4th EucheMs chemistry congress

s587 

chem. Listy 106, s587–s1425 (2012) 

CoNtENts 

list of CoNtENts 

A b s t r A c t b O O K 

4 th EucheMs chemistry congress 


AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc 

Plenary lectures s588 

Parallel sessions 

Analytical chemistry Electrochemistry, Analysis, Sample manipulation s593 

Education and History, Professional chemists Ethics, Employability, Labels s619 

Environment and Green Chemistry s635 

European Young Chemists’ Network s667 

Food Chemistry Food/Agriculture/Agrochemistry /Nanotechnology, food and processing s671 

Inorganic Chemistry plus Young inorganic chemistry day s678 

Life Sciences s703 

Nanochemistry/Nanotechnology/Molecular machines, Carbon tubes, sheets, balls s729 

Organic Chemistry, Polymers – I s754 

Organic Chemistry, Polymers – II s780 

Physical, Theoretical and Computational Chemistry s807 

Solid State Chemistry Materials chemistry /New materials s832 

Special Symposium: Jam Session plus Young National Winners in Bio-Organic Chemistry s853 

Poster session I s859 

Poster session II s1109 

List of Authors s1368 

List of Keywords s1402 

AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc

Sunday, 26-Aug 2012 | Monday, 27-Aug 2012 

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chem. Listy 106, s587–s1425 (2012) 

Plenary lectures 

Plenary lecture i 

P L - 0 1 

PerSPeCtiveS in CheMiStry: froM 

SuPrAMoLeCuLAr CheMiStry towArdS 

AdAPtive CheMiStry 

J. M. Lehn 1 

1 University of Strasbourg, ISIS, Strasbourg, France 

Supramolecular chemistry is actively exploring systems 

undergoing self-organization, i.e. systems capable of spontaneously 

generating well-defined functional supramolecular architectures 

by self-assembly from their components, on the basis of the 

molecular information stored in the covalent framework of the 

components and read out at the supramolecular level through 

specific non-covalent interactional algorithms, thus behaving as 

programmed chemical systems. 

Supramolecular chemistry is intrinsically a dynamic 

chemistry in view of the lability of the interactions connecting the 

molecular components of a supramolecular entity and the 

resulting ability of supramolecular species to exchange their 

components. The same holds for molecular chemistry when the 

molecular entity contains covalent bonds that may form and break 

reversibility, so as to allow a continuous change in constitution 

by reorganization and exchange of building blocks. These features 

define a Constitutional Dynamic Chemistry (CDC) covering both 

the molecular and supramolecular levels. 

CDC introduces a paradigm shift with respect to 

constitutionally static chemistry. The latter relies on design for the 

generation of a target entity, whereas CDC takes advantage of 

dynamic diversity to allow variation and selection. Whereas 

self-organization by design strives to achieve full control over the 

output molecular or supramolecular entity by explicit 

programming, self-organization with selection operates on 

dynamic constitutional diversity in response to either internal or 

external factors to achieveadaptation. 

In the process of reaching higher levels of self-organisation, 

CDC gives access to the generation of networks of dynamically 

interconverting constituents connected either structurally 

(molecular and supramolecular arrays) or reactionnally (set of 

connected reactions) or both. They define a class of constitutional 

dynamic networks (CDNs), presenting agonistic and antagonistic 

relationships between their constituents, that may couple to 

thermodynamic or kinetic processes and respond to perturbations 

by physical stimuli or to chemical effectors. 

These concepts and their implementation in biological 

systems as well as in materials science will be described. 

The merging of the features: 

– information and programmability, 

– dynamics and structural diversity, 

– constitution and selection, points to the emergence of 

adaptive and evolutive chemistry, towards systems of increasing 

complexity. 

references: 

1. Lehn, J.-M., Supramolecular Chemistry: Concepts and 

Perspectives, VCH Weinheim, 1995. 

2. Lehn, J.-M., Toward complex matter: Supramolecular 

chemistry and self-organization, Proc. Natl. Acad. Sci. 

USA, 2002, 99, 4763. 

3. Lehn, J.-M., From supramolecular chemistry towards 

constitutional dynamic chemistry and adaptive chemistry, 

Chem. Soc. Rev., 2007, 36, 151. 

Plenary lecture ii 


P L - 0 2 

CAtALySiS At SurfACeS: froM AtoMS to 

CoMPLexity 

G. ertL 1 

1 Fritz-Haber-Institut der Max-Planck-Gesellschaft, Physcal 

Chemistry, Berlin, Germany 

Catalysis by solid surfaces is, among others, the basis of 

chemical industry (such as the Haber-Bosch process for ammonia 

synthesis from the elements), as well as of importance for 

environmental chemistry (e.g. car exhaust catalyst). Surface 

physical techniques enable with single crystals as model systems 

elucidation of the underlying elementary processes on atomic 

scale. In special cases the rate under continuous flow conditions 

may become oscillatory or even chaotic, and the adsorbed species 

may form spatio-temporal concentration patterns on mesoscopic 

scale. These complex phenomena are manifestations of the 

underlying nonlinear dynamics and may be considered as models 

for self-organisation in various areas. 


Monday, 27-Aug 2012 | tuesday, 28-Aug 2012 

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Plenary lecture iii 

P L - 0 3 

direCted evoLution of StereoSeLeCtive 

MonooxyGenASeS AS CAtALyStS in orGAniC 

CheMiStry 

M. t. reetz 1 

1 Philipps-University Marburg, Department of Chemistry, 

Marburg, Germany 

Enzymes have been used as catalysts by organic chemists 

for a long time, but this approach to catalysis has suffred from 

traditional limitations which include the often observed poor 

stereoselectivity, limited substrate scope and/or insufficient 

stability. Directed evolution is a protein engineering technique 

which provides a means to address and solve these problems. It 

involves repeated cycles of gene mutagenesis, expression and 

screening (or selection), thereby exerting evolutionary pressure 

on the system. Ever since the first report of directed evlution of 

enhanced enantioselectivity of a lipase as the catalyst in the 

hydrolytic kinetic resolution of a racemic ester, which we 

published 15 years ago (Angew. Chem.Int. Ed. Engl. 1997, 36, 

2830–2832), this approach to generating catalysts for asymmetric 

transformation has been generalized as shown by numerous 

contributions from us and many other groups. Since the bottleneck 

of directed evolution is the screening of libraries, we have also 

focused on the development of more efficient ways to probe 

protein sequence space in the quest to generate mutant libraries 

of higher quality having an enhanced frequency of hits. 

Accordingly, Iterative Saturation Mutagenesis (ISM) has emerged 

as a powerful method in directed evolution, especially in the 

embodiment of Combinatorial Active-Site Saturation Test 

(CAST). 

The lecture will focus on the use of ISM/CAST in the 

creation of stereoselective mutants of two types of 

monooxygenases: 1) Baeyer-Villiger monooxygenases as 

catalysts in enantio- and diastereoselective Baeyer-Villiger 

reactions, and 2) P450 enzymes as catalysts in regio- and 

stereoselective CH-activating oxidative hydroxylation of steroids 

and other types of compounds. None of the selective 

transformations presented can be achieved by synthetic transition 

metal catalysts or organocatalysts, which underscores the 

complementarity of the different approaches to asymmetric 

catalysis. 

references: 

Recent review of directed evolution of stereoselective 

enzymes in organic chemistry and biotechnology: 

M. T. Reetz, Angew. Chem. Int. Ed. 2011, 50, 138-174. 

Keywords: asymmetric catalysis; enzymes; oxidation; 

Plenary lecture iV 


P L - 0 4 

SiMuLAtion And ControL of PhotoCheMiStry 

v. BonACiC-KouteCKy 1 

1 Department of Chemistry, Humboldt-University Berlin, Berlin, 

Germany 

Fundamental photochemical processes such as internal 

conversion, isomerization, electron or proton transfer involve 

nonadiabatic dynamics which couple the nuclear and electronic 

motion. Development of efficient methods for the simulation of 

these processes and for determination of ultrafast spectroscopic 

observables in complex systems involving also their environment 

will be presented. [1] This will be illustrated by comparison of 

simulated and measured time-resolved photoelectron spectra of 

furan, allowing to unravel its underlying photodynamics. [2] The 

extension to the condensed phase will show how water influences 

the photodynamics of indole. [3] 

Furthermore, we present control of photodynamics by 

including and tailoring laser fields within the recently developed 

semiclassical field-induced surface hopping (FISH) method, [4] thus 

allowing to enhance or suppress a chosen photochemical process. 

In this approach we combine quantum electronic state population 

dynamics with classical nuclear dynamics carried out “on the fly” 

without precalculation of potential energy surfaces. Our theoretical 

approach allows us to explore the controllability of photochemistry 

in complex systems and to unravel the mechanisms underlying the 

control of molecular processes. We illustrate the scope of the 

method by steering the cis-trans isomerization in prototype Schiff 

base molecular switches by shaped laser fields. Control of dynamics 

in the condensed phase by FISH method will be presented using 

designed laser fields that are capable to invoke fluorescence in the 

DNA base adenine. [5] We also show that our FISH method can be 

used to reveal fundamental dynamical processes responsible for 

optimal dynamic discrimination of the two molecular species flavin 

mononucleotide (FMN) and riboflavin (RBF), which exhibit almost 

identical spectroscopical features. [6] The selective identification of 

target molecules in the presence of structurally and 

spectroscopically similar background using optimally shaped laser 

fields opens prospects for new applications in multiple areas of 

science and engineering. As outlook, the application of optimal 

discrimination for label-free bioassays that take advantage of the 

twofold role of metallic nanoclusters for nanostructuring of ordered 

arrays and enhancement of absorption and fluorescence in proteins 

will be presented. 

references: 

1. R. Mitric, J. Petersen, V. Bonacic-Koutecký, “Multistate 

Nondadiabatic Dynamics on the fly in Complex Systems and 

its Control by Laser Fields”, in Conical Intersections: Theory, 

Computation and Experiment, Springer Verlag, 2011. 

2. T. Fuji, Y. Suzuki, T. Horio, T. Suzuki, R. Mitric, U. 

Werner, V. Bonacic-Koutecký, J. Chem. Phys. 133, 

234303 (2010) 

3. M. Wohlgemuth, R. Mitric, V. Bonacic-Koutecký, 

J. Chem. Phys. 135, 054105 (2011). 

4. R. Mitric, J. Petersen. V. Bonacic-Koutecký, Phys. Rev. A, 

79, 053416 (2009). 

5. J. Petersen, M. Wohlgemuth, B. Sellner, V. Bonacic- 

Koutecký, H. Lischka, R. Mitric, Phys. Chem. Chem. 

Phys. 14, 4687 (2012). 

6. J. Petersen, R. Mitric, V. Bonacic-Koutecký, J. P. Wolf. J. 

Roslund, H. Rabitz, Phys. Rev. Lett., 105, 073003 (2010). 


tuesday, 28-Aug 2012 | wednesday, 29-Aug 2012 

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Plenary lecture V 

P L - 0 5 

nMr SPeCtroSCoPy – A CheMiSt’S tooL for 

StudieS of the Protein univerSe 

K. wuthriCh 1 

1 The Scripps Research Institute, Molecular Biology, La Jolla, 

USA 

My research group uses nuclear magnetic resonance (NMR) 

spectroscopy for studies of proteins and protein complexes. In 

classical “structural biology”, protein structure determination was 

primarily focused on systems of well-known biological or 

biomedical interest, with examples from my laboratory in the 

areas of oxygen transport, immune suppression, differentiation in 

higher organisms and neurodegenerative diseases such as 

transmissible spongiform encephalopathies. With the availability 

of the complete genomic DNA sequences of a wide range of 

organisms, “structural genomics” provides new opportunities by 

focusing on gene products with unknown functions and minimal 

structural similarity to previously studied proteins. A precisely 

formulated initial goal of structural genomics was to determine 

representative structures for all protein families and thus cover a 

large part of the protein universe with three-dimensional 

structures. In both structural biology and structural genomics the 

NMR method is complementary to X-ray crystallography by the 

fact that atomic resolution structures and other function-related 

data can be obtained under solution conditions close to the 

physiological milieu in body fluids. NMR thus has an exciting 

role in the longer-term challenge leading from the expanding 

protein structure universe to new insights into protein functions 

and chemical biology. 

Keywords: Proteins; NMR; Structural Biology; Structural 

Genomics; 

Plenary lecture Vi 


P L - 0 6 

BreedinG And BuiLdinG MoLeCuLeS to iMAGe 

CeLLS, eLeCtriC fieLdS, And diSeASe 

ProCeSSeS 

r. y. tSien 1 

1 Univ. California San Diego, Howard Hughes Medical Institute, 

La Jolla, USA 

Molecules to observe and manipulate biological systems and 

disease processes can be devised by a variety of strategies, ranging 

from pure chemical design and total synthesis to genome mining 

and high-throughput directed evolution. Examples will be chosen 

from my own experience, including fluorescent protein-based 

indicators, molecular voltmeters and photosensors, and peptides 

that light up tumors and nerves by fluorescence and magnetic 

resonance imaging. Synthetic nanoparticles that highlight diseased 

tissue by magnetic resonance imaging are valuable for 

noninvasive early detection of cancer, while analogous fluorescent 

probes can improve the accuracy of surgery. Successful molecules 

engage multidisciplinary and sculptural creativity, provide 

colorful images and movies, reveal new biological insights, and 

may eventually help diagnose and treat important diseases such 

as cancer and atherosclerosis. 

Keywords: Fluorescent Probes; Protein engineering; Electron 

transfer; Nanoparticles; Cancer; 


wednesday, 29-Aug 2012 | thursday, 30-Aug 2012 

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Plenary lecture Vii 

P L - 0 7 

CheMiStry with MethAne: ConCePtS rAther 

thAn reCiPeS 

h. SChwArz 1 

1 Technical University Berlin, Institute of Chemistry Sekr. C 4, 

Berlin, Germany 

Four seemingly simple transformations related to the 

chemistry of methane will be addressed from mechanistic 

and conceptual points of view, i.e.: 1) metal-mediated 

dehydrogenation to form metal carbene complexes, 2) the 

hydrogen-atom abstraction step in the oxidative dimerization 

of methane, 3) the mechanisms of the CH ? CH OH conversion, 

4 3 

and 4) the initial bond scission as well as the rate-limiting step in 

the selective CH OH ? CH O oxidation. State-of-the-art gas-phase 

3 2 

experiments, in conjunction with electronic-structure calculations, 

permit to identify the elementary reactions at a molecular level 

and thus to unravel detailed mechanistic aspects. Where 

appropriate, these results are compared with findings obtained 

from related, more conventional studies in solution or on surfaces. 

Three aspects deserve special mentioning: 1) the prominent role 

of relativistic effects exerted by 5d elements, 2) two-state 

reactivity as a (new) reaction paradigm, and 3) unparalleled 

cluster-size and ligand effects on reactivity, all of which matter in 

the organometallic chemistry with methane at ambient conditions. 

Keywords: Alkanes; Cations; C-H activation; Computational 

chemistry; Density functional calculations; 

Plenary lecture Viii 


P L - 0 8 

diSCovery of MetAL-CAtALyzed reACtionS 

for SuStAinABLe CheMiStry 

d. MiLStein 1 

1 Department of Organic Chemistry, The Weizmann Institute of 

Science, Rehovot 76100, Israel 

The design of ”green” synthetic methodology and new 

approaches to sustainable energy are major goals of modern 

catalysis. We have developed a new approach to bond activation 

by metal complexes, involving metal-ligand cooperation 

of pincer-type complexes, and have discovered several 

environmentally benign catalytic reactions, including 

(a) ruthenium-catalyzed dehydrogenative coupling of alcohols to 

form esters and H (b) hydrogenation of esters to alcohols under 

2 

mild conditions (c) coupling of amines with alcohols to form 

amides with liberation of H2 (d) selective synthesis of primary 

amines directly from alcohols and ammonia (e) direct formation 

of acetals by dehydrogenative coupling of alcohols (f) generation 

of imines and hydrogen from coupling of alcohols with amines 

(g) dehydrogenative amidation of esters (h) dehydrogenative 

acylation of alcohols with esters (i) hydrogenation of amides to 

amines and alcohols (j) mild iron-catalyzed hydrogenation of 

ketones to acohols (k) iron catalyzed CO hydrogenation to 

2 

formate salts (l) hydrogenation of CO -derived organic 

2 

carbonates, carbamates, ureas and formates as alternative routes 

for the conversion of CO to methanol. These reactions are 

2 

efficient, proceed under neutral conditions and produce no waste. 

They are catalyzed by pincer-type complexes and mechanistically 

involve aromatization – dearomatization of the hetero-aromatic 

ligand core. Metal-ligand cooperation of this type has led also to 

a distinct approach towards water splitting, based on consecutive 

thermal H2 generation and light-induced O liberation, using no 

2 

sacrificial oxidants or reductants, and involving an unprcedented 

O-O bond-forming step. 


thursday, 30-Aug 2012 

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Plenary lecture iX 

P L - 0 9 

deSiGn And APPLiCAtionS of SeLeCtive 

reACtionS of oLefinS 

r. h. GruBBS 1 

1 California Institute of Technology, Department of Chemistry 

and Chemical Engineering, Pasadena, USA 

Olefin metathesis catalysts have become one of the tools for 

the efficient synthesis of complex molecules. Until recently, the 

catalysts demonstrated poor catalyst controlled selectivity. Over 

the past couple of years, complexes based on molybdenum, 

tungsten and ruthenium have been discovered that will produce 

olefins good to excellent selectivity for the generation of Z olefins 

both in cross and ring closing metathesis. New ligands have been 

developed that result in different selectivities and open new 

applications of metathesis in the synthesis of an array of complex 

molecules. 

Keywords: olefin; metathesis; catalysts; ruthenium; 



Monday, 27-Aug 2012 

s593 

chem. Listy 106, s587–s1425 (2012) 

Analytical chemistry Electrochemistry, Analysis, sample manipulation 

Elektroanalytical methods - i 

o - 0 0 1 

ArrAyS for GAS PotentioMetry And 

AMPeroMetry 

J. JAnAtA 1 , A. JonKe 1 , M. JoSowiCz 1 

1 Georgia Institute of Technology, School of Chemistry and 

Biochemistry, Atlanta GA 30332-0400, USA 

Selectivity of gas sensors based on chemical modulation of 

work function depends on the affinity of the gas or vapor for the 

sensing material. In potentiometric sensors using organic 

semiconductors, it can be affected by the choice of the polymer 

and by the type and level of the doping. Incorporation of specific 

binding sites is another possibility, which proved to be successful 

in materials based on organic semiconductor/metal composites. 

The prime example of such sensing layer is composite of 

polyaniline and Pd for selective sensing of hydrogen in the 

presence of ammonia. [1] Rapid response and broad dynamic range 

has been obtained. Selectivity to ammonia can be tuned by the 

presence of ionic liquid in the polyaniline-ionic liquid gel. [2] 

Selectivity coefficient can be evaluated from the quantitative 

relationship linking partial pressure of gas and work function of 

the sensing material. [3] 

On the other hand the selectivity of amperometric sensors 

is kinetic. It depends on catalytic activity of the selective layer to 

facilitate electron transfer between the species of interest, in 

preference to other species. We have been able to synthesize 

atomic metal/polyaniline composites in which the number of 

metal atoms determines the electrode kinetics. [4] The composition 

of our selective layers is PANI*Au Pd where stoichiometric 

m n 

factors n and m are in the range 0–8. The atomic metals and alloys 

follow theoretically predicted variation of the HOMO-LUMO 

energy gap. This control over synthesis of electroactive electrode 

materials offers unprecedented possibility for design of selective 

amperometric gas sensors. 

references: 

1. K. Domansky, et al., Anal. Chem. 70 (1998) 473-481 

2. A.Saheb, et al., Anal.Chem., 80 (2008) 4214-4219 

3. J. Janata, Coll.Czechoslov.Chem.Commun. 74 (2009) 

1623–1634 

4. A. P. Jonke, et al., J. Electrochem.Soc.159 (2012) P40-P43 

Keywords: gas sensors; potentiometric selectivity; atomic 

metals; atomic alloys; 



o - 0 0 2 

CArBon nAnoMAteriAL-BASed 

eLeCtroCheMiCAL SenSorS in MiCrofLuidiC 

totAL AnALySiS SySteMS 

G. o’neiL 1 , S. KounAveS 1 , K. MCeLhoney 1 , 

n. ChAniotAKiS 2 , M. Lee 3 , A. AuBrey 3 

1 Tufts University, Department of Chemistry, Medford, USA 

2 University of Creete, Department of Chemistry, Iraklion 

Creete, Greecea 

3 NASA Jet Propulsion Laboratory, Microdevices Laboratory, 

Pasadena, USA 

Carbon nanomaterials have become a much-discussed topic 

in chemical research after the discoveries of the remarkable 

properties of monolayer graphene, nanotubes and fullerenes. 

These nanostructures are robust, extremely conductive, and have 

unique electrochemical properties. These materials and others 

have recently been employed in chemical sensors, biosensors and 

reference electrodes with great success. 

The wet chemistry laboratory onboard NASA’s 2007 

Phoenix mission performed the first wet chemical analysis of 

Martian soil using an array of electrochemical sensors. Currently, 

we are developing a microfluidic total analysis system, which is 

capable of delivering small volumes of calibration solutions, 

reagents and sample to miniaturized ion-selective electrodes for 

analysis. Until recently, the major obstacle in the development of 

this effort has been the successful miniaturization of ISEs. 

Miniaturization of ISEs is limited due to the high resistance of 

ion-selective electrodes smaller than ~0.5 mm causing large 

amounts of noise in the measurement. Traditionally, lipophilic 

salts have been used to decrease membrane resistance in ionselective 

membranes, however these compounds are unstable in 

some instances and drastically affect sensor lifetime. It was 

recently shown that carbon nanofibers and graphene are 

effectively able to reduce the resistance of a polymer membrane. 

Here we present the use of nanostructured carbon materials 

in ion-selective electrodes and microelectrodes for sensitive and 

selective sensing of geologically relevant inorganic species. The 

results discussed will focus on using these carbon materials, 

capitalizing on their unique properties. Emphasis will be placed 

on their chemistry and behavior within ion-selective membranes 

fabricated with these materials. With this work we will show that 

nanomaterials may provide a solution for robust microelectrode 

development that can be successfully deployed in extraterrestrial 

and other harsh environments, providing the scientific community 

with high accuracy analytical data and insights into the existence 

of possible life in these environments. 

Keywords: Electrochemistry; Nanostructures; Graphene; 

Nanotubes; 



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o - 0 0 3 

A deSALinAtion BAttery 

M. PAStA 1 , y. Cui 1 , f. LA MAntiA 2 

1 Stanford University, Materials Science and Engineering, 

Stanford, USA 

2 Ruhr-Universität Bochum, Zentrum für Elektrochemie, 

Bochum, Germany 

Water desalination is an important approach to provide fresh 

water around the world, although its high energy consumption, 

and thus, high cost call for new, efficient technologies. Here we 

demonstrate a novel concept of a “desalination battery” [1] , which 

operates by performing cycles in reverse on our previously 

reported “mixing entropy battery” [2] . It exploits an electrical 

energy input to extract sodium and chloride ions from seawater, 

generating fresh water. It consists of a cationic sodium insertion 

electrode made of Na Mn O nanorods and a chloride-capturing 

2-x 5 10 

Ag/AgCl anionic electrode. 

A four-step charge/discharge process allows these electrodes 

to separate seawater into fresh water and brine streams. In the first 

step, the fully charged electrodes are immersed in seawater. A 

constant current is then applied in order to remove the ions from 

the solution. In the second step, the fresh water solution in the cell 

is extracted and then replaced with additional seawater. The 

electrodes are then recharged in this solution, releasing ions and 

creating brine (third step). In the final, fourth step, the brine 

solution is replaced with new seawater, and the desalination 

battery is ready for the next cycle. Fresh water is produced during 

Steps 1-2, while Steps 3-4 result in the production of a brine 

stream. 

The circular integral of the potential profile of a desalination 

battery as a function of charge state is equal to the net amount of 

electrical energy needed to drive the desalination. We 

demonstrated an energy consumption of 0.29 Wh l-1 for the 

removal of 25% salt, which is promising when compared to 

reverse osmosis (~0.2 Wh l-1 ), the most efficient technique 

presently available. 

references 

1. M. Pasta, et.al., Nano Letters 12, 839 (2012) 

2. F. La Mantia and M. Pasta, et.al., Nano Letters 11, 1810 

(2011) 

Keywords: Electrochemistry; Nanotechnology; 



o - 0 0 4 

new ASyMMetriC SuPerCAPACitor BASed on 

hiGh SurfACe AreA PorouS Mno And 2 

ACtivAted CArBon in ProtiC ioniC LiquidS 

C. A. CAStro ruiz 1 , d. roChefort 1 , d. BéLAnGer 2 

1 Université de Montréal, Chemistry, Montréal (Québec), 

Canada 

2 Université du Québec, Montréal, Chemistry, Montréal 

(Québec), Canada 

Pseudocapacitors are devices that store charges via faradic 

redox reactions taking place, at least to some extent, in the bulk 

of the electrode material. MnO due to its low cost and good 

2 

electrochemical performance is considered one of the most 

promising materials in many technological applications. 

Protons and/or cations are involved in the faradic reactions 

leading to pseudocapacitance and many studies on metal 

oxide-based supercapacitors (SCs) have been limited to aqueous 

solutions. Considering that the energy density (E) of a SC is 

proportional to the specific capacitance (Cs) and the voltage (V) 

[E=CsV2 /2], one strategy to enhance the cell voltage in terms of 

the energy density is to replace the aqueous electrolyte with protic 

ionic liquids (PIL) to take advantage of their intrinsic ionic 

conductivity and large electrochemical window of stability. Here, 

two PIL obtained by a mixture of a base like 2-methyl or 

2-methoxy-pyridine and an acid (TFA) were shown to sustain 

pseudocapacitance in MnO . Even if these PIL afford to obtain 

2 

good Cs values, the narrow potential window of these PIL 

(between 0.8 and 0.6V) limits the SC to reach high energy 

densities (E) values. 

Another strategy, to overcome this problem is to increase 

the cell voltage by using an asymmetric configuration that 

combines two kinds of electrode materials: one electrode (Carbon 

based) stores charge by a reversible non faradic reaction and the 

other one utilizes a reversible faradic reaction in a transition metal 

oxide (MnO ). In this contribution, we will report on the 

2 

electrochemical behavior of a hybrid AC/MnO SC in PIL 

2 

electrolytes. Further information about synthesis, characterization 

by SEM, XRD, CV and performance upon charge/discharge 

cycling will be reported. 



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Electroanalytical methods - ii 

o - 0 0 5 

MAteriALS StrAteGieS for eLeCtroAnALytiCAL 

SenSorS And BioSenSorS 

C. M. A. Brett 1 

1 University of Coimbra, Department of Chemistry, Coimbra, 

Portugal 

The development of efficient and reliable electroanalytical 

sensors and biosensors, with fast response, depends primarily on 

the materials used for their construction. Appropriate materials 

can confer enhanced selectivity and stability whilst, at the same 

time, increasing electrocatalytic effects for the desired species 

which can contribute to reducing interference problems. 

Nanostructured materials are essential for this purpose and can 

include metals, different forms of carbon, redox and conducting 

polymers. Their use can enhance performance and the reduction 

of response times by improving diffusion or reducing diffusion 

lengths Sensors and biosensors will be illustrated, prepared using 

such approaches and which are useful in the clinical, food and 

environmental areas. 

Recent research has included using metal hexacyanoferrates 

and polyazine layers as electrode modifier materials and for redox 

mediators in biosensors. [1] The incorporation of carbon nanotubes 

in these assemblies has been investigated, also including 

nitrogen-doped carbon nanotubes. Electrocatalytic and synergistic 

effects are found, for example in the detection of hydrogen 

peroxide for oxidase-based biosensors. [2] The immobilization of 

functionalized carbon nanotubes by reticulation and covalent 

bonding in chitosan or dihexadecylphosphate film matrices has 

been studied, [3] giving evidence for unmediated electron transfer 

in biosensors. Stability is enhanced, sensitivities are higher, with 

comparable or lower detection limits and linear ranges. 

A layer-by-layer approach using self-assembly to create 

multilayer modified electrodes for biosensors will also be 

described, particularly concerning the hyaluronic acid/myoglobin 

system and the minimum number of bilayers necessary to achieve 

efficient sensor/biosensor operation. [4] 

references: 

1. R. Pauliukaite, M.E. Ghica, M.M. Barsan, C.M.A. Brett, 

Anal. Lett. 43 (2010) 1588. 

2. R.C. Pena, M. Bertotti, C.M.A. Brett, Electroanalysis 23 

(2011) 2290. 

3. B.C. Janegitz, R. Pauliukaite, M.E. Ghica, C.M.A. Brett, 

O. Fatibello-Filho, Sens. Actuat. B 158 (2011) 411. 

4. M.M. Barsan, E.M. Pinto, C.M.A. Brett, Phys. Chem. 

Chem. Phys. 13 (2011) 5462. 

Keywords: Electrochemistry; Sensors; Biosensors; 

Voltammetry; Materials science; 



o - 0 0 6 

An oriGinAL Method to ProduCe JAnuS 

MiCro- And nAnoPArtiCLeS in the BuLK PhASe 

d. ziGAh 1 , C. KuMSAPAyA 1 , G. LoGet 1 , 

L. Bouffier 1 , C. wArAKuLwit 2 , J. LiMtrAKuL 2 , 

A. Kuhn 1 

1 ISM - Institut des Sciences Moléculaires-UMR 5255 CNRS, 

University of Bordeaux, Talence, France 

2 Center of Nanotechnology and Chemistry Department, 

Kasetsart University, Bangkok, Thailand 

Janus particles are asymmetric particles. This type of 

particles has a lot of applications in different areas from molecular 

electronics, to targeted drug delivery. In order to break the 

symmetry and produce Janus particles, most of the technics are 

based on using interfaces. Just a few bulk procedures are known 

to produce these particles. We propose an original method to 

obtain Janus particles in bulk phase, based on bipolar 

electrochemistry. Bipolar electrochemistry is a technique which 

allows to perform electrochemistry at a conductive objet exposed 

in solution to an electric field. The electric field polarizes the 

object and when the potential difference is big enough, oxidation 

and reduction reactions can take place on the two opposite sides 

of the object. This technique is already used in the nanoscience 

field and to build analytical devices. In this contribution we use 

this concept to make electrodeposition. This approach allows us 

to produce a large variety of asymmetric compounds with 

characteristic features in the micro- or nanometer range. It is 

possible to modify either anisotropic or isotropic objects and to 

deposit metals, semiconductors, polymer and organic layers with 

a high spatial control. Due to its versatility and because these 

modifications are carried out in the bulk phase, this process might 

become a major technology for the production of Janus particles, 

also at an industrial scale. 

Keywords: Electrochemistry; Diazo compounds; Fluorescent 

probes; Nanoparticles; Polymerization; 



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o - 0 0 7 

nAnoteChnoLoGy And MuLtiAnALyte 

PLAtforM fLow SySteMS 

J. K. f. vAn StAden 1 , r. i. vAn StAden 1 

1 INCDEMC Timisoara Timus Romania, PATLABProcess 

Analytical Technology Laboratory, Bucharest, Romania 

Email: koosvanstaden@yahoo.com www.patlab.ro, 

Sustainable development forms a key objective of the 

European Union with primary concern about natural resources 

(waste water management, water quality and quantity), food 

processing and distribution, health issues, climate change, clean 

energy as some key issues. This can be seen from the large 

number of research consortiums with current projects from the 

European Commission where Nanotechnology is one of the main 

areas with a budget reaching into millions of Euros. As a result 

microsystems technology with PAT, MPAT and NPAT become 

increasingly important in various operations in real-time and new 

innovations linking the different PAT systems successfully to 

microsystems technology may create fruitful solutions to the 

problems above. It will be shown how the establishment of 

PATLAB in Bucharest, Romania served as a catalyst for PAT, 

MPAT and NPAT. Different scenarios regarding the innovation, 

development, implementation and application of flow-based 

systems will be outlined. This will be compared with 

non-flow-based systems. Careful attention will be given to the 

reality of microfluidics as marketable applications with flowbased 

PAT, MPAT and NPAT, the incorporations of micro- or/and 

nanosensors as detection devices and if real-time is always 

possible. It will be discussed if there is any improvement in the 

configuration and construction of downscaled chemically devices 

and if the movement to remote sensing with innovation of 

high performance real-time intelligent interactive multi-point 

multi-species process analytical technological microsystems show 

that a marriage between these devices are possible. The reality of 

the current situation with possible future solutions will be 

highlighted and outlined. 

Acknowledgements: The authors would like to acknowledge 

the financial support received from the project Program Ideas 

PN-II-ID-PCE-2011-3-0538/2012-2014, financed by contract 

100/27-10-2011. 

Keywords: nanotechnology; multianalyte; microsystems; flow 

systems; 

Electroanalytical methods - iii 


o - 0 0 8 

eLeCtroCheMiStry CouPLed to 

eLeCtroSPrAy MASS SPeCtroMetry 

L. nyhoLM 1 

1 Uppsala University, Department of Chemistry - The Angström 

laboratory, Uppsala, Sweden 

The on-line coupling of electrochemistry (EC) to 

electrospray mass spectrometry (ESI-MS) provides a very 

powerful tool for studies of electroactive compounds and 

electrochemical reactions. With EC/ESI-MS it is possible to 

identify and quantitate electrochemically produced oxidation and 

reduction products1,2 . It is also possible to utilise electrochemical 

reactions for preconcentration and/or ionisation of selected 

analytes, as well as for tagging purposes3 . The coupling of 

electrochemical cells to ESI-MS, however, requires decoupling 

of the electrochemical cell from the ESI-MS high voltage, and is 

also complicated by the fact that the electrospray process itself 

involves electrochemical reactions. Care also needs to be taken 

to ensure that the electrochemically generated products do not 

undergo unwanted redox reactions between the electrochemical 

cell and the mass spectrometer4 and to reduce the transfer time 

between the electrochemical cell and the mass spectrometer5 . 

In the present communication, the advantages and 

limitations of combining electrochemistry and ESI-MS technique 

will be discussed based on selected applications. It will be 

demonstrated that the choice of electrolyte as well as the design 

of the electrochemical cell and the flow system, can affect the 

obtained mass spectra and the possibilities to detect 

electrochemically generated species. 

references: 

1. J. Gun, S. Bharathi, V. Gutkin, D. Rizkov, A. Voloshenko, 

R. Shelkov, S. Sladkevich, N. Kyi, M. Rona, Y. Wolanov, 

D. Rizkov, M. Koch, S. Mizrathi, P. V. Pridkhochenko, 

A. Modestov, O. Lev, Isr. J. Chem., 50 (2010) 360. 

2. C. Zettersten, Ph. D. Thesis, Uppsala University, 2009. 

3. T. C. Rohner, J. S. Rossier and H. H. Girault, Electrochem. 

Commun., 4 (2002) 695. 

4. F. C. Bökman, C. Zettersten, P. J. R. Sjöberg and 

L. Nyholm, Anal. Chem., 76 (2004) 2017. 

5. G. Liljegren, A. Dahlin, C. Zettersten, J. Bergquist and 

L. Nyholm, Lab Chip, 5 (2005) 1008. 

Keywords: Electrochemistry; mass spectrometry; Analytical 

Methods; Oxidation; Redox chemistry; 



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o - 0 0 9 

PoSSiBiLitieS And LiMitAionS of AMALGAM 

eLeCtrodeS 

J. BAreK 1 , J. fiSCher 1 , K. PeCKovA 1 , v. vySKoCiL 1 

1 Charles University in Prague Faculty of Science, Department 

of Analytical Chemistry, Prague 2, Czech Republic 

For the determination of electrochemically reducible organic 

substances, mercury is undoubtedly the best available electrode 

material. [1] However, mercury has some disadvantages (toxicity, 

low mechanical robustness, etc.) so that there is a constant search 

for other suitable electrode materials. Probably the most 

promising alternative are non-toxic and mechanically robust silver 

solid amalgam electrodes suitable both for voltammetry and for 

amperometry in flowing liquids. [2] The newly developed single 

crystal silver amalgam electrode [3] and other types of solid or 

paste amalgam electrodes can be very useful in this filed as well. 

Practical applications of voltammetric and amperometric 

determination of micromolar and submicromolar concentrations 

various types of organic substances (environmental polutants, 

chemical carcinogens, drugs and their metabolites, explosives, 

etc.) will be demonstrated together with construction of these 

novel electrodes and detectors based on various forms of silver 

amalgams. 

Acknowledgments: Financial support of this research by the 

Ministry of Education, Youth and Sports of the Czech Republic 

(Projects MSM 0021620857), by the Grant Agency of the 

Czech Republic (project PG 206/12/G151) and by Charles 

University (projectSVV 265201) is gratefully acknowledged. 

references: 

1. J. Barek, V. Vyskocil, Curr. Org. Chem.15 (2011) 3059. 

2. B. Yosypchuk, J. Barek, Crit. Rev. Anal. Chem. 39 (2009) 

189. 

3. J. Tvrdikova, A. Danhel, J. Barek, V. Vyskocil, 

Electrochimica Acta, in press. 

Keywords: Electrochemistry; Amalgams; Voltammetry; 



o - 0 1 0 

voLtAMMetry of AntioxidAntS in SurfACtAnt 

MediA And itS AnALytiCAL APPLiCAtion 

G. ziyAtdinovA 1 , e. ziGAnShinA 1 , h. BudniKov 1 

1 Kazan (Volga Region) Federal University, Department of 

Analytical Chemistry, Kazan, Russia 

Surfactants are widely put into practice of analytical 

chemistry at present time. Two important properties of them 

namely adsorption at the interface and aggregation into the 

organized structures are advantageously used in electrochemistry. 

Therefore, surfactants are able to modify and control the 

properties of electrode surfaces leading to changes in reaction 

rates and pathways. From other side, surfactants provide 

solubilization of organic compounds in water media and can be 

used in electrochemical studies. 

Lipophilic antioxidants being widely distributed in foodstuff 

form important group of compounds playing key role in 

antioxidant defense system of living systems. Development of 

new methods for their determination is of interest. Lipophilic 

antioxidants are usually determined in organic media due to 

hydrophobic nature and the limited solubility of analyte in other 

solvents. Surfactant media can be used as less hazardous and 

versatile substitute for organic solvents in electrochemical 

determinations. 

Voltammetric characteristics of retinol, β-carotene and 

eugenol have been studied in organic and water-organic media. 

All compounds under investigation are irreversibly oxidized on 

glassy carbon electrode. Effect of different types of surfactants 

and their concentration on voltammetric behavior of lipophilic 

antioxidants has been evaluated. The application of surfactant 

media leads to enlargement of linear working range for 

antioxidants determination. The decrease of low detection limits 

have been observed for all compounds under investigation. 

Simple, express and reliable voltammetric methods for the 

retinol, β-carotene and eugenol determination in vegetable oils, 

spices, fruits and vegetables have been developed using 

preliminary extraction of analytes. 

The application of surfactant media in voltammetry of 

lipophilic antioxidants allows to analyze them in water media or 

to decrease the organic solvent portion. The methods proposed is 

characterized by good reproducibility, speed and could be 

recommended for food quality control. 

Keywords: voltammetry; surfactants; antioxidants; 



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o - 0 1 1 

eLeCtroAnALytiCAL deteCtion of 

CyAnoBACteriAL hePAtotoxinS 

MiCroCyStin-Lr And noduLArin And 

their interACtion with dnA 

A. M. oLiveirA-Brett 1 , i. C. LoPeS 1 , P. v. f. SAntoS 1 , 

v. C. diCuLeSCu 1 

1 University of Coimbra, Department of Chemistry, Coimbra, 

Portugal 

Microcystin-LR (MC-LR) and nodularin (NOD) are among 

the most commonly reported cyclic heptapeptides produced by 

certain strains of freshwater cyanobacteria (blue-green algae), 

hepatotoxic for humans and animals. These hepatotoxins act 

mainly through the binding and consequent inhibition of 

serine/threonine protein phosphatases inside the liver cells. 

Beyond protein inhibition, other adverse toxicological effects 

have been reported concerning MC-LR and NOD exposure, such 

as intracellular glutathione alteration, reactive oxygen species 

production and lipid peroxidation. 

The electroanalytical behaviour of MC-LR and nodularin 

NOD at a glassy carbon electrode was investigated using cyclic, 

square-wave and differential pulse voltammetry. The oxidation of 

MC-LR and NOD is an irreversible, diffusion-controlled and 

pH-independent process that occurs with the transfer of only one 

electron. Chemical degradation of MC-LR and NOD, upon 

incubation in different pH electrolytes, was electrochemically 

detected by the appearance of a new oxidation peak at a lower 

potential, mainly in mild acid media. The MC-LR and NOD 

chemical degradation product, formed homogenously in the buffer 

solution, undergoes an irreversible pH-dependent oxidation. 

The electrochemical study showed that oxidation and 

cyanotoxins chemical degradation in aqueous media follow a 

complex redox mechanism, and their electroanalytical 

determination with a detection limit of one microgram per litre is 

foreseen, which will provide very important and useful data for 

toxicity evaluation. 

The evaluation of the dsDNA interaction with MC-LR and 

NOD was undertaken using a dsDNA-electrochemical biosensor 

immersed in MC-LR or NOD solutions during different periods 

of time. The in situ evaluation of the MC-LR and NOD interaction 

with dsDNA using a DNA-electrochemical biosensor showed that 

both MC-LR and NOD caused dsDNA structural modifications 

in a time-dependent manner, adding more data to the studies of 

genotoxicity and carcinogenic potential associated to these toxins. 

Keywords: Microcystin-LR; nodularin; electroanalysis; 

cyanobacterial hepatotoxins; DNA interaction; 



o - 0 1 2 

SiMuLtAneouS neurotrAnSMitterS AnALySiS 

uSinG MiCroeLeCtrodeS BASed on 

PorPhyrinS 

r. i. StefAn-vAn StAden 1 , i. MoLdoveAnu 1 , 

J. f. vAn StAden1 1INCDEMC Timisoara Timus Romania, Laboratory of 

Electrochemistry and PATLAB Bucharest, Bucharest, Romania 

Email: iustinavanstaden@yahoo.com 

Determination of neurotransmitters had an essential role in 

assessment of neurological diseases. Maps of brain can be drawn 

using the determination of the content of dopamine in different 

parts of brain tissue. Therefore it is very important to develop 

reliable and fast/real time methods of analysis for the 

simultaneous assay of neurotransmitters such as dopamine, 

epinephrine and norepinephrine. New amperometric 

microelectrodes were designed and used for the simultaneous 

assay of neurotransmitters. The microelectrodes used were based 

on porphyrins immobilized in diamond paste. The optimization 

of working conditions was done using cyclic voltammetry, for 

different electrolyte solutions (e.g., KCl, NaCl, KNO ) at different 

3 

pH values. Response characteristics for the proposed 

microelectrodes were determined for optimized working 

conditions using differential pulse voltammetry. The 

microelectrodes were used to determine the neurotransmitters 

from biological fluids, such as urine samples. The performances 

of the proposed microsensors were compared with the 

performance obtained using a graphite paste based 

microelectrode. 

Acknowledgments: The present work was supported by 

the European Commission through the DENAMIC project 

(Contract-No. 282957). 

Keywords: elecroanalysis; neurotransmitters; microelectrode; 


tuesday, 28-Aug 2012 

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separation methods – i 

o - 1 2 7 

MonoLithiC CoLuMnS for hPLC: uSe of 

nAnoSCienCe to tAiLor their PoroSity 

And CheMiStry 

f. SveC 1 

1 Lawrence Berkeley National Laboratory, Molecular Foundry, 

Berkeley California, USA 

The first generation of porous polymer monoliths emerged 

in the late 1980s and proved to be excellent stationary phase for 

the separation of large molecules. Their well known advantages 

include ease of the preparation, robustness, high permeability to 

flow, mass transfer via convection, and a vast variety of 

chemistries. However, these monoliths had a small surface area 

since they lacked the mesopores. This made them quite useful for 

the separation of large molecules such as synthetic polymers and 

proteins as well as particles including nanoparticles and viruses. 

Thus, achieving good column efficiency for small molecules has 

been a challenge due to irregular morphology, a lack of 

mesopores, and a small surface area typical of these monoliths. 

We have recently developed and demonstrated the second 

generation monoliths using a new two-step approach to the control 

of porous properties that includes hypercrosslinking reaction. This 

technique includes the preparation of generic monoliths followed 

by their solvation and rapid crosslinking. This process enables the 

preparation of porous polymer monoliths possessing large surface 

areas of several hundreds m2 /g. 

Traditionally, the surface chemistry of the monoliths is 

controlled via copolymerization with monomers bearing the 

desired functionality, chemical modification of preformed 

monolith, and photografting of pore surface with polymer chains 

bearing the desired functionalities. Now, we have introduced 

novel approaches involving nanochemistry. For example, we 

modify the pore surface within our monoliths with gold 

nanoparticles affording columns with a specific selectivity 

enabling separation and/or fishing out thiol-containing 

compounds. We are also developing processes for the 

immobilization of nanostructures such as multiwalled carbon 

nanotubes and functionalized C nanoparticles that afford 

60 

monolithic columns exhibiting high efficiency in the separations 

of small molecules. 

Keywords: Proteins; Polymers; 



o - 1 2 8 

SePArAtionS of “diffiCuLt” PoLAr 

CoMPoundS: AvAntAGeS And PitfALLS of 

AqueouS norMAL-PhASe And reverSed-PhASe 

Liquid ChroMAtoGrAPhy 

P. JAnderA 1 , t. háJeK 1 , J. SouKuP 1 , v. SKeríKová 1 , 

M. StAnKová 1 

1 University of Pardubice, Analytical Chemistry, Pardubice, 

Czech Republic 

Increasing demand for the analysis of polar compounds in 

complex matrices has triggered the development of “Hydrophilic 

Interaction Liquid Chromatography” (HILIC) methods. The 

HILIC mode, which is essentially Aqueous-organic 

“normal-phase” (NP) chromatography, enables separation of 

strongly polar compounds, which are too weakly retained in the 

RP mode, but too strongly retained in the organic NP systems. 

Another reason for increased HILIC popularity is that highly 

organic mobile phases are usually compatible with mass 

spectrometry coupled to liquid chromatography. Many polar 

columns with (poly)oxyethylene (PEG), hydroxy (DIOL), mixed 

oxyethylene-hydroxy (Luna HILIC) or sulfobetaine stationary 

phases bonded either on unmodified or hydrosilated silica gel 

support, show dual retention mechanism in aqueous-organic 

mobile phases. The retention mechanism can be flexibly tuned to 

suit specific separation problems by selecting suitable mobile 

phase composition and by adjusting the temperature. 

Commercial ZIC-HILIC sulfobetaine columns show 

excellent separation properties in the HILIC mode, whereas the 

RP retention range is rather limited in low-organic mobile phases. 

We prepared efficient and highly permeable (poly)methacrylate 

monolithic capillary sulfobetaine columns, showing, e.g., similar 

separation selectivity for phenolic acids and flavones as the 

ZIC-HILIC column in the NP mode, but significantly 

higher retention and improved separation selectivity in the 

reversed-phase mode. 

A single column can be used alternately in the HILIC and 

RP modes by switching the acetonitrile–acetate buffer mobile 

phase gradient program between highly aqueous (RP)mode and 

highly organic (HILIC) mode. The differences in selectivity 

between the HILIC and the RP modes can be used to improve the 

separation and the peak capacity of complex samples cpntaining 

polar compounds in two-dimensional LC-LC. The approach was 

applied to the analysis of natural antioxidants in beer, wine, tea 

and herbal extracts. 

Acknowledgement: The support of this work by the Grant 

Agency of the Czech Republic under the project P206/12/0398 

is acknowledged. 

Keywords: Liquid Chromatography; Analytical methods; 



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o - 1 2 9 

AnALySiS of voLAtiLe frACtion of thyMuS 

PAnnoniCuS And CorreLAtionS with 

inorGAniC PLAnt CoMPoSition By StAtiC 

heAdSPACe GAS ChroMAtoGrAPhy, MASS 

SPeCtroMetry And AtoMiC SPeCtroMetry 

S. rAziC 1 , J. ArSeniJeviC 2 , z. MAKSiMoviC 2 , 

J. MArKoviC 3 , i. SoStAriC 4 

1 University of Belgrade Faculty of Pharmacy, Department of 

Analytical Chemistry, Belgrade, Serbia 


Pharmacognosy, Belgrade, Serbia 

3 University of Belgrade, Vinca Institute of Nuclear Sciences, 

Belgrade, Serbia 

4 University of Belgrade Faculty of Agriculture, Department of 

Botany, Belgrade, Serbia 

Depending on specific analytical technique producing 

samples, the term “volatile fraction” could be related to analytical 

headspace, essential oil, flavor, fragrance, aroma or extract. There 

is a large and usually puzzling diversity of volatile organic 

compounds (VOCs) emitted by plants and only partly explained 

functions in biotic and abiotic media. On the other hand inorganic 

components, especialy trace elements require a different 

experimental approach in analysis. For elucidation of their role 

and learning about possible relations with specific organic 

components additional chemometrics approach will be applied. 

Inorganic plant composition explains only a small part of variation 

in essential oil composition but, is there any correlation with 

volatile compounds sampled differently? 

Fifteen plant individuals of Thymus pannonicus All. 

(Lamiaceae) were collected during flowering period in southern 

Banat (Serbia). Dry leaves were immediately after comminuting 

hermetically sealed and subjected to static headspace extraction 

(SHS), followed by GC and GC-MS analysis. After SHS-GC 

analysis, the same samples were subjected to microwave-assisted 

acid digestion. The resulting solutions were used for 

determination of several elements (Na, K, Ca, Mg, Fe, Mn, Zn, 

Cu, Cr, Mo, Co and Ni) by atomic absorption and emission 

spectroscopy (FAAS, GF-AAS and ICP-AES). 

Monoterpenes dominated in all examined headspace 

extracts, ranging 57.85–96.11%. Extracts with monoterpene 

hydrocarbons as principal compounds contained limonene, 

myrcene, α-pinene, E-β-ocimene and camphene in amounts up to 

42.99 %, 39.54 %, 35.58%, 23.56% and 15.81%, respectively. In 

oxigenate monoterpenes-rich extracts geranial, neral, 1,8-cineole 

and linalool were the most abundant (23.44%, 22.10%, 

12.52% and 11.99%, respectively) and also contained non 

terpenic compounds in substantial amounts (13.15–25.20%), 

mainly 6-methyl-5-hepten-2-one (8.85 – 16.01%). Sesquiterpene 

hydrocarbons and oxygenate sesquiterpenes constituted a small 

fraction of analyzed headspace extracts, 1.53–5.20% in total. 

The obtained results are subjected to the chemometrics 

analysis (PCA and CA) in order to highlight possible 

relationships. 

Keywords: Analytical Methods; 



o - 1 3 0 

deveLoPMent of hydroPhiLiC interACtion 

Liquid ChroMAtoGrAPhy (hiLiC) StAtionAry 

PhASeS in MonoLithiC CAPiLLAry forMAtS 

A. e. funA 1 , L. BArron 1 , n. w. SMith 1 

1 King’s College London (University of London), Micro 

Separations Group, London, United Kingdom 

The interest in hydrophilic interaction liquid 

chromatography (HILIC) stationary phases largely lies on their 

potential for effective separation of small, highly polar molecules: 

a problem distinctly besetting conventional reversed-phase 

materials. Development in capillary formats could further support 

important micro-separation applications in pharmaceutical 

analysis, toxicology and proteomics, amongst others. The wide 

availability of monomers opens possibilities to tailor polymeric 

monoliths to exhibit HILIC behaviour. One of these is exploiting 

the zwitterionic nature of polymerisable betaines, e.g. N-(3- 

-Sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylammonium 

betaine (SPE). The challenge lies in maximising as much 

zwitterionic moieties available for surface interaction as well as 

achieving the most favourable morphology. This study 

investigated the separation of selected nitrogenous bases and 

nucleosides in monoliths prepared by thermally-initiated 

co-polymerisation of SPE and ethylene glycol dimethacrylate in 

fused silica capillaries of different internal diameters 

(50–200 µm). The influence of monomer concentration, 

porogenic solvent polarity and polymerisation temperature on 

selectivity was studied. Reduction in reaction time and increase 

in capillary diameter have distinctly resulted in higher efficiencies. 

HILIC behaviour was very predominant when acetonitrile 

concentration in the mobile phase was higher than 70 %. The 

effect of buffer salt concentration and pH in the mobile phase was 

also demonstrated. Further optimisations are carried out, 

ultimately towards developing applied methods for drug analysis 

using LC-MS. 

Keywords: liquid chromatography; polymers; microporous 

materials; 



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separation methods – ii 

o - 1 3 1 

new fiBerS for SPMe And LC/MSn MonitorinG 

of SeLeCted druGS And their MetABoLiteS 

B. BuSzewSKi 1 

1 Nicolaus Copernicus University F. of Chemistry, Chair of 

Environmental Chemistry & Bionanalytics, Torun, Poland 

The quantitative and qualitative determination of drugs and 

biologically active compound becomes more and more important 

in pharmacokinetic analysis and therapeutic drug monitoring. The 

most relevant matrices to be analyzed for this purpose are plasma 

or blood, due to providing a good correlation between their 

concentration and pharmacological effects. One of the major tools 

in the pharmacokinetic studies is the combination of 

high-performance liquid chromatography and mass spectrometry 

(HPLC-MS). This simple and selective method has been used for 

the determination of drugs belonging to different medicinal 

classes in human plasmaPolypyrrole (PPy) and polythiophene 

(PTh) SPME coatings and their derivatives with molecular 

template were used and their ability to extract selected drugs from 

different classes with different physico–chemical properties and 

of widely varying polarities were evaluated. SPME fibers 

are manufactured electrochemically by coupling the 

homemade electropolymerization system to a new generation 

potentiostat/galvanostat in three-electrode array. 

Physico-chemical properties, mechanical and chemical stabilities 

were characterized by scanning electron microscopy and infrared 

spectrometry. The SPME coatings were evaluated by analyzing 

clinically relevant antibiotic drugs – linezolid, daptomycin, 

amoxicillin and moxifloxacin. Important factors in the 

optimization of SPME were discussed. Finally, the 

chromatographic measurements were performed by HPLC/MS. 

The potential of polymeric SPME sorption coatings for selective 

extraction of the drugs was demonstrated considering the results 

obtained for the standard solutions and applied to human plasma 

samples. 

Developed method can be used for the quantitative analysis 

of selected biologically active compounds, and provide a potential 

application to study the metabolism and pharmacokinetics of other 

drugs from different medical classes from the biological matrices. 

The results demonstrate the potential of in vivo SPME as a useful 

sample preparation tool for chromatographic based metabolomics 

drug monitoring in the biomedical application from patients 

receiving therapeutic dosages. 

Acknowledgments: This work was supported by National 

Science Center (Cracow, Poland), no. 2011/01/N/ST4/03178. 

Keywords: fibers; spme; drug; metabolites; 



o - 1 3 2 

ChroMAtoGrAPhiC deterMinAtion of 

CArBohydrAteS in PLAntS – An overview of 

SeverAL AtteMPtS 

M. rAeSSLer 1 

1 MPI Biogeochemie, SpecLab, Jena, Germany 

Carbohydrates and sugar alcohols are important plant 

components the composition of which may markedly vary with 

season, light availability and status of plant growth. Apart from 

plant growth status, carbohydrates also reflect changes of 

photosynthetic activity and abiotic stress phenomena, such as 

hyperosmosis. In addition to plant physiology, the exact 

identification and reliable quantification of carbohydrates in plant 

material is also of growing importance for the calculation of more 

sophisticated carbon balances of numerous biogeochemical 

processes. 

Today, liquid chromatography is the most suited method for 

the accurate analysis of carbohydrates and sugar alcohols. 

Carbohydrates can be subdivided in mono- (e.g. glucose), di- (e.g. 

sucrose), oligo- (e.g. raffinose) and polysaccharides (e.g. starch, 

inulin, polyfructans). The several components can be detected by 

either pulsed amperometry (PA), refrective index (RI), evaporate 

light scattering (ELS), or mass spectrometry (MS). 

This presentation is based on both the research of our group 

[1-3] dealing with the development of analytical methods for the 

determination of carbohydrates, sugar alcohols and 

polysaccharides in several plant species, and a recent review 

article by myself [4]. 

references: 

1. M. Raessler, Proceedings of the 33rd International 

Symposium on High Performance Liquid Phase 

Separations and Related Techniques (HPLC 2008), 

Kyoto, Japan, 101. 

2. M. Raessler, B. Wissuwa, A. Breul, W. Unger, T. Grimm, 

J. Agric. Food Chem. 56 (2008) 7649. 

3. M. Raessler, B. Wissuwa, A. Breul, W. Unger, T. Grimm, 

Anal. Methods 2 (2010) 532. 

4. M. Raessler, Sample preparation & current applications 

of liquid chromatography for the deter-mination of 

non-structural carbohydrates (NSC) in plants. 

TrAC-Trends in Analytical Chemistry 30 (2011) 1833. 

Keywords: Carbohydrates; 



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o - 1 3 3 

MoLeCuLAr StruCture on the BALAnCe in 

the xxi Century – rAPid hiGh reSoLution And 

tAndeM MASS SPeCtroMetry 

y. tSyBin 1 , u. LASKAy 1 , L. forneLLi 1 , K. zhurov 1 , 

A. Kozhinov 1 

1 Ecole Polytechnique Federale de Lausanne, Biomolecular 

Mass Spectrometry Laboratory, Lausanne, Switzerland 

Understanding fundamental chemical processes requires the 

knowledge of the elemental composition, structure, quantity, and 

interaction networks of the participating molecules. The necessary 

molecular information on organic, inorganic and biological 

molecules can be deduced from the accurately measured masses 

of the molecules of interest and their fragments. Mass 

spectrometry (MS) and tandem mass spectrometry (MS/MS) are 

currently the best analytical methods for these undertakings. 

Fourier transform MS (FTMS) provides superior resolution and 

mass accuracy among the palette of the MS instruments. 

However, modern comprehensive structure analysis of molecules 

and macromolecules present in extremely complex biological and 

environmental samples and/or performed under time-constrained 

experimental conditions demands a substantial increase in the 

acquisition speed of high-resolution and high mass accuracy MS 

and MS/MS data. For this reason, absorption mode spectra 

representation has been implemented in FTMS as a part of 

enhanced FT (eFT) signal processing. On the other hand, filter 

diagonalization method (FDM) is capable of overcoming the FT 

resolution limitation. Recently, we described the first 

implementation of FDM for FTMS [1, 2] and the first application 

of electron-mediated MS/MS for structural analysis of intact 

150 kDa monoclonal antibodies. [3] Here, we will discuss the 

state-of-the-art in eFT and FDM MS method development, then 

present and compare the advantages of eFT and FDM MS for 

(i) MS/MS-based top-down structure analysis of large intact 

proteins, including the monoclonal antibodies; and (ii) MS-based 

analysis of extremely complex environmental samples, e.g., crude 

oils and biofuels, where we will show, i.e, how eFT and FDM MS 

push the upper mass limit for separation of closely, e.g., 1.1 mDa 

13 (C vs. SH C), spaced molecular peaks. 

3 3 

references: 

1. Kozhinov A. N., Tsybin Y. O. Analytical Chemistry (2012) 

84, 2850–2856 

2. Miladinovic S. M., et al. Analytical Chemistry (2012) 84, 

4042–4051 

3. Tsybin Y. O., et al. Analytical Chemistry (2011) 83, 

8919–8927 

Keywords: mass spectrometry; proteomics; antibodies; 

structure elucidation; environmental chemistry; 


life science, clinical and environmental applications 

o - 1 3 4 

enAntioSeLeCtive ChroMAtoGrAPhy, A Key 

teChnoLoGy in Life SCienCeS 

w. Lindner 1 , n. M. MAier 1 

1 University of Vienna, Departmant of Analytical Chemistry 

Faculty of Chemistry, Vienna, Austria 

To date there is a large set of diverse so-called “chiral 

columns” available from many companies which are the result of 

a long way of developments in academia and industry of 

enantioselective chromatographic materials (chiral stationary 

phases, CSPs) in order to master the challenge of resolving 

enantiomers and steroisomers in various matrices. It is an 

analytical task but also of preparative relevance as it is now state 

of the art to separate chromatographically e.g. chiral drugs up to 

a production scale of several tons per year. 

The current standard of chiral liquid chromatography stands 

on several pillars, namely (i) the steadily increasing understanding 

of molecular recognition principles and thus of chiral 

discrimination concepts, (ii) advancements of material sciences 

in producing highly efficient and robust CSPs, (iii) the 

optimization of separation process parameters in terms of speed, 

sensitivity etc. in implementing LC and SFC operation modii, and 

(iv) optimising loadability and productivity to enter chemical 

production processes. 

Central to all concepts of direct enantiomer separation 

techniques is the formation of intermediate diastereomeric 

associates of the chiral selector (SO) with the chiral target 

compounds, the selectands [(R)-SA and (S)-SA] which are 

sufficiently different in Gibbs binding energy (?G) to allow 

resolution. It is based on simultaneously activated intermolecular 

interactions of specific sites of the SO and the SA moieties 

characteristic for the SO and the SA molecular motifs. It all is 

spatially demanding and some conformational flexibility is of 

advantage to allow induced fit phenomena. Chemically speaking 

the SOs can vary widely from chiral polymers, e.g. CSPs derived 

from polysaccharides which are the most successful ones, to chiral 

monomers of charged and non-charged state. In this context our 

chiral ion exchanger type CSPs are unique and will be discussed 

more specifically in context of molecular recognition aspects and 

life science applications. 

Keywords: chromatography; enantiomer separations; 



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o - 1 3 5 

dynAMiC MethodS for frACtionAtion of 

trACe MetALS And MetALLoidS in the 

SPeCiAtion AnALySiS of SoiLS And SediMentS: 

A CoMPArAtive Study 

P. fedotov 1 , e. SAvoninA 1 , B. SPivAKov 1 

1 Vernadsky Institute of Geochemistry and Analytical Chemistry, 

Department of Analytical Chemistry, Moscow, Russia 

Continuous-flow (dynamic) fractionation has been 

recognized as an attractive alternative to conventional batch 

sequential extraction procedures for partitioning of trace metals 

and metalloids in environmental solids. Recently, two promising 

continuous-flow extraction systems have been comparatively 

studied, a microcolumn (MC) packed with the solid sample and a 

rotating coiled column (RCC) in which the particulate matter is 

retained under the action of centrifugal forces. Resemblances and 

discrepancies of two methods were evaluated by the fractionation 

of Cu, Pb, Zn, As, Sb, and Se according to their physicochemical 

mobility and bioaccessibility in soil, sludge, and sediment 

samples. The eluents (leachants) were applied in correspondence 

with three different four- and five-step sequential extraction 

schemes for partitioning of trace metals, arsenic/antimony, and 

selenium, correspondingly. The data obtained were correlated with 

peculiarities of samples under investigation and operational 

principles of RCC and MC. 

In general, similar trends were found for the distribution of 

trace metals (metalloids) between extractable and residual 

fractions. However, some evident deviations were observed. The 

content of organic matter (organic carbon) in a sample can be 

regarded as an important physicochemical parameter affecting the 

leaching efficiency. As an example, for a forest soil sample 

(C < 0.2%), RCC and MC fractionation lead to quite similar 

org 

results for arsenic and antimony despite the different extraction 

conditions set by two dynamic methods. In contrary, for a dumped 

waste (soil) sample (C = 11.5%), RCC extraction provides 

org 

higher recoveries of environmentally relevant leachable fractions 

of these metalloids and the discrepancy of data obtained using 

RCC and MC methods becomes unacceptable for their 

harmonization. This problem may be resolved by optimizing 

operational parameters of extraction (e.g. sample, weight, volume 

and flow rate of eluents) as well as design parameters of 

microcolumns. In addition, a wide range of samples with variable 

composition and physicochemical parameters should be analyzed. 



o - 1 3 6 

inveStiGAtinG trACe eLeMent SPeCiAtion 

in the MArine environMent uSinG CheMiCAL 

SePArAtion StrAteGieS CoMBined with 

SPeCtroMetriC deteCtion 

P. worSfoLd 1 

1 University of Plymouth, SoGEES, Plymouth (Devon), United 

Kingdom 

Email: pworsfold@plymouth.ac.uk 

Instrumental analytical techniques with environmentally 

relevant detection limits are often the limiting factor in our ability 

to understand how trace elements are cycled in the marine 

environment, and hence determine their impact on environmental 

processes and ecosystem health. This presentation outlines robust 

methods for quantifying the different chemical forms of key 

elements in marine systems. Aspects of method design will be 

discussed, including separation strategies based on selective 

chemical reactions, detection techniques, analytical performance 

and sample presentation. The potential of the flow injection 

approach as a means of automating these methods for remote 

deployment and their capacity for high temporal and spatial 

resolution measurements will also be demonstrated. [1] 

Examples will be used to illustrate the application of 

chemical separation with spectrometric detection to investigate 

trace element biogeochemistry. The use of sequential enzyme 

reactions with spectrophotometric detection to separate and 

quantify organic phosphorus species in estuaries will be described. 

Flow injection manifolds with chemiluminescence detection, 

incorporating solid phase preconcentration/matrix separation 

chelating columns, for the determination of trace metal 

micronutrients (iron and cobalt) in remote, open ocean 

environments will also be presented. Finally, TEVA extraction 

chromatography combined with multi-collector ICP-MS detection 

as a methodology for investigating the spatial and temporal 

distribution of plutonium isotopes in coral archives will be 

outlined. These examples demonstrate how chemical separation 

strategies combined with spectrometric detection can enhance our 

understanding of trace element biogeochemistry and the link 

between chemical, physical and biological processes in aquatic 

systems. 

references: 

1. Flow analysis with spectrophotometric and luminometric 

detection, E.A.G. Zagatto, C.C. Oliveira, A. Townshend 

and P.J. Worsfold, Elsevier Handbooks in Analytical 

Science Series, 471 pp, Elsevier, 2012. 

Keywords: biogeochemistry; marine environment; flow 

injection; spectrometric detection; separation strategies; 



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o - 1 3 7 

ChirAL AnALySiS of ACyCLiC nuCLeoSide 

PhoSPhonAteS-BASed Anti-AidS druGS By 

CAPiLLAry eLeCtroPhoreSiS 

v. KASiCKA 1 , v. SoLinovA 1 , P. SAzeLovA 1 , 

h. MiKySKovA 1 , P. JAnSA 2 , M. KreCMerovA 2 , 

A. hoLy 2 

1 Institute of Organic Chemistry and Biochemistry AS CR v.v.i., 

Electromigration Methods, Prague 6, Czech Republic 


Antimetabolites of Nucleic Acids Components, Prague 6, 


Acyclic nucleoside phosphonates (ANPs) are broadly used 

for treatment of virus diseases. [1] Oral prodrug of 9-(R)-[2- 

-(phosphonomethoxy)propyl]adenine, (R)-PMPA (tenofovir), was 

approved for treatment of AIDS, and 1-[(S)-3-hydroxy-2- 

-(phosphonomethoxy)propyl]cytosine, (S)-HPMPC (cidofovir), 

is used for treatment of cytomegalovirus retinitis in patients with 

AIDS. Enantiomeric purity control of these drugs is necessary 

prior to their medical applications. For this purpose, a new 

capillary electrophoretic (CE) method was developed for chiral 

analysis of these drugs and related ANPs-based antivirals using 

native and derivatized α-, β- and γ-cyclodextrins (CDs) as chiral 

selectors. The chiral CE analysis was elaborated using R,S-PMPA 

as model stereoisomers, for which the chiral selector, its 

concentration, and composition and pH of the background 

electrolyte (BGE) were selected. [2] The best CE separation of 

(R,S)-PMPA enantiomers was obtained in 30 mM sodium 

tetraborate BGE adjusted by NaOH to pH 10.0, with the addition 

of 20 mg/mL β-CD. Very good separation resolution, 2.18, was 

achieved within a short time, 9 min. The developed and/or slightly 

modified CE methods were applicable for chiral analysis of some 

related ANPs and subsequently they were employed for 

enantiopurity control of several batches of 9-(S)-[3-hydroxy-2- 

-(phosphonomethoxy)propyl]-2,6-diaminopurine, (S)-HPMPDAP, 

and 9-(R)-[2-(phosphonomethoxy)propyl]-2,6-diaminopurine, 

(R)-PMPDAP. Using the UV-absorption detection at 206 nm and 

254 nm, the concentration detection limits of the analyzed ANPs 

were in the submicromolar level. In addition, association 

constants of the complexes of ANPs enantiomers with CDs were 

determined from the dependence of effective electrophoretic 

mobilities of ANPs enantiomers on CDs concentration in the BGE 

by the non-linear regression analysis. 

Acknowledgement: The work was supported by GACR 

(203/08/1428, P206/12/0453), ASCR (Res. Project 

AV0Z40550506, RVO 61388963), and MSMT CR (Centre for 

New Antivirals and Antineoplastics 1M0508). 

references: 

1. A. Holy, Antiviral Res. 2006, 71, 248-253. 

2. V. Solinova, V. Kasicka, P. Sazelova, A. Holy, 

Electrophoresis 2009, 30, 2245-2254. 

Keywords: Analytical Methods; Electrophoresis; 

Enantioselectivity; Nucleosides; Nucleotides; 

spectrometric methods – i 


o - 2 5 2 

MeChAniSMS of enerGy diSSiPAtion And 

uLtrAfASt PriMAry eventS in PhotoStABLe 

SySteMS: h-Bond, exCeSS eLeCtron, 

BioLoGiCAL PhotoreCePtorS 

h. ABrAMCzyK 1 , B. BrozeK-PLuSKA 1 

1 Technical University of Lodz, Chemistry, Lodz, Poland 

The fundamental property of biological systems is 

photostability. Without photostability no life would be possible. 

Molecular structures responsible for harvesting of the solar energy 

must be photostable and resistant to photo-induced chemical 

changes or must find a way for a recovery. To answer the 

questions about the photostability we have to understand 

mechanisms of relaxation and energy dissipation upon an optical 

excitation. There is a common agreement that such channels are 

provided by some special features of the potential energy surfaces 

including the conical intersections. The mechanism seems to be 

universal both for simple species such as H-bond systems, 

solvated electrons, and biologically important photoreceptor 

proteins such as bacteriorhodopsin. [1] This paper reviews recent 

progress of understanding light-energy collection and dissipation, 

with a special emphasis on the role of the vibronic coupling in 

H-bonded systems, solvated electrons and light-initiated 

biological photoreceptors. We will concentrate on the 

spectroscopic methods such as Raman imaging, the time resolved 

coherent anti-Stokes Raman spectroscopy (CARS) and the pumpprobe 

transient femtosecond absorption spectroscopy. Detailed 

understanding the paths of energy dissipation will reveal 

mechanisms that mediate light-induced signal transduction as well 

as the role of photoreceptors in photostability protection and 

reparation mechanisms in living cells. Recently we have obtained 

the results on the normal and cancerous human breast tissue by 

Raman spectroscopy and Raman imaging. [2] The results 

demonstrate that Raman spectroscopy is able to accurately 

characterize pathology of tissue and distinguish between normal, 

malignant and benign types. 

Acknowledgements: The support through the NSC grants: 

2940/B/T02/2011/40 and 3845/B/T02/2009/37. 

references: 

1. H. Abramczyk, Mechanisms of energy dissipation and 

ultrafast primary events in photostable systems: H-bond, 

excess electron, biological photoreceptors. Vibrational 

Spectroscopy, 2012, 58, 1-11 

2. H. Abramczyk, B. Brozek-Pluska, J. Surmacki, J. 

Jablonska, R. Kordek, Raman ‘optical biopsy’ of human 

breast cancer, Prog. Biophys. Mol. Biol. 108(1–2), 74–81 

(2012). 

Keywords: energy dissipation; H-bonded systems; solvated 

electron; bacteriorhodopsin; breast cancer; 


wednesday, 29-Aug 2012 

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o - 2 5 3 

direCt oPtiCAL detCtion of BioMoLeCuLAr 

interACtion 

G. GAuGLitz 1 

1 University of Tuebingen, Chemistry, Tuebingen, Germany 

Reflectometry, has gained interest in recent years for 

monitoring biomolecular interaction processes beside evanescent 

field techniques. Both principles measure the product of refractive 

index and physical thickness. Whereas evanescent field 

techniques such as surface plasmon resonance or Mach-Zehnder 

interferometers measure changes in the refractive index through 

an evanescent field which is exponentially decaying into a layer 

next to a waveguide, reflectance measurements concentrate on the 

changes in physical thickness in a layer next to the transducer, 

which can be a glass slide or even a transparent polymer. Also 

thin layer metal-coated slides can also be used. Since changes in 

the refractive index caused by changes in temperature are to a 

large part compensated by the changes in the physical thickness, 

this method is robust against temperature fluctuations. Since the 

sensitivity does not decay in the range of half the wavelength as 

is the case with evanescent field techniques, reflectance can also 

easily be used for measuring nanoparticles or even whole cells. A 

variety of examples for the combination of interference and 

reflectance as tool for monitoring biomolecular interaction 

processes will be discussed, including their limitations and 

advantages; and the different possibilities ranging from 

spectroscopic detection to either single-wavelength monitoring or 

imaging of an array of spots. 

In clinical diagnostics and environment using matrices such 

as sera or water, the detection of hormones and endocrine 

disruptors in samples such as milk or food will be discussed. 

Protein-protein interaction and receptor-ligand assays are another 

type of application. Thus reflectometry opens new possibilities to 

measure behavior of cells. Future trends, with special 

consideration to nanoparticles, effect-based analytics and 

point-of-need measurements will be given. 

references: 

1. G. Gauglitz, ABC, 398(6), 2363-2372 (2010) 

2. S. Rau, G. Gauglitz, Anal Bioanal Chem, 402(1), 529-536 

(2012) 

INSTANT, FP7-NMP-2011-SME-5, NMP4-SE-2012-280550 



o - 2 5 4 

deterMinAtion of hePArin By SequentiAL 

inJeCtion AnALySiS with 

SPeCtroPhotoMetriC And 

SPeCtrofLuoriMetriC deteCtion 

J. hrAniCeK 1 , K. SorMovA 1 , L. BAr 1 , v. Cerveny 1 , 

P. ryChLovSKy 1 

1 Charles University in Prague Faculty of Science, Analytical 

chemistry, Prague 2, Czech Republic 

A perspective method of flow analysis – the sequential 

injection analysis (SIA) – with spectrophotometric and 

spectrofluorimetric detection was applied for determination of 

heparin. 

The SIA is suitable for the serial analysis, while achieving 

the high sensitivity and the low consumption of all reagents 

(a sample including), with respect to the environment. In both cases 

the heparin determinations are based on the interaction between 

heparin and phenothiazine dye (Methylene Blue), resulting in the 

decrease of the absorbance in the spectral maximum (664 nm) 

and fluorescence intensity in its emission maximum (687 nm, 

ex. 297 nm), respectively, of the phenothiazine dye (Methylene 

Blue). 

The absorption, excitation and fluorescence spectrum of the 

Methylene Blue were measured in the batch mode. After the 

optimization of the dye concentration (2 × 10 –5moldm –3 ) and pH 

(7.0), the batch mode calibration was measured. Subsequently the 

laboratory made SIA apparatus was assembled and the influences 

of basic working parameters (the concentration of dye, the ratio 

of the batch dye and analyte volume, the volume of mixing and 

reaction coil) were studied. Under the optimum conditions the SIA 

calibration and the basic characteristic of the heparin 

determination were found. Other phenothiazine dyes (Azure A 

and Azure B) were tested for comparison under the same 

experimental conditions. 

For the sequential injection analysis the concentration 

4 × 10 –5moldm –3 of Methylene Blue, flow rate 2.5 ml min –1 

for all reagents, the sampling volume of Methylene Blue and 

Heparin 150 + 150 µl and the volume 300 µl of mixing coil, 

without reaction coil, were selected as the optimum. The 

detection limit / repeatability for the spectrophotometric (spectro - 

fluorimetric) detection, 54 µg dm –3 / 1.15 %, 25 µg dm –3 / 3.07 % 

respectively, were achieved. The similar results were obtained 

with other dyes; slightly better with Azure A 

Keywords: UV / Vis spectroscopy; fluorescence; sequential 

injection analysis; heparin; 



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o - 2 5 5 

LuMinoL CheMiLuMineSCenCe deteCtion of 

AMino ACidS with enzyMAtiC reACtionS 

A. KuGiMiyA 1 , t. hAMAoKA 1 

1 Hiroshima City University, Center for Industry and Public 

Relations, Hiroshima, Japan 

The determination of amino acids is greatly important in 

clinical settings and food technologies such as the measurement 

of diagnosis of diseases in clinics and the measurement 

of freshness and taste of foods in food technologies. The 

conventional methods of detection for amino acids are pre-column 

labeling for High-Performance Liquid Chromatography (HPLC) 

of amino acids with fluorescence derivatives, or post-column 

labeling for HPLC with ninhydrine, but large amounts of organic 

solvents and an experimental step for labeling amino acids are 

necessary. 

In this study, for the rapid and easy measurement of amino 

acids, luminol chemiluminescence detection method of amino 

acids was developed with enzymatic reactions. Aminoacyl-tRNA 

synthetases (ARSs) were used as the molecular recognition 

element for amino acids. The biosensing system for asparagine 

was constructed with asparaginyl-tRNA synthetase (AsnRS) for 

recognition of asparagine and the luminol chemiluminescence 

intensity was measured by way of several enzymatic reactions. 

By using this sensing system, up to 200 μM of asparagine could 

be measured selectively. 

This work was partly supported by the Hiroshima City 

University Grant for Special Academic Research (General Studies). 

Keywords: amino acid; biosensor; protein; chemiluminescence 

detection; enzyme; 

spectrometric methods – ii 


o - 2 5 6 

intrA-oPerAtive APPLiCAtion of viBrAtionAL 

SPeCtroSCoPy 

r. SALzer 1 , G. Steiner 2 , M. KirSCh 3 

1 Dresden University of Technology, Department of Chemistry 

and Food Chemistry, Dresden, Germany 

2 Dresden University of Technology, Faculty of Medicine 

Clinical Sensoring and Monitoring, Dresden, Germany 

3 Dresden University of Technology, Faculty of Medicine and 

University Hospital Neurosurgery, Dresden, Germany 

Various techniques are established for biochemical 

characterization of tissue and for clinical diagnosis, several other 

methods based on new technology are under development. [1] 

Unfortunately, even well-established methods like histochemistry, 

magnetic resonance imaging (MRI), X-ray tomography, or 

positron emission tomography (PET), are not really suitable for 

regular intra-operative use. However, there is a clear need for an 

intra-operative diagnostics especially in brain surgery. Vibrational 

spectroscopy techniques (both Raman and infrared) complement 

the standard methods for tissue diagnostics. [2] This contribution 

shall review the current status of applicability of vibrational 

spectroscopy under intra-operative conditions. 

Both Infrared and Raman spectroscopy have the potential 

for intra-operative use, because they can provide a biochemically 

based profile of tissue in real time and without requiring additional 

contrast agents. [3] Such marker-free techniques are particularly 

required, because they avoid any perturbation of the sample under 

investigation. Infrared spectroscopy is being used to examine 

freshly resected tissue ex vivo in the operating theater while the 

surgery is going on. The main potential in this case is the 

identification of the borderline between normal and tumor tissue. 

Other promising approaches include Raman fiber techniques and 

non-linear Raman methods. Raman fiber techniques can easily be 

combined with commercial endoscopes. Of the non-linear Raman 

methods, Coherent Anti-Stokes Raman Scattering (CARS) attracts 

the greatest research interest. 

references: 

1. Reiner Salzer, Biomedical Imaging: Principles and 

Applications, John Wiley & Sons 2012, ISBN 

0470648473 

2. Reiner Salzer, Heinz W. Siesler, Infrared and Raman 

Spectroscopic Imaging, Wiley-VCH 2009, ISBN 

352731993X 

3. Allison Stelling, Reiner Salzer, Matthias Kirsch, Stephan 

B. Sobottka, Kathrin Geiger, Edmund Koch, Gabriele 

Schackert, Gerald Steiner; Anal Bioanal Chem 400 (2011) 

2745–2753. 

Keywords: Vibrational spectroscopy; IR spectroscopy; Raman 

spectroscopy; CARS (Coherent Anti-Stokes Raman Scattering); 



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o - 2 5 7 

LuMineSCent AnALySiS BASed on the enerGy 

trAnSfer 

S. ShtyKov 1 

1 Saratov State University, Institute of Chemistry, Saratov, 

Russia 

Sensitized luminescence spectroscopy based on the excited 

energy transfer became a powerful tool for sensitivity and 

selectivity enhancement in analysis of many biologically-active 

substances (BAS) and especially in bioanalysis. Three general 

types of electronic excited energy transfer are distinguished. First, 

is Förster resonance energy transfer (FRET), based on the transfer 

of energy between two fluorophore molecules, where one acts as 

an energy donor and the other as an acceptor. The emission 

spectrum of the donor and the absorption spectrum of the acceptor 

must overlap and this is a diffusion-controlled process. There is a 

variety of FRET fashions exists especially in a time resolve 

manner but most of them apply in bioanalysis. 

Second strategy that has attracted considerable interest in a 

variety of chemical and biological applications involves use of 

lanthanide chelates formation resulting in exclusion the diffusion 

control. In such complexes, the energy absorbed by organic BASligand 

(donor) is first transferred to its triplet state through 

intersystem crossing and then intramolecularly transferred to a 

closest resonance level of the lanthanide ion (acceptor) which 

finally emits sensitized fluorescence displaying “antenna” effect. 

Three possibilities to enhancing the lanthanide sensitized 

fluorescence will be discussed. 

Third kind of energy transfer is sensitized room temperature 

phosphorescence (SRTP) results from triplet-triplet (T-T) energy 

transfer between the organic donor and acceptor molecules mainly 

in micellar solutions of surfactants. In this case two possibilities 

for enhancing of the analytical selectivity will be discussed: the 

indirect and direct SRTP analyte detection of polycyclic aromatic 

hydrocarbons. 

The aim of the report is to reveal major factors influencing 

the efficiency of energy transfer in all kinds of sensitized 

luminescence and discuss their practical application in 

fluorimetric analysis of antibiotics, amino acids, anticoagulants, 

pesticides and bioanalysis including cell analysis. 

Acknowledgement: The work was supported by Russian 

Foundation for Basic Research, project N 12-03-00450a 



o - 2 5 8 

StABiLity And CheMiCAL inertneSS StudieS of 

noveL GAdoLiniuM CoMPLexeS uSed in Mri 

v. MoGiLireddy 1 , i. déChAMPS 1 , C. CAdiou 1 , 

S. Chevreux 1 , S. ArChiBALd 2 , S. roux 3 , 

G. LeMerCier 1 , f. ChuBuru 1 

1 Institut de chimie Moléculaire de Reims, Department of 

Chemistry, Reims, France 

2 University of Hull, Department of Chemistry, Hull, United 

Kingdom 

3 Institut UTINAM - UMR 6213, Department of Chemistry, 

Besancon, France 

The use of contrast agents as tools for diagnosis is a common 

practice during medical examinations. Their role is to improve the 

quality of images by enhancing the contrast between normal and 

diseased tissues. Gadolinium chelates are the commonly available 

commercial contrast agents for MRI examinations. Since Gd3+ is 

toxic in its ionic form, it has to be administered as a stable 

complex which can be rapidly excreted from the body. [1] To ensure 

that the inherent toxicity of the contrast agent is reduced, the 

knowledge of two physicochemical parameters are essential for 

the gadolinium chelate: its thermodynamic stability and chemical 

inertness. 

In this context, our approach is to determine the 

thermodynamic stability of complexes by potentiometry and 

evaluate their inertia in the presence of competitive cations 

(Cu (II) and Zn (II)) by UV-visible and / or relaxometry. [2] Two 

candidates for MRI imaging (i) a macrocyclic ligand, tricarboxylic 

substituted benzimidazole moiety DO3A-BIM (ii) a linear ligand, 

DTDTPA, [3] will be presented. 

The analysis of the results were as follows: 

• from thermodynamic point of view, DO3A-BIM complexes are 

very stable in aqueous solution which suits well for their use in 

biological media. 

• from kinetic point of view, the demetallation mechanisms of 

GdDTDTPA and its commercial analogue GdDTPA 

(Magnevist ® ) are different. Furthermore, their half-life indicated 

that GdDTDTPA is more inert than GdDTPA in biological 

environment. Therefore, GdDTDTPA associated with 

nanoparticles contain the properties required for use in MRI. 

references: 

1. J. M. Idée, M. Port, C. Medina, E. Lancelot, E. Fayoux, 

S. Ballet, C. Corot, Toxicology, 2008, 248, 77–88 

2. L. Sarka, L. Burai, Z. Brücher Chem. Eur. J. 2000, 6, 

719–724. 

3. C. Alric, J. Taleb, G. Le Duc, C. Mandon, C. Billotey, 

A. Le Meur-Herland, T. Brochard, F. Vocanson, M. Janier, 

P. Perriat, S. Roux, O. Tillement J. Am. Chem. Soc. 2008, 

130, 5908-5916. 

Keywords: Gadolinium; Thermodynamic stability; 



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Biosensor strategies 

o - 2 5 9 

SynthetiC BioLoGy And new MAteriALS for 

BioSenSorS 

e. hALL 1 , G. BorGhei 1 , S. AKrAM 1 , M. neuMAnn 1 , 

A. wonG 1 , S. deMin 1 

1 University of Cambridge, Chemical Engineering & 

Biotechnology, Cambridge, United Kingdom 

This paper now describes how synthetic biology can 

be employed to create and tune materials for biosensors. 

For example, a polyQ fibre, based on the primary 

RFP-polyQ amyloid fibre-forming unit is described which is 

77 

able to self assemble into self supporting fibrous material. The 

RFP demonstrates that the fibre can be made to be functional and 

the properties of this material are examined. 

Bio-luminescence Resonance Energy Transfer materials can 

be created with luciferase (a) to shift the emission to longer 

wavelengths by energy transfer with a fused proten, making the 

assay more versatile for applications where shorter wavelengths 

are difficult to measure (b) to investigate constructs with abiotic 

materials where energy capture and emission can be enhanced 

through the use of semi-conducting nano-materials (c) to look at 

self-assembly of functional fibres containing the luminescent 

protein system. 

BRET constructs are demonstrated between luciferase and 

(i) red fluorescent protein or (ii) cherry fluorescent protein. 

However, >50% energy transfer from the luciferase-luciferin to 

the fluorescent protein is difficult to achieve in a one-one 

construct. We examine this and propose ways to improve this 

yield by making the first double construct Cherry-Luc-Cherry and 

by other active site manipulations. 

The future use of synthetic biological materials as analytical 

reagents is a core theme of this presentation. 

Keywords: biosensors; protein engineering; 



o - 2 6 0 

uLtrA-SPeCifiC viruS BioSenSor uSinG redox 

AntiBody ProBe interACtion with 

nAnoChAnneL AdSorBed viruS PArtiCLeS 

C. S. toh 1 , A. e. K. Peh 1 , B. t. t. nGuyen 1 , C. Chee 1 , 

L. Judy 1 , K. finK 2 , v. GAn 3 , y. S. Leo 3 

1 Nanyang Technological University, Division of Chemistry and 

Biological Chemistry School of Physical and Mathematical 

Sciences, Singapore, Singapore 

2 Singapore Immunology Network, Agency for Science 

Technology and Research ASTAR, Singapore, Singapore 

3 Tan Tock Seng Hospital, Communicable Disease Centre, 

Singapore, Singapore 

Development of immune-based and DNA-based methods 

constitute an interesting topic for enhancing selectivity of sensor 

performance for environmental, biomedical and clinical analysis 

through the incorporation of high specificity binding agents 

including antibodies, DNAs and others. However, specific 

identification remains challenged by cross-reactivities between 

similar protein or DNA analytes such as between same antibody 

types raised against different antigens or between different 

antibody types raised against the same antigen. Recently, 

nanochannel-membrane electrochemical biosensors provide an 

alternative approach to achieve high sensitive and selective 

detection of biomolecules. At same time, the high density array 

of nanochannel structure permits high surface loading of 

biorecognition agents, over a sub-micrometer thickness 

membrane layer. In this talk, the recent interesting development 

of a much thicker (in micrometer dimension) membrane allows 

multiple site interactions between a traversing redox labled 

antibody target and surface attached protein targets within the 

nanochannels, will be presented. Selective identification of virus 

serotypes is based on the rate of diffusive movement of a 

ferrocene-labeled antibody probe through nanochannels 

immobilized with virus particles at the nanochannel walls. The 

time taken for the probe to elute from the nanochannels is readily 

measured using differential pulse voltammetry which gives a peak 

signal in response to the redox-labeled antibody probe and 

electrode fouling by the same antibody protein. This strategy 

exploits the large number of nanochannels to achieve large signal 

outputs using a low cost electrochemical setup and reusable 

nanoporous membranes. 

Keywords: biosensor; nanochannel; membrane; virus; 

differential pulse voltammetry; 



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o - 2 6 1 

BioSenSorS BASed on CArBon nAnotuBeS: the 

roLe of CALiBrAtion on the reProduCiBiLity 

of deviCeS 

A. duArte 1 , C. JuStino 2 , J. P. AMArAL 3 , 

S. CArdoSo 3 , t. roChA-SAntoS 4 

1 University of Aveiro, Department of Chemistry, Aveiro, 

Portugal 

2 University of Aveiro, Department of Chemistry and CESAM, 

Aveiro, Portugal 

3 INESC-MN, INESC-MN, Lisbon, Portugal 

4 Instituto Piaget / University of Aveiro, ISEIT / Department of 

Chemistry and CESAM, Viseu /Aveiro, Portugal 

The analytical performance of biosensing technologies has 

been enhanced by the incorporation of carbon nanotubes (CNT), 

which display excellent electronic, chemical and structural 

properties. Furthermore, the portability, functionality, and 

reliability of CNT-based biosensors have been improved, thus 

contributing to real-time, fast and accurate diagnosis. Recently, 

biosensors based on networks of CNT with field effect transistors 

(NTFET) have been developed to enhance the miniaturization of 

devices and associated advantageous characteristics. However the 

reproducibility of such biosensing devices has been affected when 

analytical data of individual devices (with the same configuration 

and characteristics) are compared. Such is due to the random 

nature of CNT, i.e., variation on their diameter and chirality and 

CNT density on networks. In this communication, some analytical 

approaches such as the calibration of biosensing devices were 

discussed as a way to solve the device-to-device variation; then, 

the reproducibility of nanomaterials-based FET devices could be 

improved for their practical application and commercialization. 

Furthermore, an additional example based on the development of 

NTFET devices for the detection of C-reactive protein is 

demonstrated, where the variation on the analytical response was 

checked, and a data analysis was performed to find analytical 

similarities among individual devices. 

Acknowledgements: FEDER under the Operational Program 

for Competitiveness Factors – COMPETE, FCT (Fundacao 

para a Ciencia e a Tecnologia, Portugal) within the framework 

of research project CARDIOSENSOR (references FCOMP-01- 

-0124-FEDER-010902 and PTDC/SAU-BEB/099042/2008). 

This work was also funded through scholarships (references 

SFRH/BD/60429/2009, and SFRH/BPD/65410/2009) under 

QREN-POPH funds, co-financed by the European Social Fund 

and Portuguese National Funds from MCTES. 

Keywords: biosensors; nanotubes; immunochemistry; 



o - 2 6 2 

GLuCoSe oxidASe-funCtionALized 

MeSoPorouS zirConiA thin fiLMS for 

eLeCtroCheMiCAL GLuCoSe deteCtion 

y. S. Ko 1 , S. y. Choi 2 , y. u. Kwon 1 

1 Sungkyunkwan University, Chemistry, Suwon, Republic of 

Korea 

2 Sungkyunkwan University, SKKU Advanced Institute of 

Nanotechnology, Suwon, Republic of Korea 

We synthesized mesoporous zirconia thin films (MZTFs) by 

using a mixed solution in which zirconium hydroxide 

nanoparticles were self-assembled with a structure directing agent, 

F127 (PEO PPO PEO , EO = ethylene oxide, PO = propylene 

106 70 106 

oxide). The mesostructures of these films were characterized by 

low-angle X-ray diffraction, scanning electron microscopy, 

transmission electron microscopy, and grazing incidence small 

angle X-ray scattering. The 3D pore structures were identified by 

two distinct ones with the Fmmm structure and the P6 /mmc 3 

structure. The Fmmm structure has interconnected pores and the 

P6 /mmc one less accessible pores. The MZTFs, formed on 

3 

fluorine-doped tin oxide electrodes, were functionalized with 

glucose oxidase (GOx) and were studied for their potentials as 

electrochemical sensor for glucose. The MZTF with the Fmmm 

structure shows a large capacity for the adsorption of GOx. Thus, 

the GOx-functionalized electrode of this MZTF showed high 

sensitivity to glucose in a broad range of glucose concentration 

of 1 - 7 mM. The electrochemical data of this electrode suggest a 

surface-controlled mechanism, high degree of reproducibility, and 

a long life time. 

Keywords: Mesoporous film; Zirconia; Electrochemical 

glucose detection; 



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o - 2 6 3 

the intrinSiC non-CovALent interACtionS 

within CoMPLexeS of A-CyCLodextrin And 

BenzoAte derivAtiveS 

z. Li 1 , x. zhAnG 1 

1 ETH Zurich, Laboratory of Organic chemistry, Zürich, 

Switzerland 

Dissociation energies and structural assignments of 

α-cyclodextrin (α-CD) complexes with three benzoate derivatives 

3-methylbenzoic acid (3-MeBA), benzoic acid (BA) and 

3-hydroxylbenzoic acid (3-OHBA) were for the first time studied 

by the combination of experiments and theoretical calculations. 

Qualitative experiments were performed for these α-cyclodextrin 

complexes to obtain the relative stability order that [a-CD·3- 

-MeBA] - (1) < [a-CD·BA] - (2) < [a-CD·3-OHBA] - (3). [1] 

Threshold collision-induced dissociation experiments were 

performed on a customized 24-pole Finnigan TSQ–700 tandem 

mass spectrometer to get absolute dissociation energies. [2] The 

obtained experimental quantitative non-covalent interactions for 

complexes 1, 2 and 3 are 40.8, 41.1 and 41.8 kcal mol –1 

respectively. 

DFT calculations were carried out to further interpret 

non-covalent interactions within host-guest complexes. The bond 

dissociation energies for complexes 1, 2 and 3 are 40.6, 40.7 and 

44.0 kcal mol –1 respectively according to DFT calculations. 

Furthermore, hydrogen bonding interactions, such as O–H···O, 

C–H···O and C–H···π interactions contribute mainly for the 

stability of gaseous complexes. Inclusion geometries are still 

favored according to the experimental and computational results. 

The experimental stability order and absolute dissociation 

energies are in excellent agreement with DFT calculation results. 

references: 

1. Li, Z.; Couzijn, P. A.; Zhang, X. J. Phys. Chem. B. 2012, 

116, 943. 

2. Narancic, S.; Bach, A.; Chen, P. J. Phys. Chem. A. 2007, 

111, 7006. 

Keywords: non-covalent interactions; a-cyclodextrin; 

dissociation energies; DFT calculations; mass spectrometer; 

New analytical methodologies 


o - 2 6 4 

the inveStiGAtion of enerGetiC 

BenzALdoxiMeS with therMoAnALytiCAL And 

CoMPutAtionAL MethodS. 

A. AtAKoL 1 , M. KundurACi 2 , e. ÖzKArAMete 2 , 

n. yiLMAz 2 , o. AtAKoL 2 , M. A. AKAy 2 

1 METU, Chemistry, Ankara, Turkey 

2 Ankara University, Chemistry, Ankara, Turkey 

3,5-dinitro-2-hydroxybenzaldehyde and 3,5-dinitro-4- 

-hydroxybenzaldehyde were synthesized by nitration of 

salicylaldehyde and 4-hydroxybenzaldehyde, respectively. [1] 

These nitroaldehydes were converted into oximes with 

hydroxylamine [2] and were investigated by thermoanalytical (TG, 

DSC) and computational methods (G09W). It was observed from 

IR and MS spectra that 3,5-dinitro-2-hydroxybenzaldehyde yields 

4,6-dinitrobenzoxazine by elimination of water via Beckmann 

rearrangment at 210–215 °C. On the other hand, 3,5-dinitro-4- 

-hydroxybenzaldoxime was converged into benzonitrile by 

elimination of water at 160-190°C. The released heat for each 

exothermic reaction was measured analytically by DSC. 

All theoretical calculations were carried out using the 

Gaussian G09W (revision B.01) program package. [3] DFT-based 

structure optimizations and frequency analyses were performed 

at the B3LYP/cc-pVDZ level of theory. The enthalpies of 

formation of both reactants and products were calculated using 

complete basis set (CBS-4M) method of Petersson and coworkers 

in order to obtain accurate energies. From the calculated heat of 

formations, the enthalpies of decomposition were calculated 

according to Hess’s Law and were compared with the 

experimental values which were available from DSC analysis. 

The good agreement between the experimentally observed 

enthalpies of decomposition and the CBS-4M calculated values 

gives credence to the accuracy of the applied CBS-4M method. 

references: 

1. P. Ionita, S. Af. J. Chem, 61, 123-126, 2008 

2. J. Hull, S.T. Hilton, R. H. Crabtree, Inorg. Chim. Acta, 

363, 1243-1245, 2010 

3. a) Gaussian 09 Software, Revision B01.2009 

b) A. D. Becke, J. Chem. Phys., 88, 1053-1062, 1988 

c) Jr. A. J. Montgomery, M. J. Frisch, J. W. Ochterski, 

G. A. Petersson, J. Chem. Phys. 112, 6532-6553, 2000 

Keywords: Oxygen heterocycles; Computational Chemistry; 

Elimination; Nitrides; Rearrangement; 



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o - 2 6 5 

SiMuLtAneouS or inCreMentAL 

identifiCAtion of reACtion SySteMS? 

J. BiLLeter 1 , S. SrinivASAn 1 , d. Bonvin 1 

1 Ecole Polytechnique Fédérale de Lausanne (EPFL), Automatic 

Control Laboratory (LA), Lausanne, Switzerland 

Identification of kinetic models is essential for monitoring, 

control and optimization of industrial processes. Robust kinetic 

models are often based on first-principles and described by 

differential equations. Identification of reaction kinetics, namely 

rate expressions and rate parameters, represents the main 

challenge in building first-principles models. The identification 

task can be performed in one step via a simultaneous approach or 

over several steps via an incremental approach. 

In the simultaneous approach, a kinetic model that 

encompasses all reactions is postulated and the corresponding 

parameters are estimated by comparing predicted and measured 

concentrations. The procedure is repeated for all combinations of 

model candidates and the combination with the best fit is typically 

selected. This approach can handle complex reaction rates and 

leads to optimal parameters in the maximum-likelihood sense. 

However, it is computationally costly when several candidates are 

available for each reaction, and convergence problems can arise 

for poor initial guesses. Furthermore, simultaneous identification 

often leads to high parameters correlation, and a structural 

mismatch in one part of the model can result in errors in all 

estimated parameters. 

In the incremental approach, the identification task is 

decomposed into sub-problems of lower complexity. In the 

differential method, reaction rates are first estimated by 

differentiation of measured concentrations. Then, each estimated 

rate profile is used to discriminate between several model 

candidates, and the candidate with the best fit is selected. 

However, because of the bias introduced in the differentiation 

step, the estimated rate parameters are not statistically optimal. In 

the integral method, measured concentrations are first transformed 

to ‘experimental extents’. Subsequently, postulated rate 

expressions are integrated for each reaction individually and rate 

parameters are estimated by comparing predicted and 

experimental extents. 

This contribution reviews the simultaneous and incremental 

methods of identification and compares them via simulated 

examples taken from homogeneous and heterogeneous chemistry. 

Keywords: Kinetics; Kinetic resolution; Industrial Chemistry; 

Analytical Methods; 



o - 2 6 6 

SACChAride ProBeS for enzyMe ASSAyS And 

MoLeCuLAr LoGiC 

A. SChiLLer 1 

1 Friedrich-Schiller-University Jena, Institute for Inorganic and 

Analytical Chemistry, Jena, Germany 

A two-component glucose sensing concept based on anionic 

fluorescent dyes as reporters and boronic acid-appended 

bipyridinium salts as receptors was formulated by Singaram et 

al. [1–5] Going beyond glucose monitoring, real-time label-free 

fluorescent enzyme assays have been developed for sucrose 

phosphorylase (SPO) and phosphoglucomutase (PGM). [1, 2, 6] The 

assays are suitable for high-throughput screening of novel 

carbohydrate enzymes for industrial applications. [9] Glycoside 

phosphorylases and transglycosidases are biocatalysts for the 

glyco-sylation of small molecules which can be assayed with the 

saccharide probes. [10] These probes can also perform Boolean logic 

operations for “chemical computing”. The combination of a 

boronic acid-appended viologen and perylene diimide was able 

to perform a complementary implication (IMP) / notimplication 

logic function. Fluorescence quenching and recovery with 

fructose was analyzed with a conventional plate reader and by 

fluorescence correlation spectroscopy on few molecule level of 

the reporting dye. [11] IMP and FALSE operations are able to form 

adder, subtractor and multiplicator logic systems, based on the 

saccharide probe and fructose. 

references: 

1. A. Schiller, B. Vilozny, R. A. Wessling, B. Singaram, in 

Reviews in Fluorescence 2009, Springer, 2011, 155. 

2. A. Schiller, in Molecules at Work. Selfassembly, 

Nanomaterials, Molecular Machinery (Ed.: B. Pignataro), 

Wiley-VCH, Weinheim, 2012, 315. 

3. B. Vilozny, A. Schiller, R. A. Wessling, B. Singaram, 

J. Mater. Chem. 2011, 21, 7589. 

4. A. Schiller, R. A. Wessling, B. Singaram, Angew. Chem., 

Int. Ed. 2007, 46, 6457. 

5. A. Schiller, B. Vilozny, R. A. Wessling, B. Singaram, 

Anal. Chim. Acta. 2008, 627, 203. 

6. B. Vilozny, A. Schiller, R. A. Wessling, B. Singaram, Anal. 

Chim. Acta. 2009, 649, 246. 

9. www.novosides.eu. 

10. T. Desmet, W. Soetaert, P. Bojarová, V. Kren, 

L. Dijkhuizen, V. Eastwick-Field, A. Schiller, Chem. Eur. 

J.2012, in press. 

11. M. Elstner, K. Weisshart, K. Müllen, A. Schiller, J. Am. 

Chem. Soc. 2012, DOI: 10.1021/ja303214r 

Keywords: Sensors; Supramolecular chemistry; Enzyme 

catalysis; Fluorescent probes; Fluorescence spectroscopy; 



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o - 2 6 7 

SCoPe And LiMitAtionS of SurfACe 

funCtionAL GrouP quAntifiCAtion MethodS 

A. henniG 1 , h. BorCherdinG 2 , A. hoffMAnn 1 , 

C. JAeGer 1 , S. hAtAMi 1 , C. würth 1 , t. thieLe 2 , 

K. hoffMAnn 1 , u. SChedLer 2 , u. reSCh-GenGer 1 

1 BAM Federal Institute for Materials Research and Testing, 

Analytical Chemistry, Berlin, Germany 

2 PolyAn GmbH, -, Berlin, Germany 

Micro- and nanoparticles are emerging as key components 

in numerous application areas ranging from materials sciences to 

life sciences and medicine. Their properties and interactions with 

other molecules are largely controlled by the number, chemical 

nature, and spatial distribution of their surface functional groups. 

While the total number of surface functional groups determines 

their materials properties such as colloidal stability, the number 

of accessible functional groups indicates which fraction can be 

principally derivatized with application-relevant molecules such 

as peptides, proteins, antibodies or DNA. 

We have quantified the total and accessible number of 

carboxylic acid groups on polymer particles by conductometry, 

13C solid-state NMR, fluorophore labeling, a supramolecular assay 

based on high-affinity inding of cucurbit[7]uril (CB7 assay), and 

two colorimetric assays based on toluidine blue and Ni2+ complexation by pyrocatechol violet (Ni2+ /PV assay), whereas the 

CB7 and the Ni2+ /PV assay were recently introduced by us as 

simple, straightforward and reliable methods to determine the 

number of total and accessible functional groups, respectively. [1] 

The results demonstrated that only a small but constant fraction 

of the surface functional groups is accessible to covalent surface 

derivatization independently of the total number of surface 

functional groups. All methods were thoroughly validated and 

compared with respect to reproducibility, sensitivity, and ease of 

use. Most importantly, absolute quantum yield measurements after 

fluorophore labeling indicated a major uncertainty for this 

routinely used surface group quantification method, which is 

directly relevant for biochemical assays and medical diagnostics. 

This comprehensive comparison of surface group quantification 

methods is now extended to copolymer-functionalized surfaces 

and different fluorescent dyes. [2] 

references: 

1. a) Anal. Chem. 2011, 83, 4970-4974. 

b) Chem. Commun. 2011, 47, 7842-7844. 

c) J. Am. Chem. Soc. 2012, DOI:10.1021/ja302649g. 

2. unpublished results 

Keywords: Analytical Methods; Fluorescence spectroscopy; 

Nanoparticles; Polymers; Surface analysis; 



o - 2 6 8 

deteCtion of ethyLene GAS uSinG CArBon 

nAnotuBe BASed deviCeS: utiLity in the 

deterMinAtion of fruit riPeneSS 

B. eSSer 1 , J. M. SChnorr 1 , t. M. SwAGer 1 

1 Massachusetts Institute of Technology, Chemistry, Cambridge 

MA, USA 

Ethylene as the smallest plant hormone plays a role in many 

developmental processes in plants. For example it initiates the 

ripening of fruit, promotes seed germination and flowering, and 

is responsible for the senescence of leaves and flowers. In the 

horticultural industries, the selective detection of ethylene at low 

concentrations is highly desirable to avoid over ripening of fruit. 

Single-walled carbon nanotubes were modified with an 

ethylene binding copper(I) complex creating a reversible 

chemoresistive sensor for ethylene. The devices are able to detect 

sub-ppm concentrations of ethylene in a highly sensitive and 

selective manner and are simply prepared in few steps from 

commercially available materials. The utility of the sensor was 

demonstrated by following ripening stages in different fruits. 

Keywords: ethylene; copper; hormones; nanotubes; sensors; 



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o - 2 6 9 

feASiBiLity of AttenuAted totAL refLexion 

SPeCtroSCoPy in MonitorinG And 

quAntifiCAtion of AntiBody And hoSt CeLL 

ProteinS uSinG MAMMALiAn CeLL CuLture 

f. CAPito 1 , r. SKudAS 2 , B. StAniSLAwSKi 2 , 

h. KoLMAr 1 

1 Technische Universität Darmstadt, Organic Chemistry and 

Biochemistry, Darmstadt, Germany 

2 Merck KGaA, MM-PTD, Darmstadt, Germany 

For the first time, we present a feasibility study for 

quantifying host cell proteins (HCPs) and monoclonal antibody 

(mAb) during fermentation of mammalian cell cultures, using 

Fourier transform infrared spectroscopy. Our method is a 

non-invasive alternative to traditional monitoring of protein levels 

by ELISA, 2D-SDS-PAGE and chromatography. 

The robustness of our approach was tested with 66 NS0 and 

40 CHO cell culture samples. To obtain a wide range of HCP and 

mAb concentrations, we treated the samples with polyelectrolytes 

at different concentrations for semi-selective protein precipitation. 

The obtained samples were measured in situ by attenuated total 

reflexion with Fourier transform infrared spectroscopy in the mid 

infrared range and analyzed using multivariate data-analysis. 

We were able to quantify HCPs in the range of 

2,000–55,000ng ml-1 and mAb in the range of 0.2- 1.7g l-1 . 

Obtained values of HCPs and mAb were in good agreement with 

results measured by HCP-ELISA or determined by fluorophore 

labeling, respectively, suggesting the suitability of this method for 

mAb and HCP monitoring and quantification. 

Keywords: attenuated total reflexion; host cell protein; 

monoclonal antibody; monitoring; fermentation; 

Chemometrics – i 


o - 4 1 8 

CheMoMetriCS for Pre-ProCeSSinG of 

quAntitAtive ProteoMiCS dAtA 

P. wentzeLL 1 , J. BoutiLier 1 , B. wieLenS 1 

1 Dalhousie University, Chemistry, Halifax Nova Scotia, Canada 

Among modern high-throughput biological methods, the 

measurement of protein expression has perhaps the greatest 

potential for providing useful information, since the proteome is 

most directly linked to the biological state of an organism. To date, 

however, this potential has not been fully realized due to the many 

challenges of comprehensive quantitative proteomics. These 

include diversity of protein properties and abundance, the number 

of analytes, difficulties in quantitation, the lack of standardized 

platforms, and the long sample analysis times. Extended analysis 

times are particularly problematic in the large scale biological 

studies needed to validate conclusions across a large number of 

samples. The goal of the present research is to explore methods 

for rapid, high-throughput screening in proteomics. 

A popular platform for relative protein quantitation 

(comparative proteomics) is differential labelling of peptide 

digests from two or more biological states using isotopic tags, 

where the ratio of the two signals is indicative of up- or 

down-regulation of an associated protein. Current approaches use 

tandem mass spectrometry (MS/MS) to identify peptides prior to 

quantitation. A drawback of this method is a significant loss in 

mass spectrometer duty cycle to tandem scans. This presentation 

will describe strategies to improve throughput by relying only on 

MS scans to locate and quantify peptide pairs in the mixture. This 

presents significant challenges in dynamic signal processing to 

account for differences in charge state, number of tags, and 

isotopic patterns. The end result is a map of peptides present in 

the mixture, together with ion state and ratio. While MS resolution 

with the current instrument is generally not sufficient to uniquely 

identify peptides, the goal is to first locate differentially expressed 

proteins and then identify them by other means. Other challenges 

in this process, such as chromatographic alignment and peak 

overlap, will also be discussed. 

Keywords: Proteomics; Analytical Methods; Mass 

spectrometry; Peptides; Bioinformatics; 



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o - 4 1 9 

diSSiMiLArity BASed ModeLinG of CheMiCAL 

dAtA 

B. wALCzAK 1 

1 University of Silesia, Institute of Chemistry, Katowice, Poland 

Studying complex non-linear chemical and/or bio-chemical 

systems, we need fast and effective methods of their modeling. 

As it will be demonstrated, dissimilarity representation (known 

also as pairwise representation) reveals data structure, which is 

not revealed in the vectorial representation, and thus widens 

the sets of possible approaches to data modeling. Performance 

of the dissimilarity based methods (e.g., Dissimilarity – Partial 

Least Squares ) [1] , will be demonstrated for calibration and 

discrimination of real and simulated data sets of different structure 

and complexity. Practical aspects of dissimilarity based modeling 

(e.g., the choice of dissimilarity measure, pre-selection of the 

so-called ‘prototypes’, and fusion of different dissimilarity 

measures or different data blocks) will be discussed, as well. 

It will also be demonstrated how the dissimilarity based methods 

applied to instrumental signals such as, e.g., LC-MS signals, allow 

applications of no-warping strategies for data modeling. 

As main advantages of the proposed approach, we can 

mention its conceptual simplicity, flexibility, and very short 

computations time. 

references: 

1. P. Zerzucha, M. Daszykowski, B. Walczak, Dissimilarity 

partial least squares applied to non-linear modeling 

problems, Chemometrics and Intelligent Laboratory 

Systems, 110 (2012) 156-162 

Keywords: non-linear modeling; analysis of variance; 

Euclidean distance; 



o - 4 2 0 

APPLiCAtion of nAture-inSPired MethodS in 

CheMoMetriCS 

f. MArini 1 , B. wALCzAK 2 

1 University of Rome “La Sapienza”, Chemistry, Rome, Italy 

2 University of Silesia, Analytical Chemistry, Katowice, Poland 

Natural Computing models, inspired in part by nature and 

natural systems, are a family of powerful data analysis methods 

able to transform available heterogeneous data into knowledge. 

They include Neural Networks mimicking the mechanisms of the 

nervous system, [1] general optimization techniques, such as 

Genetic Algorithms based on simulation of biological evolution [2] , 

Swarm Intelligence based on simulation of social behavior of 

animals. [3] 

In recent years, many Nature-inspired models have been 

successfully applied to the solution of complex problems related 

to signal processing, classification, clustering, feature selection, 

and regression. 

In this communication, some successful application of 

natural computing to solve chemical problems will be presented 

and discussed. In particular, the use of feed-forward artificial 

neural networks to operate non linear classification in the cases 

where sample distribution would require complex decision 

boundaries will be shown. Additionally, the use of Kohonen 

architecture for nonlinear projection aimed at exploratory data 

analysis will be exemplified. 

As far as Genetic Algorithms are concerned, examples of 

their fruitful use in variable selection will be given. 

Lastly, some recent applications of a swarm intelligence 

algorithm (Particle Swarm Optimization) in chemometrics will be 

described. In particular, the use of PSO for parametric time 

warping, peak deconvolution and clustering will be discussed. 

references: 

1. F. Marini, Anal. Chim. Acta 635 (2009) 121-131. 

2. R. Leardi, J. Chemometr. 15 (2001) 559-569. 

3. J. Kennedy, R.C. Eberhardt, Y. Shi, Swarm Intelligence, 

Morgan Kaufmann, 2001. 

Keywords: Analytical Methods; Chemoinformatics; 



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Chemometrics – ii 

o - 4 2 1 

fuSion of MetABoLoMiCS dAtA for A Better 

underStAndinG of MuLtiPLe SCLeroSiS 

L. BuydenS 1 

1 Radboud University Nijmegen, IMM, Nijmegen, Netherlands 

While Multiple sclerosis is a major disabling disease of the 

Central nervous System (CNS) in young adults, little is known on 

the real cause of this disease; Even diagnosis in an early stage is 

a non-solved issue.Cerebrospinal Fluid (CSF) is the bio fluid, 

which is in closest interaction with the Central Nervous System 

(CNS). It is therefore the bio fluid that best mirrors the 

biochemical status and processes in brain and CNS. Biochemical 

changes are therefore most likely to be found by means of a 

comprehensive analysis of the CSF Other bio fluids such as 

plasma may also contain crucial information; 

Comprehensive analysis by a large variety of analytical 

technologies, yield however complex data for which chemometric 

data analysis and data mining have become crucial tools. Since 

no analytical platform on its own yields a comprehensive image 

of the biochemical status, data fusion has become widespread in 

the last decade. Many methods have been proposed, most of them 

restrict to a linear fusion strategy However, it is not realistic to 

assume that all biological or (bio)chemical data display this simple 

linear behavior. In that case linear methods are bound to fail. In 

this lecture alternative approaches will be presented. One is based 

on the hierarchical fusion of mid-level fusion models. Non-linear 

kernel fusion model allow to cope specifically with 

nonlinearities. [1] We use our pseudo-sample approach [2, 3] to reveal 

the contribution of the individual variables. 

In the lecture we will present results of fusion of CSF and 

plasma analysis data for a better diagnosis and search for 

biomarkers for Multiple Sclerosis 

references: 

1. S. Yu et al., Kernel-based Data Fusion for Machine 

Learning. Methods and applications in Bioinformatics and 

Text mining. Springer: Berlin 2011. 

2. P. Krooshof et al., Analytical Chemistry 82 (2010) 

7000–7007 

3. Postma et al. Analytica Chimica Acta 705 (2011) 123–134 

Keywords: data fusion; metabolomics data analysis; multiple 

sclerosis; chemometrics; 



o - 4 2 2 

SiMuLtAneouS SiGnifiCAnt fACtor deteCtion 

And vAriABLe SeLeCtion uSinG MuLti-BLoCK 

AnALySiS MethodS 

d. rutLedGe 1 

1 AgroParisTech/INRA, UMR 1145 “Génie industriel 

Alimentaire”, Paris, France 

Multivariate methods are nowdays widely used in the study 

of data matrices containing thousands or hundreds of thousands 

of variables. In spite of their ability to work with many correlated 

and noisy variables and to separate the significant variation from 

the noise, these methods can still be improved by a relevant 

selection of variables. 

In this presentation, we propose to split the data variablewise 

into a certain number of segments, each considered as an 

individual block of data, and to detect the relevant segments with 

a Multiple-Block method. 

In the case of data sets where the values of the variables are 

thought to vary with the levels of experimental factors, it is 

possible simultaneously to detect which factors have a significant 

effect. 

Application of the proposed methods to several data sets, 

increasing in complexity, has shown satisfactory results. 

Keywords: Variable Selection; Factor detection; 



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o - 4 2 3 

how to ACCeSS hidden inforMAtion in 

ChroMAtoGrAPhiC dAtA 

L. JohnSen 1 

1 Faculty of Life Sciences, Department of Food Science, 

Copenhagen, Denmark 

In chromatographic data it is often seen that one peak reflect 

more than one compound. Commercial software for multichannel 

data handling (e.g. GC-MS) often offers the possibility 

for performing deconvolution. However, the solutions given by 

such software are often unreliable and in many cases there is little 

or no possibility for the user to evaluate the quality of the resulting 

model. An alternative to the manufacturing software is fitting of 

Gaussian or Lorentzian models to the signal. However, the 

solutions from such models are not unique. Another problem is 

that the user must know how many compounds the model should 

evaluate. Another approach is to use PARAlel FACtor analysis 2 

(PARAFAC2), which has previously been shown to be a powerful 

tool for resolution of overlapping peaks. [1, 2] 

In the presentation it will be demonstrated how PARAFAC2 

can help the analyst in the task with deconvolution of peaks. 

New developments concerning automation will also be 

presented. These developments enable the possibility for 

non-chemometricians to make models with PARAFAC2 and will 

result in a more unbiased result than if the models where 

to be evaluated manually. 

references: 

1. J.M Amigo, M.J. Popielarz, R.M. Callejón, M.L. Morales 

A.M. Troncoso, M.A. Petersen, T.B. Toldam-Andersen. 

Journal of Chromatography A, 1217, 4422 (2010). 

2. J.M. Amigo, T. Skov, J. Coello, S. Maspoch, R. Bro. 

Trends in analytical Chemistry, 27, 714, (2008) 

Chemometrics – iii 


o - 4 2 4 

MuLtioBJeCtive exPeriMentAL oPtiMizAtion 

L. A. SArABiA 1 , M. S. SánChez 1 , M. C. ortiz 2 

1 University of Burgos, Mathematics and Computation, Burgos, 

Spain 

2 University of Burgos, Analytical Chemistry, Burgos, Spain 

Most problems posed in an experimental framework have 

several facets to be taken into account, starting with the 

experimental factors and their influence in different analytical 

responses. These different aspects tend to exhibit a conflicting 

behaviour, the improvement of one of them results in deterioration 

of some other(s). 

Instead of weighting the different responses into a single one 

to be optimized, the present work tackles the multicriteria 

optimization from its vector nature to search for the 

Pareto-optimal solutions, i.e. solutions that are optimal in at least 

one of the criteria maintaining the rest in their best allowable 

values. This multiresponse optimization is addressed from two 

perspectives. 

The most usual context: optimization refers to the searching 

of experimental conditions to optimize several analytical 

responses of interest. In general, this has to be approached from 

an experimental perspective. Consequently, whether these 

responses are individually or jointly optimized, the reliability of 

the optimal solutions is dependent on a proper experimental 

design. 

For some experimental procedures, above all when there are 

several experimental factors, the number of experiments in a 

standard design may make it unaffordable. Hence, the other 

perspective is the selection of the experimental design itself, based 

on its characteristics. There are several criteria to measure the 

quality of an experimental design (variance inflation factors, 

values of the variance function and related to them the alphabetic 

criteria). The search of a reduced design that maintains the 

required quality is again a problem of multicriteria optimization. 

By using analytical problems as guiding examples, Paretooptimal 

solutions are computed for choosing suitable 

experimental designs and for simultaneously optimizing several 

analytical responses of interest. Besides, to study the information 

in these optimal solutions a graphical way, an adapted version of 

the parallel coordinates plot, is also shown. 

Acknowledgments: Financial support through projects 

CTQ2011-26022 and BU108A11-2 

Keywords: Chemometrics; Experimental design; Analytical 

methods; Gas chromatography; 



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o - 4 2 5 

CouPLinG 2d-wAveLet deCoMPoSition And 

MuLtivAriAte iMAGe AnALySiS 

M. CoCChi 1 , M. Li viGni 1 , J. M. PrAtS MontALBAn 2 , 

A. ferrer 2 

1 University of Modena and Reggio Emilia, Chemistry, Modena, 

Italy 

2 Politechnical University of Valencia, Department of Applied 

Statistics Operations Research and Quality, Valencia, Spain 

Wavelet transform (WT) is mainly used in image analysis 

as a preliminary step for denoising or compression and/or in order 

to extract textural features, [1] in this case yelding global image 

descriptors to be used for classification or properties prediction. 

In the present work, we develop an approach that uses the 

2D-DWT (discrete wavelet transform) multiresolution advantage 

in the context of defects detection in single images. The basic idea 

is to combine the potentiality of the MIA approach [2, 3] with the 

wavelet decomposition scheme to take into account pixels 

correlation pattern. 

To this purpose, given a wavelet filter, the resulting blocks 

(Approximation, Horizontal, Vertical and Diagonal coefficients) 

from a 2D-WT decomposition of the image (DWT2 and SWT2 

decomposition schemes are compared), applied separately to each 

color channels, are used as different “versions” of the original 

image capturing the different patterns present in the image. We 

consider a redundant representation, i.e. including approximations 

of every decomposition level considered. In this way, as many 

images as 4 times L (decomposition level) times N (color 

channels) are obtained. These are unfolded to obtain a data matrix 

of dimensions: pixels × (4×L×N). At this point the usual MIA 

approach is followed, afterwards constructing multivariate control 

charts for Hotelling-T2 and residual sum of squares on the basis 

of one or few normal operating images (NOC) so that defects can 

be detected in faulty ones. 

The new proposal has been tested on different data sets, such 

as tiles images with quite difficult to detect defects, oranges 

images corresponding to several damages and multispectral bread 

images to detect surface defect. The main goal is to highlight, on 

one hand, the tipology of defects that can be handled by this 

method and how it may be used alternatively or complentary to 

the Bharaty and McGregor one, taking advantage of the unique 

features of WT, i.e. the fact that the different frequency content 

(related to texture) are depicted in disjoint subspaces and on the 

other to point out the critical aspects of the methodology. 

references: 

1. M. Reis, A. Bauer, Wavelet texture analysis of on-line 

acquired images for paper formation assessment and 

monitoring, Chemometrics and Intelligent Laboratory 

Systems 95 (2009) 129–137. 

2. Multivariate Image Analysis: a review with applications. 

Chemometrics and Intelligent Laboratory Systems, in 

press, doi:10.1016/j.chemolab.2011.03.002 

3. M.H. Bharati, J.F. MacGregor, Texture analysis of images 

using Principal Component Analysis, SPIE/Photonics 

Conference on Process Imaging for Automatic Control, 

Boston, 2000, pp. 27–37. 

Keywords: Multivariate image analysis; texture; wavelets; 

fault detetection; 



o - 4 2 6 

CheMoMetriCS AS A tooL to inCreASe 

effiCienCy of SPeCtroSCoPiC AnALySiS of 

food And environMentAL MAtriCeS 

t. KuBALLA 1 , S. MuShtAKovA 2 , A. tSiKin 2 , 

d. LAChenMeier 1 

1 Chemisches und Veterinäruntersuchungsamt (CVUA), 

Karlsruhe, Karlsruhe, Germany 

2 Saratov State University, Chemistry Department, Saratov, 

Russia 

Chemometrics is the use of mathematical and statistical 

methods to improve the understanding of chemical information 

and to correlate quality parameters or physical properties to 

analytical instrument data. In this study we show how 

chemometric methods can be efficiently coupled with two 

spectroscopic techniques – nuclear magnetic resonance (NMR) 

and ultraviolet-visible (UV-VIS) spectroscopy for analysis of 

complex matrices. 

First, 400 MHz 1H NMR spectroscopy and nontargeted 

approach based on principal component analysis (PCA) was 

applied to reveal potentially unsafe samples of unrecorded alcohol 

as well as for checking the floral origin of honeys, labeling of milk 

and milk substitute products and geographical origin of pine nuts. 

Validation using the independent test sets by Soft Independent 

Modeling of Class Analogy (SIMCA) showed correct 

classification in all cases. 

The second direction for the application of chemometric 

methods in analytical spectroscopy is the quantification of 

substances whose signals overlap with signals of other 

compounds. This possibility was demonstrated by applying partial 

least squares (PLS) regression to quantify several parameters in 

alcoholic beverages such as ethyl carbamate, methanol, higher 

alcohols, 2-phenyl alcohol and ethyl acetate by means of NMR 

spectroscopy and four anions (bromide, bicarbonate, nitrate and 

sulphide) in sea water samples based on UV-VIS measurements. 

Furthermore, we have applied different multivariate curve 

resolution techniques (Alternating Least Squares, Independent 

Component Analysis) for self-modeling decomposition of NMR 

and UV-VIS spectra. The performance of the algorithms was 

shown on several experimental case studies in food science. 

The examples provided clearly demonstrate the suitability 

of spectroscopic measurements for analysis of food stuffs and 

environmental objects. The combination of these spectroscopic 

techniques with chemometric methods is a valuable tool to 

develop screening methods for checking the authenticity and 

quality of these samples. 

Keywords: chemometrics; NMR spectroscopy; principal 

component analysis; multivariate curve resolution; food 

analysis; 



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o - 4 2 7 

GC x GC-tofMS CoMBined to MuLtivAriAte 

Curve reSoLution for the AnALySiS of 

CoMPLex MixtureS of PoLyCyCLiC AroMAtiC 

hydroCArBonS 

r. tAuLer 1 , h. PArAStAr 2 

1 IDAEA-CSIC, Environmental Chemistry, Barcelona, Spain 

2 Isfahan University, Department of Chemistry Faculty of 

Sciences, Isfahan, Iran 

Comprehensive two-dimensional gas chromatography 

time-of-flight mass spectrometry (GC×GC-TOFMS) combined to 

multivariate curve resolution-alternating least squares 

(MCR-ALS) is proposed to improve resolution and quantification 

of very complex sample mixtures of polycyclic aromatic 

hydrocarbons. In full scan multivariate mode, different 

GC×GC-TOFMS data slices acquired during the analysis of 

samples and standards can be simultaneously analyzed and the 

pure component elution profiles in the two chromatographic 

dimensions as well as their pure mass spectra are resolved. In this 

case, problems ubiquitously associated to GC×GC, such as 

retention time peak shifting for within and between runs, are not 

affecting the results obtained using the proposed strategy and 

proper resolution of strongly co-eluted compounds, baseline and 

background contributions are achieved. Calibration curves can be 

built up using standard samples of PAHs and allow their 

quantification in complex oil aromatic fractions. In case of 

univariate detector responses like in flame ionization detection 

(FID) or in total ion chromatogram (TIC) mass spectrometry (MS) 

detection, a combination of peak alignment methods and 

multivariate curve resolution (MCR) is proposed for handling 

retention time shifts and modeling. A new “bilinear peak 

alignment” method based on MCR is proposed to correct for 

progressive within run retention time shifts in GC×GC due to the 

effect of the temperature program on the second dimension. In 

addition, Multivariate Curve Resolution-Alternating Least 

Squares (MCR-ALS) method under proper constraints is also 

proposed to analyze the already aligned bilinear augmented 

GC×GC data matrix for the resolution and quantification of the 

target compounds in complex mixtures in case of their incomplete 

separation and co-elution problems. The results showed the 

successful application of the proposed strategy for resolution and 

quantification of target compounds in GC×GC analysis of 

simulated and real samples. 

Keywords: Chemometrics; GCxGC-MS; MCR-ALS; 




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Education and History, Professional chemists Ethics, Employability, labels 

Ethics and Employability of Professional Chemists – i 

o - 0 1 3 

ethiCS And CheMiStry 

h. frAnK 1 

1 University Bayreuth, Environmental Chemistry, Bayreuth, 

Germany 

Cultural development and chemical activities have always 

been associated with each other; mastering the conversion of 

matter by controlled use of energy, the Promethean gift, meant 

progress in humanity. All pre-historic and historic eras were 

associated with new chemical abilities: from the earliest phases 

of “unconscious chemistry”, e.g. of improving the palatability of 

food or of creating useful materials such as ceramics and metals, 

followed by a phase of “intuitive chemistry” conventionally 

referred to as the era of alchemy, until the mechanistic-analytical, 

intellectual “scientific chemistry” emerged after Paracelsus and 

Descartes. The historical path of chemistry culminated in the 

tremendous scientific advances of the 20th century, a story of the 

devotion of protagonists - but also of failures, controversies, and 

catastrophes. Nevertheless, it is exemplary for the power of 

internationalism, freedom-mindedness, and interdisciplinary 

thinking of those who were active – a success story. On the other 

hand, accidents and environmental problems also showed that we 

need, in order to progress, a more comprehensive, necessarily 

ethical understanding of the chemist’s activities. Chemists make 

chemicals – so they are responsible for them. If not, who else? 

Lawyers? Politicians? Economists? Obviously, in order to 

understand the whole truth, methods for the synthesis of the 

puzzle in front of us are required, i.e. the development of a holistic 

view. The technical prerequisites are emerging with the Internet. 

The main barrier is the too strongly competitive mind between 

those who are practicing science today. The challenge for the 

future is to develop the philosophy and psychology, to envisage 

the ideal of global fraternity/sorority, so the next generations are 

able to implement their full potential in cooperative modes. This 

way, the chemists (and other scientists) have the chance to 

outgrow from a magician’s apprenticeship to become true masters 

- largely a matter of education in science ethics. 

Keywords: Ethics; education; Chemoinformatics; History; 

Future; 



o - 0 1 4 

the MAn And the ProGreSS of CiviLizAtion. 

who Are we And where Are we GoinG? 

B. BuSzewSKi 1 

1 Department of Environmental Chemistry and Bioanalytics, 

Chair of Environmental Chemistry & Bionanalytics, Torun, 

Poland 

For many years, considering various philosophical trends 

and by acting in ecosystem we ask ourselves a weighty question: 

what is the environment? What is the universalism? What is the 

relationship between the progress of civilization and attitude of 

nowadays man, scholar, teacher? In a one word what is the 

reaction between these entities?, And how a man may find himself 

in this Space. Answer is not simple and its complexity does not 

simplify us to interpret of these phenomena, for using various 

types of arguments and facts that we are trying to use in 

interpretation of that relationship. Yes, one can recall the great 

names and attitudes of the world, from Confucius, by Aristoteles, 

Plato, Copernicus, Humboldt, Sklodowska-Curie or Czochralski, 

however these asked questions will be open to question and to 

individual interpretation. 

Similar question to ask yourself: “What chemistry copies of 

nature? How it can be used for the civilization progress?” And in 

this case we will not get a straight answer, on contrary, many 

factors will pose a problem in precise determiniation of positive 

arguments relationship. Because if it is, why and for what 

purpose? Still, there will be an open question Quo Vadis sciences, 

Quo Vadis life sciences? Is today, by the progress of civilization 

and the rush towards the innovation, need a man - an interpreter? 

Versatile scholar? What is the relationship such as master - pupil 

and if the explanation of concepts in the context of sustainable 

development gives us a sufficient dose of information and 

satisfaction? This applies particularly to the attitude, behavior and 

seek of answers by nowadays educated man. Who we are and 

what we want to achieve through learning, activity, creativity and 

ambition? 

These issues will be the subject of my discussion in the 

context of human-science-ethics-the progress of civilization and 

sustainable development. 

Keywords: man; science; civilization; 



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o - 0 1 5 

euroPeAn woMen in CheMiStry – A tASte of 

the BooK 

L. SiMon SArKAdi 1 , J. APotheKer 2 

1 Budapest University of Technology and Economics, Applied 

Biotechnology and Food Science, Budapest, Hungary 

2 University of Groningen, University of Groningen, Groningen, 

Netherlands 

The publication European Women in Chemistry is one of the 

contributions of EuCheMS for the International Year of Chemistry 

(IYC) 2011. Its aim is to celebrate the role of women in chemistry. 

The book was published by Wiley VCH and we are especially 

pleased that Professor Nicole Moreau (President, IUPAC 

International Union of Pure and Applied Chemistry) agreed to 

write foreword to the book. 

The book chapters cover women from alchemical times up 

to the 19 and 20th centuries, from famous and well-known women, 

such as Nobel Laureates Marie Curie, Irene Joliot-Curie, Dorothy 

Crowfoot Hodgkin, and Ada Yonath, to women whose reputations 

are less well-known, but whose contributions have, nevertheless, 

been vital. The stories reflect the range of activities and emphasise 

just how difficult it was for female chemists to develop rewarding 

careers for themselves. 

Whilst there has been progress throughout the 20th century 

women chemists in academia and industry are still not represented 

well at the upper levels. There is, thus, a need to continue to 

promote, support and encourage women chemists and women 

scientists and technologists, especially those at the start of their 

careers. The opportunities, challenges and satisfaction of a career 

in European science, in general, and European chemistry, in 

particular, should be stated clearly to schoolchildren so as to 

encourage future generations. The benefits to society and to 

economic development from the application and exploitation of 

science must be clearly presented at every opportunity. This is the 

responsibility of each and everyone of us. 

Keywords: book; women; history; 


Ethics and Employability of Professional Chemists – ii 

o - 0 1 6 

fLexiBLe And MuLtidiSCiPLinAry trAininG of 

younG CheMiStS 

A. de PACe 1 

1 Private Professional, Consiglio Nazionale Chimici, Padova, 

Italy 

The value of practical applications in the field of Chemistry, 

in either the public or private sector, is often underestimated with 

respect to the real possibilities that this type of formation offers. 

A background knowledge of Chemistry can make decisive 

improvements in various sectors of production and cost 

considerations, especially in product improvement and production 

processes, the creation of quicker and safer control procedures, 

better packaging methods, stocking and delivery, as well as 

distribution chains. 

In fields dealing with ecological issues, waste recycling, 

renewable energy, chemical risk evaluations, and scheduled plant 

maintenance, chemists are called upon not only to resolve 

technical problems, but to contribute also to the overall 

organization and general management of the firm. 

Some concrete examples of the above assertions are 

presented to students, as well as teachers, in order to illustrate the 

ample opportunities in the workplace that Chemistry offers to 

young graduates with broad multidisciplinary training. 

Keywords: multidisciplinarity; risk management; stockings; 



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Ethics and Employability of Professional Chemists – ii 

o - 0 1 7 

younG CheMiSt exPeCtAtionS froM A CAreer 

in induStrywhAt do younG GrAduAteS wAnt 

froM A JoB in induStry? 

G. PoiSSon 1 

1 Nancy Universite, UMR 7565 SRSMC, Vandoeuvre-les-Nancy, 

France 

All young chemists from generation Y1 also known as the 

Millennial Generation, Net Generation, … are borne between the 

mid-70s and the mid-2000s. In media, we often hear that youth 

are lazy, undisciplined, hard to manage, etc. This generation, 

which enters on the jobs market, is as they say? Is it really 

different from previous generation? How young people perceive 

job word? What do young graduates wait from a job in Industry? 

It’s to these questions that we’ll try to answer. 

Three dimensions must be taken into consideration, which 

are the dimension instrumental, social and symbolic2 . The 

instrumental dimension refer to material care, i.e. the wage and 

promotion opportunity, the social dimension concern human 

relation in firm and the symbolic dimension include the possibility 

of personal development, the ability to grow and express itself in 

its activity, the sense of achievement, social utility, etc. Many 

surveys and studies have been conduct on this topic in several 

countries. Conclusions are same for all; young chemist 

expectations are important, but not so different from previous 

generations’ expectations. Warning! For if expectations are high, 

deceptions that are linked are equally important. 

references: 

1. Strauss, William & Howe, Neil. Generations: The History 

of America’s Future, 1584 to 2069. Perennial, 1992 

(Reprint). ISBN 0-688-11912-3 pp. 31, 327 

2. a) Nicole-Drancourt C., Roulleau-Berger L.,Les jeunes et 

le travail. 1950-2000, Puf, Paris, 2001 ; 

b) Riffault H. et Tchernia J.-F., « Les Européens et le 

travail: un rapport plus personnel », Futuribles, n°227, 

2002, pp. 63-77 

Chemistry for Cultural Heritage 


o - 0 1 8 

PreServinG SCientifiC heritAGe: PrAGue 

MonuMentS reLAted to hiStory of 

CheMiStry 

S. StrBAnovA 1 

1 Institute for Contemporary History Academy of Sciences of the 

Czech Republic, Centre for the History of Sciences and 

Humanities, Prague, Czech Republic 

The identity of a city is shaped by various sets of 

characteristics by which the city is recognizable or known, like 

its visual image, architecture and natural setting. Less conspicuous 

features contribute to various parallel identities of a city, as well. 

Prague has been molded for centuries not only by architects, 

artists, musicians and artisans, but also scholars and engineers, 

therefore we may discover among the various identities of Prague 

also its scientific identity. 

Material objects that constitute the scientific or in our case 

chemical identity of a city are, for example: 

• Buildings, sites and landscapes related research and 

education, like universities, laboratories, observatories, 

hospitals, pharmacies, industrial units, etc. 

• Places related to the lives and achievements of individual 

scholars, like birthemeteries. 

• Museums, libraries and archives with collections related 

to the development of science and lives and work of 

scholars. 

• Artistic objects reminding of significant personalities or 

important achievements in science (statues, monuments, 

memorial plaques). 

Such physical objects are part of the world’s scientific 

heritage and mankind’s cultural memory, an area where science 

and humanities overlap. These items have versatile historical, 

esthetic, didactic and even economic values (tourism), and 

represent invisible links between science, technology and culture. 

The complex process of science and circulation and appropriation 

of ideas, have always been embedded in a particular setting 

– country, city, institution, laboratory – and performed in this 

setting by unique individuals, therefore these objects can serve to 

the historian of science as valuable tools for investigating 

scientific progress in its interaction with the society’s intellectual, 

political, cultural and spiritual development. To demonstrate this, 

the paper focuses on Prague’s chemical historical legacy in the 

19th century, when chemistry and related industries became 

leading branches in the Czech Lands. 

Keywords: History of Science; 



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Chemistry for Cultural Heritage 

o - 0 1 9 

ALCheMiCAL CryPtoGrAPhy 

M. nováK 1 

1 Institute of Chemical Technology, Social Sciences, Prague 6, 


Having had no rational way of notation, medieval European 

alchemists used a very complicated system of diverse graphical 

symbols for description of chemical substances, laboratory 

devices and operations. These symbols, besides their shorthand 

role, also serve as a specific cryptographic system, for very often 

the alchemists tried not only to depict their experimental results, 

but also to conceal them from the Christian church, avaricious 

noblemen and possible competitors. Origin of alchemical symbols 

was diverse: some symbols stood for simplified images of 

instruments or substances, some ones distinctly proceeded from 

Egyptian hieroglyphs or ancient Greek glyphs, on certain symbols 

influence of other graphical systems, e.g., Phoenician and 

Hebrew alphabets, Tironian notes, etc., can be traced. Of course, 

in most cases invention of an alchemist, usually influenced by 

esoteric concepts, played a not negligible role. In spite of a useful 

shorthand role the alchemical symbols, just due to their 

cryptographic effects and multiplicity, complicated 

intercommunication between alchemists and have complicated 

reading of alchemical documents up to the present days. On the 

other hand, the idea to describe chemical elements and 

compounds by certain glyphs, whose originally graphic form was 

step by step transformed to the alphabetical one, represented the 

basis of contemporary chemical logograms – probably the most 

perfect nomenclature system among other professional ones. 

European Chemistry thematic Network – i 


o - 1 3 8 

the roLe of eCtn And eC2e2n in the 

deveLoPMent of hiGher eduCAtion in 

CheMiStry in euroPe 

A. SMith 1 

1 Ecole Superieure de Chimie Physique Electronique, Chemistry, 

Villeurbanne, France 

Created in 1996 as part of the Socrates-Erasmus programme, 

the European Chemistry Thematic Network (ECTN) is a network 

that brings together all the actors in higher education in chemistry 

in Europe (universities, national chemical societies, and the 

chemical industry). The network has been continuously funded 

under the Erasmus or LifeLong Learning programme, and the 

current (fifth) three-year project is called the European Chemistry 

and Chemical Engineering Education Network (EC2E2N), and 

involves both chemistry and chemical engineering higher 

education. There are 118 partners from 27 European countries in 

this project. 

This presentation will outline the major activities and 

achievements of the network since its inception, concentrating on 

activities not discussed in other presentations in this session. 

Past activities have included: the definition of what 

constitutes core chemistry in bachelor programmes throughout 

Europe; the creation of bachelor and master frameworks for 

chemistry and at the interface of chemistry and chemical 

engineering; identifying key generic skills; summer schools for 

newly appointed university teaching staff; employability of 

chemistry graduates; entrepreneurial skills; internet-based 

chemistry and chemical engineering tests at several levels and 

covering all areas of chemistry; linguistic issues in chemistry 

education; the image and attractiveness of chemistry; improving 

learning outcomes in chemistry and chemical engineering; and a 

database of chemistry programmes at bachelor and master levels 

as an aid to student mobility. 

These areas will be briefly discussed to show how the 

network has played an important role in the development of higher 

education in chemistry over the past 16 years. 



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o - 1 3 9 

virtuAL CoMMunitieS in SCienCe And 

eduCAtion 

A. LAGAnA 1 

1 University of Perugia, Department of Chemistry, Perugia, Italy 

The evolution of networked distributed computing 

technologies is fostering the advent of virtual communities and 

service oriented approaches. Such evolution is bound to provide 

“integrated services through unified access to and seamless 

integration of the underlying networking, computing and data 

infrastructures” to research, innovation and education. 

At European level distributed technologies can rely on the 

European Grid Infrastructure (EGI) and, for Chemistry, on 

COMPCHEM a virtual organization committed to design, 

implement and develop specific Grid services as well as tools 

carrying out the evaluation of the quality of the services. As to 

Education, a protagonist of this evolution is the European 

Chemistry Thematic Network (ECTN) Association that has 

undertaken the highly innovative engagement of pursuing long 

term sustainability by building a Virtual Educational Community 

(VEC) aimed at developing a distributed service oriented 

environment. 

Cooperative/competitive educational approaches leveraging 

on the specific features of the VEC are already being adopted to 

allow software reuse and interoperability by developing 

repositories of higher education electronic teaching and learning 

materials and Learning Objects (LO) are being created. The most 

important shared patrimony of VEC is a set of electronic selfevaluation 

tests (EChemTest) in chemistry and related support 

material meant to enhance knowledge and skills in chemistry. 

EChemTest covers the European Core Chemistry topics at three 

different levels, corresponding to the end of compulsory studies 

and the beginning of university studies and the completion of the 

core chemistry syllabus in analytical, biological, inorganic, 

organic, and physical chemistry. Moreover, tests are provided for 

synthetic and computational chemistry and specialized question 

banks have been created for chemistry applied in cultural heritage 

preservation. EChemTest contents are based on a syllabus 

developed by analysing the major European educational system 

and related teaching program contents. 

Keywords: virtual community; learning object; self evaluation; 

compchem; service oriented; 



o - 1 4 0 

e-tooLS for the CheMiStry virtuAL 

eduCAtion CoMMunity 

A. LAGAnA 1 

1 University of Perugia, Department of Chemistry, Perugia, Italy 

Among the integrated services built for the Virtual 

Educational Community (VEC) established by the European 

Chemistry Thematic Network (ECTN) are some e-tools useful for 

carrying out the activities of VEC. Some of these tools are focused 

on the management of the knowledge developed within ECTN, 

on the support to the association activities and some others to 

communication. In this contribution we shall focus on two 

communication products: the Newsletter and the Magazine with 

the aim and the structure of the two e-tools being quite different. 

The Newsletter is a way of disseminating the activities 

carried out by the community and illustrating their nature. ECTN 

has published its first “News” information in 1999, renamed 

ECTN Newsletter in March 2000. Following the evolution of the 

various ECTN projects the Newsletter has become the EC2E2N 

one about the end of the year 2009. At present it consists of a 

bimonthly electronic bulletin freely accessible on the ECTN 

website (http://ectn-assoc.cpe.fr/news/index.htm) dealing with the 

activities of the eCtn Association and the european Chemistry 

and Chemical engineering education network. More in 

general, however, it deals also with any information related to the 

chemistry education in the European Higher Education Area and 

the extended European area. The announcement of the publication 

of the issues of the Newsletter is widely disseminated throughout 

Europe and abroad. Chemical Societies are also receiving our 

Bulletin, as well as the Members of the ACEN (Asia-Pacific 

Chemical Education Network). 

The electronic magazine is a biannual publication addressed 

to Virtual Innovation Research Teaching & Learning 

Communities. The magazine is the result of a joint endeavour of 

the COMPCHEM Virtual Organization (VO), of the European 

Chemistry Thematic Network (ECTN) Association and of the 

University of Perugia spinoff MASTER-UP. The magazine is 

specialized in Molecular and Materials Science, Teaching and 

Learning, Computer Science research, education and innovation 

and focuses on Service Oriented approaches. In addition to full 

papers, it publishes reports of (successful or failed) attempts to 

build services relevant to the field of interest, lists of best 

practices, products used, the advantages and disadvantages of the 

solutions adopted will be considered for publication. In particular, 

all the information useful to build the puzzle of innovative 

complex applications in education, ICT and Molecular and 

Materials science are accepted. 



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European Chemistry thematic Network – ii 

o - 1 4 1 

teAChinG Key CoMPetenCeS to CheMiStry 

StudentS – An initiAtive in the frAMe of the 

euroPeAn CheMiStry theMAtiC networK 

e. vAreLLA 1 , i. KozAriS 1 

1 Aristotle University of Thessaloniki, Chemistry, Thessaloniki, 

Greece 

The Budapest Descriptors, a detailed adaptation of the 

Dublin Descriptors in the area of chemical sciences, as well as 

their extension in interdisciplinary areas, are defining key 

competences for all academic levels. Less demanding for the first 

cycle, these indispensable abilities and mind-settings increase in 

complexity at master’s and doctoral level, or for subjects at the 

interface of chemistry and other disciplines. 

Although frequently acquired within standard study and 

research environments, key competences would as often be 

obtained by attending specialised workshops or following relevant 

course modules. In this context, the European Chemistry 

Thematic Network Association adopted a multifaceted scheme for 

supporting young scientists in their attempts to enter a globalised 

labour market. 

The structure implemented consists in Centres for Key and 

Specific Competences in Science, addressing generic skills and 

attitudes, necessary for effectively responding to requirements set 

by stakeholders. In the same frame, Units on Languages for 

Specific Purposes handle linguistic issues. The Centres apply a 

hybrid operation pattern, combining wide-ranging e-learning 

possibilities to systematically organised intensive schools. 

The on-line educational environment is designed on the 

basis of a three-fold pattern, encompassing a preliminary study 

phase; videoconferencing frontal hours; and post-course training 

and self-assessment opportunities. In this context, a specially 

developed web portal has been established. 

The intensive schools on key competences for scientists 

are structured as tailor-made interactive workshops and 

problem-solving classes, preparing young scientists from all over 

Europe for the conditions encountered in the labour market. 

The feedback to this two-fold activity of the Centres for Key 

and Specific Competences in Science, consisting in the evaluation 

of questionnaires, did not present noteworthy discrepancies, 

except for the somehow different expectations formulated in each 

academic level. 

Keywords: key competences; e-learning; intensive workshops; 

European Chemistry thematic Network – ii 


o - 1 4 2 

intenSive SChooLS And unitS on LAnGuAGeS 

for SPeCifiC PurPoSeS – hyBrid eduCAtionAL 

initiAtiveS in the frAMe of the euroPeAn 

CheMiStry theMAtiC networK 

e. vAreLLA 1 , B. whiddon frAnCiLLArd 2 , 

i. KozAriS 1 

1 Aristotle University of Thessaloniki, Chemistry, Thessaloniki, 

Greece 

2 CPE Lyon, Chemistry, Lyon, France 

In the frame of most educational initiatives taken by the 

European Chemistry Thematic Network Association at a transnational 

level, crucial open questions have been the harmonisation 

of student knowledge and competences in intensive programmes; 

and the communication gap in the multi-lingual European 

environment. An efficient low-cost answer lies in implementing 

a hybrid scheme, combining e-learning activities and intensive 

face-to-face training. 

The intensive schools address students and professionals, 

wishing to acquire a solid knowledge on the ways chemical 

sciences are applied in safeguarding tangible works of art. 

A multinational team of experts deliver frontal lectures, 

problem-solving classes and hands-on experimental exercises to 

attendees originating from Europe and beyond. Being highly 

interdisciplinary and international, the schools are confronted with 

serious complications while attempting to form levelled 

classrooms; a further permanent concern being how far the 

overload of information will not too quickly be discarded. Both 

problems are met with the implementation of a virtual campus 

combining synchronous and asynchronous techniques; and 

presenting 

e-learning possibilities for self-paced pre- and post-school use. 

A closely interrelated activity is the implementation of Units 

on Languages for Specific Purposes, divisions of pertinent Centres 

for Key and Specific Competences in Science. In their context, a 

web portal on key competences for scientists has been developed, 

including a well-built learning and self-assessment section for 

English as a foreign language. Moreover, synchronous training is 

served by an especially designed manual on teaching languages 

for chemists & chemical engineers. In a parallel way, intensive 

schools include structured language courses on topics relevant to 

their curriculum; pre- and post-school study and self-assessment 

benefiting from appropriate web-portal contents. 

The feedback to these parallel activities, consisting in the 

evaluation of questionnaires, permits judging the efficiency of 

hybrid educational schemes in intensive training and in language 

teaching. 

Keywords: intensive schools; virtual campus; languages for 

specific purposes; 



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European Chemistry thematic Network – iii 

o - 1 4 3 

A roAdMAP for euroLABeLS in CheMiStry 

t. MitCheLL 1 

1 TU Dortmund, Chemistry, Dortmund, Germany 

Chemistry was one of the subjects which was involved since 

the beginning in the project “Tuning Educational Structures in 

Europe”. Thus the Chemistry Subject Area Group in Tuning, run 

by ECTN, thought and discussed for many years about how 

chemistry degree structures across Europe could be made 

compatible. 

From there it was a short step to consider the aspect of 

quality assurance. We soon realised that, although accreditation 

was set to become a normal feature of degree programmes in 

many European countries, the international perspective was 

missing completely. 

Thus we decided to set up our own QA labels, the 

Eurolabels ® , with the support of the EU Commission. First came 

the Eurobachelor ® , then the Euromaster ® , and work has just been 

completed on a Label for doctoral programmes. 

This talk will outline the development, past and present, of 

the Eurolabel ® concept. 

European Chemistry thematic Network – iii 


o - 1 4 4 

entrePreneuriAL Attitude: whAt we 

ALreAdy teACh And whAt not (yet) 

r. SALzer 1 

1 Dresden University of Technology, Department of Chemistry 

and Food Chemistry, Dresden, Germany 

We educate high-level scientists. Do all our graduates need 

entrepreneurial skills? Can we really improve their employability 

by stimulating entrepreneurial attitude? A recent workshop took 

inventory. [1] Here we report on the results of this workshop. 

Although promotion of entrepreneurship may appear to be 

of peripheral importance to universities committed to advancing 

science and humanities, entrepreneurs can anchor intellectual 

endeavors in reality by deploying the practical output of 

knowledge. Given the role of entrepreneurship in economic 

growth and social progress, the training of entrepreneurs can be 

deeply connected to public service, central to the mission of 

universities. [2] 

Key recommendations of the workshop are: 

Graduates should be better trained to think in processes. 

Improvement in this field does not require new components in the 

curriculum; it only requires a new approach in the educational 

process. 

Teaching entrepreneurial skills is not only about setting up 

a company. Entrepreneurial skills are extremely useful in any job, 

including jobs in administration. 

A severe challenge is the business plan. A business plan is 

similar to a project plan, which should be established for any 

larger undertaking within the study programme - like a thesis. A 

project plan including well define milestones and including a plan 

B in case the milestones cannot be met would be helpful to reduce 

extended study times in several cases. 

Stimulating entrepreneurial skills is a necessary step during 

the educational process. Guidance for young entrepreneurs is 

similarly important to anchor intellectual endeavours in reality. 

references: 

1. http://ectn-assoc.cpe.fr/network/ec2e2n/wp/ 

wp06_StimulEntrepreneurship.htm 

2. I. Z. Quadir, Science 335, 6075 (2012) 1445-1446. 



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History of Chemistry 

o - 2 7 0 

hiStoriCAL And PhiLoSoPhiCAL APProACheS 

to the teAChinG/LeArninG of SoMe 

fundAMentAL CheMiStry ConCePtS. 

e. MAiA 1 

1 Centro de Filosofia das Ciencias da Universidade de Lisboa, 

University of Lisbon, Lisboa, Portugal 

By the middle of the 20th century, there was a profound 

change in science education, both in curricula and in 

methodological approaches. In what chemistry was concerned the 

curricula started giving more emphasis to a conceptual approach 

than to factual chemistry, in an attempt to get better trained 

scientists, what made the study of chemistry much more difficult 

for students and also more distant from the real world. This led to 

a new change in curricula, in view of making chemistry more 

appealing to students, with the idea that chemistry education 

should be aimed at forming citizens, and not specialists, capable 

of understanding and participating in public discussions about 

important problems related to chemical issues. And so a new trend 

appeared in the curricula, derived from the so called STS 

approach, meaning Science, Technology and Society, and later on 

STSE approach, which adds Environment. This approach stresses 

the importance of contextualizing chemistry concepts in terms of 

technology and society, integrating aspects of daily life and 

environmental concerns. Some curriculum developers also 

stressed the importance of history and philosophy of science that, 

besides allowing students to get a more general perspective of 

science could be useful didactic tools for the teaching and learning 

of several topics. 

The importance of history and philosophy of science in 

scientific education has been gradually recognized in the last 

years. In the case of chemistry, the historical evolution of some 

fundamental concepts, like acid, oxidation, atom, valence, mole, 

complemented with a philosophical reflection on them and on the 

process of the construction of this science, may facilitate students’ 

understanding of our modern way of viewing these fundamental 

concepts. History and philosophy of science also can allow 

clarifying the meaning of the duality theory-experimentation that 

accompanied the development of chemistry, and also the fruitful 

dialog between science and technology. 

Keywords: History of chemistry; Philosophy of chemistry; 

Chemistry education; 



o - 2 7 1 

you Are MAde uP of eLeMentS. A theAtriCAL 

PerforMAnCe of the PeriodiC tABLe of the 

eLeMentS for the reSeArCherS niGht 

A. MArChAL inGrAin 1 

1 University of Jaén, Inorganic and Organic Department, Jaen, 

Spain 

In the context of the “International Year of Chemistry” 

celebrated last year, an entertaining play about the story of the 

periodic table of the elements has been written and successful 

performed in several Spanish cities as a vehicle for highlighting 

the contribution of some researchers to the development of 

science, chemistry in particular. The text has been written by 

Antonio Marchal, Professor at the University of Jaén and the stage 

adaptation of the script has been carried out by Noelia Rosa, a 

local actress who has ensured that the actors and actresses were 

fully identified with the characters, some of them from different 

countries and in different historical contexts. All this despite its 

unscientific education. Thus, the story has brought alive, among 

other characters, Antonio de Ulloa and Juan Jose Delhuyar, the 

only Spanish researchers who have been credited with having 

discovered, respectively, platinum and tungsten, Marie Curie who 

discovered two radioactive elements, radium and polonium, and 

scientists Dimitri Mendeleev and Lothar Meyer, who, working 

independently, put in order all the known elements and thereby 

facilitated the study of their properties, leading to the 

establishement of Periodic Table of the Elements that we all know 

and study. 

To emphasize the educational value of the play, we have 

developed a few questions that we think might help study the topic 

of the Periodic Table and that can be answered, before the 

performance, during and at the end of it in class. Furthermore, 

the Unit Scientific Culture at the University of Jaen has edited 

the text of the play along with the recording of the first 

performance in order to enable the play to be represented and 

adapted to the characteristics of students in all schools who 

request it. 

Keywords: history of science; 



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o - 2 7 2 

the internAtionAL ConGreSS of APPLied 

CheMiStry, 1912: different viewS on the roLe 

of SCienCe in feedinG worLd PoPuLAtion 

M. tAddiA 1 

1 University of Bologna, Chemistry “G. Ciamician”, Bologna, 

Italy 

Two notable events in the history of chemistry happened in 

Europe and United States during the year 1912: (a) the foundation 

of the International Solvay Institutes for Physics and Chemistry 

by Ernest Solvay (Brussels) and (b) the International Congress of 

Applied Chemistry that took place in U.S.A. The object of the 

Eighth Congress of Applied Chemistry (Washington and New 

York, September, 1912) was the advancement of all applications 

of chemical science to practical life. This work concerns lectures 

delivered by two European chemists: August Bernthsen 

(Krefeld, 1855 – Heidelberg, 1931) and Giacomo Ciamician 

(Trieste, 1857 – Bologna, 1922). They expressed different points 

of view about the role of chemistry in feeding growing world 

population. The American press followed the meeting with 

interest, stressing differences between the speakers. On September 

12, two New York Times headlines drawn the attention of the 

reader: Gives Out Secrets of Making Ammonia and Sun To Do 

Work of Steam. The speeches by Bernthsten and Ciamician were 

the subjects. Speaking about “Synthetic Ammonia”, Bernthsen 

(Badische Co.) informed the Congress that problems for the 

synthetical manufacture of ammonia from the elements were 

solved. BASF promoted the technical work and, in order to meet 

the farmers requirements of nitrogen fertilizers, the first factory 

for synthetic ammonia was rising at Oppau. Unlike Bernthsen, 

Ciamician trusted less to the fulfillement of an happy future in 

synthetical discovery than to resupplying the earth with the energy 

which it is gradually losing. Ciamician pointed out that coal 

deposits were not endless and that people should ask themselves 

whether coal was the only energy source that could benefit 

civilization. The answer was to be found in the fact that most of 

the energy which the earth receives from the sun is wasted. 

Ciamician’s lecture “The Photochemistry of the Future” proposed 

a change in perspective. 

Keywords: History of Science; Photochemistry; Industrial 

Chemistry; 



o - 2 7 3 

euroPeAn ConGreSS? euroPeAn SoCiety? … 

And the firSt inStitute of teChnoLoGy 

SinCe 1762 

d. veLiC 1 , i. herCKo 1 , v. MiLAtA 1 , M. SALiSovA 1 

1 Slovak Chemical Society, Associated Universities 

The town of Banská Štiavnica (Banska Stiavnica, 

Schemnitz, Selmecbánya) was in Middle Ages the main producer 

of silver and gold in the Kingdom of Hungary, a part of 

Austrian-Hungarien Monarchy, nowadays Slovakia. The place 

was called “terra banensium” (the land of miners) as early as in 

1156 and gained the status of a royal town in 1238. The town 

Banská Štiavnica was a foremost center of innovation in mining 

industry, in 1627 gun powder was used here for the first time in a 

mine and water reservoirs and channels, known as tajchy, were 

designed to drain water from the flooded mines and also to 

provide energy for the early industrialization. In 1735, the first 

mining school in the Kingdom of Hungary was founded there and 

in 1762 the Hofkammer in Vienna, with support from Queen 

Maria Theresa, transformed the school into the famous Mining 

Academy, establishing the first institute of technology or the first 

technical university in the world. Department of chemistry and 

mineralogy was formed as the very first one and his head was 

Nicolaus Jacquin from Leyden, who joined theory with practice 

and lectures were based on his own laboratory experiments. 

The school organized in 1786 in Sklene Teplice also the First 

International Scientific Congress, where even Lavoisier 

participated, who considered Jacquin as the founder of 

experimental education in chemistry. At this meeting, the first 

International Society “La Société de l Exploration des Mines” was 

also established. The most prestigious credit was given to the 

Mining Academy by Fourcroy in French National Convent in 

1794, appreciating laboratory experiments in chemistry education. 

The Mining Academy in Banská Štiavnica became an example 

for establishing Parisien Polytechnique and other polytechnics in 

Europe and today we are celebrating 250 years of this tradition. 

Associated universities: 

Miskolci Egyetem Bányamérnöki Kara Miskolci, Hungary 

Nyugat-Magyarországi Egyetem Erdmérnöki Kara Sopron, 

Hungary Montanuniversität Leoben, Austria 

Hornícko-geologická fakulta Technické univerzity Ostrava, 


Fakulta baníctva, ekológie, riadenia a geotechnológií Technickej 

univerzity v Košiciach, Košice, Slovakia 

Lesnícka fakulta Technickej univerzity vo Zvolene, Zvolen, 

Slovakia 



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Education in Chemistry – i 

o - 2 7 4 

CheMiCAL, Life And environMentAL SCienCeS 

Meet BuSineSS ethiCS, CorPorAte SoCiAL 

reSPonSiBiLity: An inteGrAted APProACh And 

PerSPeCtive ShAPeS An entire univerSity 

S. fränzLe 1 , A. LÖhr 2 , o. tettenBorn 3 

1 Internationales Hochschulinstitut, Bio- and Environm. 

Sciences, Zittau, Germany 

2 Internationales Hochschulinstitut, Social Sciences, Zittau, 

Germany 

3 Internationales Hochschulinstitut, Public Affirs spokesman of 

IHI, Zittau, Germany 

IHI Zittau is dedicated to academic research, studies, and 

cross-regional cooperation providing an intercultural focus for 

(graduate) students from nearby Cz/D/PL border triangle, and 

elsewhere abroad. This implies intercultural education and intense 

foreign language training. E.g., students of project management 

are made aware of their sphere of responsibility (influence) 

and thus to keep environmental and social standards 

during production. On various levels, (MSc/MA/MBA, PhD, 

Habilitation), we strive to educate responsibly acting 

professionals, in turn confronting students of life sciences with 

ethical and economic drawbacks. 

What kind of ethics do we talk about? If ethics, ethical and 

responsible behavior, including issues of scientific integrity, were 

taught just in an abstract principle-based approach one would 

spread vague ideas and probably disappointment among students: 

rather than considering ethics an integral part of their professional 

life, this would be perceived as an demand put exogenously on 

them by principles remote from their own personal and 

professional situation. The students hence are expected to regard 

ethical criteria and demands from other spheres while subjected 

to professional tasks in their particular business. 

Practically this integrative approach is pursued by 

cooperation with real enterprises and other organizations. There, 

outside our rooms and labs, most of our MSc/MA and PhD theses 

are prepared, and there a graduate or postgrad gets familiar with 

“real-life” problems, including ethically relevant drawbacks such 

as environmental damages due to possible scale-up of their 

approaches and innovations. 

Philosophically, this goes in line with modern concepts of 

ethics, particular dialogue ethics, which rest on three pillars of 

modern philosophy, i.e. (a) the linguistic turn, (b) practical turn, 

and (c) cultural turn. In sum, the cultural-based approach to ethics 

means that students have to develop a practical (chemical, 

economic, etc.) professional culture rather than learning 

theoretical principles. 

Keywords: ethics; transdisciplinary education; scientific and 

enterprise responsibility; 

Education in Chemistry – i 


o - 2 7 5 

ASSeSSMent of toPiCS deeMed reLevAnt in A 

nurSinG CheMiStry CourSe 

C. e. Brown 1 , J. BArBerA 1 , M. L. M. henry 2 , 

r. M. hySLoP 3 

1 University of Northern Colorado, Chemistry and Biochemistry, 

Greeley, USA 

2 University of Northern Colorado, School of Nursing, Greeley, 

USA 

3 University of Northern Colorado, Department of Chemistry 

and Biochemistry, Greeley, USA 

This two-stage study focused on the undergraduate nursing 

course that covers topics in general, organic, and biological 

(GOB) chemistry. In the first stage, the central objective was to 

identify the main concepts of GOB chemistry relevant to the 

clinical practice of nursing. The collection of data was based on 

open-ended interviews of both nursing and chemistry teaching 

faculty as well as practicing nurses. From the resulting interviews, 

three themes emerged: topics that are Important – have a direct 

application in the nursing clinical practice; topics that are 

Foundational – are not directly important for the nursing clinical 

practice but facilitate the understanding of the important topics; 

and topics that are Not Important – do not have a direct application 

or are not significant in the nursing clinical practice. Utilizing the 

data collected, a list of clinically relevant chemistry concepts was 

developed. The resulting list was then evaluated by nursing and 

chemistry faculty at the national level. 

The second stage involved the design and development of 

an assessment in the form of a concept inventory. The General, 

Organic, and Biological Chemistry Concept Inventory 

(GOB-CCI) is a 47 item multiple-choice instrument designed to 

assess students’ conceptual understanding of the main chemistry 

concepts identified as essential in clinical nursing practice. Items 

for this instrument are based on the most relevant concepts as 

identified in the first stage of the research. In producing the current 

version of the instrument, data from a large-scale (n~600) pilot 

study was used to evaluate and edit each item. A psychometric 

analysis performed on the data was used to evaluate validity, 

reliability and item statistics. It is hoped that data from this 

instrument will facilitate the assessment of the GOB chemistry 

curriculum and courses as well as providing chemistry instructors 

a better understanding of the difficulties their nursing students 

have in chemistry. 



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special symposium: Ethics in science – i 

o - 2 7 6 

ModerAtion And CoMMon SenSe 

A. PAvLAth 1 

1 American Chemical Society, California Section, Albany, USA 

Seventy-five years ago chemists were depicted in movies as 

absentminded benign scientists who worked day and night in the 

laboratory immersed totally in their experiments and oblivious to 

the world around them. The stereotype was neglecting his family, 

if he had one, and was exuberated by making a new discovery. 

Nowadays, chemists are more social, but especially many of those 

in the Ivory Tower, they still do research for the sake of research 

and not necessarily for helping our everyday life. Frequently, the 

goal of the research is to get recognition and awards. 

Today the image of the “mad scientist” disappeared. The 

media now increasingly concentrates on any negative effect of 

chemistry on the environment. The side effects whether true or 

not receives headlines, while the benefits of chemical discoveries 

are relegated at best to the back pages. The effect of DDT on bird’s 

eggs was considered hundred times more important than the 

eradication of mosquitoes, which were responsible of millions of 

people dying of malaria. 

The public image of chemistry has declined during the past 

twenty-five years. It is “politically correct” to vilify chemicals. 

We should not ignore the possible side effects of chemical 

discoveries, but we must continuously communicate to the 

population the hundreds benefits chemistry provides to our life. 

Obviously, nothing is perfect in life and there is no zero risk. 

However, even when chemicals sometime may contribute to the 

problems, chemists develop new chemicals to decrease or 

eliminate them. Poor public image decrease funding for research 

and frequently direct our students to select chemistry as their 

profession. The lecture will highlight responsibilities of chemists 

both in research and communication using common sense and 

moderation. 

Keywords: Public Image; Scientific responsibility; 



o - 2 7 7 

LivinG ethiCS for the GLoBAL CheMiStry 

youth 

M. frontASyevA 1 

1 Joint Institute for Nuclear Research, Head of Dept. of NAA 

and Applied Research Frank Laboratory of Neutron Physics, 

Dubna, Russia 

The philosophy of the Cosmic Reality, known as the 

teaching of “Living Ethics” (German: Lebendige Ethik, French: 

Éthique de Vie) by the Russian thinkers Elena I. and Nicholas K. 

Roerich gives a theoretical basis for understanding the cosmic 

evolution, its features and the place of humankind in this process. 

The Roerichs’ work consists of 15 books written between 1924 

and 1937 (with unknown co-authors) on the main principles of 

new cosmic thinking. E.I. and N.K. Roerich believed that the 

proclamation of a coming new world was their task, an awakening 

of humanity which they said to be in deep crisis. The Living 

Ethics is in continuity with the principles of classical Indian 

philosophy, of Buddhism, Taoism, Confucian teachings, 

Christianity, and of the philosophy of Plato. The ideas of cosmic 

thinking and the modern scientific image of the world are briefly 

summarized: (a) evolution as a central idea in the ontology of 

Living Ethics; (b) the invisible world, an aggregation of other 

states of matter; (c) the universality of the principle of vibration 

(superstring theory); (d) the multidimensional universe with the 

latest observations indicating a non-Euclidian geometry of the 

universe and, according to some models, of a dodecahedral 

dimension; (e) Big Universe or Multiverse; (f) perspectives for 

the space-time; (g) the phenomenon of life, the origin of mind; 

(h) the Mind as the primary creative power of the Universe; 

(i) experiment and consciousness. Evolution is approaching 

the point of singularity where its rate reaches an infinite value, 

and its character must change in the near future. Our 

scientific-technical scope is becoming so vast that simple rational 

answers will not be sufficient to cope with its complexity; the 

Roerich’s humanity or Living Ethics may present a solution. 

Keywords: Living Ethics; 



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o - 2 7 8 

BetrAyAL in the LAB – internAL ethiCS of 

SCienCe 

J. MehLiCh 1 

1 Europäische Akademie GmbH, Bad Neuenahr-Ahrweiler, 

Germany 

Science ethics is one of the relevant and often debated fields 

in the area of “Applied ethics”. Apart from several controversies 

it is agreed upon distinguishing two levels of ethics: internal 

ethics as role ethics focus on the behavior of a scientist within the 

scientific community, whereas external ethics as causal action 

ethics describe the implications and external concerns of a 

scientist’s actions. While the latter are addressed by technology 

assessment (involving sociology, regulatory issues, governance, 

and others), this presentation focusses on the former approach, 

dealing with issues of fraud, betrayal and other kinds of 

misbehavior that, unfortunately, are more up-to-date than ever. 

Recently several prominent examples of betrayal in 

scientific practice are publicly discussed. Betrayal in this context 

means either deceptive behavior such as forgery and invention of 

research results, the publication of other people’s results under 

the own name (plagiarism), or insufficient information about 

references and knowledge or finance sources. According to a poll 

by Nature in 2005, 30% of the 3200 participating scientists 

confessed to have betrayed already in one or another way. Motives 

reach from academic publishing pressure to financial incentives 

of sponsors. Ethical values (or virtues) that make a stand against 

this phenomenon are intellectual honesty and truthfulness, 

bringing the scientist to commit himself to objective truth 

seeking and truth assurance. 

Another aspect often raised is the call for objectivity and 

dedicated disinterestedness. The selfless devotion to the 

ambitious goal of knowledge increase should not be blurred by 

selfish careerism or the interests of any sponsors. Methods for 

obtaining these ideals are systematized doubt and disciplined 

self-control. Apart from that, it is justified to expect fairness from 

a scientist towards his colleagues and competitors. 

Keywords: Sustainable Chemistry; Ethics of science; 



o - 2 7 9 

ethiCAL ProBLeMS in South AfriCAn 

eduCAtion 

J. vAn der weSthuizen 1 

1 University of the Free State, Chemistry, Bloemfontein, 

Republic of South Africa 

The political transformation since 1994 has solved major 

ethical and moral issues in South Africa. However, a number of 

well-intentioned but ill-conceived initiatives have wreaked havoc 

in primary and secondary education. Consequently, tertiary 

education is threatened. The universities are overwhelmed by 

poorly prepared, academically illiterate students. Government 

subsidy is determined by the number of students passed and the 

number of ISI publications, irrespective of quality. So we neglect 

the bright and waste energy on the weak. The National Research 

Foundation is baffled by an inverse relationship between the 

number of publications and the number of patents. Research for 

the subsidy has replaced research for curiosity or utility at many 

universities. 

Without students very little funding is available for research 

to build our CVs and careers. Should I write the student’s thesis 

myself? Either I do so or accept a poorly written script. Some 

researchers claim that it is easier to do the research as well. 

Scientific careers are built on a plethora of trivial papers. 

A principled approach might carry a price tag. Mediocre and 

dishonest bureaucrats, often in well-entrenched positions, do not 

tolerate criticism. It is easy to make enemies who can destroy your 

career. If you resist too much, you will be replaced by a less well 

qualified person who will pass more students. Is it ethical to claim 

to be an excellence driven university when this is the case? 

In my opinion, speaking out against wrongs, unethical 

practices and dishonesty is the ultimate ethical requirement. 

Ethical behaviour requires actions that are not in our short-term 

interest. Should I show empathy towards poor students and take 

non-academic issues (poverty and lack of background) into 

account and pass their poor academic skills on to their future 

employers and society at large? How do I act in everyone’s best 

interest? 

Keywords: South African Education; Chemistry Ethics; 

Subsidy Driven Research; 



s631 

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special symposium: Ethics in science – ii 

o - 2 8 0 

CuLturAL reStrAinS of SCienCe 

J. vetuLAni 1 

1 Institute of Pharmacology Pol. Acad. Sci, Brain Biochemnistry, 

Krakow, Poland 

Humans invented two strategies to dominate the world: 

science and culture. Those two components of civilization are 

often in conflict. 

Culture is older. Social groups always functioned basing on 

beliefs which may be objectively false but determine the social 

activities and norms of conduct which serve the survival of the 

group. Those beliefs, rules, and resulting activities form culture. 

Science aims at objective understanding the world, regardless of 

its consequences on human emotions, worldview, and social 

functioning. 

Both science and culture were formed by the brain, which 

is the organ of survival and not of cognition of the world, and it 

often gives solutions which are at odds with science but 

pragmatically relevant. The biological purpose of religion is not 

understanding the universe but securing the group’s cohesion 

necessary for its survival. Science emerged only when it appeared 

that the objective knowledge of the world may increase fitness. 

The conflicts between science and culture emerge when the 

scientific methods of gathering knowledge offend cultural norms, 

or when scientific discoveries demonstrate that the foundations 

of those norms are based on misconceptions. 

Biomedical research was particularly often blocked by 

rulings resulting from cultural norms: today vivisection 

experiments on humans would be unthinkable. Bioethics, a very 

modern cultural product, effectively interferes with the progress 

of science (moratoria on human cloning, restrictions on studying 

genetically modified organisms and limitation on animal 

experiments). 

Culture is threatened by development of science, resulting 

in constant downgrading of the position of man from its culturally 

sanctioned place at the top of material world. 

One source of the culture-science conflict is the fact that 

axioms, methodology, and emotional involvement of humanists 

in the discussed problems are often completely alien to scientists. 

Better understanding of the world requires looking for a common 

language and mutual tolerance of science and culture. 



o - 2 8 1 

the ethiCAL BASiS of MuLtiLAterAL 

environMentAL AGreeMentS 

f. MoSer 1 , f. Prof. dondi 1 

1 University of Ferrara, Chemistry, Ferrara, Italy 

The United Nations Conference on Environment and 

Development held in Rio de Janeiro in 1992 saw a number of 

groundbreaking outcomes, such as Agenda 21, a blueprint for a 

global partnership for sustainable development in the 21st century 

and the Rio Declaration on Environment and Development with its 

27 principles. The Conference was also the birthplace for a series 

of Multilateral Environmental Agreements (MEAs). 

In the chemicals field, the Conference gave impetus for the 

adoption of the Stockholm Convention on Persistent Organic 

Pollutants, which entered into force in May 2004. Being the most 

recent MEA for the management of chemical substances, the 

underlying values of the Convention embrace contemporary 

principles in the context of environmental ethics, such as sustainable 

development, the principle of common but differentiated 

responsibilities [1] , the ‘polluter pays’ principle [2] or the precautionary 

principle [3] . 

We argue that particularly chemists nowadays should have a 

moral obligation to put into practice the ethical commitments that 

are inherent to those MEAs. It is thus highly relevant to consider 

[4, 5] 

these aspects both as research and educational topics. 

references: 

1. Principle 7 of the Rio Declaration on Environment and 

Development 

2. Principle 16 of the Rio Declaration on Environment and 

Development 

3. White Paper: Strategy for a Future Chemicals Policy. 

Commission of the European Communities, Brussels. 

http://eur-lex.europa.eu/LexUriServ/site/en/com/ 

2001/com2001_0088en01.pdf 

4. Frank, Hartmut, Luigi Campanella, Francesco Dondi, 

Jan Mehlich, Erich Leitner, Giuseppe Rossi, 

Karine Ndjoko Ioset, and Gerhard Bringmann. 2011. 

Ethics, Chemistry, and Education for Sustainability. 

Angew. Chem. Int. Ed. 50, 8482–90 

5. Moser, Frank and Francesco Dondi. On the road to Rio + 20: 

the evolution of environmental ethics for a safer world 

(editorial). Toxicological and Environmental Chemistry, 

forthcoming. 

Keywords: Environmental Ethics; Multilateral Environmental 

Agreements; Stockholm Convention on Persistent Organic 

Pollutants; Rio Earth Summit; 



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o - 2 8 2 

PriMo Levi: CheMiStry, LiterAture And 

ethiCS 

L. dei 1 

1 University of Florence, Department of Chemistry “Ugo 

Schiff”, Florence, Italy 

The present talk aims to offer a reading of astory from Primo 

Levi’s book The PeriodicTable in a scientific vein, suggesting that 

chemistry and literature arethe two banks of a same river we call 

culture. Moreover, the contributionenhances the ethical 

implications of Primo Levi’s lesson. The reader isaccompanied 

within the story Cerium, making him to go into the foldings of 

the sentences that dealwith scientific laws, phenomena, and 

discoveries. The purpose is to catch thebond between narration 

and scientific knowledge, in a setting - that of lager’s life - where 

the tragedy and the existential upset obfuscate and certainly 

fadeinto the background the technical aspects of which Primo 

Levi’s writing isgreatly soaked in. The narrative thread is not only 

maintained but it goes toconstitute the essential skeleton onto 

which the chemical knowledge isexplained rigorously as concerns 

the content, even though with simplicity inthe form. The aim is 

to stimulate a critical interpretation and a punctualattention 

towards those parts, only apparently lacking in literary 

glamour,that reveal the chemist Primo Levi. The contribution 

concludes with an outlookof ‘memory’ that takes cue from another 

story of the same book, Carbon. Thisoriginal view of ‘memory’ 

deals only with matter and energy and generates atrue pathos and 

suggestiveness for people who devote themselves or manifesttheir 

interest for the scientific rationalization of natural phenomena. 

Keywords: History of science; 

Education in Chemistry – ii 

o - 4 2 8 

SChooL teACherS trAininG 

i. PArChMAnn 1 


1 Leibniz-Institute for Science Education, Chemistry Education, 

Kiel, Germany 

The training of chemistry teachers at universities is highly 

diverse in Europe. Regardless the diversity of structures, common 

content areas of university studies for teachers aiming at a degree 

for teaching at upper secondary /high level have been identified 

in a survey carried out in a common project of the network 

EC2E2N and the division of chemistry education of EuCheMS. 

Based on this survey and an additional literature research, a 

framework for chemistry teacher training in Europe has been 

developed. The framework describes structures to support 

transition phases between school, university and school again, 

content areas based on the content descriptions of the 

EuroBachelor and expected outcomes as skills and abilities both 

in chemistry and chemistry education. 

The talk will present exemplary results form the survey and 

the literature review and will discuss important feautures of the 

framework. 



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o - 4 2 9 

Another ten iMPortAnt ideAS for 

univerSity LeCturerS 

i. MACieJowSKA 1 

1 Jagiellonian University, Faculty of Chemistry, Krakow, Poland 

New lecturers do not always receive appropriate or timely 

training before undertaking teaching. To address this the first ‘Ten 

important ideas for university lecturers’ were presented in the 

framework of 3rd ECC in Nuremberg. 

There were: 

Relations with students and within student’s group 

Start each new group session with a short icebreaker. 

Be fair. 

Teaching & learning 

Be aware/accept/take into account/think about 

goals/learning outcomes. 

Help your students develop their critical skills. 

Organise the course/environment friendly for students 

activity/creativity. Let students do mistakes. 

Make sure that lectures are not just “transmit-receive” 

occasions. 

Evaluation 

Try your questions out. 

Feed back the results to your respondents. 

Reflect your own teaching 

General 

Be prepared and flexible, ready for the question “why?” 

In this key-note next ten practical advices [1] for university 

chemistry teaching staff (especially for those who have recently 

or will shortly be facing their first class of students) will be 

presented and discussed. The author will reflect also her own 

experience of helping diverse groups of doctoral students (future 

academic teachers) and lecturers in different European countries 

over last years. [2–4] 

references: 

1. Race, P. 2000 Tips for Lecturers, Kogan Page, London, 

1999. 

2. Jak ksztalcic studentów chemii i kierunków pokrewnych? 

Podrecznik nauczyciela akademickiego. Maciejowska I. 

(ed.), Wydzial Chemii UJ, Kraków 2008. 

3. Innovative Methods of Teaching and Learning Chemistry 

in Higher Education, Eilks, I. and Byers, B. (eds.), RSC 

Publishing, London, 2009. 

4.. ECTN3, Newly Appointed University Teaching Staff 

Working group, http://ectn-assoc.cpe.fr/network/wg_pres/ 

ECTN30n_NewAppUTeachStaff.htm, retrieval 02.05.2012 

Keywords: chemistry lecturer; staff development; 



o - 4 3 0 

outCoMeS And BenefitS of internAtionAL 

CoLLABorAtion: evALuAtionS of the ACS 

GLoBAL reSeArCh exPerienCeS, exChAnGeS, 

And trAininG (Greet) ProGrAM 

S. MeyerS 1 , B. MiLLer 1 

1 American Chemical Society, Office of International Activites, 

Washington D.C., USA 

The concomitant shifting realities of international 

collaboration and innovation and the need for problem solving on 

a global scale provided the rationale for the creation of the 

American Chemical Society Global Research Experiences, 

Exchanges and Training (ACS GREET) program. Through 

GREET, research teams—typically a faculty mentor and a 

graduate or undergraduate student—receive up to US$11,000 in 

seed funding to engage a colleague abroad in a new international 

collaboration. 

Over a period of several on-site weeks at an international 

host institution of their choice, the selected teams initiate a project 

that enhances their professional skills, knowledge, intercultural 

competence, and personal networking while advancing the 

progress of science. The GREET program also facilitates 

high-risk, high-reward research to be evaluated by enabling U.S. 

chemical scientist teams and their new partners abroad to collect 

the feasibility data required to seek additional support; a process 

that is not always straightforward with current nationally-focused 

research funding structures. 

While the GREET experience is intended as a first step on 

a long collaborative journey, to date program alumni have already 

achieved remarkable outcomes that have resulted in: 1) advances 

that directly address the grand challenges facing science and 

society; 2) the obtainment of large-scale follow-on funding, 

peer-reviewed publications, and secondary exchanges; and 

3) benefits and enrichments to local communities and home 

institutions. Quantitative data collected from program alumni and 

current participants before and after their experience also shows 

a pronounced impact on their opinions and perceptions of 

international collaborations. 

This paper will provide additional information on the 

GREET programmatic model and present further details on 

significant individual, institutional, and global outcomes. 

Acknowledgement: The authors wish to acknowledge ACS and 

the ACS Committee on International Activities for their support, 

and the recommendations from former ACS President Joseph 

Francisco’s International Center Taskforce which provided 

guidance for the program. 

Keywords: Education; Collaboration; International Exchange; 

Research funding; Model program; 



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Workshop for University teaching staff 

o - 4 3 1 

worKShoP for univerSity teAChinG StAff 

i. MACieJowSKA 1 , P. yAteS 2 

1 Jagiellonian University, Faculty of Chemistry, Krakow, Poland 

2 The Higher Education Academy, STEM, York, United Kingdom 

Feedback and evaluation workshop 

In this interactive workshop we will explore the related 

activities of the feedback that university teachers give to their 

students and the evaluation by students of the teaching that they 

receive. The United Kingdom’s National Student Survey will be 

used as an example of how evaluation takes place on a national 

scale, and to demonstrate that feedback continues to pose 

challenges for teaching staff across the range of universities. 

The ways in which effective feedback can be given will be 

considered by asking participants to work on a simple example. 

They will then be asked to discuss a written case study in which 

expectations have not been adequately managed, and to comment 

on a conversation between a group of students in which they 

discuss the feedback they have received. 

The need for university teachers to evaluate their 

performance will then be considered. The ways in which this can 

be done through self reflection and seeking information from 

students, colleagues and external sources will be discussed, 

including the advantages and disadvantages of each source of 

information. The need to reflect on such evaluation will be 

stressed, before deciding whether to act upon it and if so to what 

extent. 

Evaluation was a topic investigated by one of the European 

Chemistry Thematic Network’s working group1 . 

The workshop is open to all who are interested in improving 

their teaching, and opportunity will be provided to compare 

existing practice within the countries that will be represented. 

references: 

1. Working group report 

TEACHER/TEACHING EVALUATION BY STUDENTS 

http://ectn-assoc.cpe.fr/archives/lib/2006/N05/ 

200612_TeachTeachEvalByStudents.pdf 

Keywords: chemical education; teaching; feedback; 

evaluation; 




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Environment and Green Chemistry 

Environmental Radiochemistry – fukushima and Chernobyl 

o - 0 2 0 

environMentAL effeCtS of the fuKuShiMA 

ACCident – CoMPAred to the ChernoByL 

ACCident 

t. K. iKAheiMonen 1 

1 Radiation and Nuclear Safety Authority, Research and 

Environmental Surveillance, Helsinki, Finland 

On 11 March 2011 Japan suffered a large earthquake. The 

epicentre was just over 180 km from the site of the Fukushima 

Daiichi nuclear power plant. At the time of the earthquake, three 

of the site’s six nuclear reactor units were operating at power. The 

reactors were automatically shut down when the earthquake 

struck. Furthermore, in less than an hour a massive tsunami 

generated by the earthquake flooded the coast of Fukushima. The 

damage caused by the flooding resulted in loss of cooling to the 

reactor units. This led to overheating, hydrogen explosions and a 

partial melting of the reactor cores. As a consequence, major 

releases of radioactive material to the environment occurred. 

These releases were mainly gaseous releases to air, but 

subsequently there were also liquid releases to the sea through 

discharge of water used to cool the reactors. The nuclear accident 

was classified at Level 7, the highest on the International Nuclear 

and Radiological Event Scale (INES), the same level as for the 

Chernobyl accident in 1986. 

The most significant released nuclides were isotopes of 

Iodine and Caesium, but a large spectrum of other nuclides was 

detected, too. Small amounts of radionuclides originating from 

Fukushima were detected in air samples all over the world. 

Measured Iodine-131 and Cs-134+137 concentrations in the sea 

water near the Fukushima Daiichi were also considerable. 

Radioactive deposition contaminated heavily the nearby land 

areas of Fukushima Daiichi, and the distribution of contamination 

levels in other parts of the Fukushima prefecture exhibit 

significant variation with location. Foodstuffs like milk, 

vegetables and meat as well as tap water were contaminated soon 

after the accident in Fukushima but also in neighbouring 

prefectures. Contamination of the seafood occurred later. 

In this presentation, environmental effects of the Fukushima 

accident will be discussed and compared to the Chernobyl 

accident. 

Keywords: Environmental chemistry; Radiochemistry; 



o - 0 2 1 

eStABLiShinG CS-137 And CS-134 LeveLS in 

SeAwAter in the PACifiC oCeAn Between 

fuKuShiMA And hAwAii 

K. StAStnA 1 , h. duLAiovA 2 , J. KAMeniK 2 , 

f. SeBeStA 3 

1 Czech Technical University in Prague, Department of Nuclear 

Chemistry - Faculty of Nuclear Sciences and Physical 

Engineering, Prague 1, Czech Republic 

2 University of Hawaii at Manoa, Department of Geology and 

Geophysics - School of Ocean and Earth Science and 

Technology, Honolulu, USA 

3 Czech Technical University in Prague, Centre for 

Radiochemistry and Radiation Chemistry, Prague 1, Czech 

Republic 

The Fukushima NPP accident after the March 11, 2011 

earthquake and tsunami led to large releases of radioactive 

contaminants into the ocean. To determine the Pacific Ocean 

radioactivity spread and levels that might reach Hawaii, seawater 

samples were collected at eleven stations along the transect from 

Fukushima to Hawaii from June 21 to July 2, 2011. The surface 

seawater samples were pumped through a 1-µm filter, acidified 

to pH 1 with nitric acid, and stable cesium carrier was added. 

Cesium seawater monitoring required quick sensitive 

method allowing to detect ambient levels as well as new releases 

of 137Cs and 134Cs. We used the AMP-PAN composite absorber, 

containing ammonium molybdophosphate as an active 

component and polyacrylonitrile as a binding polymer, and 

gamma-spectrometry. Samples of about 20 L were passed through 

10 mL of AMP-PAN in a glass column by gravity. Dry loaded 

AMP-PAN was counted using HPGe coaxial detector. Cesium 

activities calculated from the peak areas at 662 keV for 137Cs and 

605 and 796 keV for 134Cs were corrected for decay to the date of 

collection. Cesium recovery yields determined from carrier 

concentration difference in seawater before and after the sorption 

analyzed by ICP-MS ranged from 90 to 97 %. 

The cesium radionuclide content in seawater samples taken 

along the transect from Fukushima to Hawaii ranged from 

background pre-Fukushima levels (1-2 Bq.m-3 ) for 137Cs and 

values bellow the limit of detection (tenths of Bq.m-3 ) for 134Cs south of the Kuroshio current up to 12 Bq.m-3 for 137Cs and 

10 Bq.m-3 for 134Cs at the transect and southern boundary of the 

current intersection. These values are far below limits of concern 

regarding human health, but they give information about the 

radionuclides pathways in the Pacific Ocean. The results confirm 

models predicted very little radioactivity spreading south of the 

Kuroshio current. 

Keywords: cesium; AMP-PAN; seawater; Fukushima; 



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o - 0 2 2 

BehAvior of rAdioACtive CeSiuM durinG 

inCinerAtion of MuniCiPAL wASteS 

ContAMinAted By rAdioACtive fALLout froM 

the fuKuShiMA nuCLeAr ACCident 

h. KurAMoChi 1 , M. oSAKo 1 

1 National Institute for Environmental Studies (NIES), 

Center for Materia Cycles and Waste Managemnet Research, 

Tsukuba, Japan 

In Japan, radioactive contamination was widely spread by 

radioactive fallout from explosions of the Fukushima Dai-ichi 

Nuclear Plant. Within Kanto and Tohoku regions, therefore, not 

only soils and plants but also municipal solid wastes and sewage 

sludges were contaminated. Incineration of those wastes has been 

performed to reduce their volume and mass since before the 

accident. Unfortunately, radioactive cesium in their incineration 

ash was highly concentrated compared with untreated wastes. In 

this study, the incineration of contaminated municipal solid waste 

was investigated in terms of the partitioning behavior of 

radioactive cesium between fly and bottom ashes. The 

investigation shows that the content of cesium in the fly ash, 

which is particulate matter in the flue gas, was much higher than 

that in the bottom ash, which is coarse residue left on the grate of 

waste incinerators. To understand the difference in the content of 

cesium between fly and bottom ashes, we tried to calculate the 

thermodynamic equilibrium of the combustion system using a 

commercial calculation software (FACTSage). The calculated 

result indicated that cesium preferred to form cesium chloride 

(CsCl) gas at the combustion temperature, and partially formed 

solid aluminosilicate (CsAlSi2O6). We considered that the former 

was the major cesium component of the fly ash and the latter was 

that of the bottom ash. This consideration was in a good 

agreement with the additional examination result on a leaching 

test of fly and bottom ashes, in which the fly and bottom ashes 

predominantly contained water-soluble and water-insoluble 

cesium compounds, respectively. Furthermore, the equilibrium 

calculation also indicated that the inorganic component of 

combustion waste affected the chemical composition of 

incineration ash. 

Keywords: Radioactive cesium; Waste incineration; 

Contaminated municipal waste; Thermodynamic equilibrium 

calculation; Radioactive contamination; 


o - 0 2 3 

iMPortAnCe of CheMiCAL SPeCiAtion on the 

MoBiLity of rAdioCAeSiuM in the 

terreStriAL environMent 

e. SteinneS 1 , h. thorrinG 2 , r. GJeLSviK 2 , 

L. SKuterud 2 

1 Norwegian University of Science and Technology, Department 

of Chemistry, Trondheim, Norway 

2 Norwegian Radiation Protection Authority, Environmental 

protection, Osteraas, Norway 

Norway was one of the countries most seriously affected by 

the Chernobyl accident. Radioecological research in Norway after 

1986 has emphasized the importance of chemical speciation of 

the radionuclides for their behaviour in soil, water, and sediments. 

The mobility of 137Cs in boreal soils of Scandinavia with high 

organic matter content has shown to be much greater than in the 

previously studied agricultural soils with high content of mineral 

matter including clay minerals fixing Cs ions strongly. Thus the 

uptake of Cs in plants from these soils is much greater than 

previously experienced, and strongly dependent on the chemistry 

of the soil solution. Particularly high mobility of 137Cs is observed 

in southernmost Norway where the soils are more acidified than 

elsewhere. Results from repeated nationwide surveys of natural 

surface soils show that the decline of 137Cs is greater in coastal 

regions than in areas farther inland, probably attributable to much 

greater deposition of Mg2+ and Na + in the former areas replacing 

Cs ions on soil particle surfaces. This effect appears to be 

particularly strong near the southern coast where deposition of 

NH 4 


+ from transboundary pollution is evident in addition to the 

marine cations. The effect of precipitation chemistry on the 137 Cs 

mobility is found to decline with time, indicating that the 137 Cs 

cations are gradually moving to sites where they are more strongly 

bound. Experiments where identical soil columns, containing 

137 Cs from Chernobyl and freshly added 134 Cs, are exposed to 

precipitation of different quality in amounts corresponding to ten 

years of deposition, largely confirm the conclusions from the 

repeated soil surveys. 



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Environmental Radiochemistry – Environmental studies 

using radionuclides 

o - 0 2 4 

CheMiStry on AeroSoL PArtiCLeS And iCe 

M. AMMAnn 1 

1 Paul Scherrer Institute, Laboratory of Radiochemistry and 

Environmental Chemistry, Villigen, Switzerland 

Condensed matter – air interactions in the environment 

became a prominent topic in atmospheric science since the 

discovery that stratospheric ozone depletion is linked to surface 

reactions of halogen and nitrogen containing species on aerosol 

particles and ice. Since then, heterogeneous and multiphase 

chemistry has developed into an active area of environmental 

chemistry due to the impact of these processes on the budget of 

many atmospheric gases, to human health and global climate. 

Driven by the specific needs of laboratory experiments pertaining 

to the low partial pressure conditions in the atmosphere, we 

developed a program based on using the short-lived isotope 13N as a tracer to follow the kinetics of reactions of nitrogen oxides 

with aerosol particles and ice. An overview of these activities with 

some of the major recent highlights will be given. While the tracer 

technique allows detecting sparingly low amounts of reactants or 

products on aerosol particles or ice, the chemical identification 

can only be achieved through other analytical methods. To that 

end, we have recently explored synchrotron based ambient 

pressure X-ray photoelectron spectroscopy and near edge X-ray 

absorption fine structure spectroscopy (NEXAFS) techniques as 

a tool to unravel so far unexplored details from the surface and 

the interior of aqueous solutions, mineral oxides and ice under 

environmental conditions. In combination with the tracer 

technique we have built up powerful tools to tackle current 

challenges in environmental sciences. 

Keywords: Nitrogen oxides; Isotopic labelling; Atmospheric 

chemistry; X-ray absorption spectroscopy; Kinetics; 




o - 0 2 5 

rAdioCArBon dAtinG of iCe CoreS 

A. zAPf 1 , S. SzidAt 2 , L. wACKer 3 , 

M. SChwiKowSKi 4 

1 Paul Scherrer Institute, Radio- and Environmental Chemistry, 

Villigen, Switzerland 

2 University of Bern, Radio- and Environmental Chemistry, 

Bern, Switzerland 

3 ETH Zürich, Ion Beam Physics, Zürich, Switzerland 

4 Paul Scherrer Institut, Radio- and Environmental Chemistry, 

Villigen, Switzerland 

Dating of ice cores from high-alpine glaciers is a non-trivial 

task. Particularly in the deepest parts of the ice core where 

thinning of the annual layers does not allow for conventional 

dating such as annual-layer counting on seasonally varying 

parameters, other techniques are needed to establish precise 

age-depth relationships. 

Recently we developed, published and thoroughly tested a 

novel approach to apply radiocarbon dating on alpine ice cores. 

Independent from the presence of large, organic remnants we use 

the ubiquitously present carbonaceous aerosol particles in the ice 

to date the samples, thus allowing a much wider and more 

continuous application. Carbonaceous particles are extracted from 

the ice samples via filtration prior to a combustion step where the 

fractions of organic carbon (OC) and elemental carbon (EC) are 

separated. By means of the compact radiocarbon accelerator mass 

spectrometry system MICADAS with a gas ion source gaseous 

CO samples from the combustion step are directly measured. 

2 

The method was applied to ice samples from various 

glaciated regions from the tropics to the poles and conclusive age 

information could be given for most of them.Ice cores from the 

Mongolian Altai, the Bolivian Andes and the Swiss Alps were 

investigated in detail and ages reaching from 1 000 up to 15 000 

years before present (BP) have been obtained, thus demonstrating 

a good performance of the method on Holocene timescales. Polar 

samples however, which usually contain rather little carbon 

amounts have to be interpreted with caution as analytical 

uncertainties are directly linked to sample size. Nevertheless, also 

thanks to recent improvements in small scale 14C analysis of 

gaseous samples (sample size down to 3 µg C) we have a dating 

tool with great potential for ice core related paleoclimate studies 

to improve and extend new and existing chronologies. 

Keywords: Radiochemistry; Environmental Chemistry; 

Analytical Methods; Carbon; 



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o - 0 2 6 

nuCLeAr footPrint 

J. JAnAtA 1 , L. dALLAS 2 , A. e. wALtAr 3 

1 School of Chemistry and Biochemistry, Chemistry, Atlanta 

GA 30332-0400, USA 

2 Sam Nunn School of International Affairs, Nonproliferation, 

Atlanta GA 30332, USA 

3 Texas A&M University, Nuclear Engineering (ret.), College 

Station TX 77843, USA 

The successful exploitation of nuclear fission is a defining 

event in human history. Originally harnessed for purely military 

purposes, nuclear energy was next utilized for civilian electrical 

energy production. The latter has become controversial due to 

several nuclear industrial mishaps. Of these, the Three Mile Island 

(1979) and Chernobyl (1986) accidents, and the more recent 

Fukushima Daiichi event (2011), have dominated the discussion. 

The consequences of the military use of fission have been largely 

ignored; the radiation legacy of the Cold War is perceived as a 

thing of the past. In reality, nuclear materials production 

activities [1,2] and weapons testing [3] between 1945 and 1998 have 

introduced more radiation into the biosphere than all civilian 

mishaps combined. [4] It is estimated that the Chernobyl accident 

represents less than 5% of the total military environmental 

radiation burden, and that each of the 2053 nuclear weapons tests 

by far exceeds either the Three Mile Island or Fukushima 

accidents. 

Misconceptions regarding the relative military and civilian 

contributions to our collective “nuclear footprint” must be 

reexamined. There exists a pervasive and fundamental 

misunderstanding of nuclear and radiation issues by politicians, 

the media and the general public – that is, by the very people 

whose thoughts and ideas drive public policy. We can only address 

this issue with unbiased education. That is the goal of the Nuclear 

Footprint project. 

references: 

1. R.E.Gephart, “Hanford: A Conversation about Nuclear 

Waste and Cleanup”, Battelle Press, 2008 

2. Isao Hashimoto,“Nuclear Weapons Tests 1945-1998” 

http://www.youtube.com/ 

watch?v=PffDtH4-6Kc&feature=player_embedded 

3. Yu.A. Izrael, et al., “Nuclear Explosions and their 

Environmental Contamination” - in “NUCLEAR TEST 

EXPLOSIONS, Environmental and Human Impacts”, 

J. Wiley & Sons, New York 2000 

4. Qin-Hong Hu, et al., J.Env.Radioact. 101 (2010) 426–437, 

“Sources of anthropogenic radionuclides in the 

environment” 

Keywords: Isotopes; 


Environmental Radiochemistry – speciation of actinides in 

the environment 

o - 0 2 7 

environMentAL APPLiCAtionS of xAfS 

SPeCtroSCoPy 

t. reiCh 1 

1 Institute of Nuclear Chemistry, Johannes Gutenberg- 

Universität Mainz, Mainz, Germany 

X-ray absorption fine structure (XAFS) spectroscopy is a 

powerful tool for the speciation of heavy metals in environmental 

samples and related model systems. During the past decade an 

increasing number of experimental stations for XAFS 

spectroscopy on radioactive samples has become available at 

different synchrotron radiation facilities worldwide. This lecture 

will review recent environmental applications of XAFS 

spectroscopy to fission products and actinides to highlight the 

impact these studies have on our understanding of the 

biogeochemical behavior of radiotoxic contaminants such as Tc, 

U, Np, and Pu. XAFS studies related to the sorption and diffusion 

of Np in natural clay will be presented in greater detail. 

Keywords: X-ray absorption spectroscopy; Environmental 

chemistry; Radiochemistry; Actinides; 



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o - 0 2 8 

ACtinide And LAnthAnide SPeCiAtion with 

x-rAy SPeCtroSCoPy: MiCro- to nAno- And 

other diMenSionS 

M. A. deneCKe 1 

1 Karlsruhe Institute of Technology - Campus North, Institut fuer 

Nukleare Entsorgung, Karlsruhe, Germany 

One of the key safety issues associated with high level 

nuclear waste disposal is the potential release of radionuclides 

following water intrusion into a repository, followed by corrosion 

and leaching of waste forms, subsequent breach of the 

multi-barrier system and radionuclide transport into the 

surrounding environment. Predicting, ultimately controlling or 

prohibiting transport of released radionuclides requires detailed 

understanding of the physical and chemical factors and processes 

determinant in their transport. Of central importance is the 

radionuclide speciation, or its chemical and physical form. 

Synchrotron-based X-ray techniques are extremely useful 

speciation methods for such investigations related to the safe 

disposal of high level nuclear waste. Growing sophistication of 

these techniques and increased brilliance of modern synchrotron 

sources is helping surmount challenges in speciation 

investigations of systems with inherent high chemical and 

physical heterogeneity including waste forms, containers, backfill, 

hostrock and ground water, to name a few. In my presentation 

I will show results from X-ray spectroscopy studies combined 

with imaging techniques for actinide speciation in spent fuel 

models, granite, sediment and colloids. Each example is selected 

to both illustrate several processes affecting radionuclide 

mobilization or immobilization and to demonstrate the utility of 

different state-of-the-art techniques on varying length scales. 

Keywords: XANES/EXAFS; actinide; speciation; X-ray 

techniques; 




o - 0 2 9 

urAniuM CheMiStry in CitriC ACid SoLution 

r. Steudtner 1 , K. MüLLer 1 , e. JäCKeL 1 , 

r. Meyer 1 , K. SChMeide 1 , A. Günther 1 

1 Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource 

Ecology, Dresden, Germany 

For the long-term safety assessment of radioactive waste 

disposal sites, detailed knowledge of the actinides’s migration 

behavior as a function of pH, temperature, redox potential of the 

solution and concentration of complex partners is mandatory. The 

majority of the studies on the uranium chemistry in the presence 

of carboxylic acids was performed in the acidic pH range and at 

room temperature. Thermodynamic data of the complexation of 

U(IV) and U(VI) by citric acid was given by Hummel. [1] The 

complexation was comprehensively studied by Bonin [2] and 

Guenther [3] and the photoreduction by Ohyoshi. [4] However, the 

mechanistic understanding of the basic interaction processes is 

very fragmentary. 

This study is focused on the mechanism and kinetics of the 

uranium complexation and redox reactions as a function of 

carbonate and visible light in citric acid solution. To evaluate the 

impact of these reaction parameters on the uranium – citric acid 

– system we used UV-Vis, ATR FT-IR and TRLF spectroscopy. 

In all systems the uranium citrate complexes were detected as 

solved species. The variation of reaction parameters strongly 

influence the complexation and redox reactions. The highest 

reduction rate could be determinate between pH ~3.5 at anaerobic 

conditions. Especially the presence of carbonate strongly 

influenced the mechanism of the redox processes. The uranium is 

stabilized as U(VI) carbonate complex in the U(VI) – as well as 

in the U(IV) – citric acid – system. The determination and 

verification of thermodynamic and kinetic parameters of 

complexation and redox processes will improve the safety 

assessment of nuclear waste disposal sites. 

references: 

1. Hummel et al. (2005), Chemical Thermodynamics Vol. 9., 

OECD Nuclear Energy Agency. 

2. Bonin et al. (2008), Radiochimica Acta 96, 145–152. 

3. Günther et al. (2011), Radiochimica Acta 99, 535–541. 

5. Ohyoshi & Ueno (1974), Journal of Inorganic & Nuclear 

Chemistry 36, 379–384. 

Keywords: Complexation; Redox processes; Uv-vis; 

ATR FT-IR; 



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o - 0 3 0 

CoMPArAtive inveStiGAtion of the 

nePtuniuM(v) SorPtion onto GiBBSite By 

MeAnS of Atr ft-ir SPeCtroSCoPy 

K. GueCKeL 1 , h. foerStendorf 1 , v. BrendLer 1 

1 Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource 

ecology, Dresden, Germany 

The molecular reactions of actinides at the solid-water 

interface play an important role in the retardation of radionuclides 

in the environment. Hence, the investigation of the interactions 

of actinides with metal oxides such as Al(OH) , Fe(OOH) , TiO , 

3 x 2 

or SiO , serving as model phases for more complex, naturally 

2 

occurring minerals in aqueous solution, becomes essential for the 

safety assessment in the near and far field of nuclear repositories. 

In recent years, the sorption behavior of neptunium (Np) onto 

synthetic and naturally occurring minerals was insufficiently 

studied. The majority of these studies provide macroscopic results 

presenting sorption capacities of the substrates and the effect of 

selective parameters on the sorption behavior. However, for a 

better understanding of the sorption mechanisms, structural 

information on a molecular level of the type of surface complex 

is still needed. 

Comprehensive studies using ATR FT-IR spectroscopy have 

been carried out to investigate the in situ formation of neptunyl(V) 

surface complexes on aluminum hydroxide, namely gibbsite. This 

substrate serves as a model phase for more complex mineral 

systems, e.g. clay minerals. The surface complexation of Np(V) 

on amorphous and crystalline gibbsite was studied in detail by a 

multiplicity of experiments in the presence and absence of 

atmospherically derived carbonate. In the absence of carbonate, 

one inner-sphere complex is formed on amorphous gibbsite, 

whereas no sorption occurs on the crystalline gibbsite. In the 

presence of carbonate and dependent on the crystal structure, 

different surface species (inner-, outer-sphere and ternary) were 

derived from the spectra. 

Keywords: Absorption; Radiochemistry; 


Mining and the Environment – Biogeochemical processes 

governing mining 

o - 1 4 6 

SuStAinABiLity in MetAL MininG froM the 

exPLorAtion, throuGh exPLoitAtion to finAL 

wASte MAnAGeMent – the 

BioGeoMetALLurGiCAL APProACh 

B. doLd 1 

1 University of Chile, Department of Geology, Santiago de 

Chile, Chile 

Exploitation of sulfidic ore deposits is still an inefficient 

process forming enormous amount of reactive waste material, 

which undergoes oxidation and can produce acid mine drainage 

(AMD), resulting in a threat for water and environment. 

Additionally, this waste material often still contains other 

elements or minerals of economic values or hazardous potential, 

which were not considered during exploitation. This is mainly due 

to poor mineralogical, geochemical, and microbiological 

characteriaztion of the material from the start of exploration and 

during the day-by-day mining operation. In order to improve the 

eficiency of the exploitation of the ore, but also the low-ore grade 

material of a ore deposit and minimize environmental impacts, a 

thorough characterization by advanced mineralogical and 

geochemical techniques in combination with optimized kinetic 

tests is needed in order to predict how the different geological 

units will behave in relation to metal recovery or environmental 

issues. A new integrated approach combining quantitative 

mineralogy by QEMSCAN ® , with sequential extractions 

(including Rare Earth Elements) was developped. The data is then 

used for a high resolution acid-base accounting (ABA) in order 

to predict if the different materials will produce AMD. Modified 

kinetic cell tests combined with geomicrobiological studies show 

the evolution and controling parameters in order to improve 

recovery for example in a leach operation or inhibit element 

mobility in case of environmental management strategies. The 

produced data is then integrated into a biogeometalurgical 

block-model of the deposit, which permits to designate an 

optimized extraction process to each block due to its specific 

mineral assemblage and reactivity in metal realease. This give the 

oportunity to optimize metal recovery and minimize the 

environmental impact. 

Keywords: Acid mine drainage; geomicrobiology; 

biogeometallury; Rare Earth Elements; Sustainability; 



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o - 1 4 7 

uSinG BioProCeSSinG teChnoLoGieS to 

reduCe the environMentAL iMPACt of MetAL 

MininG on the environMent 

d. B. JohnSon 1 

1 Bangor University, Biological Sciences, Bangor, United 

Kingdom 

Mining of metal ores has often been viewed as a “necessary 

evil” in terms of its impact on the environment, and the global 

demand for metals is projected to continue escalate as the size and 

aspirations of the human population increases. Among the more 

significant environmental impacts of mining has are its carbon 

footprint (energy consumed in comminution and extracting 

metals), and its legacy of waste materials that give rise to highly 

polluted waste waters that can be released from mine sites long 

after they are abandoned. Biotechnologies – some established and 

some novel – can be used to offset some of these negative aspects, 

and offer more “environmentally benign” approaches for 

recovering metals from primary ores and solid and liquid mine 

wastes. Biomining technologies have been used for almost 

50 years to recover copper from otherwise waste (“run of mine”) 

rocks, and more recently for extracting gold, nickel, cobalt and 

other metals from higher grade (reduced) sulfide ores and mineral 

concentrates. Bio-processing allows metals to be extracted at 

much lower temperatures (generally 30–50°C) than conventional 

pyrometallurgy, and the liquid wastes produced allow pollutants 

such as arsenic to be more readily contained and stored then when 

released in smelter gases. Recently, a new approach has been 

described that uses bacteria to extract metals from oxidized ores, 

such as nickel laterites, again at low temperatures (30–35°C in the 

“Ferredox” process), thereby greatly expanding the scope of 

biomining. Microorganisms can also be used to selectively 

remove metals from acidic waste waters, such as acid mine 

drainage, as sulfides or oxidized minerals. Acidophilic, 

sulfidogenic bacteria facilitate the recovery and recycling of base 

metals, such as copper and zinc, while schwertmannite (a biogenic 

ferric iron mineral produced from mine waters) has commercial 

value as a pigment or an absorbent of anionic pollutants. 

Keywords: environmental chemistry; green chemistry; sulfur; 

water chemistry; 




o - 1 4 8 

GeoCheMiCAL And MinerALoGiCAL 

iMPLiCAtionS At deCoMMiSSioned Mine 

tAiLinGS for ChooSinG A reMediAtion 

SCheMe 

A. PArviAinen 1 

1 Aalto University, Department of Civil and Environmental 

Engineering, Helsinki, Finland 

Mineralogical and geochemical investigations play a key 

role in choosing remediation scheme for decommissioned mine 

tailings with advanced sulfide oxidation. Mineralogical 

characteristics of two abandoned mine tailings in SW Finland 

were studied using conventional techniques (reflected-light 

microscopy, scanning electron microscopy, electron microprobe 

analysis, bulk powder X-ray diffraction) and techniques based on 

synchrotron radiation (µ-XRF, µ-XAS, and µ-XRD), and 

geochemical distribution of elements was assessed using a 

five-step sequential extraction method. Additionally, tailings water 

chemistry was studied. 

The surface layers of both tailings exhibited depletion in 

sulfides, generation of acid mine drainage and elemental 

mobilization. Dissolved elements and sulfate were partially 

retained by adsorption and co-precipitaion in 

Fe(III)(oxy)hydroxides (goethite and ferrihydrite) and 

Fe(III)(oxy)hydroxylsulfates (jarosite) at Haveri Au–Cu mine 

tailings, whereas Fe(III)(oxy)hydroxides (arsenical ferrihydrite) 

and Fe(III)arsenates (scorodite and kankite) precipitated at 

Ylöjärvi Cu–W–As tailings. The secondary Fe(III) minerals were 

particularly abundant in cemented layers, and As, Cu, and Zn were 

enriched in these layers at Haveri, whereas As, Cu, and Co at 

Ylöjärvi. The Fe(III) minerals proved to be especially important 

for As retention, with up to 40–100 % of As in the secondary 

minerals fraction of the total amount in sequential extractions at 

Haveri tailings. At Ylöjärvi tailings, the respective amount of As 

in the secondary minerals fraction was 83–94 % in the highly 

altered samples. 

The results highlighted the importance of Fe(III) minerals 

in the natural attenuation processes. These phases, stable at 

oxidized ambient, should not be placed under oxygen deficient 

conditions to prevent reductive dissolution. Hence, after-care and 

remediation methods common in closing mine sites (such as 

capping or raising the water table to prevent oxygen transport for 

sulfide oxidation) are not applicable in abandoned tailings areas. 

Other passive treatment methods (e.g. passive reactive barrier) 

should be considered according to the site-specific data 

evaluation. 

Keywords: Adsorption; Arsenic; Water chemistry; 



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Mining and the Environment – Remediation of pollution 

o - 1 4 9 

ACid Mine drAinAGe in the iBeriAn Pyrite 

BeLt: SourCeS And reMediAtion StrAteGieS 

C. AyorA 1 

1 Institute of Environmental Assessment and Water Research, 

Geosciences, Barcelona, Spain 

The Iberian Pyrite Belt (SW Spain and Portugal) contains 

the highest reserves of pyrite in the world with mining activities 

dating back to prehistoric times. About one hundred abandoned 

mine wastes and galleries release a huge acidity and metal load 

to the Tinto and Odiel rivers. Once the mining activity is over, 

polluting discharges can remain for centuries with no specific 

responsible entity. In-situ passive remediation technologies are 

especially suitable for these orphan sites. The concept is to insert 

a reactive porous material in the natural flowpath of surface and 

ground waters, and it is implemented through infiltration ponds 

and reactive barriers, respectively. Calcium carbonate pea-size 

gravel is the common alkalinity supplier to neutralize acidity and 

precipitate metals. These remediation systems have been 

traditionally implemented in coal mines. However, the acid 

drainages from the Iberian Pyrite Belt contain metal 

concentrations one to two orders of magnitude higher than those 

from coal mines and require special designs to avoid quick 

clogging or passivation (coating) of the grains of reactive material. 

To overcome these problems, a Dispersed Alkaline Substrate 

(DAS) mixed from fine-grained calcite sand and a coarse inert 

matrix (wood chips) was developed. The small grains provide a 

large reactive surface and dissolve almost completely before the 

growing layer of precipitates passivates the substrate. The high 

porosity and dispersion of nuclei for precipitation retard clogging. 

However, calcite dissolution only raises pH to values around 6.5, 

which is sufficient to precipitate the hydroxides of trivalent metals 

(Al, Fe), but it is not alkaline enough to remove divalent metals. 

Magnesium oxide buffers the solution pH between 8.5 and 10. A 

DAS system replacing calcite with caustic magnesium oxide was 

tested to be very efficient to remove divalent metals (Zn, Cd, Mn, 

Cu, Co, Ni, Pb) from the water previously treated with calcite. 

Keywords: acid mine drainage; passive remediation; disperse 

alkaline substrate; calcite; caustic magnesia; 



o - 1 5 0 

PerforMAnCe of A BioLoGiCAL PerMeABLe 

reACtive BArrier for in-Situ reMediAtion of 

ACid Mine drAinAGe: SuCCeSSeS And 

ShortCoMinGS 

o. GiBert 1 , J. L. CortinA 1 , J. de PABLo 1 , C. AyorA 2 

1 Universitat Politecnica de Catalunya, Chemical Engineering, 

Barcelona, Spain 

2 Consejo Superior de Investigaciones Científicas, Institut de 

Diagnosi Ambiental i Estudis de l’Aigua, Barcelona, Spain 

Goal, Scope and Background. Acid mine drainage (AMD) 

is a major environmental concern at numerous mining sites 

worldwide. AMD is characterised by a high acidity and elevated 

concentrations of heavy metals and sulphate and, because of its 

negative impact on the subsurface systems, much attention is 

focused on rehabilitating AMD-contaminated groundwater. 

Biological Permeable Reactive Barriers (bPRBs) have emerged 

in the last decades as a promising technology for this purpose. 

objectives. This work aims at reporting the 3-year 

performance of a bPRB for the bioremediation of an 

AMD-contaminated groundwater. From a broader perspective, 

and given the scarce data on full-scale bPRBs within this field, 

the ultimate goal is to provide insights into such systems and aid 

design of other future bPRBs. 

Methods. Following a throughout investigation of a site 

seriously affected by AMD, a bPRB was installed at the 

underlying aquifer. The bPRB was divided into three modules 

containing different proportions of compost, limestone and 

zero-valent iron. A network of piezometers upstream, inside and 

downstream the bPRB was used to monitor changes in 

groundwater quality by the passage through the bPRB. 

results and discussion. Overall, the bPRB proved to be 

effective at neutralizing pH and removing heavy metals from 

groundwater (removals >95%). However, shortcomings were also 

evident. Sulphate was far from being completely depleted, 

probably due to the poor degradability of compost and to the too 

short residence time within the bPRB. From a hydraulic 

perspective, the low permeability of some modules prevented the 

bPRB from properly intercepting the entire contaminated 

groundwater plume. 

Conclusions. The results demonstrated that bPRBs can 

be an effective technology for in-situ bioremediation of 

AMD-impacted aquifers. Considering the expansion of this 

technology, more data will predictably be generated within the 

coming years and will provide a good base for better identifying 

benefits and limitations of this technology. 

Keywords: acidity; biological activity; environmental 

chemistry; transition metals; 



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o - 1 5 1 

the red Mud diSASter of AJKA in hunGAry 

And itS ConSequenCeS 

A. redey 1 , z. KovACS 1 , t. yuzhAKovA 1 , r. Kurdi 1 , 

e. horvAth 1 , A. utASi 1 , v. vinCze-CSoM 1 , 

i. rAduLy 2 , L. rAduLy 2 , J. LAKo 1 

1 University of Pannonia, Institute of Environmental 

Engineering, Veszprem, Hungary 

2 Babes-Bolyai University, Faculty of Economics and Business 

Management, Sfantu Gheorghe, Romania 

The worst and the largest environmental disaster occurred 

on October 4, 2010 in Hungary, when the wall of a waste reservoir 

disrupted and a hazardous spill of red sludge burst outside of the 

territory MAL Hungarian Aluminium Production and Trade 

Company Limited by Shares. 

The caustic sludge flooded three villages and contaminated 

the rivers and streams including the nearest Stream Torna, which 

flows through Rivers Marcal and River Rába into the River 

Danube. The heavy metals contents of soil samples taken from 

the critical points were investigated as well. Monitoring of 

particulate matter (PM10) was required in areas affected by red 

mud especially at settlements situated close to catastrophe site 

where the particle levels of air were suspected to be high. 

The aim of the paper presented the disaster after the 

intervention and its effects. 

Gypsum originating from the neutralization of stack gases 

of coal-fired power plant was added under controlled conditions 

and under continuous monitoring at several points along the 

Stream Torna and River Marcal. In October 2010 the Accredited 

Water Quality Telemetry System was installed in the direct 

vicinity of Stream Torna in Devecser. The PM10 concentrations 

were measured by the Environmental Mobil Laboratory of 

University of Pannonia. 

According to the results the pH level presently is below 8.5 

due to the complex impacts of the interventions and natural 

self-cleaning, good weather and human activities (riverbed 

cleaning). Introduction of the dry red mud technology was 

commenced by MAL Co. Ltd. on April 3, 2011. So the water 

content of red mud sludge was decreased from 80 % to 30 % as a 

consequence of the modification in technology. 

Acknowledgments: This work was supported by the European 

Union and co-financed by the European Social Fund in the 

frame of the TÁMOP-4.2.2/B-10/1-2010-0025. 

Keywords: water chemistry; basicity; Materials science; 


Mining and the Environment – Assessing environmental 

impacts 

o - 1 5 2 

iMPACt of urAniuM MineS CLoSure And 

ABAndonMent on GroundwAter quALity 

n. rAPAntovA 1 , M. LiCBinSKA 1 , o. BABKA 1 , 

A. GrMeLA 1 , P. PoSPiSiL 1 

1 VSB Technical University of Ostrava, Institute of Geological 

Engineering, Ostrava, Czech Republic 

Purpose: The aim of article is to assess the evolving mine 

water quality of abandoned uranium mines in the Czech Republic. 

This paper focuses on the changes in mine water quality over time 

and spatial variability. 

Methods: In 2010 systematic monitoring of mine water 

quality at all available locations of previous uranium exploitation 

was performed. Gravity flow discharges (mine adits, uncontrolled 

discharges) or shafts were sampled. Since the mine water quality 

results from multiple conditions – geology, type of sample, 

sampling depth, time since mine flooding, the assessment was 

done taking into account all these conditions. Multivariate 

analyses were applied in order to identify samples groups based 

on their similarity. Hydrogeochemical evolution of mine waters 

was assessed using the Geochemist’s Workbench and PHREEQC. 

results: The sampling proved that uranium concentrations 

in mine waters predominantly did not exceed 0.45 mg/L. In case 

of discharges from old adits abandoned more than 40 years ago 

uranium concentrations were below US EPA MCL for uranium 

in drinking water (0.03 mg/L). Higher concentrations up to 

1.23 mg/L of U were found only at active dewatered mine. 

Concentration of 226Ra varied from 0.03 up to 1.85 Bq/L except 

for two sites with increased background values due to rock 

formation (granites). Radium has typically increasing trend after 

mine abandonment with large variability. Concerning metals, Al, 

Co and Ni exceeded legislative limits on two sites with low pH 

waters. 

The mine water quality changes with a focus on uranium 

mobility were described from recently dewatered mines to shafts 

with maintained water level in order to prevent outflows to surface 

water and finally to stagnating shafts and discharges from old 

adits. The results were in good agreement with experience on 

mine water stratification, its disturbance by pumping or natural 

water decant and the “first flush” phenomenon after mine 

flooding. 

Keywords: uranium; environmental chemistry; 



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impacts 

o - 1 5 3 

the iMPACt of MetAL MininG on SeLeCted 

river SySteMS in roMAniA 

M. SiMA 1 , J. zoBriSt 2 , G. Bird 3 , B. doLd 4 , 

M. SeniLA 5 , d. BALteAnu 1 

1 Romanian Academy, Institute of Geography, Bucharest, 

Romania 

2 Eawag, Water Resources and Drinking Water, Duebendorf, 

Switzerland 

3 Bangor University, School of Environment Natural Resources 

and Geography, Bangor, United Kingdom 

4 University of Chile, Geology Department, Santiago de Chile, 

Chile 

5 Research Institute for Analytical Instrumentation, Donath 

Street, Cluj-Napoca, Romania 

Base and precious metal mining is one of the human 

activities with significant impact on the rivers, introducing large 

quantities of heavy metals and other contaminants into the river 

drainage. Romania has a long tradition in metal mining, the ore 

exploitation and processing being now closed, which impose a 

new perspective on sustainable long-term management of mine 

waste and mining site rehabilitation, as many such deposits 

continue to produce acid drainage with adverse effects on the 

environment. 

The paper aims to provide an overview of the most 

contaminated river systems in Romania, assessing their behavior 

in time, starting from the year 2000, when two tailings dam 

failures in Maramures County strongly affected the Tisza-Danube 

river systems. The study utilizes geochemical data to assess the 

dispersal of metal contaminants from the mining source along the 

river systems by assessing metal concentration in several 

environments: surface and underground water, channel and 

floodplain sediments and mine tailings. An example of acid mine 

drainage formation within an active mine tailings dam (e.g. Mialu, 

Certej catchment) will be given, this being an importance source 

of mining-related contaminants in the fluvial system. Lead 

isotopes ( 204Pb, 206Pb, 207Pb and208Pb) have been utilized as 

geochemical tracers of the anthropogenic activities in the lower 

Danube Basin (mainly from Romania, Serbia and Bulgaria) in 

order to identify the isotopic signature of different ore deposits 

and to characterize mining affected river catchments, representing 

important information for the management and remediation 

practices. Even the metal mining is now closed in Romania, the 

improperly managed mine deposits continue to introduce large 

quantities of metal contaminants into the river systems, and thus 

a robust ecological remediation programme is needed, also 

considering that several mining sites have proved to be 

economically viable to be re-opened in the near future. 



impacts 

o - 1 5 4 

PASt And Current MetAL And MetALLoid 

ContAMinAtion froM ABAndoned MininG 

SiteS in the SurfACe wAterS of the GArdon 

river wAterShed (SoutheAStern frAnCe) 

e. reSonGLeS 1 , C. CASiot 1 , r. freydier 1 , 

L. deziLeAu 2 , f. eLBAz-PouLiChet 1 , J. vierS 3 

1 Hydrosciences UMR 5569, CNRS Universités Montpellier I 

and II IRD, Montpellier, France 

2 Géosciences UMR 5243, CNRS Université Montpellier II, 

Montpellier, France 

3 Géosciences Environnement Toulouse UMR 5563, CNRS 

Université Paul Sabatier IRD, Toulouse, France 

The Gardon River basin, located in the southeast of the 

Massif Central (France), drains many disused mine sites. Metalrich 

wastes remaining at these sites represent potential sources of 

metals and metalloids to the Gardon River. Besides post-mining 

related pollution, current industrial and urban activities may also 

contribute to metal enrichment. Considering the important cost of 

remediation efforts, it is important to determine the relative 

contribution of abandoned mining sites to contaminant loads in a 

river system. 

In this study, metal and metalloid concentrations were 

determined in water (dissolved and particulate phases) and 

sediment samples collected during high and low flow conditions 

throughout the Gardon watershed. Element concentration ratios 

were used to identify the main contaminant sources. Zinc isotopic 

composition in suspended particulate matter and sediment 

samples was also determined in order to evaluate the possible use 

of Zn isotopes as tracers of anthropogenic contaminations in this 

context of multiple pollution sources. Current metal 

contamination status of the Gardon River was compared to 

historical record. For this, metal and metalloid concentration, 

element ratios and Zn isotopic composition were determined in 

flooding layers of a sediment core sampled on the river bank in 

downstream Gardon River. 

The sediment core has recorded an increase of metals and 

metalloids enrichment from the late 19th century, in association 

with the beginning of the industrial era. This core also reveals high 

levels of contamination in 1976 related to the breaking of a tailing 

dam. Nowadays, some tributaries remain severely impacted by 

old mining sites and constitute an important input of contaminants 

to the Gardon River mainly during floods. However, other 

tributaries impacted by urban and industrial areas are emerging 

as significant pollution sources for the Gardon River. 

Keywords: Mine-affected river; Metal and metalloid 

contamination; Zinc isotopy; Sedimentary archive; 



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impacts 

o - 1 5 5 

Mine wAter GeoCheMiStry And MetAL fLux in 

A MAJor hiStoriC PB-zn-f orefieLd 

w. MAyeS 1 , A. JoneS 1 , G. GreenwAy 2 , 

M. roGerSon 3 

1 University of Hull, Centre for Environmental and Marine 

Sciences, Hull, United Kingdom 

2 University of Hull, Department of Chemistry, Hull, United 

Kingdom 

3 University of Hull, Department of Geography, Hull, United 

Kingdom 

Recent studies have shown up to 6% of rivers in England 

and Wales to be impacted by discharges from abandoned metal 

mines. Despite the large extent of impacts, there are still many 

areas where mine water impact assessments are limited by data 

availability. This study provides an overview of water quality, 

trace element composition and flux arising from one such area; 

the Yorkshire Pennine Orefield in the UK. Mine drainage waters 

across the orefield are charectrised by Ca–HCO –SO type waters, 

3 4 

with moderate mineralization (specific electrical conductance: 

160 to 514 µS cm-1 ) and enrichment of dissolved Zn (≤2003 µg L-1 ), 

Ba (≤ 971 µg L-1 ), Pb (≤ 183 µg L-1 ) and Cd (≤ 12 µg L-1 ). 

The major ion composition of the waters reflects the 

Carboniferous gritstone and limestone-dominated country rock, 

the latter of which is heavily karstified in parts of the orefield, 

while sulphate and trace element enrichment is a product of the 

oxidation of sphalerite, galena and barite mineralization in 

particular. Many of the discharges and receiving streams are close 

to saturation, or supersaturated with respect to calcite, with 

secondary instream carbonates and biofilms likely to be crucial 

in controlling downstream mobility of divalent metals. The overall 

flux of metals released from 26 monitored adit discharges is 

estimated from baseflow measurements to be in the region of 

2890kg Zn year-1 , 160kg Pb year-1 and 16kg Cd year-1 . These 

figures are put in context with national inventories of metal release 

and the impacts of the discharges are assessed with regard to the 

physico-chemical nature of receiving watercourses. 

Keywords: mine water; zinc; lead; cadmium; pollution; 



impacts 

o - 1 5 6 

hydroCheMiCAL ChArACteriStiCS of Mine 

wAterS froM ABAndoned MineS in SerBiA And 

their iMPACt on the environMent 

n. AtAnACKoviC 1 , v. drAGiSiC 1 , P. PAPiC 1 , 

J. StoJKoviC 1 , v. zivAnoviC 1 

1 Faculty of Mining and Geology, Hydrogeology, Belgrade, 

Serbia 

Research and exploitation of gold, bismuth, wolfram, 

copper, zinc, lead, coal and uranium deposits were very intense 

in Serbia. Upon completion of the research and exploitation of 

mineral resources, many mining sites were abandoned, without 

previous establishing environmental protection measures, from 

which mine waters have been discharged uncontrollably in surface 

flows. Research on wide area were conducted to determine the 

chemical characteristics of mine waters from abandoned mines of 

various types of ore deposits. 

Based on conducted research it was concluded that in cation 

composition predominates Ca2+ , while the most common anions 

2- - are SO and HCO3 . Statistical analysis of 20 selected samples 

4 

showed strong correlations between pH value and content of 

metals (Fe, Mn, Zn, Cu) in mine waters, whereby with decrease 

of pH value concentrations of these metals increase. Cluster 

analysis was applied on all analyzed parameters and, as a result, 

four groups of mine waters were separated. Mine waters were also 

classified on the basis of parameters that in high concentrations 

2- can have harmful effects on the environment (pH, TDS, SO , Fe, 4 

Mn, Zn, Cu, As, Ni). With this approach, in a separate group were 

abstracted mine waters related to Cu and Pb-Zn deposits, whose 

composition is the result of AMD (Acid Mine Drainage). 

According to their chemical composition, they are sulfate waters 

with increased concentrations of total iron, manganese, copper, 

zinc, arsenic, and other metals. Uncontrolled discharge of these 

waters directly into surface waters leads to degradation of quality 

of the latter, which is further influenced by old mine tailings, in 

which low grade ores are deposited. 

Keywords: water chemistry; environmental chemistry; acidity; 



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impacts 

o - 1 5 7 

LeGACy MerCury in SoiLS And tree rinGS in 

the CzeCh rePuBLiC 

M. hoJdovA 1 , t. nAvrAtiL 1 , J. rohoveC 1 

1 Institute of Geology AS CR, Laboratory of Env. Geology & 

Geochemistry, Prague 6, Czech Republic 

Metal mining and processing in the central Czech Republic 

has led to the contamination of surrounding soils and vegetation. 

Here we studied vertical distribution and Hg speciation in soils 

to evaluate the extent of contamination and potential Hg mobility 

in the area. Mercury speciation was determined by 

thermo-desorption analysis. Results showed that HgS 

contamination in a former mining area occurs in most surface soil 

horizons, but contamination of mineral horizons appears to be 

limited. Mercury concentrations ranged from 8 to 10 μg g-1 in 

surface soil horizons and from 3 to 9 μg g-1 in the underlying 

mineral horizons. In soils high impacted by mining approximately 

50-80% of total Hg was present as relatively insoluble HgS in all 

soil horizons. The remaining of total Hg was attributed to 

adsorbed phases on mineral surfaces. Soils in greater distance 

from mine shaft contained HgS only in surface horizons, likely 

deposited as fine particles. Mercury in mineral horizons was 

present exclusively as Hg(II) weakly-bound to mineral particles. 

Mercury in tree rings was investigated to reconstruct past 

atmospheric pollution in the area. The highest Hg concen trations 

were found in spruce at HgS smelting contaminated site 

(up to 15 ng g-1 ). In the vicinity of a Pb smelter, Hg concentrations 

increased from the 1950s to maxima (up to 8.4 ng g-1 ) in the 

1970s, corresponding with a peak of metallurgical production and 

smelter emissions. Trees growing at a site between two smelters 

seem to reflect deposition from both point sources. Results 

indicated that tree rings may serve as a reliable archive of Hg 

deposition in areas affected by ore mining and smelting. 

Keywords: mercury; speciation; mining; contamination; 

geochemical archive; 


Environmental Chemistry – Emerging contaminants, PoPs, 

phototransformation 

o - 1 5 8 

hexABroMoCyCLododeCAne (hBCdd) 

– A BroMinAted fLAMe retArdAnt uSed in 

PoLyStyrene inSuLAtion 

A. A. JenSen 1 

1 Nordic institute of product sustainability environmental 

chemistry and toxicolo, Frederiksberg, Denmark 

Hexabromocyclododecane (HBCDD or HBCD) is an 

emerging chemical with POP-properties used mainly as a flame 

retardant in the very much used polystyrene-based building 

insulation products (EPS/XPS), and the consumption of HBCDD 

is increasing. In addition HBCDD is used in electronics as a 

substitute for banned flame retardants (PBDEs). HBCDD is a 

lipophilic and persistent organic pollutant which accumulates in 

natural organisms and magnifies through the food chain, leading 

to progressively increasing background levels in human tissues 

and in wildlife, especially of the most stable α-isomer. The extent 

of this accumulation correlates directly with its ever-more 

prevalent use. HBCDD has been detected in air, water, soil and 

sediments in many countries, and it occurs in indoor air and dusts 

and in building waste. Very high levels have been found especially 

in aquatic sediments at close-to-point sources, such as industries 

producing or using the substance. In recent years, background 

levels have increased significantly. In 2008 The European 

Chemicals Agency identified HBCDD as 1 of 14 substances of 

“Very High Concern”, and in September 2010 HBCDD was added 

to REACH’s Authorization List. In February 2011 HBCDD was 

among 6 chemicals added to Annex XIV of the EU REACH 

Regulation selected to be phased out before August 2015, if 

authorisation is not granted before. On 5th March 2012 ECHA 

published information about the content (> 0.1%) of the 

53 substances of very high concern in consumer articles. ECHA 

based that info on 203 notificactions from companies notifying 

18 chemicals in April to December 2011. HBCDD was the second 

most notified with 30 notification and it was used in articles in 

the construction and building sectors such as plastic panels for the 

thermal insulation of buildings. It was also notified in polystyrene 

foam used for packaging and in the plastic housing of electronic 

appliances. 

Keywords: environmental chemistry; toxicology; 



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o - 1 5 9 

AdSorPtion of orGAniC CoMPonentS ono 

nAturAL PerLite And verMiCuLite CLAyS 

P. deMirCivi 1 , G. nASun-SAyGiLi 2 

1 Yalova Unilversity, Chemical and Process Engineering, 

Istanbul, Turkey 

2 Istanbul Technical University, Chemical Engineering, Istanbul, 

Turkey 

Email: nasun@itu.edu.tr 

Clays are the main components of the mineral fraction of 

soils. They are effective natural adsorbents due to their particle 

size and lamellar structure. Numerous works have been done for 

using clays as adsorbents to remove organic and inorganic 

components from water. Perlite and vermiculite are the natural 

clays that used for the adsorption of the components from water. 

Perlit is a glassy volcanic rock which is essentially a 

metastable amorphous aluminum silicate, expands to about 

20 times its original volume upon heating within its softening 

temperature range of 760 to 1090oC. Also, vermiculite is the 

another natural clay which has 2:1 layer silicate. Vermiculite also 

expands to 30 times its original volume depending on the presence 

of combined water. After the expantion process of perlite and 

vermiculite minerals, they have larger pore sizes and that makes 

them to have good adsorption capacities. 

In this study, modification of natural clay minerals 

has been studied. For the modification process 

hexadecyltrimethylammonium bromide (HDTMA), which is a 

cationic surfactant, and gallic acid have been used. Experiments 

were run in batch system. Adsorption capacities of perlite and 

vermiculite minerals and isotherm models have been investigated. 

Sorption mechanisms of organic components onto perlite and 

vermiculite minerals are also studied. In the experiments various 

concentrations (50%–300% of CEC of the clays) of HDTMA and 

gallic acid have been used. For both perlite and vermiculite 

samples, adsorption capacity increased with increasing 

concentration and we found that experimental data were 

correlated well by the Freundlich isotherm model. Furthermore, 

isotherm parameters of Langmuir and Freundlich isotherm models 

were also calculated. Removal percentage of HDTMA on to 

vermiculite was 99%, while adsorption percentage onto perlite 

was around 75%. Gallic acid was adsorbed onto vermiculite 

around 60%, while it was 45% onto perlite surface. 

Keywords: Adsorption; Perlite; Vermiculite; 

Hexadecyltrimethylammonium bromide; Gallic Acid; 




o - 1 6 0 

CoMBined eLeCtroCoAGuLAtion And AnodiC 

oxidAtion ProCeSSeS for SAnitAry LAndfiLL 

LeAChAte treAtMent 

A. LoPeS 1 , A. fernAndeS 1 , P. Luz 1 , M. J. PACheCo 1 , 

L. CiriACo 1 

1 University of Beira Interior, Chemistry, Covilha, Portugal 

The generation of municipal solid waste grows 

exponentially in urban society as a consequence of population 

growth, concentration of population in urban centres and new 

patterns of consumption. Sanitary landfills are the primary method 

currently used for municipal solid waste disposal in many 

countries. One of the main problems generated by this common 

practice is the production of leachate that is a very complex 

wastewater containing different heavy metals, organic and 

inorganic compounds, some of them refractory and toxic, which 

possesses color and odor. There is a great concern about the 

contamination caused by landfill leachates, mainly because they 

are particularly difficult to treat. Thus, it is very important to 

apply reliable and effective treatment technology. In this 

study, the electrochemical treatment of leachate samples from 

an intermunicipal sanitary landfill, collected before 

the biological treatment, was carried out using combined 

electrocoagulation/anodic oxidation processes. 

The samples collected at the leachate treatment plant and 

those from the electrochemical assays were analyzed by chemical 

oxygen demand (COD) and biochemical oxygen demand (BOD ), 5 

dissolved solids, total or dissolved organic carbon and UV-Visible 

absorption spectrophotometric analyses. The electrocoagulation 

assays were performed with iron consumable anodes, at different 

initial pH conditions, with and without stirring, at different applied 

current densities. In the anodic oxidation experiments a 

boron-doped diamond anode was used and different applied 

current densities were tested. The influence of the experimental 

conditions of the electrocoagulation pre-treatment on the anodic 

oxidation performance was also assessed, as well as the variation 

of the ratio BOD /COD during the electrocoagulation and anodic 

5 

oxidation processes. 

Acknowledgements: Financial support from FEDER, Programa 

Operacional Factores de Competitividade – COMPETE, and 

FCT, for the project PTDC/AAC- AMB/103112/2008. ICI- 

Santander Totta Investigacio, for the grant awarded to A. 

Fernandes. 

Keywords: Landfill leachate; Electrocoagulation; Anodic 

oxidation; BDD electrode; 



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o - 1 6 1 

diStriBution, fAte And BioAvAiLABiLity of 

AntidePreSSAntS And their MetABoLiteS in 

wAStewAter effLuentS And AquAtiC 

environMent 

C. GAGnon 1 , A. LAJeuneSSe 1 , f. GAGne 1 , S. LouiS 1 , 

y. de LAfontAine 1 , S. A. SMyth 2 , S. SAuve 3 

1 Environment Canada, Science & Technology branch, 

MONTREAL, Canada 

2 Environment Canada, Science & Technology branch, 

Burlington, Canada 

3 Universite de Montreal, Chemistry, Montreal, Canada 

Municipal effluents are important source of contaminants 

including many pharmaceuticals and their metabolites, whose 

potential impacts on the receiving environment are poorly 

understood. Substances like anti-depressant, and anti-convulsive 

drugs, are now being frequently measured in municipal 

wastewaters. These substances undergo major transformation at 

the treatment plant and again in the receiving waters, and thus 

their bioavailability and toxicity may be modified considerably. 

The influence of different wastewater treatment processes on 

pharmaceutical products was investigated. Results showed strong 

evidence that primary treatment and trickling filter/solids contact 

has limited capacity to remove antidepressants from sewage, 

while activated sludge, biological aerated filter, and biological 

nutrient removal processes yielded moderate results (mean 

removal rates: 30%). Parent compounds were removed to a 

greater degree than their metabolites. The target antidepressants 

were also detected in samples taken from effluent 

receiving waters, but at lower concentrations (0.41 to 69 ng/L). 

Bioaccumulation in top predator fish that are exposed to effluent 

dispersion plumes was investigated. Bioaccumulation potential 

was also investigated in brook trout exposed for 3 months and 

significant amounts of the antidepressants were found in fish 

tissue—in decreasing order: liver > brain > muscle. Sertraline and 

its metabolite desmethylsertraline were the predominant 

substances observed in most tissues (0.04–10.3 ng g-1 ). Biological 

effects on fish brain were observed as Na/K-ATPase activity in 

brain synaptosomes was significantly correlated with 

brain tissue concentrations of fluoxetine (r = -0.57; p < 0.03), 

desmethylsertraline (r = -0.84; p < 0.001), and sertraline (r=-0.82; 

p < 0.001). To assess the impacts of all these drug residues on the 

environment and human health, we still need to better understand 

their chemical and physical transformations occurring at the 

treatment plant and in the receiving waters. 

Keywords: pharmaceuticals; bioaccumulation; antidepressant; 

wastewater; 




o - 1 6 2 

dynAMiCS of BioCide And BioCide MetABoLite 

ConCentrAtionS in StorM wAter in A 

reSidentiAL CAtChMent AreA 

K. BeSter 1 , u. e. BoLLMAnn 1 , J. CArMeLiet 1 , 

J. voLLertSen 1 , t. wAnGLer 1 

1 Department of Environmental Science, Aarhus University, 

Roskilde, Denmark 

In suburban areas biocides may be used in two applications 

relevant for storm water: protection of facades and urban 

gardening. Houses are increasingly equipped with thermal 

insulation to increase the energy efficiency of heating. The 

plasters of these systems are often equipped with biocides – from 

these surfaces the respective compounds may be washed off. As 

rain water run-off is directly discharged into the aquatic 

environment via separated sewer systems, storm water overflow 

and rain water infiltration, discharge of storm water run-off needs 

consideration. Urban gardening agents (herbicidal compounds) 

may runoff from parking lots, roads, ways etc. 

Within this study the storm water run-off in a well described 

residential catchment area in Silkeborg (Denmark) was analyzed 

during a long term study in order to investigate the relevance of 

leaching from “natural” urbanised areas. No new buildings or 

major fresh treatment were identified in a spatial assessment. 

The samples were taken as time resolved samples from 

a separated sewer system, and analysed for a multitude of 

biocides, e.g. terbutryn, tebuconazole, diuron, carbendazim, 

octylisothiazolinone, dichloroisothiazolinone, as well as BAM 

and atrazine. Temporal developments of concentrations and massflows 

are determined. Both concentrations and mass flows were 

very dynamic with two to three orders of magnitude between peak 

and background concentrations. The peak concentrations reached 

up to 1800 ng/L while the mass transports reached up to a few 

10000 ng/s or 77 mg/event (e.g. terbutryn, carbendazim). At least 

two different release mechanisms are obvious for different 

compounds. One might be connected to first flush events 

(possibly emissions from newly treated materials from small 

areas) while others are classical leaching emissions in which the 

mass transport is directly related to the hydraulic flow. 

Keywords: biocide leaching; facade coating; carbendazim; 

BAM; storm water; 



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o - 1 6 3 

ASSeSSinG the indireCt PhotoreACtion of 

PArtiCLe-Bound PoLLutAntS 

e. APPiAni 1 , K. MCneiLL 1 

1 Biogeochemistry and Pollutant Dynamics, ETH Zurich, 

Zürich, Switzerland 

Humic substances (HS) are known to sensitize the 

photochemical production of reactive oxygen species, such as 

singlet oxygen ( 1O ). 2 1O is highly reactive and has an important 

2 

role in photodegradation of aquatic pollutants. The relative 

importance of dissolved organic matter (DOM) and particulate 

organic matter (POM) is almost certainly dependent on whether 

the reaction is occurring in the bulk solvent or on the particle. 

Some studies have shown no difference in 1O production upon 

2 

irradiation of natural samples before and after filtration, using a 

probe molecule localized in the bulk aqueous phase. In order to 

better understand the problem, a well-controlled model system 

was used. Monodisperse particles of known composition 

containing organic matter were synthesized. 1O production 

2 

rates were compared between DOM and POM samples. 

1O2 measurements were performed with two probe 

molecules that are localized in the bulk of the solvent and 

in the organic matter microphase: furfuryl alcohol 

(FFA) and 2-[(1-(3-tert-butyldimethylsiloxy)phenyl)-1-methoxy- 

-methylene]tricycle[3.3.1.1]decane (TPMA), respectively. The 

1O2 steady state concentrations ([ 1O ] ) detected upon irradiation 

2 ss 

of POM and DOM solutions, using TPMA as probe molecule, are 

similar. Those [ 1O ] are also significantly higher than the one 

2 ss 

obtained using FFA as probe molecule (up to four order of 

magnitude for POM containing solutions). These results confirm 

the strong dependence of the apparent [ 1O ] on the localization 

2 ss 

of the probe molecule in the system. It also offers evidence of the 

importance of POM in the indirect photodegradation of 

hydrophobic pollutants. 

Keywords: Environmental chemistry; Singlet oxygen; 

Sensitizers; Photolysis; 




o - 1 6 4 

KinetiC StudieS on the Photo-oxidAtion 

reACtion of wAter By quinoneS 

K. oSz 1 , e. JozSA 1 , v. KiSS 1 

1 University of Debrecen, Department of Physical Chemistry, 

Debrecen, Hungary 

One way to utilize solar energy uses photochemical 

reactions oxidizing water (preferably in aqueous medium), then 

the reduced reaction partner can be used directly or indirectly to 

produce energy. In the indirect way, the reducing agent reacts with 

another redox system (e.g. carbonates) and reduces it to a form 

which is finally suitable for energy storage (e.g. methanol). 

One possibility is to use unsubstituted and/or substituted parabenzoquinones 

(1,4-benzoquinone; a2-methyl-1,4-benzoquinone; 

2,6-dimethyl-1,4-benzoquinone; 2,6-dimethoxy-1,4-benzoquinone; 

2,6-dichloro-1,4-benzoquinone; 2,5-dichloro-1,4-benzoquinone) as 

photosensitive compounds. They are readily soluble in water 

depending on their substituents. When reacted with light, there 

are two major reaction types occurring in their solutions. The first 

is formally a disproportionation reaction, which together with 

water addition, gives hydroquinone and hydroxyquinone, the 

latest being a highly absorbing species in the Vis wavelength 

range responsible for the color of the resulting solutions. The 

second way is a redox reaction with water, where water acts as a 

reducing agent and gives oxygen gas and hydroquinone. This 

scheme is valid for simple substituted quinones as well, with 

different quantum yields and product ratios. pK values of the 

hydroxyquinone products also depend on the substituents and 

were determined from spectrophotometric titrations. 

In a further reaction, the light induced decomposition of the 

side product hydroxyquinone was also detected. 

For the detailed mechanistic studies, a UV-Vis diode array 

spectrophotometer was used in addition to a specially designed 

pH-stat pH-potentiometric system in combination with a high 

intensity UV lamp emitting at 365 nm. These techniques provide 

the possibility to detect the spectral changes or change of pH as a 

function of illumination time. CV measurements gave further 

information about the redox properties of the different quinones 

to find the best candidate for solar energy utilization. 

Keywords: Photochemistry; Kinetics; Quinones; UV/Vis 

spectroscopy; Cyclic voltammetry; 



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o - 1 6 5 

PhotodeGrAdAtion of thALidoMide: 

identifiCAtion of trAnSforMAtion ProduCtS 

By LC-uv-fL-MS/MS, ASSeSSMent of 

BiodeGrAdABiLity, CytotoxiCity And 

MutAGeniCity 

w. M. M. MAhMoud 1, 2 , A. P. tooLArAM 1 , 

M. SChneider 1 , K. KüMMerer 1 

1 Sustainable Chemistry and Material Resources, Institute of 

Sustainable and Environmental Chemistry, Leuphana 

University of Lüneburg, DE-21335 Lüneburg, Germany 

2 Pharmaceutical Analytical Chemistry Department, Faculty of 

Pharmacy, Suez Canal University, 41522 Ismailia, Egypt 

The presence of pharmaceuticals in the environment has 

become an important emerging environmental issue. The 

ecological impacts, possible human health effects, and potential 

risks associated with releases of pharmaceuticals into the 

environment have become an increasingly important issue for 

scientists, the public, and environmental regulators. 

In 1998, Thalidomide (TD), notorious for its teratogenicity, 

was approved by the FDA for the treatment of erythema nodusum 

leprosum associated with leprosy. Recently, TD is a promising 

drug in the treatment of a number of cancers and inflammatory 

diseases. [1] Consequently, a potential increased influx of TD into 

the environment makes it imperative to assess the fate of TD and 

its possible degradation products. In this study the behavior of TD 

was monitored during photoirradiation using medium-pressure 

Hg-lamp in different reactors. Biodegradation of TD and its 

phototreaction products was assessed in Closed Bottle Test (CBT). 

Cytotoxicity and Mutagenicity of TD and photodegradation 

products (after 2, 4, 8, 16 and 32 min of irradiation) were done 

with Salmonella typhimurium strains TA 98, and TA 100 in the 

Ames MPF with and without metabolic activation. 

The primary elimination of TD was monitored and 

structures of photodegradation products (PPs) were assessed by 

LC-UV-FL-MS/MS. New PPs were formed of which two were 

isomers of TD with the same molecular mass. Further, TD and its 

PPs were neither readily biodegradable in CBT nor exhibited 

cytotoxic nor mutagenic activities at the highest tested 

concentration of 50 mg/L. 

Additional toxicity studies with other endpoints (bacterial 

toxicity, genotoxicity) and structure-activity relationship will be 

applied for the further characterization of the environmental and 

human risks connected with the presence TD and its PPs in the 

environment. 

references: 

1. M. E. Bosch, A. R. Sánchez, F. S. Rojas, C. B. Ojeda. 

Journal of Pharmaceutical and Biomedical Analysis 2008, 

46 (1), 9. 

Keywords: Pharmaceuticals; Environment; Transformation 

products; UV treatment; Toxicity; 


Environmental Chemistry – Metals, transformation 

o - 2 8 3 

teStinG PrediCtive CAPABiLitieS of 

SPeCiAtion ModeLS in freShwAterS uSinG A 

LABorAtory-ASSAy APProACh 

i. AhMed 1 , J. hAMiLton-tAyLor 1 , h. zhAnG 1 , 

w. dAviSon 1 

1 University of Lancaster, The Lancaster Environment Centre, 

Lancaster, United Kingdom 

A potential problem of speciation models used for predicting 

binding of metals to natural organic matter is that they are 

parameterised using extracted humic and fulvic acid (HA and FA). 

A series of 7 standardised laboratory assays were developed to 

measure the binding characteristics of Cu to dissolved organic 

matter (DOM) rather than extracted HA and FA. To obtain DOM, 

~80 L samples (per site) of freshwater were collected from two 

headwater streams in the North Pennines, England, filtered and 

cleaned from major cations by ion–exchange. The DOM was 

concentrated using rotary evaporation to reduce the sample 

volume to ~500 cm3 . Quality control standard solutions of 

Suwannee River HA and FA were also prepared. The free Cu2+ ion activity in solution was determined using ion–selective 

electrode (ISE). The lower detection limit on the calibration curve 

of the Cu–ISE was extended from pCu of ~7.0 to ~14 by 

complexometric titration with ethylenediamine. To maintain an 

extended detection window of Cu, the ratio [DOM]: [Cu ] was 

total 

varied between 62 and 3100 while maintaining the ionic strength 

constant. The free ion activities in solutions were calculated using 

WHAM 7 and NICA–Donnan speciation models and compared 

to those obtained from the laboratory assays. For most of the 

assays the difference between experimental data and WHAM 

predictions for both isolated DOM and FA and HA was < 0.7 pCu 

units. NICA–Donnan and WHAM model predictions agreed 

within 0.5 pCu units. A systematic increase in the activities of 

Cu2+ was observed in solutions at pH 6.0 following the addition 

of Ca, Zn and Ni. This was attributed to metal competition at the 

HA or FA sites. As expected this competition effect was negligible 

in more acidic solutions. More waters need to be tested, but this 

study suggests that paremeterisation of models using extracted FA 

and HA is appropriate. 

Keywords: Dissolved Organic Matter; Ion selective electrode; 

Freshwater; WHAM model; Chemical Speciation; 



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o - 2 8 4 

tASK SPeCifiC ioniC LiquidS SyntheSiS: 

APPLiCAtion to MetAL ionS extrACtion 

A. MeSSAdi 1 , S. BoudeSoCque 1 , L. duPont 1 , 

A. MohAMAdou 1 

1 Institut de chimie Moléculaire de Reims, Groupe GCC, Reims, 

France 

Our work aims to design cationic organic chelating synthons 

derived from vegetal or animal renewable resources (betaine, 

glycine or alanine), which can generate original task specific ionic 

liquids by association with an inorganic anion. These ionic liquids 

(ILs) are used in order to develop process for pollution 

remediation. 

The cationic synthons, obtained in the form of bromide salts, 

can generate ionic liquids by metathesis reactions in the presence 

- - - of the desired anionic salt [BF , PF6 , NO3 , (NC)2N 4 

- - (Dca), ClO4 and (CF SO ) N- (NTf )]. A series of ionic liquids (ILs) are 

3 2 2 2 

isolated and characterized by various physicochemical methods 

(elemental analysis, 1H and 13C NMR, IR, DSC, viscosity, 

Karl Fischer titration, crystal XRD). 

The extraction of the different metal cations (Cu2+ , Ni2+ and 

Pb2+ ) in aqueous solution by ionic liquids synthesized was 

performed. The extraction yields, determined by the 

measurements of the residual metal concentration in aqueous 

solution, depend not only the length of the alkyl chain appending 

to the ammonium nitrogen but also on the nature of the associated 

anion. The most promising results are obtained with ILs whose 

anion has a chelating ability. The mechanism of metal transfer has 

been studied and was related to the hydrophobicity of the cationic 

synthon. Increasing the hydrophobicity of the cationic synthon 

leads to an increase of extraction yield, thus limiting ion-exchange 

(transfer of the cation of LI in the aqueous phase) and promoting 

ion pairing extraction. 

Keywords: Ionic liquids; Ion pairs; Amino acids; Ion 

exchange; Transition metals; 



o - 2 8 5 

CorK APPLiCAtion for CLeAninG MetAL 

ContAMinAted wAterS 

C. B. LoPeS 1 , i. noGueirA 1 , r. neveS 1 , 

d. S. tAvAreS 1 , A. C. duArte 1 , e. PereirA 1 


Portugal 

Metals have become of utmost importance due to our 

planet’s increasing populations and their requirements for natural 

resources and metals-based goods. The continuous demand for 

metals has originated metal rich wastewaters and metal 

contamination problems all over the world. Today, metal 

contamination has accomplished high visibility and is garnering 

public concern, since population is less and less tolerant of any 

risks to their health, safety and quality of life. The impacts that 

metal contamination has on both public health and ecosystems 

have forced the regulatory entities to the drive for strict 

environmental standards and reduction in metal releases and 

discharges. All over the world, industries are forced to reduce the 

metal contents in industrial waters to limit levels. Activated 

carbon is one of the most used sorbent to remove metals from 

waters, but due to its expensive cost, waste based sorbents have 

been emerging as a low cost alternative. 

Cork stoppers are an abundant waste from households and 

restaurant units. They are composed mostly by natural cork, and 

its main polymeric components are suberin, lignin and 

polysaccharides. Their chemical groups are the main responsible 

for their capacity to uptake metals. In this study the efficiency of 

this biomass to uptake Hg, Cd and Pb from different types of 

water have been studied in batch stirred vessels at room 

temperature. 

Cork have shown higher appetence to remove Hg(II) and 

Pb(II), achieving removal percentages as higher as 95%.The 

sorption process was studied under the effects of competing ions 

and organic matter content, and it is well described by well-known 

kinetics models. This study suggests that this waste based sorbent 

may be effectively used to reduce metal content in low and 

moderate contaminated waters. 

Acknowledgements: Cláudia B. Lopes thanks Fundacio para 

a Ciencia e Tecnologia-FCT, for financial support through a 

Post-Doctoral grant SFRH/BPD/45156/2008 

Keywords: Metals; Cork; Sorption; Competing ions; Organic 

matter; 



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o - 2 8 6 

reduCtion of SeLenite to eLeMentAL red 

SeLeniuM By the rhizoBACteriuM 

AzoSPiriLLuM BrASiLenSe 

A. v. tuGArovA 1 , e. P. vetChinKinA 2 , 

e. A. LoShChininA 2 , v. A. vLASov 1 , v. e. niKitinA 2 , 

A. A. KAMnev 1 

1 Institute of Biochemistry and Physiology of Plants and 

Microorganisms, Laboratory of Biochemistry, Saratov, Russia 

2 Institute of Biochemistry and Physiology of Plants and 

Microorganisms, Laboratory of Microbiology, Saratov, Russia 

Bacteria of the genus Azospirillum which form associative 

symbioses with many higher plants are among the most studied 

plant-growth-promoting rhizobacteria (PGPR). As the rhizosphere 

is the common natural habitat of azospirilla, they have high 

resistance and adaptability to different unfavourable 

environmental conditions: starvation, drought, etc. Selenium is a 

trace element which is required for all organisms but becomes 

toxic at higher concentrations. 

2– We have studied the impact of selenium(IV), SeO , on the 

3 

bacterial species Azospirillum brasilense (strains Sp7, Sp245, Cd). 

Concentrations of 0.5–1 mM Na SeO completely inhibited the 

2 3 

growth of all the strains at the end of the logarithmic phase of 

growth (18 h) in the liquid medium. However, bacterial growth 

and a red staining of the culture medium was observed upon 

further cultivation (stationary phase of growth, from 66 h) at the 

same concentrations. The red color of colonies was also observed 

on solid medium in the presence of selenite up to 1 mM. 

Using TEM, the presence of intracellular electron-dense 

spherical nanoparticles (50–400 nm) was shown. X-ray 

fluorescence revealed a significant accumulation of selenium by 

bacterial cells. Electron energy loss spectroscopy (EELS) was 

used to create an elemental map of selenium. The results obtained 

suggest the electron-dense nanospheres generally found inside the 

cell to be elemental selenium. 

A possible mechanism for the SeIV –>Se0 reduction involves 

2– the inclusion of SeO in the already existing denitrification 

3 

process well studied for Azospirillum, and may not be due solely 

to SeIV detoxification. 

This is the first report on the ability of Azospirillum to 

reduce selenite to Se0 . The results obtained show that these PGPR 

may be suitable for bioremediation of selenite-contaminated 

environments. The ability of Azospirillum to synthesize 

Se nanoparticles can also be of interest to nanobiotechnology. 

Keywords: Biotransformations; Green chemistry; Selenium; 

Reduction; Nanoparticles; 



o - 2 8 7 

hydrodefLuorinAtion And hydroGenAtion 

of PoLyfLuorinAted BenzeneS under MiLd 

AqueouS ConditionS 

r. BAuMGArtner 1 , K. MCneiLL 1 

1 Biogeochemistry and Pollutant Dynamics, ETH Zürich, 


Fluorinated organic compounds are increasingly used and 

important emerging pollutants. Due to their growing use, release 

to the environment is expected. In the environment, they are 

expected to be rather persistent, as fluorinated compounds show 

increased stability and lipophilicity compared to their 

non-fluorinated counterparts. Current approaches to C-F bond 

cleavage either use harsh conditions or homogeneous complexes 

that are not suitable for use in water or environmental matrices. 

In this work, we have developed a simple heterogeneous 

rhodium-based catalytic system for complete hydrodefluorination 

and hydrogenation of polyfluorinated benzenes with molecular 

hydrogen under mild aqueous conditions. Degradation kinetics, 

product and intermediate distributions, as well as data on 

catalyst–fluoroaromatic interactions will be presented, with a 

focus on their implications for the underlying reaction 

mechanisms involved. 

Keywords: environmental chemistry; heterogeneous catalysis; 

fluorine; reaction mechanisms; rhodium; 



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Green Chemistry – i 

o - 2 8 8 

the CLiMAte And enerGy PoLiCy of the 

euroPeAn union: ChALLenGeS for Green 

CheMiStry 

M. GrASSerBAuer 1 

1 Vienna Universty of Technology, Technical Chemistry, Vienna, 

Austria 

A key element of the EU efforts to promote sustainable 

development is its “Integrated Climate and Energy Policy”, 

providing for substantial reductions of the green house gas 

emissions in the EU with a reduction of the consumption of 

natural resources and a lowering of air pollution as co-benefits. 

This is a first step towards a conceived massive global effort to 

limit global warming to 2 degrees, which would correspond to 

reducing the green house gas emissions globally by 50 % till the 

year 2050. 

New “sustainable and green” technologies have to be 

developed and implemented. Key development areas refer to new 

efficient transport systems, houses and consumer devices, 

renewable energies, carbon sequestration and storage and new 

energy carriers providing a huge challenge for many scientific 

disciplines. This lecture aims at presenting key elements of this 

challenge for “green chemistry”, which can be seen as the 

molecular science of sustainable development. 



o - 2 8 9 

enerGy ConverSion effiCienCy of 

A dieSeL Power GenerAtor fueLLed with 

ethAnoL-BiodieSeL-dieSeL oiL BLendS 

J. r. Sodre 1 , A. Lodi 1 , P. SouzA 1 , t. CoStA 1 

1 Pontifical Catholic University of Minas Gerais, Department of 

Mechanical Engineering, Belo Horizonte, Brazil 

This work presents a study on fuel consumption and fuel 

conversion efficiency of a diesel power generator fuelled with 

blends of biodiesel, ethanol and diesel oil. Experiments were 

carried out on the engine fuelled with blends of 5 % (B5), 10% 

(B10), 20% (B20) and 50 % (B50) of soybean biodiesel in diesel 

oil. In addition, anhydrous ethanol was used as an additive to B20 

blend at the concentrations of 2% (B20E2) and 5% (B20E5). The 

engine load was varied from 0 kW to 37.5 kW. The results showed 

that engine fuel consumption is increased as biodiesel and ethanol 

concentrations are increased in the fuel. However, the use of 

ethanol as an additive improves engine fuel conversion efficiency. 

Keywords: Fatty acids; Alcohols; Biomass; Energy 

Conversion; Renewable Resources; 



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o - 2 9 0 

MeSoStruCtured y zeoLite AS SuPerior fCC 

CAtALySt—froM LAB to refinery 

J. GArCiA MArtinez 1 , 2 , L. KunhAo 2 , 

M. JohnSon 2 , J. vALLA 2 , J. y. yinG 3 

1 University of Alicante, Inorganic chemistry, Alicante E-03690 

and Monmouth Junction NJ 08852, Spain 

2 Rive Technology Inc, Rive Technology Inc, Monmouth 

Junction NJ 08852, USA 

3 Institute of Bioengineering and Nanotechnology (Singapore) 

and Massachusetts Institute of Technology (Cambridge), 

Institute of Bioengineering and Nanotechnology (Singapore) 

and Massachusetts Institute of Technology (Cambridge), 

Cambridge MA 02139, USA 

Y zeolite with well-controlled intracrystalline mesoporosity 

is prepared by a post-synthetic surfactant-templating approach. 

The mesostructured Y zeolite maintains good crystallinity, 

excellent hydrothermal stability, and strong acidity, which are 

critical features for catalysis (e.g. Fluid Catalytic Cracking of 

petroleum). FCC catalysts made from the mesostructured Y 

zeolite show much improved product selectivity, i.e. significantly 

more desirable transportation fuels (gasoline and diesel) and 

less undesirable products (coke and bottoms) compared to 

conventional zeolite catalysts, which can be attributed to the 

improved diffusion of reactants and products in and out of the 

micropores through the intracrystalline mesopores. 

Keywords: zeolites; mesoporous materials; catalyst; structureacidity 

relationship; cracking; 

Green Chemistry – ii 

o - 2 9 1 

Green enerGetiC MAteriALS 

C. Miro SABAte 1 , h. deLALu 1 


1 University of Lyon, Hydrazines and Polynitrogen Energetic 

Compounds, Villeurbanne, France 

Oxydation of 1,1-dimethylhydrazine using our recently 

patented method led to the formation of (E)-1,1,4,4-tetramethyl- 

2-tetrazene (1) in high yields and purities. Compound 1 was 

oxidized with potassium permanganate to form functionalized 

formyl 2-tetrazenes (E)-1-formyl-1,4,4-trimethyl-2-tetrazene (2) 

and (E)-1,4-diformyl-1,4-dimethyl-2-tetrazene (3). Additionally, 

compound 1 underwent oxidative addition with chloramine 

(Cl–NH ) to form the (E)-1-aminomethylidene-1,4,4-trimethyl-2- 

2 

tetrazenium cation (TAT + ) as its chloride salt (4). Metathesis 

reactions of salt 4 with energetic anion transfer reagents led 

to the formation of ionic compounds based on the TAT + cation 

and the following anions: nitrate (5), perchlorate (6), 

5,5?-azobistetrazolate (7*6H O), picrate (8) and azide (9). All 

2 

materials described in this work were characterized by analytical 

(elemental analysis and mass spectrometry) and spectroscopic 

(multinuclear NMR spectroscopy: 1H, 13C and 15N NMR and 

vibrational spectroscopy: infrared and Raman) methods and the 

solid state structures of compounds 2, 3, 4, 5, 6, 7*6H O and 8 

2 

were determined by low temperature X-ray crystallography. 

Additionally, we computed the natural bond orbital charges of 

compounds 2 and 3 and of the TAT + cation (B3LYP method). 

Furthermore, we used preliminary energetic testing to gain insight 

into the sensitivities of all the materials in this work towards 

impact and friction and we assessed their thermal stability by 

differential scanning calorimetry (DSC) measurements. 

Additionally, the heats of formation of the energetic materials 

were computed using quantum mechanical methods (CBS-4M) 

and these values were used to determine the detonation parameters 

(pressure and velocity) and specific impulses for the pure 

compounds and for their formulations with an oxidizer. Lastly, we 

calculated the expected decomposition gases of the pure 

compounds as well as those of the mixtures with an oxidizer. 

Based on our studies, the new compounds are of interest as a new 

type of less sensitive and more environmentally friendly energetic 

materials. 

Keywords: Ion exchange; X-ray diffraction; NMR 

spectroscopy; Ab initio calculations; Azo Compounds; 



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o - 2 9 2 

one-Pot SynthetiC ProCeSSeS By 

BetA-nitroACryLAteS: PrePArAtion of 

PentASuBStituted AniLineS 

r. BALLini 1 , S. GABrieLLi 1 , A. PALMieri 1 

1 School of Science and Technology, Chemistry Division, 

Camerino, Italy 

The synthesis of complex molecules is traditionally 

performed by a sequence of separate steps, each of which requires 

its own conditions, reagents, solvent, and catalyst. After each 

reaction is complete, the solvent and the waste products are 

removed and discardered, and the intermediate product is 

separated and purified. Environmental and economic pressure are 

now forcing the chemical community to search for more efficient 

ways of performing chemical transformations. These issue can be 

addressed by the development of new synthetic methods which, 

by bringing togherer simple components, can generate complex 

structures in one-pot, in much the same way as occurs in nature. [1] 

In this contest, β-nitroacrylates have demonstarted to be a key 

starting material for the one-pot synthesis of a variety of fine 

chemicals, such as dihydroquinoxalinones, [2] benzoxazinones, [3] 

a,β-unsaturated esters, [4] furans, [5] indoles [6] and pyrroles. [] 

Following our studies on the reactivity of β-nitroacrylates, we 

have now found that their reaction with ylidene malonitriles, 

under basic conditions, affords the one-pot synthesis of pentasubstituted, 

densely functionalized anilines in satisfactory to good 

overall yields. 

Reaction conditions and results will be reported. 

references: 

1. Ballini, R.; Palmieri, A.; Righi, P. Tetrahedron 2007, 63, 

12099–12121. 

2. Ballini, R.; Gabrielli, S.; Palmieri, A. Synlett 2009, 

965–967. 

3. Ballini, R.; Palmieri, A.; Talaq, M. A., Gabrielli, S. Adv. 

Synth. Catal. 2009, 351, 2611–2614. 

4. Palmieri, A.; Gabrielli, S.; Ballini, R. Adv. Synth. Cat. 

2010, 352, 1485–1492. 

5. Ballini, R.; Gabrielli, S.; Palmieri, A. Synlett 2010, 

2468–2470. 

6. Gabrielli, S.; Lanari, D.; Vaccaro, L.; Ballini, R. Adv. 

Synth. Catal. 2011, 353, 1429–1437. 

7. Palmieri, A.; Gabrielli, S.; Cimarelli, C.; Ballini, R. Green 

Chem. 2011, 13, 3333–3336. 



o - 2 9 3 

KeePinG hiGh SurACe AreA of CAtALytiC 

SuPPortS At hiGh teMPerAture with feCrAL 

MetALLiC foAM 

d. h. KiM 1 , B. y. yu 1 , S. h. KiM 1 , w. y. yoon 2 , 

J. y. Byun 2 

1 Korea Institute of Science and Technology, Ceter for Materials 

Architecturing, Seoul, Republic of Korea 

2 Korea University, Materials Science and Engineering, Seoul, 

Republic of Korea 

Conventional catalyst supports made of ceramic materials 

have problem such as low thermal conductivity and low 

mechanical shock resistance. In contrast, metallic catalyst 

supports have superior thermal and mechanical properties over 

ceramic supports. Although metallic supports have many 

advantages over ceramic supports as mentioned above, adhesion 

of coated oxide carrier layer to metallic support surface is weak 

due to the difference of the respective thermal expansion 

coefficients. 

In this study, we tried porous FeCrAl metallic foam as a 

support in order to improve those shortcomings of metallic 

supports mentioned above. γ-Al O powder was used as oxide 

2 3 

carrier for active catalytic materials. γ-Al O powder in distilled 

2 3 

water was ground by attrition milling. FeCrAl foam was dipped 

in the γ-Al O slurry from milling. BET, Scanning electron 

2 3 

microscopy, and X-ray diffraction were used to characterize our 

γ-Al O carrier/support complexs. In order to investigate the 

2 3 

adhesion strength of the γ-Al O powder particles to FeCrAl 

2 3 

foams, the washcoated metallic foams went through 1200 cyclic 

thermal shock tests. Each cycle was composed of 1 minute hold 

at 700degree, and 5 minutes of cooling from 700degree to RT. 

In order to investigate catalytic activity of the sample, 

Rh nanoparticles were impregnated in the γ-Al O carrier 

2 3 

particles. Those Rh-impregnated carrier/support complexs were 

put into a micro reactor and partial oxidation of DME was carried 

out in the reactor. Hydrogen yield from the partial oxidation of 

DME was measured by gas chromatography. In order to compare 

catalytic efficiency of our FeCrAl foams to that of conventional 

spherical γ-Al O supports, we also prepared Rh-impregnated 

2 3 

spherical γ-Al O supports and put them in a conventional 

2 3 

pack-bed reactor. In the reactor, we measured hydrogen yield from 

the same reaction mentioned above and compared the results with 

those from our FeCrAl foams. Our carrier/support complex 

showed better efficiency than the conventional pack-bed type 

catalyst. 

Keywords: metal foam; catalyst support; adhesion; washcoat; 

FeCrAl; 



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o - 2 9 4 

deSiGninG Greener PLAStiCizerS: infLuenCe 

of GeoMetry of CentrAL GrouP And Side 

ChAinS 

h. C. erythroPeL 1 , r. L. LeASK 1 , M. MAriC 1 , 

d. G. CooPer 1 

1 McGill University, Chemical Engineering, Montreal, Canada 

Plasticizers are important additives for brittle polymers such 

as poly(vinyl chloride) (PVC). Their addition lowers the glass 

transition temperature (Tg) making the blends soft and flexible. 

Because plasticizers are not bound to the polymer matrix, they 

slowly leach out of the blend into the environment. Many studies 

have shown di (2-ethylhexyl phthalate) (DEHP) and some of its 

toxic stable metabolites such as its monoester (MEHP) to be 

ubiquitous environmental contaminants due to their slow 

breakdown by soil bacteria. This has led to efforts to design new, 

“green” plasticizers. 

Small diester molecules that resemble DEHP were formed 

from maleic or succinic acid and esterified with alcohols ranging 

from ethanol to n-octanol and 2-ethyl hexanol were prepared and 

tested for their plasticizer properties such as reduction of Tg 

and tensile strength in blends with PVC. To assess their 

biodegradability, the compounds were exposed to the common 

soil bacterium Rhodococcus rhodocrous to determine hydrolysis 

rates and metabolite buildup. 

Studies with 2-ethylhexyl diesters showed the importance 

of the geometry of the central structure in diester plasticizers on 

biodegradation. When the two esters were in a cis-position to one 

another (maleate), the hydrolysis step of the diester was hindered, 

while for the saturated succinate, which was free to rotate about 

the intervening bond, was quickly hydrolysed. Also, no buildup 

of monoester could be observed for the succinate. Both 

compounds showed comparable plasticizer properties to DEHP. 

On this basis, further studies were undertaken with linear 

succinate compounds in order to avoid the production of a known 

toxic metabolite (2-ethyl hexanoic acid). Plasticizer properties 

were similar to the branched compounds and improved with the 

overall length of the diester. Hydrolysis rates increased when no 

branching was present, and were inversely proportional to chain 

length. The data suggest these small diester molecules are green 

plasticizers. 

Keywords: Green Chemistry; Environmental Chemistry; 

Polymers; 



o - 2 9 5 

BALL MiLLinG: An eMerGinG tooL for 

orGAniC SyntheSiS 

A. StoLLe 1 , r. SChMidt 1 , r. thorwirth 1 , 

t. SzuPPA 1 , f. BernhArdt 1 , B. ondruSChKA 1 

1 Friedrich-Schiller University Jena, Institute for Technical 

Chemistry and Environmental Chemistry, Jena, Germany 

Over the last two decades a major trend in the field of 

Organic Chemistry could be observed: environmentally friendly 

processes using safer reagents, generating fewer side products, as 

well as a decreased utilization of solvents are en vogue. Taking 

advantage of this general trend, the performance of reactions 

under ball milling conditions in the absence of solvents is an 

increasing field of research, resulting in various publications 

covering this topic from synthetic point of view, not only 

dedicated to organic but also to inorganic chemistry as well as to 

materials and polymer science. 

Due to the high energy density during ball milling, reaction 

times can often be kept short comparable to typical experimental 

procedures with radiation based energy entry (thermal or dielectric 

heating). System inherent high mixing efficiency allowed for 

efficient mixing of lipophilic and hydrophilic compounds without 

the need for employment of phase transfer reagents or similar 

additives used in solvent-based processes. Furthermore, 

continuous particle refinement accounts for the formation of small 

crystallites with high defect concentration, thus high chemical 

reactivity. Improving the reactivity of solid materials due to 

comminution in combination with reduction of mass transport 

limitations leads to high reactivity of substrates in the solid state 

allowing several reactions, sometimes with unique selectivity. 

Using model reactions from different fields of research like 

cross-coupling, selective oxidation, or cycloaddition the 

advantages and disadvantages of this technique compared to other 

methods of energy entry will be demonstrated with regard to 

feasibility, energy efficiency, and scale-up potential. 

Overall results showed that the performance of reactions in 

ball mills is often beneficial over classical experimental 

procedures. Reduced reaction times, reduction of solvent 

utilization, and the suppression of side reactions result in 

increased yields of the target products and an improved overall 

energy efficiency and mass intensity. 

Keywords: solvent-free synthesis; solid-state chemistry; metal 

catalyzed reactions; green chemistry; process intensification; 



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o - 2 9 6 

fABriCAtion of hierArChiCALLy StruCtured 

zno PhotoAnodeS for hiGhLy effiCient dye 

SenSitized SoLAr CeLLS 

i. ConCinA 1 , n. MeMAriAn 2 , S. M. rozAti 2 , 

A. voMiero 1 , G. SBerveGLieri 1 

1 CNR-IDASC, SENSOR Laboratory, Brescia, Italy 

2 University of Guilan, Physics Department, Rasht, Iran 

ZnO photoanodes are recently applied as promising 

alternatives to traditional TiO in dye sensitized solar cells 

2 

(DSCs). We report hierarchically structured ZnO films as 

photoanodes in DSCs for the enhancement of photoconversion 

efficiency, based on three main concepts: (i) high optical density 

of the sensitized layer, allowing complete light absorption in the 

spectral range of the dye; (ii) high light scattering of the absorbing 

layer, in order to both enhance the residence time of light inside 

the sensitized film and improve light absorption; (iii) inhibition 

of back reaction. The films are prepared by the simple, cheap and 

large area scalable spray pyrolysis method and are composed of 

polydispersed ZnO aggregates consisting of nanosized crystallites. 

The aggregates are submicrometer-sized and can act as efficient 

light scattering centers, while the nanoparticles deliver the 

mesoporous structure and the high specific surface area needed 

for high dye loading. Additionally, a ZnO compact buffer layer is 

formed between the conducting substrate and the layer composed 

of polydispersed aggregates. Such a layer efficiently acts as a 

blocking layer for the back reaction between the conducting glass 

at the anode and the electrolyte, preventing electron 

recombination and improving the functional properties of the 

cells. Optimized structure led to high light absorption, efficient 

electron transport and collection, inhibition of back reaction 

electron recombination, and resulted in unprecedented overall 

photoconversion efficiency up to 7.4% [1] , which is higher than 

6.58% for ZnO nanoparticles [2] and 5.4% for hierarchically 

structured ZnO without blocking layer. [3, 4] 

references: 

1. N. Memarian et al., Angew. Chem. Int. Ed. 2011, 50, 

12321–12325 

2. M. Saito, S. Fujihara, Energy Environ. Sci. 2008, 1, 

280–283 

3. Q. Zhang et al., Angew. Chem. Int. Ed. 2008, 47, 

2402–2406 

4. H.-M. Cheng et al., Energy Environ. Sci. 2010, 3, 442–447 

Keywords: third generation photovoltaics; hierarchically 

assembled ZnO; spray deposition; 

Green Chemistry – iii 


o - 2 9 7 

the CeLLuLoSiC SuGAr PLAtforM: 

SuStAinABLe BiofueLS And Green CheMiCALS 

u. KettLinG 1 , 

1 Clariant/Süd-Chemie, Munich Germany 

Facing limited fossil resources and rising and fluctuating oil 

prices, the challenge of this century will be the exploitation of 

alternative resources to secure growth and quality of life for an 

ever growing population. Glucose and other sugars are nature’s 

building blocks. The conversion of sugars offers new alternative 

routes to biobased chemicals and biofuels independent from 

fossil-based production and with substantial savings in CO2 emissions. 

Therefore, the concept of the biorefinery will become more 

and more important. Efficient use of resources and energy is 

essential to secure sustainability as well as economic viability. In 

particular, second generation products that are based on cellulosic 

plant components, as for instance wheat straw, corn stover or 

bagasse, show a significantly improved energy balance and reduce 

the competition to food production and for arable land. 

The presentation will analyze the potential of sugars as a 

platform for renewable, biobased chemicals. It will furthermore 

explore technologies and concepts for wholly integrated, 

2nd generation biorefineries. The development of economically 

competitive system solutions for biofuels and biorefineries is of 

important strategic interest for Süd-Chemie, a member of the 

Clariant Group. Süd-Chemie’s sunliquid ® process uses 

lignocellulosic feedstock such as agricultural residues for the 

production of cellulosic ethanol and matches the ambitious targets 

for economically and ecologically sustainable production and 

greenhouse gas reduction. It was developed using an integrated 

design concept. Highly optimized, feedstock and process specific 

biocatalysts and microorganisms ensure a highly efficient process 

with improved yields and feedstock-driven production costs. 

Integrated, on-site enzyme production further reduces production 

costs substantially and assures independence from external 

suppliers. In July 2011 construction started on a demonstration 

plant with an annual ethanol output of 1,000 tons. The plant will 

demonstrate the economic competitiveness to first generation 

processes and constitutes the last step from laboratory to 

commercial production. Additionally, the technology opens up a 

pathway to a second generation sugar platform to ultimately 

produce green chemicals for a wide range of applications, e.g. 

organic acids, alcohols, furanics, green solvents and other 

specialty and bulk chemicals which can be further converted into 

biobased plastics and polymers. 



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o - 2 9 8 

BAeyer-viLLiGer oxidAtionS with ioniC 

LiquidS interCALAtion CoMPoundS into 

LAyered zirConiuM PhoSPhAteS 

G. roChA 1 , C. AMAdor 1 

1 University of Aveiro, Chemistry, Aveiro, Portugal 

In the last decades, the use of metal phosphates and ionic 

liquids in various catalysis reactions received considerable 

attention. [1–3] However, in contrast to the behaviour of metal 

phosphates, the separation of ionic liquids from the reactants and 

products is, frequently, a difficult process. This drawback may be 

avoided if the ionic liquids are intercalated into suitable materials, 

such as, α- and γ-zirconium phosphates. [3] 

The oxidation of p-methoxybenzaldehyde, o-methoxy - 

benzal dehyde and 2,4,6-trimethylbenzaldehyde is a very useful 

reaction, since its products are important starting materials for the 

production of fine chemicals used in medicine, cosmetics and 

perfumery. 

In our laboratory, their oxidation was performed by 

hydrogen peroxide catalysed by 1-ethyl-3-methylimidazolium 

chloride (C mim)Cl and 1-hexyl-3-methylimidazolium chloride 

2 

(C mim)Cl intercalated into α- and γ-zirconium phosphates 

6 

(α- and γ-ZrP),without solvent and in acetic acid at 60 °C. 

The molar ratio between the substrate and the oxidant was 1:4. 

The reaction mixtures were analysed after 3 and 6 hours of 

reaction by GC and GC/MS chromatography. 

The best results, when compared with the blank reaction, 

were achieved with α-ZrP[C mim]Cl, α-ZrP[C mim]Cl and 

6 2 

γ-ZrP[C mim]Cl after 3 hours of reaction without solvent. Good 

2 

results have also been obtained after 6 hours of reaction and acetic 

acid. These catalysts have basic properties, so, we suggest that 

their structure can play a decisive role in the conversion of the 

2,4,6-trimethylphenyl, p-methoxyphenyl and o-methoxyphenyl 

formates into the respective phenols since the hydrolysis of 

formates in basic media is irreversible. 

references: 

1. G. M. S. R. O. Rocha, T. M. Santos, C. S. S. Bispo, 

Catalysis Letters, 141, 100-110 (2011) 

2. G. M. S. R. O. Rocha, R. M. A. Domingues, 

M. M. Q. Simões, A. M. S. Silva, Applied Catalysis 

A-General, 353(3), 236-244 (2009) 

3. H. Wang, M. Zou, N. Li, K. Li, Journal of Materials 

Science, 42, 7738 (2007) 

Keywords: Heterogeneous catalysis; Oxidations; Layered 

compounds; Intercalations; 



o - 2 9 9 

new ChitoSAn BASed CAtALyStS for 

Azide-ALKyne huiSGen’S [1,3-diPoLAr] 

CyCLoAddition reACtion 

f. quiGnArd 1 , A. PriMo 1 , M. roBitzer 2 , 

M. ChtChiGrovSKy 3 , f. tArAn 3 

1 ICGM - UMR5253, CNRS, Montpellier Cedex 5, France 

2 ICGM - UMR5253, ENSCM, Montpellier Cedex 5, France 

3 CEA, Service de Chimie Bioorganique et de Marquage, Saclay, 

France 

Chitosan is particularly attractive for application in catalysis 

in regard to the presence of amino groups and its insolubility in 

organic solvent. The capacity of chitosan for metal chelation can 

be strongly increased by the introduction of a ligand. The most 

straightforward route to functionalizing primary amine containing 

materials is the reaction with an aldehyde to form an imine (Schiff 

base formation). Chitosan was functionalized with 11 different 

ligands and Cu (I) was complexated. 

Solids were dried under CO supercritical conditions in 

2 

order to afford high surface area materials. [1] We evaluated the 

putative catalytic activity of the solids for the azide-alkyne 

Huisgens [3+2] cycloaddition reaction under a panel of reaction 

conditions,. The reaction was monitored by a simple fluorescence 

measurement of the corresponding triazole producted with a 

coumarin-based fluorogenic probe. One system appeared more 

active than the homogeneous system itself, and displayed 

particularly high efficiency, with only 0.1 mol catalyst. [2] This 

result was confirmed by kinetic experiments and by a series of 

experiments conducted at the mmole scale on a target reaction. 

references: 

1. R. Valentin, K. Molvinger, C. Viton, A. Domard, 

F. Quignard, Biomacromol. 2005, 6, 2785 

2. M. Chtchigrovsky, A. Primo, P. Gonzalez, K. Molvinger, 

M. Robitzer, F. Quignard, F. Taran, Angew. Chem. Int. Ed. 

2009, 48, 5916 

Keywords: Click chemistry; natural product; green chemistry; 



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o - 3 0 0 

SurfACtAnt effeCtS on CryStAL Growth of 

CLAthrAte hydrAte At interfACe Between 

wAter 

M. MitArAi 1 , M. KiShiMoto 1 , r. ohMurA 1 

1 Keio university, Mechanical Engineering, Yokohama, Japan 

This paper reports visual observations of the effect of 

surfactants on the clathrate hydrate crystal growth at the interface 

of water and cyclopentane. Recently, surfactants are used in gas 

pipeline to prevent the hydrate agglomeration which causes flow 

channel blockage. On the other hand, surfactants have the effect 

of promotion of hydrate formation. These two effects are 

apparently contradictory and the physical mechanism of the 

surfactant effects is unknown. Surfactants used in the present 

study are sorbitan monooleate (Span80), polypropylene glycol 

(PPG), and naphthenic acid. These were used at the concentration 

of 1000 ppm and 10000 ppm. These are soluble in cyclopentane 

liquid phase. Cyclopentane hydrate crystals grew at the interface 

of cyclopentane and water to form a polycrystalline layer. We 

visually analyzed the individual crystals and classified the 

morphology of the hydrate crystals according to the subcooling 

(Δ.T ) from the cyclopentane hydrate equilibrium temperature 

sub 

of atmospheric pressure. It was found that the size of the 

individual cyclopentane hydrate crystals decreased with 

increasing ΔT . The results showed that the morphology of the 

sub 

individual cyclopentane hydrate crystals in any surfactant system 

is qualitatively similar at a given ΔT . The observations also 

sub 

showed the three patterns of the behavior of the cyclopentane 

hydrate crystal growth depending on ΔT , the chemical species 

sub 

of the surfactants and their concentration. (i) Crystal growth was 

similar to that in pure cyclopentane system without surfactant; (ii) 

Surfactants worked as inhibitors and prevented the crystal growth; 

and (iii) After the crystals grew at the interface, the hydrate 

crystals detached from the interface and fell into the water phase. 

These observations indicate that the surfactants have the effect of 

inhibitor and change the wettability of hydrate, cyclopentane and 

water. 

Keywords: clathrate; hydrates; Crystal enginnering; Crystal 

growth; Energy transfer; 



o - 3 0 1 

noveL CAtALyStS froM wASte BioMASS: 

SyntheSiS, ProPertieS And APPLiCAtion to 

the oBtAinMent of BiodieSeL froM ALGAe 

e. tAGLiAvini 1 , C. SAMori 2 , d. fABBri 3 , G. fALini 1 , 

P. GALLetti 1 , C. torri 2 

1 University of Bologna, Department of Chemistry and Centro 

interdipartimentale di ricerca industriale (CIRI), Bologna, 

Italy 

2 University of Bologna, Centro Interdipartimentale di Ricerca 

Industriale, Ravenna, Italy 

3 University of Bologna, Department of Chemistry Centro 

Interdipartimentale di Ricerca Industriale (CIRI), Ravenna, 

Italy 

Some important sources of oil, as waste cooking oils and 

oils from cultured microalgae, cannot be used for synthesizing 

biodiesel by alkaline catalysis because of their high free fatty acids 

content. Acids catalysts, homogeneous (e.g. H SO ) or 

2 4 

heterogeneous (e.g. ion-exchange resins) could represent an 

alternative, but they suffer of some important drawbacks. Ion 

exchange resins are expensive and do not resist to mechanical 

stress; H SO is highly corrosive and require neutralization extra 

2 4 

step. 

Solid acid catalysts, prepared from cheap and easily 

available renewable sources represent a more sustainable 

alternative. In the present study, new solid acid catalysts have been 

prepared from sulfonation of carbonaceous material resulting 

from the pyrolysis of sugar beet molasses, the cheap viscous 

by-product of the production of sugar, and waste products, like 

potato peels. Pyrolysis conditions for molasses and potatoes peel 

carbons preparation (temperature and time) was very important 

in determining the performances of the catalysts; the best 

combination came from pyrolysis at low temperature (420 °C) for 

relatively long time (between 8 and 15 h), which ensured a better 

stability to the final material. The catalyst resulted to be highly 

active in the methanol esterification of fatty acids (100% yield 

after 3 h) as well as in the transesterification of acidic vegetable 

oils (55–96% yield after 8 h). Finally a “tandem process” using 

solid acid molasses catalyst followed by potassium hydroxide in 

methanol was developed to effectively convert algal oils 

containing high amounts of free fatty acids into biodiesel. [1] 

references: 

1. Samori C. et al., 2011. ChemSusChem, DOI: 

10.1002/cssc.201100822 

Keywords: Solid acid catalyst; esterification; biodiesel; 

pyrolytic carbon; sulfonation; 



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o - 3 0 2 

inveStiGAtion of CAtALytiC And 

PhotoCAtALytiC ProPertieS of zno 

nAnofLowerS with noveL fACetinG 

C. CAdiGAn 1 , f. Lin 1 , L. Chen 1 , C. Chou 1 , n. LinCK 1 , 

r. riChArdS 1 

1 Colorado School of Mines, Chemistry & Geochemistry, 

Golden CO, USA 

A novel flower-like and holes-rich ZnO nanostructured 

catalyst, possessing 6-fold building blocks and wurtzite structure 

with [011-0] orientation that shows activity for the hydrogenation 

of CO is investigated. The evidence for this activity was shown 

2 

with a Diffuse Reflectance Infrared Fourier Transform 

Spectroscopy (DRIFTS) study. From the DRIFTS analysis it is 

known that methanol is formed at atmospheric pressure and 

relatively low temperatures with this novel ZnO catalyst. The 

photocatalytic decomposition of methylene blue was also studied 

using nanostructured ZnO that was modified with Li, Au and Ag. 

Results show that Li is detrimental to the photocatalytic activity, 

while Au and Ag increase the activity due to the electron transfer 

between ZnO and novel nanoparticles. 

Keywords: Nanostructures; Heterogeneous catalysis; 

Photocatalysis; Green Chemistry; 



o - 3 0 3 

SuStAinABLe CheMiStry in PrACtiCe 

h. MAndery 1 

1 CEFIC aisbl, Directorate General, Brussels, Belgium 

The world is facing unprecedented challenges, which are 

powerful drivers for change in society and economy. The 

developments in Sustainable chemistry (SC) are essential to 

master these through innovation, while balancing the 3 aspects of 

Sustainable Development (SD) (ecologic, economic and societal 

dimension). For society these can offer major global market 

opportunities for jobs and growth, if research on SC can be 

successfully transferred into broadly available innovative products 

and processes. In order to be successful academia and industrial 

players from the chemical sector and along the value chain have 

to work together. 

Parameters to measure the progress on SC have to include 

molecular work (like on “Green Chemistry”) as well as the 

specific uses along the value chain till disposal. Validated 

approaches are urgently needed including acceptable screening 

criteria as neither raising unwarranted expectations in policy and 

the public nor “green washing” by any stakeholder is acceptable 

anymore. Life cycle assessment approaches can be useful as a 

measuring tool and guiding principle. However it must be 

recognized that these complex tools are not easily suited for 

communication to the general public and dependent on regional 

parameters. At global level it is essential to optimize a variety of 

parameters in the direction of SD due to the different framework 

conditions. Improved education on sustainability as part of 

students and employees curricula is vital. Interested stakeholders 

have to find new ways of cooperation like around the EU 

Technology and Innovation Platform for Sustainable Chemistry 

(SusChem). 

The European Chemical Industry has established a coherent 

open and cooperative program to tackle these challenges, which 

will be presented and discussed. 



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Green Chemistry – iV 

o - 4 3 2 

SyntheSiS of CyCLiC CArBonAteS froM wASte 

CArBon dioxide 

M. north 1 

1 Newcastle University, Chemistry, Newcastle Upon Tyne, 

United Kingdom 

World-wide production of oil and gas is expected to peak 

before 2020. Therefore, since over 90% of all commercially 

available organic chemicals are sourced from crude oil, a major 

challenge for chemistry over the next 10 years is to find 

alternative, sustainable feedstocks for the chemicals industry. One 

particularly attractive reaction in this respect is the 100% atom 

economical reaction between CO and epoxides leading to cyclic 

2 

carbonates. Cyclic carbonates are already manufactured 

commercially and have a number of applications including as 

electrolytes for lithium ion batteries and as polar aprotic solvents. 

In this presentation, the development of bimetallic 

aluminium(salen) based catalysts which, in the presence of a 

tetraalkylammonium cocatalyst, allow this reaction to be achieved 

at atmospheric pressure and room temperature will be discussed. 

Mechanistic studies on cyclic carbonate synthesis using these 

catalysts will be presented, which subsequently led to the 

synthesis of one–component versions of the catalysts. The 

immobilisation of the one–component catalysts on inorganic 

supports and their use in gas–phase flow reactors at temperatures 

and pressures suitable for direct utilization of power station 

flue–gas will be described. The tolerance of the catalysts to the 

NO and SO impurities present in simulated flue–gas will be 

x x 

reported as will the results of studies in which the catalysts were 

exposed to real flue gas from a combustion test–rig burning 

natural gas or coal. 

In view of the scale of the possible use of the catalysts 

(up to 50 tonnes of catalyst per reactor), it is essential that the cost 

of catalyst production is as low as possible. Therefore, a cost 

analysis of the catalysts will be presented along with a modified 

synthesis which avoids all of the expensive reagents and solvents. 

Keywords: carbon dioxide fixation; aluminium; sustainable 

chemistry; 



o - 4 3 3 

diMethyL CArBonAte AS Green reAGent for 

ChLorine-free SyntheSiS 

f. AriCo 1 , P. tundo 1 

1 Universita Ca’ Foscari, Dept of Environmental science 

informatics and statistics, Venezia, Italy 

Dialkyl carbonate (DACs) in general, and dimethyl 

carbonate (DMC) in particular, are well recognized green reagents 

and solvents for new synthetic pathways. DMC, nowadays 

synthesized by CO insertion into epoxides, has shown surprising 

2 

high selectivity with different monodentate and bidentate 

nucleophiles. DMC can act as methoxycarbonylation agent via a 

B 2 mechanism at reflux temperature and as methylating agent 

Ac 

via a B 2 mechanism at higher temperature. Both reactions give 

Al 

as only by-product methanol and eventually CO . 2 

In this work, we report recent advances in DMC chemistry 

for chlorine-free synthesis of 5- and 6-membered heterocycles and 

for the synthesis of nitrogen and sulphur half-mustards carbonate 

analogues. 

In particular, the reaction of 1,4-diols with DMC in the 

presence of a base resulted in the chlorine-free synthesis of 

5-membered cyclic compounds. This reaction pathway to cyclic 

ethers is of general application as it can be employed for the 

preparation of small heterocycles as well as of industrially 

relevant compounds i.e. (-)-norlabdane oxide and isosorbide. This 

synthetic procedure can be also used for the quantitative 

intramolecular heterocyclisation of bifunctional compounds i.e. 

4-amino-1-butanol to achieve pyrrolidine. 

Six-member cyclic carbamates have also been synthesised 

by chlorine-free approach employing DMC chemistry. In fact, 

reacting a primary amine or a hydrazine with a di(methyl 

carbonate) derivative of 1,3-diols oxazinan-2-ones can be 

synthetised in a one-pot chlorine-free reaction. 

Recently we also investigated the replacement of the 

chlorine by a carbonate moiety in half-nitrogen and -sulphur 

mustard compounds. This resulted in new, unexplored and safe 

compounds that showed good reactivity. Results collected 

demonstrated that the novel mustard carbonates are easily 

synthetised, don’t show any toxicity and react with a wide range 

of nucleophiles in the absence of any base. 

Keywords: Dimethyl Carbonate; Cyclisation; Heterocycles; 

Mustard Compounds; Green Chemistry; 



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o - 4 3 4 

trACeS of deGrAdAtion By PyroLySiS under 

uLtrASound: it’S GettinG hot in ioniC 

LiquidS! 

G. ChAteL 1 , r. PfLieGer 2 , e. nAffreChoux 1 , 

S. niKitenKo 2 , J. SuPtiL 1 , C. Goux-henry 3 , 

n. KArdoS 1 , B. AndrioLetti 3 , M. drAye 1 

1 Université de Savoie, LCME, Le Bourget du Lac, France 

2 Institut de Chimie Séparative de Marcoule, ICSM, Bagnolssur-Ceze, 

France 

3 Université de Lyon I, CASYEN, Villeurbanne, France 

More than eight decades after the discovery of 

ultrasound-induced chemical processes, known as sonochemistry, 

they remain a subject of attractive research. It is generally 

accepted that the chemical effects of ultrasound result from the 

phenomenon of acoustic cavitation, which is the formation, 

growth and collapse of bubbles in an elastic liquid. By imploding, 

these bubbles create locally extreme conditions that can lead to 

high-energy radical mechanisms but also generate some 

interesting physical effects that can improve catalyst activity. 

Since the use of ionic liquids in organic chemistry as 

solvents and/or as catalysts and since the development of organic 

sonochemistry, the combination of these two technologies has 

presented unsuspected and very beneficial effects for certain 

organic reactions. However, the effects of ultrasound on ionic 

liquids are unknown, except the observation of a darkening of the 

ionic liquid of the study by several research groups. 

For the first time, we have determined the origin of this 

coloration through the behaviour of hydrophobic ionic liquids to 

the phenomenon of cavitation. We have studied the 

sonoluminescence of pyrrolidinium and piperidinium ionic 

liquids. We have identified, from recent and advanced analytical 

methods, the main traces of degradation products in order to 

propose mechanisms of degradation of ionic liquids under 

ultrasound. Moreover, we have developed a simple and 

convenient method to significantly reduce the impact of 

ultrasound on ionic liquids and thus protect them from 

degradation. For the first time, we determine the acoustic power 

when they are submitted to ultrasound. Ionic liquids heat up 

almost three times faster than water leading to interesting effects 

as solvent for organic reactions. 

Our original studies present a real important impact for 

researchers for a better understanding of ionic liquids/ultrasound 

combination for various organic chemistry applications, and not 

only for specialized scope. 

Keywords: ionic liquids; analytical methods; green chemistry; 



o - 4 3 5 

PhASe equiLiBriA of CLAthrAte hydrAteS 

SuitABLe for CArBon dioxide CAPture 

K. iino 1 , t. SuGinAKA 1 , h. SAKAMoto 1 , 

r. ohMurA 1 

1 Keio university, science and engineering, Yokohama, Japan 

This study is concerned with the technology for CO2 separation from gas mixture utilizing clathrate hydrate 

formation/dissociation. CO separation may be applied for flue 

2 

gas from combustion power plants (CO and N mixture) or for 

2 2 

unconventional natural gas such as coal bed methane and biogas 

(CO and CH mixture). The obstacle of this hydrate technology 

2 4 

is high pressure for hydrate formations. Hence, it is favorable to 

moderate equilibrium conditions by adding hydrate formation 

promoters such as ionic guest substances which form 

semiclathrate hydrates. In the present study, ionic guest substances 

were selected based on the following three requirements: 

(a) moderate the equilibrium conditions, (b) non-toxic, 

non-flammable and non-corrossive effect on metal and (c) store 

large amounts of gas. Among the selected candidate guests, we 

particularly focused on tetrabutylphosphonium bromide (TBPB) 

hydrate and tetrabutylphosphonium chloride (TBPC) hydrate. 

This paper reports an experimental study on the phase equilibrium 

measurements in three-component systems of (CO , CH or 

2 4 

N + TBPB + water) and (CO or CH + TBPC + water). These 

2 2 4 

experimental data were measured by isochoric method in the 

pressure (p) range of (0.1 to 2.1 MPa) and temperature (T) range 

of (282 to 289 K) at mass fraction 0.35 for TBPB and 0.36 for 

TBPC. The measurement uncertainties were ±0.1 K for T, 

±5.0 kPa for p, and ±1.0×10-4 for mass fraction of each species in 

the liquid phase. It was found that equilibrium conditions for the 

(CO or CH + water) systems were more moderated by TBPB 

2 4 

than by TBPC. The results also indicated that TBPB was better 

ionic guest substance for CO separation from CO and CH 2 2 4 

mixture than TBPC. 

Keywords: Clathrates; Hydrates; Carbon dioxide fixation; 

Green chemistry; Phase diagrams; 



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Green Chemistry – V 

o - 4 3 6 

new SynthetiC tooLS for the definition of 

SuStAinABLe ContinuouS-fLow reACtorS 

L. vACCAro 1 , d. LAnAri 1 , f. Pizzo 1 , A. MArroCChi 1 

1 Universita’ di Perugia, Dipartimento di Chimica, Perugia, 

Italy 

Our research program is committed to the definition of 

waste-minimized and eco-friendly synthetic procedures for the 

production of fine chemicals using water [1] or solvent-free 

conditions (SolFC). [2] 

Our goal is to take green chemistry principles in flow by 

defining novel sustainable processes based on the combination of 

heterogeneous catalysts and continuous-flow reactors able to 

operate in safer media and to drastically reduce waste production. 

This approach should allow a) the highest intimacy between 

the reactants and their optimal access to the catalytic sites, 

b) to avoid mechanical stirring and high pressures and c) the 

recovery of the final products using the minimal amount of 

organic solvents and therefore minimizing the production of 

waste. 

Commercially available solid supports (organic or 

inorganic) have been developed to be used in the presence of a 

reaction medium and designed to deal with the related swelling 

processes. Besides, mechanical stirring of the reaction mixture 

often causes the complete crunching of the solid catalyst 

hampering its recovery and reuse. 

Our current studies are mainly directed towards the design 

and synthesis of tailor-made supports able to be effectively used 

in continuous-flow reactors operating under SolFC or in the 

presence of a dispersion medium such as water. The novel solid 

supports should mainly solve the problems related to their 

swelling and the consequent internal pressure. 

Some examples from our laboratory will be presented in this 

communication. 

Acknowledgement: This research has been supported by MIUR 

within the programs: PRIN 2008, FIRB – Futuro in Ricerca 

2008 

references: 

1. a) L. Vaccaro et al. a) Org. Lett. 2011, 13, 2150; 

b) Eur. J. Org. Chem. 2011, 2587 

2. a) L. Vaccaro et al. J. Catal. 2012, 285, 216; 

b) Green Chem. 2012, 14, 164; 

c) Adv. Synth. Cat. 2010, 352, 2489; 

d) Green Chem. 2010, 12, 1301 

Keywords: clean synthesis; flow chemistry; heterogenous 

catalysis; water; solvent-free conditions; 



o - 4 3 7 

SuCCeSSfuL APPLiCAtion of PorouS GLASSeS 

AS SuPPort for MethAne eMiSSion reduCtion 

CAtALyStS 

M. hoffMAnn 1 , S. wohLrAB 1 

1 Leibniz Institute for Catalysis, Inorganic Functional Materials, 

Rostock, Germany 

The use of methane as fuel for natural gas vehicles is 

increasing, although a still unsolved problem is the remaining 

methane content of 500 to 5000 ppm in the exhaust gas stream. [1] 

For the abatement of these emissions low temperature methane 

oxidation can be used, which has been extensively studied [2, 3] 

but not yet applied for this purpose. Apart from complete 

conversion at low temperatures the long term stability is the major 

requirement that can often not be fulfilled. [4] 

This work presents the application of porous glasses as 

support for Pd/CeO catalysts providing a protective framework, 

2 

reducing the methane activation temperature and increasing the 

long term stability. 

Catalysts composed of Pd on CeO in porous glasses were 

2 

prepared by simultaneous or consecutive impregnation. The 

influence of impregnation procedure, glass pore size and 

palladium loading on the catalytic activity for CH oxidation was 

4 

investigated and interpreted by H -TPR. Consecutive 

2 

impregnation of the glass support with cerium nitrate melt and 

palladium nitrate solution yielded outstanding results in 

combination with a glass pore size of 151 nm. Methane 

conversion reached 100% at temperatures as low as 350 °C in case 

of a 1% Pd loading related to CeO and 305 °C with 10% Pd 

2 

loading respectively. Long term stability tests were carried out 

showing the steadiness of the catalysts during 50 hours on stream. 

No pre-treatment of the catalysts was necessary, granting a fast 

start-up. 

references: 

1. M. Zanoletti, D. Klvana et al., Chem. Eng. Sci. 2009, 64, 

945–954. 

2. P. Gélin and M. Primet, Appl. Catal. B-Environ. 2002, 39, 

1–37. 

3. G. B. Hoflund and Z. H. Li, J. Nat. Gas Chem. 2003, 12, 

153–160. 

4. L.-h. Xiao, K.-p. Sun et al., Catal. Commun. 2005, 6, 

796–801. 

Keywords: Heterogeneous catalysis; Oxidation; Palladium; 

Cerium; Glasses; 



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o - 4 3 8 

heteroGeneouS CAtALytiC oxidAtion And 

CArBonyLAtion reACtionS in A GAS/Liquid 

ContinuouS fLow reACtor 

G. dorMAn 1 , L. LenGyeL 1 , v. GyoLLAi 1 , L. KoCSiS 1 , 

r. JoneS 1 

1 ThalesNano Inc., Chemistry, Budapest, Hungary 

Gas/liquid phase heterogeneous catalytic reactions with 

simple added gas components (hydrogen, oxygen, carbon 

monoxide, etc.) are very efficient and green processes in the 

pharmaceutical, agro and fine chemical industry as well as in 

R&D. Employing traceless gaseous reagents over chemicals 

allows to develop greener processes reducing the waste and the 

purification burden. While hydrogenation is extensively used in 

continuous flow processes due to the availability of safe in situ 

generation of this gas in a flow reactor oxidation with molecular 

oxygen or (hydro)formylation with CO are not fully exploited due 

to the strict technological requirements for safe operation. In a 

recent edition of a fixed-bed continuous flow reactor various 

external gas components can be applied including O , CO or CO . 

2 2 

In the presentation various oxidation reactions with elementary 

oxygen (including aromatization, convertion of primary and 

secondary alcohols to aldehydes vs. ketones, Baeyer-Villiger 

oxidation etc.) as well as carbonylation and carboxylation will 

demonstrate the various novel opportunities in continuous flow. 

The reactor cartridge could be pre-packed with various types of 

catalysts including Au/TiO , Ru/C, Ru/Al O , Pd/C etc, which 

2 2 3 

avoids leakage (external purification) and allows the reuse of the 

catalyst. 

Keywords: continuous flow chemistry; microreactors; 

heterogeneous catalytic oxdation; 

Green Chemistry – Vi 


o - 4 3 9 

noveL MethodoLoGieS for ABAteMent, 

ConCentrAtion And utiLizAtion of fLue GAS 

PoLLutAntS BASed on ioniC LiquidS 

y. SASSon 1 , z. BArneA 1 

1 The Hebrew University of Jerusalem, Institute of Chemistry, 

Jerusalem, Israel 

Burning of fossil fuels for power generation is always 

accompanied with formation of awfully undesired pollutants 

which are environmentally damaging and typically highly toxic. 

Even renewable fuels such as biodiesel, bioethanol and even 

hydrogen are expected to generate toxic contaminants particularly 

oxides of nitrogen. Although some upstream purification methods 

are exercised e.g. hydrodesulfurization at the oil refinery, the large 

majority of cleansing techniques are end of pipe solutions. While 

the traditional abatement methods focused on neutralization and 

decontamination of the pollutants, novel technologies are seeking 

approaches to convert the pollutants into useful products e.g. 

sulfate or nitrite fertilizers, sulfuric or nitric acid and purified 

heavy metals. 

We have recently found that ionic liquids (ILs) are superb 

conduit for the abatement of flue gas pollutants using standard 

gas liquid scrubbers. Typical ILs such as BMIM (1-butyl-3- 

-methylimidazolium) halides form stable adducts with sulfur 

dioxide that allow the swift and quantitative removal of SO from 2 

the gas phase. After absorption the BMIM-SO complex can be 

2 

straightforwardly decomposed by a temperature swing or by using 

a recycleable polar solvent, such as alcohol, that readily releases 

pure SO The latter can be directly used as raw material for 

2. 

various commercial products. 

It was further realized that the absorption characteristics of 

imidazolium based ILs can be considerably upgraded by 

incorporation of oxidizing agents. Mercury was shown to be 

swiftly oxidized and captured from flue gas of burning coal under 

very mild conditions, using iodine adducts of BMIM halides. 

Another interesting hybrid reagent, developed in our laboratory 

is the complex of ClO with BMIM halide. This novel adduct was 

2 

demonstrated to function as a three way absorption reagent in a 

common gas/liquid scrubber. The reagent simultaneously captures 

mercury, SOx and NO by an oxidation process converting the 

x 

latter into aqueous sulfate and nitrates that can be used as 

fertilizers. The mercury, trapped as a complex BMIM + - HgX , can 3 

be recovered in a pure form e.g. by reduction with aqueous 

sodium formate. This example exhibits an incredible 

concentration factor (109 ) achieved via a remarkably simple and 

cost effective operation. 

Further details will be presented at the lecture. 

Keywords: Mercury; Sulfur oxides; Nitrogen oxides; Flue gas 

purification; 



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o - 4 4 0 

non AqueouS SoLvent forMuLAtionS BASed 

on 2-AMino-2-MethyL-1-ProPAnoL (AMP) for 

effiCient Co ABSorPtion And Low 

2 

teMPerAture deSorPtion 

f. MAni 1 , f. BArzAGLi 2 , M. Peruzzini 2 , 

P. StoPPioni 1 

1 University of Florence, Department of Chemistry, Firenze, 

Italy 

2 CNR, ICCOM, Firenze, Italy 

Although the CO capture using aqueous alkanolamines is 

2 

considered the most efficient and feasible technique, the energy 

required for the solvent regeneration and the alkanolamine 

degradation are the bottleneck of the process still requiring 

unacceptable energy and economic costs. [3] We have formulated 

non aqueous solvents with the objective of minimizing the 

drawbacks of the aqueous alkanolamines without reducing their 

advantages. The solvents are based on AMP-alkanolamine 

blends (alkanolamine: 2,2'-iminodiethanol, DEA; N-methyl-2,2'- 

-iminodiethanol, MDEA; N-methyl-2-aminoethanol, MMEA; 

bis(2-hydroxypropyl)amine, DIPA; overall, 2.0 M; 18.3-22.6 wt %) 

and either single alcohols or mixtures with ethylene glycol. 

Throughout the experiments of CO capture (12 % v/v in air), both 

2 

carbonated and regenerated solvents are continuously circulated 

in a closed system between the absorber (20 °C) and the desorber 

(65, 70, 75, 80 °C). The CO loading capacity and the absorption 

2 

efficiency at equilibrium are in the range 0.65–0.81 (on molar 

scale, with respect to the amine) and, respectively, 73.1–95.9 %, 

depending on the composition of the solvents and the desorption 

temperature. The carbon containing species in the CO -amine- 

2 

-alcohol equilibria have been analysed by 13C NMR spectroscopy [2] 

and have been found to originate from alcohol and amine 

carboxylation. The lower stripping temperatures should reduce 

the thermal and oxidative degradation of the amines, whereas the 

lower heat capacity of alcohols combined with the lower stripping 

temperatures could offer potential advantages in terms of energy 

saving with respect to conventional aqueous alkanolamines. In 

some experiments, AMP carbamate has been obtained in the solid 

state and its peculiar reactivity towards some alcohols has been 

tested. 

Acknowledgements: This work was financially supported by 

ENEA (Rome). 

references: 

1. A.J. Reynolds, T.V. Verheyen, S.B. Adeloju, E. Meuleman, 

P.Feron, Environ. Sci. Technol. 2012, 46, 3643-3654. 

2. F. Barzagli, F Mani, M. Peruzzini, Energy Environ. Sci. 

2010, 3, 772 - 779. 

Keywords: carbon dioxide fixation; carboxylation; 



o - 4 4 1 

deveLoPMent And APPLiCAtion of noveL 

BioinSPired ioniC LiquidS 

K. zALewSKA 1 , L. BrAnCo 1 

1 Faculty of Sciences and Technology Universidade Nova de 

Lisboa, Departamento de Quąāmica, Caparica Lisbon, 

Portugal 

Biological molecules are considered as building blocks of 

life. The understanding and use of their chemistry represents a 

crucial role in modern research science. [1] In last decades, Ionic 

Liquids (ILs) have emerged as a possible environmentally benign 

alternative to common organic solvents, due to use in a variety of 

areas. [2] In this context, Novel Functional Bioinspired ILs (FBILs) 

based on the incorporation of relevant biological molecules by 

simple dissolution (e.g. ILs and cyclodextrins) or by sustainable 

synthetic combinations (e.g. chiral ILs based on aminoacids such 

as L-cysteine derivatives) have been developed. 

The main goal is related with the development of novel 

Chiral biomaterials based on the interaction of biocompatible ILs 

and cyclodextrins as well as the preparation of L-cysteine 

derivatives as chiral ILs. Applications of this novel Chiral ILs 

include their use for chiral recognition processes and chiral media 

for asymmetric catalysis. [3] 

Two different approaches have been investigated: 

(i) dissolution and interaction studies of a, b and g cyclodextrins 

(CDs) with several ILs. Their dissolution performance and 

interaction behavior have been studied. Novel biomaterials based 

on simple combination of ILs and CDs can be applied for 

host-guest and drug delivery processes [4] ; (ii) preparation and 

characterization of novel chiral ILs based on L-cysteine derivatives 

such as S-methyl-L-cysteine and S-carboxymethyl-L-cysteine 

combined with appropriate counter-ions. The most promising 

chiral ILs has been applied for enantiomeric resolution and 

asymmetric catalytic reactions. 

Novel biocompatible materials based on the combination of 

ILs and CDs can be explored for relevant chiral discrimination or 

separation processes. Novel L-cysteine ILs have been tested for 

resolution of racemates as well as chiral media for asymmetric 

aldol and Michael reactions. [5] Their efficiency should be 

dependent of the combination of L-cysteine as cation or anion 

with appropriate counter-ions. 

references: 

1. W. Chuanlong, F. Xiangkai, L. Shi, Eur. J. Org. Chem.; 7, 

(2011), 1291–1299. 

2. Wasserscheid P., Welton T., Ionic Liquids in Synthesis, 

VCH-Wiley, Weinheim, 2002. 

3. K. Bica, P. Gaertner, Eur. J. Org. Chem.; 19, (2008), 3235. 

4. N. Zhong, H. S. Byun, R. Bittrnan, Tetr. Lett; 39, 1998, 

2919-2920. 

5. W. Chuanlong, F. Xiangkai, L. Shi, Eur. J. Org. Chem.; 

2011, 7, 1291–1299. 

Keywords: Amino acids; Ionic liquids; Green chemistry; 

Asymmetric catalysis; Chirality; 



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o - 4 4 2 

redox-ACtive vAnAdiuM PoLyoxoMetALAteS 

for enerGy ProduCtion And StorAGe 

P. MoLinA SAnChez 1 , M. SyMeS 1 , C. Lydon 1 , 

C. BuSChe 1 , h. MirAS 1 , d. L. LonG 1 , L. Cronin 1 

1 University of Glasgow, School of Chemistry, Glasgow, United 

Kingdom 

Email: L.Cronin@chem.gla.ac.uk 

Polyoxometalates (POMs) are anionic molecular oxides of 

early transition metals, such as Mo, W, V and Nb, which possess 

an unmatched ability to incorporate almost every single element 

from the periodic table in their structure. This rich elemental 

composition together with a vast diversity in size and topology 

help to explain their extraordinary flexibility in a range of physical 

properties. For instance, POMs are generally soluble in water yet 

they can be made soluble in a range of organic solvents and they 

tend to exhibit a wealth of redox processes whilst keeping their 

structure intact. These, in particular, make POMs ideal candidates 

for energy storage and catalytic applications related to green 

energy production. 

In this light, we present [P V W O ] 4 6 30 120 10- , a Wells–Dawson 

polyoxometalate sandwich compound with a double cubane core 

consisting of six vanadium atoms1 . The formation of the cluster 

is followed by mass spectrometry and the reduction of the double 

cubane is studied by a novel technique combining mass 

spectrometry and spectroelectrochemistry. Catalytic properties of 

[P V W O ] 4 6 30 120 10- are evaluated in connection with solar fuels 

production and compared to other members of the vanadium 

polyoxotungstate family. A new device concept is also presented 

linking the ideas of energy production and storage in one 

molecular system. 

references: 

1. Lydon, C., Busche, C., Miras, H.N., Delf, A., Long, 

D. L.,Yellowlees, L., Cronin, L. Angew. Chem. Int. Ed. 

2012, 51, 2115-2118. 

Keywords: Polyoxometalates; Vanadium; Mass spectrometry; 

Electrochemistry; 



o - 4 4 3 

exPeriMentAL And theoretiCAL CoMPAriSon 

of An equAtion of StAte for Pore-Confined 

fLuidS 

P. LóPez-ArAnGuren oLiver 1 , L. f. veGA 2 , 

C. doMinGo 1 , e. h. ChiMowitz 3 

1 ICMAB (CSIC), Solid State Chemistry, Bellaterra, Spain 

2 Matgas Research Center and Carburos Metalicos Air Products 

Group, Matgas, Bellaterra, Spain 

3 University of Rochester, Chemical Engineering, Rochester, 

USA 

The prediction of properties in porous materials is of 

continuing interest in the fields of chemical and materials 

engineering. Application areas include, among others: (a) the use 

of supercritical fluids to modify porous materials, (b) physical 

adsorption of trace components from gaseous effluents, (c) gas 

storage using micro-porous materials, and (d) chemical 

separations using inorganic membranes. 

There is a need for useful thermodynamic models in this 

area and here we present an equation of state (EOS) for 

calculating the thermodynamic properties of both bulk and poreconfined 

fluids. We illustrate for the first time the application of 

this EOS to both realistic bulk and single component adsorption 

systems. The model is a mean field type derived from a statistical 

mechanics approach carried out in the grand canonical ensemble. 

In pure fluids, the only properties required are the bulk fluid’s 

critical properties. In adsorption systems, the fluid-solid matrix 

interaction parameter is required. 

We show comparisons between the model and the 

Peng-Robinson (PR) equation of state, for methane and carbon 

dioxide in the bulk fluid case. However, our EOS has an important 

advantage over the original PR EOS in that it seamlessly carries 

over into predictions of the pore-confined fluid thermodynamic 

properties. We illustrate this point using recently published 

adsorption data in a carbon dioxide-silica aerogel system. 

Keywords: Supercritical fluids; Adsorption; Statistical 

thermodynamics; 



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European Young Chemists’ Network 

EYCN – the art of writing 

o - 1 6 6 

the Art of writinG: froM teLL to SeLL 

S. GoMez-ruiz 1 

1 Universidad Rey Juan Carlos, Department of Inorganic and 

Analytical Chemistry, Mostoles (Madrid), Spain 

Writing a scientific paper is something that many scientists 

enjoy and others dread. The value of writing a paper in a concise, 

engaging and clear way, normally translates to a higher impact of 

your scientific work. Top articles are normally well-written, read, 

remembered and highly cited, whilst poorly written papers are 

easily forgotten. 

However, good writing is not simple and depends on many 

different factors as the journal, type of manuscript, concepts to 

report and readers, for example. So that, there is not a single, 

correct way to write, because many different solutions to the 

problem are possible. 

In this communication, an overview of the elements of style 

and composition of a scientific paper will be discussed. In 

addition, different approaches for an effective and successful 

writing outcome will be reviewed and adapted to young chemists 

that are in the early stage of their career. 

Keywords: Inorganic Chemistry; Organic Chemistry; Physical 

Chemistry; Writing; 

EYCN – the art of writing 


o - 1 6 7 

writinG ProPoSALS effiCientLy And 

effeCtiveLy 

S. GoMez-ruiz 1 

1 Universidad Rey Juan Carlos, Department of Inorganic and 

Analytical Chemistry, Mostoles (Madrid), Spain 

This workshop will be focused on the art of writing a grant 

proposal. Usually, the process of planning and of presenting your 

research ideas or results to the right person takes time and 

persistence to succeed. 

Techniques and advices for an efficient way of writing will 

be discussed in this lecture. It will emphasize topics such as idea 

development and identification of the most appropriate funding 

sources and the basic components of a proposal. 

Participants will learn the common mistakes and reasons 

why sometimes well written proposals finally fail. Budget 

preparation and review criteria and tips for writing succeessful 

proposals will be also examined. 

The final part will be for discussion of questions and doubts 

from the Audience. 

Keywords: writing; grant proposals; chemistry proposals; 



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EYCN – Putting your degree to work 

o - 1 6 8 

PuttinG your deGree to worK 

S. hoBBS 1 

1 Royal Society of Chemistry, Member Networks, Cambridge, 


What does a set of keys and a Chemistry degree have in 

common? They both open many doors. Wondering what you can 

do with your Chemistry degree? Come along to the RSC’s careers 

talk to find out more. The talk will cover career profiles from a 

selection of chemists, demonstrating the wide variety of options 

open to those with a chemistry background. The careers focus will 

be looking at the path from a PhD to a non-academic profession 

and learning to cope with the change in environment. Additionally 

we will be looking at an example of a graduate scheme from 

application to assessment day and interview. 

Finally, there will be additional information highlighting the 

resources available from the RSC Careers Service. The RSC’s 

careers service offers its members the support they need to 

enhance their skills or develop new ones, help with a change of 

direction in their career, advice with job hunting including advice 

on the recruitment process, including CVs, application forms and 

interviews. The importance of effective individual career planning 

can’t be overestimated in today’s volatile job market, so whether 

you are just starting out on your career path or well on your way 

through it, the RSC has resources to help its members. 

Please bring a copy of your CV to this session, they will not 

be checked individually but will form part of an exercise. 

EYCN – Chemethics and eCV 


o - 1 6 9 

ethiCS in SCienCe And teChnoLoGy 

A. quintAniLhA 1 

1 Instituto de Ciencias Biomedicas Abel Salazar (ICBAS), 

Biologia Molecular, Porto, Portugal 

As human beings our way of dealing with curiosity and 

imagination has evolved significantly over the centuries. 

Whatever the field of knowledge, whether astronomy, chemistry, 

biology, sociology or philosophy, it was always because we were 

disatisfied with existing ideas, that new questions and tentative 

new answers took shape, which required novel ways of validation. 

At the interface of science and philosopy new forms of ethics, 

namely bio-ethics, gen-ethics or eco-ethics have flourished over 

the last decades. We will discuss current issues in these emerging 

domains of knowledge. Risk, equity and fraud will be used as 

examples to illustrate the presentation. 



s669 

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EYCN – Chemethics and eCV 

o - 1 7 0 

your e-Cv: oPtiMizinG SoCiAL MediA 

M. AGoStinho 1 

1 Instituto de Medicina Molecular, Communication Unit, Lisboa, 

Portugal 

Finding a job is getting more and more difficult under the 

current economy. Nowadays, social media plays a big role in 

employee hiring, and therefore it is important to think outside the 

box. It is also crucial to make use of such tools in promoting soft 

and hard skills to achieve maximum impact in companies and 

academia. Tools such as ResearchGate, LinkedIn, Twitter and 

Facebook, are a privileged platform of professional promotion 

and networking. For instance, LinkedIn, a vast professional social 

network, enables users to demonstrate what they can convey to 

prospect employers. With the current challenges that Science 

poses to young researchers, it is essential to develop and promote 

a set of skills that leads to a higher rate of employability. With this 

lecture we intend to give some highlights on how to use social 

media in the search for a new job or simply to endorse the work 

researchers carry out and to establish a solid scientific career. 

As part of a CV, young researchers are encouraged to 

demonstrate their personal attributes that enhance not only 

interactions with fellows in the field, but also job performance 

and career prospects. Through the use of these digital platforms, 

it is possible to show positive attitude, self-confidence, 

communicational skills and team spirit, essential characteristics 

to succeed in any work field. 

EYCN – Making chemistry work for you 


o - 3 0 4 

eyCn MAKeS CheMiStry worK for you 

v. fLuxA 1 

1 EYCN, EYCN board, Berne, Switzerland 

The European Young Chemists’ Network (eyCn) is an 

organisation representing the young members of the European 

Association for Chemical and Molecular Sciences (EuCheMS). 

Every chemist under 35 within the EuCheMS framework is part 

of EYCN. For the last 6 years we have worked towards promoting 

the exchange of knowledge among chemists in academia and 

industry, as well as professional institutions and government 

bodies across Europe. 

In a friendly environment, we aim to bridge the gap between 

your studies and your chemical career. Are you thinking of going 

to the U.S. for a Postdoc or PhD? During this session, a delegation 

of American students will be there for you. To answer and discuss 

your doubts and help you plan your decision of going abroad. 

Initially launched with 12 participating societies, EYCN 

today encompasses the knowledge and enthusiasm of young 

chemists from 24 chemical societies in Europe and abroad. Our 

energy goes to support and encourage young chemists at the 

beginning of their careers. Following from that idea we have 

organised activities designed to develop the tools for 

undergraduate and graduate students to improve their career 

possibilities. Workshops in interview skills and CV writing and 

seminars about development of soft skills are our main events 

during the EYCN Satellite Event during the Prague Congress. 

You can follow us on Facebook, Twitter, LinkedIn, and on 

our web page www.eycn.eu. Join our informal session, get to know 

the network and become part of a giant multicultural voice. 

Keywords: eycn; career days; young chemist; network; 



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EYCN – Making chemistry work for you 

o - 3 0 5 

Beer: froM the firSt GLASS to A hAnGover 

K. roth 1 

1 Institute for Chemistry and Biochemistry, Freie Universität 

Berlin, Berlin, Germany 

Beer brewed according to the German “Reinheitsgebot” or 

purity law is regarded as the quintessence of an unadulterated food 

produced without any “chemistry”. What an error! There is so 

much exciting chemistry involved all the way from barley to a 

glass of beer in front of us. The chemical climax is the conversion 

of some hop constituents into bittering substances via a 

breathtaking a-ketol- or Oktoberfest-rearrangement. This is just 

another proof that chemistry cannot only be exciting but can also 

taste good. But there is a dark side. After too much beer drinking 

there arises what is colloquially referred as a “hangover” with all 

its terrible symptoms. How can a tiny molecule like ethanol be at 

the root of so much human misery. Let’s get to the bottom of the 

chemical consequences of a night of celebrating to excess. Well 

then: Na Zdraví! 

Keywords: alcohols; medical chemistry; metabolism; 

rearrangement; 




s671 

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food Chemistry food /Agriculture/Agrochemistry/Nanotechnology, food and processing 

sustainable food production – i 

o - 0 3 1 

CheMiStry for SuStAinABLe food 

ProduCtion 

B. wedziChA 1 

1 University of Leeds, Emeritus Professor of Food Science, 

Leeds, United Kingdom 

The word ‘sustainable’ means different things to different 

people, and it is difficult to reach a consensus with regard to its 

significance with regard to food production. On the one hand, the 

energy equation and environmental aspects (e.g., water, emissions, 

distribution) feature strongly in the sustainability argument, 

whereas the scope of sustainable food production must include 

manufacture efficiency, the utilisation of by-products 

(e.g., chemical, mechanical, heat), and reduction in waste up to 

the point of consumption. However, unless the food is good to eat 

and consumers are offered adequate choice (in both quality and 

type of food) the industry fails to main itself in a financially 

sustainable condition. Thus food quality (texture, flavour, safety) 

and shelf-life considerations are an important aspect of the 

sustainable food industry. This talk will explain these 

considerations and show how they will be addressed through the 

contributions to the conference. 

Keywords: KInetics; 

sustainable food production – i 


o - 0 3 2 

food ProduCtion And food quALity: 

A SuStAinABLe MAtCh 

M. vAn BoeKeL 1 

1 Wageningen University, Agrotechnology & Food Sciences, 

Wageningen, Netherlands 

The production of food is obviously of high importance 

from a societal point of view, but at the same time it can be stated 

that food production systems are not (yet) optimized in terms of 

sustainability. The focus so far has been much more on being 

effective than on being efficient, in terms of the use of available 

resources. Scarcity of resources (energy sources, raw materials, 

clean water) in the very near future will be a challenge to produce 

food in enough amounts for a growing world population. In the 

past 100 years or so, much has been achieved in terms of food 

security, food safety and food quality. The challenge to keep these 

high standards while the resources are becoming scarcer is 

enormous. It becomes all the more necessary to involve 

a scientific and engineering approach to tackle this challenge. 

To calculate the impact of using scarce resources and producing 

waste and side-streams that are given back to the environment, 

a thermodynamic approach is proposed by modelling food 

production activities in terms of entropy production. At the same 

time, food quality should be maintained and optimized, and this 

requires another modelling approach in order to get a grip on the 

multidimensional aspects involved. Thus, understanding, 

controlling, and prediction of food quality and safety by using 

mathematical models is proposed as a way forward to make food 

production more sustainable while still delivering high quality 

foods. This lecture will address some of the basic principles that 

are needed to come to such an approach. 

Keywords: food quality; food production; sustainability; food 

safety; thermodynamics; 



s672 

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food Chemistry food /Agriculture /Agrochemistry / Nanotechnology, food and processing 

Analytical chemistry supports sustainable food production 

o - 0 3 3 

AnALytiCAL CheMiStry SuPPortS SuStAinABLe 

food ProduCtion 

h. SteinhArt 1 

1 Institute of Food Chemistry, University of Hamburg, Hamburg, 

Germany 

Food analysis must be considered in regard to the type of 

matrix, the amount of information required, the legislation, and 

the possibilities of the laboratory. Developments in the creation 

of new analytical tools can help to improve the quality of food as 

well as to assist sustainable production of food. The aims of 

sustainable production of food are to protect the natural sources 

and to produce food with high quality. Food quality cannot only 

be described by single parameters such as contaminant content 

and major nutritional constituents. It comprises the consumer 

expectations like nutritional, sensory, technological value as well 

as food safety aspects. The analytical process of food comprises 

sampling, extraction, sample preparation and analysis, it is a 

complex system. Analytical methods can be divided into fast 

methods used during food. production, sensitive methods for 

known compounds used during food surveillance and most 

sensitive and versatile methods for unknown compounds and 

metabolites used in research institutes. 

In the lecture are given examples how to solve recent 

analytical problems which are connected with food safety and 

food production. These examples comprise food allergenicity, 

contaminations and residues, GMO identification and 

identification of trans fatty acids (TFA). 

Microconstituents and analysis 


o - 0 3 4 

the roLe of the fLAvour CheMiSt in 

MAintAininG SuStAinABLe food ProduCtion 

J. PArKer 1 

1 University of Reading, Food and Nutritional Sciences, 

Reading, United Kingdom 

With the UN predicting that world food production must rise 

by 50% by 2030 to meet increasing demand, and additional threats 

from climate change, agronomists are selectively breeding high 

yielding, drought resistant crop varieties for the future. Process 

engineers are tasked with reducing energy and water 

requirements, for which a parallel increase in demand is forecast. 

How can we, as chemists, and particularly flavour chemists, 

contribute to sustainable food production? 

Whilst yield and nitrogen efficiency are key indicators of 

success, it is recognised that the consumer still expects a high 

quality product and is unwilling to sacrifice the flavour when 

selecting a product which is more healthy, ethical or sustainable. 

It is, therefore, of utmost importance that flavour quality is 

considered when manipulating varieties or processing conditions 

in search of a more sustainable product. This is where it becomes 

crucial to understand the chemistry involved in flavour generation. 

Flavour can either be generated in situ from endogenous 

precursors, or it can be added as part of a flavouring preparation. 

Flavour houses are already addressing the sustainability issue. 

Biochemists are involved in “white biotechnology” generating 

flavour compounds (or their precursors) from renewable resources 

using fermentations and biocatalysis. Synthetic chemists are 

designing novel pathways from renewable starting materials and 

developing highly selective, and ever increasingly efficient, 

catalysts. 

As flavour chemists, our role is to maximise flavour 

production from raw materials where selective breeding has bred 

out flavour precursors, or minimal processing conditions have 

diminished flavour forming pathways. The major route to flavour 

generation during thermal processing is the Maillard reaction, a 

complex cascade of interdependent reactions. The flavour chemist 

of the future needs to have a thorough understanding of the 

mechanism involved and the critical control parameters, in order 

to maximise flavour formation in unfavourable, though 

sustainable, conditions. 

Keywords: sustainable food production; flavour formation; 

Maillard reaction; 



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o - 0 3 5 

ChArACterizAtion of CyPriot honeyS By 

uSinG nuCLeAr MAGnetiC reSonAnCe 

SPeCtroSCoPy 

M. vLASiou 1 , C. drouzA 2 , M. KontoMinAS 3 , 

C. PAPAStefAnou 4 , A. KerAMidAS 5 

1 University of Cyprus, Chemistry, Nicosia, Cyprus 

2 Cyprus University of Technology, Department of Agricultural 

Sciences, Limasol, Cyprus 

3 University of Ioannina, Department of Chemistry, Ioannina, 

Greece 

4 Food lab Ltd, Chemistry, Nicosia, Cyprus 

5 Univercity of Cyprus, Department of Chemistry, Nicosia, 

Cyprus 

Honey is an expensive natural food that has been, for a long 

time, target for adulteration and/or intentional misdescription of 

its botanical and geographical origin. Current, 

melissopalynilogical methods used for honey discrimination do 

not meet the quality standards of modern validated analytical 

methods. In this study, the geographical and botanical origin of 

Cypriot and Greek honey is investigated utilizing the NMR 

spectroscopy. Proton and carbon NMR are the well known 

techniques used for analytical purposes. NMR spectroscopy is a 

very useful tool for food analysis because (a) it is non catastrophic 

method for the sample, (b) it doesn’t require a lot of quantity of 

the sample (c) it is fast, and (d) gives high resolution: in a single 

run it is able to give a rich of information for many components. 

Proton and carbon NMR spectra have been recorded for 

deuterium oxide solutions of honey samples and standards at room 

temperature. From spectral analysis, the sugars content, amino 

acids, and the glucose/fructose ratio of honeys have been 

determined. It has been found that the profile of sugars isoforms 

is strongly dependent on the flora diversity located at different 

altitudes of the island providing a good separation for Cypriot and 

Greek honeys. The prior classification of the honeys based on the 

altitude facilitated the geographical and regional discrimination 

of the honeys. Because honey is objected to adulteration through 

mixing with honey originated from non European countries these 

chemometrics promote the detection of adulteration of the Cypriot 

and Greek honeys. The determination of the glucose/fructose ratio 

alone consists an effective indicator for the origin of the samples, 

and in combination with the NMR spectroscopy provides a fast 

identification /quantification method for the product which highly 

concerns the food industry and the consumer’s society. 

Funding from Research Promotion Foundation and the 

European Structural Funds program: 

ANABAΘMISH/ΠAΓIO/0308/32 

Keywords: honey; NMR; chemometrics; adulteration; origin; 



o - 0 3 6 

BotAniCAL diSCriMinAtion of oLive oiLS 

uSinG 19f nMr SPeCtroSCoPy 

C. drouzA 1 , K. tSAouSi 1 

1 Cyprus University of Technology, Agriculture Sciences 

Biotechnology and Food Science, Limassol, Cyprus 

In the last decade there has been a rapidly increasing use of 

NMR spectroscopy in the field of Food Science, because of the 

advances in high field magnets and probe design that amplified 

the analytical capacities of modern NMR spectrometers. The most 

common applications are on food analysis, authentication and 

quality control of food stuff. The disadvantage of the lower 

sensitivity of NMR compared to other spectroscopic techniques 

such us UV-Vis, fluorescence, EPR etc. is compensated by its high 

resolution: a single scan provides a rich of information for many 

components in the assay. 1H and 13C nuclei are the target nuclei 

of the majority of the NMR experiments because of their high 

sensitivity, while other nuclei such 31P have also been utilized. In 

this study, we develop a new method utilizing the 19F NMR 

spectroscopy for exploitation to the olive oils analysis and apply 

for olive oil discrimination. The 19F active adduct is chemically 

bound to the components containing -OH or –COOH groups. The 

fluorinated products exhibit hydrolytic and redox stability for long 

time and the 19F NMR spectra were run in CDCl , giving chemical 

3 

shifts ranged from -74 to -77 ppm, referenced to CFCl (0 ppm). 

3 

30 samples of Olive oils from different botanical origin cultivated 

inCyprus have been examined with the above method. Utilizing 

19F NMR spectroscopy several components such as 

a-tocopherol, tyrosol, mono- and diglycerides, b-sitosterol, 

desmesterol and free acids have been determined. PCA statistical 

analysis has been applied to the results and it has been found that 

there is a discrimination of the samples based on their botanical 

origin. 

Acknowledgement: The authors acknowledge financial 

supporters: This work has been co-funded by the European 

Regional Development Fund and the Republic of Cyprus 

through the Research Promotion Foundation (Infrastructure 

Project: ANABAQMISH/0308/32) 

Keywords: Analytical Methods; NMR spectroscopy; 



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o - 0 3 7 

the free rAdiCAL invoLved in the oxidAtion 

of fLAvonoidS By LACCASe. An ASSAy for 

Pro-oxidAnt reACtivity 

A. C. Mot 1 , G. dAMiAn 2 , C. SArBu 1 , 

r. SiLAGhi duMitreSCu 1 

1 Babes-Bolyai University, Faculty of Chemistry and Chemical 

Engineering, Cluj-Napoca, Romania 

2 Babes-Bolyai University, Faculty of Physics, Cluj-Napoca, 

Romania 

Under certain conditions polyphenolics may display 

prooxidant rather than antioxidant properties, and this may lead 

to undesirable consequences such as inhibition of mitochondrial 

respiration, direct DNA damage, lipid peroxidation and 

mutagenicity - but also to benefic effects such as tumor cell 

apoptosis, cytoprotective enzyme induction, or activation of 

oxidative-stress-responsive transcription factors. 

Here, we describe a transient species that may be detected 

with UV-vis and EPR spectroscopy during turnover of a laccase 

with a polyphenolic compound – quercetin. This transient species 

is assigned as a quercetin-derived radical, based on EPR spectra as 

well as based on UV-vis similarities with previously reported data 

obtained via a non-enzymatic route. The formation and decay of 

this species correlate well with the prooxidant reactivity manifested 

by flavonoids in the presence of laccase. An assay for the 

prooxidant reactivity of natural compounds is proposed based on 

the results reported here and applied on several propolis extracts; 

this assay has the advantages of using a biologically-relevant 

process (hemoglobin oxidation), and of not needing added 

oxidizing agents such as peroxide or superoxide. A series of 

flavonoids are assayed with this method and their characteristics 

are discussed. Correlations, or the lack thereof, between the 

prooxidant parameters and the redox potentials, antioxidant 

capacities and lipophilicities are analyzed. 

The advantage of using a laccase instead of a peroxidase is 

that it does not use H O as co-substrate but O ; indeed, H O 2 2 2 2 2 

might have direct action on some compounds or it may generate 

reactive oxygen species due to traces of transition metals. 

Moreover, laccases are multicopper oxidases structurally and 

functionally similar to ceruloplasmin. This proposed assay for 

pro-oxidant activity would thus involve direct action of phenoxyl 

radicals of flavonoids, with no other reactive species needed. 

Acknowledgement: Financial support from 

POSDRU/88/1.5/S/60185 – “Innovative doctoral studies in a 

knowledge based society” is gratefully acknowledged by ACM. 

Keywords: quercetin; flavonoid; radical; laccase; pro-oxidant; 



o - 0 3 8 

AntirAdiCAL CAPACity And redox PotentiAL 

of PhenoLiC BetALAinS 

L. GonCALveS 1 , e. BAStoS 2 

1 Universidade Federal do ABC, Centro de Ciencias Naturais e 

Humanas, Santo André, Brazil 

2 Instituto de Química, Departamento de Química Fundamental, 

Sao Paulo, Brazil 

Betalains are natural pigments with high antioxidant 

capacity, which have been used as therapeutic agents in several 

conditions related to oxidative stress. In this work, we describe 

the semi-synthesis of artificial phenolic betalains and the pH 

dependence of antiradical capacity and redox potentials. 

Betalamic acid was obtained by alkaline hydrolysis of betanin and 

coupled with ortho-, meta- and para-aminophenol under acid 

conditions resulting in BtPh-2-OH, BtPh-3-OH and BtPh-4-OH 

(average yield = 50%). Products were purified by reversed-phase 

column chromatography and characterized by LC/ESI(+)-MS and 

NMR spectroscopy. 

The antiradical capacity of the three regioisomers was 

evaluated using the TEAC/ABTS method and reported as Trolox 

equivalents. All betalains prepared have higher antiradical 

capacity than ascorbic acid and the vitamin E analogue Trolox. 

BtPh-3-OH has the highest TEAC (5.1 ± 0.3, pH = 7.4). The 

TEAC of BtPh-2-OH and BtPh-4-OH in the same experimental 

conditions was found to be 3.8 ± 0.3 and 3.0 ± 0.1, respectively. 

The antiradical capacity increases with the pH for all isomers until 

the hydrolysis limit (pH = 9.0). Square-wave voltammetry on 

boron-doped diamond electrode was used to determine the redox 

potentials of the phenolic betalains. Anodic potentials (E (mV, p 

Ag vs. AgCl) 482 and 842 (BtPh-2-OH); 803 (BtPh-3-OH); 

348 and 830 (BtPh-4-OH)) might indicate the oxidation of the 

phenolic portion as well as the 1,7-diazaheptamethine moieties. 

Control experiments with indicaxanthin (non-phenolic betalain of 

L-Pro) were performed (TEAC = 1.6 ± 0.1; E = 1044 mV 

p 

(Ag vs. AgCl)). Results indicate that the phenol portion decreases 

the oxidation potential as well as increases the antiradical capacity. 

Keywords: betalain; antioxidant; natural pigment; 



s675 

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Water, contaminants and food waste 

o - 1 7 1 

SuStAininG wAter reSourCeS in AGriCuLture 

h. tAft 1 

1 St. John’s University, Chemistry, New York, USA 

Population growth and climate change will create 

widespread water stress worldwide within the next 40 years. The 

uneven distribution of freshwater globally, exacerbated by floods 

and increasing periods of drought, has a destructive impact on 

crop yields. Novel technologies have been developed to augment 

the world’s finite freshwater systems but their applications each 

carry economic and/or ecological consequences. The objectives 

of this paper are to highlight key problems associated with regions 

undergoing agricultural stress and to present potential 

remediation. Three practical methodologies will be discussed: 

conservation, reclamation and desalination. Technologies for 

improving water retention are critical to conservation. The World 

Bank’s 2006 report estimates that 25–30% of freshwater supply 

disappears, costing $14 billion annually to the global economy. 

Implementing sustainable drip irrigation conserves water 

effectively without incurring major capital investments. Recycling 

sewage water is a powerful tool for recuperating fresh 

groundwater. The Tel Aviv Dan Project, where 100% of municipal 

wastewater is recycled, has converted the Negev desert into arable 

agricultural land that is independent of drought; however the 

filtration and precipitation of salts has increased the salinity of the 

surrounding soils. Desalination produces water low in buffering 

capacity and thus needs to be remineralized both to reduce 

corrosion risks in the metal distribution pipes and to prevent 

stunted plant growth. Desalination is currently still highly energy 

intensive but reverse osmosis is far more ecofriendly than 

multi-flash distillation. Desalination becomes ecofriendly when 

linked to cogeneration with a power plant, where the cooling 

waters provide the diluent for brine disposal. Incompatible with 

sustaining resources for food is the growing of crops for biofuels. 

Instead research on cellulosic biomass or microalgae could 

provide more viable alternative energy sources. The feasibility of 

these methods has been demonstrated and further advances and 

implementation at a global scale require serious financial 

commitment. 

Keywords: renewable resources; water chemistry; biomass; 

Water, contaminants and food waste 


o - 1 7 2 

ALternAtive MethodS of AddinG vALue to 

food wASte 

M. Gronnow 1 , J. CLArK 1 , v. BudArin 1 , 

d. MACquArrie 1 , L. herrero-dAviLA 1 

1 University of York, Department of Chemistry, York, United 

Kingdom 

Food waste is one of the most abundant sources of carbon 

on the planet with millions of tonnes generated from both the 

manufacturing process and dinner table. The Green Chemistry 

Group investigates a variety of methods by which these wastes 

can be converted into chemical products and in turn disposal costs 

into profits. From food waste a whole range of materials and 

products can be created ranging from high value platform 

molecules for conversion to pharmaceuticals, to materials, 

fermentable sugars and commodity chemicals. This presentation 

will present 3 cases studies from the Green Chemistry Group in 

this field. 

Double Green Ltd and University of York won the 

Innovator10 Award. The company, who process high fat food 

wastes into biodiesel, developed a new technology for the use of 

glycerine, a co-product from biodiesel production, in various 

applications, including the generation of biogas. The work 

contributed to the characterisation of glycerin at different stages 

of production as well as the development of protocols for the 

synthesis of added value chemicals from glycerine. 

Orange juicing is carried out worldwide and generates 50% 

waste from the juicing process, current best practice is to use the 

waste as animal feed, burn or turn into the land. Application of 

microwave assisted hydrothermal treatment of the orange peel 

waste can be used to extract valuable chemicals such as limonene 

and materials such as pectin and cellulose. The system can also 

be used to perform further downstream chemistry on the 

chemicals in-situ. 

By integration of clean chemical technologies numerous 

higher value products can be generated from agricultural residues. 

Supercritical solvent can be used to extract cosmetic waxes, the 

straw can be directly converted to furniture boards and microwave 

technology can be used to generated energy products and 

chemicals. 

Keywords: Food waste; Biorefining; 



s676 

chem. Listy 106, s587–s1425 (2012) 


sustainable food production – ii 

o - 1 7 3 

‘thouGht for food’: CheMiStry AS the 

BridGe Between the MoLeCuLAr And the 

GLoBAL 

J. C. hAneKAMP 1 

1 Roosevelt Academy, Science, Middelburg, Netherlands 

Food is chemistry. A familiar remark that nevertheless has 

far-reaching consequences when viewed from the regulatory 

emphasis on antibiotics, pesticides, contaminants, and other socalled 

man-made molecules. Food then, in the public eye, seems 

nothing other than natural produce that has diminished nutritional 

value because of man-made contamination. That the chemistry of 

antibiotics, pesticides and the like has greatly improved food 

accessibility, reduced crop losses, and tackled many a disease that 

has its source in food seems forgotten in a world of ostensible 

nutritional and financial affluence. Not to get bogged down in a 

polarised debate, we want to address (i) the chemistry of food; 

(ii) sources of regulated chemicals; (iii) profiles of risk; and 

precaution (iv) a regulatory future for the globe. Concisely, as 

chemists we can bridge the chasm between the molecular and the 

global nature of food production and consumption. 

Keywords: Chemistry; Food; Antibiotics; Risk; Precaution; 



o - 1 7 4 

MAtheMAtiCAL ModeLS: A Key tooL in 

SuStAinABLe food ProduCtion 

B. wedziChA 1 

1 University of Leeds, Emeritus Professor of Food Science, 

Leeds, United Kingdom 

Manufacture efficiency, food quality change, shelf-life and 

food demand management are aspects of the food chain which 

are amenable to the application of mathematical models. 

Interestingly, these different aspects illustrate different types of 

mathematical modelling (i.e., kinetic, sequential, probabilistic, 

and self-learning) which will be discussed alongside their 

potential as predictive tools. Thus, this lecture will aim to 

demonstrate the applicability of mathematical modelling in this 

context and its accessibility to those involved in food production. 



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o - 1 7 5 

effeCt of hiGh hydroStAtiC PreSSure on 

BioGeniC AMine forMAtion in ferMented 

foodS 

L. SiMon SArKAdi 1 , P. SiMon 1 , i. dALMAdi 2 , 

K. PASztor-huSzAr 2 , G. KiSKo 3 , C. BALLA 2 

1 Budapest University of Technology and Economics, Applied 

Biotechnology and Food Science, Budapest, Hungary 

2 Corvinus University of Budapest, Department of Refrigeration 

and Livestock Products Technology, Budapest, Hungary 

3 Corvinus University of Budapest, Department of Microbiology 

and Biotechnology, Budapest, Hungary 

Biogenic amines (BAs) are present in many foods, mainly 

in fermented products. Biogenic amines in food have great interest 

from both health protection and food quality control aspects. 

Consumption of food containing high quantities of BAs is 

responsible for many pseudo-allergic food related reactions and 

increased amounts of BAs are indicators of poor microbiological 

quality of the food. 

Food scientists and the food industry made efforts to find 

and develop techniques to reduce or to prevent formation of BAs 

in food. The most implicated food group concerning high biogenic 

amine contents is fermented food. 

The aim of this work was to study the effect of high 

hydrostatic pressure treatment (HHP) on the formation of BAs 

during production and storage of cheese and sausages. 

Samples were pressurized at 500 MPa for 10 mins, total 

viable cell count (TVC) was determined on TPC agar and 

biogenic amine analysis was carried out by an automatic amino 

acid analyzer. 

The HHP treatment reduced the level of TVC by 3.5-4 log 

cycles in cheese samples and by 1-3 log cycles in sausage 

depending on sample type (dry, semi-dry, extra thick sausage). 

The total biogenic amine content ranged between 3-207 μg/g in 

the controls and between 10-100 μg/g in the HHP-treated cheese 

samples. The total BA content of the extra thick sausage was the 

highest both in the control (118-35 μg/g) and in HHP treated 

samples (116-45 μg/g), followed by the dry sausage 

(c:103-46 μg/g; HHP:112-36 μg/g) and the semi-dry sausage 

(c:73-32 μg/g; HHP:84-13 μg/g). 

HHP treatment improved the microbial stability of cheese 

and sausage and it was effective in the reduction of biogenic 

amine formation during storage. 

Acknowledgement: This research was supported 

by Hungarian Scientific Research Fund and the National Office 

for Research and Technology (NKTH-OTKA CK-78013) 

and the National Development Agency of Hungary 

(TÁMOP 4.2.1/B-09/1/KMR/-2010-0005). 

Keywords: biogenic amines; high hydrostatic pressure; cheese; 

sausage; fermented food; 




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chem. Listy 106, s587–s1425 (2012) 

inorganic Chemistry plus Young inorganic chemistry day 

New trends in organometallic chemistry – i 

o - 0 3 9 

ControLLinG And utiLizinG the CAtALytiC 

Pro- And Anti-oxidAnt ProPertieS of 

CorroLe MetAL CoMPLexeS 

z. GroSS 1 

1 Technion, Faculty of Chemistry, Haifa, Israel 

Heme containing enzymes are responsible for both the 

destruction and the utilization of reactive oxygen species (ROS), 

for protecting vital biomolecules against damage thereby and for 

biosynthesis, respectively. The most outstanding examples are 

catalases and peroxidases: they have the same prosthetic group 

(iron(III) protopophyrin IX), but the former disarm H O by 2 2 

catalyzing its disproportionation and the latter utilize H O as 2 2 

oxidant. One major challenge for using synthetic metal complexes 

for similar purposes is to gain control on the two conflicting 

aspects: their capability to both catalyze and prevent the oxidation 

of organic molecules by ROS. 

Corrole and porphyrin metal complexes share many 

properties, but the trivalent states are more reactive and the high 

valent oxo-meal species are much more stable in the former case. [1] 

Several years ago we have started using these characteristics for 

several purposes: selective oxidation of organic molecules, small 

molecule activation, and decomposition of ROS in biological 

environments. Examples that will be presented include the 

enantioselective synthesis of an approved drug via biocatalysis, [2] 

clean four-electron electrocatalytic reduction of oxygen to water, [3] 

and the utilization of amphipolar metallocorroles as catalytic 

antioxidants in preclinical studies of diseases that are affected by 

ROS and reactive nitrogen species. [4] 

references: 

1. I. Aviv-Harel and Z. Gross “Coordination chemistry 

of corroles with focus on main group elements”, 

Coord. Chem. Rev. 2011, 255, 717-736. 

2. I. Nigal-Etinger, A. Mahammed, and Z. Gross 

“Covalent versus non-covalent (biocatalytic) approaches 

for enantioselective sulfoxidation catalyzed by corrole 

metal complexes”, Cat. Sci.Tech. 2011, 1, 578-581. 

3. A. Schechter, M. Stanevsky, A. Mahammed, and Z. Gross 

“Four Electron Oxygen Reduction by Brominated Cobalt 

Corrole” Inorg. Chem. 2012, 51, 22-24. 

4. A. Haber, M. Aviram, and Z. Gross, “Protecting 

the beneficial functionality of lipoproteins by 1-fe, 

a corrole-based catalytic antioxidant”, Chemical Science 

2011, 2, 295-302. 

Keywords: Catalysis; manganese; iron; antioxidants; 

porphyrin; 



o - 0 4 0 

CAtALytiC PotentiAL of rutheniuM 

nAnoPArtiCLeS interCALAted in heCtorite 

for SeLeCtive hydroGenAtion reACtionS 

G. SuSS-finK 1 , f. KhAn 1 , B. Sun 1 

1 University of Neuchatel, Institut de Chimie, Neuchatel, 

Switzerland 

Email: georg.suess-fink@unine.ch www2.unine.ch/chim 

Benzene ruthenium(II) aqua complexes can be reduced in 

water or alcohols to give ruthenium(0) nanoparticles, the size of 

which varies from 2 to 50 nm depending on the reaction 

conditions. These nanoparticles can be stabilized by 

intercalation into layered clays such as hectorite (idealized cell 

formula Mg Li Si O (OH) Na · n H O). Thus, ruthenium(0) 

5.5 0.5 8 20 4 2 

nanoparticles are intercalated in hectorite by ion exchange of 

sodium against [(C H )Ru(H O) ] 6 6 2 3 2+ cations between the anionic 

layers, followed by reduction with molecular hydrogen. [1, 2] 

n [(C H )Ru(OH ) ] 6 6 2 3 2+ + 7n H Ru + 2n H O 2 n 3 + + n H O+nCH 2 6 12 

Hectorite-supported ruthenium(0) nanoparticles proved to 

be highly active for the catalytic hydrogenation reactions. Thus, 

benzene can be hydrogenated to give cyclohexane under mild 

conditions (50°) with turnover frequencies up to 6500 cycles per 

hour. [2] 

Highly selective hydrogenation reactions, catalyzed by 

nanoRu@hectorite under mild conditions, will be discussed: 

Furfuryl alcohol from renewable sources can be cleanly converted 

into tetrahydrofurfuryl alcohol, [3] a green solvent with a potential 

of fuel additive. The hydrogenation of α,β-unsaturated ketones 

gives exclusively the corresponding saturated ketones without 

reduction of the C=O function, [4] and the hydrogenation of 

quinoline yields selectively 1,2,3,4-tetrahydroquinoline. After a 

catalytic run, the nanoRu@hectorite catalyst can be recycled and 

reused without loss of activity and selectivity. 

references: 

1. G. Süss-Fink, B. Mollwitz, B. Therrien, M. Dadras, 

G. Laurenczy, A. Meister, G. Meister, J. Cluster Sci. 18 

(2007), 87. 

2. G. Süss-Fink, F.-A. Khan, J. Boudon, V. Spassov, J. Cluster 

Sci. 20 (2009), 341. 

3. F.-A. Khan, A. Vallat, G. Süss-Fink, Catal. Commun. 12 

(2011), 1428. 

4. F.-A. Khan, A. Vallat, G. Süss-Fink, J. Mol. Catal. A: 

Chemical 355 (2012), 168. 

Keywords: Hydrogenation; Nanoparticles; Ruthenium; 



s679 

chem. Listy 106, s587–s1425 (2012) 



o - 0 4 1 

iodide ACtivAtion of CoordinAted 

white PhoSPhoruS: forMAtion And 

trAnSforMAtion of 1,3-dihydride-2iodideCyCLotetrAPhoSPhAne 

P. StoPPioni 1 , C. BAzziCALuPi 1 , S. Seniori 1 , 

M. Peruzzini 2 

1 University of Florence, Chemistry, Firenze, Italy 

2 ICCOM, C.N.R., Firenze, Italy 

The activation of elemental phosphorus mediated by 

transition metals represents a still challenging task that has been 

widely explored in the last decades. [1] Our group has found that 

the intact P molecule may be bound to ruthenium fragments and 

4 

that its reactivity, according to the electronic and/or steric 

requirements of the metal fragments, is significantly modified 

with respect to the free molecule. In particular the coordinated 

molecule undergoes easily dismutation in the presence of water 

to yield phosphanes [PH , 3 1P H , 2 4 2P H OH 3 4 3 4 and P H (OH) ] and 

4 3 3 

oxoacids; the former being stabilized through coordination to 

ruthenium fragment(s) which, therefore, promote both the 

reactivity of the coordinated P and the stabilization of the 

4 

hydrolysis products, practically unknown as free ones. [5] 

Here we report that the nucleophilic addition of I to P 2 4 

coordinated to two CpRu(PPh ) fragments affords a monocation 

3 2 

of formula [{CpRu(PPh ) } (μ 3 2 2 1:3 ,h1:1-P HI )] 4 2 + containing 

the 1,3-dihydride-2-iodidecyclotetraphosphane coordinated to two 

ruthenium fragments; the reactive P H I 4 2 - anion easily dissociates 

iodide to yield the bicyclotetraphosphane, P H , which in turn 

4 2 

undergoes dismutation in the presence of water to yield 

quantitatively the triphosphane, P H , and phosphorous acid, 

3 5 

H PO . Both the bicyclotetraphosphane and the 

3 3 

triphosphane, which are unknown as free ones, are 

stabilized through double metallation to yield the new 

compounds [{CpRu(PPh ) } (μ 3 2 2 1 : 3 ,h 1 : 1-P H )]OTf and 

4 2 2 

[{CpRu(PPh ) } (μ 3 2 2 1:3 ,h 1:1-PH PHPH )]OTf , respectively. 

2 2 2 

Acknowledgement: Thanks are expressed to COST action 

phoscinet for supporting this research activity. 

references: 

1. M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini, Chem. 

Rev. 2010, 110, 4178. 

2. P. Barbaro, Di Vaira, M. Peruzzini, S. Seniori Costantini, 

P. Stoppioni, Chem. Eur. J. 2007, 13, 6682. 

3. P. Barbaro, M. Di Vaira, M. Peruzzini, S. Seniori 

Costantini, P. Stoppioni, Angew. Chem., Int. Ed. 2008, 47, 

4425. 

4. P. Barbaro, M. Di Vaira, M. Peruzzini, S. Seniori 

Costantini, P. Stoppioni, Inorg. Chem. 2009, 48, 1091. 

5. M. Baudler, K. Glinka, Chem. Rev. 1994, 94, 1273. 

Keywords: White phosphorus; Activation; 



o - 0 4 2 

reACtionS of A PhoSPhinito BridGed 

diPLAtinuM(i) CoMPLex with CoinAGe MetAL 

eLeCtroPhiLeS 

v. GALLo 1 , P. MAStroriLLi 1 , M. LAtroniCo 1 , 

S. SAnChez 2 

1 Polytechnic of Bari, DIAC, Bari, Italy 

2 Departamento de Quimica, University of La Rioja, Logrono, 

Spain 

We have recently described the synthesis of the complex 

[(PHCy )Pt 2 1 (m-PCy ){k 2 2P,O-m-P(O)Cy }Pt 2 2 (PHCy )] (Pt-Pt) 

2 

(1), the first unsymmetrical phosphinito bridged Pt(I) species. [1] 

The phosphinito bridge differentiates the charge distributions on 

the two platinum atoms as confirmed by NMR spectroscopy 

(d = -4798 ppm, d = -5207 ppm) and DFT studies. Complex 

Pt(1) Pt(2) 

1 shows a rich chemistry as it reacts with nucleophiles [PHCy , 2 

PCy , P(S)HCy ], 3 2 [2] protic species HX [P(OH)Cy , PhSH, HF, 

2 

HCl, HBr, HI, HBF ], 4 [3, 4] and small molecules such as H . 2 [5] 

Recently, we started investigations on the reactivity of complex 1 

towards Au and Ag based electrophiles. 

In this communication, it will be shown that, differently 

from the isolobal H + (which attacks the phosphinito oxygen and 

migrates onto the Pt-Pt bond), 3 the [Ag(PPh )] 3 + electrophile 

attacks complex 1 selectively to the Pt2-mP bond to afford the 

cationic cluster [(PHCy )Pt 2 1 (m-PCy ){k 2 2P,O-m-P(O)Cy }Pt 2 2 {m- 

-Ag(PPh )}(PHCy )] 3 2 + (Pt–Pt) (2 + ) in which the [Ag(PPh )] 3 + 

moiety bridges the mP-Pt2 bond. Analogous reactivity is observed 

also when phosphane free electrophiles such as AgOTf, AgBF , 4 

AgClO and AgCl are used. Moreover, the reactivity of 1 towards 

4 

Au(I) electrophiles such as AuCl and [Au(PPh )Cl] was dependent 

3 

on the reagent and on the experimental conditions. 

references: 

1. Gallo, V.; Latronico, M.; Mastrorilli, P.; Nobile, C. F.; 

Suranna, G. P.; Ciccarella, G.; Englert, U.; Eur. J. Inorg. 

Chem., 2005, 4607–4616. 

2. Gallo, V.; Latronico, M.; Mastrorilli, P.; Nobile, C. F.; 

Polini, F.; Re, N.; Englert, U.; Inorg. Chem., 2008, 47, 

4785–4795. 

3. Latronico, M.; Polini, F.; Gallo, V.; Mastrorilli, P; 

Calmuschi-Cula B.; Englert, U.; Re, N.; Repo T., 

Raisanen M.; Inorg. Chem., 2008, 47, 9979-9796. 

4. M. Latronico, P. Mastrorilli, V. Gallo, M.M.Dell’Anna, 

F. Creati, N. Re, U. Englert, Inorg. Chem. 2011, 50, 

3539–3558 

5. Mastrorilli P., Latronico M., Gallo V., Polini F., Re N., 

Marrone A., Gobetto R., Ellena S.. J. Am. Chem. Soc. 

2010, 132, 4752–4765 

Keywords: Platinum; silver; gold; Phosphane ligands; 

Bridging ligands; 



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New trends in organometallic chemistry – ii 

o - 0 4 3 

triAzoLe And tetrAzoLe fe(ii) CoordinAtion 

CoMPoundS exhiBitinG SPin CroSSover. 

o. rouBeAu 1 

1 Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC 

and Universidad de Zaragoza, Zaragoza, Spain 

Triazole and tetrazole ligands are known to provide Fe(II) 

complexes the ideal range of ligand-field strength for the 

occurrence of spin crossover (SCO) [1] , a stimuli-induced change 

of spin from a ground state low spin state (LS, S= 0 in the case of 

Fe(II)) to a metastable high spin state (HS, S = 2 here). In these 

systems, small synthetic variations in organic substituents or 

counteranions are means to tailor the SCO, either its temperature 

range or its cooperativeness in the solid-state, as well as to design 

nanostructures or soft matter phases. 

This contribution will first illustrate such tuneability with 

recent advances based on triazole-based one-dimensional 

coordination polymers, with a focus on physical gels and liquid 

crystalline SCO materials [2] . Using these materials, we will also 

show that IR spectroscopy is a powerful tool to monitor the SCO, 

induced either thermally or through applied pressure at room 

temperature. 

In a second part, the structural and magnetic properties of a 

new family of complexes [Fe(mtz) ](MX ) (mtz = 1-methyl - 

6 4 2 

tetrazole, M = Fe(III) or Ga(III), X = Cl or Br) will be presented. 

They represent the first SCO compounds with paramagnetic 

tetrahalo anions [3] . These latter implement ferromagnetic 

interactions and magnetic order at lower temperatures, 

in coexistence with the SCO, thus providing with original 

two-component multi-functional materials. 

references: 

1. G. Aromí, L. A. Barrios, O. Roubeau, P. Gamez, Coord. 

Chem. Rev. 2011, 255, 485-546 

2. P. Grondin, O. Roubeau, M. Castro, H. Saadaoui, A. Colin, 

R. Clérac, Langmuir 2010, 26, 5184-5195; P. Grondin, 

D. Siretanu, O. Roubeau, M-F. Achard, R. Clérac, Inorg. 

Chem. 2012, 51, 5417-5426 

3. O. Roubeau, E. Natividad, M. Evangelisti, submitted to 

Chem. Commun. 

Keywords: Spin crossover; Iron; Magnetic properties; 

Metallomesogens; N ligands; 



o - 0 4 4 

BiMetALLiC MoLeCuLAr CArBonyL CLuSterS 

ContAininG interStitiAL CArBide AtoMS: 

StruCturAL feAtureS And PhySiCAL 

ProPertieS 

S. zACChini 1 , i. CiABAtti 1 , C. feMoni 1 , 

M. C. iAPALuCCi 1 , G. LonGoni 1 

1 Universita di Bologna, Dipartimento di Chimica Fisica ed 

Inorganica, Bologna, Italy 

Much attention has been devoted in recent years to metallic 

nanoparticles and colloids from both a fundamental and 

applicative point of view. [1] Nonetheless, some major drawbacks 

remain due to the fact that they still are collections of species 

differing in sizes, shapes and compositions. Therefore, only 

average properties can be determined. Conversely, large molecular 

metal clusters are perfectly defined in composition and all 

structural details, and enter in the field of nanomaterials from the 

lowest limit. [2] 

Herein, we describe some new nanometric bimetallic 

molecular carbonyl clusters stabilised by interstitial carbide 

atoms. The comparison of the structures of different Co-Ni, 

Co-Pd and Co-Pt carbido clusters shows the tendency, depending 

on the nature of the metals, to give species with complete, partial 

or none segregation of the two metals. Moreover, the extra 

stability of these molecular clusters allows the development of 

some interesting physical properties. For instance, paramagnetism 

in the even electron [Co Pt C (CO) ] 8 4 2 24 2– has been unequivocally 

demonstrates via SQUID and ESR measurements. [3] 

In addition, electrochemical experiments show the tendency 

of larger clusters to undergo several reversible redox processes, 

as exemplified by [H Ni Co C (CO) ] 6–n 22 6 6 36 n– (n = 3-6). The 

polyhydride nature of these species will be presented as well. 

Finally, the robustness of molecular polycarbide clusters 

containing labile ligands makes them good candidates as 

nanometric building blocks for self-assembly. 

references: 

1. A. P. Alivisatos, Y. Yadong, Nature, 2005, 437, 664. 

2. C. Femoni, F. Kaswalder, M. C. Iapalucci, G. Longoni, 

S. Zacchini, Coord. Chem. Rev., 2006, 250, 1580; S. 

Zacchini, Eur. J. Inorg. Chem., 2012, 4125. 

3. C. Femoni, M. C. Iapalucci, G. Longoni, J. Wolowska, 

S. Zacchini, P. Zanello, S. Fedi, M. Ricci, D. Pontiroli, 

M. Mazzani, ‘J. Am. Chem. Soc., 2010, 132, 2919. 

Keywords: Cluster compounds; Carbonyl ligands; 

Nanoparticles; Structure elucidation; Carbides; 



s681 

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o - 0 4 5 

tAiLor-MAde PhotoSenSitized 

PoLyoxoMetALAteS; towArdS the 

deveLoPMent of deviCeS for 

PhotoCuMuLAtive eLeCtron trAnSfer 

G. izzet 1 , B. MAtt 1 , J. MouSSA 1 , h. AMouri 1 , 

A. ProuSt 1 

1 University Pierre and Marie Curie, UMR 7201, Paris, France 

Polyoxometalates (POMs) form a remarkable class of welldefined 

nanoclusters with an unmatched diversity of structures 

and properties. [1] They receive considerable interest because of 

their wide range of applications in many fields such as analytical 

chemistry, catalysis, materials science, or even medicine. [2] An 

important property of POMs is their ability to reversibly accept 

and release specific numbers of electrons under minor structural 

rearrangement. Therefore, POMs are attractive candidates 

for the development of photochemical devices aiming at 

photocumulative electron transfer. In this context, we recently 

reported the synthesis of inorganic/organic POM-based hybrids 

in which the POM is covalently connected to different types of 

photoactive antenna (pyrene, carbocyclometalated ruthenium and 

iridium complexes). [4–6] We herein describe the synthetic strategy 

of covalent attachment of these organic and organometallic 

chromophores to organo-silyl or organo-tin POM-based 

derivatives via Sonogashira couplings. The electronic and 

photophysical properties of the resulting hybrids will be 

presented, including transient absorption spectroscopy, which in 

some cases indicates the formation of unprecedented long-lived 

charge separation states. 

references: 

1. Special issue devoted to polyoxometalates, ed. C. L. Hill, 

Chem. Rev., 1998, 98, 1–390. 

2. D.-L. Long, R. Tsunashima, and L. Cronin, Angew. Chem. 

Int. Ed. 2010, 49, 1736-1758. 

3. A. Proust, R. Thouvenot, and P. Gouzerh, Chem. 

Commun., 2008, 1837-1852. 

4. B. Matt, S. Renaudineau, L-M. Chamoreau, C. Afonso, 

G. Izzet, A. Proust, J. Org. Chem., 2011, 76, 3107-3112. 

5. B. Matt, C. Coudret, C. Viala, D. Jouvenot, F. Loiseau, 

G. Izzet, A. Proust, Inorg. Chem., 2011, 50, 7761-7768. 

6. B. Matt, J. Moussa, L-M. Chamoreau, C. Afonso, 

A. Proust, H. Amouri, G. Izzet Organometallics., 2012, 

31, 35-38. 

Keywords: Polyoxometalate; Photochemistry; Electron 

transfer; 

New trends in organometallic chemistry – iii 


o - 0 4 6 

C-C Bond forMinG reACtionS At BridGinG 

LiGAndS in diiron CoMPLexeS 

v. zAnotti 1 , L. BuSetto 1 , f. MArChetti 2 , 

r. MAzzoni 1 , M. SALMi 1 , S. zACChini 1 

1 University of Bologna, Dipatimento di Chimica Fisica e 


2 University of Pisa, Dipatimento di Chimica e Chimica 

Industriale, Pisa, Italy 

Interest toward iron mediated bond forming reactions has 

grown exponentially in recent years as consequence of increased 

attention to sustainability, and interest in replacing toxic and 

expensive metal catalysts with more cost-effective and benign 

transition metal compounds. In this growing effort aimed at new 

sustainable synthetic methodologies, diiron complexes can play 

a distinctive role in that they combine advantages associated to 

iron with those due to the presence of two adjacent metal centres. 

These include possible cooperative effects and multisite 

coordination of bridging organic fragments, which frequently 

results in peculiar reactivity patterns. A most relevant example of 

activation by diiron compounds is given by natural metallo- 

-enzymes [FeFe] hydrogenases, which have inspired extensive 

investigation in the design of new sustainable energy process. 

However, diiron complexes might provide reasonable alternatives 

to precious metals in other research areas, such as C-C bond 

formation. Our report focuses on C-C bond forming reactions 

occurring at the at bridging hydrocarbyl ligands X (X = carbyne, 

vinlylcarbene, vinyliminium etc.) in diiron complexes of type 

[Fe (m-X)(m-CO)(CO) Cp ]. (n = 1, 2) A few selected examples 

2 n 2 

will be presented, including: 

i) insertion of alkynes into the metal-carbyne carbon bond; 

ii) nucleophilic addition at vinyliminium ligands (non-conjugated 

additions); iii) activation of aC-H and gC-H in bridging vinylimiums; 

iv) 1,3 dipolar cycloadditions, and [3+2] cycloadditions of bridging 

C3 ligands with alkynes; v) [3+2+1] cycloadditions of alkynes, 

CO and vi) -vinylcarbenes; alkyne incorporation by enyne 

metathesis. 

references: 

1. Zanotti, V. Pure Appl. Chem. 2010, 82, 1555; 

2. Busetto, L.; Marchetti, F.; Renili, F.; Zacchini, S.; 

Zanotti, V. Organometallics 2010, 29, 1797; 

3. Busetto, L.; Marchetti, F.; Mazzoni, R.; Salmi, M.; 

Zacchini, S.; Zanotti, V. Chem. Commun. 2010, 46, 3327. 

Keywords: diiron complexes; 



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o - 0 4 7 

SoL-GeL CoordinAtion CheMiStry: 

A noveL APProACh to inCorPorAte CheMiCAL 

funCtionALity in PorouS MAteriALS 

J. GArCiA MArtinez 1 , n. LinAreS 1 , 

A. e. SePuLvedA 2 , e. SerrAno 1 , J. r. BerenGuer 2 , 

e. LALinde 2 

1 University of Alicante, Inorganic Chemistry, Alicante, Spain 

2 University of La Rioja, Inorganic Chemistry, Logrono, Spain 

A novel methodology to incorporate chemical functionalities 

into the framework (not on the surface) of porous materials has 

been developed via co-condensation of a silica precursor 

(typically a silicon alkoxide) and trialkoxysilanes bonded to 

different chemical moieties. Following this strategy, different 

functionalities, including metal nanoparticles, [1] organometallic 

compounds and metal complexes [2–3] as well as inorganic 

clusters, [4] have been effectively incorporated into the framework 

of the mesoporous silica and organosilica materials. This approach 

has been recently extended to titania and other metal oxide 

supports. A critical overview of the various strategies on this novel 

strategy and its main advantages over more traditional 

functionalization method, like grafting, can be found elsewhere 

[5]. 

references: 

1. a) E. Coronado, A. Ribera, J. Garcia-Martinez, N. Linares, 

L.M. Liz Marzán, J. Mater. Chem. 2008, 18, 5682; 

b) J. Garcia-Martinez, N. Linares, S. Sinibaldi, 

E. Coronado, A. Ribera, Micropor. Mesopor. Mater. 

2009, 117, 170. 

2. N. Linares, A. E. Sepúlveda, M. C. Pacheco, J. R. 

Berenguer, E. Lalinde, C. Nájera and J. García-Martínez, 

New J. Chem. 2011, 35, 225. 

3. N. Linares, A. E. Sepúlveda, J. R. Berenguer, E. Lalinde 

and J. García-Martínez, Micropor. Mesopor. Mater., 2012, 

http://dx.doi.org/10.1016/j.micromeso.2012.03.0363. 

4. A. I. Carrillo, J. García-Martínez, R. Llusar, E. Serrano, 

I. Sorribes, C. Vicent, J. A. Vidal-Moya, Micropor. 

Mesopor. Mater., 2012, 151, 380. 

5. N. Linares, E. Serrano, M. Rico, A.M. Balu, E. Losada, 

R. Luque, J. García-Martínez, Feature Article, Chem. 

Commun. 2011, 47, 9024. 

Keywords: sol-gel processes; mesoporous materials; 

nanoparticles; complexes; condensation; 



o - 0 4 8 

StruCture And reACtivity of fiSCher 

BiSCArBene CoMPLexeS 

S. Lotz 1 

1 University of Pretoria, Chemistry, Pretoria, Republic of South 

Africa 

The application of alkoxycarbene ligands as active synthons 

in template reactions in organic synthesis and catalysis is mainly 

focused on monocarbene complexes.Very few larger assemblies 

of carbene units and metal fragments (polymers, dendrimers, 

metal organic frameworks, etc.) have been reported. Hence, 

multimetal carbene and multicarbene metal complexes are 

becoming increasingly more important. [1, 2] 

Thiophenes with two alkoxycarbene ligands in chelate rings 

and attached to group 6 transition metals were synthesized after 

activating atypical positions by lithium-halogen exchange 

reactions or by selectively blocking activated positions on the 

thiophene ring. The carbene carbon atoms in the α-positions 

differed in their reactivity from those in the β-positions of 

thiophene. [3] 

Biscarbene complexes expose activated sites and can be used 

as precursors to synthesize modified monocarbene complexes or 

shed light on intermediates involving the metal-carbon double 

bond during conversions or formation of reactive intermediates. [4] 

Piggybacking alkoxycarbene complexes as substituents of 

amine and phosphine ligands into the coordination sphere of 

transition metals was successfully accomplished for group 6 to 10 

transition metals. Structural features and the availability and 

potential reactivity of these carbene-containing complexes in 

template reactions were investigated. Alternatively, this method 

can be used to import carbene complexes in larger assemblies of 

group 7 and 10 transition metalorganic frameworks. 

references: 

1. Bezuidenhout, D. I., Lotz, S., Liles, D. C., Van der 

Westhuizen, B. Coord. Chem. Rev. 2012, 256, 479–524. 

2. Sierra, M. A. Chem. Rev.2000, 100, 3591–3638. 

3. Van Jaarsveld, N. A.; Lotz, S.; Liles, D. C. Dalton Trans., 

2010, 39, 5777–5779. 

4. Lotz, S., Landman, M., Olivier, A. J., Bezuidenhout, D. I., 

Liles, D. C., Palmer, E. R. Dalton Trans., 2011, 40, 

9394–9403 

Keywords: Carbene; Structure; Reactivity; 



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o - 0 4 9 

MetAL-CAtALyzed, MetAL-ProMoted And 

MetAL-free funCtionALizAtion of ALKAneS 

A. PoMBeiro 1 

1 Technical University of Lisbon, Departamento de Engenharia 

Quimica, Lisbon, Portugal 

Email: pombeiro@ist.utl.pt 

On account of their inertness, alkanes are normally used as 

fuels, and their selective conversion into functionalized organic 

compounds is a current challenge, with significance in search for 

alternative raw materials. Of particular meaning would be the 

development of systems operating under mild and green 

conditions. 

Results obtained by the author’s Group on the following 

reactions will be described: 

i- Peroxidative oxidations of alkanes to alcohols and 

ketones, catalyzed by metal complexes; 

ii- Metal-free and metal-promoted hydrocarboxylations of 

alkanes to carboxylic acids, with water as hydroxylating 

agent; 

iii- Metal-catalyzed alkane carboxylations to carboxylic 

acids. 

Some of systems feature the highest reported catalytic 

activities in the field. 

Acknowledgements: Co-authors in references are 

acknowledged. Work supported by FCT, Portugal, and PTDC 

program. 

references: 

1. M.V. Kirillova, A.M. Kirillov, A.J.L. Pombeiro, 

Chem. Eur. J., 2010, 16, 9485. 

2. M.V. Kirillova, A.M. Kirillov, A.J.L. Pombeiro, 

Adv. Synth.Cat., 2009, 351, 2936. 

3. M.V. Kirillova, A.M. Kirillov, M.L. Kuznetsov, 

J.A.L. Silva, J.J.R. Fraústo da Silva, A.J.L. Pombeiro, 

Chem. Commun., 2009, 2353. 

4. T.C.O. Mac Leod, M.V. Kirillova, A.J.L. Pombeiro, 

M.A. Schiavon, M.D. Assis, Appl. Cat. A: Gen., 2010, 

372, 191 

5. R. Fernandes, M.V. Kirillova, J.A.L. Silva, J.J.R. Fraústo 

da Silva, A.J.L. Pombeiro, Appl. Cat. A.: Gen., 2009 353, 

107. 

6. M. Kuznetsov, A.J.L. Pombeiro, Inorg. Chem., 2009, 48, 

307. 

7. T.F.S. Silva, G.S. Mishra, M.F. Guedes da Silva, R. 

Wanke, L.M.D.R.S. Martins, A.J.L. Pombeiro, 

Dalton Trans., 2009, 9207. 

8. M.V. Kirillova, M.L. Kuznetsov, P.M. Reis, J.A.L. Silva, 

J.J.R. Fraústo da Silva, A.J.L. Pombeiro, J. Am. Chem. 

Soc., 2007, 129, 10531. 

9. A.M. Kirillov, M.N. Kopylovich, M.V. Kirillova, M. 

Haukka, M.F.C. Guedes da Silva, A.J.L. Pombeiro, 

Angew. Chem., Int. Ed., 2005, 44, 4345. 

Keywords: Alkanes; Carboxylation; Oxidation; Peroxides; 

Alcohols; 


inorganic/bioinorganic reaction mechanisms – i 

o - 1 7 6 

Green MeChAniStiC ChALLenGeS of CAtALySiS 

viA tAML iron(iv)- And iron(v)oxo SPeCieS 

(tAML = tetrAAMidoMACroCyCLiC LiGAnd) 

A. ryABov 1 

1 Carnegie-Mellon University, Department of Chemistry, 

Pittsburgh, USA 

Iron(III) complexed to four deprotonated amide nitrogens 

of tetraamidomacrocyclic ligands (TAML) are unique catalysts 

for various green oxidations by hydrogen peroxide. 

Mechanistically, the catalysts have features typical of peroxidase 

and monooxygenase enzymes. Two generations of TAML ligands 

have been introduced using a rational design approach. In aqueous 

media, the catalyst iron reaches the oxidation state of IV in the 

presence of peroxides, whereas the oxidation state of V is 

reachable in a more than 95% yield in organic solvents. Therefore 

the reactivity of the TAML iron(V)oxo species have directly been 

investigated with respect to several target molecules. The 

iron(V)oxo units are normally by four orders of magnitude more 

reactive than the iron(IV)oxo analogues. In this lecture, diverse 

mechanistic aspects of catalysis by the iron TAML compounds in 

water will be discussed with the emphasis at the catalysts of 

second generation together with the recent kinetic results on the 

reactivity of iron(V)oxo TAML derivatives generated at lower 

temperatures in acetonitrile as a solvent. The two closely related 

topics should highlight broad prospects of the catalysts in green 

and sustainable environmental chemistry. 

Keywords: iron; catalysis; green chemistry; kinetics; 

mechanism; 



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o - 1 7 7 

PhySiCoCheMiCAL StudieS And AntiCAnCer 

PotenCy of rutheniuM(P-CyMene) CoMPLexeS 

ContAininG AntiBACteriAL quinoLoneS 

i. tureL 1 , 3 , J. KLJun 1 , A. K. BytzeK 2 , 

w. KAndioLLer 2 , C. BArteL 2 , M. A. JAKuPeC 2 , 

C. G. hArtinGer 2 , B. K. KePPLer 2 

1 University of Ljubljana, Faculty of Chemistry, 1000 

LJUBLJANA, Slovenia 

2 University of Vienna, Institute of Inorganic Chemistry, Vienna, 

Austria 

3 EN-FIST Centre of Excellence, Dunajska 156, SI-1000 

Ljubljana 

Quinolone antibacterial agents are used in clinical practice 

for nearly fifty years. It is known that metal ions coordinate to 

quinolones and some complexes exert biological activity. [1] The 

synthesis and study of metal complexes with drugs used in clinical 

practice, which may exhibit synergistic activity, have attracted 

much attention in last years. 

Recently organometallic ruthenium complex of quinolone 

ofloxacin (oflo), [(η6-p-cymene)RuCl(O,O-oflo)] (1), was isolated 

and characterized. [2] In this “piano-stool” complex, quinolone is 

bidentately coordinated to the metal through the ring carbonyl and 

one of the carboxylic oxygen atoms. Interactions of this complex 

with DNA were studied by different spectroscopic methods and 

atomic force microscopy. Later, analogous compounds of the 

quinolones nalidixic acid (2) and cinoxacin (3) were synthesized, 

and their properties were compared to those of 1. [3] All compounds 

undergo a rapid ligand exchange reaction from chlorido to aqua 

species. In contrast, 2 and 3 are significantly more stable than 1 

and undergo minor conversion to an unreactive species. In the 

presence of human serum albumin 1–3 form adducts within 

20 minutes of incubation. With guanosine 5'-monophosphate rapid 

reactions yielding adducts via its N7 atom were observed, 

illustrating that DNA is a possible target for this compound class. 

A moderate capacity of inhibiting tumor cell proliferation in vitro 

was observed for 1 in CH1 ovarian cancer cells, whereas 2 and 3 

turned out to be inactive. 

Acknowledgement: Financial support from the Slovenian 

Research Agency through project J1-4131 is gratefully 

acknowledged. 

references: 

1. I. Turel, Coord. Chem. Rev., 232, 27-47 (2002). 

2. I. Turel, J. Kljun, F. Perdih, E. Morozova, V. Bakulev, 

N. Kasyanenko, J. A. W. Byl, N. Osheroff, Inorg. Chem., 

49, 10750-10752 (2010). 

3. J. Kljun, A. K. Bytzek, W. Kandioller, C. Bartel, M. 

A. Jakupec, C. G. Hartinger, B. K. Keppler, I. Turel, 

Organometallics, 30, 2506-2512 (2011). 

Keywords: Bioinorganic chemistry; Ruthenium; Antibiotics; 

Biological activity; 



o - 1 7 8 

reACtivity of ni(0)-CoMPLexeS towArdS 

ALKeneS And ALKyneS 

L. vALentin 1 , A. henSS 1 , L. KohLer 1 , 

A. de MeiJere 2 , S. SChindLer 1 

1 Justus-Liebig-Universität Gießen, Institut für Anorganische 

und Analytische Chemie, Giessen, Germany 

2 Georg-August-Universität Göttingen, Institut für Organische 

und Biomolekulare Chemie, Göttingen, Germany 

In regard to the application of Ni(0) compounds as catalysts 

in organic synthesis [1] there is high interest in better understanding 

of the reactivity of these complexes. Detailed kinetic 

investigations have been performed previously on 

substitution reactions of [Ni(bipy)COD] (bipy = 2,2'-bipyridine, 

COD = 1,5-cyclooctadiene) by Schindler and co-workers. [2] 

Furthermore, de Meijere and co-workers have synthesized 

and characterized bicyclopropylidene bcp [3] and 

dicyclopropylacetylene dcpa [4] and their reactivity. Based on 

this background it seemed interesting to investigate the 

according Ni(0) complexes of these compounds. Both 

complexes, [Ni(bipy)bcp] and [Ni(bipy)dcpa] were structurally 

characterized. The formation of these complexes could be 

investigated by UV-VIS spectroscopy using “stopped-flow” 

techniques. 

Despite the negative entropy of activation a dissociative 

mechanism was proposed for the reaction of [Ni(bipy)COD] with 

bcp according to previous kinetic studies with other olefinic 

ligands. 

The reaction of [Ni(bipy)(COD)] with dcpa is slower 

compared with bcp. Nevertheless, it was not possible to obtain 

acceptable fittings to single-exponential functions for all 

concentrations applied over the selected temperature range. 

Therefore, the reaction with another alkine, dimethoxybutyne 

dmbu was investigated. Detailed kinetic studies of this reaction 


references: 

1. Tamaru, Y., Modern Organonickel Chemistry, Wiley-VCH 

Verlag GmbH & Co. KGaA, 2005 

2. Geyer, C; Schindler, S., Organometallics 1998, 17 (20), 

4400–4405 

3. Zhao, L.; de Meijere, A. Adv. Synth. Catal. 2006, 348, 

2484–2492 

4. Emme, I.; Labahn, T.; Meijere, A. d. Eur. J. Org. Chem. 

2006, 399 

Keywords: Nickel; alkenes; alkynes; UV/Vis spectroscopy; 



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o - 1 7 9 

no And Co reLeASinG MAteriALS 

A. SChiLLer 1 

1 Friedrich-Schiller-University Jena, Institute for Inorganic and 

Analytical Chemistry, Jena, Germany 

Nitric oxide (NO) and carbon monoxide (CO) are messenger 

molecules in the human body. [1] NO- and CO-releasing materials 

(NORMAs & CORMAs) can act as gasotrans-mitter delivering 

devices in therapy; toxic metabolites after gas release are kept in 

the matrix. NO and CO photodonors use light as a trigger allowing 

the accurate control of site, timing and dosage. [2] Here we report 

the concept of embedding water-insoluble, photoactive NO and 

CO metal complexes into nanofibrous polymer non-wovens. [3] NO 

and CO release is performed by light stimu-lation of the high 

surface area materials. For the generation of NORMAs, novel 

rutheniumnitrosyl complexes {RuNO} 6 have been synthesized. [4] 

For the CORMAs, Mn (CO) and Fe(CO) were used. 2 10 5 [5] These 

metal complexes were non-covalently embedded into polylactide 

non-wovens by electrospinning. Identity of the metal complexes 

was retained in the electrospinning process. Leaching of the metal 

complexes out of the polymeric matrices into water was 

negli-gible due to their water insolubility (verified by AAS, 

ICP-MS, UV/Vis). Cytotoxicity tests with 3T3 mouse fibro-blasts 

revealed a very low mortality rate. Irradiation at λ = 366 nm 

(UV-A, 3 mW/cm2 ) in water, using Anslyn’s fluores-cent NO 

assay, showed a significant phototriggered NO release from the 

non-wovens. [4] Rapid CO release from CORMAs was detected by 

the myoglobin assay and vibrational spectroscopy. [5] 

references: 

1. R. Motterlini, L. E. Otterbein, Nat. Rev. Drug Discov. 

2010, 9, 728. 

2. D. Crespy, K. Landfester, U. S. Schubert, A. Schiller, 

Chem. Commun. 2010, 46, 6651. 


Nanomaterials, Molecular Machinery, (Ed.: B. Pignataro), 

Wiley-VCH, Weinheim, 2012, 315-338. 

4. C. Bohlender, M. Wolfram, H. Görls, W. Imhof, 

R. Menzel, A. Baumgärtel, U.S. Schubert, U. Müller, 

M. Frigge, M. Schnabelrauch, R. Wyrwa, A. Schiller, 

J. Mater. Chem. 2012,22, 8785. 

5. R. Wyrwa, M. Schnabelrauch, C. Altmann, A. Schiller, 

DE10 2012 004 132.2, patent pending. 

Keywords: Nanostructures; Ruthenium; Polymers; Nitrogen 

oxides; Immobilization; 


inorganic/bioinorganic reaction mechanisms – ii 

o - 1 8 0 

StruCturAL And SPeCtroSCoPiC 

ChArACterizAtion And reACtivitieS of 

MetAL-oxyGen interMediAteS 

w. nAM 1 

1 Ewha Womans University, Department of Bioinspired Science, 

Seoul, Republic of Korea 

Dioxygen is essential in life processes, and enzymes activate 

dioxygen to carry out a variety of biological reactions. One 

primary goal in biomimetic research is to elucidate structures of 

reactive intermediates and mechanistic details of dioxygen 

activation and oxygenation reactions occurring at the active sites 

of enzymes. During the past decade, we have been studying the 

chemical and physical properties of various reactive intermediates 

in oxygenation reactions, such as high-valent iron(IV)-oxo 

complexes of non-heme ligands in oxo-transfer and C-H 

activation reactions, metal-peroxo complexes in nucleophilic 

reactions, and metal-superoxo complexes in electrophilic 

reactions. In this presentation, I will present our recent results on 

the synthesis and structural and spectroscopic characterization of 

mononuclear nonheme metal-dioxygen intermediates. Their 

reactivities in electrophilic and nucleophilic oxidation reactions 

will be discussed as well. 

Keywords: bioinorganic chemistry; enzyme models; reactive 

intermediates; 



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o - 1 8 1 

noveL hydroquinonAte/P-SeMiquinonAte 

vAnAdiuM(iv/v) BioinorGAniC ModeLS, 

effeCtive CAtALyStS for the SeLeCtive 

reduCtion of o 2 to h 2 o 2 

A. KerAMidAS 1 , C. drouzA 2 , M. StyLiAnou 1 


2 Cyprus University of Technology, Agricultural Production and 

Biotechnology and Food Science, Lemesos, Cyprus 

Transition metal centered reductive O activation is a 

2 

fundamental process in various O oxidation reactions and 

2 

physiological O metabolism. Enzymes exhibiting in the active 

2 

site two redox centers one inorganic and one organic, such as 

galactose oxidase and copper amine oxidase, utilizes O to oxidize 

2 

organic substrates releasing H O . Synthesis of model compounds 

2 2 

that will mimic this activity is of particular interest because of the 

applications can be found in the use of O as green oxidant and in 

2 

the facile on-site production of H O which is also a powerful 

2 2 

green oxidant and can be used for clean energy storage. The last 

few years, we have pursued the synthesis of two redox center 

metal bioinorganic model complexes and stabilization of 

p-semiquinonate radicals. In particular, vanadium complexes 

because vanadium based enzymes and compounds utilize O2 and/or H O , catalyzing oxidative C-H activation, epoxidation and 

2 2 

alcohol oxidation reactions. Although, O is the most preferable 

2 

oxidant, the more reactive peroxides are used in combination with 

the vanadate catalysts. Paramagnetic vanadyl compounds are 

expected to be better choice for overcoming the spin restrictions 

and activate O than vanadates. In this work we have developed 

2 

dinuclear vanadyl hydroquinone/p-semiquinonate complexes that 

catalytically reduce O producing H O . Although these 

2 2 2 

complexes have been isolated in very acidic conditions with 

excess of chlorides, crystallographic characterization showed that 

the positive charge of the semiquinonate compound is neutralized 

with hydroxide anions. UV-Vis, electrochemistry and EPR 

support that between pH 2.2 and 2.8 the VIV-semiquinonate exhibit 

a slow reversible pH metal to ligand electron transfer towards the 

formation of hexanuclear VIV-O-V V bridged hydroquinonate 

species. The two redox center vanadyl complex is a very effective 

catalyst for the selective reduction of O to H O and 

2 2 2 

the mechanism of this activation was investigated. Financial 

support from RPF and European Structural Funds, 

ANABAUMISI/PAGIO/0308/32. 

Keywords: Vanadium; Reaction mechanisms; O-O activation; 

Bioinorganic chemistry; Redox chemistry; 



o - 1 8 2 

APPArent or reAL? the intereStinG CASe of 

wAter exChAnGe reACtionS on 

[zn(h o)4(L)] 2 2 +•2h o (L = nitroGen donor 

2 

LiGAndS) 

r. PuChtA 1 , M. wALther 1 , B. M. ALzouBi 1 

1 Friedrich-Alexander-University Erlangen-Nuremberg, Chemie 

und Pharmazie, Erlangen, Germany 

Detailed knowledge of the reactivity of the Zn(II)-cation is 

a necessity since Zn2+ is one of the most important ions in 

bioinorganic chemistry and plays a crucial rule in catalysis. [1] 

While solvent exchange reactions are the most fundamental 

substitution processes that a solvated metal ion can undergo and 

do not necessarily lead to a chemical conversion, they contribute 

fundamentally to our understanding of reactivity and substitution 

mechanisms. Experiments will lead to knowledge about reactions 

under realistic conditions, in contrast to quantum chemical 

calculations that permit detailed investigations unbiased by 

external effects. Earlier work reported I - or D-mechanisms for 

d 

H O exchange at six-fold coordinated [Zn(H O) ] 2 2 6 2+ . [1] 

In the present work we found for all ligands (L) in five-fold 

coordinated [Zn(L)(H O) ] 2 4 2+ an associative type of water 

exchange mechanism, depending on the ligand (L) and its 

properties, e.g. pK values, proton affinity, etc. focusing on ligands 

a 

with N-donors (e.g. HCN, py, NH , etc.).[2,3] The complete 

3 

reaction consists of an associative binding of one H O from the 

2 

second coordination sphere leading to a six-coordinate 

intermediate [Zn(H O) (L)] 2 5 2+ ·H O, followed by the 

2 

dissociation of a water molecule to reach the product state 

[Zn(H O) (L)] 2 4 2+ ·2H O. For a real water exchange reaction to 

2 

occur, two different transition states have to be included, 

otherwise only an apparent water exchange reaction takes place. 

For the water exchange reaction in [Zn(H O) (L)] 2 4 2+ ·2H O nearly 

2 

iso-energetic cis- and trans-orientated transition states are 

crossed. [4] 

references: 

1. J. Weston, Chem. Rev. 2005, 105, 2151. 

2. R. Puchta, B. Alzuobi, R. van Eldik, Aust. J. Chem., 2010, 

63, 236. 

3. B. M. Alzoubi, R. Puchta, R. van Eldik, Chem. Eur. J., 

2010, 16, 7300. 

4. B. M. Alzoubi, M. Walther, R. Puchta, R. van Eldik, 

Dalton Trans., DOI: 10.1039/C2DT30158J 

Keywords: Reaction mechanisms; Zinc; Quantum Chemistry; 



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inorganic/bioinorganic reaction mechanisms – iii 

o - 1 8 3 

CAtALytiC trAnSforMAtion of SuPeroxide, 

nitriC oxide, Peroxynitrite And hydroGen 

SuLfide for MediCAL And induStriAL 

APPLiCAtionS 

i. ivAnoviC-BurMAzoviC 1 

1 University of Erlangen-Nuremberg, Department of Chemistry 

and Pharmacy, Erlangen, Germany 

Superoxide, nitric oxide, peroxynitrite and hydrogen sulfide 

are small inorganic species that have diverse roles in biological 

systems. On the one hand they are toxic species involved in 

different pathologies but on the other hand they are signaling 

molecules with important physiological effects. Metal centers are 

one of their first targets in biological milieu, however the 

elementary reaction steps behind these interactions, which can 

both have stoichiometric and catalytic nature, are still unrevealed. 

New fundamental insights into these interactions and their 

potential pharmaceutical and catalytic applications will be 

presented. 



o - 1 8 4 

A fret enzyMe-BASed ProBe for MonitorinG 

hydroGen SuLfide 

M. StriAneSe 1 , G. J. PALM 2 , S. MiLione 1 , o. KühL 2 , 

w. hinriChS 2 , C. PeLLeCChiA 1 

1 University of Salerno, Chemistry and Biology, Salerno, Italy 

2 University of Greifswald, Institute for Biochemistry, 

Greifswald, Germany 

Hydrogen sulfide (H S) is among the oldest and simplest of 

2 

molecules whose reaction chemistry has very recently attracted 

attention from several research groups. In particular, recent efforts 

are mostly devoted to implement sensitive and selective detection 

techniques to monitor the distribution and function of this 

molecule in complicated biological systems. [1] For hundreds of 

years it has been known solely as a harmful gas. [2] More recently, 

H S has emerged as the “third gaseous transmitter” in biology. 2 [3] 

Recently we and others proposed an innovative method to 

make proteins suitable for sensing applications. The scheme 

builds on the translation of the binding event occurring at the 

enzyme cofactor binding-site into a change in the emission of a 

fluorescent probe covalently attached to the protein through a 

Förster Resonance Energy Transfer (FRET) mechanism. [4, 5] 

In the present contribution we show that fluorescently 

labeled cobalt peptide deformylase (Co-PDF) can be efficiently 

used as a FRET-based sensing device for H S. DFT calculations 

2 

were performed to gain insight into the characteristics of the 

coordination adduct between H S and Co-PDF. Mercaptoethanol 

2 

coordination to Co-PDF was verified by X-ray crystallography. 

We also report the crystal structure analysis of the 

monohydrogensulfide Co-PDF complex as proof of our method 

in H S detection. 

2 

references: 

1. Xuan, W.; Sheng, C.; Cao, Y.; He, W.; Wang, 

W. Angew. Chem Int. Ed Engl. 2012, 51, 2282-2284. 

2. Smith, R. P. American Scientist 2010, 98, 6-9. 

3. Chen, C. Q.; Xin, H.; Zhu, Y. Z. Acta Pharmacol. Sin. 

2007, 28, 1709-1716. 

4. Strianese, M.; Zauner, G.; Tepper, A. W.; Bubacco, L.; 

Breukink, E.; Aartsma, T. J.; Canters, G. W.; Tabares, L. C. 

Anal. Biochem. 2009, 385, 242-248. 

5. Strianese, M.; De Martino F.; Pavone, V.; Lombardi, A.; 

Canters, G. W.; Pellecchia, C. J. Inorg. biochem. 2010, 

104, 619-624. 

Keywords: biosensors; fluorescence; 



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o - 1 8 5 

new inSiGhtS into the PoLyMeriSAtion 

MeChAniSMS for PoLyPhoSPhAzene 

PreCurSorS 

S. PfirrMAnn 1 , v. BLACKStone 1 , M. BendLe 1 , 

h. heLten 1 , i. MAnnerS 1 

1 University of Bristol, School of Chemistry, Bristol, 


Polyphosphazenes, [N = PR ] , represent one of the most 

2 n 

versatile classes of inorganic polymers. The ability to tune the 

chemical and physical properties of these materials through the 

substituents R has enabled a broad range of promising 

applications. [1] Most of the synthetic methods to phosphazene 

polymers suffer from poor molecular weight control and the 

formation of broad molecular weight distributions. In 1995 the 

first example of the living polymerization route to 

polyphosphazenes was reported which involved the treatment of 

trichloro(N-trimethylsilyl)-phosphoranimine, Cl P = NSiMe , with 

3 3 

PCl . 5 [2] In contrast to other routes, this method allows the 

molecular weight of the polymer to be controlled by altering the 

monomer to initiator ratio to give polydichloro-phosphazenes in 

high yield with relatively narrow molecular weight distributions. 

Although the discovery of this living polymerization of Cl P = 3 

NSiMe has permitted a range of synthetic advances, its 

3 

mechanism has not been fully elucidated. 

Based on recent results using model chemistry [3] we have 

now further investigated the mechanism of the PCl -initiated 

5 

living polymerization of Cl P = NSiMe . These studies give 

3 3 

interesting results and have shown that the polymerization process 

is much more complex than originally proposed. 

Furthermore, the phosphite-initiated polymerization 

of bromophosphoranimine BrMePhP = NSiMe [4] has been 

3 

investigated in more detail. It was found that alternative 

compounds to phosphites can act as much more active initiators. 

references: 

1. Allcock, H. R. Chemistry and applications of 

polyphosphazenes; Wiley-Interscience: Hoboken, N.J, 

2003. 

2. Honeyman, C. H.; Manners, I.; Morrissey, C. T.; Allcock, 

H. R. J. Am. Chem. Soc. 1995, 117, 7035. 

3. Blackstone, V.; Lough, A. J.; Murray, M.; Manners, I. 

J. Am. Chem. Soc. 2009, 131, 3658. 

4. Huynh, K.; Lough, A. J.; Manners, I. J. Am. Chem. Soc. 

2006, 128, 14002. 

Keywords: polyphosphazenes; mechanisms; polymerizations; 

main group chemistry; 


o - 1 8 6 

redox reACtionS of the 

PeroxoMonoSuLfAte ion in the 

ferroin/ferriin SySteM 

i. fABiAn 1 , G. BeLLer 1 , G. Lente 1 


1 University of Debrecen, Department of Inorganic and 

Analytical Chemistry, Debrecen, Hungary 

- Peroxomonosulfate ion (oxone, HSO ) is a strong, two- 

5 

electron oxidant also used as an inexpensive and environmentally 

friendly agent in advanced oxidation procedures. Experiments 

involving oxone add valuable information to the study of reactive 

intermediates, may confirm mechanistic considerations regarding 

the autoxidation of various substrates and may explore important 

aspects of industrial applications. 

This presentation reports a kinetic study on the reactions of 

oxone in the ferroin/ferriin system (the tris-1,10-phenanthroline 

complexes of FeII and FeIII ), which is frequently used for 

modelling the redox activity of biological compounds. A complex 

kinetic behavior was observed: the concentration of ferroin 

decreases in the first stage of the reaction; however, after reaching 

a minimum the concentration increases to a maximum and then 

decreases again. A similar behavior was described previously in 

the reaction of ferroin with Ce(IV). [1] 

Detailed kinetic study and ESI mass spectrometry confirmed 

the formation of an 1:1 adduct between the reactants in the initial 

- phase of the ferroin-HSO reaction. [2] The oxidation product, 

5 

1,10-phenanthroline-mono-N-oxide was identified in the reaction 

mixture with several methods (UV-Vis, ESI-MS, 1H-NMR). The 

N-oxide has significant inhibiting effect: upon the addition of the 

N-oxide to the initial mixture, a slower consumption of ferroin 

was observed. A kinetic model was proposed for the reaction and 

independent measurements were carried out with ferriin which is 

also formed in the reaction. 

Ferriin decomposes in strongly acidic solutions 

producing ferroin and 1,10-phenanthroline-mono-N-oxide. 1,10- 

Phenanthroline-mono-N-oxide has a slight autocatalytic effect on 

the decomposition and increases the rate of ferroin formation. We 

4+ propose the formation of Fe(phen) as a minor intermediate in 

3 

the overall process. [3] 

references: 

1. M. Melichercik; J. Treindl; J. Phys. Chem. 1989, 93, 7652. 

2. G. Bellér; G. Lente; I. Fábián; Inorg. Chem. 2010, 49, 

3968. 

3. G. Bellér; G. Bátki; G. Lente; I. Fábián; J. Coord. Chem. 

2010. 63, 2586. 

Keywords: oxone; redox chemistry; reactive intermediate; 

AOP; reaction mechanism; 



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symposium on Co2 chemistry – i 

o - 3 0 6 

Co CAPture froM fLue GASeS: exiStinG 

2 

oPtionS And PerSPeCtiveS 

t. KAtz 1 , i. CLAuSen 1 

1 BASF SE, OASE Gas Treatment Excellence, Ludwigshafen, 

Germany 

Over the past 10-20 years, a variety of processes for 

capturing carbon dioxide from flue gases have been developed. 

In particular chemical absorption processes have meanwhile 

reached a level of maturity that these processes nowadays can be 

applied on an industrial scale. 

The paper provides an overview over the most relevant 

technologies and focuses on some key performance figures and 

characteristics: purity of the processed streams, energy 

consumption, solvent circulation rates as well as emissions and 

product availability and process reliability are important 

parameters, when it comes to process selection. 

In public discussion, chemical absorption processes are 

often criticized for their high energy consumption. With an 

entropy evaluation, the paper will show, where the 

thermodynamic minimum energy consumption will be, what level 

can be realized under reasonable boundary conditions and how 

this compared to today’s technologies. The approach is 

independent on the type of process and can also be used to predict 

the separation efficiency of e.g. adsorption or membrane 

processes. 

Atop, the latest developments to further improve the process 

performance of carbon dioxide absorption will be presented and 

some of the major challenges will be discussed. 

Keywords: Chemisorption; Absorption; 



o - 3 0 7 

Co - inSertion into Si-n-BondS - A 

2 

MeChAniStiC Study 

K. KrAuShAAr 1 , u. BÖhMe 1 , A. SChwArzer 1 , 

e. KroKe 1 

1 TU Bergakademie Freiberg, Institute for Inorganic Chemistry, 

Freiberg, Germany 

CO may be used as starting material for chemical syntheses, 

2 

e. g. for the synthesis of urea, methanol, and several carbonates. 

Hence, CO is mainly used as a C1 source. One of the several 

2 

[1] methods known for the activation of CO is the insertion into a 

2 

main group or transition metal nitrogen bond. [2] Most of the 

literature focus on the reactions of Me SiCl with primary and 

3 

secondary amines, e. g. using the TMS substituent as directing 

group in organic synthesis. [3] In contrast, we report here the use 

of Me SiCl and a primary amine as starting materials for the 

2 2 

synthesis of diaminosilanes Me Si(NHR) . Subsequent 

2 2 

quantitative bis-insertion of CO yields the corresponding 

2 

[4, 5] 

di(alkylcarbamoyloxy)dimethylsilanes Me Si(OCONHR) . 2 2 

Diaminosilanes of the type (RHN) SiMe , obtained from 

2 2 

Me SiCl and primary amines, were subjected to a double 

2 2 

insertion of CO at room temperature to afford the 

2 

carbamoyloxysilanes. The latter reaction is exothermic and 

proceeds with very good yields. To gain further insight into the 

reaction mechanism of the CO insertion, we performed DFT 

2 

calculations with a simple model aminosilane, Me Si(NHMe) . 2 2 [6] 

references: 

1. D. Belli Dell‘Amico, F. Calderazzo, L. Labella, 

F. Marchetti, Chem. Rev. 2003, 103, 3857. 

2. C. A. Stewart, D. A. Dickie, M. V. Parkes, J. A. Saria, 

R. A. Kemp, Inorg. Chem. 2010, 49, 11133. 

3. M. J. Fuchter, C. J. Smith, M. W. S. Tsang, A. Boyer, 

S. Saubern, J. H. Ryan, A. B. Holmes, Chem. Commun. 

2008, 2152. 

4. C. Wiltzsch, K.Kraushaar, A. Schwarzer, E. Kroke, 

Z. Naturforsch., B: J. Chem. Sci. 2011, 66, 917. 

5. C. Wiltzsch; J. Wagler; G. Roewer; E. Kroke, 

Verfahren zur Herstellung von Oligo- und Polysiloxanen, 

DE 10 2009 045 849.2, 2010. 

6. K. Kraushaar et al., Organomet. 2012, submitted. 

Keywords: Insertion; Silicon; Amines; Carbon dioxide 

fixation; Density functional calculations; 



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o - 3 0 8 

unPreCedented ALKyLzinC CArBonAte viA 

Bio-inSPired route invoLvinG rznoh And Co2 K. SoKoLowSKi 1 , w. Bury 2 , i. JuStyniAK 1 , 

M. woLSKA 2 , K. SoLtyS 1 , A. CieSLAK 2 , J. LewinSKi 1 

1 Institute of Physical Chemistry, Department of Physical 

Chemistry of Supramolecular Complexes, Warsaw, Poland 

2 Warsaw Univeristy of Technology, Faculty of Chemistry, 

Warsaw, Poland 

Over the last decade, bio-fixation approaches for the CO2 sequestration have received much attention because of their great 

environmental significance as well as very promising practical 

applications in materials chemistry. [1] This bio-inspired solution 

for chemical activation of CO is mostly based on ZnOH type 

2 

reaction systems patterned on active centre of carbonic anhydrase 

(CA). [2] However, despite numerous inorganic complexes 

investigated as CA mimics, the organozinc RZnOH compounds 

have not yet been investigated in this context. 

Here we report on the activation of CO by the model 

2 

alkylzinc hydroxide [3] ( tBuZnOH) (1) in the absence and presence 

6 

of tBu Zn as proton acceptor, and the isolation of the 

2 

unprecedented dodecanuclear alkylzinc carbonate [( tBuZn) (µ - 2 5 

-CO )] cluster (2). Compound 2 was fully characterized in the 

3 6 

solid state by X-ray diffraction studies and the presence of the 

carbonate group is substantiated by CP-MAS 13C NMR and IR 

spectroscopy. The 1H NMR spectroscopic studies clearly indicate 

that the presence of an excess of tBu Zn in the 1/CO reaction 

2 2 

system greatly accelerates the proton transfer from an 

intermediate Zn(HCO ) bicarbonate and significantly improves 

3 

the reaction yield. Moreover, the existence of the reactive 

M-C bond in the reported complexes is a unique feature qualifying 

these systems for further post-synthetic modification in order to 

design of a new class of carbonate secondary building blocks for 

materials chemistry. Further biologically inspired studies on the 

reactivity of organozinc Zn–OH systems supported by organic 

ligands towards effective CO bio-fixation and other small 

2 

molecules are in progress. 

references: 

1. J. R. Long et al., Angew. Chem. Int. Ed., 2010, 49, 

6058–6082. 

2. G. M. Whitesides et al., Chem. Rev., 2008, 108, 946–1051. 

3. W. Bury, E. Krajewska, M. Dutkiewicz, K. Sokolowski, 

I. Justyniak, Z. Kaszkur, K. J. Kurzydlowski, T. Plocinski 

and J. Lewinski, Chem. Commun., 2011, 47, 5467–5469. 

Keywords: carbon dioxide; bio-fixation; zinc hydroxide; zinc 

alkyls; proton acceptor; 


o - 3 0 9 

MeChAniStiC inSiGht froM ACtivAtion 

PArAMeterS for the reACtion of A 

rutheniuM hydride CoMPLex with CArBon 

dioxide in ConventionAL SoLventS And An 

ioniC Liquid 

S. Kern 1 , r. vAn eLdiK 1 

1 Friedrich-Alexander-University Erlangen-Nuremberg, 

Department of Chemistry and Pharmacy, Erlangen, Germany 

The reduction of carbon dioxide to a useable resource (fuel 

or otherwise) is a major goal in current chemical research. One 

possible way would be to use a hydride transfer reaction by which 

CO will first be reduced to formic acid. The reaction rate of the 

2 

reaction of a ruthenium hydride complex (RuII (terpy)(bpy)H] + 

(terpy = 2,2',6',2''-terpyridine; bpy = 2,2'-bipyridine) with 

CO 2 


to form a formate adduct strongly depends on 

the solvent [1] . Detailed kinetic studies in conventional 

solvents (water, methanol and ethanol) and in the ionic liquid 

[emim][NTf ] ([emim] = 1-ethyl-3-methyl-imidazolium; 

2 

[NTf ] = bistrifluoromethylsulfonylamide) using stopped-flow 

2 

methods were performed and second-order rate constants and 

activation parameters (ΔH # , ΔS # and ΔV # ) were determined for 

the reaction in all solvents. The second-order rate constants 

correlate with the acceptor number of the solvent, whereas the 

activation parameters support the nature of the insertion 

mechanism of the reaction. The results in water, especially the 

activation entropy (+14 ± 2 J K-1 mol-1 ) and activation volume 

(-5.9 ± 0.6 cm3 mol-1 ), differ significantly from those found for 

the other solvents, underlining the importance of hydrogen bond 

formation in the transition state. 

references: 

1. a) Konno H.; Kobayashi A.; Sakamoto H.; Fagalde F.; 

Katz N. E.; Saitoh H.; Ishitani O.; Inorg. Chim. Acta 

2000, 299, 155–163 

b) Creutz C.; Chou M. H. J. Am. Chem. Soc. 2007, 129, 

10108-10109 

Keywords: reaction mechanisms; kinetics; insertion; carbon 

dioxide; 



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symposium on Co2 chemistry – ii 

o - 3 1 0 

CheMiCALS And fueLS froM Co : the exiStinG 

2 

BArrierS to exPLoitAtion 

A. diBenedetto 1 

1 University of Bari, Department of Chemistry, Bari, Italy 

The use of carbon dioxide (CCU) to produce chemicals and 

fuels through biotechnological, biological, chemical, photo-chemical 

and photo-electrochemical processes is nowadays considered a 

way to reduce its atmospheric loading. Time is now to step 

towards the “Artificial photosynthesis”. CCU can be 

advantageously integrated within the Carbon Capture-CC and 

Carbon Capture and Storage-CCS technologies for improving 

their economic costs. 

Noteworthy, to use carbon dioxide means to reduce both the 

use of fossil C and the carbon dioxide emission into the 

atmosphere with the double benefit of preserving reserves and 

improving our environment. 

In this paper, the possible uses of CO as source of carbon 

2 

for chemicals and fuels will be summarized. A deeper insight into 

the synthesis of organic acyclic carbonates will highlight the 

existing barriers to a full exploitation of the CO -based technology 

2 

and will show how such barriers can be circumvented. 



o - 3 1 1 

exPeriMentAL inveStiGAtionS of 

nonStoiChioMetry for A SiMPLe CLAthrAte 

hydrAte of CArBon dioxide 

S. MuroMAChi 1 , S. tAKeyA 2 , r. ohMurA 3 

1 Keio university, Mechanical Engineering, Yokohama, Japan 

2 National Institute of Advanced Industrial Science and 

Technology, Research Institute of Instrumentation Frontier, 

Tsukuba, Japan 

3 Keio University, Mechanical Engineering, Yokohama, Japan 

The technologies using clathrate hydrates are promising as 

energy storage and environmental technologies. They are one of 

host-guest materials and include nonstoichiometric number of 

guest molecule within host water cages, and the contents of a 

guest substance could be varied depending on forming conditions. 

The technology using clathrate hydrates of carbon dioxide are 

expected to be the one for the carbon capture and storage. 

Therefore, the contents of CO in clathrate hydrates, i.e., cage 

2 

occupancies, are significant properties for industrial use. 

However, there was a difficulty to determine them correctly, based 

on diffraction measurements, due to the disorder of the CO2 molecule positions in the hydrate cages. This paper reports an 

attempt to improve the experimental determination of cage 

occupancies for simple clathrate hydrates of CO . The powder 

2 

X-ray diffraction (PXRD) measurement technique was applied to 

estimate the cage occupancies by the Rietveld method with the 

aid of the direct space method for clathrate hydrates [Takeya et 

al., J. Am. Chem. Soc., 2010]. The method allows to optimize 

guest-molecule positions in hydrate cages and to determine cage 

occupancies from powder samples. The hydrate samples were 

formed at the pressure over or nearly equal to the phase 

equilibrium pressure. The forming conditions were ranged in 

the temperatures from 274 K to 280 K and the pressures from 

1.5 MPa to 3 MPa. Mass measurements for carbon dioxide and 

water were also performed in order to verify the data obtained 

from the PXRD measurements. The contents of CO could be 

2 

obtained on the basis of an absolute measurement technique. The 

pressure dependence for the small cage occupancy was clearly 

observed. The data of cage occupancies obtained in this study 

were compared with the experimental data and predictions 

reported in the literature, and discussion was made based on the 

comparison. 

Keywords: Clathrates; Carbon dioxide fixation; hydrates; 

Nonstoichiometric compounds; Inclusion compounds; 



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o - 3 1 2 

CAtALytiC SyntheSiS of 

2-hydroxyMethyL-oxAzoLidinoneS froM 

GLyCeroL CArBonAte or GLyCeroL And ureA 

L. di Bitonto 1 , A. diBenedetto 1 , M. AreStA 2 , 

f. noCito 3 

1 Interuniversity Consortium Chemical Reactivity and 

Catalysis – CIRCC, Department of Chemistry, Bari, Italy 

2 Interuniversity Consortium Chemical Reactivity and Catalysis, 

CIRCC, Bari, Italy 

3 METEA Research Center, Valbior Project, Bari, Italy 

2-oxazolidinones are important heterocyclic compounds that 

find several applications in particular as antibiotics, pesticides, 

and in drug or fibers production. Industrially, 2-oxazolidinones 

are synthesized starting from amino alcohol and phosgene, [1] 

CO [2] or cyclic carbonates. [3] All such routes are affected by the 

2 

formation of polymers, harsh reaction conditions and high cost. 

In this work, we report the synthesis of hydroxymethyl-2- 

-oxazolidinones obtained reacting glycerol carbonate (GC) and 

urea or glycerol and urea. GC is a non toxic and easy 

biodegradable compound that can be prepared in high yields and 

at low cost under mild reaction conditions by glycerolysis of 

urea [4] . Such approach represents from one side a new application 

of GC or glycerol and from the other a new “green” route to 

oxazolidinones. γ -ZrP has been used as catalyst and we show that 

the modulation of the acid/base properties of the catalyst play 

a key role in the transformation of either substrate into 

2-oxazolidinones. GC and urea in presence of non calcined γ-ZrP, 

at 20 Pa and 408 K react to afford 2-oxazolidinones with a 

selectivity close to 100% and a conversion of 21%. At 453 K 

the conversion of GC into 2-oxazolidinones increases but 

the selectivity decreases and new molecular products are formed. 

In absence of catalyst the reaction does not occur under the same 

conditions. The reaction conditions and the reaction mechanism 

have been investigated and will be discussed. 

Acknowledgements: The authors acknowledge funding from 

the EU Seventh Framework Programme (FP7/2007-2013) 

under grant agreement n° 241718 EuroBioRef. 

references: 

1. Ager D. J. et al., Chem. Rev., 96, (1996), 835-875 

2. Gabriele B. et al., J. Org. Chem, 68 (2), (2003), 601-604 

3. Xiao L.F. et al., Green Chem. 9, (2007) 369-372 

4. Aresta M. et al., J. Cat., 268, (2009), 106-114 

Keywords: 2-hydroxymethyl-oxazolidinones; glycerol 

carbonate; heterogeneous catalysts; 

symposium on Co2 chemistry – iii 


o - 3 1 3 

fixAtion of Co AS CArBonAteS of MAGneSiuM 

2 

or CALCiuM 

r. zevenhoven 1 

1 Abo Akademi University, Thermal and Flow Engineering, 

Abo/Turku, Finland 

The fixation of CO in (hydro-)carbonates brings together 

2 

the goals of CO emissions reduction, valorization or stabilization 

2 

of waste streams and more sustainable or otherwise advanced 

chemical processing. While CO mineral sequestration using the 

2 

world’s vast magnesium silicate resources was recognized as a 

CCS (carbon dioxide capture and storage) route in the early 1990s, 

most CCS efforts aim at underground storage of pressurized CO . 2 

Only recently the large-scale carbonation of minerals was again 

recognized as a serious alternative for underground storage as it 

gives leakage-free, permanent storage that won’t require 

post-storage monitoring and seems to be applicable more widely. 

Moreover, it is suitable for trapping CO from streams that contain 

2 

oxygen as well, making it not only more versatile but also presents 

the option of removing the problematic and expensive capture step 

from the CCS process chain. Finally, uses for the significant 

amounts of solid (hydro-)carbonate product and by-products 

obtained are being recognized, ranging from land reclamation to 

specialized products. These increasingly patent-driven 

developments that define an overlap of CCS and CCU (carbon 

dioxide capture and utilization) shall be summarized here. 

More developed and closer to commercial application are 

process routes that utilize CO for the production of calcium 

2 

carbonates including the highly valuable precipitated 

calcium carbonate (PCC). Roughly since year 2000 many 

calcium-containing by-products, residues and wastes are 

investigated for the potential to bind CO which offers emissions 

2 

reduction potential while reducing (costly) landfill and the use of 

natural resources. Slag residue from iron and steel-making or 

ashes from for example oil shale combustion are important 

examples of calcium-based CCU methods addressed in this 

presentation. 

references (Further reading): 

1. Chapter 14 in: “Developments and innovation in CCS 

technology” M. Maroto-Valer (Ed.), Vol. 2 (2010) 

2. Chapter 16 in: “Carbon dioxide utilization”, M. Aresta 

(Ed.) (2010) 

3. Zevenhoven et al., doi:10.1002/ghg3 (2010) 

Keywords: CO2; mineral; carbonation; magnesium; calcium; 



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o - 3 1 4 

Photo-eLeCtroCheMiCAL nAdh 

reGenerAtion for enzyMAtiC CArBon 

dioxide reduCtion to MethAnoL: effiCient 

MetAL-Modified SeMiConduCtor eLeCtrodeS 

P. StufAno 1 , z. M. detweiLer 2 , e. L. zeitLer 2 , 

A. diBenedetto 3 , M. AreStA 3 , A. B. BoCArSLy 2 

1 University of Bari, Department of Chemistry, Bari, Italy 

2 Princeton University, Department of Chemistry, Princeton NJ, 

USA 

3 Interuniversity Consortium Chemical Reactivity and Catalysis, 

CIRCC, Bari, Italy 

The enzymatic reduction of carbon dioxide into methanol 

through the dehydrogenase enzyme cascade F DH, F DH and 

ate ald 

ADH represents a unique process for CO reduction as it occurs 

2 

under very mild conditions (water, 37°C, pH = 7) and with optimal 

yield and selectivity (close to 100%). [1] Nevertheless there still is 

a limitation associated with the consumption of the cofactor 

NADH that is converted into the oxidized form NAD + . 

Enzymatic, chemical and photochemical approaches have been 

attempted, [2] but over all these strategies electrochemical 

regeneration is considered the most attractive one. [4] 

Herein we report the use of p-type semiconductor electrodes 

in order to utilize solar energy for photo-electrochemical NADH 

regeneration modeling the “light reactions” occurring in 

chloroplasts. All-solid electrodes with no organometallic 

mediators were employed, in order to perform the in situ NADH 

regeneration without enzymes deactivation. While bare 

semiconductors were shown to produce only enzymatically 

inactive dimers (NAD ), modification of the surface by 

2 

electro-deposition of a thin layer of Pt or Ru metal caused the 

formation of 1,4-NADH as the main product. In particular a 

Pt/p-GaAs photocathode, illuminated by pure visible light 

(>600 nm), showed an increased efficiency in NAD + reduction at 

low overpotentials (-0.75V vs Ag/AgCl) when compared to metal 

electrodes (>7 fold), with no dimer detection. The latter evidence 

suggested a reaction pathway with no NAD . intermediate 

formation. This hypothesis was supported by electrochemical 

investigations on the reaction mechanism. This study represents 

the first example of NADH regeneration at an illuminated 

semiconductor electrode. 

references: 

1. R. Obert, B.C. Dave, J. Am. Chem. Soc., 1999, 121, 

12192. 

2. a) B. C. Dave, M. S. Rao, M. C. Burt, US Patent 0042479, 

2007; 

b) A. Dibenedetto, P. Stufano, W. Macyk, T. Baran, 

C. Fragale, M. Costa, M. Aresta, ChemSusChem, 2012, 

5, 373. 

3. F. Hollmann, I.W.C.E. Arends, K. Buehler, 

ChemCatChem, 2010, 2, 762. 

Keywords: Enzymatic CO2 reduction; NADH regeneration; 

photo-electrochemistry; p-type Gallium Arsenide; 



o - 3 1 5 

AeroBiC deGrAdAtion of triCLoSAn in 

ACtivAted SLudGe -MethyLAtion And other 

ProCeSSeS 

K. BeSter 1 , x. Chen 2 , J. L. nieLSen 3 

1 Aarhus University, Environmental Science, Roskilde, Denmark 

2 AalborgUniversity, Environmental Engineering, Aalborg, 

Denmark 

3 AalborgUniversity, Environmental Biotechnology, Aalborg, 

Denmark 

Triclosan is an antimicrobial agent which is widely used in 

personal care products such as toothpaste, soaps, deodorants, 

cosmetics and skin care lotions as well as other consumer goods. 

It is released after use via sewer system into sewage treatment 

plants. It has been demonstrated, that the elimination 

of Triclosan is very effective in waste water treatment with 

removal rates > 90%. However, the elimination pathways and the 

role of adsorption and biodegradation have not been identified 

yet. Transformation products may be emitted and of future 

concern. 

In this study we present data on the degradation and 

methylation of Triclosan in activated sludge systems. Degradation 

products are elucidated by means of GC-MS and HPLC-MS/MS. 

Degradation products include chlorinated phenols as well as 

methylated products. Kinetic data for the different steps and 

conditions are presented for selected reactions. A mass balance of 

Triclosan in dissolved and particulate phases is performed to 

estimate the fraction of sorption and biodegradation. Samples 

from the environment are compared to the technical processes. 

Keywords: Triclosan; activated sludge; degradation; waste 

water treatment; 



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New trends in organometallic chemistry – iV 

o - 3 1 6 

AMMoniA ACtivAtion ProCeSSeS LeAdinG to 

noveL AMido And iMido iridiuM And rhodiuM 

CoMPLexeS 

L. A. oro 1 , M. A. CASAdo 1 , i. MenA 1 

1 University of Zaragoza, Inorganic Chemistry, Zaragoza, Spain 

Amido-bridged polynuclear complexes [{M(µ -NH ) 2 2 

(diolefine)}x] (M = Ir, Rh; diolefin = 1,5-cyclooctadiene (cod) or 

tetrafluorobenzobarrelene (tfbb)) can be prepared by treatment of 

the methoxo-bridged compounds [{M(µ-OMe)(diolefine)} ] with 2 

gaseous ammonia in diethyl ether at atmospheric pressure. [1] The 

nuclearity of these unprecedented parent amido complexes 

depends on the olefin (trinuclear for tetrafluorobenzobarrelene 

and dinuclear for 1,5-cyclooctadiene). They are active catalysts 

in hydrogen transfer reactions from isopropanol to unsaturated 

substrates. The studies performed on the diiridium(I) complex 

[{Ir(µ -NH )(cod)} ] evidences the dinuclear nature of the species 

2 2 2 

involved and the participation of the two iridium centers in the 

catalytic hydrogen transfer reactions. Interestingly, under the 

absence of unsaturated substrates the concerted alcohol 

dehydrogenation process gives rise to the formation of unusual 

mixed amido/imido tetraiiridium and bis(imido) triiridium 

clusters. 

references: 

1. I. Mena, M. A. Casado, P. García-Orduna, V. Polo, 

F. J. Lahoz, A. Fazal and L. A. Oro, Angew. Chem. Int. Ed., 

2011, 50, 11735-11738. 

Keywords: N ligands; Rhodium; Iridium; Cluster compounds; 

Homogeneous catalysis; 



o - 3 1 7 

SurPriSeS froM oLd friendS: nitron, the 

ALder CArBene, And reLAtiveS 

u. SieMeLinG 1 , C. färBer 1 , t. SChuLz 1 , C. Bruhn 1 , 

M. LeiBoLd 1 , t. PorSCh 2 , M. hoLthAuSen 2 

1 University of Kassel, Institute of Chemistry, Kassel, Germany 

2 University of Frankfurt, Institute of Inorganic and Analytical 

Chemistry, Frankfurt am Main, Germany 

The paradigm-shifting report of the first stable crystalline 

N-heterocyclic carbene (NHC) 1,3-di-1-adamantylimidazol-2- 

-ylidene (IAd) by Arduengo in 1991 showed that singlet carbenes 

may be sufficiently stable for isolation. IAd is an iconic carbene, 

which triggered the tremendous development of NHCs and related 

diaminocarbenes from laboratory curiosities to powerful 

workhorses in synthesis and catalysis. Conveniently, a limited 

number of NHCs have become commercially available, with 

1,3,4-triphenyl-1,2,4-triazol-5-ylidene (1) introduced by Enders 

being the earliest such example. Unfortunately, prices exceed 

several hundred US$ per gram. We found that the low-cost 

analytical reagent Nitron, a relative of 1 that has been 

commercially available for more than a century, exhibits a hitherto 

unrecognised reactivity which is not compatible with its 

conventional mesoionic Lewis structure 2, but rather is expected 

for its NHC-type tautomer 2’ and closely resembles that of 1. In 

fact, the properties of 1 and 2’ as ligands in coordination 

chemistry turn out to be very similar. [1] We have investigated 

several other mesoionic instant carbenes related to Nitron, which 

are easily accessible from readily available starting materials. 

Another iconic carbene is (iPr N) C, which was published by 

2 2 

Alder in 1996 as the first acyclic diaminocarbene to be isolated 

and structurally characterised. The ‘Alder carbene’ is commonly 

known as the simplest stable diaminocarbene. However, its 

reactivity has been much underestimated. We found that (iPr N) C 2 2 

is suitable for small-molecule activation [2] and even undergoes a 

β-fragmentation in solution already at room temperature. 

This is in stark contrast to the previous claims of inertness. The 

β-fragmentation process which we uncovered very recently is not 

limited to the ‘Alder carbene’. 

references: 

1. C. Färber, M. Leibold, C. Bruhn, M. Maurer, 

U. Siemeling, Chem. Commun. 2012, 48, 227. 

2. U. Siemeling, C. Färber, C. Bruhn, M. Leibold, D. Selent, 

W. Baumann, M. von Hopffgarten, C. Goedecke, 

G. Frenking, Chem. Sci. 2010, 1, 697. 

Keywords: Carbenes; Nitrogen heterocycles; Carbene ligands; 

C-H activation; Carbonylation; 



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o - 3 1 8 

ASyMMetriC P-C CAGe CoMPoundS And their 

trAnSition MetAL CoMPLex CheMiStry 

L. rohwer 1 , C. hÖhn 1 , i. KeLLer 1 , 

f. w. heineMAnn 1 , t. ShuBinA 1 , w. BAuer 1 , 

u. zenneCK 1 



Becker’s famous phosphaalkyne and its phosphaalkene 

precursor have opened the field of P-C cage chemistry. During 

the process of working out this chemistry more systematically, we 

became aware of the high diastereoselectivity of the cage forming 

reactions. In the case of pentaphosphadeltacyclene studied 

intensively in our group, two consecutive cycloaddition reactions 

led to one pair of enantiomeric P-C cages containing 7 stereogenic 

centers. [1] By introducing a chiral auxiliary we were able to obtain 

both enantiomers separately. [2] Further investigations revealed a 

rapid epimerization equilibrium on the secondary phosphane unit 

of the molecule. 

Since we regard asymmetric P-C cages as compounds of 

interest as highly space filling ligands in stereoselective catalysis, 

we investigated the transition metal complex chemistry of 

pentaphosphadeltacyclene in more detail. After successful 

complexation of the transition metal fragments M(CO) (M = Cr, 

5 

Mo, W), the study was expanded to suitable redox-active metals 

like Ru(II) and Rh(I). Pentaphosphadeltacyclene complexes with 

M(CO) were obtained as a mixture of four isomers, whereas the 

5 

ruthenium complex consisted only of one isomer because of 

sterical reasons. In contrast to that, coordination with rhodium 

resulted in unique dinuclear complexes. 

Pentaphosphadeltacyclene is also prone to rearrangement 

reactions. Two rearranged P-C cages viz. iso-pentaphosphadeltacyclene 

and pentaphosphahomocuneane could be synthesized selectively 

under basic conditions. CD spectroscopy showed that these cages 

are again formed under complete stereo control. The complex 

chemistry properties of these sterically even more demanding 

cages were tested with the transition metal fragments M(CO) . 5 

references: 

1. A. Elvers, F. W. Heinemann, B. Wrackmeyer, U. Zenneck, 

Chem. Eur. J. 1999, 5, 3143-3153. 

2. M. Hofmann, C. Höhn, F. W. Heinemann, U. Zenneck, 

Chem. Eur. J. 2009, 15, 5998-6007. 

Keywords: Cage compounds; Cycloaddition; Phosphane 

ligands; Rearrangement; Steric hindrance; 



o - 3 1 9 

LithiuM CArBenoidS -unCoverinG new 

reACtivitieS for LonG-Known CoMPoundS 

v. h. GeSSner 1 

1 Institut für Anorganische Chemie, Universität Würzburg, 

Wuerzburg, Germany 

Since the pioneering work of Simmons and Smith 

carbenoids are frequently used reagents in organic syntheses, 

above all in cyclopropanation reactions. [1] However, giving their 

potential as carbene precursors it is surprising that there are only 

few examples of the application of carbenoids in the formation of 

transition metal carbene complexes. Furthermore, compared to 

carbenes – which have experienced dramatic research interest 

over the past two decades – carbenoids have almost been 

neglected despite their versatile reactivity as ambiphilic reagents. 

This ambiphilicity of free carbenes has opened a wide range of 

applications including their use in organocatalysis or in the 

stabilization of reactive species and the activation of small 

molecules such as dihydrogen or ammonia. [2] 

Here we present the use of lithium/chloride carbenoids in 

the preparation of transition metal carbene complexes and bond 

activation reactions. Due to the high reactivity of carbenoids we 

focus on stabilized representatives, above all thiophosphinoyl 

substituted compounds. We show that depending on the stabilizing 

ability of a second functional group different reactivities are 

observed. As such, treatment of silyl substituted Li/Cl carbenoids 

with a palladium(0) precursor delivers either a thioketone 

complex – resulting from the reduction of the thiophosphinoyl 

moiety to the free phosphine – or a carbene complex. [3] 

Furthermore, these carbenoids show unexpected reactivities 

towards small molecules such as boranes, which clearly 

demonstrate their different reactivity compared to simple 

organolithium reagents and free carbenes. [4] 

references: 

1. H. E. Simmons, R. D. Smith, J. Am. Chem. Soc. 1959, 81, 

4256. 

2. For example, see: D. Martin, M. Melaimi, 

M. Soleilhavoup, G. Bertrand, Organometallics, 2011, 30, 

5304. 

3. V. H. Gessner, Organometallics 2011, 30, 4228. 

4. V. H. Gessner, S. Molitor, 2012 submitted. 

Keywords: carbene ligands; carbenoids; lithium; transition 

metals; carbanions; 



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o - 3 2 0 

PALLAdiuM(ii) CoMPLexeS with SMALL 

n-heteroCyCLiC CArBene LiGAndS AS hiGhLy 

ACtive CAtALyStS for the SuzuKi-MiyAurA 

reACtion 

A. trzeCiAK 1 , M. SzuLMAnowiCz 1 , A. GnieweK 1 

1 University of Wroclaw, Faculty of Chemistry, Wroclaw, Poland 

Palladium complexes, bearing bulky N-heterocyclic carbene 

ligands (NHC), found many applications in catalytic reactions 

and, in particular, in the Suzuki-Miyaura cross-coupling. In 

contrast, much less is known about reactivity of carbene palladium 

complexes bearing small substituents at N-atoms of imidazole 

ring. Consequently, we synthesized two groups of palladium(II) 

complexes, namely monomeric, of the type Pd(NHC) X and 

2 2 

dimeric of [PdX (NHC)] composition with the aim to apply them 

2 2 

in the Suzuki-Miyaura reaction. Moreover, mechanistic studies 

were undertaken in order to recognize structural transformations 

of palladium complexes under reaction conditions. All new 

complexes were characterized by spectroscopic and X-ray 

methods and, in particular, for Pd(bmim-y) Br , (bmim-y = 1- 

2 2 

-methyl-3-butylimidazol-2-ylidene) both isomers, cis and trans, 

were obtained. All of the complexes studied exhibited very high 

activity in Suzuki-Miyaura cross-coupling in ethylene glycol, 

achieving TONs of up to 760000. High activity was also noted 

when NaBPh was used instead of PhB(OH) . ESI-MS studies of 

4 2 

the reaction mixtures allowed to identify dimeric forms of the type 

+ Pd (NHC) X and trimeric intermediates of the composition 

2 4 3 

Pd (NHC) Ph 3 4 + , most probably participating in the catalytic cycle. 

Further studies, performed with TEM method, confirmed the 

presence of Pd(0) nanoparticles in the reaction mixture. 

Interestingly, the size of nanoparticles decreased during 

Suzuki-Miyaura reaction indicating on their solubilization with 

formation of soluble palladium species. Consequently, we 

proposed a homogeneous pathway of the reaction with the 

participation of palladium species bearing imidazolium cations or 

N-heterocyclic carbenes as key intermediates. 

Keywords: palladium; carbene ligands; cross-coupling; 

homogeneous catalysis; ligands effects; 

Young inorganic chemistry day – i 


o - 4 4 4 

BASe-ASSiSted MetAL-CAtALyzed C-h Bond 

funCtionALizAtionS 

L. ACKerMAnn 1 

1 University of Goettingen, Institute for Organic and 

Biomolecular Chemistry, Goettingen, Germany 

Direct C–H bond functionalizations of (hetero)arenes are 

highly attractive tools for an overall streamlining of synthetic 

chemistry, since these methods avoid the preparation and use of 

prefunctionalized starting materials. [1] Recently, we introduced 

carboxylates as efficient cocatalysts for site-selective direct 

arylations and alkylations employing inexpensive ruthenium 

complexes, [2] which were found to display complementary 

selectivities as compared to palladium(0)- or copper(I) catalysts. [3] 

Detailed mechanistic insight into the C–H bond ruthenation step 

set the stage for the development of ruthenium-catalyzed twofold 

C–H bond functionalizations, as well as step-economical 

oxidative annulations of alkynes. [4] These oxidative C–H bond 

functionalizations could be performed in an aerobic fashion under 

ambient air, [5] and provided step-economical access to various 

important bioactive heterocycles. [4] 

references: 

1. a) L. Ackerman, R. Vicente, A. Kapdi, Angew. Chem. Int. 

Ed. 2009, 48, 9792. 

b) L. Ackermann, Modern Arylation Methods, 

Wiley-VCH, Weinheim, 2009. 

c) D. Alberico, M. E. Scott, M. Lautens, Chem. Rev. 2007, 

107, 174. 

2. a) L. Ackermann, P. Novák, R. Vicente, N. Hofmann, 

Angew. Chem. Int. Ed. 2009, 48, 6045. 

b) L. Ackermann, R. Vicente, A. Althammer, Org. Lett. 

2008, 10, 2299. Reviews: 

c) L. Ackermann, Chem. Commun. 2010, 46, 4866. (d) L. 

Ackermann, Chem. Rev. 2011, 111, 1315. 

e) L. Ackermann, A. Althammer, R. Born, Angew. Chem. 

Int. Ed. 2006, 45, 2619. 

f) L. Ackermann, R. Born, P. Álvarez-Bercedo, Angew. 

Chem. Int. Ed. 2007, 46, 6364. 

3. a) L. Ackermann, A. Althammer Angew. Chem. Int. Ed. 

2007, 46, 1627. 

b) L. Ackermann, A. Althammer, S. Fenner, Angew. Chem. 

Int. Ed. 2009, 48, 201. 

4. a) L. Ackermann, A. V. Lygin, N. Hofmann, Angew. Chem. 

Int. Ed. 2011, 50, 6503. 

b) L. Ackermann, J. Pospech, Org. Lett. 2011, 13, 4153. 

5. L. Ackermann, L. Wang, A. V. Lygin, Chem. Sci. 2012, 3, 

177. 

Keywords: C-H activation; Ruthenium; Carboxylate ligands; 

Green chemistry; Homogeneous catalysis; 



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o - 4 4 5 

noBLe MetALS – ContAininG 

PoLyoxoMetALAteS 

n. izArovA 1 , u. Kortz 1 

1 Jacobs University, School of Engineering and Science, 

Bremen, Germany 

Polyoxometalates (POMs) [1] containing noble metals, in 

particular palladium and platinum, have gained special attention 

over the last years. [2-4] Incorporation of noble metal ions in POM 

frameworks allows keeping the former soluble in aqueous or 

organic media and at the same time encapsulated in a fully 

inorganic, thermally and redox stable metal-oxo matrix. Such 

features offer a distinct advantage over noble metal coordination 

complexes displaying a set of organic ligands or organometallic 

moieties, susceptible to oxidative degradation. 

Here we report on a novel series of PdII containing 

polyoxotungstates based on the monolacunary Keggin-type 

[Pd (α-XW O ) ] 2 11 39 2 n- (X = PV , n = 10; [5] X = SiIV , GeIV , n = 12) and 

Dawson-type [Pd (α -P W O ) ] 2 2 2 17 61 2 16- [5] polyanions comprising two 

POM ligands linked via two PdII centers in square-planar 

coordination environment. Several structural isomers vary by 

relative orientation of POM ligands have been isolated. The 

stability of the PdII containing POMs in both aqueous and organic 

solutions has been investigated using 31P and 183W NMR 

spectroscopy. The PtII analogue [Pt (α-PW O ) ] 2 11 39 2 10- has also been 

prepared and characterized in the solid state and solution whereas 

reaction of [α-PW O ] 11 39 7- with PtIV led to rather unexpected 

products. 

references: 

1. Pope M.T., Heteropoly and Isopoly Oxometalates; 

Springer-Verlag: Berlin, 1983. 

2. Putaj P., Lefebvre F., Coord. Chem. Rev. 2001, 255, 

1642–1685. 

3. Lee U., Joo H.-C., Park K.-M., Mal S.S., Kortz U., Keita 

B., Nadjo L., Angew. Chem. Int. Ed. 2008, 47, 793–796. 

4. Izarova N.V., Vankova N., Banerjee A., Jameson G.B., 

Heine T., Schinle F., Hampe O., Kortz U., Angew. Chem. 

Int. Ed. 2010, 49, 7807–7811. 

5. Izarova N.V., Banerjee A., Kortz U., Inorg. Chem. 2011, 

50, 10379–10386. 

Keywords: Polyoxometalates; Noble metals; Palladium; 

Platinum; NMR; 



o - 4 4 6 

PoMziteS: A new CLASS of MiCroPorouS 

inorGAniC frAMeworKS froM A MiniMAL 

BuiLdinG BLoCK LiBrAry 

t. Boyd 1 , S. MitCheLL 1 , d. GABB 1 , d. LonG 1 , 

L. Cronin 1 


Kingdom 

Email: Lee.Cronin@glasgow.uk 

The crown-type heteropolyanion, [P W O ] 8 48 184 40- (hereafter 

referred to as {P W }) is notable for several properties including 

8 48 

its high-negative charge, nanometer-sized cavity and remarkable 

electrochemistry. [1] Its inherent pore space means {P W } is an 

8 48 

ideal candidate as a network synthon, to prepare open framework 

materials with microporosity. [2] The preparation of such 

“POMzite” materials, and open frameworks with designed 

topologies in general, requires control of two main factors; 

statistics (molar ratios of the components) and geometry 

(transition metal coordination modes). Recently, such structures 

have been prepared by introducing first row transition metals to 

aqueous solutions of {P W }, however the desired control in 

8 48 

preparing {P W }-based porous frameworks remains a challenge. 

8 48 

In the case of {P W } assemblies, framework extension is 

8 48 

highly dependent on experimental conditions such as pH, 

temperature and the presence of secondary cations. To understand 

this, and crucially to manipulate it in the formation of targeted 

networks, the binding properties of {P W } were investigated 

8 48 

revealing crown ether-like behaviour of the {P W } ring. 8 48 [3] 

Mapping the binding sites around the ring has enabled structural 

classification and comprehensive topological analysis, shedding 

light on a fascinating class of porous materials. Among many 

desirable properties, POMzite materials have shown remarkable 

single-crystal to single-crystal transformations, tunable and 

gateable guest uptake dependent on the redox state of the 

framework, and great potential as radioactive sequestrants. [2] 

references: 

1. R. Contant, A. Tézé, Inorg. Chem., 1985, 24, 4610-4614. 

2. S. G. Mitchell, C. Streb, H. N. Miras, T. Boyd, D.- 

L. Long, L. Cronin, Nat. Chem., 2010, 2, 308–312. 

3. T. Boyd, S. G. Mitchell, D. Gabb, D.-L. Long, L. Cronin, 

Chem. Eur. J., 2011, 17, 12010-12014. 

Keywords: Polyoxometalates; Supramolecular chemistry; 

Microporous materials; 



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o - 4 4 7 

towArdS rooM teMPerAture 

PhotoMAGnetiC MoLeCuLAr SwitCheS: 

trAnSition MetAL CoMPLexeS with 

PhotoACtive LiGAndS 

M. KhuSniyArov 1 , M. MiLeK 1 , A. witt 1 


Chemistry and Pharmacy, Erlangen, Germany 

Spin-crossover (SCO) and valence-tautomeric (VT) metal 

complexes are among the best known classes of molecular 

bistable systems. Their optical, magnetic and other 

physicochemical properties can be reversibly switched by 

changing the temperature, applied pressure, or irradiation with 

light. Although photoswitching in SCO complexes is well 

documented as a light-induced excited spin state trapping 

(LIESST) effect, this phenomenon is usually operative at low 

temperatures T < 50K. This imposes serious limitations for its 

application in genuine photodevices. The photoswitching in VT 

systems is even more difficult to achieve: temperatures below 20K 

are necessary to stabilize a photoinduced state. 

We develop molecular coordination compounds that should 

overcome low-temperature limitations of the LIESST effect and 

would allow the photoswitching in SCO and VT systems at room 

temperature. To accomplish this we introduce photoactive ligands 

to metal ions in SCO and VT complexes in such a way that 

photoisomerization of the photoactive ligand modifies the ligand 

field. This light-driven modulation should induce a spin transition 

at the metal ion in SCO complexes or a photoinduced electron 

transfer in VT systems. Since the photoisomerization of the ligand 

can be easily accomplished at room temperature, the 

photoswitching of electronic states for both SCO and VT systems 

can be accomplished at room temperature as well. 

We will report on the synthesis, characterization 

and investigation of photophysical properties of a series of 

photoactive ligands and their first-row transition metal 

complexes. Diarylethene-based ligands, capable of 

photocyclization/photocycloreversion in the solid state, are used 

to achieve a photoinduced spin transition in SCO complexes in 

solution and in the solid state. Whereas cis-trans 

photoisomerizable ligands are utilized to obtain a photoinduced 

electron transfer in VT complexes in solution. 

Keywords: Spin crossover; Valence isomerization; Magnetic 

peoperties; Molecular devices; Photochemistry; 

Young inorganic chemistry day – ii 


o - 4 4 8 

rutheniuM CoMPLexeS hoPPinG At LiPid 

BiLAyerS viA A LiGht-SenSitive 

SuPrAMoLeCuLAr Bond 

S. Bonnet 1 

1 Leiden Institute of Chemistry, MCBIM, Leiden, Netherlands 

Our general interest lies in understanding coordination 

chemistry at lipid bilayers. Lipid bilayers represent well-defined 

surfaces, on which individual molecules may be moved by light. 

We have synthesized ruthenium complexes of the type 

[Ru(terpy)(N-N)(SRR’)]2+, where N-N is a diimine chelate, and 

SRR’ a thioether-cholesterol conjugate. Coordination of the sulfur 

atom to the metal complexes and insertion of the cholesterol 

moiety into the lipid bilayer allows for preparing Ru-decorated 

large unilamellar vesicles that were characterized by DLS, 

cryo-TEM, and UV-vis spectroscopy. [1] Upon visible light 

irradiation, the Ru-S coordination bond is selectively cleaved, 

releasing the aqua complex [Ru(terpy)(N-N)(OH2)]2+. When the 

bilayer is made of anionic lipids the “free” aqua Ru complex stays 

close to the membrane and coordinates back to the membraneembedded 

thioether ligand, thus making a new Ru-S bond at the 

bilayer-water interface. With unhindered N-N chelates such 

coordination reaction only takes place upon heating, but with 

hindered N-N chelates it takes place at room temperature within 

tens of minutes. [2] In such case [Ru(terpy)(N-N)(SRR’)]2+ and 

[Ru(terpy)(N-N)(OH2)]2+ are in thermal equilibrium, and the 

Ru-S bond appears as a light-sensitive supramolecular interaction. 

By repeatedly shining light on the vesicular system and leaving it 

in the dark we were able to cleave photochemically and attach 

thermally the Ru complex from and to the membrane, thus 

realizing light-controlled hopping of the metal complex at a lipid 

bilayer surface. We will discuss the influence of the charge of the 

lipids on the ruthenium-membrane interaction, and the possible 

application of such ruthenium-decorated vesicles for drug delivery 

purposes. 

references: 

1. S. Bonnet, B. Limburg, J. D. Meeldijk, R. J. M. Klein 

Gebbink, J. A. Killian, J. Am. Chem. Soc. 2011, 133, 252 

2. Azadeh Bahreman, B. Limburg, R. I. Koning, B. Koster, 

S. Bonnet, submitted. 



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o - 4 4 9 

StruCturAL ControL of PhotoinduCed 

dynAMiCS in 4h-iMidAzoLe rutheniuM 

CoMPLexeS 

M. wäChtLer 1 , S. KuPfer 1 , J. GuthMuLLer 2 , 

M. MAiuri 3 , d. BridA 3 , G. CeruLLo 3 , S. rAu 4 , 

L. GonzALez 5 , J. PoPP 1 , B. dietzeK 6 

1 Friedrich-Schiller University Jena, 

Institute of Physical Chemistry and Abbe Center of Photonics, 

Jena, Germany 

2 Gdansk University of Technology, 

Faculty of Applied Physics and Mathematics, Gdansk, Poland 

3 Polytecnico di Milano, Dipartimento di Fisica, Milano, Italy 

4 University of Ulm, Institute of Inorganic Chemistry I, Ulm, 

Germany 

5 University of Vienna, Institute of Theoretical Chemistry, 

Vienna, Austria 

6 Institute of Photonic Technology (IPHT) e.V. Jena, Jena, 

Germany 

Ruthenium-polypyridine complexes containing 4H-imidazole 

ligands constitute an interesting class of dyes, which are capable 

of absorbing light over a wide range of the visible spectrum. [1, 2] 

This renders these structures interesting for light-harvesting 

applications as, e.g., sensitizers in dye-sensitized solar cells. 

Combining the results of resonance Raman and ultrafast 

transient absorption spectroscopy with TDDFT calculations, the 

photophysical properties of these systems were investigated in 

detail. The results indicate clear structure-dynamics relationships, 

relating excited-state properties to, e.g., the substitution pattern 

of the 4H-imidazole ligand and the polypyridine fragment. In 

terpyridyl-4H-imidazole complexes the introduction of electron- 

-donating/electron-withdrawing substituents in the 4H-imidazole 

sphere allows to tune the relative energetic position of the excited 

states involved in the photoinduced dynamics and hence influence 

the path of intramolecular electron transfer. Surprisingly, upon 

exchanging the terpyridyl-complex fragment by a bipyridyl 

fragment, the decay is significantly accelerated. From these 

investigations conclusions will be drawn for the applicability of 

4H-imidazole based Ruthenium dyes as, e.g., sensitizers in 

dye-sensitized solar cells. 

Acknowledgement: This work was financially supported 

by the Studienstiftung des deutschen Volkes (M.W.), the 

Carl-Zeiss-Stiftung (J.G.), the Fonds der Chemischen 

Industrie (B.D.) and the Thüringer Ministerium für Bildung, 

Wissenschaft und Kultur (Grant-No. B 514-09049, PhotoMIC). 

We acknowledge support from the European Community Access 

to Research Infrastructure Action, Contract RII3-CT-2003- 

506350 (Centre for Ultrafast Science and Biomedical Optics, 

LASERLAB-EUROPE). 

references: 

1. Kupfer, S.; Guthmuller, J.; Wächtler, M.; Losse, S.; Rau, 

S.; Dietzek, B.; Popp, J.; Gonzalez, L. Physical Chemistry 

Chemical Physics 2011, 13, 15580. 

2. Wächtler, M.; Kupfer, S.; Guthmuller, J.; Popp, J.; 

Gonzalez, L.; Dietzek, B. Journal of Physical Chemistry C 

2011, 115, 24004. 

Keywords: Ruthenium; Photophysics; time-resolved 

spectroscopy; ligand effects; substituent effects; 



o - 4 5 0 

ChroMoPhore ContAininG inorGAniCorGAniC 

hyBrid SiLiCA for PhotoniC 

APPLiCAtionS: deSiGn, SoL-GeL SyntheSiS And 

LuMineSCenCe ProPertieS 

M. heMGeSBerG 1 , S. BAy 2 , S. SChütz 3 , y. SChMitt 1 , 

G. dÖrr 1 , S. ernSt 1 , M. GerhArdS 1 , w. KowALSKy 3 , 

t. J. J. MüLLer 2 , w. r. thieL 1 

1 Technische Universität Kaiserslautern, Fachbereich Chemie, 

D-67663 Kaiserslautern, Germany 

2 Heinrich-Heine-Universität, Institut für Organische und 

Supramolekulare Chemie, D-40225 Düsseldorf, Germany 

3 Technische Universität Braunschweig, Institut für 

Hochfrequenztechnik – Labor für Elektrooptik, D-38106 

Braunschweig, Germany 

A variety of arene chromophores has been converted into 

sol-gel precursors for the synthesis of different kinds of micro- or 

mesoporous materials. Using both „classic’ organic synthesis, 

e. g. N-alkylation or ester aminolysis as well as palladium 

catalyzed C-C and C-Si couplings, a large number arenes carrying 

one or more hydrolyzable siloxane groups has been made 

available. For a series of 5-(trimehoxysilyl-)thien-2-yl arenes, the 

detected fluorescences cover almost every part of the VIS 

spectrum. The fluorescence may as well be tuned by treating the 

organosilica with strong Lewis or Bronsted acids or via 

electrochemical processes, as it is the case with hybrid materials 

featuring covalently bound acridone or phenothiazine moieties. 

Depending on the sol-gel method and the precursors used, 

meso- and microstructured hybrid materials have been obtained 

either via co-condensation or post-synthetic grafting. The 

morphology and structure of the silica range from monolithic 

xerogels to finely dispersed MCM-41 or SBA-15. Some of the 

materials incorporate high contents of organic chromophores of 

up to 24 weight-%. Colored or white light emitting glasses can be 

easiliy obtained by immobilization of very low dye contents inside 

a SiO or organosilica framework. 

2 

Non-porous “Fluorogels”, which could be produced in a 

one-pot sol-gel synthesis using the described chromophores, have 

proven to be more stable towards thermal stress than their 

microporous xerogel analogues. The compounds and materials we 

describe may therefore be suitable for a variety of photonic 

applications, including thin film silica coatings and membranes 

for sensors, polymeric optical fibres (POFs) and light emitting 

diodes (LEDs). 

references: 

1. Thiel, W. R. et al., Eur. J. Org. Chem. 2012 (11), 

2142–2151. 

2. Thiel, W. R. et al., Beilstein J. Nanotech. 2011, 2, 

284–292. 

Keywords: Organic-inorganic hybrid composites; Sol-gel 

processes; Mesoporous materials; Microporous materials; 

Fluorescence; 



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Young inorganic chemistry day – iii 

o - 4 5 1 

LiBrArieS of MonodentAte PhoSPhoruS 

LiGAndS for rhodiuM-CAtALyzed 

ASyMMetriC reACtionS 

u. PiAruLLi 1 

1 University of Insubria, Departimento di Scienza e Alta 

Tecnologia, Como, Italy 

In the last decade, monodentate phosphorus ligands (e.g. 

phosphites, phosphonites, phosphoramidites and phosphinamines) 

have held the stage in asymmetric catalysis (Reetz, M. T. Angew. 

Chem. Int. Ed. 2008, 47, 2556-2588). The modular nature of all 

these ligands allows the synthesis of a wide variety of 

representatives, thereby making a combinatorial approach 

possible. An important breakthrough in this area was the use of 

binary mixtures of chiral monodentate P-ligands in several 

asymmetric rhodium catalyzed reactions: by mixing two ligands 

(La and Lb ) in the presence of Rh, three species can be formed: 

RhLaLa , RhLbLb (homocomplexes), and RhLaLb (heterocomplex). 

The heterocombination is often more reactive and more 

(regio-, diastero- and enantio-) selective than either of the two 

homocombinations. The ideal case would constitute an 

equilibrium completely in favor of the heterocomplex [RhLaLb ] 

because then only a single well-defined catalyst would exist in 

the reaction, and the undesired competition of the less selective 

homocomplexes would be avoided. 

More recently, supramolecular approaches to the 

development of new ligands for asymmetric catalysis gained 

momentum (Carboni, S.; Gennari, C.; Pignataro, L.; Piarulli, U. 

Dalton Trans. 2011, 40, 4355-4373). The term ‘supramolecular 

ligand’ encompasses all the ligands possessing, besides the 

atom(s) coordinating the catalytic metal, an additional 

functionality capable of non-covalent interactions (mainly 

hydrogen or coordinative bonds) which can play the following 

role: (i) self-assemble two monodentate ligands to form a 

so-called ‘supramolecular bidentate ligand’; (ii) bind the 

substrate(s) in proximity to the catalytic metal center in analogy 

to metalloenzymes. 

Here we present our approaches to the assembly 

of monodentate P-ligands and their application to several 

Rh-catalyzed asymmetric reactions. 

Keywords: Asymmetric catalysis; Hydrogenation; 

Supramolecular chemistry; Hydrogen bonds; Combinatorial 

Chemistry; 



o - 4 5 2 

noveL n,n'-diAryLAted BiS(MeSoioniC 

CArBene) AMido PinCer LiGAndS And 

APPLiCAtionS of their MetAL CoMPLexeS 

d. Bezuidenhout 1 , G. GuiSAdo-BArrioS 2 , 

B. donnAdieu 2 , G. BertrAnd 2 


Africa 

2 University of California Riverside, UCR-CNRS Joint Research 

Chemistry Laboratory (UMI 2957) Department of Chemistry, 

Riverside, USA 

The tendency of carbenes to bind more strongly to metalcentres 

compared to nitrogen- or phosphorous-based ligands, and 

the robust nature of the corresponding complexes, render the 

search for new stable carbenes as highly desirable due to the wide 

number of potential applications. 

Recently, the preparation of free triazolylidenes (mesoionic 

carbenes MICs) has been reported, exhibiting greater donor 

properties than those of NHCs. [1] In addition, MICs have also 

proven to be competent ligands for transition metal-catalysis. 

Pincer-type ligands are widely known to form robust metal 

complexes, due to the chelating effect. This has been 

demonstrated by the isolation of reactive species, such as metal 

hydride complexes, and has contributed to their application in 

catalysis. [2] Attempts to prepare Ni(II) complexes of bis(NHC) 

amino pincer ligands from the free carbenes have been 

unsuccessful, and only possible via transmetallation. [3] Recently, 

an N-amido-N Ni hydride complex has been isolated but only at 

very low temperature. [4] Access to more stable Ni-H complexes 

should be possible using ligand scaffolds of carbene-amido- 

-carbene type. However, few examples of such ligands exist, and 

none has been complexed to nickel. [2] Therefore, the synthesis of 

novel N,N'-diarylated 1H-1,2,3-triazol-5-ylidene amido pincer 

ligands, featuring either a rigid 3,6-di-tert-butyl-9H-carbazole or 

a more flexible and more donating dialkyl-amido backbone, will 

be presented as well as the corresponding nickel complexes. 

references: 

1. G. Guisado-Barrios, J. Bouffard, B. Donnadieu, G. 

Bertrand, Angew. Chem. Int. Ed., 2010, 49, 4759. 

2. M. Poyatos, J.A. Mata, E. Peris, Chem. Rev. 2009, 109, 

3677. 

3. D. Pugh, A. Boyle, A.A. Danopoulos, Dalton Trans. 2008, 

1087. 

4. J. Breitenfeld, R. Scopelliti, X. Hu, Organometallics 2012, 

31, 2128. 

Keywords: Ni(II) complexes; mesoionic carbenes; pincer 

ligands; 



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chem. Listy 106, s587–s1425 (2012) 



o - 4 5 3 

MoLeCuLAr MetAL-oxideS AS viSiBLe-LiGht 

driven SynthetiC oxyGen evoLvinG 

CAtALyStS 

C. StreB 1 

1 Friedrich-Alexander-University Erlangen-Nuremberg, Institute 

of Inorganic Chemistry II, Erlangen, Germany 

Over the last decades, the activation of small molecules such 

as H O has attracted increasing interest from a wide variety of 

2 

fields of research, as the photochemical splitting of water into 

molecular oxygen and hydrogen can be used to convert solar 

energy into secondary energy carriers. 

Water oxidation is the particularly challenging half-reaction 

and the development of highly stable and highly active water 

oxidation catalysts (WOCs) based on economically viable 

materials is at the forefront of chemical research. 

In our work, we focus on the development of 

purely inorganic, metal-oxide-based systems, so-called 

polyoxometalates, [1] where 3d transition metals are incorporated 

as catalytic sites in a redox-active metal-oxide cluster shell. 

Conceptually, this incorporation can lead to the stabilization of 

catalytic metal centres in high oxidation states [2] which can 

subsequently be used as photoactive redox-centres for visiblelight 

driven electron transfer reactions. [3] 

Here, we show how this concept is employed to access a 

manganese vanadium oxide cluster, {Mn V } as a synthetic mimic 

4 4 

of the oxygen evolving complex (OEC) of Photosystem II. The 

{Mn V } unit features a high-valent [Mn O ] 4 4 4 4 6+ cubane which is 

stabilized by coordination to a tripodal vanadium oxide cluster, 

[V O ] 4 13 6- . The compound can be used as a homogeneous oxygen 

evolving catalyst and it is shown that this water oxidation can be 

driven photochemically using [Ru(bpy) ] 3 2+ as a visible-light 

photosensitizer. The compound shows turnover numbers of ca. 20 

and shows high reversible redox-activity and solution stability. 

The deactivation mechanism under turnover conditions, 

deactivation products and possible stabilization routes are 

discussed. 

references: 

1. D. L. Long, R. Tsunashima, L. Cronin, Angew. Chem. 

Intern. Ed. 2012, 49, 1736. 

2. C. Streb, Dalton Trans. (Perspective), 2012, 41, 1651. 

3. J. Tucher, Y. Wu, L. C. Nye, I. Ivanovic-Burmazovic, M. 

M: Khusniyarov, C. Streb, Dalton Trans. 2012, 41, DOI: 

10.1039/C2DT30304C 

Keywords: water splitting; Photochemistry; Energy 

conversion; Sustainable Chemistry; Catalysis; 



o - 4 5 4 

nuCLeoPhiLiC AryL-fLuorinAtion And 

AryL-hALide exChAnGe reACtionS MediAted 

By A Cu(i)/Cu(iii) CAtALytiC CyCLe 

A. CASitAS 1 , M. CAntA 1 , M. CoStAS 1 , M. SoLA 1 , 

x. riBAS 1 

1 Universitat de Girona, Departament de Química, Girona, 

Spain 

The insertion of a fluorine atom at an aryl group through 

halide exchange reactions is a highly desired transformation 

because of the importance of fluorinated pharmaceuticals and 

agrochemicals. [1] Moreover, the ability to exchange a given halide 

in an aryl group for another halide would facilitate the versatility 

of many transition metal catalyzed cross-coupling reactions, 

[2, 3] 

limited for many processes to the most reactive aryl iodide. 

Copper-catalyzed halide exchange reactions under very mild 

reaction conditions are described for the first time using a family 

of model aryl halide substrates. [4] All combinations of halide 

exchange (I, Br, Cl, F) are observed using catalytic amounts of 

copper(I) in the presence of excess of halide salt in moderate to 

high yields. Strikingly, quantitative fluorination of aryl halide 

substrates is also achieved catalytically at room temperature, using 

common fluoride sources, via the intermediacy of well-defined 

aryl-copper(III)-halide complexes. [4, 5] Experimental and 

computational data support a redox Cu(I)/Cu(III) catalytic cycle 

that involves aryl halide oxidative addition at the copper(I) center, 

followed by halide exchange and reductive elimination steps. 

Additionally, defluorination of the aryl fluoride model system can 

be also achieved with copper(I) at room temperature operating 

under a Cu(I)/Cu(III) redox pair. 

references: 

1. Furuya, T.; Kamlet, A. S; Ritter, T. Nature, 2011, 473, 

470–477. 

2. Sheppard, T. D. Org. Biomol. Chem., 2010, 7, 1043–1052. 

3. Kaplars, A., Buchwald, S. L., J. Am. Chem. Soc., 2002, 

124, 14844-14845. 

4. Casitas, A.; Canta, M.; Sola, M.; Costas, M.; Ribas, X. J. 

Am. Chem Soc. 2011, 133, 19386–19392. 

5. Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.; 

Ribas, X. Chem. Sci., 2010, 1, 326–330. 

Keywords: copper; cross-coupling; fluorides; homogeneous 

catalysis; hypervalent compounds; 



s702 

chem. Listy 106, s587–s1425 (2012) 



o - 4 5 5 

SyntheSiS, StruCture And CAtALytiC 

ProPertieS of trAnSition MetAL CoMPLexeS 

with SPACer-SePArAted BiS-SiLyLene LiGAndS 

S. inoue 1 , M. drieSS 1 

1 Technische Universität Berlin, Institut für Chemie, Berlin, 

Germany 

Silylenes, heavier analogues of carbenes, have attracted 

enormous research interest due to their interesting properties and 

reactivity. Despite the fact that isolable silylenes are no longer 

laboratory curiosities and can serve at the same time as much 

stronger σ-donor and π-acceptor ligands toward transition-metals 

than phosphine ligands, [1] bidentate bis-silylene ligands are 

unknown to date. In the present work, we have synthesized 

spacer-separated bis-silylenes 1,3 and 5 and their 

transition metal complexes 2,4 and 6. Bis-silylene oxide 

LSiOSiL (L7 = 7PhC(NtBu) ) 1 was prepared by 

2 

dehydrochloration of the corresponding disiloxane with base. 

The reaction of 1 with [Ni(COD) ] leads to the first bis-silylene 

2 

oxide nickel complex 2. [2] Catalytic application of nickel 

complex2 as a pre-catalyst for C-C coupling reactions will be 

presented. Furthermore, we will show the synthesis and isolation 

of the first Si(II)-based SiCSi pincer arene 3 and its unusual 

coordination behaviour towards palladium. [3] The electron-rich 

Lewis-donor character of Si(II) in pincer arene 3 gives facile 

access to new oligosilylene-silyl(phenyl) transition-metal 

complexes with potential application in catalytic chemical 

transformations. The successful synthesis, characterization and 

reactivity of the first bis(silylenyl)-substituted ferrocene LSiFcSiL 

5 will be reported. [4] Compound 5 represents one of the strongest 

bidentate M(II)-based s-donor ligands as shown by coordination 

of 5 to [CpCo] to give the cobalt complex 6. In addition, catalytic 

abilities of 6 for the Co-mediated [2+2+2] cycloaddition reactions 

of phenylacetylene and acetonitrile will be reported. 

references: 

1. Inoue, S.; Driess, M. Angew. Chem., Int. Ed. 2011, 50, 5614 

2. Wang, W.; Inoue, S.; Yao, S.; Driess, M. J. Am. Chem. Soc. 

2010, 132, 15890. 

3. Wang, W.; Inoue, S.; Irran, E.; Driess, M., Angew. Chem., 

Int. Ed. 2012, 51, 3691. 

4. Wang, W.; Inoue, S.; Enthaler, S.; Driess, M., Angew. 

Chem., Int. Ed. 2012, accepted. 

Keywords: Silicon; Transition metals; Main group elements; 

Carbene homologues; Si ligands; 




s703 

chem. Listy 106, s587–s1425 (2012) 

life sciences 

Biocatalysis session – i 

o - 0 5 0 

in SiLiCo diSCovery And APPLiCAtion of 

trAnSAMinASeS in orGAniC SyntheSiS 

C. viCKerS 1 , M. hohne 1 , u. BornSCheuer 1 

1 Institute of Biochemistry, Dept. of Biotechnology & Enzyme 

Catalysis, Greifswald, Germany 

Transaminases are versatile enzymes for the synthesis of 

optically pure amines. [1] We have developed a protecting group 

strategy to broaden the substrate range, enhance reaction rates and 

enantioselectivity in w-transaminase-catalyzed kinetic resolutions. [2] 

To enable an efficient asymmetric synthesis to obtain the desired 

amine in high yield, the w-transaminase-catalyzed reaction was 

coupled with pyruvate decarboxylase. [3] This led to a 

considerable shift in the reaction equilibrium by formation of 

carbon dioxide and acetaldehyde. Furthermore, two 

high-throughput methods for the rapid determination of 

conversion and amino donor/acceptor spectrum were developed. [4, 5] 

Finally, a detailed in silico analysis algorithm was designed. This 

enabled the discovery of a toolbox of 17 (R)-selective 

transaminases [6] from >5,000 protein sequences of enzymes from 

the PLP-superfamily with predicted substrate type and 

enantiopreference. These new transaminases showed excellent 

activity and strict (R)-selectivity in the asymmetric synthesis of a 

broad set of chiral amines. [7] 

references: 

1. Höhne, M., Bornscheuer, U.T. ChemCatChem, 2009, 1, 42. 

2. Höhne, M., Kühl, S., Robins, K., Bornscheuer, U.T. 

ChemBioChem, 2007, 9, 363. 

3. Höhne, M., Robins, K., Bornscheuer, U.T. Adv. Synth. 

Catal., 2008, 350, 807. 

4. Schätzle, S., Höhne, M., Robins, K., Bornscheuer U.T. 

Anal. Chem., 2010, 82, 2082. 

5. Schätzle, S., Höhne, M., Redestad, E., Robins, K., 

Bornscheuer U.T. Anal. Chem., 2009, 81, 8244. 

6. Höhne, M., Schätzle, S., Jochens, H., Robins, K., 

Bornscheuer, U.T. Nature Chem. Biol., 2010, 6, 807. 

7. Schätzle, S., Steffen-Munsberg, F., Thontowi, A., Höhne, 

M., Robins, K., Bornscheuer, U.T. Adv. Synth. Catal., 

2011, 353, 2439. 

Keywords: Biocatalysis; Enantioselectivity; Asymmetric 

synthesis; 



o - 0 5 1 

SynthetiC StudieS towArdS dihyPoeStoxide 

M. urooS 1 , C. J. hAyeS 1 

1 The University of Nottingham, School of Chemistry, 

Nottingham, United Kingdom 

The synthetic studies have been described towards 

diterpene derived complex natural product dihypoestoxide via a 

hetero-Diels-Alder dimerisation of its proposed biosynthetic 

precursor, hypoestoxide. The tricyclic spirochroman core of 

dihypoestoxide has been synthesised from geranoic acid in seven 

steps using a hetero-Diels-Alder cycloaddition as a key step, thus 

providing support for the proposed biosynthesis of the natural 

product. Furthermore, analysis of the 13C NMR data obtained 

for all four diastereoisomers of the synthetic spirochroman core 

has allowed us to propose a full stereochemical assignment 

for dihypoestoxide. [1] Our synthetic strategy towards 

hypoestoxide was based on a biomimetic approach by converting 

epiverticillol into its more oxygenated variant, hypoestoxide, 

A hetero-Diels-Alder dimerisation of hypoestoxide would then 

result into dihypoestoxide. 

references: 

1. Uroos, M.; Hayes, C. J. Org. Lett. 2010, 12, 5294. 

Keywords: Synthesis design; Synthetic methods; Natural 

products; biomimetic synthesis; biosynthesis; 



s704 

chem. Listy 106, s587–s1425 (2012) 

life sciences 


o - 0 5 2 

SoLution StruCtureS And ModeLS deSCriBinG 

the thioredoxin SySteM froM 

MyCoBACteriuM tuBerCuLoSiS 

t. neuMAnn 1 , A. oLSon 2 , S. CAi 3 , d. SeM 4 

1 Marquette University, Chemistry, Milwaukee Wi, USA 

2 North Carolina State University, Department of Structural and 

Molecular Biology, Raleigh NC, USA 

3 Marquette University, Chemistry, Milwaukee WI, USA 

4 Concordia University Wisconsin, School of Pharmacy, Mequon 

WI, USA 

Mycobacterium tuberculosis (M. tb) resists oxidative killing 

in part by using the thioredoxin (Trx) system. [1] Trx catalyzes 

thiol-disulfide exchange reactions using redox active cysteine 

thiols to reduce disulfides of other essential proteins, including 

metabolically essential enzymes. [2–4] Oxidized Trx is then reduced 

by thioredoxin reductase (TrxR) in an NADPH dependant 

reaction. [5] The M. tb Trx system consists of three Trx’s (TrxA, 

TrxB, and TrxC) and one Trx reductase (TrxR). TrxR is essential 

for survival. TrxB and TrxC are known substrates of TrxR. [1] TrxA, 

meanwhile, has been reported to not bind to TrxR and to possibly 

be “cryptic”. [1] The M. tb Trx system is dissimilar to the human Trx 

system (25–35% indentity) such that inhibitor specificity for the 

M. tb Trx system should be obtainable. Thus, the M. tb Trx system 

appears to be a viable drug target. [6] 

The objective of this study was to structurally characterize 

oxidized and reduced Trx’s. Solution structures have been 

calculated using standard NMR solution experiments. [7] Our 

studies indicate that TrxA is well-folded in both oxidized and 

reduced states. Structures of the individual Trx’s and binding 

models of the TrxN(N = A, B, or C)-TrxR, constructed from NMR 

titrations of each 15N enriched TrxN and unlabeled TrxR, are 

discussed. [7] These binding models show an empty pocket between 

the Trx and the TrxR, that is targeted for structure-based design 

of uncompetitive inhibitors. 

references: 

1. Akif, M., et. al. J. Bacteriol. 2008, 190, 7087-7095. 

2. Gleason, F. K., et. al. FEMS Microbiol. Lett. 1988, 54, 

271-297. 

3. Ortenberg, R., et. al. Proc. Natl. Acad. Sci. U. S. A. 2004, 

101, 7439-7444. 

4. Powis, G., et. al. Pharmacol. Ther. 1995, 68, 149-173. 

5. Williams, C. H., et. al. Eur. J. Biochem. 2000, 267, 

6110–6117. 

6. Zhang, Z., et. al. Arch. Biochem. Biophys. 1999, 363, 

19–26. 

7. Olson, A.L., et. al. Biochemistry. (under review) 

Keywords: Mycobacterium tuberculosis; nuclear magnetic 

resonance; structural biology; thioredoxin system; 



o - 0 5 3 

the LiGht MAKeS it worKS. MoLeCuLAr 

reACtion dynAMiCS inveStiGAtion At 

uLtrAfASt tiMe SCALe on 

nAdPh:ProtoChLoroPhyLLide 

oxidoreduCtASe 

A. GArrone 1 , S. fey 1 , J. SChäfer 2 , G. herMAnn 1 , 

B. dietzeK 2 

1 Friedrich-Schiller Universität Jena, Institut für Biochemie und 

Biophysik, Jena, Germany 

2 Institut für Photonische Technologien - IPHT, Ultrafast 

Spectroscopy Group, Jena, Germany 

The light driven NADPH:protochlorophyllide 

oxidoreductase (POR) is a key enzyme of chlorophyll 

biosynthesis in angiosperm and cyanobacteria. POR’s unique 

requirement of light to became active, makes the enzyme an 

attractive model to study the dynamics of enzymatic reaction in 

real time. It catalyzes one of the later steps in the chlorophyll 

synthesis pathway: the light-dependent reduction of 

protochlorophyllide (PChlide) to chlorophyllide by trans addition 

of hydrogen across the C17-C18 double bond in the porphyrin 

ring. 

The ternary complex NADPH-POR-PChlide has been 

reconstituted in vitro and the initial reaction steps were followed 

using various spectroscopic tools such as femtosecond/picosecond 

time-resolved absorption and fluorescence spectroscopy in the 

UV/vis spectral range. To highlight the mechanistic interplay 

between the protein moiety and enzyme function, point mutations 

were introduced into the catalytic site. 

Two point mutants, have been produced: an aspartate was 

substituted by methionine and a serine by alanine. Here we report 

our first results on three POR isoforms: POR A and POR B from 

barley (Hordeum vulgare) and POR from Synechocystis. We 

observed that the fluorescence decay time of PChlide when bound 

to the protein WT (wildtype) is about 1 ns longer than in solution. 

We compared the kinetic parameters of the photoreaction with the 

fluorescence decay time for the different isoforms and mutants. 

We also discuss the role of these substitutions in the substrate 

binding site and their effect on the H-bond network, which we 

suggest to play a prominent role in first fast reaction steps. 

Keywords: Enzyme models; Mutagenesis; Time-resolved 

spectroscopy; Oxidoreductases; 



s705 

chem. Listy 106, s587–s1425 (2012) 

life sciences 

Biocatalysis session – ii 

o - 0 5 4 

BioCAtALytiC CArBoxyLAtion 

K. fABer 1 , C. wuenSCh 1 , S. M. GLueCK 1 , J. GroSS 1 , 

G. SteinKeLLner 2 , K. GruBer 2 

1 University of Graz, Department of Chemistry, Graz, Austria 

2 University of Graz, Department of Molecular Biosciences, 

Graz, Austria 

The use of CO as raw material for the synthesis of well- 

2 

defined organic compounds has been rapidly developed over the 

last couple of years. [1] The Kolbe-Schmitt reaction, [2] which is one 

of the major protocols for the production of aromatic carboxylic 

acids on industrial scale, requires harsh reaction conditions (high 

pressure and temperature). In contrast, a biocatalytic method 

based on decarboxylases catalysing the reverse (carboxylation) 

reaction represents a promising ‘green’ alternative for the 

regioselective carboxylation of aromatics. 

In order to evaluate the potential of this novel strategy, 

several benzoic and phenolic acid decarboxylases were applied to 

a range of aromatic substrates, using bicarbonate buffer as 

CO -source. Whereas benzoic acid decarboxylases catalysed the 

2 

selective o-carboxylation of phenolic substrates yielding the 

corresponding o-hydroxybenzoic acids, such as salicylic acid, 

phenolic acid decarboxylases enabled the side-chain 

carboxylation of hydroxystyrene derivatives at C . beta [3] For the 

latter transformation, no chemical counterpart exists. 

Acknowledgements: This study was performed in cooperation 

between the Austrian Centre of Industrial Biotechnology 

(ACIB, funded through the FFG-COMET-Program) and the DK 

Molecular Enzymology (project W9) and support by the FWF, 

BMWFJ, BMVIT, SFG, Standortagentur Tirol and ZIT is 

gratefully acknowledged. 

references: 

1. S. M. Glueck, S. Gümüs, W. M. F. Fabian, K. Faber, 

Chem. Soc. Rev. 2010, 39, 313. 

2. A. S. Lindsey, H. Jeskey, Chem. Rev. 1957, 57, 583. 

3. C. Wuensch, S. M. Glueck, J. Gross, D. Koszelewski, 

M. Schober, K. Faber, Org. Lett. 2012, 14, in press; DOI: 

10.1021/ol300385k. 

Keywords: Carboxylation; carboxylic acids; 

Biotransformations; Biocatalysis; 



o - 0 5 5 

PePtide AdSorPtion on zro , tizr And tio 2 2 

SurfACeS 

t. SChAefer 1 , d. SChArnweBer 2 , M. dArd 3 , 

B. SChwenzer 1 

1 TU Dresden, Biochemistry, Dresden, Germany 

2 TU Dresden, Max Bergmann Center of Biomaterials, Dresden, 

Germany 

3 New York University, College of Dentistry, New York, USA 

Interactions between peptides and inorganic materials are in 

the focus of different research fields like nanotechnology or 

biotechnology as peptides offer new possibilities for surface 

modifications. Utilizing specific surface binding peptides as 

anchor allows adapting various properties such as corrosion 

behavior and surface hydrophobicity or developing sensor 

surfaces. Another important application consists in the 

development of biocompatible implant materials. 

Biofunctionalization of materials can be achieved by the 

conjugation of surface binding peptides with biologically active 

proteins for the oriented immobilization. 

This work investigated on the peptide adsorption on 

different implant materials. The ceramics zirconium oxide (ZrO ), 2 

the metal alloy titanium zircon (TiZr) and the metal titanium 

(c.p.Ti) were examined in regard to the peptide adsorption, the 

kind of interactions and the influences of ion concentration, pH 

value and temperature. 

Eight different peptides were selected from literature. Three 

have already been proven to adsorb to TiO and TiZr and two 

2 

peptides were chosen for adsorption testing on ZrO surfaces. The 

2 

presence of immobilized peptides was confirmed and quantified 

by the following surface analysis methods: an enzymatic assay 

based on biotin-streptavidin interactions, surface plasmon 

resonance (SPR) and fluorescence measurements. 

Three of the eight examined peptide sequences showed 

stable binding to all investigated materials. The surface densities 

of immobilized peptides on ZrO TiZr and TiO range from 20 to 

2, 2 

50 pmol/cm2 . The comparison of the surface densities gained by 

enzymatic assay and the SPR measurements showed equivalent 

results. 

Herein, promising linker molecules for a modification of the 

typical implant materials ZrO , TiZr and Ti were identified. They 

2 

showed stable adsorption even under physiological conditions 

which enables them for biofunctionalization of implants to 

improve their biocompatibility. 

Keywords: Adsorption; Immobilization; Materials science; 

Medicinal chemistry; Peptides; 



s706 

chem. Listy 106, s587–s1425 (2012) 

life sciences 


o - 0 5 6 

MiChAeL Addition of wAter: An enzyMAtiC 

enAntioSeLeCtive APProACh 

u. hAnefeLd 1 

1 Delft University of Technology, Biotechnology, Delft, 

Netherlands 

The addition of water to carbon-carbon double bonds at first 

glance seems straightforward. However, both chemically and 

enzymatically this reaction is very difficult to perform. Indeed the 

Michael addition of water is virtually unknown. [1] However, 

recently a Michael hydrates was identified. Interestingly, the 

hydration product is further oxidized to a 1,3-diketone by the same 

enzyme which was therefore named Michael hydratase ÷ alcohol 

dehydrogenase MhyADH. [2] Fascinatingly, this bifunctional 

enzyme can also be used to catalyze only one of the two steps. 

The hydroxylation of alpha beta unsaturated ketones can be 

uncoupled because in the absence of electron acceptors MhyADH 

functions only as a hydratase, considerably extending the scope 

of the enzyme. To efficiently work with MhyADH, it was purified 

from A. denitrificans and the gene was cloned. The sequence of 

MhyADH revealed that this enzyme belongs to the molybdenumcontaining 

hydroxylases which contain two Fe -S clusters, one 

2 2 

FAD and two molybdopterins which coordinate a molybdate. [3] 

We will report on the purification, characterization and application 

of MhyADH. The focus will be on the enantioselective addition 

of water to the unsaturated conjugated carbonyl compounds. 

Enantioselectivity and substrate scope of the enzyme will be 

discussed and first mechanistic studies will be presented. Another 

problem of this reaction, the position of the equilibrium, will be 

addressed. Although one might assume that the reaction will 

always give quantitative yields since the reaction is performed in 

water and a powerful driving force is therefore present, this is not 

the case. 

references: 

1. Jianfeng Jin and Ulf Hanefeld, Chem. Commun. 2011, 47, 

2502–2510. 

2. Jianfeng Jin, Philip C. Oskam, Sanjib K. Karmee, Adrie J. 

J. Straathof and Ulf Hanefeld, Chem. Commun. 2010, 46, 

8588–8590. 

3. Jianfeng Jin, Adrie J. J. Straathof, Martijn W. H. Pinkse, 

and Ulf Hanefeld, Appl. Microbiol. Biotechnol. 2011, 89, 

1831–1840. 

Keywords: Michael Addition; enzyme catalysis; 

Enantioselectivity; Metalloenzymes; 

Biocatalysis session – iii 


o - 0 5 7 

the queSt for MiLd And effiCient oxidAtive 

AGentS: SynthetiC exPLoitAtion of LACCASeS 

S. rivA 1 

1 Istituto di Chimica del Riconoscimento Molecolare, C.N.R., 

Milano, Italy 

Laccases are oxidoreductases belonging to the multinuclear 

copper-containing oxidases. The overall outcome of their catalytic 

cycle is the reduction of one molecule of oxygen to two molecules 

of water and the concomitant oxidation of four substrate 

molecules to give four radicals. [1, 2] 

Typical substrates of laccases are phenols and aliphatic or 

aromatic amines, the reaction products being mixtures of dimers 

or oligomers derived by the coupling of the reactive radical 

intermediates. For instance, we have exploited these 

biotransformations to isolate new dimeric derivatives of natural 

phenolic derivatives (resveratrol and its analogues, β-estradiol, 

totarol, sylibin). In these studies we have also observed a 

significant influence of the solvent on the reaction outcomes. 

More recently, we have described the use of laccasecatalyzed 

reactions for the selective hydroxylation of ergot 

alkaloids and for the synthesis of the bisindole alkaloid 

anhydrovinblastine. 

Additionally, laccases oxidation of non-phenolic groups, 

particularly benzyl and – more generally – primary alcohols, is 

also possible thanks to the ancillary action of the so-called 

“mediators” (i.e., TEMPO, HBT, ABTS): the oxidation step is 

performed by the oxidized form of a suitable mediator, generated 

by its interaction with the laccase. Accordingly, we have oxidized 

a series of sugar derivatives and of natural glycosides. 

references: 

1. D. Monti, G. Ottolina, G. Carrea, S. Riva Chem. Rev. 

2011, 111, 4111-4140. 

2. S. Riva, Trends Biotechnol. 2006, 24, 219-226. 

Keywords: biocatalysis; oxidoreductases; oxidation; natural 

products; 



s707 

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life sciences 


o - 0 5 8 

quAntitAtive CoMPAriSon of ChirAL 

CAtALyStS’ SeLeCtivity And PerforMAnCe:A 

GeneriC ConCePt iLLuStrAted with 

CyCLododeCAnone MonooxyGenASeAS 

BAeyer-viLLiGer BioCAtALySt 

M. J. finK 1 , f. rudroff 1 , M. d. MihoviLoviC 1 

1 Vienna University of Technology, Institute for Applied 

Synthetic Chemistry, Vienna, Austria 

This work establishes a generic tool for chiral catalyst 

evaluation based on the application-oriented properties activity 

and selectivity, aiming at the prospect to quantitatively compare 

catalysts’ general performance on a multitude of substrates. It is 

designed and intended to serve as decision guidance for 

challenges in catalysis and comprehensible information extraction 

from already recorded but unrefined data sets. The underlying 

algorithm assigns function points to catalytic entities via a 

statistically solid model possessing high flexibility and thus 

generates a relative ranking. This is coupled to an automated 

iterative refinement process towards maximum information 

content in the results employing Shannon Entropy optimization. 

Consequently, the developed work-flow facilitates high 

distinguishability between catalysts even in low-scattering data 

sets. Complementing this, a clearly arranged graphic 

representation permits ready and reliable visual interpretation of 

generality or niche capabilities of catalysts. Usefulness of the title 

concept is demonstrated with the performance evaluation 

of cyclododecanone monooxygenase, a highly versatile 

Baeyer-Villiger enzyme. To retain broad applicability, an opensource 

MATLAB ® script is made available in electronic form. 

Keywords: Biocatalysis; Asymmetric synthesis; Asymmetric 

catalysis; 



o - 0 5 9 

froM rinGS And ChAinS – SyntheSiS 

of hiGh vALue CoMPoundS viA 

MonooxyGenASe-CAtALySed reACtionS 

K. neufeLd 1 , J. PietruSzKA 1 

1 Institute of Bioorganic Chemistry, Chemistry, Juelich, 

Germany 

Chemo-, regio- and enantioselective oxyfunctionalisation of 

carbon-hydrogen bonds is a hot topic in organic chemistry 

enabling scientists to streamline synthetic routes. [1] Therefore, 

monooxygenases as the nature’s key to these transformations bear 

high potential for organic chemistry due to their ability to catalyse 

the selective insertion of an oxygen atom from atmospheric 

dioxygen into carbon-hydrogen bonds of a variety of 

organic compounds. [2] In the current project the P450 BM3 

monooxygenase from Bacillus megaterium was chosen as an 

excellent platform for biocatalysis. It is a well characterised, 

highly active and self-sufficient enzyme [3] which was frequently 

turned into a powerful biocatalyst with desired properties 

concerning substrate spectra and hydroxylation patterns in 

engineering approaches. [4] The design of a versatile mutant library 

for the biocatalyst in combination with the application of stateof-the-art 

assays enables to search for variants that allow the 

selective functionalisation of sterically varying compounds in 

preparative scale. The respective products are required as key 

intermediates in the synthesis of (natural) active compounds. We 

will present our most recent efforts towards the chemoselective 

generation of benzylic alcohols and enantioselective formation of 

allylic alcohols via monooxygenase mutants. 

references: 

1. C. Che, V. K. Lo, C. Zhou, J. Huang, Chem. Soc. Rev. 

2011, 40, 1950. 

2. H. M. Girvan, C. W. Levy, P. Williams, K. Fisher, 

M. R. Cheesman, S. E. J. Rigby, D. Leys, A. W. Munro, 

Biochem. J. 2010, 427, 455. 

3. a) A. M. Sawayama, M. M. Y. Chen, P. Kulanthaivel, 

M. Kuo, H. Hemmerle, F. H. Arnold, Chem. Eur. J. 

2009, 15, 11723; 

b) D. Appel, S. Lutz-Wahl, P. Fischer, U. Schwaneberg, 

R. D. Schmid, J. Biotech. 2001, 88, 167. 

4. R. Fasan, M. M. Chen, N. C. Crook, F. H. Arnold, Angew. 

Chem. Int. Ed. 2007, 48, 8414. 

Keywords: Biocatalysis; Oxidation; Alcohols; 



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o - 0 6 0 

KnowLedGe-BASed (re)deSiGn of 

fLAvin-ContAininG BioCAtALyStS 

M. frAAiJe 1 

1 University of Groningen, Molecular Enzymology group, 

Groningen, Netherlands 

The catalytic potential of enzymes is more and more 

appreciated by the industry and many industrial processes already 

rely on these sophisticated biocatalysts. However, the number of 

reactions catalyzed by enzymes is restricted as enzymes only have 

evolved to catalyze reactions that are physiologically relevant. 

Furthermore, enzymes have adapted to the cellular environment 

in which they have to function. This excludes the existence of 

enzymes that do not fit within the boundaries set by nature. It is a 

great challenge to go beyond these natural boundaries and develop 

methodologies to design ‘unnatural’ tailor-made enzymes. Ideally 

it should become possible to (re)design enzymes to convert 

pre-defined substrates. Such designer enzymes could theoretically 

exhibit unsurpassed catalytic properties and, obviously, will be of 

significant interest for industrial biotechnology. 

Recent work in my research group has focused on discovery 

of new oxidative enzymes and using them as template for enzyme 

redesign studies. Examples of newly discovered and redesigned 

redox enzymes, flavoprotein oxidases and Baeyer-Villiger 

monooxygenases, will be presented. Mechanistic studies on these 

biocatalysts have revealed new insights in how these enzymes 

function. Using this knowledge, it has been possible to create 

artificial enzymes that display catalytic properties not observed 

in nature. Results on some recent enzyme redesign studies will be 

highlighted in which new artificial enzymes were created by 

cofactor redesign. 

Keywords: Biocatalysis; Enzyme catalysis; Oxygenation; 

Oxidation; 

life science Multisymposium – i 


o - 1 8 7 

CheMiCAL BioLoGy thAt ControLS dnA 

StruCture And funCtion 

h. SuGiyAMA 1 , 2 

1 Department of Chemistry, Kyoto University, Japan 

2 Institute for Integrated Cell-Materials Science (iCeMS), Kyoto 

University, Japan 

Fifty years after the discovery of the double-helical structure 

of DNA, the complete sequence of the human genome has been 

determined. Many diseases, including cancer, hereditary, and viral 

diseases, can now be understood at the DNA sequence level. 

Recently, it has been revealed that epigenetic modification plays 

an important role in gene expression, which controls the gene 

expression through DNA methylation and histone modification. 

This is closely related to the cell reprogramming and 

differentiation. We have been undertaking original research on the 

molecular recognition of DNA by antitumor antibiotics, and the 

analysis of atom-specific chemical reaction toward DNA with 

these agents. By reconstituting such knowledge, various 

functionalized sequence-specific DNA binders were synthesized 

as an artificial genetic switch. [1] Furthermore we have 

demonstrated to control the reactions with DNA methylase and 

repair enzymes in a designed DNA nanostructure, DNA origami, 

and analyzed the single reaction using high-speed atomic force 

microscope (AFM). [2] Recent progress of regulation of the 

epigenetic gene expression using designed molecules, and 

elucidation the mechanism using single molecular imaging 

technique will be discussed. 

references: 

1. a) Synthetic Small Molecules for Epigenetic Activation of 

Pluripotency Genes In Mouse Embryonic Fibroblasts. 

Pandian, G.N.; Shinohara, K.; Ohtsuki, A.; Nakano, Y.; 

Masafumi, M.; Bando, T.; Nagase, H.; Yamada, Y.; 

Watanabe, A.; Terada, N.; Sato, S.; Morinaga, H.; 

Sugiyama, H. ChemBioChem, 2011, 12, 2822–2828. 

b) A Synthetic Small Molecule for Rapid Induction of 

Multiple Pluripotency Genes in Mouse Embryonic 

Fibroblast. Ganesh Pandian, N.; Nakano, Y; Sato, S; 

Morinaga, H; Bando, T; Nagase, H; Sugiyama, H. 

Scientific Reports, In Press. 

c) Programmable Genetic Switiches to Control 

Transcrpitional machinery of Pluripotency. Ganesh 

Pandian, N; Sugiyama, H. Biotechnol. J. 2012, 7, 

798–809. 

2. a) A DNA-Based Molecular Motor that can Navigate a 

Network of Tracks. Wickham, S.F.J; Bath, J.; Katsuda, 

Y.; Endo, M.; Hidaka, K.; Sugiyama, H.; Tuberfield, 

A.J. Nature Nanotechnol., 2012, 7, 169–173. 

b) Single-Molecule Analysis Using DNA 

Origami. Rajendran, A.; Endo, M.; Sugiyama, 

H. Angew. Chem. Int. Ed., 2012, 51, 874–890. 

Keywords: 



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o - 1 8 8 

new BiSPidine-derivAtive for duAL-ModALity 

iMAGinG 

S. fähneMAnn 1 , M. wALther 1 , h. StePhAn 1 , 

w. KrAuS 2 , f. eMMerLinG 2 , J. SteinBACh 1 

1 Helmholtz-Zentrum Dresden-Rossendorf, Institute of 

Radiopharmacy, Dresden, Germany 

2 Bundesanstalt für Materialforschung und -prüfung, 

Röntgenstruktur- und Phasenanalyase, Berlin, Germany 

The diagnostic evaluation and treatment of complex 

diseases, like cancer, is very difficult using only standing alone 

methods with their individual limitations. To overcome these 

restrictions, a combination of different imaging modalities will be 

conceivable. The radionuclide based positron emission 

tomography (PET) and single photon emission computed 

tomography (SPECT) are useful for functional imaging. To obtain 

anatomical information, computer tomography (CT) and 

magnetic resonance imaging (MRI) can be used, whereas 

fluorescence-based optical imaging finds application in surgery 

guidance. [1] 

Extensive research effort has shown, that 

3,7-diazabicyclo[3.3.1]nonane-derivatives (bispidines) built up 

thermodynamic and kinetic very stable complexes with copper(II) 

ions (logK = 16.28). [2] Different functional groups of the backbone 

(hydroxyl and carboxyl groups) provide the opportunity for 

simultaneous attachment of dyes and biomolecules 

(e. g. peptides, proteins, antibodies) as vector molecules. After 

that functionalization, the complexation of radioactive copper 

isotopes (61Cu, 64Cu, 67Cu) allows visualization of cancer tissue 

with PET and radiotherapy. 

The hydroxyl group at C9 was functionalized using 

nitrophenyl chloroformate for active ester generation. Therefore, 

a fluorescence label could be coupled to the bispidine by urethane 

bond formation. 

We will report about the versatility of bispidines as 

compounds to realize different functionalities in one molecule. 

The synthesis and characterization of such derivative, and 

radiolabeling experiments with the PET-radionuclide 64Cu 

will be discussed. 

references: 

1. Kuil, J., Velders, A. H., van Leeuwen, F. W. B.; 

Bioconjugate Chem. 2010, 21, 1709-1719. 

2. Juran, S., Walther, M., Stephan, H., Bergmann, R., 

Steinbach, J., Kraus, W., Emmerling, F., Comba, P.; 


Keywords: copper; radiopharmaceuticals; imaging agents; 



o - 1 8 9 

MuLtifunCtionAL PePtide nuCLeiC ACidS (PnA) 

for MiCrornA tArGetinG 

r. CorrAdini 1 , A. MAniCArdi 1 , f. AiMi 1 , 

t. tedeSChi 1 , S. SforzA 1 , r. MArCheLLi 1 , 

e. fABBri 2 , n. BiAnChi 2 , r. GAMBAri 2 

1 University of Parma, Department of Organic and Industrial 

Chemistry, Parma, Italy 

2 University of Ferrara-BioPharmaNet, Department of 

Biochemistry and Molecular Biology, Ferrara, Italy 

Peptide nucleic acids (PNA), and their modification are 

extensively used for targeting mRNA in the antisense approach 

for the down-regulation of the expression of target genes. [1] 

Micro-RNA (miR) are regulatory short (19–23 bp) dsRNA which 

modulate gene expression of highly relevant biological functions 

such as differentiation, cell cycle and apoptosis, through mRNA 

degradation. Inhibition of miR activity by specific molecules 

(anti-miR,) has been shown to be of great interest in drug 

development. [2] 

In the present communication we describe the synthesis of 

anti-miR PNA either conjugated with a carrier peptide or bearing 

modified residues along the chain, PNA of high affinity and high 

specificity for miR210 and miR 221, involved in erythroid 

differentiation and tumor progression respectively were obtained. 

Modified PNA showed improved biovailability and effectively 

entered into tumor cells and exerted anti-miR acivity, [3] leading to 

up-regulation of genes. Backbone modified PNAs, bearing 

arginine side chains either at C2 or C5 carbon atom of the PNA 

backbone showed improved cellular uptake, and higher 

biostability than the peptide-conjugated, and effectiveness of these 

compounds was shown to depend on the type of substitution; and 

on the distribution of charges within the PNA strand. [4] 

references: 

1. R. Corradini, S. Sforza, T. Tedeschi, F. Totsingan, 

A. Manicardi, R. Marchelli. Curr Top Med Chem 2011, 11, 

1535-1554 

2. R. Gambari, E. Fabbri, M. Borgatti, I. Lampronti, 

A. Finotti, E. Brognara, N. Bianchi, A. Manicardi, R. 

Marchelli, R. Corradini Biochemical Pharm 2011, 82, 

1416-1429. 

3. E. Fabbri,A. Manicardi , , T. Tedeschi, S.Sforza,N. Bianchi, 

E. Brognara, A. Finotti,G. Breveglieri , M. Borgatti, 

R. Corradini, R. Marchelli, R. Gambari ChemMedChem 

2011, 6, 2192-2202. 

4. A. Manicardi, E. Fabbri, T. Tedeschi, S. Sforza, 

N. Bianchi, E. Brognara, R. Gambari, R. Marchelli, 

R. Corradini ChemBiochem 2012, in press 

Keywords: Peptide Nucleic Acid; Modified Backbone; 

Anti-miR; 



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life sciences 


o - 1 9 0 

SinGLe verSuS douBLe LAyer fiBriLLAr 

AMyLoid-BetA oLiGoMerS: Size doeS MAtter 

A. h. C. horn 1 , A. KAhLer 1 , h. StiCht 1 

1 Institute for Biochemistry, Medicine, Erlangen, Germany 

Alzheimer’s disease (AD), the most common form of 

dementia world-wide, belongs to the class of protein misfolding 

diseases. The associated molecule is the 39 to 42-residues long 

amyloid-β peptide, that aggregates into oligomers, filaments, and 

fibrils found in plaque deposits in the brain of AD patients. 

Notwithstanding the large efforts of the past decades, a 

viable cure for this disease is still not available. One reason for 

this is Aβ’s conformational flexibility and structural heterogeneity 

in solution paired with its aggregation tendency. This renders the 

determination and isolation of distinct Aβ structures 

experimentally challenging. Especially the soluble oligomers, that 

are nowadays thought to be the causative agents in AD, may adopt 

a plethora of conformations in vivo. 

In this context, we used molecular dynamics simulations to 

investigate the structural stability of fibrillar single and double 

layer Aβ42 oligomers of different size (4-mer to 48-mer), because 

it is known from experiment, that Aβ fibrils can be dissolved into 

toxic oligomers. 

We found that there is a clear correlation between oligomer 

size and preference for double layer structure: Large oligomers 

display an enhanced stability in double layer conformation, 

whereas small oligomers prefer the single layer structure. On the 

other hand, large single layer oligomers disrupt into smaller 

oligomers, while small double layer oligomers collapse or are 

energetically unfavorable. From our simulations, we deduce that 

the critical number of oligomers to construct a stable Aβ double 

layer is in the range of 10 to 12. 

In a more general picture, longitudinal growth along a single 

layer is limited by the increasing structural instability. Lateral 

growth, i.e. forming a double layer, creates stable mini-fibrils. 

These may act as seeds for further stable fibril growth. Our 

findings are important for the de-novo design of potential drugs 

targeting Aβ aggregation. 

Keywords: Molecular dynamics; Amyloid beta-peptides; 

Conformation analysis; 

life science Multisymposium – ii 


o - 1 9 1 

nAnoMAteriAL And Protein enGineerinG for 

ModuLAtinG iMMune reSPonSeS 

J. huBBeLL 1 

1 Ecole Polytechnique Federale de Lausanne, Institute of 

Bioengineering, Lausanne, Switzerland 

Biomaterials research has advanced to a state where 

materials are desined to possess specific biological, drug-like 

activity. Here, we will present work on materials and protein 

engienering approaches for applications in immunotherapeutics. 

Nanomaterials present intersting opportunities in the context of 

vaccination. Very small particles, in the sub-100 nm range, can 

traffic by interstitial flow to into the draining lymphatics and thus 

efficiently access dendritic cells resident there. Trafficking across 

mucosal surfaces can be efficient as well. We hae developed 

approaches by which to conjugate antigen and adjuvant molecules 

in a manner that leads to particularly efficient antigen 

cross-presentation and inducation of cellular immune responses, 

of relevance in vaccination versus infectious diseases and cancer. 

We are also interested in approaches by which to prevent or 

erase immune responses, exploiting the body’s mechanisms for 

maintenance of peripheral tolerance. Antigen collected from 

apoptotic cells is presented in a manner such that peripheral 

tolerance is induced or maintained to those antigens. We are 

exploring protein engineering approaches that might harness this 

mechanism, engineering peptide and protein antigens to bind to 

the surfaces of circulating erythrocytes, wich are cleared and 

processed as they age. We have observed that this leads to antigenspecific 

deletion of both CD4+ and CD8+ T cells. We will show 

potential applicability of this approach in both preventing 

immunity to protein drugs and in blunting autoimmune-induced 

pathology. 

Keywords: Biomaterial; Nanoparticle; 



s711 

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life sciences 


o - 1 9 2 

SyntheSiS, ProPertieS, And APPLiCAtionS of 

CovALentLy tethered MiniCoLLAGenS 

f. weiher 1 , A. Geyer 1 

1 Philipps University Marburg, Organic Chemistry, Marburg, 

Germany 

C-terminal capping of three collagen peptides yields 

synthetic minicollagens of scalable lengths and melting 

temperatures. The covalently tethered triple helix is a 

non-bendable rod whose thermodynamic stability significantly 

differs from a monomeric PUG strand. Minicollagens adopt triple 

helical conformations independent of pH and buffers and 

therefore can serve as building blocks for molecular bionic 

designs. Their spectroscopic properties and an example of a 

[1, 2] 

possible application in material science are presented here. 

Chiral triamines can fit the required stagger of the triple 

helix. These capping groups contribute to triple helix stabilization 

by ensuring an in-phase start of the triple helix. The cap optimized 

in length and chirality is improving the melting temperature by 

more than 20 °C. In this presentation we show that trimeric 

architectures of minicollagens up to sizes of almost 90 amino 

acids can be synthesized within one day in good qualities. [3] 

Higher melting temperatures increase the range for 

minicollagens of certain lengths to exhibit a sigmoid melting 

behaviour. Physicochemical analyses also state a fast folding of 

those collagen derivatives. Contrasting previously synthesized 

collagens, the molecules presented here exhibit triple helical 

folding without incubation times. This opens new application 

fields for the minicollagens. One example from Material Science 

will be presented. [4] 

references: 

1. A. Persikov, J. Ramshaw, A. Kirkpatrick, B. Brodsky, 

J. Am. Chem. Soc. 2003, 125, 11500. 

2. M. D. Shoulders, R. T. Raines, Annu. Rev. Biochem 2009, 

78, 929. 

3. F. Weiher, A. Geyer, manuscript in preparation. 

4. F. Weiher, M. Schatz, C. Steinem, A. Geyer, manuscript in 

preparation. 

Keywords: Peptides; Collagen; Sold-Phase Peptide-Synthesis; 



o - 1 9 3 

dnA reCoGnition: new SPeCifiC AGentS And 

fLuoreSCent ProBeS 

o. vázquez 1 , M. i. SánChez 1 , M. e. vázquez 1 , 

J. L. MASCArenAS 1 

1 Centro Singular de Investigación en Química Biológica y 

Materiales Moleculares, Departamento de química orgánica, 

Santiago de Compostela (A Coru, Spain 

Deciphering the human genome has opened new 

perspectives in biomedical research, promising improved 

diagnostic techniques and personalized therapies. However, to 

fully exploit the knowledge about our genes, it is necessary to 

develop probes capable of targeting and sensing specific DNA 

sequences. In the recent decades there have been significant 

contributions in the area of dsDNA recognition. However, despite 

the enormous developments in this area, specific targeting of 

particular DNA sequences still remains an unsolved problem in 

chemical biology. 

In this context, during the last decade our group has reported 

some successful discoveries in the design, synthesis and study of 

non-natural peptide derivatives, which despite being structurally 

simpler, are capable of mimicking the DNA binding properties of 

the transcription factors. [1] Here, we present our steps forward in 

this field. 

a) Development of specific DNA recognition by synthetic, 

monomeric Cys His Zinc finger peptide conjugated to a 

2 2 

minor groove binder. [2] 

b) Discovery of the fluorogenic properties of the DNA 

minor groove binder BAPPA and applications. [3] 

c) Straightforward access to bisbenzamidine DNA binders 

and use as versatile adaptors for DNA-promoted process. [4] 

references: 

1. a) Vázquez, M. E.; Caamano, A. M. Martínez-Costas, J; 

Castedo, L.; Mascarenas, J. L., Angew. Chem. Int. Ed. 

2001, 40, 4723–4725; 

b) Blanco, J. B.; Vázquez, M. E.; Castedo, L.; Mascarenas, 

J. L., ChemBioChem 2005, 6, 2173–2177. 

2. Vázquez O.; Vázquez, M. E.; Blanco, J. B.; Castedo, L. 

Mascarenas, J. L., Angew. Chem. Int. Ed. 2007, 46, 

6886–6890; 

3. a) Vázquez, O.; Sánchez, M. I.; Martínez-Costas, J.; 

Vázquez, M. E.; Mascarenas, J. L. Org. Lett. 2010, 12, 

216–219. 

b) Vázquez, O.; Sánchez, M. I.; Mascarenas, J. L.; 

Vázquez, E. M. Chem. Commun. 2010,14, 5518–20. 

4. Sánchez, M. I.; Vázquez, O.; Martínez-Costas, J.; 

Vázquez, M. E.; Mascarenas J. L. Chem. Sci in press 

DOI:10.1039 / C2SC00027J. 

Keywords: Molecular recognition; DNA; Fluorescence; 

Peptides; Transcription factors; 



s712 

chem. Listy 106, s587–s1425 (2012) 

life sciences 

life science Multisymposium – iii 

o - 1 9 4 

oLiGonuCLeotideS for SPLiCe-SwitChinG And 

StrAnd-invASion 

C. i. e. SMith 1 

1 Karolinska Institutet, Laboratory Medicine, Stockholm, 

Sweden 

Email: edvard.smith@ki.se 

Synthetic nucleic acid chemistry has made possible the 

generation of oligonucleotides (ONs) with special features 

allowing potent effects in biological systems. We have recently 

developed highly efficient ONs for the correction of pseudo-exon 

inclusions secondary to mutations in the BTK gene causing 

recessive, X-linked agammaglobulinemia (XLA). In XLA there 

is a differentiation block in the B-lymphocyte lineage resulting 

the absence of B-lymphocytes and plasma cell in affected 

individuals. Bacterial artificial chromosome (BAC) transgenic 

mice carrying the mutated human BTK gene were generated as a 

new model for the study of splice-switching. Following 

algorithm-based identification of suitable target sequences 

efficient correction of both mRNA and protein was observed using 

locked nucleic acid (LNA) as well as morpholino-based ONs in 

both reporter cell assays and in primary cells from both patients 

and BAC-transgenic mice. 

We have also developed methods for strand-invasion into 

duplex DNA. The original “Zorro-LNA” construct is formed by 

two ONs, each targeting one of the two strands in a DNA duplex, 

and tethered by a hybridizing linker sequence. We have also 

studied single-stranded Zorro-LNAs devoid of any hybridizing 

region, but instead equipped with a single linker of different 

chemistry. Both of these compounds strand-invade DNA as 

evidenced by S1 nuclease assays. We have recently investigated 

the effect of Zorro-LNA on the expression of Huntingtin (HTT) 

mRNA in transfected cells. The HTT gene is mutated in patients 

with the dominantly inherited, neurodegenerative disorder named 

Huntington’s disease. By scanning the HTT gene, six different 

regions were identified and tested. Two of them showed robust 

down-regulation of HTT transcripts, when targeted by 

Zorro-LNAs. Reduced expression was also obtained in cell-lines 

from patients with Huntington’s disease. 

Keywords: DNA; Oligonucleotides; 



o - 1 9 5 

inK-Jet PrintinG for druG SCreeninG By 

droPLet MiCroArrAyS 

B. PiGnAtAro 1 , G. ArrABito 2 

1 University of Palermo, Department of Chemistry, Palermo, 

Italy 

2 Scuola Superiore di Catania, Chemistry Department, Catania, 

Italy 

Drug screening is the complex process of retrieving 

chemical compounds able to modulate the activity of biological 

targets which are of interest for a disease. Conventional 

miniaturized drug screening technologies require time and reagent 

consuming (micro-, nanoliter scale) instrumental tools, liquid 

handling robotics and complex detectors. Here we show a 

low-cost and efficient drug screening methodology based on 

inkjet printing for delivering molecular systems in picoliter 

volumes coupled with easily-implemented detection tools for 

probing target-drug interaction. We firstly show up a screening 

platform for a model enzyme/substrate couple and we extend this 

approach to systems of clear interest for medicinal chemistry. 

The approach was initially proved with a model enzyme 

system like Glucose Oxidase substrate covalently linked to a 

functionalized silicon oxide support. [1] On this support an 

enzymatic substrate (D-glucose)/inhibitor (D-glucal) couple was 

dispensed. A simple colorimetric detection method based on the 

production of a red quinoneimine dye in a reaction catalyzed by 

Horseradish Peroxidase proved the screening capability of the 

microarray at the single spot. Occurrence of competitive inhibition 

was verified at the solid-liquid interface with a similar behavior 

occurring for such system in a solution phase. [2] 

Afterwards, this methodology has been extended to other 

systems including CYP450 enzymes like CYP3A4, one of the 

main targets for the phase I drug metabolism via a droplet 

microreactors arrays containing CYP3A4 enzyme mixed 

with model inhibitors (i.e. ketoconazole and erythromycin) 

and enzymatic chemiluminescent substrates (Luciferin- 

Isopropylacetate). Enzymatic activity in picoliter liquid spots was 

detected by using a low cost optical method. Accordingly, 

bioluminescence given by D-luciferin leads to a production of 

photons that increase spot brightness which can be quantified by 

Charge-coupled device camera. 

references: 

1. G. Arrabito, C. Musumeci, V. Aiello, S. Libertino, 

G. Compagnini and B. Pignataro, Langmuir, 2009, 25, 

6312-6318. 

2. G. Arrabito and B. Pignataro, Analytical Chemistry, 2010, 

82, 3104-3107. 

Keywords: drug screening; inkjet printing; enzymes; 

microarrays; biotechnology; 



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life sciences 


o - 1 9 6 

deSiGn And SyntheSiS of noveL GquAdruPLex 

dnA StABiLizinG MoLeCuLeS 

S. GeorGiAdeS 1 , r. viLAr 2 


2 Imperial College London, Chemistry, London, 


G-Quadruplex DNA structures have gained enormous 

attention in recent years, due to their implication in critical 

biological processes, most notably cancer cell “immortalization” 

by means of telomere elongation by the enzyme telomerase, and 

the regulation of transcription of key proto-oncogenes (e.g. c-myc, 

c-kit). Both processes are linked to tumor formation, which has 

prompted efforts in the direction of development of small 

molecules with the ability to stabilize or induce G-quadruplexes 

in the G-rich DNA sequences of the human telomere or oncogene 

promoter regions. Stabilization of a G-quadruplex in these regions 

prevents recognition of the affected sequences by telomerase or 

the transcriptional machinery respectively, which results in 

arresting telomere elongation or oncogene expression, thus 

providing new promising anti-cancer mechanisms. As part of a 

broader effort to develop new classes of anti-cancer therapeutic 

agents and chemical probes for investigating yet unknown aspects 

of cancer biology pertaining to G-quadruplexes, we have designed 

and synthesized both organic and organometallic platinum-based 

compounds, as well as their conjugates with peptide nucleic acids 

(PNAs). Our design and synthetic methods for the preparation of 

these compounds, intended to be evaluated for their ability 

to induce or stabilize the G-quadruplex structure in 

biologically-relevant G-rich DNA sequences, will be described. 

Keywords: antitumor agents; cancer; G-quadruplexes; solidphase 

synthesis; platinum; 



o - 1 9 7 

dnA dAMAGe CheMiStry in nuCLeoSoMe Core 

PArtiCLeS 

M. GreenBerG 1 

1 Johns Hopkins University, Chemistry, Baltimore, USA 

At one time the histone proteins were believed only to 

provide structural support for nuclear DNA. It is now understood 

that histone post-translational modification within nucleosomes 

plays a large role in gene regulation. The nucleosome is also 

increasingly recognized to affect other biochemical processes, 

including the rate at which DNA lesions are repaired. Due to the 

instability of some DNA lesions, such as abasic sites, decreased 

repair efficiency poses other problems such as increased amounts 

of strand scission. We have asked whether the histone proteins, 

which contain a large number of basic amino acids, actively 

participates in DNA damage chemistry? By taking advantage of 

methods that enable one to reconstitute nucleosomes containing 

DNA lesions at defined sites, we have shown that the histone 

proteins in nucleosome core particles catalyze DNA strand 

scission at abasic sites. The details of this chemistry and 

implications will be discussed. 

Keywords: DNA damage; nucleosomes; mechanism; 



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life sciences 

Medicinal Chemistry session – i 

o - 3 2 1 

StereoSeLeCtive ACCeSS to new SCAffoLdS 

By PhotoCheMiCAL reACtionS 

t. BACh 1 

1 Technische Universität München, Lehrstuhl für Organische 

Chemie I, Garching, Germany 

Among all light-driven reactions, the [2+2] photo - 

cycloaddition is the synthetically most useful transformation. [1] 

In this lecture, most recent developments in the field will be 

discussed. [2] Particular emphasis is given on all aspects of 

stereoselectivity and on applications to the synthesis of new 

scaffolds. The quest for enantioselective [2+2] photocycloaddition 

reactions employing appro-priate chiral photocatalysts presents a 

formidable challenge for the pro-duction of biologically relevant 

compounds. Chiral catalysts for this endeavour have been 

developed in our laboratories and will also be presented in the 

course of the lecture. [3, 4] 

references: 

1. J. P. Hehn, T. Bach, Angew. Chem. Int. Ed. 2011, 50, 

1000–1045. 

2. P. Lu, T. Bach, Angew. Chem. Int. Ed. 2012, 51, 

1261–1264. 

3. C. Müller, A. Bauer, M. M. Maturi, M. C. Cuquerella, 

M. A. Miranda, T. Bach, J. Am. Chem. Soc. 2011, 133, 

16689–16697. 

4. R. Brimioulle, H. Guo, T. Bach, Chem. Eur. J. 2012, 18, 

in print. 

Keywords: cycloaddition; enantioselectivity; medicinal 

chemistry; photochemistry; strained molecules; 



o - 3 2 2 

ConCiSe routeS for exPAndinG the diverSity 

of SeLeCtive CyCLoPePtideS hiStone 

deACetyLASe inhiBitorS 

M. trAoré 1 , M. PeuChMAur 2 , y. S. wonG 2 , 

f. Mietton 3 , d. MAuBon 3 , A. BouGdour 3 , 

h. PeLLoux 3 , M. A. hAKiMi 3 

1 Université Joseph Fourier-Grenoble 1, Département de 

Pharmacochimie Moléculaire, Grenoble cedex 9, France 



3 Université Joseph Fourier-Grenoble 1, Laboratoire Adaptation 

et Pathogénie des Micro-organisme, Grenoble cedex 9, France 

Recently, we identified the natural product cyclopeptide 

FR235222, as a highly potent histone deacetylase inhibitor 

(HDACi), efficient at 8 nM on Toxoplasma gondii, the 

apicomplexa parasite responsible for toxoplasmosis, albeit with a 

poor selectivity index (efficiency against the parasite compared 

to cytotoxicity on human cell) with SI = 12. [1] We demonstrated 

that the inhibition of histone deacetylase HDAC3 with this 

HDACi induced epigenetic modifications, which strongly affected 

strain virulence at the tachyzoite and bradyzoite stages of the 

parasitic life cycle. [1, 2] This dual efficiency with a bioactive 

molecule on two distinct stages of the parasitic life cycle is 

unprecedented and outlines the key role of targeting the epigenetic 

mechanisms to control parasite proliferation. 

The design of easy adjustable/customisable syntheses and 

according to the Diversity Oriented Synthesis principles 

(variations on appendages and skeletal diversities) is essential to 

reduce the time in the optimizing process by a direct access to 

structurally diverse and relevant bioactive products. We present 

in this communication our new synthetic strategy involving 

post-transformation reactions (appendage and skeletal 

modulations) on a common cyclopeptide scaffold that affords new 

bioactive HDACi in only one or two steps. These new structures 

combine structural features ranging from FR235222 to largazole 

and have shed light on important structure-activity relationships. 

As a result, we managed to optimize new synthetic cyclopeptide 

HDACi, which retain their efficacy against the parasite at 

10-20 nM, and with better selectivity indexes (SI = 40-60). 

Interestingly, for analogues related to largazole family, we 

observed a reversal selectivity of our new HDACi. 

references: 

1. A. Bougdour, D. Maubon, P. Baldacci, P. Ortet, O. 

Bastien, A. Bouillon, J.-C. Barale, H. Pelloux, R. Menard 

and M.-A. Hakimi, J. Exp. Med., 2009, 206, 953-966. 

2. D. Maubon, A. Bougdour, M.-P. Brenier-Pinchart, 

Y.-S. Wong, A. Curt, M.-A. Hakimi and H. Pelloux, 

Antimicrob. Agents Chemother., 2010, 54, 4843-4850. 

Keywords: Antiprotozoal agents; Molecular diversity; Medical 




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chem. Listy 106, s587–s1425 (2012) 

life sciences 


o - 3 2 3 

PoLyoxoMetALAteS AS verSAtiLe enzyMe 

inhiBitorS 

h. StePhAn 1 , C. e. MüLLer 2 

1 Helmholtz-Zentrum Dresden-Rossendorf, 

Institute of Radiopharmacy, Dresden, Germany 

2 Universität Bonn, Pharmaceutical Institute, Dresden, Germany 

Polynuclear metal compounds may have considerable 

potential as metallic drugs. The most prominent representatives 

are polyoxometalates (POMs) which have been investigated since 

the last third of the 19th century. In addition to applications in 

catalysis, separation, analysis, and as electron-dense imaging 

agents, some of these substances have been shown to exhibit 

biological activity in vitro as well as in vivo ranging from anticancer, 

antibiotic, and antiviral to anti-diabetic effects. 

Polyoxometalates represent a diverse ensemble of 

nanostructures with an almost infinite variability of chemical, 

physical and biological properties. The size of typical covalent 

bridged cluster compounds is in the range from 1 to 3 nm. The 

attachment of special surface groups on the periphery of cluster 

compounds may result in self-assembled non-covalent organized 

structures larger than 5 nm which are characteristic for biomolecules, 

such as enzymes. Cells of mammalian organisms are 

typically 10 to 30 µm. However, sub-cellular organelle 

dimensions are smaller and range in sub-µm sizes. This 

comparison of size dimension illustrates that polymetalates are 

small enough to allow the cell membrane to be penetrated without 

too much interference. Evidently, some types of polyoxometalates 

are able to be transported into cells, particularly into mitochondria. 

However, many of such polyanions are only slightly taken up by 

cells, obviously caused by negatively charged membranes. 

On the way to explore the biological activity of polynuclear 

cluster compounds, we recently recognised POMs as a new class 

of potent enzyme inhibitors. Certain polyanionic complexes are 

able to inhibit extracellular E-NTPDases (ecto-nucleoside 

triphosphate diphosphohydrolases) that are surface-located 

nucleotide-hydrolyzing enzymes involved in the regulation of 

signaling cascades by activating P2 (nucleotide) receptors. 

We want to present a brief overview about the potential of 

POMs as E-NTPDase inhibitors and P2 receptor antagonists. 

Keywords: Enzyme; Inhibitors; Polyoxometalates; 



o - 3 2 4 

CyCLAMMonoProPioniC ACid- A ProMiSinG 

CheLAtinG SySteM for rAdioCoPPer iSotoPeS 

M. KuBeiL 1 , L. PeSCheL 1 , h. StePhAn 1 , 

J. SteinBACh 1 

1 Helmholtz-Zentrum Dresden-Rossendorf, 

Institute of Radiopharmacy, Dresden, Germany 

A wide variety of radiometal-chelating bioconjugates have 

been studied intensively to design effective radiopharmaceuticals 

for diagnostic and therapeutic purposes. Azamacrocycles offer an 

enormous potential to achieve highly stable radiometal complexes 

and allow the covalent attachment of targeting and/or fluorescence 

units at the ligand skeleton. In this context, 1,4,8,11- 

-tetraazacyclotetradecane-1,4,8,11-tetraacetic acid (TETA) is 

quite often used for the development of copper-based 

target-specific radiopharmaceuticals, although demetallation and 

transchelation occur in biological systems. In contrast, 

radiolabeling of propionic acid analogues has not been reported 

so far. 

An appropriate building block to form very stable 

complexes with copper(II) is N-mono-(2-(carboxy)ethyl)- 

-1,4,8,11-tetraazacyclotetradecane (Cyclammonopropionic acid, 

CMPA) which permits the formation of stable radiocopper 

complexes as well as a facile approach to obtain peptide 

multimers. An improved pharmaceutical targeting might be 

utilized due to the multimeric peptide functionalization of the 

chelating agent. The Epidermal-Growth-Factor-Receptor (EGFR), 

which is overexpressed on a multitude of tumors, has been chosen 

as target system to be studied. 

Herein, we want to report about coupling reactions of the 

model dipeptide H-(L)-Leu-(L)-Ala-OH, which is a part of an 

EGFR-specific peptide, with the cyclammonopropionic acid 

skeleton. Radiolabeling of CMPA-peptide conjugates with 

copper-64 indicate high in vitro stability of the complexes formed. 

So far, this promising behavior may pave the way to develop 

attractive candidates for radiopharmaceutical applications. 

Keywords: chelates; copper; peptide; radiopharmaceutical; 



s716 

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life sciences 

Medicinal Chemistry session – ii 

o - 3 2 5 

C-2 funCtionALizAtion of PiPeridineS viA 

direCted trAnSition MetAL-CAtALyzed SP3 Ch 

ACtivAtion 

B. MAeS 1 

1 University of Antwerp, Chemistry, Antwerp, Belgium 

The development of transition metal-catalyzed methods for 

the direct functionalization of sp3 C-H bonds is one of the current 

challenges in organic chemistry. [1] Within this area, the 

transformation of a C-H bond in alpha-position to the nitrogen 

atom of saturated cyclic amines is of great importance [2] since 

such heterocyclic motifs can be found in an impressive number 

of natural products and marketed drugs. To date, examples of 

direct C2-H functionalization of cyclic amines using transition 

metal-catalysis are still rare. The direct functionalization studies 

published thus far have mainly focused on pyrrolidines and only 

show (if any) a limited number of piperidine examples. 

We have developed a direct Ru-catalyzed C-2 arylation and 

alkylation protocol which can be used on unsubstituted and 

substituted piperidines. The arylation protocol employs 

arylboronate esters and the alkylation alkenes as reagents. [3, 4] 

The procedures require a directing group on the piperidine 

nitrogen. We used a pyridine directing group which has always 

been considered as a non removable group and developed 

protocols to remove it in a straightforward manner. 

references: 

1. a) Jazzar, R.; Hitce, J.; Renaudat, A.; Sofack-Kreutzer, J.; 

Baudoin, O. Chem. Eur. J. 2010, 16, 2654. 

b) Baudoin, O. Chem. Soc. Rev., 2011, 40, 4902. 

2. Campos, K. R. Chem. Soc. Rev. 2007, 36, 1069. 

3. Prokopcová, H.; Bergman, S.D.; Aelvoet, K.; Smout, V.; 

Herrebout, W.; Van der Veken, B.; Meerpoel, L.; 

Maes, Bert U.W. Chem. Eur. J. 2010, 16, 13063. 

4. Bergman, S.D.; Thomas, E.S.; Aelvoet, K.; Diels, G.; 

Meerpoel, L.; Maes, Bert U.W. Chem. Eur. J. 2012, 18, 

in press. 

Keywords: C-H activation; Homogeneous catalysis; 

Ruthenium; 



o - 3 2 6 

deveLoPMent And APPLiCAtion of reverSiBLe 

enriChMent tAGS for nAturAL ProduCt 

diSCovery 

d. trAder 1 , A. SideBottoM 1 , e. CArLSon 1 

1 Indiana University, Chemistry, Bloomington, USA 

Although natural product isolation can be a laborious task, 

it has yielded myriad drug candidates and inspired synthetic 

chemists for over a century. Considerable advances have been 

made in separation technology; however, additional methods are 

needed to streamline drug discovery efforts. Purification of the 

active components of a crude extract, which often represent less 

than 1% by weight, is considered a major bottleneck in natural 

products discovery. Current isolation techniques are dependent 

upon the physicochemical properties of the molecules such as 

polarity or charge. These strategies often provide mixed 

fractions upon purification, increasing the difficulty of bioassay 

assessment or structural determination of unknown molecules. 

To address these issues, we have developed a new method to 

isolate natural products based upon an orthogonal property, their 

functional group composition. This technique utilizes reversible 

enrichment tagging reagents, which react chemoselectively with 

the desired functional group class faciliting enrichment from 

complex mixtures. Our previous studies yielded the 

development of a functional group-specific method for 

enrichment of hydroxyl group-containing natural products based 

upon the formation of a silyl ether bond. We were then able to 

extend our developed silicon chemistry to yield a novel 

diisopropylsiloxane-functionalized resin that chemoselectively 

captures natural products containing a carboxylic acid moiety. 

With these two enrichment tags in hand our goal is to isolate 

previously undiscovered molecules from well-characterized 

strains of Streptomyces. Additionally, work on a third and fourth 

enrichment tag, one that is chemoselective for the aldehyde or 

ketone functionality and the phenol, is also under way. 

Keywords: natural products; Immobilization; Solid-phase 

synthesis; Antibiotics; 



s717 

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life sciences 


o - 3 2 7 

BiofunCtionALiSAtion And 64Cu-LABeLinG of 

Pyridine-ContAininG tACn LiGAndS for 

SPeCifiC tArGetinG of eGf-reCePtor 

J. heSSe 1 , K. viehweGer 1 , h. StePhAn 1 , 

J. SteinBACh 1 

1 Helmholtz-Zentrum Dresden-Rossendorf, Radiopharmacy, 

Dresden, Germany 

The application of radiolabeled peptides in biomedicine is 

increasing rapidly and offers excellent prospects for the 

development of target-specific tumor imaging agents. In this 

perspective, the incorporation of the positron-emitting 

radionuclide 64CuII into ligand-peptide conjugates would permit 

the use of positron emitting tomography (PET) for tumor 

identification. An important requirement is that the resulting 

radiocopper-ligand complex is both kinetically and 

thermodynamically stable in vivo. We have developed a ligand 

scaffold based on bis(2-pyridylmethyl)triazacyclononane 

(DMPTACN) that forms very stable CuII complexes. This 

structure allows for the introduction of linker groups, such as 

carboxylic acids, maleimide or isothiocyanate, thereby facilitating 

coupling of targeting molecules. 

Among many characteristic targets of cancer tissue, the 

epidermal growth factor receptor (EGFR) is one of the most 

important mediators involved in the development of highly 

malignant tumors. This surface receptor is overexpressed in 

several tumor entities. The altered expression of EGFR during 

tumor growth, invasion, and metastasis present an interesting 

molecular target for tumor diagnosis and therapy. 

Meanwhile, some specific peptides are identified capable of 

recognition EGFR-rich cancer tissue. Among these, the 

hexapeptide D4 (Leu-Ala-Arg-Leu-Leu-Thr) has been described. 

We want to present the synthesis of a DMPTACN-peptide 

conjugate, applying thiourea coupling of the hexapeptide D4 by 

a DMPTACN isothiocyanate derivative. Radiochemical and 

radiopharmacological properties will be reported. In vitro binding 

characteristics of the [ 64Cu]CuII-labeled DMPTACN-peptide 

conjugate in EGFR overexpressing cancer cells (FaDu, A431) 

using an immunoprecipitation protocol point to specific 

interactions. 

Keywords: Copper; Imaging agents; Radiopharmaceuticals; 

Medicinal Chemistry session – iii 


o - 3 2 8 

MoLeCuLAr reCoGnition At Protein 

SurfACeS 

e. GirALt 1 

1 Institute for Research in Biomedicine, Programme of 

Chemistry and Molecular Pharmacology Programme, 


There is no doubt that proteins can be considered as 

privileged targets for binding of small ligands. In this context the 

design of ligands able to disrupt protein-protein interactions is 

emerging as an even more relevant issue. The breakthrough 

concept that proteins function as a contact network rather than as 

independent individuals is not only one of the most important 

advances in our comprehension of living systems, but also 

translates to a new era in drug discovery. The few reported 

examples of diseases caused by “impolite” protein social behavior 

certainly represent only the tip of the iceberg. Therapeutic 

intervention through molecules designed to selectively modulate 

the strength and specificity of protein-protein interactions is 

becoming a reality. This will not only feature molecules with 

inhibitory capacity: equally or even more interesting are those 

compounds which can rescue pre-established interactions or 

structures whose loss results in disease. 

Protein-protein interactions are the result of an ensemble of 

exquisitely regulated molecular recognition events that take place 

at protein surfaces. This can be referred to as a ‘protein 

recognition code’. In order to understand protein-protein 

interactions and to achieve the efficient design of molecules with 

the capacity to modulate these protein-protein interactions, it is 

necessary to decipher this molecular recognition code, the 

language that proteins use to communicate. Unfortunately, 

progress in this field is highly unsatisfactory. Indeed, we are not 

completely illiterate, in the sense that we know the letters of this 

alphabet. They are the non-covalent interactions, such as hydrogen 

bonds, electrostatic interactions, ?-cation interactions, Van der 

Waals forces, and the others. However, we could be compared 

with a child who is learning to read and attempts Dickens’s Oliver 

Twist. 

Keywords: NMR; Protein surface; Protein; Peptide; 

Molecular recognition; 



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life sciences 


o - 3 2 9 

duAL AntiCoAGuLAnt/AntiPLAteLet 

PoLySuLfAted SMALL MoLeCuLeS: A MediCinAL 

CheMiStry CASe-Study 

M. CorreiA-dA-SiLvA 1 , e. SouSA 1 , B. duArte 2 , 

f. MArqueS 2 , f. CArvALho 3 , L. M. CunhA-riBeiro 4 , 

M. Pinto 1 

1 Faculdade de Farmácia da Universidade do Porto, Ciencias 

Químicas Laboratório de Química 

Organica e Farmaceutica CEQUIMED, Porto, Portugal 

2 Faculdade de Farmácia da Universidade do Porto, 

Ciencias Biológicas Unidade de Análises Clínicas, Porto, 

Portugal 

3 Faculdade de Farmácia da Universidade do Porto, 

Ciencias Biológicas Laboratório de Toxicologia REQUIMTE, 

Porto, Portugal 

4 Hospital de S. Joao, Servico de ImunoHemoterapia Centro de 

Trombose Hemostase e Biologia Vascular, Porto, Portugal 

With the increasing rates of cardiovascular diseases, the 

need for new antithrombotic drugs is considered of great 

importance since many of the current drugs are insufficiently 

effective, often affected by severe adverse effects and require 

routine monitoring. The search for new alternatives to heparins 

with a well defined composition associated to feasible synthesis 

is a strong challenge to medicinal chemists. Thus, a new 

strategy was designed by the hybridization of an oligo-sulfated 

moiety with a small-molecule scaffold.Polysulfation of 

carbohydrate-small molecules used as venotropic agents or 

nutraceutics was achieved with triethylamine:SO adduct by 

3 

conventional heating and/or microwave irradiation. The 

anticoagulant activity was evaluated in human plasma (APTT, 

PT, and TT clotting times) and in human whole blood 

(thromboelastography). Enzyme inhibition assays were 

performed against factor Xa, thrombin, and antithrombin III. 

Platelet aggregation induced by different agonists was 

evaluated in whole blood (platelet aggregometry). Three 

representative compounds were administered intraperitoneally 

in mice (150 μmol/kg) to measure clotting times and 

transaminases levels.Eighteen polysulfated small molecules 

were successfully obtained. The polysulfated compounds 

prolonged the clotting times and some structure-activity 

relationships could be inferred, particularly related to the 

number of sulfate groups. The most active compounds were 

rutin and 3,6-(O-β-glucopyranosyl)xanthone persulfates 

exhibiting double concentration values in the micromolar range. 

Human whole blood also became hypocoagulable, and there 

were no signals of fibrinolysis. While inactive against thrombin, 

some derivatives showed selectivity for factor Xa (directly or 

with antithrombin III). Some sulfated compounds inhibit both 

arachidonic acid and ADP-induced platelet aggregation. In vivo, 

compounds showed a rapid onset of action and a sustained 

duration of anticlotting effects with no signals of acute hepatic 

toxicity. A new class of small-molecules with dual 

anticoagulant/antiplatelet activity was identified and might 

offer an opportunity, in contrast to known antithrombotic 

agents, for the treatment of both venous and arterial thrombosis. 

Keywords: Medicinal Chemistry; Drug Discovery; 

Glycoconjugates; Heterocycles; Polyanions; 



o - 3 3 0 

SyntheSiS of PiPerine AnALoGS AS GABAA 

reCePtor LiGAndS 

L. wiMMer 1 , A. SChÖffMAnn 2 , t. SChwArz 3 , 

M. SChnürCh 1 , S. KhoM 2 , t. erKer 3 , S. herinG 2 , 

M. d. MihoviLoviC 1 

1 Vienna University of Technology, Institute of Applied Synthetic 

Chemistry, Vienna, Austria 

2 University of Vienna, Department of Pharmacology and 

Toxicology, Vienna, Austria 

3 University of Vienna, Department of Medicinal Chemistry, 


Black pepper is traditionally used in Asian folk medicine as 

antiepileptic, antianxiety, sedative, and sleep inducing preparation. 

One of the ingredients of piper nigrum, it’s natural pungent 

alkaloid piperine, was recently identified as a positive allosteric 

modulator of the GABA receptors, the major inhibitory 

A 

neurotransmitter receptors in the brain. [1] The importance of 

GABA receptors as a drug target and the side effect profile of 

A 

drugs targeting this receptors at present result in a unbowed 

demand for new scaffolds. 

This study is dedicated to the optimization of the piperine 

scaffold in terms of ligand potency. A number of 106 derivatives 

of natural product piperine were synthesized. Compounds were 

tested for GABA receptor activity using a two-electrode 

A 

voltage clamp essay on Xenopus laevis oocytes. In an early 

stage of the project the amide functionality was modified. Here, 

the di-n-propyl, di-iso-propyl and di-n-butyl amides were 

identified as the most efficacious residues. With this 

knowledge, the modification of the double bond system of the 

natural product was approached. Under application of transition 

metal catalyzed cross coupling reactions derivatives with 

1,2-, 1,3- and 1,4-substituted phenylene, 1,5-naphthalene 

and 2,5-thiophene as substitute for the double bond system were 

synthesized. The aromatic benzodioxole ring system was 

extended to naphtho[2,3-d]dioxole, incorporating one of the 

double bonds. Here, new and efficient synthetic routes, 

involving aryne chemistry or iridium catalyzed direct borylation 

reactions, to 5- and 6-substituted naphtho[2,3-d]dioxoles were 

developed and applied in the synthesis of piperine derivatives. 

references: 

1. Zaugg, J; Baburin, I; Strommer, B; Kim, H-J.; Hering, S; 

Hamburger, M; HPLC-Based Activity Profiling: 

Discovery of Piperine as a Positive GABAA Receptor 

Modulator Targeting a Benzodiazepine-Indipendent 

Binding Site. J Nat Prod 2010, 73, 185-191 

Keywords: Medicinal chemistry; Ion channels; Natural 

products; 



s719 

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life sciences 


o - 3 3 1 

deSiGn And SyntheSiS of SMALL MoLeCuLeS 

AiMed At new AntiBiotiCS 

f. rutJeS 1 

1 Radboud University Nijmegen, Institute for Molecules and 

Materials, Nijmegen, Netherlands 

Since the 1960s, defeating antibacterial resistance has 

mainly relied on the modification of existing antibiotics. It has 

appeared, however, increasingly difficult to come up with 

modifications that evade resistance without sacrificing activity 

and as a result, the pressure for finding new classes of antibiotics 

is higher than ever before. In this respect, the discovery of potent 

new antibiotics such as platencin represented a potential 

breakthrough in antibiotic research. Platencin shows 

broad-spectrum Gram-positive antibacterial activity and acts on 

the type II bacterial fatty acid synthesis. However, the 

pharmacokinetic properties are rather poor and preclude use as an 

antibiotic drug. To investigate whether platencin can be turned 

into a successful drug, the development of analogues is a pivotal 

first step. 

In this lecture, synthetic studies directed toward the 

synthesis of (–)-platencin and several analogues will be described. 

Furthermore, a recently developed entirely new strategy to 

disrupt bacterial fatty acid synthesis, based on pantothenic acid 

derivatives, will be highlighted. 

Keywords: antibiotics; total synthesis; platencin; fatty acid 

biosynthesis; platensimycin; 

Medicinal Chemistry session – iV 


o - 3 3 2 

SMALL MoLeCuLe MediAted reGenerAtive 

MediCine – noveL LeAd CoMPoundS for 

CArdioMyoGeneSiS 

M. d. MihoviLoviC 1 

1 Vienna University of Technology, Institute for Applied 

Synthetic Chemistry, Vienna, Austria 

Regenerative Medicine is understood as one of the most 

promising therapeutic approaches to alleviate a multitude of 

diseases. While there is significant progress in the experimental 

development of this approach related to gene therapeutic 

intervention often in combination with employing embryonic stem 

cells, the regulatory implications of such therapies are yet unclear 

and ethical aspects represent a major obstacle in the further 

development of such strategies. Hence, small molecules capable 

to affect cell differentiation towards particular tissues have 

received significant attention, as the prospect of employing such 

agents in regenerative medicine seem highly attractive. 

Within the past years we have been developing several 

compounds capable to trigger differentiation of certain progenitor 

cells towards particular tissues otherwise difficult to regenerate. 

This particular case study aims at the development of novel lead 

structures for cardiomyogenesis. We will disclose recent results 

on the identification of heterocyclic scaffolds capable to 

efficiently induce differentiation towards functional 

cardiomyocetes starting from embryonic or progenitor cells, 

ultimately leading to independently beating heart cells. 

Considering the fact, that cardiac infarctation represents one of 

the major death causes in the developed world, the prospect of 

tissue regeneration of damaged heart muscle tissue offers a highly 

innovative perspective of regaining heart function, as this organ 

in not capable to functional repair on its own. 

Synthetic approaches towards the individual target 

compounds exploited modular strategies based on metal assisted 

catalysis, in particular sequential coupling strategies (C-C, C-N, 

and C-H activation). Optimization of functional decorations of 

the particular heterocyclic scaffolds will be discussed in detail. 

Keywords: Medicinal chemistry; Heterocycles; Drug design; 

Cross-coupling; 



s720 

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life sciences 


o - 3 3 3 

duAL-LABeLed PePtide dendriMerS for 

fLuoreSCenCe And SPeCt/Ct iMAGinG of 

CxCr4-exPreSSinG CeLLS And tuMorS 

J. KuiL 1 , t. BuCKLe 1 , h. yuAn 2 , L. JoSePhSon 2 , 

f. vAn Leeuwen 1 

1 Leiden University Medical Center, Radiology, Leiden, 

Netherlands 

2 Massachusetts General Hospital, Center for Translational 

Nuclear Medicine and Molecular Imaging, Charlestown, USA 

The chemokine receptor 4 (CXCR4) is over-expressed in 

more than 23 types of cancer were it plays a role in, among others, 

the metastatic spread. Therefore, it is an emerging biomarker in 

the field of tumor imaging. [1] CXCR4 is also used as a target 

for cancer therapy and chemosensitization. The 14 amino 

acid-containing disulfide-bridged Ac-TZ14011 cyclic peptide has 

proven to be a potent inhibitor of CXCR4. 

We have synthesized monomeric, dimeric and tetrameric 

Ac-TZ14011 dendrimers. These dendrimers were labeled with a 

multimodal (hybrid) label, consisting of a Cy5.5-like fluorophore 

and a DTPA chelate for indium labeling. This combination allows 

for both (in vitro/in vivo) fluorescence imaging and (in vivo) 

SPECT/CT imaging. 

Confocal microscopy revealed that all three multimodal 

dendrimers were membrane-bound at 4 degrees Celsius, 

consistent with the location of CXCR4. The unlabeled dimer and 

tetramer had a somewhat lower affinity for CXCR4 than the 

unlabeled monomer. However, when labeled with the multimodal 

label the CXCR4 affinity of the dimer and tetramer (K = 93.1 nM 

D 

and 80.5 nM, respectively) were considerably higher compared 

to the labeled monomer (K = 186.9 nM). SPECT/CT tumor 

D 

visualization in mice was possible with all three compounds. 

Biodistribution studies revealed that the additional peptides in the 

dimer and tetramer reduced nonspecific muscle uptake compared 

to the monomer, resulting in tumor-to-muscle ratios of 7.41 for 

the dimer and 5.47 for the tetramer. In conclusion, multimerization 

improved the efficacy of multimodal labeled peptide. [2–3] 

references: 

1. Kuil, J., Buckle, T., van Leeuwen, F.W.B., Chem. Soc. 

Rev., accepted 

2. Kuil, J., Buckle, T., Yuan, H., van den Berg, N.S., 

Oishi, S., Fujii, N., Josephson, L., van Leeuwen, F.W.B., 

Bioconjugate Chem., 2011, 22, 859-864 

3. Kuil, J., Buckle, T., Oldenburg, J., Yuan, H., Borowsky, 

A.D., Josephson, L., van Leeuwen, F.W.B., Mol. Pharm., 

2011, 8, 2444-2453 

Keywords: Peptides; Dendrimers; Imaging agents; Fluorescent 

probes; Radiochemistry; 



o - 3 3 4 

dehydro-BetA-AMino ACid ContAininG 

PePtidoMiMetiCS AS inteGrin reCePtor 

LiGAndS 

A. toLoMeLLi 1 , L. GentiLuCCi 1 , A. vioLA 1 , 

M. BAiuLA 2 , S. SPAMPinAto 2 , L. BeLviSi 3 , 

M. CiverA 3 

1 Department of Chemistry “G.Ciamician”, University of 

Bologna, Italy 

2 Department of Pharmacology, University of Bologna, Italy 

3 Department of Organic and Industrial Chemistry and CISI, 

University of Milan, Italy 

Design and synthesis of non proteinogenic amino acids 

represent a central issue for chemists working in the area of 

medicinal chemistry and among them, unsaturated β-amino acids 

have attracted high interest as valuable intermediates in the 

synthesis of dehydropeptides, allowing the preparation of 

conformationally constrained sequences with improved biological 

activity and selectivity. In particular, we are interested to the 

synthesis of receptor-selective peptides and peptidomimetics, 

mimicking the RGD motif, present in a wide number of 

extracellular matrix proteins. These ligands bind to α β and α β v 3 5 1 

integrins, a large family of heterodimeric transmembrane 

glycoproteins, involved in the pathogenesis of several diseases, 

such as atheroschlerosis, osteoporosis, cancer and a variety of 

inflammatory disorders. In view of the application as central cores 

of peptidomimetics, we have developed synthetic strategies for 

the preparation of linear and cyclic dehydro-β-amino acids, using 

alkylidene acetoacetates and malonates as starting materials. 

The use of five membered heterocycles as proline analogues 

has been extensively explored to induce conformational restraints 

in peptidomimetics. We have recently developed the synthesis of 

5-hydroxyisoxazolidine-4-carboxylate, and related functionalized 

isoxazolines, as heterocycles containing the dehydro-β-amino 

carboxylate fragment. Lewis acid induced Michael addition of 

hydroxylamine derivatives to alkylidene acetoacetates, followed 

by intramolecular hemiketal formation, allowed to obtain a small 

library of functionalized isoxazoline-based integrin ligands. 

Moreover, transformation of alkylidene derivatives 

into the corresponding allylic carbonates furnished linear 

dehydro-β-amino acids, through regio- and stereoselective allylic 

amination in the presence of palladium and iridium catalysts. 

Introduction of an allylamino moiety through the S 2' reaction, 

N 

gave also access to an intermediate containing two unsaturations, 

thus suggesting that RCM could be a valuable tool for the 

preparation of dihydropyrrole scaffold. 

Decoration of the dehydro-β-amino acid cores with the 

proper appendages to mimic aspartate and arginine side chains, 

afforded structures possessing excellent receptor affinity as 

confirmed by cell adhesion inhibition assays. 

Keywords: Ligand design; Michael addition; Amino acids; 

Peptidomimetics; Cancer; 



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life sciences 


o - 3 3 5 

diSCovery of new her2/eGfr duAL KinASe 

inhiBitorS BASed on AniLinoquinAzoLine 

SCAffoLd AS PotentiAL tArGetinG Anti- 

CAnCer AGentS 

K. ABouzid 1 , r. SerryA 1 , A. h. KAfAfy 2 , 

M. MohSen 3 

1 Faculty of Pharmacy Ain Shams University, Pharmacetical 

Chemistry, Cairo, Egypt 

2 Faculty of PharmacyAssuit University, Organic Chemistry, 

Assuit, Egypt 

3 Faculty of Pharmacy MSA University, Organic Chemistry, 

Cairo, Egypt 

Dual inhibitors of human epidermal growth factor receptor 

(HER2) and epidermal growth factor receptor (EGFR) have been 

investigated for breast, lung, gastric, prostate, and other cancers. 

Herein, we designed and synthesized anilinoquinazoline 

derivatives bearing bulky such as arylpyridinyl and arylpyrazolyl 

moieties at the 4' position of the anilinoquinazoline, as 

HER2/EGFR dual kinase inhibitors, capable of fitting into the 

receptor ATP binding sites. Binding modes of the designed 

compounds in the ATP binding sites for both EGFR and HER2 

was carried out by means of docking study which demonstrated 

distinctive binding mode for these compounds with MET793 and 

MET 801 at the hinge region of both EGFR and HER2 

respectively. The synthesized compounds were further tested for 

their inhibitory activity on EGFR and HER2 tyrosine kinases. Two 

2-imino-1,2-dihydropyridine derivatives displayed the most 

potent inhibitory activity on EGFR with IC equal to 2.09 μM 

50 

and 1.94 μM respectively and for HER2 with IC equal to 

50 

3.981 μM and 1.036 μM respectively. Furthermore, 

antiproliferatve activity against MDA-MB-231 breast cancer cell 

lines, known to overexpress EGFR. showed an IC range 

50 

of 0.5–0.6 μM. 

Keywords: antiproliferation; bioorganic chemistry; drug 

discovery; 



o - 3 3 6 

PoLySACChAride-ASSiSted CLuSterinG of 

PALLAdiuM nAnoPArtiCLeS 

e. GASiLovA 1 , n. ShevChenKo 2 , L. BoroviKovA 2 , 

G. MAtveevA 1 , G. ALeKSAndrovA 3 , B. SuKhov 3 

1 Institute of Macromolecular Compounds Rassian Academy of 

Science, Physical Department, Saint-Petersburg, Russia 

2 Institute of Macromolecular Compounds Rassian Academy of 

Science, Chemical Department, Saint-Petersburg, Russia 

3 Institute of Chemistry Russian Academy of Science, Chemical 

Department, Irkutsk, Russia 

Clusters of metal nanoparticles (NP) functionalized by 

biomacromolecules are used in a rapidly emerging field of 

nanobiotechnology. Palladium NPs are noticeable for forming 

various self-assembled structures, though the effect of polymer 

templates on the (Pd)NPs aggregation is poorly understood. 

Recently,(Pd)NPs were obtained by using arabinogalactan (ARB) 

as the nanoreactor, reducing Pd ions to a zero-valent state, and the 

stabilizing agent preventing the NPs from aggregation. [1] We study 

the NPs clustering in the ARB@(Pd)NP colloids by dynamic 

(DLS) and static (SLS) light scattering at 632.8 nm, resonantly 

enhanced by surface plasmon resonances (SPR) of NPs. Broad 

size dispersion of spherical ARB@(Pd)NP aggregates is 

evidenced by scanning and transmission electron microscopy. 

The red shift of the SPRs with the colloidal size increasing is 

demonstrated by the difference UV/Vis spectroscopy of the 

colloids fractionated by centrifugation. The proximity of SPR of 

the largest aggregate to the incident light wavelength determines 

their most efficient role in scattering. Therefore, SLS and DLS 

probe the gyration (R ) and hydrodynamic (R ) radii of largest 

g h 

colloids. R of the colloidal aggregate is governed by the NPs’ 

g 

distribution because the NP’s density is much higher than that of 

the polysaccharide. The structure-sensitive ratio R /R ≈ 1 points 

g h 

out that the NPs form the spherical layer at the colloidal surface. 

Negative colloidal zeta-potentials show that the NPs layer is 

covered by a layer of ARB. Zero scattered light depolarization 

also indicates the spherically symmetric distribution of Pd 

nanoparticles within colloidal aggregates. Spherically symmetric 

ARB@NP(Pd) colloids with the shell of NPs at the surface can 

serve for creating new NPs’ self-assemblies. 

references: 

1. Sukhov B., et al. J. Struct. Chem. 2007, 48, 922. 

2. Trofimov B., et al. Doklady Chem. 2007, 417, 261. 

3. Gasilova E., et al. J. Phys. Chem. B 2010, 114, 4204. 

Keywords: Nanostructures; Nanoparticles; Colloids; 

Aggregation; 

[2, 3] 



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o - 3 3 7 

MonoCyCLiC BetA-LACtAMS And CyStiC 

fiBroSiS: fACinG AntioxidAnt And 

AntiMiCroBiAL ACtivity of n-thioMethyL- 

-AzetidinoneS 

d. GiACoMini 1 , P. GALLetti 1 , M. Pori 1 , 

r. CerveLLAti 1 , C. CoCuzzA 2 , r. MuSuMeCi 2 

1 University of Bologna, Department of Chemistry 

“G.Ciamician”, Bologna, Italy 

2 University of Milano-Bicocca, Department of Clinical 

Medicine and Prevention, Milan, Italy 

Beta-lactam antibiotics are the main class of agents used 

to treat bacterial infections. Notwithstanding their pivotal role, 

the treatment of bacterial infections became tangled because 

of the increasing emergence of multidrug-resistant 

microorganisms.Staphylococcus aureus (SA) is a major pathogen 

causing significant morbidity and mortality in both communityand 

hospital-acquired infections. Many staphylococcal infections 

which tend to become chronic, are associated with multiple 

recurrences and developed antibiotic resistance. This concern is 

important in the cystic fibrosis (CF) disease where a persistent 

colonization of pathogen bacteria occurred and a constant use of 

antibacterial agents selected resistant strains. 

We actively contributed to the field with the design and 

synthesis of new monocyclic beta-lactams as scaffolds for 

antibiotics against resistant bacteria and as effective enzymatic 

inhibitors against HLE, MMPs, HDACs, and as antiaggregating 

agents. 

We recently evaluated a series of N-thiomethyl-azetidinones 

against Gram-positive and Gram-negative bacteria, particularly 

methicillin resistant SA strains (MRSA) from clinical isolates of 

CF patients. The combination of specific groups on the 

beta-lactam ring strengthened the potency against MRSA. 

We also evaluated the antioxidant activity and redox 

potentials of the new beta-lactams with the aim to develop new 

promising molecules which associated antibacterial and 

antioxidant activities able to contrast the adverse conditions in CF 

due to MRSA and extensive epithelial damages by chronic 

pulmonary oxidative stress. 

references: 

1. P. Galletti, D. Giacomini Curr. Med. Chem. 2011, 18, 

4265; 

2. F. Broccolo, G. Cainelli, G. Caltabiano, C. Cocuzza, 

C. G. Fortuna, P. Galletti, D. Giacomini, G. Musumarra, 

R. Musumeci, A. Quintavalla, J.Med.Chem. 2006, 49, 

2804 

3. G. Cainelli, P. Galletti, S. Garbisa, D. Giacomini, L. Sartor, 

A. Quintavalla, Bioorg.Med.Chem. 2005, 13, 6120 

4. C. Ventrici, G. Giannini, W. Cabri, S. Penco, G.Gallo, 

S. Incenti, D. Giacomini ChemMedChem 2009, 4, 1991 

5. G. Cainelli, C. Angeloni, R. Cervellati, P. Galletti, 

D. Giacomini, S. Hrelia, R. Sinisi Chem.Biodivers. 2008, 

5, 811 

6. P. Galletti, C. Cocuzza, M. Pori, A. Quintavalla, 

R. Musumeci, D. Giacomini, ChemMedChem 2011, 6, 

1919. 

Keywords: Antibiotics; Lactams; Synthesis Design; Inhibitors; 

Antioxidants; 



o - 3 3 8 

SeLeCtiveLy LABeLLed BetuLinineS 

M. vLK 1 , P. MiCoLovA 1 , t. SvehLAKovA 1 , J. SAreK 2 , 

t. eLBert 3 , P. dzuBAK 4 , M. hAJduCh 4 

1 Czech Technical University in Prague, Dpt. Nuclear 

Chemistry, Prague 1, Czech Republic 

2 Faculty of Science Palacky University in Olomouc, Dept. of 

Organic Chemistry IMTM, Olomouc, Czech Republic 

3 Institute of Organic Chemistry and Biochemistry Academy of 

Sciences, Laboratory of Radioisotopes, Prague, Czech 

Republic 

4 Palacky University and University Hospital in Olomouc, 

Laboratory of Experimental Medicine IMTM, Olomouc, Czech 

Republic 

Betulin and betulinic acid belong to the group of natural 

triterpenoids.Together with their semisynthetic derivatives form 

basis for extensive medicinalresearch, because they have shown 

various biological activities, [1] e.g.:antiviral, anti-inflammatory, 

antimicrobial activities, hepato- andcardioprotective effects; and 

reveal a great potential for pharmaceuticalapplications when their 

cytotoxic and anti-HIV activities were described. [1, 2, 3] 

Betulinines, as we named that group of derivatives, have 

provedmultispectral cytotoxic activity on the panel of 10 cell 

tumor lines ofdifferent histogenetical origin, including multidrug 

resistance. [1, 2, 3] 

One of our leading compound 3β,28-diacetoxy-18-oxo- 

-19,20,21,29,30-pentanorlupan-22-oicacid fast and selective 

apoptosis of tumor cells, [3] comparable toconventional anticancer 

drugs. Selectivelylabelled analogues of the most cytotoxic active 

compounds are used for theinvestigation of mechanism of action 

and binding interactions. Until the present time hasbeen 

synthesized over twenty deuterated, five tritiated and six 

compoundslabelled with 15N, which were fully characterized by 

all availablespectral data. 

references: 

1. P. Dzubak, M. Hajduch, D. Vydra,A. Hustova, 

M. Kvasnica, D. Biedermann, L. Markova, M. Urban, 

J. Sarek, Nat. Prod. Rep. 2006, 23, 394. 

2. E. Pisha,H. Chai, I. S. Lee, T.E. Chagwedera, 

N. R. Farnsworth, G. A. Cordell, C. W. W. Beecher, 

H- H. S. Fong, A. D. Kinghorn, D. M. Brown, M. C. Wain, 

M. E. Wall,T. J. Hieken,T. K.Gupta, J. M. Pezzuto, 

Nat. Med. 1995, 1,1046. 

3. J. Sarek, M. Kvasnica,M. Vlk, D. Biedermann in: 

PentacyclicTriterpenes as Promising Agents in Cancer 

(Ed: J. A. R. Salvador), NovaPublishing, New York, 2011, 

pp. 159. 



s723 

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life sciences 


o - 3 3 9 

deveLoPMent of MuLti-ModAL MoLeCuLAr 

ProBeS for BetA-CeLL iMAGinG 

d. SAhoo 1 , 2 , J. GouLLey 1 , n. LAnGe 2 , P. MedA 1 

1 University of Geneva, 1Department of Cell Physiology and 

Metabolism, Geneva, Switzerland 

2 University of Geneva, 2Department of Pharmaceutical 

Science, Geneva, Switzerland 

According to the World Health Organization 346 million 

people worldwide have diabetes. The patho-physiology of 

diabetes is complex; it results from the impairment of insulin 

secretion and/or function. Type-I diabetes is characterized by the 

loss of most insulin producing Beta-cells, leading to the loss of 

endogenous insulin secretion. Type-II diabetes is characterized by 

impaired insulin secretion and insulin resistance, and a reduction 

of Beta-cell mass. Thus monitoring the changes in Beta-cell mass 

is of great interest. Glucagon like peptide-1 (GLP-1), an incretin 

peptide which binds to its membrane receptor (GLP-1R) at the 

surface of Beta cells is a suitable candidate for imaging. 

Therefore, we designed molecular probes using GLP-1 

analog exendin-4 as ligand. A fifth generation poly(amido amine) 

dendrimer (PAMAM) was chosen as the carrier; thanks to its high 

degree of molecular uniformity, narrow molecular weight 

distribution, and highly functional terminal surface. 

The PAMAM surface was labeled with 5(6)-carboxy-x- 

-Rhodamine-NHS ester to obtain a Rhodamine labeled PAMAM, 

which was further modified with suitable linkers specific to thiolmaleimide 

chemistry and oxime ligation. By using these two 

different strategies probes were synthesized with a loading of 

1-5 Exendin-4. An in vitro approach using glucose responsive 

cell-line model (MIN6) for Beta-cell and two non insulin 

producing cell-lines (PANC1, and HeLa, respectively) were used 

to challenge our probes and verify their localization and affinities 

to the GLP1 receptor. Our primary data confirm the specificity of 

our probes for insulin producing cells and show a similar pattern 

of localization between our probes and the GLP1 receptor at a 

nano molar concentration. In this poster we will present the 

synthesis details of these probes and the imaging studies that are 

being conducted to test their usefulness for the imaging of 

Beta-cell both in vitro and in vivo. 

Keywords: Diabetes; Beta-Cell; Molecular Probes; Molecular 

imaging; 

Mass spectrometry in life science – i 


o - 4 5 6 

tAndeM MASS SPeCtroMetry in CLiniCAL 

enzyMoLoGy: reCent ProGreSS in newBorn 

SCreeninG of inBorn errorS of MetABoLiSM 

f. tureCeK 1 

1 University of Washington, Chemistry, Seattle, USA 

Lysosomal storage disorders (LSD) represent a group of 

inherited metabolic diseases caused by malfunctioning of one of 

the ca. 60 specialized enzymes in the lysosome. Lysosomal 

enzyme deficiencies result in accumulation of unprocessed 

substrates (sphingolipids, glycogen, glycosaminoglycans, 

peptides, etc.) leading to cell death and progressing to organ or 

system failure. 

In the last decade there has been substantial development of 

treatments for LSD. The currently used therapies are based on 

enzyme replacement therapies or hematopoietic stem cell 

transplantation. The common feature of these therapies is that they 

have the highest success rate if applied before the onset of 

symptoms characterizing the disease phenotype. This requirement 

places emphasis on early detection of affected individuals by 

high-throughput methods such as those used in newborn 

screening. 

Our labs at University of Washington have been developing 

specific assays of lysosomal storage disorders to be applied to 

DBS. The assays use synthetic substrates that are converted to 

products upon incubation with a small punch of a DBS. The 

products are detected by electrospray tandem mass spectrometry 

(MS/MS) and quantified by comparing the ion currents from 

selected reaction monitoring (SRM) with those produced by 

internal standards, which are either isotopologues or close 

homologues. There are currently MS/MS assays for the detection 

of eleven LSD, namely, Gaucher, Krabbe, Niemann-Pick, Fabry, 

Pompe, mucopolysaccharidoses Hurler, Hunter, Maroteaux-Lamy, 

Morquio A, and neuronal lipofuscinoses I and II. Progress has 

been made on a multiplex assay for MPS-III (Sanfilippo A, B, C, 

and D). The analytical procedures have been validated by an 

ongoing large-scale pilot program of triplex screening for Fabry, 

Pompe and Hurler diseases (>80,000 samples) at the Washington 

State Newborn Screening Laboratory. 

Keywords: mass spectrometry; glycolipids; oligosaccharides; 



s724 

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life sciences 


o - 4 5 7 

the noveL AntiMiCroBiAL PePtide froM the 

venoM of SoLitAry Bee MACroPiS fuLviPeS 

And itS AnALoGS 

L. MoninCovA 1 , J. SLAninovA 2 , v. fuCiK 2 , 

L. BednArovA 3 , z. voBurKA 4 , J. StrAKA 5 , 

v. CerovSKy 2 

1 Faculty of Science Charles University in Prague, Department 

of Biochemistry, Prague, Czech Republic 


Sciences of the Czech Republic, Chemistry of Natural 

Products, Prague, Czech Republic 


Sciences of the Czech Republic, Molecular Spectroscopy, 

Prague, Czech Republic 


Sciences of the Czech Republic, Medicinal Chemistry, Prague, 



of Zoology, Prague, Czech Republic 

Antimicrobial peptides (AMPs), which are part of the innate 

defense system of practically all living organisms, are among the 

most promising lead compounds for developing medicines in the 

fight against resistant pathogenic bacteria. During recent years we 

have isolated, determined the structure, prepared synthetically and 

characterized several novel AMPs from the venom of different 

species of Hymenoptera. The most interesting AMPs were 

identified in the venom of wild bees. The novel AMP, named 

MAC-1, was isolated from the venom of the solitary bee Macropis 

fulvipes. By Edman degradation and mass spectrometry, its 

primary sequence was established as GFGMALKLLKKVL-NH . 2 

MAC-1 possesses potent antimicrobial activity against both 

Gram-positive and -negative bacteria and moderate hemolytic 

activity against human red blood cells. CD spectra confirmed that 

MAC-1 can form an amphipathic α-helical secondary structure in 

the presence of membrane-mimicking substances as sodium 

dodecyl sulfate or organic solvents like trifluoroethanol. We 

prepared a series of MAC-1 analogs to study the effect of 

incorporating D-amino acid into the sequence on antimicrobial 

and hemolytic activity, α-helicity and serum stability. 

Keywords: peptides; Circular dichroism; Biological activity; 



o - 4 5 8 

PrePArAtion of Modified oLiGonuCLeotideS 

By niCKinG enzyMe AMPLifiCAtion reACtion 

P. Ménová 1 , M. hoCeK 1 

1 Academy of Sciences of CR v.v.i., Institute of Organic 

Chemistry and Biochemistry, Prague 6, Czech Republic 

Nicking enzymes are a class of restriction enzymes which 

cut one strand of the DNA duplex to produce shorter DNA 

fragments. One of the major applications of nicking enzymes is 

in Nicking Enzyme Amplification Reaction (NEAR), which has 

been reported to rapidly synthetize short oligonucleotides under 

mild isothermal conditions. The amplification is based on the 

continuous repetition of two steps: polymerase-mediated primer 

extension and nicking enzyme-mediated cleavage. The cleaved 

oligonucleotide is too short to form a stable duplex with the 

template and leaves the duplex, thus regenerating the initial dimer 

primer-template. 

NEAR has so far been used on an analytical scale for the 

detection and quantification of DNA. Here, we present a method 

based on NEAR developed for the preparation of modified 

oligonucleotides. In the initial experiments the most efficient 

combination of DNA polymerase and nicking enzyme was 

established. These enzymes were used for the incorporation 

of m-aminophenyl-modified nucleobases. The reaction 

temperature, time, and amounts as well as the ratio of both 

enzymes were also optimized. To evaluate the scope of the 

optimized procedure, a series of modified dCXTPs bearing various 

modifications used previously in DNA labelling, protection and 

bioconjugation was incorporated using three different templates. 

Thus, three different sequences of 12-mer ONs bearing either one 

or three modifications were prepared. 

Apart from working on an analytical scale, we also 

transferred the procedure to nanomolar amounts. A protocol for 

the isolation of pure modified oligonucleotides including a 

separation on HPLC was developed. The products were 

characterized by HPLC retention time, UV-VIS spectroscopy and 

MALDI spectrometry. 

Our methodology is complementary to the synthesis of 

medium-length single-stranded oligonucleotides by PEX followed 

by magnetoseparation on streptavidine-coated beads. Thus 

prepared short modified oligonucleotides can find applications as 

modified primers for PEX and PCR as well as in diagnostics. 

Acknowledgement: This work was supported by the Grant 

Agency of the Academy of Sciences of the Czech Republic 

(IAA400040901), by the Czech Science Foundation 

(203/09/0317) and by Gilead Sciences, Inc. (Foster City, CA, 

USA). 

Keywords: oligonucleotides; DNA cleavage; 



s725 

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o - 4 5 9 

deterMinAtion of thC MetABoLiteS in SALivA 

uSinG GC-MS 

z. vAGfoLdi 1 , G. KoCSiS 2 

1 HDF NBC Area Control Center, HDF Havaria Laboratory, 

Budapest, Hungary 

2 HDF Military Hospital, Toxicological Research Department, 


A sensitive analytical method has been developed for the 

determination of metabolites of THC (Δ9-THC-COOH) in the 

saliva. In our hands, the method described produced the best 

reproducibility and the best match for determining metabolites of 

THC in saliva (1 ± 0.05 g). We stable isotope labeled the 

specimens with deuterium (Δ9-THC-COOH-d9) prior to testing, 

and thereby could use the resulting compound as an internal 

standard (ISTD). The resulting substance was subjected 

to alkaline hydrolysis, afterward solid-phase extraction 

(SPE) was preformed, followed by derivatization with 

N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA). Finally the 

result was obtained using the GC-MS system, using the Selective 

Ion Monitoring (SIM) measuring mode. The results of the target 

and qualifier ions were m/z 371 [100], 473 [25], 488[9] in the case 

of 11-nor-9-carboxy-Δ9-THC, and m/z 380[100], 479[24], 482[5] 

in case of 11-nor-9-carboxy-Δ9-THC. During our measurements, 

the calibration curve was linear between 5 and 100 ng/ml. The 

Limit of Detection (LOD) was 1.15 ng/mL and the Limit of 

Quantification (LOQ) was 4.53 ng/ml. During the analysis, we 

did not notice any interference, either in the determination of 

11-nor-Δ 9-carboxy-Δ9-THC nor 11-nor-9-carboxy-Δ9-THC-D9, 

either in the specific testing nor the selective testing. All the results 

of the qualifications were in line with the German Standards 

DIN 32645, which were checked with the B.E.N. computer 

program. 

Keywords: gas chromatography/mass spectrometry; 

Mass spectrometry in life science – ii 


o - 4 6 0 

Liquid ChroMAtoGrAPhy/MASS 

SPeCtroMetry in AtMoSPheriC fine 

PArtiCuLAte MAtter And SeCondAry orGAniC 

AeroSoL reSeArCh 

M. CLAeyS 1 , A. KAhnt 1 , M. SAfi ShALAMzAri 1 , 

f. yASMeen 1 , r. verMeyLen 1 , w. MAenhAut 1 

1 University of Antwerp, Pharmaceutical Sciences, Antwerp, 

Belgium 

During the past decade considerable progress has been made 

in our understanding of the fate of biogenic volatile organic 

compounds (BVOCs), mainly isoprene and monoterpenes, which 

are emitted in large amounts from the vegetation (estimated at 

1150 TgC/year globally) into the atmosphere. Secondary organic 

aerosol (SOA) formation through ozonolysis or photooxidation 

(hydroxyl radical-initiated reactions) of these BVOCs has been 

studied under atmospherically relevant conditions in 

environmental chambers. Molecular characterization of organic 

aerosol constituents is important because it allows one to gain 

insights into aerosol sources and the underlying mechanisms of 

SOA formation and transformation (or aging). A common term to 

denote analytically accessible organic compounds, which provide 

this valuable information in a complex matrix such as ambient 

fine aerosol containing biogenic SOA, is “tracer”. 

Emphasis will be given to the chemical characterization of 

several novel SOA tracers from the photooxidation of isoprene, 

monoterpenes (i.e., α-pinene, β-pinene, and Δ3-carene) and a 

green leaf volatile (i.e., cis-3-hexenal), using liquid 

chromatography/negative ion electrospray ionization mass 

spectrometry [LC/(–)ESI-MS], high-resolution MS, and detailed 

interpretation of MS data. The structural elucidation of the 

following SOA tracers will be addressed: 

• terpenylic acid and related lactone-containing terpenoic 

acids, which are early photooxidation products; 

• di-esters formed between pinic acid and terpenylic 

acid, which are major high-MW products in ambient fine 

aerosol from forested sites; and 

• polar organosulfates derived from isoprene and 

cis-3-hexenal. 

By now the major biogenic SOA tracers in ambient fine 

aerosol from forested sites have been structurally characterized. 

This is a prerequisite to develop quantitative LC/MS methodology 

and perform field studies in the future where time series, day/night 

chemistry, and dependence on meteorological parameters can be 

explored in more detail. 

Keywords: structure elucidation; environmental chemistry; 

oxidation; ozonolysis; mass spectrometry; 



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o - 4 6 1 

MS-BASed PePtidoMiCS for AuthentiCAtion 

of food And non-food CoMModitieS 

S. SforzA 1 , B. PrAndi 1 , S. PAoLeLLA 1 , 

M. BenCivenni 1 , C. vineiS 2 , C. tonetti 2 , 

P. d. Pozzo 2 , t. tedeSChi 1 , G. GALAvernA 1 , 

A. doSSenA 1 

1 University of Parma, Organic and Industrial Chemistry, 

Parma, Italy 

2 CNR, ISMAC, Biella, Italy 

The authenticity of quality products is an issue of paramount 

importance in the production of many food and non food products. 

Authenticity is usually intended as the adherence to defined 

production methods, the use of particular ingredients (for foods) 

or raw materials (for non foods) or a well defined place of 

production. The detection of frauds and the objective assessment 

of authenticity are essential, also because of the high market prices 

of the high-quality brand products. In the present communication, 

it will be shown how MS analysis of proteolytic peptides is a 

useful tool for rapidly and reliably determining the authenticity 

of food and non-food products at the molecular level. Proteolytic 

peptides, generated from the casein breakdown which takes place 

during the production and the ageing of cheeses, were used as 

markers for the mammalian species from which the milk for 

cheese production was obtained. In particular, LC/ESI-MS 

analysis of homologous, but not identical, proteolytic peptides 

derived from alfa -casein allowed to rapidly and reliably assess 

S1 

the presence of cows’ milk in cheeses supposedly made only from 

sheep milk or water-buffalo milk. Marker peptides, derived from 

enzymatic digestion of gluten extracted from wheat, allowed the 

determination of the presence of common wheat in flours declared 

to be made of pure durum wheat varieties. LC/MS analysis also 

allowed to quantify the amount of common wheat, which, 

according to the Italian law, cannot exceed 3%. Enzymatic 

digestion of keratin extracted from textile fibres and peptide 

analysis by LC/ESI-MS allowed to determine not only the 

presence of fibres derived from different species (yak, cashmere 

goat, sheep) but also to assess the relative percentage of usage. In 

all these cases MS-based peptide analysis turned out to be 

essential in order to obtain objective data on the authenticity of 

the specified products. 

Keywords: Peptides; Proteomics; Mass Spectrometry; Liquid 

Chromatography; 



o - 4 6 2 

A noveL CAGed CArBonyL for BioMAteriAL 

ModifiCAtion And CeLL PAtterninG 

L. o’donovAn 1 , P. de BAnK 1 

1 University of Bath, Department of Pharmacy and 

Pharmacology, Bath, United Kingdom 

Patterning cells to mimic the arrangements found in vivo is 

highly desirable for a number of applications, including tissue 

engineering. Photolabile protecting groups (PPGs) have been used 

to “cage” functional groups such as carboxylic acids and amines 

on biomaterial surfaces. [1, 2] “Uncaging” specific areas by masked 

exposure to UV light allows cell-adhesive biomolecules to be 

ligated to the free groups, enabling cell patterning. However, cells 

are rich in these groups, so sequential patterning of different 

species is impossible without modification of both the scaffold 

and existing biomolecules. 

A novel bi-functional linker, possessing a “caged” carbonyl 

(a functional group not naturally found in biology) at one end and 

a free amine for facile attachment to natural and synthetic 

biomaterials was synthesized. [3] This molecule was subsequently 

attached to collagen. Attachment and subsequent PPG loss 

following UVA exposure (10 minutes) was confirmed by UV/vis 

spectroscopy, HPLC and mass spectrometry. 

Cell adhesion and viability on modified biomaterials was 

investigated. Collagen films were modified with PPG and 

photolysed. The presence of PPG on the collagen surface and 

resultant free carbonyls prevented cell adhesion. Surfaces were 

treated with a cell adhesive protein (gelatin) chemically modified 

to incorporate hydrazide functionality. As a control, ligation with 

unmodified gelatin was attempted. Only selective ligation of 

hydrazide functionalised gelatin resulted in reintroduction of cell 

adhesion. 

UVA exposure of collagen films and gels using 

photo-resistant masks resulted in the creation of patterns, 

visualized via treatment with fluorescein-5-thiosemicarbazide. 

The ability to control cell adhesion and create patterns on 

modified biomaterials using a novel caged carbonyl has been 

demonstrated. This approach has great potential for recapitulating 

natural microenvironments and guiding 3D cell growth with 

patterned molecular cues. 

references: 

1. J. Nakanishi et al (2008) Anal Sci 24:67-72. 

2. D. Falconnet et al (2006) Biomaterials 27:3044-63. 

3. L. O’Donovan, P. A. De Bank (in preparation). 

Keywords: Materials Science; Photochemistry; Cell Adhesion; 



s727 

chem. Listy 106, s587–s1425 (2012) 

life sciences 

Mass spectrometry in life science – iii 

o - 4 6 3 

enhAnCed underStAndinG of ion CheMiStry 

for – And throuGh – the ChArACteriSAtion 

of PePtideS By MASS SPeCtroMetry And ion 

MoBiLity SPeCtroMetry 

S. GASKeLL 1 

1 Queen Mary University of London, Office of the Principal, 

London, United Kingdom 

The heavy reliance on tandem mass spectrometry of both 

qualitative and quantitative analyses of the proteomes of both 

simple and complex organisms has emphasised the importance of 

understanding the underlying ion chemistry of peptides. Some of 

the basic concepts are now well established, such as the notion 

that the multiplicity of charge-driven fragmentation pathways 

associated with low energy collisional activation of protonated 

peptides derives from a precursor ion population heterogeneous 

with respect to site of charge - a situation itself derived from the 

“mobility” of the ionising proton(s). In many cases, the resulting 

fragmentation is simple and it is correspondingly straightforward 

to relate fragment ions to precursor structure. In some instances, 

however, ion rearrangements may occur which, unless they are 

understood (or avoided by manipulation of the experiment), may 

lead to erroneous structural conclusions. 

In some instances, for example, rearrangement at the 

C-terminus results in loss of the C-terminal residue to give ions 

denoted as (b +H O) (where the b ion would represent formally 

n-1 2 n-1 

simple cleavage). One such example is the apparent formation of 

macrocyclic forms of b-ions (derived from peptide bond cleavage 

and charge association with the N-terminal fragment); subsequent 

ring opening and further cleavage may afford ions apparently 

misleading of the original sequence. 

The coupling of ion mobility separation with tandem mass 

spectrometry combines analytical techniques based on orthogonal 

ion properties (collision cross-section and mass/charge ratio), and 

allows direct observation of the possible presence of macrocyclic 

structures, assuming their lifetime is long in comparison with the 

timeframe of the experiment. This paper reviews observations 

around this process, and considers factors that favour or disfavour 

this chemistry. 

Keywords: mass spectrometry; ion mobility; proteomics; gas 

phase reactions; 



o - 4 6 4 

utiLizAtion of PhotoACtivABLe nAnoProBe 

And MASS SPeCtroMetry for StruCturAL 

deterMinAtion of CytoChroMe P450 2B4 And 

CytoChroMe B5 interACtion 

t. JeCMen 1 , M. KoBerovA 1 , P. novAK 2 , P. hodeK 1 , 

J. hudeCeK 1 , M. SuLC 2 


of Biochemistry, Prague, Czech Republic 

2 Institute of Microbiology Academy of Sciences of the Czech 

Republic, Laboratory of Molecular Structure Characterization, 


Cytochromes P450 (P450) are terminal monooxygenases of 

mixed function oxygenase system participating in xenobiotics 

detoxification, drug metabolism and unfortunately also carcinogen 

activation. Catalytic activity of some P450s is modulated by 

facultative redox partner cytochrome b which can mediate the 

5 

second electron transfer in P450 catalytic cycle. 

We developed new photolabeling method to expand our 

structural knowledge of P450 interactions, especially in the region 

of membrane domains. Three methionines localized in the 

hydrophobic anchor of cytochrome b were exchanged for 

5 

methionine photoactivable analog during recombinant expression. 

After its photoactivation, covalent bond to proximal amino acid 

is formed fixating potential interaction. Photoactivable 

cytochrome b was employed as a probe for P450 2B4 membrane 

5 

topology mapping. We reconstituted “in vitro” both cytochromes 

in lipid membrane, UV illuminated the mixture and 

electrophoretically separated formed reaction products. Detected 

P450:cytochrome b complexes were most likely in molar ratios 

5 

1:1, 1:2 and 2:1 according to molecular weight standards. 

Afterwards, they were cut off the gel and proteolytically digested. 

Resulting peptide mixture was analyzed employing high 

resolution LC-FT-ICR mass spectrometry. 

We identified cytochromes’ amino acids interacting in the 

lipid membrane environment and like so directly confirmed 

interaction of studied proteins’ membrane helixes for the first 

time. Depending on experimental approach of “in vitro” protein 

reconstitution the different types of cytochrome b binding to the 

5 

membrane is supposed according to our acquired mass 

spectrometric data of covalently cross-linked peptides. 

Obtained structural information is utilized for “in silico” 

refinement of proteins’ interaction models, their “in vitro” 

reconstitution protocols validation and also certification of 

pharmacological and toxicological tests carried on this system. 

Acknowledgement: Supported by GACR (P207/12/0627 and 

305/09/H008) and the Charles University project UNCE #42. 

Keywords: Cytochromes; Membrane proteins; Photoaffinity 

labeling; Mass spectrometry; Structure-activity relationships; 



s728 

chem. Listy 106, s587–s1425 (2012) 

life sciences 


o - 4 6 5 

MASS SPeCtroMetriC inveStiGAtion of in 

vitro SyntheSized PoLyPhenoLiC 

BioPoLyMerS: LiGninS And euMeLAninS 

S. reALe 1 , M. CruCiAneLLi 1 , A. PezzeLLA 2 , 

M. d’iSChiA 2 , f. de AnGeLiS 1 

1 University of L’Aquila, Department of Chemistry, L’Aquila, 

Italy 

2 University of Naples “Federico II”, Department of Organic 

Chemistry and Biochemistry, Napoli, Italy 

MALDI-ToF mass spectrometry has shown to be an 

extremely useful technique for the structural characterization and 

elucidation of the biosynthetic pathway for the in vitro formation 

of the polyphenolic biopolymers lignins and eumelanins. 

Eumelanins and lignins share quite similar biosynthetic pathways. 

The monomeric starting materials are polyphenolic in nature; the 

polymerization processes are both triggered by oxidative enzymes 

and are known to proceed according to radical steps; the final 

polymers themselves, highly heterogeneous in their overall 

structure, are totally insoluble and do not degrade by any 

conventional chemical and/or enzymatic treatment. 

In particular by MALDI-ToF mass spectrometry we were 

able to fully characterize a model coniferyl alcohol lignin 

(the so-called dehydrogenative polymerizate, DHP), produced by 

the action of peroxidase/H O on the alcohol monomer in different 

2 2 

reaction media, namely: pure buffer, organic solvent mixtures, and 

in water under homogeneous conditions guaranteed by the 

presence of a micellized cationic surfactant. The structural 

features of the polymers obtained under such reaction conditions 

allowed us to drive some conclusion as to its in vitro biosynthesis. 

Based on the grounds of the results on lignin biosynthesis, 

an unprecedented breakthrough into the mechanism of synthetic 

eumelanin buildup came from a detailed investigation of the 

oxidative polymerization of DHI (5,6-dihydroxyindole) and its 

N-methyl derivative (NMDHI) by linear and reflectron 

MALDI-MS. Regular collections of oligomers at increasing 

masses, spanning the entire m/z range up to 5000 Da (>30-mer) 

and 8000 Da (>50-mer) for the two buiding blocks respectively, 

were disclosed. It is the first time that the in vitro polymerisation 

of dihydroxyindoles to form synthetic eumelanins is explored up 

to its high mass limits, giving at the same time information on the 

polymerisation mode, whether it follows a stepwise pattern (being 

this the conclusion in our case) or a staking sequencing of small 

sized entities. 

Keywords: Mass spectrometry; Natural Products; biopolymers; 



o - 4 6 6 

differentiAL AnALySiS of An exoSoMe 

ProteoMe 

C. fenSeLAu 1 , M. BurKe 1 , 

S. oStrAnd-roSenBerG 2 

1 Univ of Maryland, Chemistry & Biochemistry, College Park, 

USA 

2 UMBC, Biological Sciences, Baltimore, USA 

Myeloid derived suppressor cells (MDSC) are hypothesized 

to contribute to increased cancer risk by suppressing anti-tumor 

immunity. Inflammation has been observed to enhance MDSC 

activity and to increase cancer risk. To determine how 

inflammation drives MDSC function, mass spectrometry-based 

proteomic strategies have been employed to identify and compare 

proteins in exosomes shed by MDSC developed in the tumor 

environment in mice bearing BALB/c mouse-derived 

4T1 mammary carcinomas, and in mice exposed to the 

pro-inflammatory mediator interleukin-1β. Eight hundred and 

seventy-five proteins were identified in exosomes (80 µg) from 

conventional MDSC using 1D gel electrophoresis, a bottom-up 

proteomic workflow and a meta-search program 

(htts://edwardslab.bmcb.georgetown.edu/PepArML/) that 

integrates MASCOT and six open source search engines. Protein 

identifications were based on two or more peptides with a false 

discovery rate < 10%, and were compared to entries in the 

international exosome database ExoCarta.org. A quantitative 

comparison of protein abundances in exosome samples from 

conventional and inflammatory MDSC (combined total 48 µg) 

was carried out using the iTRAQ protocol. Four repetitive 

analyses were made using a three hour gradient on a 

C-18 nanobore column in a Shimadzu Prominent HPLC 

interfaced to a Thermo LTQ-orbitrap. Isotope ratios were 

automatically determined using Proteome Discoverer v.1.2 

(Thermo Fisher Scientific). Of 1164 unique ratios determined, the 

relative abundances of 87 proteins were found to be altered greater 

than 2-fold. These proteins will be discussed, along with analyses 

of ontology and function. 

Keywords: proteomics; mass spectrometry; 



s729 

chem. Listy 106, s587–s1425 (2012) 

Nanochemistry/Nanotechnology/Molecular machines, Carbon tubes, sheets, balls 

Nanochemistry, nanotechnology and nanostructured 

materials – i 

o - 0 6 1 

MetAL-orGAniC frAMeworKS with dynAMiC 

interLoCKed CoMPonentS 

S. J. LoeB 1 , v. n. vuKotiC 1 , K. zhu 1 

1 University of Windsor, Department of Chemistry, Windsor, 

Canada 

A variety of artificial molecular switches and machines have 

been reported that are based on the relative motion of the 

components of mechanically interlocked molecules (MIMs). 

However, these and other elaborate systems only operate in 

solution or in a condensed phase where the molecular devices are 

randomly dispersed and their motion incoherent. If these tiny 

devices could be organized in a predictable and orderly manner, 

the ideas of creating ultra-dense molecular-based memory or 

controlling electronic properties of materials at the molecular level 

would be very much closer to realization. One way to achieve a 

higher level of molecular organization and coherency would be 

to precisely place the “soft” dynamic molecular components that 

undergo motion (e.g.rotation or translation) into the pores of metal 

organic framework (MOF) materials In this way, the soft MIM 

would be clearly separated from the “hard” structural skeleton of 

the MOF that holds it in place. If this could be accomplished, the 

small size of a MIM unit (~1 nm3 ) and the regularity of a MOF 

framework would allow for an incredibly high density of dynamic 

components in a material: ~1021 per cm3 . The ability to arrange 

mobile and functional molecular components in a highly dense 

and predictable array is a crucial step towards the generation of 

solid-state devices with multiple functions and properties. This 

presentation will describe our newest results in the design, 

synthesis and characterization of MOFs with mechanically 

interlocked components. 

Keywords: Metal-organic frameworks; Rotaxanes; 




o - 0 6 3 

PrePArAtion of ordered MetALLiC 

nAnoStruCtureS for the inveStiGAtion of 

nonLineAr oPtiCAL ProCeSSeS 

v. MondeS 1 , C. GrAf 1 , J. PLenGe 1 , M. BuChhoLz 1 , 

M. KLinG 2 , e. rühL 1 

1 Freie Universität Berlin, Institute of Chemistry and 

Biochemistry - Physical and Theoretical Chemistry, Berlin, 

Germany 

2 Max-Planck Institute of Quantum Optics, Laboratory for 

Attosecond Physics, Garching, Germany 

In the last years there has been an increasing interest in the 

nonlinear optical properties of metallic nanostructures. 

Assemblies of noble metal particles support local surface plasmon 

oscillations leading local field enhancement in such systems. This 

enables us to study multiphoton processes at relatively weak 

excitation power. 

Though lithographic methods yield well-defined 

nanostructures of various morphologies in the micrometer range, 

the preparation of large arrays of ordered metallic structures by 

self-organization of nanoparticles appears to be favorable. This is 

because the nanoparticle approach yields structures with 

dimensions well below 100 nm on areas reaching up to square 

centimeters. Gold nanoparticles of different size and shape are 

prepared by colloidal chemistry. These are arranged in arrays of 

ordered structures by self-organization on sapphire substrates and 

characterized by scanning electron microscopy. The controlled 

distance between the nanoparticles is adjusted by variable size 

organic ligands or the application colloidal masks. 

For the excitation of the plasmonic nanostructures 80 fs, 

800 nm pulses from a Ti:sapphire oscillator were used. 

Multiphoton processes, such as the two-photon 

photoluminescence, second and third harmonic generation were 

investigated in order to characterize the nanostructures and to map 

out and optimize their plasmonic field enhancement. 

Keywords: Nanostructures; Nonlinear optics; Self-assembly; 



s730 

chem. Listy 106, s587–s1425 (2012) 

Nanochemistry / Nanotechnology / Molecular machines, Carbon tubes, sheets, balls 



o - 0 6 4 

Mixed AeroGeLS froM MetAL And 

SeMiConduCtor nAnoPArtiCLeS 

t. hendeL 1 , L. Kühn 2 , v. LeSnyAK 2 , 

A. K. herrMAnn 2 , n. GAPoniK 2 , A. eyChMüLLer 2 

1 Humboldt-Universität zu Berlin, Institut für Chemie, Berlin, 

Germany 

2 Technische Universität Dresden, Institut für Physikalische und 

Elektrochemie, Dresden, Germany 

Self-assembled structures are currently of great interest for 

nanochemistry and chemical nanotechnology. Aerogels consisting 

of nanoparticles combine promising advantages like high porosity, 

low density and huge internal surface, whilst retaining the unique 

properties of their building blocks like quantum-confined optics 

and catalytic behavior. 

Following the recent success in fabrication of new types of 

aerogels from semiconductor and noble metal nanocrystals, we 

demonstrate the water-based formation of mixed aerogels 

consisting of strong emitting, thiol-capped CdTe nanoparticles 

and thiol-functionalized gold seeds. The formation is carried out 

by photochemical treatment and supercritical drying resulting in 

homogeneous and voluminous monoliths. 

The composition and topography of the gel was examined 

by SEM/EDX and TEM proving the highly porous architecture 

and the control of particle ratios in the network through the initial 

colloid mixtures. Optical behavior was studied by diffuse 

reflection and fluorescence spectroscopy verifying the retained 

optical properties. With increasing metal ratio the fluorescence 

intensity is decreased due to the quenching of the metallic system 

on the fluorescence process. By carrying out lifetime 

measurements of the produced gels this effect was examined. 

Porosity measurements by nitrogen adsorption characterized the 

highly porous gel network with specific internal surfaces of 

170 m2 /g which is in good accordance to porosity values of such 

structures found earlier. 

The formation of those gels provides a controllable method 

to produce highly porous hybrid materials of special interest for 

applications in nanoplasmonic devices and photocatalysis 

Keywords: nanoparticles; sol-gel processes; mesoporous 

materials; photooxidation; heterogeneous catalysis; 



materials – ii 

o - 0 6 5 

three-diMenSionAL dnA nAnoStruCtureS for 

BioLoGiCAL And MAteriALS APPLiCAtionS 

h. SLeiMAn 1 , C. MCLAuGhLin 1 , J. fAKhoury 1 , 

G. hAMBLin 1 , K. BuJoLd 1 , C. SerPeLL 1 

1 McGill University, Department of Chemistry, Montreal 

Quebec, Canada 

Three-dimensional structures made of DNA hold the 

potential to encapsulate and release drugs, selectively encage 

nanomaterials, regulate the activity of proteins, and assemble 

networks for catalysis and biomolecule crystallization. A number 

of strategies for DNA construction have been developed, through 

weaving together DNA strands into tiles, or stapling a DNA strand 

into origami structures. Our group has been examining a different 

approach to build DNA nanostructures, in which synthetic 

molecules are used to control and modify DNA self-assembly. 

We will describe the use of this approach to generate 

3D-DNA structures, such as DNA cages and nanotubes, with 

deliberate variation of geometry, size, single- and double-stranded 

forms, permeability and length. These can be dynamically 

switched to different internal volumes, and can be ‘opened’ or 

closed with specific DNA strands. The size-selective 

encapsulation of gold nanoparticles within these host structures 

and the release of this cargo when specific DNA strands are added 

will be shown. Moreover, these compact 3D-DNA structures can 

travel across the plasma membrane of a number of mammalian 

cells, without the aid of any transfection reagents. The molecules 

shown here represent a new class of selective cellular probes and 

drug delivery tools, and can assist the development of nucleic acid 

therapeutic routes. Finally, the use of these cages for the 

3D-organization of synthetic polymer chains in their core or 

corona will be described. 

references: 

1. Science, 2008, 321, 1795. 

2. Chem. Science, 2012, 3, 1980. 

3. J. Am. Chem. Soc., 2012, 134, 4280. 

4. J. Am. Chem. Soc. 2012, 134, 2888. 

5. J. Am. Chem. Soc., 2010, 132, 10212. 

6. Nature Chem. 2010,2, 319. 

7. Nature Chem., 2009, 1, 390 

8. Nature Nanotech., 2009, 4, 349. 

9. J. Am. Chem. Soc., 2007, 13376. 

Keywords: DNA Structures; Supramolecular chemistry; 

Nanostructures; Drug delivery; 



s731 

chem. Listy 106, s587–s1425 (2012) 




o - 0 6 6 

SeLf-ASSeMBLy And oPtiCALLy triGGered 

diSASSeMBLy of dendron-viruS CoMPLexeS 

M. KoStiAinen 1 , o. KASyutiCh 2 , J. CorneLiSSen 3 , 

r. noLte 3 

1 Aalto University, Department of Applied Physics, Aalto 

University, Finland 

2 University of Bristol, H.H. Wills Physics Laboratory, Bristol, 




Nature offers a vast array of biological building blocks that 

can be combined with synthetic materials to generate a variety of 

hierarchical architectures. Viruses are particularly interesting in 

this respect because of their well-defined structure and their 

possibility to function as scaffolds for the preparation of new 

biohybrid materials. We have shown that Cowpea Chlorotic 

Mottle Virus (CCMV) particles can be assembled into 

well-defined micron-sized objects and be reversed back into 

individual viruses by a short optical stimulus. Assembly is 

achieved by employing photo-sensitive dendrons that bind on the 

virus surface through multivalent electrostatic interactions and 

ultimately act as molecular glue between the virus particles. 

Individual virus particles can adopt hexagonal close packing 

within the complex. Optical triggering induces the controlled 

decomposition and charge-switching of dendrons, which results 

in loss of the multivalent interactions and the release of the virus 

particles. Furthermore, the method is not limited to the virus 

particles alone, but can also be applied to other functional protein 

cages, such as magnetoferritin. 

Keywords: Viruses; Dendrimers; DNA; Nanoparticles; 

Magnetic properties; 




o - 0 6 7 

SuPrAMoLeCuLAr funCtionALSiAtion of 

MwCntS with eu(iii) CoMPLexeS: noveL 

LuMineSCent MAteriALS for PhotoniC 

APPLiCAtionS 

L. MAGGini 1 , d. BonifAzi 1 

1 University of Namur (FUNDP), Chemistry, Namur, Belgium 

The luminescence output of a lanthanide complex (LnC) 

results dramatically dependent from the local chemical 

environment and its susceptibility to chemical and photochemical 

degradation. Moreover, the tendency of these luminescent 

modules to aggregate in solution inducing multi-chromophoric 

interactions, dramatically alters the colour quality and the 

intensity of their emission. In principle self-aggregation, together 

with similar parasite electronic interactions, can be attenuated by 

controlling the relative arrangement of the individual 

luminophores. In this respect, carbon nanotubes (CNTs) revealed 

an interesting scaffold for the regulated positioning of LnCs. 

Specifically, as we herein report, we have attempted several non 

covalent supramolecular methodologies for the arrangement of 

Eu(III) complexes onto multi-walled CNTs (MWCNTs), leading 

to novel luminescent materials characterised by the synergetic 

combination of both the luminescent properties of the LnCs and 

the mechanical and electrical properties of MWCNTs. These 

hybrids indeed revealed exceptional features exploitable in both 

the fields of biology and materials science. 

Keywords: Luminescence; Nanotechnology; Lanthanides; 

Nanotubes; Supramolecular chemistry; 



s732 

chem. Listy 106, s587–s1425 (2012) 


Nanoscale particles, cages, sheets and tubes – i 

o - 0 6 8 

reACtion And ProPerty ControL in 

SeLf-ASSeMBLed CoordinAtion CAGeS 

M. fuJitA 1 

1 University of Tokyo, Department of Applied Chemistry, Tokyo, 

Japan 

Since our first report on a metal-cornered molecular square 

(JACS, 1990, 112, 5645), we have been working on molecular 

self-assembly based on coordination chemistry. We have shown 

the highly efficient self-assembly of various cages and capsules 

with large cavities. In this talk, focus will be on the cavity-directed 

reaction and property control of organic molecules, which 

represent one of the most important features of three-dimentional 

hosts. 

references: 

Major references include: 

1. Nature 1995, 378, 469; 

2. Nature 1999, 398, 794; 

3. Science 2006, 312, 251; 

4. PNAS 2009, 106, 10435; 

5. Nature Chem. 2009, 1, 53. 



o - 0 6 9 

teMPLAted SyntheSiS of MoLeCuLAr wire 

nAnorinGS 

h. AnderSon 1 

1 University of Oxford, Department of Chemistry, Oxford, 


This lecture will discuss the use of templates for building 

large pi-conjugated macrocycles, and will demonstrate that it is 

possible to go beyond simple 1:1 template:product stoichiometries 

to direct the synthesis of very large nanorings using small 

templates. For example we have synthesized a covalent nanoring 

consisting of 24 porphyrin units with a molecular weight of 

26 kDa and a diameter of 10 nm. This is well into the size range 

of proteins. The 24 porphyrin units are clearly evident in the STM 

images, providing excellent confirmation of the structure. The 

tertiary structure of the nanoring can be fixed by formation of a 

26-component sandwich complex with DABCO. Denaturation of 

this complex is extremely cooperative, and resembles denaturation 

of a protein. Pi-conjugated nanorings of this type are expected to 

exhibit unusual electronic and photophysical behavior, and to 

mimic light-harvesting chlorophyll arrays. 

references: 

1. “Vernier templating and synthesis of a 12-porphyrin 

nanoring”, M. C. O’Sullivan, J. K. Sprafke, D. 

V. Kondratuk, C. Rinfray, T. D. W. Claridge, A. Saywell, 

M. O. Blunt, J. N. O’Shea, P. H. Beton, M. Malfois, 

H. L. Anderson, Nature 2011, 469, 72–75. 

2. “All-or-nothing cooperative self-assembly of an annulene 

sandwich”, J. K. Sprafke, B. Odell, T. D. W. Claridge, 

H. L. Anderson, Angew. Chem. Int. Ed. 2011, 50, 

5572–5575. 

3. “Two Vernier-templated routes to a 24-porphyrin 

nanoring”, D. V. Kondratuk, L. M. A. Perdigao, 

M. C. O’Sullivan, S. Svatek, G. Smith, J. N. O’Shea, 

P. H. Beton, H. L. Anderson, Angew. Chem. Int. Ed. 2012, 

51, DOI: 10.1002/anie.201202870. 

Keywords: Porphyrinoids; Molecular electronics; Molecular 

recognition; Self-assembly; Nanostructures; 



s733 

chem. Listy 106, s587–s1425 (2012) 



o - 0 7 0 

GuAnidiniuM BindinG ModuLAteS GueSt 

exChAnGe within A MetAL-orGAniC 

tetrAhedrAL CAPSuLe 

S. zArrA 1 , M. M. J. SMuLderS 1 , q. LefeBvre 1 , 

J. K. CLeGG 1 , J. r. nitSChKe 1 

1 University of Cambridge, Department of Chemistry, 

Cambridge, United Kingdom 

In recent years significant attention has been given to the 

synthesis of new metal-organic capsules. These systems have been 

used in diverse fields such as molecular recognition, reactivity 

modulation and catalysis. Our group has previously reported 

the synthesis of a tetrahedral [FeII 4L6 ]4- capsule, 1, as 

tetramethylammonium salt. [1] 1 is water soluble and encapsulates 

guests such as cyclohexane, P and furan within its hydrophobic 

4 

cavity. [2] Moreover, the exterior of this capsule is decorated with 

twelve sulfonate groups that are ideally orientated to undergo 

hydrogen-bonding with the C -symmetric guanidinium cation 

3 

(Gnd + ). 

Herein we demonstrate the use of guanidinium-sulfonate 

interactions [3] to close the faces of a metal-organic container 

molecule, resulting in the modulation of guest exchange kinetics 

between bulk solution and the host’s cavity. [4] 

Host 1 was prepared as guanidinium salt (Gnd 1). Gnd 1 

4 4 

was characterised by NMR spectroscopy, mass spectrometry, 

elemental analysis, and X-ray diffraction. Kinetic studies of 

cyclohexane uptake into host 1 in the presence of various Gnd + 

concentrations showed a linear relationship between the amount 

of bound guanidinium and the rate of guest exchange. 

In conclusion, we have demonstrated that it is possible to 

modulate the kinetics of guest exchange in a self-assembled 

container molecule by capping its faces with hydrogen-bonded 

guanidinium cations. Studies of the uptake kinetics for other 

guests are currently underway. 

references: 

1. P. Mal, D. Schultz, K. Beyeh, K. Rissanen, J. R. Nitschke, 

Angew. Chem. Int. Ed. 2008, 47, 8297-8301; 

2. a) P. Mal, B. Breiner, K. Rissanen, J. R. Nitschke, Science 

2009, 324, 1697-1699; 

b) M. M. J. Smulders, J. R. Nitschke, Chem. Sci. 2012, 3, 

785-788. 

3. V. A. Russell, C. C. Evans, W. Li, M. D. Ward, Science 

1997, 276, 575-579. 

4. S. Zarra, M. M. J. Smulders, Q. Lefebvre, J. K. Clegg, 

J. R. Nitschke, Angew. Chem. Int. Ed. 2012, DOI: 

10.1002/anie.201202665. 

Keywords: Supramolecular chemistry; Kinetics; Water 

chemistry; Host-guest systems; Hydrogen bonds; 



o - 0 7 1 

oSCiLLAtory teMPLAte exChAnGe in 

PoLyoxoMetALAte CAPSuLeS: A LiGAnd 

triGGered, redox Powered, CheMiCALLy 

dAMPed oSCiLLAtion 

h. MirAS 1 , M. SoruS 1 , J. hAwKett 2 , d. SeLLS 2 , 

e. MCinneS 2 , L. Cronin 1 

1 University of Glasgow, Chemistry, Glasgow, United Kingdom 

2 University of Manchester, Chemistry, Manchester, United 

Kingdom 

Polyoxometalates are solution-processable molecular metaloxides 

with nanoscale structures and they are governed by 

self-assembly processes. Their facile one-pot syntheses, high 

conductivity, wide range of composition, size and architecture 

play an important role in the discovery of new materials and 

technologies from bottom-up strategies. 

Unfortunately, self-assembly processes lack of specific 

mechanistic details. These details are crucial for the on-going 

efforts to understand, control, predict and then design 

multifunctional materials utilizing molecular synthons, with 

well-defined structure and geometries. Therefore, becomes 

apparent the necessity to utilize a combination of techniques in a 

smart and constructive way in order to gain access to the 

underlying chemistry which will allow better control over the 

self-assembly process. 

In this work we we describe the redox-driven template 

exchange-oscillation which causes the exchange of the two 

hetero-atom guests, (XO ) 4 3- , contained within the 

{M O (XO ) } 18 54 4 2 6- capsule (X = P 1 V and X = V 2 V ) for two complete 

oscillation cycles (P ?V ?P ?V ?P ) before being ‘chemically’ 

2 2 2 2 2 

damped and we also show that the oscillations can be restarted by 

‘resetting’ the process allowing up to additionally four complete 

cycles as shown by preliminary in-situ UV-Vis experiments. [1] The 

present discovery constitutes the first example of a controlled 

chemical oscillation in supramolecular chemistry accompanied 

with major structural rearrangement. 

These results bring us one step closer to understanding the 

formation of self-assembled systems. The findings presented here 

show the potential of polyoxometalate cluster capsules for the 

design of “smart” molecules and responsive materials. 

references: 

1. H. N. Miras, L. Cronin et. al J. Am. Chem. Soc. 2012, 134, 

6980–6983. 

Keywords: self-assembly; polyoxometalates; nanostructures; 

mass spectrometry; molybdenum; 



s734 

chem. Listy 106, s587–s1425 (2012) 


Molecular devices and machines – i 

o - 1 9 8 

froM MoLeCuLAr SwitCheS to MoLeCuLAr 

MAChineS 

S. frASer 1 

1 Northwestern University, Department of Chemistry, Evanston 

Illinois, USA 

For the best part of 20 years now, the wonder of artificial 

molecular switches (AMSs) acting as nanomachines has inspired 

engineers as well as physicists and chemists. Despite the fact that 

significant progress has been made in the preparation of AMSs of 

increasing complexity and sophistication, the goal of obtaining 

useful energy/work from these switches has eluded us for the most 

part. There have been a few examples of molecules acting as 

primitive machines. These systems are rudimentary, however, and 

fall short of performing useful tasks on any length scale, be it on 

the nano-, micro-, or macroscopic levels. In order to transform 

AMSs into artificial molecular machines (AMMs), we need to 

learn (1) how the coupling/uncoupling to the environment of 

AMSs can be achieved and (2) how these switches can be 

organized into hierarchical assemblies in order to perform work 

at various different length scales. At the single molecule level, the 

focus should be on harnessing the ineluctable effects of thermal 

noise. The principle of microscopic reversibility, which prevents 

a system from doing work on the environment, needs to be 

circumvented. This goal can be achieved, in theory, by either 

externally modulating the conditions (stochastic pumping) of a 

reaction or using a catalyst that can be switched back and forth 

between different states to drive a reaction away from equilibrium. 

At the macroscopic level, one of the major challenges inherent in 

the building of machine-like assemblies lies in the ability to 

control the spatial ordering of switchable molecules in highly 

interactive and robust architectural domains in order to maximize 

the power generated as a result of synchronous switching of 

individual molecules. The development of AMMs holds 

promise for addressable nanomaterials, such as “breathing” 

nanomembranes, “folding” nanosheets, “mechanized” 

enzyme-like mimics, and even perhaps “responsive” nanorobotic 

arms. 

Keywords: molecular machines; molecular switches; 

nanomaterials; 



o - 1 9 9 

PhotoACtivAted direCtionALLy ControLLed 

trAnSit of A non-SyMMetriC MoLeCuLAr 

AxLe throuGh A MACroCyCLe 

M. BAronCini 1 , S. SiLvi 1 , M. venturi 1 , A. Credi 1 

1 University of Bologna, Department of Chemistry “G. 

Ciamician”, Bologna, Italy 

The ability to control motion at the nanoscale is of 

fundamental importance in living organisms, and one of the most 

difficult challenges in nanoscience. In the last few years different 

research groups have developed artificial molecular machines able 

to control the movement of molecules and implemented such 

systems to make responsive materials and surfaces, to control 

catalytic processes, and to develop systems capable of controlling 

the storage of informations and the delivery of drugs upon 

controlled stimulation. But despite all this advancements, the 

development of synthetic molecular motors capable of 

directionally controlled linear or rotary movements is still a big 

challenge. In this work we show as a simple supramolecular 

assembly constituted by a dibenzylammonium axle with two 

different end groups, namely an azobenzene unit at one end and 

a cyclopentyl unit at the other, can be operated to unidirectionally 

thread through a crown ether macrocycle, DB24C8, using UV 

light and potassium ions as stimuli. The described system 

constitutes a first step towards the realization of an artificial 

molecular pump and can also be further developed to synthesize 

molecular linear motors based on rotaxanes and rotary motors 

based on catenanes. Moreover the described system is 

characterized by a minimalist design, facile synthesis, convenient 

switching, and reversibility; all this features constitute essential 

requirements for future real-world applications. 

Keywords: azobenzene; crown ethers; molecular devices; 

supramolecular chemistry; hydrogen bonds; 



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o - 2 0 0 

A rotAxAne-BASed SwitChABLe 

orGAnoCAtALySt 

v. BLAnCo SuArez 1 , A. CArLone 1 , K. d. hAnni 1 , 

d. A. LeiGh 1 , B. LewAndowSKi 1 

1 University of Edinburgh, School of Chemistry, Edinburgh, 


In biology the activity of enzymes is often modulated by cofactors, 

phosphorylation, or allosteric binding. [1] Achieving similar 

control over synthetic catalysts [2] could be useful for influencing 

both the rate and outcome of chemical transformations, the latter 

perhaps by switching ‘on’ and ‘off’ different catalysts that 

promote alternative reactions in the same pot. Rotaxane-based 

molecular shuttles have previously been used for information 

storage, control macroscopic properties of materials, to do 

mechanical work and in various controlled substrate-release 

systems. [3] 

Here we show that the positional changes of a macrocycle 

in a switchable rotaxane can be exploited to conceal and reveal 

an organocatalytically-active functional group. The design of this 

switchable rotaxane consists of a dibenzo-24-crown-8 macrocycle 

and an axle containing both triazolium rings and a 

dibenzylamine/ammonium moiety, [4] which is able to carry out 

iminium catalysis. 

The catalyst can be switched ‘on’ or ‘off’ by addition of acid 

or base which acts to move the rotaxane ring between the binding 

sites. When the rotaxane is protonated the macrocycle 

encapsulates the ammonium group blocking access of reactants 

to the catalytic site. When the secondary amine of the rotaxane is 

not protonated, the triazolium groups are the preferred binding 

sites for the macrocycle and the dibenzylamine group on the axle 

is exposed and available to perform catalysis. 

The switchable catalyst was demonstrated to effectively 

control the rate of Michael addition of an aliphatic thiol to 

trans-cinnamaldehyde. 

references: 

1. T. Traut, Allosteric Regulatory Enzymes, Springer, 

New York, 2008. 

2. a) H. J. Yoon, J. Kuwabara, J.-H. Kim, C. A. Mirkin, 

Science 2010, 330, 66. 

b) J. Wang, B. L. Feringa, Science 2011, 331, 1429. 

3. E. R. Kay, D. A. Leigh, F. Zerbetto, Angew. Chem. Int. Ed. 

2007, 46, 72. 

4. F. Coutrot, E. Busseron, Chem. Eur. J. 2008, 14, 4787. 

Keywords: Rotaxanes; Organocatalysis; Molecular devices; 




o - 2 0 1 

deSiGn And SyntheSiS of PoLyrotAxAneS for 

BiModAL iMAGinG 

J. w. fredy 1 , e. MoreL 1 , A. Guenet 1 , G. viveS 1 , 

v. MArvAud 1 , B. hASenKnoPf 1 

1 University Pierre and Marie Curie, IPCM, Paris, France 

In the past few years, the development of new methods for 

bimodal imaging has known a growing interest for the diagnosis 

and understanding of biological processes. [1] Bimodal imaging 

agents are designed to foster the advantages of two 

complementary imaging techniques on a single object. For 

example, joining a fluorescent probe and a magnetic resonance 

imaging (MRI) contrast agent combines respectively the spatial 

resolution of MRI and sensitivity of optical imaging. [2] 

In our approach, a supramolecular structure for bimodal 

imaging based on a polyrotaxane has been designed. [3] The 

polyrotaxane is based on a water soluble polymer threaded by 

cyclodextrins functionalized by MRI contrast agent or fluorescent 

probe. Stoppers could be positioned at the extremities of the 

polymer chain to avoid unthreading. This supramolecular 

approach presents the advantages of modularity, flexibility and 

potential biodegradability. Moreover, the use of biocompatible 

moieties such as cyclodextrin should permit its use for in vivo 

studies. 

The synthesis of cyclodextrins functionalized by contrast 

agents, and the design of the corresponding polyrotaxanes will be 

presented. 

references: 

1. R. Weissleder, M. J. Pittet, Nature, 2008, 452, 580-589 

2. L. Frullano, T. Meade, J. Biol. Inorg. Chem. 2007, 12, 

939–949 

3. S. Loethen, J-M. Kim, D. H. Thompson, Polymer Reviews, 

2007, 47, 383-418 

Keywords: polyrotaxane; bimodal imaging; cyclodextrin; 



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Molecular devices and machines – ii 

o - 2 0 2 

MoLeCuLAr rotAry MotorS 

B. ferinGA 1 

1 University of Groningen, Chemistry, Groningen, Netherlands 

In our body a fascinating collection of ingenious molecular 

motors and machines make it possible that our cells divide, that 

we can use our muscles and that the consumption of ATP can be 

used to generate force and mobility. A billion times larger than 

these nanoscale protein motors in Nature are the plethora of 

macroscopic motors that power the cars and machinery in daily 

life. The ingenious structures and complex functions present in 

biological systems offer a great challenge to develop synthetic 

nanostructured materials with functions controllable at the 

molecular level. Molecular motors stand out among the most 

challenging goals in nanoscience and will provide the heart of 

future molecular level machinery. Both linear and rotary motors 

are shown as well as the principle of a chemical powered 

molecular motor. Progress in the construction of molecular motors 

anchored to surfaces, the realization of autonomous movement 

and the application of molecular motors to perform useful 

functions is discussed. 

Keywords: molecular motor; molecular machines; 



o - 2 0 3 

An APPLied voLtAGe-triGGered SinGLe 

MoLeCuLAr SPin SwitCh 

G. hArzMAnn 1 , r. friSendA 2 , 

e. Burzuri LinAreS 2 , h. vAn der zAnt 2 , 

M. MAyor 1 

1 University of Basel, Department of Chemistry, Basel, 

Switzerland 

2 Kavli Institute of Nanoscience Delft University of Technology, 

Department of Quantum Nanoscience, Delft, Netherlands 

Herein we report design and successful synthesis of several 

homoleptic and heteroleptic Fe-bisterpyridine complexes. 

Especially the implementation of heteroleptic Fe-bisterpyridine 

complexes into miniaturized electronic devices is of high interest 

in the field of molecular electronics due to the complexes’ 

potential capability of acting as applied voltage-triggered single 

molecular spin switches. 

To allow a spin switching behavior on a single molecular 

level the accordant tailor-made molecules had to be immobilizable 

between two Au-electrodes. Additionally they had to contain a 

core Fe(II)-ion exhibiting an externally controllable spin state. 

Therefore we came up with different heteroleptic 

Fe-bisterpyridine complexes each bearing a symmetric thiolfunctionalized 

terpyridine ligand to enable the complexes’ 

immobilization between two electrodes. The varying second 

terpyridine ligand incorporated customizable push-/pull-systems 

exhibiting a strong dipole moment needed to provide the desired 

sensitivity of the described system towards an applied 

electric field. The challenge to assemble the uncommon 

4,4''-disubstitution pattern required for the terpyridine core moiety 

was overcome by the development of an unprecedented synthetic 

route. We applied Suzuki-Miyaura cross coupling reactions 

utilizing suitable 4-substituted lithium triisopropyl 

2-pyridylborates to form the desired 4,4''-disubstituted 2,2':6',2''- 

-terpyridine ligands. Remarkably this coupling methodology, 

though inevitably depending on α-boronylated heteroaryls, allows 

a successful assembly of several 2,2':6',2''-terpyridines avoiding 

the concurring and usually favored proto-deboronation 

previously described in literature. Finally a cascade of further 

Suzuki-Miyaura reactions led to the desired target compounds. 

For all Fe-bisterpyridine complexes characterized by X-ray 

crystallography consistently almost perfect octahedral geometries 

were revealed indicating the required low-spin configurations of 

the Fe(II)-ions. In the ongoing physical experiments an alternation 

of the applied electric field strengths between the Au-electrodes 

should result in a distortion of the original octahedral geometry 

towards pseudo-planarity triggered by the alignment of the 

push/pull-ligand with the externally applied electric field. This 

should then result in a reversible switching of the Fe(II)-ion’s spin 

state. 

Keywords: Molecular Electronics; Cross-coupling; Tridentate 

ligands; Spin crossover; Single-molecule studies; 



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o - 2 0 4 

deSiGn And SyntheSiS of MoLeCuLAr deviCeS 

for inSuLAtinG SurfACeS 

A. PuJoL 1 , A. Gourdon 2 

1 CEMES - UPS, 31, Toulouse, France 

2 CEMES -CNRS, 31, Toulouse, France 

For many years, one of the key challenges in nanosciences 

has been the design and synthesis of molecule-devices with 

electronic (switches…) or mechanical (rotor, nanocar…) 

functions. These nano-objects are generally well-studied at the 

single molecule level by Scanning Tunnelling Microscopy (STM) 

on metallic surfaces. However electronic coupling between the 

adsorbed molecules and these substrates prevents the study of 

molecular electronical or photophysical properties. In contrast, 

recent advances in Non-Contact Atomic Force Microscopy 

(NC-AFM), which now allows precise imaging at the 

sub-molecular level, have opened the possibility to explore 

molecular devices on bulk insulators surfaces [1] and to study 

electronic and optical properties of nano-objects. Unfortunately, 

molecules strongly diffuse on these surfaces leading to 3D 

clustering. 

In this context, we design and synthesize molecules prone 

to be observed as single objects by NC-AFM on insulating 

surfaces (NaCl, KBr). To do so, we have prepared a family of 

molecules comprising planar and rigid aromatic cores to facilitate 

image interpretation, equipped with several alkylated chains with 

various sizes ending by anchoring groups to maximize the 

molecule/substrate interaction. [2] The anchoring groups are 

chemical functions with a strong dipolar moment (ex. nitrile, 

carboxylic acid...) or local charges (zwitterions). One of these 

molecules (2,3,6,7,10,11-hexacyanopropyloxytriphenylene) has 

recently been studied on KBr(001) and results are encouraging to 

continue in this direction. [3] 

references: 

1. M. Bammerlin, R. Luthi, E. Meyer, A. Baratoff, J. Lu, 

and al., Appl. Phys. A Mater., 1998, 66, S293-S294. 

2. T. Trevethan, B. Such, T. Glatzel, A. L. Shluger, E. Meyer, 

P. de Mendoza, and A. M. Echavarren, Small, 2011, 7, 

1264-1270. 

3. A. Hinaut, A. Pujol, F. Chaumeton, D. Martrou, A. 

Gourdon, and S. Gauthier, Belstein J. Nanotechnol., 2012, 

3, 221-229. 

Keywords: Synthesis design; Click chemistry; Zwitterions; 

Molecular electronics; Adsorption; 

Molecular devices and machines – iii 


o - 2 0 5 

dnA nAnoMAChineS And nAnodeviCeS 

i. wiLLner 1 

1 The Hebrew University of Jerusalem, Institute of Chemistry, 


The information encoded in the base sequence of nucleic 

acids allows the design of DNA nanostructures with emerging 

properties. This will be exemplified with the following systems: 

(i) The design of different DNA machines, including “tweezers”, 

a “walker”, a “stepper” and a “crane”, using Hg2+ , H + , and 

DNA strands as “fuels”. Specifically, the synthesis of two- and 

three-ring DNA catenanes will be addressed, and the programmed, 

dynamic and reversible translocation of the catenane rings across 

pre-designed topologies will be described. The catenane machines 

will be used as functional units for the programmed organization 

of different sized Au nanoparticle nanostructures. 

Machine-dictated switchable plasmonic effects will be discussed. 

(ii) DNA provides an organizing scaffold for controlling chemical 

reactivity on surfaces. This will be exemplified with the design 

of a “walker” DNA on surfaces and with the organization of 

relay/semiconductor quantum dots on the scaffolds as 

photosynthetic model systems. (iii) Catalytic DNAs (DNAzymes) 

act as isothermal autocatalytic replication machineries that, upon 

interaction with a target fuel, lead to the self-assembly of catalytic 

DNA nanowires. Application of the systems for the ultrasensitive 

detection of DNA will be discussed. 

Keywords: Nanostructures; DNA; Self-assembly; 

Autocatalysis; Catenanes; 



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o - 2 0 6 

AnALoG And diGitAL ControL of MoLeCuLAr 

funCtion By PhotoChroMeS 

d. GuSt 1 , t. A. Moore 1 , A.L. Moore 1 

1 Arizona State University, Department of Chemistry and 

Biochemistry, Tempe Arizona, USA 

Photochromes can interact with covalently linked 

chromophores via energy or electron transfer and modification of 

electronic coupling. Because these interactions are different for 

the different isomers of the photochrome, these species may act 

as digital switches to turn some properties of other chromophores 

on or off. Molecules constructed in this way can perform logic 

operations or other binary functions. The inputs and outputs of 

these molecular devices can all be photonic, which avoids product 

buildup, a need for physical access for reagents, and other 

limitations inherent in the use of chemical inputs and outputs. 

Such molecular digital devices may also be reconfigured to 

perform other operations by changes in the wavelengths of the 

inputs and outputs. For example, a molecule capable of carrying 

out 13 different logic operations has been reported. In addition, 

ensembles of photochromic molecules can carry out analog 

control functions. In one example, a photochrome controls the 

quantum yield of photoinduced electron transfer in an artificial 

photosynthetic antenna-reaction center, thus mimicking a natural 

photoprotective mechanism found in cyanobacteria. In another, 

irradiation of a photochrome with modulated long-wavelength 

light in turn modulates fluorescence of an attached chromophore 

at a shorter wavelength. Such function could be useful in reducing 

interference in fluorescent probe applications. 

Keywords: Photochemistry; Photochromism; Molecular 

devices; 



o - 2 0 7 

LiGht-hArveStinG AntennAe BASed on 

LuMineSCent dendriMerS 

P. Ceroni 1 , M. BAronCini 1 , G. BerGAMini 1 , 

e. MArChi 1 

1 University of Bologna, Chemistry Ciamician, Bologna, Italy 

Dendrimers are ideal candidates to build up molecular 

antennae since a large number of different chromophoric units can 

be arranged in a nanoobject with a predetermined pattern. Because 

of their tree-like multi-branched structure, they can also form 

internal dynamic cavities in which small molecules or ions can be 

hosted, so that supramolecular structures can be self-assembled. 

The value of the resulting supramolecular systems relies not only 

on the total number of self-assembled molecules, but also on the 

diversity of the components and on the functions resulting from 

their mutual interactions. 

In this view, we have studied self-assembled supramolecular 

structures, based on dendrimers and metal 

complexes [1] or molecular clips, which can perform also as 

sensitizers of lanthanide ions. For example, we have 

investigated several families of dendrimers containing a 

1,4,8,11-tetraazacyclotetradecane (cyclam) core, [2] one of the most 

extensively investigated ligands in coordination chemistry, to 

build up metal complexes with dendritic ligands. [2] Particularly 

interesting results have been obtained in the case of a dendrimer 

constituted by two cyclam units linked by a photoswitchable 

azobenzene chromophore and 12 naphthalene units at the 

periphery. In this dendrimer, the distance between the two 

cyclam units can be modulated by light stimuli thanks to the 

presence of an azobenzene moiety which can be reversibly 

switched between trans and cis isomer by light irradiation. 

Therefore, the trans and cis isomers display different 

coordination ability toward Zn(II) ion in CH CN:CH Cl 3 2 2 

solution. Moreover, upon naphthalene excitation photosensitized 

azobenzene isomerization takes place. To the best of our 

knowledge, this represents the first example of a dendrimer 

containing photochromic, luminescent and metal coordinating 

units. 

references: 

1. C. Giansante, P. Ceroni, V. Balzani, F. Vögtle, 


2. G. Bergamini, E. Marchi, P. Ceroni, Coord. Chem. Rev. 

2011, 255, 2458. 

Keywords: photophysics; azobenzene; metal complex; energy 

transfer; photoisomerization; 



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o - 2 0 8 

A hyBrid donor-ACCePtor1-ACCePtor2 triAd 

BASed on different eLeCtron ACCePtinG 

fuLLereneS 

C. viLLeGAS 1 , J. L. deLGAdo 1 , P. A. Bouit 1 , 

B. GriMM 2 , w. Seitz 2 , d. M. GuLdi 2 , n. MArtín 1 

1 universidad Complutense De Madrid, Organic Chemistry, 

Madrid, Spain 

2 Friedrich-Alexander-University, Chemistry and Pharmacy 

&Interdisciplinary Center of Molecular Materials, Erlangen, 

Germany 

Donor-acceptor (D-A) systems have been extensively 

studied in order to understand the electron transfer (E.T.) process 

that takes place in the photosynthesis of plants. [1] The mechanism 

of this process is based on an unidirectional flow of electrons to 

generate a long-lived charge separation state, thus, the existence 

of a redox gradient between different fragments of the molecule, 

is an important issue to be addressed. Fullerenes and their 

derivatives have been used as electron acceptor compounds of 

these artificial models due to their electronic characteristics, 

providing an accelerate charge separation and decelerate charge 

recombination in the charge separation state. [2] 

A great variety of dyads, triads and tetrads containing one 

fullerene unit have been reported, although the preparation of 

related systems bearing different fullerenes units have been 

explored in a lesser extent. [3] 

Considering the unique properties of fullerenes and 

porphyrins, here we report the design and preparation of 

a new donor-acceptor -acceptor (D-A -A ) triad formed by 

1 2 1 2 

Zn-porphyrin as electron donor and C /C fullerene dimer as 

60 70 

electron acceptor fragment. [4] 

The new triad displays an electron gradient due to the 

two different fullerene fragments present in the molecule. 

Photophysical studies reveal the existence of two processes of 

electron transfer. This triad represent one of rare case in which 

the E.T. goes from a primary electron acceptor (C ) to a 

60 

secondary electron acceptor (C ) affording the radical ion par and 

70 

the corresponding charge separation state. 

references: 

1. D. Gust, T. A. Moore and A. L. Moore, Acc. Chem. Res., 

2001, 34, 40. 

2. G. Accorsi and N. Armaroli, J. Phys. Chem. C, 2010, 114, 

1385. 

3. B.M. Illescas, J. Santos, M. Wielopolski, C. M. Atienza, 

N. Martín and D. M. Guldi, Chem. Commun., 2009, 5374. 

4. C. Villegas, J.L. Delgado, P.-A. Bouit, B. Grimm, W. 

Seitz, N. Martín, D.M. Guldi, Chem. Sci., 2011, 2, 1677. 

Keywords: Fullerenes; Electron transfer; 


Nanoscale particles, cages, sheets and tubes – ii 

o - 3 4 0 

SuPrAMoLeCuLAr CheMiStry with CArBon 

nAnoStruCtureS 

M. PrAto 1 

1 Universita di Trieste, Dipartimento di Scienze Chimiche e 

Farmaceutiche, Trieste, Italy 

Among the wide range of novel nanometer scale structures 

available, single-wall carbon nanotubes (SWNT) and multi-wall 

carbon nanotubes (MWNT) and more recently, graphene, stand 

as unique materials for fundamental research and potential 

applications. However, manipulation and processing of NTs has 

been difficult because of their intractability and insolubility in 

most common solvents. Considerable effort has therefore been 

devoted to the chemical modification of NTs and graphene, which 

might pave the way to many useful applications. 

Our group has been involved in the organic functionalization 

of various types of nanocarbons, including carbon nanotubes, 

nanohorns, fullerenes, graphene and nanoonions. During this talk, 

we will report on the most recent advances in our group, which 

have led to several interesting applications in many fields. For 

instance, functionalized carbon nanotubes stimulate neuronal 

communication or can serve as carriers for innovative drug 

delivery systems. Especially the use of carbon nanotubes as active 

substrates for neuronal growth has given so far very exciting 

results. Not only nanotubes are compatible with neurons, but 

especially they play a very interesting role in interneuron 

communication. Improved synaptic plasticity is just one example. 

On the other hand, carbon nanostructures are ideal supports 

for catalysts useful in water splitting devices. Low overpotentials 

and high turnover numbers can be achieved using carbon 

nanostructures as active supports. 

Keywords: Carbon Nanotubes; Graphene; Supramolecular 

Chemistry; Water Splitting; 



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o - 3 4 1 

fABriCAtion, ChArACteriSAtion, And heALth 

CAre APPLiCAtionS of CArBohydrAte-CArBon 

hyBrid nAnoMAteriALS 

M. hArtMAnn 1 , P. Betz 2 , y. Sun 2 , S. n. GorB 3 , 

t. K. LindhorSt 4 , A. KrueGer 2 , C. BLAnford 5 , 

S. L. fLitSCh 1 

1 Manchester Interdisciplinary Biocentre, School of Chemistry, 

Manchester, United Kingdom 

2 Institute for Organic Chemistry, Department of Chemistry, 

Würzburg, Germany 

3 Zoological Institute, Department of Functional Morphology 

and Biomechanics, Kiel, Germany 

4 Otto Diels Institute of Organic Chemistry, Department of 

Chemistry, Kiel, Germany 

5 Manchester Interdisciplinary Biocentre, School of Materials 

Science, Manchester, United Kingdom 

Diamond and graphite are two allotropes of carbon with 

interesting, but completely differing chemical and mechanical 

properties. In diamond, the carbon atoms form a tetrahedral 

lattice, whereas in graphite they build up layers of sheets with the 

atoms in honeycomb arrangements. Their nanoscale structures, 

namely nano diamond (ND) and graphene sheets (GS), share a 

promising feature: low cytotoxicity. [1, 2] Therefore, functional 

ND- und GS-materials will become valuable tools for future 

health care applications. 

We functionalised ND and GS covalently, using 

carbohydrates as biological recognition unit to yield gylco-ND [3] 

and glyco-GS, respectively. Glycoconjugates are ubiquitous 

biological structures, which serve as recognition site in many 

different cellular health- and disease-related processes. [4] 

Carbohydrate-carbon hybrids are thus benign biologically active 

nanoscale materials with a large potential in health care 

applications. 

They can be applied for the quick, straightforward and 

efficient removal of pathogens from water samples [3] and further 

urgent health care issues. 

references: 

1. A. Krueger, J. Mater. Chem. 2011, 21, 12571.12578. 

2. V. C. Sanchez, A. Jachak, R. H. Hurt, A. B. Kane, 

Chem. Res. Toxicol. 2012, 25, 15-34. 

3. M. Hartmann, P. Betz, Y. Sun, S. N. Gorb, T. K. Lindhorst, 

A. Krueger, Chem. Eur. J. 2012, DOI: 

10.1002/chem.201104069. 

4. A. Varki, Glycobiology, 1993, 3, 2, 97-130 

Keywords: Nanoparticles; Glycoconjugates; Carbohydrates; 

Carbon; Biological activity; 



o - 3 4 2 

SyntheSiS of StAPLed Pi-ConJuGAted heLiCAL 

SCAffoLdS. A BottoM-uP APProACh to ChirAL 

CArBon nAnoCoiLS 

A. MArtin-LASAntA 1 , n. fuenteS 1 , 

L. ALvArez de CienfueGoS 1 , 

d. ChoqueSiLLo-LAzArte 2 , J. M. GArCiA-ruiz 2 , 

A. J. MotA 3 , d. J. CArdenAS 4 , M. riBAGordA 4 , 

M. C. CArreno 4 , J. M. CuervA 1 

1 Facultad De Ciencias Universidad de Granada, Quimica 

Organica, Granada, Spain 

2 IACT CISC-UGR, Laboratorio de Estudios Cristalograficos, 

Granada, Spain 

3 Facultad De Ciencias Universidad de Granada, Quimica 

Inorganica, Granada, Spain 

4 Universidad Autonoma de Madrid, Quimica Organica, 

Madrid, Spain 

Carbon nanocoils (CNCs) are carbon allotropes with tubular 

diameters down to 20 nm. CNCs have been used to generate 

magnetic fields emulating the behaviour of a solenoid and they 

have shown pseudoelastic properties allowing elongations up to 

42%. In a broad sense, [n]-helicenes and o-phenylenes can be 

considered CNCs but they have extremely rigid backbones in the 

axial direction and densely packed pi-systems. Hence, the 

expected electron transport (ET) through the helical backbone 

could be hindered by ET through the p-stacked rings. On the other 

hand, conformationally flexible o-phenylene-ethynylene 

oligomers (o-PEOs) can adopt helical arrangements by means of 

supramolecular interactions. The covalent stapling of 

conformationally dynamic o-PEOs would lead to the 

corresponding less tight CNCs. Here, we report on the synthesis 

and chiroptical properties of the smallest flexible member of 

CNCs family able to retain their striking properties. 

Firstly, we screened some hydroxylated o-PEOs with 

different diacids and nanocoils were obtained in good yields. 

Using a chiral l-tartaric acid, an intramolecular central-to-helix 

chirality transfer was revealed by CD spectroscopy. However, 

mono-stapled compounds were too flexible and underwent 

racemization at room temperature. To increase the stiffness, we 

synthesized bis-stapled nanocoils and alkene methatesis was used 

to obtain asymmetrically stapled compounds. Computer models 

and CD measurements agreed that meta- and para- substituted 

compounds have P and M helical configuration respectively. DFT 

calculations also revealed that elongations up to 2 A (55% longer) 

were accessible with low energetic requirements (< 3 Kcal mol- 1 ). An inspection of the HOMO-LUMO gaps during the stretching 

suggested that the p-stacking stabilisation was not present when 

the two final benzene rings were separated 0.75 A. In that case, 

the ET along the backbone would be favoured over the axial 

through-space ET emulating the behaviour of a solenoid. 

Keywords: helical structures; chirality; electron transport; 



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o - 3 4 3 

eLeCtroACtive CArBon-nAnoforMS: 

funCtionALizAtion And ProPertieS 

L. rodriGuez Perez 1 , J. MAteoS GiL 1 , r. GArCiA 1 , 

C. viLLeGAS 1 , J. L. deLGAdo 1 , M. A. herrAnz 1 , 

n. MArtín 1 

1 Facultad De Química Universidad Complutense De Madrid, 

Quimica Organica, Madrid, Spain 

Carbon-based materials such as fullerenes, carbon nanotubes 

or graphene, play a major role in today’s science and technology. 

In particular, carbon nanotubes and more recently graphene offer 

promising opportunities for electronic devices and chemical 

sensors due to its striking mechanical, optical and electrical 

properties. 

The development of functional structures, between 

different electroactive units and the previously mentioned 

carbon-nanoforms, able to transform sunlight into electrical or 

chemical energy are important features for the fabrication of 

innovative optoelectronic devices. 

In this regard, the remarkable gain of aromaticity and 

planarity that π-extended TTF (exTTF) derivatives reveals upon 

oxidation renders them an interesting donor unit that has been 

extensively used in the preparation of different donor-acceptor 

ensembles. In the same way, heptamethine cyanine derivatives 

have been used for the preparation of donor-acceptor dyads 

considering fullerenes as electron acceptor fragments. On the 

other hand, interfacing strong electron-acceptors with different 

carbon-nanoform has been scarcely explored and, in this sense, 

tetracyanoanthraquinodimethane derivatives (TCAQ) are suitable 

electron-acceptor systems that have been investigated with respect 

to their charge-transfer efficiency to conjugated polymers and 

fullerenes. 

However, for pursuing the practical applications of these 

carbon nanostructures, one major drawback is their difficult 

processability and/or dispersability which decrease the overall 

yields of usable material and interfere with most of the desired 

properties. A fair amount of work focuses on their non-covalent 

and the covalent functionalization as a means to overcome the 

obstacles of low solubility. While the supramolecular modification 

depends on interactions affected by multiple parameters 

(concentration, solvent,..), the covalente functionalization 

improves the stability of the nanoconjugates making them suitable 

for practical applications. 

In this contribution, we will present different covalent 

approaches towards the formation of nanohybrids based on carbon 

nanotubes or graphene and different electron-donor (exTTF, 

cyanines) and electron-acceptor (TCAQ) moieties. The detailed 

characterization of these nanostructures will be discussed. 

Keywords: Nanotubes; Graphene; Donor-acceptor systems; 

Electron transfer; 


Nanoscale particles, cages, sheets and tubes – iii 

o - 3 4 4 

CheMiCAL funCtionALizAtion of SynthetiC 

CArBon ALLotroPeS 

A. hirSCh 1 

1 University Erlangen-Nuremberg, Institute of Organic 

Chemistry II, Erlangen, Germany 

Chemical functionalization of new C-allotropes is of 

fundamental interest and opens the door to unprecedented 

materials applications. In principle, the physical and chemical 

properties of fullerenes, carbon nanotubes (CNTs) and graphene 

are related to each other, although their levels of development vary 

considerably. In order to efficiently explore the reactivity of the 

less developed CNTs and especially that of graphene it is our goal 

to provide a unifying approach for the chemistry of all three new 

carbon allotropes. The fullerenes present the first family of 

synthetic carbon allotropes. Since their availability in macroscopic 

quantities numerous investigations with respect to their physical 

characterization and chemical functionalization have been carried 

out. CNTs - the second new family of C-allotropes – exhibit at 

least the same potential for unprecedented applications. Their 

chemistry, however, is much less developed. Although many 

protocols for covalent and non-covalent CNT functionalization 

have been published there are still many fundamental problems 

to be solved. This includes inter alia the highly selective 

functionalization of metallic- or semiconducting SWNTs, the high 

throughput isolation of SWNTs with single helicity, the 

development of general concepts allowing for tunable doping of 

individualized tubes with single helicity or least defined transport 

characteristics (metallic – semiconductive). Finally, the youngest 

representative in the list of new C-allotropes is graphene and the 

exploration of its chemistry has just begun to start. So far only 

investigation on the functionalization of defect rich graphene 

oxide (GO) but not intact graphene itself have been published. 

Compared to the various flavours of CNTs (broad variation of 

helicities, single walled, multi walled) graphene is a much more 

uniform material. This will facilitate the development of its 

chemistry considerably. We will present a series of new results of 

covalent and non-covalent functionalizations of fullerenes, carbon 

nanotubes and graphene. 

Keywords: graphene; fullerene; carbon nanotube; synthetic 

carbon allotrope; 



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o - 3 4 5 

SiLiCon nAnoCryStALS: why do SoMe exhiBit 

Size dePendent PhotoLuMineSCenCe whiLe 

otherS SiMPLy hAve the BLueS? 

J. veinot 1 

1 University of Alberta, Chemistry, Edmonton, Canada 

Silicon nanocrystals (SiNCs) offer many benefits over 

prototypical CdSe quantum dots including biocompatibility. 

Adding to their appeal, SiNCs are also compatible with standard 

electronics and communications platforms, some exhibit size 

dependent photoluminescence and evidence to date suggests 

stabilizing surface groups are not labile. Numerous innovative 

solution-, gas-, and solid-phase methods have been developed to 

realize size-controlled SiNC synthesis. All procedures afford 

SiNCs that appear seemingly identical. However, based 

upon SiNC optical response it is clear they are not. SiNCs 

prepared using high-temperature methods routinely exhibit 

photoluminescence agreeing with the effective mass 

approximation. SiNCs prepared via solution methods exhibit blue 

emission that is independent of particle size. Despite many 

creative proposals, a concrete explanation for this difference has 

eluded the nanomaterials community for no less than a decade. 

This apparent dichotomy brings into question our understanding 

of SiNC properties and potentially limits the full scope their 

applications. This presentation will introduce SiNCs and many of 

the standard literature procedures used for their preparation. Focus 

will then shift to oxide-embedded and surface functionalized 

freestanding SiNCs prepared using procedures developed in the 

Veinot Laboratory and our deermination of the origin of the blue 

emission noted above. A detailed comparison of blue-emitting 

SiNCs synthesized by the Kauzlarich (UC Davis) and Tilley 

(Victoria University of Wellington) groups will also be described. 

Keywords: nanoparticles; quantum dots; silicon; 

semiconductors; fluoresence; 



o - 3 4 6 

funCtionALized SiLiCon nAnoCryStALS for 

PhotoLuMineSCenCe BASed CheMoSenSorS 

J. diAn 1 , M. KoneCny 1 , G. BronCovA 2 , i. JeLineK 3 , 

J. JindriCh 4 

1 Charles University in Prague Faculty of Mathematics and 

Physics, Chemical Physics and Optics, Prague 2, Czech 

Republic 

2 Institute of Chemical Technology Faculty of Chemical 

Technology, Analytical Chemistry, Prague 6, Czech Republic 



4 Charles University in Prague Faculty of Science, Organic 


Physical properties of nanocrystalline silicon are 

substantially different as compared to crystalline silicon. One of 

the most striking is bright visible photoluminescence observed at 

room temperature. In the presence of chemical species 

photoluminescence changes and this behavior is employed in 

sensors of chemical compounds. Porous silicon is a 

nanocrystalline silicon based material with complex morphology 

especially useful for detection of chemical species. 

Photoluminescence detection of organic compounds with 

porous silicon sensors is based on photoluminescence quenching. 

The magnitude of this quenching depends on both the 

concentration and quenching strength of analyte. The role of 

principal mechanisms of photoluminescence quenching in porous 

silicon - exciton dielectric quenching and capillary condensation 

effect – will be discussed and their manifestation in gas and liquid 

phase will be demonstrated. For applications in electronic noses 

or tongues an improvement of sensor selectivity response is 

needed. This task was achieved by functionalization of the porous 

silicon surface by molecules with molecular recognition 

properties. Examples of surface functionalization via several 

routes like oxidation (replacement of Si-H bonds with Si-O 

bonds), hydrosilylation with methyl-10-undecenoate and various 

beta-cyclodextrin derivatives (replacement of Si-H bonds with 

Si-C bonds) and electrodeposition of polymer films (polypyrrole) 

will be presented together with specific challenges in chemical 

manipulation of nanocrystalline silicon. Modification of 

photoluminescence sensor response due to surface 

functionalization will be presented and possible mechanisms 

behind modified sensors response will be discussed for various 

classes of organic molecules. Additional information about 

chemical nature of detected analytes can be obtained from 

measurements of photoluminescence decay time; advantages of 

simultaneous measurements of photoluminescence intensity and 

photoluminescence decay changes will be presented. Several 

topics connected with operation of porous silicon sensor in real 

applications will be addressed. 

Acknowledgement: Financial support of Technological Agency 

of the Czech Republic in the frame of the project TA01011363 is 

acknowledged. 

Keywords: silicon nanocrystals; porous silicon; chemosensors; 

photoluminescence; molecular recognition; 



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materials – iii 

o - 3 4 7 

MuLtifunCtionAL SuPrAMoLeCuLAr 

eLeCtroniCS 

P. SAMori 1 

1 University of Strasbourg - CNRS, ISIS, Strasbourg, France 

Multifunctional materials are key in organic 

(opto)electronics. However, their practical use requires the 

optimization of the self-assembly of multimodular architectures at 

surfaces using non-conventional methods, their controlled 

manipulation and responsiveness to external stimuli, and the 

quantitative study of various physicochemical properties at distinct 

length-/time-scales. My lecture will review our recent results on: 

(i) Development of novel (post)processing methods to 

produce ordered supramolecular electroactive 

architectures. [1] 

(ii) Supramolecular scaffolding, based on H-bonding or 

metallo-ligand interactions, to control the position of 

functional units at surfaces. [2] 

(iii) Responsive interfaces like the realization of the first 

dynamer operating at surfaces visualized on the sub-nm 

scale by Scanning Tunneling Microscopy, [3] and 

prototypes of light-powered mechano-chemical 

switches. The bistable nature of the latter were exploited 

to develop optically-modulable nanoscopic and 

macroscopic junctions. [4] 

(iv) Scanning Probe Microscopies beyond imaging to 

explore electronics processes, like photovoltaic 

activities, in multicomponent architectures. [5] Further, 

the electrochemical local reduction of graphene oxide 

with and AFM tip followed by the C-AFM study of the 

electrical properties of the manipulated architecture will 

be presented, [6] towards blueprinting macromolecular 

electronics. [7] 

(v) Supramolecular approaches to organic electronics allow 

improvement of the performance of devices, e.g. 

through the tailoring of percolation pathways for 

charge transport in polycrystalline films for FETs, [8] 

bottom-up fabrication of asymmetric electrodes for 

ambipolar FETs, [9] and realization of bi-functional 

FET. [10] 

references: 

1. Adv. Funct. Mater. 2011, 21, 1279. 

2. a) Angew. Chem. Int. Ed. 2007, 46, 245. 

b) Adv. Mater. 2008, 20, 2433. 

3. Angew. Chem. Int. Ed. 2010, 49, 1963 

4. a) PNAS 2007, 104, 9937. 

b) JACS 2008, 130, 9192. 

c) Angew. Chem. Int. Ed. 2008, 47, 3407. 

5. Acc. Chem. Res. 2010, 43, 541. 

6. JACS 2010, 132, 14130. 

7. Nat. Chem. 2011, 3, 431. 

8. Chem. Commun. 2012, 48, 1562. 

9. Adv. Mater. 2010, 22, 5018. 

10. Adv. Mater. 2011, 23, 1447. 

Keywords: supramolecular electronics; self-assembly; 

nanochemistry; 




o - 3 4 8 

MoLeCuLAr eLeCtroniCS At the uLtiMAte 

LiMit of SinGLe MoLeCuLeS interroGAted in 

SoLid-StAte deviCeS 

t. BJornhoLM 1 

1 University of Copenhagen, Nano-Science Center & 

Department of Chemistry, Copenhagen, Denmark 

One of the challenging goals of molecular electronics is to 

understand and master electronic devices at the single-molecule 

level. Based on recent progress employing three terminal 

solid-state devices [1-5] it is possible to interrogate a single molecule 

in a metal gap in great detail. The talk will focus on new 

insight into the physics and chemistry of such molecules in 

particular the influence of metal electrodes on the molecular 

energy spectrum [1] , controlling molecular spin [2] and progress 

towards chemical preparation of single molecule devices in which 

the molecule/metal interface can be controlled with atomic 

precision. [3, 4] Finally, the talk will present very recent 

developments in the fabrication of molecular solid-state devices 

employing graphene as soft top-contacts [5]. 

references: 

1. K. Moth-Poulsen, T. Bjornholm, Nature Nanotechnology 4 

551-556 (2009); S. Kubatkin, et al., Nature 425, 698-701 

(2003). 

2. E. A. Osorio et al., Nano Letters 10 105 - 110 (2010). 

3. C.A. Martin et al., J. Am. Chem. Soc. 130 13198-13199 

(2008). 

4. T. Jain et al., ACS Nano 3 828 (2009); J. Colloid Int. Sci, 

in press (2012) ; ACS Nano, in press (2012). 

5. T. Li et al., Adv Mater 24 1333-1339 (2012); Z. Wei et al, 

Langmuir 28 4016-4023 (2012). 

Keywords: Single-molecule studies; Supramolecular 

chemistry; Molecular electronics; Nanotechnology; 



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o - 3 4 9 

ControLLed MoLeCuLAr SeLf-orGAnizAtion 

for eLeCtroniC deviCeS with enhAnCed 

PerforMAnCe 

B. PiGnAtAro 1 

1 University of Palermo, Chemistry, Palermo, Italy 

The realization of well-defined and ordered structures on the 

nanoscale is a main issue in nanoscience and nanotechnology, 

biotechnology and other related fields like plastic or organic 

electronics. Among the bottom-up approaches, to date, 

self-assembly of molecular systems (equilibrium aggregates) 

received a major attention. In spite of this, far from equilibrium 

conditions allow for the generation of a wider landscape of 

organized systems depending on the set of control parameters 

employed. Under an evolutionary vision of the structures, here 

some case studies show how it is possible to programme 

and control the nanoscale features of ordered super- or 

supra-molecular aggregates at wet interfaces by modulating static 

and/or dynamic parameters. [1, 2, 3] In this contest, speed is foreseen 

as a threshold factor for changing the aggregation mechanism 

along with the shape and degree of order of the structures as well 

as their size and defectivity. The second part of the presentation 

is dedicated to important properties of well-defined 

self-assembled/organized organic or hybrid structures in 

electronic devices. Also in collaboration with other groups, our 

efforts have been recently directed to develop molecular devices 

including single layer polymer transistors, [4] high-k smart 

nanodielectrics [5] and thin film bulk heterojunction solar cells [6] 

by employing new materials and deposition strategies including 

far-from-equilibrium processes. New strategies for the realization 

of 2D and 3D supramolecular ordered thin films for electronic 

devices with enhanced performance are highlighted. 

references: 

1. B. Pignataro, J. Mater. Chem. 19 (2009) 3338 

2. S. Fabiano, B. Pignataro, Physical Chemistry Chemical 

Physics 12 (2010) 14848 

3. M.H. Rosnes, C. Musumeci, C.P. Pradeep, J.S. Mathieson, 

D.L. Long, B. Pignataro, R. Cogdell, L. Cronin, 

J. Am. Chem. Soc. 132 (2010) 15490 

4. C. Musumeci, A. Luzio, C.P. Pradeep, H.N. Miras, 

M.H. Rosnes, Y.F. Song, D.L. Long, L. Cronin, 

B. Pignataro, J. Phys. Chem. C 115 (2011) 4446 

5. S. Fabiano, C. Musumeci, Z. Chen, A. Scandurra, 

H. Wang, Y.L. Loo, A. Facchetti, B. Pignataro, Adv. Mater. 

24 (2012) 951–956 

6. C. Musumeci, M.H. Rosnes, F. Giannazzo, M.D. Symes, 

L. Cronin, B. Pignataro, ACS Nano 5 (2011) 9992 

7. S. Cataldo, S. Fabiano, F. Ferrante, F. Previti, S. Patane, 

B. Pignataro, Macromolecular Rapid Communication 31 

(2010) 1281-1286 

Keywords: molecular electronics; self-assembly; selforganization; 

functional thin films; nanoscale order; 




o - 3 5 0 

trAnSLAtion, rotAtion And LevitAtion of 

MiCro And nAno-oBJeCtS ByBiPoLAr 

eLeCtroCheMiStry 

G. LoGet 1 , z. fAttAh 1 , d. ziGAh 1 , L. Bouffier 1 , 

A. Kuhn 1 

1 ISM - Institut des Sciences Moléculaires, University of 

Bordeaux, Pessac, France 

Molecule and particle transport inside microdevices such as 

lab-on-chip or in biological systems is attracting an increasing 

attention. In this contribution, we propose new original concepts 

based on bipolar electrochemistry. When a conducing object is 

placed in an electric field, it gets polarized. Consequently, a 

potential difference appears between its two extremities that can 

be used to drive localized redox reactions. By using this 

phenomenon of bipolar electrochemistry, we were able to create 

in a straight forward way a large variety of asymmetric particles 

composed of different materials ranging from microfibers to the 

nanotubes. Some of these objects can be used as microswimmers. 

Indeed, the influence of an external magnetic field allows 

controlling the orientation of carbon microtubes functionalized 

with nickel. More recently, we could use the same substrates but 

modified with platinum to create micromotors in the presence of 

hydrogen peroxide. 

The asymmetric reactivity that is induced by bipolar 

electrochemistry can also be used directly to generate motion of 

non-hybrid objects. Using this concept, it is possible to propel 

linearly metallic micro-dendrites using a deposition/dissolution 

mechanism. Electrogenerated hydrodynamics, either at both or 

one extremity of a conductive microobject can also be used for 

controlled propulsion. We recently demonstrated that this 

mechanism allows inducing rotations, translations and levitation. 

Bipolar electrochemistry is thus an original and competitive tool 

for generating motion at the micro- or sub-microscale, which 

opens new perspectives in micro- and nanosystem technologies. 

Keywords: Micromotors; Carbon nanotubes; bipolar 

electrochemistry; Swimmers; 



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materials – iV 

o - 3 5 1 

nAnoCheMiStry At SurfACeS: froM SinGLe 

MoLeCuLeS to CoMPLex enSeMBLeS 

J. BArth 1 

1 Technical University of Munich, Physics Department E20 and 

Catalysis Research Center, Garching, Germany 

Molecules are versatile entities conferring structural 

integrity and multi-faceted functional properties to both natural 

and artificial systems. By single-molecule positioning and 

supramolecular engineering at interfaces we can advance 

molecular science and nanochemistry. The insights thus gained 

affect various fields of application, including catalysis, sensing, 

light-harvesting, magnetic materials and organic electronics. The 

intriguing details of surface-confined molecular nanosystems, 

their special configuration, electronic characteristics, chemical 

reactivity and dynamics emerge from systematic scan-ning probe 

microscopy investigations, frequently employed in combination 

with a powerful range of space-averaging spectroscopy techniques 

and accurate computational modeling. 

Here we explore molecular modules, steer their 

organization, and afford novel functions using well-defined 

surfaces as anchoring or construction platforms. The presented 

real-space observations visualize structural features with atomistic 

precision and reveal the molecular recognition and self-assembly 

phenomena mediating the expression of genuine 

nanoarchitectures. The multitechnique study of flexible species 

such as metalloporphyrins exemplifies the delicate interplay 

between conformational adaptation, electronic signature and axial 

ligation of adducts. We describe single-molecule conductance 

switching via prototropy within a tetrapyrrole macrocycle and 

stimulate rotational movements of rare-earth porphyrinato 

sandwich complexes created in vacuo. The devised bottom-up 

fabrication protocols implement biological and de novo 

synthesized building blocks and exploit error-corrective 

noncovalent bonding or metal-directed assembly. They yield 

distinct nanoarchitectures: supramolecular gratings, hierarchic 

structures, and metal-organic cyclic supramolecules, flexible 

chains and regular networks. Using porous nanomeshes we 

demonstrate tunable electron confinement, and follow the 

supramolecular dynamics of caged species. The developed 

strategy presents a rationale for the control of adaptive molecular 

species at interfaces and the design of highly organized molecular 

nanosystems with complex features and tunable functional 

properties. 

Supported by ERC-AdG MolArt. 

references: 

NatureNanotech. 7p41 (2012); ACSNano 6p549 (2012); 

NatureChem. 3p114 (2011); Angew.Chem.I.E.50p3872 (2011); 

Phys.Rev.Lett. 106p026802 (2011); Proc. Nat. Acad. Sci. 

107p21332 (2010); ACSNano4p4936 (2010); Phys. Rev. 

B80p245403 (2010); JACS132 p6783(2010); NanoLett. 10p122 

(2010); Surf. Sci. 603p1533 (2009); NatureMat. 8p189 (2009); 

JACS130p11778 (2008); NanoLett. 7p3813 (2007); 

PNAS104p5279 (2007); Annu. Rev. Phys. Chem.58p375 

(2007); Nature 437p671 (2005) 




o - 3 5 2 

nAnoPAtterninG By MoLeCuLAr PoLyGonS 

S. S. JeSter 1 

1 Rheinische Friedrich-Wilhelms-Universität Bonn, Kekulé- 

Institut für Organische Chemie und Biochemie, Bonn, 

Germany 

The self-assembly of shape-persistent molecules with 

flexible alkyl/alkoxy side chains provides an efficient approach 

towards two-dimensional supramolecular crystalline surface 

patterns at the solution/solid interface. In-situ scanning tunneling 

microscopy yields a submolecularly resolved insight into the 

adlayer structures and thus a conclusion on the driving forces for 

their formation. Of particular interest is how the nanoscale 

architectures depend on the symmetry and substitution pattern of 

the molecular building blocks. One approach towards tailored 

adlayers is based on the adsorption of shape-persistent 

arylene-alkynylene macrocycles at the interface of 1,2,4trichlorobenzene 

and highly oriented pyrolytic graphite. [1] Recent 

work has focused on macrocycles involving dithiophene corner 

building blocks connected via linear phenylene-ethynylenebutadiynylene 

units that can be viewed as molecular polygons of 

distinct symmetry (i.e. triangles, squares, pentagons, and 

hexagons). [2] Concepts of discrete geometry are applied to design 

and describe such nanoscale surface patterns. The results gain 

insight into the 2D crystallization of nanoscale pentagons, binary 

mixtures of triangles and hexagons, and how large periodicities 

of >10 nm become accessible. 

references: 

1. S.-S. Jester, N. Shabelina, S. M. Le Blanc, S. Höger, 

Angew. Chem. 2010, 49, 6101. 

2. S.-S. Jester, E. Sigmund, S. Höger, J. Am. Chem. Soc. 

2011, 133, 11062. 

Keywords: self-assembled monolayers; scanning tunneling 

microscopy; solid/liquid-interface; shape-persistent 

macrocycles; 



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o - 3 5 3 

SeLf-ASSeMBLy of ChArGed nAnoPArtiCLeS At 

fLuid interfACeS 

v. SAShuK 1 , M. fiALKowSKi 1 

1 Institute of Physical Chemistry, Soft Condensed Matter and 

Fluids, Warsaw, Poland 

Inspired by nature, self-assembly phenomena are currently 

the subject of intensive studies in modern science. Autonomous 

organization of individual elements into complex structures is 

increasingly considered the best “bottom-up” approach to 

fabricating novel materials. 

Herein we present self-assembly of charged nanoparticles 

(NPs) into hexagonally close-packed lattices at fluid interfaces. [1] 

We employ gold NPs covered with a mixture of ionic (charged) 

and hydrophobic ligands. At a certain ligand ratio, the NPs display 

a property to absorb spontaneously at fluid interfaces producing 

monolayers. We found that such self-assembled NPs exhibit 

Janus-type amphiphilic structure and possess well defined and 

constant charge. At oil-water interface, the NPs autonomously 

form hexagonally packed lattices as a result of a fine balance 

between repulsive electrostatic and attractive hydrophobic forces. 

In turn, at air-water interface, the NPs arrange into sparse 

monolayers which then can be readily compressed to give dense 

films by using Langmuir-Blodgett technique. The NP monolayers 

squeezed into such films can be used for coating of various 

materials. 

references: 

1. Sashuk et al., Chem. Eur. J. 2012, 18, 2235 

Keywords: Nanoparticles; Self-assembly; Interfaces; 

Monolayers; 




o - 3 5 4 

CheMiStry in nAno-SCALe oPtiCAL CAvitieS 

J. A. hutChiSon 1 , t. SChwArtz 1 , e. devAux 1 , 

C. Genet 1 , t. w. eBBeSen 1 

1 Université de Strasbourg and CNRS, ISIS, Strasbourg, France 

Chemistry is normally controlled by reaction conditions 

such as the type of solvent, the concentration of reactants, and 

temperature. The reaction barrier can be lowered by the use of 

catalysts or bypassed by the absorption of thermal or photonic 

energy by one of the reactants. In this contribution we explore the 

notion that one can influence a chemical reaction via a very 

different path: by the strong coupling of molecules and photons 

to form new, hybrid light/molecule states. 

Strong coupling phenomena are most familiar to chemists 

in the exchange of electron density between atomic orbitals to 

form molecular bonding and anti-bonding orbitals. Physical 

chemists are likewise familiar with the strong coupling of resonant 

transitions of molecules in aggregates (exchange of excitation 

energy) generating hybrid states of higher and lower energy, 

sometimes labelled H- and J-aggregate bands respectively 

depending on their geometry. Less intuitive is that strong coupling 

can also be found at the level of molecules exchanging photons 

with a resonant optical cavity, forming hybrid light/matter states 

(or cavity polaritons). [1, 2] 

We will present studies of molecular systems inside 

nano-scale optical cavities formed by two metallic mirrors, 

demonstrating clearly that molecular reactivity is modified by 

strong interaction with cavity optical fields. 

references: 

1. Hutchison, J.A., Schwartz, T., Devaux, E., Genet, C., 

Ebbesen, T.W. Modifying chemical landscapes by 

coupling to vacuum fields. Angew. Chem. Int. Ed., 2012, 

51, 1592-1596. 

2. Schwartz, T., Hutchison, J.A., Genet, C., Ebbesen, T.W. 

Reversible switching of ultra-strong light-molecule 

coupling. Physical Review Letters, 2011, 106, 196405(4). 

Keywords: Nanostructures; Reaction mechanisms; 

Photophysics; Energy transfer; Photochromism; 



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o - 3 5 5 

exPLoitinG P CheMiStry for GAP fine-tuninG 

And CoordinAtion-driven ASSeMBLy of 

PoLyCyCLiC AroMAtiC hydroCArBonS 

P. A. Bouit 1 , M. hiSSLer 1 , r. reAu 1 

1 UMR 6226 CNRS - Université de Rennes 1, OMC, Rennes, 

France 

Among the different families of π-conjugated systems, 

polycyclic aromatic hydrocarbons (PAHs) proved to have a great 

potential in the field of molecular electronics. [1] Due to the high 

flexibility of organic synthesis, many strategies can be considered 

to tune the bandgap and the supramolecular organization of PAHs. 

A fruitful approach involves the incorporation of heteroatoms 

(N, S, B) within the C-sp2 frameworks. [2] Here, we report that this 

appealing strategy can be extended to P-modified PAHs. 

We report on the synthesis, structural and optical properties 

of the first family of P-containing PAHs, namely 

dibenzophosphapentaphenes. [3] In addition to the synthetic 

challenge that represented the insertion of a reactive 

σ3 ,λ3-P-moiety in a PAH backbone, we show that P-chemistry 

allows an unprecedented molecular engineering of both the 

bandgap and the supramolecular organization of PAH. In 

particular, P-chemistry allows readily preparing, from one single 

precursor, a new family of PAHs with tunable optical 

(absorption/emission) and redox properties. Furthermore, the 

coordination ability of P-ligands, illustrated with the coordination 

to AuI , allows for unprecedented coordination-driven assembly of 

PAHs. This molecular engineering strategy based on 

organophosphorus chemistry shows the potential of introducing 

P into planar p-extended frameworks. 

references: 

1. K. Müllen et al. Chem. Rev. 2007, 107, 718. 

2. a) S. Draper et al. J. Am. Chem. Soc. 2002, 124, 3486; 

b) K. Müllen et al. Org. Lett. 2009, 11, 5686; 

c) C. Nuckolls et al. Angew. Chem. Int. Ed. 2010, 49, 

7909; 

d) S. Yamaguchi et al. J. Am. Chem. Soc. 2012, 134, 4529. 

3. Bouit, P.A.; Escande, A.; Szucs, R. ; Szieberth, D.; 

Lescop, C.; Nyulászi, L.; Hissler, M. ; Réau, R. 

J. Am. Chem. Soc. 2012, 134, 6524-6527. 

Keywords: aromatics; graphene; phosphorus; coordination; 




o - 3 5 6 

rAtionAL SyntheSiS of 2d PoLyMerS 

A. d. SChLüter 1 , J. SAKAMoto 1 

1 ETH Zurich, Institute of Polymers, Zurich, Switzerland 

The present interest in graphene, a naturally occurring 

two-dimensional polymer, makes clear that there is no synthetic 

method available that would allow accessing a covalently bonded 

molecular sheet with internal periodicity and a thickness of one 

monomer unit only in a non-thermolytic rational way. [1] After a 

brief historic overview, the concepts will be presented which are 

presently being pursued in the authors’ laboratory. They rest upon 

carefully designed monomers, interfacial as well as single 

crystalline ordering, and both metal-complexation [2] and 

light-induced topochemical polymerizations. [3] The lecture 

introduces the first case of a 2D polymer with internal periodicity 

composed of areal repeat units. This is an extension of 

Staudinger’s polymerization concept but in two dimensions. 

references: 

1. J. Sakamoto, J. van Heijst, O. Lukin, A. D. Schlüter, 

Angew. Chem. Int. Ed. 2009, 48, 1030-1069. 

2. T. Bauer, Z. Zheng, A. Renn, R. Enning, A. Stemmer, 

J. Sakamoto, A. D. Schlüter, Angew. Chem. Int. Ed. 2011, 

50, 7879-7884 

3. P. Kissel, R. Erni, W. B. Schweizer, M. D. Rossell, 

B. T. King, T. Bauer, S. Götzinger, A. D. Schlüter, 

J. Sakamoto, Nat. Chem. 2012 in press. 

Keywords: periodic network; areal repeat units; molecular 

sheets; topochemical reaction; 



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chem. Listy 106, s587–s1425 (2012) 


Nanoscale particles, cages, sheets and tubes – iV 

o - 4 6 7 

ControLLinG the PhotoeMiSSion of 

quAntuM dotS By MetAL And redox ACtive 

CoMPLexeS 

h. MAttouSSi 1 

1 Florida State University, Department of Chemistry and 

Biotechemistry, Tallahassee Florida, USA 

We have developed the use of polyethylene glycol 

(PEG)-based modular multifunctional ligands to functionalize a 

variety of inorganic nanoparticles and transfer them to buffer 

media. We have also designed approaches to conjugate various 

biomolecules to CdSe-ZnS core-shell semiconductor quantum 

dots (QDs), Au nanoparticles (AuNPs) and magnetic nanocrystals. 

In this presentation, we investigate the charge transfer 

interactions between luminescent QDs and metal or redox-active 

complexes. In one system we use ZnS-overcoated CdSe 

QDs surface-capped with poly(ethylene glycol)-appended 

dihydrolipoic acid (DHLA-PEG) covalently coupled to 

dopamine-isothiocyanate. For this system in particular, we found 

that in addition to the effects of conjugate valence the QD PL 

quenching efficiency can be (a) substantially increased in alkaline 

buffers compared to acidic conditions, and (b) strongly affected 

by changes in the buffer pH and the presence (or absence) of 

oxygen. These produce valence-and pH-dependent PL quenching 

combined with shortening of the exciton lifetime, while altering 

the recombination kinetics of both the electron and hole of 

photoexcited QDs. 

We will provide the experimental details, discuss 

steady-state and time-resolved data, and provide results from 

transient absorption measurements where a simultaneous change 

in the electron and hole intraband relaxation dynamics has been 

measured when the pH was switched from acidic to alkaline. 

Keywords: quantum dots; fluorescence; charge transfer; 

quenching; pH; 



o - 4 6 8 

LuMineSCent quAntuM-dot/PoLyMer/GoLd 

nAnoPArtiCLe ASSeMBLieS 

J. P. fArinhA 1 , t. riBeiro 1 , M. Moffitt 2 

1 Instituto Superior Técnico, Centro de Quimica-Fisica 

Molecular, Lisboa, Portugal 

2 University of Victoria, Department of Chemistry, Victoria, 

Canada 

Metal-semiconductor hybrid nanostructures have attracted 

increasing attention, with many potential applications in 

functional optoelectronic devices, sensors, imaging, photocatalyst, 

etc. Here we present the preparation of hierarchical structures by 

self-assembling amphiphilic block copolymer chains, using the 

micelle cores as nanoreactors to prepare CdS quantum dots (QDs), 

and the thiol chain-end groups in the polymer shell to anchor gold 

nanoparticles (GNPs). The GNP surface plasmons create 

locally-enhanced electromagnetic fields in the vicinity of the 

metal surface that can be used to increase the emission of QDs in 

close proximity to the metallic nanoparticles. 

We synthesized a symmetric amphiphilic block copolymer, 

composed by two long polystyrene (PS) inner blocks and two 

short poly(acrylic acid) (PAA) outer blocks connected by a central 

trithiocarbonate (TTC) group, using a sequential RAFT controlled 

polymerization technique. In 1,4-dioxane, the block copolymer 

chains self-assemble to form spherical micelles with a PAA core 

and a flower-like PS shell. The cores were then used as 

nanoreactors to prepare cadmium sulfide (CdS) semiconductor 

nanoparticles. We transformed the micelle shell TTC groups into 

thiol groups, which were then used to anchor GNPs. The size of 

the PS blocks is used to control the GNP-QD distance, in order to 

obtain a strong GNP-QD interaction, while avoiding the 

possibility of luminescence quenching occurring at close contact. 

Using different ratios of GNP:QD we observed an increase in the 

QDM luminescence intensity for higher gold concentrations, after 

a correction for the GNPs inner filter effect. The GNP-decorated, 

polymer coated QDs provide an excellent platform for tunable 

photonic and biolabeling materials. 

Keywords: hybrid nanostructures; RAFT polymerization; 

quantum dots; metal nanoparticles; luminescence; 



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o - 4 6 9 

LuMineSCent Core-SheLL nAnoPArtiCLeS for 

iMAGinG And SenSinG 

n. zACCheroni 1 , S. BonACChi 1 , d. GenoveSe 1 , 

r. JuriS 1 , M. MontALti 1 , L. Prodi 1 , e. rAMPAzzo 1 

1 University of Bologna, department of chemistry ‘G. 

Ciamician’, Bologna, Italy 

Luminescence finds important applications in many 

different fields and the development of new emissive components 

for real-time and space-resolved detection is still an issue. 

Nanosciences have opened up many new possibilities to this aim 

allowing the creation of promising platforms for the 

implementation of new luminescent targeting materials. 

We recently proposed a new versatile synthetic approach to 

obtain very mono-disperse, water soluble core-shell nanoparticles 

(NPs) presenting a silica core (10 nm of diameter) and an organic 

shell (7 nm thick) that can host organic dyes, even of different 

nature. These NPs are brightly luminescent, photostable, and their 

spectral profile can be easily tuned with a proper choice of the 

doping dyes. [1] The NPs can be obtained with a one pot approach 

even with modified terminal groups on the organic shell, this 

introduces a large chemical versatility that allows coupling with 

suitable species (e.g biomolecules) for specific target. This 

feature, together with the biocompatibility of the materials, and 

the use of dyes absorbing and emitting in the Near Infrared Region 

(NIR) (a transparent region for biological tissues) make these 

species particularly suitable for application in in-vivo and in-vitro 

imaging. Examples will be discussed together with other designs 

of the same platform for multiplexed analysis and nanosensor 

applications. [2] 

references: 

1. Rampazzo, E.; Boschi, F.; Bonacchi, S.; Juris, R.; 

Montalti, M.; Zaccheroni, N.; Prodi, L.; Calderan, L.; 

Rossi, B.; Becchi, S.; Sbarbati, A. Nanoscale 2012, 4, 

824 830. 

2. S. Bonacchi, S.; Genovese, D.; Juris, R.; Montalti, M.; 

Prodi, L.; Rampazzo, E.; Zaccheroni, N. Angew. Chem. 

Int. Ed. 2011, 50, 4056–4066 

Keywords: nanoparticles; luminescence; imaging agents; 



o - 4 7 0 

SuPerPArAMAGnetiC Core-SheLL 

nAnoPArtiCLeS AS CoLLoidAL SuPPort for 

PePtide SyntheSiS 

C. Stutz 1 , h. G. BÖrner 1 

1 Humboldt-Universität zu Berlin, Department of Chemistry, 


A fast and facile microwave assisted synthesis of core-shell 

nanoparticles is presented, resulting in monodispers colloids with 

magnetite cores [1] coated by functionalized silica shells, which 

have been applied as solid supports to facilitate peptide synthesis. 

Solid-phase supported peptide synthesis (SPPS), introduced 

by Merrifield in 1963, has revolutionized molecular biochemistry, 

pharmacology, biomedicine and biophysics, but also enabled 

means of combinatorial chemistry. Since the initial work of 

Merrifield, the applied solid supports have not been dramatically 

changed. Lightly cross-linked polystyrene resins with 1% 

divinylbenzene are the most used solid supports for peptide 

synthesis. Using nanoparticles as solid supports would overcome 

several difficulties, inherent to the micro gel supports as direct 

accessibility of the functionalities on permanent surfaces are 

provided and diffusion limitations of reactions in micro gel 

particles will be overcome. 

Here we present our study applying monodispers core-shell 

nanoparticles as a solid support for SPPS. [2] Superparamagnetic 

magnetite monodomain nanoparticles are coated in a microwave 

assisted Stöber-process with a functional silica shell carrying 

amino-groups that are used to introduce linkers required for SPPS. 

Average particle sizes of 70 nm allow ‘quasi homogeneous’ 

synthesis in solution. An external magnetic field is used to 

separate the solid support reversible and effectively from the 

reaction mixture, ensuring ease of purification. Magnetic 

sedimentation of the particles means ease of purification and core 

shell structure effectively improves resistance of the magnetite 

core particles against strong acids and bases. 

Several peptides were synthesized, using sequential 

assembly of Fmoc-protected α-amino acid derivatives, 

implementing colloidal supports to standard SPPS procedures. As 

model a tetrapeptide with a sequence Phe-Lys-Leu-Gly was 

synthesized. The peptide could be conveniently isolated from the 

cleavage solution with yields of ~70% and analysis of the 

resulting crude peptide exhibits remarkable product purity of ca. 

95%. 

references: 

1. Bilecka, Niederberger, Nanoscale 2010, 2, 1358-1374. 

2. Stutz, Bilecka, Thünemann, Niederberger, Börner, 

submitted. 

Keywords: Nanoparticles; Solid-phase synthesis; Microwave 

chemistry; Magnetic properties; 



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Nanoscale particles, cages, sheets and tubes – V 

o - 4 7 1 

LuMineSCent nAnoSwitCheS 

f. rAyMo 1 

1 University of Miami, Department of Chemistry, Coral Gables 

Florida, USA 

The goal of our research program is the identification of 

viable strategies to switch luminescence under optical control. In 

this context, we are developing two families of nanostructured 

constructs with photoswitchable luminescence. One of them is 

based on the ability of amphiphilic polymers to trap fluorescent 

and switchable components in their hydrophobic interior. The 

other relies of the passivation of luminescent quantum dots with 

switchable polymer ligands. In both instances, optical stimulations 

can be exploited to control the state of the switchable components 

and in turn regulate the emission of the luminescent components. 

The resulting photoswitchable luminescent constructs can be 

operated in aqueous environments, can cross the membrane of 

living cells and are not cytotoxic. Furthermore, their unique 

photoswitchable character offers the opportunity to record images 

with subdiffraction resolution as well as to monitor the diffusion 

of species. As a result, our luminescent nanoswitches might 

evolve into valuable analytical tools for a diversity of biomedical 

applications. 

Keywords: Luminescence; Photochromism; Photocages; 

Polymer Micelles; Quantum Dots; 



o - 4 7 2 

ConJuGAted PoLyMer nAnoPArtiCLeS for 

CeLL LABeLLinG, iMAGinG And druG deLivery 

d. tunCeL 1 , v. iBrAhiMovA 1 , o. GeziCi 1 

1 Bilkent University, Chemistry, Ankara, Turkey 

Nanoparticles based on conjugated polymers are emerging 

as a new class of luminescent nanoparticles. These nanoparticles 

have many potential applications including imaging agents, 

biosensors, and photonics owing to their high quantum yields, 

high molar absorptivity, photo stability and easy synthesis. The 

recent cell assay studies have also showed that these nanoparticles 

were not cytotoxic. 4 Moreover, conjugated polymer nanoparticles 

can be modified easily to deliver therapeutic agents such as cancer 

drugs, genetic materials (e.g. RNA, siRNA) and biomolecules to 

the desired targets. 

Here, we present the resent studies in our lab involving the 

synthesis and applications of nanoparticles using various 

conjugated polymers which emit blue, green, yellow and red. In 

order to obtain shape-persistent and stable nanoparticles, a novel 

method was developed in which the nanoparticles were prepared 

either via Cu-catalyzed or cucurbit[6]uril (CB6)-catalyzed 

click reactions between azide groups containing hydrophobic 

fluorene-based conjugated polymers and a hydrophilic 

diaminodialkyne containing cross-linker. Through the click 

reaction, not only does the cross-linking confer stability, but it 

also introduces functional groups, such as triazoles and amines, 

to the nanoparticles. TEM images of the nanoparticles also 

showed that they display very interesting morphologies. 

Incorporation of hydrophilic functional groups to the hydrophobic 

conjugated polymers resulted in a distinct phase separation, 

producing Janus-like or patchy particles. 

We have also demonstrated the applications of these 

conjugated polymer nanoparticles in the in vitro cell labelling and 

imaging of a number of different cell lines (e.g. multipotent 

mesenchymal stem cells, RAW264.7 and Huh7). The conjugated 

polymer nanoparticles have also been loaded with various 

anti-cancer drugs and the delivery of drugs has been investigated 

in vitro in the cancer cell lines. The cell assay studies show that 

the drug loaded nanoparticles are up-taken by the cells efficiently 

and more effective comparing to the free-drugs in killing the 

cancer cells. 

Keywords: Nanoparticles; Nanotechnology; Polymers; drug 

delivery; fluorescent nanoparticles; 



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o - 4 7 3 

PhotoACtivAted nAnoASSeMBLieS with 

BiModAL PhotodynAMiC ACtion 

S. Sortino 1 , n. KAndoth 1 , A. frAix 1 , r. Gref 2 , 

J. MoSinGer 3 

1 University of Catania, Laboratory of Photochermistry 

Department of Drug Sciences, Catania, Italy 

2 University Paris Sud, CNRS Faculty of Pharmacy, ChItenay 

Malabry, France 

3 Charles University of Prague, Faculty of Science, Prague, 


Multimodal therapies aim to exploit either additive or 

synergistic effects arising from the generation of multiple active 

species in the same region of space with the final goal to 

maximize the therapeutic effectiveness. [1] Light is a powerful 

mean for the non invasive introduction of therapeutic agents in a 

desired bio-environment, mimicking an “optical syringe” with an 

exquisite control of site, timing and dosage of the released species, 

factors playing key roles in determining a positive therapeutic 

outcome. [2] Singlet oxygen ( 1O ) and nitric oxide (NO) play a key 

2 

role in anticancer cancer and antibacterial therapy. Typical for 

both species is their easy diffusion in the cellular environment due 

to their very small size compared to some conventional drugs, 

lack of charge and lipophilic character. Moreover, common to 

both 1O and the NO radical is their potential to attack biological 

2 

substrates of different nature representing multitarget therapeutic 

agents and avoiding Multiple Drug Resistance problems 

encountered with several conventional drugs often target-specific. 

Finally since the NO release from the NO photodonors is 

independent from O availability it can potentially very well 

2 

complement the 1O effects at the onset of hypoxic conditions. In 

2 

this contribution we report the design and fabrication of 

biocompatible cyclodextrin-based nanoparticles and nanogels able 

to combine the simultaneous delivery of 1O and NO with imaging 

2 

capacity under excitation with visible light. In this view, these 

multifunctional nanoconstructs represent appealing candidates for 

applications in biomedical research. 

references: 

1. Goeld M, Givens R (Eds.), 2005. Dynamic Studies in 

Biology, Wiley-VCH, New York. 

2. Sortino S. J. Mater. Chem. 2012, 22, 301-318 

Keywords: Light; therapy; nanoparticles; singet oxygen; nitric 

oxide; 


Nanoscale particles, cages, sheets and tubes – Vi 

o - 4 7 4 

unexPeCted eLeCtroCAtALytiC ProPertieS 

of MonoLAyer ProteCted GoLd CLuSterS 

M. BruSt 1 , G. GordiLLo 2 

1 University of Liverpool, Department of Chemistry, Liverpool, 


2 Universidad de Buenos Aires, INQIMAE, Buenos Aires, 

Argentina 

The high catalytic activity of nanoscopic gold surfaces 

initially surprised the scientific community but is now well known 

and has given rise to a burgeoning new field of research. Most 

work in this area has been carried out on clean gold clusters in the 

1 to 5 nm range deposited on oxide supports such as titania, while 

practically no attention has been paid to ligand-protected gold 

nanoparticles, so called monolayer protected clusters (MPCs), 

since these are generally assumed to be catalytically inactive due 

to the presence of the passivating ligand shell. Here we report that 

MPCs protected by mercaptoalkyl ethyleneglycol ligands exhibit 

unexpected catalytic activity for the electrochemical reduction of 

protons to adsorbed molecular hydrogen. There is no detectable 

equivalent reaction on macroscopic gold surfaces, where 

hydrogen evolution occurs at significantly more negative 

potentials and without a preceding adsorptive step. Similarly, 

under potential deposition (UPD) of certain metals including Cd 

can be observed on the same type of MPC. It is argued that the 

clusters exhibit highly reactive unsaturated surface sites (atoms) 

that are not covered by the thiol ligand and are therefore accessible 

to react with small molecules and ions capable of penetrating the 

ligand shell. The number of these active sites has been quantified 

for cluster sizes of 3 and 15 nm. Electrical contact is established 

by the spontaneous adsorption of the clusters to a hanging Hg drop 

electrode. The contact to the Hg electrode is very robust and does 

not lead to the formation of amalgams even after many hours of 

cycling the potential. We believe that, apart from its fundamental 

interest, this very unusual electrocatalytic behaviour of 

ligand-protected gold nanoparticles reported here, may lead to 

new strategies for the design of catalysts for the selective 

reduction or hydrogenation of small molecules. 



s752 

chem. Listy 106, s587–s1425 (2012) 



o - 4 7 5 

nAnoStruCtured MAteriALS By CovALent 

SeLf-ASSeMBLy 

K. KiM 1 

1 Pohang University of Science and Technology, Center for 

Smart Supramolecules Department of Chemistry and Division 

of Advanced Materials Science, Pohang, Republic of Korea 

We recently reported a novel approach to the synthesis of 

polymer nanocapsules, which offer a wide range of applications 

including drug delivery, using a rigid, disk-shaped monomer with 

multiple polymerizable groups at the periphery. Without needs 

for any pre-organized structures or templates, and core-removal, 

this method directly produces polymer nanocapsules with a 

highly stable structure and relatively narrow size distribution. 

The polymer shell made of cucurbituril, a hollowed-out 

pumpkin-shaped host molecule, allows tailoring of its surface 

properties by host-guest interactions. The easy synthesis and 

unique ability to tailor surface properties in a noncovalent 

manner make the polymer capsule potentially useful in many 

applications including targeted drug delivery. This approach has 

been extended to include a wide range of cores, linkers and 

polymerization methods to synthesize new nanocapsules with 

interesting physical and chemical properties, and application 

perspectives. This strategy can also be extended to synthesize 

other nanostructured materials including two-dimensional 

polymers with single monomer thickness. The details of the 

work will be presented. 

Keywords: self-assembly; nanostructures; polymers; 



o - 4 7 6 

SteP By SteP Growth of GoLd nAnoPArtiCLeS 

And GoLd nAnorodS And their BehAvior in 

CAtALySiS 

r. fenGer 1 , f. fiSCher 1 , K. rAdeMAnn 1 


Germany 

Catalytic site effects for colloidal nanoparticles at the 

transition point from heterogeneous to homogenous catalysis are 

in the focus of on-going research because of the tunability of size, 

shape, stabilizer, and material. Thus, these systems have been 

[1, 2] 

studied intensively in oxidative and reductive catalysis. 

A standard system for the investigation of reductive catalytic 

reactions in aqueous media is the reduction of 4-nitrophenol to 

4-aminophenol with sodium borohydride. The monitoring can be 

done using UV-Vis spectroscopy following the intensities at 400 

nm. In our study, we have investigated the reduction catalysis 

using gold nanoparticles and nanorods synthesizes with the 

seeding growth method. [3, 4] Different sizes of narrow size 

distributed gold nanoparticles and different length of gold 

nanorods, their reaction rates and the activation energies of the 

reactions were determined. The size parameters of the gold 

nanorods were measured by TEM, AFM, DLS and SAXS. The 

highest activity was found for particles with 13 nm diameter. [5] 

Furthermore, we have shown that longer gold nanorods have an 

higher catalytic activity in the tested systems. [6] These unexpected 

findings will be discussed systematically. 

references: 

1. A. Arcadi, Chem. Rev. 2008, 108, 3266. 

2. A. S. K. Hashmi, G. J.Hutchings, Angew. Chem. Int. Ed. 

2006, 45, 7896. 

3. N. R. Jana, L. Gerhardt, C. J. Murphy, Langmuir 2001, 22, 

6782. 

4. J. Pérez-Juste, L. M. Liz-Marzán, S. C. Carnie, P. 

Mulvaney, Adv. Funct. Mat. 2004, 14, 571 (2004). 

5. R. Fenger, E. Feritta, H. Kirmse, A. F. Thünemann, 

K. Rademann, Phys. Chem. Chem. Phys. 2012, in print. 

6. R. Fenger, F. Fischer, Ch. Schaumberg, K. Rademann, 

in preparation (2012). 

Keywords: Gold; Heterogeneous catalysis; Nanoparticles; 

Nanostructures; 



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o - 4 7 7 

intrinSiCALLy ChirAL thioLAte-ProteCted 

GoLd CLuSterS: enAntioSePArAtion, 

ChiroPtiCAL ProPertieS And fLexiBiLity of 

Au38 

t. BürGi 1 

1 University of Geneva, Department of Physical Chemistry, 

Geneva, Switzerland 

Bestowing chirality to metal surfaces and nanoparticles has 

become an intensive field of research. Such systems are promising 

candidates for enantioselective catalysis and for other applications 

in chiral technology in general. 

Chirality in metal nanoparticles leads to optical activity, i.e. 

the differential absorption of left- and right-circularly polarized 

light. [1, 2] The origin of this optical activity is still debated, as 

several competing mechanisms may be responsible for it. Up to 

now optical activity was only observed for particles that are 

covered by chiral thiols. However, from X-ray structural analysis 

it became clear very recently that even particles covered by achiral 

thiols can be chiral due to the arrangement of the ligands in their 

surface. [3, 4] The importance of this type of surface chirality for the 

observed optical activity could not be studied yet, because all the 

samples prepared up to now were racemic and were therefore not 

optically active. 

In our contribution we demonstrate for the first time the 

separation of a gold particle or cluster, Au (SCH2CH2Ph) , 

38 24 

covered by achiral thiols into its enantiomers using chiral HPLC. 5 

The optical activity of the separated enantiomers is very strong 

and the observed anisotropy factors are the largest ever observed 

for gold nanoclusters. This demonstrates the importance of the 

surface structure of the particles for their optical activity. 

references: 

1. Schaaff, T. G.; Knight, G.; Shafigullin, M. N.; Borkman, 

R. F.; Whetten, R. L. J. Phys. Chem. B 1998, 102, 10643. 

2. Gautier, C.; Burgi, T. ChemPhysChem 2009, 10, 483. 

3. Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Bushnell, D. A.; 

Kornberg, R. D. Science 2007, 318, 430. 

4. Qian, H.; Eckenhoff, W. T.; Zhu, Y.; Pintauer, T.; Jin, R. 

J. Am. Chem. Soc. 2010, 132, 8280. 

5. Dolamic, I; Knoppe, S.; Dass, A.; Bürgi, T. Nature Commun. 

2012, 3, 798. 

Keywords: chirality; optical activity; gold nanoparticles; 

enantioseparation; 




s754 

chem. Listy 106, s587–s1425 (2012) 

organic Chemistry, Polymers – i 

organometallic Chemistry, catalysis, new frontiers – i 

o - 0 7 2 

PoLyfunCtionAL orGAnoMetALLiCS AS Key 

interMediAteS in orGAniC SyntheSiS 

P. KnoCheL 1 

1 Ludwig-Maximilians-Universität, Department Chemie, 

München, Germany 

Polyfunctional zinc, magnesium, and lithium 

organometallics are key organometallic intermediates in organic 

synthesis and new advances in the preparation and synthetic use 

of these organometallics will be presented. Thus, a stereoselective 

preparation of cyclohexyl-lithiums and related reagents by 

using a novel iodine-lithium exchange will be shown. The 

configurational stability of secondary cycloalkyl lithium, 

magnesium, and zinc reagents will be discussed as well as the 

stereochemistry (retention or inversion) of their reactions with 

various organic electrophiles. By using sterically hindered 

magnesium amides, selective directed metalations of 

functionalized aromatics and heterocycles will be performed. Also 

the preparation of air-stable zinc aryl and heteroaryl zinc 

pivalates will be shown. Applications of these new reagents in 

palladium-catalyzed cross-couplings as well as in the construction 

of heterocyclic scaffolds will be reported. 

Keywords: Cross-coupling; Lithium; Magnesium; Palladium; 

Zinc; 



o - 0 7 3 

new MethodS of enAntioSeLeCtive 

SyntheSiS with SCAndiuM And SiLAnedioL 

CAtALySiS 

A. frAnz 1 

1 University of California Davis, Department of Chemistry, 

Davis, USA 

Our goal is to develop catalysts and synthetic methodology 

that mini-mize the use of reagents and or-ganic sol-vents, increase 

efficiency, and approach 100% selec-tivity. We are investigating 

the activity and selectivity of various catalyst systems for 

carbon-carbon bond-forming reactions and the enantioselective 

synthesis of complex molecules such as oxindoles and 

spirooxindoles will be presented. Catalysts discussed will include 

scandium- and indium-based chiral Lewis acids, Bronsted acids, 

and silanediols as a new class of hydrogen-bonding catalysts. 

Of particular interest, a catalytic asymmetric [3+2] annulation 

reaction of allylsilanes with bidentate electrophiles will be 

presented to generate carbocycles and heterocycles. This lecture 

will also discuss mechanism and molecular insights for catalyst 

activity and design. 

Keywords: Asymmetric catalysis; Asymmetric synthesis; 

Hydrogen bonds; Heterocycles; Silicon; 



s755 

chem. Listy 106, s587–s1425 (2012) 



o - 0 7 4 

CyCLoPentAdienyL titAniuM(iv) CoMPLexeS 

with fLuorouS PonytAiLS iMMoBiLized on 

CArBoSiLAne dendriMerS viA A ti-o Bond 

J. CerMAK 1 , A. KruPKovA 1 

1 Institute of Chemical Process Fundamentals ASCR v.v.i., 

Organic Synthesis and Analytical Chemistry, Prague 6, Czech 

Republic 

Recently we synthesized light [1] and heavy [2] fluorous 

cyclopentadienes with silyl substituents bearing up to three 

fluorous ponytails. Both monocyclopentadienyltrichlorotitanium 

and dicyclopentadienyldichlorotitanium (titanocene) complexes 

were prepared starting from the new ligands. We wondered, 

whether the monocyclopentadienyl complexes could be 

immobilized on a soluble polymeric support with low 

polydispersity, i.e. a carbosilane dendrimer. To provide 

comparison, reactions with nonfluorinated complexes were also 

carried out. 

Dendritic polyols of the second and third generation 

2G-OH , 2G-OH , and 3G-OH were prepared by 

8 16 16 

hydroboration/oxidation of allyl terminated carbosilane 

dendrimers and used as supports for immobilization of 

cyclopentadienyltrichlorotitanium(IV) complexes via alcoholysis. 

Their reaction with CpTiCl gave metallodendrimers 

3 

2G-(OTiCpCl ) , 2G-(OTiCpCl ) , and 3G-(OTiCpCl ) , 

2 8 2 16 2 16 

respectively, whereas the reaction of the dendrimers with 

CpSi FTiCl (CpSi 3 F = C H SiMe CH CH C F ) yielded 

5 4 2 2 2 8 17 

peripherally fluorinated metallodendrimers 2G-(OTiCpSiFCl ) 2 8 

and 

3G-(OTiCpSi FCl ) . All metallodendrimers were 

2 16 

characterized by multinuclear NMR spectroscopy and the 

proposed structure was further confirmed by comparison with 

model 1-propoxycomplexes. [3] 

references: 

1. Cermák, J.; Stastná, L.; Sýkora, J.; Císarová, I.; Kvícala, J. 

Organometallics 2004, 23, 2850-2854. 

2. Cervenková Stastná, L.; Cermák, J.; Curínová, P.; Sýkora, 

J. J. Organomet. Chem. 2010, 695, 537-545. 

3. Krupková, A.; Cermák, J. J. Inorg. Organomet. Polym. 

2012, 22, 470-477. 

Keywords: Fluorinated ligands; Cyclopentadienyl ligands; 

Dendrimers; Silanes; Titanium; 



o - 0 7 5 

BidentAte LewiS ACid CAtALySiS – A new entry 

to hiGhLy SuBStituted nAPhthALeneS 

h. A. weGner 1 , S. n. KeSSLer 1 


Switzerland 

Multidentate interactions are the secret to nature’s catalysis. 

Nonetheless, the application of these principles remains an 

extremely challenging endeavor. In organic synthesis the Lewis 

acid catalysis presents a very effective tool for a variety of 

different transformations. Although effort has been made towards 

bidentate Lewis catalysts still they react in a monodentate 

fashion. [1] 

Recently, we were able to show the catalysis of the inverse 

electron-demand Diels-Alder (IEDDA) reaction of 1,2-diazines 

by a bidentate Lewis acid in a bidentate fashion. [2] The general 

principle is based on the following rational: The twofold 

coordination of the bidentate Lewis acid to the 1,2-diazine 

decreases the energy level of the LUMO facilitating the 

cycloaddition step. Consecutive elimination of N generates the 

2 

product and also liberates the catalyst. 

This new concept of catalysis is furthermore combined with 

a novel one-pot synthesis of 1,2-diazino aromatics, developed in 

our group, to produce highly substituted naphthalenes in two steps 

from aromatic aldehydes. This strategy was applied for an 

efficient preparation of Naproxen. 

references: 

1. Maruoka, K. Catal. Today 2001, 66, 33. 

2. a) S. N. Kessler, H. A. Wegner, Org. Lett. 2010, 12, 4062; 

b) S. N. Kessler, M. Neuburger, H. A. Wegner, Eur. J. Org. 

Chem. 2011, 3238; c) H. A. Wegner, S. N. Kessler, 

Synlett 2011, 699. 

Keywords: Lewis acids; Cycloaddition; Homogeneous 

catalysis; Heterocycles; 



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chem. Listy 106, s587–s1425 (2012) 


organometallic Chemistry, catalysis, new frontiers – ii 

o - 0 7 6 

ArtifiCiAL MetALLoenzyMeS BASed on 

Biotin-Avidin teChnoLoGy: reCent AdvAnCeS 

And ChALLenGeS 

t. wArd 1 


Switzerland 

Artificial metalloenzymes result from incorporation of a 

organometallic moiety within a protein. We have been exploiting 

the potential of the biotin-avidin technology for the creation of 

artificial metalloenzymes. Thanks to the remarkable affinity of 

biotin for either avidin or streptavidin, covalent linking of a biotin 

anchor to a catalyst precursor ensures that, upon stoichiometric 

addition of (strept)avidin, the metal moiety is quantitatively 

incorporated within the host protein. 

Such artificial metalloenzymes are optimized either by 

chemical (variation of the biotin-spacer-ligand moiety) or genetic 

(mutation of (strept)avidin) means. Such chemogenetic 

optimization schemes were applied to various organic 

transformations. The reaction implemented thus far include: 

1) The rhodium catalyzed hydrogenation of N-protected 

dehydroaminoacids (ee up to 95 %). 2) The palladium catalyzed 

allylic alkylation (ee up to 95%). 3) The ruthenium pianostool 

catalyzed transfer hydrogenation of prochiral ketones and imines 

(ee up to 97 %). 4) The vanadyl catalyzed oxidation of prochiral 

sulfides (ee up to 93 %). 5) The osmium catalyzed 

dihydroxylation of olefins (ee up to 97 %). 6) The ruthenium 

catalyzed oxidation of alcohol to ketones and the ruthenium 

catalyzed olefin metathesis. 

Noteworthy features, reminiscent of homogeneous catalysis 

include: the straightforward access to both enantiomers of the 

product; broad substrate scope; organic solvent tolerance and 

reactions typical of homogeneous catalysis. Enzyme-like features 

include: genetic optimization; aqueous medium as the preferred 

solvent; Michaelis-Menten behaviour; single substrate 

derivatization. X-ray characterization of artificial metalloenzymes 

provide a fascinating insight into possible enantioselection 

mechanims involving a well defined second coordination sphere 

environment. Thus, such artificial metalloenzymes combine 

attractive features of both homogeneous and enzymatic kingdoms. 

After presenting an overview of recent results for the above 

reactions, the last part of the talk will outline our current efforts 

on performing catalysis on crude cell extracts, thus paving the 

way towards directed evolution of artificial metalloenzymes. 

Keywords: Artificial metalloenzymes; Biotin-avidin 

technology; Enzyme design; enantioselective catalysis; 

bioinorganic chemistry; 



o - 0 7 7 

ALternAtive MethodS for CArBonyLAtion 

reACtionS of ALKeneS And ALKyneS 

i. fLeiSCher 1 , r. JennerJAhn 1 , d. CozzuLA 1 , 

K. dyBALLA 1 , r. frAnKe 2 , r. JACKSteLL 1 , 

M. BeLLer 1 

1 LIKAT, Rostock, Germany 

2 Evonik Industries AG, Marl, Germany 

Metal-catalyzed carbonylation reactions represent a very 

efficient and attractive synthetic method for carbonyl 

compounds. [1] Carbonylations of olefins belong to the most 

important industrially applied homogeneous catalytic 

transformations. Among them, alkoxycarbonylation, also called 

hydroesterification of olefins represents a very efficient method 

for the conversion of olefins, CO and alcohols to the 

corresponding esters. [2] On the other hand, selective 

carbonylations of tripple bonds can provide valuable 

intermediates for organic synthesis, such as unsaturated 

carboxylic acid derivatives. 

Herein, we would like to present few novel methods for 

carbonylations of alkenes and alkynes. On the one hand, reactions 

based on use of non-gaseous CO-sources, such as formic acid 

derivatives, will be shown. [3] They are promising alternatives to 

the toxic and gaseous carbon monoxide. 

Furthermore, the use of unusual, non-precious metals for 

carbonylations will be described. Recently, we have developed 

efficient iron-catalyzed mono- and diaminocarbonylations of 

alkynes. [4] Depending on the CO-pressure, either succinimides 

(10 bar) or cinamic amides (20 bar) can be obtained. 

references: 

1. L. Kollár (Ed.), Modern Carbonylation Methods, Wiley- 

VCH, Weinheim, 2008. 

2. B. El Ali, H. Alper, in Transition Metals for Organic 

Synthesis (Eds. M. Beller, C. Bolm), Wiley-VCH, 

Weinheim, 2008, pp. 113. 

3. T. Morimoto, K. Kakiuchi, Angew. Chem. Int. Ed. 2004, 

43, 5580. 

4. a) K. M. Driller; H. Klein, R. Jackstell, M. Beller, Angew. 

Chem. Int. Ed., 2009, 48, 6041; 

b) K. M. Driller, S. Prateeptongkum, R. Jackstell, 

M. Beller, Angew. Chem. Int. Ed., 2011, 50, 537. 

Keywords: homogeneous catalysis; carbonylation; Sustainable 

Chemistry; 



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o - 0 7 8 

deSiGn And CAtALytiC ACtivity of nitroxide 

orGAnoCAtALyStS 

A. SzPiLMAn 1 

1 Technion Israel Institute of Technology, Schulich Faculty of 

Chemistry, Haifa, Israel 

Nitroxides are intriguing compounds with many potential 

applications such as polymerization initiators, radical trapping 

reagents and catalysts for the oxidation of alcohols. Key to their 

catalytic reactivity is the integrity of the nitroxyl/oxoammonium 

functionality under the reaction conditions. However, this stability 

can normally only be insured by attaching two alkyl groups on 

either side of the nitroxide. Nitroxides bearing alfa hydrogen, 

although potentially more reactive catalysts undergo rapid 

decomposition to the corresponding catalytically inactive nitrones. 

We have developed a new design concept to ensure the 

stability of nitroxides with alfa hydrogens. We will present the 

first C2-symmetric nitroxide prepared according to this concept. 

This compound is able to efficiently oxidize even highly sterically 

alcohols at low catalyst loadings (2 mol%). We will discuss the 

properties of these compounds and their potential applications in 

asymmetric catalysis. 

organometallic Chemistry, catalysis, new frontiers – iii 

o - 0 7 9 

weLL-defined CAtioniC GALLiuM(iii) 

CoMPLexeS: A new tooL in orGAniC SyntheSiS 

v. GAndon 1 

1 Université Paris-sud, Institut de chimie moléculaire et des 

matériaux d’Orsay, Orsay Cedex, France 

Well-defined neutral and cationic gallium(III) halide 

complexes have been synthesized and evaluated in catalysis. Both 

the (NHC)GaX /AgSbF catalytic mixture and isolated 

3 6 

(NHC)GaX 2 


+ species function as exquisite π-Lewis acids in 

typical GaX -catalyzed reactions. The cationic complexes are 

3 

more active than GaX and yet more resistant to hydrolysis, which 

3 

allows lower catalytic loadings and faster reactions. Reactions that 

are not catalyzed by standard π-acids such as gold or platinum 

complexes are now possible with these new gallium species. 

Keywords: cycloisomerization; gallium; homogeneous 

catalysis; Lewis acids; N-heterocyclic carbenes; 



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o - 0 8 0 

new ru(ii) CAtALyStS for the ASyMMetriC 

reduCtion of KetoneS. 

M. wiLLS 1 , r. Soni 1 , K. JoLLey 1 , t. JohnSon 1 , 

M. dArwiSh 1 

1 University of Warwick, Chemistry, Coventry, United Kingdom 

The Wills group at Warwick University have developed a 

number of Ru(II)-based enantiomerically pure catalysts for use in 

the asymmetric transfer and pressure hydrogenation of ketones 

and imines. 

The latest developments in our programme of development 

of catalysts for asymmetric reduction will be described in this 

presentation including; 

i) The application of Ru(II)/arene/TsDPEN complexes 

containing a ‘tethering group’ for the catalysis of 

asymmetric hydrogenation of ketones and aldehydes, i.e. 

using hydrogen gas as the reducting agent in place of 

transfer hydrogenation conditions. 

ii) A new process for the efficient synthesis of a series of 

‘tethered’ Ru(II) catalysts for use in asymmetric transfer 

and pressure hydrogenation of ketones, and the synthesis 

of a number of new examples of catalysts. The 

application of these new catalysts to asymmetric 

reduction of ketones and imines will be described. 

iii) A new class of tridentate ligands for use in Ru-catalysed 

asymmetric ketone hydrogenation; synthesis, 

characterisation and applications to asymmetric 

transformation. The proposed mechanism of action of 

these new catalysts will be described. 

iv) the expansion of our Ru-based catalysts to a range of 

target substrates, including hindered ketone substrates, 

C = N bond-containing substrates and aldehydes, 

unsaturated substrates and substrates containing a 

substantial level of functionality, including heterocyclic 

groups. 

This will detail the latest developments from our 

group’s research and proposed future research work in this 

rapidly-developing and challenging research area. 

Keywords: Hydrogenation; Asymmetric catalysis; Reduction; 

Alcohols; Ruthenium; 



o - 0 8 1 

deSiGn, SyntheSeS And APPLiCAtionS of 

tAddoL-derived ASyMMetriC PhASe-trAnSfer 

CAtALyStS 

M. wASer 1 

1 Johannes Kepler University Linz, Institute of Organic 

Chemistry, Linz, Austria 

Tartaric acid, TADDOLs and analogous compounds are 

easily obtained and extraordinary versatile chiral auxiliaries, 

which have found numerous and widespread applications as chiral 

ligands in asymmetric metal catalyzed transformations. [1] 

Surprisingly, their use as chiral organocatalysts has so far been 

limited to a few applications only. [2] 

Thus we started a project aiming at the development of 

TADDOL derived asymmetric organocatalysts with a special 

focus on asymmetric phase transfer catalysis (PTC). [3] We recently 

developed a route to access novel TADDOL-derived N-spiro 

quaternary ammonium salts which were found to be useful 

catalysts for the asymmetric a-alkylation of glycine Schiff bases. 

Further structural modifications of these catalysts are currently 

underway and applications of these PTCs in other reactions are 

investigated. 

references: 

1. D. Seebach; A. K. Beck; A. Heckel, Angew. Chem. Int. Ed. 

2001, 40, 92. 

2. a) M. Shibasaki; T. Ohshima, In Asymmetric Phase 

Transfer Catalysis; Maruoka, K., Ed.; Wiley-VCH: 

Weinheim, 2008, 115. 

b) S. Arai; R. Tsuji; A. Nishida, Tetrahedron Lett. 2002, 

43, 9535. 

c) Y. N. Belokon; K. A. Kochetkov; T. D. Churkina; 

N. S. Ikonnikov; A. A. Chesnokov; O. V. Larionov; 

I. Singh; V. S. Parmar; S. Vyskocil; H. B. Kagan, J. Org. 

Chem. 2000, 65, 7041. 

d) T. Akiyama; Y. Saitoh; H. Morita; K. Fuchibe, 

Adv. Synth. Catal. 2008, 347, 1523. 

e) Y. Huang; A. K. Unni; A. N. Thadani; V. H. Rawal, 

Nature, 2003, 424, 146. 

3. M. Waser, K. Gratzer, R. Herchl, N. Müller, Org. Biomol. 

Chem. 2012, 10, 251. 

Keywords: organocatalysis; Phase-Transfer catalysis; 

asymmetric catalysis; 



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o - 0 8 2 

CAtALytiC MoLeCuLAr reArrAnGeMentS AS 

tooLS for C-C Bond forMAtion 

n. MAuLide 1 

1 Max-Planck-Institut für Kohlenforschung, Homogeneous 

Catalysis, Mülheim an der Ruhr, Germany 

Email: maulide@kofo.mpg.de 

The advent of the 21st century brought about a pressing need 

for new, efficient and clean strategies for rapid elaboration of 

molecular complexity. Our group has studied the use of 

atom-economical transformations, domino pericyclic reactions 

and redox-neutral rearrangement sequences as particularly 

appealing means towards achieving those ambitious goals. 

In this presentation, we will cover in detail some of our 

research in these areas. We have been recently interested in the 

development of an original and concise synthesis of functionalised 

cyclobutenes, [1,2] exploiting palladium catalysis to manipulate a 

bicyclic lactone photoproduct. This work has unearthed intriguing 

aspects of diastereo- and enantioselectivity which are 

unprecedented in asymmetric allylic alkylation chemistry. [3] 

An additional, recent research focus in our team has been 

the controlled manipulation of sp3 C-H bonds. The strategy we 

chose to employ (Scheme 2) takes advantage of the internal 

redox-reaction of specifically designed tethered amines, which 

effectively achieves oxidation of the relevant C-H linkage at the 

expense of a sacrificial, removable oxidant. Applications of this 

approach to the streamlined total synthesis of relevant natural 

products will be presented and discussed. [4] 

references: 

1. F. Frébault, M. Luparia, M. T. Oliveira, R. Goddard, 

N. Maulide, Angew. Chem. Int. Ed. 2010, 49, 5672; 

Angew. Chem. 2010, 122, 5807. 

2. M. Luparia, D. Audisio, N. Maulide, Synlett 2011, 735. 

3. M. Luparia, M. T. Oliveira, D. Audisio, F. Frébault, 


Angew. Chem. 2011, 123, 12840. 

4. I. D. Jurberg, B. Peng, E. Wöstefeld, M. Wasserloos, 


Angew. Chem. 2012, 124, 1986. 

Keywords: asymmetric catalysis; deracemisation; 

total synthesis; alkaloids; C-H activation; 



o - 0 8 3 

SyntheSiS of BioLoGiCALLy ACtive 

CoMPoundS viA direCt Arene-ASSeMBLinG 

reACtion 

J. yAMAGuChi 1 

1 Nagoya University, Department of Chemistry, Nagoya, Japan 

Direct C–H functionalization has garnered significant 

attention from the synthetic community as an “ideal” method for 

carbon–carbon and carbon–heteroatom bond formation. Although 

the development of new reactions and catalysts continues to 

evolve at a rapid pace, successful applications of this method to 

the synthesis of natural products and pharmaceuticals are still rare. 

Thus, our research program focuses on synthesis-oriented 

methodology development in catalytic C–H coupling. 

We developed the transition metal-catalyzed C–H coupling 

of heteroarenes such as 1,3-azoles, indoles, pyrroles, azines and 

thiophenes, and applied it to the synthesis of complex natural 

products and pharmaceutical candidates. 

Keywords: Cross-coupling; Total synthesis; Transition metals; 

Synthetic methods; C-H activation; 



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chem. Listy 106, s587–s1425 (2012) 


organometallic Chemistry, catalysis, new frontiers – iV 

o - 2 0 9 

new BondinG And reACtivity in SynthetiC 

CheMiStry 

M. GAndeLMAn 1 



Unlike N-heterocyclic carbenes (NHCs) that are now 

ubiquitously employed in metal based chemistry, the nitrogen 

derived analogue - where a carbon is replaced with the 

isoelectronic nitrogen cation (a nitrenium ion) - has remained 

elusive as a ligand for metals. This is especially intriguing since 

a number of other main group analogues of NHCs, such as 

silylenes, germilenes, phosphenium and arsenium salts, proved to 

coordinate to transition-metal complexes. We will demonstrate 

the first example of nitrenium ions as ligands for transition metal 

chemistry. 1 Preparation, structures, properties and reactivity of 

metal complexes based on these novel nitrenium ligands will be 

discussed. 

In the second part of the lecture, new types of well-defined 

halogen bonds will be presented. These non-covalent assemblies 

were fully characterized in solution and solid state, and their 

stereoelectronic parameters were evaluated. Moreover, a concept 

of halogen bond utilization for an activation of the electrophilic 

substrates in catalysis will be demonstrated. 

Keywords: carbenes; ligand design; homogeneous catalysis; 

noncovalent interactions; 



o - 2 1 0 

the iron APP – PrACtiCABLe iron-CAtALyzed 

C-C And C-h Bond forMAtionS 

S. GruPe 1 , A. Prof. dr. JACoBi von wAnGeLin 1 

1 Institute of Organic Chemistry, Organic Chemistry, 

Regensburg, Germany 

Email: sabine.grupe@ur.de 

Iron is an essential metal for the life cycle of all living 

things. Mimicking metabolic oxygenations, many protocols for 

iron-catalyzed oxidations have been reported in the past. The 

realization of efficient iron catalysis for reductive transformations 

has only recently gained momentum. Today, iron-catalyzed 

cross-coupling reactions have been developed to a multi-faceted 

class of C-C bond-forming reactions with wide substrate scope 

and significant functional group tolerance. 

We wish to report on our recent results in the application of 

simple iron catalysts to cross-coupling, dehalogenation, and 

hydrogenation reactions. The operationally simple protocols 

utilize cheap pre-catalyst and exhibit high sustainability. The 

catalysts are reactive toward non-activated substrates such as 

organic chlorides and simple alkenes. 

references: 

1. Angew. Chem. Int. Ed. 2009, 48, 607; 

2. Adv. Synth. Catal. 2010, 352, 2147; 

3. Chem. Commun. 2010, 6350. 

Keywords: iron; cross-coupling; dehalogenation; catalysis; 



s761 

chem. Listy 106, s587–s1425 (2012) 



o - 2 1 1 

iron-CAtALySed, hydride-MediAted 

reduCtive CroSS-CouPLinG 

S. thoMAS 1 



Iron catalysis has become an increasingly important and 

powerful method for carbon-carbon and carbon-heteroatom bond 

formations due to the inherent cost, environmental and 

toxicological benefits of iron-based protocols. [1] Although the 

iron-catalysed reduction of carbonyl functionalities is well 

established, the reduction of olefins is still a challenge. [2] Our 

research is focussed on the use of bench-stable iron catalysts for 

the concurrent reduction and functionalisation of olefins. 

An iron-catalysed, hydride-mediated reductive 

cross-coupling reaction has been developed for the preparation of 

alkanes. Using a bench-stable iron(II) pre-catalyst, reductive 

cross-coupling of vinyl iodides, bromides and chlorides with 

aryl- and alkyl Grignard reagents successfully gave the products 

of formal sp3–sp3 cross-coupling reactions. [3] 

references: 

1. a) E. Nakamura and N. Yoshikai, J. Org. Chem. 2010, 75, 

6061. 

b) W. M. Czaplik, M. Mayer, J. Cvengros and A. Jacobi 

von Wangelin, ChemSusChem, 2009, 2, 396 

c) A. Leitner, in Iron Catalysis in Organic Chemistry: 

Reactions and Applications, ed. B. Pleitker, 

Wiley-VCH, Weinheim, Germany, 2008, pp. 147–176. 

2. a) P. J. Chirik, in Catalysis without Precious Metals, ed. 

R. M. Bullock, Wiley-VCH, Weinheim, Germany, 2010, 

pp. 83–110. 

b) K. Junge, K. Schröder and M. Beller, Chem. Commun. 

2011, 47, 4849 

c) B. F. Le Bailly and S. P. Thomas, RSC Advances, 2011, 

1, 1435. 

3. B. A. F. Le Bailly, M. D. Greenhalgh and S. P. Thomas, 

Chem. Commun. 2012, 48, 1580. 

Keywords: Catalysis; Iron; Hydrogenation; Cross-coupling; 

Synthetic methods; 



o - 2 1 2 

uSe of MAGnetite nAnoPArtiCLeS AS CAtALySt 

for C-C And C-n CouPLinG reACtionS under 

MiCrowAve irrAdiAtion 

J. f. MendeS dA SiLvA 1 , r. Stutz yAunner 1 , 

A. f. PrAdo vAreLA 1 

1 Instituto de Quimica, Organic Chemistry, Rio de Janeiro, 

Brazil 

Transition metal catalyzed C-C and C-N coupling reactions 

are among the most important methodologies used in Organic 

Synthesis nowadays. Palladium and copper catalysts have been 

exhaustively studied for these reactions, but the use of iron and 

iron oxides is growing steadily, due to their low cost and 

versatility. 

In our group we are interested in studying the applications 

of magnetite (Fe O ) nanoparticles as catalysts for C-C and 

3 4 

C-N coupling, analogous to Sonogashira and Buchwald-Hartwig 

reactions. We performed the reaction between phenylacetylene 

and halobenzenes using ethylene glycol as solvent, potassium 

carbonate as base and magnetite (5 mol%) as catalyst and found 

that only iodobenzene was reactive enough to furnish the desired 

diphenylacetylene under these reaction conditions. The use of 

bromopyridine also led to the recovery of the starting products. 

When the reaction between phenylacetylene and iodobenzene in 

the same conditions was performed under microwave irratiadion, 

the major products found were ketals derived from iron-promoted 

water addition to phenylacetylene, followed by ketalization with 

ethylene glycol. 

We further investigated the effect of magnetite over 

C-N coupling reaction between halopyridines and piperidine and 

we found that this iron oxide was not able to enhance the products 

yields further than those obtained without any catalyst. 

In resume, we found that although magnetite can be used for 

C –C coupling of iodobenzene and phenylacetylene, this catalyst 

failed in promoting the same reaction under microwave irradiation 

or promoting C-N coupling reactions. On the other hand, it was 

efficient in promoting the one-step ketalization of 

phenylacetylene. 

Acknowledgement: The authors wish to thanks CNPq, CAPES 

and FAPERJ for the financial grant. 

Keywords: Nanoparticles; C-C coupling; Amination; Iron; 



s762 

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organometallic Chemistry, catalysis, new frontiers – V 

o - 2 1 8 

CAtALySiS for totAL SyntheSiS 

A. fuerStner 1 

1 Max-Planck-Institut für Kohlenforschung, Organometallic 

Chemistry, Mülheim an der Ruhr, Germany 

My lecture intends to provide an up-date on our programs 

concerning the activation of π-systems, most notably alkynes, 

with the aid of transition metal catalysts. Specifically, I will cover 

advances in the area of alkyne metathesis, for which new catalysts 

with a much improved application profile have recently been 

introduced. These new catalysts are highly active, remarkably 

selective, and at the same time easy to handle. On the other hand, 

alkynes are privileged substrates in gold- and platinum catalysis. 

Recent mechanistic studies in this field and the development of 

asymmetric variants pave the way to applications of catalytic 

alkyne activation chemistry to the total synthesis of bioactive 

natural products of biological significance. 



o - 2 1 9 

A ModuLAr APProACh to ChirAL iMidAteS: A 

new CLASS of nitroGen-BASed ChirAL LiGAndS 

J. vAn der eyCKen 1 , t. noeL 1 , K. Bert 1 , 

K. vAndyCK 1 

1 Ghent University, Organic Chemistry, Gent, Belgium 

Nitrogen-containing ligands are known as cheap, readily 

accessible and stable alternatives for phosphane ligands [1] , which 

are often very sensitive to air and require a multistep synthesis [2] . 

We wish to present a combinatorial approach to a novel type of 

nitrogen-based mono- and bidentate ligands [3, 4] . These ligands 

are characterized by their modular structure, allowing an easy 

one-step synthesis by simply combining two readily variable 

precursors which are either commercially available, or can be 

reached in only a few steps: a cyclic imidate and a (chiral) amine, 

respectively diamine. These ligands show promising results in 

e.g. the Cu(I)-catalyzed asymmetric aziridination of methyl 

cinnamate, in asymmetric diethylzinc additions to benzaldehydes, 

in the Pd(0)-catalyzed asymmetric allylic alkylation and 

amination, and in Ir(I)-based asymmetric hydrogenation of 

alkenes. 

references: 

1. a) Caputo, C.A.; Jones, N.D. Dalton Trans. 2007, 

4627–4640. 

b) Fache, F.; Schulz, E.; Tommasino, M.L.; Lemaire, 

M. Chem. Rev. 2000, 100, 2159–2231. 

2. a) Federsel, H.-J. Nat. Rev. Drug Discov. 2005, 4, 685–697. 

b) Hawkins, J.M.; Watson, T.J.N. Angew. Chem. Int. Ed. 

2004, 43, 3224–3228. 

3. a) Noel, T.; Vandyck, K.; Robeyns, K.; Van Meervelt, L.; 

Van der Eycken, J. Tetrahedron 2009, 65, 8879–8884; 

b) Noel, T.; Robeyns, K.; Van Meervelt, L.; Van der 

Eycken, E.; Van der Eycken, J. Tetrahedron: Asymmetry 

2009, 20, 1962–1968; 

c) Noel, T.; Bert, K.; Van der Eycken, E.; Van der Eycken, 

J. Eur. J. Org. Chem. 2010, 21, 4056–4061. 

4. For some of our previous work in the ligand field, see: 

a) Noel, T.; Vandyck, K.; Van der Eycken, J. Tetrahedron, 

2007, 63, 12961–12967. 

b) Vandyck, K.; Matthys, B.; Willen, M.; Robeyns, K.; 

Van Meervelt, L.; Van der Eycken, J. Org. Lett. 2006, 8, 

363–366. 

Keywords: asymmetric catalysis; chiral imidate ligands; 

transition metal catalysis; asymmetric allylic alkylation; 

asymmetric hydrogenation; 



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o - 2 2 0 

tAMinG the reACtivity of orGAnoMetALLiC 

reAGentS in ASyMMetriC CAtALySiS: new 

viStAS in CoPPer(i) CheMiStry 

S. r. hArutyunyAn 1 , f. CAPrioLi 1 , M. AdriAAn 1 , 

M. AShoKA 1 

1 University of Groningen, Stratingh Institute, Groningen, 

Netherlands 

The addition of highly reactive organometallic reagents to 

functionalized substrates is in principle one of the most 

straightforward methods to construct asymmetric carbon-carbon 

bond. Copper(I) based catalysts have been used as the 

synthetic tool par excellence to achieve 1,4-selectivity and 

SN2'-substitution with reactive organometallic compounds such 

as organozinc, aluminium and Grignard reagents. 

This talk will focus on our current discovery which shows 

that the longstanding paradigm of copper(I) based catalysts 

favouring 1,4-selectivity over 1,2-selectivity in the addition of 

Grignard reagents is not fully justified and that highly valuable 

chiral tertiary and secondary alcohols can be now accessed via 

copper(I) chemistry. 2 In this talk it will be shown how, employing 

chiral copper phosphine complex, catalytic enantioselective 

synthesis of tertiary alcohols can also be achieved for the first time 

using Grignard reagents with both enones, enals and alkyl aryl 

ketones with near perfect stereocontrol. Beneficially, the catalytic 

system provides already the highest level of enantioselectivity 

using the chiral ligand with e.r. of only 60:40. Mechanistic studies, 

structure of the active species and scope of the reaction will be 

discussed. 

Keywords: asymmetric catalysis; tertiary alcohol; copper 

catalysis; ferrocenyl diphosphine; 1,2-addition; 

General synthetic methods – i 


o - 2 1 3 

ASyMMetriC orGAnoCAtALytiC doMino 

reACtionS 

d. enderS 1 

1 RWTH Aachen University, Organic Chemistry, Aachen, 

Germany 

The research field of organocatalysis has developed rapidly 

since about the turn of the millennium and can now be seen as a 

third pillar of asymmetric catalysis beside metal and biocatalysis. 

Numerous basic organocatalytic protocols for very efficient and 

highly stereoselective carbon-carbon and carbon-heteroatom bond 

formations are now part of the strategic arsenal of synthetic 

chemistry. 

In this short lecture the development of simple, triple and 

even quadruple organocatalytic domino (cascade) reactions [1] using 

i.a. diphenyl prolinol-TMS-ether as catalyst will be presented. 

Some applications of these organocascade reactions in the 

short and efficient asymmetric synthesis of thiadecalines [2] , 

3H-pyrrolo[1,2-a]indole-2-carbaldehydes 3 , novel GABA 

derivatives [4] , polyfunctionalized 3-(cyclohexenyl-methyl)-indoles [5] 

and tetracyclic indol structures will be reported. 

references: 

1. For reviews from our group, see: 

a) A. Grossmann, D. Enders, Angew. Chem. Int. Ed. 2012, 

51, 314; 

b) C. Grondal, M. Jeanty, D. Enders, Nature Chemistry 

2010, 2, 167. 

c) D. Enders, C. Grondal, M. R. M. Hüttl, Angew. Chem. 

Int. Ed. 2007,46, 1570. 

2. D. Enders, B. Schmid, N. Erdmann, G. Raabe, Synthesis 

2010, 2271. 

3. D. Enders, C. Wang, G. Raabe, Synthesis 2009, 4119. 

4. D. Enders, C. Wang, J. W. Bats, Angew. Chem. Int. Ed. 

2008, 47, 7539. 

5. D. Enders, C. Wang, M. Mukanova, A. Greb, Chem. 

Commun. 2010, 46, 2447. 



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o - 2 1 4 

ACetyLeneS CArryin fLuorinAted 

CArBorAte AnionS 

f. SeMBerA 1 , M. vALASeK 1 , J. hAJduCh 1 , 

S. KeSArKAr 1 , i. StiBor 1 , J. MiChL 2 


Organic synthesis, Prague 6, Czech Republic 

2 University of Colorado, Department of Chemistry and 

Biochemistry, Boulder 80309, USA 

One of the best known and most studied among electrically 

conducting polymers is polyacetylene, which has a long 

π-conjugated linear polyene backbone and becomes conducting 

after doping. [1] We try to synthesize deeply doped polyacetylenes 

carrying the HCB11F11- anion, [2] whose synthesis by direct 

fluorination of [CsHCB11H11] with elemental fluorine in HF we 

have improved. This carborate anion is expected to be resistant 

to oxidation and electrophilic attack. The nucleophile 

LiCB11F11- generated from [CsHCB11F11] with BuLi or MeOLi 

was alkylated with acetylene derivatives TMSC =C-CR2- 

-(CH2)n-X (X = Br, I, MsO). The trimethylsilyl group was then 

removed with CsF in DMF and the desired acetylenes HC = C- 

-CR2-(CH2)n-CB11F11- (R = Me or H) were obtained. We have 

attempted to polymerize these acetylenes with several common 

polymerization catalysts but so far have obtained only oligomers. 

Acknowledgments: The research leading to these results has 

received funding from the European Research Council under 

the European Community’s Seventh Framework Programmme 

(FP7/2007-2013) / ERC grant agreement no. 227756 and was 

supported by the Academy of Sciences of the Czech Republic 

RVO: 61388963 and the Grant Agency of the Czech Republic 

203/09/J058. 

references: 

1. Shirakawa, H. Angew. Chem. Int. Ed. 2001, 40, 2574; 

MacDiarmid, A.G. Angew. Chem. Int. Ed. 2001, 40, 2581; 

Heeger, A.J. Angew. Chem. Int. Ed. 2001, 40, 2591. 

2. Ivanov, S. V.; Rockwell, J. J.; Polyakov, O. G.; 

Gaudinski, C. M.; Anderson, O. P.; Solntsev, K. A.; 

Strauss, S. H. J. Am. Chem. Soc. 1998, 120, 4224. 

Keywords: carborate anion; polyacetylene; fluorinated; 



o - 2 1 5 

reGio- And StereoSeLeCtive rinG 

trAnSforMAtionS of SMALL-rinG 

AzAheteroCyCLeS viA AziridiniuM And 

AzetidiniuM interMediAteS 

M. d’hooGhe 1 , n. de KiMPe 1 

1 Ghent University - Faculty of Bioscience Engineering, 

Sustainable Organic Chemistry and Technology, Gent, Belgium 

Three- and four-membered azaheterocyclic systems have 

acquired a pivotal position as building blocks in organic 

chemistry. In particular, aziridines and azetidines have been 

shown to be eligible synthons for the construction of a broad 

variety of stereodefined heterocyclic frameworks, often endowed 

with pronounced bioactivities. In this presentation, the synthetic 

flexibility of functionalized aziridines and azetidines toward the 

preparation of different types of aza- and oxaheterocyclic 

structures will be explained. These transformations proceed 

through the transient generation of mono- and bicyclic aziridinium 

or azetidinium intermediates, which are intercepted by various 

nucleophiles in a regio- and stereoselective manner. 

Selected examples in that respect include the use of 

2-(4-chloro-2-cyanobutyl)aziridines for a microwave-promoted 

stereoselective rearrangement into 2-(chloromethyl)piperidin-4- 

-carbonitriles [1] and for a one-step LiAlH -induced transformation 

4 

into 2-aminomethyl-1-azabicyclo[2.2.1]heptanes, the deployment 

of 2-(2-cyanoethyl)aziridines for an enzyme-catalyzed 

rearrangement into 5-hydroxypiperidin-2-ones and for a ring 

transformation to 4-(aminomethyl)butyrolactones via intermediate 

3-(aziridin-2-yl)propanoates, [2] a solvent-mediated selective 

transformation of 2-bromomethyl-2-methylaziridines into either 

functionalized aziridines or azetidines, [3] a stereoselective 

ring enlargement of chiral 2-(1-chloroalkyl)azetidines into 

3-chloropyrrolidines [4] and of 2-(2-mesyloxyethyl)azetidines 

into 4-substituted piperidines, [5] thermodynamically- or 

kinetically-controlled ring-opening reactions of aziridinium 

salts by halides, [6] and a peculiar rearrangement of 

1-(2-chloropropyl)aziridines into 2-aminopropanes via elusive 

N-spiro bis-aziridinium intermediates. 7 

In summary, a variety of new ring-rearrangement protocols 

for the selective transformation of aziridines and azetidines into 

different heterocyclic systems, mediated by the formation of 

highly reactive strained intermediates, will be presented. 

references: 

1. J. Org. Chem. 2010, 75, 7734–7744. 

2. Org. Lett. 2012, 14, 106–109. 

3. a) J. Org. Chem. 2011, 76, 2157–2167. 

b) J. Org. Chem. 2012, 77, 3181–3190. 

4. J. Org. Chem. 2010, 75, 5934–5940. 

5. J. Org. Chem. 2011, 76, 8364–8375. 

6. a) Eur. J. Org. Chem. 2010, 4920–4931. 

b) J. Org. Chem. 2010, 75, 4530–4541. 

7. J. Org. Chem. 2011, 76, 264–269. 

Keywords: Heterocycles; Ring expansion; Synthetic methods; 

Reactive intermediates; 



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o - 2 1 6 

uMPoLed tAndeM reACtion of ALPhA-iMino 

eSterS 

M. ShiMizu 1 

1 Mie University, Chemistry for Materials, Tsu, Japan 

Nucleophilic addition to the nitrogen atom of simple imines 

is, in principal, difficult due to the electron negativity of the imino 

functionality. Only limited examples have been available for the 

nucleophilic addition to the nitrogen atom of alpha-imino esters. 

The reactivity of alpha-imino esters is of interest and several 

intriguing features have been discovered. N-Alkylation of the 

imines derived from glyoxylate esters was conducted 

with dialkylaluminum chloride in acetonitrile to give an 

N-monoalkylated intermediate, which in turn underwent a 

subsequent addition reaction with another imine. When the 

N-monoalkylated intermediate was oxidized with BPO in the 

presence of allyltributyltin or cyanotrimethylsilane, tandem 

N-alkylation-C-allylation or N-alkylation-C-cyanation products 

were respectively obtained in good yields. Thus, alpha-imino 

esters behave as acceptors of two nucleophiles which attack across 

the C = N double bond. 

When an imine had two electron-withdrawing groups, i. e., 

2-[N-(p-methoxyphenyl)imino]malonate, this derivative served as 

an excellent N-alkylation reagent for Grignard reagents. 

Subsequent oxidative removal of the malonate and 

p-methoxyphenyl moieties offered a new amination methodology 

for carbanions. 

In a similar mannner, the alkoxycarbonyl iminium salt is 

easily prepared using the oxidation of amino ketene silyl acetal 

with DDQ, and subsequent nucleophilic addition to this iminium 

species proceeds efficiently to afford the amino esters in good 

yields. This methodology provides us with a new and easy entry 

into reactive iminium salts, which are important synthetic 

intermediates for many nitrogen-containing bioactive compounds. 

references: 

1. Cf. J. Am. Chem. Soc., 2003, 125, 3720: 

2. J. Am. Chem. Soc., 2005, 127, 3296; 

3. Chem. Commun., 2009, 874; 

4. J. Org. Chem., 2011, 76, 9670; 

5. Pure Appl. Chem., 2012, 84, in press. 

Keywords: Umpolung; Domino reactions; Amino acids; 

Regioselectivity; Mannich bases; 



o - 2 1 7 

deCArBoxyLAtive etherifiCAtion of 

AroMAtiC CArBoxyLiC ACidS 

w. i. dziK 1 , S. BhAdrA 1 , L. J. GooSSen 1 

1 Technische Universität, Fachbereich Chemie – Organische 

Chemie, Kaiserslautern, Germany 

The regioselective formation of aryl-oxygen bonds is a 

synthetic transformation of fundamental importance, as the aryl 

ether moiety is a common motif in many biologically active 

molecules and functional materials. Traditional synthesis of aryl 

ethers via sp2-C–O bond formation, e.g. nucleophilic aromatic 

substitutions of haloarenes or the Ullmann coupling of phenols 

with aryl halides, proceed under harsh conditions which renders 

them unsuitable for the late-stage derivatization of functionalized 

molecules. The current state-of-the-art methods are the 

Buchwald-Hartwig approach for coupling aryl halides with 

phenols or alcohols in the presence of a palladium or copper 

catalyst, and the copper-mediated Chan-Evans-Lam coupling of 

boronic acids and phenols in the presence of oxygen. 

We have developed a decarboxylative variant of the 

Chan-Evans-Lam-type coupling in which aromatic carboxylic 

acid salts are regiospecifically coupled with alkoxysilanes to form 

aryl ethers. The bimetallic catalyst system consists of a silver 

catalyst which allows for the generation of an aryl nucleophile by 

decarboxylation of an ortho-substituted benzoic acid, and of 

copper(II) acetate that mediates the C–O coupling with alkoxides 

in the presence of an oxidant. This protocol allows for a 

regioselective synthesis of aryl ethers from aromatic carboxylates 

with various electron-withdrawing and donating groups. Thus, 

diaryl and linear or branched alkyl aryl ethers containing i.a. nitro, 

methoxy, dimethylamino, sulfonyl, chloro, fluoro, trifluoromethyl 

or phenyl groups in the orthoposition could be obtained in good 

yields. 

The key advantage of the decarboxylative etherification 

reaction as a synthetic entry to aryl ethers is that it is based on 

widely available carboxylic acids as the starting materials, which 

often have substitution patterns complimentary to those of aryl 

halides or boronic acids as they draw on different starting material 

pool. 

The new reaction sets the stage for the development of 

related decarboxylative C–heteroatom bond forming reactions, 

e.g. decarboxylative aminations. 

Keywords: Carboxylic acids; C-C activation; Homogeneous 

catalysis; C-O coupling; Arenes; 



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General synthetic methods – ii 

o - 3 5 7 

SyntheSiS of CoMPLex MoLeCuLeS. ProBLeMS 

And SoLutionS 

J. CoSSy 1 

1 ESPCI ParisTech, Laboratoire de Chimie Organique, Paris, 

France 

Email: janine.cossy@espci.fr 

During the synthesis of complex bioactive compounds, 

some synthetic steps revealed problematic however, these 

problems were a good source of inspiration to develop methods. 

One major challenge to access complex molecules is the 

design and execution of concise approaches and strategies that are 

using reactions that rapidly lead to the skeleton framework of 

natural and/or biologically active compounds. In the case of 

bioactive complex oxygenated molecules, the problems 

encountered during their synthesis, forced us to find a solution 

and to explore their construction by utilizing new conditions 

involving organometallics to realize coupling reactions, 

cyclizations as well as diastereo- and enantioselective 

condensations. 

These methods and their applications to the synthesis of 

biologically active complex natural and non-natural heterocycles 


Keywords: total synthesis; bioactive molecules; coupling 

reactions; organometallics; Natural products; Synthetic 

methods; C-C coupling; Heterocycles; 



o - 3 5 8 

triAnGuLene-derived PuSh-PuLL 

ChroMoPhoreS 

M. KivALA 1 , B. GLieMAnn 1 , n. Gruner 1 


Lehrstuhl für Organische Chemie I, Erlangen, Germany 

Push-pull chromophores consisting of strong donor and 

acceptor moieties connected through various π-conjugating 

linkers have attracted much attention due to their strongly 

bathochromically shifted UV/vis absorption bands as absorbers 

in bulk heterojunction organic solar cells or as functional dyes for 

nonlinear optics. [1] 

Bridged triphenylamine derivatives, so-called triangulenes, 

have been realized by Hellwinkel and co-workers about 40 years 

ago. [2] However, the potential of these scaffolds for the 

construction of π-systems with interesting optoelectronic 

properties have by far not been exhausted to date. Here, we 

present the synthesis and optoelectronic properties of a series of 

novel triangulene chromophores featuring intramolecular 

charge-transfer interactions. 

references: 

1. A. Mishra, P. Bäuerle, Angew. Chem. Int. Ed. 2012, 51, 

2020–2067. 

2. D. Hellwinkel, M. Melan, Chem. Ber. 1971, 104, 

1001–1016. 

Keywords: Conjugation; Heterocycles; Charge transfer; 

Chromophores; Fused-ring systems; 



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o - 3 5 9 

hydroGenAtion of heteroCyCLiC 

CALixAreneS 

r. neier 1 , G. Journot 1 , L. CeriSoLi 2 , 

A. GuALAndi 2 , d. SAvoiA 2 

1 University of Neuchatel, Department of Chemistry, Neuchatel, 

Switzerland 

2 University of Bologna, Department of Chemistry, Bolgona, Italy 

The simple and efficient synthesis of calix[4]furan and 

calix[4]pyrrole has been known for more than 125 years. The 

connectivity of the heterocyclic calix[4]arenes is identical with 

the skeleton of the «pigments of life». The chemical properties, 

especially the ability to form complexes with transition metals, 

are totally different when comparing the artificial systems with 

the natural products. A direct way to confer metal binding 

capabilities to compounds derived from heterocyclic 

calix[4]arenes is hydrogenation. We present our systematic studies 

of the hydrogenation reactions of calix[4]furan and 

calix[4]pyrrole. The hydrogenation of the calix[4]pyrrole proved 

to be challenging. The major products obtained first were the half 

reduced macrocycles of the type calix[2]pyrrole[2]pyrrolidine. 

The totally reduced macrocycle was isolated only in small 

amounts. To understand the sequence of this heterogenous 

catalytic hydrogenation the synthesis of mixed calix[n]furan[4- 

-n]pyrrole was undertaken. These mixed macrocycles were good 

model compounds for studying the sequence of the reduction 

process. The macrocycles were preferentially hydrogenated on 

the furan rings, whereas the hydrogenation of the pyrrole rings 

consistently needed much harsher conditions. Exploiting this 

difference in reactivity we were able to determine the sequence 

of the hydrogenation reaction. Based on these mechanistic data 

an improved synthetic procedure has been developed for the 

hydrogenation process, which allowed us to obtain the totally 

reduced macrocycle calix[4]pyrrolidines in quantitative yield. The 

calix[2]pyrrole[2]pyrrolidine showed a very strong intramolecular 

hydrogen bond network. This network determines the structure, 

the conformational behavior and the chemical reactivity of 

this novel macrocycle. The metal binding of the totally 

reduced calix[4]pyrrolidines will be presented. The new 

calix[4]pyrrolidines can be classified as new stiffened macrocyclic 

crown ethers or as saturated analogues of the porphyrin derived 

«pigments of life». 

Keywords: Heterogenous catalysis; Calixarenes; 

Hydrogenation; Hydrogen bonds; Heterocycles; 



o - 3 6 0 

one-Pot nuCLeoPhiLiC rAdiCAL Addition to 

KetiMineS GenerAted in Situ 

B. roSSi 1 , n. PAStori 1 , A. CLeriCi 1 , S. ProSPerini 1 , 

C. PuntA 1 

1 Politecnico di Milano, Dipartimento di Chimica Materiali ed 

Ingegneria Chimica “G. Natta”, Milano, Italy 

In the last years we reported that the Ti(III)/hydroperoxide 

(H O , t-BuOOH) system was able to promote both radical 

2 2 

Mannich-type reactions and a radical version of the Strecker 

synthesis, starting from an aldehyde and an amine in ether, alcohol 

or formamide co-solvent, respectively. [1] The optimization of the 

previously reported protocol allowed us to develop the 

nucleophilic free radical addition of formamide to ketimines 

generated in situ by replacing the aqueous solution of TiCl with 3 

the more convenient and efficient Ti(IV)-Zn system, providing 

instant access to quaternary α-aminonacid precursors. [2, 3] The new 

catalytic system was successfully applied for the nucleophilic 

radical hydroxymethylation of ketimines, leading to the synthesis 

of β-amino alcohols [4] and the selective radical aminoalkylation 

of ethers. [5] 

references: 

1. a) Cannella, R.; Clerici, A.; Panzeri, W.; Pastori, N.; Porta, 

O. Tetrahedron 2006, 62, 5986–5994; 

b) Clerici, A.; Ghilardi, A.; Pastori, N.; Punta, C.; Porta, 

O. Org. Lett. 2008,10, 5063–5066; 

c) Cannella, R.; Clerici, A.; Panzeri, W.; Pastori, N.; Punta, 

C.; Porta, O. J. Am. Chem. Soc. 2006, 128, 5358–5359. 

2. Pastori, N.; Greco, C.; Clerici, A.; Porta, O. Org. Lett. 

2010,12, 3898–3901. 

3. Prosperini, S.; Pastori, N.; Ghilardi, A.; Clerici, A.; Punta, 

C. Org. Biomol. Chem., 2011, 9, 3759-3767 

4. Rossi, B.; Pastori, N.; Clerici, A.; Punta, C., submitted. 

5. Rossi, B.; Pastori, N.; Clerici, A.; Punta, C. manuscript in 

preparation. 

Keywords: Radical reactions; Titanium; Multicomponent 

reactions; Nucleophilic addition; Amino alcohols; 



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General synthetic methods – iii 

o - 3 6 1 

reCent deveLoPMentS of new 

StereoSeLeCtive MuLtiPLe Bond-forMinG 

trAnSforMAtionS 

J. rodriGuez 1 

1 Aix-Marseille University, Institut des Sciences Moleculaires de 

Marseille, Marseille cedex 20, France 

The presentation will be devoted to some of our recent 

contributions on the utilization of activated carbonyls towards the 

development of new MBFTs involving organocatalyzed 

asymmetric Michael addition, selective intramolecular trapping 

of iminiums and microwave-promoted both olefin metathesis and 

acyl-Wolff rearrangement allowing the facile preparation of 

polyheterocyclic systems with a high level of complexity and 

diversity. 

Keywords: Michael addition; Multicomponent Reactions; 

Carbanions; Molecular diversity; Synthetic Methods; 



o - 3 6 2 

PrePArAtionS of reGioSeLeCtiveLy 

MonoSuBStituted ALPhA-, BetA- And GAMMA- 

CyCLodextrin derivAtiveS – PreCurSorS for 

further SyntheSiS. 

J. JindriCh 1 , M. rezAnKA 1 , M. BLAhovA 1 , 

e. BednArovA 1 


of Organic and Nuclear Chemistry, Prague 2, Czech Republic 

Alkylation of α-, β- or γ-cyclodextrin with allyl, cinnamyl 

or propargyl bromide followed by peracetylation of remaining 

hydroxyl groups and separation of isomers resulted in the sets of 

peracetylated 2I-O-, 3I-O- and 6I-O-alkylated cyclodextrins. 

Ozonolyzis or oxidative cleaveage of peracetylated allyl or 

cinnamyl derivatives resulted in complete sets of peracetylated 

2I-O-, 3I-O- and 6I-O- formylmethyl or carboxymethyl derivatives 

which are, as well as the propargyl derivatives, useful precursors 

for preparation of regioselectively monosubstituted derivatives of 

cyclodextrins. All compounds were characterized by 2D-NMR 

techniques. The carboxymethyl derivatives were used as chiral 

selectors in capillary electrophoresis. Substantial differences in 

separation abilities among the regioisomers were observed. Thus, 

the importance of performing supramolecular interaction 

experiments with pure regiosomers of cyclodextrin derivatives 

was confirmed. 

Keywords: cyclodextrins; synthetic methods; electrophoresis; 

NMR spectroscopy; supramolecular chemistry; 



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o - 3 6 3 

Convenient SiLyLAtion of PhenoLS By uSinG 

ChLoroSiLAneS in Br/MG-exChAnGe reACtion 

G. StrLe 1 , J. CerKovniK 1 

1 University of Ljubljana, Faculty of Chemistry and Chemical 

Technology, Ljubljana, Slovenia 

Preparation of aryl Grignards bearing unprotected OH group 

in halogen-magnesium exchange reaction represent a synthetic 

chalenge. [1, 2] Some literature data for preparation of 

trialkylsilyl-substituted phenols by other synthetic methods are 

available, however, there is no reports on direct preparation of 

silyl-substituted phenols bearing one or two hydrogen atoms on 

silicon atom. Namely, such compounds are usually unstable under 

reaction conditions and readily lose silyl functional group by 

forming phenols. 

Herein, we wish to report efficient direct silylation of 

bromo-substituted phenols in a Br/Mg-exchange reaction by 

using various disubstituted chlorosilanes in presence of catalytic 

amounts of LiCl. [2] Chlorosilane act at the same time as Lewis 

acid activating magnesium for bromine exchange to in situ 

generate Grignard reagent, and as an electrophilic reagent. By 

applying this method we successfully isolated various 

substituted alkylsilyl-, dialkylsilyl-, alkylphenylsilyl- and 

diphenylsilylphenols in satisfactory to good yields. This approach 

can be also extended to various heterocyclic compounds bearing 

a hydroxy group like pyridines and quinolines. 

Recently we have found an efficient direct catalytic 

transformation of some silyl hydrotrioxides (ROOOH). [3] To 

prepare some polymer-bound silylated substrates we were 

challenged with the preparation silyl-substituted phenols. In this 

contribution attempts to prepare polymer-bound substrates via 

silyl-substituted phenols will also be discussed. 

references: 

1. a) Gottardo, C.; Aguirre, A. Tetrahedron Lett. 2002, 43, 

7091. 

b) Kopp, F.; Krasovskiy, A.; Knochel, P. Chem. Commun. 

2004, 2288. 

2. Piller, F. M.; Metzger, A.; Schade, M. A.; Haag, B. A.; 

Gavryushin, A.; Knochel, P. Chem. –Eur. J. 2009, 15, 

7192. 

3. Bergant, A.; Cerkovnik, J.; Plesnicar, B.; Tuttle, T. J. Am. 

Chem. Soc. 2008, 130, 14086. 

Keywords: Grignard reaction; Silanes; Electrophilic 

substitution; Synthesis design; Polymers; 

General synthetic methods – iV 


o - 3 6 4 

C-h ACtivAtion reACtionS At SP2- And 

SP3-CArBon CenterS 

t. BACh 1 

1 Technische Universität München, Lehrstuhl für Organische 

Chemie I, Garching, Germany 

C-H activation reactions at sp2-carbon centers allow for the 

direct, regioselective introduction of substituents into arenes and 

hetarenes. Particular focus of our work in this area is the installation 

of alkyl groups into biologically relevant heterocycles. [1] 

In the area of C-H activation at sp3-carbon centers we have 

studied the diastereoselective amination reaction in the benzylic 

position of chiral substrates. [32] One of the ultimate goals in C-H 

activation chemistry is the regio- and enantioselective activation 

of aliphatic C-H bonds. Towards this goal, we have developed 

transition metal catalysts, to which a ligand with a hydrogen 

bonding site is attached. [3] Hydrogen bonding allows to perfectly 

position the substrate in an enzyme-like approach. Most recent 

results will be discussed. 

references: 

1. L. Jiao, T. Bach, J. Am. Chem. Soc. 2011, 133, 

12990–12993. 

2. A. Nörder, P. Herrmann, E. Herdtweck, T. Bach, Org. Lett. 

2010, 12, 3690–3692. 

3. P. Fackler, C. Berthold, F. Voss, T. Bach, J. Am. Chem. 

Soc. 2010, 132, 15911–15913. 

Keywords: amination; C-H activation; enantioselectivity; 

homogenous catalysis; hydrogen bonds; 



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o - 3 6 5 

the SyntheSiS of GiAnt CALixAreneS 

C. MArtini 1 , M. roLLet 2 , d. GiGMeS 2 , S. vieL 3 , 

B. LePoittevin 4 , v. huC 4 

1 University Pierre and Marie Curie, Laboratoire de Chimie de 

la Matiere Condensée, PARIS, France 

2 Laboratoire Chimie Provence, Chimie Radicalaire Organique 

et Polymeres de Spécialité, Marseille, France 

3 Laboratoire Chimie Provence, Spectrométries Appliquées a la 

Chimie Structurale, Marseille, France 

4Universite Paris-Sud 11, Institut de Chimie Moléculaire et des 

Matériaux d’Orsay, Orsay, France 

Calixarenes are a versatile class of cyclic oligomers 

successfully applied to ions recognition, for example, thanks to 

their tunable cavity and their ability to be readily functionalized. 

Their synthesis involves a reaction between formaldehyde and 

positions ortho to the hydroxyl group of phenol derivatives under 

basic or acidic catalysis. The ring shape of calixarenes is induced 

by intramolecular H-bonding as oligomers grow. Among 

calixarenes family, the most studied are those including 4 to 8 

monomer units since they are easily accessible from standard 

synthesis methods. Very few examples of larger calixarenes are 

available in the literature and the larger one, synthesized in very 

small amount, doesn’t exceed 20 units. We propose here the 

synthesis of “giant calixarenes” with a size well above the current 

state of art. These macrocycles are obtained easily in one step and 

can be purified by simple selective precipitation processes. We 

found that, depending mainly on the choice of para group and 

catalyst, and on reaction time, calixarenes are able to reach 

unsuspected size. In contrast with the classic synthesis of 

macrocyclic polymers, needing a high dilution to prevent an 

intermolecular linkage, the giant calixarenes are obtained using a 

high concentration and produced in very large scale (above 50 g 

in a 1L-flask). Furthermore, taking advantage of the chemical 

versatility of calixarenes, we successfully performed the 

functionalization of giant calixarenes lower rims with different 

reactants. These new compounds represent a very promising 

platform for the design and the production of functional 

macrocyclic polymers, and will probably open new perspectives 

in material science. 

Keywords: Calixarenes; polymers; macrocycles; 



o - 3 6 6 

froM iMidAzoquinoLineS to 

iMidAzoquinoLineS throuGh triCyCLiC 

quinoLineS 

v. MiLAtA 1 , J. SALon 1 , M. BeLLA 2 

1 Slovak University of Technology FCHPT, Organic Chemistry 

Catalysis and Petrochemistry, Bratislava, Slovak Republic 

2 FCHPT STU and SAS, OCCP and IC, Bratislava, 

Slovak Republic 

2-Aminoimidazoquinoline, compounds with interesting 

biological properties, was found, like similar pyrazinoquinolines, 

in thermally treated meats (HCA, heterocyclic amines). [1, 2] The 

synthetic strategy leading to them is based on closing the 

quinoline or the azole/pyrazine ring. 

Aminobenzimidazoles/triazoles/selenadiazoles/ 

/quinoxalines we prepared mainly from the corresponding 

nitroderivatives. After reduction to corresponding amine and 

applying the Gould-Jacobs protocol with activated enolethers 

under S V conditions we obtained aminoethylene derivatives 

N 

– precursors of target compounds. Thermal cyclization of the 

aminoethylenes gave exclusively the angularly annelated 

azolo/pyrazinoquinolines, which could be converted to parent, 

non-substituted heterocycles by following reactions: hydrolysis, 

decarboxylation, chlorination/aromatization and dechlorination. 

During reductive dechlorination of the 7-chloropyrido[2,3- 

-f]quinoxaline we found that an unknown coupled ring contraction 

of the fused pyrazine ring into a condensed imidazole ring takes 

place. The ring transformation of condensed selenadiazole ring 

gave us a tool to prepare various selectively alkylated tricyclic 

heterocycles. Another approach afforded food borne carcinogen, 

2-amino-3-methylimidazo[4,5-f]quinoline (IQ) obtained in total 

20% yield using unique strategy. 

Acknowledgements: The authors are grateful to the Slovak 

Grant Agency for Science (contract No. 1/0660/11) and to 

Slovak Research and Development Agency (contracts No. 

APVV-0339-10 and APVV-0038-11) for the financial support. 

references: 

1. Milata V.: Tricyclic Azoloquinolines, Advances in 

Heterocyclic Chemistry, ed. A. R. Katritzky, vol. 78, 

189–268, Academic Press, San Diego, 2001. 

2. Nagao, M.; Sugimura, T. Food Borne Carcinogens; 

John Wiley & Sons: Chichester, 2000. 

Keywords: imidazoquinoline; selediazoloquinoline; 

pyrazinoquinoline; nucleophilic vinylic substitution; 

Gould-Jacobs reaction; 



s771 

chem. Listy 106, s587–s1425 (2012) 



o - 3 6 7 

wAter MediAted Proton-CouPLed eLeCtron 

trAnSfer in enzyMeS And in free-rAdiCAL 

CheMiStry By CoordinAtion to MetAL 

CoMPLexeS 

A. G. CAMPAnA 1 , M. PArAdAS 1 , t. JiMénez 1 , 

i. rodríGuez-Márquez 1 , e. BunueL 2 , 

d. J. CárdenAS 2 , J. M. CuervA 3 

1 Facultad De Ciencias, Quimica Organica, Granada, Spain 

2 Facultad De Ciencias, Quimica Organica, Madrid, Spain 

3 Facultad de Ciencias, Quimica Organica, Granada, Spain 

Efficient proton and electron transfer lies at the heart of the 

remarkable success of energy conversions in photosynthesis and 

respiration. In many biological systems proton transfer (PT) is 

coupled to electron transfer (ET) allowing the assembly of 

thermodynamically favored reaction pathways, and avoiding 

high-energy intermediates. 

Here we show theoretical evidences of an unprecedented 

water mediated long-range PCET process between metal 

complexes. [1] Water mediates the long-range proton-coupled 

electron transfer between two Cu complexes separated by 11 ? in 

the peptidylglycine α-hydroxylating monooxygenase (PHM) 

cofactor. The proposed mechanism, which involves three H-atom 

exchanges, accounts for long-range electron transfer in 

metalloenzymes, and may be ubiquitous in nature. 

Taking into account that aquo or hydroxo complexes of 

other transition metals are generally present in vital processes in 

nature, those complexes could also play an essential role in many 

organic synthetic reactions. In this sense, water would be an 

extraordinary safe and cheap hydrogen atom transfer (HAT) 

reagent in the reduction of carbon-based radicals. Therefore in 

recent years solid evidence of HAT reductions involving water as 

hydrogen atom source have been presented. 

Water becomes an excellent hydrogen atom donor in the 

presence of bis(cyclopentadienyl)titanium(III) chloride (Cp TiCl) 2 

towards carbon radicals. In this work we also show that the 

efficiency of Ti(III) aqua complexes as an unique class of HAT 

reagents is based on two key features: (a) excellent binding 

capabilities of water towards titanocene(III) complexes and 

(b) a low activation energy for the HAT step. [2] 

references: 

1. Cárdenas, D. J.; Cuerva, J. M.; Alías, M.; Bunuel, E.; 

Campana, A. G. Chem. Eur. J. 2011, 17, 8318-8323. 

2. Paradas, M.; Campana, A. G.; Jiménez, T.; Robles, R.; 

Oltra, J. E.; Bunuel, E.; Justicia, J.; Cárdenas, D. J.; 

Cuerva, J. M. J. Am. Chem. Soc. 2010, 132, 12748-12756. 

Keywords: Density functional calculations; Hydrogen transfer; 

Metalloenzymes; Radical reactions; Water chemistry; 



o - 3 6 8 

CASCAde reArrAnGeMent of enediyneS with 

MeMory of ChirALity 

M. neChAB 1 , S. MondAL 1 , d. CAMPoLo 1 , 

n. vAnthuyne 2 , M. P. BertrAnd 1 

1 CMO, Institut Chimie Radicalaire, Marseille France, France 

2 Chirosciences, ISM2, Marseille France, France 

During the past decade, Memory of Chirality (MOC) has 

emerged as a powerful tool in organic synthetic. [1] This strategy 

allows the enantioselective construction of a chiral tetrasubstituted 

stereocenter. We have recently developed a polar/radical crossover 

cascade rearrangement of enediynes bearing a sulfone moiety as 

a precursor of an intermediate enyne-allene. [2-3] The reaction 

proceeded with retention of the configuration of the starting 

material to afford tetracyclic heterocycle with high memory effect. 

Deuterium labelling and theoretical calculations were used to 

demonstrate that an 1,5-hydrogen atom transfer was exclusively 

involved in this cascade. [4] 

Heterocyclic analogues of aspartic esters bearing two 

contiguous quaternary stereogenic centers were also reached 

through copper catalyzed five-step cascade rearrangement of 

terminal enediynes with diazoesters. [5] The copper carbenoid acts 

as a reactant and catalyst to promote carbene insertion and 

one-pot allene formation. 

In order to overcome the lack of diastereoselectivity which 

is the main drawback of this process, we devised a tandem Crabbe 

homologation-radical rearrangement of terminal enediynes 

leading the synthesis of six- and seven-membered ring 

α-aminoesters. [6] 

references: 

1. For review, see:K. Fuji, T. Kawabata, Chem. Eur. J. 1998, 

4, 373; 

2. M. Nechab, D. Campolo, J. Maury, P. Perfetti, 

N. Vanthuyne, D. Siri, M. P. Bertrand, J. Am. Chem. Soc. 

2010, 132, 14742-14744. 

3. M. Nechab, E. Besson, D. Campolo, P. Perfetti, 

N. Vanthuyne, E. Bloch, R. Denoyel, M. P. Bertrand, 

Chem. Commun. 2011, 47, 5286–5288. 

4. D. Campolo, A. Gaudel-Siri, S. Mondal, D. Siri, E. 

Besson, N. Vanthuyne, M. Nechab, M. P. Bertrand, 

J. Org. Chem., 2012, 77, 2773-2783. 

5. S. Mondal, M. Nechab, D. Campolo N. Vanthuyne and 

M. P. Bertrand, Adv. Synth. Cat. in Press. 

6. S. Mondal, M. Nechab, N. Vanthuyne and M. P. Bertrand, 

Chem. Commun, 2012, 48, 2549-2551. 

Keywords: Memory of chirality; Enediynes; Myers-Saito 

cyclization; Radical cascades; Tetrasubstituted stereocenters; 



s772 

chem. Listy 106, s587–s1425 (2012) 


General synthetic methods – V 

o - 3 6 9 

nuCLeoPhiLe SeLeCtive CroSS-CouPLinG 

reACtionS 

A. StAuBitz 1 , J. LinShoeft 1 , A. C. J. heinriCh 1 , 

S. A.w. SeGLer 1 , B. thiedeMAnn 1 , P. J. GAteS 2 

1 Otto-Diels-Institute for Organic Chemistry, Chemistry, Kiel, 

Germany 

2 Organic Chemistry, School of Chemistry, Bristol, United Kingdom 

In cross-coupling reactions, the reactivity of the electrophilic 

functional group typically decreases in the order I > OTf > Br > Cl. 

This enables reactions to be performed with a very high degree 

of chemo selectivity. 

In contrast, nucleophile selective cross-coupling reactions, 

where there is a differentiation between different nucleophilic 

groups, have received little attention to date. 

We wish to report a systematic investigation into a 

cross-coupling procedure with complete differentiation between 

two nucleophilic sites, a boronic ester and a stannyl group. [1] 

We will discuss the synthesis of the starting materials and 

potential applications in materials science. 

references: 

1. Julian Linshoeft, Annika C. J. Heinrich, Stephan A. W. Segler, 

Paul J. Gates, and Anne Staubitz, manuscript submitted. 

Keywords: cross-coupling; heterocycles; 



o - 3 7 0 

SoLid-PhASe SyntheSiS of diverSeLy 

ConStrAined PePtidoMiMetiCS 

A. LA veniA 1 , v. KrChnAK 2 

1 Palacky University in Olomouc, Organic Chemistry, Olomouc, 


2 University of Notre Dame, Department of Chemistry and 

Biochemistry, Notre Dame, USA 

Methodology providing access to an array of diverse 

secondary structure peptidomimetics, with complete control of 

their stereochemistry, is an indispensable tool for investigation 

complex structure-function relationships of biologically 

significant peptides and proteins, and also to obtain highly active 

and selective compounds with enhanced proteolytic stability. [1] In 

particular, tandem N-acyliminium ion cyclization – nucleophilic 

addition, which represents a powerful strategy to generate 

fused-ring systems, has been useful to synthesize constrained 

peptidomimetics. [2] The concept of these tandem cyclizations 

inherently enables sequential and independent synthesis of the 

lineal precursors for cyclic iminiums followed by incorporation 

of precursors for the nucleophilic addition, allowing the 

combination of the precursors of both rings to produce 

combinatorial libraries. The aim of this work has been to develop 

a general methodology for efficient and expeditious solid-phase 

synthesis of diversely constrained peptidomimetics, in which the 

constraints would be assembled from simple building blocks using 

the N-iminium chemistry during solid-phase synthesis, rather than 

typical incorporation of pre-formed scaffolds. Thus a library of 

varied heterocycles with functional as well as skeletal diversity 

was efficiently synthesized with full stereocontrol, achieving 

several ring sizes and including different internal nucleophiles 

(N, O, S, C). The analysis of these experiments allowed to 

recognize the internal nucleophile’s requirements to promote the 

second cyclization, concluding in the case of N nucleophiles that 

sulfonamides achieved the best results. In addition a strong 

influence of the different tested aminoacids in products’ 

stereochemistry was observed, mainly of those aminoacids 

present in the first ring. All the fused-rings generated are available 

to be introduced in a larger peptide, but are also interesting 

per se, being their biological activity measurement in process. 

references: 

1. a) Grauer, A.; König, B., Eur. J. Org. Chem. 2009, 5099. 

b) Eguchi, E.; et al., Mini-Rev. Med. Chem., 2002, 447. 

2. Kahn, M.; Chen, B., Tetrahedron Lett. 1987, 1623. 

Keywords: Fused-ring systems; Heterocycles; Solid-phase 

synthesis; Peptidomimetics; 



s773 

chem. Listy 106, s587–s1425 (2012) 



o - 3 7 1 

triPhenyLAMine BASed d-A or d-A-d P 

ConJuGAted SySteMS AS MoLeCuLAr donorS 

for orGAniC SoLAr CeLLS 

A. LeLieGe 1 , t. rouSSeAu 1 , P. BLAnChArd 1 , 

J. ronCALi 1 

1 MOLTECH-Anjou, UFR sciences, Angers, France 

The development of organic solar cells (OSCs) is currently 

the subject of considerable interest. OSCs based on bulk 

heterojunctions between conjugated polymers (electron donor 

material) and fullerene derivatives (electron acceptor material) 

have led to significant improvements over the last decade. On the 

other hand, small conjugated molecules represent attractive donor 

materials since their synthesis is more reproducible, their 

purification easier and they offer the advantage of being used for 

both the preparation of bilayer-type OSCs by vacuum deposition 

and the elaboration of bulk heterojunction OSCs by spin 

casting. [1] An interesting approach to synthesize efficient donor 

molecules relies on the introduction of an electron acceptor group 

A in the structure of the conjugated system to create an 

intramolecular charge transfer between an electron-donor group 

D and the acceptor A. [2] Thus D-π-A and D-π-A-π-D systems 

generally display a broad absorption in the visible spectrum and 

they have recently shown interesting performances in both bilayer 

and bulk heterojunction OSCs. In this context, we present here 

the synthesis and characterization of new symmetrical and 

unsymmetrical D-π-A-π-D molecules based on 

tetracyanobutadiene as central acceptor (A) and oligothienyl-TPA 

chains as donors (D),3 as well as new D-π-A systems of 

minimized length based on a bridged indenothiophenone 

derivative as acceptor. OSCs of simple bilayer architecture made 

with these new compounds show photovoltaic conversion 

efficiencies ranging from 1 to 3% which represent very promising 

results. [3, 4] 

references: 

1. J. Roncali, Acc. Chem. Res., 2009, 42, 1719. 

2. S. Roquet, A. Cravino, P. Leriche, O. Aleveque, P. Frere, 

J. Roncali, J. Am. Chem. Soc., 2006, 128, 3459. 

3. A. Leliege, P. Blanchard, T. Rousseau, J. Roncali, Org. 

Lett., 2011, 13, 3098. 

4. A. Leliege, P. Blanchard, J. Roncali, manuscript in 

preparation. 

Keywords: organic electronics; thiophene; organic solar cells; 

sulfur heterocycles; 



o - 3 7 2 

JAnuS-heAd tyPe diPhoSPhoruS triCAtion 

[Pyr P ] 3 2 3+ (Pyr =3,5-diMethyLPyrAzoLe) AS 

reAGent for the funCtionALiSAtion of 

orGAniC MoLeCuLeS 

A. K. C. eChterhoff 1 , S. yoGendrA 1 , J. J. weiGAnd 1 

1 WWU Münster, Institut für Analytische und Anorganische 

Chemie, Münster, Germany 

Email: a.echterhoff@uni-muenster.de www.agweigand.de 

Main group element-centered cations possess unusual 

reactivities. [1] Especially, multiply charged phosphorus-centered 

cations are comparable rare [2] and we have found that certain types 

of these cations can be used for unusual bond formation reactions. 

Recently, we reported on a Janus-head type diphosphorus trication 

[pyr P ] 3 2 3+ (1) as triflate salt (1[OTf] ). 3 [3] Due to the high Lewisacidity 

and the presence of the labile pyrazolyl moieties in this 

compound, we found that this highly-charged, very oxophilic 

cation 13+ allows unusual phosphorus-oxygen bond formation 

reactions. [3, 4] In this context we became interested in using 

compound 1[OTf] as deoxygenation and pyrazole transfer as well 

3 

as dehydration reagent in organic synthesis. Hence 1[OTf] 3 

enables us to functionalise organic compounds such as pyridones, 

urea-compounds or amides in a one-pot syntheses. We will present 

our recent results and discuss possible applications of our 

approach. 

references: 

1. V. G. Nenajdenko, N. E. Shevchenko, E. S. Balenkova 

Chem. Rev. 2003, 103, 229. 

2. a) J. J. Weigand, N. Burford, A. Decken, A. Schulz, 

Eur. J. Inorg. Chem. 2007, 4868; 

b) Dyker, C. A.; Burford, N. Chem. Asian J. 2008, 3, 28; 

and references therein. 

3. Weigand, J. J.; Feldmann, K.-O.; Echterhoff, A. K. C.; 

Ehlers, A.; Lammertsma, K. Angew. Chem. Int. Ed. 2010, 

49, 6178. 

4. Feldmann, K.-O.; Schulz, S.; Klotter, F.; Weigand; 

J. J. Chem. Sus. Chem., 2011, 4, 1805. 

Keywords: Phosphorus; Sustainable Chemistry; Green 

Chemistry; Functionalisation; Amides; 



s774 

chem. Listy 106, s587–s1425 (2012) 



o - 3 7 3 

Cu CAtALyzed SeLeCtive 

Mono-n-PyridyLizAtion: 

2-AMinodMAP/SuLfonAMideS AS BifunCtionAL 

orGAnoCAtALyStS 

C. tAnyeLi 1 , M. iSiK 1 

1 Middle East Technical University, Chemistry, Ankara, Turkey 

Chiral DMAP analogues offer unique reactivity and 

versatility as Lewis base catalysts in a wide array of reactions. [1] 

There is a significant demand to evolve novel practical 

methodologies targeting direct mono-N-functionalization of 

C -symmetrical diamines.Herein, we have anticipated that the chiral 

2 

2-aminoDMAP derived from trans-cyclohexane-1,2-diamine could 

serve as a versatile Lewis basic catalaphore and introduction of 

various H-bond donor entities via modification of remaining 

primary amine might led to discovery of new reactivities in 

context of bifunctional acid/base catalyst development. For this 

purpose, we have explored the possibility of 

Pd-catalyzed Buchwald-Hartwig N-arylation [2] of the 

(1R,2R)-cyclohexane-1,2-diamine with 2-haloDMAPs. However 

no trace of target compound was observed. Realizing 

unsatisfactory results with palladium chemistry, we have turned 

our attention to copper-catalyzed modified Ullmann coupling 

reaction. Successful synthesis of 2-aminoDMAP readily in only 

one step encouraged us to investigate the catalytic potential of this 

basic catalaphore unit in pursuit of efficient bifunctional acid/base 

organocatalysts. [3] Sulfonamides were chosen to chaperon 

2-aminoDMAP base as the H-bond donor counterpart. Developed 

catalysts were screened in conjugate addition of acetylacetone to 

trans-(β)-nitrostyrene, serving testing ground for bifunctional 

organocatalysis. We presented 10 examples of bifunctional 

acid/base organocatalysts incorporating 2-aminoDMAP and 

systematically varied sulfonamide moieties. The catalyst given 

above was shown to promote the conjugate addition reaction of 

acetylacetone and trans-(β)-nitrostyrene effectively with 

enantioselectivites up to 93%. 

references: 

1. a) R. P. Wurz, Chem. Rev. 2007, 107, 5570. 

b) A. C. Spivey, S. Arseniyadis, Top. Curr. Chem. 2010, 

291, 233. 

c) C. E. Müller, P. R. Schreiner, Angew. Chem., Int. Ed. 

2011, 50, 6012. 

2. a) A. S. Guram, R. A. Rennels, S. L. Buchwald, Angew. 

Chem. Int. Ed. 1995, 34,1348. 

b) J. Louie, J. F. Hartwig, Tetrahedron Lett. 1995, 36, 

3609. 

3. Y. Wang, L. Deng, in Catalytic Asymmetric Synthesis, 

3rd ed. (Ed.: I. Ojima), Wiley VCH: Newyork, 2010, 59–94. 

Keywords: copper; organocatalysis; asymmetric synthesis; 



o - 3 7 4 

MuLtiPLe Arene funCtionALizAtion uSinG 

trAnSient diAzoniuM SALtS 

B. SChMidt 1 

1 University of Potsdam, Institut fuer Chemie, Potsdam-Golm, 

Germany 

Arene diazonium salts have emerged as versatile coupling 

reagents in numerous Pd-catalyzed reactions. [1] A particular 

benefit of these reagents is the very high reactivity, the opportunity 

to suppress undesired double bond migration following Heck 

reactions, [2] and their convenient and economically advantageous 

synthesis from anilines. However, there are also a few 

disadvantages that often deter chemists from using these reagents: 

quite often the anilines are remarkably sensitive towards 

oxidation, and handling isolated diazonium salts is often 

considered as potentially hazardous. 

Over the past few years we have embarked on a project 

directed at using anilides rather than anilines as precursors for 

arene diazonium salts. This approach involves the in situ 

deacetylation, diazotation and precipitation as stable isolable 

tetrafluoroborates. [3] In this contribution we report about the 

extension of this sequence by Pd-catalyzed steps, leading to the 

establishment of anilides as electrophile precursors for Heck- and 

cross coupling reactions. We will further report how this 

methodology can be used for the synthesis of phenolic natural 

products with minimization of protecting group steps (using 

phenol diazonium salts as arylating agents) [4, 5] and for the 

synthesis of polyfunctionalized naphthalines. Finally, our first 

results on the efficient double exploitation of acetanilides as 

directing groups in dehydrogenative Heck reactions and as leaving 

group precursors in conventional Heck reactions will be 

presented. [6] 

references: 

1. Felpin, F.-X.; Nassar-Hardy, L.; Le Callonnec, F.; Fouquet, 

E. Tetrahedron 2011, 67, 2815-2831. 

2. Schmidt, B.; Hölter, F. Chem. Eur. J. 2009, 15, 

11948–11953. 

3. Schmidt, B.; Berger, R.; Hölter, F. Org. Biomol. Chem. 

2010, 8, 1406-1414. 

4. Schmidt, B.; Hölter, F.; Berger, R.; Jessel, S. Adv. Synth. 

Catal. 2010, 352, 2463-2473. 

5. Schmidt, B.; Hölter, F.; Kelling, A.; Schilde, U. J. Org. 

Chem. 2011, 76, 3357-3365. 

6. Schmidt, B.; Elizarov, N. Chem. Commun. 2012, 48, 

4350–4352. 

Keywords: Arenes; C-C coupling; Diazo compounds; 

Palladium; Synthetic methods; 



s775 

chem. Listy 106, s587–s1425 (2012) 


Natural products, Drugs – i 

o - 4 7 9 

SynthetiC AntituMor vACCineS BASed on 

MuCin GLyCoPePtide AntiGenS 

h. Kunz 1 , A. KAiSer 1 , n. GAidziK 1 , u. weSterLind 1 

1 Institute of Organic Chemistry, University of Mainz, Mainz, 

Germany 

Membrane glycoproteins of epithelial tumor cells show 

glycosylation patterns which are quite different from those of 

normal cells. Among those, tumor-associated mucin MUC1 is 

highly over-expressed on tumor cells and characterized by short, 

prematurely sialylated saccharide antigens. Glycopeptides 

of the extracellular tandem repeat region of MUC1 carrying the 

Tn- T-, Sialyl-Tn-, and Sialyl-T-antigen saccharides are 

considered promising target structures for a selective 

immunological attack on epithelial tumor cells. 

In order to construct synthetic vaccines, Fmoc-protected 

O-glycosyl threonine and serine building blocks containing these 

tumor-associated saccharide antigens were synthesized and 

applied to solid-phase syntheses of tumor-associated 

MUC1 glycopeptides. These glycopeptides were coupled to T cell 

epitope peptides from ovalbumin [1] to furnish fully synthetic 

vaccines A. Antibodies induced by these vaccines A in transgenic 

mice showed a high selectivity in binding to MUC1 glycopeptide 

antigens. 

In addition, the tumor-associated MUC1 glycopeptide 

antigens were conjugated to Tetanus Toxoid to give highly 

immunogenic vaccines. [2, 3] Immunization with these vaccines 

elicited antibodies which strongly bound to tumor cells in culture 

and in tissues. 

references: 

1. U. Westerlind, A. Hobel, N. Gaidzik, E. Schmitt, 

and H. Kunz, Angew. Chem. Int. Ed. 2008, 47, 7551. 

2. A. Kaiser, N. Gaidzik, U. Westerlind, D. Kowalczyk, 

A. Hobel E. Schmitt and H. Kunz, Angew. Chem. Int. Ed. 

2009, 48, 7551. 

3. A. Hoffmann-Röder, A. Kaiser, S. Wagner, N. Gaidzik, 

D. Kowalczyk, U. Westerlind, B. Gerlitzki, E. Schmitt, 

H. Kunz, 2010, Angew. Chem. Int. Ed. 49, 8498. 

4. N. Gaidzik,, A. Kaiser, D. Kowalczyk, U. Westerlind, 

B. Gerlitzki, H. P. Sinn, E. Schmitt, H. Kunz, 2011, 

Angew. Chem. Int. Ed. 50, 8498. 

Keywords: Synthetic vaccines; Glycopeptides; Solid-phase 

synthesis; Mucin MUC1; 

Natural products, Drugs – i 


o - 4 8 0 

SyntheSiS of BioLoGiCALLy iMPortAnt 

oLiGoSACChArideS ContAininG 

ALPhA(2,8)oLiGoSiALiC ACidS 

t. tAKAhAShi 1 , y. niShiurA 1 , h. tAnAKA 1 

1 Tokyo Institute of Technology, Department of Applied 

Chemistry Graduate School of Science and Engineering, 

Tokyo, Japan 

α(2,8) Oligosialic acids are frequently located at the 

non-reducing end of biologically active glycoconjugates such 

as glycoproteins and glycolipids. Ganglio-series 

gangliosides are a family of glycolipids involving a 

tetrasaccharide (Galβ(1,3)GalNAcβ(1,4)Galβ(1,4)Glc) bearing 

α(2,8) di/oligosialic acids at the 3-position of the both galactose 

moieties. They further are classified by the presence of the sialic 

acid residues linked to the inner galactose moiety; one (a-series), 

two (b-series), and three (c-series). GP1c glycolipid is one of the 

most complex c-series gangliosides involving α(2,8) tri- and 

di-sialic acid units. 

Chemical synthesis of these di-/oligo-sialo-containing 

glycolipids and their derivatives would facilitate identification of 

their biological roles. However, synthesis of both the 

α(2,8) oligosialic acid unit and the compact and rigid 

3,4 dibranched galactoside unit is challenging. We recently 

reported on a new and effective method for α-sialylation using the 

5,4-N,O-carbonyl protected sialyl donor, which enabled 

preparation of α(2,8) and α(2,9) tetrasialic acid in stereoselective 

manner. The 5,4-N,O-carbonyl protection permitted a-sialylation 

without use of nitrile solvents. Herein, we report the synthesis of 

a set of the ganglio-series of ganglioside epitopes varying the 

number of sialic acid residues. 

Keywords: ganglioside; sialic acids; glycosylation; library; 



s776 

chem. Listy 106, s587–s1425 (2012) 


Natural products, Drugs – ii 

o - 4 8 1 

BioinSPired CheMiStry with PePtideS 

h. wenneMerS 1 

1 ETH Zürich, Laboratorium für Organische Chemie, Zürich, 

Germany 

In nature, proteins fulfill manifold different functions and 

are crucial as, for example, enzymes or templates for the 

controlled formation of structural components such as bones or 

seashells. My research group is intrigued by the question whether 

also peptides with significantly lower molecular weights 

compared to proteins, can fulfill functions for which nature 

evolved large macromolecules. For example, we are engaged in 

the development of peptides as asymmetric catalysts and 

templates for the controlled formation of inorganic nanoparticles. 

1. Tripeptides of the general type H-Pro-Pro-Xaa 

(Xaa = amino acid with a carboxylic acid) are effective catalysts 

for aldol reactions [1, 2] and conjugate addition reactions between 

aldehydes and nitroolefins. [3, 4] The peptides allow for enamine 

catalysis with catalyst loadings of as little as 0.1-1 mol % and 

provide the synthetically versatile products in high to excellent 

stereoselectivities. The scope of these peptide catalyzed reactions 


2. The development of peptides as templates for the 

controlled formation of silver nanoparticles (AgNPs) in defined 

sizes will be presented. Utilizing combinatorial chemistry 

different tripeptides were identified that allow for the formation 

of AgNPs in significantly different sizes. [5] More recently, a 

correlation between the length of oligoproline-based templates 

and the size of the resulting AgNPs was observed. [6] 

references: 

1. P. Krattiger, R. Kovasy, J. D. Revell, S. Ivan, 

H. Wennemers, Org. Lett. 2005, 7, 1101. 

2. J. D. Revell, H. Wennemers, Adv. Synth. Catal. 2008, 350, 

1046.. 

3. M. Wiesner, J. D. Revell, H. Wennemers, Angew. Chem. 

Int. Ed. 2008, 47, 1871. 

4. J. Duschmalé, H. Wennemers, Chem. Eur. J. 2012, 18, 1111. 

5. K. Belser, T. V. Slenters, C. Pfumbidzai, G. Upert, 

L. Mirolo, K. M. Fromm, H. Wennemers, Angew. Chem. 

Int. Ed. 2009, 48, 3661-3664. 

6. G. Upert, F. Bouillere, H. Wennemers, Angew. Chem. Int. 

Ed. 2012, 124, 4307-4310. 

Keywords: Peptide; Nanoparticles; 

Natural products, Drugs – ii 


o - 4 8 2 

PePtido SuLfonyL fLuorideS AS new 

ProteASe inhiBitorS 

r. LiSKAMP 1 

1 Utrecht University, Pharmaceutical Sciences, Utrecht, Netherlands 

We have employed the sulfonamide moiety as a transitionstate 

isostere of the hydrolysis of the amide bond. Incorporation 

of the sulfonamide moiety led to peptidosulfonamide-peptide 

hybrids capable of protease inhibition or resistant to proteolytic 

degradation. The versatile preparation of b-peptidosulfonamides, 

in which all peptide-amide bonds have been replaced by 

sulfonamide moieties, enticed investigation of the foldamer 

properties of this class of peptidomimetics. 

We have found that the required amino acid derived sulfinyl 

chlorides or amino acid derived sulfonyl chlorides intermediates 

can also be employed for the preparation of new “electrophilic 

traps” useful for the synthesis of protease inhibitors. Thus, amino 

acid based sulfinyl chlorides were converted into the 

corresponding a-chloromethylsulfoxides capable of inhibition of 

for example papain. Moreover, amino acid derived sulfonyl 

chlorides could be converted into the corresponding sulfonyl 

fluorides, which are crucial building blocks in the preparation of 

peptido sulfonyl fluorides comprising a new class of protease 

inhibitors. Apart from inhibition of chymotrypsin, protease 

activity of the proteasome can be efficiently inhibited. This offers 

opportunities for using peptido sulfonyl fluorides as powerful 

selective protease inhibitors in cancer treatment but also as 

potential anti-malaria compounds. Both the presence of a peptide 

fragment and the amino acid derived sulfonyl fluoride offer great 

possibilities for profiling but also for tuning the reactivity and 

specificity of the protease of interest. 



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Natural products, Drugs – iii 

o - 4 8 3 

PhytohorMoneS AS LeAdS for AntiCAnCer 

druG deveLoPMent 

M. StrnAd 1 , v. KryStof 1 , L. hAvLiCeK 1 , r. JordA 1 , 

L. rArovA 1 , J. oKLeStKovA 1 

1 Institute of Experimental Botany ASCR and Palacky University, 

Laboratory of Growth Regulators, Olomouc, 


Throughout history, natural products have afforded a rich 

source of compounds that have found many applications in the 

fields of medicine, pharmacy and biology. Our research focused 

on cell division cycle showed that natural phytohormones 

cytokinins are also rather non-specific inhibitors of various protein 

kinases. Surprisingly, among aromatic cytokinin derivatives, 

2-(2-hydroxyethylamino)-6-benzylamino-9-methylpurine, named 

olomoucine (OC), which specifically inhibits some CDKs at 

micromolar concentration was discovered. The total lack of the 

inhibitory effect of olomoucine on major kinases, such as cAMPand 

cGMP-dependent kinases, protein kinase C, and others, 

suggests that OC might be a useful tool for cell cycle regulation 

studies. The design and inhibitory activity of OC was further 

improved by modifications at positions 2, 6, and 9, i.e., the 

positions that control binding to CDK1. This led to discovery of 

novel specific CDK inhibitors named roscovitine, olomoucine II, 

purvalanol A, and LGR1406, which display an enhanced 

inhibitory activity toward CDK1, a higher selectivity toward 

some CDKs, an increased antimitotic activity at the G1/S and 

G2/M points of the cell cycle, and stronger and more selective 

antitumour effects. The compounds are also effective in vivo and 

one of them is already in clinical trials in USA and Europe 

(roscovitine ? Seliciclib, Cyclacel Pharmaceuticals Ltd, U.K.). 

Seliciclib is currently in Phase IIb clinical trials as a single therapy 

in multiple myeloma as well as two other B-cell hematological 

malignancies: B-cell Chronic Lymphocytic Leukemia and Mantle 

Cell Lymphoma. An additional Phase IIb clinical trial is in 

progress investigating the effects of Seliciclib in patients with 

Non-Small Cell Lung Cancer in combination with gemcitabine 

and cisplatin. Recently, we have developed also first CDK9 

inhibitors and discovered whole range of new structural motifs 

for development of CDK inhibitors which are derived from 

anticytokinin structures. 



o - 4 8 4 

CheMiCAL And BioLoGiCAL PotentiAL of new 

Azetidinone derivAtiveS 

P. GALLetti 1 , d. GiACoMini 1 , M. Pori 1 , r. SoLdAti 1 

1 University of Bologna, Department of Chemistry “G.Ciamician”, 


Beta-lactam compounds are really “evergreen” molecules. 

Beside bicyclic b-lactam substrates such as penicillins, 

cephalosporins, and carbapenems, monocyclic compounds, 

azetidinones, emerged for their interesting and variegated 

biological activities. [1] We developed the synthesis of a new class 

of monocyclic b-lactam derivatives, 4-alkyliden-azetidinones, 

characterized by a C = C bond on the C-4 position of the ring. [2] 

4-Alkyliden-azetidinones proved to be interesting scaffold for 

antibiotics against resistant bacteria [3] and effective enzymatic 

inhibitors against Human Leukocyte Elastase (HLE) and matrix 

metallo-proteases (MMPs), and as antiaggregating agents. [4] In 

exploring their use as synthons we observed that the C = C double 

bond in 4-alkyliden-azetidinones revealed an unexpected 

characteristic of low reactivity towards addition reactions of 

electrophiles or nucleophiles, whereas we succeeded in an 

unexpected oxidative substitution of vinylic hydrogen or 

halodecarboxylation reaction which led to the synthesis of mono 

and di-vinylhalides of 4-alkylidene-azetidinones. [5] 

Our interest in the design of new beta lactam compounds 

with specific biological activities recently allowed us to extend 

our strategies to the synthesis of new monocyclic derivatives with 

specific inhibitory potency against integrins and histone 

deacetylase enzymes (HDAC). [6] 

references: 

1. P.Galletti, D.Giacomini Curr.Med.Chem. 2011, 18, 4265. 

2. G.Cainelli, D.Giacomini, P. Galletti, A. Quintavalla Eur. 

J.Org.Chem. 2003, 1765. 

3. F.Broccolo, G.Cainelli, G.Caltabiano, C.Cocuzza, 

C.G.Fortuna, P.Galletti, D.Giacomini, G. Musumarra, 

R.Musumeci, A.Quintavalla, J. Med. Chem. 2006, 49, 

2804. 

4. G. Cainelli, P. Galletti, S. Garbisa, D. Giacomini, 

L. Sartor, A. Quintavalla, Bioorg. Med. Chem. 2005, 13, 

6120. 

5. P.Galletti, A.Quintavalla, C. Ventrici, D.Giacomini 

Eur.J.Org.Chem. 2009, 4541; G. Cainelli, P.Galletti, 

D. Giacomini, S. Licciulli, A. Quintavalla 

Eur.J.Org.Chem. 2007, 2526. 

6. P. Galletti, A. Quintavalla, C.Ventrici, G.Giannini, 

W.Cabri, S.Penco, G.Gallo, S.Vincenti, D..Giacomini 

ChemMedChem 2009, 4, 1991. P.Galletti, A.Quintavalla, 

C.Ventrici, G.Giannini, W.Cabri, D.Giacomini, 

New J. Chem. 2010, 34, 2861. 

Keywords: Lactams; Inhibitors; Synthesis Design; Small ring 

systems; Heterocycles; 



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o - 4 8 5 

noveL AnioniC Steroid inhiBitorS of 

PhASiCALLy And toniCALLy ACtivAted nMdA 

reCePtorS 

e. KudovA 1 , h. ChodounSKA 1 , B. SLAviKovA 1 , 

v. vyKLiCKy 2 , J. BorovSKA 2 , B. KrAuSovA 2 , 

L. Jr. vyKLiCKy 2 


Neuroprotectives, Prague 6, Czech Republic 

2 Institute of Physiology AS CR v.v.i., Department of Cellular 

Neurophysiology, Prague 4, Czech Republic 

N-methyl-D-aspartate receptors (NMDARs) play important 

roles in development, synaptic plasticity, learning, and memory, 

however, abnormal activation of NMDA receptors is thought to 

mediate neuronal degeneration. NMDA Receptor activity can be 

influenced by exogenous and endogenous ligands, including 

neurosteroids - endogenous steroids that are synthesized and act 

in the central nervous system. 20-Oxo-5β-pregnan-3α-yl sulfate 

(pregnanolone sulfate; PA-S) is an endogenous neurosteroid that 

inhibits NMDARs and is neuroprotective. However, the low 

bioavailability and poor metabolic stability of PA-S limit its 

in vivo application. Therefore, we have prepared a series of new 

pregnanolone derivatives bearing negatively charged substituents 

at C-3 connected via linkers of various lengths. As such, 

pregnanolone 3α-hemiesters of oxalic, malonic, succinic, glutaric, 

adipic, pimelic, and suberic acids were prepared. Subsequently, 

the patch-clamp and imagining recordings from HEK293 cells 

expressing NR1/NR2B receptors and cultured rat hippocampal 

neurons were used to establish the NMDARs inhibition and IC50 values. We conclude that the values of IC assessed for novel 

50 

synthetic C-3 analogs of PA are correlated with the 

length/lipophilicity of the substituents at C-3. Moreover, we have 

showed that these compounds differ by a rate of inhibition of 

tonically and phasically activated NMDA receptors. Defining the 

properties of pharmacophore for pregnanolone inhibitors of 

NMDA receptors and improving inhibitor pharmacological 

properties could bring practical results in the treatment of serious 

neuronal diseases and disorders such as brain injuries, 

consequences of brain stroke, epilepsy, and in a number of others. 

Keywords: steroids; receptors; lipophilicity; Structure-activity 

relationships; Drug design; 



o - 4 8 6 

CheMoenzyMAtiC nAturAL ProduCt 

SyntheSiS 

J. PietruSzKA 1 

1 Institute of Bioorganic Chemistry, Heinrich Heine University 

Duesseldorf im, Juelich, Germany 

Biocatalytic approaches towards new building blocks for 

organic synthesis have increa-singly emerged as an important tool 

in recent years. Nowadays, a number of biotrans-formations are 

primarily applied in the chemical and pharmaceutical industries 

delivering fine chemicals, e.g. for drugs. The mild reaction 

conditions - also triggering high stereo-, regio-, and 

chemoselectivity - and the often elegant short-cuts in synthetic 

en-deavours lead to economic and ecological advantages of the 

enzymatic conversions. [1] 

The focus of our projects is on natural product syntheses and 

the development of new synthetic methods (see e.g. ref. [2] ). The 

synthesis of the highly selective antitumor reagent psymberin 

(Figure 1), isolated from the sponge Psammocinia spp., [3] is one 

of the more recent target molecules in our group, but also marine 

oxylipins such as the constanolactones caught our attention. The 

progress on a chemoenzymatic approach towards key building 

blocks for organic synthesis will be presented. Enzymes utilized 

range from hydrolases, aldolases and (ene)reductases to 

monooxygenases. 

references: 

1. T. Fischer, J. Pietruszka, Top. Cur. Chem. 2010, 297, 1-43. 

2. a) M. Bischop, V. Doum, A. C. M. Nordschild (née 

Rieche), J. Pietruszka, D. Sandkuhl, Synthesis 2010, 

527-537; 

b) J. Pietruszka, R. C. Simon, Eur. J. Org. Chem. 2009, 

3628-3634; 

c) M. Korpak, J. Pietruszka, Adv. Synth. Catal. 2011, 353, 

1420-1424. 

3. a) R. H. Cichewicz, F. A. Valeriote, P. Crews, Org. Lett. 

2004, 6, 1951–1954; 

b) G. R. Pettit, J. Xu, J. Chapius, R. K. Pettit, L. P. Tackett, 

D. L. Doubek, J. N. A. Hooper, J. M. Schmidt, J. Med. 

Chem. 2004, 47, 1149–1152. 

Keywords: Biocatalysis; Asymmetric catalysis; Natural 

products; Total synthesis; 



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o - 4 8 7 

CASe StudieS of ASyMMetriC hydroGenAtion 

of ChALLenGinG PhArMACeutiCALLy 

reLevAnt SuBStrAteS 

v. JurCiK 1 

1 Johnson Matthey Catalysts, Chiral Catalysts and 

Technologies, Cambridge, United Kingdom 

Two recent case studies of asymmetric hydrogenation of 

unusual and challenging pharmaceutically relevant substrates will 

be presented. Emphasis on challenges of industrially applicable 

catalytic transformations will be given. 

First case study will show efficient asymmetric 

hydrogenation of (1-chlorovinyl) boronates. [1] 

Broad range of substituted (1-chlorovinyl) boronates, with 

different steric and electronic properties, can be successfully 

hydrogenated in the presence of P^N-iridium catalysts without 

significant cleavage of the C-Cl bond. 

It will be shown how rational modification of the 

structural properties of the P^N ligands can result in new 

N-acyl-imidazoline ferrocenyl-based iridium catalysts with broad 

substrate acceptance. With these catalysts, excellent conversions, 

high chemoselectivities (with dechlorinated byproducts in the 

range of 3–19%), and enantioselectivities of up to 94%ee can be 

obtained. The utility of the hydrogenation method presented will 

be demonstrated on preparation of a key precursor for the 

construction of the anticancer drug bortezomib. 

Second case study will deal with development of 

asymmetric hydrogenation of a pyridyl benzo thiophene alkene. [2] 

Studied transformation represents a key step in enantioselective 

synthesis of NBI-75043, a selective and potent H1 antagonist for 

the treatment of insomnia. 

Reduction can be successfully accomplished using 

[BoPhoz Rh] catalysts. By tailoring the steric properties of the 

BoPhoz ligand, the ee of the product can be increased from just 

12% to 90%. This research further expands the substrate scope 

of the conventional class of functionalized alkenes amenable 

to catalytic asymmetric hydrogenation. 

references: 

1. Angew. Chem. Int. Ed. 2012, 51, 1014–1018 

2. Tet. Lett. 2012, 53, 1025–1028 

Keywords: Asymmetric catalysis; Hydrogenation; 




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organic Chemistry, Polymers – ii 

Physical organic methods – i 

o - 0 8 4 

SySteMS CheMiStry: CAtALySiS And 

SeLf-rePLiCAtion in dynAMiC MoLeCuLAr 

networKS 

S. otto 1 

1 University of Groningen, Stratingh Institute for Chemistry, 


How the immense complexity of living organisms has arisen 

is one of the most intriguing questions in contemporary science. 

We have started to explore experimentally how organization and 

function can emerge from complex molecular networks. [1, 2] 

We focus on networks of molecules that can interconvert, to give 

mixtures that are can change their composition. Molecular 

recognition between molecules in such mixtures leads to their 

mutual stabilisation, which drives the synthesis of more of the 

privileged structures. [3, 4] We show for the first time how a substrate 

of a chemical reaction can induce the formation of a catalyst for 

this reaction. We also demonstrate how self-recognition can lead 

to self-replication. [5] We also show that the self-assembled 

structures can be covalently cross-linked through photo-initiated 

disulfide exchange, resulting the in the formation of hydrogels. [6] 

references: 

1. R. F. Ludlow, S. Otto, Chem. Soc. Rev. 2008, 37, 101-108. 

2. P. T. Corbett, J. Leclaire, L. Vial, K. R. West, J.-L. Wietor, 

J. K. M. Sanders, S. Otto Chem. Rev. 2006, 106, 3652- 

3711. 

3. K. R. West; R. F. Ludlow; P. Besenius; P. T. Corbett; 

P. A. G. Cormack; D. C. Sherrington; S. Otto, J. Am. 

Chem. Soc. 2008, 130, 10834-10835. 

4. R. F. Ludlow; S. Otto, J. Am. Chem. Soc. 2008, 130, 

12218-12219. 

5. J. M. A. Carnall; C. A. Waudby; A. M. Belenguer; 

M. C. A. Stuart, J. J.-P. Peyralans, S. Otto Science 2010, 

327, 1502-1506. 

6. J. Li; J. M. A. Carnall; M. C. A. Stuart; S. Otto Angew. 

Chem. Int. Ed. 2011, 50, 8384-8386. 

Keywords: Supramolecular chemistry; Molecular recognition; 

Self-assembly; Macrocycles; Autocatalysis; 



o - 0 8 5 

noveL PhotoChroMiC SurfACtAnt for 

orGAniC reACtionS in AqueouS MediA 

e. LeonArd 1 , n. driLLAud 1 , i. Pezron 1 , C. Len 1 

1 UTC/ESCOM, TIMR, Compiegne, France 

With the concept of green chemistry and its twelve 

principles, organic chemists are strongly encouraged to use water 

as solvent in the largest number of synthetic steps. The reaction 

of water-insoluble substrates requires the use of molecules that 

can induce the transfert of reagent from organic solvent to water, 

or in a privileged way from air to the reactive aqueous mixture. 

Among those molecules, micelles or aggregates composed of 

amphiphilic moieties can be used. Numerous reports on the 

subject showed that surfactants have a significant effect on the 

yield and selectivity of the reactions studied. 

Based on those results, the synthesis of a novel 

photochromic surfactant that can form aggregates reversibly in 

water was studied. [1] The main aim was the formation/disruption 

of aggregation by a simple UV irradiation, leading to the 

capture/release of the reagents or products. The targeted molecule 

obtained has a hydrophilic head derived from D-glucose, and a 

hydrophobic tail of alkyl type associated to an azobenzene 

chromophore. The hydrophilic and hydrophobic parts were 

clicked together. 

To compare and test the properties of our system on a model 

reaction we chose the acetylation of anilines. Indeed, this reaction 

is an important and widely used transformation in organic 

synthesis and a number of reagents coupled with promoters or 

catalysts have been put forth. So our surfactant was used to allow 

the acetylation of amines in aqueous medium and the recycling 

of the media from experience to experience. The process was 

simply to release the acetamide formed thanks to a UV irradiation, 

to filtrate and purify the residue, and to carry out again another 

reaction in the filtrate medium collected. 

The design, synthesis and physico-chemical studies will be 

detailed. 

references: 

1. Drillaud, N.; Banaszak-Leonard, E.; Pezron, I.; 

Len C. submitted to Angew. Chem. Int. Ed. 

Keywords: Photochromism; Surfactants; Azo compounds; 

Isomerization; Acylation; 



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o - 0 8 6 

PhotoinduCed dynAMiCS in A 

terPyridine-BASed zinC(ii) CoordinAtion 

PoLyMer And their MoLeCuLAr frAGeMentS 

B. dietzeK 1 , A. winter 2 , u. S. SChuBert 2 , 

i. SCheBLyKin 3 , J. PoPP 4 

1 IPHT, Research Group Ultrafast Spectroscopy, Jena, Germany 

2 Friedrich-Schiller-University Jena, Jena Center for Soft 

Matter, Jena, Germany 

3 Lund University, Department of Chemical Physics, Lund, 

Sweden 

4 Friedrich-Schiller-University Jena, Institute of Physical 

Chemistry, Jena, Germany 

This contribution focuses on the photoinduced dynamics in 

a ZnII-bis-terpyridine coordination polymer and its molecular 

fragments – in particular the bis-terpyridine ligands bearing 

conjugated chromophore units, which resemble 

the structural features of poly[2-methoxy-5-(2-ethylhexyloxy)- 

-1,4-phenylenevinylene] (MEH-PPV). The ZnII coordination 

polymer, which forms ridgid linear macromolecular structures, 

combines up to about 35 such individual MEH-PPV-like 

chromophores and is investigated by single molecule fluorescence 

spectroscopy. Upon incorporation of the individual chromophores 

into the coordination polymer the fluorescence quantum yield of 

an individual chromophore is found to be reduced. The molecular 

mechanism underlying this finding is addressed by investigating 

the brightness of isolated polymer molecules in various 

environments. The SMS results show that the ZnII-bis-terpyridine coordination polymer with the MEH-PPV-like chromophore 

structure contains a significantly larger fraction of bright 

chromophores compared to MEH-PPV alone. This finding is 

attributed to the particularly rigid geometry of the system at hand. 

The single-molecule fluoresecence experiments will be correlated 

with ultrafast time-resolved spectroscopy pointing to the 

photoinduced geometrical rearrangement in the bis-terpyridine 

chromophores. Finally, experiments on the ZnII coordination 

polymer under different atmospheric conditions offer further 

insights into the molecular mechanism and the nature of the 

quenchers involved in the blinking. 

Acknowledgement: Support by the Fonds der Chemischen 

Industrie is acknowledged. 

references: 

1. R. Siebert et al. Central Eur. J. Chem. 2011, 9, 990–999. 

2. R. Siebert et al. J. Phys. Chem. C 2011, 115, 12677–12688 

3. R. Siebert et al. Phys. Chem. Chem. Phys 2011, 13, 

1606–1617. 

4. R. Siebert et al. J. Phys. Chem. C 2010, 114, 6841–6848. 

5. R. Siebert et al. Macromol. Rapid Comm. 2010, 31, 

883–888. 

6. R. Siebert et al. Macromol. Rapid Comm. 2012, doi: 

10.1002/marc.20110075 

Keywords: Zn(II) coordination polymers; photophysics; 

terpyridine coordination compounds; excited-state dynamics; 

luminescence properties; 



o - 0 8 7 

fLuoreSCenCe SPeCtrA PrediCtion of 

oLiGothioPhene derivAtiveS: CoLor tuninG 

By SuBStituent vAriAtion 

e. horKeL 1 , B. hoLzer 1 , d. LuMPi 1 , f. PLASSer 2 , 

h. LiSChKA 2 , J. frÖhLiCh 1 



2 University of Vienna, Institute for Theoretical Chemistry, 


Organic electronics [1] has gained both academic and 

industrial interest during recent years. Especially organic light 

emitting devices (OLEDs) have drawn much attention on them, 

as they show superior properties, e.g. a higher viewing angle and 

lower power consumption when compared to their inorganic 

counterparts. Thus, tools assisting the efficient development of 

novel materials suitable for the fabrication of OLEDs are highly 

appreciated. Bis(triarylamine) substituted oligothiophenes, [2] 

often described as cap-linker-cap systems, are typical 

representatives for a whole class of OLED materials. Variation of 

conjugation length of the oligothiophene linker as well as the 

decoration of the triarylamine cap with different substituents R 

enable tuning of spectral properties. Aim of this study was to 

investigate the influence of the substituent R on the fluorescence 

characteristics. In order to have knowledge upon this critical 

property before time consuming synthesis, we evaluated the 

possibility to predict fluorescence spectra by means of 

computational chemistry. For this purpose time-dependent density 

functional theory (TDDFT) was used, giving in the first step 

information on the vertical emission, both in gas phase and in 

solution. To move one step further, vibrational information was 

used to get insight into the particular band shapes of the entire 

spectra. Simulations based on the Wigner distribution, as 

implemented in the framework of the Newton-X program 

package, proved to be appropriate to perform this task. [3] 

The hereby obtained spectra were compared to experimental data 

to show scope and limitation of the methods under investigation. 

references: 

1. Organic Electronics: Materials, Manufacturing and 

Applications, Hagen Klauk (editor), Wiley-VCH 2006 

2. Mishra, A.; Ma, C.-Q.; Ba¨uerle, P. Chemical Reviews 

2009, 109, 1141. 

3. http://www.univie.ac.at/newtonx/ 

Keywords: Density functional calculations; Fluorescence; 

Sulfur heterocycles; Semiconductors; 



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chem. Listy 106, s587–s1425 (2012) 


Physical organic methods – ii 

o - 0 8 8 

ProBinG Proton trAnSfer reACtionS in 

CAtALySiS: PhySiCAL orGAniC tooLS 

A. o’donoGhue 1 

1 Durham University, Chemistry, Durham, United Kingdom 

Proton transfer reactions are ubiquitous in chemical and 

biological processes, and are often key to efficient catalysis. We 

use a physical organic chemistry approach towards deciphering 

reaction mechanisms based on organic synthesis, reaction kinetics 

and structure-activity studies. This presentation will focus on the 

physical organic methodology that we use to probe the dynamics 

of proton transfer and for pK determination. In particular, the 

a 

study of proton transfer at carbon is central to our research and 

recent results of the proton transfer reactions of N-heterocyclic 

carbenes will be used to showcase our methodology. Analysis of 

the kinetics of hydrogen/deuterium exchange at carbon has 

allowed us to access the kinetic and thermodynamic acidities of a 

broad range of conjugate acids of imidazol-2-ylidenes, 

imidazolin-2-ylidenes, trihydropyrimidin-2-ylidenes and 

triazol-3-ylidenes. Notably, pD-rate profiles for deuterium 

exchange reveal that protonation to give dicationic triazolium 

species occurs under acidic conditions, allowing the carbon acid 

pK values for the conjugate acid precursors to cationic 

a 

triazol-3-ylidenes to be estimated. As a further illustration of the 

tools used to probe proton transfer, our recent studies of a range 

of key Bronsted acid and base organocatalysts will be outlined. 

Keywords: Acidity; Protonation; Isotopic labeling; 

organocatalysis; kinetics; 



o - 0 8 9 

SyntheSiS And dynAMiCS of CryStALLine 

PoLyfunCtionAL ChirAL rotorS 

G. BAStien 1 , C. LeMouChi 1 , C. Meziere 1 , 

K. iLioPouLoS 1 , d. Gindre 1 , M. ChrySoS 1 , 

P. BAtAiL 1 

1 Moltech-Anjou, UFR Sciences, Angers, France 

We present the synthesis and structures of a variety of 

amphidynamic solids based on symmetrically and dissymmetrically 

functionalised 1,4-Bis(ethynyl)bicyclo[2.2.2]octane (BCO) 

moieties. The stochastic rotational motion of the BCO helixes in 

the condensed phase is investigated by variable-temperature 

X-ray and 1H spin-lattice relaxation. In addition the torsional 

motion that switches the right-left configuration of the three rotor 

blades is analysed and discussed in the context of the modulation 

of the electro-optical properties of the systems. 

Keywords: Ligand design; Metal-organic frameworks; NMR 

spectroscopy; X-ray diffraction; Nonlinear optics; 



s783 

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o - 0 9 0 

tuninG of trAnSPArAnt SuBStrAteS: 

SeLeCtive Anti-BiofouLinG And/or SPeCifiC 

CeLL Growth onto ito viA orGAniC 

MonoLAyerS. 

h. zuiLhof 1 , y. Li 1 

1 Wageningen University, Organic Chemistry, Wageningen, 

Netherlands 

Covalently attached organic layers on indium tin oxide 

(ITO) surfaces can be prepared by the photochemical grafting 

with 1-alkenes. THis is relevant, since ITO is not only fully 

transparant, but also electrically conducting. By taking suitably 

substituted alkene substrates, a tailor-made and extremely mild 

functionalization of the surface can be obtained in one step! 

The surface modification was monitored with static water 

contact angle, X-ray photoelectron spectroscopy (XPS) and 

atomic force microscopy (AFM) measurements. Hydrophobic 

methyl-terminated ITO surfaces can be obtained via the grafting 

of tetradec-1-ene, whereas the attachment of w-functionalized 

1-alkenes leads to functionalized ITO surfaces. The use of a CΞC- 

Ge(CH3)3 terminus allows for facile tagging of the surface with 

an azido group via a one-pot deprotection/click reaction, resulting 

in bio/electronically active interfaces. The combination of 

non-aggressive chemicals (alkenes), mild reaction conditions 

(room temperature) and a light-induced grafting that facilitates 

the direct patterning of organic layers possible makes this simple 

approach highly promising for the development of ITO-based 

(bio) electronic devices. The presentation will outline the 

methodology and provide a detailed surface characterization to 

demonstrate the potential for local biofunctionalization of ITO 

with complex bio-organic moieties (reference 1). 

In addition, it will outline current developments for the local 

attachment of functionalizable zwitterionic polymers that fully 

repel any protein deposition and cell growth of human colon 

(Caco-2) cells. The local deposition of the polymer layer can be 

used to enable the local cell growth on this transparant substrates 

onto uncoated or RDG-coated areas. In this manner, covalently 

attached polymeric layers (20 nm) can be used to direct patterned 

cell growth, and allow the construction of bio-electronic 

architectures. 

references: 

1. Li, Y.; Zuilhof, H. Langmuir 2012, 28, 5350–5359. 

Keywords: cell adhesion; monolayers; surface chemistry; 

photochemistry; 

Physical organic methods – iii 


o - 0 9 1 

effiCient CAtALySt reuSe By diSSoLution in 

non-ConventionAL MediA 

C. AfonSo 1 , A. roSAteLLA 1 , n. CAndeiAS 1 , 

L. GoMeS 1 , S. SiMeonov 1 , J. CoeLho 1 

1 Research Institute for Medicines and Pharmaceuticals 

Sciences, Faculty of Pharmacy University of Lisbon, Lisbon, 

Portugal 

Efficient catalysis is an important topic in modern synthetic 

transformations and provides precious contribution for the 

development of more sustainable chemistry. However, generally 

due to the high cost of required rare metals and/or necessary 

considerable synthetic demand for the synthesis of many catalytic 

systems, is very important to achieve efficient methodologies for 

catalysts reuse without affecting the main features of the catalyst. 

The major approach to catalyst reuse is based on chemical 

immobilization of the catalyst in organic or inorganic support and 

under heterogeneous conditions which in many cases leads to 

some erosion of the catalytic system performance. On the other 

hand, the use of homogeneous conditions is in general more 

efficient but the catalyst reuse needs more elaborated approaches 

such as anchoring the catalyst on polymer with tunable solubility, 

incorporation of anchoring groups on the catalyst with high 

affinity to alternative reaction media such as fluorinated 

solvents/supports, PEG, supercritical CO , water and ionic liquids. 

2 

Another simpler approach for catalyst reuse is based on the use 

of original catalytic system under homogeneous conditions and 

without any chemical manipulation just by appropriate choice of 

the reaction medium - separation process. [1] 

In line with our contribution in this area, [2] here is 

described recent achievements from this laboratory on novel 

catalyzed transformations such as: a) Bronsted acid-catalyzed 

dihydroxylation of olefins in aqueous medium; b) Asymmetric 

Rh(II) carbenoid C-H insertion of alpha-diazo-acetamides and 

c) Production and isolation of 5-hydroxymethylfurfural(HMF) 

from carbohydrates. 

Acknowledgment: We would like to thank FCT and FEDER for 

financial support. 

references: 

1. Q.H.Fan, Y.M.Li, A.S.C.Chan, Chem. Rev. 2002, 102, 

3385. A.F.Trindade, P.M.P.Gois, C.A.M. Afonso, Chem. 

Rev., 2009, 109, 418. M.Yoon, R.Srirambalaji, K.Kim, 

Chem. Rev. 2012, 112, 1196. 

2. C.A.M.Afonso, L.C.Branco, N.R.Candeias, P.M.P.Gois, 

N.M.T.Lourenco, N.M.M.Mateus, J.N.Rosa, Chem. 

Comm, 2007, 2669, Feature Article. 

Keywords: Asymmetric catalysis; Carbohydrates; Green 

chemistry; Insertion; Oxidation; 



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o - 0 9 2 

MiCrowAve-ASSiSted Cu(i)-CAtALyzed 

CouPLinG of AMineS, ALdehydeS And 

ACetyLeneS 

d. erMoLAtev 1 

1 Katholieke Unversiteit Leuven, Chemistry Deparment, 

Heverlee, Belgium 

The three-component coupling of an amine, an aldehyde and 

an acetylene (A3-coupling) attracts attention of chemists for the 

last decade. Among other catalysts, Cu(I) salts proved to be the 

most efficient and economical catalysts. The outcome of the 

A3-coupling reaction depends on the nature of the starting 

compounds. For example, the coupling of primary amines with 

aldehydes and acetylens provides secondary propargylamines. 

The same reaction with propiolic acids leads to the trisubstituted 

oxazolidinones. We have also developed the decarboxylative 

A3-coupling reaction affording tertiary propargylamines. Finally, 

the Cu(I)-catalyzed decarboxylative A3-coupling using glyoxalic 

acid provided interesting aminoenynes. 

references: 

1. J. B. Barival, D. S. Ermolat’ev, E. V. Van der Eycken, 

Chem. Eur. J. 2010, 16, 3281. 

2. D. S. Ermolat’ev, J. B. Barival, H. Steenackers, 

S. De Keersmaecker, E. V. Van der Eycken, Angew. Chem. 

2010, 49, 9465. 

3. Feng, H. D.; Ermolat’ev, D. S.; Song, G. H.; Van der Eycken, 

E. V. Adv. Synth. Catal. 2012, 354, 505. 


E. V. J. Org. Chem. 2011, 76, 7608. 


E. V. Org. Lett. 2012, 14, 1942. 

Keywords: A3-coupling; organic catalysis; propargylamines; 

microwave-assisted organic synthesis; copper catalyst; 



o - 0 9 3 

A SerieS of BiS-triAzoLyL 

BenzoChALCoGendiAzoLe triMerS And their 

uSe AS MetAL ion SenSorS 

J. J. BryAnt 1 , B. d. Lindner 1 , u. h. f. Bunz 1 

1 Universität Heidelberg, Organisch Chemisches Institut, 

Heidelberg, Germany 

The prevalence of metal ions in the environment and their 

occurrence in biological systems has created a need for the 

detection and differentiation of such species. Spectrophotometric 

methods have emerged as a powerful tool for metal ion detection 

due to their simplicity, sensitivity, and versatility. Previously we 

reported on the metal-binding properties of bis-triazolyl 

heteroaromatic trimers, benzothiadiazole in particular. We have 

already shown that variation of the heteroatom from oxygen to 

sulfur to selenium affects the electronic properties of 

benzochalcogendiazoles; in this work we examine the effect of 

this structural variation on the metal-binding properties of their 

bis-triazolyl cycloadducts. 

These fluorescent metal sensors were synthesized via ‘click’ 

coupling of an azide with the bis-ethynyl heteroaromatic core. 

Because aqueous solution is the ideal media for metal ion sensing, 

an azide with a water-soluble substituent was used. The branched 

oligo(ethylene glycol) substituent chosen provides excellent 

water-solubility and improved quantum yields. 

The chalcogen atom in the heteroaromatic core of these 

sensors plays an important part in the electronic properties of the 

cycloadducts. Moving down the group from oxygen to selenium 

induces bathochromic shifts in the absorption and emission 

spectra. Selenium shows the largest effect on the photophysical 

properties; the oxo- and thiadiazole click products are both 

green-fluorescent, while the seleno- congener fluoresces orange. 

The effect of the heteroatom on the metal-binding properties 

was also investigated. Binding constants of different metals were 

determined from the fluorescence quenching response. The click 

product containing the more electronegative oxygen atom showed 

very weak metal ion binding. The counterparts containing sulfur 

and selenium were able to efficiently bind Ag(I), Cu(II), and Ni(II) 

ions. The fluorophore containing selenium, the largest and least 

electronegative atom, displayed the strongest binding. 

Additionally, the absorbance response pattern of these 

fluorophores is different for each metal, allowing differentiation 

of copper, silver, and nickel. 

Keywords: nitrogen heterocycles; fluorescent probes; 

fluorescence spectroscopy; click chemistry; 



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o - 0 9 4 

MiCrowAveS And MuLti-CoMPonent 

reACtionS in the SyntheSiS of MediuM-Sized 

rinGS 

e. vAn der eyCKen 1 

1 KU Leuven BE0419052173, Chemistry, Leuven, Belgium 

Medium-sized rings are abundantly present in many 

biologically active (natural) products as e.g. the alkaloids 

aphanorphine, lennoxamine and cephalotaxine and the 

noncompetitive N-methyl-D-aspartate (NMDA) receptor 

antagonist Dizocilpine, also known as MK-801. However, the 

synthesis of medium-sized rings is known to be rather 

cumbersome and no good generally applicable procedures have 

been described so far. Some time ago we have elaborated an 

efficient synthesis of the 3-benzazepine framework via an 

intramolecular Heck reductive cyclization. We have demonstrated 

that the application of microwave irradiation is beneficial for this 

process. As a result of these investigations we extended our 

research towards the synthesis of indoloazocines, 

dibenzoazocines, dibenzoazepines, 3-benzazepines and 

dibenzo[c,e]azepinones. To assure the generation of diversity we 

utilized multicomponent reactions as the aldehyde/amine/alkyne 

(A3) coupling and the Ugi 4CR which will be run in an 

intramolecular fashion. The beneficial effect of the application of 

microwave irradiation in each of these processes will be 

commented. 

references: 

1. Efficient Synthesis of the 3-Benzazepine Framework via 

Intramolecular Heck Reductive Cyclization, P. A. Donets, 

E. Van der Eycken, Org. Lett., 9, 3017-3020, 2007. 

2. Unprecedented Cu(I)-Catalyzed Microwave-Assisted 

Three-Component Coupling of a Ketone, an Alkyne 

and a Primary Amine, O. P. Pereshivko, V. A. Peshkov, 

E. V. Van der Eycken, Org. Lett., 12, 2638-2641, 

2010 and references cited. 

3. A walk around the A3-coupling reaction and related 

protocols, V. A. Peshkov, O. P. Pereshivko, 

E. V. Van der Eycken, Chem. Soc. Rev., 

DOI:10.1039/C2CS15356D, 2012 

Keywords: Microwave chemistry; Medium-ring compounds; 

Multi-component reactions; 



o - 0 9 5 

PhoSPhoreSCent iridiuM CoMPLexeS 

ConJuGAted to CxCr4-tArGetinG PePtideS 

for LifetiMe iMAGinG 

J. KuiL 1 , P. SteunenBerG 2 , P. Chin 1 , K. JALinK 3 , 

A. veLderS 4 , f. vAn Leeuwen 1 

1 Leiden University Medical Center, Radiology, Leiden, 

Netherlands 

2 Wageningen University, Laboratory of Organic Chemistry, 

Wageningen, Netherlands 

3 Netherlands Cancer Institute – Antoni van Leeuwenhoek 

Hospital, Cell Biology I, Amsterdam, Netherlands 

4 Wageningen University, BioNanoTechnology, Wageningen, 

Netherlands 

Fluorescence lifetime imaging microscopy (FLIM) is an 

optical imaging technique that produces contrast based on 

differences in luminescence decay rates (lifetime). Standard 

organic dyes such as fluorescein generally have lifetimes 

of < 10 ns, which is also the case for autofluorescence generated 

by cells and tissue. On the other hand, transition metal complexes 

possess lifetimes of > 100 ns, which makes discrimination from 

autofluorescence unambiguous. To benefit from these long 

lifetimes in targeted imaging applications, we have prepared 

phosphorescent iridium(III) complexes for chemokine receptor 

4 (CXCR4) targeting. CXCR4 over-expression is found in many 

types of cancer, where it plays a role in, among others, the 

metastatic spread. For this reason it is an interesting biomarker 

for the field of molecular imaging. [1] 

Three iridium complexes, containing one, two or three 

β-alanine spacers, were synthesized. [2] They had luminescent 

lifetimes of 200-220 ns, absorption maxima of approximately 

400 nm and emission maxima of approximately 570 nm. The 

iridium complexes were functionalized with one, two or three 

targeting peptides to allow for CXCR4 visualization. The CXCR4 

receptor affinities of the mono-, di- and trimeric peptide 

derivatives were determined using flow cytometry and amount 

84.4, 254.4 and 66.3 nM, respectively. All three derivatives did 

not cause cytotoxicity up to 3 µM concentrations and could 

distinguish between cell lines with different CXCR4 expression 

levels. FLIM showed that the peptide–iridium complex conjugates 

can be used to visualize CXCR4 expression in tumor cells with 

very high contrast. [3] 

references: 

1. Kuil, J., Buckle, T., van Leeuwen, F.W.B., Chem. Soc. 

Rev., accepted 

2. Steunenberg, P., Ruggi, A., van den Berg, N.S., Buckle, T., 

Kuil, J., van Leeuwen, F.W.B., Velders, A.H., Inorg. 

Chem., 2012, 51, 2105-2114 

3. Kuil, J., Steunenberg, P., Chin, P.T.K., Oldenburg, J., 

Jalink, K., Velders, A.H., van 

Leeuwen, F.W.B., ChemBioChem, 2011, 12, 1897-1903 

Keywords: Luminescence; Metal-organic frameworks; 

Peptides; Fluorescence spectroscopy; Synthesis design; 



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Polymer chemistry – i 

o - 2 2 1 

MuLtiCoMPArtMent MiCeLLeS froM 

MuLtiBLoCK MuLtiCoMPonent PoLyMerS in 

SeLeCtive SoLventS 

n. hAdJiChriStidiS 1 , n. houBenov 1 

1 King Abdullah university of science and Technology (KAUST), 

Chemical and Life Sciences and Engineering, Thuwal 23955- 

6900, Saudi Arabia 

Controlled formation of compartmentalized spherical 

micelles with self-assembled complex hierarchical structures was 

demonstrated by using linear and non-linear 

multiblock multicomponent polymers {ABCD, ABCED, 

and (ABC) D, where A:polystyrene; B:polyisoprene-1,4; 

2 

C:poly(dimethylsiloxane); D:poly(2-vinylpyridine) and 

E:poly(tert-butylmethacrylate)} in selective solvents. These 

tetrablock quarter and pentablock quinto polymers were 

synthesized by using anionic polymerization high vacuum 

techniques and appropriate chlorosilane-based heterofunctional 

linking agents. The molecular characteristics of the multiblock 

multicomponent polymers were obtained by osmometry, light 

scattering, size exclusion chromatography (SEC) and NMR. The 

multicompartment character of the micellar aggregates was 

studied by Static/Dynamic Light Scattering (SLS/DLS), 

Transmission Electron Microscopy (TEM/Tomography), and 

Atomic Force Microscopy (AFM). Using suitable solvent systems 

we have constructed well-defined micellar hierarchies 

with collapsed unprecedented tri-componential core and 

compartmentalized or mixed corona. The ratio of the different 

blocks in the core and corona was varied by the quality of the 

solvents and solvent mixtures used in the experiments. 

Keywords: multiblock multicomponent copolymers; selective 

solvents; multicompartment micelles; transmission electron 

microscopy; static/dynamic light scattering; 



o - 2 2 2 

CryStALLine ProPertieS of PvAC-B-PCL BLoCK 

CoPoLyMerS: infLuenCe of the SyntheSiS 

route 

S. BiStAC 1 , C. deLAite 1 , o. GLAied 2 

1 Université de Haute Alsace, LPIM, Mulhouse cedex, France 

2 Hochschule für Life Sciences, Institut für Chemie und 

Bioanalytik, Muttenz, Switzerland 

Poly(vinyl acetate)/poly(ε-caprolaclone) block copolymers 

(PVAc-b-PCL) were synthesized using two different approaches: 

a “coupling reaction” approach and a “macroinitiator” one. For 

the coupling approach, a chain transfer agent, with an azide 

function, was used to initiate the polymerization of VAc. PCL 

containing an alkyne termination was also prepared. These two 

reaction products, PVAc and PCL, were then coupled by a click 

chemistry reaction to obtain the corresponding block copolymer. 

For the macroinitiator approach, PCL-b-PVAc block copolymers 

were obtained by a two-step procedure: first, a macroinitiator PCL 

with a xanthate end group was prepared, then, the polymerization 

of VAc was initiated by RAFT polymerization from the PCL, 

allowing to obtain PVAC-b-PCL block copolymers. Different 

copolymers, varying by their blocks lengths, were prepared with 

both methods. Elsewhere, PCL is a semi-crystalline polymer, and 

consequently, PCL blocks of PVAc-b-PCL are able to 

crystallize.The objective of this work is then to analyse the 

influence of the synthesis way of copolymers on the crystallinity 

of PCL blocks. Crystalline properties have been investigated by 

differential scanning calorimetry (DSC). 

The results indicate a decrease of the crystallinity of the PCL 

block in copolymers obtained by the “coupling” method, 

compared to PCL homopolymers, contrary to copolymers 

obtained through the “macroinitiator” approach for which the 

crystallinity of the PCL was much less affected. This influence of 

the synthesis method was explained by the presence, in the 

copolymers obtained by click reaction, of a rigid triazol cycle 

(cycle binding the two blocks of polymer). This triazol cycle limit 

the relative mobility of the two blocks and decrease the possibility 

of organization and the crystal formation. This study has 

evidenced the great influence of the synthesis route on copolymers 

crystallinity and the major effect of the presence of the triazol 

cycle, inducing a high decrease of the crystallinity degree 

Keywords: Crystal growth; Polymers; Calorimetry; 



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o - 2 2 3 

SuLfonAtion of PoLyButAdiene And 

ButAdiene-Styrene CoPoLyMerS AS verSAtiLe 

route for the ProduCtion of 

PoLyeLeCtroLyteS And ionoMerS with 

enhAnCed therMAL StABiLity And 

ControLLed MorPhoLoGy 

A. GrASSi 1 , A. BuonerBA 1 , v. SPerAnzA 2 

1 University of Salerno, Chemistry and Biology, Salerno, Italy 

2 University of Salerno, Chemical Engineering, Salerno, Italy 

Sulfonated ionomers find applications ranging from ion 

exchange membranes for fuel cells to superacid catalysts, 

surfactants, compatibilizers and sensors. Typical examples are 

sulfonated polystyrene, polybenzimidazole and polyphenylene 

oxide in which the sulfonic acid groups are randomly introduced 

onto the aromatic rings of the polymer chains. The selective 

functionalization of polymer segments in block copolymers is 

more challenging but of interest for the production of phase 

separated materials containing polar domains homogeneously 

dispersed in hard polymer matrices. 

In this presentation we describe a two steps process which 

allows the fast and selective sulfonation of olefinic carbon-carbon 

double bonds of polybutadiene and polystyrene-b-polybutadieneb-polystyrene 

triblock copolymers (SBS), without producing 

crosslinking of the polymer chains and functionalization of aryl 

groups. High level of sulfonation and ion exchange capacities 

(IEC) were thus obtained. Sulfonation of semicrystalline 

multiblock syndiotactic polystyrene-co-cis-1,4-polybutadiene 

(sPSB) [1] led tosPSB-SA in which the polybutadiene segments are 

completely sulfonated and the crystallinity of the syndiotactic 

polystyrene domains is preserved. A thin film by spin-coating of 

sPSB-SA (12 mol% of -SO H) showed at AFM analysis a phase 

3 

separated morphology, consisting of conductive regions of few 

tens of nanometers embedded in a non conductive matrix of 

syndiotactic polystyrene. The thermal stability of sPSB-SAs was 

investigated by DSC and TGA-FTIR analysis. sPSB-SA samples 

debated in water/chloroform solvent mixture produced micelles 

of 200-300 nm highlighted by TEM analysis. The selective 

staining with Pb(II) revealed the core-shell nature of the micelles, 

exhibiting -SO H groups on the surface. 

3 

references: 

1. a) Cuomo, C.; Serra, M. C.; Gonzalez Maupoey, M.; 

Grassi, A.; Macromolecules, 2007, 40, 7089. 

b) Buonerba, A.; Cuomo, C.; Speranza, V.; Grassi, A.; 

Macromolecules, 2010, 43, 367. 

Keywords: sulfonation; polyanion; Nanostructures; Block 

copolymers; 



o - 2 2 4 

AMPhiPhiLiC CAtioniC CArBoSiLAne-PeG 

dendriMerS: SyntheSiS And APPLiCAtionS in 

Gene therAPy 

J. SAnChez-nieveS 1 , P. frAnSen 2 , d. PuLido 3 , 

r. Lorente 4 , M. A. Munoz-fernández 4 , M. royo 3 , 

f. ALBeriCio 5 , r. GóMez 1 , f. J. de LA MAtA 1 

1 Universidad de Alcalá, Inorganic Chemistry, Alcalá de 

Henares (Madrid), Spain 

2 Barcelona Science Park, Institute for Research in Biomedicine, 


3 Barcelona Science Park, Combinatorial Chemistry Unit, 


4 Hospital General Universitario Gregorio Maranón, 

Laboratorio de Inmunología Molecular, Madrid, Spain 

5 University of Barcelona, Organic Chemistry, Barcelona, Spain 

The interest on treating diseases by gene therapy has clearly 

bloomed as consequence of the increase knowledge on disease 

molecular pathways and human genome. This method requires 

guiding functional genetic material (plasmids, nucleic acids, 

oligonucleotides) to the target cells. [1] Macromolecules, polymers 

and nanosystems, which can be rationally designed, have been 

employed as synthetic gene vectors. These vectors have to interact 

with the nucleic acids, usually forming electrostatic complexes 

compacting them and preventing their degradation. Thus, different 

systems functionalized with cationic groups have been employed 

for this objective. In the particular case of dendritic 

macromolecules, their properties such as well defined size and 

structure, flexibility, monodispersity and multivalency molecular 

surface have attracted attention for biomedical applications. [2] 

Carbosilane dendrimers present a hydrophobic framework. 

The introduction of ammonium groups at the periphery turn them 

water soluble and have been successfully tested as gene transfer 

agents. [3] However, the major drawback of cationic dendrimers is 

their intrinsic toxicity. An adequate procedure to overcome this 

problem has been PEGylation of these systems, increasing also 

the solubility of the macromolecule. [4] 

We described here the synthesis of cationic amphiphilic 

carbosilane-PEG dendrimers with ammonium groups via click 

chemistry coupling of carbosilane (generation 1 to 3) and 

PEG-based dendrons functionalized at the periphery with NHBoc 

groups. The cationic heterodendrimers thus obtained have been 

evaluated in gene therapy against HIV in Peripheral Blood 

Mononuclear Cells, and their results compared with a carbosilane 

homodendrimer. 

references: 

1. Verma, I. M.; Somia, N. Nature 1997, 389, 239. 

2. Astruc, D.; Boisselier, E.; Ornelas, C. Chem. Rev. 2010, 

110, 1857. 

3. Bermejo, J. F.; Ortega, P.; Chonco, L.; Eritja, R.; 

Samaniego, R.; Mullner, M.; de Jesús, E.; de la Mata, F. J.; 

Flores, J. C.; Gómez, R.; Munoz-Fernández, A. Chem. 

Eur. J. 2007, 13, 483. 

4. Sousa-Herves, A.; Riguera, R.; Fernández-Megia, E. 

New J. Chem. 2012, 36, 205. 

Keywords: Dendrimers; Antiviral agents; Amphiphiles; 

Cations; 



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Polymer chemistry – ii 

o - 2 2 5 

Photo, eLeCtro, Bio And therMALLy 

funCtionAL PoLyMerS By CLiCK CheMiStry 

y. yAGCi 1 

1 Istanbul Technical University, Department of Chemistry, 


Recently, 1,3-dipolar cycloadditions, from the reactions 

between azides and alkynes or nitriles, known as ‘click reaction 

have been recognized as a useful synthetic methodology and 

applied to macromolecular chemistry offering materials ranging 

from the block copolymers to the complex macromolecular 

structures. These cycloaddition reactions enabled the C-C bond 

formation in a quantitative yield without side reactions and 

requirement for additional purification steps. The click reactions 

are particularly important in preparative methods, in which high 

conversion of functional groups is desirable. Numerous 

applications of Click chemistry in polymer science as well as 

molecular biology and nanoelectronics have recently been 

reviewed. In recent years, several other click reactions based on 

Diels-Alder cycloaddtion, thiol-ene chemistry and keten 

chemistry have been proposed. 

In this presentation, various click reactions, namely 

1,3-dipolar cycloadditions, Diels-Alder cycloaddition, thiol-ene 

chemistry and keten chemistry for the preparation of block and 

graft copolymers, and polymers possessing electro, bio, photo and 

thermo active groups will be presented. Moreover, several new 

photo-induced click reactions developed in author’s laboratory 

will be addressed. 

references: 

1. Gacal B, Durmaz H, Tasdelen MA, Hizal G, Tunca U, 

Yagci Y, Demirel AL, Macromolecules 2006, 39, 5330 

2. Ergin M, Kiskan B, Gacal B, Yagci Y. Macromolecules 

2007, 40, 4724 

3. Temel G, Aydogan B, Arsu N, Yagci Y. Macromolecules, 

2009, 42, 60 

4. Gacal BN, Koz B, Gacal B, Kiskan, B, Erdogan M, Yagci 

Y. J.Polym. Sci., Polym.Chem. Ed.,, 2009, 47, 1317 

5. Kiskan B, Demiray G, Yagci Y. J.Polym. Sci., Polym. 

Chem. Ed., 2008, 46, 3512 

6. Durmaz YY, Kumbaraci V, Demirel AL, Talinli N, Yagci Y. 

Macromolecules, 2009, 42, 3743 

7. Tasdelen MA, Kreutzer J, Yagci Y. Macromol. Chem. 

Phys., 2010, 211, 279 

8. Tasdelen MA, Yilmaz G, Iskin B, Yagci Y, 

Macromolecules, 2012, 45, 56-61. 

Keywords: click chemistry; polymers; biological activity; 

photochemistry; electrochemistry; 



o - 2 2 6 

CAtALyStS iMMoBiLizAtion: A SiMPLe And 

effiCient tooL to enforCe StereoSeLeCtive 

ProduCtion of CoMModity And 

BiodeGrAdABLe PoLyMerS 

r. GAuvin 1 , M. tSChAn 2 , C. M. thoMAS 2 , 

i. deL roSAL 3 , L. MAron 3 , L. deLevoye 1 

1 UCCS UMR CNRS 8181, CNRS, Villeneuve d’Ascq, France 

2 Laboratoire Charles Friedel, Chimie ParisTech, Paris, France 

3 Université Paul Sabatier, LPCNO, Toulouse, France 

Commodity polymers such as polymethylmethacrylate or 

polydienes are ubiquitous in everyday life. On the other hand, 

biodegradable polymers such as aliphatic polyesters are attracting 

an ever growing attention, as potential answers to key 

environmental issues. They can be accessed by lactone 

ring-opening polymerization using rare-earth metal initiators. The 

polymers mechanical properties are chiefly governed by their 

microstructure, which in turn can be controlled through catalyst 

design, using ligands derived from multistep synthesis. [1] A simple 

way to produce stereoselective catalysts without time-consuming 

synthetic procedures is therefore of considerable interest. 

This problem can be efficiently tackled by use of 

well-defined supported catalytic systems based on rare-earth 

metal species. [2] Indeed, in sharp contrast to their homoleptic 

molecular counterparts, immobilized derivatives provide 

polymers with high degree of stereocontrol. [3] This has been 

shown for several monomers (methylmethacrylate, isoprene, 

styrene, beta-butyrolactone). We will show that this is linked to 

the grafting chemistry, by determining structure-selectivity 

relationships: a precise control over the surface species structure 

is of prime importance. Furthermore, understanding of this 

beneficial “surface effect” has been addressed through DFT 

calculations, which clearly demonstrate the impact of the silica 

surface on successive stereoselective monomer enchainments. [4] 

references: 

1. C. M. Thomas, Chem. Soc. Rev. 2010, 39, 165. 

2. a) R. M. Gauvin, A. Mortreux, Chem. Commun. 2005, 

1146, 

b) R. M. Gauvin, L. Delevoye, R. Ali Hassan, J. 

Keldenich, A. Mortreux, Inorg. Chem. 2007, 46, 1062. 

3. a) N. Ajellal, G. Durieux, L. Delevoye, G. Tricot, 

C. Dujardin, C. M. Thomas, R. M. Gauvin, Chem. 

Commun. 2010, 46, 1032, 

b) M. Terrier, E. Brulé, M. J. Vitorino, N. Ajellal, 

C. Robert, R. M. Gauvin, C. M. Thomas, Macromol. 

Rapid Comm.2011, 32, 215. 

4. I. Del Rosas, M. Tschan, R. M. Gauvin, L. Maron, 

C. M. Thomas. Polym. Chem. DOI: 10.1039/C2PY00472K. 

Keywords: Ring-opening polymerization; Rare Earths; 

Supported catalysts; Polymerization; Density functional 

calculations; 



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o - 5 2 6 

PerfLuorinAted AMPhiPoLAr PoLyMerS At 

interfACeS 

M. KLAPPer 1 , f. e. GoLLinG 1 , t. SChuSter 1 , 

C. GeideL 1 , L. MAMMen 1 , d. voLLMer 1 

1 Max Planck Institute for Polymer Research, Ackermannweg 

10, 55128 Mainz, Germany 

Surface active compounds play a decisive role for various 

applications. While in most cases one focuses on hydrophilic/ 

hydrophobic structures herein the use of perfluorinated 

amphiphiles is discussed. In three different examples, it is 

demonstrated that these molecules are very powerful surface 

active compounds. Their synthesis and application is highlighted 

and described in regard to adjusting liquid-liquid and solid-liquid 

interactions: In particular, (i) fluorous amphiphilic block 

copolymers were designed to stabilize nonaqueous emulsions 

even suitable for metallocene catalyzed polymerisations, (ii) 

statistical copolymers were utilized to functionalize and 

compatibilize the surface of inorganic nanoparticles, and finally 

(iii) terpolymers were applied to obtain superhydrophobic 

properties. 

references: 

1. Nenov, S.; Clark, C. G. Jr.; Klapper, M.; Muellen, K. 

Macromol. Chem. Phys. 2007, 208, 1362–1369. 

2. Klapper, M; Nenov, S.; Haschick, R.; Mueller, K.; 

Muellen, K. Acc Chem. Res. 2008, 41, 1190-1201. 

3. Stelzig, S. H.; Menneking, C.; Hoffmann, M. S.; Eisele, K.; 

Barcikowski, S.; Klapper, M.; Muellen, K. Eur. Polym. J. 

2011, 47, 662–667. 

4. Golling, F.E.; Schuster, T.; Geidel, C.; Mammen, L.; 

Vollmer, D.; Klapper, M.; Muellen, K. The Power of 

Perfluorinated Amphiphilic Polymers at Interfaces, in 

Advances in Fluorine-Containing Polymers 2012, ACS 

Books. 

Polymer chemistry – iii 


o - 2 2 7 

SyntheSiS AS Key towArdS iMProved 

(oPto)eLeCtroniC MAteriALS 

u. SCherf 1 

1 University of Wuppertal, Chemistry, Wuppertal, Germany 

The lecture presents recent synthesis driven approaches 

towards systematic control on morphology and (opto)electronic 

properties of conjugated oligomers and (co)polymers. The 

examples include conjugated (co)polymers for application in 

organic solar cells, [1 2] all-conjugated rod-rod block copolymers 

and their self-assembly in solvent mixtures and in the bulk, [1,3-5] 

as well as hyperbranched, multichromophoric conjugated 

polymers. [6] 

references: 

1. J. H. Seo, A. Gutacker, Y. Sun, H. Wu, F. Huang, Y. Cao, 

U. Scherf, A. J. Heeger, G. C. Bazan, J. Am. Chem. Soc. 

2011, 133, 8416. 

2. P. Li, O. Fenwick, S. Yilmaz, D. Breusov, D. J. Caruana, 

S. Allard, U. Scherf, F. Cacialli, Chem. Commun. 2011, 

47, 8820. 

3. Tu, G., Li, H., Forster, M., Heiderhoff, R., Balk, L. J., 

Sigel, R., Scherf, U.; Small 2007, 3, 1001. 

4. U. Scherf, A. Gutacker, N. Koenen, Acc. Chem. Res. 2008, 

41, 1086. 

5. A. Gutacker, S. Adamczyk, A. Helfer, L. E. Garner, 

R. C. Evans, S. M. Fonseca, M. Knaapila, G. C. Bazan, 

H. D. Burrows, U. Scherf, J. Mater. Chem. 2010, 20, 1423. 

6. J.-M. Koenen, S. Jung, A. Patra, A. Helfer, U. Scherf, 

Adv. Mater. 2012, 24, 681. 

Keywords: Conducting materials; Polymers; Semiconductors; 

Block copolymers; Amphiphiles; 



s790 

chem. Listy 106, s587–s1425 (2012) 



o - 2 2 8 

SurfACe funCtionALized PoLyPhenyLene 

dendriMerS 

r. StAnGenBerG 1 , K. MüLLen 1 

1 Max-Planck-Institute for Polymer Research, Synthetic 

Chemistry, Mainz, Germany 

Modifying the periphery of dendrimers affects properties 

such as solubility, aggregation and membrane penetration. A new 

type of amphiphilicity on the periphery of polyphenylene 

dendrimers (PPDs) is investigated by designing the periphery in 

an unprecedented way and scale. Polar (sulfonic acids) and 

non-polar groups (alkyl chains) were placed alternating close to 

each other on a sub-nanometer length scale (7?) to create small 

hydrophilic and hydrophobic domains on the surface. 

While in case of amphiphilic nanoparticles the surface 

patterning relies on self-assembly, dendrimer synthesis allows the 

right placement of different functional groups at assigned 

positions. Thus the number and arrangement of functional groups 

as well as the distance between them can be adjusted. Backward 

folding of the periphery into the dendrimer interior is prevented 

by the rigid PPD scaffold so that functional groups of different 

polarity are fixed on the surface. Polarity differences lead to a 

permanent repulsion between the different functional groups. 

These functional groups cannot rearrange into a fully phase 

segregated state due to their fixed positions. This frustration leads 

to unique solubility i.e in polar and non-polar solvents as well. An 

application of such an amphiphilic PPDs as a transport agent for 

phase transfer (i.e. drug delivery via membranes) is presently 

being investigated. 

On the other hand two polyphenylenedendrons of different 

polarity can be combined to a so called “JANUS”-dendrimer. 

Such type of a PPD containing a hydrophilic and a lipophilic 

hemisphere should form supramolecular structures due to their 

strong aggregation. 

Furthermore, the switchability of the surface polarity and 

thereby the solubility is enabled by the incorporation of 

photoswitchable azobenzenes in the scaffold of our PPDs is under 

investigation. We aim to be able to switch the solubility in polar 

solvents on and off by light. 

Keywords: Dendrimers; Amphiphiles; 



o - 2 2 9 

new Low enerGy GAP PoLyMerS for 

APPLiCAtion in SoLAr CeLLS 

A. irAqi 1 , h. yi 1 , A. ALGhAMdi 1 , 

M. S. SArJAdi SArJAdi 1 , S. AL-fAifi 1 , d. wAtterS 2 , 

J. KinGSLey 2 , d. G. Lidzey 2 

1 University of Sheffield, Chemistry, Sheffield, United Kingdom 

2 University of Sheffield, Physics & Astronomy, Sheffield, United 

Kingdom 

Research into the use of conjugated polymers for application 

in bulk heterojunction solar cells has been the subject of much 

interest in recent years in view of their potential technological 

value for energy generation. Major advances have been achieved 

in this area; however, new polymer systems with high absorption 

coefficients and extended absorption spectra are still being sought 

for use in this area. 

The design of low energy-gap conjugated polymers can be 

achieved by introduction of alternate electron donor and acceptor 

repeat units along the polymer chains which results in 

intra-molecular charge transfer. This approach proved successful 

in the preparation of a range of narrow energy gap polymers for 

application in bulk heterojunction solar cells. Donor/acceptor 

systems comprising copolymers with alternating 2,7-carbazole 

repeat units along with acceptor repeat units have been described 

by Leclerc et al. and showed great promise when used with PCBM 

in bulk heterojunction photovoltaic cells with good power 

conversion efficiencies. We have reported recently the preparation 

of a series of donor / acceptor alternating copolymers comprising 

dithienyl benzothiadiazole with alkoxy substituents and 2,7-linked 

carbazole repeat units. The polymers showed higher open circuit 

voltage (V ) values than that of PCdtBt and good power 

oc 

conversion efficiencies with PCE values of 4.22 and 4.12%. 

In this work, we report the preparation and 

characterization of new classes of low energy gap 

donor/acceptor alternating copolymers, comprising 2,7-linked 

carbazole repeat units and alternate repeat units 

including selenophenyl benzo[1,2,5]thiadiazole units and 

thienothiophenyl benzo[1,2,5]thiadiazole units. We also present 

studies on the physical properties of the polymers and their ability 

to act as electron donors to PCBM as well as their performance 

in bulk heterojunction solar cells in blends with PCBM. 

Keywords: Conjugated polymers; Organic photovoltaics; Bulk 

heterojunction solar cells; 



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o - 2 3 0 

SeLf-heALinG PoLyMer CoAtinGS BASed on 

the (retro) dieLS-ALder reACtion 

M. d. hAGer 1 , J. KoetteritzSCh 1 

1 Friedrich-Schiller-University Jena, Laboratory of Organic and 

Macromolecular Chemistry (IOMC), Jena, Germany 

Self-healing materials feature the extraordinary property that 

a damage inflicted to them can be healed (partially or completely). 

Hereby the original function of the material can be restored. In 

Nature this process is very common: a cut in the finger can be 

healed, broken bones merge,... 

However, man-made materials very often lack this special 

ability. In contrast to natural materials they were designed in order 

to prevent the damage, not to manage and handle damage, which 

will inescapable occur during usage of common materials. 

Self-healing coatings are of particular interest, because coatings 

are very prone to damage. Latter will lead to a loss of the function 

of the coating: protection of the underlying material and 

aesthetical exterior. 

Self-healing can be achieved in coatings by extrinsic 

materials, i.e. a healing agent is embedded into the coating 

(e.g., within capsules). In addition, the polymeric material of the 

coating itself can feature the ability for healing. In this context, 

we report the synthesis of novel acrylic polymers, which contain 

both binding units for the Diels-Alder reaction (i.e. the maleimide 

and the furan moiety). The ATRP was utilized to synthesize 

well-defined functional terpolymers, which could be crosslinked 

via thermal treatment. Different comonomers have been utilized 

to tune the thermal and mechanical properties of the resulting 

polymer networks. 

Moreover, the healing of scratches in polymer coatings, 

based on these materials, was investigated. The influence of the 

crosslinking density, the kind of the comonomer and the healing 

temperature on the ability for self-healing was investigated in 

detail. Efficient healing of polymer coatings could be obtained. 

Keywords: Polymers; Materials science; Cycloaddition; 

Pericyclic reaction; 



o - 2 3 1 

deSiGn And SyntheSiS of noveL Serine BASed 

GeMini SurfACtAntS: how doeS StruCturAL 

ModifiCAtion AffeCt MiCeLLizAtion And 

CytotoxiCity 

M. L. C. do vALe 1 , S. G. SiLvA 1 , C. M. ALveS 1 , 

A. M. S. CArdoSo 2 , M. C. PedroSo de LiMA 2 , 

A. S. JurAdo 2 , e. f. MArqueS 1 

1 Faculty of Sciences of the University of Porto, CIQ 

- Centro de Investigacio em Química and Department of 

Chemistry and Biochemistry, Porto, Portugal 

2 CNC - Centre for Neurosciences and Cell Biology and 

Department of Life Sciences, University of Coimbra, Coimbra, 

Portugal 

Gemini surfactants represent a new generation of 

compounds composed of two surfactant monomers linked 

chemically at or near the head groups by a rigid or flexible spacer. 

Owing to their excellent performance and enhanced 

physicochemical and biological properties in comparison to the 

corresponding monomeric counterparts, gemini surfactants have 

a broad range of applications, ranging from cosmetic and food 

formulations, models for membranes and microreactors, to drug 

and gene delivery systems, among others. [1] Therefore, considerable 

efforts have been made to design and synthesize new forms of 

gemini surfactants, focusing on the effect of the nature of the polar 

head group and of the spacer length and hydrophobicity on the 

aggregation properties as well as on the toxicological profile of 

the compounds. 

In this context, our research group has been engaged in the 

synthesis and evaluation of the basic physicochemical properties 

of amino acid based monomeric and dimeric surfactants. [2] In the 

present work, the results obtained with two novel series of cationic 

gemini surfactants based on serine are presented. The most 

efficient synthetic pathway was established and involves the 

introduction of the spacer into the N, N-dialkylated monomeric 

precursors by peptide condensation methods, subsequent 

methylation and deprotection. The final target surfactants have 

either an amide or an ester bond between the polar head group 

and the spacer. These surfactants showed enhanced micellization 

properties compared to the conventional bis-quats. A study 

on the influence of the nature of the spacer linkage as well as of 

the spacer chain length has been performed. The cytotoxicity 

of the compounds has also been evaluated. 

Acknowledgement: Thanks are due to FCT 

(PTDC/QUI-BIQ/103001/2008; PTDC/QUI/115212/2009; 

SFRH/BD/61193/2009; CIQUP); 

FEDER (REDE/1517/RMN/2005). 

references: 

1. F. M. Menger, J. S. Keiper, Angew. Chem. Int. Ed. 2000, 

39, 1906–1920; [2] S. Goreti Silva, Ricardo F. Fernandes, 

Eduardo F. Marques, M. Luísa C. Vale, Eur. J. Org. Chem. 

2012, 345–352. 

Keywords: surfactants; synthesis; cytotoxicity; self-assembly; 

amino acids; 



s792 

chem. Listy 106, s587–s1425 (2012) 


Polymer chemistry – iV 

o - 3 7 5 

PoLyMerizAtion-induCed SeLf-ASSeMBLy of 

AMPhiPhiLiC BLoCK CoPoLyMerS in wAter 

B. ChArLeux 1 , w. zhAnG 1 , x. zhAnG 1 , 

f. d’AGoSto 1 , J. rieGer 2 , o. Boyron 1 

1 Chimie Catalyse Polymeres et Procédés, CPE Lyon, 

Villeurbanne, France 

2 Laboratoire de Chimie des Polymeres, UMPC, Paris, France 

The presentation will describe the formation of amphiphilic 

block polymer nanoparticles in water via an in situ process based 

on polymerization-induced self-assembly. This method relies on 

the employment of a hydrophilic living polymer precursor 

prepared via controlled free-radical polymerization that is 

extended with a hydrophobic second block in an aqueous or 

hydroalcoholic environment. The process thus leads to 

amphiphilic block copolymers that self-assemble in situ into 

self-stabilized nano-objects in the frame of an emulsion or 

dispersion polymerization process. Depending on the nature and 

the structure of the so-formed copolymer, not only spherical 

particles can be achieved but also all morphologies that can be 

found in the phase diagram of an amphiphilic block copolymer in 

a selective solvent. The presentation will focus mainly on the 

RAFT (reversible addition-fragmentation chain transfer) 

controlled free-radical polymerization technique using various 

hydrophilic and hydrophobic comonomers. 

Keywords: self-assembly; amphiphilic block copolymer; 

controlled-radical polymerization; reversible additionfragmentation 

chain transfer; polymerization in dispersed 

systems; 



o - 3 7 6 

SyntheSiS And ControLLed iMMoBiLizAtion 

of AMPhiPhiLiC BLoCK CoPoLyMerS on SoLid 

SuPPortS 

S. touGhrAi 1 , J. L. Perin 1 , C. K. PAndiyArAJAn 2 , 

n. BrunS 1 , w. Meier 1 

1 Institute of Physical Chemistry, Department of Chemistry, 

Basel, Switzerland 

2 Institut für Mikrosystemtechnik, Department of Chemistry, 

Freiburg, Germany 

Functionalization of surfaces using biomimetic block 

copolymer membranes enhances the development of smart 

surfaces for biotechnological applications that include biosensing 

and the local production and release of drugs. Instead of lipid 

membranes, amphiphilic block copolymer membranes have been 

chosen as mimics of biological membranes, due to properties such 

as tunable thickness, chemical and mechanical stability, lower 

permeability, fluidity, mobility, etc. Upon insertion of membrane 

proteins, these systems could allow for the preparation of 

mechanically and chemically robust, air-stable biosensing and 

drug delivery devices. 

Surface-initiated atom transfer radical polymerization 

(ATRP) was used because it provides good control of 

brush thickness by controlling polymer molecular weight. 

Poly(2-hydroxyethyl methacrylate)-block-poly(n-butyl methacrylate)- 

-block-poly(2-hydroxyethyl methacrylate), PHEMA-b-PBMA-b- 

-PHEMA block copolymers were synthesized with the first 

PHEMA block anchored to a self-assembled monolayer of 

initiators on a gold surface, while the other PHEMA block was 

exposed to the outside. To achieve this, a self-assembled 

monolayer of (BrC-(CH ) COO(CH ) S) ) initiator was formed 

3 2 2 11 2 

by disulphide ? gold covalent bonding. 

The formation of the self-assembled monolayer was 

successfully characterized by AFM, contact angle- and X-ray 

photoelectron spectroscopy (XPS), providing information on the 

presence of chemical elements and their binding energies, and 

therefore on the structure of the initiator on the surface. Contact 

angle, ATR-FTIR, and AFM measurements were taken to monitor 

the ATRP synthesis. PHEMA brushes render the surface smoother 

and more hydrophilic, whereas PBMA brushes result in a rougher, 

more hydrophobic surface. The thickness was measured layer by 

layer by surface plasmon resonance (SPR), with an overall 

thickness of 39 nm. 

ATRP was successfully applied to the grafting of 

ABA-triblock copolymer membranes from gold supports. 

Polymer brushes such as these, exhibiting a hydrophilic- 

-hydrophobic-hydrophilic sequence, could be regarded as the first 

example of solid supported, biomimetic block copolymer 

membranes prepared by a “grafting-from” approach. 

Keywords: Biosensors; Block copolymers; Surface chemistry; 

Membrane proteins; 



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chem. Listy 106, s587–s1425 (2012) 



o - 3 7 7 

new PdMS-B-PCL And PCL-B-PdMS-B-PCL BLoCK 

CoPoLyMerS for SurfACe nAno And MiCro- 

PAtterninG 

M. BroGLy 1 , C. ALzinA 1 , S. BiStAC 1 , C. deLAite 1 

1 Université de Haute Alsace, LPIM - Equipe CPCP, Mulhouse 

cedex, France 

Polydimethylsiloxane (PDMS) are particularly interesting 

polymers due to their broad combination of desirable properties 

as a low glass transition temperature (-120 °C), a high chain 

flexibility, a high resistance to chemical oxidation, high thermal 

and UV stability, a very pronounced hydrophobic character, as 

well as high biocompatibility. However, silicone polymers have 

so far been little used for the control of chemical modification of 

surfaces due to a strong dewetting tendency during adsorption on 

solid surfaces. To increase the chemical compatibility and 

promote irreversible adsorption, the synthesis of new block 

copolymers with a viscoelastic PDMS block was investigated. 

More precisely PDMS was copolymerized with e-caprolactone 

(e-CL) that is currently reconsidered with particular attention 

because of its biodegradability when polymerized. 

The purpose of this study is to create micro-patterned 

surfaces with specific and adjustable properties (hydrophobic vs 

hydrophilic or rigid vs soft). Several block copolymers were 

synthesized by reacting hydroxy-functional PDMS oligomers 

with e-caprolactone. The synthesis of block copolymers AB and 

ABA were made by anionic coordinated polymerization. A wide 

range of combinations of well-defined diblock PDMS-b-PCL and 

tribloks PCL-b-PDMS-b-PCL copolymers were obtained. The 

molecular weights of block copolymers synthesized were 

determined by 1H NMR and SEC. The thermal and structural 

properties of copolymers were determined by DSC and FTIR 

spectroscopy. The structure of copolymers in the adsorbed state 

was studied by Atomic Force Microscopy (AFM) to reveal the 

impact of block copolymer microstructure on the micro-patterning 

properties. 

The results show that the surface morphology of the 

adsorbed copolymer films can be tuned by the copolymer 

microstructure. In particular, the adsorption on a hydrophobic 

surface allows obtaining a 2D “porous” surface, for which the size 

of “cells” is determined by the microstructure of the copolymer. 

Keywords: Block copolymers; Polydimethylsiloxane; 

Polycaprolactone; Adsorption; Surface patterning; 



o - 3 7 8 

ChitoSAn-BASed LeAther funCtionAL 

CoAtinGS with iMProved AntiMiCroBiAL 

ProPertieS 

J. S. AMArAL 1 , i. P. fernAndeS 2 , v. Pinto 3 , 

M. J. ferreirA 3 , M. f. BArreiro 2 

1 REQUIMTE/Pharmacy Faculty of Porto, and Polytechnic 

Institute of Braganca, Braganca, Portugal 

2 LSRE/IPB, Polytechnic Institute of Braganca, Braganca, 

Portugal 

3 CTCP, Centro Tecnologico do Calcado de Portugal, Sao Joao 

da Madeira, Portugal 

Among the interesting biological activities that have been 

ascribed to chitosan, the antimicrobial activity is probably the one 

that generates the higher number of applications. Developing 

antimicrobial coatings for footwear components to be used in 

direct contact with the feet is of great interest; both at industrial 

level (reducing the possibility of material deterioration and quality 

loss) and from the consumer’s point of view (decreasing skin 

infections and minimizing unpleasant odours). One weakness of 

this application is addressed to the durability and efficiency of the 

product antimicrobial activity, since it is directly associated with 

+ the availability of the positively charged R–NH groups that are 

3 

depleted during use. 

In this work chitosan-based microparticles loaded with 

limonene as a model core material have been produced using an 

atomization technique followed by a coagulation step with sodium 

tripolyphosphate solution and a finishing step with 

glutaraldehyde. By using microencapsulation it is expected that 

the loaded essential oil will progressively release, reinforcing the 

antimicrobial durability and effectiveness of the developed 

coating. Moreover, the empty chitosan carriers can act as an 

additional source of chitosan. 

The chitosan-based microparticles were applied conjunctly 

with a chitosan solution (1% w/v in diluted formic acid solution) 

in a pilot scale drum during 2 hour at 50 ºC. The used leather 

samples correspond to half a hide arising from the industrial dye 

fixation stage split in two parts. After the coating process, the 

leather was dried in industrial conditions and stored in closed 

plastic bags before testing. The antimicrobial activity was tested 

using a Standard Test Method under Dynamic Contact Conditions 

based on the ASTM Standard E 2149-01. Comparatively to the 

leather impregnated with the base chitosan solution, the coatings 

reinforced with chitosan microparticles evidenced an improved 

antimicrobial activity. 

Acknowledges: Financial support from COMPETE, QREN and 

EU (project QREN-ADI-1585-ADVANCEDSHOE). 

Keywords: polymers; biological activity; natural products; 



s794 

chem. Listy 106, s587–s1425 (2012) 


supramolecular Chemistry – i 

o - 3 7 9 

ChirAL CAPSuLeS with reverSed PoLArity 

A. SzuMnA 1 

1 Institute of Organic Chemistry, Institute of Organic Chemistry, 


Molecule-sized synthetic container molecules (capsules and 

cavitands) have been of continuing interest to many researchers 

because they provide a specific, confined nanospace as a site for 

recognition and catalysis. Their unique constrictive internal 

environment and ability to eliminate solvent’s influence have been 

sown to cause stabilization of unusual conformations, transition 

states and reaction intermediates. These features can be exploited 

for the construction of selective sensors, gas storage media and 

reaction nanovessels. 

Most of the currently known synthetic container molecules 

(capsules and cavitands) have walls composed of aromatic rings. 

Therefore they have smooth and hydrophobic interiors incapable 

of directional interactions with guests, recognition of polar guests, 

distinguishing of enantiomers, performing in asymmetric 

reactions or generation of unidirectional motion. Their nonpolar 

interiors are also disadvantageous for catalytic purposes. Synthetic 

container molecules with chiral, polar walls capable of directional 

interactions with guests can potentially overcome these drawbacks 

and therefore are of great interest. 

We have succeeded in the synthesis of a series of capsular 

dimers with hydrophobic outer surfaces and polar and chiral 

interiors. High kinetic stability of the resulting polar capsules 

requires a non-covalent approach to the synthesis and isolation. 

We will discuss various aspects of supramolecular synthesis of 

the polar capsules, involving reversible formation, self- and 

nonself-sorting and denaturation. We will also show their 

applications and use for basic research. For example: a) extraction 

and encapsulation of biologically relevant polar molecules from 

water phase; b) differentiation of enantiomers with detailed 

interaction studies based on X-ray analysis; c)model studies on 

the influence of water molecules on recognition and d) model 

studies on the guests’ dynamics in restricted polar environment. 

references: 

1. Kuberski B., Szumna A. Chem. Commun. 1959 (2009). 

2. Szumna A. Chem. Commun., 4191 (2009). 

3. Szumna A. Chem. Eur. J., 15, 12381 (2009). 

Keywords: Self-assembly; NMR spectroscopy; Calixarenes; 

Cavitands; Chirality; 



o - 3 8 0 

ChirAL SuPrAMoLeCuLAr orGAnizAtion of 

oLiGo(PhenyLene ethynyLene) (oPe)-BASed 

diSCotiCS: induCtion of heLiCity And 

AMPLifiCAtion of ChirALity 

f. GArCiA 1 , L. SAnChez 1 

1 Universidad Complutense de Madrid, Química Orgánica I, 

Madrid, Spain 

The self-assembly of relative small molecules to yield 

supramolecular polymers is a matter of interest because the well 

defined and organized supramolecular structures can find 

applicability in material and biological science. [1] Many of these 

supramolecular structures exhibit a preferred handedness due to 

the incorporation of stereocenters at the peripheral substituents. 

Here in we describe the self-aggregation of two series of 

triangular shape OPEs discotics. [2] One of them is composed by 

OPE-based trisamides with a variable number of chiral side chains 

that self-assemble following a cooperative mechanism into αhelices. 

The presence of only one stereogenic center is enough in 

this series to achieve a helical organization with a preferred 

handedness. However, the ability to amplify the chirality 

decreases upon decreasing the number of stereocenters. In the 

other series the amide functionalities are replaced by ether 

linkages which impedes the α-helical columnar organization, and 

no dichroic response is observed. 

The amplification of chirality experienced by mixing some 

components of the two series has been studied. Thus, while the 

mixture of a chiral trisamide with chiral but non helical OPEs 

functionalized with 2 or 3 ether linkages does not result in an 

amplification of chirality, the combination of an achiral trisamide 

with a chiral but nonhelical bisamide-monoether OPE generates 

helical structures with a preferred handedness. These studies 

represent one of the scarce examples in which chirality is obtained 

from the formation of host-guest complexes between structurally 

analogous species that separately are CD-silent. 

references: 

1. a) T. Aida, E. W. Meijer, S. I. Stupp; Science, 2012, 335, 

813–817; 

b) A. R. A. Palmans, E. W. Meijer; Angew. Chem. Int. 

Ed. 2007, 46, 8948–8968. 

2. F. García, L. Sánchez; J. Am. Chem. Soc. 2012, 134, 

734–742. 

Keywords: Supramolecular chemistry; Self-assembly; 

Chirality; Hydrogen bonds; Helical structures; 



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chem. Listy 106, s587–s1425 (2012) 



o - 3 8 1 

PePtide nuCLeiC ACidS (PnA) BeArinG 

C5-Modified urACiL derivAtiveS: hiGhLy 

SeLeCtive ProBeS CoMBininG StACKinG 

interACtionS And BASe PAirinG 

r. CorrAdini 1 , A. MAniCArdi 1 , A. ACCettA 1 , 

A. Ghidini 1 , r. MArCheLLi 1 



Peptide nucleic acids (PNA) are among the best performing 

molecules in the recognition of DNA and RNA, and are very 

useful in the development of diagnostic as well as therapeutic 

tools. [1, 2] In the present communication we describe the synthesis 

of PNA probes containing monomers bearing uracil bases 

modified at the C5 carbon. The pendant groups were designed to 

allow to maintain the usual Watson-Crick base pairing and to 

provide additional stacking interactions (pyrene or naphthalene 

units), additional hydrogen bonds (Hoogsteen-like, through 

linking of a second uracil group) or both. Building blocks for the 

C5 modified monomers were isoorotic acid 

(5-carboxyuracil) or 5-(azidomethyl)uracil. In the former case the 

preformed modified PNA monomer was produced, whereas for 

the latter the strategy of introducing pendant groups directly on 

the solid phase, during or after the PNA synthesis, was also used. 

PNA thus synthesized bearing several pyrene units 

distributed along the chain showed remarkable recognition 

properties, due to the stabilizing effect of stacking interaction 

which allowed to form stable triplex structures. The occurrence 

of these interactions was probed by excimer band formation in 

the emission spectrum, which was highly sequence selective. Thus 

these type of derivatives turned out to be excellent fluorescent 

probes for the target point mutation on DNA. 

references: 

1. R. Corradini, S. Sforza, T. Tedeschi, F. Totsingan, 

A. Manicardi, R. Marchelli. Curr Top Med Chem 2011, 11, 

1535-1554 

2. L.M. Zanoli, M. Licciardello, R. D’Agata, C. Lantano, 

A. Calabretta, R. Corradini, R. Marchelli, G. Spoto. Anal. 

Bioanal. Chem., in press. DOI: 10.1007/s00216-011-5638-3 

Keywords: Peptide Nucleic Acid; Uracil derivatives; Stacking 

interactions; Modified Nucleobases; Fluorescent probes; 

supramolecular Chemistry – ii 


o - 3 8 2 

foLdAMerS: exPAndinG the CheMiCAL SPACe 

i. huC 1 

1 Institut Européen de Chimie et Biologie, Université de 

Bordeaux – CNRS, Pessac, France 

Our group has developed helical foldamers – oligomers that 

adopt stable helical folded conformations – derived from aromatic 

amino acids. [1] Some of these folded objects have shown 

unprecedented conformational stability, [2] and constitute 

convenient building blocks to elaborate synthetic, very large 

(protein-sized) folded architectures. [3] They possess a high 

propensity to assemble into double, triple and quadruple helices. [4] 

Cavities can be designed within such synthetic molecules that 

enable them to act as artificial receptors [5] and molecular motors. [6] 

Water soluble analogues of these foldamers show promise in 

nucleic acid recognition. 7 

references: 

1. G. Guichard, I. Huc, Chem. Commun. 2011, 47, 5933. 

2. H. Jiang, J.-M. Léger, I. Huc, J. Am. Chem. Soc. 2003, 

125, 3448; 

N. Delsuc, T. Kawanami, J. Lefeuvre, A. Shundo, H. Ihara, 

M. Takafuji, I. Huc ChemPhysChem 2008, 9, 1882. 

3. D. Sánchez-García, B. Kauffmann, T. Kawanami, H. Ihara, 

M. Takafuji, M.-H. Delville, I. Huc, J. Am. Chem. Soc. 

2009, 131, 8642; 

N. Delsuc, S. Massip, J.-M. Léger, B. Kauffmann, I. Huc, 

J. Am. Chem. Soc. 2011, 133, 3165. 

4. Q. Gan, C. Bao, B. Kauffmann, A. Grélard, J. Xiang, 

S. Liu, I. Huc, H. Jiang, Angew. Chem. Int. Ed. 2008, 47, 

1715; 

D. Haldar, H. Jiang, J.-M. Léger, I. Huc, Angew. Chem. 

Int. Ed. 2006, 45, 5483; 

Y. Ferrand, A. Kendhale, J. Garric, B. Kauffmann, I. Huc, 


5. Y. Ferrand, A. M. Kendhale, B. Kauffmann, A. Grélard, 

C. Marie, V. Blot, M. Pipelier, D. Dubreuil, I. Huc, J. Am. 

Chem. Soc. 2010, 132, 7858. 

6. Q. Gan, Y. Ferrand, C. Bao, B. Kauffmann, A. Grélard, 

H. Jiang, I. Huc, Science 2011, 331, 1172. 

7. L. Delauriere, Z. Dong, K. Laxmi-Reddy, F. Godde, 

J.-J. Toulmé, I. Huc, Angew. Chem. Int. Ed. 2012, 51, 473. 

Keywords: Supramolecular Chemistry; 



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o - 3 8 3 

SuPrAMoLeCuLAr nuCLeiC ACid StruCtureS 

for nAnoMediCine And diAGnoStiCS 

A. herrMAnn 1 , M. KwAK 1 , d. K. PruSty 1 

1 University of Groningen, Zernike Institute for Advanced 

Materials, Groningen, Netherlands 

Chimeras of DNA and different other synthetic materials 

like polymers, catalysts and dyes have gained increasing 

importance in recent years due to their ability to form functional 

supramolecular nanostructures in a modular fashion by employing 

Watson-Crick base pairing. [1] First, the combination of DNA and 

synthetic macromolecules will be discussed. Amphiphilic linear 

DNA block copolymers (DBCs) undergo microphase separation 

and form micelle aggregates in aqueous solution and their 

structural properties can be manipulated by hybridization. [2] 

Moreover, the organization of DBCs in liposomes and 

nanoelectronic devices will be demonstrated. [3] In the context of 

applications, the uptake of DNA block copolymer aggregates with 

different shapes into cells was studied. Based on these results their 

use as combinatorial platform for drug delivery was realized. [4] 

Furthermore, oligonucleotides were conjugated to dyes 

containing a heavy atom like iodine that induces quenching of the 

photoluminescence. When employed in a DNA-templated 

Heck-reaction the fluorescence signal was restored allowing DNA 

detection. [5] A strongly amplified detection system was realized by 

DNA-directed assembly of a dehalogenation catalyst resulting in 

a detection limit of only 10 fM. 

Finally, non-covalent complexes of nucleic acids with 

structurally complex natural products will be highlighted. 

The RNA supramolecular protective groups block several 

functionalities in an antibiotic bearing several chemically 

equivalent groups and enable the highly chemo- and 

regioselective derivatization of drug molecules in a single 

synthetic step. This technology will dramatically accelerate the 

drug development process avoiding costly and cumbersome 

synthetic routes. 

references: 

1. M. Kwak, et al, Angew. Chem. Int. Ed. 2010, 49, 8574. 

2. K. Ding, et al, Angew. Chem. Int. Ed. 2007, 46, 1172. 

3. M. Kwak, et al, Angew. Chem. Int. Ed. 2011, 50, 3206. 

4. F. E. Alemdaroglu, et al, Adv. Mat. 2008, 20, 899. 

5. D. K. Prusty, et al, J. Am. Chem. Soc. 2010, 132, 12197. 

Keywords: DNA; block copolymers; drug delivery; sensing; 

catalyst; 



o - 3 8 4 

BuiLdinG SynthetiC And therAPeutiC 

ProteinS 

G. BernArdeS 1 , d. neri 1 , B. dAviS 2 

1 ETH Zurich, Chemistry and Applied Biosciences, Zürich, 

Switzerland 

2 University of Oxford, Department of Chemistry and Applied 

Biosciences, Oxford, United Kingdom 

Chemical site-selective modification of proteins is a 

powerful tool for (i) accessing and understanding 

structure-activity relationships of different post-translational 

modifications (PTMs), and (ii) building homogenous therapeutic 

proteins such as carbohydrate-based vaccines or antibody-drug 

conjugates (ADCs). Here, I will present different strategies to 

install different PTM’s and cytotoxic drugs on proteins in a 

controllable and specific manner. 

Reaction engineering at cysteine: From disulfides to 

thioethers, a range of novel reactions and methods that enable 

controlled, specific modification of proteins at cysteine were 

developed. These methods are efficient strategies to access 

post-translational modifications such as phosphorylation, 

glycosylation, prenylation, or acetylation and methylation of 

lysine residues on proteins in a controllable, defined manner. 

Traceless, homogenous ADCs for cancer therapy: Using a 

vascular targeting approach, it was demonstrated for the first time 

that non-internalizing antibody-drug conjugates (ADCs) may be 

used to mediate strong anti-tumor activity in vivo. Coupling 

technology was based on direct cysteine modification with potent 

thiol containing cytotoxic drugs that yielded chemically defined, 

traceless ADCs. This novel strategy allows a) the progressive 

amplification of drug release, as tumor cell lysis mediates 

glutathione and cysteine release to the surrounding tissue and 

b) results in a strong anti-tumor activity in vivo, as demonstrated 

in three different syngeneic immunocompetent models of murine 

cancer that are not cured by conventional cytotoxic agents alone. 

Keywords: Synthetic Biology; Synthetic methods; Protein 

modifications; Bioorganic chemistry; Drug-delivery; 



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o - 3 8 5 

unPreCedented BiStABLe hoSt-GueSt 

CoMPLexeS of CuCurBit[6]uriL And AroMAtiC 

diAMMoniuM SALtS 

o. reAny 1 , K. M. SinhA 2 , M. yefet 2 , 

M. BotoShAnSKy 2 , e. KeinAn 2 

1 The Open University of Israel, Natural Sciences, Ra’anan, 

Israel 

2 Technion-Israel Institute of Technology, Chemistry, Haifa, 

Israel 

Since the first reported cucurbit[6]uril (CB[6]) complex with 

dihydrochloride salt of bis-1,4-(aminomethyl)benzene, [1] CB[6] 

complexes have been widely used for the construction of 

pseudorotaxanes and rotaxanes that exhibited interesting dynamic, 

structural, and functional properties. [2] However, while linear 

aliphatic diammonium salts readily form stable host–guest 

complexes of CB[6], [3] the ability of CB[6] to host aromatic 

compounds has not been investigated. 

Recently we have reported that 4-aminobipyridine 

derivatives form strong 1:1 inclusion complexes with CB[6], 

whereas the N,N-bis(2,2'-bipyridine)xylylenediamine analogue 

forms a strong 1:2 complex with CB[6] at room temperature [4] and 

we report here the scoop of host–guest complexes of CB[6] with 

various 1,4-bis(alkylaminomethyl)benzene guests. [5] Interestingly, 

these complexes are found to exhibit two stable binding modes 

with an unexpectedly high barrier between them. The highly 

stable 2:1 complexation mode that is formed at room temperature, 

is found to be a kinetic product, and can be converted to the 

thermodynamic 1:1 complex upon prolonged heating to 100 ºC. 

The latter is a very stable rotaxane despite the fact that it lacks 

bulky end groups. 

The structural and dynamic properties of the various 

complexes, the kinetic and thermodynamic binding parameters, 

as well as different chemical reactivity towards the azide–alkyne 

[3+2] cycloaddition reaction (click chemistry), will be discussed. 

references: 

1. W. A. Freeman, Acta Crystallogr. Sect. B 1984, 40, 

382 –387. 

2. Parvari, G., Reany, O., Keinan, E.; Isr. J. Chem., 2011, 51, 

646-663 

3. a) W. L. Mock, Top. Curr. Chem. 1995, 175, 1–24; 

b) M. V. Rekharsky, Y.-H. Ko. N. Selvapalam, K. Kim, 

Y. Inoeu, Supramol. Chem. 2007, 19, 39 –43. 

4. Mantosh, S., Reany, O., Parvari, G., Karmakar, A., 

Keinan, E.; Chem. Euro. J., 2010, 16 (30), 9056-9067. 

5. Mantosh, S., Reany, O., Yefet, M., Botoshansky, M., 

Keinan, E.; Chem. Euro. J., 2012, 18 (18), 5589-5605. 

Keywords: host-guest systems; click chemistry; rotaxanes; 

supramolecular Chemistry – iii 

o - 3 8 6 

SuPrAMoLeCuLAr SenSorS 

e. dALCAnALe 1 


1 University of Parma, Department of Chemistry, Parma, Italy 

Selectivity is one of the key issues involved in developing 

new, efficient chemical sensors. [1] The use of supramolecular 

structures has proven to be one of the best approaches to generate 

new materials with molecular specificity for chemical sensing. 

However, the direct translation of the molecular recognition 

properties of a given receptor from solution studies to the solid 

devices is not trivial, since nonspecific interactions such as 

dispersion forces, and material properties, like surface 

morphology, come into play. [2] In this lecture, I will report our 

recent efforts to produce specific supramolecular sensors using 

phosphonate cavitands as receptors. The implementation of the 

molecular recognition paradigm throughout the whole sensing 

chain will be highlighted through selected examples from our own 

work. Particular emphasis will be given to strategies to remove 

the two bottlenecks hindering the exploitation of synthetic 

receptors in supramolecular sensing, namely the precise transfer 

of the intrinsic molecular recognition properties at the gas-solid 

and liquid-solid interfaces and the high fidelity transduction of 

the interfacial molecular recognition events. 

In this contribution three examples will be illustrated: 

• Solid-gas interface: Fluorescent cavitands as selective 

layers for the specific detection of C -C alcohols in the 

1 4 

gas phase. [3] 

• Solid-liquid interface: Exclusive detection of sarcosine in 

water and urine with cavitand-functionalized SWCNTs and 

cavitand-functionalized silicon wafers. [4,5] 

• Nanomechanical recognition of N-methylated derivatives. [6] 

references: 

1. L. Pirondini, E. Dalcanale Chem. Soc. Rev. 2007, 36, 

695–706. 

2. M. Tonezzer et al. Chem. Mater. 2008, 20, 6535–6542. 

3. F. Maffei et al. Angew. Chem. Int. Ed. 2011, 4654–4657. 

4. M. Dionisio et al. J. Am. Chem. Soc. 2012, 134, 

6540–6543 

5. E. Biavardi et al. Proc. Natl. Acad. Sci. USA 2012, 109, 

2263–2268. 

6. M. Dionisio et al. J. Am. Chem. Soc. 2012, 134, 

2392–2398. 

Keywords: Cavitands; Interfaces; Sensors; 



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o - 3 8 7 

AzoBenzene MACroCyCLiC ChiroPtiCAL 

SwitCheS 

M. PutALA 1 , A. KiCKová 1 , r. MiSiCáK 1 

1 Comenius University in Bratislava, Department of Organic 

Chemistry Faculty of Natural Sciences, Bratislava, Slovak 

Republic 

Light-driven molecular machines have attracted intensive 

attention for their potential applications in the field of optical data 

processing and storage. One of the alternative strategies for the 

non-destructive readout is represented by utilization of their 

chiroptical properties. Photochromic diaryldiazene unit undergoes 

significant change in molecular geometry upon trans-cis 

isomerization which has been successfully explored for 

construction of chiroptical switches in combination with 

binaphthalene moiety as conformation sensitive chiral unit 

(changing dihedral angle between naphthyl units). 

Our results on the synthesis and characterization of 

macrocyclic switches consisting of photochromic diazene and 

binaphthalene chiral moiety attached via suitable linkers will be 

reported. In comparison to the previously reported analogues with 

more flexible propan-1,3-diyldioxy linkers, the derivatives with 

more rigid acrylamide and urea linkers exhibit advanced 

switching performance: switching of CD signal intensity up to 1:3 

for compound with acrylamide linker, or even switching the signal 

sign for compoud with urea linker. 

Keywords: azo compounds; binaphthyl derivatives; chiroptical 

switches; 



o - 3 8 8 

SeLf-ASSeMBLed ttf-BASed redox-ACtive 

reCePtorS: froM 2d PoLyGonS to 3d CAGeS 

S. BivAud 1 , S. GoeB 1 , J. y. BALAndier 1 , M. ChAS 1 , 

M. SALLe 1 

1 MOLTECH-Anjou, UFR Sciences, Angers, France 

The methodology of self-assembly driven by metals 

(typically Pt, Pd) allowed the preparation of a large number of 

molecular polygons (triangle, square,...) and polyhedrons (cubes, 

prisms, …) presenting remarkable properties. [1] For instance, the 

water-soluble cage described below by Fujita et al showed 

surprising catalytic activities. [2] 

Nevertheless, very few electro-active polygons or 

polyhedrons have been described, and none presents an 

electron-rich cavity. In this context, we have initiated a project to 

elaborate new self-assembled discrete structures incorporating 

redox-active walls based on tetrathiafulvalene (TTF). [3] 

We recently described the first self-assembled molecular 

square and triangle integrating TTFs units, reversibly oxidizable 

and able to complex the electron-poor fullerenes C or C . 60 70 4 

In this communication, we will focus on our last results in 

this area, and in particular on several new three dimensional 

capsules based on TTF, bispyrrolo-TTF (BPTTF) and 

extended-TTF (exTTF) based-ligands (see below), and on their 

capability to bind electro-deficient units. 

references: 

1. R. Chakrabarty, P. S. Mukherjee, P. J. Stang, Chem. Rev. 

2011, 111, 6810-6918. 

2. a) S. Horiuchi, Y. Nishioka, T. Murase, M. Fujita, Chem. 

Commun. 2010, 46, 3460-3462 ; 

b) T. Murase, S. Horiuchi, M. Fujita, J. Am. Chem. Soc. 

2010, 132, 2866-2867. 

3. D. Canevet, M. Sallé, G. Zhang, D. Zhang, D. Zhu, Chem. 

Commun. 2009, 2245-2269. 

4. a) J. Y. Balandier, M. Chas, P. Dron, S. Goeb, D. Canevet, 

A. Belyasmine, M. Allain, M. Sallé, J. Org. Chem. 

2010, 75, 1589 ; 

b) J. Y. Balandier, M. Chas, S. Goeb, P. I. Dron, D. Rondeau, 

A. Belyasmine, N. Gallego, M. Sallé, New J. Chem. 

2011, 35, 165 ; 

c) S. Goeb, S. Bivaud, J. Y. Balandier, P. I. Dron, M. Chas, 

M. Sallé, Chem. Commun. 2012, 48, 3106-3108. 

Keywords: Sulfur heterocycles; Self-assembly; Supramolecular 

chemistry; Molecular recognition; 



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o - 3 8 9 

ModuLAr SyntheSeS of PorouS orGAniC CAGe 

CoMPoundS 

M. w. SChneider 1 , M. MAStALerz 1 

1 Ulm University, Chemistry II & Advanced Materials, Ulm, 

Germany 

Discrete organic cage compounds are a new family of 

porous materials besides the well investigated metal organic 

frameworks or zeolites. [1] They are synthesized from readily 

available precursors in one-pot by reversible Schiff-base 

reactions. In contrast to porous networks, cage compounds are 

soluble in common solvents and thereby, for example porous thin 

films can be casted. [2] Recently, the reaction of triptycene triamine 

with different salicyldialdehydes to [4+6] cage compounds was 

introduced. The amorphous material as well as the crystalline 

material of the [4+6] cage compounds have a high nitrogen gas 

uptake at 77 K which results in Brunauer-Emmett-Teller (BET) 

surface areas up to 2071 m2 g-1 . [3] By a similar approach, using 

other dialdehydes, various shape persistent cage compounds of 

different sizes and functionalities in the interior or exterior of the 

molecules can be rationally constructed. [4, 5] The syntheses and 

material properties of those cage compounds will be discussed. 

references: 

1. M. Mastalerz, Angew. Chem. Int. Ed. 2010, 49, 5042-5053. 

2. M. Brutschy, M. W. Schneider, M. Mastalerz, 

S. R. Waldvogel, unpublished results 

3. a) M. W. Schneider, I. M. Oppel, H. Ott, L. G. Lechner, 

H.-J. S. Hauswald, R. Stoll, M. Mastalerz,Chem. Eur. J. 

2012, 18, 836-847; 

b) M. Mastalerz, M. W. Schneider, I. M. Oppel, O. Presly, 


4. M. W. Schneider, I. M. Oppel, M. Mastalerz, Chem. Eur. J. 

2012, 18, 4156-4160. 

5. M. W. Schneider, M. Mastalerz, unpublished results. 

Keywords: Cage compounds; Crystal engineering; Schiff 

bases; 



o - 3 9 0 

one-Pot reGioSeLeCtive SyntheSiS And x-rAy 

CryStAL StruCture of A StABLe [60]fuLLerene 

triSAdduCt with the eedGe,efACe,trAnS-1 

Addition PAttern 

n. ChronAKiS 1 , M. riALA 1 , M. MArKouLideS 1 


The tether-directed remote functionalization method is a 

sophisticated and powerful approach which has been applied 

successfully for the regioselective functionalization of C . To 60 

access three-dimensional fullerene architectures, absolute control 

of the regioselectivity of tris-additions on the spherical fullerene 

carbon network is needed, since compared with bis-additions on 

C the number of the possible trisadducts is dramatically 

60 

increasing. As such, the design of appropriate tethers becomes a 

more demanding task. Among the 46 possible trisadducts of C60 (excluding the ones having a cis-1 position relationship), we 

targeted the e,e,trans-1 for the following reasons: a) this addition 

pattern cannot be accessed by stepwise Bingel cyclopropanations 

on C , b) the e,e,trans-1 trisadduct is a synthetically valuable 

60 

precursor for the synthesis of mixed [3:3] hexakisadducts with 

different types of addends located at octahedral sites. By varying 

the nature or the hydrophobic/hydrophilic character of the 

different organic addends, globular dendrimers, lipofullerenes and 

novel functional materials were synthesized and studied, and c) 

the synthesis of the e,e,trans-1 trisadduct of C has been reported 

60 

before but required multiple synthetic steps and chromatographic 

separations. The Bingel functionalization of C with a structurally 

60 

novel tether equipped with three reactive malonate groups 

afforded a C -symmetrical e ,e ,trans-1 trisadduct in a 

2v edge face 

complete regioselective manner and in the excellent yield of 65 %. 

The [60]fullerene trisadduct showed pronounced ability to 

crystallize and gave X-ray quality single crystals for analysis. 

The synthesized e ,e ,trans-1 fullerene trisadduct represents 

edge face 

a novel and attractive molecular structure due to the 

three-dimensional cavities that form between the tether and the 

fullerene skeleton, equipped with oxygen atoms and aromatic 

rings. Furthermore, the designed tether enhances the 

crystallizability of fullerene adducts and this might be useful for 

the functionalization of higher fullerenes where the assignment 

of the addition patterns is difficult by NMR spectroscopy. 

Keywords: Fullerenes; Macrocycles; Regioselectivity; 

Template Synthesis; X-ray Diffraction; 



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o - 3 9 1 

Anion-Pi interACtionS And hALoGen BondS in 

ACtion 

A. vArGAS JentzSCh 1 , d. eMery 1 , J. MAredA 1 , 

n. SAKAi 1 , S. MAtiLe 1 

1 University of Geneva, Organic Chemistry, Geneva, 

Switzerland 

The creation of supramolecular functional systems is of 

paramount importance. In this context, the available interactions 

to create function should be widened as much as possible. Ion 

transport systems are practically well suited to probe for the 

functional relevance of otherwise elusive interactions, because 

only weak contacts are needed for activity, whereas stronger 

contacts cause inactivation; a similar Goldilock-type situation 

exists in catalysis. 

Whereas most of the synthetic transport systems relay on 

intrinsically hydrophilic non-bonding interactions, especially 

hydrogen bonds, the possibility to use hydrophobic analogs 

appeared very promising. Therefore, the application of less 

recognized non-covalent interactions to anion transport systems 

seemed most fitting. 

Early work includes transport with anion-π interactions [1] , 

here the focus is on anion transport systems that operate with 

halogen-bond donors. Their strength, directionality and 

hydrophobic nature seemed ideal for this purpose. 

Exploiting known scaffolds (i.e. calixarenes), we have 

shown that anion transport in bilayer model systems can be 

achieved with halogen bonds. However, these initial examples 

required assistance from ion pairing and were too complex [2] . 

Therefore, we simplified the concept and minimized the system 

to the extreme. This approach provided access to extremely small 

molecules, down to highly volatile transporters containing one 

single carbon only, that are capable to self-assemble in lipid 

bilayer membranes and form supramolecular anion transport 

systems. 

These systems were studied for anion transport in 

fluorogenic vesicles as well as in planar bilayer conductance 

experiments, in the solid state with x-ray crystal structures and 

modeled in silico. The outcome is a surprisingly clean, leakage 

free, highly selective, non-ohmnic and minimalist transport 

system. 

references: 

1. Mísek, J.; Vargas Jentzsch, A.; Sakurai, S.; Emery, D.; 

Mareda, J.; Matile, S. Angew. Chem. Int. Ed. 2010, 49, 

7680. 

2. Vargas Jentzsch, A.; Emery, D.; Mareda, J.; Metrangolo, 

P.; Resnati, G.; Matile, S. Angew. Chem. Int. Ed. 2011, 50, 

11675. 

Keywords: Supramolecular chemistry; Noncovalent 

interactions; Anions; 



o - 5 2 5 

PhoSPhonAted SMALL MoLeCuLeS - A 

MuLtitALent in fueL CeLL APPLiCAtionS - 

J. weGener 1 , A. KALtBeitzeL 2 , M. KLAPPer 1 , 

K. MüLLen 1 


Chemistry, Mainz, Germany 

2 Max-Planck-Institute for Polymer Research, Physical 

Chemistry of Polymers, Mainz, Germany 

State-of-the-art separator materials often consist of sulfonic 

acid based perfluorinated polymers such as Nafion ® . The 

operation temperature of these materials is limited to the boiling 

point of water since proton conductivity strongly depends on the 

hydration of the membrane. Water-based proton-exchange 

membranes (PEMs) show certain disadvantages such as poor 

carbon monoxide tolerance and significant water transport 

through the electrolyte. Therefore, non-water-based PEMs 

providing high protonconductivity at intermediate temperatures 

(110 - 150°C) and low humidity are one of the biggest challenges 

for new separator materials. 

On-going research has focused on the development of 

Nafion ® -like materials which present a nanophase separation 

between a hydrophobic polymer main chain and acidic moieties. 

Another concept concerns the use of anhydrous protic ionic 

liquids which do not require humidification for proton transport. 

However, despite high conductivities a critical issue that still 

severely hampers the use of these electrolytes in fuel cell 

applications is their volatility as well as their instability. 

A different approach to achieve proton mobility by 

self-organization of small phosphonated molecules such as 

hexakis(p-phosphonatophenyl)benzene could be recently 

demonstrated. [1,2] 

For the development of novel separator materials based on 

this concept phosphonic-acid containing molecules with different 

geometry and substitution patterns were synthesized and 

characterized. These crystalline materials self-assemble into 

well-defined superstructures containing a proton-conducting 

periphery and present high as well as constant proton 

conductivities in the solid state. By incorporation of electronconducting 

moieties into these organic crystals, a mixed 

proton-electron-conducting material is being envisaged which has 

only been achieved for inorganic or composite materials up to 

now. 

references: 

1. L. Jiménez-García, A. Kaltbeitzel, W. Pisula, 

J. S. Gutmann, M. Klapper, K. Müllen, Angew. Chem. Int. 

Ed. 2009, 48, 9951. 

2. L. Jiménez-García, A. Kaltbeitzel, J. S. Gutmann, 

V. Enkelmann, M. Klapper, K. Müllen, Adv. Funct. Mater. 

2011, 21, 2216. 

Keywords: Conducting material; Fuel cells; Phosphorylation; 

Proton transport; Self-assembly; 



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chem. Listy 106, s587–s1425 (2012) 


frontiers and Advances of organic Chemistry – i 

o - 4 8 8 

new direCtionS in orGAnoCAtALySiS 

K. A. JorGenSen 1 

1 Aarhus University, Chemistry, Aarhus C, Denmark 

The lecture will present new activation modes in 

organocatalysis which allow for the development of new reaction 

concepts 



o - 4 8 9 

MiCro fLow CheMiStry – new PoSSiBiLitieS 

for SynthetiC CheMiStS 

t. noeL 1 , S. BuChwALd 2 , v. heSSeL 1 

1 Technische Universiteit Eindhoven, Chemistry and Chemical 

Engineering, Eindhoven, Netherlands 

2 Massachusetts Institute of Technology, Chemistry, Cambridge, 

United States Pacific Island Wildli 

Until recently, many reactions have been exclusively 

performed in batch processes. With the advent of microfluidics, 

significant effort has been devoted to develop a wide variety of 

continuous-flow techniques to facilitate organic synthesis. [1, 2] 

Microreactor technology offers several advantages compared to 

traditional batch reactors, such as, enhanced heat- and masstransfer 

and the possibility to integrate several reaction steps and 

subsequent separations in a single streamlined process. 

In this presentation, we will give an overview of some 

interesting aspects of flow chemistry within the realm of so-called 

Novel Process Windows. [3] This involves microflow results 

obtained in: 

• Buchwald-Hartwig Aminations: this section details on 

handling of solid forming reactions in microfluidic 

systems; [3a, 3e] 

• Suzuki-Miyaura Cross-Coupling Reactons: the feasibility 

to perform multistep reactions in microflow will be 

described in this part; [3b, 3d] 

• Pd-catalyzed Fluorinations: our efforts towards the 

development of an accelerated fluorination process in flow 

will be discussed in this fragment; [3c] 

• Click chemistry: we will conclude with a discussion of 

our efforts to develop a continuous copper scavenger 

unit. [3f] 

references: 

1. T. Noel, S. L. Buchwald, Chem. Soc. Rev. 2011, 40, 5010. 

2. V. Hessel, I. Vural-Gursel, Q. Wang, T. Noel, J. Lang, 

Chem. Eng. Technol. 2012, in press. 

3. a) T. Noel, J.R. Naber, R.L. Hartman, J.P. McMullen, 

K.F. Jensen, S.L. Buchwald, Chem. Sci. 2011, 2, 287. 

b) T. Noel, S. Kuhn, A.J. Musacchio, K.F. Jensen, 

S.L. Buchwald, Angew. Chem. Int. Ed. 2011, 50, 5943. 

c) T. Noel, T.J. Maimone, S.L. Buchwald, Angew. Chem. 

Int. Ed. 2011, 50, 8900. 

d) T. Noel, A.J. Musacchio, Org. Lett. 2011, 13, 5180. 

e) S. Kuhn, T. Noel, L. Gu, P.L. Heider, K.F. Jensen, Lab 

Chip 2011, 11, 2488. 

f) A.C. Varas, T. Noel, Q. Wang, V. Hessel, 2012 

manuscript in preparation. 

Keywords: Microreactors; Amination; fluorine; Click 

chemistry; Cross-coupling; 



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o - 4 9 0 

nitroAroMAtiC exPLoSiveS SenSinG uSinG 

non PorouS, nAno-orGAnized fLuoreSCent 

oLiGoPhenyLeneethynyLene fiLMS: how 

doeS it worK? 

e. PASquinet 1 , t. CAron 1 , P. MontMeAt 1 , 

A. vAn der Lee 2 , r. PAnSu 3 , v. roueSSAC 2 , 

M. BouhAdid 1 , f. Serein-SPirAu 4 , 

J. P. Lere-Porte 4 

1 CEA LE RIPAULT, Department of Explosives, Monts, France 

2 IEM, Institut Européen des Membranes, Montpellier, France 

3 ENS CACHAN, PPSM, Cachan, France 

4 Institut Charles Gerhardt, ENSCM, Montpellier, France 

The use of explosives in terrorist attacks has created a strong 

demand for explosives vapor sensors that would be suitable for 

suspicious luggage checking and forensic analysis. Fluorescence 

quenching of phenyleneethynylene compounds by nitroaromatic 

explosives is now a well-established method for sensing purposes. 

A great deal of attention has been focusing on the design of 

polymer structures incorporating sufficient porosity to allow 

diffusion of the nitroaromatic molecules in the film. However, 

some efficient non polymeric phenyleneethynylene derivatives 

have been reported. For these compounds, a rationale explaining 

their ability to detect nitroaromatic vapors is clearly lacking. 

The crystal structures of films of two similar 

phenyleneethynylene compounds displaying different behaviors 

were investigated. The first, Di8, bearing diimine moieties, is very 

sensitive to nitroaromatics but the second, unsubstituted 

compound shows poor responses. First it was shown that both 

non-porous films exhibited a high degree of crystallization and a 

preferred orientation, and that the crystal structure was identical 

in films or single crystals. Analysis of the very specific molecular 

arrangement within the crystals revealed that the fluorescent 

conjugated pi-structure of the non-responsive compound is highly 

tilted from the surface so that it can hardly be accessed by 

nitroaromatic vapors. On the contrary, the pi-structure of the 

efficient compound Di8 is readily available since it is almost 

parallel to the surface. This arrangement was also observed in 

films of another related product that also exhibited excellent 

sensing performances, thus consolidating the hypothesis. 

Moreover, exciton migration within the films of Di8 was 

clearly observed through time-resolved fluorescence experiments. 

This explains how most of the fluorescence of these non-porous 

films can be quenched even at very low concentrations of 

nitroaromatic species. 

Therefore, for the first time, structural data are provided on 

organic thin films to better understand the structure/sensing ability 

relationships for non porous phenyleneetynylene compounds. 

Keywords: sensors; fluorescence; thin films; nanostructures; 

supramolecular chemistry; 



o - 4 9 1 

redox-neutrAL Bio-CASCAde to AMineS froM 

PriM-ALCohoLS 

J. SAttLer 1 , M. fuChS 1 , K. tAuBer 1 , f. G. Mutti 1 , 

K. fABer 1 , J. Pfeffer 2 , t. hAAS 2 , w. KroutiL 1 

1 Karl-Franzens-Universität Graz, Institute of organic and 

bioorg. Chemistry, Graz, Austria 

2 Evonik Industries AG, Creavis Technologies, Marl, Germany 

While to transform primary alcohols to amines has been 

vividly investigated for metal catalysts applying the so called 

“borrowing hydrogen” methodology, [1–3] no such process has been 

reported for primary alcohols employing biocatalytic methods. 

A biocatalytic cascade was thus designed: In the first step 

an alcohol dehydrogenase (ADH) [4, 5] catalyzed the oxidation of 

the alcohol consuming NAD + leading to the formation of the 

aldehyde and NADH. 

In the second sequential simultaneous step, an 

ω-transaminase (ω-TA) is doing the amination reaction 

transferring the amine group from L-alanine to the aldehyde 

creating pyruvate, which is recycled by an NADH-dependent 

alanine dehydrogenase (AlaDH) using an ammonium salt as the 

nitrogen source regenerating the cofactor as well as the amine 

donor. 

Acknowledgement: The research leading to these results has 

received funding from the European Union’s Seventh 

Framework Programme FP7/2007-2013 under grant agreement 

no 245144 (AmBioCas) and Evonik. 

references: 

1. D. Pingen, C. Müller, D. Vogt, Angew. Chem. Int. Ed. 

2010, 49, 8130. 

2. S. Imm, S. Bähn, L. Neubert, H. Neumann, M. Beller, 


3. C. Gunanathan, D. Milstein, Angew. Chem. Int. Ed. 2008, 

47, 8661. 

4. T. Orbegozo, J. G. d. Vries, W. Kroutil, Eur. J. Org. Chem. 

2010, 3445. 

5. C. V. Voss, C. C. Gruber, K. Faber, T. Knaus, P. 

Macheroux, W. Kroutil, J. Am. Chem. Soc. 2008, 130, 

13969. 

Keywords: amination; primary alcohols; biocatalysis; Nylon; 

cascade reaction; 



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chem. Listy 106, s587–s1425 (2012) 


frontiers and Advances of organic Chemistry – ii 

o - 4 9 2 

ArtifiCiAL PhotoSyntheSiS – Low 

diMenSionAL CArBonS 

d. GuLdi 1 



Carbon is the key to many technological applications that 

have become indispensable in our daily life. Altering the periodic 

binding motifs in networks of sp3-, sp2-, and sp-hybridized 

C-atoms is the conceptual starting point for a wide palette of 

carbon allotropes. To this end, the past two decades have served 

as a test-bed for measuring the physico-chemical properties of 

low-dimensional carbon with the advent of fullerenes (0D), 

followed in chronological order by carbon nanotubes (1D), carbon 

nanohorns, and, most recently, by graphene (2D). These species 

are now poised for use in wide-ranging applications. 

Expanding global needs for energy have led to a significant 

effort to develop alternatives to fossil fuels. While alternative 

sources for energy are already in use, they comprise a small 

percentage of the energy demands needed to carry us through the 

21st century. No single source will solve the global needs, but the 

development of photovoltaics has vast potential as a point-of-use 

power source. Recent work has shown that hybrid 

photoelectrochemical efforts with a percolation network of photon 

absorbers coupled to anelectron/hole transporter in combination 

with advanced photon management are the ideal design for 

realizing breakthroughs in high photon conversion efficiencies 

suitable for the catalysis of water. 

I will report on our efforts regarding a unifying strategy to 

use the unprecedented charge transfer chemistry of 0D fullerenes, 

the ballistic conductance of 1D carbon nanotubes, the 

semiconducting features of carbon nanohorns, and the high 

mobility of charge carriers in 2D graphene, together in a 

groundbreaking approach to solving a far-reaching challenge, that 

is, the efficient use of the abundant light energy around us. 

Keywords: Carbon Allotropes; Solar Energy Conversion; 



o - 4 9 3 

ACtivAtion of ePoxide By PhenoLiC 

oxidAtion, A new entrAnCe in CASCAde 

reACtion 

y. S. wonG 1 , v. GoBé 1 , M. trAoré 1 



Phenol is ubiquitous in nature and is a common starting 

material for the building of various and complex secondary 

metabolites. Over the past few years, we have been involved in 

the study of cascade reactions triggered by phenolic oxidation. [1] 

By oxidizing phenol with hypervalent iodine reagent, we 

demonstrated that an intramolecular ketone can be trapped by the 

corresponding phenoxenium species resulting in the activation of 

subsequent reactive species in cascade manner. [2] 

In this communication, we wish to report our last 

endeavours by the transposition of this activation process from 

ketone to epoxide groups. The resulting species turns out to be 

highly efficient to initiate new cascade sequences giving rise to 

complex structures. We will also present examples of 

enantioselective cascade reactions involving enantioselective 

epoxidation and phenolic oxidation. 

references: 

1. M. Traore, S. Ahmed-Ali, M. Peuchmaur, Y.-S. Wong, 

Tetrahedron 2010, 66, 5863-5872. 

2. M. Traoré, M. Maynadier, F. Souard, L. Choisnard, 

H. Vial, Y.-S. Wong, J. Org. Chem. 2011, 76, 1409-1417. 

Keywords: Domino reaction; Epoxidation; Hypervalent 

compound; oxidation; Spiro compound; 



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o - 4 9 4 

BuiLdinG PriviLeGed CoMPLexity with 

CASCAde trAnSforMAtionS: froM rinG- to 

funCtionAL diverSity 

K. KuMAr 1 

1 Max-Planck-Institute for molecular Physiology, Chemical 

Biology, Dortmund, Germany 

Compound collections designed on the basis core scaffolds 

of of natural products or the privileged motifs are expected to be 

enriched in biochemical and biological activity. This calls for 

developing efficient chemical transformations wherein further 

molecular complexity (ring-structures and sp3 character) and 

diversity (functional groups and carbo- and heterocyclic rings) 

can be generated around these core-structures and which should 

be amenable to compound collection format. [1] Cascade or domino 

reaction sequences can rapidly built up molecular complexity and 

thus could prove highly useful in synthesis of focused compound 

libraries based on natural products core structures. [2] We have 

successfully developed new cascade reaction sequences leading 

to compound collections around benzopyrone, indoloisoquinoline 

and indoloquinolizine core structures of natural products. This 

presentation will summarize the implementation of different 

modes of catalysis i.e. organo-, nucleophilic and Bronsted acid 

and coinage metal catalysis to facilitate diverse cascade reactions 

that transform the easily available substrates into the desired 

complex natural product inspired compounds. A glimpse into how 

such molecules help understand complex biological phenomenon [3] 

and how the ring-diversity translates into functional-diversity shall 

also be presented. 

references: 

1. K. Kumar, H. Waldmann, Angew. Chem. Int. Ed. 2009 48, 

3224. 

2. B. Baskar, P.-Y. Dakas, K. Kumar Org. Lett. 2011, 13, 

1988. 

3. H. Dückert, V. Pries, V. Khedkar, S. Menninger, H. Bruss, 

A. W. Bird, Z. Maliga, A. Brockmeyer, P. Janning, 

A. Hyman, S. Grimme, M. Schürmann, H. Preut, K. 

Hübel, S. Ziegler, K. Kumar, H. Waldmann Nature Chem. 

Biol. 2012, 8, 179. 

Keywords: Alkaloids; Annulation; Domino reactions; 

Molecular diversity; Natural products; 


frontiers and Advances of organic Chemistry – iii 

o - 4 9 5 

SynthetiC SuPrAMoLeCuLAr SySteMS At 

worK 

S. MAtiLe 1 

1 University of Geneva, Department of Organic Chemistry, 


This lecture will summarize recent progress with design, 

synthesis and evaluation of functional supramolecular systems. 

The unifying theme is transport, topics of interest include the 

transport of electrons and holes in photosystems, the transport of 

anions and cations across lipid bilayers, and the transport of larger 

molecules for sensing applications and cellular uptake. 

To create oriented photosystems, we will have to learn how 

to build with high precision directly on surfaces. To contribute 

new solutions for this old problem, zipper assembly has been 

introduced first. Combining LBL with stick-end technology, 

zipper assembly has afforded double-channel architectures with 

oriented antiparallel redox gradients. Looking for more 

user-friendly alternatives, self-organizing surface-initiated 

polymerization (SOSIP) has been developed next. This method 

uses ring-opening disulfide exchange polymerization from 

templating initiators on the surface. Hard to get but easy to use, 

SOSIP is now being applied to topics such as templated 

self-sorting for the transcription of 2D information into 

3D architectures. Moreover, stack exchange has been introduced 

to drill big holes into SOSIP architectures and build multi - 

channel systems with multicomponent gradients, ultimately 

composed of naphthalenediimides, perylenediimides, squaraines, 

phthalocyanines, porphyrins and fullerenes. 

As far as the transport of ions in lipid bilayers is concerned, 

current interest focuses on the expansion our repertoire of 

established interactions we have in hand to create function. 

Examples include anion-macrodiple interactions, anion-π 

interactions, and halogen bonds. To proof the functional relevance 

of these less common interactions beyond any doubt, the size of 

the transporters had to be reduced to an absolute minimum. 

Driven to the extreme, this reductionism resulted in the 

first example of clean, leakage-free, cooperative, highly 

voltage-dependent and highly anion selective transport with the 

smallest possible organic transporter, a molecule with one single 

carbon only, and a boiling point of -22 ºC. 

Keywords: photosystems; ion transport; surface-initiated 

polymerization; templated self-sorting; halogen bonds; 



s805 

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o - 4 9 6 

PreCiouS MetAL doPed zeoLiteS in 

environMentAL CAtALySiS 

f. KLoSe 1 , o. MAnoyLovA 1 , A. tiSSLer 1 

1 Clariant/SüdChemie, Germany 

Precious metal exchanged zeolites can be used for various 

environmental applications allowing the reduction off necessary 

precious metal doping in comparison to conventional combustion 

catalysts. A typical example is the use of Pt and Pd exchanged 

zeolites for stationary VOC combustion. The main feature of 

zeolite based catalysts is the possibility to incorporate the precious 

metals into the pores and cavities of the zeolite framework. This 

will hinder the precious metal clusters to grow up resulting in a 

decreased catalytic activity. 

However, the capability of the zeolite cavities to take up 

precious metal species is limited. The excess of precious metals 

which are then deposited on the outer crystallite surface can 

undergo rapid sintering during exposure of the catalyst to elevated 

temperatures. For effective incorporation of precious metals into 

zeolites, the kind of precursor applied and calcination conditions 

are of significant relevance. To discriminate between “internal” 

and “external” precious metal clusters, infrared spectroscopy with 

application of sensor molecules and selective poisoning 

techniques can be applied. 



o - 4 9 7 

doPed Pi-ConJuGAted orGAniC eMitterS: 

SyntheSiS, ProPertieS And SuPrAMoLeCuLAr 

orGAnizAtion 

d. BonifAzi 1 

1 University of Namur (FUNDP), Namur Research College 

(NARC), Namur, Belgium 

The development of organic-based polymers and of their 

hybrid derivatives paves the way towards materials with a 

continuously tunable energy gap from the IR to the deep UV. 

Specifically, there is a growing demand for light-emitting devices 

(LEDs) in the deep UV region, for a variety of applications where 

high photon energy is necessary for either processing or 

sensing/characterisation purposes (UV lamps for photodynamic 

therapy, water sterilization systems, “solar-blind” photodetectors, 

to name a few). A possible engineering strategy meeting these 

requirements would be to tune the electronic properties of the 

material by combining molecules with a similar carbon-based 

structures replacing every pair of carbon atoms rings by boron 

and nitrogen atoms. In this respect, borazine rings (Stock in 1926) 

are good candidates. However, the sensitivity toward water has 

hampered their exploitation in current technologies. In this report, 

we will describe the synthetic efforts toward the synthesis of 

water-stable borazine derivatives. Fluorescence studies in solution 

and at the solid state showed the presence of a strong UV-emission 

band in the UV region. The synthesis of unprecedent 

unsymmetrical borazine derivatives and borazene linear modules 

will be shown as well as their organization on surfaces. 

Novel H-bonding interactions involving boronic acids will be also 

discussed showing their potentials as alternative molecular 

synthones in molecular recognitions. 

Keywords: Boron; Hydrogen bonds; Donor acceptor systems; 

Self-assembly; Supramolecular Chemistry; 



s806 

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o - 4 9 8 

hiGhLy diSPerSed PALLAdiuM nAnoPArtiCLeS 

on MeSoCeLLuLAr foAM: An effiCient And 

reCyCLABLe heteroGeneouS CAtALySt for 

ALCohoL oxidAtion 

o. verho 1 , e. JohnSton 1 , M. KärKäS 1 , 

M. ShAKeri 1 , C. w. tAi 2 , P. PALMGren 3 , 

K. eriKSSon 1 , S. oSCArSSon 1 , J. e. BäCKvALL 1 

1 Stockholm University, Organic Chemistry, Stockholm, Sweden 

2 Stockholm University, Materials and Environmental 

Chemistry, Stockholm, Sweden 

3 Uppsala University, Physics and Astronomy, Uppsala, Sweden 

Oxidation reactions are of fundamental importance in 

nature, and they are key transformations in organic synthesis. 

During the past decades, a large number of oxidation methods 

have been developed. Despite the development, traditional 

oxidation methods employing stoichiometric amounts of 

high-valent metal reagents are still commonly used in the 

production of a large number of organic compounds. These 

oxidations lead to large amounts of toxic metal waste and 

therefore it exists a considerable need for the development of new 

and more efficient catalytic oxidation methods in industrial 

chemistry. To meet the needs of high efficiency and 

“green chemistry”, processes that employ transition metals as 

substrate-selective catalysts and use environmentally friendly and 

cheap oxidants, such as molecular oxygen, have consequently 

emerged as a topic of major research. In these oxidations the 

substrate is oxidized and molecular oxygen is converted to water. 

The catalyst is essential since direct oxidation of organic 

substrates by molecular oxygen is associated with high energy 

barriers of electron transfer. 

We have recently developed a heterogenous catalyst 

consisting of palladium nanoparticles immobilized on siliceous 

mesocellular foam and it has been shown to be able to efficiently 

catalyze the oxidation of a wide scope of primary and secondary 

alcohols, using molecular oxygen as terminal oxidant. 

Furthermore, the catalyst displayed excellent recyclability and 

negligible leaching, which are two important factors to consider 

when applying a catalyst in industrial and pharmaceutical 

applications. 

Keywords: Oxidation; Heterogeneous Catalysis; Green 

Chemistry; Alcohols; Nanoparticles; 



o - 4 9 9 

MetAL-CAtALyzed CASCAde reACtionS of 

ALKyneS: uSefuL ProtoCoLS for SyntheSiS 

of PoLyCyCLiC AroMAtiC hydroCArBonS 

And oLiGoeneS 

y. t. wu 1 

1 National Cheng Kung University, Department of Chemistry, 

Tainan, Taiwan 

Metal-catalyzed reactions for carbon-carbon bond formation 

are the focus of extensive research in organic synthesis. These 

reactions are useful tools for constructing a variety of valuable 

and important products. Unsaturated substrates, such as alkenes, 

alkynes, and others, are suitable for use in these reactions because 

they easily form π-complexes, and subsequently undergo 

migratory insertion from their coordination sphere. This 

phenomenon makes the reaction very efficient, even under mild 

conditions. Recently, my coworkers and I have successfully 

developed several synthetic methods for preparing numerous 

polycyclic aromatic hydrocarbons and oligoenens, including 8,8a- 

-dihydro-cyclopenta[a]indenes, [1] cyclopenta[def]phenanthrenes, [2] 

zethrenes, [3] pyrroloarenes, [4] benzo[k]fluoranthene-based linear 

acenes, [5] phenanthroindolizidine alkaloids, [6] highly curved 

buckybowls [7] and octatetraenes. [8] Most of these compounds 

exhibit interesting physical properties, and can be applied to 

organic materials. For example, benzo[k]fluoranthene-based 

linear acenes display strong blue photoluminescence, and are used 

for efficient deep blue organic light-emitting devices. [9] In 

addition, phenanthroindolizidine alkaloids have strong antitumor 

effects. 

references: 

1. Angew. Chem. Int. Ed. 2008, 47, 9891; Chem. Eur. J. 2011, 

17, 7220. 

2. Adv. Synth. Catal. 2010, 352, 3267. 

3. Angew. Chem. Int. Ed. 2010, 49, 7059. 

4. Chem. Eur. J. 2011, 17, 1930. 

5. Chem. Eur. J. 2010, 16, 5909. 

6. Adv. Synth. Catal. 2011, 353, 1756. 

7. J. Am. Chem. Soc. 2011, 133, 16319; Chem. Commun. 

2010, 7241. 

8. Org. Lett. 2011, 13, 4794. 

9. J. Mater. Chem. 2012, 22, Advance Article. 

Keywords: Alkyne; Palladium; Polycyclic Aromatic 

Hydrocarbon; Oligoene; 



s807 

chem. Listy 106, s587–s1425 (2012) 

Physical, theoretical and Computational Chemistry 

Novel Materials – i 

o - 0 9 6 

Pi-SiGMA* StAteS in the PhotoCheMiStry of 

heteroAroMAtiC MoLeCuLeS 

M. AShfoLd 1 



Imidazoles, pyrroles and phenols are key components of the 

long wavelength chromophores in nucleobases and aromatic 

amino-acids like histidine, tryptophan and tyrosine, which 

dominate the UV absorption spectra of many biological 

molecules. π*-π transitions are responsible for these strong UV 

absorptions, but such heteroaromatic molecules also possess 

excited states formed via σ*-π electron promotions. The latter 

excitations have much smaller absorption cross-sections, and have 

only recently started to attract much detailed attention. High 

resolution photofragment translational spectroscopy methods and 

complementary ab initio theory have been used to study H atom 

loss processes following UV photo-excitation of a progressively 

more complex range of such heteroaromatics in the gas phase. [1] 

These studies: 

(i) demonstrate that heteroatom–H bond fission following 

direct excitation to the 11πσ* state or, in phenols, by 

tunneling under the conical intersection between the 

11ππ* and 11πσ* potential energy surfaces, can be an 

important non-radiative decay process in such 

molecules, 

(ii) show that the radical co-fragments are formed in a very 

limited sub-set of the vibrational states that are 

accessible, energetically. Identification of these product 

states provides detailed insights into the non-adiabatic 

couplings that enable the evolution from parent 

molecule to eventual fragments, and 

(iii) open the way to studies of analogous fragmentation 

processes in solution – in collaboration with the group 

of Professor Steve Bradforth at the University of 

Southern California. [2] 

references: 

1. M.N.R. Ashfold, A.L. Devine, R.N. Dixon, G.A. King, 

M.G.D. Nix, T.A.A. Oliver, Proc. Nat. Acad. Sci. 2008, 

105, 12701. 

2. T.A.A. Oliver, Y. Zhang, M.N.R. Ashfold and S.E. Bradforth, 

Farad Disc. 2011, 150, 439. 



o - 0 9 7 

ConforMAtionAL effeCtS in SuGAr ionS: 

SPeCtroSCoPiC inveStiGAtionS of the 

ProtonAted ALPhA And BetA AnoMerS of 

d-xyLoPyrAnoSyL iMidAzoLiuM in the GAS 

PhASe And in SoLution 

S. rudiC 1, 2, 3 , r. SAGAr 2 , d. P. GAMBLin 2 , 

e. M. SCAnLAn 2 , t. d. vAden 3 , B. odeLL 2 , 

t. d. w. CLAridGe 2 , J. P. SiMonS 3 , B. G. dAviS 2 

1 Rutherford Appleton Laboratory STFC, ISIS Facility, Didcot, 


2 University of Oxford, Chemistry Research Laboratory 

Department of Chemistry, Oxford, United Kingdom 

3 University of Oxford, Physical and Theoretical Chemistry 

Laboratory Department of Chemistry, Oxford, United 

Kingdom 

We present direct investigations of the conformational 

preferences of sugars with a positively charged substituent at their 

anomeric centre, C-1, which display in solution, a preference for 

an equatorial conformation - an apparent reversal of the normal 

anomeric effect. The investigations focus on the protonated 

monosaccharide, D-xylopyranosyl imidazolium in its α and β 

forms, first probed in a range of different solvents through NMR 

measurements and then in the gas phase, i.e. free of solvent or 

counterion interactions which may have clouded or even 

overwhelmed the normal anomeric effect. The sugar ions in the 

gas phase were generated at a temperature ~300-350 K and were 

subsequently probed through mass selected infrared multiphoton 

dissociation spectroscopy. The results, when compared and 

discussed in the light of density functional theory, ab initio and 

natural bond orbital calculations, expose the possible origins of 

the reversed conformational preference and provide a better 

understanding of the factors controlling conformational choice. 

Keywords: conformational effects; sugars; spectroscopy; gas 

phase; biomolecules; 



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o - 0 9 8 

CAtALytiC StudieS of feS towArdS AMMoniA 

2 

SyntheSiS under AMBient ConditionS 

i. teMPrAno 1 , t. Liu 1 , S. JenKinS 1 , S. driver 1 , 

d. KinG 1 

1 University of Cambridge, Chemistry, Cambridge, 


The synthesis of ammonia over an iron catalyst, via the 

Haber-Bosch process, is one of the most important large-scale 

industrial reactions underlying the modern global economy. 

Essential for the manufacture of artificial fertilisers, this single 

process is reckoned to be responsible for feeding up to one sixth 

of the world population. On the other hand, such high 

temperatures and pressures are necessary to achieve economic 

performance that the Haber-Bosch process alone is thought to 

consume up to one percent of all man-made energy production. [1] 

At this scale, even a marginal improvement in efficiency would 

imply enormous environmental benefits, not to mention inevitable 

economic rewards. Of all the industrial processes, ammonia 

synthesis is arguably the instance for which tuning catalytic 

efficiency is most urgently required. 

In nature, by way of contrast to the Haber-Bosch process, 

the enzyme nitrogenase achieves much the same end under 

ambient conditions. Efforts of protein crystallography have 

gradually unveiled that the active sites of nitrogenase are 

composed of three distinct FeS nanoclusters which cooperatively 

x 

accomplish the electron transfer and the N reduction processes. [2, 3] 

2 

In the light of the above understanding, we are investigating 

NH -related reactions on Iron sulfide surfaces. In the presentation, 

3 

we will discuss the surface chemistry of N , H and NH on a 

2 2 3 

pyrite single crystal surface. The gas-surface interactions are 

investigated by a combination of spatially averaging and localized 

surface science techniques to ascertain whether NH synthesis is 

3 

favourable iron sulphide, with a view to establishing their 

corresponding reaction mechanisms. 

references: 

1. Schlögl, R. Angewandte Chemie International Edition 

2003, 42, 2004. 

2. Howard, J. B.; Rees, D. C. Proceedings of the National 

Academy of Sciences 2006, 103, 17088. 

3. Einsle, O.; Tezcan, F. A.; Andrade, S. L. A.; Schmid, B.; 

Yoshida, M.; Howard, J. B.; Rees, D. C. Science 2002, 

297, 1696. 

Keywords: Ammonia synthesis; Iron sulphide; Surface science; 



o - 0 9 9 

uv PhotodiSSoCiAtion dynAMiCS of 

thioAniSoLeS: the effeCt of SuBStitution 

d. K. zAouriS 1 , A. M. wenGe 1 , t. n. v. KArSiLi 1 , 

S. J. hArriS 1 , M. CottereLL 1 , M. n. r. AShfoLd 1 



In this work, both experimental and theoretical, results from 

the UV photodissociation of thioanisole [1] in the gas phase are 

reported. The effect of substitution on the dynamics of the 

photodissociation has also been studied, by introducing a methyl 

(CH ) group, as a substituent, in para- position. The dissociation 

3 

has been studied using Velocity Map Imaging (VMI) technique 

and detecting the produced, after the S-CH bond fission, methyl 

3 

fragments in their ground vibrational state (v = 0). Both velocity 

and angular information are presented. The experimental results 

are accompanied by high accuracy ab initio calculations, which 

give the shape of the Potential Energy Cuts (PECs) of the ground 

and the first two excited electronic states, along the S-CH3 coordinate. Such gas phase studies are an essential precursor to 

on-going ultrafast pump-probe investigations of the 

photochemistry of these molecules in solution. 

references: 

1. J.S. Lim and S.K. Kim, Nature Chemistry 2, 627 (2010). 

Keywords: Photochemistry; Ab initio calculations; Substituent 

effects; UV/Vis spectroscopy; Laser spectroscopy; 



s809 

chem. Listy 106, s587–s1425 (2012) 


Novel Materials – ii 

o - 1 0 0 

the hyBrid LAnGMuir-SChAefer dePoSition 

– A new BottoM-uP APProACh to CreAte Low 

diMenSionAL funCtionAL nAnoStruCtureS 

P. rudoLf 1 

1 University of Groningen, Zernike Institute for Advanced 

Materials, Groningen, Netherlands 

In recent years, low-dimensional assemblies have assumed 

remarkable importance due to their outstanding physical, chemical 

and biological properties which make them attractive for 

photophysical and electrical applications as well as for catalysis, 

molecular separation, drug delivery and biosensing. Controlling 

both the organization of the assemblies and their properties 

through simple external parameters led to the creation of new 

tailored functional materials. 

An easy method to produce such materials with excellent of 

control combines self-assembly and Langmuir-Blodgett assembly. 

I shall demonstrate how this method allows the assembly of 

hybrid materials based on the fact that graphene oxide or clay 

nanosheets act as 2D template for reaction or grafting of a variety 

of guest species (in our case: C , Ni molecular magnets, Prussian 

60 8 

Blue analogues, metal nanoparticles). Prefect layer-by-layer 

growth and control at the molecular level allow one create entirely 

novel architectures whose final structure is encoded in the shape 

and properties of the clusters or molecules that are used. 

Interesting new properties emerge: for example 2D or 0D Prussian 

Blue analogue structures can be formed, which differently from 

3D crystals, show new superparamagnetic-spin glass properties 

with high blocking glass temperature. The versatility of the 

approach will be illustrated also in the case of grapheme 

oxide – metal nanoparticle assemblies where one can choose to 

either synthesize the nanoparticles in situ or graft already formed 

nanoparticles on the sheets obtaining materials with different 

magnetic properties. 

Keywords: Self-assembly; Clays; Graphene; Langmuir- 

Blodgett films; Materials Science; 



o - 1 0 1 

theoretiCAL SeArCh for environMentALLy 

friendLy fire extinGuiShinG SuBStAnCeS 

v. KuKuevA 1 

1 Academy of Fire Safety, Combustion Chemistry, Cherkassy, 

Ukraine 

Since the advent of the Montreal Protocol in the 1990, which 

banned the manufacture of a variety of halogenated compounds 

including the fire suppressant CF Br (because of ozone depletion 

3 

action), there has been a strong interest in development of new 

chemically active fire suppressants. One of the classes of 

compounds, that are under consideration are phosphorus-based 

agents, such as DMMP (dimethyl methylphosphonate), TMP 

(trimethylphosphate) and others. Extinction measurements on 

non-premixed, atmospheric-pressure flames have demonstrated 

DMMP to be a highly effective suppressant (2-4 times more 

effective than CF Br). 3 [1] The mechanism for phosphorus-based 

inhibition is believed to be catalytic recombination of flame 

radicals (H ? , O ?? , OH ? ) by phosphorus-containing radicals [2, 3] 

formed following the decomposition of parent compounds. [2, 4] The 

influence of phosphorus-containing compounds (PCCs) on radical 

concentrations in flames has been demonstrated experimentally, 

but there are still some not properly understood details of 

inhibition mechanisms. The ab initio quantum-chemical 

calculations in the 6-31G** basis set of the destruction ways of 

phosphorus-containing fire suppressant compounds as well as the 

interaction energy of destruction products with flame radicals 

have been provided to investigate the inhibition mechanisms. 

It was shown, that the inhibition action could be done by 

molecules of DMMP and TMP but much more extend by the 

destruction products: HOPO , HOPO, PO and PO. This results 

2 2 

are in good agreement with experimental papers. [3, 4] 

references: 

1. MacDonald, M. A., Gouldin, F. C., Fisher, E. M., 

Temperature Dependence of Phosphorus-based flame 

inhibition., Combust. Flame 125: 668–683 (2001). 

2. Hastie, J. W., and Bonnell, D. W., Molecular Chemistry of 

Inhibited Combustion Systems, National Bureau of 

Standards, Final NBSIR 80-2169; PB81–170375, 1980. 

3. Twarowski, A., Combust. Flame 94:91–107 (1993). 

4. Korobeinichev, O. P., Il’in, S. B., and Mokrushin, V. V., 

Combust. Sci. Technol. 116–117:51–67 (1996). 

Keywords: quntum-chemical calculation; flame radicals; fire 

extinguishing substances; 



s810 

chem. Listy 106, s587–s1425 (2012) 



o - 1 0 2 

infLuenCe of SuPPort ConfineMent on ioniC 

Liquid CryStAL BASed CAtALyStS 

B. MorAin 1 , M. SoBotA 1 , x. wAnG 2 , f. KohLer 3 , 

B. MeLCher 3 , P. wASSerSCheid 3 , K. Meyer 2 , 

M. LAurin 1 , J. LiBudA 1 

1 Universitaet Erlangen Nürnberg, Lehrstuhl für Physikalische 

Chemie II, Erlangen, Germany 

2 Universitaet Erlangen Nürnberg, Lehrstuhl für Anorganische 

und Allgemeine Chemie, Erlangen, Germany 

3 Universitaet Erlangen Nürnberg, Lehrstuhl für Chemische 

Reaktionstechnik, Erlangen, Germany 

Thermodynamic and physical properties of liquid crystalline 

systems are modified by confinement in volumes of mesoscopic 

dimensions. Ionic Liquids (ILs) are molten salts with melting 

point below 100 °C. They have a liquid crystalline behaviour 

(ILC) when containing long alkyl chains. We aim at understanding 

the influence of confinement on transition metal catalysts 

dissolved in ILCs into porous supports, for the resulting ordered 

mesophase should lead to increased catalytic selectivity. These 

IL-based systems are called “Supported Ionic Liquid Phase” 

(SILP) catalysts. In a first step, different loadings of the ILCs 

1-octadecyl- and 1-hexadecyl-3-methylimidazolium trifluorosulfate 

[C C Im][OTf] and [C C Im][OTf] confined in increasing 

18 1 16 1 

support pore sizes are studied using Differential Scanning 

Calorimetry (DSC) and Diffuse Reflectance IR Fourier Transform 

Spectroscopy (DRIFTS). The results reveal an influence of the 

confinement on the smectic-to-liquid phase transition and the 

existence of a contact layer in the order of 2 nm thickness. The 

latter shows a single glass transition at temperatures 30 K lower 

than that of the bulk. [1] In a second step, Ni-based and Rh-based 

complexes are dissolved in the ILC 1,3-didodecylimidazolium 

tetrafluoroborate [C C Im][BF ], and in [C C Im][OTf] 

12 12 4 18 1 

respectively. Investigations on these systems using IR Reflection 

Absorption Spectroscopy (IRAS) on extended surfaces and 

DRIFTS on powders show retained liquid crystalline transitions 

for a ratio from 1 to 10 wt%. [2] This behaviour remains while 

measuring operando during the hydroformylation of olefins, thus 

permitting to measure the influence of the phase transition on the 

catalytic selectivity. 

references: 

1. Morain et al, ChemPhysChem, 2011, 12, 3539-3546. 

2. Wang et al, J.Mater.Chem, 2012, 22, 1893. 

Keywords: confinement; infrared; operando; ionic liquid; 

transition metal; 

Biointerface and Colloids 


o - 1 0 3 

inorGAniC routeS to SeLf-ASSeMBLed 

CoMPLex ShAPeS 

J. M. GArCiA-ruiz 1 

1 Instituto Andaluz de Ciencias de la Tierra, Laboratorio de 

Estudios Cristalográficos, Armilla Granada, Spain 

The morphology of crystals is controlled by their growth 

environment and crystal structure. But above all, structural control 

restricts the symmetry of any crystal shape to one of the 

32 point-symmetry groups (35 when quasicrystals are 

considered). Crystal structure also imposes discrete angles 

between faces and discards the possibility of continuous 

curvature. To break this constriction, life has developed several 

strategies to built crystalline complex morphologies with 

continuous curvature but hierarchical textural organization. The 

formation of such architectures is usually directed by organic 

molecules or matrices and it is thought they are privative of life 

and distinguish biogenic shapes from their inanimate, mostly 

euhedral counterparts. I will review in this communication the 

existence of chemical routes to complex shapes with continuous 

curvature made of purely inorganic materials. One of them, called 

silica biomorphs, are simply made by precipitation of 

alkaline-earth carbonates in silica-rich media. Thus, aggregates 

of highly oriented carbonate nanocrystals can be obtained, which 

display striking non-crystallographic morphologies that mimic 

primitive life forms. [1] These precipitates are made of millions of 

nanocrystals that self-assemble expanding the symmetry of the 

crystalline phase 2/m 2/m 2/m forming first fractal aggregates, 

then two-dimensional lamellae and finally three-dimensional 

morphologies with non-crystallographic symmetry. I will present 

the details of the morphogenesis of these materials at a 

phenomenological level [2, 3] and will propose a plausible physicochemical 

explication based on coupling of silica-carbonate 

precipitation. Finally, I will comment the advances in the 

formation of silica gardens, [4] a second type of inorganic route to 

materials with complex shapes. 

references: 

1. J.M. García-Ruiz, et al., Science 302 (2003) 1194-1197. 

2. J. M. García-Ruiz, et al., Science 323 (2009) 362-365. 

3. M. Kellermeier, et al, Chemistry A European Journal, 18 

(2012) 2272 –2282. 

4. F. Glaab et al., Angewandte Chemie, (2012) in press 

Keywords: Self-assembly; Nanoparticles; crystal growth; 

Biomimetic synthesis; Bioinorganic chemistry; 



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o - 1 0 4 

hoMotAurine nitroSAtion: A KinetiC Study 

J. ArenAS-vALGAnón 1 , M. GonzáLez-JiMénez 1 , 

i. f. CéSPedeS-CAMACho 1 , e. CALLe 1 , J. CASAdo 1 

1 Facultad de Ciencias Químicas, Química Física, Salamanca, 

Spain 

Homotaurine (3-aminopropanesulfonic acid) is a taurine 

analogue present in red alga (Ito, K et al. Hiroshima Daigaku 

Suichikusangakubu Kiyo 1977, 16, 77). In spite of being rejected 

in the treatment of Alzheimer’s disease, in some countries it is 

actually a nutraceutical used as a memory protector (Swanoski, 

M. T. Am. J. Health Syst. Pharm. 2009, 66, 1950). Due to its 

similarity to taurine, homotaurine is expected to react with nitrite 

(widely present in meat as an antibotulinic agent) in the conditions 

of the stomach lumen. 

The nitrosation of taurine affords an unstable sultone as an 

intermediate product (Arenas-Valganón, J. et al. Food Chem. 

2012, 134, 986) and since some sultones are “possibly 

carcinogens for human” (IARC, IARC monograph 71 1999), the 

study of the nitrosation of homotaurine is of interest. 

The nitrosation reaction of homotaurine was studied by 

measuring the variation in absorbance of the nitrosation mixtures 

at λ=371 nm. Nitrosation mixtures were made by the addition of 

0.1 ml of nitrite solution to 3 ml of an acidic solution of 

homotaurine contained in a cuvette. The initial rate method was 

used. 

The experimental rate equation observed for nitrosation of 

taurine was: 

The order with respect to the initial concentrations of 

reagents was studied, as well as the influence of temperature and 

ionic strength on k . A strong dependence on pH was observed, 

obs 

a maximum value for k being observed at pH ≈ 3.3. 

obs 

The results have led us to propose a mechanism of 

nitrosation by N O in which the reaction is controlled by a 

2 3 

diffusion process, as in taurine nitrosation. 

Acknowledgement: The authors thank the Spanish 

Ministerio de Ciencia e Innovación and FEDER Fund 

(Project CTQ2010-18999). J.A.V thanks Junta de Castilla y 

León for a Ph. D. grant. 

Keywords: homotaurine; nitrite; nirosation; kinetics; 



o - 1 0 5 

deteCtion of ChAin BACKfoLdinG in 

SiMuLAtion of dnA in nAnofLuidiC ChAnneLS 

t. BLehA 1 , P. CifrA 1 

1 Polymer Institute SAS, Bratislava, Slovak Republic 

With recent nanotechnology advances single DNA 

molecules can be manipulated and analyzed in new ways. 

Stretching of double-stranded (ds)DNA in nanofabricated 

channels has emerged as an innovative technique for the fragment 

length analysis and genome mapping. Molecular simulations 

combined with the theories of polymer confinement expand our 

understanding of single molecule experiments. Since the channel 

dimensions used in measurements (~ 100 nm) much exceed the 

DNA chain diameter, the confined DNA chains involve various 

folds of chain on itself, loops and knots. 

In series of papers we have earlier employed Monte Carlo 

simulations based on a discrete worm-like chain model to 

compute the chain extension R of DNA as a function of channel 

dimension. (e.g. J. Phys. Chem. B, 2009,113,1843). In this report 

simulations are used to estimate the amount of backfolding in 

DNA confined in nanochannels. Since folded structures are much 

shorter than the straight forms, they tend to significantly reduce 

the equilibrium extension R. The individual folding-unfolding 

events can be identified in MC traces. 

Simulations revealed that the amount of folded structures 

(hairpins) in channel-confined DNA molecules can be 

considerable. At the DNA ends an extensive folding (mainly as 

the J-type hairpins) is detected in narrow and moderate channel 

widths representing progressively the Odijk, transition and blob 

regimes from the polymer confinement theories. In contrast, in 

DNA internal segments the folding into the Z-type hairpins is 

substantial only at moderate channel widths in the blob regime; 

such a folding is limited in the transition region and practically 

absent in narrow channels in the Odijk regime. The importance 

of accounting for the local folding in interpretation of the DNA 

experiments in nanochannels is pointed out. 

Keywords: Computational chemistry; DNA; Molecular 

modeling; 



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o - 1 0 6 

new KinetiC StudieS of the nitroSAtion of 

CoMPLex MoLeCuLeS 

M. GonzALez JiMenez 1 , J. ArenAS-vALGAnón 1 , 

i. f. CéSPedeS-CAMACho 1 , e. CALLe 1 , J. CASAdo 1 

1 Facultad de Ciencias Químicas, Química Física, Salamanca, 

Spain 

The report by Magee and Barnes (Magee, P. N.; Barnes, 

J. M. Br. J. Cancer. 1956, 10, 114) that dimethylnitrosamine 

induces liver cancer when fed to rats prompted the study of the 

Chemistry and Biology of nitroso compounds. Since then, 

biologists have mainly been interested in the use of these 

compounds as models for producing a broad range of cancers, 

whereas chemists are more interested first in the mechanisms of 

formation of nitroso compounds and then in blocking or inhibiting 

the mechanisms of these species (Lijinsky, W. (Chemistry and 

Biology of N-nitroso compounds, Cambridge Univ. Press., 

Cambridge, 1992). 

While N-nitrosation reactions are well known, the 

mechanism for generating C-and O-nitroso compounds are 

subject to discussion, especially when a molecule has several 

competing potentially nitrosatable groups (Williams, D. L. H., 

Nitrosation reactions and the chemistry of nitric oxide, Elsevier, 

Amsterdam, 2004; González Jiménez, M. et al., Org. Biomol. 

Chem. 2011, 9, 7680). 

In this work, the nitrosation mechanisms of ethylbenzene, 

2-phenethylamine and tyramine (2-(4-hydroxyphenyl)ethylamine) 

in perchloric aqueous solutions of sodium nitrite were 

investigated. The mechanisms for the reactions of N-nitrosation 

and aromatic C-nitrosation are proposed and discussed. The 

activation of the aromatic ring and the basicity of the substrate 

proved to be crucial factors in the rate of the C-nitrosation 

reaction, which was sometimes faster than that of N-nitrosation. 

Nitrosation reactions were followed kinetically by 

UV-visible spectrography, measuring the absorbance of the 

reaction products with a spectrophotometer equipped with a 

thermoelectric six-cell holder temperature-control system 

(± 0.1 ºC). 

Acknowledgments: The authors thank the Spanish Ministerio 

de Ciencia e Innovación and the European Regional 

Development Funds (Project CTQ2010-18999) for supporting 

the research reported in this article. M.G.-J. and J.A.-V. thank 

the Spanish Ministerio de Economía y Competitividad for a 

PhD Grant. 

Keywords: kinetics; nitrosation; catecholamines; tyramine; 



o - 1 0 7 

Low-teMPerAture, SoLid-StAte nMr of the 

v49A BACteriorhodoPSin MutAnt 

v. L. Mooney 1 , M. n. SAndBerG 2 , S. SenGuPtA 1 , 

e. A. fry 1 , n. L. wAGner 2 , r. r. BirGe 2 , K. w. ziLM 1 

1 Yale University, Chemistry, New Haven CT, USA 

2 University of Connecticut, Chemistry, Storrs CT, USA 

Bacteriorhodopsin is a proton pump which activates when 

absorption of a photon causes isomerization of the all-trans retinal 

ligand present in the protein’s binding pocket. The V49A mutant 

changes the retinal binding pocket, resulting in alterations in the 

retinal isomer composition and in the kinetics of the protein’s 

photoactivation mechanism. It has also been suggested that the 

V49A mutation disrupts the interaction between the retinal-K216 

protonated Schiff base and its counterion, D85. For these reasons, 

we chose to investigate the retinal environment in the V49A 

mutant using solid-state NMR. After acquiring 1D and 

2D 13C spectra of the dark-adapted bacteriorhodopsin mutant 

possessing a retinal ligand labeled at positions C8-C15, C19 and 

C20, we were able to assign many of the peaks due to labeled 

carbons. We found that both all-trans and 13-cis retinal isomers 

are present and that some of the labeled carbons chemical shifts 

differ from those previously seen in wild-type bacteriorhodopsin. 

Our results thus far indicate that the environments of certain 

carbons along the retinal chain in the V49A bacteriorhodopsin 

mutant are significantly different from those in wild-type 

bacteriorhodopsin. Experiments are currently underway to resolve 

the identities and chemical shifts of overlapping peaks. This data 

should provide insight into the interaction of the protonated Schiff 

base and the D85 counterion in the V49A mutant and also the 

changes in the retinal isomer composition. In addition, the 

sensitivities of our 1D and 2D spectra are such that we are now 

able to investigate other bacteriorhodopsin mutants’ retinal 

environments. 

Keywords: NMR spectroscopy; Schiff bases; Chromophores; 

Membrane proteins; 



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theoretical Chemisry – i 

o - 2 3 2 

reCent exAMPLeS on reLAtiviStiC effeCtS in 

CheMiStry 

P. PyyKKo 1 

1 University of Helsinki, Department of Chemistry, Helsinki, 

Finland 

Relativistic effects often explain the special properties of 

6th-Period elements (Cs-Rn), as compared to their 5th-Period analogues (Rb-Xe). It was recently shown using solid-state 

calculations that about 80% of the voltage of the lead-acid battery 

come from relativistic effects. [1] Cars start due to relativity. For the 

mercury battery, the corresponding contribution is about 30 %. [2] 

The form of the periodic table up to Z = 172 was recently 

reconsidered using average-of-configuration Dirac-Fock 

calculations on atoms and ions. [3] The last valence electron left 

upon ionisation was used to classify the chemical group to which 

the element should be assigned. Two recent reviews have been 

compiled, one on the fundamental, mainly QED aspects [4] and 

another on chemical properties, influenced by relativity. [5] As 

discussed there, more information is now available on spin-orbit 

(SO) effects in structural chemistry. The relativistic origin of the 

yellow colour of gold is now confirmed. The use of quantum 

chemistry to predict new, simple inorganic species was also 

reviewed. [6] 

references: 

1. R. Ahuja, A. Blomqvist, P. Larsson, P. Pyykkö and 

P. Zaleski-Ejgierd, Phys. Rev. Lett. 106 (2011) 018301. 

2. P. Zaleski-Ejgierd and P. Pyykkö, Phys. Chem. Chem. 

Phys. {\bf 13} (2011) 16510. 

3. P. Pyykkö, Phys. Chem. Chem. Phys. 13 (2011) 161. 

4. P. Pyykkö, Chem. Rev. 112 (2012) 371. 

5. P. Pyykkö, Ann. Rev. Phys. Chem. 63 (2012) 000. 

6. P. Pyykkö, Phys. Chem. Chem. Phys., Advance Article 1 

February 2012, DOI: 10.1039/c2cp24003c. 

Keywords: Relativistic effects; heavy-element chemistry; Gold; 

lead; quantum chemistry; 



o - 2 3 3 

why Are the interACtion enerGieS of 

ChArGe-trAnSfer CoMPLexeS ChALLenGinG 

for dft? 

S. SteinMAnn 1 , C. PieMonteSi 1 , A. deLAChAt 1 , 

C. CorMinBoeuf 1 

1 Ecole Polytechnique Federale de Lausanne, Institute of 

Chemical Sciences and Engineering, Lausanne, Switzerland 

The description of charge transfer complexes by standard 

density functionals is highly challenging. [1] Illustrative examples 

include large overestimation of charge transfer by local and 

semi-local functionals and inaccurate binding energies in the 

ground state. We demonstrate that standard density functionals 

fail to accurately describe interaction energies of charge-transfer 

complexes not only because of the missing long-range exchange 

as generally assumed [2] but mostly because of the neglected 

ubiquitous dispersion interactions. [3] Accounting for the missing 

dispersion interactions is thus of key importance. These assertions 

are based on the evaluation of the extent of stabilization due to 

dispersion using both DFT coupled with our recent 

density-dependent dispersion correction (dDsC) [4] and high-level 

ab initio computations and reflects the imperfect errorcancellation 

between the overestimation of charge-transfer and 

the missing long-range interactions. An in-depth energy 

decomposition analysis of an illustrative series of 4 small 

ambidentate molecules (HCN, HNC, HF and ClF) bound 

together with NF provides the main conclusions which are 

3 

validated on a typical organic charge-transfer complex 

(i.e., tetrathiafulvalene-tetracyanoquinodimethane). Only 

well-balanced functionals such as PBE0-dDsC, LC-BOP-LRD 

and M06-2X can overcome the difficulties of standard density 

functionals for charge transfer complexes. These results parallel 

the benchmarking on 341 diverse reaction energies where these 

functionals were among the best hybrid density functionals. [4] 

references: 

1. Ruiz E., Salahub D.R., Vela A., J. Am. Chem. Soc. 1995, 

117, 1141. 

2. Sini G., Sears J.S., Bredas J.-L., J. Chem. Theory Comput. 

2011, 7, 602. 

3. Steinmann S.N., Piemontesi C., Delachat A., Corminboeuf 

C., J. Chem. Theory Comput., doi 10.1021/ct200930x. 

4. Steinmann S.N., Corminboeuf C., J. Chem. Theory 

Comput. 2011, 7, 3567. 

Keywords: Density functional theory; noncovalent 

interactions; 



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o - 2 3 4 

AdJuStinG eLeCtroniC StruCture And 

ConduCtive ProPertieS of Li3n viA 

PhoSPhoruS And ArSeniC SuBStitution 

S. wu 1 , S. S. neo 2 , z. donG 2 , f. Boey 2 , P. wu 1 

1 Institute of High Performance Computing, Materials Science 

& Engineering, Singapore, Singapore 

2 Nanyang Technological University, School of Materials 

Science and Engineering, Singapore, Singapore 

Lithium nitrides have emerged as promising anode materials 

in lithium recharged batteries. The effect of phosphorus and 

arsenic substitution on electronic structure and conductive 

properties of Li N is investigated based on first-principles density 

3 

functional theory within the generalized gradient approximation 

as implemented in the Vienna Ab-initio Package (VASP). The 

Li(2) site vacancy is found to be the dominant defect with the 

lowest formation energy under nitrogen-rich conditions. Vacancy 

formation brings about delocalization of valence electrons to 

increase electronic conduction. Partial P and As substitution 

reduces Li vacancy formation energy with inappreciable 

discrepancy of electronic structure, which suggests an 

improvement in Li ionic conduction. However, a full substitution 

of P and As for N results in variation of crystal structure from the 

space group P6/mmm to P6 /mmm, and the energy band gaps of 

3 

Li P and Li As are reduced to 0.72 eV and 0.65 eV respectively 

3 3 

in comparison with 1.14 eV of Li N, which implicates an 

3 

enhancement of electronic conduction. A full substitution also 

brings about an increase of Li vacancy formation energies, 

suggesting degradation in Li ionic conduction. Therefore, our 

calculations suggest that it would be viable to achieve balanced 

electronic and ionic conduction of Li N by controlled P and As 

3 

substitution. It provides instructive information for experimental 

researches on synthesizing ternary lithium nitride compounds with 

designed electrochemical properties. 

Keywords: electronic structure; vacancy formation; ionic 

conduction; lithium nitride; structure variation; 



o - 2 3 5 

iMPortAnCe of vAn der wAALS forCeS to 

SurfACe StudieS 

J. KLiMeS 1 , A. MiChAeLideS 2 

1 University of Vienna, Faculty of Physics and Center for 

Computational Materials Science, Vienna, Austria 

2 University College London, London Centre for 

Nanotechnology and Department of Chemistry, London, 


Dispersion interactions are ubiquitous in nature and 

contribute to the binding in biomolecules, the adsorption of 

molecules on surfaces, and the condensed phases of water, to 

name but a few. However, due to their non-locality and small 

magnitude, they are difficult to describe accurately by electronic 

structure methods. For example, density functional theory (DFT) 

with standard functionals can give misleading results for systems 

where dispersion is important. The van der Waals density 

functional (vdW-DF) of Dion et al. [Dion et al., Phys. Rev. Lett. 

92, 246401 (2004)] is one of several promising approaches for 

accounting for dispersion. We have shown recently that with an 

improved treatment of the exchange part it can offer much better 

than chemical accuracy for a range of weakly interacting 

molecular systems [Klimes et al., J. Phys.: Cond. Matt. 22, 022201 

(2010)]. Here we will show applications of the method to systems 

which are not in the weakly bonded regime such as solids and 

molecules adsorbed on solid surfaces. We show that in some 

cases, including dispersion turns out to be crucial to reconcile 

theory with the experiment, for example for water adsorption on 

metals [Carrasco et al., Phys. Rev. Lett. 106, 026101 (2011)]. 

Keywords: Density functional calculations; Adsorption; Solidstate 

structures; Hydrogen bonds; 



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theoretical Chemisry – ii 

o - 2 3 6 

qM/CLASSiCAL MethodS to deSCriBe 

ProPertieS And ProCeSSeS of exCited StAteS 

in CoMPLex environMentS 

B. MennuCCi 1 

1 University of Pisa, Chemistry, Pisa, Italy 

Email: bene@dcci.unipi.it 

Nowadays molecular systems in their excited states play a 

fundamental role in many fields of science. In most cases, their 

photochemistry and photophysics are strongly affected, if not 

entirely determined, by the surrounding environment. For this 

reason, the accurate modelling of their properties, and of the 

phenomena and processes they undergo, requires to integrate 

proper quantum-mechanical (QM) descriptions with models 

which take into account the effects of the environment. In this 

talk, it will be shown that models based on hybrid QM/classical 

descriptions (either continuum or discrete) represent a valid 

computational strategy but only if mutual polarization effects 

between the QM and the classical part are possible and all the 

main physical specificities of the environment are properly taken 

into account. Examples of applications of these methods to 

phenomena involving molecular excited states (absorption, 

emission and energy transfer) in the presence of environments of 

increasing complexity will be presented and discussed. 

Keywords: Solvent effects; Quantum Chemistry; Energy 

transfer; Photophysics; Computational chemistry; 



o - 2 3 7 

towArdS A detAiLed CoMBuStion ModeL for 

furAn And itS derivAtiveS throuGh 

theoretiCAL Study of their h-ABStrACtion 

rAte ConStAntS 

r. x. fernAndeS 1 , S. vrAnCKx 1 , 

h. K. ChAKrAvArty 1 

1 RWTH Aachen University, Physico Chemical Fundamentals of 

Combustion, Aachen, Germany 

The scarcities of fossil fuels in the transportation sector have 

motivated the interest in search of potential alternative reliable 

energy resources. An important alternative is to use biomass 

derived fuels as they are both renewable and have the potency to 

reduce pollutant emissions. Furan based biofuels (furanics) have 

been proposed as promising alternative fuels and studies to 

develop detailed kinetic models of their combustion are ongoing. 

The main consumption of these fuels in combustion processes is 

initiated by abstraction of a hydrogen-atom. Our first objective is 

to determine the rate coefficients of H-abstraction reactions from 

furanics by OH and HO accurately. Therefore, the present work 

2 

focuses on the computational investigation at DFT and G3B3 

level of theories from 200-2000 K through canonical transition 

state theory incorporating Wigner’s and Eckart’s symmetrical and 

unsymmetrical tunneling corrections in order to calculate highly 

accurate Arrhenius parameters for these abstraction reactions. 

The accurate abstraction rate expressions will be applied to 

construct a detailed combustion model for the furanics. The model 

development relies on both our detailed theoretical calculations 

for the abstractions as well as literature data and estimations for 

other reaction classes to construct the mechanism starting from 

an elaborate C -C base chemistry set. The detailed kinetic model 

0 4 

is validated against auto-ignition time results over wide 

temperature and pressure range for the fuels of interest. These 

experiments have been performed in our group within the cluster 

of excellence “Tailor made fuels from biomass” at the RWTH 

Aachen using a high-pressure shock tube and rapid compression 

machine. The goal of the model development is to capture and 

explain the interesting ignition chemistry observed at low to 

intermediate combustion temperatures of relevance to new engine 

concepts such as HCCI. The final combustion models will be 

applied for engine simulations for these novel fuels. 

Keywords: kinetics; ab initio calculations; 



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o - 2 3 8 

theoretiCAL Study for LithiuM diffuSion in 

SoLid StAte MAteriALS 

M. M. iSLAM 1 , t. Bredow 1 

1 University of Bonn, Mulliken Center for Theoretical Chemistry, 

Bonn, Germany 

Lithium diffusion in lithium containing transition element 

disulphide and fluoride is investigated theoretically with periodic 

quantum-chemical methods. The calculated lithiation energies for 

the hexagonal titanium disulphide (h-Li TiS , x = 0.88,1.0) 

x 2 

confirm that Li preferentially occupies the octahedral site rather 

than the tetrahedral site. Among the considered point defects, V , Li 

V , and Ti , Li point defects are thermodynamically preferred in 

Ti i 

h-Li TiS . Competing pathways for Li diffusion in 

x 2 

h-Li TiS are investigated using the climbing-image 

x 2 

Nudged-Elastic-Band (cNEB) approach. Li + ions can migrate 

within the crystallographic ab plane either in a direct pathway 

through shared edges of neighboring octahedra or via vacant 

tetrahedral sites. The possibility of three-dimensional Li + diffusion 

along the c direction is investigated via inclusion of Ti point 

defects and Ti Frenkel defects. The calculated energetic properties 

show that ferromagnetic phase is more stable than the 

anti-ferromagnetic phase of lithium vanadium fluoride (α-Li VF ). 3 6 

Three different inequivalent Li sites (Li(1), Li(2) and Li(3)) are 

observed where Li(1) occupies the middle position of the triplet 

Li(2)–Li(1)–Li(3). The calculated Li vacancy formation energy 

shows that vacancy formation at the Li(1) and Li(3) sites are easier 

than that in Li(2) site. The Li exchange processes between Li(1) 

to Li(3), Li(1) to Li(2) and Li(2) to Li(3) are studied by calculating 

the Li + migration between various sites. It is observed that Li 

exchange in α-Li VF may take place in the following order: Li(1) 

3 6 

to Li(3) > (Li(1) to Li(2) > Li(2) to Li(3). This is in well accord 

with the available experiment. 

Keywords: Lithium titanium disulphide; Lithium vanadium 

fluoride; Defects; Li Ion Diffusion; Activation energy; 

theoretical Chemisry – iii 


o - 2 3 9 

theoretiCAL StudieS of enzyMAtiC 

reACtionS 

w. thieL 1 

1 Max-Planck-Institut für Kohlenforschung, Theory, 

Mülheim an der Ruhr, Germany 

Combined quantum mechanical/molecular mechanical 

(QM/MM) approaches have emerged as the method of choice for 

treating local electronic events in large molecular systems, for 

example, chemical reactions in enzymes or photoinduced 

processes in biomolecules. The lecture will outline the theoretical 

background and commonly chosen strategies for QM/MM studies 

of biomolecular reactions. [1–3] It will then describe some of our 

recent work on biocatalysis by enzymes which includes 

mechanistic studies on cytochrome P450cam, [4, 5] xanthine 

oxidases [6, 7] , cyclohexanone monooxygenase (CHMO) [8] , and 

glycosyltransferases (LgtC) [9] . These studies have addressed, 

inter alia, the competition between coupling and uncoupling 

reactions in the wild-type P450cam enzyme and its mutants, the 

crucial role of active-site residues in the reductive half-reaction 

of xanthine oxidases, the origin of enantioselectivity in 

CHMO-catalyzed reactions, and the favored reaction mechanism 

in LgtC. The examples presented will illustrate the chemical 

insights and the improved mechanistic understanding of 

enzymatic reactions that can be provided by QM/MM 

calculations. 

references: 

1. H. M. Senn, W. Thiel, Angew. Chem. Int. Ed. 48, 

1198–1229 (2009). 

2. H. M. Senn, J. Kästner, J. Breidung, W. Thiel, 

Can. J. Chem. 87, 1322–1337 (2009). 

3. T. Benighaus, W. Thiel, J. Chem. Theory Comput. 7, 

238–249 (2011). 

4. M. Altarsha, T. Benighaus, D. Kumar, W. Thiel, J. Am. 

Chem. Soc. 131, 4755–4763 (2009). 

5. S. Shaik, S. Cohen, Y. Wang, H. Chen, D. Kumar, 

W. Thiel, Chem. Rev. 110, 949–1017 (2010). 

6. S. Metz, D. Wang, W. Thiel, J. Am. Chem. Soc. 131, 

4628–4640 (2009). 

7. S. Metz, W. Thiel, J. Am. Chem. Soc. 131, 14885–14902 

(2009). 

8. I. Polyak, M. T. Reetz, W. Thiel, J. Am. Chem. Soc. 134, 

2732–2741 (2012). 

9. H. Gomez, I. Polyak, W. Thiel, J. M. Lluch, L. Masgrau, 

J. Am. Chem. Soc. (2012); doi:10.1021/ja210490f. 

Keywords: QM/MM; reaction mechanisms; enzymes; 



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chem. Listy 106, s587–s1425 (2012) 



o - 2 4 0 

oPtiCAL ProPertieS And uLtrAfASt dynAMiCS 

of PorPhyrin ArrAyS 

M. roehr 1 , J. PeterSen 1 , v. BonACiC-KouteCKy 2 , 

r. MitriC 1 

1 Freie Universität Berlin, Fachbereich Physik, Berlin, Germany 

2 Humboldt Universität zu Berlin, Fachbereich Chemie, Berlin, 

Germany 

Multiporphyrin arrays represent ideal building blocks for 

optoelectronic and light-harvesting materials since they can be 

produced in different shapes including oligomers and 

two-dimensional polymers. Great variability of possible 

multiporphyrin arrays allows to tailor their optical properties. We 

present here the theoretical study of the optical properties and 

ultrafast dynamics of different classes of porphyrin oligomers. 

We assign the optical spectra of these systems by using 

semi-empirical multi-reference and configuration interaction 

(MR-CI) method. Furthermore, we investigate the influence of 

specifically designed charged ligands on the optical absorption 

and the optical band gap of porphyrin oligomers. Since the 

functionality of optoelectronic and light-harvesting materials is 

determined by the interplay between the radiative and 

nonradiative relaxation processes, we perform surface hopping 

simulations of the ultrafast dynamics in order to determine the 

mechanism of the excited state relaxation in porphyrin oligomers. 

Keywords: Molecular dynamics; Porphyrinoids; 



o - 2 4 1 

StoChAStiC KinetiC ModeLinG of the SoAi 

reACtion 

L. GABor 1 , d. evA 1 

1 University of Debrecen, Institute of Chemistry Department of 

Inorganic and Analytical Chemistry, Debrecen, Hungary 

The Soai reaction, which involves carbon-carbon bond 

formation using an organozinc reagent, is the best known example 

of absolute asymmetric synthesis [1] . In this presentation, it will be 

demonstrated how the experimentally observed distribution of 

enantiomers in the Soai reaction can be interpreted based on a 

chemical mechanism using a newly developed stochastic kinetic 

method, accelerated Monte Carlo simulation combined with 

deterministic continuation and symmetrization. The method is in 

principle suitable for handling large mechanisms with realistic 

particle numbers and could be useful for any case where the 

kinetics of a process shows inherent random fluctuations. The 

mechanism shows how a slow initial reaction combined with 

efficient and highly enantioselective autocatalysis can give rise to 

chiral symmetry breaking under completely nonchiral external 

conditions [2] . 

Acknowledgement: This work was supported by the TÁMOP 

4.2.1/B-09/1/KONV-2010-0007 project, which is co-financed by 

the European Union and the European Social Fund. 

references: 

1. Soai, K.; Sato, I.; Shibata, T.; Komiya, S.; Hayashi, M.; 

Matsueda, Y.; Imamura, H.; Hayase, T.; Morioka, H.; 

Tabira, H.; Yamamoto, J.; Kowata, Y. Tetrahedron: 

Asymm. 2003, 14, 185–188. 

2. Dóka, É.; Lente, G. J. Am. Chem. Soc. 2011, 133, 

17878–17881. 

Keywords: Kinetics; Asymmetric amplification; Autocatalysis; 

Enantioselectivity; Chirality; 



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o - 2 4 2 

An ir And dft Study of AMMoniA interACtion 

with foSSiL PAttern in KBr MAtrix 

i. vorotyntSev 1 , i. GreenvALd 2 , i. KALAGAev 2 , 

e. SutyAGinA 2 , A. PetuKhov 1 , n. PetuKhovA 1 

1 Nizhny Novgorod State Technical University n.a. R.Y. Alekseev, 

PTMCET department, Nizhny Novgorod, Russia 


OCSM department, Nizhny Novgorod, Russia 

The role of ammonia in biological processes is not quite 

clear yet. Nevertheless in the last years the interest to the 

interaction of ammonia and fossil patterns is becoming immense. 

The problem of ammonia action in nature is connected in the first 

regard with the possibility of complex formation as an initial step 

in molecular transformation.The presented work the mechanism 

of appearance and structure of ammonia intermediates with water, 

cellulose acetate and betuline, employing IR experimental and 

DFT theoretical approaches is presenting.Usually the unstable 

adducts are fixed in the low temperature films. We have suggested 

a new variant of spectral method, using the stabilization of 

intermediates in KBr-matrix. The mentioned experimental tactic 

permits to investigate the complexes and their conversion at 

normal conditions. In this way we have revealed in IR-spectra of 

KBr-pallets, saturated by ammonia/water mixture before the 

pressing,in 3600-3000cm-1and 1600-1400cm-1region the new 

bands, which can be assigned to the water intermediates and 

ammonium cation vibrations. The experiments have shown that 

both weak water complexes and hydroxonium adducts can be 

stabilized in KBr-matrix. These data can be considered to some 

extent as the evidence of hydrogen transfer from water to 

ammonia molecule. At the interaction of cellulose acetate and 

ammonia it was established the existance of ammonia adducts 

with cellulose pattern in KBr-matrix. However for this system the 

hydrogen transfer between coupled molecules is not observed. In 

the case of betuline/ammonia system the IR-study indicates the 

hydrogen transfer in the intermediates of both betuline and 

ammonia. 

The conducted DFT-calculations in terms of GAUSSIAN 

procedure have manifested the complex formation in the 

presented systems. We have considered different species of 

intermediates, including the varied ratio of components.The 

calculated frequencies agree well with the experimental values in 

general. 

Acknowledgments: This work has been financially supported by 

Russia Foundation of Basic Research (11-08-00707) 

Keywords: ammonia; cellulose acetate; betuline; hydrogen 

bones; IR-spectroscopy; 



o - 2 4 3 

CAr-PArrineLLo MoLeCuLAr dynAMiCS 

SiMuLAtionS with GriMMe vdw CorreCtion 

for CLAthrAte hydrAteS ConSiStinG of 

ALCohoL And fLuoroCArBon MoLeCuLeS 

M. hirAtSuKA 1 , r. ohMurA 1 , S. AMAdeu K. 2 , 

K. yASuoKA 1 

1 Keio University, Department of Mechanical Engineering, 

Yokohama, Japan 

2 Colorado School of Mines, Center for Hydrate Research 

Department of Chemical & Biological Engineering, Golden, 

USA 

Clathrate hydrates are crystalline compounds consisting of 

hydrogen-bonded water molecules forming cages that enclose 

guest molecules. Clathrate hydrates are expected to be used in 

transport of natural gas, storage of unstable molecules, and future 

energy resource. Since the phase equilibrium conditions of the 

clathrate hydrates are significant for these applications, variety of 

experimental measurements and theoretical studies have been 

performed to understand the stability of the hydrate phases. 

Although many guest substances are known to form hydrates, 

alcohol and fluorocarbon molecules are most important ones. 

Recently, several alcohol and halogenated hydrocarbon molecules 

such as ethanol, butanol, fluorocarbons are reported as promoters 

for hydrate formation. However, in the previous understanding, 

the guest molecules that have large dipole moment and coulomb 

interactions between cage water molecules like methanol are 

known as inhibitor for hydrate. Therefore the mechanisms of the 

stabilizations of hydrate phase by the alcohol and halogenated 

hydrocarbon molecules that have large dipole moments are still 

missing. Furtherer understanding of the effect for phase 

equilibrium conditions from the interactions between the guest 

and cage water molecules is important for future applications of 

clathrate hydrates. 

The ab initio molecular dynamics simulation is a suitable 

way to observe the molecular behavior of the guest molecules in 

the hydrates. We performed Car-Parrinello MD simulation with 

vdW correction based on the Grimme model for the alcohol 

hydrates and fluorocarbon hydrates to calculate molecular 

motions of guest in the cages. As result, the hydrogen-bonding 

between guest and water molecules were observed and the 

vibrational spectrum was changed for alcohol hydrate. The 

differences of the molecular motions of fluorocarbons were also 

reported. The CH2F2 and CHF3 molecule moved along the long 

axis in the 51262 cages. 

Keywords: Inclusion compounds; Molecular dynamics; Ab 

initio calculations; Vibrational spectroscopy; 



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chem. Listy 106, s587–s1425 (2012) 


Computational Chemistry – i 

o - 3 9 2 

the vALenCe Bond wAy in CheMiStry 

S. ShAiK 1 

1 Chemistry, Organic Chemistry, Jerusalem, Israel 

“Give us insight, not numbers” was Coulson’s admonition 

to theoretical chemists. My talk will show that Valence Bond (VB) 

theory provides insight and good numbers, and creates a great deal 

of order in Chemistry [1, 2] . In this talk I will show its application 

to bioinorgnic and organic chemisry. Potentially, if time permits, 

I may cover the following two stories: 

(a) The first story concerns the reactivity of the iron-oxo 

species of Cytochrome P450 in H-abstraction, 

sulfoxidation, and aromatic hydroxylation, and how VB 

theory creates order and makes predictions in this 

complex field [1]. I will further teach how the VB model 

enables one to estimate H-abstraction barriers for 

reactions that range from H+H to the etard reaction, 

2 

permanganate oxidation, and all the way to Cytochrome 

P450 oxidation. A bridge will be created between normal 

hydrogen atom abstraction (HAT) and the proton 

coupled electron transfer (PCET) mechanism [1]. 

(b) The story of the oxy complexes of Myoglobin and 

Hemoglobin (Mb.O ; Hb.O ), which were “discovered” 

2 2 

about 333 years ago, and their bonding features, which 

were outlined first in 1936, remain disputed for 75 years. 

We shall see how VB theory resolves the dispute 

by transforming the CASSCF/MM wave function to 

a VB/MM wave function, which shows clearly the 

bonding mechanism of O to the ferrous heme complex 2 [2] . 

It will be argued that VB theory and VB reading of the wave 

function is a productive future paradigm in chemistry. 

references: 

1. W.Z. Lai, C. Li, H. Chen, Angew. Chem. Int. Ed. DOI: 

10.1002/anie.201108398. 

2. H. Chen, M. Ikeda-Saito, S. Shaik, J. Am. Chem. Soc., 

130 (2008) 14778-14790. 

Keywords: ab initio calculations; bioinorganic chemistry; 

C-H activation; iron; molecular modeling; 



o - 3 9 3 

dyotroPiC And douBLe GrouP trAnSfer 

reACtionS: oriGinS of the reACtion 

BArrierS 

i. fernAndez 1 , f. P. CoSSio 2 , f. M. BiCKeLhAuPt 3 

1 Universidad Complutense De Madrid, Departamento 

de Química Orgánica Facultad de CC. Químicas, Madrid, Spain 

2 Universidad del País Vasco, Facultad de Química, San 

Sebastián, Spain 

3 Vrije Universiteit, Department of Theoretical Chemistry, 

Amsterdam, Netherlands 

Double group transfer (DGT) reactions are a general class 

of pericyclic reactions that occur through the simultaneous 

migration of two atoms or groups from one compound to another 

in a concerted reaction pathway. [1] The process is suprafacial on 

both reaction sites and therefore these [σ2 +σ2 +π2 ] 

s s s 

transformations may be considered to be a thermally allowed 

pericyclic reaction according to the Woodward–Hoffmann rules. 

Strikingly, DGT reactions share a common feature, namely, they 

proceed in a concerted and synchronous fashion through a 

transition state featuring a six-membered ring that is highly 

in-plane aromatic. [2] 

Despite the aromatic character of these transition states, 

DGT reactions are associated with relatively high barriers. The 

origins of these barrier heights have been studied with the help of 

the so-called Activation Strain Model. We found that, similar to 

other pericyclic processes, the activation strain associated with 

the structural rearrangement of the reactants is also the controlling 

factor for the high energy of the DGT reaction barriers. [3] 

In addition, the origins of the reaction barriers of related dyotropic 

reactions shall be also discussed. [4] 

references: 

1. a) S. Sankararaman, Pericyclic Reactions-A Textbook: 

Reactions, Applications and Theory, Wiley, Weinheim, 

2005; pp. 326 –329, and references therein. 

b) I. Fernández, F. P. Cossío, M. A. Sierra, Chem. Rev. 

2009, 109, 6687. 

2. a) I. Fernández, M. A. Sierra, F. P. Cossío, J. Org. Chem. 

2007, 72, 1488. 

b) G. Frenking, F. P. Cossío, M. A. Sierra, I. Fernández, 

Eur. J. Org. Chem. 2007, 5410. 

3. a) I. Fernández, F. M. Bickelhaupt, F. P. Cossío, Chem. 

Eur. J. 2009, 15, 13022. 

b) I. Fernández, F. P. Cossío, Curr. Org. Chem. 2010, 14, 

1578. 

4. a) I. Fernández, F. P. Cossío, M. A. Sierra, Chem. Eur. J. 

2006, 12, 6323. 

b) I. Fernández, F. M. Bickelhaupt, F. P. Cossío, Chem. 

Eur. J. 2012, in press. 

Keywords: Pericyclic Reaction; Reaction Mechamisms; 

aromaticity; Computational Chemistry; 



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o - 3 9 4 

theoretiCAL ChArACterizAtion And 

identifiCAtion of eLeCtrideS 

e. MAtito 1 , v. PoStiLS 1 , M. GArCiA 1 , M. SoLA 1 , 

J. M. LuiS 1 

1 Institut de Química Computacional Universitat de Girona, 

Department of Chemistry, Girona, Spain 

The electrides [1-2] are intriguing chemical species with an 

electron not formally assigned to any atom. This situation is, 

however, completely different to that given in a metal where the 

electrons are delocalized between positively charged metal ions. 

The electron in an electride acts as a formal anion, which is 

bonded to positively charged species in the molecule. This 

particular feature of electrides prompts very particular chemical 

and physical properties: they are powerful reducing reagents, 

exhibit exalted electric linear and non-linear optical properties as 

well as a particular magnetic behavior. 

In this work, we analyze the electronic structure and the 

identification of several electride structures by means of the 

Quantum Theory of Atoms in Molecules (QTAIM) and the 

Electron Localization Function (ELF). [3] Our results show that 

these tools make possible the classification of candidate species 

as electrides or not. It was already proved that one could 

distinguish the electride behavior in insulating high-pressure 

forms of alkali metals from ELF analysis [4] but now we show that 

with QTAIM and ELF is possible to characterize the electride 

behavior in all sorts of molecules. 

references: 

1. Dye, J. L. Science, 2003, 301, 607-608. 

2. Dye, J. L. Science, 1990, 247, 663 

3. Matito, E.; Sola, M. Coord. Chem. Rev., 2009, 253, 

647–665 

4. Marqués et al., Phys Rev. Lett. 103, 115501 (2009) 

Keywords: electronic structure; ELF; Nonlinear optics; bond 

theory; Density functional calculations; 



o - 3 9 5 

underStAndinG the diffuSion of SMALL GASeS 

throuGh PorouS orGAniC CAGe 

nAnoCryStALS viA MoLeCuLAr dynAMiCS 

d. hoLden 1 , t. hASeLL 1 , A. trewin 1 , h. ShePherd 1 , 

A. CooPer 1 

1 University of Liverpool, Chemistry, Liverpool, United Kingdom 

Email: abbiet@liv.ac.uk, aicooper@liv.ac.uk 

Most organic molecules pack in such a way to minimise free 

space therefore exhibiting minimal void volume and hence 

permanent porosity is rare. However, previously we have shown 

that tetrahedral organic cages can be synthesized and then 

desolvated to generate porous crystals that adsorb small guest 

molecules such as nitrogen, hydrogen, methane and carbon 

dioxide. [1] We have also shown that it is possible to control the 

particle size of these systems by altering the building blocks used 

within the makeup of the material. [2] These all exhibit a 

3D-diamondoid pore network and by altering the modulus there 

is an impact on the pore size; as a result the diffusion of gases 

through them changes. 

Upon the generation of a bespoke force field, it has been 

possible to simulate how the diffusion of small gases alter 

dependant on their particle size. Using molecular dynamic 

simulations we have unlocked phenomena such as gas selectivity, 

rare-event hopping and displacement of gases to regions 

previously considered inaccessible; all of which help to rationalize 

experimental observations. The aim here is to predict materials 

which show good selectivity to one gas over another. 

references: 

1. Tozawa, T.; Jones, J. T. A.; Swamy, S. I.; Jiang, S.; 

Adams, D. J.; Shakespeare, S.; Clowes, R.; Bradshaw, D.; 

Hasell, T.; Chong, S. Y.; Tang, C.; Thompson, S.; Parker, J.; 

Trewin, A.; Bacsa, J.; Slawin, A. M. Z.; Steiner, A.; 

Cooper, A. I. Nat. Mater.2009, 8, 973. 

2. Hasell, T.; Chong, S. Y.; Jelfs, K. E.; Adams, D. J.; 

Cooper, A. I. Journal of the American Chemical Society 

2012, 134, 588. 

Keywords: Molecular dynamics; Nanostructures; Microporous 

materials; Cage compounds; Computational chemistry; 



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chem. Listy 106, s587–s1425 (2012) 


Computational Chemistry – ii 

o - 3 9 6 

how to treAt exCited StAteS of 

BioMoLeCuLeS 

x. ASSfeLd 1 , t. very 1 , A. MonAri 1 

1 Universite De Lorraine, Chimie et Biochimie Théoriques 

UMR 7565, Vandoeuvre les Nancy, France 

For the UV/Visible absorption of molecules in the gas phase, 

the Franck-Condon principle is very often invoked. It states that, 

the electronic motion being so fast compared to the nuclear 

motion, the molecular geometry can be considered fixed. 

In solution, the geometry of the chromophore is still 

considered unchanged during the absorption process, but the 

internal geometry of solvent molecule and their relative 

orientations also. A contrario, the electrons of the solvent 

molecules can react instantaneously to the modification of the 

electronic cloud of the chromophore. This is called the electronic 

response of the surrounding (ERS). A solvent is generally an 

isotropic media, in average, that can be modeled by a polarizable 

continuum characterized by the relative dielectric constant with 

separated electronic and nuclear contributions. Hence, extracting 

the electronic contribution is trivial in so called self-consistent 

reaction field approaches (SCRF). 

Oppositely, macromolecules need an atomic description 

using hybrid methods combining quantum mechanics and 

molecular mechanics (QM/MM). Usual force fields, describing 

the surrounding of the chromophore, consider atoms as a whole 

and do not explicitly consider the electrons. This clearly prevents 

the ERS to be taken into account. Instead of using polarizable 

force fields, we propose a simple method which combines hybrid 

QM/MM techniques with SCRF approaches to evaluate the ERS 

in macromolecules. This method will be detailed and applied to 

the interpretation of the absorption spectra of various systems of 

biological interest. 

In addition, a modification of the QM/MM method we 

developed will be presented in order to avoid spurious excitations. 

references: 

1. Jacquemin, D.; Perpete, E. A.; Laurent, A. D.; Assfeld, X.; 

Adamo, C. Phys. Chem. Chem. Phys. 11 (2009) 

1258–1262. 

2. Laurent, A.; Assfeld, X. Interdisciplinary Sciences: 

Computational Life Sciences, 2 (2010) 38–47. 

3. Very, T.; Monari, A.; Assfeld, X. Phys. Chem. Chem. Phys. 

(2012) submitted 

Keywords: QM/MM; excited state; polarization; 



o - 3 9 7 

therMAL iSoMerizAtion of CoMPoundS froM 

the PinAne SerieS AS ModeL SySteMS for 

KinetiC Study And ModeLLinG of SuBStituent 

effeCtS 

A. StoLLe 1 , J. Leiner 1 , B. ondruSChKA 1 

1 Friedrich-Schiller University Jena, Institute for Technical 

Chemistry and Environmental Chemistry, Jena, Germany 

Monoterpenes and Monoterpenoids from the pinane series 

are interesting compounds for the study of structural influences 

of the reaction kinetics. The thermal isomerization of those 

compounds is not only from scientific interest but also from 

industrial importance since products arising from the reactions are 

valuable intermediates for fine and specialty chemicals. For 

instance the pyrolysis of β-pinene affords via ring-opening of a 

strained vinylcyclobutane-system myrcene, a valuable building 

block for Vitamin E and A precursors as well as for industrial 

synthesis of carotinoids. The bottleneck in those processes is the 

thermal rearrangement, since different parallel reaction channels 

affording a series of products. Fundamental understanding of the 

reaction kinetics as well as of the elementary steps going on are 

from importance for an industrial application of such reactions. 

Therefore, the thermal isomerization of α-pinene, β-pinene, 

pinane, and pinan-2-ol has been studied using a flow type 

apparatus allowing the performance of the reactions in the gas 

phase with nitrogen as carrier and diluting gas. Kinetic analysis 

of the experimental results allowed for the identification of 

individual reaction pathways, whereas the product distribution 

strongly correlates with the structural entities of the bicyclic 

starting molecules. Additionally, the reactivity of the molecules 

depend on the occurrence of vinylcyclobutane or cyclobutane 

substructures in the bicyclic carbon skeleton. The starting 

materials can be rearranged via biradical intermediates to either 

acyclic reaction products ([2+2] cycloreversion) or monocyclic 

isomers ([1,5]H shift). The first type of reaction products is able 

to undergo rearrangement to cyclopentanes derivatives following 

an Ene-type cyclization mechanism. Reaction mechanism is 

supported by computational studies and kinetic models allow the 

prediction of experimental conditions leading to high yields of the 

target products. 

Keywords: Rearrangement; Gas-phase chemistry; Kinetic 

modelling; Reaction mechanism; Computational study; 



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o - 3 9 8 

quAntuM-CheMiCAL Study of the reACtion 

MeChAniSM of PoLyPePtide udP-GALnAC 

trAnSferASe 2, A retAininG 

GLyCoSyLtrAnSferASe 

t. trnKA 1 , S. KozMon 2 , i. tvAroSKA 3 , J. KoCA 2 

1 Masaryk University, National Centre for Biomolecular 

Research, Brno, Czech Republic 

2 Masaryk University, CEITEC MU, Brno, Czech Republic 

3 Slovak Academy of Sciences, Institute of Chemistry – Centre 

for Glycomics, Bratislava, Slovak Republic 

Glycosylation of cell surface proteins plays a crucial role in 

cell communication and recognition. Alterations in glycan 

structures are linked to many diseases with the most prominent 

example being cancer. To understand the regulation of 

glycosylation and to be able to modify it, reaction mechanisms 

of involved glycosyltransferases have to be known. However, 

reaction mechanism of the configuration-retaining group 

of glycosyltransferases hasn’t been sufficiently explained yet. 

For this reason we have chosen a retaining 

glycosyltransferase – polypeptide UDP-GalNAc transferase 

(ppGalNAcT) – as the subject of our quantum-chemical study. 

This enzyme catalyses the transfer of N-acetylgalactosamine 

moiety onto serine or threonine hydroxyls, forming the first bond 

of the so-called O-linked glycosylation pathway. Increased 

activity of ppGalNAcT has been found to enable metastasis of 

breast and colorectal cancer. 

We’re studying human ppGalNAcT2 by a hybrid QM/MM 

approach using density functional theory for the important part of 

the active site. We have found that the commonly used 

Becke-Perdew functional completely fails to describe the shape 

of the potential energy surface, while the OPBE functional 

provides results in good agreement with state-of-the-art metahybrid 

functional M06-2X. Structures of reactant and product 

have been successfully obtained on the OPBE-D3/TZP level, 

enabling a 2D potential energy surface scan to locate the transition 

state candidates for final optimisation. Results suggest that the 

reaction proceeds via a one-step S i mechanism, initiated by 

N 

proton transfer from acceptor hydroxyl to donor phosphate. This 

conclusion agrees well with recent experimental evidence. 

Acknowledgement: This work was realized in CEITEC - Central 

European Institute of Technology with research infrastructure 

supported by the project CZ.1.05/1.1.00/02.0068 financed from 

European Regional Development Fund. 

The research has been supported by the EU Seventh Framework 

Programme under the “Capacities” specific programme 

(Contract No. 286154). 

Tomáš Trnka is a Brno Ph.D. Talent Scholarship Holder – Funded 

by the Brno City Municipality. 

Keywords: glycosylation; reaction mechanisms; quantum 

chemistry; transferases; density functional calculations; 

Computational Chemistry – iii 


o - 3 9 9 

oxideS fiLMS At the nAnoSCALe: new 

StruCtureS, new funCtionS And new 

MAteriALS 

G. PACChioni 1 

1 University of Milan-Bicocca, Department of Materials Science, 

Milano, Italy 

SiO films of few nanometers thickness have been the basis 

2 

of the microelectronics revolution but ultrathin oxide films grown 

on a metal have a wide range of properties and applications [1] . 

They are essential to confer a specific property to a material 

(biocompatibility of titania implants in medical applications via 

formation of a thin titania layer, corrosion protection of metals by 

passive layers) or are fabricated in devices especially designed to 

exploit the reduced thickness of the oxide layer (e.g. tunneling 

magnetoresistance sensors, solar energy materials, ferroelectric 

ultrathin film capacitors). Oxides at the nanoscale may exhibit 

specific surface morphology, physical properties, chemical 

reactivity, thus providing new opportunities for the design of 

innovative materials. Theory has a very important role in this field 

and can answer several important questions. Are the electronic 

properties of an oxide film of just a few atomic layers similar to 

those of the corresponding bulk material? How important is the 

formation of a metal/oxide interface for the surface properties? 

What is the role of the strain in the epilayer? How thick an oxide 

film has be to recover typical bulk properties? Are the nature of 

the defects and even the chemical composition of the film similar 

to those of the bulk crystalline phase? These and other related 

questions will be addressed in this talk by discussing transport 

phenomena across the ultrathin insulating oxide barrier (charging 

effects), the structural flexibility of oxide ultrathin films and their 

relevance in catalytic processes, nanoporosity and the possibility 

to stabilize atomic species at the metal/oxide interface, change in 

electronic properties by selective doping of oxide nanostructures [2] . 

references: 

1. G. Pacchioni, S. Valeri (Editors), Oxide Ultrathin Films: 

Science and Technology, Wiley-VCH, Weinheim 2012, 

pp. XVI, 352. 

2. L. Giordano, G. Pacchioni, Accounts of Chemical 

Research, 44, 1244-1252 (2011). 



s823 

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o - 4 0 0 

the frozen CAGe ModeL: A CoMPutAtionALLy 

Low-CoSt tooL for PrediCtinG the 

exohedrAL reGioSeLeCtivity of 

CyCLoAddition reACtionS invoLvinG 

endohedrAL MetALLofuLLereneS 

M. GArCiA-BorrAS 1 , S. oSunA 2 , M. SwArt 3 , 

J. M. LuiS 1 , M. SoLA 1 


Departament de Química, Girona, Spain 

2 University of California Los Angeles, Department of Chemistry 

and Biochemistry, Los Angeles, USA 

3 Institució Catalana de Recerca i Estudis Avancats (ICREA), 

Departament de Química Universitat de Girona, Girona, Spain 

Functionalization of endohedral metallofullerenes (EMFs) 

is an active line of research that is important for obtaining 

nanomaterials with unique properties that might be used in a 

variety of fields, ranging from molecular electronics to biomedical 

applications. Such functionalization is commonly achieved by 

means of cycloaddition reactions. The scarcity of both 

experimental and theoretical studies analyzing the exohedral 

regioselectivity of cycloaddition reactions involving 

EMFs translates into a poor understanding of the EMF reactivity. 

From a theoretical point of view, the main obstacle is the high 

computational cost associated with this kind of studies. 

To alleviate the situation, we propose an approach named Frozen 

Cage Model (FCM). [1] The FCM represents a fast and 

computationally inexpensive manner to perform accurate 

qualitative predictions of the exohedral regioselectivity of 

cycloaddition reactions in EMFs. The Diels-Alder (DA) 

cycloaddition of 1,3-cis-butadiene to X@D -C 3h 78 

(X = Ti C , 2 2 [2] Sc N, 3 [3] and Y N 3 [4] ) EMFs provides a justification 

of the method. Moreover, the efficiency and successfully of the 

FCM is corroborated by the regioselectivity prediction of the DA 

addition of 1,3-cis-butadiene over all X@I -C (X = Sc N, Lu N, 

h 80 3 3 

Y N, Y , Sc NC, Sc C , Sc O , Sc CH, Sc O , Sc C , La , and Ce ) 

3 3 3 3 2 4 2 3 4 3 4 2 2 2 

EMFs species synthesized until nowadays. [5] 

references: 

1. Garcia-Borras, M.; Romero-Rivera, A.; Osuna, S.; Luis, J. M.; 

Swart, M.; Sola, M. J. Chem. Theory Comput. 2012, 8, 

1671. 

2. Garcia-Borras, M.; Osuna, S.; Luis, J. M.; Swart, M.; 

Sola, M. Chem. Eur. J. 2012, DOI: 

10.1002/chem.201103701. 

3. Osuna, S.; Swart, M.; Campanera, J. M.; Poblet, J. M.; 

Sola, M. J. Am. Chem. Soc. 2008, 130, 6206. 

4. Osuna, S.; Swart, M.; Sola, M. J. Am. Chem. Soc. 2009, 

131, 129. 

5. Garcia-Borras, M.; Osuna, S.; Luis, J. M.; Swart, M.; 

Sola, M. 2012, (in preparation). 

Keywords: Regioselectivity; fullerenes; cycloadditions; Density 

functional calculations; Cage compounds; 



o - 4 0 1 

oxidAtion of ALKAneS: in SiLiCo CAtALySt 

deSiGn 

P. C. AndriKoPouLoS 1 , C. MiCheL 1 , S. Chouzier 2 , 

P. SAutet 1 

1 Ecole Normale Supérieure de Lyon, Laboratoire de Chimie, 

Lyon, France 

2 Centre de Recherches et Technologies de Lyon, Laboratoire 

Intermédiaires Polyamide, Saint-Fons, France 

Alkane C-H activation, and in particular, selective oxidation 

under mild conditions has been an enduring challenge in catalysis. 

In an effort to match the in vivo effectiveness of metallo-enzymes 

such as cytochrome P-450, much attention has been drawn to 

metal-oxo systems that can mimic their reactivity. [1] The selective 

oxidation of alkanes into various oxidized products employing a 

transition metal catalyst together with the oxidative agent (i.e. 

hydrogen peroxide in Fenton chemistry processes) has been 

thoroughly investigated by computational means. [2] Various metalcentred 

catalysts have been proposed for the above 

functionalization ranging from [FeO(H O) ] 2 5 2+ and the ammonia 

substituted equivalent [2, 3] to Mn-heme containing systems. [4] 

A plausible mechanism that governs the C-H bond activation is 

the oxygen rebound mechanism [5] which applies to remarkably 

diverse systems. 

Theory can assist in tailoring an efficient catalyst, finding 

the optimum compromise between a fast H-abstraction/O-rebound 

step but also a facile regeneration of the iron-oxo active site. The 

latter part of the catalytic cycle is often neglected in the literature 

but represents a determining factor for the functionality of the 

catalyst. In the present DFT study, the complete catalytic cycle is 

considered, so that complexes that are known to perform well in 

the H-abstraction/O-rebound step are also assessed at the 

regeneration step. Heme and non-heme containing systems such 

as the ones mentioned above are included in the study. 

Furthermore, the effect of the equatorial or axial position of the 

ligands on the spin state and reactivity of the species is also taken 

into account, throughout the catalytic cycle. 

references: 

1. S.Ye, F.Neese, Proc.Natl.Acad.Sci.USA 2011, 108, 

1228–1233; S.Shaik, H.Chen, D.Janardanan, Natur.Chem. 

2011, 3, 19–27. 

2. F.Buda, B.Ensing, M.C.M.Gribnau, E.J.Baerends, 

Chem.Eur.J. 2001, 7, 2775-2783; C.Michel, E.J.Baerends, 

Inorg.Chem. 2009, 48, 3628–3638. 

3. L.Bernasconi, M.J.Louwerse, E.J.Baerends, 

Eur.J.Inorg.Chem. 2007, 3023–3033. 

4. D.Balcells, C.Raynaud, R.H.Crabtree, O.Eisenstein, 

Chem.Comm. 2009, 13, 1772–1774. 

5. J.T.Groves, G.A.McClusky, J.Am.Chem.Soc. 1976, 98, 

859–861. 

Keywords: C-H activation; Density Functional Calculations; 

Homogeneous Catalysis; 



s824 

chem. Listy 106, s587–s1425 (2012) 



o - 4 0 2 

BridGeS Between the PhySiCS And CheMiStry 

of MoLeCuLAr ConduCtorS 

e. CAnAdeLL 1 

1 ICMAB (CSIC), Laboratory of Electronic Structure of 

Materials, Bellaterra, Spain 

Molecular conductors are low-dimensional materials at the 

crossroads of chemistry and physics. They offer fertile ground 

where new ideas from the two disciplines can be brought together 

to induce new phenomena or test new concepts. To have some 

control over their properties it is advisable to understand their 

electronic structure which provides the simplest link between the 

chemical nature and the physical properties. These solids are 

usually build from two different sublattices put together to induce 

conducting properties in one of them. 

Although simple tight-binding approaches have been 

extremely successful in understanding many aspects of the 

electronic structure of these solids, some features require a more 

precise evaluation for a comparison with experimental results to 

be meaningful. Accurate first-principles density-functional theory 

(DFT) calculations are now possible for systems with large and 

complex unit cells like many molecular conductors. However, to 

fully exploit this potential, chemically oriented ways to analyze 

the results are needed. In this presentation we will report the 

results of DFT calculations using localized basis sets, which are 

very well suited for this goal, for several of these solids. 

Systems to be discussed include alpha-type BEDT-TTF 

conductors and Bechgaard salts. Despite the fact that these salts 

have been intensely studied for longtime some quite fundamental 

aspects of their physical behavior are still not well understood. In 

particular, we will discuss the origin of the low-temperature 

modulation exhibited by alpha-(BEDT-TTF) KHg(SCN) and the 

2 4 

charge-ordering transition in alpha-(BEDT-TTF) I both of which 

2 3 

are associated with anomalies in their electrical conductivity. The 

interaction of the conducting properties of one of the two 

sublattices with other properties of the remaining sublattice will 

also be considered. 

Keywords: Electronic Structure; Conducting Materials; 

Density Functional Calculations; Materials Science; Electronic 

Transport; 

Computational Chemistry – iV 


o - 4 0 3 

tuninG CAtALytiC reACtivity on MetAL And 

oxide SurfACeS: inSiGhtS froM dft 

P. SAutet 1 

1 University of Lyon and CNRS, Ecole Normale Supérieure de 

Lyon Laboratoire de Chimie, Lyon, France 

Tuning catalytic reactivity by atomic scale modifications of 

the catalyst’s surface is a key aspect of fundamental catalysis. In 

this lecture we will present and compare insights obtained from 

DFT calculations on metal and oxide surfaces. 

The first example will deal with the modification of Pt by 

alloying. Mixing with Sn forms a PtSn surface alloy, decreasing 

the reactivity of the Pt atoms, especially with C and H atoms. This 

weakening has a direct influence on the selectivity for the 

hydrogenation of unsaturated aldehydes by lowering the 

adsorption energy of unsaturated alcohol, and allowing its 

desorption from the catalyst. [1] In the case of butadiene selective 

hydrogenation, the lower Pt-C interaction opens a new 

hydrogenation pathway, where the C = C bond to be hydrogenated 

in not coordinated to the surface. [2] This strongly reduces the 

barrier for the selective pathways towards butene formation. [3] 

The second example will deal with the influence of 

coadsorbates on the surface, and we will focus on H O and OH 

2 

groups. On alumina, water can have a beneficial effect by 

increasing the basicity of surface O atoms, hence favouring the 

surface reactivity for methane or H dissociation. 2 [4] On a Rh or Pt 

surface, OH groups form strong hydrogen bonds with alcohol 

reactants, rendering OH activation easier, but disfavouring 

C-H bond breaking [5, 6] 

references: 

1. D. Loffreda et al., Angewandte Chemie International 

Edition, 48, 4978 (2009) 

2. F. Delbecq, D. Loffreda, P. Sautet, J. Phys. Chem. Lett., 

1, 323-326 (2010) 

3. F. Vigné, J. Haubrich, D. Loffreda, P. Sautet, F. Delbecq, 

J. Catal. 275, 129 (2010) 

4. R. Wischert et al., Angewandte Chemie International 

Edition, 50, 3202-3205 (2011) 

5. F. Auneau et al., Chem. Eur. J. 17, 14288-14299 (2011) 

6. C. Michel, F. Auneau, F. Delbecq, P. Sautet, ACS catalysis, 

1, 1430 (2011) 

Keywords: heterogeneous catalysis; surface chemistry; 

reaction pathways; Density Functional Theory; 



s825 

chem. Listy 106, s587–s1425 (2012) 


structural research for tomorrow 

o - 5 0 0 

MiCroSCoPiC inSiGhtS on CheMiCAL StAte And 

MorPhoLoGy of Key CoMPonentS in 

oPerAtinG ModeL fueL CeLLS uSinG 

SynChrotron-BASed MethodS 

M. KiSKinovA 1 

1 Elettra Laboratory, Experimental Division, Trieste, Italy 

Fuel cells are one of the most appealing environmentally 

friendly devices for effective conversion of chemical energy into 

electricity and heat, but still there are key barriers to their broad 

commercialization. Along with efficiency a major challenge of 

fuel cell technology is durability of the key components 

(interconnects, electrodes and electrolytes) that can be subject of 

corrosion or undesired morphology and chemical changes 

occurring under operating conditions. The complementary 

capabilities of synchrotron-based x-ray microscopes in terms of 

imaging, spectroscopy, spatial and time resolution and variable 

probing depths have opened unique opportunities to explore the 

structure and chemical composition of these technologically 

relevant complex materials and correlate them to the actual 

operating conditions. [1, 2] The most recent achievements in this 

respect, which are prerequisite for understanding and controlling 

the performance and durability of such devices, will be illustrated 

by selected results obtained with simplified versions of proton 

exchange membrane fuel cells (PEMFC) [3] and solid oxide fuel 

cell (SOFC) [4] . The reported results will demonstrate in-situ 

monitoring of the red-ox reactions or side reactions resulting in 

undesired deposits at the interconnects and electrodes, interactions 

at the interfaces of the electrodes and electrolyte and release of 

corrosion products to the electrolyte phase of PEMFC, mass 

transport processes and structural changes occurring at the high 

operation temperatures of SOFC and promoted by the 

polarization. 

references: 

1. A. Barinov et al, Nucl. Instr. Meth. Phys. Res. A 601 

(2009) 195. 

2. B. Kaulich et al, J. Phys.: Condens. Matter 23 (2011) 

083002. 

3. B. Bozzini et al, ChemSusChem 3 (2010) 846; J. Power 

Sources 196 (2011) 2513 and under preparation. 

4. B. Bozzini et al, ChemSusChem 4, (2011) 1099 and under 

preparation 

Keywords: surface chemistry; electrochemistry; interfaces; 

x-ray absorption pectroscopy; photoelectron spectroscopy; 



o - 5 0 1 

voLuMetriC ProPertieS of SoMe ALiPhAtiC 

Mono And diCArBoxyLiC ACidS And their 

SodiuM SALtS in wAter At 298.15 K 

z. KinArt 1 , A. BALd 1 

1 Univesity of Lodz, Department of Physical Chemistry of 

Solutions, Lodz, Poland 

On the base of densimetric measurements the apparent 

molar volumes of aliphatic carboxylic acids of the type: 

H(CH ) COOH [n = 1– 8] and (CH ) (COOH) [n = 0 – 6], sodium 

2 n 2 n 2 

salts of saturated aliphatic carboxylic acids of the type: 

H(CH ),COONa [n = 1– 8], (CH ) (COONa) [n = 1– 8] and 

2 2 n 2 

Cl(CH ) COONa [n = 1– 4], sodium salts of unsaturated 

2 n 

aliphatic acids of H(CH ) CH = CHCOONa [n = 2 – 7] and 

2 n-2 

CH = CH(CH ) COONa [n = 2 – 4] types and monosodium 

2 2 n-2 

salts of aliphatic dicarboxylic acids of the type: 

HOOC(CH ) (COOH) [n = 0– 6] in dilute aqueous solution were 

2 n 2 

determined at T = 298.15 K. The density of studied solutions of 

electrolytes was measured at the concentration range 

0.0050 ≤ m / (mol • kg-1 ) ≤ 0.3000 using a vibrating-tube 

densimeter (DMA 5000, Anton Paar, Austria).Suggested by us 

modification of the equation describing the apparent molar 

volume, derived after taking into account all existing in a solution 

ions, undissociated molecules and all present here equilibria, 

allowed us to determine the limiting apparent molar volumes 

(partial molar volumes) of all anions and undissociated acids. In 

the case of salts of the NaHA type the entirely new method of 

determining the partial molar volume of HA- anions was used 

based on treatment of a solution of monosodium salt as a mixture 

of different types of electrolytes. The variations of these values 

were analysed as a function of length of the aliphatic chain of 

studied electrolytes. 

Keywords: density; apparent molar volumes; carboxylic acid; 



s826 

chem. Listy 106, s587–s1425 (2012) 



o - 5 0 2 

MoLeCuLAr ModeLinG of zno nAnoPArtiCLe 

nuCLeAtion: froM Pre-nuCLeAtion CLuSterS 

to funCtionALized PArtiCLeS 

t. MiLeK 1 , P. duChStein 1 , d. zAhn 1 

1 Friedrich-Alexander-Universität Erlangen-Nürnberg, 

Computer Chemie Centrum, Erlangen, Germany 

We demonstrate the molecular modeling of ion cluster 

formation, ripening reactions, nucleation and growth of zinc oxide 

nanomaterials. Key issues are the molecular mechanisms of 

self-organization, growth control and surface stabilization by 

surfactants. This is aiming at the fundamental understanding 

needed for the guided formation of nanostructures with 

tailor-made properties. Our simulation scheme (Kawska-Zahn 

method [1, 2] ) allows to explore the evolution of a forming aggregate 

ion-by-ion. In doing so, the method combines Molecular 

Dynamics, Monte-Carlo and quantum/classical modeling to tackle 

the time/length-scale problem inherent to crystallization from 

solution [3] . At first we show the very initial steps of pre-nucleation 

cluster formation from Zn2+ and OH-ions and Zn O(OAc) 4 6 

precursors. The mechanistic insights include the emerging of 

transition clusters as well as the influence of counterions on the 

stability of the aggregates. Moreover, we present for 

ZnO/Zn(OH) core/shell nanoparticles cluster ripening and 

2 

nucleation of early wurtzite domains [4] . Exploring subsequent 

stages of particle growth for various crystal surfaces, we reveal 

the association and surfaces structure of organic molecules like 

carboxylates and amines. Eventually we propose mechanisms of 

stabilization and growth inhibition by those surfactants. 

references: 

1. A. Kawska, J. Brickmann, R. Kniep, O. Hochrein, 

D. Zahn, J. Chem. Phys., 2006, 124, 24513 

2. T. Milek, P. Duchstein, G. Seifert, D. Zahn, 

ChemPhysChem, 2010, 11, 847. 

3. J. Anwar, D. Zahn, Angew. Chem. Int. Ed., 2011, 50, 

1996. 

4. A. Kawska, P. Duchstein, O. Hochrein, D. Zahn, 

Nano Letters, 2008, 8, 2336. 

Keywords: Molecular dynamics; Nanoparticles; Surfactants; 


o - 5 0 3 

qA of dye-SenSitized nio nAnoPArtiCLe 

LAyerS viA reSonAnCe rAMAn 

MiCroSPeCtroSCoPy: dye deSorPtion 

dynAMiCS in wAter 

M. BräutiGAM 1 , J. PoPP 1 , B. dietzeK 1 

1 Friedrich-Schiller University Jena, Institute of Physical 

Chemistry and Abbe Center of Photonics, Jena, Germany 

Dye-sensitized solar cells (DSC) have gained a significant 

scientific impact in the last years. State-of-the-art DSCs consist 

of a dye-sensitized nano-porous TiO electrode and a passive 

2 

counter-electrode (usually Pt). [1] Recently, efforts have been made 

to activate the cathode to build so-called tandem solar cells which 

achieve theoretically higher efficiencies. Promising materials are 

p-type semiconductors, e. g. NiO that exhibits an appropriate 

x 

band position, is chemically stable and accessible. [2] 

Monolayer and bilayer (2-step synthesis) NiO substrates 

x 

are produced and sensitized with modified Ruthenium bipyridine 

dyes. In order to characterize the quality of these dye-sensitized 

NiO x 


layers spectroscopic techniques such as UV-vis 

spectroscopy, luminescence spectroscopy, and resonance Raman 

(rR) microspectroscopy are applied. Thereby, it is possible to 

detail with rR microspectrsocopy the distribution of the dye on 

the surface and to map inhomogeneities or vacancies in the layer. 

Furthermore, a statistically profound analysis of the dye 

desorption dynamics upon addition of water, which influences the 

long-term stability of the solar cell, is performed. The desorption 

on the monolayer is faster than on the bilayer and the rR signal 

ratio of the dye on the monolayer compared with the bilayer 

changes from 1 to 2 without a washing step to about 1 to 5.8 after 

washing in water for 20 min. This change in ratio can be attributed 

to binding sites on the NiO x surface that are passivated with regard 

to water penetration. These passivated “vaults” are introduced 

upon the second synthesis step that is needed to build the bilayer. 

Acknowledgement: This work is financially supported by the 

Fonds der Chemischen Industrie and the Studienstiftung des 

deutschen Volkes. 

references: 

1. Hagfeldt, A.; Boschloo, G.; Sun, L.; Kloo, L.; Pettersson, H. 

Chemical Reviews 2010, 110, 6595–6663. 

2. He, J.; Lindström, H.; Hagfeldt, A.; Lindquist, S.-E. Solar 

Energy Materials and Solar Cells 2000, 62, 265–273. 

Keywords: Raman spectroscopy; Ruthenium; Laser 

spectroscopy; Vibrational spectroscopy; Nickel; 



s827 

chem. Listy 106, s587–s1425 (2012) 


Ultra fast Processes – i 

o - 5 0 4 

uLtrAfASt oPtiCAL And x-rAy StudieS of the 

ChArGe, SPin And StruCturAL dynAMiCS in 

SoLutionS 

M. CherGui 1 

1 Ecole Polytechnique Fédérale Lausanne, Laboratory of 

Ultrafast Spectroscopy, Lausanne, Switzerland 

We will present results of our studies of metal-based 

molecular complexes in solution. We will show how with a 

combination of ultrafast fluorescence up-conversion and ultrafast 

optical and X-ray absorption spectroscopy, and quantum chemical 

simulations, we have obtained a detailed description of the 

photocycle of Fe-based complexes, which implies a large spin 

transition (DS = 2) on an ultrafast time-scale (< 150 fs). We have 

recently implemented a new set-up for ultrafast 2 dimensional 

spectroscopy in the UV around 300 nm. we will show how this 

technique allows us to retrieve additional information about the 

relaxation dynamics in Fe-complexes. Finally, we will present our 

ultrafast fluorescence studies of metalloporphyrins yielding new 

insight into their relaxation pathways. 

Keywords: ultrafast; X-ray; solutions; structural dynamics; 



o - 5 0 5 

uLtrAfASt dynAMiCS, CoMPoSition And 

StruCture of Confined SySteMS towArdS 4d 

ChArACterizAtion 

d. veLiC 1 , e. JAne 2 , v. SzoeCS 3 , t. PALSzeGi 4 , 

i. BuGAr 4 , o. GrAnCiCovA 2 , J. SePeLAK 2 , 

d. rePovSKy 2 , G. CiK 5 , S. hALASzovA 2 

1 International laser center, Comenius University, Bratislava, 


2 Comenius University, Physical Theoretical and Computational 

Chemistry, Bratislava, Slovak Republic 

3 Comenius University, Institute of Chemistry, Bratislava, 


4 International laser center, International laser center, 

Bratislava, Slovak Republic 

5 Slovak University of Technology, Department of environmental 

engineering, Bratislava, Slovak Republic 

A correlation between a structure and a function is a well 

defined concept in biochemistry and it is clearly relevant also for 

other fields of natural sciences. However, there is a third 

component - a time domain. To determine the changing structure 

in real time is then of interest, especially on molecular level. 

This contribution represents an attempt to provide a unique 

overlap between the dynamics in 1D time and the structural 

characterization in 3D along with the chemical composition. Our 

experiments are based on time-resolved laser fluorescence 

spectroscopy providing ultrafast dynamics, secondary ion mass 

spectrometry providing the chemical composition within 3D 

location, and atomic force microscopy providing topography and 

morphology of the structure surfaces. 

The concept is discussed on two examples. The first is the 

double confined system of 

coumarin C522 (C522) in aqueous solution of 

b-cyclodextrin and additionally in AOT (natrium 

dioctyl-sulphosuccinate) /n-heptane/water micelle. The micelle 

diameter is systematically changed. The dependence of the 

micelle diameter and presence of b-cyclodextrin on fluorescence 

dynamics is discussed. The second is a copolymer of dimethyl 

ester of 3,3````- bisdecyl [2,2`; 5`,2``; 5``,2```; 5```, 2````; 5````, 

2`````] sexithiophene-5,5`````- dicarboxylic acid with polyethylene 

oxide. The film preparation reveals the differences in fluorescence 

dynamics supported by details of local composition and structure. 

Keywords: Femtochemistry; Mass spectrometry; Micelles; 

Cyclodextrins; 



s828 

chem. Listy 106, s587–s1425 (2012) 



o - 5 0 6 

StruCturAL dynAMiCS of CovALent 

PeryLene-BASed SySteMS ProBed with 

feMtoSeCond StiMuLAted rAMAn 

SPeCtroSCoPy 

K. Brown 1 , B. veLdKAMP 1 , d. Co 1 , 

M. wASieLewSKi 1 

1 Northwestern University, Chemistry, Evanston, USA 

Understanding the charge transfer (CT) dynamics on the 

femtosecond to picosecond timescale provides crucial information 

to the development of bio-inspired photocatalytic systems for 

solar fuels and solar energy. For several donor-acceptor systems, 

the CT state remains a convolution of locally excited states (ES) 

or radical ion pairs, which prove difficult to understand using time 

resolved spectroscopy. However, spectroscopic techniques such 

as transient absorption give little useful information relaying 

structural information in the excited state and CT processes that 

occur on the fs to ps time scale. In order to obtain simultaneous 

high temporal and spectral resolution, it is necessary to have a 

structural probe with sub-picosecond time resolution. The recent 

development of femtosecond stimulated Raman spectroscopy 

(FSRS) enables observation of vibrational structural information 

with resolution comparable to vibrational dephasing times. FSRS 

also has the advantage of being insensitive to fluorescence, which 

can hinder the use of structural techniques such as spontaneous 

Raman spectroscopy for broadly used, solar-driven chromophores 

such as perylene diimide (PDI, ε=80,000 M-1 cm-1 ). 

We demonstrate the use of FSRS to elucidate ES and CT 

dynamics of various perylene-based chromophores. Here we 

present a study of picosecond vibrational dynamics of the CT and 

ES of perylene, PDI, and perylene monoimide (PMI). Evaluation 

of these chromophores reveals strong C = C core stretching 

vibrations that, though consistent in the ground state, vary 

significantly upon excitation to the first excited state, S1 . For 

instance, a strong, dispersive feature at 1593 cm-1 is solely present 

in the ES of PDI, suggesting the utilization of a new vibrational 

coordinate. Analysis of the photoreduced PDI anion in a dyadic 

system demonstrates significant contributions from these 

additional modes. Understanding the structural motion of different 

states will provide needed insight as we move to effectively design 

an efficient solar fuel. 

Keywords: Electron Transfer; Charge Transfer; Photophysics; 

Raman spectroscopy; Time-resolved Spectroscopy; 

Ultra fast Processes – ii 


o - 5 0 7 

uLtrA-fASt LASer MAteriALS ProCeSSinG 

w. KAuteK 1 

1 University of Vienna, Department of Physical Chemistry, 


Femtosecond Nanoscale Processing is reviewed for a wide 

variety of representative material classes, such as metals, 

semiconductors, dielectrics, ceramics, polymers, and biopolymers. 

The photo-electronic excitation mechanisms of these materials are 

compared in terms of incubation phenomena and material-specific 

electronic behaviours [1, 2] . An increase of pulse duration and pulse 

repetition rate into the megahertz range yielded a rising 

contribution of thermal excitation. Non-thermal and thermal 

processes, which determine the extent of the heat-affected zones, 

could be identified during the ablation process. Laser-induced 

periodic surface structures depend on the pulse length, the laser 

fluence, the number of laser pulses, the polarization, and on the 

shape of temporally tailored pulses [3, 4] . New insights into such 

self-assembly phenomena induced by femtosecond laser treatment 

on solid materials were gained. Current work with optical-field 

enhancement and confinement for an asymmetrically illuminated 

nanoscopic SFM tip illuminated by fs-laser pulses suspended over 

different materials is shortly reported. Since the first fundamental 

femtosecond pulse laser ablation studies on human corneas [5] , 

the use of sub-picosecond laser experienced vivid attention in 

surgery [6] . These processes involve non-linear optical coupling 

being highly dependent on the local intensity. 

references: 

1. W. Kautek, in “Laser Ablation and its Applications”, 

Ed. C. Phipps, Springer, Norwell, Mass. USA 2006, p. 215. 

2. W. Kautek and M. Forster, Springer Series in Materials 

Science 135 (2010) 189. 

3. M. Forster, L. Égerházi, C. Haselberger, C. Huber and 

W. Kautek, Appl. Phys. A 102 (2011) 27. 

4. M. Forster, W. Kautek, N. Faure, E. Audouard, and 

R. Stoian, Phys. Chem. Chem. Phys. 13 (2011) 4155. 

5. W. Kautek, S. Mitterer, J. Krüger, W. Husinsky, and 

G. Grabner, Appl. Phys. A58 (1994) 513. 

6. G. Grabner, Spektrum Augenheilkd. 23 (2009) 187. 



s829 

chem. Listy 106, s587–s1425 (2012) 



o - 5 0 8 

deGenerAte feMtoSeCond PuMP ProBe 

StudieS of LeAd SuLfide nAnoCryStALS At the 

BAnd GAP 

d. M. BuCKLey 1 , t. L. Courtney 1 , w. K. PeterS 1 , 

A. P. SPenCer 1 , d. M. JonAS 1 

1 University of Colorado at Boulder, Chemistry & Biochemistry, 

Boulder, USA 

One method of creating high efficiency third generation 

photovoltaics is to exploit carrier multiplication observed in 

narrow band gap light absorbers. Bi-exciton formation in different 

semiconductor quantum dots has been shown to occur when 

single photon excitation occurs via photons of energy 3 times the 

band gap or greater. The potential for carrier multiplication from 

photons at the peak of the solar spectrum, motivate the study of 

nanomaterials with band gaps between 0.6 to 1.2 eV in the 

near- and short-wave infrared. Femtosecond four-wave mixing in 

the short-wave infrared can be used to measure dynamics in both 

isolated colloidal quantum dots and, most importantly, coupled 

quantum dot arrays suitable for device applications. 

Disagreements exist about timescales for fundamental 

photophysical processes, such as carrier cooling and impact 

ionization: timescales reported in different studies vary from tens 

of femtoseconds to picoseconds. Degenerate pump-probe 

spectroscopy is used to investigate and compare relaxation times 

in arrays and colloidal solutions of lead sulfide quantum dots. 

The time-dependent behavior of different sizes of PbS nanocrystal 

arrays and solutions is measured at the respective band gaps with 

25 fs to 85 fs time resolution. 

Keywords: quantum dots; ultrafast spectroscopy; 



o - 5 0 9 

roLe of ChroMoPhoreS ArrAnGeMent 

in Coherent enerGy MiGrAtion in 

LiGht-hArveStinG CoMPLexeS 

e. CoLLini 1 

1 University of Padova, Dept. of Chemical Sciences, Padova, 

Italy 

The rapid development of two-dimensional electronic 

spectroscopy (2DES) has been central to the discovery of subtle 

quantum-coherent mechanisms in the natural light-harvesting 

process [1] as well as in artificial systems. [2] The role of such 

mechanisms in enhancing the efficiency of energy transfer (ET), 

although very appealing, is still not well understood. Moreover, 

still unknown are the factors regulating the presence of such 

effects although many theories have now been proposed about the 

role of structure and environment. [3] 

From a practical perspective, the possibility of correlating 

the presence of quantum-coherent dynamics to special structural 

motifs would opens the door for the design of new molecular 

assemblies by exploiting quantum attributes built into the system 

Hamiltonian, essentially by the choice of the nature and the 

structural arrangement of chromophores. 

With the aim of identifying if and which structural motifs 

play a major role in the coherent driving of energy migration, in 

this work two evolutionary-related light-harvesting proteins 

isolated from marine algae were studied by means of 2DES. The 

two complexes, named PC645 and PE555, are characterized by 

analogous structures but they present slight differences in the 

nature and in the arrangement of the absorbing chromophores. 

The measurements, performed at room temperature and 

physiologically relevant conditions, revealed for both complexes 

exceptionally long-lasting excitation oscillations with distinct 

anti-correlations, attributable to electronic quantum-coherences. 

The most interesting result is that, while in PC645 the quantum 

beating associated with electronic coherence lasts for at least 

300 fs1 , in PE555 the anticorrelated beating was recorded for less 

than 100 fs. The differences in the coherent dynamics of the two 

complexes are tentatively discussed in terms of their structural 

differences. 

references: 

1. E. Collini et al., Nature 463, 644 (2010). 

2. E. Collini, G.D. Scholes, Science 323, 369 (2009). 

3. G. D. Scholes et al., Nature Chemistry 3, 763 (2011). 



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o - 5 1 0 

GAS-SoLid-Shift in MoLeCuLAr inner-SheLL 

trAnSitionS 

e. ruehL 1 , r. fLeSCh 1 , e. SerdAroGLu 1 , 

P. feuLner 2 , f. BLoBner 2 , n. KoSuGi 3 , 

A.A. PAvLyChev 4 , x. o. BryKALovA 4 , y. zhAnG 1 , 

B. wASSerMAnn 1 

1 Freie Universitaet Berlin, Physical and Theoretical Chemistry, 


2 TU Munich, Physik Department, Berlin, Germany 

3 Institute for Molecular Science, UVSOR, Okazaki, Japan 

4 St. Petersburg State University, Institute of Physics, St. 

Petersburg, Russia 

Clusters and nanoparticles are known to bridge the gap 

between the condensed and the gaseous state of matter. Inner-shell 

excitation has been shown earlier to be a suitable approach to 

probe size effects of matter. However, accurate comparisons of 

core-to-valence transitions between gaseous molecules and the 

corresponding condensed phase are scarce. 

We present results on spectral changes that are observed 

between gaseous and condensed molecules in the inner-shell 

excitation regime. The experiments are carried out at the electron 

storage ring BESSY II (HZB Berlin). Condensed phase spectra 

are obtained from multilayers of condensed molecules. Gas phase 

spectra are simultaneously recorded, so that the energy scale is 

constant within 5 meV. 

Specifically, the C 1s-π * transition in benzene (C H ) is 6 6 

studied where a red-shift by 60 meV is observed in the condensed 

phase relative to the gas phase spectrum. This spectral shift is 

slightly smaller than that observed earlier for free benzene 

clusters. These findings are discussed in the context of structural 

changes occurring between molecular solids and micro-clusters, 

which are studied by ab initio calculations. 

Spectral shifts upon cluster formation in solution have also 

been observed in liquid microdroplets, when they reach 

supersaturation. These studies are performed in the hard X-ray 

regime, where the formation of Bjerrum pairs as well as solute 

clusters are formed in highly concentrated solutions. Structural 

information of such clusters is also inferred from model 

calculations. 

Keywords: clusters; X-ray absorption spectroscopy; 

nanoparticles; 



o - 5 1 1 

exCited-StAte ProPertieS in Ph-SwitChABLe 

rutheniuM dyeS 

M. wäChtLer 1 , M. BräutiGAM 1 , S. KuPfer 1 , 

J. GuthMuLLer 2 , S. rAu 3 , J. PoPP 1 , L. GonzALez 4 , 

B. dietzeK 5 



2 Gdansk University of Technology, Faculty of Applied Physics 

and Mathematics, Gdansk, Poland 


Germany 

4 University of Vienna, Institute of Theoretical Chemistry, 


5 Institute of Photonic Technology (IPHT) e.V. Jena, Jena, 

Germany 

Ruthenium polypyridine dyes are amongst the most studied 

compounds due to their unique combination of chemical stability 

and redox and optical properties, which are exploited in the design 

of e.g. artificial light-harvesting systems and molecular sensors. 

By incorporating extended ligand structures bearing basic/acidic 

positions, complex structures sensitive to environment pH can be 

designed. The resulting effects may be useful for pH-sensing 

applications and the design of pH-switchable optical devices. By 

de(protonation) the character of individual excited states is 

influenced, changing not only the absorption properties. Lifetimes 

of excited states and general decay mechanisms of the 

photoexcited structures may alter significantly. [1] 

Here we present a series of pH-sensitive structures which 

were investigated combining experimental and theoretical 

approaches. Applying resonance Raman spectroscopy and DFT 

calculations a detailed picture of the initial excited states and the 

changes induced by (de)protonation is developed. [2] Additionally, 

a comparison of calculated and experimental absorption and 

resonance Raman spectra allows for unambiguous identification 

of the protonated species present at certain pH ranges, which is 

especially important in the case of multiple positions available for 

protonation. [3] Applying time-resolved transient absorption 

spectroscopy the interplay between relative energetic positions of 

excited states in dependence on the protonation state and the 

excite state decay mechanism is revealed. 

Acknowledgement: This work was financially supported by the 

Studienstiftung des deutschen Volkes (M.W.), the Fonds der 

Chemischen Industrie (B.D.) and the Thüringer Ministerium für 

Bildung, Wissenschaft und Kultur (Grant-No. B 514-09049, 

PhotoMIC). 

references: 

1. Bräutigam, M.; Wächtler, M.; Rau, S.; Popp, J.; Dietzek, 

B. Journal of Physical Chemistry C 2012, 116, 1274. 

2. Kupfer, S.; Guthmuller, J.; Wächtler, M.; Losse, S.; 

Rau, S.; Dietzek, B.; Popp, J.; Gonzalez, L. Physical 

Chemistry Chemical Physics 2011, 13, 15580. 

3. Wächtler, M.; Kupfer, S.; Guthmuller, J.; Popp, J.; 

Gonzalez, L.; Dietzek, B. Journal of Physical Chemistry C 

2011, 115, 24004. 

Keywords: Ruthenium; Photophysics; time-resolved 

spectroscopy; computational chemistry; protonation; 



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o - 5 1 2 

KinetiC deterMinAtion of the ALKyLAtinG 

PotentiAL of vinyL CoMPoundS 

i. f. CeSPedeS-CAMACho 1 , J. A. MAnSo 1 , e. CALLe 1 , 

J. CASAdo 1 

1 Universidad de Salamanca, Química física, Salamanca, Spain 

Humans are exposed to alkylating compounds present in the 

environment and also produced endogenously. Many of these 

compounds are mutagenic and genotoxic due to their ability to 

interact with proteins and DNA [Gates, K. S. Chem. Res. Toxicol. 

2009,22, 1747]. The alkylating potential of four vinyl compounds 

(VC) was investigated: acrylamide (AM), acrylonitrile (AN), 

acrolein (AC) and acrylic acid (AA). As common substrate of 

alkylation, 4–(p–nitrobenzyl)pyridine (NBP) -that forms colored 

adducts with them- was used. These reactions occur through an 

enthalpy-controlled Michael addition mechanism, being 

moderately accelerated by electron-withdrawing groups. The 

sequence of alkylating potential was as follows: 

AN > AM > AA > AC. 

The alkylating potentials of the same VC on the nucleosides 

guanosine (Guo) and uridine (Urd) were also investigated. A novel 

Ultra Fast Liquid Chromatography (UFLC) technique was used 

to monitor the alkylation reactions. The following conclusions 

were drawn: i) AC presents the higher alkylating potential, 

showing reaction over Guo and Urd at cellular pH, which support 

its biological importance [Feng, Z. Proc. Natl. Acad. Sci. U.S.A. 

2006, 103, 15404]; ii) the alkylation reactions of Urd and Guo by 

the UC occur through a Michael addition mechanism; 

iii) a correlation between chemical reactivity (alkylation rate 

constants and thermodynamic activation parameters) and 

mutagenicity was found; iv) The sequence of alkylating potential 

with the nucleosides was as follows: AC > AN > AM ~ AA; 

v) the coherence between the results obtained with the nucleosides 

and NBP allow one to consider NBP-test as a simple biomimetic 

assay with predictive character. 

Acknowledgement: We thank the Spanish Ministerio de Ciencia 

e Innovación and FEDER Funds (CTQ2010-18999). I.F.C.C. 

also thanks the Spanish Ministerio de Asuntos Exteriores y 

Cooperación (MAEC–AECID) for Ph.D. grant. 

Keywords: alkylation; nucleosides; kinetics; 




s832 

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solid state Chemistry Materials chemistry/New materials 

self-assembly, Molecular Recognition and Biomaterials – i 

o - 1 0 8 

PLAnt CyStoLithS: CoMPLex funCtionAL 

BioCoMPoSiteS deSiGned to SCAtter LiGht 

L. AddAdi 1 , A. GAL 1 , S. weiner 1 

1 Weizmann Institute of Science, Structural Biology, Rehovot, Israel 

Plant cystoliths are mineralized objects formed by 

specialized cells in the leaves of certain plants. The main mineral 

component of cystoliths by volume is amorphous calcium 

carbonate (ACC), but a silica stalk, which is found to be essential 

for ACC formation, is always the first formed mineral. The 

cystolith is composed of four distinct mineral phases with 

different chemical properties: An initial silica phase blends into a 

Mg-rich silica phase, which in turn mediates the transition to a 

highly stable ACC phase. Encapsulating the first ACC phase, a 

bulky and less stable ACC phase is deposited. This complex 

architecture poses interesting questions not only about the strategy 

for ACC stabilization, [1–2] but also about the physiological function 

of the mineralized objects. 

Cystoliths are regularly distributed in the epidermis of leaves 

and protrude into the photosynthetic tissue. The photosynthetic 

pigments generate a steep light gradient in the leaf. Under most 

illumination regimes the outer leaf layer is light saturated, thus 

the photosynthetic apparatus is kinetically unable to use the excess 

light for photochemistry. Using micro-scale modulated 

fluorometry, we demonstrated that light scattered by the cystoliths 

is distributed from the photosynthetically inefficient upper tissue 

to the efficient, but light deprived, lower tissue. The presence of 

the cystoliths functioning as light scatterers thus reduces the steep 

light gradient, enabling the leaf to use the incoming light flux 

more efficiently for photosynthesis. [3] 

references: 

1. Assaf Gal, Steve Weiner, Lia Addadi, J Am Chem Soc, 

132, 13208–13211 (2010) 

2. Assaf Gal, Anna Hirsch, Stefan Siegel, Chenghao Li, 

Yael Politi, Peter Fratzl, Steve Weiner and Lia Addadi, 

Chemistry European J, submitted 

3. Assaf Gal, Vlad Brumfeld, Steve Weiner, Lia Addadi, 

Dan Oron, Adv. Mater. 2012, 24, OP77–OP83 

Keywords: Bioinorganic chemistry; Amorphous materials; 

X-ray diffraction; Materials science; Photosynthesis; 



o - 1 0 9 

SeLf-ASSeMBLed Bio-inSPired 

nAnoStruCtureS of unique CheMiCAL, 

PhySiCAL, And MeChAniCAL ProPertieS 

e. GAzit 1 

1 Nano-Biology, Tel Aviv University, Tel Aviv 69978, Israel 

The significant progress and novel discoveries made in the 

past two decades in the field of nanoscience and nanotechnology 

have enabled the fabrication of nano-scale materials and structures 

with unique and often unprecedented physical and chemical 

properties. The self-assembly of short peptide building blocks 

derived from functional biological modules results in the 

formation of nanostructures of unique chemical and physical 

properties. By the inspiration from the minimal recognition 

modules used by nature to mediate coordinated processes of 

self-assembly, we had developed building blocks that could be 

directed to form well-ordered nanostructures including nanotubes, 

nanospheres, nanoplates, and hydrogels with nano-scale order. 

Based on the molecular architecture of the ultra-rigid aromatic 

polyamide polymers (such as Kevlar) presenting the aromatic 

interactions, hydrogen bonds and the stacking of the planar amide 

bond, these nanostructures represent a new and novel family that 

is completely different from all other organic nanostructures. 

These structures also share the heat resistance and chemical 

stability of the aromatic polyamides. The compact design of the 

building blocks and therefore their unique structural organization 

resulted in metallic-like Young‘s modulus of up to 275 GPa, blue 

luminescence due to high quantum confinement at the nano-scale, 

and piezoelectric properties comparable to LiNbO3. 

references: 

1. Reches, M. and Gazit, E. (2003) Casting Metal Nanowires 

within Discrete Self-Assembled Peptide Nanotubes. 

Science 300, 625-627. 

2. Reches, M. and Gazit, E. (2006) Controlled Patterning of 

Aligned Self-Assembled Peptide Nanotubes. nature 

nanotechnol. 1, 195-200. 

3. Adler-Abramovich L., Aronov D., Beker P., Yevnin M., 

Stempler S., Buzhansky L., Rosenman G. and Gazit E. 

(2009) Self-Assembled Arrays of Peptide Nanotubes by 

Vapour Deposition. nature nanotechnol. 4, 849-854. 

4. Carny, O., Shalev, D., and Gazit, E. (2006) Fabrication of 

Coaxial Metal Nanowires Using Self-Assembled Peptide 

Nanotube Scaffold. nano Lett. 6, 1594-1597. (Featured in 

the Research Highlights of nature nanotechnol.; 

doi:10.1038/nnano.2006.23). 

5. Amdursky, N., Molotskii, M., Gazit, E., and Rosenman, G. 

(2010) Elementary Building Blocks of Self-Assembled 

Peptide Nanotubes. J. Am. Chem. Soc. 132, 15632-1563. 

(Featured in the News and Views of nature 468, 516-517). 



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o - 1 1 0 

deSiGn, PrePArAtion, And Study of 

Steroid-BASed GeLAtorS, their GeLS And 

MetALLoGeLS 

h. SvoBodovA 1 , e. KoLehMAinen 1 

1 University of Jyväskylä, Department of Chemistry, Jyväskylä, 

Finland 

Supramolecular gels, composed of low-molecular-weight 

organic compounds, have received a lot of attention over the past 

two decades [1] . During this time gelation has moved from being a 

phenomenon observed sporadically in particular molecules, to a 

controllable and functional process. Supramolecular gels have 

evolved as a fascinating class of smart and functional nanoscale 

materials with high potential for a wide range of advanced 

applications, e.g. in sensing, molecular electronics, catalysis, 

tissue engineering and drug delivery, and as templates for the 

synthesis of nanoporous materials [2] . 

The gel formation stems from the spontaneous but 

controlled self-assembly of low-molecular-weight compounds 

into fibrous architectures through non-covalent interactions 

including hydrogen bonding, π-π stacking, electrostatic, and van 

der Waals interactions, where solvent molecules are entrapped by 

the entangled three dimensional networks. In the last few years, 

there has been an increase of interest in the use of coordination 

chemistry as a rational design route towards self-assembled gel [3] . 

The binding of a metal ion to a gelator molecule containing an 

appended ligand site can affect self-aggregation modes and allow 

the gelation ability to be finely tuned. Although various 

low-molecular-weight hydro- and organogelators have been 

reported thus far, examples of gels based on coordination bonds 

and stimuli- responsive gels generally are still relatively rare. We 

deal with the design, preparation and study of steroid-based gel [4] 

responsive to various stimuli (pH, ionic strength, light, redox, etc.) 

and in this work, examples of pH-responsive systems as well as 

metallogels will be presented. 

references: 

1. e.g.: Chem. Commun. 2011,47,1379; 

J. Mater. Chem. 2011,21,2024; 

J. Mater. Chem. 2009,19,6649; 

Chem. Soc. Rev. 2008,37,2699. 

2. e.g.: Chem. Asian J. 2011,6,266; 

Angew. Chem. Int. Ed. 2008,47,8002; 

Chem. Soc. Rev. 2005, 34,821. 

3. e.g.: Chem. Rev. 2010,110,1960; 

Angew. Chem. Int. Ed. 2006,45,1680. 

4. J. Colloid Inter. Sci. 2011,361,587. 

Keywords: Gels; Supramolecular chemistry; Materials 

science; Steroids; Amino acids; 


self-assembly, Molecular Recognition and Biomaterials – ii 

o - 1 1 1 

MACroSCoPiC SeLf-ASSeMBLy And SeLfheALinG 

throuGh MoLeCuLAr reCoGnition 

A. hArAdA 1 

1 Osaka University, Dept. of Macromolecular Science Graduate 

School of Science, Toyonaka Osaka, Japan 

In the past three decades much attention has been attracted 

to molecular recognition and supramolecular complexes. 

Although there have been numerous attempts on self-organization 

of molecules, there are a few on self –assembly on macroscopic 

scale. If molecular recognition works in macroscopic scale, we 

will be able to realize a variety of architectures and functions. 

Here we found that macroscopic soft materials can be 

differentiated each other through molecular recognition. This is 

the first example of specific molecular recognition events on 

macroscopic-scale. The concept of supramolecular science will 

be pushed up as a powerful way on the production of practical 

materials. 

First, a host gel containing β-cyclodextrin(CD) was found 

to bind a guest gel containing adamantane (Ad) strongly through 

molecular recognition. In addition, α-CD gel was found to bind 

the guest gel containing n-butyl group specifically and β-CD gel 

binds that of t-butyl groups selectively to give self-assembly on 

macroscopic scale only by mixing and shaking in water. We used 

acrylamide gels containing CDs as host gels, and those containing 

various alkyl groups as guest gels. Each gel was prepared by 

copolymerization of acrylamide, bis-acrylamide, and acrylamide 

CD or alkyl acrylates, respectively. Although α-CD gel bound 

linear alkyl gels, β-CD gel bound cyclic alkyl gels. 

We found that a β-CD polymer and a ferrocene-polymer 

formed a gel. Even when the gel was cut in half, if the gel pieces 

were brought in contact, the gel pieces were bound and self-healed 

to the original gel. This gel is redox-responsive. 

α-CD gel was found to bind to trans-azobenzene gel 

(Azo-gel). When Azo-gel was irradiated by UV light, the Azo-gel 

turned to cis-azobenzene. Eventually, Azo-gel left α-CD gel and 

bound to β-CD gel. This is reversible. This is the first discovery 

that molecular recognition event work in our real world. 

Keywords: Cyclodextrin; Self-assembly; Self-healing; 




s834 

chem. Listy 106, s587–s1425 (2012) 


self-assembly, Molecular Recognition and Biomaterials – ii 

o - 1 1 2 

ChArGe-ASSiSted hydroGen BondS And weAK 

interMoLeCuLAr interACtionS AS tooLS to 

fABriCAte CoMPLex SuPrAMoLeCuLAr 

ArChiteCtureS 

A. CoMotti 1 , S. BrACCo 1 , M. BerettA 1 , 

M. d. wArd 2 , P. SozzAni 1 

1 University of Milano Bicocca, Department of Materials Science, 

Milano, Italy 

2 New York University, Department of Chemistry, New York, USA 

The rational design of synthetic supramolecular 

architectures based on well-defined structure-directing forces and 

hydrogen bonding is still a challenge. We present a 

supramolecular cage assembled through 72 hydrogen bonds 

which is constructed from two kinds of hexagonal molecular tiles 

forming a truncated octahedron, one of the thirteen Archimedean 

polyhedra (Science 2011, 333, 436). The framework displays an 

extraordinary ability to encapsulate a wide range of differently 

charged species, not observed otherwise. 

By the exploitation of the same kind of interactions, 

orientation of polyconjugated guest molecules is obtained in 

tunable host cavities. The framework host architectures can be 

controlled systematically in a manner that enables the regulation 

of the guest orientation and aggregation (J. Am. Chem. Soc. 2010, 

132, 14603). The effects of the distinct packing motifs is 

manifested as bathochromic shifts in the absorption and emission 

spectra of the guests as interpreted by ab initio TDDFT 

calculations. 

Interestingly, through CH···pi interactions, the molecular 

recognition of specific blocks of triblock copolymers by a host 

molecule promotes the formation of hierarchical periodic 

structures. The formation of the supramolecular architectures is 

followed by in situsynchrotron X-ray diffraction while the 

specific CH···pi intermolecular interactions are highlighted by 

fast-1H MAS NMR and GIAO HF ab initio calculations (J. Am. 

Chem. Soc. 2011, 133, 8982). 

Moreover, weak intermolecular interactions play a key role 

in modulating the dynamics of molecular rotors in amphidynamic 

materials. Indeed, the precise engineering of highly-organized 

porous silica scaffolds supporting organic elements allows the 

fabrication of fast molecular rotors (k>108 Hz) entirely exposed 

to the guest molecules which act as regulators (Angew. Chemie 

Int. Ed. 2010, 49, 1760). 

Keywords: Crystal Engineering; Block Copolymers; Hydrogen 

bonds; Materials science; 


self-assembly, Molecular Recognition and Biomaterials – iii 

o - 1 1 3 

dnA MAteriALS And nAnoMAChineS 

n. SeeMAn 1 

1 New York University, Department of Chemistry, New York, USA 

We build branched DNA species that can be joined using 

sticky ends to produce N-connected objects and lattices. We have 

used ligation to construct DNA stick-polyhedra and topological 

targets, such as Borromean rings. Branched junctions with up to 

12 arms have been produced. 

Nanorobotics is a key area of application. We have made 

robust 2-state and 3-state sequence-dependent devices that change 

states by varied hybridization topology. Bipedal walkers, both 

clocked and autonomous have been built. We have constructed a 

molecular assembly line by combining a DNA origami layer with 

three 2-state devices, so that there are eight different states 

represented by their arrangements. We have demonstrated that all 

eight products (including the null product) can be built from this 

system. 

A central goal of DNA nanotechnology is the self-assembly 

of periodic matter. We have constructed 2-dimensional DNA 

arrays with designed patterns from many different motifs. We 

have used DNA scaffolding to organize active DNA components. 

Active DNA components include DNAzymes and DNA 

nanomechanical devices; both are active when incorporated in 2D 

DNA lattices. We have used pairs of 2-state devices to capture a 

variety of different targets. Multi-tile DNA arrays have been used 

to organize gold nanoparticles in specific arrangements. 

We have self-assembled a 3D crystalline array and have 

solved its crystal structure to 4 A resolution, using unbiased 

crystallographic methods. More than ten other crystals have been 

designed following the same principles of sticky-ended cohesion. 

We can use crystals with two molecules in the crystallographic 

repeat to control the color of the crystals. Thus, structural DNA 

nanotechnology has fulfilled its initial goal of controlling the 

structure of matter in three dimensions. A new era in nanoscale 

control awaits us. 

Acknowledgement: This research has been supported by the 

NIGMS, NSF, ARO, ONR and the W.M. Keck Foundation. 

Keywords: DNA Nanotechnology; Self-Assembled 3D Crystals; 

Nanomechanical Devices; N-Connected Objects; Topological 

Control; 



s835 

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o - 1 1 4 

fundAMentAL And APPLied ASPeCtS of SoLid 

orGAniC inCLuSion CoMPoundS 

K. hArriS 1 

1 Cardiff University, School of Chemistry, Cardiff, United Kingdom 

The lecture will highlight some contemporary challenges in 

understanding properties of molecular solids, and will focus on 

strategies that may be implemented to tackle these challenges. 

In many respects, solid host-guest materials based on 

one-dimensional tunnel host structures (e.g. urea and thiourea 

inclusion compounds) serve as model systems for exploring and 

understanding fundamental properties of wider relevance to other 

classes of materials. Issues of interest include structural properties 

(including the fundamental understanding of commensurate 

versus incommensurate behaviour), dynamic properties, 

host-guest chiral recognition, and order-disorder phase transitions. 

In addition to these fundamental properties, our recent research 

has been directed increasingly towards aspects of more direct 

relevance to potential applications of solid inclusion compounds, 

including the control of crystal growth processes, studies of guest 

exchange and guest transport processes, the development of 

materials for applications as X-ray dichroic filters, and 

explorations of the related phenomenon of X-ray birefringence. 

The lecture will present an overview of several inter-related 

aspects of our research on these materials, as well as highlighting 

other areas of recent research focused on fundamental aspects of 

crystallization processes: 

(a) fundamental and applied aspects of solid inclusion 

compounds, [1,2] 

(b) new insights on crystallization processes by confocal 

Raman microspectrometry, [3] 

(c) in-situ solid-state NMR studies of crystallization from 

solution. [4,5] 

references: 

1. K.D.M. Harris, Supramol. Chem., 2007, 19, 47. 

2. B.A. Palmer, A. Morte-Ródenas, B.M. Kariuki, K.D.M. 

Harris, S.P. Collins, J. Phys. Chem. Lett., 2011, 2, 2346. 

3. B.A. Palmer, K.D.M. Harris, F. Guillaume, Angew. 

Chemie Int. Ed., 2010, 49, 5096. 

4. C.E. Hughes, K.D.M. Harris, J. Phys. Chem. A, 2008, 112, 

6808. 

5. C.E. Hughes, K.D.M. Harris, Chem. Commun., 2010, 46, 

4982. 

Keywords: Solid-state structures; Inclusion compounds; Phase 

transitions; Crystal growth; 



o - 1 1 5 

towArdS ChArGe StorAGe MeMory deviCeS 

BASed on eLeCtroACtive orGAniC 

MoLeCuLeS 

J. veCiAnA 1 , C. SiMAo 1 , M. MAS-torrent 1 , 

n. CriviLLerS 1 , C. rovirA 1 

1 Institut de Ciencia de Materials de Barcelona (ICMAB-CSIC), 

Molecular Nanoscience and Organic Materials, Barcelona, 

Spain 

The increasing interest in miniaturizing electronic devices 

to achieve denser memories will eventually entail the utilization 

of molecules as active components. In particular, self-assembled 

monolayers attached to substrates appear as suitable candidates 

inMolecular Electronics for the development of switchable and 

memory devices based on electroactive molecules grafted on 

surfaces. [1] Polychlorinated triphenylmethyl (PTM) radicals are 

persistent electroactive organic radicals that can be easily reduced 

to the corresponding anionic species which also show a high 

stability in solution. Tetrathiafulvalenes are another electroactive 

species that can be easily oxidized to the corresponding 

radical-cation and dication states. All such species exhibit 

different optical and magnetic properties and can be reversibly 

interconverted in solution by electrochemical techniques. [2] In 

addition PTM and TTF compounds can be covalently 

grafted/deposited on surfaces of different nature (Au, SiO , 2 

HOPG) where they keep their bistability and switchability without 

degradation. [2] 

We will report efforts addressed to functionalize transparent 

and conducting ITO and Gold surfaces with appropriately 

functionalized PTM radicals and TTF derivatives. Such hybrid 

organic/inorganic surfaces behave as chemical and 

electrochemical redox switches with bistable optical (absorption 

and fluorescence), magnetic, and wetting responses exhibiting an 

exceptionally high long-term stability and excellent reversibility 

and reproducibility. [2] Moreover, such hybrid surfaces can be 

patterned as well as electrochemically locally addressed enabling 

to write-store-read information reversibly on the patterned clusters 

of electroactive molecules. Examples of such nonvolatile 

molecular memory devices will be presented and discussed. 

references: 

1. Veciana, J., Ratera, I. in “Stable Radicals: Fundamentals 

and Applied Aspects of Odd-Electron Compounds”, Ch. 2., 

Ed. by Hicks, R.G., John Wiley & Sons, Ltd, 2010. 

2. Simao, C. et al. Nature Chem., 3, (2011) 359. 

Keywords: Self-assembly; Radicals; Anions; 



s836 

chem. Listy 106, s587–s1425 (2012) 


supramolecular Chemistry and Nanostructured Materials – i 

o - 2 4 4 

‘fruStrAted’ orGAniC SoLidS 

J. Atwood 1 

1 University of Missouri-Columbia, Department of Chemistry, 

Columbia MO, USA 

Physical adsorption of gases by a wide variety of materials 

is an active area of endeavor. Contributions from our group have 

revolved around solid-solid phase transformations with regard to 

organic solids. In the process of going from a solvated to a 

desolvated form of host solid, we have discovered and published 

on a type of material, which we believe involves a frustration of 

the solvate lattice as it moves toward the desolvated state. The 

frustration arises from a reduction in the solvent content within 

the structure during the desolvation process and results in the 

formation of a porous material that rapidly sorbs a variety of gases 

under ambient conditions. In this discussion we further develop 

applications of frustrated organic solids. Ramifications of early 

discoveries will also be discussed. 



o - 2 4 5 

reACtivity in hALoGen Bonded CryStALLine 

MAteriALS 

G. reSnAti 1 , J. MArti ruJAS 2 , P. MetrAnGoLo 1 , 

G. terrAneo 1 , K. hArriS 3 

1 Politecnico di Milano, Chemistry Materials Chemical 

Engineering “Giulio Natta”, Milano, Italy 

2 Italian Institute of Technology, Centre for Nano Science and 

Technology, Milano, Italy 

3 Cardiff University, School of Chemistry, Cardiff, United 

Kingdom 

Discrete and extended cavities are used in many different 

applications, e.g. gas absorption, transport, and conductivity. They 

can also function as nanoreactors and products formed in such 

confined environments can differ significantly from those formed 

in the bulk solution due to the unique constrains the cavity 

imposes on the reagents. 

The dynamic behavior and reactivity in crystalline solids is 

a field of increasing interest and solid-state reactions induced by 

external stimuli are useful as they can be employed to synthesize 

new classes of responsive materials. Recently, we demonstrated 

that α,ω-bis(trimethilammonium)alkanes diiodides are 

dynamically porous materials capable of selective uptake of 

α,ω-diiodoperfluoroalkanes in solution and gas-solid 

self-assembly processes driven by halogen bonding, the non 

covalent interaction where halogen atoms work as electron density 

acceptors. 

In this communication we will exploit further the unique 

and useful opportunities offered by the dynamic behavior of 

crystalline bis(trimethylammonium)alkane salts. We will 

describe that the size matching between the cation and 

self-assembled supramolecular anions allows unstable and 

previously unknown species to be prepared in quantitative yields. 

Specifically, we will report that the encapsulating ability of the 

1,6-bis(trimethylammonium)hexane cation (hexamethonium 

2 cation) and its tendency to pin a tetrahalide dianion X Y ? 2 2 

(X, Y = Cl, Br, I) via a net of hydrogen bonds is robust enough to 

drive the quantitative formation of hexamethonium salts 

2- 2- 2- containing the discrete dianions I , I2Br , and I2Cl . These 

4 2 

2 

dianions are formed via a thermally induced I elimination from 

2 

- hexamethonium salts containing the I , I2Br 3 

- , and I Cl 2 - anions 

respectively. Halogen bonding, hydrogen bonding, and 

components prearrangement are crucial in allowing for the 

solid-gas reaction. The reported results prove that the relevance 

of interactions involving polyhalides can be engineered in the 

purposeful obtainment of new polyhalides if interactions and their 

selectivity are maximized in the constrained environment of 

crystalline solids. 

Keywords: Polyhalides; Self-assembly; Solid-state reactions; 

Iodine; Gas-phase reactions; 



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o - 2 4 6 

SoLution-LiKe CheMiStry in CryStALS of 

networKed MoLeCuLAr hoStS 

y. inoKuMA 1 , M. fuJitA 1 

1 The University of Tokyo, Applied Chemistry School of Engineering, 

Tokyo, Japan 

While many molecular hosts are known to encapsulate 

specific guest molecules and to induce unusual chemical events 

in solution, most of them become inactive when they are closely 

packed in the crystalline state. In porous crystals, however, 

molecules in fluid pores maintain their solution-like mobility and 

reactivity. We utilized this pseudo-solution state in porous crystals 

to transfer solution chemistry into the solid state. 

By means of self-assembly strategy, we synthesized 

porous coordination networks composed of an infinite array of 

Co L (L: 2,4,6-tris(4-pyridyl)triazine) molecular hosts as single 

6 4 

crystals. The host subunit was isostructural to a molecular 

Pd L cage which hosts a lot of guests in solution. The crystalline 

6 4 

Co L host combines molecular-size host cavities and large 

6 4 

interstitial pores of 1.2 nm diameter, and solution-like guest 

accommodation occurs even in a crystalline state. Since guest 

binding takes place in a single-crystal to single-crystal fashion, 

the crystal structures of host-guest complexes have been 

unambiguously determined by X-ray crystallography. 

With a pair of solution and crystalline hosts, we can easily 

transfer unique reactions induced by molecular hosts in solution 

into a heterogeneous system. When a host-guest complex 

of Pd L cage and 4-hydroxydiphenylamine was treated with 

6 4 

EtNCO, chemoselective acylation occurred only on the OH group. 

The same selectivity was reproduced in the cavity of networked 

Co L cages. Furthermore, this unusual chemoselectivity was 

6 4 

explained by crystallographic analysis with crystalline host. 

In this presentation, we will present new results of solutionlike 

chemistry observed in crystals of networked molecular hosts. 

Keywords: host-guest systems; X-ray diffraction; Solid-state 

reactions; 


supramolecular Chemistry and Nanostructured Materials – ii 

o - 2 4 7 

PerSPeCtiveS in MoLeCuLAr teCtoniCS 

M. w. hoSSeini 1 

1 Universite de Strasbourg Institut Le Bel, Laboratoire de 

Chimie de Coordination Organique, Strasbourg, France 

The design and construction of periodic architectures in the 

crystalline phase or at surfaces are attracting considerable interest 

over the last two decades. For both design and analysis of 

molecular crystals, we have developed a strategy called molecular 

tectonics which is based on the formation of molecular networks 

through the design of complementary tectons or molecular 

construction units. The generation of molecular networks and 

subsequently of crystals is achieved by self-assembly processes 

based on repetitive molecular recognition events. This approach, 

combining supramolecular synthesis and self-assembly processes 

in the solid state, is operational and versatile and allows the design 

and construction of a variety of complex purely organic or hybrid 

architectures. The approach will be presented and illustrated by a 

variety of tectons and networks. 

references: 

1. Hosseini, M. W. Acc. Chem. Res., 2005, 38, 313. 

2. Hosseini, M. W. Chem. Commun., Focus Article, 2005, 582. 

3. Hosseini, M. W. Cryts.Eng.Comm., 2004, 6, 318 

4. Hosseini, M. W. Actualité Chimique., 2005, 290-291, 59. 

5. Hosseini, M. W. “LES AVANCEES DE LA CHIMIE”, 

Actualité Chimique, 2011, 348-349, 36. 

Keywords: Supramolecular Chemistry; Solid-state structures; 

Crystal engineering; Crystal growth; Cyanides; 



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supramolecular Chemistry and Nanostructured Materials – ii 

o - 2 4 8 

interfACiAL SySteMS CheMiStry: 

SurfACe-teMPLAted ASSeMBLy of 

three-diMenSionAL funCtionAL 

frAMeworKS. 

C. woeLL 1 

1 Karlsruhe Institute of Technology, Institute of Functional 

Interfaces, Karlsruhe, Germany 

Supramolecular chemistry holds unique prospects for the 

fabrication of novel functional materials. Molecularly precisely 

defined, nanometer-sized subunits which may already be rather 

complex self-assemble to form even more complex structures 

which exhibit functionalities not provided by the individual 

building blocks. 

We extend the fabrication of surface-anchored networks 

beyond the formation of planar, two-dimensional adlayers [1] by 

demonstrating the synthesis of highly-ordered, three-dimensional 

porous metal-organic frameworks (MOFs) nucleated on modified 

Au substrates. We will demonstrate the principle of liquid phase 

epitaxy [2] for the case of [Cu (BTC) (H O) ] (HKUST-1) grown 

3 2 2 n 

on COOH- and OH-terminated SAMs using Cu(II) acetate as the 

metal precursor and BTC (benztricarboxylic acid) as the organic 

ligand. The rather different fabrication mechanisms underlying 

the LPE-process – alternating exposure to the reactants in contrast 

to the standard solvothermal synthesis – allows to access novel 

MOF-structures and makes it possible to control the phenomenon 

of interpenetration. [5] 

The availability of porous frameworks rigidly anchored to 

solid surfaces opens the prospect of adding additional 

functionality to these ultrathin surface coatings [7] by placing 

nanoobjects inside the pores within the MOFs, e.g. metal clusters 

or dye molecules. [6] We will demonstrate the potential of this 

approach by loading the three-dimensional porous scaffolds with 

metal-containing molecules such as ferrocene and then 

characterizing their properties using electrochemistry. 

references: 

1. J.V. Barth, Annual Review of Physical Chemistry 58, 375 

(2007) 

2. O. Shekhah et al., J.Am.Chem.Soc. 129, 15118 (2007) 

3. C. Munuera et al., PCCP. 10, 7257 (2008) 

4. O. Shekhah et al., Angew. Chem. Int. Ed., 48, 5038 (2009) 

5. O.Shekhah et al., Nat.Mater. 8, 481 (2009) 

6. H.K. Arlsan et al., J. Am. Chem. Soc., 133 (21), 

8158–8161 (2011) 

7. O.Shekhah et al., Chem.Soc.Rev. 40, 1081 (2011) 

8. A.Dragässer et al., Chem. Comm., 48, 663 (2012) 

Keywords: Metal-Organic Frameworks; Surface Chemistry; 

Nanotechnology; 


supramolecular Chemistry and Nanostructured Materials – iii 

o - 2 4 9 

SuPrAMoLeCuLAr-tiLt-ChirALity for 

deSiGninG orGAniC CryStALS And PoLyMerS 

M. MiyAtA 1 

1 Graduate School of Engineering Osaka University, 

Department of Material and Life Science, Suita Osaka, Japan 

Studies on inclusion compounds of steroids and alkaloids 

led us to the finding about handedness of two-fold helical 

assemblies. This finding in supramolecular chirality has been 

connected with the following two facts. First, the handedness lie 

in seventy percent of over 600,000 crystal data according to the 

Cambridge Structural Database. Second, one can catch the 

handedness in the form of two-fold helical molecular assemblies, 

bundles of the helical assemblies, as well as complimentary 

helical assemblies of host and guest components. 

This presentation deals with discrimination of right- or 

left-handedness in supramolecular-tilt-chirality on the basis of 

two- or multi-point approximation method. The discrimination in 

supramolecular-tilt-chirality for organic crystals has consistency 

with that of molecular chirality for chiral molecules and helical 

polymers. The conventional crystallographic theory is surely 

correct in the case of atoms and ions with spherical symmetry, but 

is not always correct in the case of organic molecules with various 

shapes. 

The supramolecular-tilt-chirality method is effective for 

designing organic crystals and polymers with two-fold helices. 

We applied this to bundling of two-fold helical hydrogen-bonded 

networks as well as so-called asymmetric crystallization of achiral 

organic molecules, such as polyaromatic compounds. We now 

know that most of organic crystals consist of helical assemblies 

with right- or left-handedness, likewise biopolymers such as DNA 

and proteins. 

A series of aliphatic ammonium anthracenedisulfonates have 

enabled us to diversely arrange their anthracene moieties in the 

crystalline state. These moieties allowed us to observe static and 

dynamic modulations of optical and electrical properties. 

The systematic investigation indicates a relationship between the 

arrangements and the properties. Finally, this presentation covers 

a hierarchical construction of inclusion crystals consisting of 

1,8-anthracenedisulfonate and triphenylmethylamine through 

chairlike hydrogen bonding networks. Such crystals have stacked 

ellipsoidal supramolecular beads which exhibit guest-responsive 

fluorescence. 

Keywords: solid-state structures; helical structures; chirality; 

fluorescence; supramolecular chemistry; 



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o - 2 5 0 

MeSoPorouS And MiCroPorouS MAteriALS 

for BioMediCAL APPLiCAtionS 

L. de CoLA 1 , S. Kehr 1 , z. Li 1 

1 Westfalische Wilhelms-Universitat Munster, Center for 

Nanotechnology, Muenster, Germany 

Porous materials such as zeolites L, and ordered mesoporous 

silica systems are interesting containers which can reach small 

dimensions and can with appropriate functionalization be 

biocompatible. In this talk I will show that silica based materials 

can be used to target label and kill antibiotic resistant bacteria 

using light. The multifunctional nanocontainers can be used for 

diagnostics purposes and their uptake by different type of cell 

will be shown. The combination of imaging and deliver will be 

demonstrated with a very recent result. Cellular uptake of 

nano-size zeolites can be followed by fluorescence microscopy 

and molecules entrapped inside the channels of the zeolites can 

be delivered into the nucleus of the cells. Indeed the channels can 

be opened upon degradation of a polymer used to coat the entire 

crystals. 

Finally the use of these silica materials for the patterning of 

surfaces will be discussed. The pattern can be obtains using micro 

contact printing and the functionalization with biomolecules will 

lead to the cell adhesion only in desired patterns. The use of chiral 

systems will allows the immobilization of only desired type of 

cells. 



o - 2 5 1 

CheMiCAL reACtionS of MoLeCuLAr CryStALS 

And AGGreGAteS under hiGh PreSSureS 

v. SChettino 1 

1 Universita di Firenze, Dipartimento di Chimica, Sesto 

Fiorentino Firenze, Italy 

In the last years information on chemical reactions at high 

pressures in molecular crystals and other molecular aggregates 

has been growing steadily involving a variety of systems and 

among others simple second row diatomics and triatomics, 

hydrocarbons, energetic materials, alcohols, clathrate hydrates. 

With the available data it is feasible to attempt a classification of 

high pressure chemical reactions primarily into reversible and 

irreversible processes depending of the free energy profile from 

reactants to products and its modification going from ambient to 

high pressures and the heigth of the enrgy barriers. In several 

experiments and in ab initio molecular dynamics modeling the 

role of excited electronic states in high pressure reactivity has 

been highlighted and a novel dynamic view of the topochemical 

principle has been brougth forward as a source of selectivity in 

high pressure processes as a subsection of solid state chemistry. 

The collective character of high pressure solid state reactions has 

also been evidenced. The synergy of the combined use of 

pressurization and photoactivation has been shown to be an 

invaluable source of information on the the high pressure reaction 

mechanisms. 

These concepts will be discussed with results on high 

pressure reactions in simple hydrocarbons (condensation, 

polymerization, amorphization), on simple alcohols and on 

clathrate hydrates. 

references: 

1. V.Schettino, R. Bini, M. Ceppatelli, L. Ciabini, M. Citroni 

Adv. Chem. Phys. 131 (2005) 105 

2. L. Ciabini, F. A Gorelli, M. Santoro, Roberto Bini, 

V. Schettino, S. Raugei 

Nature Mater. 6 (2007) 39 

3. R. Bini, V. Schettino 

Chem. Soc. Rev. 36 (2007) 869 

4. M. Citroni, R. Bini, P. Foggi and V. Schettino 

PNAS 105 (2008) 7658 

5. M. Ceppatelli, R. Bini, V. Schettino 

PNAS 106 (2009) 11454 

6. S. Fanetti, M. Ceppatelli, M. Citroni, R.Bini 

J. Phys. Chem. B, 115 (2011) 15236; 114 (2010) 15437 

Keywords: high pressure chemistry; solid state chemistry; 

photoactivation; 



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Nanoporous Materials – i 

o - 4 0 4 

ControLLinG And MAintAininG the 

StruCture of teMPLAted PorouS MAteriALS 

A. Stein 1 

1 University of Minnesota, Department of Chemistry, 

Minneapolis, USA 

Nanoporous and nanostructured materials are becoming 

increasingly important for advanced applications involving, for 

example, bioactive materials, catalytic materials, energy storage 

and conversion materials, photonic crystals, membranes, and 

more. Templating methods based on hard templates (colloidal 

crystal templating, nanocasting) and soft templates (surfactant 

systems) provide access to nanostructured porous materials in 

which both the internal pore architecture and the material’s 

morphology can be controlled at a range of length scales from the 

subnanometer to the millimeter scale. Significant benefits of 

materials with structural features of nanometer and submicrometer 

dimensions have been demonstrated for numerous applications, 

at least at the proof-of-concept stage. Some applications profit 

from short diffusion paths in hierarchical nanostructures. Other 

applications take advantage of the relatively high surface areas of 

nanoporous solids and the often associated improved reactivity. 

However, in many applications the operating environment puts 

extreme demands on the material, perhaps due to external and 

internal mechanical forces, high temperatures needed for efficient 

operation, or involvement of the material in a reaction. It can be 

difficult to maintain structural features at small length scales and 

even bulk morphologies under those conditions. This presentation 

highlights methods of controlling pore architecture and materials 

morphology and will then outline limitations and recent advances 

in stabilizing porous materials under reactive or high temperature 

conditions. 

Keywords: Template synthesis; Mesoporous materials; 



o - 4 0 5 

SiLiCA MeSoPorouS CryStALS with 

iCoSAhedrAL And dodeCAGonAL-PriSM 

MorPhoLoGieS; MuLtiPLy twinned or 

quASiCryStALLine? 

o. terASAKi 1, 2 , C. xiAo 1 , n. fuJitA 3 , K. MiyASAKA 1, 2 , 

1, 4 

y. SAKAMoto 

1 MMK, Bezelii Center EXSELENT, Stockholm University, 

Sweden 

2 EEWS, WCU program, Kaist, Daejeong, Republic of South 

Korea 

3 Inst. of Multidisciplinary Research for Advanced Materials, 

Tohoku Univ., Japan 

4 Nanoscience and Nanotechnology Research Centre, Osaka 

Prefecture Univ., Japan 

A mesoporous silica crystal is formed through co-operative 

self-organisation of surfactant and silica in water. We have 

confirmed by electron crystallography that sphere packing 

(Space groups (SGs): Fm-3m, P6 mmc), polyhedra packing 

3 

(SGs:Fd-3m,Pm-3n, Cmmm, P4 /mnm), cylindrical (SG:p6mm) 

2 

and bi-continuous (SGs: Ia-3d, Pn-3m) structures are formed in 

this order as surfactant concentration increases. Most of 

mesoporous silica crystals show characteristic morphology which 

is commensurate with crystallographic point group symmetries. 

We have synthesized a crystal which shows well-resolved 

powder XRD profile but its icosahedral morphology does not fit 

any crystallographic point group symmetry in the sphere-packing 

regime. [1] Furthermore, recently we have succeeded in 

synthesising a mesoporous silica crystal, which indicates twelvefold 

symmetry in both morphology and electron diffraction 

pattern in polyhedra-packing regime. [2] 

From electron microscopy (EM), the crystal with 

icosahedral morphology is multiply-twined particle (MTP) of 

FCC structure and the second one is a dodecagonal quasicrystal 

in the center surrounded by twelve fans of crystalline domains in 

the peripheral part.The details will be given at the Conference. 

references: 

1. K. Miyasaka, L.Han, S. Che & O. Terasaki, Angew.Chem. 

Int. Ed., 45, 2006, 6516. 

2. C. Xiao, N. Fujita, K. Miyasaka, Y. Sakamoto & 

O. Terasaki; Submitted to Nature. 



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o - 4 0 6 

ionoSiLiCAS: PeriodiC MeSoPorouS 

orGAnoSiLiCAS froM ioniC PreCurSorS 

P. heSeMAnn 1 

1 Institut Charles Gerhardt, CMOS, Montpellier, France 

Ionosilicates (or so-called ‘i-silicas’) are defined as silica 

based materials containing covalently tethered ionic groups. 

These materials, situated at the interface of silica hybrid materials 

and ionic liquids, have large potential in catalysis, molecular 

recognition and separation. This talk will summarize our ongoing 

efforts in different areas related to the synthesis and applications 

of i-silicas. In a first part, we will focus on different aspects of 

the formation of i-silica phases displaying defined architectures 

on a mesoscopic level. I-Silicas are obtained via template 

directed hydrolysis-polycondensation reactions using ionic 

trialkoxysilylated precursors. Nanostructured phases can be 

obtained thank to specific interactions of these ionic precursors 

with complementary surfactants. We will show that the 

formation of structured phases can be achieved from suitable 

surfactant-precursor ion pairs. This approach is particularly 

appealing as both the nature of the organo-ionic part of the 

precursor and the the chemical constitution of the surfactant can 

be modulated. The second part is devoted to applications 

of i-silicas in catalysis and separation. I-Silicas show interesting 

catalytic properties in various organocatalytic reactions. In several 

cases, synergistic effects between silica support and the tethered 

ionic substructure allow increasing significantly the catalytic 

activity compared to pure ionic liquids. Finally, i-silicas appear 

as efficient ion exchange materials displaying Hofmeister 

selectivity. 

Keywords: Periodic mesoporous organosilica; Ionic liquids; 

Template syntheses; 

Nanoporous Materials – ii 


o - 4 0 7 

nAnoPorouS orGAniC-inorGAniC hyBrid 

MAteriALS: PoroSity MeetS SurfACe 

CheMiStry 

M. froeBA 1 

1 University of Hamburg, Institute of Inorganic Chemistry, 

Hamburg, Germany 

Nanoporous organic-inorganic hybrid materials with ordered 

pore structures exhibit a high potential for important applications 

like gas storage and separation, heterogenous catalysis, sensors 

and drug release. The usage of appropriate organic-inorganic 

precursors in the presence of structure-directing agents allows the 

synthesis of micro- or mesoporous hybrid materials with defined 

high porosity and tailored surface chemistry. This lecture is 

dealing with the principles of the synthesis strategy of 

microporous metal-organic frameworks (MOFs) and periodic 

mesoporous organosilicas (PMOs) as well as with the application 

of these materials for storage, separation and light harvesting. 

Keywords: Metal-organic Frameworks; Mesoporous materials; 



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Nanoporous Materials – ii 

o - 4 0 8 

PorouS orGAniC MAteriALS 

S. BrAeSe 1 

1 Karlsruhe Institute of Technology, Insitute for Organic 

Chemistry, Karlsruhe, Germany 

Porous organic materials such as Hyper-Cross-linked 

Polymers (HPCs) and Polymeric Porous Networks (PPNs) have 

raised considerable interest in the material science community due 

to their host-guest interactions. The pores within these materials 

are indeed capable of specific host uptake and release. This opens 

the door to applications such as gas storage and separation but 

also to racemic resolution and asymmetric synthesis if materials 

bearing enantiomerically pure pores are used. 

In contrast to inorganic material such as zeolites or hybrid 

networks like Metal organic frameworks (MOFs), purely 

organic porous materials convince by unreached low densities 

which are particularly appealing for the automotive sector and by 

their ease of processing, post-functionalization and of introducing 

chirality. 

We have developed an easy and rapid access to 

tetraphenylmethane (TPM) and tetraphenyladamantane (TPA) as 

well as to hexaphenyl-p-xylene (HPX) cores. These tetrahedral 

and pseudo-octahedral molecules serve as precursors out of which 

a whole range of different tectons can readily be prepared and 

serve directly for network generation. 

Using the same concept of modularity, we also prepared 

some fullerene hexakis adducts bearing octahedral topology. 

These tectons will again serve for networks generation. 

references: 

1. W. Lu, D. Yuan, D. Zhao, C. I. Schilling, O. Plietzsch, 

T. Muller, S. Bräse, J. Guenther, J. Blümel, R. Krishna, 

Z. Li, H.-C. Zhou, Chem. Mater. 2010, 22, 5964–5972. 

Porous Organic Frameworks: Porosity and Clean Energy 

Applications 

2. A. Singh, M. Tolev, M. Meng, K. Klenin, O. Plietzsch, 

C. I. Schilling, T. Muller, M. Nieger, S. Bräse, W. Wenzel, 

C. Richert, Angew. Chem. 2011, 123, 3285-3289; Angew. 

Chem. Int. Ed. 2011, 50, 3227–3231. Branched DNA that 

Forms a Solid at 95 °C 

3. O. Plietzsch, C. I. Schilling, T. Grab, S. L. Grage, 

A. S. Ulrich, A. Comotti, P. Sozzani, T. Muller, New 

J. Chem. 2011, 15, 1577–1581. Click Chemistry Produces 

Hyper-Cross-linked Polymers with Tetrahedral Cores 

Keywords: Organic Materials; Click chemistry; Porous 

networks; Gas storage; 

Nanoporous Materials – iii 


o - 4 0 9 

PorouS AroMAtiC frAMeworKS: SyntheSiS, 

StruCture, And funCtionS 

t. Ben 1 , q. ShiLun 1 

1 Jilin University, Department of Chemistry, Changchun, China 

In last decades, many efforts were applied to improve the 

surface area and heat of adsorption of artificial porous materials. 

Among those synthesized ultrahigh surface area porous solids, 

porous aromatic frameworks (PAFs) express highest Brunauer- 

Emmett-Teller (BET) surface area and excellent physicochemical 

stability to meet the criteria of post-combustion. In 2009, our 

group have developed a method to synthesis the first long range 

ordered PAFs with dia topology (PAF-1), which show a record 

surface area (S = 5640 m BET 2 g-1 ) at that time and exceptional 

physicochemical stability via a nickel(0)-catalyzed 

Yamamoto-type Ullmann cross-coupling. Besides, PAF-1 also 

shows very high uptakes of carbon dioxide (1.3 g g-1 at 40 bar, 

298 K) to make it a good candidate for carbon dioxide storage. 

Recently, this record was broken by a porous aromatic polymer 

network PPN-4, which shows the BET surface area as high as 

6461 m2 g-1 . Combined with such an impressive surface area, 

PPN-4 can adsorb 2121 mg g-1CO (212 wt %) at 50 bar and 

2 

295K. Before PPN-4 was reported, same porous organic 

framework had already been synthesized by Cooper’s group 

(S =1102 m BET 2 g-1 ) and our group as PAF-3 (S = 2932 m BET 2 g-1 ) 

independently via Yamamoto type Ullmann cross-coupling with 

different synthesis conditions. In addition to the dramatic CO2 storage properties of PAFs, we also find that PAFs have high 

selective adsorption properties on green house gas such as CO2 and CH . Zhou also report high selectivity of CO /N by grafting 

4 2 2 

sulfonic acid and its lithium salt on the framework of PAF-1. 

These progresses indicated that PAFs is such a robust material 

that not only store large amount CO at high pressure but also 

2 

selectively adsorb green house at ambient condition which meet 

the criteria of post-combustion capture of CO . 2 

Keywords: Adsorption; Microporous materials; Host-guest 

systems; Carbon dioxide fixation; Molecular recognition; 



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o - 4 1 0 

MetAL orGAniC frAMeworKS for CLeAn 

enerGy APPLiCAtionS 

G. ShiMizu 1 , r. vAidhyAnAthAn 1 , S. ireMonGer 1 , 

J. tAyLor 1 

1 University of Calgary SA 109, Department of Chemistry, 

Calgary Alberta, Canada 

Until affordable green options are available, fossil fuels will 

remain a primary source of energy. Carbon capture represents a 

means of mitigating the greenhouse effects of fossil fuel 

combustion. This approach also presently carries significant costs 

making widespread adoption challenging. Part of this presentation 

will focus on the opportunities and challenges to make fossil fuel 

energy production greener including the idea of solid sorbents, 

such as metal organic frameworks (MOFs), for gases. 

MOFs represent tunable molecular scaffolding that can be 

adjusted for a breadth of applications. This presentation will 

concern our efforts towards tailoring the properties of MOFs 

towards energy challenges. [1] The first concerns our efforts to 

make MOFs with amine lined pores for CO capture. In contrast 

2 

to liquid amines which chemisorb CO and have high energy costs 

2 

for regeneration, the MOF approach gives physisorbed gases and 

hence more facile release. Despite the weaker binding mode, we 

will show that high selectivities are possible owing to heats of 

adsorption over 40 kJ/mol. [2] A key challenge for this field is to 

make MOFs that are more hydrolytically stable. Some of our 

recent results concern efforts to make more water stable MOFs 

using phosphonates and related linkers. [3] 

references: 

1. a) J. Long, O. Yaghi,Chem. Soc. Rev., 2009, 38, 1213. 

b) G. Férey et al., Chem. Soc. Rev. 2011, 40, 550. 

c) K. Sumida et al., Chem. Rev., 2012, 112, 724. 

d) J. Li et al. Chem. Rev., 2012, 112, 869. 

e) S. Keskin et al. ChemSusChem, 2010, 3, 879. 

2. a) R. Vaidhyanathan et al. Science, 2010, 330, 650-653. 

b) R. Vaidhyanathan et al. Angew. Chem, 2012, 51, 1826. 

3. Iremonger, S. S. et al., J. Am. Chem. Soc. 2011, 133, 20048. 

Keywords: MOFs; CO capture; Porous solids; 

2 



o - 4 1 1 

LuMineSCent MoLeCuLeS Confined 

in PorouS And LAyered MAteriALS: 

enhAnCed PhotoeMiSSion ProPertieS 

And oPtoeLeCtroniC APPLiCAtionS 

L. MArCheSe 1 , CArniAto f. 1 , CuCinottA f. 1 , 

C. BiSio1 1 Dipartimento di Scienze e Innovazione Tecnologica and 

Nano-SiSTeMI Interdisciplinary Centre, Universitá del 

Piemonte Orientale A. Avogadro, Viale T. Michel 11, I-15121 

Alessandria, Italy 

The confinement of luminescent dyes and polymers into the 

nanospaces of porous or layered materials may prevent molecules 

aggregation and improve their thermal and photochemical 

stability along with their photoemission properties. These 

requirements are key points for the development of efficient 

hybrid optoelectronic devices (HLED). In this field, our research 

group recently developed novel hybrid luminescent solids based 

on nano-sized MCM-41 and platelet SBA-15 silica containing 

inside the pores fluorescein and electroluminescent 

polyphenylenevinylene (PPV) co-polymer (super yellow), 

respectively. [1] Higher quantum efficiency, mainly related to a 

reduction of aggregates of the pure dyes, and improved 

photostability were observed in both host-guest systems. 

Moreover, hybrid photonic antenna based on SBA-15 solid, where 

an encapsulated donor (PPV co-polymer) transfers the 

photoexcitation energy directly to an acceptor (cyanine dye) 

covalently linked on the external surface was also developed as 

promising candidate for use in optoelectronic devices. 

Recently, luminescent organo-modified layered materials 

were syntesized and tested as light-emitting film in HLED 

devices. The structural properties along with their tunable 

hydrophilicity/hydrophobicity render these solids suitable to host 

and stabilize different luminescent entities. In this respect, two 

systemes will be described: i) a synthetic saponite intercalated 

with a luminescent polyhedral oligomeric silsesquioxane (POSS) 

bearing in the structure a cyanine molecule and ii) a hydrotalcite 

decorated on the surface with electroluminescent semiconductor 

quantum dot crystals. [2] Both systemes were used as emitting films 

in LED devices, because of their enhanced quantum yield 

efficiency and improved photostability. 

references: 

1. F Cucinotta, F. Carniato, C. Bisio, L. Marchese et al., 

Chem. Mater., 2011, 23, 2803; F. Carniato, C. Bisio, L. 

Marchese et al., J. Mater. Chem., 2010, 20(26), 5504. 

2. J.S. Bendall, L. Marchese et al., Adv. Funct. Mater., 2010, 

20, 3298. 



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Novel Materials and Molecular interactions 

o - 4 1 2 

PorouS AMorPhouS orGAniC CAGeS: 

An exPeriMentAL And MoLeCuLAr dynAMiC 

SiMuLAtion Study. 

S. JiAnG 1 , A. trewin 1 , A. CooPer 1 

1 University of Liverpool, Department of Chemistry, Liverpool, 


Email: aicooper@liv.ac.uk 

The design of porous organic molecular solids where 

packing is dictated by weak van der Waals forces is attracting 

considerable attention. We have developed a series of organic cage 

molecules that can be used for the construction of self-assembled 

crystalline porous materials. Furthermore, we have found these 

cage molecules can badly pack, creating permanent porosity in 

the amorphous solid state. Interestingly, the gas selectivity in these 

amorphous cage materials can be fine tuned by varying the ratio 

of reagents in the reaction. A better understanding of this 

phenomenon will aid in the optimization and development of 

industrial applications of these amorphous materials in separation 

and catalytic process. 

An alternative approach for characterizing these amorphous 

materials is based on molecular simulations. We developed a 

methodology to generate simulated structures of amorphous cage 

materials. All simulated models are characterized by their porosity 

with surface area, pore size distribution, density and microporous 

volume. The results show good agreement with available 

experimental data. The dynamic diffusion of gas molecules 

(mainly H , N ) through cavities or pores of amorphous organic 

2 2 

cages were investigated using MD simulations. The trajectory of 

H in amorphous cage 1 exhibits a broader range of displacement 

2 

compared to N , which indicates a faster diffusion of H . 

2 2 

Therefore, amorphous cage 1 displays gas selectivity for H over 2 

N . We also suggest that the enhanced porosity in these amorphous 

2 

solids results predominantly from the extrinsic porosity. 

references: 

1. Jiang, S.; Jones, J. T. A.; Hasell, T.; Blythe, C. E.; 

Adams, D. J.; Trewin, A.; Cooper, A. I. Nat Commun 

2011, 2, 207 

Keywords: Molecular dynamics; Micropore materails; Cage 

compounds; Nanostructures; 



o - 4 1 3 

AMinoGuAnidine And diAMinoGuAnidine AS 

AdAPtive CAtioniC BuiLdinG BLoCKS in 

orGAnoSuLfonAte StruCtureS 

d. G. duMitreSCu 1 , M. BArBoiu 2 , A. vAn der Lee 2 , 

y. M. LeGrAnd 2 

1 University Politehnica of Bucharest, FACSM Organic 

Chemistry Department, Bucharest, Romania 

2 Institut Européen des Membranes, Adaptive Nanostructures, 


Crystal engineering is a very delicate process which depends 

on many factors, and, as a consequence the final structure can 

rarely be predicted. Crystal engineering usually overcomes these 

obstacles by relying on strong, directional interactions like 

hydrogen bonding and dipolar forces. 

The structural backbone of one of the most versatile and 

widely used systems, guanidinium-sulfonate assemblies, is a 

honeycomb lattice of R2 (8) H-bond rings which assemble into 

2 

ribbons and larger R3 (12) patterns. The numerous papers 

6 

published on this subject provide ample amounts of data on the 

effect of organic R substituent on crystal packing and overall 

structure type (bilayer, brick etc.). 

To our knowledge no attempt was made to change the 

cationic component in these systems, the guanidinium moiety. 

The aim of the current work is to investigate the structural 

versatility of aminoguanidine and diaminoguanidine as cationic 

components together with representative organic sulfonates. 

The 7 new crystal structures demonstrate the versatility of 

these new cationic components to form supramolecular 

hydrogen-bonding assemblies. Furthermore, aminoguanidine 

proved to be adaptable, by forming a R2 (10) dimer in the 

2 

structures where the total number of hydrogens available of 

H-bonding exceeds the total number of H-bond acceptors. 

Diaminoguanidine presented this motif in all the structures 

studied, with the orientation of the elongated dimer mimicking 

the width of the organic group from the sulfonates. 

Keywords: crystal engineering; hydrogen-bond patterns; 



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o - 4 1 4 

MAtrix-iSoLAtion And AB initio Study of the 

CoMPLex Between forMiC ACid And xenon 

q. CAo 1 , L. KhriAChtChev 1 , M. MeLAvuori 1 , 

M. räSänen 1 , J. LundeLL 2 

1 Universitty of Helsinki, Chemistry, Helsinki, Finland 

2 Universitty of Jyväskylä, Chemistry, Jyväskylä, Finland 

Formic acid (HCOOH, FA) is a useful model compound for 

understanding the properties of more complicated molecules and 

the intermolecular interactions, in particular, of biological interest. 

As the simplest organic acid, FA exhibits the conformational 

isomerism with respect to the rotation about the single C-O bond, 

which is a typical phenomenon in the conformational processes 

in carboxylic acids. Light-induced conformational change has 

allowed preparing dimers and complexes of the higher-energy 

conformer. Since rare-gas matrices are widely used to study 

conformational changes, understanding of the interactions 

between rare-gas atoms and different conformers is important. In 

present work, we study the complexes of trans- and cis-FA with 

a Xe atom using IR spectroscopy in an argon matrix. The 

geometries, interaction energies, reaction barriers, and vibrational 

spectra of the 1:1 FA···Xe complexes are calculated by the ab 

initio method at the MP2 level of theory. The calculations reveal 

four structures for the trans-FA···Xe complex and four structures 

for the cis-FA···Xe complex. In the experiments, two structures 

of the trans-FA···Xe complex are observed after deposition of 

FA/Xe/Ar matrices, with and without OH···Xe interaction 

(H-bonded and non-H-bonded structures). The cis-FA···Xe 

complex was synthesized by vibrational excitation of the 

non-H-bonded trans-FA···Xe complex. The non-H-bonded and 

H-bonded structures of the cis-FA···Xe complex are observed 

after the excitation. The decay of the H-bonded and non-H-bonded 

cis-FA···Xe complexes in an argon matrix is, respectively, 

substantially slower and faster compared to the cis-FA monomer. 

This observation is explained by the different tunnelling barriers 

for these species. This is the first experimental report of the 

non-H-bonded complex for cis-FA. This work is partially 

motivated by anaesthetic properties of xenon, which enhances the 

importance of research on the interaction between Xe atoms and 

organic molecules. 

Keywords: Ab initio; formic acid; xenon; Tunnelling; Matrix 

isolation; 



o - 4 1 5 

ioniC nAnoPArtiCLe networKS: new 

verSAtiLe hyBrid MAteriALS 

M. neouze 1 

1 Vienna University of Technology, Institute of Materials 


Recently ionic nanoparticle networks (INN) were 

reported in the frame of the remarkable development of new 

inorganic-organic hybrid materials based on nanoparticle 

assembly. The original method we developed to synthesize 

3-D networks is based on the functionalization of metal oxide 

nanoparticles with ionic linkers, the bridging ligands containing 

imidazolium units. Recent publications pointed out the powerful 

synergy of ionic species with nanoparticles. Such synergy makes 

those new inorganic-organic hybrid materials promising 

candidates for many applications such as catalysis or luminescent 

devices, as will be exemplified in this communication. 

Focusing on catalysis for CO activation reactions, the 

2 

combination of high imidazolium content with the presence of 

metal centers, also able to coordinate to CO molecules, makes 

2 

the hybrid materials INN highly promising catalysts. In addition 

the imidazolium bridging units in the final hybrid material renders 

the INN tailorable, while the INN materials are solid, which 

allows an easy separation of the catalyst after reaction. Thus, INN 

materials, with mono- and di-imidazolium bridging units as well 

as with various counter anions, were investigated as catalysts for 

the cycloaddition of CO into different starting epoxides. 

2 

The photoluminescent properties of INN were also studied. 

It appears that INN materials are luminescent in the visible range. 

The excitation wavelength as well as the wavelength of maximum 

emission can be tailored when modifying the imidazolium linker 

used to link the nanoparticles. In parallel, the short-range order of 

the network was investigated via small-angle X-ray scattering. 

This short-range order was interpreted as originating from 

self-organization of the aromatic rings of the ligands bridging the 

nanoparticles by means of pi-pi stacking. This hypothesis was 

validated by luminescence investigations on the hybrid materials. 

Keywords: Materials Science; Nanoparticles; Luminescence; 

Stacking interactions; Cycloaddition; 



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o - 4 1 6 

A new MonAzite PhASe forMed froM 

StrontiuM fLuoroPhoSPhAte 

J. rutter 1 , A. wriGht 1 

1 University Of Birmingham, School of Chemistry, Birmingham, 


Fluorophosphates (PO F 3 2- ) are a fluorine derivative to an 

3- orthophosphate (PO ), with the tetrahedral unit possessing at 

4 

least one P-F bond. Although these materials have been known 

since the early 1920’s, with a number of uses, particularly in 

dental care, their exploitation as a structural building block to new 

materials has been limited. To date, fewer than 25 structurally 

characterized monofluorophosphates have been reported. 

Our research has initially focused on the substitutional 

3- chemistry possible when PO is replaced by PO3F 4 

2- . To this end, 

we report the novel synthesis of a monazite structured SrPO F, 3 

formed from a readily available PO F 3 2- precursor via a 

precipitation reaction. 

Detailed structural studies, performed using neutron powder 

diffraction, X-ray fluorescence and Raman spectroscopy confirm 

SrPO F adopts the important monazite structure type (MXO ), 

3 4 

which is more commonly associated with rare earth phosphates 

[1] such as LaPO . This compound crystallises with space group 

4 

(P2 /n) and unit cell parameters a = 6.97293(6) ?, 

1 

b = 7.11850(5) ?, c = 6.71991(5) ? and β = 101.7629(7)°. The 

structure consists of distorted PO F 3 2- tetrahedron which form 

chains both parallel and perpendicular to the a axis, with an 

apparent ordering of the P-F bond and consequently the 

orientations of the distorted PO F 3 2- tetrahedra. This study also 

investigates the stability of these new materials. 

references: 

1. N. Clavier, R. Podor and N. Dacheux, J. European Ceram. 

Soc., 2011, 31, 941-976. 

Keywords: Materials Science; 



o - 4 1 7 

hiGhLy PorouS CArBon MAteriALS froM 

diCyCLoPentAdiene hiGh internAL PhASe 

eMuLSionS (hiPeS) 

S. KovACiC 1 , n. MAtSKo 2 , C. SLuGovC 1 

1 Graz University of Technology, Institute for Chemistry and 

Technology of Materials, Graz, Austria 

2 Graz Centre for Electron Microscopy, Graz Centre for 

Electron Microscopy, Graz, Austria 

Email: s.kovacic@tugraz.at 

The present work relates to the preparation of a threedimensional 

carbonaceous polyHIPE material using a high 

internal phase emulsion (HIPE) templating technology. Porous 

carbonaceous materials represent outstanding candidates for a 

range of applications such as water and air purification, 

adsorption, catalysis, electrodes and energy storage materials [1] . 

Using high internal phase emulsion (HIPE) templating 

technology [2] , porous carbonaceous materials can be obtained after 

the carbonization and the pyrolysis with fully accessible network, 

high (macro)pore volume of up to 10 cm3 /g and in a different 

shapes. 

Carbon precursor used in present work is an economically 

interesting monomer while it is a by-product of steam cracking of 

naphta and gas oils namely dicyclopentadiene (DCPD) which is 

cheap and readily available. PolyDCPD HIPEs posses very 

favourable mechanical properties. [3] After the pyrolysis material 

undergoes major dimensional shrinkage (by factor of 2) however, 

interconnected porous morphology is completely maintained whit 

additional microporosity in the polymer walls. 

references: 

1. Suramoney S., Adv. Mater. 1998, 10, 1157-1171. 

2. Cameron, N. R., J. Chrom. Libr., 2003, 67, 255-276. 

3. a) Kovacic, S., Krajnc, P., Slugovc, C. Chem. Commun. 

2010, 46, 7504-7506, 

b) Kovacic, S., Jerabek K., Krajnc, P., Slugovc, C. Polym. 

Chem. 2012, 3, 325-328. 

Keywords: microporous carbon polymers; ring opening 

metathesis polymerization; 



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Molecular and Hybrid Porous Crystals 

o - 5 1 3 

PerMAnent PorouS MAteriALS froM 

ShAPe-PerSiStent orGAniC MoLeCuLeS 

M. MAStALerz 1 

1 University of Ulm, Institute of Organic Chemistry II & 

Advanced Materials, Ulm, Germany 

Porous materials derived from discrete organic compounds 

became a real alternative to systems like zeolites, metal-organic 

frameworks, covalent organic frameworks or amorphous porous 

organic polymers. 

The rational construction of molecular organic precursors, 

their synthesis and formation of functional porous materials are 

discussed. The compounds form porous materials with very high 

specific surface areas for both types of materials, intrinsic and 

extrinsic, achieving values of up to 2796 m2g-1 . [1–3] Furthermore, 

the processing porous molecules into functional devices is 

presented. 

references: 

1. M. Mastalerz, M. W. Schneider, I. M. Oppel, O. Presly, 


2. M. W. Schneider, I. M. Oppel, H. Ott, L. G. Lechner, H.- 

J. S. Hauswald, R. Stoll, M. Mastalerz, Chem. Eur. J. 

2012, 18, 836-847. 

3. M. Mastalerz, I. M. Oppel, Angew. Chem. Int. Ed. 2012, 

DOI: 10.1002/anie.201201174. 

Keywords: Crystal engineering; Materials science; Schiff 

bases; 



o - 5 1 4 

GAS StorAGe And SeLeCtivity in PorouS 

MetAL orGAniC frAMeworK MAteriALS 

M. SChroder 1 

1 The University of Nottingham, School of Chemistry, 

Nottingham, United Kingdom 

Metal-organic framework (MOF) complexes, constructed 

via combination of metal nodes with designed polychelate 

bridging ligands, are important hybrid materials that can show 

permanent porosity and excellent gas storage capabilities. 

Understanding the molecular mechanisms by which these porous 

materials trap gases is essential for the design of improved 

systems. In this lecture we focus on MOFs for the selective 

capture of CO from flue gases, and describe the synthesis, 

2 

properties and structures of a series of new porous materials 

derived from Al(III) and In(III) with isophthalate carboxylate 

bridging ligands showing novel structures and pore decoration. 

Materials functionalised with amine-groups dominate the 

area of CO capture largely because of their potential to form 

2 

carbamates via H N(δ-)—C(δ+)O interactions, thus trapping CO 2 2 2 

covalently. We report the synthesis and structure of a unique nonamine-containing 

porous solid NOTT-300 in which hydroxyl 

groups within the pores bind selectively to CO . NOTT-300 

2 

exhibits highly selective uptake of CO versus N , CH , H , CO, 

2 2 4 2 

O , Ar, and in situ powder X-ray diffraction (PXRD) and inelastic 

2 

neutron scattering (INS) studies, combined with density functional 

theory (DFT) modelling, reveal that these hydroxyl groups bind 

CO via the formation of O = C = O(δ-)···H(δ+)—O hydrogen 

2 

bonds. These are reinforced further by weak supramolecular 

interactions with C-H hydrogen atoms on the phenyl rings. This 

offers exciting potential for the application of new capture systems 

based on the soft binding of CO via the use of an ‘easy-on’ and 

2 

‘easy-off’ model. Parallel studies using PXRD, INS and DTF on 

the capture of SO have defined the structure of SO -loaded 

2 2 

NOTT-300. Furthermore, with In(III) we report an unprecedented 

partially-interpenetrated network showing high selectivity for CO2 based upon a defect structure that can be modelled by grand 

canonical Monte Carlo simulations. 

Keywords: metal organic framework materials; gas storage; 

inelastic neutron scattering; powder x-ray diffraction; CO2 and 

SO2; 



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o - 5 1 5 

ModeLLinG CoMPLex StruCture, PoroSity, 

And Co-oPerAtive diffuSion BehAviour in 

MoLeCuLAr PorouS orGAniC MAteriALS 

A. trewin 1 , M. LewiS 1 , d. hoLden 1 , 

J. JordAnoviC 1 , K. JeLfS 1 , A. CooPer 1 

1 University of Liverpool, Chemistry, Liverpool, United Kingdom 

Materials with molecular-scale porosity are important in a 

wide range of applications such as gas storage, molecular 

separation, and heterogeneous catalysis. Understanding complex 

gas sorption behaviour can give important information about the 

[1, 2] 

structural properties of a material and gas uptake mechanisms. 

We are developing novel methodologies for investigating the 

structure, time-dependent pore connectivity, co-operative 

diffusion mechanisms, and stepped gas sorption uptake behaviour. 

Discrete molecules tend to pack efficiently in the solid state 

resulting in minimal void volume, hence very few molecular 

materials exhibit permanent porosity. Molecular porous materials 

are able to respond locally to the presence of a guest leading to 

the potential for diffusion of molecules that would not be expected 

by analysis of the static crystalline structure. 

Here, we analyse molecular porous solids, for example Cage 

3 that packs to form a diamondoid 3-D pore structure running 

through restrictive cage windows. [3, 4] We show that by analysing 

the dynamic surface area properties of the molecular material 

as guest molecules diffuse, we can identify and understand 

the co-operative diffusion mechanisms. This will allow us to 

potentially design materials with porosity tailored for a specific 

application. 

references: 

1. T. Tozawa et al,Nature Mater. 2009, 8, 973–978. 

2. J. T. A. Jones et al, Angewandte Chemie 2011, 123, 775–779; 

3. J. T. A. Jones et al, Nature 2011, 474, 367–371; 

4. S. Jiang et al, Nat Commun 2011, 2, 207. 

Keywords: Microporous materials; Molecular dynamics; 

Surface analysis; Solid state structures; 

Hybrid Zeolites and Nanochemistry 


o - 5 1 6 

eni CArBon SiLiCAteS: truLy hyBrid 

orGAniC-inorGAniC zeoLiteS 

r. MiLLini 1 

1 Eni s.p.a. - refining&marketing division, San Donato Milanese 

Research Center - Physical Chemistry Dept., San Donato 

Milanese, Italy 

ECS materials form a new class of porous crystalline 

organic-inorganic hybrid aluminosilicates recently discovered, 

whose synthesis resembles that of zeolites, involving the 

hydrothermal treatment of a reaction mixture composed by 

NaAlO and a bridged silsesquioxanes [(R'O) Si–R–Si(OR') , 

2 3 3 

R = alkyl or aromatic groups; R' = Me or Et] as sources of alumina 

and silica, respectively. A set of ECS materials has been 

synthesized so far, by varying the nature of the bridged 

silsesquioxanes and the synthesis conditions. The characterization 

of these materials demonstrated that most part of the silica 

precursor does not undergo Si-C hydrolysis and are present 

unchanged in the crystalline phases. Though challenging because 

of the complexity of the XRD patterns, the determination of the 

crystal structure of some ECS materials was successful, providing 

important information on their characteristics. The ECS structures 

known so far consist of a stacking of alternating inorganic and 

organic layers and possess microporous systems, whose 

architecture varies from a phase to another. Taking into account 

the materials obtained with R = phenylene, different situations 

exist. ECS-2 is a clathrasil-like structure since the arrangement of 

the phenylene rings in the organic layers produces large cages not 

open to the exterior. In the structure of ECS-3 the relative 

arrangement of the phenylene rings generates an open porosity 

running within the organic layer only. More interesting is 

ECS-14 because it represents the first example of hybrid material 

with the structure related to a known zeolite framework type, i.e. 

AFI common to AlPO-5 and the silica SSZ-25 phases. 

The 12-membered ring linear channels are present even in 

ECS-14, crossing the inorganic and organic layers which stack 

along [001]. For other ECS materials, the structure determination 

is in progress and the results will be illustrated and discussed to 

provide an overview of this interesting class of materials. 

Keywords: Zeolites; Microporous materials; Layered 

compounds; X-ray diffraction; Electron diffraction; 



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o - 5 1 7 

hiGh PreSSure wAter intruSion 

inveStiGAtion on Pure SiLiCA CAGe-LiKe StttyPe 

zeoLite: infLuenCe of the 

MinerALizinG AGent 

L. tzAniS 1 , M. SouLArd 1 , J. PAtArin 1 

1 Université de Haute Alsace, Haut Rhin, Mulhouse cedex, 

France 

Crystalline pure silica polymorphs of microporous nature 

are attractive materials for several applications, especially in the 

energetic field. In these hydrophobic materials, the adsorption of 

water is extremely weak when the pressure is below the water 

saturation vapor pressure. By submitting these porous solids 

(zeosils) to an increasing hydrostatic pressure, the intrusion of 

water into the microporous matrices is observed. Depending on 

various physical parameters related to the porous material, the 

“zeosil-water” system is able to restore, dissipate or absorb the 

supplied mechanical energy during the compression step and 

therefore displays a spring, shock-absorber or bumper behavior. 

Cage-like system as STT-type zeosils has been studied and their 

experimental water intrusion–extrusion isotherms were performed 

at room temperature. These “zeosil–water” systems behave like a 

molecular spring and the phenomenon is reproducible over several 

cycles. The samples were obtained using two synthesis routes: 

hydroxide (SSZ-23(OH)) and fluoride media (SSZ-23(F)). 

Different characterizations have been realized before and after 

water intrusion–extrusion experiments in order to reveal the 

presence or not of defects after such experiments. For all samples, 

no structural modifications at the long range order were observed 

by XRD analysis. 29Si solid state NMR spectroscopy confirmed 

the presence of a small amount of silanol defects in the calcined 

materials which is more pronounced for the SSZ-23(OH) sample. 

Nevertheless, the amount of silanol defects observed is quite low 

(< 3% for SSZ- 23(F) and < 6% for SSZ-23(OH)). After 

intrusion-extrusion of water, due to the breaking of some siloxane 

bonds, the number of defect sites increases and consequently part 

of water still remains in the structure. However, for both 

SSZ-23 samples the “STT zeosil-water” can restore more than 

80 % of the stored energy corresponding to about 7.0 J.g-1 . 

Keywords: Hydrophobic zeolite; STT-type zeolite; water 

intrusion-extrusion experiments; 



o - 5 1 8 

SurfACe ModifiCAtion of ito LAyerS By 

AfM-BASed eLeCtrooxidAtive LithoGrAPhy 

d. Meroni 1 , S. Ardizzone 1 , S. hoePPener 2 , 

u. S. SChuBert 2 

1 Universita’ di Milano, Chemistry, Milano, Italy 


Macromolecular Chemistry, Jena, Germany 

Transparent conductive oxides like indium tin oxide (ITO) 

are fundamental components in manifold technological 

applications. The modulation of ITO surface properties, such as 

wettability, adhesion, and conductivity, is crucial to its integration 

in complex frameworks. Silane-based self-assembled monolayers 

(SAMs) have proved reliable systems to tailor the oxide 

surface properties. [1] The site-selective oxidation of SAMs by 

electro-oxidative probe lithography enables the assembly of 

nanoscale structures by supramolecular chemistry. [2] 

Here, we report for the first time the nanoscale oxidation of 

octadecyltrichlorosilane (OTS) monolayers onto ITO films by 

electro-oxidative probe lithography. The lithographic process 

results in a local overoxidation of the substrate, as confirmed by 

tests onto bare ITO. Moreover, the monolayer oxidation causes 

the conversion of –CH groups into hydrophilic functionalities. 

3 

This phenomenon was exploited to further modify the surface by 

site-selective growth of Ag nanoparticles. The oxidation process 

was studied by Scanning Kelvin Probe Microscopy (SKPM) and 

compared to the oxidation of the non-coated oxide and of the 

“reference” OTS-Si. Marked difference related to the oxidized 

monolayer are appreciable in SKPM images, which are not 

observable in topography or lateral force images. SKPM thus 

represents a powerful tool to investigate the monolayer oxidation. 

references: 

1. D. Meroni et al. J. Phys. Chem. C 2011, 115, 18649–18658. 

2. S. Hoeppener et al. Angew. Chem. Int. Ed. 2009, 48, 

1732–1739. 

Keywords: ITO; octadecyltrichlorosilane; electro-oxidative 

lithography; scanning Kelvin probe microscopy; atomic force 

microscopy; 



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solid state Chemistry and Nanochemistry 

o - 5 1 9 

MetAL-ASSiSted Growth of GerMAniuM 

nAnowireS: oPPortunitieS uSinG SoLid MetAL 

SeedS 

S. BArth 1 



One-dimensional (1D) semiconductor nano-architectures 

with tunable morphologies, dimensions, crystallographic phases 

and orientation are of tremendous interest for a broad range of 

applications. [1] Metal-seeded growth of 1D semiconductor 

nanostructures is still a very active field of research, despite the 

huge progress which has been made in understanding this 

fundamental phenomenon. Liquid growth promoters allow control 

of the aspect ratio, diameter and structure of 1D crystals via 

external parameters, such as precursor feedstock, temperature and 

operating pressure. However the transfer of crystallographic 

information from a nanoparticle seed to a growing nanowire has 

not been described in the literature. We investigated the formation 

of Ge nanowires using solid metal growth promoters in a process 

based on thermal decomposition of diphenylgermane. The 

theoretical requirements for transferring information such as 

defects from nanoparticle seeds to growing semiconductor 

nanowires have been defined and we describe why specific metal 

nanoparticles are ideal candidates for this purpose. [2] Significantly, 

under certain reaction conditions {111} stacking faults in the 

noble metal seeds can be directly transferred to a high percentage 

of -oriented Ge nanowires, in the form of radial twins in 

the semiconductor crystals. In addition, we will detail the 

influence of solid growth seeds on the crystal quality of Ge 

nanowires and demonstrate size-selective growth in the sub-20 nm 

diameter regime. [3] Controlled defect transfer from nanoparticles 

to nanowires could open up the possibility of engineering 1D 

nanostructures with new and tuneable physical properties and 

morphologies. 

references: 

1. S. Barth, F. Hernandez-Ramirez, J. D. Holmes, 

A. Romano-Rodriguez. Prog. Mater. Sci. 2010, 55, 

563–627. 

2. S. Barth, J. J. Boland, J. D. Holmes. Nano Lett. 2011, 11, 

1550-1555. 

3. S. Barth, M. M. Kolesnik, K. Donegan, V. Krstic, 

J. D. Holmes. Chem. Mater. 2011, 23, 3335–3340. 

Keywords: Crystal growth; Chemical vapor deposition; 

Nanostructures; Electron diffraction; 



o - 5 2 0 

StruCturAL ChArACterizAtion And 

trAnSPort ProPertieS of Cvt Grown zrSe3 

And zrS3 CryStALS. 

A. dASAdiA 1 , B. nAriyA 1 , A. JAni 1 

1 Sardar Patel University, Department Of Physics, Vallabh 

Vidyanagar, India 

Single crystals of ZrSe3 and ZrS3 are family of materials 

with low symmetry structure were grown by chemical vapour 

transport technique using iodine as a transporting agent. The 

grown crystals were characterized by energy dispersive analysis 

of X-ray (EDAX) for confirmation of stochiometric proportion of 

constituent elements and structure of grown crystals was 

determined by X-ray diffraction (XRD) technique. The resistivity 

and thermoelectric power measurements were carried out in the 

temperature range 308 K to 573 K. The Hall coefficient, carrier 

concentration and Hall mobility were determined from Hall Effect 

measurements at room temperature. 

Keywords: Crystal Growth; CVT; structure characterization; 



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o - 5 2 1 

StruCture PrediCtion And AB initio enerGy 

LAndSCAPe exPLorAtion of PBS And of the 

PernitrideS of CA, LA And ti 

J. C. SChoen 1 , d. zAGorAC 1 , A. KuLKArni 1 , 

K. doLL 2 , M. JAnSen 1 

1 Max Planck Institute for Solid State Research, Inorganic Solid 

State Chemistry, Stuttgart, Germany 

2 University Ulm, Institute for Electrochemistry, Ulm, Germany 

A fundamental issue in solid state chemistry and materials 

science is the rational planning of syntheses. [1] The basic 

requirements for success in this endeavor are the ability to predict 

possible target compounds, including metastable modifications at 

real thermodynamic conditions, and to devise synthesis routes to 

access these predicted compounds. 

Predicting which crystalline modifications can exist in a 

chemical system requires the global exploration of its energy 

landscape. [1] Due to the large computational effort involved, in the 

past this search for sufficiently stable minima has been performed 

employing a variety of empirical potentials and cost functions 

followed by a local optimization on the ab initio level. However, 

this might introduce some bias favoring certain types of chemical 

bonding and entails the risk of overlooking important 

modifications that are not modeled accurately using empirical 

potentials, necessitating the use of ab initio energy functions 

during the global optimization phase of the structure prediction. 

Thus, we have applied a global optimization tool, simulated 

annealing, to the study of the ab initio energy landscape of PbS [2] 

and the pernitrides of Ca, La and Ti, exhibiting various types of 

chemical bonding. For the PbS system, we recover the 

experimentally known structures, clarify the experimental 

structures at intermediary pressures, predict the existence of an 

a-GeTe modification that competes with the known rock salt 

modifcation at standard pressure and analyze its electronic and 

vibrational structure and its kinetic stability. For the pernitrides, 

our explorations confirm the recent discovery of a new 

CaN -modification 2 [3] , and predict kinetically stable polymorphs 

for LaN and TiN . 

2 2 

references: 

1. J. C. Schön, M. Jansen, Angew. Chem. Int. Ed., 1996, 

35:1286. 

2. D. Zagorac, K. Doll, J. C. Schön, M. Jansen, Phys. Rev. B, 

2011, 84:045206; Chem. Eur. J., submitted. 

3. S. B. Schneider, R. Frankovsky, W. Schnick, Inorg. Chem., 

2012, 51:2366. 

Keywords: structure prediction; energy landscape; lead 

sulfide; pernitride; 



o - 5 2 2 

new therMoeLeCtriCS By CoMBinAtion of 

CoSB3 with Ge/SB/te MAteriALS 

f. fAhrnBAuer 1 , t. roSenthAL 1 , S. MAier 1 , 

t. SChrÖder 1 , o. oeCKLer 2 

1 LMU Munich, Department of Chemistry, Munich, Germany 

2 Leipzig University, IMKM, Leipzig, Germany 

The reduction of the lattice thermal conductivity is the 

method of choice for improving the figure of merit ZT of 

thermoelectric materials. Inducing nanostructures is one 

promising way to achieve this, and structures that are 

heterogeneous on the nanoscale represent an intriguing 

approach.[Kanatzidis et al., Angew. Chem. Int. Ed. 2009, 48, 

8616.; Zhang et al., J. Electron. Mater. 2011, 40, 932.] 

Nanocomposites of CoSb and Ge/Sb/Te (GST) compounds 

3 

– which both exhibit interesting thermoelectric properties – are a 

promising class of materials, and their synthesis involves 

challenging solid-state syntheses. We have shown that the ZT 

values of GST materials strongly depend on the type 

and distribution of the nanostructures present.[Oeckler et al., 

Chem. Mater. 2011, 23, 4349.] Heterostructures of cubic 

skutterudite-type crystals in a bulk matrix of trigonal GST were 

obtained by quenching melts of stoichiometric mixtures of the 

elements, followed by annealing. Quenched samples exhibit 

interesting features: Over wide regions of the bulk, triangular 

holes with edge lengths from 0.2 to 1.5 µm are uniformly arranged 

along parallel lines. In these holes, there are small skutteruditetype 

precipitates. Subsequent thermal treatment has a great 

influence on the size and shape of the CoSb crystals, in which up 

3 

to 50 % of the Sb sites are occupied by Ge/Te. In addition, 

octahedrally shaped aggregates are formed. These consist of 

grown-together layered heterostructures of GST and CoSb . 3 

This combination of heterogeneous nanostructures with 

anion substitution in CoSb crystallites may be an intriguing 

3 

way to further improve thermoelectric characteristics. 

The skutterudite-type precipitates occur with a variety of crystal 

morphologies and are firmly intergrown with the matrix. 

The CoSb /GST octahedra exhibit well-defined relationships 

3 

between the crystallographic orientations of their components. 

The different kinds of heterostructures were analyzed on the 

atomic level by means of HRTEM. 

Keywords: GST; skutterudite; thermoelectrics; intergrowth; 

nanostructure; 



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o - 5 2 3 

vAryinG the nAnoStruCture of ternAry 

GerMAniuM teLLurideS And itS infLuenCe on 

therMoeLeCtriC ProPertieS 

t. roSenthAL 1 , t. SChrÖder 1 , M. SChneider 1 , 

C. Stiewe 2 , o. oeCKLer 3 

1 LMU Munich, Department of Chemistry, Munich, Germany 

2 DLR, Köln, Germany 

3 IMKM, Leipzig, Germany 

Multinary tellurides – especially nanostructured ones – have 

turned out to be promising novel thermoelectrics with high figures 

of merit ZT = S2σT/k. In multinary systems, the charge carrier 

concentration is flexible, allowing one to optimize the Seebeck 

coefficientS. Real-structure effects and nanostructures enhance 

phonon scattering and thus reduce thermal conductivity k, which 

means an increase of ZT. 

At ambient conditions, stable compounds of the 

“homologous” series (GeTe) (Sb Te ) exhibit trigonal layered 

n 2 3 

structures. In the rocksalt-type high-temperature phase, 

Ge/Sb/vacancies are randomly distributed on the cation sites. The 

GeTe content n determines both the vacancy concentration in the 

cubic phase and the thickness of the rocksalt-type slabs in the 

trigonal phase. In addition to the thermal treatment, this has a 

strong impact on the nanostructures formed when the diffusion 

required for the phase transition occurs incompletely. For n = 12 

or 19, ZT values up to 1.3 are reached. [1] Se and Sn doping result 

in more pronounced nanostructures at lower n combined with new 

features probably related to phase separation. In-substituted 

samples exhibit less short-range vacancy ordering resulting in a 

less pronounced nanostructure, while Li can be used to stabilize 

the cubic phase by filling vacancies. Additional Sb sheets in 

layered phases lead to translation periods of up to 10 nm in (often 

metastable) compounds like (MTe)(Sb Te )(Sb ) (M = Ge, Sn). 2 3 2 4 [2] 

The average domain size of GeBi Te quenched under 

2 4 

high-pressure (12GPa) depends on the quenching rate. The 

associated grain and domain boundary effects strongly influence 

the electrical conductivity σ, which changes form metallic to 

semiconducting with decreasing domain size and more randomly 

oriented domains. [3] 

references: 

1. T. Rosenthal et al., Chem. Mater. 2011, 23, 4349. 

2. M. N. Schneider et al., Chem. Eur. J. 2012, 18, 1209. 

3. T. Schröder et al., Phys. Rev. B 2011, 84, 184104. 

Keywords: Tellurides; Nanostructure; Thermoelectric; 



o - 5 2 4 

the roLe of doMAin Size, StruCture And 

trAnSforMAtion in defininG P-x-t hyStereSiS 

in hydroGen SorPtion By trAnSition MetAL 

oxideS (ton) And SuLPhideS (tSn) to forM 

hxton And hxtSn BronzeS when ACtivAted By 

SPiLLover 

P. SerMon 1 , A. BerzinS 2 

1 Brunel University, Wolfson Materials Centre, Uxbridge, 


2 Johnson Matthey Research Centre, Blounts Court, Sonning 

Common, United Kingdom 

A non-stoichiometric bronze is a solid formed by 

intercalation via electron and cation insertion into the host oxide 

or sulphide. Hydrogen bronzes (H TO and H TS ) are of 

x n x n 

particular interest since they contain the smallest guest ion and 

the consequent high charge density tends to polarize the 

surrounding host lattice. Following early studies on H WO and 

x 3 

H MoO a considerable number of well-characterised hydrogen 

x 3 

bronzes have been prepared from transition metal oxides and 

chalcogenides with either a layer structures or three dimensional 

matrices containing tunnels; proton mobilities therein approach 

those in water. 

We describe significant rates and extents of H sorption by 

2 

transition metal oxides and sulphides in the presence (but not in 

the absence) of Pt at 323K and 5-101kPa, where anion removal 

by bulk reduction was not thought to be significant. Preliminary 

in-situ X-ray diffraction has revealed the development and 

decomposition of H TO and H TS phases as a function of T and 

x n x n 

p . The results are relevant to the optimisation of (i) catalysts, 

H2 

(ii) reversible electrode materials, (iii) electrochromic devices and 

(iv) hydrogen storage. 

XRD is an ideal non-invasive technique for probing 

transformations of such solids. -WO under present conditions is 

3 

normally monoclinic (and only orthorhombic or tetragonal at 

higher temperatures). By varying the partial pressure of hydrogen 

in the presence of activating Pt at a temperature of 323K, WO3 undergoes reversible phase changes to a tetragonal structure 

(a = 0.375nm; c = 0.379nm) that exists at 1-40kPa H , and 2 

thereafter a cubic phase (a = 0.397nm) is found. Upon reducing 

the p tetragonal domains are reformed, one of which is identical 

H2 

to that found in adsorption. Upon flushing for 12h with N2 a 

orthorhombic structure (a = 0.725nm; b = 0.750nm; c=0.384nm) 

is found. 

Data are presented on reversible sorption of hydrogen by 

Pt/MoO , Pt/WO , Pt/Mo W O , Pt/Na WO and Pt/MoS . 

3 3 y 1-y 3 y 3 2 



s853 

chem. Listy 106, s587–s1425 (2012) 

special symposium: Jam session plus Young National Winners in Bio-organic Chemistry 

special symposium – i 

o - 1 1 6 

SuPer BronSted ACid CAtALySt And SuPer 

SiLyL enoL ether – rAPid SyntheSiS of 

PoLyKetideS 

1, 2 

h. yAMAMoto 

1 The University of Chicago, Chemistry, Chicago IL, USA 

2 Institute of Molecular Catalyst, Chubu University, JP 

Acid is the classical reagent in organic synthesis. Lewis and 

Bronsted acids can be utilized as more effective tools for chemical 

reactions by sophisticated engineering such as “designer acids”. 

Needless to say, the ultimate goal of such “designer acids” is to 

achieve high reactivity, selectivity, and versatility as a useful tool 

of organic synthesis. Even now, the full potential of acid catalysts 

has not yet been realized. 

We are interested the combination of super Bronsted acid 

and super silyl group to establish a cascade reaction to generate 

complex molecules in a single pot. This successive aldol process 

is a completely new version of the Mukaiyama aldol reaction and 

provides numerous opportunities to flexible control the 

stereochemistry of the product molecule with high selectivity. The 

long-term goal of the project is to assemble a route to polyketides 

in one-pot using multi-component condensations enabled by 

unique reactivity of super sily enol ethers and super Bronsted acid 

catalyst, which will provide basic information for a polyketide 

synthesizer in the future. The objective of this particular 

application is to identify how the complex polyketide can be 

synthesized efficiently and selectively using the second generation 

of Mukaiyama aldol reactions. 



o - 1 1 7 

evoLution of ASyMMetriC orGAnoCAtALySiS 

– retroCAtALySiS And the MuLtiCAtALySt 

APProACh 

r. C. wende 1 , C. e. MüLLer 1 , r. hrdinA 1 , 

P. r. SChreiner 1 

1 Institute of Organic Chemistry, Justus-Liebig University, 

Giessen, Germany 

The combination of distinct organocatalysts performing onepot 

multistep reaction sequences, i.e., multicatalysis has become 

a powerful tool in organic synthesis. [1, 2] It allows the synthesis of 

complex molecules from simple and readily available starting 

materials, thereby achieving high levels of reaction and resource 

efficiency. [1, 2] An extension of this concept is a multicatalyst, i.e., 

an arbitrary catalyst backbone bearing orthogonally reactive 

catalytic moieties. [2] 

Based on a previously developed highly efficient 

peptide-based acylation catalyst [3] we designed the first member 

of organic multicatalysts for the one-pot acylative desymmetrization 

and subsequent oxidation of meso-alkane-1,2-diols affording the 

corresponding α-acetoxy ketones (up to 97% yield and 97:3 d.r.). [4] 

We term this strategy of reverse catalyst design as retrocatalysis 

(a step oriented approach) to emphasize the close conceptional 

[2, 4] 

relation to retrosynthesis (a target structure oriented approach). 

Recently, we reported a novel multicatalyst equipped with 

β-aspartate (epoxidation) and π-methyl histidine (acylative kinetic 

resolution) as catalytic moieties. [5] In conjunction with 

hydrazinium sulfate (epoxide opening) this catalyst enabled 

performing a three-step reaction sequence from simple 

symmetrical alkenes yielding valuable trans-alkane-1,2-diols 

(up to 99 % ee) and monoacylated trans-alkane-1,2-diols (up to 

68 % ee; corresponding S-values up to 26). [5] 

references: 

1. a) L. M. Ambrosini, T. H. Lambert, ChemCatChem 2010, 

2, 1373; 

b) J. Zhou, Chem.–Asian J. 2010, 5, 422. 

2. R. C. Wende, P. R. Schreiner, Green Chem. 2012, in press. 

3. a) C. E. Müller, L. Wanka, K. Jewell, P. R. Schreiner, 

Angew. Chem. Int. Ed. 2008, 47, 6180; 

b) C. E. Müller, D. Zell, P. R. Schreiner, Chem.–Eur. J. 

2009, 15, 9647; 

c) R. Hrdina, C. E. Müller, P. R. Schreiner, Chem. 

Commun. 2010, 46, 2689. 

4. C. E. Müller, R. Hrdina, R. C. Wende, P. R. Schreiner, 

Chem.–Eur. J. 2011, 17, 6309. 

5. R. Hrdina, C. E. Müller, R. C. Wende, L. Wanka, 

P. R. Schreiner, Chem. Commun. 2012, 48, 2498. 

Keywords: Organocatalysis; Peptides; Acylation; Sustainable 

Chemistry; 



s854 

chem. Listy 106, s587–s1425 (2012) 



o - 1 1 8 

SyntheSiS of A non-reduCinG diSACChAride 

SCAffoLd for noveL LiPid A MiMetiCS 

f. AdAnitSCh 1 , P. KoSMA 1 , A. zAMyAtinA 1 

1 University for Natural resources and applied life sciences, 

Department of Chemistry, Vienna, Austria 

Lipid A is a unique glycolipid, which anchors 

lipopolysaccharides (LPS) in the outer membrane of Gramnegative 

bacteria. Lipid A, also known as endotoxin, is recognized 

by the mammalian innate immune system via the Toll-like 

receptor 4 (TLR4) -myeloid differentiation factor 2 (MD-2) 

complex. [1] 

Lipid A consists of a β-(1-6)-linked di-glucosamine that 

carries a strain-specific pattern of β-hydroxy- and/or 

β-acyloxy- long-chain fatty acids at positions 2, 3, 2' and 3' as well 

as phosphate groups at positions 1 and 4', respectively. [2] The 

endotoxic activity of Lipid A depends on the number, length and 

position of acyl chains and on the presence of phosphate groups. [3] 

Triggering of innate immune signaling by the Lipid 

A/MD-2/TLR4 - receptor complex might be regulated by 

application of specifically designed Lipid A analogues and 

can aid in the discovery of future immunotherapeutics, vaccine 

adjuvants and anti-inflammatory agents. Based on the 

three-dimensional arrangement of Lipid A in the crystal structure 

of the TLR4-MD-2-LPS complex, [4] novel Lipid A mimetics based 

on a non-reducing 1,1'-α,α-disaccharide scaffold have been 

developed. To this end, a non-reducing disaccharide, composed 

of α-D-mannose and α-D-glucosamine carrying a set of 

orthogonal protecting groups, which allows for subsequent 

regioselective acylation and phosphorylation has been assembled. 

To achieve the demanding stereoselective formation of the 1,1'α,α-glycosidic 

bond, serveral orthogonally protected D-Man 

based 1-O-imidate glycosyl donors and orthogonally protected 

D-Glc2N glycosyl acceptors were synthesized and coupled in a 

TMSOTf-catalyzed glycosylation reaction. 

Acknowledgments: Financial support from FWF 

(grant P 22116) is gratefully acknowledged. 

references 

1. Yamamoto, M., Akira, S. Adv. Exp. Med. Biol. 2010, 667: 

59–68. 

2. Raetz, C. R. H., Whitfield, C. Ann. Rev. Biochem. 2002, 

71: 635–700. 

3. Kusumoto, S. In: Y. A. Knirel and M. A. Valvano, 

Bacterial Lipopolysaccharides. Springer Vienna, 2011: 

117–130. 

4. Park, B.S., et al. Nature 2009, 458: 1191-1195. 

Keywords: Carbohydrates; Glycoconjugates; Glycosylation; 

Protecting Groups; 



o - 1 1 9 

CoMPLexAtion of PriMAry AMineS with 

BorAne or triMethyLALuMinuM 

B. neMeth 1 , J. P. GuéGAn 2 , t. veSzPréMi 3 , 

J. C. GuiLLeMin 2 

1 Gedeon Richter Plc., Drug Polymorphism Research Division, 


2 Ecole Nationale Supérieure de Chimie de Rennes, Institut des 

Sciences Chimiques de Rennes, Rennes, France 

3 Budapest University of Technology and Economics, Inorganic 

and Analytical Chemistry, Budapest, Hungary 

Trimethylaluminum (TMA) complexes of methyl-, 

n-propyl-, cyclopropyl-, allyl- and propargylamine were 

synthesized and their experimental and theoretical properties were 

compared with the respective amine-borane analogues. It was 

shown that the amine ligand of an amine-TMA Lewis acid-base 

complex can be changed by another amine through a 2:1 

amine-TMA intermediate in pentane at room temperature. Similar 

exchange in the case of amine-borane requires more vigorous 

conditions in line with the calculated relative energy of the 

respective transition state. The 1H and 13C NMR experiments 

examining the addition of one or more equivalent amine to the 

respective Lewis acid-base complex resulted in fast exchange of 

the amine ligand in the NMR timescale only in the cases of 

amine-TMA complexes, which could also be caused by similar 

2:1 complex formation. However, in gas phase only 1:1 

amine-TMA complexes were obtained by ultraviolet 

photoelectron spectroscopy (UPS). The observed UP spectra 

indicate that the stabilization effect of the lone electron pair of 

nitrogen atom in amines during the borane complexation is 

stronger than that of the TMA complexation. In line with this 

observation, the destabilization of the σ orbitals is lower than 

Al-C 

that of σ orbitals during the formation amine-TMA complexes 

B-H 

and amine-boranes, respectively. It was calculated that the CH4 elimination of the studied amine-TMA complexes is exothermic, 

which supports the possibility of their use in metal organic 

chemical vapour deposition (MOCVD) techniques. On the other 

hand, our experimental conditions are able to avoid this methane 

elimination, resulting in the first procedure to synthesize primary 

amine-TMA complexes. 

Keywords: Lewis acids; synthetic methods; NMR spectroscopy; 

photoelectron spectroscopy; Computational chemistry; 



s855 

chem. Listy 106, s587–s1425 (2012) 


special symposium – ii 

o - 1 2 0 

CheMiCAL CroSS-LinKinG And 

hydroGen/deuteriuM exChAnGe AS An 

ALternAtive APProACh to StudyinG the 

Protein StruCture 

d. rozBeSKy 1 , P. MAn 1 , J. ChMeLiK 2 , P. novAK 1 

1 Charles University Faculty of Science, Biochemistry, Prague, 


2 Institute of Microbiology Academy of Science of the Czech 

Republic, Laboratory of Molecular Structure Charactrization, 


Determination of the three-dimensional structures of 

proteins has traditionally been realized by X-ray crystallography 

and NMR spectroscopy. Although these techniques provide high 

resolution atomic data, they have some limitations. 

Chemical cross-linking and Hydrogen/Deuterium (H/D) 

exchange combined with high resolution mass spectrometry offer 

an alternative approach to studying the protein structure. This 

method is fast, is general and uses small amounts of material. 

Our aim was to gain insight into structure of NKR-P1A and 

NKR-P1C protein, important activating receptors which play a 

key role in eliminating virally infected and tumor cells. 

We used homobifunctional cross-linking reagents DSS 

and DSG (amine-amine coupling) and heterobifunctional 

cross-linking reagent EDC (carboxyl-amine coupling). Mass 

spectrometry was used for cross-links identification and 

furthermore for precise revealing which residues were involved 

in the cross-link. The residues which were within a certain 

distance of each other were converted into covalent bonds by the 

cross-linking reagent and therefore provided distance constraints 

which were used for protein structure modeling. 

In the second approach, H/D exchange combined with mass 

spectrometry was applied to study the NKR-P1A loop 

conformation. The aim of this analysis was to compare the 

kinetics of H/D exchange for NKR-P1A and NKR-P1A in which 

the loop was removed and replaced with two alanines. H/D 

exchange revealed that the solution structure differs from the 

crystal structure in the conformation of the conserved loop. While 

the conserved loop is in close proximity to compact core in 

solution, it is extended from the core in the crystal structure where 

it interacts with the surface of a symmetry-related molecule. 

Finally, distance constraints derived from cross-linking and 

information on local solvent accessibility of proteins derived from 

H/D exchange have been implemented in the modeling of both 

receptors. 

Acknowledgement: Financial support by the Grant Agency of 

the Czech Republic (P207/10/1040) and from the Grant Agency 

of Charles University (403211/2011 and Project UNCE). 

Keywords: mass spectrometry; protein structures; structural 

biology; 


o - 1 2 1 

SyntheSiS of ferroCeneStrone 

f. heSSLer 1 , M. KotorA 1 




Ferrocene conjugates with various types of biologically 

active compounds such as saccharides, steroids or peptides have 

been studied intensively by bioorganometallic and medicinal 

chemists in the last few years for their new interesting properties 

compared to the model compounds. [1, 2] Ferrocifen may serve as a 

notable example of an interesting new substance. It is a ferrocene 

containing derivative of tamoxifen with potential effect in 

treatment of breast cancer. 

Although several conjugates of steroids with ferrocene have 

been prepared, the cyclopentadienyl ring has not been the integral 

part of the steroid skeleton in any of them. In regard of our recent 

results concerning new synthesis of estrone, [3] we decided to 

address the synthesis of first such steroid, containing ferrocene in 

place of the aromatic A-ring – ferrocenestrone. [4] 

The approach to the ferrocene-steroid framework 

construction was based on transition metal mediated reactions 

starting from a suitably substituted chiral ferrocene. The methods 

used were: zirconocene-mediated oxidative additions 

with successive alkylation sequences, palladium-catalyzed 

cross-coupling reactions, ruthenium-catalyzed skeletal 

rearrangements (enyne metathesis), palladium and iridium 

catalyzed hydrogenations etc. Also selective oxidation and 

subsequent borane reduction was used for the final change of 

skeletal configuration. Successful application of the above 

mentioned methods yielded the first metallocene based steroid 

derivative. 

references: 

1. P. Stepnicka, Ferrocenes: Ligands, Materials and 

Biomolecules, John Wiley & Sons Ltd: Chichester, 2008. 

2. U. Schatzschneider; N. Metzler-Nolte, Angew. Chem. Int. 

Ed. 2006, 45, 1504. 

3. P. Herrmann; M. Budesínský; M. Kotora, J. Org. Chem. 

2008, 73, 6202. 

4. F. Hessler, I. Císarová, D. Sedlák, P. Bartunek, M. Kotora, 

Chem. Eur. J. 2012, 18, 5515. 

Keywords: asymmetric synthesis; metallocenes; steroids; 

synthesis design; 



s856 

chem. Listy 106, s587–s1425 (2012) 



o - 1 2 2 

BrASSinoSteroidS, SynthetiC ChALLenGe for 

huMAn MediCine 

v. KhriPACh 1 , v. zhABinSKii 1 

1 Institute of Bioorganic Chemistry, Head of Laboratory of 

Steroid Chemistry, Minsk, Belarus 

Discovery of brassinosteroids (BS) later recognized as a new 

class of plant hormones became a historical event indicating 

versatile role of steroids as hormonal regulators typical to most 

organisms inhabiting the Earth. BS were found to be very active 

plant growth stimulants having at the same time adaptogenic and 

protective properties. As obligatory constituents of plants, BS 

have been consumed by mammals with food over all the 

evolution, but their role outside plant kingdom has never been 

supposed. 

Except for toxicological aspects, during the early period of 

BS investigations there were no attempts to look for their effects 

in higher organisms. Being chemists, who were lucky to solve the 

problem of BS availability for practice, and having a large variety 

of natural BS in our hands, we started systematic studies of BS 

phenomena in animals quite long ago with expectation to discover 

their possible role outside plant kingdom. Our first results were 

reported in Prachatice at 18h Conference on Isoprenoids and 

published in our monograph in 1999. This was the beginning of 

extensive research that later got development in many laboratories 

and brought us to implementation of the obtained results for 

human and animal use. 

The present paper will discuss our results in studies on 

chemical synthesis, specific properties and natural occurrence of 

BS that became critically important for their development as a 

basis for new medications. Among the most interesting results are 

the findings of regio- and stereoselective approaches to the 

synthesis of the cyclic part and steroid side chain bearing 

characteristic functionality, ways for introduction of an isotope 

label or another modifier into a BS-molecule, which are necessary 

for analytical and pharmacokinetic studies, and synthesis of new 

BS-based hybrid molecules having additional pharmacophore, 

tracer or another group influencing physico-chemical and 

physiological properties of BS into the desirable direction. 

Keywords: Brassinosteroids; Phytohormones; Synthesis; 

Medicinal application; 

special symposium – iii 


o - 1 2 3 

need to MAKe A Bond? try it in wAter At 

rooM teMPerAture 

B. LiPShutz 1 

1 University of California, Chemistry, Santa Barbara, USA 

New technology for effecting a variety of transition 

metal-catalyzed cross-coupling reactions under green chemistry 

conditions; i.e., in water at room temperature, will be described. 

These are enabled by virtue of the “designer” surfactant 

TPGS-750-M, which quickly forms nanomicelles upon 

dissolution in water, in which the reactions take place. Reactions 

to be discussed include unpublished results on Pd-catalyzed 

aromatic aminations and Stille couplings, copper-catalyzed 

conjugate additions, and Zn-mediated halide reductions. 

Keywords: green chemistry; cross-couplings; catalysis; 



s857 

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o - 1 2 4 

StrAteGieS, deSiGn And SyntheSiS 

of hiGhLy eLeCtroLuMineSCent deviCeS 

MAde with A ConvenientLy SyntheSiSed 

2-thienyL-2'-(1h-PentAfLuoroPhenyL) 

PyrroLe BuiLdinG BLoCKS 

P. tiSovSKy 1 , v. dAnieL 1 , J. KoziSeK 2 

1 Slovak University of Technology FCHPT, Department of 

Organic Chemistry, Bratislava, Slovak Republic 

2 Slovak University of Technology FCHPT, Institute of Physical 

Chemistry and Chemical Physics, Bratislava, Slovak Republic 

Synthesis of new molecules or polymers that have bipolar 

transport properties and utilization of perfluoroaromatics for 

molecular recognition has in recent years been an intensely 

studied topic. 

The convenient synthesis of substituted 2-thienyl-2'-(N- 

-pentafluorophenyl)pyrrole derivatives is described from 

5-substituted 2-thienylaldehydes by Stetter reaction [1] and 

bromoacetyl tiophenes (yielding 1,4-dicarbonyl compounds) and 

Paal-Knorr pyrrole synthesis. [2] 

This molecules labeled TP NFB is composed of 

triphenylamine or carbazole (known to transport holes) and 

oxadiazole, triazole and pyrazine (know to transport electrons) 

moieties. 

Nucleophilic displacement of a single fluorine atom in 

pentafluorophenyl group by azide anion affords new possibilities 

for cross linking, colour incorporating, efficient photosensitive 

dyes and photolabeling. The target compounds can be used as 

building blocks for novel materials with optoelectronic properties 

OLED, fotolabeling reagents or as photosensitizers in the 

so-called “Gräetzel solar cells”. [3, 4] 

Acknowledgement: This work was financially supported by 

grants from the Ministry of Education of the Slovak Republic 

No. 1/0660/11 1/1072/11, APVV-0202-10 

references: 

1. Orsini M., Chiarotto I., Sotgiu G., Inesi A.: Electrochimica 

Acta 2010, 55, 3511. 

2. Patterson J.M. Synthesis 1976, 281. 

3. Regan B. O., Grätzel M. Nature, 1991, 353, 737. 

4. Hagfeldt A., Grätzel M. Acc. Chem. Res., 2000, 33, 269. 

Keywords: Synthesis design; Polymers; 



o - 1 2 5 

retention MeChAniSM of nuCLeotideS And 

their SePArAtion with the uSe of hiGh 

PerforMAnCe Liquid ChroMAtoGrAPhy 

S. StudzinSKA 1 , B. BuSzewSKi 1 

1 Nicolaus Copernicus University Faculty of Chemistry, 

Department of Environmental Chemistry and Bioanalytics 

Faculty of Chemistry, Torun, Poland 

Nucleotides are essential for living organisms. They take 

part in many cellular and intercellular processes, playing 

important regulatory functions. Their presence and quantity has 

to be controlled for such purposes as: cardiovascular system 

monitoring, determination biomarkers of oxidative stress, 

microorganisms, cellular extracts study, erythocytes, baby foods 

and human milk determination, food investigation, human 

cerebrospinal fluid analysis. High performance liquid 

chromatography (HPLC) became the most popular for the 

determination of nucleotides. On the other hand although many 

different packings materials may be used as stationary phases for 

RP HPLC, generally only octadecyl phase is used for nucleotides 

analysis. However the resolution and peak shapes of analyzed 

compounds are often not satisfactory. For this reason the 

improvement in analysis of nucleic acids components by RP 

HPLC is of great importance. The simplest way to achieve it, is 

to change mobile phase composition or stationary phase type. 

The main goal of the study was to test variety of HPLC 

columns to chose the best one for the analysis of polar nucleotides. 

Two octadecyl columns were used, differing in the carbon load. 

On the other hand also medium polarity packing material 

have been utilized, namely: alkylamide, cholesterol and 

alkyl-phosphate. Phenyl stationary phase was also investigated. 

Most of these material have been utilized in the separation of 

nucleotides for the first time. The special attention was paid to the 

influence of mobile phase buffer pH, since this may be important 

parameter controlling resolution of nucleotides. Such systematic 

studies concerning the influence of pH on the retention of 

nucleotides on specific packings materials was performed for the 

first time. Obtained results allowed for the selection of the best 

stationary phase for the separation of nucleotides. 

Acknowledgements: Financial support was provided by the 

National Science Center (Cracow, Poland) under grant 

No. 2011/01/D/ST4/04142. 

Keywords: high performance liquid chromatography; 

nucleotides; stationary phase; 



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o - 1 2 6 

funCtionAL MoLeCuLeS BASed on AroMAtiC 

ArChiteCtureS 

J. SieGeL 1 

1 Organic Chemistry Institute, University of Zurich, Zurich, 

Switzerland 

Aromatic architectures have left the world of flat land and 

taken center stage in supramolecular and materials chemistry. The 

key parts of molecular machines, the templates for novel 

graphenoids and fullerenes as well as the active compounds in 

light-energy devices all start from aromatic scaffolds. Our 

particular interests in the stereochemistry of novel aromatic 

morphologies and topologies will be presented with an eye toward 

understanding their structure, dynamics and function. 

Keywords: Aromatic Chemistry; Materials Chemistry; 

Supramolecular Chemistry; Stereochemistry; Molecular 

Function; 



Poster Session 1 

s859 

chem. Listy 106, s587–s1425 (2012) 

Poster session 1 - Physical, theoretical chemistry 

P - 0 0 0 1 

SeCtor ModeL SCheMe for PLACeMent of 

exPLiCit wAter MoLeCuLeS for PKA 

PrediCtion 

r. ABrAMSon 1 , K. BALdridGe 1 

1 Organic Chemistry Institute, Organic Chemistry Institute, 


Accurate prediction of the properties associated with proton 

transfer reactions, in particular the acidity dissociation constant 

(K ), are a benchmark challenge for theory. Considerable efforts 

a 

have been made in the last decade towards prediction within 

0.5 units, [1] which is the minimum level of accuracy for many 

problems such as structure based drug design. [2] Hybrid 

approaches, referred to as continuum cluster (CC), are the most 

recent and promising development in pKa prediction. [1, 3, 4, 5] They 

attempt to capture some of the missing first solvation shell effects 

by adding a small number (< 4) solvent molecules explicitly 

around the solute embedded in the solvent cavity. However, 

a number of practical challenges arise in application of this 

method due to the need to have a consistent framework for 

determination of optimal number and position of solvent 

molecules surrounding the solute. We propose a sector model 

approach to investigate in greater detail the role of explicit 

first-shell solvation of a set of carboxylic acids and their conjugate 

bases. This model offers the possibility of systematizing the study 

of these effects according to the degree of solvation (S ) and the 

D 

configuration of solvation (S ), which allows a number of rules 

C 

for future prediction to be elucidated. Furthermore, prediction 

within 1kcal/mol, a chemically significant bound, is demonstrated, 

for a diverse set of carboxylic acids. 

references: 

1. Ho, J., Coote, M.L., 2011, Wires Comput. Mol. Sci., 2011, 

1(5), 649-660 

2. Klicic, J.J. Friesner, R.A., Liu, S., Guida, W., J. Phys. 

Chem. A, 2002, 106, 1327-1335 

3. Pliego, J.R., Riveros, J.M., J. Phys. Chem. A, 106, 2002, 

7434-7439 

4. Eckert, F., Diedenhofen, M., Klamt, A., Molecular 

Physics, 2010, 108 (3), 229-241 

5. Kelly, C.P., Cramer, C.J., Truhlar, D.G., J. Phys. Chem. A, 

2006, 110 (7), 2493-9 

Keywords: pKa prediction; continuum cluster; explicit solvent; 

sector model; 


P - 0 0 0 2 

theoretiCAL inveStiGAtionS on eLeCtroniCS 

StruCture, And CheMiCAL BondinG on 

iridAthiABenzene And iridAoxABenzne 

A. eLAhe 1 , r. GhiASi 1 

1 Islamic Azad University East Tehran Branch Qiam Dasht, 

Chimistry, Tehran, Iran 

The electronic structure and properties of the Iridathiabenzene 

and Iridaoxabenzne isomers have been investigated using the 

hybrid density functional mpw1pw91 theory. The energetic aspect 

shows that trans-ortho isomer is the most stable isomer. This is 

compatible with principles of minimum energy and minimum 

polarizability. Molecular orbital analysis shows a linear 

correlation between hardness and anisotropic polarizability values 

for Iridathiabenzene and iridaoxabenzene isomers. The structural 

and natural bond analysis (NBO) results illustrate electronic 

delocalization in these rings. Also, the study of non linear optical 

properties of these molecules indicate a good correlation between 

b and E(HOMO) for iridathiabenzene. The results from natural 

tot 

bond orbital (NBO) analysis have provided insights into Ir–ligand, 

P-H and P-H bonding. 

apical basal 

Keywords: Isomers; Bond energy; Analytical Methods; 

Metallacycles; 



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P - 0 0 0 3 

theoretiCAL StudieS of MetALLoPhiLiC 

interACtionS throuGh the uSe of LoCAL 

CorreLAtion MethodS 

M. AndreJiC 1 , r. MAtA 1 

1 Georg-August-Universität Göttingen, Institute of Physical 

Chemistry, Göttingen, Germany 

It has long been observed that cationic Au(I)d10 complexes 

can establish weak metal-metal interactions. This effect is 

somewhat curious, since it involves centers with the same charge 

and completely filled electronic shells. Similar interactions are 

found in complexes with Ag and Cu, but with a much smaller 

magnitude. This effect has come to be known as aurophilicity, and 

is strongly linked to electron correlation with a further 

strengthening by relativistic effects. [1] Previous theoretical works 

have shown that high levels of theory are required to reproduced 

this effect quantitatively (e.g. CCSD(T)). [2] 

We have performed a series of calculations on inorganic 

complex dimers of the type (Cl-M-X) , with M = Au, Ag. 

2 

Comparison is made to density functional theory (DFT), including 

empirical dispersion corrections, and state of the art wave 

function-based methods. Local approximations have also been 

used to treat the metal sites at the highest level of theory in a 

QM/QM hybrid scheme. [3] We show some of the challenges in the 

theoretical treatment of aurophilic interactions, with prospects on 

the treatment of further metal-metal interactions in bioinorganic 

complexes. 

references: 

1. L. Magnko, M. Schweizer, G. Rauhut, M. Schütz, H. Stoll 

and H. Werner, Phys. Chem. Chem. Phys. 2002, Vol. 4, 

1006-1013. 

2. S. Riedel, P. Pyykkö, R. Mata, Chemical Physics Letters, 

2005, Vol. 405, 148-152. 

3. R. Mata, H. Werner, M. Schütz, The Journal of Chemical 

Physics 128, 144106, 2008. 

Keywords: Ab initio calculations; Aurophilicity; Electronic 

structure; 


P - 0 0 0 4 

MoLeCuLAr dynAMiCS SiMuLAtionS of 

BioACtive GLASS nAnoPArtiCLeS 

t. Antonio 1 

1 University College London, Chemistry, London, United Kingdom 

Bioactive glasses such as the 45S5 composition (BG45) are 

clinically employed as bone defect fillers in orthopaedic and 

dental applications. Their potential in regenerative medicine has 

also been highlighted but not exploited as yet, due to the lack of 

fundamental understanding of their composition-structure-activity 

relations. For instance, nanosized BG45 particles have shown 

enhanced biological activity and antibacterial properties, which 

could be the key towards developing a new generation of 

biomaterials for regenerative medicine. However, the rational 

development of these materials requires a better understanding of 

the origin of the superior properties of BG45 nanoparticles. 

Molecular dynamics simulations of a Bioglass spherical 

nanoparticle (approximately 6 nm diameter) have been carried out 

to investigate how the reduced size affect structural and dynamical 

features, which could enhance the bioreactivity of these systems. 

Compared to the bulk glass or to the 2D-flat surface of BG45, the 

simulations reveal that the reduced size leads to a further slight 

reduction in the already low silicate connectivity on the 

nanoparticle surface, to a ring size distribution shifted towards 

three-membered rings, and to a higher Na + /Ca2+ ratio in close 

proximity of the surface. A higher mobility of Na cations in the 

external regions of the nanoparticle has also been detected. The 

possible ways in which these effects can translate into higher 

bioreactivity of BG45 nanoparticles are discussed. 

Keywords: Molecular dynamics; Nanoparticles; Glasses; 

Surface chemistry; Structure-activity relationships; 



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P - 0 0 0 5 

CALCuLAtion of 4-Bit nuMBerS with An 

ALLoSteriC indiCAtor diSPLACeMent ASSAy 

J. AxtheLM 1 , S. Sinn 2 , M. eLStner 1 , A. SChiLLer 1 

1 Friedrich-Schiller-University Jena, IAAC, Jena, Germany 

2 Friedrich-Schiller-University Jena, IOC, Jena, Germany 

Logic gates, better known as the Boolean operations, 

perform all fundamental logical circuits in electronics. In addition, 

molecular logic is becoming increasingly important. [1-2] In our 

work we have developed a 4-bit full adder system which allowed 

us to sum up two 4-bit numbers on the basis of the 

IMPLICATION-gate (IMP-gate). [3] We used a two-component 

saccharide probe for the generation of the IMP-gate which follows 

the principle of an allosteric indicator displacement assay 

(AIDA). [4] In detail the main fluorescence signal was provided by 

an anionic fluorescence dye HPTS which retains in the presence 

of fructose and decreases by the addition of quencher component 

BBV. In the case of quencher and fructose being added the 

fluorescence reaches its original intensity. For the summation of 

two 4-bit numbers four full adder units containing two half adder 

units each were connected in a row by suitable conjunction of the 

IMP and FALSE operation. The correct binary values of the total 

4-bit sum were obtained after 8 hours of preparation. 

Furthermore it is possible to establish the sum of numbers 

larger than 4-bit which is only limited by the size of the used 

wellplate. Also other operations such as subtraction and 

multiplication have been done. 

references: 

1. A. P. de Silva, S. Uchiyama, Nat. Nano 2007, 2, 399-410. 

2. A.Schiller, in Molecules at Work. Selfassembly, 



3. M. Elstner, K. Weisshart, K. Müllen, A. Schiller, 

J. Am. Chem. Soc. 2012, DOI: 10.1021/ja303214ri. 

4. A. Schiller, R. A. Wessling, B. Singaram, Angew. Chem., 

Int. Ed. 2007, 46, 6457. 

Keywords: Molecular logic; Saccharide probe; Allosteric 

indicator displacement assay; Logic gate; Fluorescence 

quenching; 


P - 0 0 0 6 

SeMi-SyntheSiS And ABSorPtion ProPertieS 

of ArtifiCiAL BetALAinS 

e. BAStoS 1 , L. GonCALveS 2 , L. CiSCAto 2 

1 Instituto de Química, Departamento de Química Fundamental, 

Sao Paulo, Brazil 


Humanas, Santo Andre, Brazil 

Betalains are natural pigments classified as yellow 

betaxanthins or violet-red betacyanins. They originate from 

spontaneous non-stereoselective addition of amines or amino 

acids to betalamic acid. Betaxanthins are responsible for visible 

fluorescence of flowers,e.g., yellow varieties of Mirabilis jalapa 

(four o’clock), whereas betacyanins are natural phenolic 

antioxidants. In this work, we describe the semi-synthesis of 

artificial betalains derived from substituted anilines and the 

experimental and theoretical study of their absorption properties. 

Eleven derivatives were prepared, purified and the absorption 

spectra were registered at room temperature in aqueous acid 

media (pH=4,5). The absorption maxima (λ ) of all compounds 

max 

are in the green region of the spectra (510 – 520 nm). The molar 

absorption coefficients (ε) were determined using second 

derivative spectroscopy and were found to be between 2.8 and 

5.5 × 104 L mol –1 cm –1 . 

The geometry of all derivatives where fully optimized at the 

DFT SMD(water)/M06-2X/6-31+G(d,p) level. Electronic 

transition energies and oscillator strengths of the molecules were 

calculated employing the semiempirical ZIndo/S method 

considering water as solvent using the SMD solvation model. 

Theoretical electronic transitions are in good agreement with the 

experimental values (error in λ < 3%). All compounds studied 

max 

belongs to the C1 point group and the observed high intensity 

bands in the visible region arises from HOMO–1?LUMO and 

HOMO ® LUMO transitions and were assigned as π?π* transitions. 

These results indicate that the substitution pattern in the aromatic 

iminic portion of such betalains has minor importance in their 

absorption properties. 

Keywords: betalain; DFT; natural pigment; 



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P - 0 0 0 7 

AB initio BASed MethodoLoGieS for 

inveStiGAtion of ChArGe trAnSfer throuGh 

orGAniC MoLeCuLeS 

L. BerStiS 1 , K. BALdridGe 1 

1 University of Zürich, Organic Chemistry Institute, Zürich, 

Switzerland 

The study of charge transfer (CT) reactivity through organic 

molecules presents vast opportunities to understand and design 

materials with desirable electronic properties. In the current work, 

a first principles methodology has been developed for the 

evaluation of CT properties in nonadiabatic systems, and 

implemented into the widely used ab initio computational suite 

GAMESS. In this implementation a broad range of levels of 

theory, including semiempirical, Hartree-Fock, DFT, or MP2, may 

be applied to the system studied, to achieve the highest possible 

accuracy for the size and complexity of the CT system at hand. 

The calculation of the electronic coupling between an electron 

donor and acceptor utilizes a localized molecular orbital effective 

Hamiltonian [1] , relating the coupling between the donor and 

acceptor through the remaining bridge localized orbitals. 

Furthermore the possible tunneling pathways available are 

calculated by means of a Greens function matrix of the bridge 

localized atomic or molecular orbitals. [2] These evaluations shed 

new light on discussions of through-bond and through-space 

coupling effects. The electronic coupling and pathway analyses 

enable a quantification of the magnitude of through-space or 

through-bond coupling, and clarify through which molecular 

orbitals these interactions are made possible. Additionally the 

impact of solvent to these CT characteristics is considered in the 

present work. Through these investigations, an understanding is 

gained of the impacts of structure, and presence of functional 

groups on the donor, acceptor or bridge, on the probability and 

mechanism of the CT reactions, contributing greatly towards the 

design of materials, which will offer desirable properties. 

references: 

1. Teklos A, Skourtis S.S. 2006 J. Chem. Phys. 125, 244103. 

2. C. Kobayashi, K. Baldridge, J.N. Onuchic. 2003 J. Chem. 

Phys. Vol. 119, No. 6. 

Keywords: Ab initio calculations; charge transfer; 


P - 0 0 0 8 

PhotoPhySiCAL dynAMiCS of A rutheniuM 

PoLyPyridine dye ControLLed By SoLvent Ph 

M. BräutiGAM 1 , M. wäChtLer 1 , S. rAu 2 , J. PoPP 1 , 

B. dietzeK 1 




Germany 

The photophysical properties of the novel trishetero - 

leptic Ruthenium dye [Ru(tmBiBzIm)(dppz)(tbbpy)] 2+ 

(tmBiBzIm = 5,5',6,6'-tetramethyl-2,2'-bibenzimidazole, 

dppz = dipyrido[3,2-a:2',3,3'-c]phenazine, tbbpy = 4,4'-di-tertbutyl-2,2'-bipyridine) 

are investigated. The dye structure 

combines the pH sensitiviy of the bibenzimidazole ligand with 

the DNA-responsive properties of the dppz ligand. Therefore, the 

complex might form the basis to develop systems for intracellular 

DNA and pH sensing. 

The combination of these different ligands allows for 

controlling the photophysics by two distinct mechanisms: 

(i) (de)protonation of the tmBiBzIm and (ii) hydrogen bonding to 

the phenazine-nitrogens of the dppz ligand. A combination of 

resonance Raman spectroscopy, to reveal the participation of the 

different ligands in the initial excitation, [1] and fs time-resolved 

transient absorption measurements, to observe the following 

development of the photoexcited complex was applied. 

As is reported, deprotonation of the tmBiBzIm ligand causes 

a bathochromic shift of the metal-to-ligand charge-transfer 

transition although the tmBiBzIm ligand itself does not directly 

contribute to the light absorption. Furthermore, tmBiBzIm 

deprotonation shortens the overall excited-state lifetime of the 

complex significantly. The overall photoinduced dynamics is 

dominated by the dppz ligand. [2, 3] Consequently, addition of water 

to the solvent affects the excited-state relaxation pathway as 

known from, e.g., [Ru(phen) dppz] 2 2+ (phen = 1,10-phenanthroline) 

complexes, anticipating similar DNA-responisve properties. 


the Studienstiftung des deutschen Volkes (M.W.), the Fonds der 

Chemischen Industrie (B.D.) and the Thüringer Ministerium für 

Bildung, Wissenschaft und Kultur (Grant-No. B 514-09049, 

PhotoMIC). 

references: 

1. Wächtler, M.; Guthmuller, J.; Gonzalez, L.; Dietzek, B. 

Coordination Chemistry Reviews 2012, 

10.1016/j.ccr.2012.02.004. 

2. Bräutigam, M.; Wächtler, M.; Rau, S.; Popp, J.; 

Dietzek, B. Journal of Physical Chemistry C 2012, 116, 

1274. 

3. Kuhnt, C.; Karnahl, M.; Tschierlei, S.; Griebenow, K.; 

Schmitt, M.; Schafer, B.; Krieck, S.; Gorls, H.; Rau, S.; 

Dietzek, B.; Popp, J. Physical Chemistry Chemical 

Physics 2010, 12, 1357. 

Keywords: Laser spectroscopy; Ruthenium; DNA; Raman 

spectroscopy; Luminescence; 



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P - 0 0 0 9 

AtMoSPheriC CheMiStry of MethyLeneiMine 

A.J. BunKAn 1 , y. tAnG 1 , S. r. SeLLevAG 1 , 

C. J. nieLSen 1 

1 University of Oslo, Department of Chemistry, Oslo, Norway 

A CO post combustion capture test facility employing 

2 

amine technology is now in operation at Mongstad, Norway. 

Given the scale of implementation of post-combustion Carbon 

Capture and Storage CCS, it is likely that there will be relatively 

small but still significant discharges of amines to the atmosphere 

during operation of a full-scale plant. There is also the potential 

for larger scale accidental discharges. CH NH and (CH ) NH are 

3 2 3 2 

among the process degradation products of the more complex 

amines used in CO capture, and these small amines will therefore 

2 

always be emitted with the cleaned flue gas to the atmosphere no 

matter which parent amine is used in the absorber. 

Methyleneimine, CH NH, and ethyleneimine, CH CHNH, 

2 3 

is identified as a major photo-oxidation product in the atmospheric 

degradation of CH NH and (CH ) NH, respectively. Possible 

3 2 3 2 

atmospheric sinks of these imines include reactions with OH, 

NO , Cl, O and hydrolysis. 

3 3 

Results from a quantum chemical study of reactions of 

methyleneimine relevant to tropospheric conditions are presented. 

Our results indicate that it reacts very rapidly with OH and Cl, 

and that HCN is formed as a major product. 

Keywords: Ab initio calculations; Kinetics; Atmospheric 

chemistry; Radical reactions; Environmental chemistry; 


P - 0 0 1 0 

qM/MM SiMuLAtionS on Anion CoMPLexeS of A 

PoSitiveLy ChArGed tetrA-triAzoLiuM 

MACroCyCLe 

S. CArvALho 1 , v. féLix 1 , n. G .white 2 , P. d. Beer 2 

1 University of Aveiro, Chemistry /CICECO, Aveiro, Portugal 



Anions play an important role in many biological and 

chemical processes. Many receptors have been synthetized for 

their recognition, although the efficient recognition of anions, 

especially in aqueous solution is still very rare. In spite of their 

high potential, the use of macrocycles incorporating triazole 

moieties in anion recognition is almost unexplored. Those 

macrocycles can be positively charged by alkylation polarizing 

the heterocycle’s C-H bond and increasing the electrostatic 

interactions between the anion and receptor. [1, 2] 

The current work reports the theoretical investigations 

carried out on the binding affinity of a tetra-triazolium macrocycle 

with a positive net charge of +4 with Cl - , Br - , F - , I - and SO 4 

anions in the competitive 1:1 DMSO:H 2 O solvent mixture. These 

studies were performed by classical molecular dynamics 

simulations followed of quantum mechanics/molecular mechanics 

(QM/MM) simulations using the Amber software. 1 In the 

QM/MM simulations the macrocycle and the anions (QM region) 

were treated by quantum mechanics using the semi-empirical 

PM3 method, while the solvent region composed of TIP3P water 

molecules and full-atom model of DMSO molecules, were 

described by classical molecular mechanics. [3] 

The results showed that C-H ... X hydrogen bonds have an 

important role in the selective binding affinity macrocyle for the 

halide and sulphate anions. 

Acknowledgement: Authors are grateful to the FCT for 

financial support under project PTDC/QUI-QUI/101022/2008 

with co-participation European Community funds from the 

FEDER, QREN and COMPETE. Sílvia Carvalho also 

acknowledges the grant from FCT (SFRH/BPD/42357/2007). 

references: 

1. N. G. White, P. D. Beer, S. Carvalho, V. Félix, “Anion 

Binding in aqueous media by tetra-triazolium macrocycle” 

submitted for publication. 

2. J. L. Sesser, P. A. Gale, W-S. Cho, “Anion Receptor 

Chemistry” RSC Publishing, 2006, UK. 

3. R. C. Walker, M. F. Crowley, D. A. Case, J. Comput. 

Chem. 2008, 29, 1019-1031. 

Keywords: QM/MM simulations; anion recognition; 

macrocycles; hydrogen bonds; 

AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc 

2


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P - 0 0 1 1 

the ConneCtion Between MACroSCoPiC And 

quAntuM ProPertieS of ALKAneS 

S. dezortSev 1 , M. doLoMAtov 1 

1 Ufa state academy of economics and service, physics, Ufa, Russia 

The estimation of physical-chemical properties of alkanes 

is essential in the theory of chemical structure of substance and 

engineering practice. Physical-chemical properties (PCP) of 

normal and iso- alkanes are most extensively studied. 

We have ascertained quantitative appropriatenessys between 

macroscopic properties of alkanes and characteristics of their 

electronic structure: 

Z=a.•e i βi•E 

where Z - physical-chemical property (for example, boiling 

point, molecular weight, density, ets.); α and β – suitable 

i i 

empirical coefficients, which depend on topological index of 

chemical structure; E - characteristic of their electronic structure 

(calculated values of highest occupied and lowest unoccupied 

molecular orbitals energy, ionization potential (IP) and electron 

affinity, as well as the width of conducting band). 

In series of n-alkanes C -C best correlations may be 

1 10 

observed for calculated values of highest occupied and lowest 

unoccupied molecular orbitals energy, as well as the width of 

conducting band with macroscopic PCPs. Designed values for IP 

of n-alkanes C -C were confirmed by outcome of experiment by 

1 10 

photoelectron spectroscopy (PES). Received relationship for nalkanes 

C -C is confirmed by statistical data manipulation, have 

1 10 

correlation coefficient R=0,95÷0,99. 

In homologous series of iso-alkanes C -C similar nature of 

4 10 

PCP and electronic structure characteristics relations is confirmed 

for calculated values of highest occupied molecular orbital energy. 

It may be presumed, that direct analysis (instrumentations) of IP 

by photoelectron spectroscopy method will confirm the results of 

quantum-chemical computations. 

Received relationship for iso-alkanes is confirmed by 

statistical data manipulation, have correlation coefficient 

R=0,89÷0,96. 

The existence of such correlations means the availability of 

the concept of physical-chemical properties forecasting direct 

from quantum computations and photoelectron spectroscopy data. 

references: 

1. Dezortsev S.V., Dolomatov M.Yu., Shutkova S.A., 

Shuyakovskaya D.V. The Connection Between Electronic 

Structure and Physical-Chemical Properties of n-alkanes 

(Report I) // XVIII International Conference on Chemical 

Thermodynamics in Russia, Samara, October 3-7, 2011. 

- Vol. 1. - p.71-73. 

Keywords: alkanes; ionization potentials; quantum chemistry; 


P - 0 0 1 2 

uLtrAfASt CirCuLAr diChroiSM 

inveStiGAtion of the rinG oPeninG in 

7-dehydroChoLeSteroL 

J. Meyer-iLSe 1 , d. AKiMov 2 , r. C. MenezeS 2 , 

B. dietzeK 1 

1 Institute of Physical Chemistry and Abbe Center of Photonics 

Friedrich-Schiller University Jena Helmholtzweg 4 07743 

Jena Germany and Institute of Photonic Technologies (IPHT) 

Jena e.V. Albert-Einstein-Str. 9 07745 Jena Germany, 

Spectroscopy and Imaging, Jena, Germany 

2 Institute of Photonic Technologies (IPHT) Jena e.V. Albert- 

Einstein-Str. 9 07745 Jena Germany, Spectroscopy and 

Imaging, Jena, Germany 

UV-femtosecond time-resolved circular dichroism (TRCD) 

spectroscopy has been used to study the ultrafast changes of 

chirality in a small molecular biological paradigm sample, 

7-dehydrocholeserol (7-DHC). Upon UV-photoexcitation, 7-DHC 

undergoes a ring opening to produce previtamin D and two of 

3 

the chiral centers of 7-DHC are removed, which impacts the 

overall chirality of the molecule. Here, measurements of this 

chirality change connected to the ring opening of 7-DHC with a 

time-resolution of 280 fs are reported. With this method a 

previously described discrepancy concerning the photophysics of 

7-DHC was clarified. With our set-up the relaxation time of the 

chirality change was measured to be 1-2 ps, which corresponds 

to the shortest time-constant in the transient absorption (TA) 

measurements, allowing us to assign that time-constant to the ring 

opening. 

Acknowledgement: Financial support by the German Science 

Foundation (Di 1517/2-1) is gratefully acknowledged. 

Keywords: Circular dichroism; Vitamins; Time-resolved 

spectroscopy; 



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chem. Listy 106, s587–s1425 (2012) 


P - 0 0 1 3 

CryStAL ShAPe reCoGnition SoftwAre 

v. eiGner 1 , J. CeJKA 1 , M. dušeK 2 

1 Institute of Chemical Technology in Prague, Department of 

Solid State Chemistry, Prague 6, Czech Republic 

2 Institute of Physics AS CR v.v.i., Department of Structure 

Analysis, Prague 8, Czech Republic 

The X-ray structure determination has seen fast 

development over last twenty years from a special method 

towards a semi-automatic tool available to any sufficiently trained 

scientist. Despite the advancements in both the instruments and 

methods, some materials still resist the routine approach. Typical 

examples are highly absorbing minerals containing heavy 

elements, but high absorption is also encountered with moderately 

heavy elements measured with copper radiation. 

Although the commonly accessible diffractometer programs 

usually contain tools for absorption correction, details of their 

functionality are unknown. Moreover, such absorption correction 

cannot be undone and repeated in later stages of structure solution 

when the data are processed by different software. For this reason 

we have started a project [1] of moving absorption correction tools 

into Jana2006 software. [2] Here we present the first successfully 

finished part, a tool for automatic shape indexing. 

The presented Crystal shape recognition software uses as an 

input photographs of the crystal shape acquired for various 

orientations of the sample with the program Crysalis [3] , which is 

delivered for laboratory diffractometers produced by Agilent 

(former Oxford Diffraction). Our software automatically assigns 

hkl indices to bordering planes, based on the contrast between the 

image of the crystal and the background. For small samples where 

the pixel size limits the precision of the mouse movement, this 

method is more precise. In the next step, the user can make 

manual corrections of the preliminary shape with a step unlimited 

by the resolution of the frame. Currently, we are implementing 

this program to the Jana2006 software [2] . 

references: 

1. Czech Science Foundation P204/11/0809. 

2. Petrícek, V., Du‰ek, M., Palatinus, L., (2006). Jana2006. 

The crystallographic computing system. Institute of 

Physics, Praha, Czech Republic. 

3. CrysAlisPro, version 1.171.35.21, Agilent Technologies 

(2012). 

Keywords: absorption correction; crystallographic computing; 

Jana2006; 


P - 0 0 1 4 

ControLinG the reGioSeLeCtivity in the 

exohedrAL funCtionALizAtion of 

fuLLereneS By SuCCeSSive fuLLerene 

reduCtionS 

M. GArCiA-BorrAS 1 , S. oSunA 2 , J. M. LuiS 1 , 

M. SwArt 3 , M. SoLA 1 



2 University of California Los Angeles, Department of Chemistry 

and Biochemistry, Los Angeles, USA 

3 Institució Catalana de Recerca i Estudis Avancats (ICREA), 

Departament de Química Universitat de Girona, Girona, Spain 

Email: marc.garcia@udg.edu 

Regioselectivity in the exohedral functionalization of 

fullerene and endohedral metallofullerenes (EMFs) species widely 

depends on the nature of the fullerene species and the metallic 

cluster encapsulated. This regioselectivity can change 

dramatically from the empty fullerene to the EMF derivative. As 

we have shown in previous studies on the C case, both geometric 

78 

and electronic effects [1–3] due to the presence of the metallic cluster 

play an important role in the regioselectivity of the reaction when 

the reactivity of an EMF is compared to that of the free fullerene. 

It is found that the electronic effects that change the shape and 

energy of the LUMOs are the most important. [4] 

In this work, [5] we present a study on the effect of successive 

reductions of C on the regioselectivity of the Diels-Alder, 

60 

1,3-dipolar and carbene additions to the fullerenic C cage. We 

60 

show that by tuning the number of electrons added to the 

fullerene, the regioselectivity of the studied reactions changes 

from the usual [6,6] addition in neutral species to addition to the 

[5,6] bond when the number of electrons added to C increases. 

60 

We also show that changes in aromaticity of the six- and 

five-membered rings of C during the reduction process helps to 

60 

understand the change of the regioselectivity. Our study provides 

a good model to describe what is happening when a metallic atom 

or cluster is encapsulated inside a fullerene cage (endohedral 

metallofullerenes, EMFs), as metal clusters formally transfer a 

certain number of electrons to the fullerene cage. 

references: 

1. Osuna, S.; Swart, M.; Campanera, J. M.; Poblet, J. M.; 

Sola, M. J. Am. Chem. Soc. 2008, 130, 6206. 

2. Osuna, S.; Swart, M.; Sola, M. J. Am. Chem. Soc. 2009, 

131, 129. 

3. Garcia-Borras, M.; Osuna, S.; Luis, J. M.; Swart, M.; Sola, 

M. Chem. Eur. J. 2012, DOI: 10.1002/chem.201103701. 

4. Garcia-Borras, M.; Romero-Rivera, A.; Osuna, S.; Luis, J. M.; 

Swart, M.; Sola, M. J. Chem. Theory Comput. 2012, 8, 

1671. 

5. Garcia-Borras, M.; Swart, M.; Luis, J. M.; Sola, M. 

in preparation 2012. 

Keywords: Regioselectivity; fullerenes; Reduction; Density 

functional calculations; cycloadditions; 



s866 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 1 5 

AdSorPtion of herBiCide niCoSuLfuron on 

ACtivAted CArBon, ALuMinA And SiLiCA 

L. iGnJAtoviC 1 , S. PetKoviC 1 , A. tASiC 1 , 

M. MiLenKoviC 1 , S. StAniSiC 1 

1 University of Belgrade, Faculty of Physical Chemistry, Belgrade, 

Serbia 

Nicosulfuron, C H N O S, belongs to the sulfonylurea’s 

15 18 6 6 

group of the herbicides, widely used in agriculture. We studied 

the possibilities to remove nicosulfuron from aqueous solution by 

adsorption on commercial activated carbon, alumina and silica. 

The adsorption has been investigated at room temperature 

applying batch equilibrium techniques. The influences of sorption 

parameters: contact time, solution pH, initial nicosulfuron 

concentration were studied in order to optimize the reaction 

conditions. 

The investigations showed that adsorption on activated 

carbon is fast and complete: in less than 5 minutes 100% of the 

initialy present nicosulfuron was adsorbed. 

Nicosulfuron uptake on alumina was evaluated using the 

Freundlich isotherm model. Freundlich constant, k , and F 

heterogenity factor, 1/n, are calculated from the intercept and 

slope of the Freundlich linear plot. Knowing the k =1.0352 mg/g, 

F 

one can calculate free energy change ΔG = -16.91 kJ/mol. The 

negative ΔG value indicates the feasibility of the process and the 

spontaneous nature of adsorption. The numerical value 

of 1/n =0.9651 indicates an adsorptive process that only slightly 

suppressed at lower equilibrium concentrations ad is atributed to 

a heterogeneous nature of the adsorbent’s surface without any 

interactions between adsorbed molecules. 

The adsorption isotherms of nicosulfuron on silica with 

different pore size (18-32, 32-64 and 64-100 ?) seem to indicate 

adsorption into two steps, where a second monolayer adsorption 

starts after the first monolayer is completed. This successive 

adsorption corresponds to the adsorption on surface sites that are 

structurally different. At low nicosulfuron concentration 

adsorption only occurs on one kind of sites. As the equilibrium 

concentration increases, these sites become saturated and other 

sites contribute significantly to the adsorption. 


P - 0 0 1 6 

StruCture of CytoChroMe P450 

1A2-CytoChroMe B5 BinAry CoMPLex PrediCted 

And evALuAted By MeAnS of MoLeCuLAr 

dynAMiC MethodS 

P. JerABeK 1 , M. StiBorovA 1 , v. MArtineK 1 

1 Charles University in Prague Faculty of Science, Biochemistry, 


Cytochromes P450 (CYPs) represent a large group of 

enzymes oxidizing drugs and chemical carcinogens. Eukaryotic 

CYPs interact with other membrane proteins located in the 

endoplasmic reticulum. Cytochrome b (cyt b ), which is also 

5 5 

present in endoplasmic reticulum (ER), may enhance, inhibit or 

have no effect on enzymatic activity of CYPs, depending on the 

particular CYP isoform and the substrate. Hence, the cyt b has 5 

the potential to significantly modulate CYP mediated metabolism 

of xenobiotics. The cyt b -mediated modulation of CYP activity 

5 

is attributed to the formation of specific protein-protein 

interaction. Exact 3D structure of the binary complex has not been 

experimentally determined. However, indirect data based on 

mutagenesis studies and chemical cross-links indicate that the 

convex and acidic surface of cyt b binds to the basic concave 

5 

surface of a CYP. 

The study is focused on prediction of the CYP1A2-cyt b5 binary complex structure, using contemporary methods of 

theoretical chemistry. In the first step, flexible protein-protein 

docking method implemented in HADDOCK software was 

employed to obtain a set of plausible orientations of soluble 

domains of both cytochromes. Further several individuals were 

selected according to rough estimations of binding energies and 

mutual orientations of both protein structures. These binary 

complexes were subjected to stability evaluation using classical 

molecular dynamic method implemented in NAMD software. 

Further we employed steered molecular dynamic protocol. This 

method was used in order to compare binding free energies of 

individual CYP1A2-cyt b complexes obtained by protein-protein 

5 

docking. 

Acknowledgement: Supported by GACR (203/09/0812, 

P207/12/0627, 305/09/H008) and Charles University 

in Prague (UNCE #42). Also the access to the METACentrum 

supercomputing facilities provided under the programme 

LM2010005 funded by the Ministry of Education, Youth, and 

Sports of the Czech Republic is highly appreciated. 

Keywords: cytochrome p450; cytochrome b5; molecular 

modeling; 



s867 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 1 7 

theoretiCAL inveStiGAtion of thetA4 for 

two nAnoMeMBrAneS in vAriouS dieLeCtriC 

environMentS 

P. dAneShGAr 1 , M. MonAJJeMi 2 

1 Nanobiotechnology, Faculty Of Science And Technology, 

Tehran, Iran 

2 Research And Science Branchislamic Azad University, Chemistry, 

Tehran, Iran 

Atomic-level molecular dynamics data for dipalmitoyl 

phosphatidylcholine (DPPC) and dimyristoyl phosphatidylcholine 

(DMPC) are approved that they have such an important role in 

nano biotechnology sciences so that they are important for new 

researches. These phosphatidylcholines are used to industry of 

drug delivery and etc. Gaussian software calculated different 

quantum descriptors for each molecule. we used ab initio 6-31G 

method for multiple linear regression, factor analysis-based 

multiple linear regression, principal component regression and 

partial least squares combined with genetic algorithm for variable 

selection were employed to make connections between structural 

parameters and stability activity. The effect of dielectric 

coefficient differences is fully studied in different critical 

temperatures, such as Manufactory, body temperature, and fever. 

In the present work, we considered the interaction between 

polar head groups and hydrophobic strains of DPPC/DMPC with 

polar molecules systems like water, ethanol and etc. by different 

dielectric coefficient that extended our ab initio calculations to 

determine the minimum energy conformation of the 

DPPC/DMPC structures. The method that has been used is initial 

Hortree Fock computation, STO-3G level to optimize the 

molecules in different solvents environments by different 

dielectric coefficients as well. The results elaborated that the 

phospholipids in ethanol and water are more compatible than the 

other solvents so that the supposed dielectric coefficient is 

appropriate to construct the PCs as well; In addition the dihedral 

angle mentioned in the article is the same as the energy that the 

pressure on the tails in ethanol and water is more than the other 

solvents. Thus, the ethanol and water seem more persuadable to 

use as the solvent in the bio molecular technologies and the most 

convenient for the biologic environments either in vitro and in 

vivo. 

Keywords: Nanomembrane; ab initio 6-31G method; 


P - 0 0 1 8 

eLeCtriCAL ConduCtivity of SoLutionS of 

SoMe eLeCtroLyteS in MixtureS of wAter 

with 2-MethoxyethAnoL At the teMPerAture 

298.15 K 

z. KinArt 1 , A. BALd 1 

1 Univesity of Lodz, Department of Physical Chemistry of 

Solutions, Lodz, Poland 

The electric conductivities of solutions of NaBr, NBu Br, 4 

NaBPh , KBr and KCl have been measured a wide concentration 

4 

range of binary mixtures of water (1) – 2-methoxyethanol (2) 

binary mixtures were measured at T = 298.15 K. In the case of 

KCl and NaCl (due to of the low solubility of these electrolytes) 

our studies have been carried out in mixtures containing a 

maximum of 2-methoxyethanol equal x = 0.5, respectively. For 

2 

measurements the apparatus of high accuracy has been used. For 

the analysis of the dependence molar conductivities (Λ) on the 

concentration of the electrolyte Fuossa-Justice equation has been 

applied (using a nonlinear least-squares method). We have found 

values ??of: limiting molar conductance of electrolytes (Λ ), ionic 

0 

association constants (K ) and the distance parameter of ions (R). 

A 

The values of Walden product (Λ ? η) have been also calculated. 

Based on the Fuoss-Hirsh assumption, the limiting molar 

conductance of individual ions have been calculated. The changes 

of values of all these parameters have been analyzed as a function 

of the composition of the studied mixtures in terms of ion - ion 

and ion – solvent interactions. 

Keywords: Electrical conductivity; Binary mixtures; 

Association constant; 



s868 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 1 9 

eLeCtriC quAdruPoLe MoMent of GrAPhene 

And itS effeCt on interMoLeCuLAr 

interACtionS 

M. KoCMAn 1 , M. PyKAL 1 , P. JureCKA 1 

1 Palacky University in Olomouc, Physical Chemistry, Olomouc, 


Understanding the nature of graphene...solvent interactions 

might help to design new and more efficient solvents for 

liquid-phase graphene exfoliation. Here we focus on the 

electrostatic component of interaction energy. Carbon atoms in a 

graphene sheet exhibit permanent quadrupole moment due to the 

aromatic pi electron distribution. In an infinite graphene sheet the 

electrostatic field of the atomic quadrupoles sums to zero and 

therefore does not contribute to intermolecular interactions. 

However, for a finite model, this field is nonzero and vanishes 

only very slowly with model size. Here we investigate magnitude 

of the graphene quadrupolar field as a function of model size and 

its influence on intermolecular interactions. Molecular dynamics 

simulations were carried out with and without explicit 

quadrupolar field and potentials of mean force are derived, 

compared and discussed. 

Keywords: graphene; electrostatic interaction; density 

functional calculations; molecular dynamics; 


P - 0 0 2 0 

eSterifiCAtion of ACryLiC ACid with 

2-ethyLhexAn-1-oL therModynAMiC And 

KinetiC Study 

t. KoMon 1 , P. niewiAdoMSKi 1 , M. JAMróz 1 , 

J. KiJenSKi 2 

1 Industrial Chemistry Research Institute, Department of 

Proecological Modernization of Technology, Warsaw, Poland 

2 Warsaw University of Technology, Faculty of Civil Engineering 

Mechanics and Petrochemistry, Plock, Poland 

2-Ethylhexyl acrylate is obtained by direct esterification of 

acrylic acid with 2-ethylhexan-1-ol. It is reversible and 

endothermic reaction, running in the presence of an acid catalyst. 

Sulfuric acid or methanesulfonic acid are the most commonly 

used catalysts in the industrial processes. However, they are 

generate heavy waste difficult to separate from the product. 

Solution to these problems can be use of an efficient 

heterogeneous catalysts. 

Designing the esterification in an industrial scale requires 

accurate thermodynamic and kinetic parameters to be determined. 

The solid acid catalysts in the form of sulfonated 

polystyrene/divinylbenzene resin are well recognized to be active 

and durable industrial catalysts. So far, the kinetic of acrylic acid 

esterification with 2-ethylexan-1-ol in the presence of acidic ion 

exchange resins has been scarcely documented in the literature. 

The reaction equilibrium was studied for equimolar alcohol 

to acid mixture in the presence of Amberlyst 70. The reaction 

enthalpy was estimated from linear dependence of equilibrium 

constant on reciprocal temperature in the range of 333 – 373 K. 

The esterification reaction rate was determined for various 

ratio of acid to alcohol and temperature range of 353 – 393 K. It 

was checked that to eliminate mass transfer limitations, it is 

sufficient to continuously stir the reaction mixture at a rate of 

500 rpm. The effect of catalyst loading was tested as well. 

The apparent (K ) and thermodynamic equilibrium constant 

x 

(K ) was estimated by the UNIQUAC method. It was found that, 

a 

reaction was first-order both in the presence of acid excess as well 

as in the alcohol excess. A quasi-homogenous kinetic model was 

used to describe the reaction. It was taking into account both mole 

fractions and activities to describe nonideality of liquid phase. 

Kinetic parameters were found. 

Participation in the conference co-financed by the European 

Union under the European Regional Development Found 

Keywords: Ion exchange resins; acrylates; equilibrium 

constant; kinetic parameters; 



s869 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 2 1 

CheMiStry inSide MoLeCuLAr ContAinerS in 

the GAS-PhASe 

A. i. LAzAr 1 , t. C. Lee 2 , e. KALeniuS 3 , K. i. ASSAf 1 , 

o. A. SCherMAn 4 , n. Kuhnert 1 , C. h. Grün 5 , 

J. JäniS 6 , w. M. nAu 1 

1 Jacobs University Bremen, Department of Chemistry, Bremen, 

Germany 

2 Max Planck Institute for Intelligent Systems, Chemistry, 

Stuttgart, Germany 


Finland 

4 Melville Laboratory for Polymer Synthesis University of 

Cambridge, Department of Chemistry, Cambridge, United 

Kingdom 

5 Unilever, R&D, Vlaardingen, Netherlands 

6 University of Eastern Finland, Department of Chemistry, 

Joensuu, Finland 

The reversible complexation of guests by supramolecular 

hosts affects their chemical reactivity in solution, [1–3] affording 

impressive examples of supramolecular catalysis and, in the case 

of reactions inside concave hosts, biomimetic activity. [4–8] In the gas 

phase, however, the situation is different – the supply of thermal 

energy favors irreversible dissociation rather than chemical 

reactions of the encapsulated guest. [9–11] While precedents for 

gas-phase reactivity of host-guest complexes exist, [12–19] inner-phase 

reactions have until now been limited to the solution phase. [20] 

We studied host-guest inclusion complexes of 

cucurbit[n]urils (CBn, n=6, 7, 8) and three water-soluble bicyclic 

azoalkane homologues in gas phase, we additionally performed 

quantum chemical calculations, and we found several examples 

of thermally activated, selective retro-Diels-Alder reactions in the 

gas phase. We observed an interesting reactivity pattern, where 

the cycloreversion inside the cavity becomes dominant when the 

packing coefficient35 of the complexes fall within a narrow range. 

We derived a potential function in the form of a Lennard-Jones 

12-6 potential to model the interaction of such spherical guests 

positioned centro-symmetrically inside a host cavity. 

Efficient inner-phase reactions for some, but not for all 

homologous complexes, disclosed fundamental insights into the 

factors governing chemical reactivity in isolated confined 

environments. We interpret the observed trends in terms of an 

interplay of three factors: (a) the intrinsic activation energies for 

chemical reaction of the guest, (b) the constrictive binding 

displayed by the particular host, and (c) the void space inside the 

host-guest complex. 

A combination of constrictive binding and void space 

emerges as an important structure-reactivity relationship. The two 

effects should directly manifest themselves on the pre-exponential 

factors and activation energies of the inner-phase reaction and, 

therefore, be transferable to catalysis and biocatalysis inside 

confined reaction space. 

references: 

1. Cram, D. J. Molecular Container Compounds. Nature 356, 

29–36, (1992). 

2. Mal, P., Breiner, B., Rissanen, K. & Nitschke, J. R. White 

Phosphorus Is Air-Stable Within a Self-Assembled 

Tetrahedral Capsule. Science 324, 1697–1699, (2009). 

3. Yoshizawa, M., Klosterman, J. K. & Fujita, M. Functional 

Molecular Flasks: New Properties and Reactions within 

Discrete, Self-Assembled Hosts. Angew. Chem. Int. Ed. 

48, 3418–3438, (2009). 


4. Chen, J. & Rebek, J. Selectivity in an encapsulated 

cycloaddition reaction. Org. Lett. 4, 327–329, (2002). 

5. Sarmentero, M. A. et al. Catalytic Hydrogenation of 

Norbornadiene by a Rhodium Complex in a Self-Folding 

Cavitand. Angew. Chem. Int. Ed. 49, 7489–7492, (2010). 

6. Pluth, M. D., Bergman, R. G. & Raymond, K. N. Acid 

catalysis in basic solution: A supramolecular host 

promotes orthoformate hydrolysis. Science 316, 85–88, 

(2007). 

7. Walter, C. J., Anderson, H. L. & Sanders, J. K. M. 

Exo-Selective Acceleration of an Intermolecular 

Diels-Alder Reaction by a Trimeric Porphyrin Host. 

J. Chem. Soc. Chem. Commun. 458-460, (1993). 

8. Marchetti, L. & Levine, M. Biomimetic Catalysis. ACS 

Catal. 1, 1090–1118, (2011). 

9. Schalley, C. A. Molecular recognition and supramolecular 

chemistry in the gas phase. Mass Spectrom. Rev. 20, 

253–309, (2001). 

10. Armentrout, P. B. Cation-ether complexes in the gas 

phase: thermodynamic insight into molecular recognition. 

Int. J. Mass Spectrom. 193, 227–240, (1999). 

11. Jiang, W. & Schalley, C. A. Tandem mass spectrometry for 

the analysis of self-sorted pseudorotaxanes: the effects of 

Coulomb interactions. J. Mass Spectrom. 45, 788–798, 

(2010). 

12.. Nuwaysir, L. M., Castoro, J. A., Yang, C. L. C. & Wilkins, 

C. L. Gas-Phase Host Guest Chemistry of Carcerands and 

Hemicarcerands. J. Am. Chem. Soc. 114, 5748–5751, 

(1992). 

13. Schalley, C. A. et al. Structural examination of 

supramolecular architectures by electrospray ionization 

mass spectrometry. Eur. J. Org. Chem. 1325–1331, (1999). 

14. Kalenius, E., Moiani, D., Dalcanale, E. & Vainiotalo, P. 

Measuring H-bonding supramolecular complexes by gas 

phase ion-molecule reactions. Chem. Commun. 

3865–3867, (2007). 

15. Massera, C., Melegari, M., Kalenius, E., Ugozzoli, F. & 

Dalcanale, E. Supramolecular Control of Single-Crystalto-Single-Crystal 

Transformation through Selective Guest 

Exchange. Chem. Eur. J. 17, 3064–3068, (2011). 

16. Dearden, D. V. et al. One Ring to Bind Them All: 

Shape-Selective Complexation of Phenylenediamine 

Isomers with Cucurbit[6]uril in the Gas Phase. J. Phys. 

Chem. A 113, 989–997, (2009). 

17. Carvalho, C. P., Uzunova, V. D., Da Silva, J. P., Nau, 

W. M. & Pischel, U. A photoinduced pH jump applied to 

drug release from cucurbit[7]uril. Chem. Commun. 47, 

8793–8795, (2011). 

18. Julian, R. R., May, J. A., Stoltz, B. M. & Beauchamp, J. L. 

Molecular mousetraps: Gas-phase studies of the covalent 

coupling of noncovalent complexes initiated by reactive 

carbenes formed by controlled activation of diazo 

precursors. Angew. Chem. Int. Ed. 42, 1012–1015, (2003). 

19. Springer, C. A. S. a. A. Mass Spectrometry and Gas-Phase 

Chemistry of Non-Covalent Complexes. Supramolecular 

Chemistry in the Gas Phase. (John Wiley & Sons, 2009). 

20. Miesset, U. H. B. a. J.-L. Molecular Encapsulation: 

Organic Reactions in Constrained Systems (John Wiley & 

Sons, 2010). 

Keywords: inner-phase reactions; gas-phase; host-guest; 



s870 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 2 2 

eLeCtrideS, nonLineAr oPtiCAL ProPertieS 

And viBrAtionS 

J. M. LuiS 1 , M. GArCiA-BorrAS 1 , M. SoLA 1 , 

B. KirtMAn 2 


Química, Girona, Spain 

2 University of California – Santa Barbara, Chemistry and 

Biochemistry, Santa Barbara, USA 

Electrides are ionic compounds in which electrons behave 

as anions. These special electrons are separated from any nuclei, 

occupying positions typically populated by anions in ionic 

compounds. It is well-known that electrides have very large NLO 

electronic properties. [1–4] The main goal of this study has been to 

determine and analyze the vibrational, as compared to the 

electronic, NLO properties for a representative set of electrides 

•+ •- including Li@Calix, Na@Calix, Li@B H , Li TCNQ and 

10 14 2 

Na 2 

•+ TCNQ •- . Our results, obtained by UB3LYP level using 

different Pople basis set, vary depending upon the electride and 

the NLO process. In general, however, we find that the average 

static vibrational first and second hyperpolarizability exceed the 

corresponding electronic property values, sometimes in the latter 

case by more than an order of magnitude. As far as dynamic 

properties are concerned, on average they are roughly the same 

as the corresponding static electronic hyperpolarizability, and in 

particular cases they may be twice as large or more. The role of 

anharmonicity in the (NR) hyperpolarizabilities is variable. It 

plays a dominant role for the Li@B H first and second 

10 14 

•+ •- hyperpolarizability, but is negligible for the Li TCNQ first 

2 

(though not the second) hyperpolarizability. 

references: 

1. W. Chen, Z. R. Li, D. Wu, Y. Li, C. C. Sun, F. L. Gu, 

J. Am. Chem. Soc., 127, 10977 (2005). 

2. Z. J. Li, F. F. Wang, Z. R. Li, H. L. Xu, X. R. Huang, 

D. Wu, W. Chen, G. T. Yu, F. L. Gu, Y. Aoki, Phys. Chem. 

Chem. Phys., 11, 402 (2009). 

3. S. Muhammad, H. L. Xu, Y. Liao, Y. H. Kan, Z. M. Su, 

J. Am. Chem. Soc., 131, 11833 (2009). 

4. F. Ma, Z. R. Li, H. L. Xu, Z. J. Li, Z. S. Li, Y. Aoki, 

F. L. Gu, J. Phys. Chem. A, 112, 11462 (2008). 

Keywords: electride; Non linear optical properties; 

hyperpolarizabilities; vibrational contributions; 


P - 0 0 2 3 

SoLvent And ioniC StrenGth effeCtS on the 

StABiLity of dioxovAnAdiuM (v) CoMPLexeS 

with idA And dtPA 

K. MAJLeSi 1 , S. BALALi 1 , z. CetvAti 1 

1 Islamic Azad University Science and Research Branch, 

Chemistry, Tehran, Iran 

Our laboratory has taken up the study of complexation of 

+ 2- various aminopolycarboxylic acids with VO and MoO4 ions in 

2 

order to study the influence of the solvents and ionic medium and 

to determine the contribution of Kamlet-Abboud-Taft (KAT) 

parameters in recent years. [1–3] Polarity of a liquid is defined as 

the sum of all possible specific and non-specific interactions 

between the solvent and a potential solute. The goal of this 

study is to investigate the H O-CH OH composition and 

2 3 

the ionic strength influences on the stability of dioxovanadium 

(V) + iminodiacetic acid (IDA) and dioxovanadium (V) + 

diethylenetriaminepentaacetic acid (DTPA) complexes 

respectively. UV data have been gathered at a fixed ionic strength 

(I = 0.1 mol.dm-3 of sodium perchlorate) and t = 25°C for the 

+ solvent effect study. Complexation of VO ion with DTPA was 

2 

studied at different ionic strengths of sodium chloride 

(0.1 ≤I/mol.dm-3 ≤ 1.0). It was concluded that the increase in 

the hydrogen-bond acceptor capability of the solvent favors a 

higher thermodynamic stability of the products with respect to the 

reactants and consequently, an increase in the corresponding 

stability constants. Determination of the activity coefficients of 

aqueous electrolyte solutions is a very important area of research. 

At higher concentrations short range and non electrostatic 

interactions have to be taken into account, and this is usually done 

by adding terms to the Debye-Hückel expression. The most 

popular models are the Pitzer and specific ion interaction theory 

(SIT) equations. The errors and R2 values for the models showed 

that the SIT model is the best for this research. 

references: 

1. K. Majlesi, S. Rezaienejad, J. Chem. Eng. Data 56, 3194 

(2011) 

2. K. Majlesi, S. Rezaienejad, J. Solution. Chem 40, DOI: 

10.1007/s0953-011-9754-7 (2011) 

3. K. Majlesi, S. Rezaienejad, A. Rouhzad, J. Chem. Eng. 

Data 56, 541 (2011) 

Keywords: Thermodynamics; Solvent effects; Hydrogen bonds; 

UV/Vis spectroscopy; 



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chem. Listy 106, s587–s1425 (2012) 


P - 0 0 2 4 

CALCuLAtion of eLeCtroniC exCitAtion 

enerGieS throuGh the uSe of inCreMentAL 

CorreLAtion SCheMeS 

r. MAtA 1 , M. PAuLiKAt 1 

1 Georg-August-Universität Göttingen, Institute of Physical 


The application of ab initio correlation methods is severely 

hindered by their computational cost. The exponential scaling of 

the latter relative to the system size only allows for the treatment 

of relatively small systems. However, electronic correlation in 

molecules is known to be a short range effect, and significant 

savings can be obtained by taking this into account, may it be 

through the use of integral screening, [1] local approximations [2] 

or many-body approaches. The latter class of methods works by 

splitting the system into fragments and computing the energy as 

a many-body expansion. Such approaches have been applied to 

the ground state correlation energy of molecular systems. [3] We 

have also recently presented an extension for the calculation of 

excited states. [4] 

In this work, the incremental scheme is applied in the 

calculation of excitation energies of a large benchmark set. We 

present several improvements to the method including new robust 

criteria to identify the main fragments involved in the excitation. 

Results show that the method is capable of reproducing full 

calculation results in only a fraction of the total computational 

time. Preliminary applications in the study of physisorbed 

molecules are also discussed. 

references: 

1. B. Doser, D. S. Lambrecht, J. Kussmann and 

C. Ochsenfeld, J. Chem. Phys. 130, 1006–1013 (2009). 

2. C. Hampel and H.-J. Werner, J. Chem. Phys. 104, 

6286–6297 (1996). 

3. J. Friedrich and M. Dolg, J. Chem. Theory Comput. 5, 

287–294 (2009). 

4. R. A. Mata and H. Stoll, J. Chem. Phys. 134, 034122 (2011). 

Keywords: Electronic structure; Ab initio calculations; 

Photochemistry; 


P - 0 0 2 5 

MuLtiCenter Bond index: A verSAtiLe tooL 

to ChArACterize eLeCtron deLoCALizAtion 

And AroMAtiCity. 

e. MAtito 1 , f. feixAS 2 , J. M. BArroSo 1 , 

J. M. uGALde 3 , M. SoLA 1 


Department of Chemistry, Girona, Spain 

2 University of California San Diego, Department of Chemistry 

and Biochemistry, San Diego, USA 

3 University of the Basque Country, Faculty of Chemistry, 

Donostia, Spain 

Multicenter indices (MCI) [1–10] are used in a number of 

situations such as the analysis of conjugation and 

hyperconjugation effects, [7] to identify agostic bonds, to account 

for electron distributions in molecules [4–5] or to study aromaticity 

in both organic [9] and all-metal compounds. [4–11] The formula of 

MCI involves the intuitive n-order central moment of the electron 

population, [12–13] which depends on the n-order RDM. The 

calculation of the n-RDM is overwhelmingly expensive for 

correlated wavefunctions and, therefore, there are so few studies 

of MCI available in the literature. In this talk we review the 

applications of MCI and suggest a new approximation for the 

3-RDM that provides more accurate MCI values than the 

approximations suggested thus far in the literature. [15–16] 

references: 

1. Giambiagi, M. et al. A. P. Phys. Chem. Chem. Phys. 2 

(2000) 3381. 

2. Bultinck, P et al. J. Phys. Org. Chem. 18 (2005) 706. 

3. Cioslowski, J. et al. J. Phys. Chem. A 111 (2007) 6521. 

4. Pendás, A. M. et al. Phys. Chem. Chem. Phys. 9 (2007) 

1087. 

5. Pendás, A. M. et al. J. Chem. Phys. 127 (2007) 144103. 

6. Ponec, R. et al. J. Phys. Chem. A 101 (1997) 1738. 

7. Feixas, F. et al. J. Phys. Chem. A 115 (2011) 13104. 

8. Bultinck, P. Faraday Discuss. 135 (2007) 347. 

9. Feixas, F. et al. J. Comput. Chem. 29 (2008) 1543. 

10. Feixas, F. et al. Theor. Chem. Acc. 128 (2011) 419. 

11. Feixas, F. et al. J. Chem. Theory Comput. 6 (2010) 1118. 

12. Giambiagi, M. et al. Struct. Chem. 1 (1990) 423. 

13. Francisco, E. et al. J. Chem. Phys 126 (2007) 094102. 

14. Feixas, F. et al. in preparation. 

15. Colmenero, F. et al. Int. J. Quantum Chem. 51 (1994) 369. 

16. Mazziotti, D. A. Phys. Rev. A 57 (1998) 4219. 

Keywords: mutiple bonds; aromaticity; bond theory; agostic 

interactions; 



s872 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 2 6 

exPLorinG the nAture of 

CArBohydrAte-AroMAtiC diSPerSion 

interACtionS viA SoPhiStiCAted 

CoMPutAtionAL CheMiStry tooLS 

S. KozMon 1 , r. MAtuSKA 2 , v. SPiwoK 3 , J. KoCA 1 

1 CEITEC - Central European Institute of Technology Masaryk 

University, Computational Chemistry Group, Brno, 


2 National Centre for Biomolecular Research Masaryk 

University, Laboratory of Computational Chemistry, Brno, 


3 Institute of Chemical Technology, Department of Biochemistry 

& Microbiology, Praha, Czech Republic 

Interactions of saccharides with receptors belong to the most 

important ones. The carbohydrates represent signalling molecules 

from so-called glycocode, which is recognized by the variety of 

proteins. There are several ways how saccharides interact with 

proteins. The role of dispersion-driven CH-π interactions in 

protein-carbohydrate interactions has been underestimated for a 

long time. This type of interaction occurs between carbohydrate 

apolar faces and aromatic amino-acids. 

We introduce first systematic study of CH-π interactions 

between carbohydrates (β-D-glucopyranose, β-D-mannopyranose, 

α-L-fucopyranose) and aromatic amino-acid models: benzene and 

naphtalene. 3D interaction energy (E ) scan was performed to 

int 

elucidate interaction energy maps for carbohydrate-benzene 

interaction. Resulting stationary complexes were reoptimized and 

their E was refined at highly-sophisticated level. To study 

int 

possible degree of additivity, we used geometries of carbohydratebenzene 

complexes to build-up monodentate (interaction with one 

CH-group) and bidentate (interaction with two CH-groups) 

carbohydrate-naphtalene complexes. 

Results show E in carbohydrate-benzene complex up 

int 

to -5,40 kcal/mol. We localized most attractive regions where the 

E is highest. The strongest interaction is localized above and 

int 

under CH-groups of carbohydrate. Additionally, benzene can 

recognize the specific hydrogens of carbohydrate in specific ideal 

distance (|(C)H-π| distance around 2,3 ?). The aromatic ring is 

coplanar with the carbohydrate cycle. 

Localization of the strongest interaction regions for 

carbohydrate-benzene complex lead us to idea about possible 

additivity of the CH-π interaction. Therefore, E of bidentate 

int 

carbohydrate-napthalene complexes were analyzed. The 

hypothesis of total additivity of the interaction was not confirmed. 

However, the E exhibits certain degree of additivity. The E of 

int int 

bidentate complex forms 2/3 of sum of E of monodentate ones 

int 

and 4/5 of sum of E of carbohydrate-benzene complexes. 

int 

Acknowledgement: Financial support by the German Science 

Foundation (Di 1517/2-1) is gratefully acknowledged. 

This work was supported within the project “CEITEC-Central 

European Institute of Technology” (CZ.1.05/1.1.00/02.0068) 

from European Regional Development Fund. Access to the 

MetaCentrum computing facilities provided under the research 

intent MSM6383917201 is acknowledged. 

Keywords: carbohydrate; benzene; naphtalene; ab initio 

calculations; density functional calculations; 


P - 0 0 2 7 

deProtonAted G8 And ProtonAted A38 in the 

GenerAL ACid/BASe MeChAniSM of the hAirPin 

riBozyMe SeLf-CLeAvAGe reACtion PAthwAy 

v. MLynSKy 1 , P. BAnAS 1 , n. G. wALter 2 , J. SPoner 3 , 

M. otyePKA 1 

1 Regional Centre of Advanced Technologies and Materials, 

Department of Physical Chemistry, Palacky University 

Olomouc, Czech Republic 

2 Department of Chemistry Single Molecule Analysis Group, 

University of Michigan, Ann Arbor MI, USA 

3 Institute of Biophysics, Academy of Sciences of the 

Czech Republic, Brno, Czech Republic 

The hairpin ribozyme is a member of the group of 

small ribozymes, performing self-cleavage and -ligation without 

direct participation of metal ions. Experiments identified two 

catalytically active residues, guanine 8 (G8) and adenine 

38 (A38), but their exact roles remain still elusive. We carried out 

all-atom molecular dynamics (MD) simulations in explicit solvent 

on 50-500 ns time scales in order to compare the impact of various 

protonation states of G8 and A38. We observed that the 

geometries with the canonical G8 and protonated A38H + agreed 

well with the crystal structures, while those bearing a 

deprotonated G8- and a canonical A38 gradually perturbed the 

active site. The geometries generated by MD simulations were 

further analyzed by the hybrid quantum-mechanical/molecular 

mechanical (QM/MM) method. We calculated energies along the 

reaction pathways and indentified activation barriers and 

rate-limiting steps. We found three possible reaction scenarios 

with activation barriers in good agreement with those derived 

from experiment (20-21 kcal/mol). These scenario were: 

(i) a general base (deprotonated G8- )/general acid (protonated 

A38H + ) mechanism with activation barrier of 20.4 kcal/mol; 

(ii) two mechanisms involving a proton shuttle via the 

nonbridging oxygen in the presence of canonical G8 together with 

either A38 or A38H + (20.5 or 21.0 kcal/mol, respectively); and 

(iii) a combined proton shuttle/general acid mechanism with 

canonical G8 and protonated A38H + (21.0 kcal/mol). In all cases, 

the initial nucleophile attack of the A-1(2'-OH) group on the 

scissile phosphate represented the rate-limiting step along the 

reaction path. We suggest that RNA self-cleavage may benefit 

from several microscopic pathways that are energetically 

comparable. Among those pathways, the reaction mechanism with 

deprotonated G8- as general base and protonated A38H + as general 

acid is the most consistent with the experimentally measured 

kinetic pH profiles. 

Keywords: Enzyme catalysis; Ribozymes; Cleavage reactions; 



s873 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 2 8 

AdSorPtion of hCn on LewiS SiteS of 

MiCroCryStALLine GAMMA-ALuMinA: A 

quAntuM CheMiCAL CLuSter ModeL Study 

i. nAStovA 1 , t. SKAPin 2 , L. PeJov 1 

1 Faculty of Natural Sciences and Mathematics, Institute of 

Chemistry, Skopje, Macedonia 

2 Jozef Stefan Institute, Department of Inorganic Chemistry and 


Adsorption of HCN on the surface-exposed acidic Lewis 

sites of microcrystalline γ-alumina was studied by a quantum 

chemical cluster model approach, with an emphasis on 

the potential usage of HCN as a test-probe molecular 

system. B3LYP/6-31++G(d,p) and HF/6-31++G(d,p) levels of 

theory were employed, considering the standard and 

counterpoise-corrected potential energy surfaces (PESs) of HCN 

attached to finite clusters modeling the surface. The main focus 

was put on the non-polar (100) and (110) crystal planes of 

microcrystalline γ-alumina. Neutral cluster models representing 

the non-polar (100) and (110) planes were derived from the crystal 

structure of γ-Al 2 O 3 . Termination of the clusters at the bulk-cluster 

interfaces was performed by OH groups or HOH molecules. Both 

the standard and the counterpoise-corrected potential energy 

surfaces of free HCN, as well as of HCN-Al(OH) x (H 2 O) y clusters 

in the ground electronic state were explored at the 

above-mentioned levels of theory. Explicit inclusion of 

dynamical electron correlation effects and the elimination of the 

basis set superposition effects in geometry optimization was found 

to be significant factor in order to reproduce the experimental 

trends in the shifts of the HCN C-H stretching mode frequencies 

upon adsorption. Both harmonic and anharmonic vibrational 

analyses of the HCN C-H stretching motion were performed. The 

later were based on sequential computation of the C-H stretching 

vibrational potentials for the free and adsorbed HCN molecule 

(on various clusters) and solution of the corresponding vibrational 

Schrodinger equation by the variational method. Bader and 

NBO analyses of the electronic density were employed in order 

to make a proper classification of the type of intermolecular 

interaction (covalent versus noncovalent) in the course 

of HCN adsorption on microcrystalline γ-alumina. 

Keywords: HCN; adsorption; Lewis adsorption sites; gammaalumina 

(?-Al2O3); 


P - 0 0 2 9 

MetAL-orGAniC MoLeCuLAr unitS for 

induCed StruCture MAniPuLAtion 

f. nAuMKin 1 

1 UOIT, Faculty of Science, Oshawa, Canada 

Interfaces between metal atoms and organic molecules are 

key units of metal-organic frameworks, connections between 

metal electrodes and molecular “wires”, catalysis-related species. 

A large class of such interfaces is represented by sandwich-type 

complexes with the molecules on both sides of the atoms. Most 

of such systems involve transition metals, while main-group light 

metals may induce features related to closer proximity of the 

molecules combined with their favourable orientation 

[Chem.Phys.Lett. 499 (2010) 203]. 

Presented are results of ab initio calculations for a series of 

complexes of light-metal atoms sandwiched between small 

unsaturated hydrocarbon molecules. Evolution of the system 

structure and stability is systematically studied for different metal 

atoms, as well as upon ionization and electron attachment. 

Predicted interesting features include non-additive stabilization 

on adding second molecule to the half-sandwich precursor, 

unusual geometries in some cases, and reversible charge- or 

excitation-governed geometry alterations. The latter variations are 

found to reflect structure similarities for isoelectronic systems. 

Such properties apparently suggest potential applications of the 

above species as stable intermolecular junctions and units with 

charge- or spin-controlled shapes in molecular devices and/or 

machines. 

Additional point of interest is the metal-atom induced fusion 

of the sandwiching molecules, leading to another isomer of the 

system. Different metals are predicted to favour different isomers, 

with such catalysis producing higher-energy species in some 

cases. Stability towards detachment of the metal atom from the 

fused molecular species (thus completing the catalytic cycle) is 

addressed. 

Also considered is a system of one or two metal atoms and 

a single larger molecule with a few suitably positioned unsaturated 

fragments. It is found to exhibit similar, although intra-molecular, 

nonadditive stabilization and metal-atom induced isomerization. 

Mutual influence of metal-attachment sites and their effect on the 

isomerization are analyzed as well. 

Keywords: Ab initio calculations; Sandwich complexes; Main 

group elements; Isomers; Molecular devices; 



s874 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 3 0 

ConforMAtionAL StudieS of BetA-PePtideS 

throuGh the uSe of LMP2-CoSMo And 

MoLeCuLAr dynAMiCS 

J. oLiveirA 1 , r. MAtA 1 

1 Georg-August-University Göttingen, Institute of Physical 


The study of β-peptides secondary structures has gained 

substantial interest over the last years. Compared to α-peptides, 

the additional carbon in their backbone provides an extra degree 

of freedom due to the added torsional angle. This feature allows 

β-peptides to adopt a large number of distinct secondary structures 

with relatively low energy differences. 

β-peptides seem to have an intrinsic tendency to fold into 

periodic structures, although the nature and relation of these 

interactions are not quite well understood. This appears to be 

related with local torsional angles as well as backbone-side chain 

and side chain-side chain interactions. [1] The use of local 

correlation methods with implicit solvent model have shown to 

be promising method to describe the properties of hexamers of 

such systems. [2] 

In an attempt to characterize and better understand the 

β-peptides conformational landscape, several oligopeptide 

geometries were optimized with DFT methods in different 

polarity environments. The energetics were then refined through 

single point energy calculations carried out at the level of local 

second order Müller Plesset perturbation theory (LMP2) [3] in 

combination with the COSMO model. [4] Density-fitting 

approximations, which reduce the computational cost relative to 

the basis set size, were also applied. Molecular dynamics 

simulations were also carried out in order to treat the solvent 

explicitly and complement the quantum mechanics studies. 

The results underline the applicability local correlated 

methods in the characterization of such systems, as well as the 

influence of the side chain groups. 

references: 

1. T. Martinek, F. Fülop, Eur. J. Biochem., 270 (2003) 3657. 

2. J. C. A. Oliveira, J. Feldt, N. Galamba, R. Mata, J. Phys. 

Chem. A, 116 (2012) 5464. 

3. H.-J. Werner, F. R. Manby and P. J. Knowles, J. Chem. 

Phys., 118 (2003) 8149. 

4. A. Klamt and G. Schürmann, J. Chem. Soc. Perkin Trans. 

II, 799 (1993). 

Keywords: Peptides; Molecular dynamics; Ab initio 

calculations; 


P - 0 0 3 1 

qSPr ModeLLinG of LiPoPhiLiCity And 

AntituBerCuLAr ACtivity of 

thioBenzAniLide derivAtiveS 

L. Pinheiro 1 , M. L. MoitA 2 , S. BorGeS 2 , M. reiS 2 , 

i. SouSA 2 , S. SAntoS 2 , C. venturA 2 , f. MArtinS 2 

1 Research Institute for Medicines and Pharmaceuticals 

Sciences FFUL, DCTB, Lisbon, Portugal 

2 Centro de Quimica e Bioquimica FCUL, DQB, Lisbon, 

Portugal 

The search for novel drugs against bacterial infections like 

tuberculosis, a disease caused by Mycobacterium tuberculosis 

(M. tb) and other mycobacterioses, is one of the goals of 

present-day pharmaceutical industry, given the enormous impact 

of these pathologies on public health worldwide1 and, in the case 

of M. tb, also due to the alarming spread of multi-drug resistance 

reported cases. Thiobenzanilides, which are relatively weakly 

toxic to higher organisms, have been found to show strong 

biological activity as anti-tubercular agents. 

In this work we have analyzed a large set of thiobenzanilide 

derivatives (189 compounds), taken from literature, and have 

derived two quantitative structure-properties relationships 

(QSPRs) relating the lipophilicity, measured as clogP, and the 

anti-tubercular activity, measured as log(1/MIC), of these 

compounds with various computed molecular descriptors. QSPR 

models were generated by multiple linear regressions (MLR) 

using a forward stepwise variable selection. 2 The database was 

divided into a training set and an independent test set with similar 

variability. The best descriptors related to either lipophilicity 

(clogP) or biological activity (MIC) were selected on the basis of 

rigorous statistical criteria. The obtained model equations were 

internally and externally validated, in order to assess the 

robustness and predictive ability of the developed QSPR models. 

The best found equations showed a good interpretative ability and 

an effective predictive power towards test set compounds and will 

be used to assist us in the rational design and synthesis of new 

active thiobenzanilide derivatives. 

Acknowledgements: This work was supported by national 

funding through FCT- Fundacio para a Ciencia e a Tecnologia, 

within the scope of projects PTDC/QUI/67933/2006 and PEst- 

OE/QUI/UI0612/2011 

references: 

1. http://www.who.int/tb/publications/ 

/global_report/2011/gtbr11_full.pdf accessed 24/05/2012 

2. Ventura C, Martins F. J Med Chem 2008, 51, 612-624. 

Keywords: thiobenzanilides; anti-tubercular activity; 

lipophilicity; quantitative structure-property relationship; 



s875 

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P - 0 0 3 2 

interACtionS Between SeLeCted BiLe SALtS 

And triton x-100 or SodiuM LAuryL ether 

SuLfAte 

M. PoSA 1 , A. SeBenyi 1 , K. KuhAJdA 2 , S. KevreSAn 3 , 

d. Cirin 4 

1 Medical faculty Novi Sad, Pharmacy, Novi Sad, Serbia 

2 Faculty of Science, Chemistry, Novi Sad, Serbia 

3 Faculty of Agriculture, Chemistry, Novi Sad, Serbia 

4 Medical Faculty, pharmacy, Novi Sad, Serbia 

Background: In order to develop colloidal drug carriers 

with desired properties, it is important to determine 

physico-chemical characteristics of these systems. Bile salt mixed 

micelles are extensively studied as novel drug delivery systems. 

The objective of the present investigation is to develop and 

characterize mixed micelles of nonionic (Triton X-100) or anionic 

(sodium lauryl ether sulfate) surfactant having oxyethylene groups 

in the polar head and following bile salts: cholate, deoxycholate 

and 7-oxodeoxycholate. 

results: The micellization behaviour of binary 

anionic-nonionic and anionic-anionic surfactant mixtures was 

investigated by conductivity and surface tension measurements. 

The results of the study have been analyzed using Clint’s, 

Rubingh’s, and Motomura’s theories for mixed binary systems. 

The negative values of the interaction parameter indicate 

synergism between micelle building units. It was noticed that 

Triton X-100 and sodium lauryl ether sulfate generate the weakest 

synergistic interactions with sodium deoxycholate, while 

7-oxodeoxycholate creates the strongest attractive interaction with 

investigated co-surfactants. 

Conclusion: It was concluded that increased synergistic 

interactions can be attributed to the larger number of hydrophilic 

groups at a side of the bile salts. Additionally, 7-oxo group of 

7-oxodeoxycholate enhance attractive interactions with selected 

co-surfactants more than 7-hydroxyl group of sodium cholate. 

Acknowledgement: This work was financially supported 

by the Provincial Secretariat for Science and Technological 

Development, AP Vojvodina, Republic of Serbia, 

Grant No. 114-451-2113/2011-02. The Hungary-Serbia IPA 

Cross-border Co-operation programme HUSRB/1002/214/193, 

Bile Acid Nanosystems as Molecule Carriers in Pharmaceutical 

Applications (BANAMOCA), is thanked as well. 

Keywords: Micelles; Molecular recognition; 


P - 0 0 3 3 

interACtionS Between SodiuM ChoLAte or 

SodiuM deoxyChoLAte And nonioniC 

SurfACtAnt (tween 20 or tween 60) in 

AqueouS SoLution 

M. PoSA 1 , d. Cirin 1 , J. trifunoviC 1 , A. SeBenyi 1 

1 Medical Faculty Novi Sad, Pharmacy, Novi Sad, Serbia 

Knowledge of physicochemical parameters of mixed 

micelles is important in order to develop drug delivery systems 

with required characteristics. Investigated bile salts and Tweens 

are relatively nontoxic surfactants, extensively studied as 

biocompatible colloidal drug carriers. The micellization behavior 

of binary anionic-nonionic surfactant mixtures built of sodium 

cholate or sodium deoxycholate and one of two Tweens 

(Tween 20 or Tween 60) was investigated by conductivity and 

surface tension measurements. The results of the study have been 

analyzed using Clint’s, Rubingh’s, and Motomura’s theories for 

mixed binary systems. The determined physicochemical 

properties, particularly the negative values of the interaction 

parameter, indicate synergism between the individual surfactants 

in the mixed micelles. It was noticed that Tween with a longer 

hydrophobic tail shows stronger interactions with selected bile 

salts. However, it was found that the more hydrophilic bile salt 

(sodium cholate) generates the stronger synergism with 

investigated Tweens. 

This work was financially supported by the Provincial 

Secretariat for Science and Technological Development, AP 

Vojvodina, Republic of Serbia, Grant No. 114-451-2113/2011-02. 

The Hungary-Serbia IPA Cross-border Co-operation programme 

HUSRB/1002/214/193, Bile Acid Nanosystems as Molecule 

Carriers in Pharmaceutical Applications (BANAMOCA), is 

thanked as well. 

Keywords: bile acids; mixed micelle; Tween; 



s876 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 3 4 

interACtion of SMALL rnA MoLeCuLeS with 

GrAPhene SurfACe 

M. PyKAL 1 , P. JureCKA 1 , P. KoSinová 1 , 

M. KoCMAn 1 , M. otyePKA 1 

1 Regional Centre of Advanced Technologies and Materials 

Palacky University Faculty of Science, Department of Physical 

Chemistry, Olomouc, Czech Republic 

Hairpins belong to the most important structural motifs in 

RNA. Many of them play key roles in relevant biological 

processes such RNA-folding and interactions that determine the 

tertiary structure of RNA molecules. In combination with 

graphene, RNA fragments may become interesting in many 

applications, for instance in sensing, similarly as DNA. But in 

comparison to DNA, little is known about RNA-graphene 

interactions to date. In this work we focused on the GAGA 

tetraloop, which is found in sarcin-ricin loop in ribosome, where 

it serves as a recognition site for some ribotoxins. We carried out 

molecular dynamics simulations of this tetraloop in water and also 

at the graphene-water interface. We used various techniques such 

as potential of mean force (PMF) or targeted MD to investigate 

the influence of graphene on the stability of these motifs. 

Keywords: Molecular dynamics; Graphene; RNA; Biosensors; 


P - 0 0 3 5 

LoCAL SPin: iMProved hiLBert-SPACe AnALySiS 

e. rAMoS-CordoBA 1 , e. MAtito 1 , i. MAyer 2 , 

P. SALvAdor 1 



2 Institut of Organic Chemistry Research Center for Natural 

Science, Hungarian Academy of Science, H-1525 Budapest 

P.O. Box 17, Hungary 

The local spin is a key concept for the characterization of 

magnetic properties of transition metal complexes and clusters, 

and also for establishing the radical character of molecules or 

reactive processes. In recent years there has been an increasing 

interest in recovering local spins from ab initio wavefunctions. [1–6] 

We have shown [6] that there is actually a continuum of 

different formulations that fulfill all physical requirements 

imposed to date to the decomposition of s2 , and this applies to 

both single- and multideterminant wave functions. In order to find 

the best local-spin decomposition scheme, we impose a new, 

additional requirement related to the one-electron distribution that 

eliminates the ambiguity. The resulting local-spin decomposition 

is thus unique and fulfills all physical requirements found so far. 

Moreover, there is an apparent ambiguity in decomposing 

two-electron quantities in the framework of Hilbert-space analysis 

that, to date, has not received due attention. This problem is 

particularly relevant in the case of the decomposition of s2 The 

numerical implementation has been carried out in the 

Hilbert-space. A series of representative closed-shell and 

open-shell systems have been used to illustrate the performance 

of this new decomposition scheme against other existing 

approaches. Unlike other decompositions of s2 , the new scheme 

provides very small local-spin values for genuine diamagnetic 

molecules treated with correlated wave functions. 

references: 

1. A. E. Clark, E. R. Davison, J. Chem. Phys. 2001, 115, 7382 

2. I. Mayer, Chem. Phys. Lett. 2007,440, 357. 

3. I. Mayer, Chem. Phys. Lett. 2009,478, 323. 

4. I. Mayer, E. Matito, Phys. Chem. Chem. Phys., 2010,12, 

11308 

5. D. R. Alcoba, A. Torre,L. Lain, R. C. Bochicchio, J. Chem. 

Theory Comput. 2011, 7, 3560–3566 

6. E. Ramos-Cordoba, E. Matito, I. Mayer, P. Salvador J. 

Chem. Theory Comput. 2012, 8, 1270–1279. 

Keywords: ab initio calculations; quantum chemistry; 



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P - 0 0 3 6 

Coherent exCitAtion of neon in the 

extreMe uLtrAvioLet reGiMe 

C. rASChPiChLer 1 , J. PLenGe 1 , A. wirSinG 1 , 

B. wASSerMAnn 1 , e. rühL 1 

1 Freie Universität Berlin, Institute of Chemistry and 

Biochemistry, Berlin, Germany 

Coherent excitation of atomic transitions is a general 

phenomenon that may result in coherent transients. These are a 

signature of interferences between resonant and non-resonant 

excitation pathways. This fundamental process has been 

investigated using ultrashort laser pulses in the near infrared 

regime [1] . An extension of the investigation of these fundamental 

processes from the optical to the extreme ultraviolet (xuv) regime 

has become feasible with the development of ultrashort xuv light 

sources. High-order harmonic generation is a well-established 

technique for producing ultrashort radiation in the xuv range. 

In this work we investigate the coherent excitation of a 

superposition of Rydberg states in neon by the 13th harmonic of 

an intense 804 nm pulse and the formation of a wave packet [2] . 

We present pump-probe experiments performed on the 3d 

manifold of neon where the 2p6 2p5 ( 2P ) 3d [1/2] and 

3/2 

2p6 2p5 ( 2P ) 3d [3/2] transitions are excited at 20.04 eV photon 

3/2 

energy. The temporal evolution of the excited wave packet is 

probed by ionization with a time-delayed 804 nm pulse. We 

demonstrate the control of the coherent transient excitation of 

neon and the wave packet dynamics in the xuv regime using the 

spectral phase of the 13th harmonic as a control parameter, where 

the modulation of the phase is achieved by propagation of the xuv 

pulse through a variable optical density of neon gas. The 

experimental results indicate the possibility to control 

fundamental coherent excitation processes in the xuv regime using 

phase-shaped high-order harmonics. 

references: 

1. S. Zamith, J. Degert, S. Stock, and B. de Beauvoir, Phys. 

Rev. Lett. 87, 033001 (2001). 

2. J. Plenge, A. Wirsing, C. Raschpichler, B. Wassermann, 

and E. Rühl, Faraday Discuss. 153, 361 (2011). 

Keywords: Time-resolved spectroscopy; Photoelectron 

spectroscopy; 


P - 0 0 3 7 

roLe of exonS in StABiLizAtion of Protein 

StruCture 

i. roterMAn-KonieCznA 1 , M. PiwowAr 1 , 

M. BAnACh 2 

1 Jagiellonian University - Medical College, Bioinformatics and 

Telemedicine, Kraków, Poland 

2 Jagiellonian University, Faculty of Physiscs Astronomy and 

Applied Computational Science, Kraków, Poland 

The role of exons can be interpreted on many aspects. One 

of them is the relation of exons to the 3-D structure of protein. It 

has been shown that fragments of the secondary structural forms 

are not accordant with sequence fragments accordant with exons. 

The relation between exon fragments and their structural 

status in 3-D structural forms is under consideration. Particularly 

the relation between tertiary structure of the protein and the 

structure of exons present in particular protein has been analyzed. 

The stabilization of tertiary structure is estimated on the basis of 

hydrophobic core structure. The participation of exons in 

hydrophobic stabilization is measured to reveal the role of each 

exon-fragment. 

The exons in selected proteins (100) were identified on the 

basis of information in GenBank files taken from nucleotide 

database in National Center of Biotechnology Information. The 

amino acid sequence representing particular exon was identified. 

The defined sequence fragments were localized in 3-D structural 

forms of proteins (PDB). 

The participation of each exon-fragment in the construction 

of hydrophobic core was measured using the divergence entropy 

calculation showing their differentiate role in the stabilization of 

tertiary structure. 

It was revealed that the presence of at least one exon, of 

which the structure of polypeptide fragment is accordant with 

expected ordered structure of hydrophobic core. It means that the 

probable role of at least one exon is to generate the hydrophobic 

core responsible for tertiary stabilization in proteins. 

Acknowledgements: The financial support – Jagiellonian 

University – Medical College grant system: K/ZDS/001531 and 

K/ZDS/002907. 

Keywords: exons; hydrophobic core; divergence entropy; 



s878 

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P - 0 0 3 8 

CALCuLAtion of frAnCK-Condon fACtor for 

hArMoniC oSCiLLAtorS 

t. SAttASAthuChAnA 1 , K. BALdridGe 1 

1 Organic Chemistry Institute, University of Zürich, Zürich, 

Switzerland 

A formula of Franck-Condon factor for harmonic oscillators 

has been derived from reference. The formula will be used as an 

implementation for calculating rate of electron transfer. Also, the 

applications of Franck-Condon factor have been conducted by 

comparing with DFT calculation of S O molecule with various 

2 

basis sets. 

Keywords: Franck-Condon factor; harmonic oscillator; 


P - 0 0 3 9 

LiGht-driven-CoordinAtion induCed 

SPin-StAte SwitCh: rAtionAL deSiGn of 

PhotodiSSoCiABLe LiGAndS uSinG denSity 

funCtionAL theory MethodS 

C. SChütt 1 , f. KÖhLer 1 , S. thieS 1 , r. herGeS 1 

1 Otto-Diels-Institut, Organic Chemistry, Kiel, Germany 

The coordination of axial ligands to porphyrins is of 

fundamental importance in many areas of chemistry, biology and 

material science. [1] Azopyridinederivates which are isomerizing 

between the cis and trans configuration upon irradiation with UV 

and visible light were used to realize a Light-Driven-Coordination 

Induced Spin-State Switch (LD-CISSS) at Ni(II)-porphyrins. [2,3] 

Upon the association/dissociation of axial ligands the Ni(II) center 

can be switched between the high spin (HS) and the low spin (LS) 

state. Whereas the trans isomer binds with its pyridine nitrogen 

the coordination of the bent cis isomer is sterically hindered. We 

performed density functional theory calculations to find a 

substitution pattern at the phenylazopyridine ligand which 

provided an optimum switching efficiency. A similar approach 

with the photochromic ligands covalently attached to the 

porphyrin has recently been published. [4] 

references: 

1. “The Porphyrin Handbook”, K. M. Kadish, K. M. Smith, 

R. Guilard Eds. Academic Press 2000, London. 

2. S. Thies, H. Sell, C. Schütt, C. Bornholdt, C. Näther, 

F. Tuczek, R. Herges, J. Am. Chem. Soc. 2011, 133, 

16243–16250. 

3. S. Thies, H. Sell, C. Bornholdt, C. Schütt, F. Köhler, 

F. Tuczek, R. Herges, Chem. Eur. J. 2012, submitted. 

4. S. Venkataramani, U. Jana, M. Dommaschk, 

F. D. Sönnichsen, F. Tuczek, R. Herges, Science 2011, 

331, 445–448. 

Keywords: Computational chemistry; Quantum Chemistry; 



s879 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 4 0 

Serine-BASed SurfACtAntS AS ProMiSinG 

CArrierS for Gene deLivery: dnA 

CoMPACtion StudieS with SinGLe-SurfACtAnt 

And CAtAnioniC LiPoSoMeS 

S. SiLvA 1 , d. féLix 1 , M. L. CArdoSo do vALe 1 , 

e. f. MArqueS 1 

1 Faculty of Sciences of the University of Porto, Centro de 

Investigacio em Química - Department of Chemistry and 

Biochemistry, Porto, Portugal 

Cationic lipoplexes have emerged as a potential alternative 

to viral vector-mediated gene delivery for in vitro and in vivo 

applications. Liposomes formed by phospholipids may show 

problems of chemical stability, as these molecules can easily 

undergo chemical degradation by hydrolysis and peroxidation. 

Furthermore, these liposome formulations are frequently 

non-spontaneous and non-equilibrium structures, with limited 

colloidal stability in time. Such shortcomings may compromise, 

in turn, the formation, stability and efficiency of lipoplexes. 

The use of amino acids for the synthesis of surfactants with 

liposome-forming properties provides the route for novel 

biofriendly liposomes that can aim at DNA compaction. These 

liposomes that either be based on single surfactant systems or in 

catanionic mixtures, in the latter case with enhanced 

chemical/colloidal stability and the possibility of charge 

manipulation [1] . 

In this context, we have been involved in the synthesis and 

evaluation of the self-aggregation properties of a variety of ionic 

amino acid-based surfactants. On the basis of previous screening 

toxicological studies, our efforts have been directed towards 

serine-based surfactants [2] . Here, we report the study of the phase 

behavior and microstructure of some serine-based catanionic 

mixtures composed by monomeric single-chained cationic 

(C12, C16) and monomeric double-chained anionic (C8-8, 

C12-12) surfactants. The phase diagrams of two serine-based 

cationic gemini surfactants, (12Ser) CON12 and (12Ser) COO12, 

2 2 

which spontaneously form vesicles, are also presented. The 

synthesis of the compounds has been performed according to a 

methodology established in our laboratory. The mixtures have 

been characterized by differential scanning calorimetry, videoenhanced 

light microscopy and cryo-scanning electron 

microscopy. DNA compaction studies have been also performed, 

by means of fluorescence microscopy. 

Acknowledgement: Thanks are due to FCT 

(PTDC/QUI/115212/2009; SFRH/BD/61193/2009; CIQUP) 

references: 

1. E.F. Marques, Encyclopedia of Surface and Colloid 

Science, 2nd ed.; Taylor & Francis, (2010) 1-19. 

2. R. O. Brito et al., Colloids Surf. B: Biointerfaces, 72, 

(2009) 80. 

Keywords: Amino acids; Surfactants; Vesicles; DNA; 


P - 0 0 4 1 

hyBrid qM/qM APProACheS uSinG LoCAL 

exPLiCitLy CorreLAted MethodS 

t. StoLPer 1 , r. MAtA 1 

1 Georg-August-University Göttingen, Institute of Physical 


Notwithstanding the popularity of DFT, wave function 

methods remain a standard for highly accurate computational 

chemistry studies. However, accuracy comes at a high price in the 

form of long computation times for even a few atoms and a decent 

basis set. To get around this inherent problem, methods such as 

QM/MM and local correlation methods have been introduced. [1] 

The former places the emphasis on a certain area of a complex 

structure, in which most of the change occurs, while the latter 

makes use of the fact that correlation is actually a short range 

effect. Both methods enable the study of much larger systems, but 

possess their own faults. QM/MM approaches may require large 

QM regions to avoid artifacts in their interaction with the 

environment. Local coupled cluster methods, even if low-order 

scaling, may still be too costly for routine applications. A solution 

to these problems is a hybrid QM/QM approach where the whole 

molecule is treated quantum mechanically. The system is divided 

into a region of interest and an outer region, computed at a lower 

level. Through the use of local orbital spaces, [2] no bonds have to 

be broken. 

In this work we apply hybrid QM/QM approaches with 

local explicitly correlated methods, i.e. LMP2-F12 and 

LCCSD(T0)-F12, [3] to calculate reaction energies and barriers of 

different reaction types (e.g. peptide bond formations). This 

method was also used to calculate barriers for an enzyme catalized 

reaction with coupling to MM. [4] Calculations with different 

region sizes support the efficiency of this approach and further 

test systems are suggested. 

references: 

1. C. Hampel, H.-J. Werner, J. Chem. Phys. 1996, 104, 6286. 

2. R. Mata, H.-J. Werner, M. Schütz, J. Chem. Phys. 2008, 128, 

144106. 

3. T. Adler, H.-J. Werner, J. Chem. Phys. 2011, 135, 144117. 

4. R. Mata, H.-J. Werner, S. Thiel, W. Thiel, J. Chem. Phys. 

2008, 128, 025104. 

Keywords: Ab initio calculations; Computational chemistry; 

Peptides; 



s880 

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P - 0 0 4 2 

APPLiCABiLity of MArCuS theory in ioniC 

LiquidS. evidenCe froM eSr Line BroAdeninG 

exPeriMentS 

B. Sudy 1 , K. rASMuSSen 1 , G. GrAMPP 1 

1 Graz University of Technology, Inst. of Physical and 

Theoretical Chemistry, Graz, Austria 

For more than half a century Marcus Theory [1] has been one 

of the cornerstones in the understanding of outer-sphere electron 

transfer reactions. The theory, together with many further 

developments [2,3] , provides a thorough theoretical description of 

the reaction energetics and kinetics and has been substantiated by 

numerous experimental findings. Since Marcus Theory was 

developed for polar liquids, using a dielectric continuum 

approach, it is interesting to know to what extent it can be applied 

to electron transfer in ionic liquids. 

In the past, ESR line broadening experiments [4] on electron 

self-exchange reactions in polar solvents have provided a wealth 

of experimental information on Marcus Theory and thus suggest 

themselves for similar studies in ionic liquids. 

Several well-known self-exchange systems [5,6] have been 

investigated in some common imidazolium based ionic liquids 

using ESR spectroscopy at room temperature and at variable 

temperatures or pressures. The experimental results, such as rate 

constants, reorganization energies or solvent dynamic effects are 

compared to their analogues from traditional solvents, as well as 

to existing findings from literature, obtained using other 

experimental methods. 

references: 

1. R. A. Marcus, J. Chem. Phys., 1956, 24, 966–978 

2. M. Bixon and J. Jortner, Adv. Chem. Phys., 1999, 106, 

35–208 

3. Sutin, N., Prog. Inorg. Chem., 1983, 30, 441–498 

4. G. Grampp, in Electron Paramagnetic Resonance, 

Specialist Periodical Report, eds. B. C. Gilbert, N. M. 

Atherton, M. J. Davies, RSC Cambridge, 1998, vol. 16 

5. G. Grampp and W. Jaenicke, Ber. Bunsenges. Phys. Chem., 

1991, 95, 904–927 

6. G. Grampp and K. Rasmussen, Phys. Chem. Chem. Phys., 

2002, 4, 5546–5549 

Keywords: ESR; Electron Transfer; Ionic Liquids; 


P - 0 0 4 3 

terMinAtion MeChAniSMS for PoLyoLefin 

LivinG CAtALySiS At dft LeveL 

v. viLLAni 1 , G. GiAMMArino 1 

1 University of Basilicata, Chemistry, Potenza, Italy 

Living polymerization is a hot topic in post-metallocene 

catalysis. [1, 3] In fact, the synthesis of ultra-high molecular weight 

polyethylene and block copolymers and the understanding of the 

reaction mechanisms of the termination step are still challenging. 

Fujita et al. [1] have been the first to highlight the living 

behaviour of bis(phenoxyimine)Ti catalysts in the polymerization 

of ethylene and propylene. 

Mecking et al. [2] showed that the new bis(enolatoimine) 

Ti catalyst, with ortho-fluorinated aryl groups, is able to achieve 

the same living behaviour. Via NMR, the key role of the F-bond 

interactions o-F···Ti in the suppression of the H -termination was 

β 

proposed. 

In this communication, we investigate the mechanism of the 

H -transfer in the termination reaction. The models used are 

β 

Mecking’s catalysts. DFT calculations were performed on a 

parallel platform using GAUSSIAN09. 

A procedure to simulate the termination reaction, usually 

based on forcing the cleavage of Ti-C bond, has been developed. 

α 

The stationary structures have been localized and energy barriers 

of activation determined. In transition states’ calculations, normal 

mode analysis has been performed. The protective role of the 

fluorine o-F···H and o-F···Ti bonds in the reactive species, and 

repulsive o-F···o-F interactions destabilizing the transition states, 

have been unraveled. An alternative H -transfer to the ligand, with 

β 

formation of an alkoxyimine, in the termination mechanism of 

ortho-hydrogenated or -methylated non-living catalysts is 

proposed. 

references: 

1. Terao, H.; Iwashita, A.; Matsukawa, N.; Ishii, S.; Mitani, M.; 

Tanaka, H.; Nakano, T.; Fujita, T. ACS Catal. 2011, 1, 

254-265. 

2. Bryliakov, K. P.; Talsi, E. P.; Möller, H. M.; Baier, M. C.; 

Mecking, S. Organometallics 2010, 29, 4428-4430. 

3. Villani, V.; Giammarino, G. Macromolecules 2010, 43, 

5917-5918. 

Keywords: Hydrogen transfer; Density functional calculations; 

Fluorinated ligands; Polymerization; Reaction mechanisms; 



s881 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 4 4 

effeCt of ethynyL And thioPhene-2-yL 

SuBStituentS on CoMPLexAtion of 

4'-SuBStituted 2,2';6',2"-terPyridineS with zn2+ And fe2+ ionS And SPeCtroSCoPiCProPertieS of 

forMed CoMPLexeS. 

t. vitvArová 1 , J. zedníK 1 , M. BLáhA 1 , 

J. vohLídAL 1 , J. SvoBodA 1 


of Physical and Macromolecular Chemistry, Prague 2, Czech 

Republic 

Metallo-supramolecular polymers are macromolecules 

composed of defined oligomeric molecules with chelate 

end-groups, which are linked to chains through reversible 

coordination to metal ions. Strength of this interaction depends 

on choice of ligand as well as metal ions. 

Appropriate combination of metal and ligand is the key to 

obtain polymer with demanding properties. 

2,2':6',2"-Terpyridine is easy to functionalized and can be 

used as chelate end-groups for oligomeric components of 

electromagnetic-field-responsive metallo-supramolecular polymers 

for photovoltaic applications. Iron (II) and zinc (II) ions are 

typical ions used in metallosupramolecular polymers composed 

of terpyridine capped π-conjugated oligomers. 

Terpyridine end-groups can be linked to molecules of 

various conjugated oligomers via ethynediyl or thiophene-2,5-diyl 

moieties. As these moieties can significantly influence their 

properties, knowledge of them is of high interest since it allows 

discriminating contributions of the oligomeric chains to the 

properties of resulting metallo-supramolecular polymers. 

Therefore, we thoroughly studied complexation of 

4'-ethynyl- and 4'-(thiophene-2-yl)-terpyridine with Zn2+ and Fe2+ ions using the UV/vis, NMR and fluorescence spectroscopy in 

order to (i) determine stability constants of complexes formed, (ii) 

obtain an insight into the spectral changes accompanying these 

complexations. In addition, we measured stability constants and 

examined spectral properties of Zn2+ and Fe2+ complexes of 

unsubstituted terpyridine in order to get a solid basis for the 

evaluation of the substituent effects. 

The obtained results show that stepwise addition of Zn2+ ions 

to ligand (L) solution, gives as first species [ZnL ] 2 2+ and then 

[ZnL] 2+ in proportions depending on the Zn/L molar ratio. In 

contrast, added Fe2+ ions give exclusively species [FeL ] 2 2+ 

that, according to UV-VIS and NMR spectra do not undergo 

transformation into [FeL] 2+ . 

Stability constants of forming complex ML and ML were 2 

calculated. All complexes were found to be stable under applied 

conditions. 

Keywords: UV/Vis spectroscopy; NMR spectroscopy; 

Supramolecular chemistry; N ligands; 


P - 0 0 4 5 

CLuSter forMAtion in SoLvAted BiSMuth 

CoMPLexeS 

M. wALther 1 , M. SChLeSinGer 2 , d. zAhn 1 

1 Friedrich-Alexander-Universität Erlangen-Nürnberg, Chemistry 

and Pharmacy, Erlangen, Germany 

2 Technische Universität Chemnitz, Fakultät für 

Naturwissenschaften, Chemnitz, Germany 

Our research is focusing on the formation of clusters in 

solvated metal systems, in this case mixed bismuth hydroxide and 

bismuth nitrate clusters in Dimethylsulfoxide, and nucleation and 

phase change in these systems. The objective is to characterize 

mechanisms by which such phase changes occur and the 

associated parameters which promote the phase change best. 

Our side of this research project centers on computational 

methods, namely molecular dynamics and statistical analysis, 

using the DL POLY package and the OPLS force field, through 

which both properties in solution and after beginning nucleation 

are assessed and quantized for dynamic and thermodynamic 

properties. The next step will be to calculate exchange energies of 

bimut octahedra in different ion caged (OH- - - - , NO , (OH )x (NO )y ) 

3 

3 

and with added ions (Na + OH- ) in solution. After this assessment 

and parameterization the Kawska-Zahn-Method of simulating 

nucleation is used to speed up the process, enabling more detailed 

studies of the nucleation. 

Thus far an inherent stability in octahedral clusters of the type 

(Bi (NO ) (OH) O ) (DMSO) has been revealed, necessitating 

6 3 6 4 4 x y 

modification of the anion cage in which the bismuth ions are 

- embedded. Associated NO -ions show some degree of a tendency 

3 

to migrate inside the solution and between bismuth octahedra, 

giving the octahedra a net charge, while OH- and O2--ions are 

stably bound. 

This research is part of the DFG SPP 1415 grant programme, 

“Crystalline Non-equilibrium phases – Preparation, 

characterization and in-situ examination of formation 

mechanisms” 

Keywords: Bismuth; Molecular Dynamics; Phase transitions; 

Cluster compounds; 



s882 

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P - 0 0 4 6 

fLuoroPhorS for inveStiGAtinG orGAniC 

reACtionS on the SinGLe MoLeCuLe LeveL 

M. wirtz 1 , A. ryBinA 2 , d. P. herten 2 , G. JunG 1 

1 Saarland University, Biophysical Chemistry, Saarbrücken, 

Germany 

2 University of Heidelberg, Bioquant, Heidelberg, Germany 

The knowledge of organic reaction mechanisms is of utmost 

relevance in synthetic chemistry. Optimization requires a deep 

insight into the mechanisms. A convenient way to determine the 

individual steps of the transformation can be accomplished by 

single molecule experiments. We designed two systems, one for 

studying the epoxidation and the other for studying the metathesis 

reaction by means of fluorescence spectroscopy. The class of 

Borondipyrromethene (Bodipy) dyes is used as fluorophor 

scaffold because of their adequate qualities for single molecule 

experiments, i.e. a high fluorescence quantum yield and a high 

photostability [1] . Furthermore, the Bodipy dyes exhibit a neutral, 

apolar chromophore which is easily accessible and modifiable [2,3] . 

Prolongation of the chromophoric unit by a chemical reaction 

leads to an orange fluorescent dye [4] . 

As a first example, we visualize the epoxidation of a double 

bond via m-Chloroperoxybenzoic acid (MCPBA). The Bodipy is 

immobilized on a surface and the reaction is detected via 

TIRF-microscopy by a blueshift of the emission-wavelength [5] . 

Currently we investigate the metathesis reaction. We 

synthesized an immobilized metathesis catalyst which reacts with 

a vinyl-Bodipy dye. Here, the transformation of the vinyl- to a 

styryl-compound is seen in the bathochrome shift of the 

fluorescence wavelength. Recent results are discussed at our 

presentation. 

With the current approach, our long-term goal of mapping 

complex potential energy surfaces comes into reach [6] . 

references: 

1. B. Hinkeldey, A. Schmitt, G. Jung, ChemPhysChem., 

2008, 9, 2019–2027. 

2. A. Loudet, K. Burgess, Chem. Rev., 2007, 107, 

4891–4932. 

3. G. Ulrich, R. Ziessel, A. Harriman, Angew. Chem. Int. 

Ed., 2008, 47, 1184–1201. 

4. A. Schmitt, B. Hinkeldey, B. Hötzer, G. Jung, J. Phys. 

Org. Chem., 2009, 22, 1233–1238. 

5. unpublished results 

6. G. Jung, A. Schmitt, K. Jacob, B. Hinkeldey, Ann. N. Y. 

Acad. Sci., 2008, 1130, 131–137. 

Keywords: single-molecule studies; Metathesis; Fluorescent 

probes; Reaction mechanisms; Ruthenium; 


P - 0 0 4 7 

GLASS-forMinG tendenCy of the BinAry 

SySteM wAter + oxyethyLAted GLyCeroL 

(n = 25) 

e. zhivotovA 1 , A. zinChenKo 2 , L. KuLeShovA 3 , 

e. duKhoPeLniKov 4 , v. CheKAnovA 5 

1 National University of Pharmacy, Department of physics, 

Kharkov, Ukraine 

2 Institute for Problems of Cryobiology and Cryomedicine of 

National Academy of Sciences of Ukraine, Department of 

cryobiophysics, Kharkov, Ukraine 


National Academy of Sciences of Ukraine, Department of Low 

Temperature Preservation, Kharkov, Ukraine 

4 Usikov Institute of Radiophysics and Electronics of National 

Academy of Sciences of Ukraine, Department of Biological 

Physics, Kharkov, Ukraine 


National Academy of Sciences of Ukraine, Department of 

Cryoprotectants, Kharkov, Ukraine 

In this study relation between low temperature phase 

behavior and intermolecular interactions in a system 

low-molecular polymer+water is discussed. At the present time 

aqueous solutions of oxyethylated glycerol of different 

polymerization degree are suggested to be used as components of 

cryoprotective media for low temperature preservation of 

biological objects. One of criteria of efficiency of a cryoprotectant 

is its ability to prevent formation of ice causing damage and death 

of biological cells. Therefore study of phase behaviour and 

glass-forming tendency of cryoprotectant-containing aqueous 

solutions is of immediate practical importance. It is known that 

compounds forming intermolecular hydrogen bonds have a strong 

glass-forming tendency. In the present work, physical states of the 

binary system water+oxyethylated glycerol of polymerization 

degree n=25 (OEGn=25) were studied below 273 K over all the 

concentration range by DSC and optical cryomicroscopy. The 

hydration number characterizing intermolecular interactions was 

determined on the basis of DSC and IR-spectroscopy data. The 

phase diagram of the water–OEGn=25 system was plotted. It has 

been found from the diagram and the optical cryomicroscopy 

results that ice crystallization occurs and concentrated unfrozen 

residues remain during cooling at low OEGn=25 concentrations. 

The system hardens in the amorphous state during cooling and ice 

crystallization occurs during heating at medium concentrations. 

Crystallization is observed neither during cooling nor the 

subsequent heating at moderately high concentrations. OEGn=25 

crystallization occurs at high concentrations. According to the 

phase diagram analysis, each OEGn=25 molecule can bind about 

72 water molecules and about 36 of them are strongly bound. The 

hydration number of OEGn = 25 is found to be about 75 by 

IR-spectroscopy. Thus the binary system water+OEGn = 25 has 

sufficiently high glass-forming tendency due to containing a large 

number of polar groups able to form numerous hydrogen bonds 

with water. 

Keywords: Hydrogen bonds; Polymers; Glasses; Phase 

transitions; Phase diagrams; 



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P - 1 0 1 6 

APPArent or reAL wAter exChAnGe 

reACtionS on [zn(h o) (L)] 2 4 2 + 2h o 2 

B. ALzouBi 1 , M. wALther 1 , r. PuChtA 1 , 

r. vAn eLdiK 1 

1 Friedrich-Alexander-University Erlangen-Nuremberg, chemie 

and pharmacy, Erlangen, Germany 

The exchange of a second coordination sphere water 

molecule in [Zn(H O) (L)] 2 4 2 +·2H O (L = N-donor Ligand) 2 [1-3] 

against a coordinated water molecule in the first coordination 

sphere was studied by quantum chemical calculations 

(RB3LYP/6-311+G**). The complete reaction consists of an 

associative binding of one H O from the second coordination 

2 

sphere leading to a six-coordinate intermediate, followed by the 

dissociation of a water molecule to reach the product state 

[Zn(H O) (L)] 2 4 2 +·2H O. For a real water exchange reaction to 

2 

occur two different transition states have to be included, otherwise 

only an apparent water exchange reaction takes place. For the 

water exchange reaction in [Zn(H O) (L)] 2 4 2 +·2H O nearly 

2 

iso-energetic cis- and trans-orientated transition states are crossed. 

The basicity (described as the gas-phase proton affinity) of L 

shows instructive correlations with structural parameters and 

energy gaps for the investigated reactions. 

references: 

1. B. M. Alzoubi, R. Puchta, R. van Eldik, Aust. J. Chem. 

2010, 63, 236. 

2. B. M. Alzoubi, R. Puchta, R. van Eldik, Eur. J. Chem. 

2010, 16, 7300. 

3. B. M. Alzoubi, M. Walther, R. Puchta, R. van Eldik, 

Dalton Trans. 2012, 41, 6932. 

Keywords: Calculated water exchange reactions; 


P - 0 0 4 8 

CytotoxiCity of new 

thiAdiAzoLo[2,3-A]Pyridine BenzAMide 

derivAtiveS on five CAnCer CeLL LineS 

f. AdhAMi 1 

1 Islamic Azad University Shahr-Ray Branch, Chemistry, 

Tehran, Iran 

Cancer is a serious clinical problem which can develop in 

almost any organ or tissue, but they are classified by the type of 

cell that is initially affected such as the skin, bone, lung, colon, 

breast and nerve cancer. 

There are some therapy options like surgery, chemotherapy, 

endocrine and radiation therapy in the treatment of cancer. 

Chemotherapy is an important treatment for cancers. However, 

toxicity and poor tolerance to current chemotherapeutic agents are 

dose-limiting factors. Therefore, discovery and development of 

apoptosis inducers as new chemotherapeutic agents is a promising 

approach. [1] 

In this study, three derivatives of Thiadiazolo[2,3-a]Pyridine 

Benzamide were synthesized in two steps. First step, 

reaction between three derivatives of 2-aminopyridine and 

benzoylisothiocyanate formed three thiourea derivatives; 

a) N-Benzoyl-N-(2-Pyridyl)Thiourea (PyTuBenzo), b) N-Benzoyl- 

-N-(4-Methyl-2-Pridyl)Thiourea (4PicTuBenzo) and c) N-Benzoyl- 

-N-(6-Methyl-2-Pyridyl)Thiourea (6PicTuBenzo). Second step, 

three thiourea derivatives were oxidized by Cu2+ . The oxidized 

products were Thiadiazolo[2,3-a]Pyridine Benzamide derivatives 

as a second group; a`) N`-(2H-[1,2,4]-Thiadiazolo[2,3-a]Pyridine- 

-2-Ylidne)Benzamide (2HThPyBenza), b`) N`-(7-Methyl- 

-2H-[1,2,4]Thiadiazolo[2,3-a]Pyridine-2-Ylidne)Benzamide 

(7MeThPyBenza) and 3`)N`-(5-Methyl-2H-[1,2,4]Thiadiazolo[2,3- 

-a]Pyridine-2-Ylidne)Benzamide (5MeThPyBenza). The products 

in two steps were characterized by FTIR, 1HNMR and 13CNMR spectroscopies and their crystal structures were determined. 

In vitro cytotoxic activity of the six products were studied 

by five human cell lines include Breast cancer cell line 

MDA-MB-231, Prostate adenocarcinoma cell line LNCap, 

Neuroblastoma cell line SK-N-MC, Nasopharyngeal epidermoid 

carcinoma cell line KB and Liver cancer cell line HEPG-2. 

The results were compared with Doxorubicin using MTT-dye 

reduction assay. 

In vitro results suggested that the second group inhibited the 

growth of cancer cell lines. Among these Benzamide derivatives 

in this group, 7MeThPyBenza showed the best results for four 

human cell lines than the other derivatives. 

references: 

1. N.I. Wenzel, et al., J. Med. Chem. 53 (2010) 3214. 

Keywords: Thiadiazolo Benzamide; Cytotoxicity; Cancer cell 

line; [2,3-a]Pyridine Benzamide; 



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chem. Listy 106, s587–s1425 (2012) 

Poster session 1 - life sciences 

P - 0 0 4 9 

tAriquidAr-reLAted ModuLAtorS of ABC 

trAnSPorterS PreferrinG the BreASt 

CAnCer reSiStAnCe Protein (ABCG2) 

M. BAuSe 1 , C. oChoA-PuenteS 1 , S. BAuer 2 , 

G. BernhArdt 2 , A. BuSChAuer 2 , B. KoeniG 1 

1 Institute of Organic Chemistry, Department of Chemistry and 

Pharmacy, Regensburg, Germany 

2 Institute of Pharmacy, Department of Chemistry and 


ABC inhibitors have been developed to overcome multidrug 

resistance and to reach tissues that express ABC efflux 

transporters. 

Aiming at structural optimization of potent and selective 

ABCG2 inhibitors, such as UR-ME22-1, from our laboratory, an 

efficient solid phase synthesis was developed to get convenient 

access to this class of compounds. 

The inhibition of ABCB1 and ABCG2 was determined in 

the calcein-AM and the Hoechst 33342 microplate assay, 

respectively. Compounds bearing triethylene-glycol ether groups 

at the tetrahydroisoquinoline moiety were more efficient in the 

testing, due to increased solubility in water. 

The stability of the ABCG2 inhibitors in serum, which is 

crucial for cell culture testing and even more for in vivo 

experiments, was determined by incubation with serum and HPLC 

measurements. Unfortunately, the amide bond of the potent 

ABCG2 inhibitor UR-ME22-1 was rapidly cleaved. Therefore, 

new generations of inhibitors with higher stability against 

enzymatic cleavage are under development. Early results are 

promising for a new series of compounds. 

Keywords: solid phase; abcg2; breast cancer resistance 

protein; stability; 


P - 0 0 5 0 

ASCorBAte PeroxidASe ACtivity with 

CytoChroMe C 

C. BiSChin 1 , f. deAC 1 , r. SiLAGhi-duMitreSCu 1 , 

J. worrALL 2 , B. rAJACoPAL 2 , G. dAMiAn 3 , 

C. CooPer 2 

1 Babes-Bolyai University, Faculty of Chem. and Chem. Eng., 

Cluj-Napoca, Romania 

2 University of Essex, Biological Sciences, Colchester, United 

Kingdom 

3 Babes-Bolyai University, Faculty of Physics, Cluj-Napoca, 

Romania 

Cytochrome c, a metalloprotein of the electron transport 

chain, is also known to be involved in apoptosis, most probably 

due to its free radical reactivity, and in particular interaction with 

peroxide. Under conditions where the sixth coordination position 

at the cytochrome c heme iron become more accessible for 

exogenous ligands (including changes in pH or temperature), this 

peroxidase activity is enhanced. Here, it is shown that treatments 

favoring liberation of the sixth coordination position at the 

cytochrome c heme iron and therefore increased accessibility for 

peroxide (by partial denaturation with guanidinium 

hydrochloride) lead to a drastic increase in the reactivity of 

cytochrome c towards hydrogen peroxide, to the point where the 

ascorbate peroxidase activity demonstrated here for native 

cytochrome c is drastically improved (both in terms of Km and 

Vmax). Moreover, a reaction intermediate is detected by 

stopped-flow UV-vis spectroscopy upon treatment of 

guanidine-treated cytochrome c with peroxide, which resembles 

the spectrum of globin Compound II and is thus proposed to be a 

high-valent ferryl species – the first of its kind to be directly 

detected in a cytochrome c at room temperature. The ability of 

physiological levels of ascorbate (10-60 μM) to interact with this 

species may have implications for mechanism of cell signaling or 

damage that are based on cytochrome c/peroxide interactions. 

Electron paramagnetic resonance (EPR) data support these 

findings. 

Keywords: cytochrome c; peroxide; ascorbate; 



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P - 0 0 5 1 

CoMPLeMent Protein C-reACtive Protein 

BindinG to Curved SuPPorted LiPid BiLAyerS 

J. C. BLACK 1 , t. CAMPBeLL 1 , M. KnowLeS 1 

1 University of Denver, Chemistry and Biochemistry, Denver, USA 

This project is advancing research into cardiovascular 

disease by investigating C-reactive protein’s (CRP) interaction 

with curved membrane surfaces, a condition present in apoptotic 

cells found in inflamed tissue of atherosclerotic plaque. By using 

nanoparticles of varying diameters, we have induced curvature in 

a phospholipid bilayer independent of other factors typically 

present in a biological system (such as oxidized lipid). 

Nanoparticles were deposited onto a glass substrate prior to 

creation of a supported lipid bilayer (SLB), which induces 

curvature in the bilayer as it forms. Liposomes are suspended in 

solution via sonication, settle onto glass, and form bilayer sheets. 

Using confocal microscopy, SLB fluidity has been observed and 

diffusion rates characterized for bilayers formed over differently 

sized nanoparticles. We have used two different diameter 

nanoparticles: 40 nm and 100 nm. No significant differences were 

seen for flat bilayers compared to patterned bilayers. Curvature 

specific binding has also been observed for native and modified 

forms of CRP to these patterned SLBs. After modification, 

localization of CRP to curvature increased significantly. Higher 

extents of curvature (lower radius particles) showed a greater 

change in binding to higher colocalization percentages than those 

of lower extents of curvature. 

Keywords: Membranes; Biophysics; Nanostructures; Proteins; 


P - 0 0 5 2 

SCLerotiniA SCLerotioruM LACCASe 

ProduCtion. inSiGhtS into the 

PhySioLoGiCAL roLe 

C. CoMAn 1 , A. C. Mot 1 , M. PArvu 2 , 




2 Babes-Bolyai University, Faculty of Biology and Geology, 


Laccases are multicopper oxidases that catalyze the 

one-electron oxidation of phenolics, aromatic amines, and other 

electron-rich substrates with the concomitant reduction of O to 2 

H O. We have recently characterized an unusual laccase from 

2 

Sclerotinia sclerotiorum. Here, we report on the expression of this 

laccase as a response of environmental stress. Various carbon 

sources as well as nitrogen sources for Sclerotinia sclerotiorum 

were tested, by monitoring the laccase activity, mycelium weight 

and morphology. 

The pH of the medium appeared to be very important both 

for growth and for laccase production; importantly, the pH of the 

culture medium prior to sterilization had a notable effect, even 

if at inoculation the pH was adjusted back to other values 

– suggesting that the composition of the medium is affected by 

sterilization in a manner that generates stressors or inducers for 

the culture. Sclerotinia sclerotiorum tolerates well alkaline pH up 

to pH 9, by a mechanism where it decreases it to a final value of 

almost 3.5 (physiological pH), with different kinetics depending 

on the initial pH value; the fungus does not develop at all bellow 

pH 3. Laccase production is maximum between pH 5-7. 

Extracts of Chelidonium majus as well as of yeast were 

found to be laccase inducers in Sclerotinia sclerotiorum through 

stress pathways as proved by mycelium morphology and protein 

profile. Fractionation experiments suggest that the nature of the 

inducer from yeast is an organic molecule, while in the 

Chelidonium majus extract it is probably a mixture of alkaloids 

or polyphenols as suggested by other authors which describe its 

antifungal properties. Overall, the extracellular laccase produced 

by this organism appears to be regulated by several variables such 

as nutrients, pH and other inducers. 

Acknowledgement: Financial support from 

POSDRU/88/1.5/S/60185 – “Innovative doctoral studies in a 

knowledge based society” is gratefully acknowledged by ACM. 

Keywords: Sclerotinia sclerotiorum; laccase induction; protein 

regulation; Chelidonium majus; yeast extract; 



s886 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 5 3 

PAnurGineS, noveL AntiMiCroBiAL PePtideS 

froM the venoM of wiLd Bee PAnurGuS 

CALCArAtuS And their interACtionS with 

PhoSPhoLiPidS veSiCLeS 

S. CuJovA 1 , L. MoninCovA 1 , J. SLAninovA 2 , 

L. BednArovA 2 , v. CerovSKy 2 

1 Faculty of Science Charles University in Prague, 

Biochemistry, Prague 2, Czech Republic 


Chemistry of natural products, Prague 6, Czech Republic 

Three novel antimicrobial peptides, named panurgines (PNG), 

were isolated from the venom of wild bee Panurgus calcaratus. 

One of them is dodecapeptide LNWGAILKHIIK-NH2 (PNG-1). The next two are almost identical peptides containing 

25 amino acid residues and two intramolecular disulfide bridges 

LDVKKIICVACKIxPNPACKKICPK-OH (X =K, R PNG-K or 

PNG-R). All peptides exhibited antimicrobial activity against 

Gram-positive and Gram-negative bacteria, antifungal activity and 

low haemolytic activity. We prepared 11 analogues of PNG-1 with 

the aim to improve its biological properties and a linear analogue 

of PNG-R to elucidate importance of disulfide bridges for its 

activity. 

In the second part of the study, we followed the effect of 

panurgines on the degree of membrane disruption by observing 

the leakage of fluorescence dye (calcein) entrapped in artificial 

phospholipids vesicles. Specifically, we investigated membrane 

interactions of PNGs with negatively charged vesicles 1:2 

DOPC/DPPG and 1:2 DOPC/DOPG as a general model of 

bacteria membrane and 15:80:5 DOPC/DOPG/CL as a possible 

model for a membrane of Bacillus subtilis. The membrane 

interaction of PNGs was also investigated on uncharged DOPC 

vesicles as potential model membrane for erythrocytes. PNGs 

exhibited weak dye-leakage activity for neutral vesicles, while 

they effectively induced dye leakage in the presence of negatively 

charged vesicles. These results indicate that PNGs have stronger 

potency to disrupt bacteria-mimicking anionic membranes than 

those which mimic eukaryotic cell membrane. 

Keywords: antimicrobial peptides; phospholipids vesicles; 


P - 0 0 5 4 

BioinduCed inveStiGAtion on MetAL ion – 

hydroxAMAte SySteMS 

e. fArKAS 1 , o. SzABo 1 

1 University of Debrecen, Inorganic and Analytical Chemistry, 

Debrecen, Hungary 

Hydroxamic acids are among the most well studied 

compounds due to their significance in so many fields. For 

example, due to their good metal binding capability, they are 

effective inhibitors of many metalloenzymes, including MMP-s 

or ureases. The inhibitory effect is in direct correlation with the 

coordination of the hydroxamate function to the metal ion 

situating in the active centre of the metalloenzyme. This is one 

reason, why transition metal ion-hydroxamate complexes have 

been in the focus of interest and interaction of metal ions with 

various hydroxamic acids and also the factors determining the 

interaction have been investigated in Debrecen for many years. 

Because there have been only a few data on Mn(II)- and 

Co(II)-hydroxamate complexes in the literature, our recent work 

has focused on such types of systems. Numerous mono-, di- and 

two trihydroxamate based natural siderophores. desferrioaxamine 

B (DFB), and desferricoprogen (DFC), have been involved into 

the study, in which the stoichiometry, the thermodynamic and 

redox stabilities of the complexes have been determined. 

Relaxometric measurements on the Mn(II)-systems provided also 

interesting information about the intramolecular motions in the 

Mn(II)-siderophore complexes. 

Surprisingly, oxidation of Mn(II)- and Co(II)-siderophore 

complexes at high pH resulted the formation of extremely high 

stability complexes. The stability of the Mn(III) complexes are 

close, while that of the Co(III) complexes is higher than the 

stability of the corresponding Fe(III) species. Whether does it 

mean the possibility of disruption of the microbial iron-uptake in 

the presence of these metal ions? This question and all the results 

obtained for the Mn(II) and Co(II) complexes are planed to 

discuss in a presentation. 

Acknowledgments: The work was supported by OTKA-NKTH 

CK77586 and TAMOP 4.2.1/B-09/1/KONV-2010-0007 National 

Hungarian Fund 

Keywords: hydroxamate complexes; equilibrium study; 

hydroxamate based siderophores; manganese and cobalt ions; 

thermodynamic and redox stability; 



s887 

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P - 0 0 5 5 

dnA dAMAGe reCoGnition By xPA/rAd14 in 

nuCLeotide exCiSion rePAir 

K. GASteiGer 1 , S. KoCh 1 , u. LiSChKe 1 , 

S. SChneider 2 , t. CAreLL 1 

1 Ludwig-Maximilians-Universität, Chemistry, München, 

Germany 

2 Technische Universität München, Biochemistry, München, 

Germany 

DNA is constantly subjected to damaging agents such as 

UV- or γ-irradiation, as well as oxidation and hydrolysis or 

chemical carcinogenes. To avoid degeneration of the genetic 

information, nature developed a variety of DNA repair pathways 

to repair the resulting lesions. One of the main genome 

maintenance systems in eukaryotes is the Nucleotide Excision 

Repair (NER). NER is a multistep process that includes damage 

recognition, assembly of repair factors at the damaged site, dual 

incision on either side of the lesion containing oligonucleotide, 

which results in an excision of the lesion, followed by DNA 

synthesis to fill the gap. A defective NER response in humans 

leads to a high predisposition to skin cancer (Xermoderma 

Pigmentosum). [1] XPC/Rad 4 is known to detect disrupted duplex 

structures [2] , whereas XPA/Rad14 is thought to be required for the 

binding of bulky DNA adducts generated by chemical 

carcinogens, like aromatic amines. We want to elucidate the exact 

mechanism of the recognition of bulky adducts by NER 

recognition factors. Therefore we investigate the binding affinity 

of the human XPA and its yeast homolog Rad14 to DNA 

containing bulky lesions by EMSA. The crystal structure of Rad14 

in complex with an acetylaminofluorene-dG containing 

oligonucleotide will give us insight into the mechanism of damage 

recognition of bulky adducts in NER. 

references: 

1. M. T. Hess, D. Gunz, H. Naegeli, Nucleic Acids Research 

1996, 24 (5), 824-828. 

2. J. H. Min, N. P. Pavletich, Nature 2007, 449, 570-575. 

Keywords: NER; XPA/Rad14; 


P - 0 0 5 6 

MonitorinG ChAnneL Protein–MediAted 

trAnSLoCAtion of ArGinine–riCh PePtideS By 

A SuPrAMoLeCuLAr SenSinG enSeMBLe 

G. GhALe 1 , h. weinGArt 1 , M. winterhALter 1 , 

w. M. nAu 1 

1 Jacobs University Bremen, School of Engineering and Science, 


The influx of xenobiotics such as antibiotics, peptides, and 

other biologically relevant molecules through channel proteins, 

or in general, through lipid bilayers, is crucial for medicinal, 

biotechnological, and analytical applications and also for 

understanding the translocation processes. [1–4] Consequently, 

assays to detect the flux of molecules through these channels with 

high sensitivity, versatility, and scalability for high-throughput 

screening is in high demand in the pharmaceutical industry, and 

biochemical research laboratories. [5–7] However, the techniques for 

accurate monitoring of this process are limited, in particular those 

allowing continuous real-time measurement of concentration 

changes. 

Drawing inspiration from supramolecular tandem assays, [8–11] 

we introduce herein a simple yet effective fluorescence based 

strategy to study the diffusion of molecules through the membrane 

or channel proteins, namely supramolecular tandem membrane 

assay. The underlying principle is to encapsulate a macrocyclic 

host and a fluorescent probe inside the liposomes. This leads to a 

compartmentalization of the sensing ensemble inside the 

proteoliposomes, such that one can follow the permeation of 

analytes in real-time via fluorescence, because the host/dye 

complex will respond only to analytes which enter into the inside 

of the vesicles, where they displace the dye from the macrocycle 

and trigger the fluorescence response. 

Owing to their impermeablity through the lipid membrane, 

a anionic macrocyclic receptor p-sulfonatocalix[4]arene (CX4) 

and a highly fluorescent dye lucigenin (LCG) were selected as a 

host/dye reporter pair to investigate the translocation of 

protamine, an arginine-rich antimicrobial peptide through a 

bacterial outer membrane channel protein F (OmpF). [10, 12, 13] The 

translocation of protamine into the liposomes was monitored as a 

time-resolved increase in fluorescence intensity due to the release 

of the dye LCG from the CX4 cavity. Furthermore, using the 

tandem membrane assay method, we were able to screen for other 

translocating analytes, the activity of mutagenized OmpF, and the 

effect of channel modulators on the translocation process. 

references: 

1. Han, J.; Nilius, B.; Earm, Y. E.; Noble, D. Progress in 

Biophysics & Molecular Biology 2010, 103, 1. 

2. Housden, N. G.; Wojdyla, J. A.; Korczynska, J.; 

Grishkovskaya, I.; Kirkpatrick, N.; Brzozowski, A. M.; 

Kleanthous, C. Proc. Natl. Acad. Sci. U. S. A. 2010, 107, 

21412. 

3. Imming, P.; Sinning, C.; Meyer, A. Nat. Rev. Drug 

Discovery 2006, 5, 821. 

4. Nestorovich, E. M.; Danelon, C.; Winterhalter, M.; 

Bezrukov, S. M. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 

9789. 

5. Dunlop, J.; Bowlby, M.; Peri, R.; Vasilyev, D.; Arias, R. 

Nat. Rev. Drug Discovery 2008, 7, 358. 

6. Mahendran, K. R.; Hajjar, E.; Mach, T.; Lovelle, M.; 

Kumar, A.; Sousa, I.; Spiga, E.; Weingart, H.; Gameiro, P.; 

Winterhalter, M.; Ceccarelli, M. J. Phys. Chem. B 2010, 

114, 5170. 



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chem. Listy 106, s587–s1425 (2012) 


7. Matile, S.; Sakai, N. In Analytical Methods in 

Supramolecular Chemistry; Wiley-VCH Verlag GmbH & 

Co. KGaA: 2007, p 391. 

8. Hennig, A.; Bakirci, H.; Nau, W. M. Nat. Methods 2007, 

4, 629. 

9. Bailey, D. M.; Hennig, A.; Uzunova, V. D.; Nau, W. M. 

Chemistry-a European Journal 2008, 14, 6069. 

10. Guo, D. S.; Uzunova, V. D.; Su, X.; Liu, Y.; Nau, W. M. 

Chemical Science 2011, 2, 1722. 

11. Florea, M.; Kudithipudi, S.; Rei, A.; Gonzalez-Alvarez, 

M. J.; Jeltsch, A.; Nau, W. M. Chemistry 2012, 18, 3521. 

12. Pages, J. M.; James, C. E.; Winterhalter, M. Nat. Rev. 

Microbiol. 2008, 6, 893. 

13. Uyttendaele, M.; Debevere, J. Food Microbiol. 1994, 11, 

417. 

Keywords: peptides; liposomes; membrane proteins; 

fluorescence; fluorescent dyes; supramolecular chemistry; 

macrocycles; lipids; 


P - 0 0 5 7 

uSe of A non-heMe iron PeroxidASe in 

heMoGLoBin And heMerythrin-BASed BLood 

SuBStituteS 

G. d. hAthAzi 1 , A. C. Mot 1 , f. deAC 1 , i. LuPAn 2 , 

e. fiSher-fodor 3 , G. dAMiAn 4 , d. M. Kurtz Jr 5 , 




2 Babes-Bolyai University, Faculty of Biology and Geology, 


3 Ion Chiricuta Cancer Institute, Comprehensive Cancer Center, 


4 Babes-Bolyai University, Department of Physics, Cluj-Napoca, 

Romania 

5 University of Texas at San Antonio, One UTSA Circle, San 

Antonio, USA 

Hemoglobin-based potential artificial oxygen carriers have 

been described and examined extensively.However, their 

applicability so far has been limited due to known in vivo toxicity 

issues. As many of these issues can be linked to oxidative stress, 

strategies were proposed for limiting this toxicity by adding 

antioxidant small molecules or enzymes to chemically-derivatized 

or encapsulated hemoglobin. Hemerythrin has distinctly smaller 

reactivity than hemoglobin towards oxidative and nitrosative 

stress agents, and also shows a remarkably smaller tendency to 

generate toxic free radicals in such reactions. 

The non-heme iron peroxidase, rubrerythrin (Rbr), shows as 

an interesting feature the ability to reduce hydrogen peroxide 

without involving strongly-oxidizing and free-radical-creating 

powerful oxidants such as Compounds I and II (formally Fe(IV) 

in contrast with heme-containing peroxidases and catalases. 

Morevoer, the K for hydrogen peroxide is two orders of 

m 

magnitude lower in Rbr compared to peroxidases and catalases. 

Therefore, it may be used as a useful ingredient in protein-based 

artificial oxygen carriers. Hemoglobin (Hb) and hemerythrin (Hr), 

can each be co-polymerized with rubrerythrin using 

gluteraldehyde as cross-linking agent. These co-polymers show 

additional peroxidase activity compared to Hb-only and Hr-only 

polymers, respectively. Reported here are protocols for chemical 

crosslinking of hemerythrin and hemoglobin with small amounts 

of rubrerythrin, leading to products with increased capability for 

removing hydrogen peroxide, offering promise as less toxic 

artificial oxygen carriers/blood substitutes. 

Tests on human umbilical vein endothelial cells (HUVEC) 

reveal slightly better performance of the Rbr co-polymers 

compared to controls, as measured at 24 hours but not at later 

times. 

Acknowledgements: the work shown here has been supported 

by the Romanian Ministry for Education and Research (grant 

PCCE 140/2008) and by PhD scholarships to ACM and FD 

(Contract POSDRU/88/1.5/S/60185 – “Innovative doctoral 

studies in a knowledge based society”). 

Keywords: blood substitutes; Rubrerythrin; co-polymers; 

hemoglobin; hemerythrin; 



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P - 0 0 5 8 

ConforMAtionAL StABiLity of A noveL 

AMyLoid-BetA tetrAMer toPoLoGy 

A. h. C. horn 1 , e. SoCher 1 , h. StiCht 1 

1 Institute for Biochemistry, Medicine, Erlangen, Germany 

The amyloid-β (Aβ) peptide is a key molecule in the 

pathogenesis of Alzheimer’s disease (AD), the most common 

neurodegenerative disorder. Originally, the Aβ fibrils were 

postulated to be the neurotoxic agents for a long time, because an 

increased presence of extracellular amyloid plaques, composed 

primarily of insoluble Aβ fibrils, is found in the brain of affected 

patients. Recent studies, however, showed a higher cytotoxicity 

for small Aβ oligomers than for the Aβ fibrils so that these soluble 

Aβ oligomers are moving to the centre of interest now. 

Because of the unstable and noncrystalline nature of these 

species, obtaining structural information for small oligomers is an 

experimentally challenging task. Novel structural insight was 

obtained from a recent crystal structure of a tetramer formed by 

the amyloidogenic residues 18-41 of the Aβ peptide. To enhance 

stability, this fragment was genetically engineered into the CDR3 

loop region of a shark Ig single variable domain antibody. 

Since the respective crystal structure is stabilized by the 

antibody moiety, we investigated, whether the respective topology 

also represents a stable fold for the isolated Aβ-peptide. 

We performed molecular dynamics simulations (200ns) in 

explicit solvent for the isolated tetrameric amyloid-β fragment in 

two different lengths (17-40 or 17-42) and the derived dimer and 

monomer structures. 

In contrast to the tetramer of Aβ , we observed a stable 

17-40 

dynamical behaviour of Aβ : The extension of the antiparallel 

17-42 

β-sheet (through the residues 41 and 42) is responsible for the 

enhanced structural stability in Aβ . 17-42 

In summary, our results suggest that the novel tetrameric 

structure represents a stable oligomer conformation for the longer 

and more neurotoxic Aβ species and thus could be a new target 

42 

in rational drug design aiming at the prevention of toxic oligomer 

formation. 

Keywords: Amyloid beta-peptides; Molecular dynamics; 

Protein structures; Aggregation; Medicinal chemistry; 


P - 0 0 5 9 

the iMPACt of the BiSPidine StruCture on 

the StABiLity of their Cu(ii) CoMPLexeS 

S. hunoLdt 1 , P. CoMBA 2 , M. MorGAn 2 , 

J. SteinBACh 1 , h. StePhAn 1 

1 Helmholtz-Zentrum Dresden-Rossendorf, Institut of 

Radiopharmacy, Dresden, Germany 

2 University of Heidelberg, Institut of Inorganic Chemistry, 


Rigid bispidine (3,7-diazabicyclo[3.3.1]nonane) derivatives 

have been shown to form stable complexes, particularly with first 

row transition metal ions. [1] The variable number, type and 

position of donor groups provide a variety of tailor-made 

coordination sites for specific metal ions. Furthermore, the 

bispidine skeleton opens suitable pathways to introduce 

biomolecules, which are important in view of the pharmaceutical 

targeting of such complexes. Due to these interesting features, 

bispidines are predestined as attractive bifunctional chelating 

agents for the development of target-specific copper-based 

radiopharmaceuticals. In this perspective, a hexadentate bispidine 

ligand consisting of pyridine units in the positions C-2, C-4, N-3, 

and N-7 was conjugated to the tumour-seeking peptide bombesin. 

The 64Cu-labeled bioconjugate is accumulated in human prostate 

tumors to allow clear visualization of the tumor tissue. [2] 

In order to optimize the radiopharmaceutical behavior, 

further bispidine ligands have been developed with different 

denticity (tetra-, penta, hexadentate) with pyridine and/or 

methoxypyridine donor groups and with the possibility to 

introduce functionalities, such as targeting units and fluorescence 

labels in view of pharmaceutical targeting as well as dual labeling 

(PET and optical imaging). 

These ligands and the important properties of their CuII complexes, e. g. stabilities, exchange kinetics and partition 

coefficients ( 64Cu: octanol/water) will be reported. 

references: 

1. P. Comba, M. Kerscher, W. Schiek, Progr. Inorg. Chem. 

2008, 55, 613-704. 

2. S. Juran, M. Walther, H. Stephan, R. Bergmann, 

J. Steinbach, W. Kraus, F. Emmerling, P. Comba, 


Keywords: ligand design; imaging agents; copper; 



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P - 0 0 6 0 

eLeCtroCheMiCAL And SPeCtroSCoPiC 

StudieS of the interACtion Between the 

neuroLePtiC druG,GABAPentin, And dnA 

f. JALALi 1 , P. dorrAJi 1 

1 Razi University, Chemistry, Kermanshah, Iran 

The interaction between gabapentin (GP), a neuroleptic 

drug, and DNA was investigated. Cyclic voltammetry and 

different spectroscopic methods (UV/Vis spectrophotometry, 

spectroflourimetry and Circular dichroism) were used to study the 

process. The oxidation current of GP was considerably decreased 

in the presence of calf-thymus DNA. The negative shift of the 

peak potential in cyclic voltammetry suggested an electrostatic 

mode of binding. The binding constant (K-=-8.33 × 103 mol-1 L) 

was obtained from voltammetric data with a standard Gibbs free 

energy change, ?G°, of -21.99 kJ mol-1 at 25 °C which indicated 

the spontaneity of the binding interaction. A hyperchromic effect 

in the maximum absorption band of DNA as well as quenching 

in fluorescence experiments were observed in the presence of GP. 

The values of binding constants obtained from UV absorption, 

spectrofluorimetry and voltammetric measurements, were in close 

agreement. 

Keywords: gabapentin; DNA; Cyclic voltammetry; 

Spectroscopy; Binding constant; 


P - 0 0 6 1 

Potent BenzeneSuLfonAMideS AGAinSt the 

PredoMinAnt CoMMunity-ASSoCiAted 

MethiCiLLin-reSiStAnt StAPhyLoCoCCuS 

AureuS StrAin uSA300 

C. JiArPinitnun 1 , w. PhetSAnG 1 , 

S. ChAturonGAKuL 2 

1 Faculty of Science Mahidol University, Department of 

Chemistry and Center for Innovation in Chemistry 

(PERCH-CIC), Bangkok, Thailand 

2 Faculty of Science Mahidol University, Department of 

Microbiology, Bangkok, Thailand 

Since first isolated in 1880, a Gram positive bacteria 

Staphylococcus aureus (S. aureus) has remained the leading source 

of bacterial infections in human and in animal worldwide. The 

treatment of S. aureus infection becomes more complicated due to 

the emergence of antibiotic resistance. The community-associated 

methicillin-resistant Staphylococcus aureus (CA-MRSA), which 

acquires resistance to the commonly used beta-lactam antibiotics 

such as penicillin, poses a serious threat in terms of infection 

control. The pathogen can colonize in healthy individuals and 

easily transmit via skin-to-skin contacts. The epidemic MRSA 

PFGE strain type USA300, in particular, has become the 

predominant CA-MRSA strain causing serious skin and soft tissue 

infections as well as life-threatening diseases. The USA300 

isolates have been currently recognized and responsible for 

infections in many continents, including Europe. As several 

USA300 isolates showed reduced susceptibility to vancomycin in 

addition to occasional resistance to the combination therapy, 

trimethoprim-sulfamethoxazole. The dramatic spread of MRSA 

USA300 in addition to the emergence of the currently used 

antibiotics resistance has greatly heightened the need for 

discoveries of novel therapeutics. Here in, we investigated the 

structural features required for the growth inhibition of S. aureus 

and MRSA USA300 strain SF8300. The small focused chemical 

library was designed and synthesized in a few steps from 

commercially starting materials. The pathogen susceptibility 

results led to the discovery of the potent S. aureus and MRSA 

USA300 growth inhibition N-(3,5-bis(trifluoromethyl)phenyl)-4- 

-bromobenzene sulfonamide [MIC = 5.6 mg/L] and other effective 

sulfonamides. Structure-activity correlations revealed that the 

benzene sulfonamide bearing electron-withdrawing substituents 

were essential for inhibiting pathogen growth effectively. 

Interestingly, these potent sulfonamides were also able to 

completely inhibit growth of the sulfonamide-resistant MRSA 

strain (COL), implicating that these active sulfonamides may 

inhibit bacterial growth via alternative mechanisms differed from 

the folate pathway inhibition, known for typical sulfonamide 

antibiotics. 

Keywords: Methicillin-resistant Staphylococcus aureus 

(MRSA); USA 300 CA-MRSA; Benzenesulfonamides; 



s891 

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P - 0 0 6 2 

reGuLAtory MeChAniSM of PhoSduCin 

funCtion 

M. KACirovA 1, 3 , L. rezABKovA 1, 3 , M. StePAneK 1 , 

M. SuLC 2 , P. herMAn 4 , J. veCer 4 , v. oBSiLovA 3 , 

1, 3 

t. oBSiL 

1 Department of Physical and Macromolecular Chemistry, 

Faculty of Science, Charles University in Prague, 12843 


2 Department of Biochemistry, Faculty of Science, Charles 

University in Prague, 12843 Prague, Czech Republic 

3 Institute of Physiology, Academy of Sciences of the Czech 

Republic, 14220 Prague, Czech Republic 

4 Faculty of Mathematics and Physics, Charles University in 

Prague, 12116 Prague, Czech Republic 

Phosducin (Pdc), a regulatory and highly conserved 30 kDa 

acidic phosphoprotein, is present in a variety of cell types, with 

especially high expression in retinal photoreceptors and 

pinealocytes. Pdc regulates the G-protein signaling by competing 

with Ga for binding to Gβγ subunits. The ability of Pdc to bind to 

Gβγ depends on its phosphorylation state as only 

unphosphorylated Pdc binds Gβγ tightly. Phosphorylation of Pdc 

within the N-terminal part inhibits its binding to Gβγ through 

unclear mechanism involving the interaction between Pdc and the 

regulatory 14-3-3 protein. The 14-3-3 proteins are conserved 

regulatory proteins expressed in all eukaryotic cells from yeast to 

human. 

In this work, we studied interactions between phosphorylated 

Pdc and 14-3-3 using analytical ultracentrifugation, dynamic light 

scattering and time-resolved fluorescence spectroscopy. Our results 

show that: (i) Pdc and 14-3-3 form a stable complex with 1:2 

molar stoichiometry; (ii) the molecule of Pdc is unfolded; and (iii) 

the 14-3-3 protein binding significantly affects the structure of 

both the N- and C-terminal domains of Pdc. 

Acknowledgement: This work was funded by Grant 

P305/11/0708 of the Czech Science Foundation, 

by Research Project MSM0021620857 and by Research 

Project AV0Z50110509 of the Academy of Sciences 

of the Czech Republic. 

references: 

1. R. Gaudet, A. Bohm, P. B. Sigler, Cell 87, (1996), 

577–588. 

2. B. Y. Lee, C. D. Thulin, B. M. Willardson, J. Biol. Chem. 

279, (2004), 54008–54017. 

Keywords: Protein-protein interactions; Biophysics; 

Fluorescence spectroscopy; Protein structures; 


P - 0 0 6 3 

teMPLAte-direCted SyntheSiS in 3'- And 

5'-direCtion with reverSiBLe terMinAtion 

A. KAiSer 1 , S. SPieS 1 , t. LoMMeL 2 , C. riChert 1 

1 University of Stuttgart, Institute of Organic Chemistry, 


2 Thyssen Krupp Rasselstein AG, Product Development 

Research and Quality, Andernach, Germany 

Chemical primer extension (CPE) involves the elongation 

of a synthetic primer on a DNA or RNA template using active 

esters of nucleoside-5'-monophosphates. [1] This reaction is known 

for RNA primers, [2] DNA primers with a 3'-terminal 3'-amino- 

-2',3'-dideoxynucleoside, [3-5] and DNA primers with a 3'-terminal 

2'-amino-2',3'-dideoxynucleoside. [6] The latter version of CPE has 

been performed with fluorophore-labeled monomers, allowing for 

the optical read-out of sequences without enzymes. [7,8] Also, 

catalyzed CPE occuring within minutes or seconds have 

been reported. [9] Here we report a method that we refer as 

template-directed synthesis with reversible termination. This 

method uses azidomethyloxycarbonyl (Azoc) moieties as 

protecting group which can be removed under non-denaturing 

conditions, [10] as well as a magnetic solid support that allows for 

the noncovalent binding of the template and the primer 

oligonucleotide. Tenfold, controlled and stepwise synthesis of 

oligonucleotides in template-directed fashion is demonstrated 

both in 3'- and 5'-direction. [11] 

references: 

1. Orgel, L.E. Crit. Rev. Biochem. Mol. Biol.2004, 39, 99. 

2. Deck, C., Jauker, M., Richert, C. Nature Chem. 2011, 3, 

603. 

3. Hagenbuch, P., Richert, C. et al. Angew. Chem. Int. Ed. 

2005, 44, 6588. 

4. Kervio, E., Richert, C. et al. Proc. Natl. Acad. Sci. USA 

2010, 107, 12074. 

5. Rajamani, S., Szostak J. W. et al. J. Am. Chem. Soc. 2010, 

132, 5880. 

6. Schrum, J.P., Szostak J.W. et al. J. Am. Chem. Soc. 2009, 

131, 14560. 

7. Griesang, N., Richert, C. et al. Angew. Chem. Int. Ed. 

2006, 45, 6144. 

8. Gießler, K., Richert, C. et al. Eur. J. Org. Chem. 2010, 

3611. 

9. Röthlingshöfer, M., Richert, C. et al. Angew. Chem. Int. 

Ed. 2008, 47, 6065. 

10. Kaiser, A., Richert, C. Synlett 2010, 2267. 

11. Kaiser, A., Richert, C. et al. Angew. Chem. Int. Ed. 2012, 

published online July 9, DOI: 10.1002/anie.201203859. 

Keywords: DNA; solid-phase synthesis; protecting groups; 



s892 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 6 4 

deveLoPMent of new no-ASA-derivAtiveS for 

the treAtMent of ChroniC LyMPhoCytiC 

LeuKeMiA (CLL) 

A. BerKeSSeL 1 , M. KrüGer 1 

1 Institute of Organic Chemistry, Department of Chemistry, 

Köln, Germany 

no-ASA was originally developed by NicOx to treat human 

colon cancer. [1] It was found later that this Aspirin-derivative is 

effective for treating many other human cancers, such as prostate, 

pancreatic, lung, skin, breast, and bladder cancers, and is also 

suitable for the treatment of type-2-diabetes and the 

cardioprotection of animal hearts. [3] Kreuzer et al. reported that 

NO-ASA is also very effective against chronic lymphocytic 

leukemia (CLL). [3] According to the current mechanistic scenario 

NO-ASA is initially metabolized to different active compounds. 

The key compounds are quinone methide (QM) and nitrate anion. 

QM contributes the major part to the anticancer effect of 

NO-ASA, due to the fact that it is a very reactive Michael 

acceptor. Various studies point out that quinone methide reacts 

with many nucleophiles, alkylates the DNA and proteins (like 

glutathion). The nitrate anion effects S-nitrosylation and tyrosine 

nitration. All reactions lead to modifications in the cell-signaling 

pathways and ultimately result in the apoptosis of cells. [2,4] Based 

on the promising results achieved with NO-ASA, we decided to 

syn-the-s-ise several new NO-ASA-de-rivatives. Our efforts 

resulted in the discovery of some more potent NO-ASA-derivatives. 

Several in vitro assays and in vivo xenograft nude mice models 

showed sig-nificantly improved and sele-ctive cytotoxicity of some 

of our com-pounds in comparison to NO-ASA. For future, 

mechanistic studies, we are intending to label our compounds in 

particular with regard to bio-orthogonal reactions and mass 

spectroscopy. 

references: 

1. P. Del Soldato, WO 02/30866 A1, PCT/EP01/11664, 2002. 

2. K. Kashfi, B. Rigas, Biochem. Soc. Trans. 2005, 33, 

701–704. 

3. R. Razavi, I. Gehrke, K.-A. Kreuzer et al., Clin. Cancer 

Res. 2011, 17, 286–293. 

4. J. L. Williams, P. Jia, N. Ouyang et al., Exp. Cell Res. 

2011, 10, 1359–1367. 

Keywords: Cancer; Synthesis design; Bioorganic chemistry; 

Biotransformations; Cytotoxicity; 


P - 0 0 6 5 

StruCturAL ASSeMBLy of hexoSAMinidASe 

CoMPLex 

z. KuKACKA 1 , P. PoMPACh 2 , P. MAn 2 , P. novAK 2 

1 Faculty of Science, Department of Biochemistry, Prague, 


2 Institute of Microbiology, Laboratory of Molecular Structure 

Characterization, Prague, Czech Republic 

Background: Fungal β-N-acetylhexosaminidases 

EC 3.2.1.52) are inducible extracellular glycosidases involved in 

many biological processes. The native enzyme from Aspergillus 

oryzae CCF 1066 is composed of two propeptides (each 10 kDa) 

and two catalytic units (each 65 kDa). The propeptides are 

noncovalently associated with the catalytic units and are essential 

for the enzyme activity. 

objectives: In this study we would like to uncover the 

position where the propeptide is associated with the catalytic unit. 

Methods: β-N-acetylhexosaminidase was purified from the 

medium of the producing organism. For EDC (1-Ethyl-3-(3- 

-dimethylaminopropyl) carbodiimide) experiment the enzyme 

was transferred by gel filtration to 50mM Pyridine pH 5.5, 

150mM NaCl and for DSG (disuccinimidyl glutarate) experiment 

to 50mM Triethylamine carbonate pH 7.5. After the cross-linking 

reaction was over, the products of enzyme were separated by SDS 

electrophoresis. In gel digestion was performed and the resulting 

peptides were analyzed by LC-ESI FT MS (Agilent 1200, 

APEX-Ultra) 

results: To obtain good reproducibility and high yields of 

cross-linking reactions, different types and concentrations of 

cross-linking reagents together with optimization of enzyme 

concentrations in the reaction was performed. The best results 

were achieved by using DSG and EDC reagents. Enzyme 

concentration was set to 0.5 mg/ml. The ratio of cross-linking 

agents over the enzyme was 100 fold access of EDC and 50 fold 

access of DSG. By LC-ESI FT MS analysis were found several 

intermolecular (A80-S96 with I347-E365) and few intramolecular 

cross-links (A102-K114 with D409-Y434). Obtained results are 

in a good agreement with X-ray diffraction data. 

Conclusions: Combinating chemical cross-linking and high 

resolution mass spectrometry we uncover the region of 

propeptide-catalytic unit ineraction. Moreover we revealed that 

the structural changes of the catalytic unit depend on the 

presence/absence of the propeptide molecule. 

Acknowledgement: This work was supported by grants 

P207/10/1040 and P207/10/1934 of the Czech Science 

Foundation. 

Keywords: Glycoproteins; Enzyme models; Mass spectrometry; 

X-Ray diffraction; 



s893 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 6 6 

SPeCtrAL AnALySiS of SeCondAry 

MetABoLiteS ProduCed in funGAL 

interACtionS 

r. C. MenezeS 1 , C. MAtthäuS 2 , e. M. JunG 3 , 

K. KrAuSe 3 , B. dietzeK 2 , e. Kothe 3 , J. PoPP 2 

1 Friedrich Schiller University, Institute of 

Microbiology/Institute of Photonic Technology, Jena, Germany 

2 Friedrich Schiller University, Institute of Physical 

Chemistry/Institute of Photonic Technology, Jena, Germany 

3 Friedrich Schiller University, Institute of Microbiology, Jena, 

Germany 

Fungal competition for territory and resources is inevitable 

in habitats with overlap between the niches of different species or 

strains. Interactions between wood-decaying basidiomycetes are 

excellent examples of such competition and the outcome 

determines the size of territory held by one mycelium, and hence 

access to nutrients. It is a major impetus of community change, 

and affects decay rates in woodland ecosystems. Competition is 

brought about by antagonistic mycelial interactions which elicit 

mycelial morphology, metabolic, secondary metabolite release 

and extracellular enzyme pattern changes. 

The basidiomycete studied, Schizophyllum commune, is a 

white-rot fungus which is most widely distributed world-wide. 

The abundance of S. commune can not only be attributed to its 

incredible mating ability (more than 23,000 different sexes), but 

also to its superior competition ability. It has been noted that 

S. commune produces secondary metabolites, especially in the 

interaction zone or zone of contact with competitor species. The 

nature of these compounds is unknown and may be the result of 

the action of the fungal oxidative enzymes in response to stress 

caused in the face of a stimulans excreted from the competitor. 

We attempted to elucidate the composition of the 

compounds produced during these interactions using Raman 

micro-spectroscopy. The principle is that Raman spectra contain 

information on molecular vibrations providing a highly specific 

fingerprint of the molecular structure and biochemical 

composition of cells and tissues. Spectra are obtained 

non-invasively without interference from water. The employment 

of external labels is not necessary and the sample requires little 

or no preparation. Moreover, the coupling of Raman spectroscopy 

with microscopy (Raman Micro-spectroscopy) enables high 

spatial resolution (below ~ 1 µm) and sensitivity. Using 

particularly resonance Raman spectroscopy, we show the presence 

of Indigo in the zones of interaction of the fungi. 

Keywords: Raman spectroscopy; Structure elucidation; 

Dyes/Pigments; 


P - 0 0 6 7 

StruCture ChAnGe of JuveniLe horMone 

BindinG Protein froM SiLKworM heMoLyMPh 

M. MiyAzAwA 1 , t. yAMAzAKi 2 , r. SuzuKi 2 , 

z. fuJiMoto 2 , w. tSuChiyA 2 , M. MoMMA 2 , A. tASe 2 , 

t. ShiotSuKi 3 

1 National Institute of Agrobiological Sciences, Insect Mimetics 

Research Unit, Tsukuba Ibaraki, Japan 

2 National Institute of Agrobiological Sciences, Biomolecular 

Research Unit, Tsukuba Ibaraki, Japan 

3 National Institute of Agrobiological Sciences, Insect Growth 

Regulation Research Unit, Tsukuba Ibaraki, Japan 

Juvenile hormones (JHs) are acyclic sequiterpenoids which 

contain an unsaturated methyl ester and a terpenoid backbone with 

an epoxide distal to the ester. JH regulates many processes, 

including the growth, development, metamorphosis and 

reproduction of insects. The JH actions are initiated by transport 

of JH in the hemolymph as a complex with JH-binding protein 

(JHBP) to target tissues. The concentration of JHBP in the 

hemolymph varies in relation to development but almost always 

exceeds the concentration of JH by some orders of magnitude. It 

has been estimated that more than 99% of the JH molecules in 

hemolymph are bound by JHBP. Here, we report structural 

properties of JHBP based on the solution and crystal structures of 

apo and JH-bound JHBP. CD measurements in buffer solution 

suggested that apo-JHBP exists in equilibrium of multiple 

conformations. The crystal structures of the apo and JH-bound 

JHBP have an unusual fold with hydrophobic pockets. JH-binding 

form results in the fully closed structure where the bound JH is 

completely buried inside the protein. JH-bound JHBP opens the 

gate helix to release the bound hormone likely by sensing the less 

polar environment at the membrane surface. Our results reveal the 

structural basis for JH transport by JHBP in hemolymph, the first 

essential process of the JH signal transfer mechanisms. 

Keywords: Juvenile hormone binding protein; CD 

spectroscopy; X-ray crystallography; 



s894 

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P - 0 0 6 8 

deveLoPMent of firSt inhiBitorS 

for BetAine-hoMoCySteine 

S-MethyLtrAnSferASe 2 

J. MLAdKovA 1 , v. vAneK 2 , t. eLBert 3 , 

M. BudeSinSKy 4 , J. JirACeK 2 

1 Faculty of Science of Charles University, Biochemistry, 

Prague 2, Czech Republic 


Sciences of the Czech Republic v.v.i., Biochemistry and 

Molecular Biology, Prague 6, Czech Republic 


Sciences of the Czech Republic v.v.i., Laboratory of 

Radioisotopes, Prague 6, Czech Republic 


Sciences of the Czech Republic v.v.i., NMR Spectroscopy, 


Only three human enzymes are able to methylate 

homocysteine to yield methionine: methionine synthase, 

betaine-homocysteine S-methyltransferase (BHMT) and 

betaine-homocysteine S-methyltransferase-2 (BHMT-2). 

BHMT-2 is a zinc metalloenzyme that catalyzes the transfer 

of a methyl group from S-methylmethionine (SMM) to 

l-homocysteine yielding two molecules of l-methionine. SMM is 

not synthesized in mammalian organism but is a universal 

component of their diet. The human BHMT-2 has 73% amino acid 

identity to BHMT. Similarly to BHMT, BHMT-2 is highly 

expressed in liver and kidney. BHMT-2 proved to be a very 

unstable enzyme. Physiological functions of BHMT-2 remain 

unknown also because no selective BHMT-2 inhibitor is available. 

The aim of this study was to purify and stabilize human 

recombinant BHMT-2 and to design, synthesize and discover first 

potent and selective inhibitors of the enzyme. The enzymes were 

expressed in transfected E. coli cells and purified using chitin 

affinity chromatography. The inhibitors were designed to mimic 

the hypothetical transition state of BHMT-2 substrates, SMM and 

homocysteine. All the inhibitors were prepared from l-methionine. 

In general, cleavage of the l-methionine methyl group by sodium 

in liquid ammonia generated a solution of l-homocysteine, which 

was alkylated in situ by appropriate halogenide. 

In our study, we purified human recombinant BHMT-2 

stabilized by co-purification with human recombinant BHMT. 

Then we synthesized first BHMT-2 inhibitors, which were tested 

with BHMT-2 and BHMT. Among these compounds, we 

identified a highly potent inhibitor, (2S,8RS,11S )-5-thia-2,11- 

-diamino-8-methyldodecanedioic acid, which represents the first 

selective inhibitor of BHMT-2. Moreover, this inhibitor inhibits 

app BHMT only weakly. We determined its IC and K towards 

50 i 

BHMT-2 and IC towards BHMT. 

50 

BHMT-2 was highly stabilized by co-purification with 

BHMT, which raises questions about co-oligomerization of the 

enzymes in vivo. Potent and selective BHMT-2 inhibitors will be 

useful in future in vivo studies of physiological functions of the 

enzyme in animal models. 

Keywords: enzyme catalysis; inhibitors; alkylation; 


P - 0 0 6 9 

noveL in vitro nonCeLL BASed ModeL for 

PrediCtinG PhoSPhoLiPidoSiS 

J. MuLLer 1 , G. t. BALoGh 2 

1 Budapest University of Technology and Economics, 

Department of Organic Chemistry and Technology, Budapest, 

Hungary 

2 Gedeon Richter Plc., Compound Profiling Laboratory, 


Phospholipidosis (PLD) is a lipid storage disorder 

characterized by the accumulation of phospholipids within cells 

and has been found to be induced by several drugs. Several studies 

have indicated that cationic amphiphilic drugs (CADs) are 

responsible for inducing this lipid accumulation in cells. In drug 

discovery and development, the accumulation of drugs in critical 

tissues such as brain, eye, liver, and heart are of major concerns 

and it is clearly a disadvantage when compared to a competitor 

without PLD indication. 

Several in silico [1, 2] , in vitro cell based [3] and noncell based [4, 5] 

methods to evaluate PLD-inducing potential with low and middle 

throughput have been available until recently. In the present study 

we have evaluated a well-known permeability model, a PAMPA 

(Parallel artificial membrane permeability assay) for predicting 

of PLD potency. 

Typical artifacts of in vitro models are caused by metabolism 

of investigated drugs which modifies PLD potency by at least two 

ways. In the present study we have investigated these metabolic 

effects of selected compounds and their metabolites by our new 

pH-gradient PAMPA system. 

references: 

1. Ploemen, J. H. T. M.et al. Experimental and Toxicologic 

Pathology 2004. 55, 347–355. 

2. Tomizawa, K. et al. Journal of Toxicological Sciences 

2006, 31(4), 315–324. 

3. Mesens, N. et al. Toxicology in Vitro 2010, 24, 1417–1425. 

4. Jiang, Z. et al. Journal of Pharmaceutical and 

Biomedicinal Analysis 2010, 61, 184–190. 

5. Zhou, L. et al. Analytical Chemistry 2011, 83(18), 

6980–6987. 

Keywords: drug discovery; Phospholipids; 



s895 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 7 0 

SiMuLtAneouSLy deterMinAtion of 

MeroPeneM And CLAvuLAniC ACid By uSinG 

derivAtive SPeCtroSCoPy 

M. PACzKowSKA 1 , J. CieLeCKA-PionteK 1 , 

P. zALewSKi 1 

1 Poznan University of Medical Sciences, Department of 

Pharmaceutical Chemistry, Poznan, Poland 

Meropenem as a carbapenem analog belongs to the group 

of β-lactam antibiotics, while clavulanic acid is a β-lactamses 

inhibitor, which increases the antibacterial activity of β-lactam 

antibiotics. Recent studies reported that the connection of 

meropenem and clanulanic acid showed the unique antibacterial 

activity, including effectiveness in the treatment of 

Mycobacterium tuberculosis [1] . 

The aim of the studies was to develop derivative 

spectroscopy for the simultaneously determination of meropenem 

and clavulanic acid. The application of derivative spectroscopy 

solved the problem of overlapping of absorption spectra of 

meropenem and clavulanic acid. In derivative spectroscopy, 

meropenem was determinated at λ =324 nm and clavulanic acid 

mer 

at λ =285 nm. The method was validated in terms of selectivity 

clav 

(the evaluation of changes of meropenem and clavulanic acid 

concentration for degraded samples), precision, accuracy, 

linearity. Limits of determination (LOD) and quantitation (LOQ) 

were established. 

The experimental results demonstrate that meropenem and 

clavulanic acid can be determined in their binary mixture and in 

the presence of their degradation products, by the first-derivative 

spectroscopy using the zero-crossing technique. The method 

meets all validation parameters and is in accordance with current 

trends of ‘green pharmaceutical analysis’. 

Acknowledgements: This study was supported by a grant from 

the Foundation for Polish Science (no. VENTURES/2011-8/7). 

references: 

1. Hugonnet J. et al. (2009) Meropenem-clavulanate is 

effective against extensively drug-resistant 

Mycobacterium tuberculosis, Science 27: 1215-1218 

Keywords: Antibiotics; UV/Vis spectroscopy; Green chemistry; 


P - 0 0 7 1 

effeCt of nAnoPArtiCLeS on huMAn 

ePiderMAL KerAtinoCyteS And huMAn 

derMAL fiBroBLAStS 

v. PivodovA 1 , A. GALAndAKovA 1 , J. frAnKovA 1 , 

B. zALeSAK 2 , J. uLriChovA 3 

1 Palacky University, Department of Medical chemistry and 

Biochemistry, Olomouc, Czech Republic 

2 University Hospital Olomouc, Department of Plastic and 

Aesthetic Surgery, Olomouc, Czech Republic 

3 Palacky University, Department of Medical Chemistry and 


Background: Wound healing processes create a very 

complex system of connected reactions which influence each 

other. Normal healing takes place in four basic stages: 

homeostasis, inflammation, reparation and remodelling. A lot of 

types of cells (neutrophils, monocytes, lymphocytes, fibroblasts 

and keratinocytes etc.) and mediators (cytokines and matrix 

metalloproteinases) are involved into the healing. The current 

investigations are shown that silver ions and nanoparticles have 

antibacterial and anti-inflammatory properties as well as gold 

nanoparticles. 

objectives: In this work, we have been studied the influence 

of nanoparticles (colloidal silver and gold solutions) on 

biomarkers involved in the wound healing process on human 

epidermal keratinocytes and human dermal fibroblasts. 

Methods: Both types of cells were isolated from samples of 

skin with the informed consent of the Ethical committee of the 

University Hospital in Olomouc and the patient’s consent. 

Cytotoxicity of nanoparticles (0.013–50 ppm; 24–72 h) was 

evaluated by cell viability (MTT) assay. The effect of 

nanoparticles on selected biomarkers interleukin-6, tumour 

necrosis factor alpha, cyclooxygenase-2, matrix 

metalloproteinase-1, matrix metalloproteinase-3 and matrix 

metalloproteinase-13 was determinated by ELISA techniques and 

western blot analysis. 

results and conclusion: Our results showed that the 

colloidal silver decreased cell viability in dose-dependent manner 

(1–50 ppm; 24–72 h) while colloidal gold did not show cytotoxic 

effect on both cell types. The effect of nanoparticles on selected 

inflammatory markers in human epidermal keratinocytes and 

human dermal fibroblasts will be discussed. 

Acknowledgement: Financial support of Grant GACR 

303/09/H048, FT-TI2/205 is acknowledged. 



s896 

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P - 0 0 7 2 

AntiCAnCer ACtivity of PhthALAzinyL 

hydrAzoneS 

J. rAK 1 , B. deJLová 1 , r. KAPLáneK 1 , J. KráLová 2 , 

v. KráL 1 

1 Institute of Chemical Technology in Prague, Dept. of 

Analytical Chemistry, Prague 6, Czech Republic 

2 Academy of Sciences of the Czech Republic, Institute of 

Molecular Genetics, Prague 4, Czech Republic 

Heteroaryl hydrazones are compounds with significant 

biological activity including anticancer activity. Therefore we 

designed set of phthalazinyl hydrazones for testing their activity 

against cancer cells. Anticancer activity evaluation on the human 

promyelocytic leukemia cells (HL60) and mouse mammary 

carcinoma cells (4T1) showed that some phthalazinyl hydrazones 

have significant inhibitory effect against both cancer cell lines. 

Complexation studies toward biologically important metal ions 

(Cu2+ , Co2+ , Cr3+ , Fe2+ , Fe3+ , Mn2+ , Ni2+ , Zn2+ ) at biologically 

relevant conditions show general ability to bind Cu2+ , Co2+ , Ni2+ and Fe3+ (with some exceptions) and rarely Zn2+ and Fe2+ . There 

is not any clear correlation of binding ability with anticancer 

activity; however many derivatives able to bind Zn2+ display very 

high activity (IC < 1 µM for HL60) and opposite way all 

50 

derivatives without binding ability towards Co2+ do not display 

any significant activity (IC > 10 µM for both lines). Phthalazinyl 

50 

hydrazones are known to display tautomerism; QD/MD 

calculations in aqueous media show significant preference of 

hydralazine form in contrast to preference of phthalazone form 

described in literature (obtained from in vacuo calculations). 

Calculations also show that metallo-complexes of derivatives are 

relatively planar and thus potentially allow intercalation into DNA 

in contrast to derivatives themselves. This is in good agreement 

with experimental observation that metallo-complexes of many 

derivatives display ability to interact with DNA but derivatives 

themselves do not. 

Acknowledgement: Financial support was provided from 

Specific university research (MSMT No. 21/2012, Grants 

A1_FCHI_2012_003 and A2_FCHI_2012_021 provided by IGS 

VSCHT) and the Grant Agency of the Czech Republic (Grants 

No. GA203/09/1311 and GAP303/11/1291). 

Keywords: Hydrazones; Schiff bases; Antitumor agents; 


P - 0 0 7 3 

SoLuBLe SynthetiC MiniAMyLoidS 

A. roeder 1 , y. rÖttGer 2 , L. Andrei-SeLMer 3 , 

A. StündeL 2 , M. BACher 2 , r. dodeL 2 , A. Geyer 1 

1 Philipps-University Marburg, Department of Chemistry, 


2 Philipps-University Marburg, Department of Neurology, 


3 Rheinische Friedrich-Wilhelms University Bonn, Department 

of Neuroanatomy, Bonn, Germany 

Based on the proposed contact surfaces between individual 

β-amyloid peptides (Aβ) within fibrillar aggregates [1] we 

synthesized soluble Miniamyloids as chemically consistent 

dimers, trimers and other oligomers, respectively. Selected Aβ 

fragments were linked in different relative orientations by a 

combination of protecting group strategy and click chemistry. 

Several unnatural amino acids were synthesized and incorporated 

into the Miniamyloids to assemble the antiparallel and parallel 

oligomers of the peptide strands. 

Aβ derivatives are characterized by their notoriously high 

aggregation tendency. To prevent fiber formation and to improve 

solubility, anionic and cationic amino acids were incorporated 

aside the native sequence. By varying the charge pattern and in 

combination with the different arrangements of the peptides 

strands a broad set of Miniamyloids was obtained. These peptides 

are a valuable and unique tool to understand how naturally 

occurring antibodies against Aβ (nAbs-Aβ) [2] recognize 

oligomeric Aβ and Aβ aggregation itself. [3] For instance they can 

be used for affinity chromatography experiments to specify the 

pool of polyclonal nAbs-Aβ. 

references: 

1. T. Lührs, C. Ritter, M. Adrian, D. Riek-Loher, 

B. Bohrmann, H. Dobeli, D. Schubert, R. Riek, 

Proc. Natl. Acad. Sci. USA 2005, 102, 17342-17347. 

2. R. C. Dodel, Y. Du, C. Depboylu, H. Hampel, L. Frölich, 

A. Haag, U. Hemmeter, S. Paulsen, S. J. Teipel, 

S. Brettschneider, A. Spottke, C. Nölker, H. J. Müller, 

X. Wei, M. Farlow, N. Sommer, W. H. Oertel, J. Neurol. 

Neurosurg. Psychiatry 2004,75, 1472-1474. 

3. R. Dodel, M. Bacher, K. Balakrishnan, A. Geyer, 

A. M. Roeder, Patent 2011, PCT/EP2011 071239. 

Keywords: amyloid-ß peptide; protein aggregation; 

Alzheimer’s disease; 



s897 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 7 4 

SuPrAMoLeCuLAr LiGAndS of ProteinS 

i. roterMAn-KonieCznA 1 , M. KroL 1 , 

B. PieKArSKA 2 , B. StoPA 2 , L. KonieCzny 2 , 

J. ryBArSKA 2 , A. JAGuSiAK 2 , G. zeMAneK 2 

1 Jagiellonian University - Medical College, Bioinformatics and 

Telemedicine, Kraków, Poland 

2 Jagiellonian University - Medical College, Chair of Medical 

Biochemistry, Kraków, Poland 

Proteins bind ligands commonly by docking them to sites 

evolutionary designed for binding. However some strongly 

assembled organic compounds have been recently found to form 

complexes penetrating as clusters of molecules into protein body 

outside the binding site. The large ligands which assume the shape 

of ribbon-like or rode-like supramolecular form affect 

significantly structure and function of proteins. Congo red is an 

example. The several or more assembled molecules of this dye 

adhere firmly to polypeptide backbone penetrating in between 

protein chains of β-conformation. The penetration and 

complexation is basically limited to low stability protein regions 

and is usually connected with the replacement of some 

polypeptide fragment from its native locus to make room for the 

ligand. Partly unfolded proteins are typical objects of binding 

supramolecular ligands but some native proteins of structure 

altered due to function-derived constraints may also become 

susceptible for binding. Bivalent antibodies bound to large 

antigens belong to such proteins. The constraints arise due to the 

imposed fitting of both antibody arms to randomly distributed 

antigenic determinants. V domains of antibodies are those which 

bind Congo red. The increased freedom of movements within 

domain results from replacing N-terminal polypeptide from 

β-plate by noncovalently stabilized ligand. It facilitates fitting of 

CDR loops to antigenic determinants increasing significantly the 

affinity of antibody to antigen. 

The selective binding of Congo red to immune complexes 

with the preserved micellar nature of the dye allows the carriage 

of many compounds and drugs incorporated by intercalation. It 

raised the idea of using supramolecular systems as carriers in 

immunotargeting technique. The confirmation of its applicability 

in vitro and in vivo is shown on the poster. 

Keywords: supramolecular ligand; Congo red; 

immunoglobulin; 


P - 0 0 7 5 

noveL SCreeninG ASSAy for A,B-unSAturAted 

CArBonyL CoMPoundS towArdS their heMe 

oxyGenASe-1 induCtion 

h. rueCKer 1 , S. AMSLinGer 1 

1 University of Regensburg, Institute of Organic Chemistry, 


Heme oxygenase 1 (HO-1) is a redox sensitive, inducible 

stress protein converting heme to CO, iron and biliverdin, which 

is further reduced to bilirubin by biliverdin reductase. As a 

member of the cytoprotective phase II enzymes the transcription 

of HO-1 is regulated by the Keap 1/Nrf2/ARE signaling pathway. 

α,β-Unsaturated carbonyl compounds possess Michael acceptor 

activity and can react with nucleophilic sulfhydryl groups of the 

Nrf2-complexing chaperon Keap1. Thereby the Nrf2 regulated 

antioxidant-responsive element (ARE) is activated which leads to 

a transcriptional induction of HO-1. Various natural products and 

synthetic molecules containing the α,β-unsaturated carbonyl 

moiety reveal an induction of the anti-inflammatory, antioxidant 

and cytoprotective enzyme HO-1. 

A novel HO-1 activity assay was established in order to 

discover new potent HO-1 inducing agents. The cell-based assay 

is a highly sensitive high-throughput screening method that 

determines HO-1 activity based on the quantification of bilirubin 

in whole cell lysates via ELISA. A diverse group of natural 

products was tested and could be assessed concerning its HO-1 

induction behaviour. 

Keywords: biological activity; immunoassays; high-troughput 

screening; antioxidant; inflammation; 



s898 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 7 6 

exPLoitAtion of veGfr2 tK SALt BridGe 

ContAininG PoLAr PoCKet for deveLoPMent 

of AryLAMinooxAzoLe inhiBitorS with 

iMProved ACtivitieS 

M. SALiSovA 1 , L. KovACiKovA 1 , L. LintnerovA 1 , 

A. BohAC 1 , M. reMKo 2 , G. hAnquet 3 , C. LAMBert 4 , 

r. deLCoMBeL 4 

1 Comenius University in Bratislava, Faculty of Natural 

Sciences Department of Organic Chemistry, Bratislava, 


2 Comenius University in Bratislava, Faculty of Pharmacy 

Department of Pharmaceutical Chemistry, Bratislava, 


3 Universite de Strasbourg Ecole europeenne de Chimie 

Polymeres et Materiaux, Laboratoire de stereochimie, 

Strasbourg, France 

4 University of Liege Tour de Pathologie, Laboratory of 

Connective Tissues Biology GIGA-R, Liege, Belgium 

An interaction analysis, molecular modelling and docking 

have been used to design new derivatives of VEGFR2 inhibitor 

AAz (N-[5-(ethylsulfonyl)-2-methoxyphenyl]-5-(3-pyridin-2- 

-ylphenyl)-1,3-oxazol-2-amine, PDB: 1Y6A). A small Salt Bridge 

Containing Polar Pocket (SBCPP) consisting from Lys866, 

Glu883 and Phe1045 amino acid residues was found to be situated 

over an internal aromatic ring of AAz ligand. SBCPP pocket is 

currently present in DFG-out VEGFR2 tyrosine kinase complexes 

hosting Type I ligand (PDB: 1Y6A, 1Y6B, 3C7Q). Intermolecular 

interactions between SBCPP pocket and AAz derivatives were 

considered to ensure a good VEGFR2 affinity for new 

compounds. Proposed substances BM1-BM3 were synthesised 

and their enzymatic and cellular VEGFR2 inhibition activity 

determined together with AAz, sorafenib tosylate and sunitinib 

L-malate. Calculated binding energies for AAz, BM1-BM3 and 

experimental IC values were found in a good agreement. Of the 

50 

analogues investigated, BM1 and BM2 demonstrated significant 

enzymatic nM inhibitory activity against the VEGFR2 kinase 

comparable to that of sorafenib tosylate and sunitinib L-malate, 

respectively. 

Acknowledgements: we are grateful for the gift of drug active 

compounds: sorafenib tosylate (Nexavar ® , Bayer HealthCare 

Pharmaceuticals) and sunitinib L-malate (Sutent ® , Pfizer Inc.) 

to both Bayer HealthCare and Pfizer companies, respectively. 

For molecular docking and structure predictions, we thank to 

Biomagi, Slovakia. The COST action CM0602 (AngioKem) 

and CM1106 (StemChem) for research networking is also 

acknowledged. This work was supported by VEGA grant 

2/0112/10. Dissemination of international collaboration was 

supported by Joint Interface Third-Cycle Degrees in Chemistry 

(PhDChem) 502271-LLP-1-2009-1-GR-ERASMUS-ECDSP. 

Keywords: Angiogenesis; Drug design; Salt Bridge Containing 

Polar Pocket; arylaminooxazoles; VEGFR2 tyrosine kinase; 


P - 0 0 7 7 

SeLeCtive inhiBition of JMJd2 hiStone 

deMethyLASeS By zinC-eJeCtion 

r. SeKirniK 1 , n. roSe 2 , A. thALhAMMer 1 , 

J. MeCinoviC 3 , C. SChofieLd 1 



2 University of Oxford, Department of Biochemistry, Oxford, 




The oxygenase JMJD2A, recently identified as a possible 

anti-cancer target, catalyzes the demethylation of Nε-lysyl methylation on histone tails. Most JMJD2A inhibitors developed 

to date chelate the active site Fe(II) and also compete with 

2-oxoglutarate, a common cofactor for all dioxygenases, making 

selective inhibition of JMJD2A difficult to achieve. 

Structures of JMJD2A revealed a Cys -His Zn(II) binding 

3 

site close to the Nε-methyl lysine-residue binding site, which is 

not present in other dioxygenases. We reasoned that the catalytic 

activity of the JMJD2 histone demethylases might be inhibited by 

compounds known to act as Zn(II) ejectors from proteins. 

Our objective was to demonstrate that Zn(II) ejection by 

selected sulphur and selenium-containing compounds is a viable 

approach for selective inhibition of JMJD2 histone demethylases. 

MALDI-MS based peptide turnover assays were thus employed 

for measuring a decrease of catalytic activity upon treatment with 

Zn(II) ejectors, differential scanning fluorimetry (DSF)-based 

protein stabilization assay was used to measure the extent of 

structural destabilization by Zn(II) ejectors, and Zn(II)-selective 

fluorophore FluozinTM-based Zn(II) ejection assay was used to 

demonstrate the loss of Zn(II) from the protein structure upon 

treatment with Zn(II) ejectors. 

Using this methodology, we have successfully demonstrated 

Zn(II) ejection as a novel approach to achieving selective 

inhibition of the JMJD2 histone demethylases over other 

dioxygenases. In particular, commercially available drug 

disulfiram, used in treatment of alcoholism, was found to be a 

potent inhibitor of JMJD2A acting by Zn(II) ejection mechanism. 

In conclusion, this new approach to selective oxygenase inhibition 

may prove useful in probing the complexity of epigenetic 

modifications and the regulatory enzymes that catalyze them. 

Keywords: Inhibitors; Enzyme catalysis; Structural biology; 

Drug discovery; 



s899 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 7 8 

quAntitAtive AnALySiS for the dnA StABiLity 

towArd the deveLoPMent of new 

funCtionAL MAteriALS 

n. SuGiMoto 1 , h. yAKu 2 , t. MurAShiMA 1 , 

d. MiyoShi 1 , S. nAKAno 1 , t. endoh 3 , 

h. tAteiShi-KAriMAtA 3 

1 Konan University, Frontier Institute for Biomolecular 

Engineering Research and Faculty of Frontiers of Innovative 

Research in Science and Technology, Kobe, Japan 

2 Konan University and Panasonic Corporation, Frontier 

Institute for Biomolecular Engineering Research and Faculty 

of Frontiers of Innovative Research in Science and Technology 

and 3Advanced Technology Research Laboratories, Kobe, 

Japan 

3 Konan University, Frontier Institute for Biomolecular 

Engineering Research, Kobe, Japan 

DNAs have been attracting attention as the advanced 

materials such as biosensors, biodevices, and biocircuits due to 

specific base-pairing interactions of DNAs. However, for DNA 

materials to become practically applicable, finding a medium in 

which they are stable for long time periods at room temperature 

is an important bottleneck in this field. Room-temperature ionic 

liquids (ILs) have generated tremendous interest as non-volatile 

media that provide favourable environments for a wide 

range of chemical and biochemical reactions. Choline 

dihydrogenphosphate (choline dhp) with 20% dissolved water is 

hydrated IL, which has been demonstrated to be a good solvent 

for proteins and DNAs for ensuring long-term stability. It is 

considered that the hydrared IL should be useful as a medium 

developing DNA materials because the hydrated IL can keep the 

activity of biomolecules for long time. However, its detail effect 

on the DNAs remains unclear. 

Here, we have investigated quantitatively thermodynamic 

stabilities of DNA duplexes, triplexes and G-quadruplexes by 

ultraviolet melting in the solution containing choline dhp. Choline 

dhp induced a drastic change in the DNA stabilities depending on 

their structures compared with an aqueous solution. In the 

presentation, we will discuss the stability changes of DNA 

structures from the perspective of thermodynamic parameters for 

the DNA structure formations. Moreover, we will show our recent 

works regarding quantitative analyses for the transcription, 

translation and telomerase elongation reactions toward the 

development of new functional materials. 

Keywords: DNA; Thermodynamics; Ionic liquids; 


P - 0 0 7 9 

SyntheSiS, AnALySiS And 

AntioxidAntProPertieS of SChiff BASe 

indoLe-AMino ACid derivAtiveS 

S. Suzen 1 , S. S. CihAner 1 , t. CoBAn 2 

1 Ankara University Faculty of Pharmacy, Pharmaceutical 

Chemistry, Ankara, Turkey 

2 Ankara University Faculty of Pharmacy, Pharmaceutical 

Toxicology, Ankara, Turkey 

Increased levels of reactive oxygen species attributed to 

oxidative stress have been found to be responsible for the 

development of some vital diseases such as cardiovascular, 

neurodegenerative and autoimmune diseases. Recently, it was 

observed that melatonin is a highly important antioxidant, and 

melatonin analogues are under investigation to find out improved 

antioxidant activity. In this study, 14 indole amino acid and 

N-protected amino acid derivatives were synthesized and 

elucidated spectrometrically. To investigate the antioxidant 

activity of the synthesized compounds and to compare with 

melatonin, butylhydroxytoluene and vitamin E, lipid peroxidation 

inhibition and 2,2-diphenyl-1-picrylhydrazyl radical-scavenging 

activities were tested. The results indicated that the synthesized 

new indole amino acid derivatives have similar activities to 

melatonin in 2,2-diphenyl-1-picrylhydrazyl radical-scavenging 

activity assay but more potent activities in lipid peroxidation 

inhibition assay. 

Keywords: indole; amino acid; synthesis; analysis; 

antioxidant; 



s900 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 8 0 

MAGiC AnGLe SPinninG (MAS) nMr in Life 

SCienCeS 

P. turAno 1 

1 University of Florence, Dept. of Chemistry, Firenze, Italy 

Magic angle spinning (MAS) averages out chemical shift 

anisotropy and weak dipolar couplings and allows the acquisition 

of high-resolution NMR spectra of solids. MAS solid state NMR 

(ssNMR) is nowadays widely used for the investigation of the 

structural and dynamical properties of integral membrane 

proteins, as well as a for the characterization of immobilized large 

soluble proteins, thus overcoming the size limitations imposed by 

the large line widths associated to slow molecular tumbling in 

solution. [1] Immobilization of soluble proteins is generally 

obtained via microcrystallization or PEG precipitation of the 

protein. MAS ssNMR of proteins has been essentially restricted 

to 13C-detection and, less commonly, 15N-detection experiments. 

MAS NMR can also be used to obtain solid state NMR spectra 

on sedimented samples. Relatively large proteins in solution, spun 

in NMR rotors for solid samples at typical ultracentrifugation 

speeds, sediment at the rotor wall, providing samples with limited 

reorientational capability. The resulting spectra are comparable in 

quality with those of the best microcrystalline samples. [2,3] 

Technical improvements that permit very fast MAS have 

started allowing the acquisition of 1H-detected spectra of 

microcrystalline and sedimented samples. On the other hands, 

slow MAS represents a useful approach for high-resolution 

1H NMR metabolic profiling of intact tissues. 

references: 

1. P. Turano, D. Lalli, I.C. Felli, E.C. Theil, I. Bertini 

Proc.Natl.Acad.Sci.USA (2010) 107, 545. 

2. I. Bertini, F. Engelke, C. Luchinat, G. Parigi, E. Ravera, 

C. Rosa, P. Turano Phys. Chem. Chem. Phys. (2012) 14, 439. 

3. I. Bertini, C. Luchinat, G. Parigi, E. Ravera, B. Reif, 

P. Turano Proc. Natl. Acad. Sci. U.S.A. (2011) 108, 10396. 


P - 0 0 8 1 

PhArMACoPhore ModeLinG And 3d-qSAr 

StudieS of ACridoneS AS CheMoSenSitizinG 

AGentS in CAnCer 

r. P. v v S 1 , d. r. G 1 

1 Vishnu Institute of Pharmaceutical Education and Research, 

Medcinal Chemistry Research Division, Narsapur Andhra 

Pradesh, India 

In the present study we have identified an efficient 

pharmacophore from a set of 38 acridones which reverts 

HL-60/DX cell line. Identified pharmacophoric features such as 

one hydrogen bond acceptor, one hydrophobic region, a positive 

ion group and three aromatic rings i.e, AHPRRR. Ligand based 

3D-QSAR was performed by employing partial least square 

regression analysis which gave a regression coefficient R2 of 0.98 

and Q2 of 0.86, and Pearson-R of 0.95. Another pharmacophore 

model of same compounds with same set of pharmacophoric 

features with different 3D spatial arrangement showed that 

0.95 (R2 ), 0.87 (Q2 ) and 0.94 (Pearson-R). Molecular docking 

study was performed for fluoro acridones against calmodulin 

dependent cAMP phosphodiesterase (PDE1c) in order to identify 

the possible protein ligand interactions and results thus obtained 

were compared with in-vitro data, good correlations were found 

between in-silico and in-vitro results. 

Keywords: Acridone; 3D-QSAR; Pharmacophore; Docking; 

MM/GBSA; 



s901 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 8 2 

AntioxidAnt ProfiLe of red CLover 

(trifoLiuM PrAtenSe L.) 

S. vLAiSAvLJeviC 1 , B. KAurinoviC 1 , M. PoPoviC 1 

1 University of Novi Sad, Chemistry Biochemistry and 

Environmental Protection, 21000 Novi Sad, Serbia 

It is well-known that polyphenolic compounds are 

responsible for the potential antioxidant activity and radical 

scavengig capacity of plant. In this context, there is an increasing 

interest in the benefical health effects of plant derived 

phytoestrogens with special focus on isoflavones. Recent research 

has shown that Red clover (Trifolium pratense L.) extract contain 

significant high amounts of all four major estrogenic isoflavones 

genistein, daidzein and their methyl ether derivatives biochanin. 

A and formononetin which are known for their potential bio-active 

antioxidant properties and radical scavenging capacity. This 

research reports the antioxidative activities of four different 

extracts and determination of dominant compound in extract 

which showed the best scavenging capacity for the free radical 

species such as: 2,2-diphenyl-1-picrylhidrazyl (DPPH · ), nitricoxide 

(NO · -· ) and super oxide anion (O ). Free radical scavenging 

2 

capacity was determined on the basis of the calculated values of 

IC The greatest antioxidant effect has an extract which shows 

50. 

the lowest value of IC . In our case it is ethyl acetate extract: 

50 

DPPH (IC = 17.82µg/mL), NO 50 · (IC = 20.35µg/mL) and 

50 

-· O (IC50 =12.90µg/mL). For this reason, this extract was used for 

2 

the determination of dominant components by HPLC analysis. 

Predominant bioactive compounds in extract are isoflavones: 

daidzein, genistein, formononetin, biochanin A, such as their 

glycosides and they are corresponding with literature data. 

Considering the mentioned above results, isoflavones are 

probably responsible for the antioxidant activity of Red clover. 

Ethyl acetate extract is suitable for isoflavones extraction, because 

they are less polar than some other flavonoides which are 

responsible for antioxidant activity. 

Keywords: Antioxidants; 


P - 0 0 8 3 

deteCtion of the AntioxidAtive ACtivity in 

CoMPoundS LACKinG the tyPiCAL StruCturAL 

deterMinAntS 

v. zAitSev 1 , e. ShMAtovA 2 , i. tyurenKov 3 , 

A. ozerov 2 , o. oStrovSKii 1 , A. yAnKovA 3 , 

S. KAveLenovA 1 

1 Volgograd State Medical University, Basic and Clinical 

Biochemistry, Volgograd, Russia 

2 Volgograd State Medical University, Pharmaceutical and 

Toxicological Chemistry, Volgograd, Russia 

3 Volgograd State Medical University, Pharmacology and 

Biopharmacy for Postgraduated Students, Volgograd, Russia 

At the present day task-oriented search of new antioxidants 

(AOs) is somewhat one-sided. Hydrogen donors (e.g., phenolic 

or thiol groups), reducing and chelating fragments are supposed 

as usual determinants of direct antioxidative activity (AOA). 

Therefore, new AOs were sought mostly among phenols, thiols 

and chelators. However, El Bakkali et al. have recently shown 

AOA can be found in aromatics without the said structural 

determinants. Aim of this study was to evaluate AOA for various 

compounds lacking typical pharmacophores. To this purpose we 

synthesized 20 derivates of adenine or quinazoline with 

substituents containing the aromatic rings and hydrogen bond 

acceptors. None of these compounds contained phenolic, thiol or 

carboxylic groups. None of them showed reducing activity with 

phosphomolybdic acid. Prediction of AOA by PASS 

(http://www.pharmaexpert.ru/passonline/) was negative for all 

synthesized compounds. However, 5 of 20 tested compounds 

exhibited AOA detected by the ABTS cation radical 

decolourization test. Range of averadge EC values was 

25 

3,74-8,18 μM for five active compounds. Thus AOA of the new 

compounds was slightly less than AOA of the well-known AOs 

gallic and ascorbic acids (values of EC were 1,32 and 2,23 μM 

25 

respectively). Three of newly found AOs (VMA-10-09, 

VMA-10-10 and VMA-10-20) contains the same substructure 

which absent in inactive compounds. This substructure is 

expressed as CC(=O)NC1=CC=C(C=C1)N(C)C in the SMILES 

notation or [#6]-[#6](=[#8])-[#7]-c1ccc(cc1)-[#7](-[#6])-[#6] in 

the SMARTS notation. Biologically relevant AOA of 

VMA-10-09 and VMA-10-10 was tested by copper-induced 

oxidative haemolysis assay. Both VMA-10-09 and VMA-10-10 

prevented RBC lysis better than quercetin or 2,6-di-tert-butyl-4- 

-methylphenol (BHT) taken at the same concentration. Hence we 

identified a new structural subfragment might be the determinant 

of AOA. 

Keywords: Antioxidants; Biological activity; Drug discovery; 



s902 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 8 4 

CoBALt-BindinG CAPACity of the Bovine 

SeruM ALBuMin treAted in vitro By vAriouS 

oxidizinG AGentS 

v. zAitSev 1 , e. LituS 1 , A. zhdAnovA 2 , 

n. KoSterinA 1 , A. ryAKShinA 1 

1 Volgograd State Medical University, Basic and Clinical 

Biochemistry, Volgograd, Russia 

2 Volgograd State Medical University, University Clinic no.1, 

Volgograd, Russia 

Various properties of the serum albumin are often used as 

basis of a number of clinical laboratory tests. One of them is the 

ACB test proposed by Bar-Or et al. to detect myocardial ischemia. 

Hypothesis which underlies this test is reduction of the serum 

albumin cobalt-binding capacity (CoBC) due to oxidative 

modification during the blood passes through hypoxic 

myocardium. However, genuine ‘ishemia-modified albumin’ 

(IMA) has not been purified yet. Moreover, controversal data 

about clinical significance of the ACB test has risen. We proposed 

diagnostic ambiguity of the ACB test might be concerned with 

IMA propeties which have not determinated clearly. We examined 

whether various oxidizing agents could change CoBC of the 

serum albumin diversely. The bovine serum albumin (BSA) was 

used as model protein. We measured CoBC by colourimetric 

dithiothreitol assay. The tested oxidizing agents were the Fenton’s 

reagents and NaOCl. All tested oxidizing agents caused weak 

accumulation of dinitrophenylhydrazine-reactive carbonyls and 

depletion of the thiol groups in BSA. However, effects of 

oxidizing agents on CoBC were different. The copper-based 

Fenton’s reagent (H O + CuSO ) significantly reduced CoBC of 

2 2 4 

treated BSA in comparison with native BSA. Effect of the 

iron-based Fenton’s reagent (H O + Mohr’s salt) on CoBC was 

2 2 

negligible. On the contrary, treatment of BSA by NaOCl increased 

CoBC value. Although the effect of NaOCl seems surprising, 

the chemical modification of ε-NH -groups of Lys by 

2 

acetylation, deamination, succinylation, or reaction with 

2,4-dinitrobenzenesulphonic acid is known to raise the cobalt 

binding by human serum albumin. Similarly NaOCl modifies 

ε-NH -group of Lys forming the chloramine groups. We suppose 

2 

the NaOCl-induced increase of BSA CoBC can be produced by 

elimination of positive charges of lysines in the protein molecule. 

Hence, we showed oxidants can act as both inhibitors and 

stimulants of cobalt-binding activity of serum albumin. 

Keywords: Proteins; Oxidation; Redox chemistry; 


P - 0 0 8 5 

SyntheSiS And StruCture-ACtivity 

reLAtionShiPS of BiS-3-ChLoroPiPeridineS 

AS BifunCtionAL dnA ALKyLAtinG AGentS 

i. zurAvKA 1 , r. GÖttLiCh 1 , A. PinGoud 2 , w. wende 2 , 

e. PetzinGer 3 , J. Geyer 3 , e. eSSid 3 

1 Justus-Liebig-University Giessen, Institute of Organic 

Chemistry, Giessen, Germany 

2 Justus-Liebig-University Giessen, Institute of Biochemistry, 


3 Justus-Liebig-University Giessen, Institute of Pharmacology 

and Toxicology Faculty of Veterinary Medicine, Giessen, 

Germany 

Bifunctional alkylating agents such as chlorambucil and 

melphalan represent an important class of clinical cancer 

chemotherapeutics. The antitumor antibiotics azinomycin A and 

B have the ability to alkylate and cross-link DNA. However, their 

poor chemical stability suggests that these natural products are 

unlikely to progress as therapeutic candidates. Yet they can act as 

lead structures from which to develop potentially useful new 

molecules. [1] 

Due to our interest in developing more effective bifunctional 

alkylating agents, we designed novel bis-3-chloropiperidines 

based upon the azinomycins backbone. [2] The nitrogen mustard 

moiety is more stable and the alkylating functions generated via 

intermediate aziridinium ions are positioned in a similar distance 

as has been observed for the azinomycins. [3, 4] To examine the 

relationship between structural modifications and DNA alkylating 

rates it appeared appealing to introduce aromatic units that might 

facilitate DNA interactions. Accordingly, we synthesised a series 

of derivatives and evaluated the alkylating properties by 

performing a DNA cleavage assay. Furthermore, in vitro cell 

cytotoxicity studies of these compounds were carried out using 

the MTT method. The biochemical and cytotoxicity results as well 

as the synthetic approach to bis-3-chloropiperidines will be 

presented. 

references: 

1. Watanabe, C. M. H. et al. Nat. Prod. Rep., 2011, 28, 693. 

2. Roesmann, R., Dissertation 2008, 

Justus-Liebig-University Giessen. 

3. Shipman, M. et al. Organic Letters, 2004, 6, 3505. 

4. Searcey M. et al. Org. Biomol. Chem., 2005, 3, 3585. 

Keywords: Antitumor agents; DNA cleavage; Structure-activity 

relationships; 



s903 

chem. Listy 106, s587–s1425 (2012) 


P - 1 0 1 8 

rAtionALLy deSiGned nir-fLuoreSCent 

nAnoPArtiCLeS for BioAnALytiCAL 

APPLiCAtionS 

K. hoffMAnn 1 , t. BehnKe 1 , C. würth 1 , 

u. reSCh-GenGer 1 

1 BAM Federal Institute for Materials Research and Testing, FB 

1.10 Biophotonics, Berlin, Germany 

Current trends in the life sciences are fluorescence-based 

techniques and concepts for signal amplification and multiplexing 

strategies to increase the overall detection sensitivity and to enable 

the ratiometric and simultaneous detection of several analytes. [1] 

This can be successfully achieved with fluorophore loaded 

or labeled particles preferably emitting in the visible or nearinfrared 

(NIR) spectral region. The detection within the diagnostic 

window (650 to 950 nm) is advantageous to reduce scattering 

effects and absorption from tissue and blood components and 

signal contributions from autofluorescence. [2, 3] Moreover, 

fluorophore incorporation into particles can reduce unspecific 

interactions between the dye molecules and the surrounding 

medium and can also minimize their potentially cytotoxic effects. 

Furthermore, encapsulated NIR dyes often show an improved 

photochemical and thermal stability as well as enhanced 

fluorescence quantum yields in polar and protic solvents like 

water. [4] For hydrophobic dyes with very low solubility in aqueous 

media, encapsulation presents the only strategy for their use in 

biologically relevant environments. 

Here, we present the synthesis and characterization of bright 

NIR-fluorescent polystyrene nanoparticles by a simple one-step 

staining procedure which can be applied to all bioanalytically 

relevant dye classes including xanthenes, cyanines, squaraines, 

oxazines, and BODIPYs. [5] The resulting particles with various 

surface functions and spectral properties have great potential for 

cellular imaging and biomarker targeting. Applications as 

ratiometric nanosensors for several analytes like oxygen, [6] and as 

labels for lifetime multiplexing detection schemes will be 

exemplary shown. 

references: 

1. U. Resch-Genger et al., Nature Methods 2008, 5, 763. 

2. J. Yan et al., NanoToday 2007, 2, 44. 

3. K.E. Adams et al., Journal of Biomedical Optics, 2007. 

12(2): 024017-1. 

4. V. Buschmann et al., Bioconj. Chem. 2003, 14, 195. 

5. T. Behnke et al., Dyes and Pigments, 2012. 94(2): 247. 

6. J. Napp et al., Analytical Chemistry, 2011. 83(23): 9039. 

P - 0 0 8 6 

forMAtion of Green ruSt SuLfAte And 

CArBonAte in the PreSenCe of zn uSinG 

tiMe-reSoLved in Situ SMALL– And 

wide–AnGLe x-rAy SCAtterinG 

i. AhMed 1 , S. ShAw 2 , L. BenninG 2 

1 University of Lancaster, The Lancaster Environment Centre, 

Lancaster, United Kingdom 

2 Leeds University, School of Earth and Environment, Leeds, 


Email: i.ahmed@Lancaster.ac.uk 

Green rusts (GR) nanoparticles are highly reactive iron 

minerals that typically form under weakly acidic to alkaline 

conditions in suboxic environments. GR have been shown to 

significantly reduce the solubility and mobility of many toxic and 

radioactive species in the environment, including Cr, U, Se, Ni 

and Zn. GR is a lamellar double hydroxide solid with Fe2+ and 

Fe3+ cations in the main hydroxide layer and anionic species (e.g., 

2– 2– SO , CO3 ) occupying the interlayer domain. 

4 

The formation mechanisms of green rust sulfate (GR-SO ) 4 

and carbonate (GR-CO ) were determined using an in situ 

3 

approach combining time-resolved synchrotron-based Wide– and 

Small–Angle X-ray Scattering with highly controlled chemical 

synthesis and electrochemical monitoring of the reaction. Both 

GR materials were coprecipitated under anaerobic conditions. The 

reaction in both systems proceeded via a three stage reaction. 

During the first stage schwertmannite [Fe O (OH) (SO ) ] 

8 8 4.5 4 1.75 

precipitated directly from solution at pH 2.8 - 4.5. With increasing 

pH (> 5) Fe2+ ions adsorb to the surface of schwertmannite and 

catalyse its transformation into goethite during the second stage 

of the reaction. In the third stage, the hydrolysis of the adsorbed 

Fe2+ ions on goethite initiates its transformation to GR-SO at pH 4 

near 7. A fourth stage was identified at pH > 8.6 in the GR–CO3 system which involves an interlayer SO 4 


2– 2– /CO3 ion–exchange 

process leading to the formation of the GR–CO phase. Evidences 

3 

on the incorporation of Zn2+ into the molecular structure of GR 

are also presented. 

references: 

1. Ahmed, I. A. M.; Benning, L. G.; Kakonyi, G.; 

Sumoondur, A. D.; Terrill, N. J.; Shaw, S. Formation of 

Green Rust Sulfate: A combined in situ time-resolved 

X-ray scattering and electrochemical Study. Langmuir 26 

(9), 6593–6603 (2010). 

Keywords: Wide Angle Scattering; Green Rust; 

schwertmannite; Synchrotron; Coprecipitation; 



s904 

chem. Listy 106, s587–s1425 (2012) 

Poster session 1 - Environmental Chemistry 

P - 0 0 8 7 

PhotoLySiS of SuLfAMethoxyPyridAzine 

in vAriouS AqueouS MediA: AeroBiC 

BiodeGrAdAtion And PhotoProduCtS 

identifiCAtion By LC-uv-MS/MS 

n. d. h. KhALeeL 1, 2 , w. M. M. MAhMoud 1, 2 , 

G. M. hAdAd 2 , r. A. ABdeL- SALAM 2 , K. KüMMerer 1 

1 Institute of Sustainable and Environmental Chemistry 

Leuphana University Lüneburg, Sustainable Chemistry and 

Material Resources, Lüneburg, Germany 

2 Faculty of Pharmacy Suez Canal University, Pharmaceutical 

Analytical Chemistry Department, Ismailia, Egypt 

In recent years, interest is growing continuously in the 

occurrence, fate, and possible effects of pharmaceutical 

compounds residues in the environment. Sulfonamides are one of 

the most frequently used antibiotics in human and veterinary 

medicines worldwide especially in Asia and Africa. Therefore 

mitigation processes are of interest. Photodegradation and 

biodegradation are the potentially significant removal 

mechanisms for pharmaceuticals in aquatic environments. 

The photolysis of sulfamethoxypyridazine (SMZ) using a 

medium pressure Hg-lamp was evaluated in three different media: 

Millipore water pH 6.1 (MW), effluent from sewage treatment 

plant pH 7.6 (STP), and buffered demineralized water pH 7.4 

(BDW). Identification of transformation products (TPs) was 

performed by LC-UV-MS/MS. The biodegradation of SMZ using 

two tests from the OECD series was studied: Closed Bottle test 

(CBT; OECD 301 D), and Manometric Respirometry test 

(MRT; OECD 301 F). 

The results showed that SMZ was removed completely 

within 128 min of irradiation in the three media, but they differ 

only in the degradation rate. However, no dissolved organic 

carbon (DOC) removal was observed in BDW and little DOC 

removal was observed in MW and STP, thus indicating the 

formation of nearly abundant TPs. Analysis by LC-UV-MS/MS 

resulted in the detection of up to six TPs of photolysis in MW, but 

only one of them was detected in STP and BDW. The observed 

difference may be due to pH or buffer salts differences. The 

hydroxylation of SMZ represents the main photodegradation 

pathway. In biodegradation tests, it was found that SMZ was not 

readily biodegradable in both CBT and MRT so it may pose a risk 

to the environment. 

Advanced oxidation process for SMZ and biodegradation 

tests for photodegradation samples will be performed. Further 

research on SMZ and its TPs, including environmental samples 

analysis, as well as toxicity tests are strongly recommended to 

know its environmental impact. 

Keywords: Sulfonamides; Photolysis; Biodegradation; 

Transformation products; Aquatic environment; 


P - 0 0 8 8 

reMovAL of PoLLutinG MetAL CAtionS froM 

wAter uSinG A Sio MAtrix entrAPPed LiGAnd 

2 

– n,n’ di(2-hydroxy-4,6 di-terButyL-BenzyL) 

iMidAzoLidine 

y. ALBo 1 , S. GoteSMAn 2 , h. Cohen 3 

1 Ariel University center of samaria, Chemical Engineering, 

Ariel, Israel 

2 Bar Ilan University, Chemistry, Tel Aviv, Israel 

3 Ariel University center of samaria, Biological Chemistry, 

Ariel, Israel 

Toxic metal ions removal from water by using chelating 

polymers is of great importance due to their high selectivity, 

efficiency and easy handling. The aim of this study is to prepare 

a novel, N,N’ di(2-hydroxy-4,6 di-terbutyl-benzyl)imidazolidine 

(L) bonded solid columns that can absorb various heavy metal 

cations. The solid chelating beads are prepared by incorporating 

the ligand to SiO matrix via the sol-gel biphasic method. The 

2 

introduction of organic functional groups to the silica matrix 

produces a new organofunctional-bonded-silica gel surface. 

The adsorption of Cu2+ , Ni2+ and Cd2+ to the chelating inorganic 

support was examined and was found to be very efficient. 

The results suggest an integrated process which links metal 

cations involving anionic groups inherent in the sol gel matrix 

(ionic atom exchange mechanism) as well as ligation by the 

“fixed” ligand, L, (coordination mechanism). 

Keywords: sol gel; 



s905 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 8 9 

PoLyMetAL(fe,AL)n-zeoLite tuff(CLn) 

CoMPoSiteS AS CoAGuLAntS for wAStewAter 

treAtMent 

i. G. BAJenAru 1 , L. SArBu 2 , v. fruth 3 , f. BACALuM 4 , 

L. MArA 5 , i. MinCA 4 , v. BAdiLitA 6 

1 University ‘POLITEHNICA’ of Bucharest, Department of 

Analytical Chemistry, Bucharest, Romania 

2 INCDCP-ICECHIM of Bucharest, Department of Chemistry 

and Petrochemistry Tech., Bucharest, Romania 

3 ICF-Ilie Murgulescu, Department of Chemistry, Bucharest, 

Romania 

4 INCDCP-ICECHIM, Department TCP, Bucharest, Romania 

5 INCDMNR-IMNR, Department, Bucharest, Romania 

6 INCDMNR-IMNR, Department, Bucharest, Romania 

Coagulation/flocculation is preferred in the primary 

purification processes of water and in industrial wastewater 

treatment mainly due to the operation ease, high efficiency and 

cost effectiveness. Also, it uses less energy than alternative 

treatments. The most commonly used coagulants are aluminium 

or iron(III)-based salts [1, 2] . 

The work aims to obtain composites with coagulation 

properties by valorising the red mud waste from the aluminium 

industry and the roumanian zeolite tuff (66-75% clinoptilolite) 

and to verify their efficiency in treating hydrocarbon-polluted 

waters. 

The polymetal (Fe,Al) -zeolite tuff(CLN) composites were 

n 

obtained by treating the red mud (RM) waste 

with acid solutions (HCl, H SO ) of different concentrations, 

2 4 

at pH values of 3-5.5, followed by the modification of the zeolite 

tuffs with polymetallic prehydrolyzed salts obtained at 45–80 °C 

with (Fe, Al) /CLN ratios of 1/0.5 -1/10. The solid phase of the 

n 

modified zeolite tuff was separated from the mix by filtration and 

drying. 

The processing conditions of the red mud(acid 

concentration, pH, RM/HCl, H ,SO ) for obtaining polymetallic 

2 4 

prehydrolyzed salts and those for the (Fe, Al) - CLN composites 

n 

influence both the structural characteristics determined by DRX, 

XRF FTIR, Raman spectroscopy, SEM and the wastewaters 

treatment process efficiency. 

The new (Fe, Al) -CLN composites efficiency in the 

n 

hydrocarbon-polluted waters(C -C , TOC=100-500 mg/L) 

12 20 

treatment process was studied by Jar tests, at 25, 45 °C. The 

experimental results emphasise the coagulant properties of the 

composites. Using the composites(0.3-0.4 mM metal content), 

generates an increase in yield for the reduction of turbidity, TOC, 

UV254nm and settling times by 50%, 67-87%, 80% and 45% 

respectively, all compared to the situation in which only the 

conventional “Alum” coagulant was used. 

The simplification of the overall treatment process and the 

cost-effectiveness are considered as the major advantages of the 

composite coagulants. 

references: 

1. N.D.Tzoupanos,A.I.Zouboulis, Water Research 45,(2011), 

3614-3626; 

2. S.Li, P.Zhou,L.Ding, K. feng, Journal of Water Resource 

and Protection, 2011, 3,253-261. 

Keywords: coagulation/flocculation; wasterwater; red mud; 


P - 0 0 9 0 

ozonAtion ProduCtS of triCLoSAn forMed in 

AdvAnCed wASte wAter treAtMent 

K. BeSter 1 , x. Chen 2 , d. eLKe 3 , t. JoChen 4 

1 Aarhus University, Environmental Science, Roskilde, Denmark 

2 Aalborg University, Biotechnology Chemistry and 

Environmental Engineering, Aalborg, Denmark 

3 University of Duisburg-Essen, Institute of Hygiene and 

Occupational Medicine, Essen, Germany 

4 Institute of Energy and Environmental Technology, Research 

Analytic Chemsitry, Duisburg, Germany 

Triclosan is an antimicrobial agent which has recently 

gained increasing interest because of its potential impacts on 

environment and public health. The high removal rate in 

biological wastewater treatment plants (> 90%) may not be 

enough as this compound is very effective on non target aquatic 

organisms. However the emitted amounts of Triclosan are present 

in surface waters with concentrations of 1-10 ng/L. Thus it is 

studied on whether ozonation of waste water may give improved 

results. 

In this study the reaction of Triclosan by aqueous ozone is 

investigated. Removal efficiency of Triclosan by ozone and 

kinetic data for the different steps are presented. Transformation 

products such as chlorophenols and hydroxy-triclosan derivatives 

are identified by GC-MS and HPLC-MS. Probably Triclosan is 

oxidized in two ways: addition of hydroxyl-groups and breaking 

of the ether bridge between the two aromatic rings. Structural 

elucidation was performed by advanced tandem mass 

spectrometry. The toxicity of selected transformation products in 

cellular systems was studied as a basis of an assessment. In total 

the concentrations go down drastically, however some of the 

transformation products are of concern. 

Keywords: triclosan; ozone; oxidation; waste water treatment; 



s906 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 9 1 

dioxinS in huMAn MiLK froM different 

reGionS of frAnCe: PiLot of the frenCh 

LonGitudinAL Study of ChiLdren (eLfe) 

M. L. Bidondo 1 , J. f. foCAnt 2 , A. SAoudi 1 , n. frery 1 , 

A. oLeKo 1 , h. Leridon 3 , L. GuLdner 1 , 

S. vAndentorren 1 

1 French Institute for Public Health Surveillance, Environment 

and Health, Saint-Maurice, France 

2 CART Mass Spectrometry Laboratory, Organic and Biological 

Analytical Chemistry, Liege, Belgium 

3 Institute of Demography, Demography, Paris, France 

Surveillance of the exposure to chemicals among pregnant 

women and their child is particularly important and constitute one 

of the objectives of the on-going Elfe (French longitudinal study 

of children) cohort study, by the use of biomarkers. 

The present work focused on the determination of 

polychlorodibenzodioxines (PCDD), polychlorodibenzofuranes 

(PCDF) and dioxin-like polychlorinated biphenyls (DL-PCBs) 

levels in the breast-milk of the mothers included in a pilot study 

of Elfe, carried out in the fall of 2007 in a random sample of 

children of several counties in France. 

A set of 35 compounds were tested: seven 2,3,7,8-substituted 

PCDDs, ten 2,3,7,8-substituted PCDFs, 12 DL-PCBs (four 

non-ortho-PCBs, eight mono-ortho-PCBs) and six NDL-PCBs. 

Fourty four samples of breast-milk were liquid-liquid 

extracted and analyzed with gas chromatography coupled to high 

resolution mass spectrometry (GC-HRMS). The limits of 

detection and quantification were optimized to obtain a good 

selectivity and sensitivity. 

Mothers were aged from 24 to 41 years old (mean and 

median: 32 years) and 50% (n = 22) were primiparous or 

secundiparous. The geometric mean concentration for total TEQ 

(PCDD/Fs and DL-PCBs), was 24.25 pg TEQ/g lipids if 

expressed in WHO1998-TEQ and 17.74 in WHO2005-TEQ. 

The comparison of these results with those from a previous 

national study conducted in 1998 shows that proportion of PCDDs 

was 78% of PCDD/Fs in 2005 versus 50% in 1998. For the sum 

of the 6 NDL-PCBs, the geometric mean concentration in milk 

was 176.3 ng/g lipids. The mean fat concentration in breast milk 

was 25.1 g/L (range from 6 to 46.7 g/L). When the comparison 

concerns only the primaparous mothers in 1998 and 2007, the 

decrease of the mean of PCDD/F levels was equal to 40%. 

Keywords: health; dioxin; environment; 


P - 0 0 9 2 

PrePArAtion And ChArACterizAtion of 

ti/Pt/PBo -tio AnodeS for iBuProfen 

2 2 

deGrAdAtion 

L. CiriACo 1 , C. ASCenCAo 1 , M. J. PACheCo 1 


Metal oxides are a promising class of anode materials that 

have been investigated in the last decades. Among the studied 

oxides, PbO already proved to be very efficient in the degradation 

2 

of organic pollutants, eliminating them from solution by 

mechanisms of conversion/combustion [1] . It can even compete 

with BDD anodes, giving similar removal rates for organic 

pollutants degradation, with the advantage of having much lower 

preparation cost. However, it presents lower service-life than 

BDD anodes. Thus, to increase anodes life time, prior to PbO2 depositions titanium substrates were platinized and, to allow 

photoelectrocatalysis applications, during the electrodeposition of 

PbO , TiO nanoparticles were also incorporated in the film. 

2 2 

Ti/Pt/β-PbO -TiO electrodes were prepared by thermal 

2 2 

electrochemical method [2, 3] . The electrodes were structural and 

morphological characterised by XRD and SEM that confirm the 

presence of β-PbO +TiO phases. The prepared Ti/Pt/β-PbO -TiO 2 2 2 2 

anodes were used in the electrodegradation of 100 ppm ibuprofen 

aqueous solutions, with Na SO 5 g L 2 4 -1 as electrolyte. The 

electrodegradation assays were run with 200 mL of solution and 

different currents densities, j, were tested, 10, 20 and 30 mA cm-2 , 

during 6 h. The samples collected during the electrochemical 

assays were analysed for the following parameters: Chemical 

oxygen demand (COD), total organic carbon (TOC) and 

UV-Visible absorption spectrophotometry. After 6 h assay, the best 

removals of Abs , COD and TOC were obtained at the highest 

224nm 

current density tested and were, respectively, 95, 76 and 63%. 

Acknowledgments: Fundacio para a Ciencia e a Tecnologia. 

references: 

1. L. Ciríaco, C. Anjo, J. Correia, M.J. Pacheco, A. Lopes, 

Electrochim. Acta 54 (2009) 1464–72. 

2. L.S. Andrade, L.A.M. Ruotolo, R.C. Rocha-Filho, 

N. Bocchi, S.R. Biaggio, J. Iniesta, V. García-Garcia, 

V. Montiel, Chemosphere 66 (2007) 2035–43. 

3. G. Li, J. Qua, X. Zhang, J. Ge, Water Res. 40 (2006) 

213–20. 

Keywords: Ibuprofen; anodic oxidation; PbO2; 



s907 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 9 3 

effeCtS of uv-B rAdiAtion And vitAMin C on 

the AntioxidAnt defenSe SySteMS in winter 

wheAt (tritiCuM AeStivuM Cv.doGu-88) And 

BArLey (hordeuM vuLGAre toKAK 157) 

SeedLinGS 

n. deMir 1 , e. tASGin 2 , h. nAdAroGLu 3 

1 Mugla University, Faculty of Sciences, Department of 

Chemistry, 48000, Mugla, Turkey 

2 Bayburt University, Faculty of Bayburt Education, 69000, 

Bayburt, Turkey 

3 Ataturk University, Department of Food Technology, 25240, 

Erzurum, Turkey 

The stratospheric ozone decrease has heightened concern over 

the ecological implication of increasing solar UV-B (280–315 nm) 

radiation on agricultural production and natural plant ecosystems. 

UV-B effects on plants include physiological damage to the 

photosynthetic apparatus, damage to DNA, effects on membranes 

and morphological damage as evidenced by stunting of plants, 

leaf discoloration and decreased vegetative biomass and grain 

yield. Therefore, antioxidant is likely to reduce the oxidative 

burden, hence tissue damage. Vitamin C is one of the most widely 

available and affordable nonenzymatic antioxidant molecules that 

have been used to mitigate oxidative damage. It is an important 

water-soluble antioxidant in biological fluids in wheat and barley. 

It readily scavenges physiological ROS such as superoxide, 

hydroxyl, and aqueous peroxyl radicals, as well as nonradical 

species such as singlet oxygen and ozone, as well as reactive 

nitrogen species (RNS). 

In this study, the effects of UV and their combinations of UV 

and vitamin C on the activities of antioxidant enzymes were 

researched in the leaves of wheat (Triticum aestivum L. Dogu 88) 

and barley (Hordeum vulgare Tokak 157) cultivars. Fifteenday-old 

wheat and barley seedlings were treated with UV radiation 

(240 nm, 3 day) prior to vitamin C treatment (20 °C). 

Supplementary UV-B radiation and UV-B+Vitamin C significantly 

decreased chlorophyll contents but total phenol contents was 

increased in both wheat and barley leaves. The activities of 

enzyme extracts; polyphenol oxidase, catalase, paraoxonase and 

peroxidase were determined in the wheat and barley leaves both 

under normal, UV-B (


s908 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 9 5 

SiLiCA fuMe ModifiCAtion for itS uSe AS 

ALternAtive AdSorBent MAteriAL for 

CAdMiuM froM AqueouS SoLutionS 

e. KALKAn 1 , h. nAdAroGLu 2 , n. CeLeBi 2 , 

n. diKBAS 3 

1 Oltu Earth Science Faculty, Geological Engineering, Erzurum, 

Turkey 

2 Erzurum Vocational Training School, Chemistry Department, 


3 Agricultural Faculty, Biotechnology Department, Erzurum, 

Turkey 

The presence of heavy metals in the environment is one of 

the major concerns because of their toxicity and threat to human 

life. Therefore, the effective removal of heavy metals from 

industrial wastewater is among the most important issues for 

many industrialized countries. Removing of cadmium from 

aqueous solutions has been studied using silica fume waste 

material after its modification with bacteria called 

Methylobacterium radiotolerans. Batch adsorption experiments 

have been performed as a function of pH, contact time and 

adsorbent dose. The experimental investigation results show that 

bacteria modified-silica fume has a high level of adsorption 

capacity for removing cadmium ions. The results revealed that 

cadmium is considerably adsorbed on the bacteria modified-silica 

fume. Consequently, it is concluded that the bacteria 

modified-silica fume can be successfully used for the removal of 

the cadmium ions from the aqueous solutions with heavy metals. 

Keywords: Wastewater; Silica fume; Bacteria-modified silica 

fume; Cadmium removal; Adsorption studies; 


P - 0 0 9 6 

BACteriA-Modified red Mud for AdSorPtion 

of CAdMiuM ionS froM AqueouS SoLutionS 

e. KALKAn 1 , h. nAdAroGLu 2 , n. diKBAS 3 


Turkey 

2 Erzurum Vocational Training School, Chemistry, Erzurum, 

Turkey 

3 Agricultural Faculty, Biotechnology, Erzurum, Turkey 

Cadmium is widely used in industry and it enters the 

environment from electroplating, smelting, alloy manufacturing, 

pigments, plastic, cadmium-nickel batteries, fertilizers, pesticides, 

mining, pigments and dyes, textile operations and refining 

industries. Cadmium is recognized as a highly toxic element and 

a serious environmental contaminant; therefore, its removal from 

water is very important. Removal, separation and enrichment of 

heavy metal ions in aqueous solutions play an important role for 

the environmental remediation of wastewater. 

The present study describes removal of cadmium from 

aqueous solutions using bacteria-modified red mud waste material 

as low cost adsorbent. Batch adsorption experiments have been 

performed as a function of pH, contact time, temperature and 

adsorbent dosage. The optimum results were obtained at pH 4.0, 

contact time of 60 min, temperature of 30 ºC and an adsorbent 

dose of 1 mg/mL. Experimental equilibrium and kinetics data 

were fitted by Langmuir and Freundlich isotherms and 

pseudo-first-order and pseudo-second-order kinetics models, 

respectively. The results show that the equilibrium data follow 

Langmuir isotherm and the kinetic data follow pseudo-second-order 

model. The maximum adsorption capacity obtained from 

Langmuir isotherm is 83.034 mg/g. The results show that the 

bacteria-modified red mud can be used for the treatment of 

aqueous solutions containing cadmium as an alternative low cost 

adsorbent. 

Keywords: Wastewater; Red mud; Bacteria-modified red mud; 

Cadmium removal; Adsorption studies; 



s909 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 9 7 

treAtMent of oLive oiL MiLL wAStewAter By 

SiLiCA-ALGinAte-funGi BioCoMPoSiteS 

A. C. freitAS 3 , C. JuStino 1 , K. r. duArte 2 , 

r. PereirA 4 , M. eL Azzouzi 5 , A. zrineh 5 , 

A. duArte 1 , t. roChA-SAntoS 3 



2 Instituto Piaget, ISEIT, Viseu, Portugal 

3 Instituto Piaget/University of Aveiro, ISEIT /Department of 


4 University of Aveiro /Faculdade de Ciencias da Universidade 

do Porto, Department of Biology, Aveiro /Porto, Portugal 

5 University Mohammed V-Agdal, Department of Chemistry, 

Rabat, Morocco 

Olive oil mill wastewater (OMW) is a liquid waste which 

constitutes a major environmental problem due to the presence 

of a wide variety of pollutants [1] . In order to mitigate the 

environmental impact of these effluents, efficient treatment 

systems have been developed to reduce the COD, color, organic 

compounds, and toxicity [2, 3] . In this study, we firstly report the 

potential of a treatment strategy for OMW (from Portugal and 

Morocco) by biocomposites of silica-alginate-fungi (Pleurotus 

sajor caju and Trametes versicolor). The treatment by 

biocomposites was processed on three steps for the efficient 

removal of the compounds, i.e., through the adsorption of 

reactants on the monolithic structure and diffusion to the 

biological active sites, biodegradation by the fungi, and diffusion 

of the products resulting from the biodegradation. We found 

potential capacity to remove organic compounds, color, COD and 

toxicity; the T. versicolor biocomposites were the most effective 

and responsible for the reduction in color, COD, and total phenolic 

content after 29 days of treatment. On the other hand, the toxicity 

reduction on Portuguese OMW was minimal, but the use of 

biocomposites on the Moroccan OMW caused a 9.5- to 19-fold 

reduction in toxicity. Furthermore the proposed treatment strategy 

shows great potential for tertiary treatment of OMW. 

Acknowledgements: FCT (Fundacao para a 

Ciencia e a Tecnologia, Portugal) scope research grants 

(SFRH/BPD/73781/2010, SFRH/BPD/65410/2009, and 

SFRH/BD/60429/2009) funded by QREN-POPH co-financed by 

the European Social Fund and Portuguese National Funds from 

MCTES, through FSE and POPH funds (Programa Ciencia 

2007) and through the bilateral cooperation FCT 

Portugal/CNRST Morocco. 

references: 

1. Justino, C.I.L, Pereira, R., Freitas, A.C., Rocha-Santos, 

T.A.P., Panteleitchouk, T.S.L., Duarte, A.C., (2012). 

Ecotoxicology, 21, 615-629. 

2. McNamara, C.J., Anastasiou, C.C., O’Flaherty, V., 

Mitchell, R., (2008). International Biodeterioration & 

Biodegradation, 61, 127-134. 

3. Roig, A., Cayuela, M.L., Sánchez-Monedero, M.A., 

(2006). Waste Management, 26, 960-969. 

Keywords: environmental chemistry; toxicology; 


P - 0 0 9 8 

iMPACt of nAturAL orGAniC MAtter on the 

toxiCity of nAnoPArtiCLeS 

f. h. friMMeL 1 , h. SChweGMAnn 1 , M. deLAy 1 

1 Karlsruhe Institute of Technology, Wasserchemie, Karlsruhe, 

Germany 

As of now, the risk posed by nanoparticles (NP) for the 

environment has not been well examined. The effects that can 

occur if NP encounter microorganisms (MO) in the environment 

are of special interest as bacteria play a critical role in ecosystems. 

In environmental aquatic systems the interaction of NP with water 

constituents such as calcium, sodium and natural organic matter 

(NOM) is of high relevance. NOM is omnipresent in aqueous 

systems and can significantly change the properties of pristine NP 

concerning their stability and their toxicological impact [1, 2] . 

In this contribution, we follow the hypothesis that the 

adsorption of NOM on the surface of NP renders their physicalchemical 

behavior and will have an effect on their toxicity towards 

MO. 

In batch systems the adsorption of fulvic acid (FA) on 

SiO -CL NP and the associated change in their zeta potential was 

2 

investigated. The FA served as a model for NOM and was isolated 

from a brown water lake (Lake Hohloh/Black Forest, Germany) 

using a standard method given in [3] . The toxicity of the NP was 

determined against Pseudomonas putida (gram-negative) and 

Lactobacillus plantarum (gram-positive). 

The adsorption of FA onto the NP could be fitted using the 

Langmuir approach. The SiO -CL NP have a point of zero charge 

2 

at pH = 9. Therefore, the adsorption was significantly higher 

at pH-values below 9 with a maximum FA loading of 

160 ± 23 µg/mg. The zeta potential of the NP changes 

from +30 mV to -20 mV (at pH = 7) caused by the adsorption of 

the FA. 

Most MO have a negative zeta potential at neutral 

pH-values. Due to the electrostatic attraction between the pristine 

NP and MO, the NP cover the surface of the MO and impair their 

proliferation [4]. Based on the adsorption of the FA and the change 

in the zeta potential, the toxicity of the SiO -CL was diminished 

2 

in the presence of FA. 

This detoxification effect is of general importance for 

aquatic systems. 

references: 

1. Delay, M. and Frimmel, F.H., Nanoparticles in aquatic 

systems. Analytical and Bioanalytical Chemistry, 2012. 

402(2): 583-592. 

2. Frimmel, F.H. and Niessner, R., Nanoparticles in the Water 

Cycle: Properties, Analysis and Environmental Relevance. 

2010: Springer. 

3. Abbt-Braun, G., Frimmel, F.H. and Lipp, P., Isolation of 

organic substances from aquatic and terrestrial systems – 

comparison of some methods. Zeitschrift für 

Wasser-Abwasser Forschung, 1991. 24: 285-292. 

4. Schwegmann, H., Feitz, A.J. and Frimmel, F.H., Influence 

of the zeta potential on the sorption and toxicity of iron 

oxide nanoparticles on S. cerevisiae and E. coli. Journal 

of Colloid and Interface Science, 2010. 347(1): 43-48. 



s910 

chem. Listy 106, s587–s1425 (2012) 


P - 0 0 9 9 

Air PoLLution StudieS in ruSSiA BASed on 

MoSS AnALySiS: PASt, PreSent And future 

M. frontASyevA 1 

1 Joint Institute for Nuclear Research, Department of Neutron 

Activation Analysis and Applied Research Frank Laboratory of 

Neutron Physics, Dubna, Russia 

The use of mosses as biomonitors of atmospheric deposition 

of trace metals and radionuclides in Russia started more than 

30 years ago in connection with the development and problems 

of the nuclear and military-industrial complexes in Siberia and 

the Urals. In the 1990s, within the framework of UNECE ICP 

Vegetation programme, systematic studies using moss were 

carried on in North-western Russia, and the results were presented 

in the European Atlas Atmospheric Heavy Metal Deposition in 

Europe – Estimations Based on Moss Analysis. In 1998–2002, 

JINR participated in the IAEA-coordinated research project 

“Biomonitoring of air pollution in the Chelyabinskregion (South 

Ural Mountains, Russia) through trace elements” in one of the 

most contaminated areas of the world experiencing strong 

ecological stress from trace metals and radionuclides. JINR 

contributed to the 2000/2001, 2005/2006, 2010/2011 European 

moss surveys reporting data on some areas of Central Russia and 

the Urals. The active moss biomonitoring (moss bag technique) 

was used to study air pollution in street canyons of the intensely 

growing megalopolis of Moscow. A combination of instrumental 

ENAA at the IBR-2 reactor at JINR, Dubna, and AAS at 

counterpart laboratories provides data on concentrations of about 

40 chemical elements (Al, As, Au, Ba, Br, Ca, Cd, Ce, Cl, Co, 

Cr, Cs, Cu, Dy, Eu, fe, Hf, hg, I, In, La, Lu, Mg, Mn, Na, Nd,ni, 

Pb, Rb, Sb, S, Sc, Se, Sm, Ta, Tb, Ti, Th, v, W, Yb, zn), which 

substantially exceed the requested by the European Atlas number 

of elements (given in bold). Distribution of the determined 

elements over the sampled areas is illustrated by the contour maps 

produced by the Russian software package GIS-INTEGRO with 

raster and vector graphics. The moss technique is supposed to be 

used for assessing sequences of the Fukushima disaster in the Far 

East of Russia. 

Keywords: air pollution; moss biomonitoring; epithermal 

neutron activation analysis; software package GIS-INTEGRO; 


P - 0 1 0 0 

PhotodeGrAdAtion of PhthALAte uSinG 

MAGnetiC hyBrid MAteriALS under viSiBLe 

LiGht 

C. ChAnG 1 , y. Liu 1 

1 Tunghai University, Environmental Science and Engineering, 

Taichung, Taiwan 

The semiconductor photocatalysts have been attracted 

attention due to the advantages of great physicochemical stability 

and the effective elimination of organic contaminants. In order to 

effectively utilize the main part of solar spectrum, the organic dye 

sensitization approach was used to prepare photosensitized TiO2 which possesses visible-light activity. The dye sensitization of 

TiO commonly adopted phthalocyanine as the sensitizer was 

2 

reported to be practical and effective. However, a major drawback 

still occurred in the system, which was the difficulty in achieving 

solid-liquid separation of nano-sized photocatalysts. 

In order to overcome the separation problem, the magnetic 

visible-light-active photocatalysts were developed in this study. 

The core-shell type of magnetic materials was commonly used as 

photocatalysts, which normally consist of the ferromagnetic core, 

an active layer of TiO2, and a passive film between the 

ferromagnetic core and the active layer. Such kinds of 

magnetically separable photocatalysts have been proved to 

effectively degrade the organics in the aqueous solution. 

Dimethyl phthalate (DMP) is one of the endocrine 

disrupting chemicals and almost ubiquitous in the environment. 

Therefore, how to effectively and economically eliminate DMP 

from aqueous solution is an important environmental issue 

nowadays. Due to the lack of previous reports on the preparation 

for magnetically hybrid materials, in this paper, we present 

experimental results on physicochemical properties of resulting 

magnetically visible-light-active photocatalysts prepared under 

various CoPc loading, and evaluation of sorption properties, 

photocatalytic activity and stability under visible light using DMP 

as a model compound in this paper. The results confirmed that the 

synthesized magnetic hybrid CoPc/TiO2 materials were 

photocatalytic active under visible light region so as to effectively 

degrade the DMP in the aqueous solution. 

Keywords: magnetic; titania; Co-phthalocyanine; dimethyl 

phthalate; photocatalysis; 



s911 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 0 1 

the effeCtS of niCKeL on the MinerAL 

nutrition of PoPLAr’S CLoneS And their 

PhytoextrACtion PotentiAL 

M. KeBert 1 , S. orLoviC 2 , B. KLASnJA 3 , d. StAJner 4 , 

B. PoPoviC 4 

1 Institute of Lowland Forestry And Environment, 

Environmental biochemistry, Novi Sad, Serbia 

2 Institute of Lowland Forestry And Environment, General 

forestry, Novi Sad, Serbia 

3 Institute of Lowland Forestry And Environment, Wood 

biotechnology, Novi Sad, Serbia 

4 Faculty of Agriculture, Chemistry department, Novi Sad, 

Serbia 

Poplars present ideal wood model system for testing 

phytoremediation of heavy metals contaminated soils as an 

emerging and cost-effective technology due to fact that they act 

as a biological filters and biomonitors. On the other hand, 

contamination with Ni2+ ions detrimentally effect biochemical and 

physiological processes as well as mineral nutrition in plants. 

Especially, due to fact that Ni2+ as a trace metal has same charge 

and similar atomic radii as some macronutrients such as Ca2+ and 

Mg2+ , disturbances in their transport are expected. 

In this study, experimental trial was settled in greenhouse, 

in half-controlled conditions with three poplar clones cuttings 

(B229, PE 19/66 and M1) which grown and were exposed to 

different concentrations of Ni2+ (25, 50, 100 and 150 mg/kg). The 

aim of this study was to asses differences in poplar’s clones 

phytoextraction potential as well as changes in mineral nutrition 

in poplar clones induced by nickel contaminated soil. Using 

atomic absorption spectrophotometry (AAS), distribution of 

absorbed Ni by organs (root, shoot and leaves) as well as contents 

of Ca and Mg were determined in poplar clones. Also, N, C and 

P contents were determined by elemental analysis (C,N) and 

spectrophotometrically (P). Gained results showed that by 

enhancement of applied Ni concentration in soil, accumulated Ni 

increased in all examined plant organs in all clones, where clone 

PE 19/66 showed highest phytoremediation potential among other 

clones by accumulating 210,12 and 143,513 ppm in roots and 

leaves, respectively at highest treatment. Obtained results should 

be used in selection of nickel tolerant poplar clone with interesting 

perspectives of application in phytoremediation technologies and 

as a platform for forestation programs of Ni polluted soils. 

Keywords: poplar; nickel; phytoextraction; mineral nutrition; 

phytoremediation; 


P - 0 1 0 2 

how to eStiMAte the PhytoextrACtion 

PotentiAL of PLAntS? 

A. KÖtSChAu 1 , G. BüCheL 1 , J. einAx 2 , 

w. von tüMPLinG 3 , d. Merten 1 

1 Friedrich Schiller University Jena, Applied Geology, Jena, 

Germany 

2 Friedrich Schiller University Jena, Environmental Analysis, 

Jena, Germany 

3 Hemholtz Centre for Environemental Research, River Ecology, 

Magdeburg, Germany 

Phytoremediation describes the cleaning of polluted 

environments by use of plants. A special way to remediate is to 

extract heavy metals from soil through uptake by plants. 

Advantages of phytoremediation are the low costs and a high 

acceptance in the population. A promising phytoextraction plant 

is the sunflower (Helianthus annuus).To test its potential under 

real conditions we grew sunflowers on the testfield 

“Gessenwiese”, which is situated in the former uranium mining 

district of Ronneburg (Thuringia). This area is contaminated with 

a broad range of heavy metals such as Cd, Cr, Co, Cu, Ni, Th, U 

and Zn and also shows elevated values for rare earth elements 

(REE). The harvested sunflowers were analyzed for the above 

named elements in roots and above-ground plant parts. The soil 

was analyzed for the total content, the bioavailable fraction and 

the specifically adsorbed fraction (Zeien and Brümmer, 1989). 

Often the phytoextraction potential of a plant is estimated based 

on first: transfer factor (TF) - content ratio of roots vs. soil, 

second: translocation factor (TL) - content ratio of above-ground 

plant part vs. roots, and third: bioaccumulation factor (BAF) 

– content ratio of above-ground plant parts vs. soil. Generally, for 

soil the total elemental content is taken into account. To our 

opinion this is not satisfying, since the content determined by total 

digestions contain a high fraction which is not available to the 

plants. Because of this drawback we additionally calculated TF 

and BAF with the bioavailable and specifically adsorbed soil 

fractions. This revealed much higher TF and BAF, compared to 

total soil calculation, so that the sunflower can be claimed as a 

good metal extractor. In addition it shows, that the plants 

solubilize even more metals, than easy available for them, which 

means a high energy effort for them. 

Keywords: Phytoextraction; Transferfactor; 

Bioaccumulationfactor; Sunflower; Heavy metals; 



s912 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 0 3 

environMentAL ProteCtion riSKS of heAvy 

MetAL ContAMinAted wood CoMBuStion. 

h. KováCS 1 , K. SzeMMeLveiSz 1 

1 University of Miskolc, Department of Combustion Technology, 

Miskolc, Hungary 

Numerous industrial activities polluted the environment in 

the past decades, whereupon heavy metals piled up in the soil in 

a bigger measure than the natural concentration. The soil pollution 

caused by means of toxic metals accelerated up since the 

beginning of the industrial revolution. Many sites were left behind 

following the industrial restructuring in Hungary, with polluted 

soil, therefore the utilization of these contaminated sites remained 

unsolved. The utilization of these sites requires the remediation 

of soil. The aim of our research is to select plant species that are 

able to decrease of the pollutant concentration of the soil by their 

accumulation ability and they grease the skids for energetic 

utilization of underutilized areas by their combustion. The heavy 

metal content of the biomass fuel is transferred into the 

combustion residues therefore it is necessary to analyze the 

hazards, the heavy-metal content and the treatment opportunities 

of these materials. The selected area in Gyöngyösoroszi was a 

mining area polluted with heavy metals. 5 wood species (Robinia 

pseudoacacia, Salix fragile, Populus tremula, Betula pendula, 

Pinus sylvestris, Quercus robur) were examined here. The 

composition of the woody materials was examined with Flame 

Atomic Absorption Spectrometry. The toxicity of the ashes was 

confirmed with leaching tests. Our studies confirmed the previous 

assumptions that before the energetic utilization of biomasses 

coming from areas polluted with heavy metals, a thorough 

examination is necessary concerning combustion technology and 

environmental protection. 

Keywords: contaminated biomass; heavy metals; combustion; 


P - 0 1 0 5 

CoMPoSition And SourCeS of fine PM in An 

induStriAL AreA: Porto MArGherA (itALy) 

M. MASioL 1 , S. SquizzAto 1 , G. rAMPAzzo 1 , 

B. PAvoni 1 

1 Universita Ca’ Foscari, Scienze Ambientali Informatica e 

Statistica, Venezia, Italy 

Industrial emissions are mainly characterized by analyzing 

PM, gaseous pollutants, involved in the secondary aerosol 

formation processes, and some hazardous air pollutants such as 

heavy metals, volatile organic compounds and polycyclic 

aromatic hydrocarbons. In this study a chemometric approach, 

including factor analysis and multiple linear regression analysis 

has been applied to PM chemical data and cluster analysis was 

used to process wind data. The aim was to identify the main 

sources of PM, their mass composition and relationship with local 

atmospheric circulation. 

Samples have been collected in Malcontenta (Venice), a site 

selected in the surroundings of the industrial zone of Porto 

Marghera to be representative of an industrial emissive scenario 

being the most extended industrial area in Italy, with chemical and 

metallurgical works, oil-refineries, incineration and thermoelectric 

power plants burning coal, gas and refuse derived fuel. 

About 190 PM samples have been analyzed to be 

2.5 

representative of different environmental conditions. Major 

inorganic ions and elements have been determined by ion 

chromatography (F- , Cl- - 2- + + + 2+ 2+ , NO , SO4 , Na , NH4 , K , Mg , Ca ), 

3 

ICP-OES (Zn, Fe, Mn, Mg, Ca, Ti, Al) and ICP-MS (V, Ni, Cu, 

As, Cd, Ba, Pb). 

Results from the factor analysis show 5 main sources of PM. 

- + The most important one links As, Cd, Pb, NO and NH4 and 

3 

represents the local contribution to PM of typical industrial 

markers such as As, Cd, Pb and secondary inorganic aerosol 

- + components (NO , NH4 ). The second source includes crustal 

3 

materials and correlates Al, Ca and Mg. The third source is 

2- characterized by the Ni – V –SO association and identifies the 

4 

fossil fuel combustion processes. The fourth source highlights a 

contribution from vehicular emissions linking Cu and Ba (tyre 

and brake abrasion) and K + and Cl- (gasoline vehicle emissions). 

The last source is related to the marine aerosol (Na + , Cl- ). 

Keywords: Transition metals; Arsenic; Cadmium; Lead; Ion 

chromatography; 



s913 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 0 6 

the MASS Size diStriBution of AeroSoL in A 

CoAStAL Site of Po vALLey (itALy): LoCAL And 

externAL oriGinS of eLeMentAL CoMPoSition 

M. MASioL 1 , S. SquizzAto 1 , d. CeCCAto 2 , 

G. rAMPAzzo 1 , B. PAvoni 1 



2 Universita di Padova, Fisica, Padova, Italy 

Venice (Italy) is located on the eastern border of the Po 

Valley, between an intensively anthropized mainland and the 

Adriatic Sea. EU limit values for many airborne pollutants are 

frequently exceeded as a consequence of peculiar weather 

conditions related to some orographic features, the closeness to 

the sea and the external transport of pollutants at continental and 

regional-scales. A total of 18 size-segregated aerosol samples were 

collected in a coastal semi-rural background site near Venice 

(Italy) in autumn and winter, i.e. in the most polluted period with 

the highest levels of airborne particulate matter. A 8-stage cascade 

impactor with nominal cut-points of 16, 8, 4, 2, 1, 0.5, 0.25 μm 

aerodynamic diameter was used, for a total of 144 samples. 

Samples were analyzed using the Particle Induced X-ray Emission 

technique for quantifying both major (Al, Si, K, Ca, Ti, Fe) and 

minor (V, Cr, Mn, Ni, Cu, Zn, Br) elements. A chemometric 

procedure was used to discriminate the weather conditions, local 

processes and remote contributions having an impact on aerosol 

chemical composition and size. Results pointed out the key role 

of the local atmospheric circulation on the sea-salt aerosol 

generation process and the accumulation effect of air mass 

stagnation on the pollutants emitted in the urban area. The 

contribution of external transports of air masses on the secondary 

inorganic aerosol formation was also clearly demonstrated. 

Finally, original and detailed information on the dimensional 

characteristics of particulate matter in the area and the main 

processes responsible for the changes in its chemical composition 

are also discussed. 

Keywords: Environmental chemistry; Sulfur; Chlorine; Silicon; 

Transition metals; 


P - 0 1 0 7 

the ChAnGeS of PoLLutinG eLeMentS, 

orGAniC CArBon And n-P-CoMPoundS in the 

SurfACe SediMentS of the LAGoon of veniCe 

(itALy) Between 1980S And 2000S 

M. MASioL 1 , C. fACCA 1 , f. viSin 1 , S. CeoLdo 1 , 

A. SfriSo 1 , B. PAvoni 1 



The sediments of the Lagoon of Venice (Italy) have been the 

sink of various pollutants from different pathways, such as direct 

discharges from a variety of urban and industrial activities, runoff 

and seepage from the draining basin and atmospheric depositions. 

This study discusses the trend of polluting elements, organic 

carbon and nutrient species in the superficial sediments of the 

central lagoon from 1987 to 2003. The period was selected for 

having undergone significant changes in the contamination impact 

due to both the drop of emissions and enhanced erosion processes. 

Twenty five sites were sampled in the central part of the lagoon 

in 1987, 1993, 1998 and 2003. The trend of the analyzed elements 

(Al, As, Cd, Co, Cu, Fe, Hg and Zn) exhibit a moderate and 

roughly linear decline in concentrations from 1987 to 2003. An 

evident anomalous peak of chromium and nickel was found in 

1998 with concentrations about 1.5–2 times greater than in the 

other sampling years. A lead clear decrease between 1998 and 

2003 superimposed to a decreasing trend similar to the other 

metals was found corresponding to the ban of tetra-alkyl lead as 

an anti-knock additive in gasoline imposed in January 2002. Four 

factors staying behind the changes in the contamination of the 

lagoon were identified through a chemometric approach: i) heavy 

metals; ii) chromium and nickel; iii) sediment mineralogy and iv) 

eutrophication. Finally, the spatial distribution of these factors was 

plotted using GIS. 

Keywords: Environmental chemistry; Heavy metals; Mercury; 

Chromium; Lead; 



s914 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 0 8 

reMovAL of CoPPer froM AqueouS SoLution 

uSinG SiLiCA fuMe with/without 

APoCArBoniC AnhydrASe 

h. nAdAroGLu 1 , e. KALKAn 2 , n. deMir 3 


Turkey 


Turkey 

3 Arts and Sciences Faculty, Chemistry, Mugla, Turkey 

Water pollution is the contamination of water bodies such 

as lakes, rivers, oceans, and groundwater caused by human 

activities, which can be harmful to organisms and plants which 

live in these water bodies. Water pollution by toxic heavy metals 

through the discharge of industrial waste is a worldwide 

environmental problem. Since copper is a widely used material, 

there are many actual or potential sources of copper pollution. 

Although a limit of 2 mg/L was proposed by the World Health 

Organization as the provisional guideline value for copper content 

of drinking water, intake of excessively large doses of copper by 

man leads to severe mucosal irritation and corrosion, widespread 

capillary damage, hepatic and renal damage and central nervous 

system irritation followed by depression. Severe gastrointestinal 

irritation and possible necrotic changes in the liver and kidney 

could occur. 

This study evaluates the use of silica fume waste material 

in the remediation of polluted heavy metal water to remove copper 

ions. For studying metal adsorption, 1 g of silica fume has been 

taken as adsorbent and then it has been suspended in 50 mL of 

1 mg/mL CuCl , at pH between 3 and 11 with / without 

2 

apocarbonic anhydrase and contacted batchwise in a thermostatic 

(t = 30 °C±0.1 °C) water-bath agitator for 1 h to enable 

equilibration of the sorbent and solution phases. The copper 

concentrations in the samples taken from the silica fume treated 

aqueous solutions of polluted river water and CuCl solution 

2 

with/without apocarbonic anhydrase have been determined by 

spectrophotometric method using 1-amino-2-hydroxy-4- 

-naphthalenesulfonic acid. The experimental investigation results 

show that activated silica fume has a high level of adsorption 

capacity for Cu2+ ion. Consequently, it is concluded that the silica 

fume can be successfully used for the removal of the copper ions 

from the aqueous solutions with heavy metals. 

Keywords: Wastewater; Silica fume; Apocarbonic anhydrase; 

Copper removal; Aqueous solution; 


P - 0 1 0 9 

CheMwAter: 2050 viSion for A SuStAinABLe 

wAter uSe 

C. neGro 1 , A. BLAnCo 1 , P. LoPéz 1 , h. dAPhne 1 

1 Universidad Complutense De Madrid, Ingeniería Química, 

Madrid, Spain 

The European chemical industry is the world’s top exporter 

and importer of chemicals with a record of €47 billion trade 

surplus in 2010 [1] .The links between the chemical industry and the 

water sector are multiple. The chemical sector is both, a main 

water consumer, it uses the 11% of the water abstracted in the 

continent and at the same time it is the provider of a great 

number of products employed in the treatment of drinking and 

waste water. 

The European Commission (EC, 2007a) [2] recognized that 

water scarcity and droughts will constitute a major challenge for 

the European Union in the near future. At least 11% of the 

European population and 17% of its territory have been affected 

by water scarcity to date. Recent trends show a significant 

extension of water scarcity across Europe threatening to increase 

the € 100 billion costs and losses associated to these phenomena 

over the past thirty years. Furthermore, the gaining importance of 

upcoming industrial sectors such as white biotechnology is 

expected to result in higher demands for water adding on the 

current one. In view of this, it is clear that water sustainability is 

a main challenge to confront in the near future. 

ChemWater is an FP7 project (NMP-2010-CSA-4-266851) 

that intends to coordinate European strategies on sustainable 

materials, processes and emerging technologies. It focuses on 

chemical and water sectors trying to establish synergies in the 

future development of both and to promote a shift in the paradigm 

of water from its current status of interminable commodity to a 

valuable raw material, what will result in an optimized industrial 

water management. The project looks at the European chemical 

industry as a provider of solutions for the whole water 

management cycle. Therefore this project fosters a new point of 

view: that of “chemistry for water” alongside the more traditional 

“water for chemistry”. 

The project brings together the WssTP and SusChem 

Technology Platforms as well as the networks of excellence EMH, 

ENMIX and ERIC. Experts from the two sectors as well as 

relevant professionals and stakeholders will jointly define a 

common long term vision that will enable a sustainable industrial 

water management in Europe. From that reference point, the 

consortium will detect the technological, legislative and social 

gaps to fill with research initiatives in order to achieve 

the 2050 Vision for ecoefficient water management. 

references 

1. The European Chemical Industry. At the Heart of 

Progress-CEFIC, 2012) 

2. EC, 2007a. Communication from the Commission to the 

European Parliament and the Council on addressing the 

challenge of water scarcity and droughts in the European 

Union. COM(2007) 414 final. 

Keywords: water; sustainable chemistry; 



s915 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 1 0 

AdSorPtion of huMiC ACid on ACid treAted 

SPent BLeAChinG eArth 

f. ozBAS 1 , M. MAhrAMAnLioGLu 1 , o. ozGen 1 , 

M. zAhoor 1 

1 Istanbul University, Engineering Faculty Chemistry 

Department, Istanbul, Turkey 

The adsorption of humic acid was studied on acid 

treated spent bleaching earth as functions of time,pH, initial 

concentration. The adsorption followed first order kinet,cs and 

rate constants for different initial concentrations were calculated. 

The Langmuir isotherm was well fit to the experimental data. The 

constants of this isotherm was calculated. The results indicated 

that the removal efficiency was influenced significantly by 

solution pH. 

The results sugest that acid treated spent bleaching earth can 

be used effectively fort he removal of humic acid. 

Keywords: Spent Bleaching Earth; Adsorption of humic acid; 


P - 0 1 1 1 

AdSorPtion of AS (iii) on ACid treAted SPent 

BLeAChinG eArth 

f. ozBAS 1 , M. MAhrAMAnLioGLu 1 , K. GuCLu 1 , 

o. ozGen 1 , M. zAhoor 1 

1 Istanbul University, Engineering Faculty Chemistry 


Spent bleaching earth (SBE) that is a solid waste from edible 

oil processing industry was chosen as raw material The aim of 

this study is to remove arsenite ions by acid treated spent 

bleaching earth.The adsorption of As (III) on acid treated spent 

bleaching earth was studied as functions of time,pH, initial 

concentration and temperature. The adsorption kinetics was 

described by the Lagergren equation. and rate constants for 

different initial concentrations were calculated. Intraparticle 

coefficients and mass transfer coefficient were also calculated. 

The Langmuir and Freundlich isotherms were fitted by the 

adsorption data obtained. The values of Langmuir and Freundlich 

constants were determined. The results indicated that the removal 

efficiency was influenced significantly by solution pH. 

The results sugest that acid treated spent bleaching earth can 

be used effectively for the removal of As (III). 

Keywords: Spent Bleaching Earth; Adsorption of As(III); 



s916 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 1 2 

treAtMent of tABLe oLive ProCeSSinG 

wAStewAter By AnodiC oxidAtion 

M. J. PACheCo 1 , J. BArBoSA 1 , L. CiriACo 1 , A. LoPeS 1 


In Mediterranean countries, olive processing industry 

generates wastewaters that contain pollutant compounds. In 

Portugal, the storage of olives in large open air tanks, filled with 

fresh water, to minimize olive deterioration while waiting for 

processing, is a common procedure. This practice yields a dark 

colored wastewater with high contents of organic matter, known 

by the negative impact on the environment. In fact, these 

wastewaters possess high concentration of phenols, which can be 

toxic to biological treatments, decreasing their efficiency. In this 

context, the introduction of advanced oxidation processes, in 

particular, the anodic oxidation with boron-doped diamond 

anodes, based on the oxidation of organics by the hydroxyl radical 

generated in situ, have been used with success for the degradation 

of biorefractory organic compounds. 

The aim of this work was to study the electrochemical 

oxidation of table olive cleaning and storage wastewaters, using 

a boron-doped diamond electrode as anode. The efficiency of the 

process was studied under different operating conditions, namely 

initial organic load and current densities. 

The experiments were conducted in a batch system with 

recirculation, using a single compartment electrochemical cell. 

All electrochemical experiments were conducted under 

galvanostatic conditions, with imposed current densities of 20 and 

30 mA cm-2 . The decay in organic content during the assays was 

monitored by measurements of COD, TOC and UV-Visible 

absorption spectrophotometric analyses. 

Although the tested wastewater is a multi-component 

solution, it behaves like a single organic synthetic wastewater and 

COD removal with time agrees very well with theoretical model 

proposed for a single component solution. For all initial organic 

load tested, the mineralization was very high. 

Acknowledgements: Financial support from Programa 

Operacional Regional do Centro 2007-2013 of QREN- 

Programa Mais Centro – FEDER for the project CENTRO-01- 

CT62-FEDER-002019 

Keywords: Table Olive Processing Wastewater; Anodic 

oxidation; Boron-doped diamond anode; 


P - 0 1 1 3 

iMPACt of oPen BurninG on PM LeveLS And 

CheMiCAL CoMPoSition 

A. di GiLio 1 , G. de GennAro 1 , P. dAMBruoSo 1 , 

M. AModio 1 , B. e. dAreStA 1 , A. MArzoCCA 1 , 

A. deMAriniS LoiotiLe 1 , M. tutino 1 , P. JoLAndA 1 

1 University Of Bari, Depatment Of Chemistry, Bari, Italy 

The burning of pruning waste of olive trees in the field is a 

common practice in South of Italy. Since fields are usually close 

to densely populated areas, the emissions from biomass burning 

may cause seasonally increasing exposure to air pollutants. The 

aims of this study is the assessment of the impact of biomass 

burning source on the levels and chemical composition of PM10 

by comparison to periods when no open fires there were. 

The experiments were made in an olive trees field, where 

daily PM10 samples were collected by an High Volume Air 

Sampler for one week and in two different years. In particular 

daily PM10 samples were collected during three days when no 

open fires there were and during three days when biomasses were 

burned. Moreover, a second High Volume Air Sampler has been 

used to collect PM10 samples at a few meters from plume of a 

bonfire only during the hours when pruning wastes of olive trees 

were burned. Finally, during monitoring campaigns the numerical 

particles concentration and the PHAs TOT concentrations have 

been determined by an Optical Particles Counters and by a PHAs 

Analyzer, respectively. The chemical characterization of PM10 

samples was performed in order to determine inorganic 

components such as ions and elements, Polycyclic Aromatic 

Hydrocarbons (PAHs) and carbonaceous fraction (OC, EC). The 

preliminary analysis of collected data showed the relevance of 

organic and inorganic tracer species for interpreting the impact of 

biomass burning source on PM levels. In fact high concentrations 

of OC, Cl, K, Pb, and PAHs, such as benzo(a)anthracene, 

benzo(a)pyrene, benzo(K)fluoranthene were observed. Finally, in 

this work will be provided the determination of enrichment factors 

(EF) for each one element and the evaluation of dimensional 

distribution patters of particles involved in biomass burning 

events. 

Keywords: conbustion; biomass burning; Chemical 

characterization; 



s917 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 1 4 

oPtiMizinG SMALL wAStewAter treAtMent 

PLAntS By MeAnS of A MoBiLe MonitorinG And 

ModeLLinG SySteM 

A. redey 1 , v. SoMoGyi 1 , e. doMoKoS 1 , z. KovACS 1 , 

B. Pinter 1 

1 Institute of Environmental Engineering, University of 

Pannonia, Veszprem, Hungary 

Small municipal wastewater treatment plants often lack 

sophisticated monitoring systems while they are subject to abrupt 

changes. This results in inefficient operation or even unwanted 

environmental pollution. 

An R+D project was carried out to develop a Wastewater 

Treatment Service Centre (WATC) (GOP-2008-1.3.1/B). The 

purpose was to create a complex service that collects and 

processes online data from wastewater treatment plants in order 

to provide a set of rules for early warning system and to carry out 

different optimization tasks based on the measurement results. 

The WATC consists of three major parts: mobile laboratories 

with built-in online analysers for the influent and the effluent, 

online communication infrastructure and software package and 

the modelling module which is coupled with an expert system. 

The mobile laboratories measure COD, ammonium, 

orthophosphate, nitrite and nitrate and sulphide on the influent 

stream and COD, ammonium, orthophosphate and nitrate 

regarding the effluent. Beside that pH, conductivity, temperature 

and turbidity are monitored on both sides and dissolved oxygen 

concentration in the aerated basins. The samples are provided 

hourly to the online communication system which provides the 

wastewater treatment proffessionals with immediate feedback on 

the measurement data. The results are used for the early warning 

system as well as the modelling module which is capable of 

optimisation tasks. 

In the pilot project the chosen facility has an average 

hydraulic load of 2300 m3 /d. In order to maintain the nitrification 

the excess sludge removal rate was kept low in wintertime. While 

normally the plant would have satisfactory nitrification capacity 

the quality of the effluent decreased heavily by the end of the 

weekends. Using the online data simulation was carried out in 

order to find an optimum concerning nitrification capacity and 

sludge removal rate. 

Acknowledgement: The authors would like to acknowledge the 

financial support of the GOP-2008-1.3.1/B project. 

Keywords: analytical methods; waste prevention; 


P - 0 1 1 5 

diStriBution of PoLyCyCLiC AroMAtiC 

hydroCArBonS in SurfACe wAter And Bed 

SediMentS of the hunGAriAn uPPer SeCtion 

of the dAnuBe river 

A. SzABo nAGy 1 , J. SzABo 1 , G. SiMon 1 , i. vASS 2 

1 Istvan Szechenyi University, Physics and Chemistry, Gyor, 

Hungary 

2 North Transdanubian Regional Environmental Protection 

Nature Conservation and Water Management Inspectorate, 

Laboratory, Gyor, Hungary 

The objective of this study was to investigate the 

concentration level and distribution of polycyclic aromatic 

hydrocarbons (PAHs) in surface water and bed sediments of the 

Hungarian upper section of the Danube River and the Moson 

Danube branch in the period of 2001–2010. The sampling sites 

were under the authority of the North Transdanubian Regional 

Environmental Protection, Nature Conservation and Water 

Management Inspectorate, designated by the Hungarian National 

Monitoring Programme. The measured data evaluation was 

supported by the Széchenyi University Main Research Direction 

Grant. 

A total of 217 samples (water and sediments) were collected 

from four different sampling sites and analysed by GC/MS 

method for the 16 priority US EPA PAHs. The total concentrations 

of PAHs in water samples ranged from 25 to 1208 ng/L, which 

were predominated by two- and three-ring PAHs. The total 

concentrations of PAHs in sediments ranged from 8.3 to 

1202.5 ng/g dry weight. Four-ring PAHs including fluoranthene 

and pyrene were the dominant species in sediment samples. A 

selected number of concentration ratios of specific PAH 

compounds were calculated to evaluate the possible sources of 

PAH contamination. The ratios reflected a pattern of pyrogenic 

input as a major source of PAHs. The results of this study add new 

data to the international database of the Danube River producing 

comparable and reliable information on water quality. 

Keywords: PAH; Danube; monitoring; surface water; 

sediment; 



s918 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 1 6 

effeCtS of uv-B rAdiAtion And ButyLAted 

hydroxyAniSoLe (BhA) on the reSPonSe of 

AntioxidAnt defenSe SySteMS in winter 

wheAt (tritiCuM AeStivuM L. yiLdiriM) 

SeedLinGS 

e. tASGin 1 , h. nAdAroGLu 2 , K. eKreM 3 

1 Bayburt Education Faculty, Chemistry, Bayburt, Turkey 


Turkey 

3 Oltu Earth Sciences Faculty, Geological Engineering, 


Due to thinness of the ozone layer, the world’s surface has 

been exposed to UV-B radiation which is potentially harmful for 

the plant growth, development and physiology. UV radiation in 

plants are caused through the production of deleterious free 

radicals/reactive oxygen species (ROS) which leads to synthesis 

of some protective substances in plants. This protective antioxidant 

system includes enzymes such as peroxidase (POX), catalase 

(CAT), paraoxonase (PON) etc.; vitamins; phytochemicals; 

minerals and food addictives. 

Butylated hydroxyanisole (BHA, 2-tert-Butyl-4-hydroxyanisole 

and 3-tert-butyl-4-hydroxyanisole) is a food additive and it is an 

aromatic organic compound. BHA has been widely used as 

antioxidants in the food industry. Effects of UV and butlated 

hydroxanisol (BHA) on the activities of antioxidant enzymes were 

studied on the leaves of wheat cultivars, in winter (Triticum 

aestivum L. Yildirim). Fifteen days old wheat seedlings were 

treated with UV radiation (240 nm, 3 day) before they are treated 

with BHA (20 °C). Supplementary UV-B radiation and 

UV-B+BHA significantly decreased chlorophyll and total phenol 

contents. The activities of enzyme extracts; polyphenol oxidase, 

catalase, paraoxonase and peroxidase were determined in the 

leaves both under normal, UV-B ( Co (88%)> Fe (78%)> Mn (78%)> Nickel (78%)> 

> Copper (66%)> Lead (63%)> Cadmium (59%). The results 

show sediment contamination by Nickel, Cadmium and Lead, 

according to the world aquatic sediments and mean earth crust 

values. Manganese and Copper have strong association with 

organic matter and are of high portion of sulfide bonded ions. 

Cluster analysis was performed in order to assess heavy metal 

interactions between water and sediment. Accordingly, Nickel, 

Cadmium and Copper are earth-originated. Zink, Copper and 

Manganese are dominated by pH. All the elemental concentrations 

in water and sediment are correlated except for sedimental copper. 

Keywords: Anthropogenic; Lithogenous; Sediment; Trace 

metal; 



s919 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 1 8 

inveStiGAtion of SurfACe funCtioAnALitieS 

And BioSorPtive ChArACteriStiCS of 

different heAvy MetALS uSinG Green MArine 

MACro ALGAe enteroMorPhA LinzA 

S. yALCin 1 

1 Istanbul University Engineering Faculty, Chemistry 


The biosorption mechanism of divalent Ni, Cd, and Pb ions 

from aqueous solutions using dried marine green macro algae 

Enteromorpha linza was investigated as a function of pH and 

contact time in a series of batch tests. The experimental data were 

evaluated by Langmuir isotherm model. The uptake capacity of 

the tested metal ions was markedly influenced from pH in the 

range of 2-3 and maximum rates were observed at pH 5 - 5. 5. 

The kinetics of the metal ions adsorption reached very rapidly to 

the equilibrium within 10 min of contact time. In addition to batch 

sorption tests, the functioanal groups on the cell wall matrix of 

dried green marine macro algae were revealed by potentiometric 

titration data and fourier-transform infrared analysis. The relative 

contribution of the chemical groups involved in metal biosorption 

such as carboxyl, amino, sulphonate was evaluated to characterize 

their binding mechanisms using these instrumental techniques. 

The density of strong and weak acidic functional groups 

in the biomass were found to be 0. 91 mmol/ g-biomass and 

3.19 mmol/ g-biomass, respectively. In conclusion, the present 

work showed that the marine algae E. linza could be used as a 

potential cost-effective biosorbent for the treatment of complex 

wastewaters containing heavy metals. 

Keywords: biosorption; heavy metal; Ni; Cd; Pb; green marine 

algae; enteromorpha linza; 


P - 0 1 1 9 

vitrifiCAtion AGentS effeCtS on Sr trAPPinG 

uSinG nAx zeoLite And Bentonite. 

S. BeLKhiri 1 , A. tABouChe 1 , y. BouCheffA 1 

1 Ecole Militaire Polytechnique, UER de Chimie, Alger, Algeria 

Zeolites are crystalline microporous adsorbents. As they are 

cationic exchangers, they have been extensively used to remove 

radionuclides from nuclear liquid wastes. Conventionally, zeolites 

containing radionuclides are vitrified at high temperatures. In this 

way, these noxious cations are safely occluded in the vitreous 

material and they can be stored for long periods until the 

radioactivity decays. Vitrified materials may in turn be sensitive 

to radiation or aging developing cracks and defects that could 

permit lixiviation. 

This work relates to the study of the influence of two 

vitrification agents; Na CO and CaCO , on the mode of strontium 

2 3 3 

retention in synthetic zeolite and Algerian bentonite.The strontium 

considered as being one of the most dangerous elements present 

in the radioactive waste (half-life = 30 years), requiring a sure and 

effective solution for its long-term adsorption and storage, by 

decreasing to the maximum any kind of diffusion and exchange 

between the environment and the trapping matrix (zeolite or 

bentonite). 

This study allowed us, to select the appropriate vitrification 

agent. The textural, structural and morphological characterizations 

of Na CO /NaX, CaCO /NaX, and CaCO /bentonite mixtures 

2 3 3 3 

treated at different temperatures (600–1000 °C) revealed that 

CaCO /NaX and CaCO /bentonite mixtures at 20/80 w/w heated 

3 3 

at 600 °C are most adequate for the safe trapping of radioactive 

strontium. Furthermore, we note the formation of new phases 

(wollastonite, αNa O.2SiO + βNa O.2SiO and quartz) even at 

2 2 2 2 

relatively low temperatures of treatment (600 °C). These new 

phases permit to improve the irreversible trapping of 

radionuclides. 

Keywords: Strontium; Vitrification; zeolite; Bentonite; 



s920 

chem. Listy 106, s587–s1425 (2012) 

Poster session 1 - Environmental Radiochemistry 

P - 0 1 2 0 

the ASSeSSMent of nAturAL And ArtifiCiAL 

rAdionuCLideS in river BottoM SediMentS 

And SuSPended SoLidS in the CzeCh rePuBLiC 

in the Period 2000–2010 uSinG 

GAMMA-SPeCtroMetriC Method 

e. hAnSLíK 1 , d. MArešová 1 , e. JurAnová 1 , 

P. StierAnd 2 

1 T. G. Masaryk Water Research Institute, Radioecology, 


2 Czech Hydrometeorological Institute, Hydrology, Prague, 


The concentrations of natural radionuclides, radium-226, 

radium-228, and potassium-40, and the artificial radionuclide 

caesium-137, in river bottom sediments and suspended solids 

were monitored in the Czech Republic by the Czech 

Hydrometeorological Institute in cooperation with T. G. Masaryk 

Water Research Institute, Public Research Institution during the 

period 2000–2010. The data were used to evaluate the natural 

background levels of these radionuclides and the impact of human 

activities on the water environment. For potassium-40 in 

sediments, the natural background level was estimated to 

be 569±161 Bq/kg. To evaluate the background level for 

radium-226, the river sites affected by human activities (mining 

and processing uranium ore, coal) were eliminated from the 

assessment, and only river sites falling into class I were used for 

the analysis. The average natural background values were 

47.8±24.1 Bq/kg for radium-226 and 47.2±23.9 Bq/kg for 

radium-228 in sediments and 87.9±45.9 Bq/kg for radium-228 

and 73.4±54.1 Bq/kg for radium-226 in suspended solids. 

The river sediments were identified as good indicators of 

radioactive contamination, especially radium-226, which recorded 

historic contamination due to former uranium mining and milling. 

The radium-226 contamination rate was assessed using the ratio 

of radium-226 to radium-228. This ratio was used to classify 

sediment according to the relative contamination from the 

uranium industry. The residual contamination of caesium-137 due 

to the Chernobyl accident in 1986 was also assessed. Average 

value of caesium-137 was 14.0 Bq/kg in sediments and 

25.0 Bq/kg in suspended solids. 

Keywords: river bottom sediments; radioactive contamination; 

radium-226; radium-228; caesium-137; 


P - 0 1 2 1 

reMovAL of StrontiuM And CeSiuM froM 

AqueouS SoLutionS uSinG nAturAL riCe 

G. KeCeLi 1 

1 Istanbul Universty, Physical Chemistry, Istanbul, Turkey 

Email: keceli@istanbul.edu.tr 

There is an increasing effort for stocking higly solube 

radioactive contaminants by transferring them from aqueous 

waste streams to solid waste forms. By doing that it is aimed to 

decrease the volüme of radioactive contaminants in aqueous waste 

streams. In this way, the high volüme aqueous streams are 

transferred from a high level radioactive waste into a low level 

radioactive waste which is much cheaper. Strontium-90 and 

Cesium-137 are dengerous radionuclides and the radioisotopes of 

these materials are produced with a high yield as a result of 

radioactive decay. As they have long life and high solublity, they 

are the primary materials in radioactive wastes. This study is done 

to find an alternative and efficient way to remove the radioactive 

wastes from aqueous waste streams. That’s why adsorption 

method is used. It is also preferred as it provides cost reduction 

in waste treatment and as it is environmental friendly. To 

investigate the adsorption properties and characteristics of 

Strontium-90 and Cesium-137 natural rice as an adsorbent, 

radioactive tracers, G-Müller and gamma counter were used. To 

investigate the impact of binding on natural rice, the parameters 

which effect binding like concentration, time and temperature, 

have been checked. The results have been applied to adsorbtion 

isotherms and kinetics models. Besides, the thermodynamic 

parameters of adsorption system like ΔH0 , ΔS0 and ΔG0 have been 

examined and ΔG0 energy has been calculated. Adsorption 

kinetics at different time intervals have been investigated, reaction 

rate and diffusion constant have been calculated. As a result, this 

study proves that natural rice can be used as good adsorbent to 

remove Strontium-90 and Cesium-137 from waste solutions. 



s921 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 2 2 

AdSorPtion KinetiCS of CeSiuM ionS on roCK 

G. KeCeLi 1 

1 Istanbul Universty, Physical Chemistry, Istanbul, Turkey 

Email: keceli@istanbul.edu.tr 

The preconcentration and separation of metal ions from the 

waste solutions have industrial importance and it has found many 

applications in nuclear industry and from the view point of 

environmental waste disposal. Fort his reason, there is a need for 

removal of metal ions from aqueous nuclear waste solutions using 

organic or inorganic adsorbents. The adsorption of metal ions in 

aqueous solution onto clay minerals is important in many areas 

of science and technology. These adsorption studies are needed 

in order to estimate rates of transport of the nuclides in the event 

of water penetration into and through the repository. The 

adsorption behaviour of cesium one of the more importent 

nuclides present in nuclear waste, has been extensively studied 

for some mineral solution systems. In this study adsorption of 

cesium ions on rock has been investigated using Cs-137 as tracer. 

The adsorption experiments were carreid out using the batch 

metod and initial concentrations of Cs ions ranged from 10-2 to 

10-6 M. It was found that % adsorption values and distribution 

coefficient decreases with increasing initial Cs ion concentration. 

Adsorption experiments were performed as a function of shaking 

time at 293 K. Initially, the % adsorption of Cs ion increases 

rapidly, but then the process slow down. The slow adsorption may 

be due to the diffusion of the ions into the pores of the clays. 

Kinetic investigations were performed to elucidate the mechanism 

of adsorption of Cs + ions. It is seen that distribution coefficient 

decrease with increase the temperature. In order to predict 

thermodynamic behaviour of the adsorption process on rock. 

Thermodynamic constants ΔH0 , ΔS0 and ΔG0 were calculated at 

293 K, 313 K, 333 K and 343 K. 


P - 0 1 2 3 

deveLoPMent of rAPid deterMinAtion 

Method of Sr-90 in environMentAL SAMPLeS 

S. neufuSS 1 , M. neMeC 1 

1 Czech Technical University in Prague, Nuclear Chemistry, 


Determination and monitoring of 90Sr (half-life 28.9 a) as 

one of the nuclear fission products (yields > 5%) belong among 

procedures to ensure and provide a radiohygienic safety. 90Sr is 

studied for its biochemical similarity with calcium and possible 

consequent incorporation into human body. Main risk presents its 

daughter product 90Y (half-life 2.67 d), which is a high energy 

β-emitter (E =2.28 MeV). 

β,max 

There are three main goals of research: environmental 

sample treatment, extraction of 90Sr from samples and 

determination of 90Sr. The poster mainly shows the first step of 

this study: the sample preparation. Moss samples from the 

surroundings of the NPP Temelín has been studied. For 

subsequent 90Sr extraction each moss sample is necessary to 

decompose and liquidize. There are several methods to 

decompose organic samples. Using a traditional ways of “wet” 

and “dry” chemistry is one of them. These methods (incineration, 

leaching and evaporation) give us very good results, but they are 

time consuming and these processes have to be repeated for each 

sample a several times. Application of new decomposition 

methods, using by microwave digestion module, where 

decomposition process is enhanced by heating with microwaves, 

lead to the better results. However, by application of microwave 

digestion another problem occurs: the volume of digestion vessel 

allows us to decompose only limited amount of the sample. 

Because of a very low concentration of 90Sr in environmental 

samples we would have to, to reach detection limit of 90Sr, decompose a lot of samples. 

The research shows the combination of analytical chemistry 

processes and microwave digestion is possibility how to eliminate 

problems mentioned above. The incineration and the consequent 

microwave digestion may lead to full decomposition of the moss 

sample and samples are more suitable for extraction. 

Keywords: strontium determination; microwave digestion; 

environmental sample; 



s922 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 2 4 

Study of urAniuM oxidAtion StAteS in 

SediMentS froM ruPreChtov AnALoGue Site 

i. PidChenKo 1 , J. SuKSi 2 , u. noSeCK 3 

1 Saint-Petersburg State University, Chemistry, Saint- 

Petersburg, Russia 

2 University of Helsinki, Chemistry, Helsinki, Finland 

3 Gesellschaft fur Anlagen-und Reaktorsicherheit, Chemistry, 

Braunsweig, Germany 

It is important to study U oxidation states in environment to 

estimate radioecological impact of U and as a natural redox 

monitor for assessing geological objects and sites considered for 

radioactive waste storage. The aim of our work was to develop 

methodology for U oxidation state analysis in solid samples by 

comparing wet chemistry [1] and SR method - XANES [2]. The 

comparison of two different methods is needed to establish the 

reliability of the wet chemistry determination of the samples with 

low U concentration, which cannot be analysed by instrumental 

techniques due to lack of sufficient sensitivity. A novel wet 

chemical method for separating U(IV) and U(VI) from solid 

samples was developed, which does not alter the oxidation state 

of U during the separation procedure. Lignite samples collected 

from the sediment layer of the Ruprechtov natural analogue site 

(Czech Republic) were studied. Redox processes during U 

extraction were monitored using 236U4+ and 236U6+ tracers. XANES 

showed for both samples that bulk of U is in U(IV) state. 234U/ 238U activities ratio(AR) were also used to assess redox behavior in 

wet chemistry method. In case of considerable 234U radionuclide 

fractionation, differences in AR can be measured depending on 

oxidizing or reducing environment was in the studied system. In 

our case, where we observed oxidizing conditions, AR in U(IV) 

fraction, with value - 0.4, does not change; whereas in U(VI) 

fraction, AR can decrease dramatically, depending on what part 

of U(IV) is oxidized during extraction. In U(VI) fraction AR is 

changing from 0.9 to 1.8 depending on experimental conditions. 

Results are in good agreement with samples from other regions 

of Ruprechtov site [3]. 

Keywords: Uranium; oxidation state; analysis; wet chemistry; 

xanes; 

P - 0 1 2 5 

ChArACterizAtion And PrePArAtion of 

tio-PAn SorBent 

J. rAindL 1 , i. SPendLiKovA 1 , M. neMeC 1 , 

A. zAvAdiLovA 1 , f. SeBeStA 1 


Chemistry, Prague, Czech Republic 

The uranium separation from natural waters was studied at 

the Department of Nuclear Chemistry in late 80’s and early 90’s. 

TiO-PAN sorbent (titanium dioxide embedded in 

polyacrylonitrile) embodied high sorption capacity for uranium. 

The purpose of this project was the thorough 

characterization of TiO-PAN sorbent with dynamic and static 

experiments which include kinetic experiments, sorption 

isotherm, effect of several ions (Ca2+ ; Mg2+ ; Fe3+ - 2- ; NO ; SO4 ; 

3 

Cl- 2- 2- 2- ; CO ) (V/m = 500 ml/g). It was found that CO3 , SO4 and 

3 

NO 3 


- ions have a positive effect on uranium sorption and on the 

other hand Cl- ions have a negative sorption effect. Specific 

surface area was measured and compared with results gained in 

2001. 

The uranium concentrations were determined by Time 

Resolved Laser Induces Fluorescence Spectrometry (TRLFS) 

which allows us to measure uranium concentrations up to ppb 

level. A strong influence of Cl- ions present in the solutions was 

seen, thus the calibration of TRLFS has to be made in order to 

determine the correct uranium concentration. 

Keywords: uranium; TiO-PAN; 



s923 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 2 6 

urAniuM SorPtion And AMS MeASureMentS 

i. SPendLiKovA 1 , M. neMeC 1 , f. SeBeStA 1 , 

P. Steier 2 , G. wALLner 3 



2 University of Vienna, Vera Laboratory, Vienna, Austria 

3 University of Vienna, Department of Inorganic Chemistry, 


The uranium separation from natural waters was studied at 

the Department of Nuclear Chemistry in late 80’s and early 90’s. 

TiO-PAN sorbent (titanium dioxide embedded in 

polyacrylonitrile) showed high sorption capacity for this element. 

This composite sorbent is planned to be used for uranium 

preconcentration for measuring environmental 236U/U ratios by 

Acceleration Mass Spectrometry (AMS) in bilateral cooperation 

with the University of Vienna. After the preliminary AMS results 

showing anthropogenic contamination in TiO-PAN sorbent, the 

preparation of titanium oxide was studied with a strong emphasis 

on elimination of this contamination. Several samples of titanium 

oxide were prepared from an organic uranium-free compound. 

These samples were studied using X-Ray Diffraction for their 

crystal structure and using selective sorption of nitrogen gas for 

their specific surface area. Their sorption properties were also 

evaluated. 

Presently we are focusing on finding a water source which 

is not anthropogenically contaminated in order to use this water 

for further experiments and on the following separation and 

concentration steps for AMS sample preparation. 

Keywords: uranium; titanium oxide; 


P - 0 1 2 7 

retention ProCeSSeS of SeLeniuM SPeCieS on 

CzeCh GrAnitiC roCK 

K. videnSKA 1 , v. hAvLovA 2 

1 Institute of Chemical Technology, Analytical Chemistry, 


2 Nuclear Research Institute Rez, Waste Management & Fuel 

Cycle Chemistry, Rez, Czech Republic 

Selenium (Se-79, T = 6.5·10 1/2 4yrs) belongs among fission 

products with long lifetime, high mobility and prevailing anionic 

character. Retention of selenium depends on its oxidation state 

therefore knowledge of migration behaviour under different 

conditions can significantly improve input into performance and 

safety assessment models. 

Granite is considered as a potential host rock for deep 

geological disposal of radioactive waste in several countries, 

including Czech Republic. Considering that, retention processes 

of selenium species on granitic rock were investigated using 

sorption and diffusion experiments. Granitic rock from Melechov 

massive (Centre Bohemian Massive, Czech Republic) was used 

as a representative for crystalline rock material. 

The sorption batch experiments were conducted on the 

crushed granite, which was sieved into several fractions with 

defined grain size. Mineral composition of each granitic fraction 

was evaluated using X-ray diffraction. The through-diffusion 

experiments were conducted on the granitic discs of the same 

origin (Melechov Massive, average 50 mm, and length 10 mm). 

Granitic discs were saturated with experimental tracer solution 

Na SeO or Na SeO . Afterwards they were placed into diffusion 

2 3 2 4 

cells. Due the saturation we can directly observed steady state 

diffusion processes. 

The X-ray diffraction results showed differences in mineral 

composition of granitic fractions (different content of quartz, 

feldspar, plagioclase, mica, chlorite, kaolinite). The 

enrichment/depletion, namely concerning Fe containing phases 

(micas) can influence the extent of both sorption and diffusion of 

observed tracers. 

Sorption experiments revealed that retention of selenite was 

higher then sorption of selenate. Granitic fractions enriched in 

mica indicated increased affinity to selenite. However, presence 

of mica did not influence sorption behaviour of selenate. The 

diffusion experiments suggested similar trend: selenite exhibited 

lower diffusion movement through rock samples in comparison 

with selenate. Selenate was proved to be rather mobile, almost 

non-sorbing specie. 

Acknowledgement: This research was supported by project of 

Ministry of Trade and Industry FR-TI1/362. 

Keywords: selenium; granite; retention; 



s924 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 2 8 

inveStiGAtinG the CheMiStry of Studtite 

A. wALShe 1 , r. J. BAKer 1 

1 Trinity College Dublin, School of Chemistry, Dublin, Ireland 

Studtite, [UO (μ-O )(H O) ].2H O, and the dehydrated form 

2 2 2 2 2 

metastudtite, [UO (μ-O )(H O) ], are the only two stable mineral 

2 2 2 2 

peroxides known. Studtite has been identified on the surface of 

spent nuclear fuel (SNF). The generally accepted mechanism of 

formation of studtite is by the reaction of UO (a primary 

2 

component of SNF) with H O (generated by the α-radiolysis of 

2 2 

water). 

One of the reasons studtite has been studied in recent years 

is the realisation that studtite has been seen to affect the mobility 

of radionuclides in SNF via sorption or incorporation into the 

uranyl-oxygen network – something that when occurring on the 

surface of SNF in repositories can have great environmental 

repercussions. 

This presentation details our investigations into the 

electronic properties of studtite via photochemical and cyclic 

voltammetric techniques and examining the redox chemistry of 

studtite. We also explore the reactivity of studtite with 

radionuclides (such as 241Am) and their analogues. 

Keywords: Spent Nuclear Fuel; Nuclear Waste; Uranium; 

Cyclic voltammetry; Radiochemistry; 


P - 0 1 2 9 

oCCurrenCe of SB(v) And SB(iii) SPeCieS ALonG 

A Ph And redox GrAdient in the CArnouL’S 

Mine wAterS (Southern frAnCe) 

C. CASiot 1 , e. reSonGLeS 1 , C. Piot 2 , S. deLPoux 1 , 

r. freydier 1 , o. BruneeL 1 , A. voLAnt 1 , 

f. eLBAz-PouLiChet 1 

1 HydroSciences, CNRS-IRD-UM1-UM2, Montpellier Cedex 5, 

France 

2 LCME, Universite de Savoie-Polytech, Le Bourget du Lac, 

France 

The concentration and speciation of antimony were 

investigated along a pH and oxygen concentration gradient in the 

Reigous-Amous-Gardon continuum downstream from the 

abandoned Pb-Zn Carnoul’s mine (Gard, France). Conditions of 

pH and dissolved oxygen concentration (DO), acquired through 

long-term monitoring study, ranged from acid suboxic in Reigous 

Creek at the outlet of sulfide tailings impoundment, to near neutral 

oxygenated at downstream sites along the rivers Amous and 

Gardon. Concentration of antimony in the fraction below 0.22 µm 

decreased from 7.7 - 409.9 μg L-1 at the source of Reigous Creek 

to 0.22 – 0.45 μg L-1 in the Gardon River. Dissolved Sb 

concentrations were predominant upon particulate Sb 

concentrations in the rivers Amous and Gardon but dissolved to 

particulate distribution coefficient log Kd exhibited a wide range 

of variations, from 2.4 L kg-1 to 4.9 L kg-1 . Speciation analysis 

carried out both in the fraction below 0.22 µm and below 10 kDa 

indicated that in the suboxic conditions of Reigous Creek water, 

Sb(III) represented up to 38% of total Sb in the fraction below 

0.22 µm, among which colloidal Sb(III) occurred. Conversely, in 

the Amous and Gardon rivers, Sb(V) was the only species present 

in the fraction below 0.22 µm and it was not associated to the 

collo?dal phase. Speciation calculations allowed to identify 

- Sb(OH) and Sb(OH)5 as the predominant Sb(V) species both in 

6 

Reigous Creek water and in the rivers Amous and Gardon, while 

Sb(III) was in the form of Sb(OH) . These calculations indicated 

3 

that the whole Sb(III) species did not represent as much as 6 % of 

total aqueous Sb concentration, which was lower than the 

proportion obtained from redox speciation measurements. This 

discrepancy was attributed to kinetic effect. 

Keywords: antimony; acid mine drainage (AMD); speciation; 



s925 

chem. Listy 106, s587–s1425 (2012) 

Poster session 1 - Mining and the Environment 

P - 0 1 3 0 

reCLAMAtion of Mine tAiLinGS uSinG BioChAr 

And SewAGe SLudGe 

e. GJenGedAL 1 , r. LiAn 1 , M. StroMMe 1 , 

P. h. heyerdAhL 2 

1 Norwegian University of Life Sciences, Dept. of Plant and 

Environmental Sciences, As, Norway 

2 Norwegian University of Life Sciences, Dept. of Mathematical 

Science and Technology, As, Norway 

In order to make barren tailings suitable for plant growth, 

amendment is necessary. The possibility of using biochar, the 

carbon-rich product of biomass heated without access to air, in 

combination with aluminium and iron precipitated sewage sludge 

in reclamation of mine tailings is explored. The biochar used was 

made from CCA (copper, chromium, and arsenic) treated wood 

sources in a microwave pyrolysis process at


s926 

chem. Listy 106, s587–s1425 (2012) 

Poster session 1 - Mining and the Environment 

P - 0 1 3 2 

ASturiAn MerCury MininG diStriCt(SPAin)And 

the environMent: A review 

J. Loredo 1 , A. ordonez 1 , r. ALvArez 1 

1 University of Oviedo, Prospecting and Mining Exploration, 

Oviedo, Spain 

Mercury is of particular concern amongst global 

environmental pollutants, with contaminated sites abundant 

worldwide, many of which are associated with mining activities. 

Northwest of Spain (Asturias) can be considered a Hg 

metallogenic province with abundant deposits, whose paragenesis 

includealso As-rich minerals. Several mines have operated in this 

region since antiquity, with evidence of activity on individual sites 

since the 1st and 2nd centuries. This leaded Asturias to become an 

important Hg producer at the world scale during the decade 

1962–1972, with average production of 15,000 flasks/year. Taking 

into account the losses during mining and inefficient smelting, the 

release of Hg and associated elements into the environment, (of 

which As is of particular note), was significant.As occurred in 

other Hg mining districts all around the world, the great decline 

on Hg prices on the 1970’s gave rise to the closure of 

Asturianmines. At that time, the environmental concern was not 

the current one, and mines were abandoned long before the 

introduction of any environmental regulations to control metal 

release from associated spoil heaps and tailings ponds. 

Aninheritanceof derelict underground and surface mine facilities 

(shafts, galleries, and external buildings) and spoil heaps, still 

remains in the sites of this district. Consequently, the environment 

is affected globally, as high metal concentrations (mainly Hg and 

As) have been found in soils, waters, sediments and air,and the 

potential adverse health effects of the exposure to these elements, 

have been assessed. 


P - 0 1 3 3 

ChArACterizAtion of MiCroALGAe iSoLAted 

froM ACid Mine drAinAGe (AMd) AS A 

PotentiAL SourCe for BiodieSeL ProduCtion 

y. PArK 1 , h. S. yun 1 , w. r. Lee 1 , J. Choi 1 

1 KIST, Gangneung Institute, Gangneung, Republic of Korea 

In an era of increasing oil prices and climate concerns, 

biodiesel has gained attention as alternative energy sources. 

Biodiesel derived from microalgae is a potential renewable and 

carbon neutral alternative to petroleum fuels. One of the most 

important decisions in obtaining oil from microalgae is the choice 

of algal species. A total of 32 microalgae cultures were isolated 

from an AMD (Acid Mine Drainage) in South Korea. 

5 microalgae isolates were selected based on their morphology 

and ease of cultivation under our test conditions. The name of 

microalgae Nephroselmis sp. KGE 1, Nephroselmis sp. KGE 2, 

Uronema sp. KGE 8, Scenedesmus obiquus KGE 9 and 

Micractinium sp. KGE 10, based on 28S rRNA (D1D2 forward 

primer 5'-AGCGGAGGAAAAGAAACTA-3',D1D2 revers 

primer 5'- TACTAGAAGGTTCGAT TA GT C-3') sequence 

analyses. Nephroselmis sp. KGE 2 maximum growth of biomass 

concentration of 1.45±0.15 g dwt L-1 with a relatively lipid 

content of 20±0.5% w/w. Also, the fatty acids compositions of the 

studied species were mainly myristic, palmitic, palmitoleic, oleic, 

linoleic, g-linolenic, and linolenic acids. High concentration of 

oleic acid was also found in Nephroselmis sp. KGE 2, which led 

us to conclude that fatty acids of microalgae incubated in growth 

media were more effective for biodiesel production due to 

relatively lower saturation degree compared to the other cultures 

algal species. Our results suggest that Nephroselmis sp. KGE 2 

can be a possible candidate species to produce oils for high quality 

biodiesel. 

Keywords: Microalgae; Biodiesel; Acid Mine Drainage; Oleic 

acid; lipid; 



s927 

chem. Listy 106, s587–s1425 (2012) 

Poster session 1 - Education and History 

P - 0 1 3 4 

SPM At SChooL: SeeinG AtoMS iS the BeSt wAy 

to LeArn ABout theM 

z. hAJKovA 1 , A. feJfAr 2 , P. SMeJKAL 1 


of Teaching and Didactics of Chemistry, Prague 2, 


2 Institute of Physics Academy of Sciences of the Czech 

Republic, Department of Thin Films and Nanostructures, 


Contemporary chemistry and physics frequently deal with 

the structure of matter at nanoscale level. One of the most 

important techniques used for imaging and measuring surfaces at 

the nanoscale (often with atomic resolution) is Scanning Probe 

Microscopy (SPM). SPM is an important up-and-coming 

technique in both academia and industry. For this reason, it should 

be mentioned in secondary education, at least for students with 

an interest in chemistry and physics. 

In order to introduce SPM into secondary education, new 

educational materials and approaches are needed. Therefore, we 

have designed an excursion concept that includes an educational 

text, a presentation, worksheets, tests and a verified proposal of 

three places in the Czech Republic where it is possible to carry 

out the excursion. As it is quite abstract and difficult for secondary 

school students to comprehend how SPM works, in addition to 

what was mentioned above, we have suggested two 

demonstrations of a visual analogy for SPM. 

Both of the demonstrations were carried out on various 

seminars arranged for secondary school physics and/or chemistry 

teachers (e.g. projects Heureka, Open Science, Open Science II, 

Project 5P, AAA science) as well as for secondary school and 

undergraduate students. They met with a surprisingly good 

response. 

Furthermore we did an orientation survey using 

questionnaires, interviews and worksheets among chemistry 

teachers from Prague and their students. Quite often students 

claimed that seeing atoms is the best way to learn about them. 

Students that had only seen demonstrations expressed that they 

would like to have an excursion to see SPM for real. Teaching 

about SPM is rather difficult, as the results of our survey showed 

occurrence of several misconceptions, so we will also show 

possible ways how to avoid them. 

Keywords: Scanning probe microscopy; 


P - 0 1 3 5 

reALizAtion of the CoMPetenCe APProACh in 

teAChinG orGAniC CheMiStry in enGLiSh 

S. iSKAKovA 1 

1 South-Kazakhstan State university, Chemistry, Shymkent, 

Kazakhstan 

Today education became a crucial criterion of «knowledge 

society» formation which is based on the leading of intellectual 

product development. The Higher education of Kazakhstan is 

included in Bologna process. Technology integration moves from 

teacher-to learner-centered methodology. Being an innovation in 

the high education, credit-hour system concerns the 

individualization of teaching-learning process. Therefore the 

contents and the organization of students’ self-directed studies are 

considerably changed, and their signification is enhanced. 

The term «student-centered approach in education» 

appeared in connection to the Bologna transformation and 

orientation at the outcome of the teaching process. Creation of 

student-centered approach in education is achieved via full-weight 

realization of a competence-based approach. The notion 

competence content itself and also goals of competences 

development bring to necessary of creation of means of both 

subject and common competences control. The most optimal 

means of control is seen such control means as Portfolio. Material 

to be included in Portfolio is, as rule, defined by teacher, 

sometimes, by student. 

The main part of a student portfolio is the student’s 

independent/ individual work. The main part of SDS is group and 

individual research projects prepared in the form of presentation. 

Themes of group and individual projects are tightly connected 

with students’ future specialty. The objectives of projects 

development, the acquired competences, and the levels of 

mastering of teaching material are give in terms of Blum’s 

Taxonomy. 

Such competences are the results of teaching the given part 

of program in Organic Chemistry; they show the individual 

achievements, knowledge and practical skills, acquired and 

presented after the successful completion of program. So, the 

student portfolio plays a crucial role in the assessment of student 

learning. 

Keywords: portfolio; Competency; innovation; 



s928 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 3 6 

CinCh – CooPerAtion in eduCAtion in 

nuCLeAr CheMiStry 

J. John 1 , v. CuBA 1 , M. neMeC 1 , t. reteGAn 2 , 

C. eKBerG 2 , G. SKArneMArK 2 , J. Lehto 3 , 

t. KoivuLA 3 , S. n. KALMyKov 4 , r. A. ALiev 4 , 

G. Cote 5 , w. MorSCheidt 5 , J. uhLir 6 , A. voKAL 6 , 

B. hAnSon 7 , B. SALBu 8 , L. SKiPPerud 8 , 

J. P. oMtvedt 9 



2 Chalmers University of Technology, Gothenburg, Sweden 

3 University of Helsinki, Helsinki, Finland 

4 Lomonosov Moscow State University, Moscow, Russia 

5 Ecole Nationale Supérieure de Chimie de Paris, Rue Pierre et 

Marie Curie, 75231 Paris, France 

6 Nuclear Research Institute Rez plc, 250 68 Rez, 


7 National Nuclear Laboratory Ltd., Daresbury Park - 

Daresbury 1100, Warrington WA4 4GB, United Kingdom 

8 Norwegian University of Life Sciences, Fougnerbakken 3, 

1432 Aas, Norway 

9 University of Oslo, P.O box 1033, Blindern, 0315 Oslo, 

Norway 

The renaissance of nuclear power is already requiring a 

significant increase in the number of the respective specialists, 

amongst others are nuclear chemists. The project Cooperation In 

education in Nuclear CHemistry (CINCH) aims to coordinate the 

current fragmented and diverse activities in Nuclear Chemistry 

education and training in Europe both at Ph.D. and undergraduate 

levels, in collaboration with Russia. The system developed should 

enable formation of a long-term Euratom Fission Training Scheme 

(EFTS) and contribute to moving the education and training in 

nuclear chemistry to a qualitatively new level. The work has been 

coordinated also with activities of ENEN association, Division of 

Nuclear and Radiochemistry of EuChemMS, and the training 

modules of EUROATOM “chemical” IPs and NOEs. 

The main results of the project with the broadest impact to 

students, teachers, industries, and research community will be a 

set of compact joint modular courses in different branches of 

modern nuclear chemistry, an e-learning platform available for 

both education and training (both applicable at the Ph.D., life-long 

learning, and MSc. levels), and a long term sustainable strategy 

for nuclear chemistry education. In this presentation, examples of 

the structures of the courses developed will be given and other 

project activities will be reviewed. 

Keywords: Nuclear Chemistry; radiochemistry; education; 

training; e-learning; 


P - 0 1 3 7 

intenSivLehrendeS PeriodenSySteM der 

eLeMente 

t. KoBer 1 

1 in Ruhestand, Wuerzburg, Germany 

Chancourtois, Newlands, Olding, Meyer, Mendeleew und 

andere Gelehrte sind unabhängig voneinander zum Periodizität 

gekommen. Dabei leisteten Mendeleew und Meyer viel mehr 

Arbeit zur Entwicklung dieser Idee als andere Wissenschaftler 

und bildeten unabhängig voneinander in den Jahren 1868/69 

Periodensysteme der Elemente (PSE) 

Das PSE wurde von mehreren Generationen von 

Wissenschaftlern vervollkommnet und in 1989 von der IUPAC 

angenommen. Dabei ist es auffällig, dass die von der IUPAC für 

gültig erklärte Variante des PSE mit dem „Kopf’ nach unten 

dargestellt ist. Aufgrund dieses Mangels der Variante kann man 

das Schema des Atombaus in normaler Weise nicht anbinden. 

Ich habe daher eine kleine aber prinzipielle wichtige 

Veränderung an der derzeitig gültigen Variante PSE 

vorgenommen werden - das PSE wird auf die „Beine’ zugestellt: 

die Elemente mit kleinen Kernladungen H und He stehen somit 

unten und die Elemente mit großer Kernladung werden 

aufsteigend nach oben angeordnet. Auf der linken Seite der 

Tabelle wird das Schema des Atombaus dargestellt. Die Stellung 

den Elementen in den Gruppen und Perioden ist mit dem Schema 

der Reihenfolge der Besetzung der Elektronen von den Hauptund 

Nebenenergieniveau logisch verbunden. 

Bei jedem Element sind die wichtigsten Daten 

(Elektronenkonfiguration, Atomradius, Elektronegativität, 

Oxidationszahlen, Standardpotentiale E0 etc.) 

angeführt. Die Spannungsreihe der Metalle mit E0 von den 

katodischen Vorgängen (2H + /H , 2H O+O /4OH 2 2 2 - etc.) ist auch 

dargestellt. Die selbstpassivierende Metalle und die Metalle, 

dessen Oxide und Hydrooxide amphoter sind werden bezeichnet. 

Auf dem Grund dieser Daten kann man die chemischen 

Eigenschaften der einfachen Stoffe beschreiben, chemische 

Formel von den verschiedenen 

Verbindungen (Hydride, Oxide, Basen, Säuren etc.) bilden 

und auch ihre chemische Eigenschaften sowie einfache und 

Redoxreaktionen beschreiben. 

Also sind in dieser Variante des Periodensystems die 

Elemente logisch und anschaulich angeordnet und aufgebaut. 

Somit stimmt hier der Aufbau des PSE mit dem Atombau überein, 

was den Lernprozess bei Schülern und Studenten vereinfacht. 



s929 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 3 8 

oPPortunity of teMPuS ?158918-At-CAndi 

ProJeCt for deveLoPMent of eduCAtionAL 

ProCeSS in heeS 

B. MutALiyevA 1 , G. MAdyBeKovA 2 , P. LieBerzeit 3 , 

A. PryAniChniKovA 3 

1 South-Kazakhstan State university, Biotechnology, Shymkent, 

Kazakhstan 

2 Kazakh-Turkish International university, Chemistry, Turkestan, 

Kazakhstan 

3 University of Vienna, Analytical Chemistry, Vienna, Austria 

One of the CANDI project objectives on theme “Teaching 

competency and infrastructure for E-learning and retraining” is a 

preparation and development infrastructure for E-learning in 

HEEs of Central Asia with a glance of European countries 

experience. 

At fulfilment of project the basic courses for distance 

education at retraining of industrial staff have been chosen, such 

as Inorganic chemistry, Analytical chemistry, Technology of 

inorganic substances, Technology of high molecular compounds. 

The new programs for learning in HEEs have been created. The 

platform Moodle have been chosen, in accordance with 

requirements of which the test tasks and checking questions on 

each lectures themes have been prepared, with account of 

self-study training of students. Student, selecting theme, prepares 

report of 10 or 20 pages, and sends this work for check and 

estimation. Also student participates in checking and estimation 

of 5 reports on given course, where he independently tries to 

acquire necessary knowledges for implementation this process. 

The program analyses some variants of estimation from different 

students and deduces total assessment of reports. 

Program includes fulfilment of laboratory experiments. So 

the methodical aids for laboratory studies fulfilment have been 

prepared, and the video-materials have been shooted. For 

acquirement on the fulfilment of laboratory experiments the 

cheching questions and tasks have been provided. 

For total assessment of course and access for exam student 

interview with lecturer. 

For preparation materials teacher should have sufficient 

skills and teaching competency, which have provided in the 

framework of project, by participation and training in workshops 

on developing components of e-learning, including work with 

camera for video-materials. Thereby, necessary skills for 

preparation of developing courses have been acquired by 

developers, and teaching aids have been prepared. 

Keywords: Infrastructure; E-learning; teaching competency; 

skills; self-study training; 


P - 0 1 3 9 

rAdioCheMiCAL tASKS deveLoPed for 

PrACtiCAL exerCiSeS in rAdioCheMiStry 

teChniqueS 

S. neufuSS 1 , S. irenA 1 , n. MoJMir 1 , C. KAterinA 1 

1 Czech Technical University in Prague, Nuclear Chemistry, 


The Department of nuclear chemistry, FNPSE CTU in 

Prague founded is one of the few institutions in central Europe 

which provides a full Bachelor’s and Master’s degree programme 

in nuclear chemistry. Our department pays strong attention to the 

familiarization with basic techniques of instrumentation in a 

radiochemical laboratory. To improve practical skills of our 

students we are now developing new practical exercises to meet 

today’s requirements and fundamental knowledge for work in 

radiochemical laboratories. Preparations of radioactive solutions, 

handling of radioactive liquids, basic extraction methods, 

detection of ionizing radiation or surface decontamination are 

basic procedures students need to get acquainted with. The 

completion of Practical exercises in radiochemistry techniques is 

the first step on their way to become “nuclear chemists”. Our 

teachers focus on the individual access and good supervision of 

the students which allow to achieve a high level of comprehension 

to those problems. The course of Practical exercises in 

radiochemistry techniques is part of Bachelor’s degree 

programme and allows students to undertake more advanced 

laboratory exercises in nuclear chemistry, radioanalytic methods, 

detection of ionizing radiation during Master’s degree 

programme. 

The poster shows and describes two tasks which relate to 

surface decontamination and solvent extraction. Simple handling, 

not any complex apparatus and good description make easier for 

students to understand a problem and give them a basic insight 

how to work in radiochemical laboratory. 

Keywords: practical exercise; nuclear chemistry; extraction; 

decontamination; 



s930 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 4 0 

iSSueS of ethiCS in CheMiStry: A PerSonAL 

oPinion 

J. Petr 1 

1 Palacky University in Olomouc, Department of Analytical 


The relation of ethics and chemistry represents an important 

connection between a classical science discipline (chemistry) and 

more sociological and philosophical discipline (ethics). However, 

the connection of such disciplines was defined in early stage of 

science e.g. with Aristotle or Plato. In 2011, Frank et al. [1] 

published an interesting article related to problems of ethics in 

chemistry and also started discussion about this theme. In my 

contribution, a personal opinion on four main themes related to 

the ethics and chemistry will be presented. First, a short review 

of issues that need to be addressed will be discussed. Then 

probably the most important problem related to the economic 

profit vs. ethics issues will be addressed. Next point will be 

connected with experiences of ethics issues in medicine that could 

serve as a model for issues of ethics in chemistry. And finally, 

some university students’ ideas on such theme will be presented 

with a proposal of questionnaire to evaluate their opinions. 

Acknowledgement: The financial support of my work by 

the Operational Program Research and Development for 

Innovations – European Regional Development Fund 

(project CZ.1.05/2.1.00/03.0058) is gratefully acknowledged. 

references: 

1. H. Frank, L. Campanella, F. Dondi, J. Mehlich, E. Leitner, 

G. Rossi, K. N. Ioset, G. Bringmann, Angew. Chem. Int. 

Ed. 2011, 50, 8482-8490. 

Keywords: ethics; chemistry; teaching; 


P - 0 1 4 1 

the nAturAL CoMPoundS in hiGh SChooL 

CheMiCAL eduCAtion 

M. PoLivKovA 1 


of Teaching and Didactics of Chemistry, Prague, Czech 

Republic 

Email: polivkova.michala@gmail.com 

Methods of learning about natural compounds have changed 

in recent years mainly due to their use in daily life. Saccharides, 

lipids, proteins and nucleic acids are found traditionally in the 

textbooks, other natural compounds are mentioned less. 

Nowadays there is emphasis on pigments, aromas, tastes, 

pheromones and food additives. 

The Framework education programme in Czech Republic 

enables the variability in the chemistry education. In every high 

school there is its own school education program, which is 

specific to the school and allows teaching natural compounds in 

less or bigger extent. 

There is a problem with laboratory works in high school due 

to allocation of hours. Somewhere they are not realized at all, 

elsewhere students have them only a few times per school year. 

Experiments with natural compounds are attractive, because 

students know the material from home or supermarket. 

We are going to interpret the results of our research about 

natural compound in high school chemical education. We will 

show that natural compounds have connection with daily life and 

experiments with them are interesting for students. 

Keywords: Natural products; Dyes/Pigments; Pheromones; 

Terpenoids; Alkaloids; 



s931 

chem. Listy 106, s587–s1425 (2012) 


P - 1 0 1 5 

the uLtiMAte frontier: A new APProACh for 

CheMiStry in A deveLoPinG Country 

f. de Leon 1 , r. MorALeS 1 , r. LetonA 1 

1 University of San Carlos, Guatemala 

As the 4th university founded in America, the University of 

San Carlos (USAC) has the responsibility for most of the higher 

education in Guatemala. Unfortunately, the role of chemistry has 

been mainly descriptive during the last years. The tools for 

education and research have been scarce and, even though 

education is being given and research is being made, the resources 

are limited. Taking this into account, some students and teachers 

have proposed a different approach: to promote the career in high 

schools, private industries and eventually make links 

internationally. The goal is to focus on theory. Theoretical 

chemistry and especially computational chemistry are branches 

which allow developing countries to make research at a low cost 

and with minimal resources. The first efforts are being made 

already. The First Central American Chemistry Congress made by 

students and professors, were students have the main role in 

selecting the lecturers, will be carried away next month. A special 

team of students is making some proposals for the renewal of the 

careers curriculum. And in the area of research, some projects in 

the field of organic synthesis, natural sea products, 

pharmaceutical, environmental, inorganic and supramolecular 

chemistry have been already carried away with promising results. 

Besides, some software and a small infrastructure have been 

acquired to take the first steps into chemical modeling and 

simulation. The idea is to form a theoretical chemistry group, a 

computational chemistry group and a high performance 

computing grid, based on GPU and cluster technology. The latter 

is thought to work between the state university and private 

universities in the country to support all experimental research 

made in Central America. In conclusion, by building a network 

of Central American chemists and working with other universities 

from other countries, especially those with the resources and tools 

to make the experimental part of a project, Guatemala could start 

making high level research and contribute with science around 

the world, producing results within international standards in a 

much more efficient and effective way. 


P - 1 0 1 9 

StudyinG rAdioCheMiStry By 1930 BrAnCA 

MArqueS A PortuGueSe woMAn CheMiSt in 

the Curie LABorAtory 

e. MAiA 1 , i. SerrA 1 

1 Centro de Filosofia das Ciencias da Universidade de Lisboa, 

Universidade de Lisboa, Lisboa, Portugal 

Branca Marques (1899–1986) was one of the first 

Portuguese women chemists in Portugal. She graduated in Physics 

and Chemistry in 1925, and even before finishing her degree she 

was invited by the Director of the Chemistry Department to be 

his assistant, thus becoming the first woman teaching in this 

department. Fascinated by the new field of radioactivity she got a 

grant of the Portuguese government to work in the Curie 

Laboratory, firstly to get acquainted with radiochemistry 

techniques, in order to come back to Portugal and install a 

radiochemistry laboratory. After some time, by suggestion of 

Marie Curie with whom she worked directly and who recognized 

her excellent qualities as experimentalist, she asked a prorogation 

of her grant and continued in the Curie Laboratory preparing her 

PhD thesis supervised by Marie Curie, and after her death in 1934, 

by Henri Debierne. 

In 1935, after defending her thesis titled « Nouvelles 

recherches sur fractionnement des sels de baryum radif?re », 

Branca Marques returned to Portugal, where she continued her 

academic career, having also succeeded in founding a 

Radiochemistry Laboratory mainly aimed at applied research. 

After her death her spoil has been conserved in the Chemistry 

Department of the Faculty of Sciences. In this spoil, among many 

other documents, there are several laboratory notebooks as well 

as other notebooks and spare notes and drawings of the period 

that she spent in Paris in the Curie Laboratory. The analysis of 

these documents is very interesting, as it gives some hints, not 

only on her work in the Laboratory, but also about safety rules 

and concerns, as well as bibliography consulted for her research. 

In this communication a brief sketch of this analysis will be 

presented. 

Keywords: history of science; radiochemistry; 



s932 

chem. Listy 106, s587–s1425 (2012) 

Poster session 1 - inorganic Chemistry 

P - 0 1 4 2 

SeLeCtive fLuoreSCent SenSinG of ChLoride 

in wAter By A CAtioniC PinCer (nCn) PLAtinuM 

(ii) CoMPLex. 

A. dorAzCo 1 , r. SCoPeLLeti 1 , K. Severin 1 

1 Ecole Polytechnique Fédérale de Lausanne, Institut des 

Sciences et Ingénierie Chimiques, Lausanne, Switzerland 

The recognition and sensing of chloride by synthetic 

receptors in water is a current challenge in supramolecular 

chemistry. We demonstrate that a luminescent platinum(II) pincer 

complex can be used for sensing of chloride in aqueous solution. 

As receptor, we employ the cyclometalated complex 

[Pt(NCN)(MeOH)]TfO (NCN = 1,3-bis(2-N-phenylbenzimidazolyl)-benzene) 

(1). The addition of chloride to a solution of 1 

in DMF-water or MeCN-water (1:1 v/v) results in quenching of 

its fluorescence. The optical response is due to coordination of 

chloride to the cationic Pt complex. The spectral response can be 

improved by mixing 1 with a surfactant. The encapsulation of 1 

inside the hydrophobic core of the surfactant micelles enhances 

the apparent binding constant for complexation of chloride 

(logK = 4.9), which allows to detect chloride in the micromolar 

concentration range. Furthermore, the micellar system displays a 

good selectivity for chloride over other common anions such as 

acetate, pyrophosphate, ect. The chemosensing system can be 

used for optical detection of chloride in bottled water. Crystal 

structures of chloro-1, iodo-1 complexes and sensing studies in 

solution will be discussed. 

Keywords: Platinum; Fluorescent probes; Anions; 


P - 0 1 4 3 

oCtAhedrAL Pd(ii) CoordinAtion And 

ferroMAGnetiC orderinG in 

PALLAdiuMdiSuLfAte 

J. BrunS 1 , M. wiCKLeder 1 , M. euL 2 , r. PÖttGen 2 

1 Institute of Pure and Applied Chemistry, Chemistry, 

Oldenburg, Germany 

2 Institute of Inorganic and Analytical Chemistry, Chemistry, 

Münster, Germany 

The reaction of elemental palladium with SO in sealed glass 

3 

tubes at elevated temperature leads to deep-blue single crystals of 

Pd(S O ) (monoclinic, P2 /n, Z = 4, a=502.20(1), b=1280.50(1), 

2 7 1 

c = 804.30(1) pm, β = 91.409(1)° [1] . Surprisingly the structure 

shows essentially undistorted octahedral oxygen coordination for 

the Pd2+ 2- ions realized by six monodentate S O groups. Up to 

2 7 

now octahedral Pd2+ coordination by oxygen atoms has only 

been achieved using rigid frameworks, e.g. in PdAs O [2] . The 

2 6 

octahedral coordination of the Pd2+ ion (electronic d8 configuration) leads to the paramagnetic behavior of the 

compound. Furthermore, at low temperature (11.7 K) even 

ferromagnetic coupling is observed, providing the first example 

of such type of magnetic behavior for a Pd(II) compound. 

Investigations of the thermal behavior of Pd(S O ) by means of 

2 7 

DSC/TG measurements and temperature-dependent powder 

diffraction reveal that in a first decomposition step PdSO forms 4 

which degrades further to PdO and finally to elemental palladium. 

The intermediate PdSO can be prepared in form of red single 

4 

crystals by the reaction of palladium with oleum. Contrastingly 

to the disulfate the palladium atoms are in square planar 

coordination in this compound. 

references: 

1. J. Bruns, M. Eul, R. Pöttgen, M. S. Wickleder, Angew. 

Chem. 2012, 124, 2247–2250; Angew. Chem. Int. Ed. 

2012, 51, 2204–2207. 

2. D. Orosel, M. Jansen, Z. Anorg. Allg. Chem. 2006, 632, 

1131–1133. 

Keywords: Palladium; magnetic properties; 



s933 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 4 4 

noveL PoLynuCLeAr niCKeL(ii)-oxo 

CoMPLexeS StABiLized By 

heterPoLytunGStAteS 

M. iBrAhiM 1 , y. xiAnG 2 , B. BASSiL 2 , y. LAn 3 , 

u. Kortz 2 , A.K. PoweLL 1 

1 Karlsruher Institut für Technologie (KIT), Institut für 

Nanotechnologie (INT), Eggenstein-Leopoldshafen, Germany 



3 Karlsruher Institut für Technologie (KIT), Institute of 

Inorganic Chemistry, Karlsruhe, Germany 

Polyoxometalates (POMs) have been found to be notably 

versatile inorganic compounds that are being practiced in many 

fields, e.g., analytical chemistry, molecular magnetism, 

nanotechnology, medicine, electrochemistry, photochemistry, and 

catalysis. 1 In order to manufacture all inorganic complexes, 

lacunary polyanions are being successfully used as multidentate 

oxo ligands to construct multinuclear magnetic materials. 2 It has 

been a matter of great challenge to encapsulate high nuclearity 

magnetic core in diamagnetic polyoxometalate shell. As part of 

our continuous effort to increase number of encapsulated 

transition metal centers in polyoxometalate, that may have 

interesting magnetic properties and potential application in 

catalysis, we have successfully made two lacunary Keggin- and 

Wells-Dawson type polyanions that encapsulate 5 NiII and 

14 NiII centers respectively. Both the polyanions were 

synthesized in a simple one-pot reaction in aqueous basic 

media (pH 8). The Wells-Dawson based polyanion 

[(Ni (H O) (OH) (PO (OH)) (α-P W O ) ] 14 2 11 5 3 4 2 15 56 4 33- (ni ) is composed 

14 

of four NiII containing {(P W O )(Ni O (OH) } sub units, a 

2 15 56 3 4 2 

central dinuclear nickel oxo cluster and four linking phosphate 

groups. 

Single crystal XRD reveals that Keggin based polyanion 

[Ni 5 (H 2 O) 4 (OH) 4 (GeW 9 O 34 )(GeW 8 O 31 )] 14- (ni 5 ) is composed of 

two asymmetric Keggin units, [β-GeW 9 O 34 ] 10- and [β-GeW 8 O 31 ] 10which 

are connected via a five nickel(II) centers. Both componds 

were characterized by single-crystal X-ray diffraction, IR 

spectroscopy, thermogravimetric analysis, elemental analysis, 

electrochemistry, and magnetochemistry. 

Keywords: Nickel; Polyoxometalates; Magnesium; 

Polynuclear; 


P - 0 1 4 5 

1,4-PhoSPhoniC And PhoSPhiniC ACid CyCLen 

derivAtiveS AS LiGAndS for Mn(ii) And Gd(iii) 

BASed Mri ContrASt AGentS 

J. BArtA 1 , J. KoteK 1 , e. tóth 2 


of Inorganic Chemistry, Prague, Czech Republic 

2 Centre National de la Recherche Scientifique, Centre de 

Biophysique Moléculaire, Orléans, France 

Magnetic resonance imaging (MRI) is one of the 

none-invasive techniques of human body examination. The only 

disadvantage of MRI is a low resolution and specificity, therefore, 

MRI contrast agents (CAs) are widely used in clinical practice 

(approximately in 40 % of all examinations). They increase not 

only resolution and specificity but also efficiency of the 

examination. The CAs consist of paramagnetic ion (Gd(III) or 

Mn(II)) and strong chelator such as DOTA or DTPA. 

Cyclen is basis of many derivatives which are being used, 

including the DOTA ligand. 1,4-phosphonic and 1,4-phosphinic 

acid cyclen derivatives could be a better alternative to 

commercially available ones. We introduced a synthetic pathway 

to three of these novel derivatives and determined the stability 

constants with metals used in CAs (Mn(II), Gd(III)) and many 

others using the potentiometric titrations. All ligands have higher 

stability constant with Mn(II) – log K around 12, than with 

LM 

Ca(II) – log K around 8, which is the closest rival for 

LM 

transmetallation under physiological conditions. The strongest 

Gd(III)-complex is formed by ligand 1,4-DO2P – log K =19.15, 

LM 

which is comparable to [Gd(DO3A)] – log K = 21.0. Also 

LM 

relaxometry studies of these derivatives were performed with 

Mn(II) and Gd(III). The complex [Mn(1,4-DO2P)] exhibits 

relaxivity 2.23 mM-1 s-1 ; [Mn(1,4-DO2POEt )] 2.32 mM-1 s-1 , and 

[Mn(1,4-DO2Bn2P H )] 1.54 mM-1 s-1 at 20 MHz and 25 °C. 

The only suitable derivative for complexation of Gd(III) is 

1,4-DO2P, which forms the complex exhibiting relaxivity 

6.96 mM-1 s-1 at 20 MHz and 25 °C. 

For all complexes 17O NMR measurements were carried out 

to determine further physico-chemistry properties. 

Acknowledgement: The research was supported by the Grant 

Agency of the Czech Republic (No. 207/11/1437) and COST 

D38 and TD1004 actions. 

Keywords: Imaging agents; Manganese; Heterocycles; 



s934 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 4 6 

StruCturAL ModifiCAtionS of the 

heteroBiMetALLiC Mn-Pt thioCyAnAto 

CoMPLexeS And their infLuenCe on the 

MAGnetiC ProPertieS 

t.SiLhA 1 , i. neMeC 1 , r. herCheL 1 , z. trávníCeK 1 


Palacky University in Olomouc, Department of Inorganic 


Manganese complexes with tetradentate Schiff base ligands 

can be used for the targeted syntheses of polynuclear or polymeric 

coordination compounds exhibiting single molecule magnetism 

(SMM) or single chain magnetism (SCM). The SMM behavior 

originates in a combination of the high spin state of the central 

metal atom and uniaxial magnetic anisotropy, which both can be 

attributed to the Mn(III) polynuclear complexes [1–2] . 

This work presents synthesis and characterization of the 

trinuclear and polynuclear heterobimetalic complexes, which 

consist of the magnetically active parts involving the manganese 

central atom (MnIII , S=2) coordinated by a tetradentate Schiff base 

(L4 = derivatives of N,N'-bis(salicylidene)-1,2-diaminethane 

dianion). These parts are bridged by the diamagnetic 

[Pt(SCN) ] 4 2- and [Pt(SCN) ] 6 2- species: [(solv)(L4 )Mn{μ - 2 

-Pt(SCN) }Mn(L 4 4 )(solv)], [(solv)(L 4 )Mn{μ -Pt (SCN) }Mn(L 2 6 4 )(solv)] 

and [(L4 )Mn{μ -Pt(SCN) }Mn(L 2 6 4 )] , solv = H O or CH OH. 

n 2 3 

The compounds were characterized by elemental analysis, 

single-crystal X-ray analysis, SQUID magnetic measurements and 

infrared spectroscopy. 

Magnetic data indicate that either a weak antiferromagnetic 

or ferromagnetic exchange interaction is present in the prepared 

complexes depending on the type of the exchange pathway. The 

magnetic interactions can be realized by several different ways in 

general, the covalent or non-covalent pathways are discussed 

within the presentation. 

Acknowledgements: The financial support from the projects 

P207/11/0841, CZ.1.05/2.1.00/03.0058, CZ.1.07/2.3.00/20.0017 

and PrF_2012_009 is gratefully acknowledged. 

references: 

1. H. Miyasak, A. Saitoh,S. Abe, Coord. Chem. Rev. 2007, 

251, 2622-2664. 

2. S. Wang, X. Ding, Y. Li., W. Huang, Coord. Chem. Rev. 

2012, 256, 439-464. 

Keywords: manganese complexes; antiferromagnetic 

interaction; ferromagnetic interaction; 


P - 0 1 4 7 

StruCturAL ChArACterizAtion of two ni(ii) 

CoMPLexeS BASed on 2-AMinoMethyLPyridine 

And tetrACyAnidoMetALAte(2-) AnionS 

J. KuChAr 1 , z. viLCeKovA 1 , J. CernAK 1 

1 Pavol Jozef Safarik University in Kosice, Faculty of Science, 

Kosice, Slovak Republic 

As a continuation of our previous studies on molecular 

magnets based on Ni(II) and cyanidometallate(2-) anions [1,2] we 

have from the aqueous systems Ni(II)–ampy–[M(CN) ] 4 2– (ampy 

= 2-aminomethylpyridine, M = Ni(II) and Pd(II)) isolated and 

characterized two novel complexes exhibiting compositions 

[Ni(ampy) ][Ni(CN) ]·H O (i) and [Ni(ampy) ][Pd(CN) ]·H O 

3 4 2 3 4 2 

(ii). Both crystal structures of i and ii are ionic and are formed 

by [Ni(ampy) ] 3 2+ cations, [M(CN) ] 4 2- (M = Ni(II) and Pd(II)) 

anions and water molecules of crystallization. The paramagnetic 

Ni(II) central atoms exhibits deformed octahedral coordination 

with amine groups occupying fac positions in the octahedron and 

M atoms within the anions exhibits usual square coordination. In 

both i and ii the hydrogen bonds of the N-H···O and O-H···N 

types link complex cations, complex anions and water molecules 

forming hydrogen bonded layers. Additionally, these hydrogen 

bonded layers are linked by π-π interactions forming a 3D 

supramolecular arrangement. The temperature variable 

susceptibility (2-300 K) and magnetization studies suggest the 

presence of weak antiferomagnetic interactions and/or single ion 

anisotropy. 

Acknowledgement: This work was supported by grant VEGA 

1/0089/09. 

references: 

1. Kuchár, J., Cernák, J., Massa, W.: Acta Cryst., C62 (2006) 

m337-m339. 

2. Paharová, J., Cernák, J., Boca, R., Îák, Z.: Inorg. Chim. 

Acta 346 (2003) 25-31. 

Keywords: nickel(II); hydrogen bonds; cyanido complexes; 

magnetic properties; 



s935 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 4 8 

whAt iS the StruCturAL ArrAnGeMent to 

AChieve hiGh in vitro AntirAdiCAL ACtivity 

of Cu(ii) CoMPLexeS invoLvinG AntioxidAnt 

Kinetin And itS derivAtiveS? 

r. novotná 1 , r. herCheL 1 , z. trávníCeK 1 


Palacky University in Olomouc, Department of Inorganic 


The metalloenzyme Cu, Zn-superoxide dismutase (Cu, 

Zn-SOD) plays a key role in the cell protection against reactive 

oxygen species because it catalyses the disproportionation of the 

superoxide radical to oxygen and hydrogen peroxide [1] . Cu, 

Zn-SOD whose active site contains the imidazole-bridged copper 

and zinc atoms [2] has become a model compound for the synthesis 

of low-molecular antioxidants based on Cu(II) complexes [3] . 

Kinetin (N6-furfuryladenine) belongs among plant growth 

hormones cytokinins [4] . At present, due to its significant 

anti-ageing effect, it has been used in medicinal cosmetics. 

Kinetin itself exhibits intrinsic antioxidative properties [4] , thus 

coordinating kinetin to copper (possible synergic effect) might 

lead to compounds with auspicious SOD-mimic activity. 

Depending on the substitution on the kinetin molecule and 

on the reaction conditions, nine structurally varied complexes 

were prepared. The polymeric [Cu (μ -L 2 3 n ) (μ -Ac) ] (1–3), 

2 2 2 n 

dimeric [Cu (μ -Ac) (HL 2 2 4 n ) ] (4, 5) [5], [Cu (μ-HL 2 2 n ) Cl ]Cl (6), 

4 2 2 

[Cu (μ-HL 2 n ) (μ-Cl) (HL 2 2 n ) Cl ] (7) and mononuclear 

2 2 

[Cu(H O) (L 2 2 n ) (phen)] (8, 9) complexes (HL 2 n = kinetin and its 

derivatives; phen = 1,10-phenanthroline) were characterized by 

elemental, thermal analyses, spectroscopic methods (IR, UV-Vis), 

conductivity, magnetochemical measurements and single crystal 

X-ray analysis. In vitro SOD-mimic activity was tested for all the 

compounds, while the best result was observed for complex 7 with 

IC = 0.71 μM (70% activity of native Cu, Zn-SOD). The 

50 

influence of the various structural types of the complexes on 

SOD-mimic activity will be discussed. 

Acknowledgement: The financial support is gratefully 

acknowledged: CZ.1.05/2.1.00/03.0058, 

CZ.1.07/2.3.00/20.0017, PrF_2012_009. 

references: 

1. Xu K.Y., Kuppusamy P.: Biochem. Biophys. Res. 

Commun. 336 (2005) 1190. 

2. Strothkamp K.G., Lippard S.J.: J. Acc. Chem. Res. 15 

(1982) 318. 

3. Starha P., Trávnícek Z., Herchel R., Popa I., Suchý P., 

Vanco J.: J. Inorg. Biochem. 103 (2009) 432. 

4. Barciszewski J., Rattan S.I.S., Siboska G., Clark B.F.C.: 

Plant Sci. 148 (1999) 37. 

5. Novotná R., Herchel R., Trávnícek Z.: Polyhedron 34 

(2012) 56. 

Keywords: Cu(II) complexes; kinetin; in vitro antiradical 

activity; 


P - 0 1 4 9 

the KinetiCS of SiLiCon tetrAChLoride 

CAtALitiC reduCtion By hydroGen on niCKeL 

ChLoride 

A. vorotyntSev 1 


FTMCET department, Nizhny Novgorod, Russia 

Nowadays it pays special attention to the reaction of silicon 

tetrachloride reduction due to its great importance in the 

technological cycle of production of polycrystalline silicon,which 

is used,for the microelectronics industry.Modern technology for 

getting silicon is based on the hydrochlorination of silicon to 

trichlorosilane with its following separation from the gas-vapor 

mixture and purification from impurities and hydrogen reduction. 

Besides, the method of thermal decomposition of silane is 

used for silicon production, which is produced by trichlorosilane 

disproportionation.In this way it forms from 14 to 16kg of silicon 

tetrachloride as a byproduct per 1kg of the receivable silicon. 

Thus from the economic and environmental points of view 

the whole amount of processing silicon tetrachloride have to be 

convert into less energy-intensive raw materials,which can be 

used in semiconductor silicon production.The purpose of realizing 

such scheme is the design of closed cycle of silicon production. 

In this work we studied the reduction reaction of silicon 

tetrachloride in the presence of a catalyst based on nickel chloride, 

investigated the kinetics of the process, as well as identify the 

order and activation energy of the reaction studied. It’s found that 

chlorine transfer from molecule of chlorosilanes to molecule of 

hydrogen and hydrogen chloride formation is one of the main 

reactions occurring on the catalyst surface.The mechanism of the 

reaction is confirmed by X-ray phase and chemical analysis. A 

quantum-chemical modeling of the studied reactions is in a good 

agreement with experimental data. 

The conversion of silicon tetrachloride at 250°C was 

obtained up to 85%.It was proved by gas chromatographic 

analysis of vapor-gas mixture, which is leaving the reactor with 

catalyst.The catalyst porosity was 60%.Thus the conversion ratio 

was increased from 30% to 85% with the process temperature 

decreeing in 4 times.These outstanding results can provide the 

opportunity to creati of green technology of silicon production. 

Keywords: silicon tetrachloride; catalytic reduction; nickel 

chloride; 



s936 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 5 0 

CoordinAtion of unSAturAted dithioetherS 

to Cu(i) hALideS: froM MoLeCuLeS to 

LuMineSCent MAteriALS 

M. Knorr 1 , f. Guyon 1 , A. Bonnot 1 , M. M. KuBiCKi 2 , 

y. rouSSeLin 2 

1 Institute UTINAM, University of Franche-Comté, Besancon, 

France 

2 ICMUB, University of Burgundy, Dijon, France 

In the context of our work on the coordination chemistry and 

organometallic chemistry of sulfur-rich organic ligands such as 

mono- and polydentate thioethers, we have recently started to use 

these compounds as building blocks to self-assemble coordination 

polymers (Metal-Organic Frameworks) of varying dimensionality 

incorporating the soft metal ions Cu(I), Ag(I), Au(I) and Hg(II). 

We demonstrate that the reaction of aromatic and aliphatic 

dithioethers of type RS-CH -CH=CHCH -SR and RS-CH - 

2 2 2 

-CΞCCH -SR with CuX gives rise to MOFs, in which dinuclear 

2 

Cu(µ -X) Cu rhomboids, tetranuclear Cu I cubane units or 

2 2 4 4 

hexanuclear Cu I clusters are present. These polymetallic 

6 6 

secondary building units (SBUs) act as connecting nodes, which 

are spanned by the organic dithioether ligands. We are currently 

investigating in detail the different parameters (metal-to-ligand 

ratio, solvent, lengths and rigidity of the spacer, substitution 

pattern of -SR), which are controlling the topologies and 

dimensionalities of the resulting networks. In order to correlate 

the temperature-dependent emissions of these strongly 

luminescent materials with the Cu...Cu distances within the SBUs, 

some X-ray diffraction studies were performed at variable 

temperature. The emission properties are also rationalized by 

means of DFT and TD-DFT calculations. 

references: 

1. P.H. Harvey, M. Knorr Macromol. Rapid Commun. 2010, 

31, 808. 

2. M. Knorr, F. Guyon, M. M. Kubicki, Y. Rousselin, 

S. M. Aly, P.D. Harvey New J. Chem. 2011, 35, 1184. 

3. M. Knorr, A. Pam, A. Khatyr, C. Strohmann, M. M. 

Kubicki, Y. Rousselin, S. M. Aly, D. Fortin, P.D. Harvey 

Inorg. Chem. 2010, 49, 5834 

4. M. Knorr, F. Guyon, A. Khatyr, C. Däschlein, 

C. Strohmann, S.M. Aly, D. Fortin, P.D. Harvey 

Dalton Trans. 2009, 948. 

5. H. N. Peindy, F. Guyon, A. Khatyr, M. Knorr, 

V.H. Gessner, C. Strohmann Z. Anorg. Allg. Chem., 2009, 

635, 2099. 

6. H.N. Peindy, F. Guyon, A. Khatyr, M. Knorr, C. 

Strohmann Eur. J. Inorg. Chem. 2007, 1823. 

Keywords: Copper; Metal-organic frameworks; Luminescence; 

S Ligands; X-ray diffraction; 


P - 0 1 5 1 

new MoLyBdenuM dinitroGen CoMPLexeS 

with Mixed ALKyL-AryL triPodAL PhoSPhAne 

LiGAndS 

L. SÖnCKSen 1 , f. tuCzeK 1 

1 Institut für Anorg. Chemie, Christian-Albrechts-Universität, 

Kiel, Germany 

Synthetic nitrogen fixation enables the reduction of 

dinitrogen ligands to ammonia. The first cyclic conversion could 

be achieved in the Chatt cycle by protonation of bis(dinitrogen) 

phosphane-Mo/W complexes. [1] Our group has been involved in 

synthetic, spectroscopic, and theoretical investigations of Chatt 

type complexes in the last years. [2] 

In the classic Chatt cycle the conjugated base of the acid, 

applied for protonation, is able to displace one of the dinitrogen 

ligands in the bis(dinitrogen) complex. The presence of anionic 

coligands leads to a disproportionation reaction at the MoI stage 

which limits the reforming of the pivotal bis(dinitrogen) complex. 

Therefore, one strategy followed in our group is to occupy 

the trans position of the dinitrogen ligand in the Mo0 complex. 

This has been fulfilled by the facially coordinated tripodal 

phosphine ligand 1,1,1-tris(diphenylphosphanylmethyl)ethane 

(tdppme) recently. [3] The activation of the dinitrogen 

ligand could be tuned by variation of the 

coligands bis(dimethylphosphanyl)methane (dmpm) and 

bis(diphenylphosphanyl)methane (dppm). 

The fact that alkylphosphane donor groups provide more 

electron density for dinitrogen activation brought us to the 

approach of applying alkyl-aryl phosphane tripodal ligands to 

synthetic nitrogen fixation. Here we present the first dinitrogen 

complexes with mixed alkyl-aryl tripod ligands of the type 

Me-C(CH PPh ) (CH P 2 2 2 2 iPr ) or H-C(CH PPh )-(CH P 2 2 2 2 iPr ) . The 

2 2 

space demanding diisopropyl phosphane groups and the usage of 

dmpm or dppm as coligands influence the coordination mode to 

the Mo0 center. [4] 

references: 

1. C. J. Pickett, J.Biol. Inorg. Chem. 1996, 1, 601. 

2. A. Dreher, G. Stephan, F. Tuczek, Adv. Inorg. Chem. 2009, 

61, 367-405 

3. J. Krahmer, H. Broda, C. Näther, G. Peters, W. Thimm, 

F. Tuczek, Eur. J. Inorg. Chem. 2011, 28, 4377. 

4. L. Söncksen, F. Tuczek, manuscript in preparation. 

Keywords: Nitrogen Fixation; Molybdenum; Tripodal 

Phosphane Ligands; 



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chem. Listy 106, s587–s1425 (2012) 


P - 0 1 5 2 

BLue PhoSPhoreSCent iridiuM CoMPLexeS 

ContAininG SuBStituted 2-PhenyLPyridine 

And PiCoLiniC ACid for orGAniC 

LiGht-eMittinG diodS 

y. KiM 1 , S. yun 1 , J. PArK 1 , S. Jin 1 

1 Pusan National University, Department of Chemistry 

Education, Busan, Republic of Korea 

Cyclometalated phosphorescent iridium(III) complexes have 

been of great interest in the study of modern organic light-emitting 

diodes (OLEDs) [1] since color and emission efficiency were tuned 

by structural modification of chromophore ligands. 

Herein we synthesized and characterized two blue 

phosphorescent iridium(III) complexes (dfpmpyCF )Ir(pic) (1) 

3 

and (dfpmpyhCz)Ir(pic) (2) using two electron density modulated 

phenylpyridine main ligands and one picolinic acid ancillary 

ligand for the fabrication of OLEDs. These complexes were 

thermally and electrochemically stable, and showed good 

photoluminescence efficiency (> 15%). The –CF substituted on 

3 

the phenylpyridine-based ligand caused a hypochromic shift in 

the emitting spectra in compound 1 and hexylcarbazole 

substituted iridium(III) complex 2 exhibited energy transfer from 

the carbazolyl moieties to the iridium(III) core with high external 

quantum efficiency [2] . The studied complexes are suitable for blue 

phosphorescent emitters in OLEDs. The best device performance 

based on compound 1 demonstrated a maximum luminance (L), 

external quantum efficiency (EQE), luminance efficiency (LE) 

and power efficiency (PE) of 5750 cd/m2 , 7.53 %, 16.86 cd/A and 

5.88 lm/W, respectively with Commission Internationale de 

L’Eclairage (CIE) coordinates of (0.17,0.40) 

references: 

1. a) Y.-C. Zhu, L. Zhou, H.-Y. Li, Q.-L. Zu, M.-Y. Teng, 

Y.-X. Zheng, J.-L. Zuo, H.-J. Zhang, Z.-Z. You, Adv. 

Mater. 2011, 23, 4041. 

b) R. Wang, D. Liu, H. Ren, T. Zhang, Z. Wang, J. Li, 

J. Mater. Chem. 2011, 21, 15494. 

2. H.-J. Seo, M. Song, S.-H. Jin, J. H. Choi, S.-J. Yun, 

Y.-I. Kim, RSC Adv. 2011, 1, 755. 

Keywords: Blue phophorescent; iridium(III) complex; OLEDs; 


P - 0 1 5 3 

fixAtion of nitrouS oxide By CArBeneS 

And the reACtivity of ACtivAted n o 2 

A. tSKhovreBov 1 , K. Severin 1 

1 Ecole Polytechnique Fédérale de Lausanne, ISIC, Lausanne, 

Switzerland 

Nitrous oxide is the main ozone-depleting substance 

nowadays, and it is around 300 times more potent greenhouse gas 

then CO . In addition, N O is an appealing oxidant due to its 

2 2 

thermodynamic potency and environmentally friendly nature 

(the only by product in oxygen atom transfer reactions is N ). 2 

Recently we discovered that N-heterocyclic carbenes are 

able to fix N O and form stable adducts. 2 1 This adducts could be 

regarded as a source of activated N O and they display unique 

2 

reactivity as evidenced by different organic and organometallic 

transformations. 1,2 

references: 

1. A.G. Tskhovrebov, E. Solari, M.D. Wodrich, 

R. Scopelliti,K. Severin, Angew. Chem. Int. Ed. 

2012,51(1),232-234. 

2. A.G. Tskhovrebov, E. Solari, M.D. Wodrich, 

R. Scopelliti,K. Severin, J. Am. Chem.Soc. 2012, 134(3), 

1471-1473. 



s938 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 5 4 

MoLyBdenuM(0)-CArBonyL CoMPLexeS with 

Mixed iMidAzoL-2-yLidene/PhoSPhino-hyBrid 

LiGAndS: whAt Are the ConSequenCeS of 

SuBStitutinG A PhoSPhine By A nhC GrouP? 

C. GrAdert 1 , f. tuCzeK 1 


Kiel, Germany 

Since the first isolation of a free N-heterocyclic carbene 

(NHC) by Arduengo and co-workers in 1991 [1] , NHCs have 

become more and more popular as ligands in organometallic 

catalysis. In spite of the high potential of molybdenum complexes 

in to olefin epoxidation or nitrogen fixation, only a limited number 

of molybdenum complexes carrying NHCs has so far been 

reported. 

A series of mixed NHC/phosphine ligands has been prepared 

[2] which comprises the bidentate ligand EtImEtPPh having one 

2 

diphenylphosphinoethyl group attached to a imidazole based 

carbene as well as two tridentate ligands (EtPPh ) Im and 

2 2 

PPh(EtImEt) ) 2 [3], [4] having two terminal diphenylphosphinoethyl 

groups bound to a central NHC and two terminal NHC groups 

bound via ethylene spacers to a central phosphine, respectively. 

Employing these ligands the new molybdenum(0) carbonyl 

complexes [Mo(CO) (EtImEtPPh )], fac-[Mo(CO) ((EtPPh ) Im)], 

4 2 3 2 2 

and fac-[Mo(CO) (PPh(EtIm-Et) )] were synthesized. The 

3 2 

complexes are investigated by X-ray structure analysis, 

vibrational and NMR spectroscopy coupled to DFT calculations. 

The mixed NHC/phosphine ligands exhibit a dramatically 

increased σ-donor strength in comparison to their classic bi- and 

tridentate counterparts exclusively carrying phosphine groups 

such as dppp (1,3-bis(diphenylphosphino)propane) and 

dpepp (bis(2-diphenylphosphinoethyl)phenylphosphine). 

Another distinctive feature of the tridentate ligands (EtPPh ) Im 2 2 

and PPh(EtImEt) is their propensity to coordinate in a fac 

2 

geometry. [5] 

references: 

1. A. J. Arduengo, R. L. Harlow, M. Kline, Journal of the 

American Chemical Society 1991, 113, 361. 

2. H. M. Lee*, P. l. Chiu, J. Yao. Zeng, Inorg. Chim. Acta 

2004, 357, 4313. 

3. H. M. Lee*, J. Y. Zeng, C.-H. Hu, M.-T. Lee, 

Inorg. Chem.2004, 43, 6822. 

4. K. W. Kottsieper, O. Stelzer*, P. Wasserscheid, 

J. Molec. Catal. A: Chem. 2001, 175, 285. 

5. C. Gradert, G. Peters, F. Sönnichsen, C. Näther, G. Henkel 

and F. Tuczek*, in preparation. 

Keywords: Molybdenum; Carbene ligands; Phosphane 

ligands; Carbonyl ligands; 


P - 0 1 5 5 

A MuLtiChroMoPhoriC dendriMer for 

intrAMoLeCuLAr enerGy uP-ConverSion 

G. BerGAMini 1 , P. Ceroni 1 , C. StefAno 2 

1 University of Bologna, Chemistry “G. Ciamician”, Bologna, 

Italy 

2 University of Firenze, Chemistry “Ugo Schiff”, Firenze, Italy 

Dendrimers are repeatedly branched macromolecules with 

a well-defined and tree-like structure. They are ideal scaffolds to 

arrange multiple and different functional units within a nanobject 

according to a predetermined pattern. Several examples of 

dendrimers containing photoactive units have been investigated 

in the last decade and photoinduced electron and energy transfer 

processes have been investigated for sensing with signal 

amplification and light-harvesting purposes [1] . 

In the present work, a dendritic structure consisting of a 

[Ru(bpy) ] 3 2+ (bpy=2,2'-bipyridine) complex as a core and four 

diphenylanthracene units (DPA) at the periphery. The blue 

emission of DPA chromophores is observed upon green-laser light 

excitation at 532 nm of the Ru(II) core both in fluid CH CN 3 

solution and in C H OH/CH Cl 1:1 (v/v) rigid matrix at 77 K. 2 5 2 2 [2] 

To the best of our knowledge, dendrimers have never been used 

for this application, apart from one example reported by us, [3] 

based on chromophores absorbing and emitting in the UV spectral 

region. 

This result is very important in view of a potential 

application of energy up-conversion in solid state device for 

wavelength shifting in spectroscopy. [4] By proper choice of the 

chromophoric units and based on previuosly reported examples 

in fluid solution, these dendritic systems may be applied to the 

sensitization of photovoltaics by harvesting the red and near 

infrared region of the solar spectrum. 

references: 

1. a) G. Bergamini, E. Marchi, P. Ceroni, Coord. Chem. Rev., 

2011, 255, 2458; 

b) V. Balzani, G. Bergamini, P. Ceroni, E. Marchi, 

New J. Chem., 2011, 35, 1944. 

2. G. Bergamini, P. Ceroni, P. Fabbrizi, S. Cicchi, Chem. 

Commun., 2011, 47, 12780. 

3. G. Bergamini, P. Ceroni, M. Maestri, V. Balzani, 

S.-K. Lee, F. Vögtle, Photochem. Photobiol. Sci., 2004, 3, 

898. 

4. For a recent review, see: T. N. Singh-Rachford, 

F. N. Castellano, Coord. Chem. Rev., 2010, 254, 2560. 

Keywords: Dendrimers; Ruthenium; Supramolecular 

chemistry; Energy transfer; Photophysics; 



s939 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 5 6 

SyntheSiS And ChArACterizAtion of 

orGAnozinK LiGAted d10 MetAL CoMPoundS 

M. MoLon 1 , C. GeMeL 1 , r.A. fiSCher 1 

1 Ruhr-University Bochum, Inorganic Chemistry II 

Organometallics and Materials Chemsiry, Bochum, Germany 

Quite recently a new family of mononuclear transition metal 

complexes containing organozinc ligands has been discovered by 

reaction of GaCp* ligated compounds [M(GaCp*) ] (M=Mo, Ru, 

n 

Rh, Ni, Pd and Pt) with ZnMe , which affords zinc rich complexes 

2 

[M(ZnR) ] (R = Cp*, Me) in selective Ga/Zn and Cp*/Me 

2n 

exchange reactions. 1 These highly coordinated complexes 

represent a new class of compounds bridging metal rich molecules 

and intermetallic phases. Also oligonuclear compounds 

like [{Mo(CO) } (Zn) (µ -ZnCp*) ] 4 4 6 2 4 2 , [(RhCp*) (Zn) (ZnCl) µ - 

6 6 12 6 

Cl][RhCp* ] 2 3 and [Pd Zn Ga (Cp*) (Me) ] 2 8-n n 5 3 4 (n = 2, 4) can be 

obtained by similar reactions. In this poster we present the 

synthetic pathway for this type of zinc ligated compounds by 

treating heteroleptic transition metal complexes such as 

[(C H ) Ni (µ -ECp*) ] (E = Ga, Al) or [Ni(GaCp*)(PMe ) ] with 

2 4 2 2 2 3 3 3 

a proper amount of ZnMe . 2 5 finally giving the first 

dinuclear and paramagnetic as well as several mononuclear 

compounds like [(Cp*Ni)µ -(ZnMe) Ni(ZnCp*) (ZnMe) ] or 

2 4 2 2 

[Ni(ZnCp*)(ZnMe)(PMe ) ], respectively. The extension of this 

3 3 

concept, a comparison of the coordination geometries with 

Continuous Shape Measures (CShM), as well as theoretical 

analysis on the DFT level of theory will be discussed. 

references: 

1. T. Cadenbach, T. Bollermann, C. Gemel, M. Tombul, 

I. Fernandez, M. van Hopffgarten, G. Frenking, 

R. A. Fischer, J. Am. Chem. Soc. 2009, 131, 16063-16077. 

2. T. Cadenbach, C. Gemel, R. A. Fischer, Angew. Chem. Int. 

Ed. 2008, 47, 9146-9149. 

3. M. Molon, T. Cadenbach, T. Bollermann, C. Gemel, 

R. A. Fischer, Chem. Commun. 2010, 46, 5677-5679. 

4. T. Bollermann, M. Molon, C. Gemel, K. Freitag, 

R. W. Seidel, M. von Hopffgarten, P. Jerabek, G. Frenking, 

R. A. Fischer, Chemistry – A European Journal 2012, 18, 

4909-4915. 

5. M. Molon, T. Bollermann, C. Gemel, J. Schaumann, 

R. A. Fischer, Dalton Trans. 2011, 40, 10769-10774. 

Keywords: organozinc; organometallic; cluster compound; 

zinc; 


P - 0 1 5 7 

CoordinAtion of oLiGodentAte n-donor 

LiGAndS to Li+ 

K. PoKorny 1 , M. SChMeiSSer 1 , A. zAhL 1 , 

A. SCheurer 1 , J. KorzeKwA 1 , r. PuChtA 1 , 




Ionic liquids (IL) are of great interest in current research. 

Due to their tunable properties, IL can be used in a wide range of 

applications. Our research interest is to study chemical reactions 

in IL in comparison with conventional molecular organic solvents. 

Therefore, we investigated the coordination behaviour of N-donor 

ligands to Li + and Na + ions. [1][2] 

The coordination of the tridentate N-donor ligand 2,2':6',2"- 

-terpyridine (terpy) to Li + ions in nitromethane and the ionic 

liquids ([EMIM][NTf ] and [EMIM][EtSO ]) was investigated 

2 4 

using 7Li NMR spectroscopy. To determine the coordination 

numbers in solution, the chemical shift of the 7Li signal was 

studied as a function of the added ligand concentration in 

reference to an external standard. The resulting plots indicate a 

terpy to Li + ratio of 2:1. The results also show a clear curvature 

of the graphs which indicates an equilibrium between the 

coordinated and free lithium ions in solution. Based on the 

difference between the observed NMR data and the best linear fit, 

the overall stability constant b for the complexation of Li 2 + ions 

by terpy in nitromethane was found to be in the range of 106 M-2 . 

Temperature dependent 7Li NMR spectroscopy was carried out to 

obtain the enthalpy (DH°) and entropy (DS°) of the reaction. 

Furthermore, the reaction between 2,6-bis(5-tert-butyl-1H- 

-pyrazol-3-yl)pyridine and Li + ions was studied. This tridentate 

ligand shows remarkable coordination behaviour. Depending on 

the ligand to Li + ratio different species were detected in the 7Li spectrum. 

references: 

1. M. Schmeisser, A. Zahl, A. Scheurer, R. Puchta, 

R. van Eldik, Z. Naturforsch. 2010, 65b, 405–413 

2. M. Schmeisser, F. Heinemann, P. Illner, R. Puchta, 

A. Zahl, R. van Eldik, Inorg. Chem. 2011, 50, 6685–6695 

Keywords: N-donor ligands; Ionic liquids; coordination 

chemistry; nmr titration; 



s940 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 5 8 

noveL PLAtinuM(ii) CheLAte CoMPLexeS 

viA A Pyridine-SuLfoxide BASed AnChorinG 

frAMeworK: froM MonoMeriC SPeCieS to 

trinuCLeAr triPodAL LiGAnd derivAtiveS 

M. r. PLutino 1 , A. BArAttuCCi 2 , C. fAGGi 3 , 

P. BonACCorSi 2 , L. MonSu SCoLAro 4 , 

M. C. AverSA 2 

1 CNR, Institute for the Study of Nanostructured Materials, 

Messina, Italy 

2 Univ. Messina, Department of Organic and Biological 

Chemistry, Messina, Italy 

3 Univ. Florence, Interdepartmental Centre of 

Crystallographylogical Chemistry, Florence, Italy 

4 Univ. Messina, Department of Inorganic Chemistry Analytical 

Chemistry and Physical Chemistry, Messina, Italy 

The past decade has seen remarkable progress in the 

development of new materials based on transition-metal ions and 

organic ligands, often termed as coordination polymers (networks) 

or metal organic frameworks (MOFs). Within this framework, the 

employment of square-planar platinum(II) complexes have 

attracted great interest due to their potential applications as 

photocatalysts and in a variety of photonic devices, such as 

light-emitting diodes, photovoltaic cells, and chemosensors, or 

anticancer agents.Here we will report the new synthesis of a 

tripodal ligand 1,3,5-tris{[1-(2-pyridinyl)-ethenylsulfinyl]- 

-methyl}-2,4,6-triethylbenzene (C or nonsymm), containing 

3symm 

both a sulfinyl and a pyridine moiety, and its utilization in 

the coordination of square planar Pt(II) complexes, such as 

cis-[PtMe (Me SO) ], and trans-[PtMeCl(Me SO) ]. Nice crystals 

2 2 2 2 2 

of the C racemic mixture have been obtained and the crystal 

3 

structure of the tripodal species has been solved by means of 

X-ray diffrattometry. With the aim of studying the coordination 

ability towards platinum(II) complexes of the tripodal k-S, k'-N 

type chelating ligand, we have thought worthwhile to synthesize 

a model compound, [1-(2-pyridinyl)-ethenylsulfinyl]-benzene 

ligand, bringing only a sulfoxide and a pyridinyl anchoring 

moiety, and to explore, as a preliminary study, its behavior in 

coordination chemistry. All the prepared species have been fully 

characterized by NMR spectroscopy from the connectivities in 

2D-COSY and 13C, 1H-HSQC experiments, as also predicted by 

molecular mechanics calculation, and by phase-sensitive NOESY 

spectra. 

Keywords: tripodal ligand; platinum(II) complexes; 

supramolecular species; coordination compounds; 


P - 0 1 5 9 

PhASe diAGrAMS Are A Key for new ideAS in 

CheMiStry: SySteM Ce-AL 

v. KoBer 1 

1 Ural Federal University, physical- technical, Oranienburg, 

Germany 

Email: kobervi@gmail.com 

In the system Ce - Al are five intermetallic compounds 

determined with the next thermal stability (t,C): Ce3Al 11 - 1235, 

CeAl 3 - 1135, CeAl 2 - 1480, CeAl - 845, Ce3Al - 655 C /1/. The 

number of compounds can be defined as a result at one after 

another filling 3p shells of the aluminium atom-acceptors with 

electrons from the conducting zone of the cerium atom-donors to 

formation virtual complete 3s2 3p6 electron configurations. But 

every new formed formal electron ensemble redistribute itself by 

take into account of the energy minimum. Therefore every 

electron configuration characterized its stability and its own 

number of bonding orbitals. The win of energy by the electrons 

transitions from the conducting zone of the cerium atom-donors 

to the aluminium atom-acceptors with formation virtual stable 

bonding configurations define the energy of the alloy formation 

and the differences of the IMC transformation temperatures. 

Decrease the 3s1 3p3 electron configuration stability for the IMC 

Ce3 Al 11 at the filling the shielding spherical 3s orbitals of the 

aluminium atom-acceptors to 3s2 3p3 electron configuration 

conditioned more low transformation temperature for the 

compound CeAl 3 - 1135 C. Formation from the 3s2 3p4 formal 

bonding configuration an 3s1(3p3d)5 stable electron ensemble 

with increase the spin multiplicity and number of bonding 

configurations define increase the melting temperature of the 

Laves phase CeAl 2 to 1480 C. The further filling the free 

3p orbitals of the aluminium atom-acceptors with electrons to 

formation 3s2 3p5 and 3s2 3p6 electron configurations define the 

electrons ensembles energy increasing and decreasing of 

the CeAl and Ce3Al IMC thermal stability to 845 and 655 C 

correspondingly. 

references: 

1. Ljakishev N.P., Constitution of Binary Metallic Systems, 

Reference Books, M., 1996, V. 1, P. 127–128. 



s941 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 6 0 

hiGhLy SeLeCtive Pd-CAtALyzed 

heCK CouPLinG reACtionS uSinG A 

PhoSPhoruS-nitroGen ContAininG LiGAnd 

M. JoShAGhAni 1 , S. JAMALi 2 , e. rAfiee 1 , A. AtAee 1 , 

S. nAdri 1 


2 Sharif University of Technology, Chemistry, Tehran, Iran 

Phosphorus–nitrogen containing ligands have particular use 

in catalysis where it is necessary for a part of ligand to dissociate 

and allow an organic fragment to coordinate and undergo 

transformations. [1–2] They have interesting dual characteristics; 

they coordinate metal ions by phosphorous and/or nitrogen sites 

depend on the hard-soft nature of the metal ion and the same time, 

the nitrogen atoms act as base whenever a base is required in the 

reaction. Among them, 2,6-bis(diphenylphosphino)pyridine 

(bdppp, (Ph P) Py) is an unique P-N ligand with rigid and 

2 2 

relatively large bite angle. This rigidity governs the P...N...P bite 

distance so that binding a metal to each donor site places the metal 

ions in very close proximity (about 2.6-2.8 ?). In the other hand, 

the rigidity of phosphine ligand is very important in selective 

Pd/phosphine-catalyzed cross-coupling reactions. Therefore, in 

continuation of our previous study on cross-coupling reactions, [3–4] 

we encourage to study the Pd-catalyzed heck coupling reactions. 

A series of aryl bromides containing electron withdrawing 

and/or electron donating groups were sufficiently used for 

aryaltion of styrene. 

references: 

1. A. Zapf, M. Beller, Chem. Commun. 2005, 431. 

2. P. Bhattacharyya, J.D. Woollins, Polyhedron 14, 1995, 

3367. 

3. Sh. Nadri, E. Azadi, A. Ataei, M. Joshaghani, E. Rafiee, 

J. Organomet. Chem. 2011, 696, 2966-2970. 

4. Sh. Nadri, M. Joshaghani, E. Rafiee, Organometallics 

2009, 28, 6281–6287. 

Keywords: Heck Reaction; Cross Coupling; Palladiujm; 

Phosphine; 


P - 0 1 6 1 

CyCLen And CroSS-BridGed CyCLen 

derivAtiveS trAnS-n-diSuBStituted for 

CoPPer(ii) CoMPLexAtion 

C. v. eSteveS 1 , L. M. P. LiMA 1 , P. MAteuS 1 , 

r. deLGAdo 1 

1 Instituto de Tecnologia Química e Biológica Universidade 

Nova de Lisboa, Chemistry, Oeiras, Portugal 

Tetraazamacrocycles such as cyclen (1,4,7,10-tetraazacyclo - 

dodecane) and their N-functionalized derivatives continue to 

interest many scientists owing to their ability to form very 

stable metal complexes. [1] In particular, cross-bridged 

tetraazacycloalkanes are proton sponges and their increased 

structural rigidity lead to kinetically inert metal complexes, making 

them interesting candidates for applications such as positron 

emission tomography (PET) (using 64Cu-labelled macrocycles) or 

radiotherapy (with 67Cu-labelled macrocycles). [2, 3] 

In this work two different types of cyclen derivatives were 

synthesized, with or without a cross-bridge, exploring different 

methylphenol-based pendant arms in search for enhanced 

copper(II) coordination ability. The cross-bridged cyclen 

derivatives were studied comparatively with the non cross-bridged 

ones regarding their acid-base and complexation behaviour. 

Copper(II) complexes were studied in solution and in solid state 

by a range of potentiometric, spectroscopic and crystallographic 

techniques. 

Acknowledgements: The authors acknowledge Fundacio para a 

Ciencia e a Tecnologia with co-participation of the European 

Community fund FEDER, POCI, QREN and COMPETE, 

for the financial support under Project PTDC/QUI/67175/2006. 

The authors also acknowledge P. Brand and V. Félix for the 

crystal structures determination. 

references: 

1. Delgado, R.; Félix, V.; Lima, L. M. P.; Price, D. W.; 

Dalton Trans. 2007, 2734-2745. 

2. Bernier, N.; Costa, J.; Delgado, R.; Félix, V.; Royal, G.; 

Tripier, R.; Dalton Trans. 2011, 40, 4514-4526. 

3. Wadas, T. J.; Wong, E. H; Weisman, G. R.; Anderson, C. J.; 

Chem. Rev. 2010, 110, 2858-2902. 

Keywords: Macrocyclic ligands; Cyclen; Cross-bridged 

cyclen; Copper Complexes; 



s942 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 6 2 

PoLyoxoMetALAteS MAde of GoLd 

y. xiAnG 1 , n. v. izArovA 1 , u. Kortz 1 



In recent years there has been an increasing interest in the 

self-assembly of polynuclear metal-oxo complexes of noble 

metals (e.g. Pt, Pd, Au), leading to the class of noble metal-based 

polyoxometalates (POMs). 1 Such discrete species have a great 

potential as models for the active intermediates of H O /O -based 

2 2 2 

oxidations catalyzed by noble metal-containing materials, 2 as well 

as catalysts and precatalysts for different, industrially relevant 

processes. 

Herein we report on two heteropolyaurates, 

[AuIII 4O4 (AsVO ) ] 4 4 8- 1c and [AuIII 4O4 (SeIVO ) ] 3 4 4- , which represent 

the only examples of POMs made of gold to date. Both POMs 

exhibit a tetrameric structure with four square-planar coordinated 

AuIII ions bridged by four oxo ligands and four arsenate or selenite 

capping groups, respectively. The polyanions were crystallized as 

hydrated alkali metal salts and characterized by single-crystal 

XRD, elemental analysis, TGA, IR as well as ESI-MS 

spectrometry. The aqueous solution stability of the selenite-based 

POM was investigated by 77Se NMR spectroscopy. The facile 

synthetic procedure for the preparation of these polyanions based 

on the condensation of in-situ formed [AuIII (OH) ] 4 - offers a 

convenient way to fully inorganic, discrete gold-oxo complexes. 

references: 

1. a) M. Pley, M. S. Wickleder, Angew. Chem. Int. Ed. 2004, 

43, 4168; 

b) E. V. Chubarova, M. H. Dickman, B. Keita, L. Nadjo, 

F. Miserque, M. Mifsud, I. Arends, U. Kortz, Angew. 

Chem. Int. Ed., 2008, 47, 9542; 

c) N. V. Izarova, N. Vankova, T. Heine, R. N. Biboum, 

B. Keita, L. Nadjo, U. Kortz, Angew. Chem. Int. Ed. 

2010, 49, 1886. 

2. a) P. Putaj, F. Lefebvre, Coord. Chem. Rev. 2011, 255, 

1642; 

b) I. A. Weinstock, A. Müller, Isr. J. Chem. 2011, 51, 176; 

d) J. C. Goloboy, W. G. Klemperer, Angew. Chem. Int. Ed. 

2009, 48, 3562. 

Keywords: Polyoxometalate; gold; cluster compounds; Mass 

spectrometry; 

P - 0 1 6 3 

new Boron-ContAininG AMino ACidS derived 

froM PoLyhedrAL Boron hydrideS 

i. SivAev 1 , M. zAKhArovA 1 , M. StoGniy 1 , 

M. BerzinA 1 , J. LASKovA 1 , A. PriKAznov 1 , 

i. LoBAnovA 1 , A. SeMioShKin 1 , v. BreGAdze 1 

1 A.N.Nesmeyanov Institute of Organoelement Compounds, 

Laboratory of Organoaluminium- and Boron Compounds, 

Moscow, Russia 

Boron neutron capture therapy (BNCT) of cancer is a binary 

method for cancer treatment based on selective accumulation of 

the non-radioactive 10B isotope in the cancer cells followed by 

their treatment with a flux of thermal neutrons [1] . One of the 

main requirements for BNCT is the availability of boron 

compounds that can be accumulated selectively in the tumor tissue 

at the concentrations sufficient for the intracellular nuclear 

reaction. In particular, amino acids and peptides can be used as 

molecules carrying out the targeted delivery of boron to a tumor. 

We prepared a wide range of new boron-containing amino acids 

based on different polyhedral boron hydrides. Two different 

approaches were used. The first one includes alkylation of sulfur 

derivatives of carboranes. The closo-carborane based amino acids 

1-HOOCCH(NH 2 )(CH 2 ) n S-1,2-C 2 B 10 H 11 


were prepared by 

alkylation of 1-mercapto-ortho-carborane with the corresponding 

ω-alkyl diethyl N-acetamidomalonates followed by acidic 

hydrolysis and decarboxylation. The treatment of the 

closo-carborane based amino acids with CsF in refluxing ethanol 

resulted in the nido-carborane based aminoacids 

[7-HOOCCH(NH 2 )-(CH 2 ) n S-7,8-C 2 B 9 H 11 ] - . Another series of the 

nido-carborane based amino acids 9-HOOCCH(NH 2 )(CH 2 ) n SMe- 

-7,8-C 2 B 9 H 11 were prepared by the alkylation of [9-MeS-7,8- 

-C 2 B 9 H 11 ] - . The second approach is based on disclosure of the 

cyclic oxonium derivatives of polyhedral boron hydride anions 

(BHA=closo-decaborate [B 10 H 10 ] 2- ,closo-dodecaborate [B 12 H 12 ] 2- , 

cobalt bis(dicarbollide) [3,3'-Co(1,2-C 2 B 9 H 11 ) 2 ] - ) with terminal 

nucleophilic centres of natural amino acids, such 

as tyrosine, serine, cysteine, etc. Using this approach a 

series of boron-containing tyrosines [BHA-(OCH 2 CH 2 ) 2 O- 

-4-C 6 H 4 CH 2 CH(NH 2 )COOH] 2/1- and [BHA-O(CH 2 ) 4 O-4- 

C 6 H 4 CH 2 CH(NH 2 )COOH] 2- were prepared [2, 3] . 

Acknowledgement: This work was supported by Russian 

Foundation for Basic Research (10-03-00698 and 12-03- 

00772). 

references: 

1. V.I. Bregadze, I.B. Sivaev, S.A. Glazun, Anti-Cancer 

Agents in Med. Chem., 2006, 6, 75-109. 

2. I.A. Lobanova, M.Ya. Berzina, I.B. Sivaev, P.V. Petrovskii, 

V.I. Bregadze, Russ. Chem. Bull., 2010, 59, 2302-2308. 

3. A.V. Prikaznov, Yu.N. Las’kova, A.A. Semioshkin, I.B. 

Sivaev, A.V. Kisin, V.I. Bregadze, Russ. Chem. Bull., 

2011, 60, 2502-2506. 

Keywords: Boranes; Carboranes; Amino acids; Synthetic 

methods; 



s943 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 6 4 

noveL SyntheSiS route for the AttAChMent 

of BioLoGiCAL GrouPS to PhotoACtive 

rutheniuM(ii) PoLyPyridine CoMPLexeS 

n. zABArSKA 1 , f. heineMAnn 2 , S. rAu 1 

1 Inorganic Chemistry I, Materials and Catalysis, Ulm, 

Germany 

2 Inorganic Chemistry, Chemistry and Pharmacy, Erlangen, 

Germany 

Ruthenium(II) polypyridine complexes might be promising 

therapeutics in the photodynamic therapy (PDT) due to their 

photophysical properties allowing the formation of reactive 

oxygen species (ROS), stability in living organisms and 

convenient synthetic access. [1, 2] Additionally, they are able to be 

taken up in cells, which was shown in the literature. [3] To provide 

a targeted cellular uptake predominantly in cancer cells, 

biocompatible groups, i.e. sugar, have been introduced into the 

periphery of ruthenium(II) polypyridine complexes. [4, 5] 

This work presents a convenient method to connect 

ruthenium(II) polypyridine complexes with biocompatible groups 

within the CuAAC (copper(I)-catalyzed azide-alkyne 

cycloaddition) click reaction. 

Hence Ru(bpy * ) Cl was substituted with an alkyne bearing 

2 2 

bipyridine forming the novel complex bis(bpy*)-4-ethynyl-2,2'- 

-bipyridine-ruthenium(II)[PF ] , which was fully characterized 

6 2 

including an x-ray structure. Furthermore the CuAAC click 

reaction was first performed with benzyl azide composing 

bis(bpy*)-4-(1-benzyl-1H-1,2,3-triazol-4-yl)-2,2'-bipyridine- 

-ruthenium(II)[PF ] . CuAAC was also successfully applied 

6 2 

to attach a glucose azide onto the above mentioned 

bis(bpy*)-4-ethynyl-2,2'-bipyridine-ruthenium(II)[PF ] 6 2 

producing bis(bpy*)-4-[(2R,3R,4S,5R,6R)-2-(acetoxy-methyl)-6- 

-(2-azidoethoxy)tetrahydro-2H-pyran-3,4,5-triyl-triacetate]-2,2'- 

-bipyridine-ruthenium(II)[PF ] . 6 2 

To the best of our knowledge this is the first reported 

CuAAC click reaction performed on a ruthenium(II) polypyridine. 

This reaction route opens an attractive way to attach any 

biocompatible group onto appropriate ruthenium(II) polypyridine 

complexes. 

references: 

1. W. Han Ang, P. J. Dyson, European Journal of Inorganic 

Chemistry 2006, 2006, 4003-4018. 

2. M. J. Clarke, Coordination Chemistry Reviews 2003, 236, 

209-233. 

3. C. A. Puckett, J. K. Barton, Journal of the American 

Chemical Society 2006, 129, 46-47. 

4. M. Gottschaldt, U. S. Schubert, S. Rau, S. Yano, J. G. Vos, 

T. Kroll, J. Clement, I. Hilger, European Journal of 

Chemical Biology 2010, 11, 649-652. 

5. S. Rau, S. Zheng, Current Topics in Medicinal Chemistry 

2012, 12, 1-13. 

Keywords: click chemistry; photochemistry; Ruthenium; 


P - 0 1 6 5 

A CheMiCALLy unLoCKed BinAry MoLeCuLAr 

SwitCh 

G. Chen 1 , J. SArriS 1 , n. wArdLe 1 , S. w. A. BLiGh 1 , 

n. ChAtterton 1 

1 London Metropolitan University, School of Human Sciences, 

London, United Kingdom 

The sensing of chemical inputs using the modulation 

lanthanide luminescence as an output was first achieved by De 

Silva [1] and has been followed by extensive work in this area aimed 

at producing practicable devices. The advantages of lanthanide 

chelate luminescence in this area are well known, constituting in 

many ways the optimum light-based sensors. They have been 

proven at analyte concentrations as low as 10-15 M due to their 

high signal to noise ratio. [2] The simplest chemical input is that of 

H + ion concentration (or pH) and this is one probably the most 

widely utilised to date in such molecular devices. [3] This 

presentation will describes a terbium macrocycle that displays 

extremely sensitive pH-dependent luminescence, conditional on 

its previous pH. 

The novel organic ligand reported here is formed by the 

conjugation of the well-known macrocyclic moiety DO3A to a 

phthalimide chromophore via a propyl-bridge. In this work we 

found that a Tb3+ complex of the initial ligand can be activated by 

changes in pH and this active form displays luminescence that can 

be reversibly switched on and off by further changes in pH. 

The active complex is highly luminescent with a quantum 

yield of 47% and an extremely long luminescence lifetime of 

2.26 ms. In addition, it acts an extremely sensitive, reversible, H + 

sensor or switch between pH values of 2 and 4: the complex loses 

60% of its luminescence within one pH unit. 

references: 

1. A.P.de Silva, H.Q.N Gunaratne, T. E. Rice, Angew. Chem. 

Int. Ed. Engl., 35, 2116 (1996). 

2. K. N. Raymond, S. Petoud, S. M. Cohen, J. Xu, US Patent 

2002/0128451 A1 

3. S. Faulkner, B. P. Burton-Pye, Chem. Commun., 2051 

(2006); A. P. de Silva, Chem. Asian J., 6, 750 (2011). 

Keywords: Terbium Complexes; Luminescence; Molecular 

Switches; Molecular Logic Gates; 



s944 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 6 6 

KinetiC StudieS of Ln(iii) CoMPLexeS 

of dotP-LiKe MACroCyCLiC LiGAndS 

r. SevCiK 1 , J. vAneK 2 , P. LuBAL 2 , z. KotKovA 3 , 

J. KoteK 3 , P. herMAnn 3 

1 Masaryk University Faculty of Science, Department of 

Chemistry, Brno, Czech Republic 


Chemistry/CEITEC, Brno, Czech Republic 

3 Charles University, Department of Inorganic Chemistry, 


The Ln(III) complexes of macrocyclic ligands (mostly 

DOTA/DOTP derivatives) are often employed in medicinal 

chemistry as MRI agents and luminescent probes. For any 

biomedical applications, these metal complexes should exhibit a 

high thermodynamic stability as well as kinetic inertness under 

physiological conditions and therefore, knowledge of their 

thermodynamic/kinetic properties (e.g. dissociation rate constants 

for an estimation of kinetic inertness) is important to evaluate their 

use in these applications. 

In this work, the formation/acid-assisted dissociation 

kinetics of chosen Ln(III) (Ln = Ce, Eu) complexes with 

DOTP-like macrocyclic ligands (H dotp = 1, 4, 7, 10 – tetraaza - 

8 

cyclododecane – 1, 4, 7, 10 – tetrakis(methylphospho nic acid) 

and their analogs: H dotp 4 OEt = tetrakis(monoethylester), 

H dotp 4 H = tetrakis(methylphosphinate), H dotp 4 Ph =tetrakis[methyl 

(phenyl)phosphinate) was studied using molecular absorption 

spectroscopy in UV region and time-resolved laser-induced 

fluorescence spectroscopy (TRLIFS). The impact of the 

coordination number of Ln(III) ion (Ce vs. Eu) and the 

softness/hardness of pendant arms of studied macrocyclic ligands 

on kinetic properties of Ln(III) complexes was investigated in 

order to optimize the structural design for synthesis of bifunctional 

chelators for potential medical applications. 

Acknowledgements: This work was done in the framework of 

EU CM1006 program. We thank to Ministry of Education of the 

Czech Republic (grants ME09065, MSM0021620857, CEITEC 

CZ.1.05/1.1.0/02.0068) for financial support. 

Keywords: Macrocycles; Lanthanides; Kinetics; 


P - 0 1 6 7 

PhotoCAtALytiC wAter reduCtion with 

rutheniuM PoLyPyridyL ChroMoPhoreS 

r. StAehLe 1 , M. fiLiPoviC 2 , S. LoSSe 3 , J. G. voS 4 , 

i. ivAnoviC-BurMAzoviC 2 , S. rAu 1 


Germany 

2 Bioinorganic Chemistry, Chemistry and Pharmacy, Erlangen, 

Germany 

3 Leibniz Institute for Catalysis, Applied Homogeneous 

Catalysis, Rostock, Germany 

4 Inorganic Chemistry, School of Chemical Sciences, Dublin, 

Ireland 

The splitting of water by solar energy, using ruthenium 

polypyridyl complexes can be divided into two half reactions; (i) 

water oxidation, to yield O and (ii) water reduction, producing 

2 

H , an alternative fuel. Systems for both separated reactions are 

2 

well-known using a multiplicity of different dyes and sacrificial 

redox reagents. For the light driven overall water splitting both 

reactions must have the ability to work parallel, i.e. H evolution 

2 

in the presence of O . This could not be obtained till now. 

2 

A supramolecular photocatalytic system for the water reduction 

consisting of a ruthenium complex with a 4,4'-dicyano-2,2'- 

-bipyridine ligand as photosensitizer has been studied. 

Surprisingly this system shows a superior catalytic activity 

under aerobic than under anaerobic conditions. The mechanism 

of this reaction was studied in detail whereby a conversion of the 

nitrile groups and efficient photocatalytic consumption of O2 could be observed. Based on these results we synthesized and 

characterized the related ruthenium complex with a 4,7-dicyano- 

-1,10-phenanthroline and a 4-cyano-1,10-phenanthroline ligand 

for comparison. 

references: 

1. S. Losse, H. Görls, R. Groarke, J.G. Vos, S. Rau, 

Eur. J. Inorg.Chem. 2008, 28, 4448-4452. 

2. S. Losse, J.G. Vos, S. Rau, Coord. Chem. Rev. 2010, 254, 

2492-2504. 

Keywords: Ruthenium; Water splitting; Homogeneous 

catalysis; Cobalt; 



s945 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 6 8 

SuBStituted fiSCher CArBene CoMPLexeS of 

tunGSten(0) 

M. LAndMAn 1 , r. PretoriuS 1 


Africa 

Fischer carbenes have a wide range of applications in 

organic synthesis. It is also known that modification of the ligand 

sphere will alter the reactivity of these complexes. [1, 2] These 

complexes are, however, not known to be metathesis active on 

their own, and require activation or co-catalysts. [3] Tungsten, 

however, is described as a metathesis-active metal, and examples 

of complexes which are useful for olefin metathesis and 

polymerisation of unsaturated compounds are known. [4] 

Phosphine and amino derivatives of tungsten Fischer 

carbenes were thus synthesised in order to study the effects of 

these changes on the catalytic activity. Theoretical studies of these 

complexes were also done to investigate the correlation between 

the distribution of the HOMO and LUMO with the activity of the 

molecule. Furyl- or thienyl-ethoxy tungsten Fischer carbenes were 

synthesised as the starting material and from there modifications 

to the ligand sphere were made. PPh and DPPE were used as the 

3 

mono and diphosphine ligands respectively. Both the cis and trans 

isomers were isolated for P(Ph) , while only the mer isomer was 

3 

isolated for the DPPE derivative. Aminolysis products of the 

complexes were also synthesised by reacting the ethoxy carbene 

with cyclohexylamine. 

For further comparison, an ethylene diamine aminolysis 

chelate was synthesised to analyse the combined effect of nitrogen 

on the ligand sphere and the carbene. Preliminary catalytic studies 

were done on the selected products. 

references: 

1. E.W. Reinheimer, K. A. Kantardjieff, S.R. Herron, 

C.G. Tisserat, J.A. Casalnuovo, J. Chem. Crys. 2003, 33, 

503–514 

2. A. Arrieta, F.P. Cossio, I. Fernández, M. Gómez-Gallego, 

B. Lecea, M.J. Mancheno, M.A. Sierra, J. Am. Chem. Soc. 

2000, 122, 11509–11510 

3. K. H. Dötz, Angew. Chem. Int. Ed. Engl. 1984, 23, 587–8 

4. S. Kotha, M.K. Dipak, Tetrahedron 2012, 68, 397–421 

Keywords: Carbenes; P ligand; Tungsten; 


P - 0 1 6 9 

A weLL-Known reACtion in A new MediuM: 

the CLASSiC “Brown rinG” reACtion in An 

ioniC Liquid 

S. BeGeL 1 , f. heineMAnn 1 , G. StoPA 2 , G. StoCheL 2 , 




2 Jagiellonian University, Chemistry, Krakow, Poland 

The properties of ionic liquids (ILs) and their 

advantages/disadvantages are presently discussed extensively in 

terms of different kinds of possible applications. [1] It is 

well-known that ILs in general greatly improve the solubility of 

gases, which could have an important effect on their activation. 

However, there is no sufficient information presently available on 

the role of the ILs in such reactions. 

The present goal of our work was to study the activation of 

small molecules, such as NO, by transition metal complexes in 

ILs. The reaction of nitric oxide (NO) with transition metal ions 

plays an important role in environmental and biological 

processes. [2] 

We report here detailed mechanistic studies on the reversible 

binding of NO to FeCl dissolved in the ionic liquid [emim][dca], 

2 

1-ethyl-3-methylimidazolium dicyanamide, as solvent. [3] The 

kinetic data and activation parameters were measured using a laser 

flash photolysis technique at ambient and high pressure for the 

first time in an ionic liquid. These data suggest that the reaction 

follows a limiting dissociative (D) ligand substitution mechanism 

in contrast to occurrences in aqueous solution, where an 

interchange dissociative (I ) ligand substitution mechanism was 

d 

found. The observed difference apparently arises from the 

participation of the ionic liquid anion as N-donor ligand, as 

verified by X-ray crystallography. In addition, Mössbauer and 

EPR spectra were recorded for the reaction product formed in the 

ionic liquid, and the parameters closely resemble those of the 

{FeNO} 7 unit in other well-characterized nitrosyl complexes. 

references: 

1. Plechkova, N. V.; Seddon, K. R. Chem. Soc. Rev. 2008, 

37, 123. 

2. a) Moreau, M.; Lindermayr, C.; Durner, J.; Klessig, 

D. F. Physiol. Plant. 2010, 138, 372-383. 

b) Pena-Altamira, E.; Petazzi, P.; Contestabile, A. Curr. 

Pharm. Des. 2010, 16, 440-450. 

3. Begel, S.; Heinemann, F. W.; Stopa, G.; Stochel, G.; 

van Eldik, R. Inorg. Chem. 2011, 50, 3946-3958. 

Keywords: ionic liquids; kinetics; nitrogen oxides; transition 

metals; UV/Vis spectroscopy; 



s946 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 7 0 

diMAnGAneSe dodeCACArBonyL And itS LiGht 

triGGered Co reLeASe froM nAnofiBrouS 

MAteriALS 

C. BohLender 1 , S. GLäSer 1 , A. SChiLLer 1 


Dimanganese dodecacarbonyl (Mn (CO) ) can release 

2 10 

biologically relevant carbon monoxide during irradiation with 

light. [1,2] 

Here, Mn (CO) has been non-covalently embedded into a 

2 10 

poly(L-lactide-co-D/L-lactide) matrix via the electrospinning 

process forming a hybrid non-woven. [3] The incorporation enables 

water-insoluble Mn (CO) to become accessible to the aqueous 

2 10 

phase. Furthermore, degradations products from the irradiation 

process will be retained in the polymeric matrix and therefore 

[4, 5] 

physiologically toxic side reactions are suppressed. 

The nanofibrous hybrid material was characterized with 

FTIR, 13C-NMR, UV-Vis, BET surface area measurement, DSC 

and SEM. Leaching of the dimanganese dodecacarbonyl from the 

non-woven was negligible as proven by UV-Vis and AAS. The 

cytotoxicity of the fibrous web was determined in a typical cell 

test. Irradiation experiments at 366 nm in water, using the 

myoglobin assay for polymeric materials, showed a significant 

photo-triggered CO release from the non-woven. [4] 

references: 

1. Motterlini, R.; Clark, J. E.; Foresti, R.; Sarathchandra, P.; 

Mann, B. E.; Green, C. J; Circ. Res. 2002, 90, e17-e24. 

2. Wyrwa, R.; Schnabelrauch, M.; Altmann, C.; Schiller, A., 

DE10 2012 004 132.2, patent pending 

3. Greiner, A.; Wendorff, J. H. Angew. Chem. 2007, 119, 

5770-5805. 

4. Bohlender, C.; Wolfram, M.; Goerls, H.; Imhof, W.; 

Menzel, R.; Baumgaertel, A.; Schubert, U. S.; Mueller, U.; 

Frigge, M.; Schnabelrauch, M.; Wyrwa, R.; Schiller, A. 

J. Mater. Chem. 2012, 22, 8785-8792. 

5. Crespy, D; Landfester, K.; Schubert, U.S.; Schiller, A. 

Chem. Commun. 2010, 46, 6651-6662. 

Keywords: Manganese; Drug delivery; Nanostructures; 

Polymers; 


P - 0 1 7 1 

SyntheSiS of “ButterfLy-LiKe” 

PoLyPhoSPhoruS diCAtionS 

[L P ] 2 4 2+ (L = Ph AS, Ph P) 

3 3 

M. donAth 1 , n. Burford 2 , J. J. weiGAnd 1 

1 WWU, Institut für Anorganische und Analytische Chemie, 

Münster, Germany 

2 Dalhousie University, Department of Chemistry, Halifax, 

Canada 

www.agweigand.de 

Several homoatomic cage compounds of Group 15 elements 

are known, and anionic and neutral derivatives of P such as 

4 

[1, 2] 

Zintl-anions and polyphosphanes have been developed. 

However, analogous cationic polyphosphorus derivatives have not 

been reported. [3] Therefore, we developed the synthesis of the 

“butterfly-like” polyphosphorus dication [L P ] 2 4 2+ (L = Ph As) as 3 

tetrachloroaluminate salt [(Ph As) P ][AlCl ] and investigated 

3 2 4 4 2 

the reaction of this cation with different Lewis bases. [4] Thus, we 

could show that the Ph As-moieties can easily be substituted by 

3 

stronger Lewis bases (L = Ph P, NHC) and, therefore, dications 

3 

[L P ] 2 4 2+ can be considered as a [P ] 4 2+ synthon. 

references: 

1. “Phosphides: Solid State Chemistry”: H. G. von Schnering, 

W. Hönle in Encyclopedia of Inorganic Chemistry 

(Ed.: R. E. King), Wiley, Chichester, 1994, pp. 3106. 

2. “Phosphides: Solid State Chemistry”: R. Pöttgen, 

W. Hönle, H. G. von Schnering in Encyclopedia of 

Inorganic Chemistry, Vol. VIII, 2nd ed. (Ed.: R. E. King), 

Wiley, Chichester, 2005, pp. 4255. 

3. I. Krossing in Molecular Clusters of Main Group Elements 

(Eds.: M. Driess, H. Nöth),Wiley-VCH,Weinheim, 2004, 

pp. 209. 

4. M. Donath, E. Conrad, P. Jerabek, G. Frenking, R. Fröhlich, 

N. Burford, J.J.Weigand, Angew. Chem. Int. Ed. 2012, 51, 

pp. 2964. 

Keywords: Cations; Phosphorus; Cage compounds; 

Pnicogens; 



s947 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 7 2 

ConCePtS for the iMPLeMentAtion of 

fuLLereneS in SuPrAMoLeCuLAr 

PhotoCAtALyStS 

C. PehLKen 1 , S. rAu 1 

1 Institute for Inorganic Chemistry I, University Ulm, Ulm, 

Germany 

The photocatalytic splitting of water is an intensively studied 

reaction, since a transformation of the sunlight’s energy into 

chemical energy seems to be possible. Studies on this research 

topic revealed that supramolecular photocatalysts consisting of a 

photocenter, a bridging ligand and a catalytic center are of great 

importance to the development of photoelectric cells. [1] One of the 

most important factors of the activity this photocatalysts is the 

electron transfer from the photocenter to the bridging ligand and 

further the catalytic center. Supramolecular photocatalysts based 

on tetrapyridophenazine as bridging ligand show an ultrafast 

photoinduced electron transfer of one electron. [2] Water reduction 

requires two electrons to form hydrogen. Therefore a bridging 

ligand that is able to store two electrons and submit them to the 

catalytic center should increase the activity of the catalytic 

systems. 

Here, we present the supramolecular interaction between the 

complex [(tbbpy) (tpphz)Ru](PF ) and the multi electron storage 

2 6 2 

C . The occurring π-π-stacking interaction between the tpphz 

60 

ligand and the fullerene was observed via 1H-NMR-, UV/Vis- and 

Emission spectroscopy. 1H-NMR analyses showed different types 

of π-π-interactions between the complex and the C . The presence 

60 

of the fullerene heavily influences the spectroscopic properties of 

the complex. The energy level of the 3MLCT-state of the 

Ruthenium complex gets lowered and its Emission gets quenched. 

Moreover we present a new Bis-tert-butylbipyridine 

Ruthenium-C complex. Thereby the fullerene is functionalized 

60 

with a 2,3-dimethylpyrazino[2,3-f][1,10]phenanthrolyl group [3] 

coordinating to the Ruthenium center. This complex was analyzed 

via UV/Vis- and Emission spectroscopy. The comparison with 

[(tbbpy) (tpphz)Ru](PF ) showed a higher intensity of the 

2 6 2 

1MLCT band and a significant quenching of the Emission of the 

3 MLCT. 

references: 

1. T. E. Mallouk, et al. Acc. Chem. Res. 2009, 42, 1966. 

2. J. Popp, S. Rau, et al. Angew. Chem. Int. Ed. 2010, 49, 3981. 

3. A. Kleineweischede, J. Mattay, Eur. J. Org. Chem. 2006, 

947. 

Keywords: Fullerenes; Ruthenium; Supramolecular Chemistry; 



P - 0 1 7 3 

towArd the deveLoPMent of A SuStAinABLe 

eLeCtroCheMiCAL reduCtion ProCeSS of 

triPhenyLPhoSPhAne oxide 

S. SChuLz 1 , K. o. feLdMAnn 1 , J. J. weiGAnd 1 

1 WWU Münster, Institut für Anorganische und Analytische 



Recycling of tertiary phosphane oxide as wastes from 

industrial processes [1] has become an important aim in the context 

of sustainable use of valuable phosphorus compounds. As an 

example, the production of vitamin A, which key step is a 

Wittig-reaction, produce large quantities of triphenylphosphane 

oxide (TPPO) as waste in stoichiometric amounts. [2] The wasteful 

synthesis of the corresponding phosphanes from valuable 

phosphorus sources is a driving force in the exploration of the 

follow-up chemistry of phosphane oxides for decades. [3] We have 

investigated new routes to phopshane oxide functionalization and 

have found, that they can qunatitatively converted to 

pyrazolylphosphonium triflates by our recently developed 

compound [pyr P ][OTf] (pyr = 1,3-dimethylpyrazole). 3 2 3 [4] The 

obtained pyrazolylphosphonium salts are used in a multitude of 

follow-up reactions to generate usefull compounds. [5] 

The electrochemical reduction of pyrazolylphosphonium 

triflates to the corresponding phosphanes would open up an 

interesting aspect in phosphane oxide recycling. We inverstigated 

this reaction by the use of cyclic voltammetry (CV). A preparative 

approach under galvanostatic conditions was developed by 

coupling of electrolysis with in-situmonitoring of the 

pyrazolylphosphonium salt and triphenylphosphane (TPP) 

concentration by CV. Coulometric measurements during the 

CV-monitored electrolysis give further insights for a plausible 

mechanism. The combination of these methods enables to further 

optimize the electrochemical conditions to develop a waste-free 

electrochemical reduction process for the synthesis of 

triphenylphosphane from TPPO. 

references: 

1. Mayer, H. Pure & Appl. Chem. 2004, 66, 931. 

2. Reif, W.; Grasner, H. Chemie-Ing.-Techn. 1973, 45, 646. 

3. Hartley, F. R. (Ed.), The Chemistry of Organophosphorus 

Compounds, Vol. 2, 1992, Wiley, Chichester. 


Ehlers, A. W.; Lammertsma, K., Angew. Chem. 2010, 122, 

6314. 

5. Feldmann, K.-O.; Schulz, S.; Klotter, F.; Weigand; J. J. 

Chem. Sus. Chem. 2011, 4, 1805. (Cover Picture) 

Keywords: Phosphanes; Oxides; Electrochemistry; Reduction; 

Sustainable Chemistry; 



s948 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 7 4 

CoordinAtion CheMiStry of 

2,6-diPhoSPhonyLPhenyL-SuBStituted 

diPhenyLPhoSPhAne ChALCoGenideS 

M. GoCK 1 , C. dietz 1 , K. JurKSChAt 1 

1 TU Dortmund, Anorganische Chemie II, Dortmund, Germany 

E,C,E-coordinating pincer-type ligands (E = heteroatoms 

such as N, P, O, S...) are well established for stabilizing numerous 

complexes of metals such as tin, platinum and palladium. [1] Beside 

that ability however, the coordination chemistry of the ligands 

themselves is not well explored. In continuation of our systematic 

studies on phosphorus-containing O,C,O-coordinating pincer-type 

ligand [2] – 4-t-Bu-2,6-[P(O)(Oi-Pr) ] C H we present here the 

2 2 6 2 

phosphorus-substituted derivatives 4-t-Bu-2,6-[P(O)(Oi- 

-Pr) ] C H P(E)Ph (E = O, S, Se, lone pair) and complexes with 

2 2 6 2 2 

a variety of transition metals. 

references: 

1. The chemistry of Pincer compounds, Morales-Morales, 

D.; Jensen, C. M. 2007, Elsevier. 

2. a) Wagner, M.; Dorogov, K.; Schürmann, M.; Jurkschat, K. 

Dalton Trans. 2011, 40, 839. 

b) Henn, M.; Deaky, V.; Krabbe, S.; Schürmann, M.; 

Prosenc, M. H.; Herres-Pawlis, S.; Mahieu, B.; 

Jurkschat, K.; Z. Anorg. Allg. Chem. 2011, 637, 211. 

c) Mehring, M.; Löw, C.; Schürmann, M.; Uhlig, F.; 

Jurkschat, K.; Mahieu, B. Organometallics 2000, 19, 

4613. 

Keywords: Phosphane ligands; Coordination modes; 



P - 0 1 7 5 

effeCtS of the PrePArAtion ConditionS in 

the ProPertieS of the Li LA tio AS 

3x 2/3-x 3 

eLeCtroLyte in SoLid-StAte LithiuM-ion 

BAtterieS 

K. vidAL 1 , A. LArrAnAGA 1 , L. orteGA 2 , 

M. ArriortuA 3 

1 Universidad del País Vasco., Mineralogía y Petrología, 

LEIOA-BIZKAIA, Spain 

2 Pontificia Universidad Católica del Perú (PUCP), 

Departamento de Ciencias Sección Químicas, Lima, Peru 

3 Universidad del Pais Vasco (UPV/EHU), Departamento 

Mineralogía y Petrología, Leioa-Bizkaia, Spain 

In recent years, all solid state lithium ion batteries have been 

attracting more attention owing to their properties of high power 

density and good safety. As an important part of the battery, 

inorganic solid state electrolytes (Li La TiO , LLTO) become 

3x 2/3-x 3 

a significant issue because they present the highest lithium ion 

electrical conductivity at room temperature (about 10-3 S.cm-1 for 

x = 0.3). [1, 2] 

It is well known that the conductivity of LLTO strongly 

depends on the exact conditions of sample preparation. Until now 

most of inorganic solid-state electrolytes have been obtained by 

solid state reaction. As known, this conventional preparation 

method needs high sintering temperature and long sintering 

time, [3] which result in serious lithium loss during sintering 

process and in a particle size increase that is negative for 

micro-electrolyte layers in battery applications. As alternatives, 

some other synthetic methods have been used to prepare LLTO 

ceramics pellets or thin films. [4, 5] Furthermore the lithium content 

(x value) and the cooling rate in the sample syntesis play a crucial 

role in the structural properties, and then, in the materials 

properties as conductivity. [2] 

In this sense, this study is focused on the synthesis route, 

sintering temperature, cooling rate and crystal stability of the 

Li La TiO electrolyte in order to find out a suitable processing 

3x 2/3-x 3 

conditions to use in Lithium-ion battery systems. 

Keywords: synthesis route; solid electrolyte; lithium battery; 

perovskite; 



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chem. Listy 106, s587–s1425 (2012) 


P - 0 1 7 6 

PhotoinduCed CAtALytiC wAter reduCtion 

to hydroGen By new CoBALt CoMPLexeS 

BASed on tetrA- And PentAdentAte 

nitroGenAte LiGAndS 

A. CALL 1 , z. CodoLA 1 , M. CoStAS 1 , 

J. LLoret-fiLLoL 1 


Spain 

Currently, one of the most appealing research areas is the 

discovery and study of new electro- or photo-chemical catalysts 

based on earth-abundant elements able to generate fast and 

efficiently H from the reduction of water. 2 [1] Remarkable example 

of electro- and photochemical water reduction catalysts has been 

shown recently. [2] Nevertheless, regardless of the fast development 

of the field, only few examples of well-defined, water and oxygen 

robust catalysts have been developed. [3] 

With this aim, we become interested in the development of 

well-defined, robust and modular homogeneous catalytic systems 

which their electronic and steric properties were easily tunable. 

Hence, we presented a new family of catalysts for water 

reduction based on iron, nickel and cobalt complexes with robust 

tetra- and pentadentate nitrogenate ligands derivates from the 

basic 1,4,7-triazacyclononane structure. Preliminary studies show 

that not only all cobalt complexes [4] are active photo-induced 

catalysts but also the H formation activity and efficiency may be 

2 

modulated by the electron-drawing properties of the ligand 

achieving up to 420 TON in less than an hour. 

In this contribution the catalytic efficiency versus the 

photosensitizers used such as Ir, Ru or organic dyes and sacrificial 

electron donors such as Et N, TEOA or ascorbic acid will be 

3 

discussed. Finally, key intermediates will the postulated based on 

ongoing mechanistic studies. 

references: 

1. Teets, T. S. Nocera, D. G. Chem. Commun. 47, 9268-9274 

(2011). 

2. a) Wang, M. Na, Y. Gorlov, M. Sun, L. Dalton Trans., 

6458-6467 (2009). 

b) Gärtner, F., et al. Chem. Eur. J. 17, 6425-6436 (2011). 

c) Helm, M. L. et al. Science 333, 863-866 (2011). 

3. a) McNamara, W. R. J. Am. Chem. Soc. 133, 15368-15371 

(2011). 

b) Singh, W. M. Angew. Chem. Int. Ed. 51, 1-5 (2012) 

4. Artero, V. Angew. Chem. Int. Ed. 50, 7238-7266 (2011). 

Keywords: water reduction; hydrogen; cobalt; water splitting; 


P - 0 1 7 7 

reACtivity of dinuCLeAr Pt(ii) CoMPLexeS 

ContAininG BidentAte n,n- And n,S-donor 

LiGAndS 

S. hoChreuther 1 , r. PuChtA 1 , r. vAn eLdiK 1 



The cytostatic activity of cis-diamminedichloroplatium(II) 

– cisplatin – was discovered in 1969 by Barnett Rosenberg and 

this development marked a turning point in the treatment of 

cancer. However, there are a number of problems that need to be 

considered using cisplatin, viz. there are numerous side effects, 

the anti-tumor activity is limited to certain types of cancer, and 

some tumors develop a resistance during the therapy. 

Besides new mononuclear complexes with improved 

properties (carboplatin and oxaliplatin), a new class of 

multinuclear Pt(II) complexes has been developed by Farrell and 

his group. [1] 

We have now synthesized a series of dinuclear Pt(II) 

complexes in our group in which the two Pt(II) centers are 

connected by an aliphatic chain of variable length. Furthermore, 

a chelating ligand system was used that contain either exclusively 

N-donor atoms (NNpy) or a mixed N- and S-donor system 

(NSpy). These chelating systems stabilize the complex toward 

further nucleophilic attack and inhibit the decomposition of the 

dinuclear system. [2] 

Cytostatic active platinum compounds react in the cell with 

DNA as well as with sulfur containing substances, which leads to 

loss of cytostatic activity. In our studies we focused on kinetic 

measurements to examine substitution reactions with thiourea as 

a strong sulfur nucleophile to gain a closer look into the reactivity 

of these complexes. The rate constants of substitution can then be 

compared for the two systems and amongst each other as a 

function of chain length. A detailed discussion of our latest results 

will be presented. [3] 

references: 

1. Farrell, N.; Qu, Y. Inorg. Chem. 1989, 28, 3416. 

2. Hochreuther, S.; Puchta, R.; van Eldik, R. Inorg. Chem. 

2011, 50, 8984 

Hochreuther, S.; Puchta, R.; van Eldik, R. Inorg. Chem. 

2011, 50, 12747. 

3. Hochreuther, S.; van Eldik, R. Inorg. Chem.2012, 51, 

3025. 

Keywords: platinum; cytotoxicity; kinetics; reaction 

mechanisms; ligand effects; 



s950 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 7 8 

SyntheSiS, ChArACterizAtion And 

AntiMiCroBiAL ACtivity of PALLAdiuM(ii) 

CoMPLexeS with SoMe ALKyL eSterS of 

(S,S)-ethyLenediAMine-n,n'-di-2-(3-MethyL)- 

-ButAnoiC ACid 

v. GLodJoviC 1 , r. GordAnA 1 , i. rAdoJeviC 2 , 

o. StefAnoviC 2 , L. CoMiC 2 , S. trifunoviC 1 

1 Faculty of Science, Chemistry, Kragujevac, Serbia 

2 Faculty of Science, Biology, Kragujevac, Serbia 

Numerous complexes based on palladium(II) ion have been 

synthesized and their different biological activities have been 

documented [1–2] . The impact of different palladium complexes on 

the growth and metabolism of various groups of microorganisms 

has been studied. Garoufis reviewed numerous scientific papers 

on antiviral, antibacterial and antifungal activity of palladium(II) 

complexes with different types of ligands [3] . 

Palladium(II) complexes with R -S,S-eddp ligands 

2 

(S,S-eddp=(S,S)-ethylenediamine-N,N’-di-2-propanoate; R=n-pr, 

n-bu, n-pe [4] were synthesized and characterized. 

Three new ligand precursors and their palladium(II) 

complexes of general formula [PdCl{(S,S)-(R)eddv}] 

(R = n-propyl, n-butyl and n-pentyl; S,S-eddv =(S,S)- 

-ethylenediamine-N,N’-di-2-(3-methyl)-butanoate) have 

been synthesized and characterized by microanalysis, infrared, 

1 13 H and C NMR spectroscopy and mass spectrometry. In vitro 

antimicrobial activity for these ligands and complexes is 

investigated. Testing is preformed by microdilution method and 

minimum inhibitory concentration (MIC) and minimum 

microbicidal concentration (MMC) have been determined. Testing 

is conducted against 15 microorganisms (five strains of 

pathogenic bacteria, three species of probiotic bacteria, two yeast 

species and five pathogenic fungi). Tested ligands, with a few 

exceptions, show very low antimicrobial activity. Palladium(II) 

complexes show selective and moderate activity. The difference 

in antimicrobial activity between ligands and corresponding 

palladium(II) complexes is noticed and it is always higher with 

palladium(II) complexes. 

Acknowledgements: The authors are grateful to the Ministry of 

Education and Science of the Republic of Serbia for financial 

support. 

references: 

1. B.T. Khan, J. Bhatt, K. Najmoddin, S. Shamsuddin, 

K. Annapoorna, J. Inorg. Biochem. 44 (1991) 55. 

2. C. Navarro-Eanninger, J.M. Peréz, F. Zamora, V.M. 

Gonzáles, J.M. Masaguer, C.Alonso, J.Inorg. Biochem. 

52 (1993) 37. 

3. A. Garoufis, S.K. Hadjikakou, N. Hadjiliadis, Coord. 

Chem. Rev. 253 (2009) 1384. 

4. G.P. Vasic, V.V. Glodovic, I.D. Radojevic, O.D. Stefanovic, 

Lj.R. Comic, V.M. ?inovic, S.R. Trifunovic, Inorg. Chim. 

Acta 363 (2010) 3606. 

Keywords: Palladium; N ligands; Antifungal agents; 


P - 0 1 7 9 

noveL diethAnoLAMine derivAtiveS of 

AntiMony And BiSMuth- SyntheSiS And 

StruCtureS 

v. ABeyAwArAthAn 1 , C. dietz 1 , K. JurKSChAt 1 

1 TU Dortmund, Anorganische Chemie II, Dortmund, Germany 

In analogy to the 5-aza-2,8-dioxa-1-stanna(III)bi - 

cyclo[3.3.01.5 ]octanes known as intermediates for the synthesis [1] 

of non-toxic catalysts for polyurethane formation [2] , 

5-aza-2,8-dioxa-1-stiba(III)bicyclo[3.3.0 1.5 ]octanes of the type 

XSb(OCR CH ) NR'(R=H, Me, R'= alkyl, aryl, X = Cl, F, N ) 2 2 2 3 [3] 

and new pseudostibatranes were synthesized. The latter 

compound shows an intramolecular MeO?Sb interaction 

at a O-Sb distance of 3.12 ?. The antimony salt 

{[Sb(OCMe CH ) NMe]GaCl } , which is isoelectronic to the 

2 2 2 4 2 

5-aza-2,8-dioxa-1-stanna(III)bicyclo[3.3.0 1.5 ]octanes mentioned 

above, shows a dimeric structure. The 5-aza-2,8-dioxa-1- 

-bismuta(III)bicyclo[3.3.01.5 ]octanes are dimeric structures in the 

solid state. The interaction of compound 2 with moisture provided 

a partial hydrolysis product that shows an interesting structure 

with two bismuth atoms. 

references: 

1. T. Berends, L. Iovkova, G. Bradtmöller, I. Oppel, 

M. Schürmann, K. Jurkschat, Z. Anorg. Allg. Chem. 2009, 

635, 369. 

2. J. Krause, S. Reiter, S. Lindner, A. Schmidt, K.Jurkschat, 

M. Schürmann, G. Bradtmöller, Patent: DE 10 2008 021 

980 Al. 

3. V.Abeyawarathan, Master Thesis 2010, TU Dortmund. 

Keywords: Diethanolamines; Antimony; Bismuth; Catalysis; 



s951 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 8 0 

vALenCe tAutoMeriC quinonoid CoBALt 

CoMPLexeS with PhotoACtive CiS-trAnS 

iSoMerizABLe LiGAndS 

A. witt 1 , f. heineMAnn 1 , M. KhuSniyArov 1 



The recently proposed ligand-driven light-induced spin 

change (LD-LISC) is one possible approach to achieve magnetic 

bistability at room temperature. It is based on the possibility to 

reversibly change the ligand field of a transition metal complex 

by photoisomerization of the ligands to such an extent, that 

the metal ion undergoes a spin transition. [1] In this contribution 

we adopt the LD-LISC concept to the well explored valence 

tautomeric quinonoid transition metal complexes [2] which 

are known to exhibit different optical, electronic and/or 

most importantly magnetic properties due to a reversible 

interconversion between their electronic isomers. 

Well studied 4-phenylazopyridine (4-papy) and 

4-styrylpyridine (4-stpy), which undergo a reversible cis-trans 

isomerisation upon irradiation, are incorporated into a redox 

active Co(3,5-DBTSQ)(3,5-DBTCat) framework as photoactive 

ligands, where 3,5-DBTSQ- and 3,5-DBTCat2- are the 

semiquinonate and catecholate forms of 3,5-di-tert-butyl-o- 

-benzoquinone, respectively. 

As confirmed by EPR spectroscopy in frozen solution at 

14 K, the electronic structure of complexes [Co(3,5-DBTSQ)(3,5- 

DBTCat)(4-papy) ] 1 and [Co(3,5-DBTSQ)(3,5-DBTCat)(4-stpy) ] 

2 2 

2 consists of a ligand π-radical attached to a low-spin Co(III) ion. 

Cyclic voltammogram of 1 at RT reveals several typical (partially) 

reversible redox processes. Magnetochemical data of 1 in solid 

state shows a low-spin Co(III) electronic structure at T < 240 K; 

however, the observed gradual increase of the effective magnetic 

moment at higher temperatures may indicate a thermally induced 

transition to a high-spin Co(II) state. Upon irradiation with UV 

light at RT in solution a trans-to-cis isomerization of the 

photoactive ligands both in 1 and 2 is suggested by electronic 

absorption spectroscopy. 

references: 

1. M.-L. Boillot, J. Zarembowitch, A. Sour, in Topics in 

Current Chemistry, Vol. 234 (Eds.: P. Gütlich, 

H. A. Goodwin), Springer Berlin / Heidelberg, 2004, 

pp. 786–786. 

2. D. N. Hendrickson, C. G. Pierpont, in Topics in Current 

Chemistry, Vol. 234 (Eds.: P. Gütlich, H. A. Goodwin), 

Springer Berlin / Heidelberg, 2004, pp. 786–786. 

Keywords: Cobalt; Valence isomerization; Spin crossover; 

Magnetic properties; UV/Vis spectroscopy; 


P - 0 1 8 1 

CoMPAriSon of C-h hydroGen AtoM trAnSfer 

reACtionS MediAted By MAnGAneSe(iv)-oxo 

CoMPLexeS with tuned eLeCtroniC 

ProPertieS 

o. CuSSó 1 , i. GArCiA-BoSCh 1 , A. CoMPAny 1 , 

x. riBAS 1 , M. CoStAS 1 

1 Universitat De Girona, Departament de Química, Girona, 

Spain 

Oxidation of C-H bonds mediated by transition metal 

complexes are fundamental steps in fine and industrial chemistry, 

and in many biochemical transformations. One of the most 

commonly metal used is iron, usually adopting high valent 

iron(IV)-oxo species. [1] The comparison of manganese systems 

with their iron analogues have also attracted the attention of 

different authors, trying to shed light into the Fe/Mn duality found 

in nature. It is known that there are some oxidative enzymes that 

can be both iron and manganese dependent. While several highvalent 

iron complexes are currently known, this is not the case for 

the manganese metal, for which mononuclear high-valent 

oxo-complexes are rather uncommon, likely because of their 

tendency to dimerize. [2] Manganese(V)-oxo species and their role 

in C-H oxidation reactions have been also explored, [3] also it have 

been studied in other oxidative transformations such as sulfide 

oxidations and epoxidations. 

In this work, we have studied the reaction of C-H oxidation 

of dihydroanthracene as model substrate mediated by 

[ RPyTacn-Mn IV (OH) ] and [ 2 RPyTacn-Mn IV (OH)(O)] species 

containing different electronic groups on the pyridine ligand. [4] 

A comparative analysis of the kinetic parameters of these 

reactions, as well as the thermodynamic driving forces for such 

reactions have been performed. 

references: 

1. M. Costas, M. P. Mehn, M. P. Jensen, L. Que, Jr., Chem. 

Rev. 2004, 104, 939 

2. G. Yin, A. M. Danby, D. Kitko, J. D. Carter, 

W. M. Scheper, D. H. Busch, J. Am. Chem. Soc. 2008, 

130, 16245 

3. J. T. Groves, J. Lee, S. S. Marla, J. Am. Chem. Soc. 1997, 

119, 6269. 

4. I. Garcia-Bosch, A. Company, C. W. Cady, S. Styring, 

W. R. Browne, X. Ribas, M. Costas, Angew. Chem., Int. 

Ed. 2011, 50, 5648. 

Keywords: C-H activation; Kinetics; Manganese; 



s952 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 8 2 

LuMineSCenCe ProPertieS of noveL 

MetAL-orGAniC frAMeworKS (MofS) BASed on 

LeAd(ii) And A funCtionALiSed BiPhenyL 

LinKer 

w. w. LeStAri 1 , P. LÖnneCKe 1 , h. C. Streit 2 , 

C. wiCKLeder 2 , e. hey-hAwKinS 1 

1 Institut für Anorganische Chemie, Fakultät für Chemie und 

Mineralogie, Universität Leipzig, Germany 

2 Institut für Anorganische Chemie II, Fakultät IV, Department 

Chemie-Biologie Universität Siegen, Germany 

The structural features of MOFs are highly influenced by 

many factors, such as the coordination chemistry of the included 

metal ions, the nature of the organic building blocks, the synthetic 

templates, solvents, counter-anions, stoichiometry and pH value 

of the solution. [1] 

Lead(II) complexes exhibit a wide variety of coordination 

numbers 2 and irregular geometries, as well as luminescence 

properties [3] . Here, we will present the synthesis of a novel MOF 

from lead(II) nitrate and the functionalised biphenyl linker 

4,4'-dicarboxy-2,2'-dimethoxy-1,1'-biphenyl (Lh 2 ) in the solvent 

mixture EtOH/H 2 O (2/10) which led to the formation of a threedimensional 

network with a Pb 6 O 2 cluster as secondary building 

unit. Interestingly, luminescence investigations of the Pb-based 

MOF show only ligand (not lead) emission and excitation, which 

is influenced by included organic molecules, such as DMF. 

Thus, [{(Pb 6 O 2 )L 4 }] n can be used as sensor for organic solvents. 

references: 

1. G. Wu, Y. Wang, X. Wang, H. Kawaguchi, W. Sun, 

J. Chem. Cryst. 2007, 37, 199. 

2. a) N. L. Rosi, J. Kim, M. Eddaoudi, B. Chen, M. O’Keeffe, 

O. M. Yaghi, J. Am. Chem. Soc. 2005, 127, 1504. 

b) D. L. Turner, T. P. Vaid, P. W. Stephens, K. H. Stone, 

A. G. DiPasquale, A. L. Rheingold, J. Am. Chem. Soc. 

2008, 130,14. 

c) Y. Tan, F. Meng, M. Wu, M. Zeng, J. Mol. Struct. 2009, 

928, 176. 

d) Z. Li, Y. Xing, C. Wang, J. Li, X. Zeng, M. Ge, S. Niu, 

Z. Anorg. Allg. Chem. 2009, 635, 1650. 

3. a) R. Hu, H. Cai, J. Luo, Inorg. Chem. Commun. 2011, 14, 

433. 

b) F. J. M. Casado, L. Canadillas-Delgado, F. Cucinotta, 

A. Guerrero-Martínez, M. R. Riesco, L. Marchese, 

J. A. R. Cheda, CrystEngComm 2012, DOI: 

10.1039/c2ce06546k. 

c) F.-Y. Meng, Y.-L. Zhou, H.-H. Zou, M.-H. Zeng, H. Liang, 

J. Mol. Struct. 2009, 920, 238. 


P - 0 1 8 3 

CoAtinG Pt nAnoPArtiCLeS with MethyLS: 

the reACtion Between MethyL rAdiCALS And 

Pt-nAnoPArtiCLeS SuSPended in AqueouS 

SoLutionS 

i. ziLBerMAnn 1 , r. BAr-ziv 2 , G. yArdeni 2 , 

h. Cohen 3 , d. MeyerStein 3 

1 NRCN, Chemistry, Beer Sheva, Israel 

2 Ben-Gurion University of the Negev and NRCN, Chemistry, 

Beer Sheva, Israel 

3 Ariel University Center of Samaria and Ben-Gurion University 

of the Negev, Chemistry, Ariel and Beer Sheva, Israel 

Transition metal nanoparticles (NPs) are known as catalysts 

of various redox processes. Radicals are often intermediates in 

these processes. Recent studies [1, 2] point out that methyl radicals 

react in fast reactions, with rate constants k > 1×108 M-1s-1 , with 

Auo , Ago and TiO NPs dispersed in aqueous solutions to form 

2 

intermediates, (NP)-(CH ) , in which the methyls are covalently 

3 n 

bound to the NPs via σ bonds. These intermediates decompose to 

form ethane. Thus formally the particles efficiently “catalyze” the 

dimerization of the methyl radicals. The reported minimal lifetime 

of the (NP)-CH transients (t) is surprisingly long, e.g. t ≥ 8 and 

3 

t ≥ 188 sec for Ago and Auo NPs, respectively [2] . 

Platinum is a known catalyst of a variety of processes and a 

common electrode. In many cases surface alkyl groups have been 

proposed as intermediates in these processes. It seemed therefore 

of interest to study the kinetics and mechanism of reaction of 

methyl radicals with Pto-NPs suspended in aqueous solutions. The 

results point out that methyl radicals react with Pto-NPs suspended 

in aqueous solutions in fast reactions. This reaction results in four 

different products The major product is stable methyl coated 

Pto-NPs, (Pto-NPs)-(CH )n. C H , C H and some polymerization 

3 2 6 2 4 

products are also formed. These observations are in accord with 

the polycrystalline nature of the Pto-NPs. Thus atoms at edges, 

corners and planes have different chemical properties. These 

results are clearly relevant to the understanding of catalytic and 

electrochemical processes occurring on Pto surfaces. 

references: 

1. O. Oster, R. Bar-Ziv, G. Yardeni, I. Zilbermann, 

D. Meyerstein, Chemistry-a European Journal 2011, 17, 

9226-9231. 

2. R. Bar-Ziv, I. Zilbermann, O. Oster, G. Yardeni, H. Cohen, 

D. Meyerstein, Chemistry-a European Journal 2012, 18, 

4699-4705. 

3. R. Bar-Ziv, I. Zilbermann, O. Oster, G. Yardeni, H. Cohen, 

D. Meyerstein, Chemistry-a European Journal 2012in 

press. 

Keywords: radicals; stable intermediates; rate constants; 

transition metal nanoparticles; mechanisms of reaction; 



s953 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 8 4 

CirCuLAr heLiCAteS And A MoLeCuLAr 

PentAfoiL Knot 

J. e. BeveS 1 , J. f. AyMe 2 , d. A. LeiGh 2 , 

r. t. MCBurney 2 , K. riSSAnen 3 

1 Nanjing University, Key State Laboratory for Coordination 

Chemistry School of Chemistry, Nanjing, China 

2 University of Edinburgh, School of Chemistry, Edinburgh, 



Finland 

Knots are being discovered with increasing frequency in 

both biological and synthetic macromolecules and have been 

fundamental topological targets for chemical synthesis for the past 

two decades. Here we present the synthesis of the most complex 

non-DNA molecular knot prepared to date: [1, 2] the self-assembly 

of five bis-aldehyde and five bis-amine building blocks about five 

metal cations and one chloride anion to form a 160-atom-loop 

molecular pentafoil knot (five crossing points). The structure and 

topology of the knot is established by NMR spectroscopy, mass 

spectrometry and X-ray crystallography, revealing a symmetrical 

closed-loop double helicate with the chloride anion held at the 

centre of the pentafoil knot by ten CH...Cl– hydrogen bonds. The 

one-pot self-assembly reaction features an exceptional number of 

different design elements. 

The synthesis of eleven pentameric related cyclic helicates 

is also reported. The factors influencing the assembly process 

(reactant stoichiometry, concentration, solvent, nature and amount 

of anion) were studied in detail: the role of chloride in the 

assembly process appears not to be limited to that of a simple 

template and larger circular helicates observed with related 

tris(bipyridine) ligands with different iron salts are not produced 

with the imine ligands. Using certain chiral amines, pentameric 

cyclic helices of single handedness could be isolated and the 

stereochemistry of the helix determined by circular dichroism. 

We anticipate that the strategies and tactics used here can be 

applied to the rational synthesis of other higher-order interlocked 

molecular architectures. 

references: 

1. J. -F. Ayme, J. E. Beves, D. A. Leigh, R. T. McBurney, 

K. Rissanen, D. Schultz, Nature Chem., 2012, 4, 15-20. 

2. J. -F. Ayme, J. E. Beves, D. A. Leigh, R. T. McBurney, 

K. Rissanen, D. Schultz, J. Am. Chem. Soc, 2012, 

accepted. 

Keywords: Supramolecular chemistry; Circular dichroism; 

Bridging ligands; Self-assembly; Anions; 


P - 0 1 8 5 

Low teMPerAture SyntheSiS of 

GeL-nAnoStruCtured SiLver vAnAdiuM 

oxideS CAthode MAteriALS 

r. fernández de LuiS 1 , M. i. ArriortuA 1 

1 Universidad del País Vasco., Mineralogy and Petrology, 

Leioa-Bizkaia, Spain 

Silver vanadium oxides (SVO) have potential applications 

in rechargeable high-energy density lithium batteries and 

photo-catalysis due to their excellent electrochemical and 

photophysical properties. Recently, several researching groups 

have obtained different nanostructured SVO via hydrothermal 

treatments. 

The main aim of this work is to determine the effect of initial 

synthesis conditions on the particle size and morphology of 

α-AgVO and β-AgVO SVO. The solution and hydrothermal 

3 3 

AgNO /NaVO /H O systems were studied, considering the 

3 3 2 

economic cost versus the health hazards and environmental risks 

of the initial reagents with respect to V O , NH VO or Ag O. 

2 5 4 3 2 

The particle size and morphology were checked by particle size 

analyzer, X-ray diffraction and electron microscopy. 

With regard to the α-AgVO and β-AgVO compounds 

3 3 

obtained at room temperature, the α-AgVO compound 

3 

transformation to β-AgVO depends on the stirring time. The 

3 

electron microscopy images indicate that in a first step tabular 

micro-sized crystals agglomerated in spherical particles 

crystallize, and in the second step nano-tubular morphologies 

of 300-400nm x10nm x 10nm grow. If ethanol is used as 

co-dissolvent, the tabular like single crystals are completely 

recovered by 300-30x200-20x10 nm nano-tabular crystals. The 

α-AgVO to β-AgVO transformation does not seem to affect the 

3 3 

particle morphology. For the hydrothermal treatments at 120 and 

180ºC, the β-AgVO obtained at neutral pH conditions crystallize 

3 

as orange powders; however those ones synthesized at slightly 

acidic pHs, and with a starting vanadium rich stoichiometry 

crystallize as orange-red gels. The electron microscopy images 

indicate that nano-tubular (100-200x0.5x0.5 nm) samples of 

β-AgVO are obtained after one hour of hydrothermal treatment 

3 

at 120ºC. 

Acknowledgments: This work was financially supported by the 

“Ministerio de Ciencia e Innovación” (MAT2010-15375) and 

the Bask Country Government (IT-177-07), which we gratefully 

acknowledge. R. Fernández thanks to “Ministerio de Ciencia e 

Innovación” for funding. The authors thanks to the technicians 

of SGIKer (UPV/EHU) for the support. 

Keywords: Silver Vanadium Oxide; Hydrothermal synthesis; 

Nanotubes; Li-Ion Batteries; 



s954 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 8 6 

CoPPer CoMPLexeS of 

dihydroxyBenzALdehyde 

thioSeMiCArBAzoneS: SyntheSiS, CryStAL 

StruCture And BioLoGiCAL ACtivitieS 

K. tAn 1 , h. L. SenG 1 , S. C. CheAh 2 , M. hd. JAMiL MAAh 1 , 

M. hd. rAiS MuStAfA 2 , S. w. nG1 , C. h. nG3 1 Universiti Malaya, Chemistry, Kuala Lumpur, Malaysia 

2 Universiti Malaya, Pharmacology, Kuala Lumpur, Malaysia 

3 Universiti Tunku Abdul Rahman, Chemistry, Perak, Malaysia 

Four thiosemicarbazones ligands, H T(1), H M(2), H E(3) 

3 3 3 

and H P(4) have been prepared with good yield by refluxing 

3 

2,4-dihydroxybenzaldehyde with N(4)-substituted thio - 

semicarbazide in ethanol (H T(1) = 2,4-dihydroxybenzaldehyde 

3 

thiosemicarbazone; H M(2) = 2,4-dihydroxybenzaldehyde 

3 

4-methylthiosemicarbazone; H E(3)=2,4-dihydroxybenzaldehyde 

3 

4-ethylthiosemicarbazone and H P(4)=2,4-dihydroxybenzaldehyde 

3 

4-phenylthiosemicarbazone). Reactions of these ligands with 

copper acetates in the presence of 2,2'-bipyridine lead to the 

formation of copper(II) complexes of formulation [Cu(bpy)L](5-8) 

(bpy = 2,2'-bipyridine; L = doubly deprotonated thiosemi - 

carbazones=HT(5); HM(6); HE(7) and HP(8)). These compounds 

were characterized and their nucleolytic, cytotoxicity and 

Topoisomerase I inhibition activities studied. X-ray diffraction 

study indicates that complex 5 is mononuclear and five 

coordinated with the doubly deprotonated thiosemicarbazone 

acting as a tridentate ligand coordinating through the phenolic 

oxygen, azomethine nitrogen and thiolate sulfur while 

2,2-bipyridine as the N,N’-bidentate ligand. The trigonality index 

τ of 0.03 for 5 indicates that the coordination geometry around 

copper is close to a perfect square pyramidal. Nucleolytic and 

topoisomerase I inhibition activities seem to be dependent on the 

N(4) substituent of the thiosemicarbazone moiety. 

Keywords: DNA; cytotoxicity; schiff bases; enzymes; copper; 


P - 0 1 8 7 

uSinG CryStALLizAtion driven SeLf-ASSeMBLy 

for ControLLed ACCeSS to 2-d ovAL ShAPed 

ArChiteCtureS 

e. dunPhy 1 , P. ruPAr 1 , G. whitteLL 1 , i. MAnnerS 1 

1 University of Bristol, Chemistry, Bristol, United Kingdom 

Crystallization driven self-assembly (CDSA) has previously 

been used to direct the controlled solution phase self-assembly of 

block co-polymers and reported morphologies have often focused 

on cylindrical structures. [1, 2, 3] 

Here we report on recent investigations using CDSA to 

access 2-D architectures involving block copolymers consisting 

of a core of polyferrocenosilane (PFS) and coronae of 

polydimethylsiloxane (PDMS), polymethylvinylsiloxane (PMVS) 

and polyisoprene (PI). By judiciously choosing experimental 

conditions we have shown it possible to obtain access to regular, 

mono-dispersed oval shaped platelet structures. We have, in 

addition, obtained remarkable control over their size and growth 

and visualization of the epitaxial growth processes. 

references: 

1. Wang, X.; Guerin, G.; Wang, H.; Wang, Y.; Manners, I.; 

Winnik, M.A. Science, 2007, (317), 644. 

2. Gilroy, J. B.; Gädt, T.; Whittell, G. R.; Chabanne, L.; 

Mitchels, J. M.; Richardson, R. M.; Winnik, M. A.; 

Manners, I. Nature Chem., 2010 (2), 566-570 

3. Gaedt, T.; Ieong, N.S.; Cambridge, G.; Winnik, M.A.; 

Manners, I. Nature Materials 2009, 8, 144 

Keywords: block co-polymers; self-assembly; 

polyferrocenosilane; 



s955 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 8 8 

CoPPer(i)-dioxyGen ACtivAtion At A noveL 

unSyMMetriC dinuCLeAtinG LiGAnd 

J. SerrAno-PLAnA 1 , A. CoMPAny 1 , x. riBAS 1 , 

M. CoStAS 1 

1 Universitat De Girona, Departament de Química, Girona, 

Spain 

Dioxygen plays important roles in many biological 

processes: it is the terminal electron acceptor in cellular 

respiration and it is used as oxidant in metabolic oxidation 

reactions catalyzed by metalloenzymes. Due to its inherent 

electronic structure, dioxygen is kinetically inert and it reacts 

slowly with organic molecules. In biological systems this kinetic 

barrier is overcome by reaction with redox active transition 

metals. For example, several dinuclear copper proteins are 

involved in dioxygen activation processes. [1] In this line, extensive 

work has been done on exploring the Cu/O reactivity in 

2 

homometallic symmetric synthetic model compounds which bind 

and activate O , forming reactive intermediates like superoxides, 

2 

peroxides or metal oxide species. 

Usually, O -activating enzymes present an unsymmetric 

2 

active site in which the two metal centers are not equivalent. This 

lack of symmetry arises either from a distinct coordination 

environment in both sites (as in tyrosinase) or from the presence 

of two different metals (as in cytochrome c oxidase). Studies of 

O activation at unsymmetric dinuclear sites are very scarce due 

2 

the difficulty in preparing an adequate ligand scaffold capable of 

holding metal ions in different coordination environments. [2] 

In this work we have studied the binding and activation of 

dioxygen at copper(I) centers using a novel nitrogen-based 

unsymmetric ligand with two different binding sites. The 

coordination site “chosen” by the copper center to perform oxygen 

activation depends on the nature of the other metal present. 

Acknowledgements: Financial support from Consolider Ingenio 

(CSD2010-00065), Generalitat de Catalunya (2009-SGR637) 

and Ministerio de Ciencia e Innovación Spain (CTQ2009- 

08464/BQU) is acknowledged. M.C. and X.R. thank 

ICREA-Academia and A.C. thanks MICNN for a Ramón y Cajal 

contract. 

references: 

1. L. M. Mirica, X. Ottenwaelder, T. D. P. Stack Chem.Rev. 

2004, 104, 1013-1045 

2. I. Garcia-Bosch, X. Ribas, and M. Costas Eur. J. Inorg. 

Chem. 2012, 179-187 

Keywords: O-O activation; copper; 


P - 0 1 8 9 

tin oxide nAnoPArtiCLeS viA twin 

PoLyMerizAtion froM noveL tin(iv) 

ALKoxideS 

S. BruMM 1 , C. LeonhArdt 1 , A. Seifert 1 , G. Cox 2 , 

A. LAnGe 2 , M. MehrinG 1 

1 Chemnitz University of Technology, Chemistry, Chemnitz, 

Germany 

2 BASF SE, Research Performance Materials, Ludwigshafen, 

Germany 

The development of synthetic strategies for nanostructured 

hybrid materials is currently a very active research area. [1] Twin 

Polymerization is a novel synthetic approach for nanostructured 

organic-inorganic hybrid materials and metal oxide nanoparticles. 

The special character of this concept is the formation of an organic 

and an inorganic framework on the same timescale starting from 

one monomer only. Interpenetrating networks are generated and 

produce the nanostructure of the material. We are interested in 

tin-containing hybrid materials, which have attracted e.g. for gas 

sensors, [3] solar cells, [4] and lithium ion batteries. [5] Here we 

present novel well-defined tin precursors for Twin Polymerisation 

such as Sn(OCH C H O) , [Sn(OCH C H S) ·HOCH C H S] , 

2 4 3 4 2 4 3 4 2 4 3 2 

[Sn(OCH -2-OCH C H ) ?HOCH -2-OCH C H ] and [Sn(OCH - 

2 3 6 4 4 2 3 6 4 2 2 

-2,4-OCH C H ) ?HOCH -2,4-OCH C H ] . By the use of such 

3 6 3 4 2 3 6 3 2 

tin precursors in polymerization reactions in melt and in solution 

we were able to prepare cross-linked nanocomposites from the 

type polymer/SnO . These materials are characterized by 2 13C and 

119Sn NMR in the solid state and in solution, IR, elemental 

analysis, BET, TEM and oxidized to give tin oxid nanoparticles. 

references: 

1. a) G. Kickelbick, Hybrid Materials-Synthesis Characterizaion, 

and Applications, Wiley-VCH, Weinheim, 2007; 

b) C. Sanchez, L. Rozes, F. Ribot, C. Laberty-Robert, 

D. Grosso, C. Sassoye, C. Boissiere, L. Nicole, C.R. 

Chimie 2010, 13,3 

2. a) T. Löschner, A. Mehner, S. Grund, A. Seifert, A. Pohlers, 

A. Lange, G. Cox, H.-J. Hähnle, S. Spange, Angew. 

Chem. 2012, 124, 3312; 

b) F. Böttger-Hiller, R. Lungwitz, A. Seifert, M. Hietschold, 

M. Schlesinger, M. Mehring, S. Spange, Angew. Chem. 

Int. Ed. 2009, 48, 8878 

3. a) G. Fagila, C. Baratto, G. Sberveglieri, Appl. Phys. Lett. 

2005, 86, 11923; 

b) B. Schumacher, R. Ochs, H. Tröße, S. Schlabach, 

M. Bruns, D. V. Szabó, J. Haußelt, Plasma Process. 

Polym. 2007, 4, 865. 

4. T. Stergiopoulos, I. M. Arabatzis, H. Cachet, P. Falaras, 

J. Photoch. Photobio. A 2003, 155, 163 

5. a) Y. Wang, J. Y. Lee, J. Phys. Chem. B 2004, 108, 17832; 

b) A. Yu, R. Frech, J. Power Sources 2002, 104, 97 

Keywords: Organic-inorganic hybrid composites; Tin; 

Nanoparticles; Polymerization; 



s956 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 9 0 

SyntheSiS And StruCturAL StudieS of 

vAnAdiuM(v) SChiff BASe CoMPLexeS derived 

froM SALiCyLALdehyde And BrAnChed-ChAin 

AMino ACidS 

L. KrivoSudSKy 1 , P. SChwendt 1 

1 Faculty of Natural Sciences Comenius University in 

Bratislava, Department of Inorganic Chemistry, Bratislava, 


Asymmetric metal catalysis is in the focus of current 

chemical research, and in recent years several major 

breakthroughs have been achieved. It was one of the 2001 Nobel 

Prize laureates, Sharpless and coworkers, who reported on a 

highly promising asymmetric vanadium catalyst based on 

[VO(acac) ] as early as 1977. Since then, the catalysis by 

2 

vanadium compounds has been studied in detail. It was found that 

vanadium complexes with tridentate Schiff bases ligands are very 

effective catalysts of asymmetric oxidation of organic sulfides to 

sulfoxides, diastereoselective epoxidation as well as 

hydroxylation, bromination and oxidation of secondary alcohols 

to corresponding ketones. This contribution deals with the 

preparation and structural characterization of three new chiral 

dioxidocomplexes of vanadium(V) with Schiff bases: 

[N(CH CH CH CH ) ][VO (N-salicyliden-L-valinato)] (1), 

2 2 2 3 4 2 

[N(CH CH CH CH ) ][VO (N-salicyliden-L-leucinato)] (2) and 

2 2 2 3 4 2 

[N(CH CH CH CH ) ][VO (N-salicyliden-L-isoleucinato)] (3). 

2 2 2 3 4 2 

Compounds 1, 2 and 3 crystallize in the enantiomorph space 

group P2 2 2 and are isostructural. The central atom of vanadium 

1 1 1 

adopts distorted square pyramidal coordination and bonds to two 

oxido ligands and one Schiff base ligand, which provides ‘ONO’ 

set of donor atoms. Using 51V NMR spectroscopy the behavior of 

the complexes in different solvents important in terms of future 

study of their catalytic properties has been studied. It was found 

that the prepared complexes do not decompose in acetonitrile even 

after 48 hours, while in aqueous solution hydrolysis takes place 

and vanadates are formed. The change in color of 

dichloromethane and chloroform solution from yellow to blue 

indicates that V(V) is reduced to V(IV) after several hours. Thanks 

to an extraordinary stability of the complexes in acetonitrile 

solution the specific optical rotation and CD spectra were 

measured, confirming that the prepared compounds are 

homochiral. The CD spectra were collected in solid state too, 

showing fine resolution of the electron transitions. 

Keywords: Vanadium; Chirality; Schiff bases; 


P - 0 1 9 1 

SyntheSiS And ChArACterizAtion 

of A3B tyPe wAter-SoLuBLe unSyMMetriCAL 

PhthALoCyAnine 

S. AriKAn 1 , y. ArSLAnoGLu 1 , A. GüL 1 

1 Istanbul Technical University, Chemistry, Istanbul, Turkey 

Email: arikans87@gmail.com 

Phthalocyanines have attracted considerable attention and 

present an important and active frontier, due to their interesting 

and useful biological, electronic, optical, catalytic, and structural 

properties. For this reason they exhibite a wide range of 

application in material science, catalysts, and medicine [1] . For 

example boron containing phthalocyanines are particularly 

promising for dual application in BNCT and PDT because of their 

strong absorptions in the near-IR where light penetration through 

tissue is substantially increased compared with visible light [2] . For 

a number of uses, phthalocyanines with two or more different 

substituents on the exterior of the ring system would be 

advantageous as in the case of water-soluble unsymmetrically 

substituted phthalocyanines. The most commonly used synthetic 

approach is the statistical condensation of two different 

phthalonitriles, diiminoisoindols, or related derivatives [3] . 

In this work, water-soluble A B type novel unsymmetrically 

3 

substituted metallophthalocyanines have been synthesized by 

statistical condensation of a mixture of 4-dimethylaminoethylthio- 

-phthalonitrile (A) and 2-hydroxyethylthio-phthalonitrile (B). All 

synthesized novel phthalocyanine compounds have been 

characterized by using their elemental analyses, FT-IR, UV-Vis, 

1 13 H NMR, C NMR and mass spectroscopic methods. 

references: 

1. Saglam Ö., Gül A., Polyhedron, 2001, 20, 269–275 

2. Li, H., Fronczek, FRM., Vicente, GH., Tetrahedron, 2008, 

49, 4828–4830 

3. Arslanoglu, Y., Nyokong, T., Polyhedron, 2011, 30, 

2733–2739 

Keywords: Phthalocyanines; Asymmetric synthesis; 

Macrocycles; 



s957 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 9 2 

PrePArAtion of MetAL-free And 

MetALLoPhthALoCyAnineS BeArinG BuLKy 

AntrACene GrouPS viA eSterifiCAtion 

S. AriKAn 1 , A. M. SeviM 1 , A. GüL 1 


Email: arikans87@gmail.com 

Phthalocyanines are close relatives of the porphyrin 

macrocycles and are the parent compound of one of the most 

studied class of functional organic materials. Phthalocyanine and 

its derivatives displaying interesting photophysical properties, 

electron transfer ability and reduction–oxidation behaviour are 

studied for applications in electrophotography, photovoltaic cells, 

fuel cells and electrochromic displays [1] . 

The main restricting factor of phthalocyanines is a rather 

low solubility in organic solvents. Periferal substitution of 

phthalocyanines with alkyl, alkoxy, alkythio chains or bulky 

groups enhances their solubility drastically [2] . The introduction of 

carboxy or amino groups gives water-soluble products. Compared 

to unsubstituted parent metal phthalocyanines, 

ester-containing porphyrazines and phthalocyanines are highly 

soluble in chlorinated hydrocarbons [3] .The synthesis of soluble 

phthalocyanines should provide them new optical, electronic, 

redox and magnetic properties which could increase the field of 

possible applications. 

In this present study, metal-free and metallophthalocyanines 

(Co, Zn) bearing peripheral thioglycolic acid groups were 

synthesized by cyclotetramerisation of the corresponding 

phthalonitrile derivative [4] . All of these thioglycolic acid 

substituents of the metal-free and metallophthalocyanines were 

esterified with antracene-9-methanol for gaining better soluble 

and combining two photoactive moieties in the same molecule. 

The novel phthalocyanine compounds were characterized by 

elemental analyses, 1H-NMR, FT-IR, UV-Vis and Mass 

spectroscopic techniques. 

references: 

1. C.C. Leznoff, A.B.P. Lever (Eds.), Phthalocyanines 

Properties and Applications, vols. 1–4, VCH, Weinheim, 

1989–1996. 

2. Z.A. Bayir, E. Hamuryudan, A.G. Gurek, O. Bekaroglu, 

J. Porphyr. Phthalocya. 1 (1997) 349. 

3. Akkus H, Gul A. Octakis(ferrocene)-substituted 

porphyrazines. Trans Met. Chem 2001;26:689e94. 

4. Sevim, A. M.; Ilgün, C.; Gül A. Preparation of 

Heterogeneous Phthalocyanine Catalysts by Cotton Fabric 

Dyeing, Dyes and Pigments, 2011, 89(2), 162-168. 


P - 0 1 9 3 

PhotoSenSitized rutheniuMnitroSyL 

CoMPLexeS for ControLLed no-reLeASe 

t. BeCKer 1 , A. SChiLLer 1 


Novel strategies in curing cancer diseases involvethe use of 

nitric oxide (NO) as a therapeutic agent. [1] Controlled release of 

NOvia light irradiation of photosensitive compounds gained a lot 

of interest inthe last years. [2] A number of rutheniumnitrosyl 

complexes are promising NO donors as metallo-pharmaceuticals. [3-4] 

The specific design ofthe NO-releasing properties of such 

compounds can be reached by the synthesisof tailor-made organic 

ligands. Novel biscarboxamide rutheniumnitrosylcomplexes 

[LRu(NO)Cl] based on the tetradentate ligands N,N'-bis(1- 

-methylimidazole-2-carboxamide)-1,2-phenazine (L=mipab)and 

N,N'-bis(1-vinylimidazole-2-carboxamide)-1,2-phenazine(L=vipab) 

have been synthesized and were characterized via NMR, MS, IR 

andUV/VIS. The synthesis was realized via novel lithiated 

biscarboxamide ligands ofstrong basicity. The UV/VIS-spectra of 

the obtained complexes compared to a rutheniumNO 

complex based on N,N'-bis(1-methylimidazole-2-carboxamide)- 

-1,2-benzene(L=bib) showed an impressive red shift of the lowest 

energy absorption bandfrom 350 nm to 470 nm, which equals the 

region of blue light. Duringirradiation with wavelengths in the 

range of 450 nm to 490 nm,the NO-release was measured by using 

a fluorescence assay (Anslyn’s NO assay). 

references: 

1. A.W. Carpenter, M. H. Schoenfisch, Chem. Soc.Rev. 2012, 

41, 3742-3752. 

2. M. J. Rose, P. K. Mascharak, Coordin. Chem. Rev. 2008, 

252, 2093-2114. 

3. D. Crespy, K. Landfester, U. S. Schubert, A. Schiller, 

Chem. Commun. 2010, 46, 6651-6662. 

4. C. Bohlender, M. Wolfram, H. Goerls, W. Imhof, R. Menzel, 

A.Baumgaertel, U. S. Schubert, U. Mueller, M. Frigge, 

M. Schnabelrauch, R. Wyrwa,A. Schiller, J. Mater. Chem. 

2012, 22, 8785-8792. 

Keywords: Antitumor agents; Nitrogen oxides; Ligand design; 

Lithium; 



s958 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 9 4 

GutMAnn donor And ACCePtor nuMBerS for 

ioniC LiquidS 

S. MAtthiAS 1 , P. iLLner 1 , r. PuChtA 1 , A. zAhL 1 , 




In recent years, ionic liquids have been discussed as an 

outstanding class of solvents, due to their wide range of properties. 

Unfortunately, a detailed understanding of the interactions 

between ionic liquids and dissolved substrates and the resulting 

effects on chemical reactions is, in many cases, still missing. 

These interactions and their strength is influenced by many 

different factors, such as the strength of intermolecular van der 

Waals forces, the ability of a solvent to form hydrogen bonds, the 

polarity of the solvent, and especially important for ILs, the 

strength of intermolecular coulomb interactions. The 

quantification of these solvent characteristics can be an important 

tool to understand physicochemical phenomena and chemical 

behavior in solution. 

One approach to express and quantify solvent properties is 

the so called “donor-acceptor concept” invented by Victor 

Gutmann. He defined the donor number, DN (also referred to as 

“donicity”), as a quantitative measure for the propensity to donate 

electron pairs to acceptors, and its counterpart, the acceptor 

number (AN), as a measure for the electrophilic properties of a 

solvent, i.e. the ability to accept electron pairs or at least electron 

density. 

For the first time, we present Gutmann donor and acceptor 

numbers for a series of 36 different ionic liquids that include 

26 different anions. The donor numbers were obtained 

by 23Na-NMR and show a strong dependence on the anionic 

component of the ionic liquid. The donor numbers measured vary 

from -12.3 kcal mol-1 for the ionic liquid containing the weakest 

coordinative anion [emim][FAP] (1-ethyl-3-methylimidazolium 

tris(penta-fluoroethyl)-trifluorophosphate), being a weaker donor 

than 1,2-dichloroethane, to 76.7 kcal mol-1 found for the ionic 

liquid [emim][Br], exhibiting a coordinative strength in the range 

of tertiary amines. The acceptor numbers were measured using 

31P-NMR and also vary as a function of the anionic and cationic 

component of the ionic liquid. 

Keywords: ionic liquids; solvent properties; NMRmeasurements; 

nucleophilicity; 


P - 0 1 9 5 

A noveL iMMoBiLized ni CoMPLex on A 

SiLiCA-SuPPort. A SPeCtroSCoPiCAL And An 

eLeCtroCheMiCAL Study 

e. MAiMon 1 , S. AttiA 2 , A. ShAMeS 3 , i. ziLBerMAnn 1 , 

d. MeyerStein 4 

1 NRCN, Chemistry, Beer Sheva, Israel 

2 Ben Gurion University of the Negev, Chemistry, Beer Sheva, 

Israel 

3 Ben Gurion University of the Negev, Physics, Beer Sheva, 

Israel 

4 Ariel University Center of Samaria and Ben Gurion University 

of the Negev, Chemistry, Ariel and Beer Sheva, Israel 

The reaction of silica gel particles with aminopropyl 

orthosilicate under a dry atmosphere gives a precursor with the 

amine group that can be readily used as a ‘padlocking’ nucleophile 

for ring closure. This study reports the first covalent binding 

of a nickel-penta-aza-cyclotetradecane complex through a 

non-coordinative nitrogen atom to silica gel particles. These 

grafted particles can serve as a good candidate for electron 

exchange columns (analogous to ion exchange columns). Redox 

cycles with persulfate as the oxidizing agent, and ascorbic acid as 

the reducing agent were performed. Modified electrodes based on 

Nafion with embedded “particles” (containing the NiL complex) 

have been prepared, and CV measurements have been conducted. 

The electrochemical measurements showed no changes in the 

redox potential (E Ni 1/2 3+/2+ L'= +0.750 volt vs. SCE) versus the 

redox potential of the analogous couple Ni3+/2+ L. The ESR 

measurements confirm the new Ni3+ formation. The redox 

behavior and full characterization of NiL' will be presented in 

detail. 

Keywords: nickel complexes; electron exchange columns; 

redox cycles; grafted particles; electrochemistry; 



s959 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 9 6 

tin-enCAPSuLAted ordered MeSoPorouS 

CArBon SPhereS for Li-ion BAtterieS 

P. y. ChAnG 1 , r. A. doonG 1 

1 National Tsing Hua University, Department of Biomedical 

Engineering and Environmental Sciences, Hsinchu City, 

Taiwan 

Tin-based materials have been considered as a good 

candidate for anodes of Li-ion battery (LIB) because of their high 

capacity (Sn, 994 mAh g-1 and SnO , 781 mAh g 2 -1 ), abundance in 

earth, nontoxic, and chemical stable. However, the large volume 

changes during charge/discharge (Li is intercalated/deintercalated) 

processes cause the internal damage to the electrode, and the loss 

of capacity. In this study, the improvement in stability with high 

capacity retention has been demonstrated by embedding Sn 

particles into ordered mesoporous carbon spheres (TOMCS) 

which was synthesized for buffering the volume expansion during 

the insertion and removal of Li ions. A series of TOMCS with 

various weight percentages of tin ranging from 15 to 75 wt% has 

been obtained via the hydrothermal and impregnation method. 

The mesoporous structures of TOMCS in terms of morphology, 

crystallization, and surface area were characterized by 

scanning/transmission electron microscope (SEM/TEM), 

small angle/wide angle X-ray diffraction (XRD), and N2 adsorption/desorption analysis, respectively. TOMCS exhibited 

the body-centered cubic mesoporous arrangement after 

calcination at 700 °C in N and showed obvious Sn(0) and 

2 

SnO phases with the high surface area of around 700 m 2 2 g-1 . 

The electrochemical performances were displayed by Li half cell. 

An extremely high coulomb efficiency of 99% with the stable 

specific capacity of around 300 mAh g-1 after 100 cycles was 

obtained, which indicates that TOMCS can successfully 

accommodate large strain after lithiated electrochemical process. 

Results obtained clearly demonstrate that TOMCS is a novel 

material for anode fabrication for potential application to high rate 

capability and good cyclability LIB. 

Keywords: Li ion battery; Ordered mesoporous carbon 

spheres; Hydrothermal; Impregnation; Cyclability; 


P - 0 1 9 7 

SoLid StAte StruCture of A new nhC-BASed 

CyCLoMetALAted PLAtinuM(ii) CoMPLex 

M. tenne 1 , y. unGer 1 , t. StrASSner 1 

1 Technische Universitaet Dresden, Chemistry and Food 

Chemistry, Dresden, Germany 

Phosphorescent platinum(II) complexes have attracted much 

attention as promising emitters for application in organic 

light-emitting diodes (OLEDs) because their exceptional 

luminescence properties. We recently reported a new class of 

platinum(II) compounds with cyclometalated N-heterocyclic carbene 

(NHC) ligands based on phenylimidazole. The complexes are 

strongly emissive in the green-blue region of the spectrum and their 

properties differ from the previously known complexes with C^N 

cyclometalating ligands derived from e.g. 2-phenylpyridine (ppy) 

or from phenylazoles like phenylpyrazole or 2-phenylimidazole. 

In this presentation we show and discuss the second solid 

state structure of this new class. The platinum(II) complex 

contains a bidentate, cyclometalated phenylimidazol-ylidene 

ligand and an acetylacetonate spectator ligand, which form a 

distorted square planar coordination sphere around the platinum 

center. In the crystal the molecules are oriented in a parallel 

fashion caused by their planarity and several intermolecular 

interactions. 

Keywords: Carbene ligands; Platinum; Solid-state structures; 



s960 

chem. Listy 106, s587–s1425 (2012) 


P - 0 1 9 8 

SyntheSiS And reduCtion of A 

hyPer-CoordinAted CAtion 

[L-PCL -AL]+ (L = nhC, AL = ABnorMAL nhC) 

2 

K. SChwedtMAnn 1 , M. h. hoLthAuSen 1 , 

J. J. weiGAnd 1 

1 WWU Münster, IAAC, Münster, Germany 


Positively charged, hyper-coordinated organophosphorus 

compounds are an interesting and rather undeveloped substance 

class. [1] They can be used as models for the mechanism of 

nucleophilic substitution reactions at a phosphorus-center. 

Therefore, we investigated the reaction of [LPCl ][otf] 2 [2] 

(L = 1.3-bis(2.6-diisopropylphenyl)imidazol-2-ylidene) and L in 

difluorobenzene. The outcome of this reaction is cation 

[L-PCl -aL] 2 + in which the phosphorus atom is pseudo-penta- 

-coordinated by two Cl-substituents, a normal (L) and abnormal 

(aL) NHC. Reaction of [L-PCl -aL] 2 + with KC or Mg leads to 

8 

the clean formation of the P(I)-centered cation [L-P-aL] + . The 

intriguing reaction and bonding situation of cations [L-PCl -aL] 2 + 

and [L-P-aL] + will be discussed. 

references: 

1. Burford N.; Phillips A. D.; Spinney H. A.; Lumsden M.; 

Werner-Zwanziger U.; Ferguson M. J.; McDonald R.; 

J. Am. Chem. Soc. 2005, 127, 3921. 

2. Weigand J. J.; Feldmann K. O.; Henne F. D.; J. Am. Chem. 

Soc. 2010, 132, 16321. 

Keywords: Maingroup; Phosphorus; Cation; Hypercoordinated; 

Reduction; 


P - 0 1 9 9 

PALLAdiuM(ii) CoMPLexeS with CheLAtinG 

BiSCArBene LiGAndS in the SuzuKi-MiyAurA 

CroSS CouPLinG reACtion 

M. MiCKSCh 1 , t. StrASSner 1 

1 Technische Universitaet Dresden, Physical Organic Chemistry, 


Palladium catalyzed cross coupling reactions are one of the 

most powerful carbon-carbon bond-forming processes. The 

Suzuki-Miyaura cross coupling reaction has become a very 

important and widely used method in fine chemical syntheses. 

Since the isolation of a stable free N-heterocyclic carbene (NHC) 

in 1991 a large number of palladium-NHC complexes have been 

investigated. 

We studied the catalytic activity of palladium(II) complexes 

with chelating imidazolium and benzimidazolium ligands in the 

Suzuki-Miyaura cross coupling reaction. N-aryl substituted 

bis-NHC-Pd complexes could be synthesized in three steps 

starting from commercially available anilines. The methylene 

bridged systems with aryl substituents carrying sterically and 

electronically different groups (F, NO , OMe, H, Me, i-Pr) show 

2 

good to excellent catalytic activities in the Suzuki-Miyaura cross 

coupling reaction of aryl bromides. We have shown that ligands 

substituted with electron donating groups lead to higher 

yields, sterically demanding ligands to lower yields in the 

Suzuki-Miyaura cross coupling of aryl bromides. The p-methoxy 

phenyl-substituted bis-NHC-Pd complex turned out to be the most 

active complex. 

Furthermore the p-methoxy phenyl-substituted bis-NHC-Pd 

complex shows a good substrate scope. Aryl bromides with 

electron withdrawing as well as donating groups in para position 

and ortho and di-ortho substituted aryl bromides were coupled in 

excellent yields. 

Keywords: Cross-coupling; Palladium; Carbene ligands; 



s961 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 0 0 

funCtionALizAtion of 

KreBS-tyPe PoLyoxotunGStAteS with 

4-iMidAzoLeCArBoxyLAte 

B. Artetxe 1 , S. reinoSo 1 , L. SAn feLiCeS 1 , 

A. iturroSPe 1 , A. PAChe 1 , 

J. M. Gutiérrez-zorriLLA 1 

1 Universidad del País Vasco, Inorganic Chemistry, Leioa- 

Bizkaia, Spain 

Functionalization of polyoxometalates (POMs) via covalent 

attachment of organic ligands represents a suitable strategy to 

obtain hybrid derivatives of this class of anionic clusters with new 

properties and applications [1] . Several routes have been explored 

to prepare such hybrids, including ligand substitution of labile 

water molecules on 3d-substituted POMs. Despite of being ideal 

candidates because of their two external 3d atoms with three water 

molecules each, Krebs-type [M (H O) (WO ) (XW O ) ] 2 2 6 2 2 9 33 2 npolyoxotungstates 

[2] remain almost unexplored as POM 

precursors in ligand substitution and only oxalate derivatives of 

iron(III) tetra-substituted clusters are known [3] . 

Here we report the direct functionalization of 

3d-disubstituted Krebs-type POMs with 4-imidazolecarboxylate 

(L), which has resulted in two complete families of 

organically derivatized [{MII (L)(H O)} (WO ) (XW O ) ] 2 2 2 2 9 33 2 12tungstoantimonate(III) 

and –bismuthate(III) species, where 

M=Mn, Co, Ni, Zn. The title POMs have been prepared by 

straightforward ligand substitution on pre-formed precursors, but 

also by addition of L to solutions of Krebs-type POMs generated 

in situ or even to solutions of addenda-metal and heteroatom 

sources. 

Functionalization has been spectroscopically determined 

prior to single-crystal X-ray studies. The title species are formed 

from two [B-β-XIIIW O ] 9 33 9- subunits linked by two octahedral 

{WO } internal moieties and two external M 2 II atoms, resulting in 

the well-known Krebs-type skeleton. Each MII center is 

octahedrally coordinated by three O atoms, one O,N-chelating 

POM 

ligand and one water molecule. The hybrid POMs show a 

one-dimensional arrangement in the solid state through triple 

hydrogen-bonding between the imidazolyl N-H groups and 

bridging O atoms of tetrameric {W O } faces. 

4 18 

references: 

1. A. Dolbecq, E. Dumas, C. R. Mayer, P. Mialane, 

Chem. Rev., 2010, 110, 6009–6048. 

2. M. Bösing, I. Loose, H. Pohlmann, B. Krebs, 

Chem. Eur. J., 1997, 8, 1232–1237. 

3. A. Dolbecq, J. D. Compain, P. Mialane, J. Marrot, 

E. Riviere, F. Sécheresse, Inorg. Chem., 2008, 47, 

3371–3378. 

Keywords: Polyoxometalates; Hybrids; Functionalization; 


P - 0 2 0 1 


CoordinAtion CAGeS verSuS SPheriCAL 

MorPhoLoGy uSinG PyridyL-ContAininG 

tridentAte LiGAndS 

t. h. noh 1 , o. S. JunG 1 

1 Pusan National University, Dept. of Chemistry, Busan, 


In order to validate the formation and behavior of cage 

containing a flexible tridentate ligand, we report cage 

compounds, [Pd (L1) ](X) (Pd = (Me en)Pd(II); X 3 2 6 4 - - = BF and 4 

- ClO ; L1 = 1,3,5-tris(isonicotinoyloxyethyl)cyanurate) via 

4 

construction of a new C -symmetric potential triangular 

3 

component with cis-protected ditopic (Me en)Pd(II) as a corner 

4 

linker. A single water molecule is nestled within the new cage, 

and is reversibly adsorbed and desorbed via a combination of the 

adequate space, polar environment, and conformational flexibility 

of the cage. Thus, the duality of liberal and restrictive properties 

of a single water molecule has been discussed based on 

spectroscopic data. In Suzuki-Miyaura C-C cross-coupling 

reactions, the cage complex shows significant catalytic activity 

along with the effects of the isolated single water molecule. On 

the other hand, reaction of (bpy)Pd(PF ) (bpy = 2,2'-bipyridine) 

6 2 

with 1,3,5-tris(nicotinoyloxyethyl)cyanurate (L2) in acetone, and 

followed by addition of water and solvent evaporation allows to 

form amorphous spherical morphology consisting of 

[(bpy) Pd (L2) ](PF ) without any template or additive. In 

3 3 2 6 6 

contrast, the reaction and slowly evaporation in acetone for 

1 month yield single crystals consisting of [(bpy) Pd (L2)(μ - 

3 3 3 

-HPO )](PF (OH) ). The formations of spherical morphology and 

4 3 3 

cage-shaped single crystal appear to be primarily associated with 

the kinetic and thermodynamic control, respectively. The present 

compounds were characterized by IR, 31P NMR, and thermal 

analyses. 

Keywords: Cage compounds; Tridentate ligands; 



s962 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 0 2 

ditoPiC Mo(vi) diAMinotetrAPhenoLAte 

CoMPLexeS 

A. riiSiÖ 1 , A. Lehtonen 2 , r. SiLLAnPää 1 

1 University of Jyväskylä, Chemistry, Jyväskylä, Finland 

2 University of Turku, Chemistry, Turku, Finland 

Oxidomolybdenum(VI) compounds act as effective catalyst 

for olefin metathesis reactions [1] , oxidation of alcohols [2] , 

epoxidation [2] , and oxotransfer [4] reactions. 

Cis-dioxidomolybdenum(VI) complexes with 

aminobisphenols are easily prepared using various molybdenum 

starting materials in polar solvents. The coordination sphere 

around Mo(VI) cation in these complexes is predominantly 

octahedral, and Mo(VI) bonds tightly to hard Lewis bases. 

In order to increase the reactivity and catalytic activity of 

the complexes, some labile ligands, e.g. halides are needed on 

the coordination sphere of Mo(VI). [5] Earlier we have 

modified aminobisphenol complexes of dioxidotungsten(VI) and 

-molybdenum(VI) by the reaction with trimethylsilylchloride. [6] 

In most cases the reaction produces cis and trans isomers of the 

new [MoOCl ] 2 2+ moiety whereas the trans isomer is more stable. [6] 

In this work we report linear ditopic dioxido - 

molybdenum(VI) diaminotetraphenolates with n-alkyl-bridged 

N,N,N’,N’-tetra(2-hydroxybenzyl)diamines. Similar ligands are 

earlier used to form cyclic dinuclear Cu(II) complexes. [7] 

Chloride-for-oxide substitution for the prepared compounds as 

well as some catalytic results are also presented. 

references: 

1. A. H. Hoveyda and A. R. Zhugralin, Nature. 2007, 450, 

243-251. 

2. S. Velusamy, M. Ahamed and T. Punniyamurthy, Org. Lett. 

2004, 6, 4821-4824. 

3. A. U. Barlan, A. Basak and H. Yamamoto, Agnew. Chem. 

Int. Ed. 2006, 45, 5849-5852. 

4. F. J. Arnaiz, R. Aguardo and J. M. M Deilardua, 

Polyhedron, 1994, 13, 3257-3259. 

5. K. J. Ivin, J. C. Mol, Olefin Metathesis and Metathesis 

Polymerisation, Academic Press, London, 1997. 

6. A. Lehtonen and R. Sillanpää, Eur. J. Inorg. Chem. 2006, 

2878–2884. 

7. A. Riisiö, M. M. Hänninen and R. Sillanpää, Eur. J. Inorg. 

Chem. 2006, 1048–1053. 

Keywords: Mo(VI); aminobisphenol; catalysis; 


P - 0 2 0 3 

noveL diene LiGAndS in rhodiuM-CAtALyzed 

1,4-Addition 

M. SChLeSinGer 1 , M. hofMAnn 1 , S. LeonhArdt 1 , 

t. rüffer 1 , M. MehrinG 1 


Germany 

The synthesis and catalytic activity of new diene ligands is 

an ongoing research topic of high interest. [1–2] Among the dienes 

bicyclic strained olefins with interesting electronic properties and 

reactivity are presented by benzobicyclo[2.2.2]-2,5,7-octatriene, 

a combination of an aromatic and a barrelene framework. [3] In the 

last decades several synthetic strategies for such benzobarrelenes 

have been developed. [4–7] Recently, the activity and 

enantioselectivity of rhodium-catalyzed 1,4-addition with chiral 

tetrafluorobenzobarrelene-based ligands was reported. [8] 

Herein, we present a novel Diels-Alder type synthesis route 

for benzobarrelenes bearing substituents at the aromatic ring. 

Starting from the Grignard reagent (2,4,6-Tribromphenyl)- 

-magnesiumbromide we obtained dibromoarynes, which were 

reacted with several benzene derivates to give 

dibromobenzobarrelenes. The synthetic concept gives access to 

diverse benzobarrelenes including carboxylic and phosphonic acid 

derivates. The high high catalytic activity of “in-situ” formed 

rhodium complexes for 1,4-addition with quantitative conversion 

is shown. 

references: 

1. F. Glorius, Angew. Chem. Int. Ed. 2004, 43, 3364. 

2. C. Defieber, H. Gruetzmacher, E. M. Carreira, Angew. 

Chem. Int. Ed. 2008, 47, 4482. 

3. H. E. Zimmerman, R. S. Givens, R. M. Pagni, J. Am. 

Chem. Soc. 1968, 90, 6096. 

4. R. G. Miller, M. Stiles, J. Am. Chem. Soc. 1963, 85, 1798. 

5. D. J. Berry, B. Wakefield, J. Chem. Soc. C 1969, 2342. 

6. N. J. Hales, H. Heaney, J. H. Hollinshead, R. P. Sharma, 

Tetrahedron 1995, 51, 7403. 

7. L. Pu, R. H. Grubbs, J. Org. Chem. 1994, 59, 1351. 

8. R. Shintani, M. Takeda, T. Nishimura, T. Hayashi, Angew. 

Chem. Int. Ed. 2010, 49, 3969. 

Keywords: diene; catalysis; benzobarrelene; 1,4-addition; 

ligand; 



s963 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 0 4 

exPeriMentAL And theoretiCAL StudieS on 

the reACtivity of SiLiCon ContAininG 

PreCurSorS for twin PoLyMerizAtion 

P. KitSChKe 1 , M. MehrinG 1 , A. A. Auer 2 


Germany 

2 Max-Planck-Institut for Bioinorganic Chemistry, Chemistry, 

Mühlheim, Germany 

There has been an increasing interest in novel synthesis 

strategies for porous materials within the last decade. This is 

related to the numerous industrial applications which take 

advantage of the particular structural features of nanomaterials. 

Especially organic-inorganic hybrid materials with well defined 

nanoscaled pore geometry, high porosity and monodisperse 

particle size distribution have become an important field of 

research. Most of the synthetic concepts for such materials 

provide organic-inorganic composite materials, which exhibit 

nanostructures in the range between 2 to 100 nm. [1] The novel 

concept of Twin Polymerization provides a synthesis route 

towards nanoscaled metal oxides as well as metal oxide based 

organic-inorganic composite materials with domains in the range 

below 2 nm. [2] For instance, Twin Polymerization of 

2,2'-Spirobi[4H-1,3,2-benzodioxasiline] gives a composite 

material composed of interpenetrating SiO /Phenol resin networks 

2 

with defined nanostructured domains of 0.5 to 3 nm. Oxidation 

of the composite material leads to highly porous SiO with a BET 

2 

surface area of 904 m2 g-1 , while carbonization and consecutive 

removal of SiO gives microporous carbon with a BET surface 

2 

area of 1018 m2 g-1 . [2a] Here we present the synthesis and 

characterization of new Twin Monomers such as 6,6'-Dimethyl- 

-4H,4'H-2,2'-spirobi[benzo-1,3,2-dioxasiline] and 6,6'-Dibromo- 

-4H,4'H-2,2'-spirobi[benzo-1,3,2-dioxasiline]. Their reaction 

behavior with regard to Twin Polymerization was studied and 

the resulting organic-inorganic composite materials were 

characterized. In order to support our hypothesis of a reactivity 

scale based on steric and electronic features of the monomers, we 

have carried out DFT calculations (B3LYP//def2-TZVPP level of 

theory) in order to obtain more detailed insight into the first 

reaction steps of this novel type of polymerization. 

references: 

1. a) G.Kickelbick, Hybrid Materials-Synthesis Characterization 

and Applications,Wiley-VCH,Weinheim,2007; 

b) P. Gómez-Romero, C.Sanchez, Functional Hybrid 

Materials,Wiley-VCH,Weinheim,2004; 

c) C.Sanchez,L.Rozes,F.Ribot, C.Laberty-Robert, 

D.Grosso, C.Sassoye, C.Boissiere, L.Nicole, C.R.Chimie 

2010,13,3 

2. a)S.Spange, P.Kempe, A.Seifert, A.A.Auer, P.Ecorchard, 

H.Lang, M.Falke, M.Hietschold, A.Pohlers, W.Hoyer, 

G.Cox, E.Kockrick and S.Kaskel, Angew. Chem., Int. 

Ed. 2009,48,8254; 

b) T.Löschner, A.Mehner, S.Grund, A.Seifert, A.Pohlers, 

A.Lange, G.Cox, H.-J.Hähnle, S.Spange, Angew. Chem. 

2012,124,3312; 

c) F.Böttger-Hiller, R.Lungwitz, A.Seifert, M.Hietschold, 

M.Schlesinger, M.Mehring, S.Spange, Angew. Chem. 

Int. Ed.2009,48,8878 

Keywords: Twin Polymerization; DFT Calculations; 

nanoscaled Hybrid Materials; 


P - 0 2 0 5 

new Mo(ii) heteroGeneouS MAteriAL for 

enAntioSeLeCtive CAtALySiS 

M. S. SArAivA 1 , C. d. nuneS 1 , t. G. nuneS 2 , 

M. J. CALhordA 3 

1 Faculty of Science of University of Lisbon, Department of 

Chemistry and Biochemistry, 1100 - 016 Lisboa, Portugal 

2 Instituto Superior Tecnico, CQE, 1049-001 Lisboa, Portugal 

3 Faculty of Science of University of Lisbon, CQB Department 

of Chemistry and Biochemistry, 1100-016 Lisboa, Portugal 

Chiral porous materials have many potencial applications in 

a wide range of areas, such as enantioseparation, chiral catalysis, 

chemical sensors, drug delivery, chiral catalysis. [1] . In this work, 

the synthesis of chiral matrix mesoporous materials was achieved 

using ammonia as co-surfactant [2] . They were used as support to 

prepare chiral molybdenum(II) heterogeneous catalysts to be 

tested in enantioselective oxidation catalysis. The materials 

prepared retain the basic structure of the silicon based matrices, 

but they also display a confined helical environment of the 

channels, as detected by SEM and TEM. 

The inner surface of the chiral material was functionalized 

by reaction of surface SiOH groups with the ligand 

C H NCH=N(CH ) CH (pyca) or a chiral ligand (glypy, a 

5 4 2 2 3 

2-aminopyridine glycidyloxypropyl derivative). Both ligands 

were modified to bear adequate Si(OR) groups, to allow covalent 

3 

binding to the walls of the material. The immoblized ligands react 

with MoI (CO) (NCMe) precursor complex, giving rise to 

2 3 2 

heterogeneous catalysts [3, 4] . All synthesized materials were 

characterized by means of adequate spectroscopic techniques, 

such as solid state NMR, FTIR, XRD, SEM/TEM, and N2 isotherms. The chiral materials were tested as precursors in 

oxidation catalysis, namely, epoxidation of olefins and allylic 

alcohols, with t-butylhydroperoxide. Several substrates were 

tested, from cyclooctene and styrene, to chiral species such as 

r-limonene, cis-hexen-3-ol, trans-2-hexen-1-ol and other allylic 

alcohols. 

Acknowledgements: We thank Fundacio para Ciencia e 

Tecnologia for financial support: PEst-OE/QUI/UI0612/2011. 

MSS (SFRH/BD/48640/2008) thanks FCT for research Grant 

references: 

1. Guo Z, Du Y, Liu X, Ng S, Chen Y (2010) 

Nanotechnology 21: 165103 

2. Yu HB, Zhao L, Ying JY (2007) Adv. Mater. 19: 

2454–2459. 

3. Vasconcellos-Dias M, Nunes CD, Vaz PD, Ferreira P, 

Brand P, Félix V, Calhorda MJ (2008) J. Catal. 256: 

301–311 

4. Silva NU, Fernandes CI, Nunes TG, Saraiva MS, Nunes 

CD, Vaz PD, Applied Catalysis A: General 408 (2011) 

105–116 

Keywords: Molybdenum; Mesoporous materials; 

Enantioselectivity; Epoxidation; 



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chem. Listy 106, s587–s1425 (2012) 


P - 0 2 0 6 

ACidiC wet CheMiCAL etChinG of SiLiCon – 

froM SurfACe CLeAninG to texturinG 

M. LiPPoLd 1 , C. GondeK 1 , e. KroKe 1 , i. rÖver 2 , 

t. BAChMAnn 2 

1 TU Bergakademie Freiberg, Inorganic Chemistry, Freiberg, 

Germany 

2 SolarWorld AG, Sunicon GmbH, Freiberg, Germany 

Acidic wet chemical etching processes are widely utilized 

in semiconductor and photovoltaic industry (cleaning silicon, 

texturing of multicrystalline silicon wafers and recycling of 

silicon). In spite of numerous industrial applications, detailed 

understanding of the etching process is still missing. However, 

dissolving silicon requires a stepwise oxidation of silicon surface 

+ + atoms by oxidants (HNO , NO , NO , H2O , …) and the 

3 2 

2 

formation of soluble complexes by fluoride containing species 

- - (HF, HF , F ). Both processes proceed simultaneously at the 

2 

silicon/etchant interface. Cleaning solar-grade silicon is realized 

by acidic and alkaline solutions. Because of environmental 

aspects, a substitution of HF-HNO -based mixtures by 

3 

HF-H O -containing solutions is of increasing interest. 2 2 [1] For 

etching silicon in HF-H O -H O mixtures concentration 

2 2 2 

depending reactivity studies were performed. Especially metal 

contaminations influence the reactivity of silicon in HF-H O -H O 

2 2 2 

solutions. Resulting surfaces were analyzed by means of scanning 

electron microscopy (SEM) and the formation of porous silicon 

was obtained. However, HF-H O -H O mixtures are suitable for 

2 2 2 

cleaning of small sized silicon particles. During processing solar 

cells, HF-HNO -based etching mixtures are used for texturing 

3 

silicon wafers. Thereby, sulphuric acid is a reasonable additive. [2, 3] 

HF-HNO -H SO etching mixtures were characterized by means 

3 2 4 

of NMR and Raman spectroscopy. For high sulfuric acid 

+ 

concentrations, a stabilization of nitrogen-oxygen cations (NO2 and NO + ) was obtained. Depending on mixture compositions, 

silicon etching rates and etched surface morphologies were 

investigated. In general, the H SO -concentration influences the 

2 4 

mixture reactivity and etched surface morphologies. Surprisingly, 

pore-like etching structures were obtained by SEM and laser 

scanning microscopy (LSM) for H SO -rich mixtures. 2 4 [4] 

references: 

1. H. Wochner, C. Gossmann, H. Lindner, 

DE102006031105A1, 2006. 

2. A. Kübelbeck, C. Zielinski, T. Gölzenleuchter, 

DE19962136A1, 1999. 

3. I. Melnyk, P. Fath, DE102007004060A1, 2007. 

4. M. Lippold, S. Patzig-Klein, E. Kroke, Z. Naturforsch., 

66b, 2011, 155-163. 

Keywords: Silicon; Surface chemistry; Surface analysis; 



P - 0 2 0 7 

SyntheSiS of new titAniuM oxo CLuSterS 

uSinG PhoSPhoniC ACid derivAtiveS 

M. CzAKLer 1 , C. Artner 1 , u. SChuBert 1 

1 Vienna Universty of Technology, Institute of Materials 


Clusters are interesting intermediates between molecules 

and nanoparticles. Unlike nanoparticles they are formed as 

defined and soluble compounds, the structure of which can be 

determined exactly by single crystal XRD and NMR. A versatile 

route to metal oxo clusters are reactions of metal alkoxides with 

carboxylic acids. The metal alkoxides are partly hydrolysed by 

water produced in situ, through esterification of the acid. 

Controlled condensation is thus achieved, and well defined 

clusters are formed, which are stabilized by the carboxylate ligand 

sphere. 

New oxo clusters were prepared by varying the carboxylic 

acids and using mixtures of different carboxylic acids. 

Furthermore, using phosphonate ligands for the clusters, new 

highly interesting compounds were synthesised. By employing 

easily hydrolysed phosphonic acids esters, namely trimethylsilyl 

esters, instead of phosphonic acids themselves, the reaction is 

convenient and the results are better reproducible. 

A new cluster, the first titanium oxo cluster with 

functionalized phosphonate ligands, was thus formed. Its structure 

consists of six titanium atoms and two oxo bridges. Six 

phosphonates are bound to three titanium atoms each, opening 

two interconnected tetrahedrons. Interestingly, the cluster has an 

overall rod-like shape, with only alkoxides ligands on both tips. 

Keywords: Cluster compounds; Titanium; 



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chem. Listy 106, s587–s1425 (2012) 


P - 0 2 0 8 

SyntheSiS of CAtionS [LPCL ] 2 + , [L PCL] 2 2+ And 

[L P] 3 3+ And SuBSequent reACtionS (L = nhC) 

f. d. henne 1 , J. J. weiGAnd 1 

1 WWU Münster, IAAC, Münster, Germany 


Several types of phosphorus-centered cations are known, 

however, most of them require stabilization via adduct formation 

with a Lewis base. [1] Multiply-charged phosphorus-centered 

cations incorporating trivalent P(III)-atoms that are suitable for 

further functionalization are rare. [2] 

In this contribution we present phosphorus-centered cations 

[LPCl ] 2 + 

, [L2PCl]2+ and [L P] 3 3+ that are synthesized from the 

reaction of PCl with “imidazolium-transfer” reagents 3 [3] which are 

prepared from N-heterocyclic carbenes (NHC’s) and 

Me SiOTf. 3 [4] The cations are formed via sequestration of the 

chloro-substituent into Me SiCl. This approach can be extended 

3 

to the arsenic derivative [LAsCl ] 2 + . Substitution reactions have 

been investigated with Me SiCN, Me SiN , (Me Si) S and 

3 3 3 3 2 

reduction reactions to access novel functionalized P(III) 

derivatives. 

references: 

1. a) Burford, N.; Ragogna, P. J.; Dalton Trans. 2002, 4307; 

b) Dyker, C. A.; Burford, N.; Chem. Asian J. 2008, 3, 28. 

2. a) Weigand, J. J.; Burford, N.; Davidson, R. J.; Cameron, T. S.; 

Seelheim, P.; J. Am. Chem. Soc. 2009, 131, 17943; 

b) Weiss, R.; Engel, S; Angew. Chem. Int. Ed. 1992, 104, 239, 

c) J. Petusakova, M. Patil, S. Holle, C. Lehmann, W.; 

Thiel, W.; Alcarazo, M.; J. Am. Chem. Soc 2011, 133, 

20758. 

3. a) Weiss, R.; Salomon, N. J.; Mien, G. E.; Roth, R.; 

Angew.Chem. 1986, 98, 925; 

b) Mendoza-Espinosa, D.; Donnadieu, B.; Bertrand, G.; 

J. Am. Chem. Soc. 2010, 132, 7264. 

4. Weigand, J. J.; Feldmann, K.-O.; Henne, F. D.; 

J. Am. Chem. Soc. 2010, 132, 16321. 

Keywords: Cations; Main Group Elements; Phosphorus; 

Sulfur Heterocycles; 


P - 0 2 0 9 

CyCLoPentASiLAne (CPS) AS A PreCurSor for 

PoLySiLAneS And SiLiCon CoAtinGS 

d. SChMidt 1 , e. KroKe 1 

1 TU Bergakademie Freiberg, Department of Inorganic 

Chemistry, Freiberg, Germany 

Chemical Vapour Deposition (CVD) of monosilane is a wellknown 

method for the synthesis of solar-grade silicon, e.g. for 

thin-film solar cells or thin-film transistors. The use of bulky 

vacuum apparatus and high energy consumption make the process 

expensive. An alternative approach is based on liquid 

perhydridooligosilanes as precursors combined with liquid 

deposition techniques such as spin- or spray-coating to yield thin 

silicon-films after a pyrolysis. Shimoda et al. [1, 2] reported on 

cyclopentasilane 3 (Si 5 H 10 / CPS) as precursor for solution-processed 

silicon thin-films. 

We report on an improved synthesis of CPS, replacement of 

the common hydrogenation agent LiAlH , which can lead to 

4 

polymerization and aluminium impurities. The use of alkylstannanes 

leads to perhydridooligosilanes. Photo-polymerisation of CPS 

provides soluble oligomers. Pyrolysis of the perhydridooligosilanes 

generates cross-linked polymers as well as amorphous and 

crystalline silicon films. Thermogravimetry and DSC experiments 

coupled with mass spectroscopy provide information on the 

thermolysis process. Analysis of the oligomeric intermediates and 

the solid products was performed with FTIR, Raman and 29Si NMR 

spectroscopy. Further information on the chemical structure and 

physical properties of the coatings is provided by ellipsometry, 

XPS, electron microscopy and conductivity measurements. 

references: 

1. Shimoda T., Matsuki Y., Furusawa M., Aoki T., Yudasaka I., 

Tanaka H., Iwasawa H., Wang D., Miyasaka M., Takeuchi Y., 

2006, Nature 440, 783–786. 

2. Tanaka H., Iwasawa H., Wang D., Toyoda N., Aoki T., 

Yudasaka I., Matsuki Y., Shimoda T., Furusawa M., 2007, 

Jpn. J. Appl. Phys. 46, L 886–L 888. 

3. Hengge E., Bauer G., 1975, Monatsh. Chem. 106, 503–512. 

Keywords: Polymerization; Silicon; Amorphous materials; 



s966 

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P - 0 2 1 0 

SoLid-StAte ion exChAnGe of Cu2+ AG+ And Li+ 

on hy zeoLite. ion exChAnGe KinetiC Study 

f. BenALiouChe 1 , y. BouCheffA 1 

1 Ecole Militaire Polytechnique, UER de Chimie Appliquée, 

Alger, Algeria 

The areas of technological applications of ion exchange 

associated to zeolite materials are progressively increasing and 

have attracted ever-growing attention during the past two decades. 

These include uses in catalysis, the removal of nuclear waste or 

other environmental pollutants, ion chromatography and 

detergency [1, 2] . Conventionally, ion exchange is commonly done 

by suspending the zeolite powder in aqueous solutions of salts, 

which contain the desired in-going cation. The major side effect 

of this ion exchange method, compared to solid-state ion exchange 

(SSIE) technique, is the hydrolysis effects that may alter the 

zeolite structure and the adsorption properties [1–3] . SSIE technique 

has not been as extensively studied because of the complexity of 

the process. Information related to the ion exchange reaction 

within zeolites and their dependence to the nature of 

in-going cation is limited and associated phenomena are not well 

understood. In the present study, Ag-, Cu- and Li-exchanged 

zeolites are prepared by the SSIE method. Reactive mixtures of 

HY zeolite and salts containing the in-going cation (AgNO , 3 

CuCl or LiNO ) are reacted at high temperature in pyrex fixed 

2 3 

bed reactor. The ion exchange kinetic is followed using pH-metry 

measurement of the acidic gas leaving the reactor (HNO or HCl) 

3 

and reacting with alkaline solution. On other hand, the produced 

acid is estimated via thermogravimetry. Both structural and 

textural investigations show good conservation of the zeolitic 

structure after ionic exchange. The ion exchange kinetic study 

highlights clearly the complexity of the diffusive mechanisms of 

ions within the micropores of exchanged zeolites. 

references: 

1. H. G. Karge and E. Geidel, in: H. G. Karge and 

J. Weitkamp (Eds). Molecular sieves-science and 

technology, Characterization I, Springer, vol 4, 2004. 

2. Yang, R. T., Adsorbents: fundamentals and applications; 

Wiley-Interscience, 2003. 

3. F. Benaliouche, Y. Boucheffa, F. Thibault-Starzyk, 

Microporous Mesoporous Mater, 147 (2012), 10-16. 

Keywords: Zeolites; Microporous materials; Ion exchange; 

Solid-state reactions; 


P - 0 2 1 1 

SyntheSiS of SinGLe SourCe PreCurSorS for 

ni/zro nAnoCoMPoSiteS 

2 

A. dAte 1 

1 Technische Universität Wien, Material Chemistry, Vienna, 

Austria 

Many natural materials consist of inorganic and organic 

building blocks, i.e. they are inorganic-organic hybrid materials. 

The concept of hybrid materials is used to study fundamental 

processes of materials formation and to transfer ideas to artificial 

materials. One of the greatest advantages of hybrid materials is 

the possibility to create multifunctional materials. 

In the work presented here, bimetallic nanocomposites are 

prepared by means of inorganic-organic hybrid intermediates. To 

this end, single-sourse precursors for sol-gel processing were 

prepared. Organic moieties containing two functional groups are 

used which 

(a) connect two different metal moieties. 

(b) are stable during sol-gel processing. 

(c) allow some pre-orientation of the two metals. 

In this presentation, a compound with both a Schiff base and 

a carboxylate group was employed as bridging ligand in the 

synthesis of heterobimetallic (Ni/Zr) complexes. The resulting 

complex was processed by the sol-gel method, followed by 

calcination to remove the organic linker. The non-hydrolytic 

sol-gel method is also promising. The complex was characterised 

by NMR and IR spectroscopy and the resulting mixed oxide by 

SAXS measurements. 

Keywords: Sol-gel processes; Zirconium; Nickel; 



s967 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 1 2 

SyntheSiS of SiLiCoPhoSPhAteS ContAininG 

Sio6 oCtAhedrA 

S. JähniGen 1 , e. BrendLer 2 , u. BÖhMe 1 , e. KroKe 1 

1 TU Bergakademie Freiberg, Institute of Inorganic Chemistry, 


2 TU Bergakademie Freiberg, Institute of Analytical Chemistry, 


In nature, silicon predominantly appears in tetrahedral 

coordination. A few high-pressure phases are known such as 

stishovite [1, 2] where silicon is in an octahedral coordination. 

Meanwhile, it was also proved that six-fold coordinated silicon is 

present in a small number of silicophosphates. Examples with 

SiO octahedra are SiP O -I 6 2 7 [3] , SiP O -III 2 7 [4] , SiP O -IV 2 7 [5] and 

Si P O [6] . However, for their synthesis high temperatures, 

5 6 25 

transport reactions or the addition of alkali or alkaline earth 

halides are frequently required. 

Here, we present a novel synthesis of silicophosphate solids 

with octahedral silicon structures at room temperature and under 

normal pressure [7] . Anhydrous H PO and alkoxysilanes were 

3 4 

used to form Si/P/O-materials comprise SiO and SiO units plus 

6 4 

PO tetrahedra. The products were fully characterized with 4 29Si-, 31 1 P-, H-NMR-, IR-spectroscopy and single crystal X-ray structure 

analysis. 

The new preparative route opens opportunities to prepare 

further silicophosphates and related materials. 

references: 

1. S. M. Stishov, S. V. Popova, Geokhimiya 1961, 837. 

2. E. C. T. Chao, J. J. Fahey, J. Littler, J. Geophys. Res. 1962, 

67, 419. 

3. E. Tillmanns, W. Gebert, W. H. Baur, J. Solid State Chem. 

1973, 7, 69. 

4. G. Bissert, F. Liebau, Acta Cryst. 1970, B26, 233. 

5. F. Liebau, K. F. Hesse, Z.Kristallogr. 1971, 133, 213. 

6. H. Mayer, Monatsh. Chem. 1974, 105, 46. 

7. S. Jähnigen, E. Brendler, U. Böhme, E. Kroke, 

Chem. Commun. 2012, submitted. 

Keywords: Silicon; Phosphorus; Coordination modes; 


P - 0 2 1 3 

C^C*-CyCLoMetALLAted PLAtinuM(ii) 

CoMPLexeS with trifLuoroMethyL-ACAC 

LiGAndS – SyntheSiS And eLeCtroniC effeCtS 

A. tronnier 1 , n. niSChAn 1 , t. StrASSner 1 

1 Technische Universitaet Dresden, Physical Organic Chemistry, 


A series of C^C*-cyclometallated platinum(II) 

trifluouromethyl-acac complexes could be synthesized via a new 

synthetic route. 

They have been characterized by standard methods 

(NMR, EA) as well as solid-state structures. Quantum chemical 

calculations on the HOMO and LUMO levels show significant 

differences to the previously reported acac-derivatives. 

Keywords: platinum; carbene ligands; Density functional 

calculations; Solid-state structures; Photophysics; 



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chem. Listy 106, s587–s1425 (2012) 


P - 0 2 1 4 

A SuLfonyL SuBStituted diLithio 

MethAndiide: froM itS eLeCtroniC 

StruCture to trAnSition MetAL CArBene 

CoMPLexeS 

v. GeSSner 1 , f. SChMitt 1 , P. SChrÖter 1 

1 Institut für Anorganische Chemie, Universität Würzburg, 

Wuerzburg, Germany 

Since the pioneering work by E. O. Fischer and R. R. Schrock, 

transition metal carbene complexes have found wide-ranging 

applications. These complexes are generally divided into two 

classes, the Fischer-type carbene and the Schrock-type alkylidene 

complexes. However in this context, carbene complexes formed 

from geminal dianions, above all dilithiated bis(iminophosphorano) 

and bis(thiophosphoryl)methanes, have gained special interest as 

they seem to contradict this general classification pattern. [1] Here, 

the metal carbon bond is formed by a four-electron donation from 

the ligand to the metal, resulting in a highly nucleophilic carbon 

atom. [2] 

Investigations have so far concentrated on the readily 

available bis(phosphonium) systems, thus leaving the impact of 

the α-substituent on the nature of the metal carbon bond and thus 

on the reactivity of the complex unknown. However, electronic 

effects of substitutents at the carbene carbon have shown to 

crucially influence the electronic properties and reactivity of 

carbene complexes. Here we present a novel sulfonyl substituted 

dilithio methandiide as precursor for transition metal carbene 

complexes. [3] The methandiide features a distorted carbon 

environment which differs from the ideal tetrahedral arrangement. 

This is mainly due to geometrical restriction of the donor 

functions and can be described by two different bonding modes 

of the lithium atoms with the sp2hybridized carbon atom. 

Transmetallation with metal salts gives way to early and late 

transition metal carbene complexes in high yields. 

references: 

1. D.J. Mindiola, J. Scott, Nature Chem. 2011, 3, 15. 

2. a) T. Cantat, N. Mézailles, A. Auffrant, P. Le Floch, 

Dalton Trans. 2008, 1957. 

b) S. Harder, Coord. Chem. Rev. 2011, 255, 1252. 

4. V. H. Gessner, P. Schröter 2012, submitted. 

Keywords: lithium; carbene; carbanions; transition metals; 


P - 0 2 1 5 

SwitCh it! – PhotoChroMiC CArBene LiGAndS 

u. MonKowiuS 1 , M. KAiSer 1 , S. Leitner 1 , 

C. hirtenLehner 1 

1 Johannes Kepler University Linz, Institut für Anorganische 

Chemie, Linz, Austria 

N-Heterocyclic carbenes (NHC) are established ligands for 

almost all transition metals and various highly active catalyst 

systems bearing NHC ligands have been reported. Nevertheless, 

the control of their catalytic performance by external stimuli is 

still a challenging task. Various concepts for the regulation of the 

activity including the variation of the pH-value, temperature or 

solubility have been introduced, but besides the activation of 

precatalysts by irreversible photolytic reactions the reversible 

regulation of catalysts by light is still in its infancy [1] . Promising 

candidates for this purpose are photochromic systems which can 

be switched between two different states, e.g. diazobenzenes or 

spiropyranes. Based on these moieties, ligands can be designed 

which are capable of reversibly shielding an active center of a 

metal complex catalyst by steric hindrance. 

We will present our first results of NHC based ligands 

bearing a diazobenzene group and demonstrate their ligand 

properties by the synthesis of the corresponding Ag(I) and Au(I) 

complexes. The Ag(I) complex is obtained by the reaction of the 

functionalized imidazolium salt with Ag O, successive 

2 

transmetallation with (Me S)AuCl yields the Au(I) complex. The 

2 

E->Z isomerisation is induced by UV-light. The thermal back 

reaction is very slow and account for minutes even at 80 °C 

making an effective switching under catalytic conditions feasible. 

references: 

1. R. S. Stoll, S. Hecht, Angew. Chem. Int. Ed. 2010, 49, 

5054-5075; 

M. D. Segarra-Maset, P. W. N. M. van Leeuwen, Z. Freixa, 

Eur. J. Inorg. Chem. 2010, 2075-2078. 

Keywords: Photochromism; Carbene ligands; Gold; Silver; 



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chem. Listy 106, s587–s1425 (2012) 


P - 0 2 1 6 

PhotoCheMiCAL, PhotoPhySiCAL And 

BioLoGiCAL ProPertieS of noveL wAter 

SoLuBLe PhthALoCyAnineS BeArinG 

trifLuoroMethyLquinoLine GrouPS 

d. evren 1 , A. KALKAn BurAt 1 , M. durMuS 2 , 

B. S. SeSALAn 1 


2 Gebze Institute of Technology, Chemistry, Istanbul, Turkey 

Email: evren@itu.edu.tr, kalkanayf@itu.edu.tr, 

sungurs@itu.edu.tr, durmus@gyte.edu.tr 

For photodynamic therapy (PDT), a combination of a 

photosensitizing drug and light in the presence of molecular 

oxygen is used to obtain a therapeutic effect, and has been 

proposed as an alternative treatment to complement conventional 

protocols in the management of malignant tumours and many 

other nononcologic diseases [1] . The use of photosensitizing agents 

for inactivation of several cancer cells has been widely 

studied [2] . Due to their high molar absorption coefficient in the red 

part of the spectrum, photostability, and long lifetimes of the 

photoexicited triplet states, phthalocyanines (Pcs) are known to be 

useful photosensitizers [3, 4] . The aggregation properties of Pcs are 

very important for the development of new photosensitizers [5] . 

The aim of our ongoing research is to synthesize 

water-soluble phthalocyanines to be used as potential PDT agents. 

In this work; photophysical, (fluorescence quantum yields and 

lifetimes), photochemical (singlet oxygen and photodegradation 

quantum yields) and biological properties of water soluble 

quarternized metal free, zinc and indium phthalocyanines 

including trifluoromethylquinoline substituents on the peripheral 

positions are presented. 

references: 

1. A.C. Tedesco, J.C.G. Rotta, C.N. Lunardi, Curr. Org. 

Chem. 7 (2003) 187–196. 

2. J. Moan, K. Berg, Photochem. Photobiol. 55 (1992) 

931–948. 

3. S. Kudrevich, N. Brasseur, C. La Madeline, S. Gilbert, 

J. E. van Lier, J. Med. Chem. 40 (1997) 3897–3904. 

4. R. Bonnett, Chem. Soc. Rev. 24 (1995) 19–33. 

5. K. Tabata, K. Fukushima, K. Oda, I.J. Okura, 

J. Porphyrins Phthalocyanines.4 (2000) 278–284. 

Keywords: DNA; Singlet oxygen; Phthalocyanines; 

Photodynamic theraphy; 


P - 0 2 1 7 

reverSiBLe PhASe trAnSforMAtion And 

MeChAnoChroMiC LuMineSCenCe of zn(ii)- 

And Cd(ii)-diPyridyLAMide CoordinAtion 

frAMeworKS 

B. C. tzenG 1 

1 National Chung Cheng University, Chemistry and 

Biochemistry, Chiayi, Taiwan 

A 1-D double-zigzag framework, {[Zn(paps) (H O) ](ClO ) } 2 2 2 4 2 n 

(1)(paps = N,N'-bis(pyridylcarbonyl)-4,4'-diaminodiphenyl thioether), 

was synthesized by the reaction of Zn(ClO ) with paps. However, 

4 2 

a similar reaction, except that dry solvents were used instead, led 

to the formation of a novel 2-D polyrotaxane framework, 

[Zn(paps) (ClO ) ] (2). The above difference relies on the fact 

2 4 2 n 

that water coordinates to the Zn(II) ion in 1, but ClO 4 

- anion 

coordination is found in 2. Notably, both structures can be 

interconverted by heating and grinding in the presence of 

moisture, and such structural transformation can also be proven 

experimentally by powder and single-crystal X-ray diffraction 

studies. The related papo (papo = N,N'-bis(pyridylcarbonyl)-4,4'diaminodiphenyl 

ether) and papc (papc = N,N'-(methylenedi-p- 

-phenylene)bispyridine-4-carboxamide) ligands were used to react 

with Zn(II) ions as well. When we performed a similar reaction with 

dry solvents, except that papo was used instead of paps, the product 

mixture contained mononuclear [Zn(papo)(CH OH) ](ClO ) (5) 

3 4 4 2 

and the polyrotaxane [Zn(papo) (ClO ) ] (4). From the PXRD 

2 4 2 n 

data, grinding this mixture in the presence of moisture 

resulted in the total conversion to the pure double-zigzag 

{[Zn(papo) (H O) ](ClO ) } (3) immediately. Upon heating 

2 2 2 4 2 n 

the double-zigzag 3, the polyrotaxane framework of 

[Zn(papo) (ClO ) ] (4) can be recovered. The double-zigzag 

2 4 2 n 

{[Zn(papc) (H O) ](ClO ) } (6) and polyrotaxane [Zn(papc) (ClO ) ] 2 2 2 4 2 n 2 4 2 n 

(7) can be synthesized in a similar reaction. Although heating the 

double-zigzag 6 can undergo structural transformation to give the 

polyrotaxane 7, grinding its solid samples in the presence of 

moisture cannot lead to the formation of the double-zigzag 6. 

Significantly, the bright emissions for double-zigzag frameworks 

of 1 and 3 and weak ones for polyrotaxane frameworks of 2 and 

4, respectively, can also show interesting mechanochromic 

luminescence. The related Cd(II)-dipyridylamide coordination 

frameworks have been also investigated for the comparison 

purpose. 

Keywords: phase transformation; mechanochromic 

luminescence; coordination frameworks; 



s970 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 1 8 

hiGhLy StruCtured And hiGh SurfACe SS-SiC 

froM PLAnt MAteriAL 

M. neuMAnn 1 , r. nÖSKe 1 , B. tierSCh 1 , P. StrAuCh 1 

1 University of Potsdam, Institute of Chemistry, Potsdam, 

Germany 

The high-temperature-resistant silicon carbide, SiC, with 

interesting mechanical, chemical as well as electrical properties 

and the potential for widespread applications in electronics, 

semiconductor industry and catalysis is experiencing a new wave 

of interest. Purity, structural parameters and morphology play a 

key role influencing the performance of final application. 

Complex morphologies, high specific surface areas and high 

silicon content offer an important potential for high performance 

ceramics from plant materials. 

Silicon carbide syntheses via carbothermal processes are 

known since years [1] . We are now able to produce highly 

structured biomorphous SiC with the possibility to transfer typical 

plant morphologies from renewable plant materials, especially for 

twoEquisetaceae species, in a one step procedure at relatively low 

temperatures (approximately 1200 °C). A silicon-carbon-mixture, 

given by the plant itself [2] , is used as precursor. The finely 

dispersed carbon precursor is prepared by pyrolysis of the organic 

plant matrix. Yields are between 3 to 100 % and we obtain high 

specific surfaces up to 660 m2 g-1 depending on reaction 

parameters for the pure β-SiC [3] . The reported thermal synthetic 

method is, therefore of interest for applications where a pure, 

porous, thermally and chemically stable, as well as a cheap and 

easily available material is needed. 

references: 

1. a) Y. L. Chiew, K. Y. Cheong, Mater. Sci. Eng. B 2011, 

176, 951-964.; 

b) R. Nöske, I. Horn, Ger. Patent DE 10 2008 042 499, 

2008. 

2. M. Neumann, R. Nöske, S. Wagner, P. Strauch, 

Z. Naturforsch., 2010, 65b, 1113-1120. 

3. a) M. Neumann, R. Nöske, A. Taubert, B. Tiersch, 

P. Strauch, J. Mater. Chem., 2012, 22, 9046-9051.; 

b) R. Nöske, M. Neumann, P. Strauch, Ger. Patent DE 10 

2011 056 122.6, 2011. 

Keywords: Ceramics; Biomass; Carbides; 


P - 0 2 1 9 

nMr inveStiGAtionS of the intrA- And 

interMoLeCuLAr exChAnGe PhenoMenA of 

the 3,5-diMethyLPyrAzoLyL SiLAne CLSi(Pz*) 3 

And reLAted CoMPoundS 

f. Bitto 1 , e. BrendLer 2 , e. KroKe 1 

1 TU Bergakademie Freiberg, Inorganic Chemistry, Freiberg, 

Germany 

2 TU Bergakademie Freiberg, Analytical Chemistry, Freiberg, 

Germany 

Chlorine substituted 3,5-dimethylpyrazolyl (pz*) silanes 

exhibit interesting inter- and intramolecular exchange phenomena. 

Intermolecular reactions involving Si-N vs. Si-Cl dismutation 

cause equilibria between the three species Cl Si(pz*) , ClSi(pz*) 2 2 3 

(main component) and Si(pz*) . Intramolecular exchange is 

4 

interpreted as a “dangling” of the pz*-moieties in every pyrazolyl 

silane molecule itself. [1] 

These phenomena were investigated with one and two 

dimensional NMR spectroscopic methods at variable 

temperatures. The “dangling” of the pz*-moieties is slowed down 

with decreasing temperature and are best visible in the spectra 

recorded at -40°C. The use of 1H-29Si-HMBC spectroscopy 

(heteronuclear multiple bond correlation) allows to assign the 

olefinic protons to the corresponding silicon species. In the EXSY 

(exchange spectroscopy) spectra the exchange between the 

pz*-methyl groups and the NOE (nuclear overhauser effect) 

correlation between the methyl groups and the olefinic protons 

are observed at the same time in one spectrum. 

The data obtained with EXSY and HMBC-spectroscopy in 

combination with variable temperature 1H NMR allows 

qualitative conclusions concerning the rate of exchange and the 

dependence on the silicon corresponding species. 

references: 

1. F. Bitto, J. Wagler, E. Kroke, Eur. J. Inorg. Chem. 2012, 

in press, doi:10.1002/ejic.201101409. 

Keywords: Silanes; NMR spectroscopy; Exchange interactions; 



s971 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 2 0 

new fe(ii) PinCer hydride CoMPLexeS And 

their APPLiCAtion in hydroGenAtion 

reACtionS 

B. BiChLer 1 , K. Mereiter 2 , K. KirChner 1 

1 Institute of Applied Synthetic Chemistry, Vienna University of 

Technology, Vienna, Austria 

2 Institue of Chemical Technology and Analytic, Vienna 

University of Technology, Vienna, Austria 

Hydrogenation for reducing ketones to alcohols is a 

common and often used reaction in modern synthetic organic 

chemistry. Particularly the stereoselective synthesis of enantiopure 

alcohols is an important topic and usually catalysts based on 

precious metals, like ruthenium, iridium or rhodium are used. Well 

defined iron complexes with similar reactivity would provide an 

excellent alternative, due to the high natural abundance, low costs 

and low toxicity. 

We here report the synthesis, characterization and reactivity 

of Fe(II) Complexes and their application in hydrogenation 

reactions. The complexes are based on PNP pincer type ligands 

with a pyridine or pyrimidine ring with a P-N bond. [1] All ligands 

are accessible in modular fashion based on simple synthetic 

methodologies. A useful feature of these ligands is that steric, 

electronic, and even stereochemical parameters can be 

manipulated by modifications of the phosphino R groups and the 

substituents at the aromatic backbone in order to control the 

reactivity at the metal center. 

The ligands are reacted with FeX (X=Cl, Br) in the 

2 

presence of CO and a silver salt to get a bis-CO PNP precatalyst 

of the type [Fe(PNP)(CO) Cl] 2 + . The CO co-ligand is essential in 

order to keep the iron center in a low-spin state throughout the 

catalytic cycle as revealed by DFT calculations. Reduction with 

elemental Zn yields the catalytic active mono-hydride species. 

references: 

1. D. Benito-Garagorri, K. Kirchner, Acc. Chem. Res. 2008, 

41, 201 - 213. 

Keywords: homogeneous catalysis; hydrogenation; iron; 

Density functional calculations; 


P - 0 2 2 1 

SyntheSiS And ChArACterizAtion of noveL 

wAter SoLuBLe PhthALoCyAnineS BeArinG 

trifLuoroMethyLquinoLine GrouPS 

d. evren 1 , A. KALKAn BurAt 1 

1 Istanbul Technical University, Department of Chemistry, 

34469, Istanbul, Turkey 

Email: evren@itu.edu.tr, kalkanayf@itu.edu.tr 

Phthalocyanine (Pc) compounds are a very important class 

of organic materials. They possess a conjugated system of 

π-electrons and exhibit the ability to chelate metal ions at the 

center of the ring. The properties of phthalocyanines are influced 

both by the nature of substituents on the ligand and by the nature 

of the metal ion in the inner core. Phthalocyanines have found 

widespread applications in various areas including printing inks, 

catalysts, display devices, chemical sensors, non-linear optical 

devices, data storage systems, liquid crystalline charge carriers and 

second generation photosensitizers for photodynamic therapy . [1–3] 

Recently, fluorinated metallophthalocyanines (MPcs) are 

receiving a great deal of attention due to their interesting 

electron-transfer and photosensitizing properties. [4] 

In the present work, we have synthesized novel water 

soluble quarternized metal free,zinc and indium phthalocyanines 

including trifluoromethylquinoline substituents on the peripheral 

positions. The structure of synthesized complexes were 

1 characterized by H-NMR, UV-Vis, FT-IR and Mass 

spectroscopic techniques. 

references: 

1. N. B. McKeown, Phthalocyanine Materials Synthesis, 

Structure and Function Cambridge University Press., 1998. 

2. C.C. Leznoff, A. B. P. Lever, Phthalocyanines; Properties 

and Applications, vol. 1-4, VCH, Weinheim, 1989-1996. 

3. A. K. Burat, A. Koca, J. P. Lewtak, D. T. Gryko, 

Synthetic Metals, vol. 161 (2011), pp. 1537-1545. 

4. A. K. Burat, Z.P. Öz, Z. A. Bayir, Monatshefte für Chemie, 

vol. 143, (2012), pp. 437-442. 

Keywords: Phthalocyanines; Indium; Zinc; Solubility; 

Quinoline; 



s972 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 2 2 

the roAd froM rodS to CheLAte CArBene 

CoMPLexeS of ChroMiuM And tunGSten on 

thienyL tyPe LiGAndS 

n. vAn JAArSveLd 1 , S. Lotz 1 , d. C. LiLeS 1 

1 University of Pretoria, Chemsirty, Pretoria, Republic of South 

Africa 

Known chelate carbene complexes are subject to the 

available reactivity of the chosen ligand [1] . This has been 

favourable for the synthesis of many mono and biscarbene 

complexes, but not chelate Fischer carbene complexes, making 

them extremely rare compared to N-heterocyclic chelate carbene 

complexes [2–3] . Reaction of dilithiated thiophene species, 

(2,5-Li C H S) with W(CO) and subsequent alkylation afforded 

2 4 2 6 

the known thienyl monocarbene complex and the novel 

biscarbene complex. To prepare chelated carbene complexes the 

ligand must be modified to divert reactivity to neighbouring 

carbon atoms. For this purpose, two options have been suggested: 

Blocking and activation (or a combination of both). Blocking an 

α-position on thiophene with a methyl substituent (2-C H (Me)S) 

4 3 

and reacting with two equivalents n-BuLi, gave the monocarbene 

and the unstable methylene biscarbene complex. Monocarbene 

complexes and the targeted 2,3-thienyl biscarbene chelated 

complexes were obtained from a lithium-halogen exchange 

reaction of 3-bromo-5-methylthiophene. Alternatively, the 

reaction of di(thiophen-2-yl)methane (DTM) with two equivalents 

n-BuLi afforded the di(thiophen-2-ylene)methane biscarbene 

rods, as the only isolated products. Blocking both 3 and 4 

positions on a thiophene ligand, the desired chelated biscarbene 

complexes were accessible only from 2,3-dibromobenzo[3,2- 

-b]thiophene, while lithiation of benzo[3,2-b]thiophene (C H S) 8 6 

only gave the known benzothienyl monocarbene. Modification of 

the blocking group allows for the reaction of dilithiated 4-methyl- 

-4H-thieno[3,2-b]pyrrole (C H N(Me)S) species with [M(CO) ] 

6 4 6 

to afford the monocarbene complex, the dimetal biscarbene rod 

and the monometal biscarbene chelated complex, after subsequent 

alkylation. 

references: 

1. E. O. Fischer, W. Röll, N. Hoa Tran Huy, and 

K. Ackermann, Chem. Ber., 1982, 115, 2951. 

2. M. A. Sierra, Chem. Rev., 2000, 100, 3591. 

3. D. I. Bezuidenhout, S. Lotz, D. C. Liles, and 

B. van der Westhuizen, Coord. Chem. Rev., 2012, 256, 479. 

Keywords: Carbene; Chelate; Reactivity; 


P - 0 2 2 3 

noveL Green-eMittinG iridiuM(iii) CoMPLexeS 

BASed on 2-(2,3,4-trifLuoroPhenyL)Pyridine 

for SoLution-ProCeSSed orGAniC 

LiGht-eMittinG diodeS 

y. KiM 1 , S. yun 1 , i. hwAnG 1 , d. KiM 1 , J. PArK 1 , S. Jin 1 

1 Pusan National University, Department of Chemistry 

Education, Busan, Republic of Korea 

In the past decades, organic light-emitting diodes (OLEDs) 

based on phosphorescent complexes have attracted increasing 

attention. Many OLEDs have been fabricated by thermal 

evaporation of several organic layers, making the fabrication 

process relatively complicated and expensive. However, solution 

processed OLEDs proved satisfactory alternative to those 

processed by vacuum deposition due to their significantly reduced 

production cost [1] . 

We synthesized three phosphorescent iridium(III) 

complexes based on 2-(2,3,4-trifluorophenyl)pyridine, and 

their structures and luminescent properties were characterized 

for solution-processed PhOLEDs; (tfppy) Ir(pic) (1), 

2 

(tfpmpy) Ir(pic) (2) and(tfpCF py) Ir(pic) (3), where 

2 3 2 

tfppy = 2-(2',3',4'-trifluorophenyl)pyridine, tfpmpy = 2-(2',3',4'- 

-trifluorophenyl)-5-(methyl)pyridine, tfpCF py = 2-(2',3',4'- 

3 

-trifluorophenyl)-5-(trifluoromethyl)pyridine and pic = picolinic 

acid. The complexes exhibited photoluminescence peaks 

at 486, 482 and 513 nm and quantum yields of 19, 18 and 27 % 

in solution for complexes 1, 2 and 3, respectively. Complex (1) 

exhibited a red shift emission compared to Firpic, indicating that 

the conjugation effect of the 3-position –F atom was significant 

and led to an increase of HOMO energy level. 3–Substituted CH3 group in pyridine caused a blue-shift in emission whereas a 

red-shift was observed for 2–CF substituted pyridine resulting 

3 

from the change of LUMO energy level due to the electronic 

effect in pyridine ring. The solution-processed PhOLED 

performance of complexes (1), (2), (3) showed CIE coordinates 

of (0.18, 0.47), (0.18, 0.47), (0.29, 0.62), maximum external 

quantum efficiency of 8.48, 6.76 and 7.23% and luminance 

efficiency of 21.18, 16.66 and 25.43 cd/A respectively. 

references: 

1. a) S.-J. Lee, J.-S. Park, M. Song, I. A. Shin, Y.-I. Kim, 

J. W. Lee, J.-W. Kang, Y.-S. Gal, S. Kang, J. Y. Lee, 

S.-H. Jung, H.-S. Kim, M.-Y. Chae, S.-H. Jin, 

Adv. Funct. Mater. 2009, 19, 2202. 

b) M. Song, J.S. Park, M. Yoon, A.J. Kim, Y.I. Kim, 

Y.-S. Gal, J.W. Lee, S.-H. Jin, J. Organomet.Chem. 

2011, 696, 2122. 

Keywords: iridium(III) complex; 



s973 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 2 4 

tetrAChLoridoCuPrAteS(ii) – SyntheSiS And 

eLeCtron PArAMAGnetiC reSonAnCe (ePr) 

SPeCtroSCoPy 

A. winter 1 , A. zABeL 1 , P. StrAuCh 1 

1 University of Potsdam, Chemistry, Potsdam-Golm, Germany 

Ionic liquids (ILs) based on metal containing anions and/or 

cations are of interest for a variety of technical applications, e.g. 

synthesis of (nano)particles, magnetic or thermochromic 

materials. 

We present the synthesis and the results of electron 

paramagnetic resonance (EPR) spectroscopic analyses of a series 

of some new potential ionic liquids on the basis of 

tetrachloridocuprates(II), [CuCl ] 4 2- , with different sterically 

demanding cations, e.g. hexadecyltrimethylammonium, 

tetradecyltrimethylammonium, tetrabutylammonium and 

benzyltriethylammonium. The cations in this series were used to 

achieve a reasonable separation of the paramagnetic Cu(II) centers 

for EPR spectroscopy because this method is very suitable for 

investigation of paramagnetic copper complexes in different 

physical states (as solids and as liquids). The spectra are all of 

axial symmetry but the hyperfine structure was not resolved. This 

is due to the exchange broadening, resulting from still incomplete 

separation of the paramagnetic Cu(II) ions. Nevertheless, the 

principal main values of the electron Zeemann g-tensor (gparallel and g ) of the complex anions could be determined. 

perpendicular 

Even though the solid substances show slightly different 

colors, the UV/Vis spectra of the solutions (acetonitrile) are nearly 

identical, indicating no structural changes of the 

tetrachloridocuprate moieties. In contrast the X-ray structures of 

this type of complexes give a proof of structural differences in 

crystalline state. 

The complexes have a promising potential, e.g. as high 

temperature ionic liquids, as precursors for the formation of copper 

chloride particles or as catalytic paramagnetic ionic liquids . [1] 

references: 

1. A. Winter, A. Zabel and P. Strauch, Int. J. Mol. Sci. 2012, 

13, 1612-1619. 

Keywords: Cuprates; Ionic Liquids; 


P - 0 2 2 5 

uSinG MeLeM AS nuCLeoPhiLiC reAGent to 

forM CyCLiC iMideS 

A. SChwArzer 1 , e. KroKe 1 

1 TU Bergakademie Freiberg, Institute of Inorganic Chemistry, 


Melem C N (NH ) is one of the most important starting 

6 7 2 3 

materials for the synthesis of tri-s-triazines. In these reactions, 

melem is usually attacked nucleophilically, e.g. to form 

melonates [1] or cyamelurates. [2] In literature, reactions describing 

the amino groups of melem as a nucleophil are rare. With 

formaldehyde it gives a methanol derivative [3] and with PCl5 iminophosphoranes are formed. [4] 

The current study presents the use of melem as nucleophilic 

reagent towards carbonyl compounds, e.g. to form cyclic imides. 

In detail, reactions with phthalic and pyromellitic derivatives were 

carried out in different solvents and as solid state reaction to 

access new types of monomeric and polymeric heptazine based 

triimides. 

The monomer exhibits a planar molecular structure as 

indicated by crystal structure analysis and interesting properties 

such as high chemical and thermal stability up to 500 °C and 

remarkable photoluminescence at 500 nm. 

These properties provide new targets and prospects using 

melem as a reagent towards other strong electrophiles. 

references: 

1. e.g. 

a) J. Liebig, Ann. Chem. 1855, 95, 257-282; 

b) J. Liebig, Ann. Chem. 1844, 50, 337-363; 

c) C. E. Redemann, H. J. Lucas, J. Am. Chem. Soc. 1939, 

61, 3420-3425; 

d) E. Horvath—Bordon, E. Kroke, I. Svoboda, H. Fuess, 

R. Riedel, New J. Chem. 2005, 29, 693-699. 

2. e.g. 

a) E. Horvath-Bordon, E. Kroke, I. Svoboda, H. Fueß, R. 

Riedel, N. Sharma, A. K. Cheetham, Dalton Trans. 2004, 

3900-3908; 

b) A. Sattler, M. R. Budde, W. Schnick, Z. Anorg. Allg. 

Chem. 2009, 635, 1933-1939. 

3. R. I. Spasskaya, A. I. Finkelshtein, E. N. Zilberman, 

V. A. Galperin, Zh. Obshch. Khim. 1976, 46, 1423. 

4. T. Saplinova, C. Lehnert, U. Böhme, J. Wagler, E. Kroke, 

New J. Chem. 2010, 34, 1893-1908. 

5. a) A. Schwarzer, U. Böhme, E. Kroke, Chem. Eur. J. 2012, 

submitted; 

b) A. Schwarzer, E. Kroke, patent application filed. 

Keywords: Heterocycles; Luminescence; X-ray diffraction; 



s974 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 2 6 

ControLed MetAL-MetAL CoMMuniCAtion in 

ferroCenyL CArBene CoMPLexeS 

B. vAn der weSthuizen 1 , P. SwArtS 2 , d. LiLeS 1 , 

J. SwArtS 2 , d. Bezuidenhout 1 


Africa 

2 University of the Free State, Chemistry, Bloemfontein, 

Republic of South Africa 

Fischer carbene complexes of the type [M(CO) =CFc(OEt)] 

5 

(Fc=ferrocenyl; M =Cr, W) has been reported.Little is known on 

the electrochemical behavior of these complexes [1] . Ambiguity 

regarding the extent of M-M communication remains [2, 3] . 

Cyclovoltammetric studies were performed on a range of 

ferrocenyl carbene complexes, exhibiting in all cases, except 

[Mn(CO) =CFc(NHBu)], quasi electrochemical reversible one 

2 

electron oxidations of the central metal (Cr, Mn) and at least one 

oxidation for Fe2+ /Fe3+ . These well resolved peaks had separations 

of more than 400mV. Thus charges on the metal centres remain 

localized. For [Mn(CO) =CFc(NHBu)], the Mn and Fc peaks 

2 

overlapped implying charges on the oxidized metal centres are 

delocalized. Aminolysis to yield this complex was done to 

investigate the greater donating ability of the amino-substituent. 

Increased contribution of its resonance structure in the 

ground state is expected and π-back donation from the Mn 

towards the carbene carbon is inhibited.The isolation of 

[M(CO) =CFc(OEt)] 5 + [PF ] 6 - , was achieved by chemical 

oxidation.Controlled electron flow is useful in molecular switches 

and nanotechnology for application in molecular computers [4] . 

Utilisation of this property in directing the site of activity in this 

type of molecules is being explored in our laboratories. 

references: 

1. D.I. Bezuidenhout, S. Lotz, D.C. Liles, B. van der Westhuizen, 

Coordination Chemistry Reviews. 2012, 256, 479. 

2. a) R. Martinez-Alvarez, M. Gomez-Gallego, I. Fernandez, 

M.J. Mancheno, M.A. Sierra, Organometallics. 2004, 

23, 4647, 

b) A. J. L. Pombeiro, J. Organomet. Chem. 2005, 690, 

6021. 

3. D. I. Bezuidenhout, W. Barnard, B. van der Westhuizen, 

E. van der Watt, D.C. Liles, Dalton Trans. 2011, 40, 6711. 

4. a) J.P. Sauvage (Ed.), July 2001, Molecular Machines & 

Motors (Structure and Bonding), 1st edition, Springer, 

New York; 

b) J. E. Green, J.W. Choi, A. Boukai, Y. Bunimovich, 

E. Johnston-Halperin, E. DeIonno, Y. Luo, B.A. Sheriff, 

K. Xu, Y.S. Shin, H-R. Tseng, J.F. Stoddart, J.R. Heath, 

Nature. 2007, 445, 414. 


P - 0 2 2 7 

SPin-CroSSover iron(ii) CoMPLexeS with A 

PhotoACtive diAryLethene-BASed LiGAnd 

M. MiLeK 1 , C. StreB 1 , M. M. KhuSniyArov 1 



Innovative materials whose magnetic properties can be 

switched reversibly by light irradiation at room temperature on a 

single molecular level offer a variety of applications, e.g. as highdensity 

memory units or photoswitches. 

The light controlled spin-change in spin-crossover (SCO) 

metal complexes is well examined as Light-Induced Excited Spin 

State Trapping (LIESST) effect, with the disadvantage of low 

operating temperatures (< 50 K). [1] To overcome this limitation 

we use the recently introduced Ligand-Driven Light-Induced Spin 

Change (LD-LISC) effect. [2] By utilizing the photoisomerizable 

diarylethene-based ligand 5,6-bis(2,5-dimethylthiophen-3-yl)- 

-1,10-phenanthroline (L) [3] coordinated to an iron(II) center we 

intend to change the spin state of the metal ion at room 

temperature via photocyclisation/-cycloreversion of the 

photoactive ligand. Auxiliary ligands are used to adjust the ligand 

field strength favourable for a spin transition. 

The synthesis, characterisation and photophysical 

properties of two photoactive FeII complexes [Fe(NCS) L ] and 

2 2 

- [Fe(H B(pz) ) L] (H B(pz) =dihydobis(pyrazolyl)borate) will be 

2 2 2 2 2 

presented. 

references: 

1. A. Hauser, Top. Curr. Chem. 2004, 234, 155-198. 

2. M.-L. Boillot, J. Zarembowitch, A. Sour, Top. Curr. Chem. 

2004, 234, 261-276. 

3. C.-C. Ko, W.-M. Kwok, V. W.-W. Yam, D. L. Phillips, 

Chem. Eur. J. 2006, 12, 5840-5848. 

Keywords: Spin crossover; Molecular devices; 

Photochemistry; Magnetic properties; Iron; 



s975 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 2 8 

fACiLe C-S, C-Se And C-P CroSS-CouPLinG 

reACtionS in A weLL-defined AryL-Cuiii 

CoMPLex. MeChAniStiC iMPLiCAtionS in 

uLLMAnn CondenSAtionS 

M. font 1 , A. CASitAS 1 , t. PAreLLA 2 , M. CoStAS 1 , 

x. riBAS 1 


Spain 

2 Universitat Autonoma de Barcelona, Servei RMN, Bellaterra, 

Spain 

Recent efforts to recover the usefulness of copper in 

cross-coupling catalysis has led to the implementation of Ullmann 

chemistry in the construction of C-heteroatom bonds. [1] In the last 

decade, the exploration of new copper catalysis protocols have 

proved utility for the formation of C-S, C-Se and C-P bonds. [2] 

Although catalytic methods have been extensively investigated 

for these type of reactions, their mechanism is still under debate. 

This work aims at shedding light into the mechanism of 

copper-catalyzed cross-coupling reactions using sulphur, selenium 

and phosphorus-based nucleophiles. Studies conducted with a 

well-defined aryl-CuIII complex revealed the capability of this 

complex to undergo aryl-S, aryl-Se and aryl-P reductive 

elimination to yield biaryl thioethers, aryl alkyl thioethers, biaryl 

selenide and aryl alkyl phosphonates upon reaction with 

thiophenols, alkyl thiols, selenols and dialkyl phosphites. 

Experimental data reveals a pKa and coordination ability 

dependence on the reaction rates. Competition experiments using 

bifunctional substrates showed the selectivity of the complex 

towards thiol functionality in presence of an alcohol in substituted 

aromatic rings. The implication of CuI /CuIII redox cycles of these 

C-S, C-Se and C-P bond-forming reactions are further assessed 

by the excellent performance of the catalytic version of the 

reactions. Our results support a mechanistic proposal involving a 

CuI /CuIII oxidative addition and reductive elimination type of 

mechanism for aryl-S, aryl-Se and aryl-P bond formation 

catalysis. [3] 

references: 

1. G. Evano, N. Blanchard, M. Toumi, Chem. Rev. 2008, 108, 

3054–3131. 

2. a) I. P. Beletskaya, V. P. Ananikov, Chem. Rev. 2011, 111, 

1596–1636; 

b) R. Zhuang, J. Xu, Z. Cai, G. Tang, M. Fang, Y. Zhao, 

Org. Lett. 2011, 13, 2110–2113. 

3. a) A. Casitas, A. E. King, T. Parella, M. Costas, S. S. Stahl, 

X. Ribas, Chem. Sci. 2010, 1, 326–330; 

b) L. M. Huffman, A. Casitas, M. Font, M. Canta, M. Costas, 

X. Ribas, S. S. Stahl, Chem. Eur. J., 2011, 17, 

10643–10650. 

Keywords: Copper; Cross-coupling; C-S; C-Se; C-P bond 

forming reactions; Ullmann-Goldberg mechanisms; 


P - 0 2 2 9 

forMAtion of PhotoCheMiCALLy ACtive zno 

fiLMS on ALuMiniuM SuBStrAteS By 

hydrotherMAL treAtMent 

A. ShiMAMurA 1 , M. JoneS 2 1, 3 

, J. MetSon 

1 University of Auckland, School Of Chemical Science, 1142 

Auckland, New Zealand 

2 University of Auckland, Department 

Of Chemical And Materials Engineering, 1142 Auckland, 

New Zealand 

3 MacDiarmid Institute for Advanced Materials and 

Nanotechnology. 

ZnO is a wide-band-gap semiconductor which has attracted 

considerable attention over recent years due to its potential 

applications in solar cells, flat-panel displays, photovoltaic 

devices and conductive composites. Aluminium is one of the most 

widely used metals because of its light weight, ease of handling 

and inexpensive price. Although aluminium has high conductivity, 

it is difficult to use aluminium as a substrate for photo- or 

electro-active devices because of the ease with which an 

insulating surface oxide is formed in atmosphere. Therefore, 

there is potential for low cost devices if active films such as ZnO 

can be deposited in intimate contact with aluminium substrates. 

In this study, thin ZnO films were formed on the surface of 

an aluminium substrate by a hydrothermal treatment method 

utilising an intermediate layered hydroxide. The thermal treatment 

conditions were optimized by changing the solution pH and 

reaction temperature. Characterization of the thin ZnO films was 

carried out by XANES, XRD, XPS, SEM and photocurrent 

measurement. Photoactive devices were successfully fabricated 

with the highest photocurrents observed from ZnO films formed 

under hydrothermal treatment conditions of 383 K and a solution 

pH of 8.0. 

Keywords: zinc oxide; photocatalysis; 



s976 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 3 0 

PrePArAtion of MeSoPorouS CAtALyStS for 

oLefin MetAtheSiS 

J. PAStvA 1 , h. BALCAr 2 , J. CeJKA 2 


of Physical and Macromolecular Chemistry, Prague, Czech 

Republic 

2 J. Heyrovsky Institute of Physical Chemistry of the ASCR v. v. 

i., Department of Synthesis and Catalysis, Prague, Czech 

Republic 

Olefin metathesis has become a powerful tool in organic 

synthesis and isnow extremely useful having numerous 

applications in fine chemicalsynthesis. Ru based complexes are 

themost popular metathesis catalysts due to their high activity and 

tolerance to thevariety of functional groups in substrate 

molecule.Mesoporous molecular sieves are siliceous materials 

withwell-defined regular architecture, large surface areas, large 

void volumes andnarrow pore size distribution of mesopores. 

They represent progressive supports for newheterogeneous 

catalysts for olefin metathesis and metathesis polymerization. 

Immobilization of solublemetathesis catalysts on siliceous 

molecular sieves promised heterogeneousmetathesis catalysts 

with high efficiency and low metal leaching. 

In the present work the heterogenouscatalysts have been 

prepared by immobilization ofcommercial Hoveyda-Grubbs 

1st generation catalyst on siliceousmesoporous molecular sieves 

(SBA-15, SBA-16 and MCM-48) of different pore sizeand 

architecture modified with linkers containing 

dicyclohexylphosphine (PCy )groups. SBA-15 (S = 688 m 2 BET 2 /g, 

V=1.1cm3 /g, d = 6.9 nm) is mesoporous silicawith hexagonal 

symmetry of uniform pores. SBA-16 (S = 796 m BET 2 /g, 

V=0.6 cm3 /g, d = 4.7 nm)is a mesoporous material with 

three dimensional cubicarrangement of mesopores. MCM-48 

(S = 756 m BET 2 /g,V = 0.9 cm3 /g, d=6.2 nm) is a mesoporoussieve 

with two independent interwoven three-dimensional channels. 

These catalystsshows low Ru leaching and can be used repeatedly. 

Filtration tests proved that the activity ofthe catalysts is bound to 

the solid phase. Effect of the architectureof the supports on catalyst 

activity (decrease in the order SBA-15 > MCM-48> SBA-16) was 

observed for the ring closing metathesis of various 

modelsubstrates (diethyl diallylmalonate, 1,7-octadiene, tert 

butyl-N, N-diallylcarbamate and N, N-Diallyl-2,2,2-trifluoro - 

acetamide)(Scheme 1). 

Keywords: olefin metathesis; mesoporous molecular sieves; 

heterogenous catalysts; 


P - 0 2 3 1 

noveL SuPrAMoLeCuLAr PhotoCAtALyStS 

BASed on nhC-LiGAndS 

L. PeterMAnn 1 , r. StAehLe 2 , d. PiLz 1 , S. rAu 1 


Germany 

2 Bioinorganic Chemistry, Chemistry and Pharmacy, Erlangen, 

Germany 

Supramolecular photocatalysts can play an important role in 

converting sunlight into usable energy. Current promising 

examples consist of a ruthenium polypyridyl moiety which is 

linked to a catalytic centre such as Pd or Pt via a bridging ligand. 

The activity of these catalysts depends on their stability 

throughout the catalytic cycle. One main deactivation mechanism 

is the release of low-valent metal species observed by 

Hammarstroem et al. in a bridged ruthenium-palladium-system [1] 

and in other related systems. [2] 

However, optimised system stability might be achieved by 

designing different coordination motifs suppressing bond 

cleavage between N-donor ligands and these catalyst centres. Here 

we introduce a new type of bridged system possessing 

N-heterocyclic carbene (NHC) ligands as anchoring sites for lowvalent 

catalyst species. Related NHC-ligands have recently been 

used to gain precise control over the electronic and steric 

properties of catalytic intermediates. [3,4] 

Here we present a series of bimetallic complexes where 

a Ru-centre is connected to a low-valent catalytic centre via an 

N,N-coordinated 1,3-substituted-1H-imidazo[4,5-f] bridge. 

The compounds were successfully used as hydrogen evolving 

catalysts and were fully characterised by spectroscopic and 

electrochemical studies. [5] Detailed investigations into the 

synthesis and spectroscopic properties are shown by NMR 

spectroscopy, absorption and emission measurements indicating 

the successful preparation of mono- and dinuclear compounds. 

references: 

1. P. Lei, M. Hedlund, R. Lomoth, H. Rensmo, O. Johansson, 

L. Hammarstroem, JACS, 2008, 130, 26–27 

2. P. Du, J. Schneider, F. Li, W. Zhao, U. Patel, F. N. Castellano, 

R. Eisenberg, JACS, 2008, 130, 5056–5058 

3. F. Glorius, N-Heterocyclic Carbenes in Transition Metal 

Catalysis: 21, Vol. 1, Springer, Berlin, 2006, 1–242 

4. R. Jackstell, M. G. Andreu, A. Frisch, K. Selvakumar, 

A. Zapf, H. Klein, A. Spannenberg, D. Roettger, O. Briel, 

R. Karch, M. Beller, Angew. Chem. Int. Ed. 2002, 41, 

986–989 

5. D. Pilz, PhD Thesis, University of Jena, 2011, 110–173 

Keywords: ruthenium; photocatalysis; NHC ligands; hydrogen 

production; 



s977 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 3 2 

the MetAL-BindinG SiteS of SuGAr AMino 

ACidS 

S. iLLi 1 , t. SChwArz 1 , P. KLüferS 1 

1 Ludwig-Maximilians-Universität, Chemie, München, Germany 

Sugar amino acids are carbohydrates containing at least one 

carboxyl and one amino group at a sugar core. Based on the 

exchangeable arrangement of the amino and carboxyl group at the 

sugar core, many different derivatives can be synthesized. Various 

types of sugar amino acids can also be found in biological 

systems. There, their extraordinary abilities were utilized in a 

variety of ways. For example, N-acetyl neuraminic acid often 

represents the last sugar unit in many glycoproteins of higher 

organisms. Furthermore, some derivatives of N-acetyl neuraminic 

acid play a decisive role in viral infections. 

However, the coordination chemistry of these important 

biomolecules has not yet been investigated satisfactorily. Through 

the study of the complexes, specific rules of metalation should be 

proposed. In the last years many PdIIN -complexes (N =bidentate 

2 2 

nitrogen ligand) with carbohydrates were studied and 

characterized by NMR spectroscopy and single crystal X-ray 

diffraction. To probe the metal-binding sites of sugar amino 

acids we used the well analyzed PdII reagents Pd-tmen 

(tmen = N,N,N’,N’-tetramethylethane-1,2-diamine) and Pd-chxn 

(chxn = (1R,2R)-cyclohexane-1,2-diamine) in aqueous solution. 

Within this poster 2-amino-2-deoxy-gluconic acids are in the 

centre of attention. Therefore, three sugar amino acids were 

investigated as representatives for 2-amino-2-deoxy-gluconic 

acids: D-glucosaminic acid, sodium 2-amino-2-deoxy-D- 

-mannonate and sodium 2-amino-2-deoxy-D-idonate. The sugar 

amino acids sodium 2-amino-2-deoxy-D-mannonate and sodium 

2-amino-2-deoxy-D-idonate were synthesized in a six-step 

synthesis each. D-Glucosaminic acid was commercially available. 

The pH value proved to be a decisive parameter to address 

the binding sites of sugar amino acids. Hence, the pH was 

thoroughly controlled in the course of the experiments. Moreover, 

di- and trimetallation of the carbohydrate was achieved by 

increasing the concentration of PdII reagent. The molecular 

structures were assigned by a combined 1H-13C-NMR-spectroscopic approach and by single crystal X-ray diffraction. 

Keywords: Coordination modes; Palladium; Carbohydrates; 

NMR spectroscopy; X-ray diffraction; 


P - 0 2 3 3 

ALiPhAtiC C–h Bond oxidAtion of toLuene 

uSinG rooM teMPerAture StABLe CoPPer 

Peroxo CoMPLexeS 

n. KeMPf 1 , C. würteLe 1 , S. SChindLer 1 

1 Institut für Anorganische und Analytische Chemie, Institut für 

Anorganische und Analytische Chemie, Giessen, Germany 

The activation of dioxygen by copper proteins and enzymes 

plays an important role for catalytic oxidation reactions in nature. 

Various mononuclear copper complexes have been synthesized as 

model compounds due to their potential to mimic the active site 

and the function of such copper proteins and enzymes. [1] The 

copper(I) complexes of tetradentate tripodal ligands showed the 

formation of thermally labile dinuclear copper peroxo complexes, 

[Cu (L) (O )] 2 2 2 2+ , in the presence of dioxygen. [2] These compounds 

have been investigated for their possible application as catalysts 

for the selective catalytic oxidation of organic substrates. 

In 2009 Lucas et al. and Würtele et al. demonstrated 

aliphatic C-H-bond oxidation in the oxidation of toluene to 

benzaldehyde using copper peroxo complexes with tetradentate 

tripodal ligands. In these studies the oxidative transfer of oxygen 

[3, 4] 

was limited to a stoichiometric conversion up to 40 %. 

Recently we succeeded to exceed the limited conversion and 

to obtain a catalytic oxidation of toluene to benzaldehyde within 30 

catalytic cycles. The investigations on aliphatic C-H-bond oxidation 

reactions were carried out systematically with a series of copper 

peroxo complexes, [Cu (L) (O )](BPh ) (L=tetradentate tripodal 

2 2 2 4 2 

ligand, Tris(2-pyridylmethyl)amine, 2-(Dimethylaminoethyl)bis(2- 

-pyridylmethyl)-amine, Bis(2-dimethyl-aminoethyl)(2-pyridyl - 

methyl)amine, Tris(2-dimethylaminoethyl)amine), that are stable 

at room temperature. 

references: 

1. Mirica, L. M.; Ottenwaelder, X.; Stack, T. D. P. Chem. 

Rev. 2004, 104, 1013-1046. 

2. Karlin, K. D.; Wei, N.; Jung, B.; Kaderli, S.; Niklaus, P.; 

Zuberbühler, A. D. J. Am. Chem. Soc. 1993, 115, 9506. 

3. Lucas, H. R.; Li, L.; Narducci Sarjeant, A. A.; Vance, M. A.; 

Solomon, E. I.; Karlin; K. D. J. Am. Chem. Soc. 2009, 

131, 3230-3245. 

4. Würtele, C.; Sander, O.; Lutz, V.; Waitz, T.; Tuczek, F.; 

Schindler, S. J. Am. Chem. Soc. 2009, 131, 7544-7545. 

Keywords: Copper; Oxidation; Tripodal ligands; 



s978 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 3 4 

Size MAtterS – infLuenCe of nAnoPArtiCLe 

Size in thePerforMAnCe of Mo-SuPPorted 

ePoxidAtion CAtALyStS 

C. i. fernAndeS 1 , M. d. CArvALho 2 , P. d. vAz 1 , 

C. d. nuneS 1 

1 Faculdade de Ciencias da Universidade de Lisboa, CQB 

Departamento de Química e Bioquímica, Lisboa, Portugal 

2 Faculdade de Ciencias da Universidade de Lisboa, CCMM 

Departamento de Química e Bioquímica, Lisboa, Portugal 

Nanochemisty is an exponentially growing research field in 

modern science that involves the synthesis and application of 

nanoparticles of different sizes and shapes. Fabrication of 

core-shell magnetic particles has recently been subject of 

extensive research, since such materials combine the unique 

magnetic properties of the core together with the possibility to 

further functionalize the research. This has motivated research to 

develop designed application in different fields like bioseparation, 

drug delivery, MRI, catalysis and others [1] . The specific 

advantages of magnetic nanomaterials include high specific 

surface area, active sites mainly distributed on the “outer” surface 

of the support which avoids pore diffusion and the application of 

an external magnetic field enables the removal of the particles in 

a simple way [1] . 

In the present work we used iron magnetic nanoparticles 

with different sizes. The particles were subsequently coated with 

a dense silica layer yielding binding sites (Si-OH units) for 

heterogenization of molecular catalysts [1] . The core/shell 

nanoparticles were derivatized with benzoic acid-4- 

-diphenylphosphine and isonicotinic acid, both suitable for 

coordination of metal centers. This latter step was accomplished 

by adding the Mo precursor complex [MoI (CO) (NCMe) ], 

2 3 2 

yielding the desired magnetic nanocatalysts. All synthesized 

materials were characterized by adequate spectroscopic 

techniques (FTIR and DRUV) or other techniques (XRD, 

Mössbauer and SEM/TEM). 

The resulting catalysts were tested in oxidation catalysis, 

namely, epoxidation of olefins and allylic alcohols, with 

t-butylhydroperoxide. 

The results demonstrate that the supported Mo materials are 

efficient recyclable catalysts for selective olefin epoxidation and 

reveal that the systems are completely selective for epoxides 

across several substrates. The reaction conditions (temperature 

and solvent) and nanoparticles size were found to influence 

catalysts performance, and will be discussed. 

references: 

1. Shylesh, S.; Schweizer, J.; Demeshko, S.; Schünemann, V.; 

Ernst, S.; Thiel, W., Adv. Synth. Catal. 2009, 351, 1789- 

1795. 

Keywords: Nanoparticles; Epoxidation; Molybdenum; 

Magnetic properties; Heterogeneous catalysis; 


P - 0 2 3 5 

d-GLyCoSyLAMineS And their CoordinAtion 

CheMiStry 

L. Lindner 1 , P. KLüferS 1 


Amino sugars are carbohydrates in which one or more 

hydroxy functions are substituted by an amino group. They occur 

in nature, for example, in antibiotics, in glycoproteins and in 

chitin. The latter is built up of β-1,4-linked N-acetyl glucosamine 

molecules and appears in the exoskeleton of arthropods. In this 

work, the glycosylamines (1-amino-1-deoxy-glycoses) are at the 

centre of attention. Since amino sugars are potential ligands but 

there is little known about their features, it is important to acquire 

more information about this substance group. By studying these 

complexes, specific rules of metalation can be proposed. 

Since glycosylamines are reducing sugars, the four different 

anomers, β-pyranose, α-pyranose, β-furanose and α-furanose may 

be accessible for metal chelation. In this poster D-ribosylamine, 

D-galactosylamine and D-lyxosylamine were discussed as 

representatives of the group of D-glycosylamines. To present the 

chelating properties of D-galactosylamine, the reactions with 

palladium(II) and cobalt(III) were analysed. It is evident that the 

reactions with the PdII (tmen) metal fragment [tmen = N,N,N',N'- 

-tetramethylethane-1,2-diamine] and the CoIII (tren) metal 

fragment [tren = tris-(2-aminoethyl)-amine] led to only one 

species in which the amino sugar binds through its N1 and O2 

atoms and exists in the 4C -β anomer. Moreover, the first 

1 

crystal structure of a cobalt complex with an unsubstituted 

D-glycosylamine was obtained. In contrast to these results, the 

reactions of D-lyxosylamine with PdII (tmen) and K PtCl showed 

2 4 

a change in the configuration of the amino sugar. Here, too, the 

1-amino function reliably participated in metal binding but the 

4C1-β pyranose educt was transformed to its 1C -α anomer. 

4 

Keywords: NMR spectroscopy; Coordination modes; 

Conformation analysis; Palladium; Cobalt; 



s979 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 3 6 

infLuenCe of CArBoxyLiC ACidS on the 

forMAtion of Mixed- MetAL oxo- CLuSter 

froM MetAL ALKoxideS 

C. Artner 1 , u. SChuBert 1 



Molecular metal oxo- cluster can act as building blocks in 

inorganic-organic hybrid materials. Strong chemical bonds 

between the components demand reactive sites on the surface of 

the cluster, which serve as connectors. In order to achieve highly 

ordered networks, the geometry of these functional ligands is 

crucial. 

The introduction of oxo- cluster containing two different 

metals opens the field to an even larger variety of building blocks 

with different physical and chemical properties. Due to the 

different bonding characteristics of the used metals and the 

asymmetric shape of the clusters an anisotropic functionalization 

can be possibly achieved. 

There are several ways to synthesise oxo- cluster, one is to 

start from the corresponding metal alkoxides and react them with 

carboxylic acids. The type of cluster formed during the reaction 

is mainly influenced by the type of alkoxides and acids used, as 

well as on the alkoxide/acid ratio. In this work, we present the 

influence of different carboxylic acids on the formation of mixed 

Ti/Zr oxo- cluster. 

Keywords: cluster compound; Carboxylic acids; X-ray 

diffraction; 


P - 0 2 3 7 

A3B tyPe fLuorinAted unSyMMetriCAL 

PhthALoCyAnineS for Pdt APPLiCAtionS 

M. B. BAyrAMoGLu 1 , y. ArSLAnoGLu 1 , 

e. hAMuryudAn 1 


Phthalocyanines are versatile molecules used as industrial 

pigments, and they have been applied in a number of applications: 

for example, photodynamic therapy, photovoltaic devices, 

catalysts, gas sensors, electrochromic displays and photovoltaic 

devices. Phthalocyanines have strong absorption at short and long 

wavelength ends of the visible spectrum and are thus well suited 

for optical applications. The optical and electrical properties of 

phthalocyanines can be tuned by changing the center metal and 

the peripheral substituents. For instance, the fluorescence and 

phosphorescence quantum yields and the corresponding lifetimes 

of singlet and triplet states of phthalocyanines depend on their 

structure. Unsymmetrically substituted phthalocyanines are 

usually prepared by three principal synthetic strategies: the 

polymer support route, the subphthalocyanine route, and the 

statistical condensation route. The most common method is the 

statistical condensation of two differently substituted dinitriles or 

diiminoisoindolines (using different ratios 3:1, 6:1, 9:1 etc..) 

followed by chromatographic separation of the resulting mixture. 

In the present work, we describe the synthesize and 

characterization of A B type novel unsymmetrically substituted 

3 

metallophthalocyanine which has been synthesized by statistical 

condensation of a mixture of sulfur containing phthalonitrile (A) 

and fluorinated phthalonitrile (B). The structures of all these 

compounds were identified by using IR, UV-VIS, 1H NMR and 

elemental analyses spectroscopic data. 

references: 

1. Nombona, N., Chidawanyika W., Nyokong, T., Polyhedron, 

2011, 30, 654-659. 

2. Arslanoglu, Y., Koca, A., Hamuryudan, E., 

Dyes and Pigments, 2011, 88, 135-142. 

3. Tempesti TC., Alvarez MG., Durantini EN., 

Dyes and Pigments, 2011,91, 6-12. 

Keywords: PDT application; Unsymmetrical Phthalocyanine; 

Fluorinated; 



s980 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 3 8 

PLAyinG with fe(ii) LiGAnd fieLd, the 

exAMPLe of (PyrAzoLyL)Pyridine-tyPe 

LiGAndS: diMeriC CoMPLexeS And their 

SPin-CroSSover BehAviour 

d. fedAoui 1 , y. BouhAdJA 1 , P. roSA 2 

1 Science Faculty, Chemistry, Annaba, Algeria 

2 ICMCB, chemistry, Bordeaux, France 

From its discovery in the 1930’s till now, spin crossover has 

been the subject of extensive applications. One of the problems 

remaining is the ability to organize at will spin crossover systems 

with the desired properties, since spin crossover remains an 

elusive property very much depending on the surroundings of the 

metallic center. 

In this context, a very interesting family is the 

bis(pyrazolyl)pyridine one. With these analogues of the widely-used 

terpyridine system, many of their homoleptic complexes show spin 

crossover behaviour [1] . It has also been shown in our laboratory 

that many complexes can be photoconverted at low temperatures, 

with long lifetimes of photoexcited high-spin state [2a, b] . They 

constitute thus interesting building blocks for the obtention of 

organized systems. 

During the course of our present investigations of 

functionalized subunits of the kind, we have also looked at the 

possibility of controlling the coordination behaviour of 

bis(pyrazolyl)pyridine ligands through the use of blocking 

ancillary ligands. This poster will show the results we have found 

with pseudohalogens in particular thiocyanate and selenocyanate. 

This leads to complex having one free coordination site so 

the choice of an appropriate ligand either monodentate or bridging 

bidentate allows to obtain both mononuclear and dinuclear 

species. Characterization, magnetic and photomagnetic properties 

of synthesized complexes will be discussed. 

Keywords: iron(II); spin crossover; magnetism; complexes; 


P - 0 2 3 9 

PiGGyBACKinG fiSCher CArBene CoMPLexeS 

n. A. hArriS 1 , S. Lotz 1 


Africa 

Fischer carbene complexes play an important role in many 

organic reactions. [1] There are numerous examples of transition 

metals that can accommodate alkoxycarbene ligands [2] , however 

there is also a wide range of transition metals that form carbene 

complexes that are difficult to isolate and also metals that do not 

readily form Fischer carbene complexes. Examples of multimetal 

Fischer carbene complexes have been synthesized where the role 

of the metal fragments was investigated for structural features and 

communication between metal fragments. [3, 4] 

In this study the main aim was to transfer Fischer carbene 

complexes as substituents on a phosphine or amine ligand into the 

coordination spheres of a variety of transition metals. The substrates 

chosen: tri(4-bromophenyl)amine and tri(2-furyl)phosphine, 

are able to accommodate more than one Fischer carbene complex 

as substituents and also act as very good ligands to a variety of 

transition metals. The newly synthesized carbene containing 

complexes of Group 6 to 10 transition metals display interesting 

spectroscopic and structural features. The study further entails 

examining the effect the carbene has on the bonding ability of the 

ligand and also the metal to which the ligand is coordinated. 

Further investigations will demonstrate the potential of the newly 

formed complexes which may display catalytic properties or play 

significant roles in template reactions. 

references: 

1. Barluenga J, Fernández-Rodriguez MA, Aguilar E. 

J. Organomet. Chem. 2005;690(3):539-587. 

2. Cardin DJ, Cetinkaya B, Lappert MF. Chem. Rev. 

1972;72:545–574. 

3. Bezuidenhout DI, Lotz S, Marilé L, Liles DC. 

Inorg. Chem. 2011;50:1521 - 1533. 

4. Bezuidenhout DI, Barnard W, van der Westhuizen B, 

van der Watt E, Liles DC. Dalton Trans. 2011;40:6711-6721. 

Keywords: Fischer carbene complex; Multimetal complex; 

Ligand coordination; 



s981 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 4 0 

BiSMuth vAnAdiuM oxide CLuSterS with 

viSiBLe-LiGht PhotoACtivity 

J. tuCher 1 , C. StreB 1 

1 Friedrich-Alexander-University Erlangen-Nuremberg, Institute 

of Inorganic Chemistry II, Erlangen, Germany 

Polyoxometalates (POMs) are anionic metal oxo clusters 

with applications in various fields of research on catalysis [1] and 

photocatalysis [2] . Structure and reactivity tuning can be achieved 

by incorporation of heterometal centers like into the cluster shell. 

In the present study, we were exploring the incorporation of 

bismuth(III) centers into polyoxovanadates as a potential route 

for the assembly of vanadates with photoactivity in the visible 

range. 

The idea is based on literature reports which show that 

solid-state bismuth vanadium oxides are promising visible-light 

photocatalysts. [3] However, thus far, no molecular analogues of 

solid-state bismuth vanadate are known. Here, we present the 

syntheses, characterization and photochemical activities of 

molecular bismuth vanadium oxide clusters. Structural analyses 

show that the bismuth vanadate clusters, H [(Bi(dmso) ) V O ] 

3 3 4 13 40 

x ca. 4 DMSO and TBA[(Bi(dmso) ) V O X], are formed 

3 2 12 33 

3- around a central, tetrahedral ortho-vanadate VO or halide 

4 

(X = Cl- , Br- ), template. [4] One of the main features of bismuth 

vanadium oxides is their visible-light photoactivity. For these 

bismuth vanadium clusters, UV-Vis spectroscopy showed a strong 

O?M LMCT transition; tailing of the LMCT transitions into the 

visible range up to ca. l=600 nm is observed. In order to study 

the visible-light induced photoreactivity of bismuth vanadium 

clusters, the dye photodegradation of a model pollutant was 

chosen as a test reaction. The results of the photochemical test 

reactions as well as the catalytic performance (TON, TOF, 

quantum efficiency) are discussed in this presentation. 

references: 

1. C. L. Hill and C. M. Prosser-McCartha, Coord. Chem. 

Rev., 1995, 143, 407-455. 

2. a) C. Streb, Dalton Trans., 2012, 41, 1651-1659; 

b) J. Tucher, Y. Wu, L. C. Nye, I. Ivanovic-Burmazovic, 

M. M: Khusniyarov, C. Streb, Dalton Trans. 2012, 41, 

DOI: 10.1039/C2DT30304C. 

3. A. Kudo, K. Omori, H. Kato, J. Am. Chem. Soc., 1999, 121, 

11459-11467. 

4. J. Tucher, A Notarnicola, L. C. Nye, I. Ivanovic-Burmazovic, 

Carsten Streb, 2012, submitted. 

Keywords: Photochemistry; Sustainable Chemistry; Vanadium; 

Catalysis; 


P - 0 2 4 1 

BuiLdinG BLoCKS And new LiGAndS in 

CheMiStry of PALLAdiuM PoLynuCLeAr 

CArBoxyLAte CoMPLexeS 

o. ShiShiLov 1 , r. PodoBedov 1 , y. rezinKovA 2 , 

n. AKhMAduLLinA 3 , A. ChurAKov 4 , i. efiMenKo 5 

1N.S. Kurnakov Institute of General and Inorganic Chemistry of 

RAS, Laboratory of power-consuming substances and 

materials, Moscow, Russia 

2 M.V. Lomonosov Moscow State University of Fine Chemical 

Technolgies, Department of physical chemistry, Moscow, 

Russia 

3 A.A. Baikov Institute of Metallurgy and Material Science of 

RAS, Laboratory of physical and chemical analysis of ceramic 


4 N.S. Kurnakov Institute of General and Inorganic Chemistry of 

RAS, Laboratory for X-Ray Diffraction Studies, Moscow, 

Russia 


RAS, Laboratory of power-consuming susbtances and 


Synthesis of platinum metal polynuclear compounds is one 

of the main challenges in modern cluster chemistry, first of all, 

due to its unique catalytic properties. Our investigations permitted 

to identify building blocks for polynuclear palladium carboxylate 

complexes with coordinated CO and NO. 

It was shown that interaction of palladium carbonyl carboxylate 

clusters Pd (μ-CO) (μ-RCO ) (1) with gaseous NO leads to 

6 6 2 6 

formation of 8-nuclear clusters Pd (μ-CO) (μ-RCO ) (μ-NO ) (2) 

8 4 2 8- 2 4 

with nitrite ligands. Clusters 1 and 2 contain 4-nuclear 

structure unit Pd (μ-CO) (μ-RCO ) , which was also fixed as 

4 2 2 4 

Pd (μ-CO) (μ-NO) (μ-RCO ) (3) complexes obtained in the same 

4 2 - 2 5 

reaction under the presence of excess of corresponding carboxylic 

acid. Comparison of structural and spectral parameters for clusters 

1-3 allows to conclude that Pd (μ-CO) (μ-RCO ) is high-stable 

4 2 2 4 

unit which can be considered as building block for palladium 

carbonyl carboxylate clusters. Another feature of the reaction 

is a formation of nitrite ligands directly from NO. 

A building block containing NO was identified 

when studying reaction of Pd 4 (NO) 2 (RCO 2 ) 6 

(4) with 

acetonitrile. New 5-nuclear complexes of a general formula 

Pd 5 (CH 3 C(=N)OC(=N)CH 3 )(NO 2 ) x (NO)(RCO 2 ) 7-x (x = 0, 1) (5) 

were obtained in the reaction. Structural and spectral parameters 

of Pd 4 (μ-RCO 2 ) 5 (μ-NO) unit in complexes 3-5 are very close, so 

the unit can be considered as building block for palladium 

nitrosyl carboxylate clusters. Complexes 5 contain a specific 

ligand – acetamide anhydride. This ligand forms under reaction 

conditions from acetonitrile as a result of acetonitrile hydrolysis 

followed by coupling of molecules of acetamide and acetonitrile 

or two molecules of acetamide. 

Finally, studying ESI-mass-spectra of complexes 2 and 3 we 

have detected Pd 3 (μ-CO) 2 (μ-RCO 2 ) 2 units, which later were 

found in the biggest palladium carboxylate cluster 

Pd 12 (μ-CO) 8 (μ-NO 2 ) 8 (μ-RCO 2 ) 8 (6). Up to date this the first cluster 

composed of 3-nuclear carbonyl carboxylate metal chains. 

Acknowledgement: We are grateful to the Council of the 

President of the Russian Federation for young scientists for 

financial support (project 966.2012.3). 

Keywords: palladium; carbonyl; nitrosyl; nitrite; carboxylate; 



s982 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 4 2 

CroSS-LinKinG of two-diMenSionAL MetAL 

CyAnide networKSBy SoL-GeL ProCeSSinG 

e. feLBerMAir 1 , u. SChuBert 1 



Ni2+ complexes with certain nitrogen-containing organic 

ligands and various metal cyanides form two-dimensional 

honeycomb-like analogues of Prussian Blue. The organic ligands 

block the four equatorial coordination sites of Ni2+ and thereby 

favour this geometrical structure. 

So far, attention has mainly been directed at networks of 

[Ni(cyclam)] 2+ (cyclam=1,4,8,11-tetraazacyclotetradecane) with 

3- Fe(CN) [1, 2] 3- or W(CN)8 [3, 4] . Research has been focused on them 

6 

because they possess interesting magnetic properties and 

microporosity. This combination leads to their classification as 

“magnetic sponges” [5] , which denotes materials that change their 

magnetic behaviour when the solvent guest molecules are 

removed. 

We are investigating whether the magnetic properties of the 

materials change upon embedding the two-dimensional sheet 

structures in an amorphous gel. This is done by cross-linking the 

layers by means of trialkoxysilylalkyl groups, which are 

introduced by derivatising the organic blocking ligands, followed 

by sol-gel processing. The obtained gels are analysed regarding 

their structure (NMR, spectroscopic measurements, elemental 

analysis) as well as functionality (magnetic susceptibility, 

conductivity). 

references: 

1. Colacio, E. et. al. Chem. Commun. 1999, 987-988 

2. Colacio, E. et. al. Inorg. Chem. 2001, 40, 4876-4883 

3. Nowicka, B. et. al. Dalton Trans. 2011, 40, 3067-3073 

4. Nowicka, B.; Rams, M.; Stadnicka, K.; Sieklucka, B. 

Inorg. Chem. 2007, 46, 8123–8125 

5. Kahn, O.; Larionova, J.; Yakhmi, J. V. Chem.–Eur. J. 

1999, 5, 3443-3449 

Keywords: cyanides; Magnetic properties; microporous 

materials; Nickel; macrocyclic ligands; 


P - 0 2 4 3 

SyntheSiS, ChArACterizAtion And 

AntiProLiferAtive ACtivity of SoMe 

trAnSition MetAL CoMPLexeS with 3-(2-(4- 

-MethoxyPhenyLCArBAMothioyL)hydrA - 

zinyL)-3-oxo-n-(thiAzoL-2-yL)ProPAnAMide 

e. eL-zAhAny 1 , S. drweeSh 1 , A. eL-Seidy 1 , M. ALi 2 , 

B. ABdeL-wAhAB 3 , n. youSSef 1 

1 National Research Centre, Inorganic chemistry, Giza, Egypt 

2 National Research Centre, Biochemistry, Giza, Egypt 

3 National Research Centre, Applied Organic Chemistry, Giza, 

Egypt 

The coordination chemistry of nitrogen-sulfur donor ligands 

such as thiazole derivatives as well as their transition metal 

complexes are well documented to have antifungal and 

antibacterial properties, beside antitumor activity. The aim of 

this work is to prepare and characterize a new thiazole ligand 

3-(2-(4-methoxyphenylcarbamothioyl)hydrazinyl)-3-oxo-N- 

-(thiazol-2-yl)propanamide h L and its complexes and to study 

4 

its antitumor activity against the human breast cancer cell line 

(MCF-7). h L structure was confirmed by elemental analysis, IR, 

4 

mass and 1H NMR spectroscopy. h L complexes with Cu(II), 

4 

V(IV), Co(II), Mn(II) and Ni(II) have been characterized by 

elemental analyses, molar conductivities, spectral (UV-Vis, IR, 

1H NMR, mass) as well as magnetic moment measurements 

technique. The IR spectra suggest that H L acts as a uni-negative 

4 

tetradentate or mono-anionic bidentate ligand. The molar 

conductance measurements proved that all complexes are 

non-electrolytes, except ni, Co and Cucomplexes behaved as 

electrolytes. The results revealed that the complexes possess a 

tetrahedral, square planar, square-pyramidal or octahedral 

geometry. The newly synthesized complexes have been tested for 

their antibacterial and antitumor activities. The effect of the new 

compounds on proliferation of human breast adenocarcinoma cell 

line MCF-7 showed that all studied compounds have anticancer 

activity except Co and v complexes, where the synthesized 

complexes have antitumor activity values more than that of the 

free ligand. The smaller value of IC50 of ni complex than that of 

the cisplatin would provide a new potential antitumor drug. 

Keywords: transition metal complexes; antiproliferative 

activity; thiazol derivatives; 



s983 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 4 4 

CoordinAtion CoMPLexeS of GALLiuM: A wAy 

to overCoMe AntiMiCroBiAL reSiStAnCe? 

K. drALLe 1 , M. ABrAMS 1 , C. orviG 1 

1 University of British Columbia, Department of Chemistry, 

Vancouver, Canada 

The World Health Organization (WHO) has identified the 

growing resistance of microbes to known antimicrobial drugs as 

one of the greatest threats to human health, because it hampers 

the control of infectious diseases, threatens a return to the 

pre-antibiotic era and jeopardizes the achievements of modern 

medicine; in addition, it increases global health care costs [1] . New 

antimicrobial agents that target new biological sites of action are 

needed to overcome the antimicrobial resistance. 

One potential target is iron metabolism. Iron is critical for 

the metabolism and growth of most organisms, and many animal 

species, including humans, limit the availability of iron at the site 

of infection as a mechanism of host defense [2] . Ga3+ shares many 

chemical similarities with Fe3+ , which makes it difficult for 

biological systems to distinguish the two metals; however, the 

3+/2+ redox chemistry essential for the iron metabolism cannot 

be accessed for gallium, which results in cellular toxicity. 

Consequently, Ga3+ has been stamped as the Trojan horse in 

biological systems [3] . 

In a bioinorganic chemistry approach to new potential 

metalloantimicrobials, our group has synthesized gallium(III) 

complexes of the (fluoro-)quinolones, a class of synthetic 

broad-spectrum antibiotics. To further explore the 

structure-activity-relationship of these new potential 

metalloantimicrobials, the corresponding iron(III) complexes 

were included in the antimicrobial susceptibility studies to test the 

Trojan horse theory. 

Acknowledgements: The University of British Columbia is 

acknowledged for a Four Year Doctoral Fellowship (K.D.) and 

the Natural Sciences & Engineering Research Council of 

Canada for a Discovery Grant. 

references: 

1. WHO (2012). Antimicrobial resistance 

[Fact sheet]. Retrieved from 

http://www.who.int/mediacentre/factsheets/fs194/en/. 

2. Schaible, U.E.; Kaufmann, S.H.E. Nat. Rev. Microbiol. 

2004, 2, 946-954. 

3. Kaneko, Y.; Thoendel, M.; Olakanmi, O.; Britigan, B.E.; 

Singh, P.K. J. Clin. Invest. 2007, 117, 877-888. 

Keywords: Antibiotics; Bioinorganic Chemistry; Gallium; 


P - 0 2 4 5 

Mixed SuGAr-Core-PhoSPhAte LiGAtion 

of d-fruCtoSe 1,6-BiSPhoSPhAte with 

the re(v)o(tMen) MetAL frAGMent 

M. SteinBorn 1 , P. KLüferS 1 

1 Ludwig-Maximilians-Universität, Chemistry, München, 

Germany 

Sugar phosphates play a decisive role in all organisms. 

They’re ubiquitous in metabolism pathways such as the pentose 

phosphate pathway or glycolysis. All reactions of these pathways 

are catalysed by enzymes. Several of these contain divalent metal 

centres, e.g. magnesium, iron or zinc, in their active site. The 

dications are chelated by the sugar phosphate substrates during 

the catalysed reaction. Well known examples for such 

metalloenzymes are class-II aldolase, fructose 1,6-bisphosphatase 

and glucose 6-phosphate isomerase. Since crystal structure 

analyses of enzymes offer only limited results about the initial 

binding of ground-state sugar-phosphate forms to metal centres, 

it’s necessary to investigate such complexes in aqueous solution 

outside enzymes. 

Sugar phosphates are able to coordinate in various ways to 

a metal centre whereby the pH is an important parameter. So at 

alkaline pH values, only the hydroxyl functions of the 

sugar-core coordinate to the metal centre while, at lower pH 

values, solely the coordination of the phosphate groups occurs. 

Close to the physiological pH, another coordination type is 

possible. In the case of D-fructose 1,6-bisphosphate, a mixed 

sugar-core-phosphate ligation exhibiting a seven-membered 

chelate ring is observed in the presence of the metal fragments 

PdII (en) and AlIII (tacn) (en = ethane-1,2-diamine, tacn = 1,4,7- 

-triazacyclononane). This coordination pattern was also found in 

the enzyme 3,4-dihydroxy-2-butanone 4-phosphate synthase. 

However, no crystal structure analysis has been available yet, 

proving this special coordination type outside an enzyme. 

Here we present the results of experiments of the 

ReVO(tmen) metal fragment (tmen = tetramethylethane-1,2- 

-diamine) with D-fructose 1,6-bisphosphate as well as its model 

glycerol 1-phosphate. It is shown, via both mass and NMR 

spectroscopy, that with an ReVO metal fragment the formation of 

a mixed sugar-core–phosphate ligation could be achieved. 

Moreover, the first crystal structure determination verifying this 

coordination pattern outside an enzyme can be presented. 

Keywords: Coordination modes; Rhenium; O ligands; NMR 

spectroscopy; x-ray diffraction; 



s984 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 4 6 

ChLoride And CArBoxyLAte CoMPLexeS of 

GoLd(iii) with n,n-donor LiGAndS 

n. AKhMAduLLinA 1 , A. BoriSovA 2 , A. ChurAKov 3 , 

o. ShiShiLov 4 , y. KArGin 1 

1 A.A. Baikov Institute of Metallurgy and Material Science of 

RAS, Laboratory of physical and chemical analysis of ceramic 


2 A.N. Nesmeyanov Institute of Organoelement Compounds of 


Russia 



Russia 


RAS, Laboratory of power-consuming susbtances and 


Chemistry of gold complexes is a growing modern area of 

coordination chemistry. First of all this is due to broadening use 

of gold compounds in homogeneous catalysis. Analysis of 

influence of ligands environment is impossible without the 

information about structure and reactivity of such compounds 

which makes study of new gold chloride and carboxylate 

complexes a topical issue. 

The general approach to synthesis of gold(III) carboxylate 

complexes with N,N-donor ligands (2,2'-bipyridine, 

phenanthroline) is a substitution of chloride ligands in complexes 

[LAuCl ]X under action of silver carboxylates. The most 

2 

common-used starting materials are complexes [LAuCl ]Cl. In 

2 

order to reduce a consumption of silver carboxylates we changed 

– inner-sphere chloride ions with BF ions. 4 

– Complexes with BF ions were used as starting materials 

4 

for reaction with silver acetate, trimethylacetate and 

trifluoroacetate. The reaction leads to formation of corresponding 

carboxylate gold(III) compounds [LAu(RCO ) ]BF . According 

2 2 4 

to X-ray diffraction and IR-spectroscopy data they are 

mononuclear complexes with chelate coordination of N,N-donor 

ligands and terminal coordination of two carboxylate groups. 

Complexes are quite stable but slowly decompose under the light. 

Trifluoroacetates are noticeably less stable than others 

carboxylates. 

Our attempts to substitute chloride ligands in 

[(phen)AuCl ]Cl without use of silver carboxylates gave 

2 

unexpected result. Reaction of [(phen)AuCl ]Cl with sodium 

2 

acetate in glacial acetic acid at 80°? leads to essential 

rearrangement of gold coordination sphere. A half of 

[(phen)AuCl ] 2 + ions lose phenanthroline and join chloride ligands 

giving [AuCl ] 4 – anions. The reaction results in formation of 

[(phen)AuCl ][AuCl ] complex, which was characterized by 

2 4 

X-ray diffraction analysis. The quantum-chemical calculations 

show that [LAuCl ][AuCl ] are products of thermodynamic 

2 4 

control in the systems [LAuCl ] 2 + – – –RCO – Cl (calculations were 

2 

carried out for L = 2,2'-bipyridine, phenanthroline and R = CH , 3 

CMe , CF ). 3 3 

Acknowledgement: We are grateful to the Council of the 

President of the Russian Federation for young scientists for 

financial support (project 977.2012.3). 

Keywords: gold; chloride; carboxylate; N,N-donor ligands; 


P - 0 2 4 7 

A BioinSPired, inorGAniC oxyGen evoLvinG 

CAtALySt BASed on A MAnGAneSe 

PoLyoxovAnAdAte CLuSter 

J. forSter 1 


Department of Chemistry Inorganic Chemistry II, Erlangen, 

Germany 

Here, we present a bioinspired, novel [Mn V O (OAc) ] 4 4 17 3 3cluster 

(= {Mn4V4}) which features a central manganese-oxo 

cubane [Mn O ] 4 4 6+ core supported by four corner-sharing [VO ] 4 

tetrahedra acting as inorganic ‘tripodal’ ligands. The cubane unit 

is stabilised by three [VO ] tetrahedra directly, which are 

4 

connected to the manganese atoms by six bridging V-O-Mn bonds 

in total. In addition, three acetate ligands fill the coordination 

sphere. Compared with other [Mn O L ] complexes this 

4 4 6 

[Mn O ]-polyoxovanadate unit is air-stable and easily accessible. 

4 4 

The four manganese centres were tentatively assigned as 

MnIII 2MnIV based on bond valance sum calculations, elemental 

2 

analysis and ESI-MS. The cyclic voltammogram of the {Mn V } 4 4 

cluster in acetonitrile shows three distinct reversible redox waves 

(-0,90 V, 0,08 V and 1,07 V) which indicate a highly redox-active 

species. ESI-mass spectrometry confirmed the existence of the 

{Mn V } cluster in solution. 

4 4 

This oxygen evolving complex (OEC) model complex is 

inspired by nature and an aqueous solution of {Mn V } is capable 

4 4 

of oxygen evolution in the presence of a stoichiometric oxidant 

like cerium ammonium nitrate (CeIV ) or light-driven by a 

2- well-known Ru-based system ([Ru(bpy) ]Cl / S O ). 

3 2 2 8 

Since these are our initial results we have to optimise the 

system and to improve the turnover numbers. Furthermore, the 

exact redox-reactions of the manganese-oxo core needs to be 

investigated. In addition, it has to be shown that the reaction is 

indeed homogeneous and does not involve the formation of 

heterogeneous particles. 

Keywords: Polyoxometalates; Oxygen evolving complex; 

Manganese; Vanadates; Oxygen evolution; 



s985 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 4 8 

BridGinG PSeudohALideS in PALLAdACyCLeS 

AS SourCe of different ASSeMBLieS 

f. viLLAfAne 1 , M. Arroyo 1 , P. GóMez-iGLeSiAS 1 , 

J. S. MeLero 1 , d. SChiLdBACh 2 , C. unKeLBACh 2 , 

C. StrohMAnn 2 

1 Univ. Valladolid, Q. Inorgánica, Valladolid, Spain 

2 Technische Universität Dortmund, Anorganische Chemie, 

Dortmund, Germany 

Background and objectives: Following our previous 

studies on the reactivity of (piperidinomethyl)silylmethyl 

cyclopalladated complexes, we decided to explore the behavior 

of this soft metallic center containing two coordinative sites 

available in cis geometry toward pseudohalides such as cyanide, 

thiocyanate or azide, which present several possible coordination 

modes and may give rise to different assemblies. 

results: The reaction of [Pd{CH SiPh (CH2NC5H10)- 

2 2 

-k2C,N}(m-Cl)] (CH NC H = piperidinomethyl) with KSCN 

2 2 5 10 

leads to the centrosymmetric dimer [Pd{CH SiPh (CH NC H )- 

2 2 2 5 10 

-k2C,N}(m-SCN-k 1S,k1N)] , which features side-on bridging 

2 

thiocyanate ligands. The analogous reaction with NaN yields the 

3 

dimer [Pd{CH SiPh (CH NC H )-k 2 2 2 5 10 2C,N}(m-N -k 3 1k1N)] , 2 

in which the azide ligands exhibit end-on coordination. 

This complex persists as a mixture of cis and trans isomers 

in solution. Lastly, the square tetrametallic complex 

[Pd{CH SiPh (CH NC H )-k 2 2 2 5 10 2C,N}(m-CN-k1C,k 1N)] , is obtained 

4 

from the reaction between the parent chloride-bridged complex 

and AgCN. In solution, this compound displays an equilibrium 

between tetrametallic and trimetallic species. Thermodynamic 

data were determined, showing that the formation of the 

trimetallic isomer is thermodynamically disfavored and that the 

variation of the enthalpy and entropy are positive. 

Conclusions: Bridging azide and bridging thiocyanate give 

rise to bimetallic species where azide is coordinated end-on, and 

thiocyanate as side-on. In contrast, linear bridging cyanide gives 

rise to a square shaped tetrametallic complex. The latter is in 

equilibrium with a trimetallic isomer in solution while the 

bridging azide dimer persists as a mixture of cis and trans isomers 

in solution. The trimetallic species is always the minor isomer, 

and its ratio increases with dilution of the solution, with increasing 

temperature, and with increase in polarity of the solvent used. 

Keywords: Self-assembly; Metallacycles; Silanes; Bridging 

ligands; 


P - 0 2 4 9 

16 CoBALt(ii)-ContAininG 

heteroPoLytunGStAte SinGLe-MoLeCuLe 

MAGnetS 

A. hAider 1 , M. iBrAhiM 1 , A. CArey 1 , B. BASSiL 1 , 

u. Kortz 1 

1 Jacobs University, Nano molecular, Bremen, Germany 

Polyoxometalates (POMs) are a large class of discrete, 

anionic metal-oxides comprising early transition metals in high 

oxidation states, such as WVI , MoVI , VV . [1] There has been 

increasing interest in this field due to potential applications of 

POMs in various fields including catalysis, magnetism, medicine, 

materials science, and chemical analysis. [2] Lacunary 

heteropolytungstates allow for incorporation of transition metal 

ions, potentially resulting in species with high nuclearity magnetic 

cores. [3] 

Very recently, we reported on the 16 CoII-containing [(PW 9 O 34 ) 4 {Co II 

4 (OH) 3 PO 4 } 4 ]28- (Co 16 -Pw 9 ), composed of four 

Keggin-type {Co 3 PW 9 } fragments encapsulating a central 

{Co 4 O 4 } cubane unit, which in addition is capped by four external 

phosphate groups, resulting overall in a polyanion with idealized 

T d point group symmetry (see Fig. 1). [4] We have now succeeded 

in preparing [(SiW 9 O 34 ) 4 {Co II 

4 (OH) 3 PO 4 } 4 ]32- (Co 16 -Siw 9 ) and 

[(GeW 9 O 34 ) 4 {Co II 

4 (OH) 3 PO 4 } 4 ]32- (Co 16- Gew 9 ), the isostructural 

silicon and germanium analogues of Co 16 -Pw 9 in a simple, 

one-pot procedure by reacting the trilacunary [A-a-SiW 9 O 34 ] 10or 

[A-a-GeW 9 O 34 ] 10- with Co II ions in phosphate buffer. 

These polyanions were investigated in the solid state by 

single-crystal XRD, FT-IR spectroscopy, thermogravimetric 

and elemental analyses. 

references: 

1. M. T. Pope, Heteropoly and Isopoly Oxometalates 

(Springer, Berlin, 1983). 

2. Eur. J. Inorg. Chem. 2009, 34, 5055 – 5276 (Issue 

dedicated to Polyoxometalates; Guest Ed.: U. Kortz). 

3. U. Kortz, A. Müller, J. van Slageren, J. Schnack, N. S. Dalal, 

M. Dressel, Coord. Chem. Rev. 2009, 253, 2315. 

4. M. Ibrahim, B. S. Bassil, Y. Xiang, Y. Lan, A. K. Powell, 

U. Kortz, Angew. Chem. Int. Ed. 2011, 50, 4708-4711. 



s986 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 5 0 

CoMPutAtionAL Study of SuBStituent effeCt 

in PArA SuBStituted PLAtinABenzene 

CoMPLexeS 

A. h. hAKiMyoun 1 , r. GhiASi 1 , h. PASdAr 2 

1 Islamic Azad University East Tehran Branch, Department of 

Chemistry Basic Science Faculty, Tehran, Iran 

2 Islamic Azad University North Tehran Branch, Department of 

Chemistry Basic Science Faculty, Tehran, Iran 

The electronic structure and properties of the platinabenzene 

and para substituted platinabenzenes have been investigated using 

the hybrid density functional mpw1pw91 theory. The substituent 

effect in structure parameters, frontier orbital energies, aromaticity 

indexes, and hyperpolarizability has been study. The calculations 

show that HOMO ® LUMO transition has most contribution in 

t the most intense electronic transition for all molecules. 

Keywords: Platinabenzene; substituent effect; 

hyperpolarizability; Nucleus-independent chemical shift 

(NICS); 


P - 0 2 5 1 

SyntheSiS, ChArACterizAtion, 

PhotoPhySiCAL, PhotoCheMiCAL And 

AGGreGAtion BehAvior 

of 4-[2-(1,4-dioxA-8-AzASPiro[4.5]deC-8- 

-yL)ethoxy-SuBStituted PhthALoCyAnineS 

e. t. SAKA 1 , C. GÖL 2 , M. durMuS 2 , h. KAnteKin 1 , 

z. BiyiKLioGLu 1 

1 Karadeniz Technical University, Chemistry, Trabzon, Turkey 

2 Gebze Institute of Technology, Chemistry, Gebze, Turkey 

Phthalocyanines (Pcs) are the most interesting materials 

because of their highly conjugatedπ-electron system and chemical 

stability. They are used extensively in biological and technological 

areas such as chemical sensors, liquid crystals, catalysis, 

non-linear optics and photodynamic therapy (PDT) of cancer [1]. 

The novel treatment is PDT in cancer therapies. PDT is 

based on a photochemical reaction, which is initiated by light 

activation of a photosensitizing drug causing tumour cell death. 

Light is mainly applied by superficial illumination of the tumour 

and the surrounding tissue causing drug activation followed by 

tumour cell death. Phthalocyanines (Pcs) and 

metallophthalocyanines (MPcs) are useful photosensitizers due to 

their intense absorbtion in red region of the visible light [2, 3]. 

In this study, the novel metal-free (4)and zinc (II) (5) 

phthalocyanine compounds substituted with four 1-(2-hydro - 

xyethyl)-4-piperidone ethylene ketal functional groups at 

peripherally positions have been prepared. These new 

phthalocyanine compounds have been characterized by IR, 1H NMR, 13CNMR spectroscopy, MS spectra data and elemental 

analysis. The synthesized phthalocyanine compounds exhibited 

excellent solubility in common organic solvents and the zinc (II) 

phthalocyanine complex (5) showed J-type aggregation in 

chloroform. The photophysical and photochemical properties of 

metal-free (4) and zinc (II) (5) phthalocyanine complexes were 

also investigated in DMSO. The investigation of the 

photophysical and photochemical properties of photosensitizers 

is very useful for photodynamic therapy (PDT) applications. 

references: 

1. M.A. Loi, H. Neugebauer, P. Denk, C.J. Brabec, 

N.S. Sariciftci, A. Gouloumis, P. Vasquez, T. Torres, 

J. Mater. Chem. 13 (2003) 700-704 

2. B. Raymond, Photodynamic Therapy in Historical 

Perspective Contemp Pharmacother, 1990, 10, 1-14 

3. H. Ali, J.E. van Lier, Chem. Rev. 99 (1999) 2379–2450. 

Keywords: Phthalocyanine; Aggregation; Photodynamic 

therapy; Zinc; Singlet oxygen; 



s987 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 5 2 

SyntheSiS And ChArACterizAtion of Co(ii) 

PhthALoCyAnine And inveStiGAtion of itS 

CAtALytiC ACtivitiy on ALCohoL oxidAtion 

z. BiyiKLioGLu 1 , e. t. SAKA 1 , d. CAKir 1 , v. CAKir 1 , 

h. KAnteKin 1 

1 Karadeniz Technical University, Department of Chemistry, 

Trabzon, Turkey 

Catalytic oxidation of alcohols is of great importance for the 

manufacture of fragrances and many synthetic intermediates for 

organic synthesis [1, 2] . Traditional methods for performing such a 

transformation involve the use of stoichiometric quantities of 

heavy inorganic oxidants, such as chromium(VI) or permanganate, 

which are toxic and pose significant environmental problems. 

Hence, the development of efficient and environment-friendly 

catalysts for alcohol oxidation using oxygen source has attracted 

great research interest. Many researchers have reported the use of 

highly active metallic catalysts for the alcohol oxidation [3] . 

Metallophthalocyanine complexes especially Co(II) 

phthalocyanines are readily available oxidation catalysts and 

found to transfer oxygen from various oxygen donors to alcohols, 

alkanes, alkenes, phenols and thiols in numerous studies [4] . 

Herein, we report the synthesis and characterization of 

{2-[3-(diethylamino)phenoxy]ethoxy} group substituted Co(II) 

phthalocyanines and the catalytic behavior of these complexes in 

oxidation of alcohol. 

references: 

1. A. B. Sorokin, A. Tuel, Cataly. Today, 2000; 57, 45. 

2. N. Sethlotho, T. Nyokong, J. Mol. Catal. A: Chem. 2004; 

219, 201. 

3. M. Chibwe, L. Ukrainczyk, S.A. Boyd, T.J. Pinnavaia, 

J. Mol. Catal. A: Chem. 1996; 113, 249. 

4. S.M.S. Chauhan, B. Kalra, P.P. Mohapatra, 

J. Mol. Catal. A: Chem. 1999; 137, 85. 

Keywords: Phthalocyanine; Cobalt; Catalysis; Oxidation; 


P - 0 2 5 3 

SyntheSiS, ChArACterizAtion And CAtALytiC 

ACtivitiy on CyCLohexene oxidAtion of 

PeriPherALLy tetrA-SuBStituted CoBALt(ii) 

PhthALoCyAnine 

e. t. SAKA 1 , z. BiyiKLioGLu 1 , i. KAni 2 , 

h. KAnteKin 1 

1 Karadeniz Technical University, Chemistry, Trabzon, Turkey 

2 Anadolu University, Chemistry, Eskisehir, Turkey 

Phthalocyanines (Pcs), a family of aromatic macrocycles 

based on an extensive delocalized 18-p electron system, have been 

extensively studied due to their unique optical, electronic, catalytic 

and structural properties. [1] The catalytic conversion of alcohols in 

to their corresponding carbonyl compounds is an important 

reaction in organic synthesis. Syntheticmetalloporphyrins have 

been investigated extensively as models for the activity of 

cytochrome P-450 [1] . 

In this work, we have synthesized and characterized 

of new cobalt(II) phthalocyanine substituted with four 

3,3-diphenylpropoxy groups. The new compound was 

characterized by IR, UV-Vis, elementel analysis and MS spectral 

data. This cobalt complex was investigated as catalyst for 

cyclohexene oxidation with TBHP, m-CPBA and H O as an 

2 2 

oxidant in organic solvent (DMF). Tert-butylhydroperoxide was 

found to be the best oxidant for cyclohexene oxidation since 

higher conversion and selectivity were observed when this oxidant 

was used. 

references: 

1. B. Meunier, Biomimetic Oxidations Mediated by Metal 

Complexes. 

Imperial College Press: London, 2000. 

Keywords: Phthalocyanine; Cobalt; Synthesis; Cyclohexene 

oxidation; Oxidant; 



s988 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 5 4 

PeriPherAL And non-PeriPherAL 

tetrA-SuBStituted wAter SoLuBLe zinC(ii) 

PhthALoCyAnineS: SyntheSiS, PhotoPhySiCS 

And PhotoCheMiStry 

z. BiyiKLioGLu 1 , d. CAKir 1 , M. durMuS 2 , 

h. KAnteKin 1 

1 Karadeniz Technical University, Department of Chemistry, 

Trabzon, Turkey 

2 Gebze Institute of Technology, Department of Chemistry, 

Kocaeli, Turkey 

Phthalocyanines (Pcs), a family of aromatic macrocycles 

based on an extensive delocalized 18 p electron system, have been 

extensively studied due to their unique optical, electronic, 

catalytic and structural properties. Owing to their strong and 

long-wavelength absorptions, high efficiency at generating 

reactive oxygen species and ease of chemical modification, 

phthalocyanines have emerged as a promising class of 

second-generation photosensitizers for photodynamic therapy 

(PDT) [1–4] . Over the last decade, a substantial number of 

phthalocyanine-based photosensitizers have been prepared and 

evaluated for their photodynamic activity, with focus on zinc, 

silicon and aluminium analogues as a result of their desirable 

photophysical properties. 

In this study, we report on the synthesis, characterization 

and spectroscopic behaviour as well as photophysical 

(fluorescence quantum yields and lifetimes) and photochemical 

(singlet oxygen and photodegradation quantum yields) properties 

of zinc phthalocyanine complexes substituted with four 

{2-[3-(dimethylamino)phenoxy]ethoxy} groups on both 

peripherally and non-peripherally positions. 

references: 

1. H. Yanik, D. Aydin, M. Durmus, V. Ahsen, J. Photochem. 

Photobiol.A Chem. 206 (2009) 18-26. 

2. H. Ali, J.E. van Lier, Chem. Rev. 99 (1999) 2379–2450. 

3. D. Phillips, Pure Appl. Chem. 67 (1995) 117-126. 

4. A. C. Tedesco, J. C. G. Rotta, C. N. Lunardi, Curr. Org. 

Chem. 7 (2003) 187-196. 

Keywords: Phthalocyanine; Zinc; Quaternization; 

Photodynamic therapy; Photosensitizer; 


P - 0 2 5 5 

PhotoCheMiCAL fAte- the LoCALizAtion of 

the initiAL eLeCtroniC trAnSition 

deterMineS the effiCienCy of CAtALytiC 

ACtion in SuPrAMoLeCuLAr PhotoCAtALySt 

B. dietzeK1 , S. tSChierLei2 , M. KArnAhL2 , 

M. SChMitt3 , J. PoPP3 , S. rAu4 1 IPHT, Research Group Ultrafast Spectroscopy, Jena, Germany 

2 Uppsala University, Department of Photochemistry and 

Molecular Sciences, Uppsala, Sweden 

3 Friedrich-Schiller-University Jena, Institute of Physical 

Chemistry, Jena, Germany 

4 Ulm University, Institute of Inorganic Chemistry, Ulm, 

Germany 

Artificial photosynthesis presents a promising solution to 

the looming energy crisis by converting sunlight into chemical 

fuels. In particular, supramolecular photocatalysts present an 

interesting class of substances in this context. These systems allow 

for synthetic optimization of the intramolecular energy- and 

electron-transfer processes by local modifications of the ligand 

architecture. 

In this contribution we discuss the photophysics and 

photocatalysis of the supramolecular photocatalyst ruPd 

(Bis-(4,4'-di-tert-butyl-2,2'-bipyridine)–ruthenium(II)-µ (tetra- 

-pyrido[3,2-a:2,3'c:3",2",-h:2'",-3'"-j]-phenazine)-dichloro- 

-palla-dium(II)).- The combination of various spectroscopic 

techniques yields a detailed picture of the photoinduced processes 

in ruPd and structurally related model systems. The dynamic 

range of the joint use of resonance Raman, femtosecond 

time-resolved transient absorptions and luminescence 

spectroscopy covers timescales of several orders of magnitude. 

Based on detailed spectroscopic characterization we shall discuss 

the correlation of the photoinduced excited-state dynamics with 

the catalytical efficiency of the ruPd system and its dependence 

on structural modifications of the ligand architecture. Based on 

the spectroscopic results presented, we shall discuss a novel 

concept for the design of artificial photosynthetic systems, which 

is based on tailoring the properties of the Franck-Condon point of 

absorption. 

Acknowledgement: This work was financially supported by the 

Fonds der Chemischen Industrie (B.D.) and by the project 

PhotoMIC of the TMBWK, grant No. B514-09049. 

Keywords: artificial photosynthesis; photophysics; 

photochemical hydrogen evolution; electron transfer; 



s989 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 5 6 

redox direCted ProCeSSeS in the deSiGn of 

noveL nAnoSCALe heteroPoLyACidS 

A. KondinSKi 1 , n. izArovA 1 , n. nSouLi 1 , B. BASSiL 1 , 

u. Kortz 1 



Polyoxometalates (POMs) are an exciting class of discrete 

metal-oxygen cage complexes with a tremendous variety of 

structures, compositions and properties. [1] . In this work we 

decided to explore the use of oxidizing agents such as sodium 

chromate in the synthesis of novel lanthanide containing 

tungstoarsenates. In particular, when using the trilacunary 

lone-pair-containing [AsIIIW O ] 9 33 9- as the POM precursor, there is 

a partial in-situ oxidation of the AsIII heteroatom of the POM 

precursor, leading to a large mixed-valent AsIII/AsV polyanions 

with formula [Ln As 12 III 

8AsV 2W90O328 (H2O) 36 (OAc) 4 ]48- (Ln=Gd III , 

TbIII , DyIII , HoIII ErIII , TmIII , YbIII , LuIII ). The same reaction 

conditions in presence of cerium(III) ions lead to in-situ oxidation 

of CeIII ions to CeIVfollowed by a self-assembly into the novel 

tetrameric polyanion [CeIV 4AsIII 4W41O149 ]24- . 

Keywords: polyoxometalate; self-assembly; in-situ oxidation; 

lanthanoids; tungstoarsenate; 


P - 0 2 5 7 

LithiAted SuLfoxideS – ALPhA-SuLfinyL 

funCtionALized CArBAnionS 

G. LudwiG 1 , A. hoPPe 1 , M. Bette 1 , t. rüffer 2 , 

d. SteinBorn 2 

1 Institute of Chemistry, Inorganic Chemistry, Halle (Saale), 

Germany 

2 Institute of Chemistry, Inorganic Chemistry, Chemnitz, 

Germany 

α-Heteroatom functionalized alkyl lithium compounds of 

the type LiCHRYR' n (Y = N, P, O, S, Cl, …) exhibit a unique 

reactivity; thus, for example, those with electronegative groups 

YR' n may react as carbenoids. 1 A further point of interest is the 

configurational stability of the carbanionic C atoms. 2 Sulfur 

functionalized lithium compounds, among them lithiated 

sulfoxides Li[CRR'S(O)R”], have been hardly investigated in this 

respect. 3–5 In the present work, lithiated sulfoxides of the type 

[Li 2 {CRR'S(O)Ph} 2 (TMEDA) 2 ] (i) were obtained by direct 

metallation of the respective sulfoxides with n-BuLi/TMEDA. In 

the solid state, in type i compounds, no Li–C interactions were 

recognized; thus, there is a “free” α-carbanionic center having a 

planar configuration (see the structural image with R/R' =Me/Me 

as example). The dynamics of type i lithium compounds in 

solution was investigated by low-temperature NMR 

measurements and, moreover, these results were confirmed by 

DFT calculations. Furthermore, here we report on reactions of 

type i compounds with various electrophiles and their 

diastereoselectivity as well as on the decomposition of type i 

compounds exhibiting a carbenoid reactivity. 

references: 

1. G. Köbrich, Angew. Chem. 1972, 84, 557. 

2. A. Basu, S. Thayumanavan, Angew. Chem., Int. Ed. 2002, 

41, 716. 

3. M. Marsch, W. Massa, K. Harms, G. Baum, G. Boche, 

Angew. Chem., Int. Ed. 1986, 25, 1011. 

4. A. Maercker, R. Schuhmacher, W. Buchmeier, H. D. Lutz, 

Chem. Ber. 1991, 124, 2489. 

5. D. J. Cram, S. H. Pine, J. Am. Chem. Soc. 1963, 85, 1096. 

Keywords: carbanion; carbenoid; lithiated sulfoxide; 



s990 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 5 8 

denSity funCtionAL theory Study of the 

deLtAhedrAL diCoBALtAdiCArBABorAneS 

hAvinG nine to tweLve vertiCeS 

A. LuPAn 1 , r. B. KinG 2 

1 Babes-Bolyai University, Chemistry, Cluj-Napoca, Romania 

2 University of Georgia, Chemistry, Athens, USA 

The basic building blocks of metal-free polyhedral boranes 

and isoelectronic carboranes have long been recognized to be the 

most spherical deltahedra, also known as closo deltahedra. Vertex 

atoms in the deltahedral dicarbaborane C B H structures can be 

2 n–2 n 

replaced with isolobal transition metal units leading to very stable 

metalladicarbaboranes and dimetalladicarbaboranes. Compounds 

having CpCo (Cp =η5-C H ) vertices in place of BH vertices in 

5 5 

carborane structures are of particular interest since CpCo vertices, 

as formal donors of two skeletal electrons, are isolobal with BH 

vertices. The theoretical predictions from this study agree well 

with experimental data on the numerous known Cp Co C B H 2 2 2 n–4 n–2 

(n = 9, 10, 11, and 12) derivatives. The lowest energy structures 

for the dicobaltadicarbaboranes Cp Co C B H (n=9, 10, and 11) 

2 2 2 n–4 n–2 

are found by density functional theory to be the most spherical 

borane deltahedra with the carbon atoms at degree 4 vertices and 

the cobalt atoms at degree 5 or 6 vertices. Thus for the nine-vertex 

Cp Co C B H system only the two lowest energy isomers are 

2 2 2 5 7 

found experimentally; these lie within 3 kcal/mol of each other 

and ~6 kcal/mol below the next lowest energy isomer. For the 

ten-vertex Cp Co C B H system three of the six lowest energy 

2 2 2 6 8 

isomers are known. The 11-vertex Cp Co C B H systems provide 

2 2 2 7 9 

examples of stable high energy isomers with direct Co–Co or 

C–C bonds arising from the synthetic methods used. Thus one of 

the experimentally known 11-vertex Cp2Co2C2B7H9 isomers is 

a high-energy structure with adjacent carbon atoms lying 

~26 kcal/mol above the global minimum. For the icosahedral 

12 vertex dicobaltadicarbaboranes Cp Co C B H with only 

2 2 2 8 10 

degree 5 vertices, the lowest energy structures are those without 

Co–Co or C–C edges. 

Keywords: metallaboranes; cobalt; density functional theory; 


P - 0 2 5 9 

froM BiSMuth oxido CLuSterS to 

MetAStABLe 

SS-Bi o nAnoPArtiCLeS ShowinG hiGh 

2 3 

PhotoCAtALytiC ACtivity 

S. MAiK 1 , d. SAttLer 2 , C. A. SChALLey 2 , d. zAhn 3 , 

M. MehrinG 1 

1 Chemnitz University of Technology, Institute of Chemistry 

Coordination Chemistry, Chemnitz, Germany 

2 Freie Universität Berlin, Institute of Chemistry Mass 

Spectrometry and Supramolecular Chemistry, Berlin, Germany 

3 Friedrich-Alexander-Universität Erlangen-Nürnberg, Institute 

of Chemistry Theoretical Chemistry, Erlangen, Germany 

Bismuth oxides are interesting materials in terms of their 

environmentally benign, non-toxic behavior and interesting 

properties. [1] For example α-Bi O /Bi O nanocomposites are 

2 3 2 4 

excellent photocatalysts and δ-Bi O exhibits high oxide ionic 

2 3 

conductivity. [2-4] However, controlled synthesis of metastable 

bismuth(III) oxides is difficult as a result of a distinctive 

polymorphism. Six different polymorphs are known until now. 

α-Bi O with its monoclinic structure is stable at room temperature. 

2 3 

Upon heating it is transformed into the cubic δ phase at 

approximately 730 °C which is stable upon its melting point. On 

cooling one out of two metastable bismuth(III) oxides, tetragonal βor 

cubic γ-Bi O , is stabilized depending on the reaction conditions. 

2 3 

So far factors that control the polymorphism in bismuth(III) oxides 

are not fully understood. In our approach we use nanoscaled bismuth 

oxido clusters [5, 6] as model compounds and starting materials for the 

synthesis of bismuth(III) oxide polymorphs. The clusters show an 

interesting structural relationship with δ- and β-Bi O . 2 3 

Here we present several bismuth oxido clusters such 

tBu)14 ], [8] 

as [Bi 6 O 4 (OH) 4 (NO 3 ) 6 (H 2 O)]·H 2 O, [7] [Bi 22 O 26 (OSiMe 2 

[Bi O (OMc) (DMSO) ]·2DMSO·7H O 38 45 24 9 2 [9] (OMc=O CC H ) and 

2 3 5 

[Bi O (NO ) (DMSO) ](NO ) ·4DMSO. 38 45 3 20 28 3 4 [5] which are promising 

precursors for the synthesis of metastable β-Bi O nanoparticles with 

2 3 

high photocatalytic activity in the visible light region. The 

investigations are supported by in-situ X-ray powder diffraction, 

electrospray mass spectrometry experiments and molecular dynamic 

simulations which provide insight into the nucleation and 

decomposition process of bismuth oxido clusters to give bismuth 

oxides. Furthermore, UV-Vis spectroscopy, transmission and 

scanning electron microscopy and nitrogen adsorption measurements 

were used for the characterization of the β-Bi O nanoparticles. 

2 3 

references: 

1. M.Mehring, Coord.Chem.Rev.2007,251,974. 

2. A.Hameed, T.Montini, V.Gombac, P.Fornasiero, 

J.Am.Chem.Soc.2008,130,9658. 

3. R.Punn, A. M. Feteira, D.C.Sinclair, C.Greaves, 

J.Am.Chem.Soc.2006,128,15386. 

4. P.Shuk, H.D.Wiemhofer, U.Guth, W.Gopel, M.Greenblatt, 

SolidStateIonics 1996,89,179. 

5. L.Miersch, M.Schlesinger, R.W.Troff, C.A.Schalley, T.Rueffer, 

H.Lang, D.Zahn, M.Mehring, Chem. Eur. J. 2011,17,6985. 

6. L.Miersch, T.Rüffer, H.Lang, S.Schulze, M.Hietschold, 

D.Zahn, M.Mehring, Eur.J.Inorg.Chem.2010,4763. 

7. F.Lazarini, ActaCryst.B1979,35,448. 

8. D.Mansfeld, M.Mehring, M.Schürmann, Angew. Chem. 

Int. Ed. 2004,44,245. 

9. L.Miersch, T.Rueffer, M.Mehring, Chem. Commun.2 011, 

47, 6353. 

Keywords: bismuth oxido cluster; bismuth oxide; 



s991 

chem. Listy 106, s587–s1425 (2012) 

photocatalysis; nanoparticles; metastable phases; 


P - 0 2 6 0 

AntiPyrine CoMPLexeS of rAre eArth 

iodideS And PerChLorAteS: StruCture And 

ProPertieS 

n. ruKK 1 , d. ALBov 2 , r. ShAMSiev 3 , G. dAvidovA 4 , 

A. SKryABinA 1 , G. APryShKo 5 , v. zAMALyutin 1 , 

e. MironovA 6 

1 M.V. Lomonosov Moscow University of Fine Chemical 

Technology (MITHT), Department of Inorganic Chemistry, 


2 M.V. Lomonosov Moscow State University (MSU), Chemistry 

Department, Moscow, Russia 

3 M.V. Lomonosov Moscow University of Fine Chemical 

Technology (MITHT), Department of Physical Chemistry, 


4 Institute of Theoretical and Experimental Biophysics Russian 

Academy of Sciences, Natural-Science Department, Pushchino 

Moscow Region, Russia 

5 N.N. Blokhin Russian Cancer Research Center Russian 

Academy of Medical Sciences, Natural-Science Department, 


6 Pushchino State Natural-Science Institute, Natural-Science 

Department, Pushchino Moscow Region, Russia 

Antipyrine (2,3-dimethyl-1-phenyl-3-pyrazolin-5-one, AP) 

and its derivatives have been widely used as analgesic, antipyretic 

and anti-inflammatory drugs, their biological activity being 

attributed to its scavenging activity against reactive oxygen and 

nitrogen species and to the inhibition of neutrophil’s oxidative 

burst [1]. It was found [2] that metal complexes generally have a 

better activity than free ligands. 

The title compounds [Ln(AP) ]X (X=I 6 3 – – , ClO , Ln=La-Nd, 

4 

Sm-Lu, Sc, Y) have been synthesized and studied. It was 

demonstrated that the complexes form two isostructural series of 

respective iodides and perchlorates. On the basis of the single 

crystal XRD and IR spectra studies it was found that the central 

atom coordinates antipyrine molecules via the oxygen atom of 

carbonyl group, the iodide-or perchlorate ions being in the outer 

sphere. The complexes are characterized by the presence of the 

intracomplex π – π stacking interaction, the phenyl rings being 

almost parallel to the five-membered pyrazole rings of the AP 

molecules from the adjacent sectors. IR spectra (Calculated using 

all-electron relativistic DFT-PBE approach) were in good 

agreement with the experimental ones. 

Cytotoxicity of the complexes was studied using the mouse 

fibroblasts NCTN clone L929 cells and the Hep-2 epithelial cells. 

It was found that [Ln(AP) ]I at approximately equal molar 

6 3 

concentrations inhibit the NCTC clone L929 cell survivability in 

more extent than antipyrine. The non-monotonous dependences 

of the cells survivability on the atomic number Z of the central 

complex-forming lanthanoid atom is observed by comparison of 

the complexes cytotoxicity with respect to the cells of both types. 

Perchlorate complexes demonstrated a more pronounced 

inhibiting effect in comparison with the iodide ones. 

references: 

1. P.M.P. Santos, A.M.M. Antunes, J. Noronha et al. 

Eur. J. Med. Chem., 45 (2010) 2258-2264. 

2. T. Rosu, E. Pahontu, C. Maxim et al. Polyhedron, 29 

(2010), 757-766. 

Keywords: Rare Earths; X-ray diffraction; Quantum 

Chemistry; Cytotoxicity; 


P - 0 2 6 1 

BiS-C-Pivot LAriAt etherS: SyntheSeS, 

SPeCtroSCoPiC ProPertieS And 

StereoCheMiStry of 15-18-MeMBered 

CoronAndS with two diALKyL PhoSPhonAte 

GrouPS 

S. BiLGe KoCAK 1 , h. uCKArdeS 1 

1 Ankara University Faculty of Science, Department of 


A large number of methods for the preparation of diverse 

α-aminoalkylphosphonates, in which the carboxylic acid group 

[C(O)(OH)] is replaced by a phosphonate group [P(O)(OR) ], 2 

have been published since the first synthesis by Fields in 1952 

but, the most convenient is the nucleophilic addition of dialkyl 

phosphites to the C=N bonds of Schiff bases. This synthetic route 

was followed in the synthesis of the bis-C-pivot macrocycles 

containing both phosphonate and amine functionalities in the 

same molecule, (CH ) {o-CH[P(O)(OR) ]NHPhO} X, using 

2 3 2 2 

dimethyl phosphite [HP(O)(OCH ) ] and diethyl phosphite 

3 2 

[HP(O)(OC H ) ] with the dibenzo-bis-imino crown 

2 5 2 

ethers {(CH ) [o-CH=NHPhO] X; X:-CH CH -, -CH CH CH -, 

2 3 2 2 2 2 2 2 

-CH CH CH CH - and -CH CH OCH CH -} in dry MeOH. 

2 2 2 2 2 2 2 2 

The nucleophilic addition of dimethyl or diethyl phosphite to 

CH=N bonds in dibenzo-bis-imino crown ethers is of paramount 

importance in providing tetra-substituted carbon atom, 

[CH(phosphonate)(amine)(arom)], which is a centre of chirality 

and as each macrocycle contains two equivalent chiral carbon 

atoms then the molecules are expected to be diastereoisomers and 

exist in meso and racemic forms. The structures of the compounds 

have been characterized by elemental analysis, FTIR, MS and 

NMR measurements. 1H, 13C and 31P NMR assignments have been 

made for the meso and racemic forms of bis-C-pivot macrocycles 

by analysis of chemical shifts, signal intensities, spin-spin 

coupling constants, splitting patterns and 2D HETCOR NMR 

techniques. Due to the presence of two chiral carbon centres, 

bis-C-pivot macrocycles can be valuable to be investigated as 

bioactive molecules and pharmacological agents. The synthesized 

bis-C-pivot macrocycles may serve as a potential new class of 

supramolecular host molecules because of their natures to give 

rise to intermolecular hydrogen bonds confirmed by 

X-ray crystallography. The phosphorylation addition reaction to 

dibenzo-bis-imino crown ethers produces adjacent N–H and 

P=O moieties in the molecule with the potential of parallel 

orientation, and hence of forming a pair of antiparallel hydrogen 

bonds with a similar grouping on a second molecule. 

Keywords: Macrocycles; Schiff Bases; NMR Spectroscopy; 

Diastereoselectivity; X-ray Difraction; 



s992 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 6 2 

MuLtinuCLeAr MAnGAneSe-ContAininG 

PoLyoxotunGStAteS:SyntheSiS, StruCture, 

And CAtALytiC CAPACity 

r. AL-oweini 1 , B. BASSiL 1 , u. Kortz 1 



Inorganic compounds are generally known to be formed 

from atoms of a metallic nature as their intrinsic building units. 

Polyoxometalates (POMs) are discrete, nano-sized metal-oxo 

anions of high oxidation state early transition metals, 

predominantly VV , NbV , TaV , MoVI , and WVI . 1a They are adaptable 

structures with natural properties in nano-sized dimensions, shape, 

charge density and surface reactivity due to the flexibility of their 

chemical composition, charge, and counterions. [1] Such properties 

render POMs highly desirable for magnetic, electronic, and 

catalytic studies amongst others. [2, 3] 

Polyanions containing several paramagnetic d-block ions are 

of interest for oxidation catalysis applications. In particular 

manganese-containing polyanions are important here, and very 

recently our group has reported the synthesis and magnetic 

properties of a new member, the Mn -containing polyanion 

19 

[Mn II 

19 (OH) 12 (SiW 10 O 37 ) 6 ]34- {Mn 19 }. [4] To date only a few 

high-nuclearity, mixed-valence polytungstates have been 

prepared, usually based on reactions of MnII - and MnO , or the 

4 

well-known {Mn }, with lacunary polytungstate precursors. 

12 

We have investigated the reactivity of {Mn } with lacunary 

12 

heteropolytungstates. This approach has enabled us to synthesize 

the polyanions [Mn III 

3 (OH) 3 (H 2 O) 3 SiW 9 O 34 ]4- {Mn 3 -Keggin}, 

[Mn III 

3 MnIV (CH 3 COO) 3 SiW 9 O 37 ] 6- {Mn 4 }, [Mn III 

3 (H 2 O) 5 (PW 9 O 34 ) 2 ]9- 

{Mn 3 -Knoth}, and [Mn III 

6 MnIV 

4 O 4 (OH) 12 (H 2 O) 12 (AsW 9 O 34 ) 4 ]22- 

{Mn 10 }, which were all characterized by single-crystal XRD, 

electrochemical studies, TGA, and IR spectroscopy. 

These compounds have tremendous potential in electro- and 

oxidation-catalysis. 

references: 

1. a) M. T. Pope, A. Müller, Angew. Chem. Int. Ed. Engl. 

1991, 30, 34–48; 

b) Chem. Rev. 1998, 98, 1–390 (Special Issue on 

Polyoxometalates; Ed.: C. L. Hill); 

2. Kortz, U., Müller, A., van Slageren, J., Schnack, J., Dalal, 

N.S., and Dressel, M. Coord. Chem. Rev. 2009, 253, 

2315–2327; 

3. Eur. J. Inorg. Chem. 2009, 34 (Issue dedicated to 

Polyoxometalates; Guest Ed.: U. Kortz); 

4. B. S. Bassil, M. Ibrahim, R. Al-Oweini, M. Asano, Z. Wang, 

J. van Tol, N. S. Dalal, K.-Y. Choi, R. Ngo Biboum, 

B. Keita, L. Nadjo, U. Kortz, Angew. Chem. Int. Ed., 

2011, 50, 5961–5964. 

Keywords: Polyoxometalates; Oxidation; Homogeneous 

catalysis; Manganese; Magnetic properties; 


P - 0 2 6 3 

hiGh-nuCLeArity, MAGnetiC 

MetAL-oxo ASSeMBLieS StABiLized By 

heteroPoLytunGStAteS 

B. BASSiL 1 , S. S. MAL 1 , M. iBrAhiM 1 , u. Kortz 1 

1 Jacobs University, Chemistry, Bremen, Germany 

Lacunary heteropolytungstates are known to act as inorganic 

multidentate ligands with oxygen atom donors at the lacunary 

sites. [1] The combination of 3d transition metals with lacunary 

heteropolutungstates is part of the TMSP (Transition 

Metal-Substituted Polyoxometalates) subclass. Recently, a 

growing interest started to show in TMSP’s comprising high 

nuclearity (>10) metal-oxo cage complexes with paramagnetic 

centers, due to their potential to exhibit Single 

Molecular Magnet (SMM) behavior. [2] Interaction of the 

wheel-shaped 48-tungsto-8-phosphate [H P W O ] 7 8 48 184 33- ({P W }) 8 48 

with copper(II) and iron (III) formed the 20-copper(II)- and 

16-iron(III)-containing species {Cu P W } and {Fe P W } 

20 8 48 16 8 48 

respectively, which correspond to the parent lacunary 

precursor {P W } encapsulating a [Cu Cl(OH) (H O) ] 8 48 20 24 2 12 9- and a 

[Fe (OH) (H O) ] 16 28 2 4 20+ core. [3] Interaction of the trilacunary 

nonatungstosilicate [SiW O ] 9 34 10- ({SiW }) with manganese(II) and 

9 

its phosphate analogue [PW O ] 9 34 9- ({PW }) with cobalt(II) ions 

9 

in basic phosphate buffer formed the 19-manganese(II)- and 

16-cobalt(II)-containing species {Mn Si W } and {Co P W } 

19 6 60 16 4 36 

respectively, corresponding to a sheet-like [Mn (OH) ] 19 12 26+ core 

stabilized by six [SiW O ] 10 37 10- units and a tetrahedrally arranged 

[Co (OH) (PO ) ] 16 12 4 4 8+ core stabilized by four {PW } units. 9 [4] 

references: 

1. Eur. J. Inorg. Chem. 2009, 34 (Issue dedicated to 

Polyoxometalates; Guest Ed.: U. Kortz). 

2. U. Kortz, A. Müller, J. van Slageren, J. Schnack, 

N.S. Dalal, M. Dressel, Coord. Chem. Rev. 2009, 253, 2315. 

3. a) S. S. Mal, U. Kortz, Angew. Chem. Int. Ed. 2005, 44, 3777 

b) S. S. Mal, M. H. Dickman, U. Kortz, A. M. Todea, 

A. Merca, H. Bögge, T. Glaser, A. Müller, S. Nellutla, 

N. Kaur, J. van Tol, N. S. Dalal, B. Keita, L. Nadjo, 

Chem. Eur. J. 2008, 14, 1186 

4. a) B.S. Bassil, M. Ibrahim, R. Al-Oweini, M. Asano, 

Z. Wang, J. van Tol, N. S. Dalal, K.-Y. Choi, U. Kortz, 

Angew. Chem. Int. Ed. 2011, 50, 5961 

b) M. Ibrahim, Y. Lan, B. S. Bassil, Y. Xiang, A. K. Powell, 

U. Kortz, Angew. Chem. Int. Ed. 2011, 50, 4708 

Keywords: Polyoxometalates; Transition metals; Magnetic 

properties; 



s993 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 6 4 

Pre-orGAnzied MetAL ALKoxideS 

C. MAurer 1 , M. PuChBerGer 1 , S. PABiSCh 2 , 

u. SChuBert 1 

1 Vienna Universty of Technology, Institute of Materials 


2 Universty of Vienna, Faculty of Physics, Vienna, Austria 

Organically modified metal alkoxides are well known as 

precursors for sol-gel materials, since substitution of part of the 

alkoxo groups opens the chance of lowering the reactivity and 

better controlling of sol-gel processing. To this end, different types 

of ligands, e.g. ß-diketonates, ß-ketoesterates, amines and oximates 

can be used. While sol-gel processing of the metal alkoxide 

complexes results in unstructured materials, pre-organized 

precursors open the possibility to prepare structured metal 

oxide-based materials. One access is through polymeric metal 

alkoxides, which retain their structure during the hydrolysis 

process, another one can be the formation of MOF-like structures. 

First experiments to react titanium alkoxides with 

bis(ß-ketoesters) and bis(ß-diketones) resulted in cyclic 

dimeric structures with two bridging ligands and two terminal 

alkoxides per titanium atom. ESI-MS- and NMR-measurements 

proved that no polymeric products were formed, as the cyclic 

dimers seemed to be thermodynamically more stable. Dimeric or 

oligomeric structures were also obtained with dioximes. As SAXS 

measurements showed no pre-organization of the precursors, the 

number of functionalities per ligand was increased to three and 

four. 1,3,5-Benzene-tri-p-benzoic acid (L ), adamantane-1,3,5,7- 

1 

-tetracarboxylic acid and others were chosen as ligands. 

Reaction of titanium isopropoxide with different proportions 

of these ligands resulted in insoluble residues, which were 

characterized by IR, SAXS and XPS. From a ratio of 

2:1 (Ti:COOH) a two-dimensional structure was built with L . 1 

Therefore, using adamantane as the spacer between the four 

carboxylic groups should open the possibility to form 

three-dimensional structures. Lower metal alkoxide to ligand 

ratios resulted in a dense material with no specific pre-structuring. 

Partial hydrolysis studies and XPS measurements will be 

performed to check whether the anticipated pre-structure is 

retained in the hydrolysed materials. 

Keywords: titanium; metal alkoxides; multifunctional ligands; 


P - 0 2 6 5 

hiGh nuCLeArity trAnSition MetAL 

ContAininG PoLyoxoMetALAteS 

y. xiAnG 1 , M. iBrAhiM 2 , B. BASSiL 1 , u. Kortz 1 



2 Karlsruher Institut für Technologie, Institut für Anorganische 

Chemie, Karlsruher, Germany 

Polyoxometalates (POMs) are a large class of discrete, 

anionic metal-oxides comprised of early transition metals in 

high-oxidation states, such as W(VI), Mo(VI), or V(V). [1] There 

has been increasing interest in this field due to potential 

applications of POMs in various fields including catalysis, 

magnetism, medicine, materials science, and chemical analysis. [2] 

Lacunary heteropolytungstates allow for incorporation of 

transition metals, and in particular POMs containing a high 

nuclearity magnetic core are of major interest. [3] 

Here we report on the 16 CoII containing 

[(PW 9 O 34 ) 4 {Co II 

4 (OH) 3 PO 4 } 4 ]28- which is composed of four 

Keggin-type {Co 3 PW 9 } fragments encapsulating a central 

{Co 4 O 4 } cubane unit, which in addition is capped by four external 

phosphate groups, resulting overall in a polyanion with 

idealized T d point group symmetry. [4] The 14 Ni II containing 

[(A-α-P 2 W 15 O 56 ) 4 (Ni 14 O 10 (OH) 6 (PO 4 ) 4 ] 58- is composed of four 

Wells-Dawson type {Ni 3 P 2 W 15 } fragments encapsulating a central 

di-nickel-oxo unit and four capping phosphate groups. Both 

polyanions were synthesized in simple one-pot reactions in 

aqueous phosphate buffer (pH 8), and structurally characterized 

in the solid state by single-crystal X-ray diffraction, FT-IR, 

and TGA. 

references: 

1. M. T. Pope, Heteropoly and Isopoly Oxometalates 

(Springer, Berlin, 1983). 

2. Eur. J. Inorg. Chem. 34, 5055 (2009), Issue dedicated to 

Polyoxometalates; Guest Ed.: U. Kortz. 

3. U. Kortz, A. Müller, J. van Slageren, J. Schnack, N. S. Dalal, 

M. Dressel, Coord. Chem. Rev. 253, 2315 (2009). 

4. M. Ibrahim, B. S. Bassil, Y. Xiang, Y. Lan, A. K. Powell, 

U. Kortz, manuscript in preparation. 

Keywords: Polyoxometalate; magnets; Co; Ni; 



s994 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 6 6 

x-rAy diffrACtion And ir SPeCtroSCoPy for 

nAno-Sized ito doPed with SoMe MetAL 

oxideS 

A. youSSef 1 , f. hAMMAd 1 , z. hAnAfi 1 , h. ABASS 1 

1 National Research Centre, Inorganic Chemistry, Cairo, Egypt 

Nanocrystalline indium tin oxide (ITO) doped with 2, 4 and 

6 mole % of CuO, Cr O , and ZrO powder have been synthesized 

2 3 2 

by pechini method. The crystalline structure of all the prepared 

samples was identified using XRD and IR spectroscopy. The 

morphology and average grain size of the prepared powder were 

determined using TEM and XRD. The effect of different dopant, 

different concentration, dopant cation valence and ionic radius on 

the crystalline structure, lattice parameter, crystallite size and 

strain were investigated. All samples have single cubic bixbyite 

phase structure except ITO samples doped with Zr. They have 

cubic bixbyite structure as predominant phase and traces of 

rhombohedral phase. Pure ITO sample has higher lattice 

parameter value than those of ITO samples doped with ZrO and 2 

lower lattice parameter value than those of ITO samples doped 

with CuO and Cr O . 2 3 

Keywords: Nano-sized doped ITO; Structural properties; IR; 

TEM; 


P - 0 2 6 7 

SoLvotherMAL SyntheSiS of new MAGnetiC 

MAteriALS BASed on rheniuM(iv) 

A. KoCheL 1 

1 University of Wroclaw, Faculty of Chemistry, Wroclaw, Poland 

ReCl L (L - aromatic amine) complexes were obtained by 

4 

solvothermal method in a Berghoff pressure reactor. 

The presented product, ReCl (2,2'-bipyrimidine)·(CH ) SO , 

4 3 2 2 

crystallizes in orthorhombic crystal system, a = 18.6257(3), 

b=12.9848(3) c = 12.4753(3) ?, V = 3017.16(11) ? 3 , Z = 4. 

Intramolecular C-H···Cl hydrogen bonds are present in the 

complex molecule (C(5)-H(5)···Cl(2): where H···Cl 2.73 ? C···Cl 

3.317(3) ?, < CHCl 122°, and C(8)-H(8)···Cl(4) where H···Cl 

2.81 ? C···Cl 3.386(3) ?, < CHCl 121°), additionally stabilizing 

the crystal structure. The magnetic properties were investigated 

from susceptibility measurements preformed on polycrystalline 

samples in the temperature range 1.7-300 K. The magnetic 

behavior found is typical of antiferromagentically coupled 

systems, and susceptibility maxima are found at 12 K. Short 

Re-Cl···Cl-Re contacts account for the observed 

antiferromagnetic behavior. 

The study on the coordination chemistry of rhenium and its 

compounds is of great interest due to several therapeutic, catalytic, 

photophysical and magnetic properties. 

One on first compounds with characterized magnetic 

properties was [ReCl (py) ] obtained via solvothermal synthesis. 4 2 [1] 

Rhenium(IV) complexes of ReCl L (L – aromatic amine) 

4 

general formula were examined with respect to their anti-tumor 

properties and they may be applied in treatment of breast, prostate 

and ovary cancer. [2] 

references: 

1. Andrzej Kochel, Jerzy Mrozinski, Tadeusz Lis, 

Journal of Molecular Structure., 2002, 610, 53-61. 

2. José Martínez-Lillo, Teresa F. Mastropietro, Rosamaria 

Lappano, Antonio Madeo, Marta E. Alberto, Nino Russo, 

Marcello Maggiolini and Giovanni De Munno Chem. 

Commun., 2011, 47, 5283-5285 

Keywords: Rhenium(IV); magnetic materials; solvothermal 

synthesis.; 



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chem. Listy 106, s587–s1425 (2012) 


P - 0 2 6 8 

[n]SiLA-ACeneS (n =2-4): the infLuenCe of rinG 

Size on the ProPertieS 

h. GhiASi 1 , r. GhiASi 1 , A. BoSShAK 1 

1 Islamic Azad University, Department of Chemistry, Tehran, 

Iran 

The structure and properties of [n]sila-acenes (n =2-4) were 

investigated by density functional theory method. The results of 

calculations were obtained at B3LYP/6-311G(d,p) level on model 

species. Energetic criteria suggest that 2-1b (n =2), 3-1b (n =3), 

and 4-1b (n = 4) isomers enjoy stabilization. By frontier orbital 

analysis, these systems are among the most stable of the family. 

Also, calculations indicate the most stable isomers have the most 

first hyperpolarizability values. The aromaticity of all molecules 

has been studied by nucleus-independent chemical shift. 


P - 0 2 6 9 

StruCture, MAGnetiC And eLeCtroCheMiCAL 

ProPertieS of Lini Mn Co o PrePAred viA 

1/3 1/3 1/3 2 

CitrAte-GeL Method 

h. ABuzeid 1 , A. hASheM 1 , A. ABdeL GhAny 1 , 

h. ehrenBerG 2 , C. JuLien 3 

1 National Research Centre, Inorganic Chemistry, Dokki, Egypt 

2 Institute for Complex Materials IFW, Inorganic chemistry, 


3 Institut des Nano-Sciences de Paris (INSP) CNRS-UMR 7588 

Universite Pierre et Marie, Inorganic Chemistry, Paris, 

France 

Layered LiNi Mn Co O oxide was synthesized by 

1/3 1/3 1/3 2 

citrate gel method with molar ratio Li/M =1, (M =Ni +Mn +Co). 

Structural properties studied by X-ray diffraction (XRD) and 

magnetic measurements carried out by superconducting quantum 

interference device (SQUID) showed the well-defined a-NaFeO2 structure with cationic distribution close to the nominal formula. 

3.2% of nickel ions were located into the Li sublattice as estimated 

from magnetic measurements. Electrochemical properties were 

investigated by both potentiostatic and galvanostatic 

charge-discharge cycling. High capacity values were observed for 

the prepared oxide from electrochemical measurement. An initial 

discharge capacity of 176 mAhg-1 was delivered at C/15-rate in 

the cut-off voltage of 2.5–4.5V vs. Li/Li + . More than 87% of its 

initial capacity was retained after 35 cycles at C/15-rate. 

Keywords: LiNi1/3Mn1/3Co1/3O2; Li-batteries; squid; 



s996 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 7 0 

Co reduCtion utiLiSinG 

2 

Photo-eLeCtro-CAtALytiC APProACh 

BASed on trAnSition MetAL CoMPLex 

CAtALyStS AnChored to SeMiConduCtorS 

S. C. PArKer 1 , J. A. weinStein 1 , r. n. Perutz 2 

1 University of Sheffield, Department of Chemistry, Sheffield, 


2 University of York, Department of Chemistry, Heslington York, 


A prominent current area of research is that of CO reduction 

2 

in which CO can be chemically reduced to one of several different 

2 

chemical feedstocks including methanol and formaldehyde. These 

feedstocks are of great importance to many sectors of industry 

and it would be highly beneficial if they could be produced 

cheaply and efficiently. There are two main approaches to 

achieving this goal, using electrocatalysts [1] or photocatalysts [2] . 

Our research is currently focusing on using systems which 

combine both a semiconductor material and an electrocatalyst in 

order to reduce CO . The semiconductor is a nitrogen doped Ta O 2 2 5 

which acts as a photosensitizer capable of absorbing photons with 

energies corresponding to the visible region of the spectrum [3] . 

The electrocatalyst is a transition metal complex with anchoring 

groups to allow attachment to the semiconductor. Upon photon 

absorption, the semiconductor generates the necessary potential 

difference and transfers an electron to the catalyst, which in turn 

reduces CO . We are presently investigating electrocatalysts based 

2 

on ruthenium and rhenium diimine complexes with two types 

of anchoring groups, 4,4'-dicarboxylic acid (dcbpy) and 

4,4'-diphosphonic acid (dpbpy). 

Results from rhenium complexes containing dpbpy 

anchoring groups will be presented. Initial electrochemical studies 

suggest that CO reduction indeed occurs using these complexes 

2 

in an acetonitrile solution at room temperature. 

We would like to thank the White Rose university consortium 

for funding and support. 

references: 

1. E. E. Benson, C. P. Kubiak, A. J. Sathrum and J. M. Smieja, 

Chem. Soc. Rev., 2009, 38, 89-99. 

2.. H. Takedaa and O. Ishitani, Coordination Chemistry 

Reviews., 2010, 254, 346-354. 

3. S. Sato, T. Morikawa, S. Saeki, T. Kajino and T. Motohiro, 

Angew. Chem. Int. Ed., 2010, 49, 5101-5105. 

Keywords: Cyclic voltammetry; Photochemistry; Rhenium; 

Semiconductors; 


P - 0 2 7 1 

CoPPer(i) CoMPLexeS of ACyCLiC 

P,n,n',P'-LiGAndS for SuStAinABLe oLed-tyPe 

deviCeS 

u. SoydAner 1 , e. C. ConStABLe 1 , C. e. houSeCroft 1 , 

M. neuBurGer 1 , J. A. zAMPeSe 1 

1 University of Basel, Chemistry, Basel, Switzerland 

Organic light-emitting devices (OLEDs) based upon 

transition metal or lanthanide metal emitters or sensitizers have 

attracted a great deal of attention due to their potential use in 

lighting as well as future panel display applications [1] . In recent 

years, copper(I) complexes showed promising results as a 

sustainable alternative to the traditionally adopted lanthanide 

emitters or sensitizers and the external quantum efficiency and up 

to 16% has been realized [2] . 

With the goal of optimizing light emitting properties of 

copper(I) complexes, we have synthesized a family of P,N,N’,P’-type 

ligands along with their mononuclear copper(I) complexes. The 

properties of these complexes and structure-property relationships 


references: 

1. M. A. Baldo, M. E. Thompson, S. R. Forrest, 

Pure Appl. Chem. 1999, 71, 2095. 

2. Q. Zhang, Q. Zhou, Y. Cheng, L. Wang, D. Ma, 

X. Jingand F. Wang, Adv. Funct. Mater. 2006, 16, 1203. 

Keywords: ligand design; luminescence; copper; N,P ligands; 



s997 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 7 2 

SyntheSiS And ChArACterizAtion of new 

PhoSPhASiLAProPeneS 

A. BArtoK 1 , r. SePteLeAn 1 , P. PetrAr 1 , G. neMeS 1 , 

L. SiLAGhi-duMitreSCu 1 

1 Babes-Bolyai University, Inorganic Chemistry, Cluj-Napoca, 

Romania 

Three new phosphasilapropenes type Mes*P = C(Cl)- 

-SiCl(Ph)R, [R = Cl (1), R = 9-methylfluorenyl (2), R = 9-tri - 

methylsilafluorenyl (3), Mes*=2, 4, 6-tri-tert-butylphenyl] were 

prepared and completely characterized by physico-chemical 

methods. Their structure in solid state was confirmed by X-ray 

diffraction studies on monocrystals. Dichlorophosphasilapropenes 

2 and 3 were obtained starting from the trichloro - 

phosphasilapropene 1. The latter derivatives were synthesized in 

an attempt to improve the steric protection around the P-C-Si 

moiety, by replacing one of the chlorine atoms from the 

silicon atom with the bulkier 9-methylfluorenyl (2) or 

9-trimethylsilafluorenyl groups (3). 

The reactivity of phosphasilapropenes is currently under 

investigation. 

Keywords: phosphasilapropene; multiple bonding; 


P - 1 0 1 7 

StruCturAL, MeChAniStiC And CAtALytiC 

ASPeCtS of CoPPer(ii) CoMPLexeS ContAininG 

2,6-BiS(iMino)PyridyL LiGAndS 

S. ShABAn 1 , A. rAMAdAn 2 , r. vAn eLdiK 1 

1 University of Erlangen-Nuremberg, Chemistry and Pharmacy, 

Erlangen, Germany 

2 Faculty of Science Kafrelsheikh University, Chemistry, 

Kafrelsheikh, Egypt 

In search for Cu(II) complexes having [CuIIN ] cores as a 

3 

catechol oxidase model, new five-coordinate trigonal bipyramidal 

complexes of the type [CuII (pyN )Cl ], with sterically constrained 

3 2 

chelate ligands, were synthesized and X-ray structurally 

characterized. The ligand substitution kinetics for chloride 

substitution by bio-relevant ligands was studied as a function of 

nucleophile concentration, temperature and pressure. Catalysis of 

the oxidation of 3,5-di-tert-butylcatechol to 3,5-di-tert-butylquinone 

was studied, and correlations between the reactivity, chloride 

substitution behaviour, and reduction potentials of complexes are 

reported. The results show that the rate of oxidation is independent 

of the rate of chloride substitution, indicating that the substitution 

of chloride by catechol as substrate occurs in a fast step. Spectral 

data show a non-linear relationship between the ability of the 

complexes to oxidize 3,5-DTBC and the Lewis acidity of their 

copper(II) centres. Electrochemical data demonstrate that the most 

effective complex has an E½ value that approaches the E½ value 

of the natural tyrosinase enzyme. 

references: 

1. S. Y. Shaban, F. W. Heinemann, R. van Eldik, Eur. J. 

Inorg. Chem., 2009, 3111-3118. 

2. S. Y. Shaban, A. M. Ramadan, R. van Eldik, J. Coord. 

Chem., 2012, 65, 2415-2431. 

Keywords: Biomemetics; amine ligands; Catechol oxidases; 

Crystal structure; 



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Poster session 1 - organic chemistry 

P - 0 2 7 3 

SyntheSiS of hiGher AMino SuGArS 

C. ALBLer 1 , r. hoLLAuS 2 , w. SChMid 1 

1 University of Vienna, Organic Chemistry, Vienna, Austria 

2 University of Natural Resources and Life Sciences, Organic 


A convenient synthesis leading to 2-amino-heptoses and - 

octoses has been developed. These higher amino sugars, although 

scarcely known, play important roles in biological systems. Thus, 

it has been shown that the cell wall LPS of certain bacteria contain 

2-amino-heptoses. [1] Furthermore, 2-amino-octodiose, which is 

formed by oxidation at C-8, is present in the antibiotics 

Apramycin and Oxyapramycin. However, previous syntheses [2] 

of octodioses lack a certain amount of stereochemical flexibility, 

which would be highly interesting in terms of biological activity. 

The title compounds are prepared starting from the unprotected 

carbohydrates D-arabinose, D-galactose and D-glucose through a 

two carbon chain elongation applying the indium mediated 

allylation strategy. [3] The acetate protected products containing a 

terminal olefin moiety were ozonized and yielded after base 

treatment the two carbon chain-elongated, α,β-unsaturated chiral 

aldehydes. These aldehydes were subsequently stereoselectively 

epoxidized utilizing a chiral, L-prolin derived catalyst following 

the JØrgenson’s protocol. [4] After transformation of the aldehyde 

via a Wittig reaction to the corresponding α,β-unsaturated-γ,δ-epoxy 

esters, the epoxide was regio- and stereoselectively opened with 

an azide nucleophile under palladium catalysis. [5] Full 

deprotection finally yields the desired higher amino sugars. 

However, an unexpected side reaction in this respect generated 

highly functionalized tetrahydrofurane derivatives, which belong 

to the class of C-glycosides. Through carefully adjusting the 

reaction conditions, both substance classes are now available. In 

summary, we developed a simple, highly versatile route for the 

synthesis of rare, 2-amino functionalized heptoses, octoses and 

the corresponding methyl acetate C-glycosides respectively. 

references: 

1. Weise, G.; Drews, G.; Jann, B. Arch. Microbiol. 1970, 89. 

2. Martin, O. R.; Szarek, W. A. Carb. Res. 1984, 195. 

3. Schmölzer C.; Fischer M.; Schmid W. Eur. J. Org. Chem. 

2010, 4886. 

4. Marigo, M.; Franzen, J.; Jorgensen, K. A. J. Am. Chem. 

Soc. 2005, 6964. 

5. Miyashita, M.; Mizutani, T.; Tadano, G. Angew. Chem. Int. 

Ed. 2005, 5094. 

Keywords: Higher Amino Sugars; Indium mediated Allylation; 

Stereoselective Epoxidation of Enals; Palladium catalyzed 

Epoxide Opening; 


P - 0 2 7 4 

quAdruPLe CLiCK reACtionS for the 

SyntheSiS of CySteine-terMinAted LineAr 

MuLtiBLoCK CoPoLyMerS 

o. ALdAS CAndAn 1 , h. durMAz 1 , G. hizAL 1 , 

u. tunCA 1 


More recently, click reactions including the copper- 

-catalyzed azide–alkyne cycloaddition (CuAAC), Diels–Alder, 

thiol-ene/thiol-yne, and nitroxide radical coupling (NRC) reactions 

widely adapted to polymer chemistry have emerged as powerful 

tools for the preparation of multisegmented block copolymers with 

a wide variety of macromolecular architectures. [1–9] 

In this work synthesis of cysteine-terminated linear 

polystyrene (PS)-b-poly(e-caprolactone) (PCL)-b-poly(methyl 

methacrylate) (PMMA)/or poly(tert-butyl acrylate)(PtBA)-b- 

-poly(ethylene glycol) (PEG) copolymers was carried out using 

sequential quadruple click reactions including thiol-ene, 

copper-catalyzed azide–alkyne cycloaddition (CuAAC), 

Diels–Alder, and nitroxide radical coupling (NRC) reactions. 

Because the thiol-ene reaction has its own limitations based on 

the polymer–polymer conjugation, instead the cysteine molecule 

was used for conjugation to the polymer blocks. Moreover, this 

quadruple click combination will be effective to prepare a variety 

of end-functional polymer blocks from molecules with thiol 

functionality. Thus, this combination displays a potential strategy 

in which biomolecule–polymer conjugates (biohybrids) from 

biomolecules with thiol functionality can be prepared. 

references: 

1. Nandivada, H.; Jiang, X.; Lahann, J. Adv. Mater. 2007, 19, 

2197–2208.. 

2. Lligadas, G.; Hahn, C.; Percec, V. J. Polym. Sci. Part A: 

Polym. Chem. 2009, 47, 3940–3948. 

3. Mansfeld, U.; Pietsch, C.; Hoogenboom, R.; Becer, C. R.; 

Schubert, U. S. Polym. Chem. 2010, 1, 1560–1598. 

4. Sumerlin, B. S.; Vogt, A. P. Macromolecules 2010, 43, 1– 

13. 

5. Jing, R.; Lin, W.; Wang, G.; Huang, J. J. Polym. Sci. Part 

A: Polym. Chem. 2011, 49, 2594–2600. 

6. Altintas, O.; Tunca, U. Chem. Asian J. 2011, 6, 2584– 

2591. 

7. Hizal, G.; Tunca, U.; Sanyal, A. J. Polym. Sci. Part A: 

Polym. Chem. 2011, 49, 4103–4120. 

8. Altintas, O.; Vogt, A. P.; Barner-Kowollik, C.; Tunca, U. 

Polym. Chem. 2012, 3, 34–45. 

9. Durmaz, H.; Sanyal, A.; Hizal, G.; Tunca, U. Polym. 

Chem. 2012, 3, 825–835. 

Keywords: Polymerization; Click chemistry; Polymers; 



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P - 0 2 7 5 

new fLuoreSCent MeMBrAne ProBeS: froM 

nAPhthALenediiMideS to oLiGothioPheneS 

d. ALonSo dovAL 1 , A. fin 1 , 

M. tAKAhAShi-uMeBAyAShi 2 , h. riezMAn 2 , 

A. roux 2 , n. SAKAi 1 , S. MAtiLe 1 , n. SAKAi 1 

1 University of Geneva, Organic Chemistry, Geneva, 

Switzerland 

2 University of Geneva, Biochemistry, Geneva, Switzerland 

New fluorescent probes are introduced as an innovative 

methodology to label lipid bilayer membranes. This system is 

based on the dynamic covalent linkage between a hydrophilic 

charged head [1] and a fluorescent tail. Dynamic amphiphiles [2] 

formed from core-substitued naphthalenediimides (cNDIs) and 

perylenediimides (cPDIs) were tested first. These probes are 

insensitive to their environment and able to partition selectively 

into liquid-disordered (Ld) microdomains of mixed lipid bilayers 

and to activate DNA transporters [3] . These results confirm the 

potential of dynamic fluorescent amphiphiles to selectively label 

extra- and intracellular membranes. Oligothiophenes have been 

selected for the second generation of dynamic fluorescent 

amphiphiles. Lessons from nature suggest that the combination 

of fluorophore polarization (push-pull fluorophores) [4, 5] and 

fluorophore planarization could provide an attractive approach to 

achieve high sensitivity to membrane fluidity (microdomains), 

membrane potential and membrane stretching (and interesting 

NLO properties at interfaces). This combination is explored 

systematically by varying number and nature of substituents along 

the oligothiophene scaffold in combination with different donors 

and acceptors at both ends. Preliminary results in large unilamellar 

vesicles (LUVs) of variable fluidity are very encouraging. 

references: 

1. Montenegro, J.; Matile, S., Chem. Asian J., 2011, 6, 

681–689. 

2. Takeuchi, T.; Montenegro, J.; Hennig, A.; Matile, S., 

Chem. Sci., 2011, 2, 303–307. 

3. Alonso Doval, D.; Fin, A.; Takahashi-Umebayashi, M.; 

Riezman, H.; Roux, A.; Sakai, N.; Matile, S., Org. Biomol. 

Chem., in press. 

4. Zambianchi, M.; Di Maria, F.; Cazzato, A.; Gigli, G.; 

Piacenza, M.; Della Sala, F.; Barbarella, G., J. Am. Chem. 

Soc., 2009, 131, 10892–10900. 

5. Yan, P.; Xie, A.; Wei, M.; Loew, L., M., J. Org Chem., 

2008, 73, 6587–6594. 


P - 0 2 7 6 

9-C-SuBStituted PhenALenoneS AS ProMiSinG 

PreCurSorS for the forMAtion of new 

StABLe oPen-SheLL heteroAroMAtiCS 

o. AnAMiMoGhAdAM 1 , d. LonG 1 , C. BuSChe 1 , 

M. SyMeS 1 , L. Cronin 1 , G. BuCher 1 

1 University of Glasgow, School of Chemistry, Glasgow, 


We report the access to a series of new phenalenyl type 

radicals using 9-C-substituted phenalenones. Phenalenyl radicals 

are usually arranged in equilibrium between a diamagnetic 

σ-dimer and a paramagnetic π-dimer. To shift the balance towards 

the π-dimer, we focus on the practical preparation of π-radicals 

without steric hindering groups but with electronic effects arising 

from the incorporation of a heteroatom in the molecular structure. 

The target compounds have open shell systems, thus they are 

amphoteric redox species and are able to form both cation and 

anion with invariant molecular structure. The analysis was carried 

out using cyclic voltammetry, X-Ray analysis, NMR-, ESR- and 

UV/Vis-spectroscopy. In the presentation, the syntheses, 

characterisation, physical properties and the importance of these 

compounds in modern applications will be presented and 

discussed. 



s1000 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 7 7 

noveL therAPeutiC AGentS for the 

treAtMent of rheuMAtoid ArthritiS 

S. Aoun 1 , f. redini 2 , d. heyMAnn 2 , J. LeBreton 1 , 

M. MAthé-ALLAinMAt1 1 Laboratoire CEISAM - UMR CNRS 6230, Loire atlantique, 

Nantes, France 

2 INSERM - UMR-S 957, Loire atlantique, Nantes, France 

the bone tissue is a connective tissue composed of a 

mineral part, made of calcium phosphate in the form of 

hydroxyapatite crystals (HA : Ca (PO ) (OH) ), and of an organic 

10 4 6 2 

part containing an extracellular matrix and numerous specialized 

cells (osteoclasts, osteoblasts...). [1] These different components are 

balanced and every malfunction leads to the appearance of 

specific pathologies such as osteoporosis which is a disease 

characterized by an important bone resorption. 

Nowadays, different drugs are proposed to treat bone 

diseases such as zoledronic acid (or zoledronate) which is the 

most efficient anti-resorptive commercialized agent. Its high 

activity on bone is particularly due to the presence of a 

hydroxy-BisPhosphonic acid (hBP) function which strongly 

chelate hydroxyapatite crystals. 

This efficient binding property of HBPs to the surface of 

bone makes them potential tools to target bone and deliver various 

drugs to it. [2] Such a concept could be expressed by the design of 

“bifunctional molecules” where a HBP function is attached to a 

linker bearing a drug on the other end. In the laboratory, we have 

recently developed this concept to potentially treat rheumatoid 

arthritis with attachment of nSAid (non-Steroidal 

Anti-inflammatory drug) to the vectors. [3] 

This communication will outline different synthetic routes 

to a family of “bifunctional molecules” with the application of a 

novel procedure to access to complex HBPs starting from 

carboxylic acid precursors. [4] 

references: 

1. Green, J. The physicochemical structure of bone: cellular 

and noncellular elements.Miner Electrolyte Metab. 1994, 

20, 7–15. 

2. Uludag, H. Current Pharmaceutical Design, 2002, 8, 

99–110. 

3. Egorov, M.; Fortun, Y.; Heymann, D.; Lebreton, J.; 

Mathe, M.; Padrines, M.; Redini, F. PCT Int. Appl. 2009, 

WO 2009083614. 

4. Egorov, M.; Aoun, S.; Padrines, M.; Redini, F.; Heymann, 

D.; Lebreton, J.; Mathe-Allainmat, M. Eur. J. Org. Chem., 

2011, 35, 7148–7154. 

Keywords: biological activity; carboxylic acids; Drug design; 

phosphorus; inflammation; 


P - 0 2 7 8 

funCtionALiSed PoLyMerS By SurfACe 

ModifiCAtion uSinG diAryL CArBeneS 

A. APhAiwonG 1 , M. MoLoney 1 



The use of diaryl diazo compounds for the direct surface 

modification of polymers is a novel post-polymerisation method, 

which is suitable for adjustment of the surface characteristics of 

materials for particular applications, without changing their bulk 

properties. The project aims to establish an efficient method for 

the introduction of two classes of organic compounds, namely 

pyridine-type metal coordinators and spiropyran-type 

photochomophores, onto materials. 

The modified materials with pyridine moiety are developed 

for ligation with zinc complexes of bis(thiosemicarbazone), or 

Zn[ATSM]. Upon transmetallation of the Zn(II) complex with 

radioactive Cu(II), the polymers provide a solution of Cu[ATSM] 

as a biologically active and hypoxia selective copper-based 

marker for detection of hypoxia in tumours. The desired diazo 

compound with a remote pyridine moiety was synthesised and 

then used for surface modification of polystyrenes. The modified 

materials were reacted with zinc complexes to demonstrate the 

ability to coordinate with metals, ligand exchange with Cu(II) 

gave a solution of copper complexes. HPLC, EPR, and UV/Vis 

spectroscopy confirmed the existence of copper complexes in the 

eluent solution. 

Spiropyrans are a type of photochromic switch that can be 

interconverted reversibly between two states upon irradiation at 

different wavelengths as a result of photocyclisation. The desired 

photochromic and diazo molecules were independently 

synthesised, and then coupled prior to surface modification of 

polymers. An examination of the photochromic properties found 

that the photoinduced process could be demonstrated by 

irradiation with UV light, with a significant change in contact 

angles on modified PET sheet. 

These two modifications demonstrate the utility of this 

approach to introduce diverse macroscopic functions. 

Keywords: surface analysis; synthetic methods; polymers; 



s1001 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 7 9 

3-StyryLfLAvoneS SyntheSiS: heCK verSuS 

wittiG reACtionS 

d. h. A. roChA 1 , d. C. G. A. Pinto 1 , A. M. S. SiLvA 1 , 

J. A. S. CAvALeiro 1 


Styrylchromones constitute a small group of natural oxygen 

heterocyclic compounds. Only 2-styryl-derivatives have been 

found in nature and these derivatives are also known for their 

significant biological activities [1] . The interest in 3-styryl- 

-derivatives is growing in the last years and some synthetic 

methods have been developed [2] . The first report on the synthesis 

of one 3-styrylflavone consist of a Wittig reaction of a 

phosphorous ylide, obtained from 3-bromomethylflavone, with 

benzaldehyde [3] . Recently we reported the synthesis of 

3-styrylflavones using the Heck reaction of 3-bromoflavones with 

styrene derivatives [4] . Having in mind the importance of 

developing new synthetic approaches towards 3-styrylflavones 

we design a new efficient route to obtain 3-methylflavones and 

to use them in a Wittig reaction strategy to obtain 3-styrylflavones. 

In this communication we will present our results on the synthesis 

of 3-methylflavone derivatives and the reaction sequence of their 

transformation into 3-styrylflavones. We will also compare this 

synthetic route with the Heck reaction one in order to discuss the 

benefits of each one. 

Acknowledgements: Thanks are due to the University of Aveiro, 

FCT and FEDER for funding the Organic Chemistry Research 

Unit (project PEst-C/QUI/UI0062/2011), the Portuguese 

National NMR Network. One of us (DHA Rocha) also thanks 

FCT for their PhD grant (SFRH/BD/68991/2010). 

references: 

1. Gomes, A., Freitas, M., Fernandes, E., Lima, J. L. F. C., 

Mini-Rev. Med. Chem., 2010, 10, 1-7. 

2. Silva, A. M. S., Pinto, D. C. G. A., Cavaleiro, J. A. S., 

Lévai, A., Patonay, T., ARKIVOC, 2004, vii, 106-123. 

3. Goyal, S., Parthasarathy, M. R. Indian J. Chem., 1992, 

31B, 391-395. 

4. Rocha, D. H. A., Pinto, D. C. G. A., Silva, A. S. M., 

Patonay, T., Cavaleiro, J. A. S., Synlett, 2012, 559-564. 

Keywords: Wittig reaction; Heck reaction; Halogenation; NMR 

spectroscopy; Synthetic methods; 


P - 0 2 8 0 

SyntheSiS of PoLy-AzAheteroAroMAtiC 

LiGAndS AS foLdAMerS CentrAL LinKerS for 

An APPLiCAtion in SuPrAMoLeCuLAr 

CheMiStry 

C. AuBé 1 , M. PiPeLier 1 , i. huC 2 , e. LéoneL 3 , 

d. duBreuiL 1 

1 Laboratory CEISAM - UMR 6230, University of Nantes, 

Nantes, France 

2 IECB - UMR 5248, University of Bordeaux, Pessac, France 

3 ICMPE - UMR 7182, University of Paris-Est Creteil, Thiais, 

France 

Polydentate nitrogen ligands represent attractive targets in 

chemistry/biology/physicochemistry. For many years, Profs. D. 

Dubreuil and E. Léonel’s groups were interested in pyridazinic 

and pyrrolic compounds particularly for their synthetic 

methodology and their various applications. [1] Indeed, molecules 

featuring these heterocycles are present in therapeutic chemistry 

as anticancer agents (Prodigiosine or metallic complex of 

cisplatine) and also in supramolecular chemistry as central linkers 

for the synthesis of foldamers as biological receptor mimics. [2] 

Our collaborative works with Dr. I. Huc in the field of synthesis 

and characterization of supramolecular structures led us to 

elaborate oligoamidic-type foldamers including an 

azaheteroaromatic ligand as central linker. We have demonstrated 

their ability to encapsulate diastereoselectively small molecules 

such as tartaric acid. [3] 

Focusing the elaboration of the central linkers, we turned 

our attention to (poly)-pyridazinic and (poly)-pyrrolic structures. 

Their preparations are based on various methodologies of 

C-C bond formation, including electrochemical and chemical 

cross-coupling processes. 

In this communication, the synthetic approach of central 

linkers will be presented following organometallic chemistry for 

cross-coupling reactions. Results obtained in supramolecular 

chemistry will also be discussed. 

references: 

1. a) Tabatchnik, A.; Aubé, C.; Bakkali, H.; Thia Manh, G.; 

Blot, V.; Thobie, C.; Ferrand, Y.; Huc, I.; Lebreton, J.; 

Pipelier, M.; Dubreuil, D. Chem. Eur. J. 2010, 16, 

11876. 

b) Bakkali, H.; Marie, C.; Ly, A.; Thobie, C.; Graton, J.; 

Pipelier, M.; Sengmany, S.; Léonel, E.; Nédélec, J.-Y.; 

Evain, M.; Dubreuil, D. Eur. J. Org. Chem. 2008, 12, 

2156. 

c) Sengmany, S.; Léonel, E.; Polissaint, F.; Nédélec, J.-Y.; 

Pipelier, M.; Thobie, C.; Dubreuil, D. J. Org. Chem. 

2007, 72, 5631. 

2. Garric, J.; Léger, J.-M.; Huc, I. Chem. Eur. J. 2007, 13, 

8454. 

3. Ferrand, Y.; Kendhale, A. M.; Kauffmann, B.; Grélard, A.; 

Marie, C.; Blot, V.; Pipelier, M.; Dubreuil, D.; Huc, I. 

J. Am. Chem. Soc. 2010, 132, 7858. 

Keywords: Nitrogen heterocycles; C-C coupling; 

Electrochemistry; Helical structures; Supramolecular chemistry; 



s1002 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 8 1 

PALLAdiuM-CAtALyzed 

heteroCyCLizAtion/reduCtive CouPLinG 

CASCAdeS of 2-ALKynyLBenzAMide-tyPe 

SuBStrAteS And MethyL vinyL Ketone 

J. AurreCoeCheA 1 , y. MAdiCh 1 , r. ALvArez 2 

1 Universidad del País Vasco., Química Orgánica II, 


2 Universidade de Vigo, Química Orgánica, Vigo, Spain 

Nucleophile-tethered unsaturated derivatives participate in 

Pd(II)-catalyzed heterocyclization/reductive coupling reactions 

with α,β-unsaturated aldehydes and ketones leading to 

heterocyclic derivatives where the carbonyl compound carbon 

framework is incorporated as an exocyclic 3-oxopropyl unit. [1] In 

these reactions, Pd(II) serves a dual role as cyclization and 

coupling promoter to eventually generate a C-palladium enolate, 

which is finally protonated. Normally, useful reactivity has 

required the use of excess amounts of halide salts as additives 

and/or acidic solvents to effectively steer the behavior of 

the palladium enolate towards protonation rather than 

β-H elimination, a competing process leading to the alternative 

Heck products. 

We now report the application of this strategy to the use 

of 2-alkynylbenzamides as novel nucleophilic partners in 

Pd-catalyzed heterocyclization/reductive coupling cascades with 

methyl vinyl ketone. In contrast to related applications, these 

reactions do not require the use of protic solvents or excess halide 

additives, and proceed effectively under Pd(II) catalysis in the 

presence of just substoichiometric amounts of added KI or 

alternatively with the use of PdI as catalyst without any other 

2 

additive. In this manner, products resulting from 

6-endo-cyclizations followed by reductive coupling are obtained 

in 76–97% yields without significant interference from Heck or 

alternative regiochemical pathways. 

High structural diversity is attained in the final products 

emanating from the choice of alkyl or aryl substituents in the 

alkyne and nitrogen moieties of the starting 2-alkynylbenzamide, 

as well as from the possibility of additional structural variations 

introduced at the benzamide-type aryl ring, including various 

heterocyclic motifs. 

references: 

1. Representative examples: 

a) Shen, Z. M.; Lu, X. Y. Tetrahedron 2006, 62, 

10896–10899. 

b) Trost, B. M.; Lumb, J.-P.; Azzarelli, J. M. J. Am. Chem. 

Soc. 2011, 133, 740–743. 

c) Trost, B. M.; Taft, B. R.; Masters, J. T.; Lumb, J.-P. 

J. Am. Chem. Soc. 2011, 133, 8502–8505. 

Keywords: Palladium; C-C coupling; Cyclization; 

Heterocycles; 


P - 0 2 8 2 

SyntheSiS of PriviLeGed SCAffoLdS: 

MiMiCKinG 1,5-BenzodiAzePine-2,4-dioneS viA A 

ModuLAr APProACh on SoLid-PhASe 

f. BACKAert 1 , h. SnAuwAert 1 , J. CAroen 1 , 

J. vAn der eyCKen 1 


Recent developments in modern drug discovery are based 

on the application of “privileged structures” defined by Evans et 

al. as structures capable of displaying activity towards 

different receptors [1] . Benzopyrans, diketopiperazines and 

1,5-benzodiazepin-2,4-diones are well-known and widely 

investigated scaffolds, e.g. the latter showing anxiolytic and 

antiarrhythmic effects. Now, we propose a new potential 

“privileged structure” containing a 1,5-disubstituted triazole 

moiety mimicking the cis-amide bond within the 

1,5-benzodiazepin-2,4-dione motif. [2] 

Molecules based on this [1,2,3]-triazolo[1,5-d]benzo-1,4- 

-diazepin-2-one scaffold are synthesized and decorated via 

a modular approach on Wang resin using α-amino acids, 

2-ethynylaniline or 2-amino-3-ethynylpyridine building blocks 

and N-alkylating agents resulting in five points of diversity. The 

methodology involves the attachment of α-amino acids onto a 

solid support, subsequent removal of the Fmoc group followed 

by an optimized diazotransfer reaction of the resulting amine 

yielding a resin-bound azide. Conversion of the latter into a 

1,5-disubstituted 1,2,3-triazole moiety is achieved quantitatively 

by addition of a range of 2-ethynylaniline or 2-amino-3- 

-ethynylpyridine building blocks using a Ru(II)-catalyst. 

The desired scaffold can be obtained in high crude purities 

(> 95%) in solution via an acid catalyzed one-step cyclisationrelease 

strategy. Solution-phase N-alkylation finally affords the 

fully diversified scaffold. In this fashion, several libraries of 

this [1,2,3]-triazolo[1,5-d]benzo-1,4-diazepin-2-one scaffold 

(62 compounds) have been synthesized in moderate yields by 

successfully varying all diversity points. 

Interestingly, fully diversified compounds exhibit 

atropoisomeric effects. This fast-slow exchange between two or 

more conformers can be studied via 1H NMR spectroscopy and 

therefore more information about the thermodynamics of this 

scaffold can be revealed. 

Taking into account future screening results of the 

synthesized libraries, a well-thought decoration of this scaffold 

leading to discovery of new lead molecules is within reach. 

references: 

1. Evans, B. E.; Rittle, K. E. et al. J. Med Chem. 1988, 31, 

2235–2246. 

2. Tron, G.C.; Pirali, T. et al. Med. Res. Rev. 2008, 28, 

278–308. 

Keywords: Solid-phase synthesis; Atropisomerism; 

Combinatorial chemistry; Click chemistry; Azides; 



s1003 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 8 3 

inveStiGAtion of Photo-induCed 

trAnSforMAtionS inSide Soft GeL MAteriALS: 

CoMPAriSon with hoMoGeneouS And 

MiCeLLAr SoLutionS 

J. BAChL 1 , A. hohenLeutner 1 , B. dhAr 2 , 

C. CAtivieLA 3 , u. MAitrA 4 , B. KÖniG 5 , B. KÖniG 5 , 

d. diAz diAz 3 



2 National Chemical Laboratory, CReST. Chemical Engineering 

Division, Pune, India 

3 Instituto de Sintesis Quimica y Catalisis Homogenea (ISQCH), 

CSIC-Universidad de Zaragoza, Zaragoza, Spain 

4 Indian Institute of Science, Department of Organic Chemistry, 

Bangalore, India 



Supramolecular gels have recently been rediscovered as a 

new field in supramolecular chemistry and soft matter because 

they represent a powerful tool to the development of new 

materials and devices of nanoscale dimensions with tailored 

functionalities such as high mechanical strength or interesting 

optical and electronic properties. In general such materials should 

also be suitable for catalyzing chemical reactions by containing 

either embedded or covalently bound catalytic moieties. 

Diffusion-controlled processes within the constrained 

environment of the dynamic gel medium have gained a lot of 

interest in scientific research because of their impact on the 

potential catalytic activity and the control of product selectivities 

of gel materials. The two key features of gel materials are 

represented by a) the two-phase nature, which allows an easy 

separation of the catalyst and products and b) a much higher 

accessibility of small reagents to the highly solvated 

three-dimensional network in comparison to most of the 

standard heterogeneous catalysts. 

In order to investigate the potential application of gels as 

reaction vessels in catalysis the well studied photo-oxidation of 

benzylalcohols by flavin derivatives and blue visible light has 

been chosen as model reaction. 

Flavins, which are versatile electron carriers in biological 

processes have recently gained much attention in chemical 

catalysis as upon irradiation the redox potential of the flavins 

increases significantly. Various both biopolymer and 

low-molecular weight based gel-materials have been applied for 

the studies. 

Structure-property relationships of the different confined 

environments and their effect on product selectivities and reaction 

process have been developed by for example oscillatory rheology, 

electron microscopy, FTIR and UV-spectroscopy, thermal 

transition temperature and oxygen permeability determinations. 

It could be shown that several of these materials can efficiently 

assist the production of desired oxidation products in moderate to 

excellent yields without byproduct-formation. 

Keywords: Photochemistry; Supramolecular Chemistry; Gels; 


P - 0 2 8 4 

AnthrAquinone AS A redox LABeL for dnA. 

SyntheSiS, enzyMAtiC inCorPorAtion And 

eLeCtroCheMiStry of AnthrAquinone- 

-Modified nuCLeoSideS, nuCLeotideS And dnA 

J. BALintovA 1 , L. hAvrAn 2 , M. foJtA 2 , M. hoCeK 3 


of Organic and Nuclear Chemistry, Prague, Czech Republic 

2 Institute of Biophysics, Academy of Sciences of the Czech 

Republic, Brno, Czech Republic 

3 Institute of Organic Chemistry and Biochemistry, Academy of 

Sciences of the Czech Republic, Prague, Czech Republic 

Electrochemical detection is a less expensive but 

comparatively sensitive alternative to common optical methods. 

Particularly efficient is the single-step synthesis of modified 

dNTPs by cross-coupling reactions followed by polymerase 

incorporation. We have used this novel approach for the synthesis 

of DNA bearing a number of redox labels [1] , which were 

successfully used for “multicolor” redox labelling of DNA. 

Anthraquinones are attractive redox labels suitable for labelling 

of biomolecules. [2] Our goal was to prepare modified dNTPs 

bearing anthraquinones attached through an acetylene or 

propargylcarbamoyl linker to the 5-position of pyrimidine (C) or 

to the 7-position of 7-deazaadenine and their polymerase 

incorporation to DNA. Polymerase incorporations of the 

AQ-labelled dNTPs into DNA by primer extension with KOD XL 

polymerase have been successfully developed. The 

electrochemical properties of the AQ-labeled nucleosides, 

nucleotides, and DNA were studied by cyclic and square-wave 

voltammetry. [3] 

Acknowledgement: This work is part of the research project Z4 

055 0506, the Ministry of Education (LC512,1M0508), Grant 

Agency of the Academy of Sciences of the Czech Republic 

(IAA400040901), Czech Science Foundation (203/09/0317) and 

by Gilead Sciences, Inc. (Foster City, CA, U. S. A.). 

references: 

1. a) Capek, P.; Cahová, H.; Pohl, R.; Hocek, M.; Gloeckner, C.; 

Marx, A.; Chem. Eur. J. 2007, 13, 6196–6203; 

b) Cahová, H.; Havran, L.; Brázdilová, P.; Pivonková, H.; 

Pohl, R.; Fojta, M.; Hocek, M.; Angew. Chem. Int. Ed. 

2008, 47, 2059–2062. 

2. a) Jacobsen, M. F.; Ferapontova, E. E.; Gothelf, K. V.; 

Org. Biomol. Chem. 2009, 7, 905-908; 

b) Abou-Elkhair, R. A. I.; Dixon, D. W., Netzel, T.L.; 

J. Org. Chem. 2009, 74, 4712-4719. 

3. J. Balintová, R. Pohl, P. Horáková, P. Vidláková, L. 

Havran, M. Fojta, M. Hocek, Chem. Eur. J. 2011, 17, 

14063-14073. 

Keywords: nucleosides; oligonucleotides; electrochemistry; 



s1004 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 8 5 

reSoLution of tert-ButyL-3-hydroxy-4- 

-PhenyLPyrroLidine-1-CArBoxyLAte 

d. BALoGh 1 , e. KovACS 1 , f. fAiGL 1 



Hungary 

In kinetic resolution two enantiomers react with different 

rates in a chemical reaction. If there is a large difference between 

the two reaction rate constants, practically only one of the isomers 

takes part in the reaction, the other one stays unreacted. Kinetic 

resolution can be carried out in the presence of chiral catalysts. 

Enzymes, such as hydrolases are highly suitable for this purpose. [1] 

Our goal was to prepare a racemic pyrrolidine derivative and 

work out its enzymatic resolution. It can be an intermediate of the 

synthesis of chiral ligands and could be useful for the 

pharmaceutical industry. Many compounds with the similar 

structure were proved to have biological effects such as 

iminosugars, which are potential inhibitors of glucosidase 

enzymes [2] or kainic acid derivatives that have a potent central 

nervous system stimulant activity [3] . 

In the course of our research, we synthesized trans 

tert-butyl-3-hydroxy-4-phenylpyrrolidine-1-carboxylate from 

tert-butyl 6-oxa-3-azabicyclo[3.1.0]hexane-3-carboxylate in a 

Grignard-reaction. Kinetic resolution of the racemic secondary 

alcohol was investigated using enzyme catalysed acylation. Series 

of experiments were accomplished in order to find the most 

efficient enzyme, solvent and temperature, thus we could prepare 

the optically active (3R,4S)-alcohol isomer with high enantiomeric 

purity. 

The optically active ester was separated from the 

(3R,4S)-alcohol by flash chromatography. Alcoholysis of the ester 

was performed in different alcohols catalysed by Novozym 435 

enzyme, which proved to be the most efficient in the previous 

experiments. With this method also the (3S,4R)-isomer of the 

alcohol can be prepared in high enantiomeric excess. 

references: 

1. Yamada H., Shimizu S., in: Biocatalysts in Organic 

Synthesis, Tramper, H. C., Plas. P., Linko P. (Eds.), 

Amsterdam: Elsevier, 1985; pp 19-37 

2. U.S. 3691198 patent (1972) 

3. P. Gill, W.D. Lubell: J. Org. Chem., 60, 2658 (1996) 

Keywords: Enzymes; Kinetic resolution; Acylation; 

Enantioselectivity; Heterocycles; 


P - 0 2 8 6 

GrowinG PoLy(diSuLfide) CeLL-PenetrAtinG 

PePtideS on thioLAted CArGo 

e. K. BAnG 1 , S. MAtiLe 1 



The activities of dynamic polyion-counterion complexes in 

lipid bilayer membranes have been studied for their scientific 

utilities as transmembrane transporters / carriers, voltage gates, 

and sensors. Our dynamic amphiphiles, having dynamic bonds 

between their charged head and their hydrophobic tails, can 

activate biomolecules (DNAs, siRNAs, CPPs) as counterion 

transporters. [1] We currently are expanding this concept to 

poly(disulfide)s, dynamic polymers with disulfide repeats in their 

main chain, to deliver biomolecules through the cellular 

membrane. [2] The disulfide bond is a dynamic covalent bond, 

which can be easily cleaved and reformed, but stronger than the 

non-covalent interactions present in supramolecular polymers. 

Moreover, it is degradable via reductive depolymerization by 

glutathione in cells. The general objective of this project is to let 

poly(disulfide) CPPs grow directly on thiolated initiators of free 

choice (siRNA, drugs, probes) before their cellular uptake, and 

have them removed afterwards in the cytosol. Here, we report the 

synthesis of guanidinium-containing disulfide propagators and 

their polymerization by thiol-initiated ring-opening disulfide 

exchange. [3] The polymerization and depolymerization processes 

were monitored by measuring transport activity in fluorogenic 

vesicles, and by size exclusion chromatography, light scattering 

and mass spectrometry, including fluorescent initiators and 

terminators for FRET-analysis. We hope that the resulting method 

will provide general access to non-toxic delivery in native form. 

references: 

1. a) T. Takeuchi, J. Montenegro, A. Hennig, S. Matile, 

Chem. Sci. 2011, 2, 303-307; 

b) J. Montenegro, E.-K. Bang, N. Sakai, S. Matile, 

Chem. Eur. J., in press (EuCheMS Issue). 

2. a) J. Montenegro, C. Gehin, E.-K. Bang, A. Fin, 

D. Alonso Doval, H. Riezman, S. Matile, Chimia 2011, 

65, 853-858; 

b) E.-K. Bang, M. Lista, G. Sforazzini, N. Sakai, S. Matile, 

Chem. Sci., 2012, DOI:10.1039/C2SC20098H. 

3. N. Sakai, M. Lista, O. Kel, S. Sakurai, D. Emery, J. Mareda, 

E. Vauthey, S. Matile, J. Am. Chem. Soc. 2011, 133, 

15224-15227. 

Keywords: Peptides; Polymers; Ring-opening polymerization; 



s1005 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 8 7 

“MetAL-free” SyntheSiS of funCtionALized 

PoLyLACtide By CAtioniC ACtivAted 

MonoMer PoLyMerizAtion 

M. BASKo 1 , M. BednAreK 1 , P. KuBiSA 1 

1 Centre Polish Academy of Sci, Department of Polymer 

Chemistry, Lodz, Poland 

Poly(lactide) (PLA) is the major bio-based polymer which 

can be produced from renewable resources. Due to biodegrability 

and biocompatibility PLA is the candidate of choice for polymeric 

commodities as well as for application in the medical field. [1] 

However a lack of functional group along the polymer 

backbone considerably limits the possibilities for further chemical 

modification of polymer chains. To overcome this limitation 

several approaches has been examined including modification of 

lactide monomer, copolymerization with suitable comonomer or 

blending. [2] 

Our goal was to develop convenient synthetic procedures 

for the synthesis of functionalized PLA using “metal-free” 

catalysts and initiators. Polymers of lactide containing at one or 

both ends reactive groups that may be used as precursors of 

segments in block copolymers or side-chains in graft copolymers 

can be obtained by cationic activated monomer polymerization. [3] 

Using functionalized alcohols as initiators we obtained PLA 

macromonomers carrying unsaturated – (meth)acrylate and 

propargyl groups at one chain end. One-pot synthesis based on 

easy available acid and alcohols prevents the possible 

contamination of the final products with metallic initiators or 

catalyst residues. 

The reactivity of functional groups (containing double or 

triple bonds) was confirmed by radical (co)polymerization of 

macromonomers or by performing azide-alkyne “click” reaction 

with model azide. [4] 

PLA containing pendant reactive groups was obtained in 

cationic copolymerization of lactide with epichlorohydrin. The 

postpolymerization modification based on these functional 

polymers may provide entry to expand the application of PLA. 

Acknowledgement: Financial support by the project POIG. 

01.01.02-10-123/09-01, acronym BIOMASA is gratefully 

acknowledged 

references: 

1. A. C. Albertsson, J. Polym. Sci. Part A: Polym. Chem. 48, 

1214, 2010 

2. M. Weck et al. Biomacromolecules 7, 1735, 2006 

3. P. Kubisa, S. Penczek, Prog. Polym. Sci. 24, 1409, 1999 

4. M. Basko, M. Bednarek, Reactive and Functional Polymers. 

72, 213, 2012 

Keywords: polymerization; 


P - 0 2 8 8 

SyntheSiS of trAditionAL MediCinAL funGAL 

MetABoLiteS. 

A. BeeKMAn 1 , r. BArrow 1 

1 Australian National University, Research School of Chemistry, 

Canberra ACT, Australia 

In 2009 Proksch et al. isolated a number of biologically 

active fungal metabolites from a Pestalotiopsis sp. of fungi, 

discovered in the medicinal plant Rhizopora mucronata, a 

mangrove found in southern China. [1] The biologically active 

compounds isolated from the endophytic fungi, may prove to be 

drug leads which have a history of internal use (non-toxic) and 

demonstrated activity. Two classes of compounds isolated by 

Proksch were of particular interest. The pestalotiopsones are a 

collection of chromone derivatives featuring an alkyl group at 

C-2 and a carboxyl group at C-5. 1a Compounds with this 

substitution pattern are part of a rare subtype of chromones found 

in nature, with only three previously recorded members. [2] 

The cytosporones are a group of 3-isochromanones, which are 

relatively scarce in the natural products literature, possessing an 

alkyl group at C-2 and varying oxygenation of the aromatic ring. 1b 

The specific rotations of the natural products containing 

chirality were measured, although the absolute stereochemistry 

of the compounds was not determined. Synthesis of these 

compounds is yet to be reported in the literature. This presentation 

will describe the work leading to the first syntheses of these 

natural products, and the determination of the absolute 

stereochemistry of the natural compounds. 

references: 

1. a) Proksch, P., et al., J. Nat. Prod. 2009, 72, 662-665. 

b) Proksch, P., et al., Bioorg. Med. Chem. 2009, 17, 

7362–7367. 

2. Kashiwada, Y., et al., Chem. Pharm. Bull. 1984, 32, 

3493–3500; 

Graziani, E. I., et al., J. Nat. Prod. 2005, 68, 1262-1265; 

Kalaitzis, J. A.; Moore, B. S., J. Nat. Prod. 2004, 67, 

1419–1422. 

Keywords: Total synthesis; Natural products; Drug discovery; 

Heterocycles; Microwave chemistry; 



s1006 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 8 9 

ChoLeSteroL-Boron CLuSter ConJuGAteS: 

SyntheSiS viA dioxAne rinG oPeninG of the 

oxoniuM derivAtive of the Boron CLuSter 

And PreLiMinAry PhySiCoCheMiCAL And 

BioLoGiCAL evALuAtion 

M. BiALeK-PietrAS 1 , A.B. oLeJniCzAK 1 , 

S. tAChiKAwA 2 , h. nAKAMurA 2 , z. J. LeSniKowSKi 1 

1 Institute of Medical Biology PAS, Laboratory of Molecular 

Virology and Biological Chemistry, Lodz, Poland 

2 Gakushuin University, Department of Chemistry, Tokyo, Japan 

Due to bioorthogonality, lipophilicity or amphiphilicity, rigid, 

spherical or ellipsoidal shape, chemical stability and resistance to 

catabolism, carboranes and metallacarboranes are often used in 

modification of biologically active compounds. The literature 

comprises numerous examples in which boron clusters are applied 

as surrogates for heterocycles, annulated carbon rings, or most 

popularly for substituted or unsubstituted phenyl rings. [1, 2] Among 

many low molecular weight compounds modified with boron 

clusters are amino acids, lipids, carbohydrates, porphyrins, nucleic 

acid bases and nucleosides, andDNA groove binders; boron cluster 

modified biopolymers include peptides and proteins, nucleic acids 

(DNA-oligonucleotides) and oligophosphates. Carboranes have 

been used also in preparation of analogues of biologically active 

steroids such as estradiol, estrogen receptor modulators or 

testosterone. [3] 

In this communication a general approach to the synthesis 

of novel type of cholesterol-boron cluster conjugates bearing 

metallacarborane moiety is described. The method is based on the 

dioxane ring opening in the oxonium derivative of the boron 

cluster.Possibility of incorporation of the selected conjugates into 

lipid bilayers and physicochemical and biological characterization 

of the obtained metallacarborane-incrusted liposomes was also 

approached. 

Acknowledgment: Research co-financed by the European 

Regional Development Fund under the Operational Programme 

Innovative Economy, grant POIG.01.01.02-10-107/09, to MBP, 

ABO and ZJL. 

references: 

1. Z.J. Lesnikowski, in “Boron Science: New Technologies 

and Applications”; 2011; H.S. Narayan Ed., CRC Press, 

Boca Raton FL, pp. 3–19 

2. Z.J. Lesnikowski et al. J. Organomet. Chem.; 1999; 581; 

156–169 

3. R.N. Grimes; Carboranes, 2011; sec. ed.; Elsevier; 

1053–1082 

Keywords: carboranes; steroids; liposomes; 


P - 0 2 9 0 

n-oxide derivAtiveS of ChoLeSteroL And 

LAnoSteroL 

u. BiLdziuKeviCh 1, 2 1, 2 

, z. wiMMer 


Chemistry of Natural Compounds, Prague 6, Czech Republic 

2 Institute of Experimental Botany AS CR v.v.i., Isotope 

Laboratory, Prague 4, Czech Republic 

Pathogenic microbes and fungi represent a significant 

hazard to multicellular organisms, including humans. In nature, 

there are substances capable of selectively inhibit the growth of 

microbes and fungi. Some of these substances contain a peroxide 

group. We assumed that substances bearing the N-oxide group 

also will have the desired properties. Our goal was to prepare 

derivatives of phytosterols containing N-oxide group for 

subsequent tests of the biological activity. 

Lanosterol and cholesterol were selected as representatives 

of sterols. For each steroid a series of derivatives was obtained. 

We obtained four series of derivatives. Each series consisted of 

derivatives containing the N-oxide fragment and derivatives 

without theN-oxide fragment. As a basis containing the 

N-oxide fragment were selected picolylamine derivatives and 

2-(4-aminomethylphenyl)pyridine-N-oxide. They were obtained 

in three synthetic stages. Synthesis consisted in protection of the 

amino group by obtaining FMOC derivative, oxidation by peracetic 

acid for obtaining N-oxide and removing protection group. From 

the initial steroids hemiesters of succinic acid were obtained. 

Modified amines bearing N-oxide group were coupled with the 

sterol hemiesters by amide bond. For comparing biological 

activity, we obtained derivatives of phytosterol hemiesters 

with picolylamines and 2-(4-aminomethylphenyl)pyridine. 

The resulting derivatives were tested for cytotoxicity on the 

cells of human T-lymphoblastic leukemia, breast adenocarcinoma, 

cervical cancer, and also on normal human fibroblasts. 

Acknowledgment: A financial support from specific university 

research (MSMT No. 21/2012), project P503/11/0616 (GACR) 

and the research program MSM6046137305 (MSMT) is 


Keywords: steroids; amines; amides; cytotoxicity; 



s1007 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 9 1 

AdheSion ProPertieS of PoLyurethAneS 

PrePAred froM CiS-1, 4-PoLyiSoPrene 

S. BiStAC 1 , e. AnAnJAroenvonG 2 , 

i. CAMPiStron 2 , J.f. PiLArd 2 

1 Université de Haute Alsace, LPIM, Mulhouse cedex, France 

2 UCO2M, Université du Maine, Le Mans, France 

Hydroxyl compounds currently used in the production of 

polyurethanes (PU) are petrochemical products (polyester and 

polyether polyols). However, they have some disadvantages as 

they are non-renewable resources, they may cause environmental 

pollution, and they tend to be exhausted in the near future. Natural 

rubber (NR), mainly composed of polyisoprene, is an interesting 

choice to use as a starting material in PU synthesis, due to the fact 

that they are renewable source, abundant polymer and they have 

good mechanical properties and are easy to chemically modify. 

Polyisoprene was modified to lead oligomers with reactive 

terminated groups. The objective of these chemical modifications 

of polyisoprene is to prepare new polyurethane adhesives using 

environmentally friendly sources such as NR latex. 

The first step of the adhesives preparation is the synthesis 

of hydroxytelechelic cis-1,4-polyisoprene of various molecular 

weight. The second step is then the preparation of epoxidized 

hydroxytelechelic cis-1,4-polyisoprene with different epoxidation 

levels. Polyurethane adhesives were finally obtained by reaction 

of hydroxytelechelic oligomers with toluene diisocyanate. 

Steel/polyurethane/steel assemblies were obtained after 

curing of adhesive at 60 °C. A wedge test was used to quantify 

adherence level of assemblies. A wedge is introduced in the 

assembly, in air at 20 °C, is then stopped and the crack length is 

followed until equilibrium. The final crack length was measured 

for different polyurethanes, prepared from hydroxytelechelic 

cis-1,4-polyisoprene of various molecular weight and epoxidation 

degree. Microscopy analysis was used to precisely localize the 

locus of failure. Surface properties of polyurethane films were 

also investigated by FTIR spectroscopy (ATR mode) and 

wettability. 

Wedge test results show that some polyurethanes exhibit 

high adherence level. Adhesive behaviour is discussed as a 

function of isoprene molecular weight and epoxidation degree. 

Keywords: Polymers; Interfaces; Natural products; 


P - 0 2 9 2 

froM ProPArGyLiC AMideS to 

funCtionALized oxAzoLeS: doMino GoLd 

CAtALySiS/oxidAtion By MoLeCuLAr oxyGen 

M. C. BLAnCo JAiMeS 1 , A. S. K. hAShMi 1 , 

f. roMinGer 1 

1 University of Heidelberg, Organic Chemistry Institut, 


The oxazole nucleus is present in different natural and nonnatural 

compounds possessing biological and pharmaceutical 

properties. Recently, we have reported the gold-catalyzed 

cycloisomerization of propargylic amides to alkylideneoxazolines 

and oxazines. [1] While studying this reaction, it was observed that 

a different product could be isolated when the reaction mixture 

was exposed to air. The unexpected product was formed as a result 

of a spontaneous oxidation mediated by the oxygen present in the 

air. Such an oxidation is only reported in presence of metals or 

radical initiators and none of them have been used for the 

synthesis of oxazoles. 

In order to investigate the autoxidation process, different 

solvents, substrate concentrations and temperatures were tested. 

It was established that with 0.5 M of the substrate in 

tetrahydrofuran (THF) at 50°C a faster conversion and higher 

yields were achieved. Although experiments in absence of oxygen 

indicated that molecular oxygen is the main oxidizing agent that 

promotes the conversion, the presence of THF peroxide 

accelerates the formation of the hydroperoxide. To have a better 

idea of the possible pathway, some additional experiments were 

conducted. The oxidation does not take place in presence of the 

well know butylated hydroxytoluene, and it is accelerated by the 

radical initiator azobisisobutyronitrile.From these results it is 

possible to deduce that the oxidation of methyleneoxazolines 

follows a radical pathway, probably triggered by the combination 

of high temperature and light and promoted by the presence of 

oxygen and THF peroxides. The study of the reaction scope 

proved that the reaction performs with good yields by a wide 

range of substrates with different electron withdrawing and 

electron donating groups in the benzene ring, offering a novel 

access to functionalized 2,5-disubtituted oxazoles with full atom 

economy. 

references: 

1. A.S.K. Hashmi, A. Schuster, M. Schmuck, F. Rominger, 

Eur. J. Org. Chem., 2011, 24, 4595-4602. 

Keywords: Autoxidation; Gold; Oxygen; Peroxides; 

Cyclization; 



s1008 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 9 3 

SeLf-ASSeMBLed trAnSition MetAL 

CoordinAtion PoLyhedrA 

P. BonAKdArzAdeh 1 , K. riSSAnen 1 

1 University of Jyväskylä, Department of Chemistry Nanoscience 

Center, Jyväskylä, Finland 

Pyridine based organic ligands have been widely used with 

transition metals in self-assembly. With this approach different 

kinds of structures have been reported such as spheres, cubes and 

tetrahedra. 1-3 In this study different kinds of pyridine ligands were 

prepared. These ligands have usually two pyridine binding sites 

with a ligand bend angle varying from 120° to 180°. Depending 

on the coordination geometry of the transition metals, the bend 

angle of the ligand and an appropriate stoichiometric ratio of the 

components can lead self-assembly into specific and discrete 

three-dimensional assemblies. The ligands have to have a certain 

amount of rigidity. Too rigid or too flexible ligands may not form 

discrete structures. Therefore, for achieving a certain defined 

supramolecular structure the ligand design and the transition metal 

ion have to be chosen carefully. Preliminary results on the studies 

of the prepared ligands and their Pd2+ and Fe2+ ion based 

assemblies will be presented. 

references: 

1. J. Bunzen, J. Iwasa, P. Bonakdarzadeh, E. Numase, 

K. Rissanen, S. Sato and M. Fujita, Angew. Chem. Int. Ed., 

2012, 51, 3161. 

2. M. Yoshizawa, J. K. Klosterman and M. Fujita, Angew. 

Chem. Int. Ed., 2009, 48, 3418. 

3. R. Chakrabarty, P. S. Mukherjee and P. J. Stang, Chem. 

Rev., 2011, 111, 6810. 

Keywords: Self-assembly; Supramolecular chemistry; N 

ligands; Ligand design; 


P - 0 2 9 4 

eSterifiCAtion under MiCrowAve ConditionS 

in orGAnoPhoSPhoruS CheMiStry 

e. BottGer 1 , n. z. KiSS 1 , G. KeGLeviCh 1 

1 Budapest University of Technology and Economics, Organic 

Chemistry and Technology, Budapest, Hungary 

It is known that phosphinic acids cannot be esterified under 

traditional conditions. Phosphinic esters are usually synthesized 

by the reaction of the corresponding P-acid chlorides with 

alcohols and phenols. This method is not environmentally friendly 

because of the hydrocloric acid liberated. Despite of this it is 

widely used in the industry. Recent experiments showed that 

direct esterification of phosphinic acids with primary alcohols 

under microwave (MW) conditions may be a possible 

environmentally friendly solution. The fact that the beneficial 

effects of the MW irradiation causes the novel reaction was 

proved by comparative thermal experiments. 

Our research group has already studied the esterification of 

phosphinic acids to phosphinates under MW conditions. The 

direct esterifications using short chain alcohols in 15 times excess 

were optimized. Applying a reaction temperature of 160–200 °C, 

the preparative yields were around 45–60%. 

Our aim was to study the esterification with branched chain 

and less volatile (longer carbon chain) alcohols in order to 

investigate the direct esterification in detail and to synthesize new 

phosphinates. The new products were characterized by 31P NMR, 

13 1 C NMR and H NMR, as well as HRMS spectrometry. 

Our model compounds were the cyclic 

hydroxyphospholene- and phospholane oxides, and an acyclic 

compound, the 1-H-phenyl phosphinic acid. 

The novel reaction is promoted by the beneficial MW effect 

that was proved by comparative thermal experiments. 

Keywords: Phosphorus; Microwave chemistry; Environmental 

chemistry; Green chemistry; 



s1009 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 9 5 

A SiMPLe new Method of the SyntheSiS of 

MethyL 1,4,5-triSuBStituted-1h-PyrAzoLe-3- 

-CArBoxyLAteS 

B. Broz 1 , P. SiMuneK 1 

1 University of Pardubice, Faculty of Chemical Technology - 

Institute of Organic Chemistry and Technology, Pardubice, 


A new method for the synthesis of methyl 1,4,5- 

-trisubstitued-1H-pyrazole-3-carboxylates which doesn’t involve 

using of hydrazines has been studied. This method can be carried 

out very simply and under mild conditions. Regarding the 

complex topic of the synthesis of persubstituted 1H-pyrazoles and 

the importance of pyrazole derivatives as pharmacophores and 

pesticides, this procedure could be a useful expansion of existing 

synthetic methods for the preparation of these substances. 

Several derivatives have been prepared by means of t 

he basic-catalyzed reaction of “push-pull”-polarized 

β-enaminoesters with benzenediazonium-tetrafluoroborates. The 

reaction mechanism has not been completely described yet, but it 

probably comprises a double azo-coupling with a subsequent 

intramolecular cyclization followed by releasing of nitrogen and 

the corresponding arene. The crucial effect of the basic catalyst 

has been determined: the reaction does not proceed without its 

presence and the right choice of the catalyst can affect the 

regioselectivity of the reaction. 

This work follows the recent studies on the synthesis of 

3-acyl-4-amino-1-aryl-1H-pyrazoles [1–3] . The structures of the 

prepared products have been verified by means of GC/MS and 

NMR spectroscopy, some of them also by X-ray diffraction. 

The reaction conditions and procedures will be further discussed. 

Acknowledgement: The work was supported by Ministry of 

Education, Youth and Sports (MSM 002 162 7501). 

references: 

1. Simunek P., Svobodova M., Bertolasi V., Machacek V.: 

Synthesis, 2008, 11, 1761. 

2. Simunek P., Svobodova M., Machacek V.: 

J. Heterocycl. Chem., 2009, 46, 650. 

3. Simunek P., Machacek V., Svobodova M., Ruzicka A.: 

J. Heterocycl. Chem., 2011, 48, 780. 

Keywords: Heterocycles; Diazo compounds; Synthetic 

methods; 


P - 0 2 9 6 

towArdS the SyntheSiS of SPeCifiCALLy 

13-C-rinG LABeLLed PhenyLALAnine 

f. CAPPA 1 , r. LiChteneCKer 1 , C. LentSCh 1 , 

w. SChMid 1 

1 University of Vienna, Institut of Organic Chemistry, Vienna, 

Austria 

The development of new isotope labelling strategies for 

proteins has boosted the development of new methods to study 

the structure and dynamics of these molecules. 

In this study new tools for structural biological problems 

will be developed. Focus will be set on the preparation of 

specifically 13-C ring-labeled aromatic amino acids and their 

precursors, which should be versatile starting points for structural 

assignments of biopolymers utilizing novel NMR experiments. 

The aim of this project is to synthesize specifically 

13-C-ring labelled phenylalanine precursors via metathesis 

reaction. The reaction sequence utilizes the easily accessible 

protected D-glyceraldehyde, obtained from commercially 

available D-mannitol, as starting material. The metathesis reaction 

precursor needed is generated via an indium promoted chain 

elongation reaction of the aldehyde using α-bromomethacrylate 

as allyl component. Ring closing metathesis (RCM) yields a 

cyclohexene derivative which should easily aromatize to benzoic 

acid. Reduction of the ester moiety to the corresponding aldehyde 

and further hydantoin elongation should make phenylalanine 

13 accessible. The origins of the C-labels are the 

α-bromomethacrylate which has been synthesized in all 

possible13C-labeling patterns in our group. This route opens the 

possibility to label exactly defined positions in the aromatic ring. 

The second optional source of 13-C-labels is the hydantoin, which 

enables establishing a variety of labelling patterns in the 

C-3-sidechain of the final amino acids. 

Keywords: Isotopic labeling; Amino acids; Metathesis; 



s1010 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 9 7 

hArneSSinG heLiCity for enhAnCed funCtion 

d. CArBery 1 

1 University of Bath, Chemistry, Bath, United Kingdom 

Helical structures are manifest in nature over many 

magnitudes of scale from galaxies to biochemistry. Helical 

structures are chiral yet, arguably underutilised as a design elemnt 

in asymmetric organic synthesis. This presentation will focus 

upon our efforts to harness helicity, in the form of helicene-like 

molecules (helicenoids), examining their efficacy in the context 

of organocataysis. 

Our synthetic efforts to “helical DMAP” and “helical 

m-CPBA” catalysts will be discussed. Key issues and contexts 

under discussion in this presentation will be catalyst resolution, 

point-to-helicity transfer, kinetic resolutions, enantioselective 

reactions and metal organic frameworks. 

Keywords: Helical structures; Organocatalysis; Synthetic 

methods; 


P - 0 2 9 8 

tAndeM MetAtheSiS for the totAL SyntheSiS 

of LyCorine tyPe ALKALoidS 

S. CArret 1 , C. verrier 1 , A. viCeriAt 1 , 

J. f. PoiSSon 1 

1 DCM - Departement de Chimie Moleculaire, SERCO, 

Grenoble, France 

Our organic synthesis group have developed over the past 

five years strategies for the synthesis of complex natural alkaloids 

relying on ring closing metathesis (RCM). This program has led 

to the efficient asymmetric total synthesis of biologically 

active natural products such as (+)-castanospermine and 

(+)-1-deoxynojirimycin, through the development of an original 

one pot procedure of enol ether RCM – hydroboration that lead 

exclusively, and in high yield, to a specific trans-trans substitution 

pattern present in numerous alkaloids. 

Our attention is now focused on the exploration of tandem 

ring closing metathesis containing an ynol ether as a partner and 

its application to the total synthesis of lycorine type alkaloids. The 

synthesis of the key intermediate for the novel tandem sequence 

requires the development of two new methods: firstly, the 

unprecedented addition of alkoxyacetylide to chiral sulfinylimine, 

and secondly a crucial direct aldolisation of sulfinylimidate. The 

alkoxyacetylide additions to sulfinylimine proceed with excellent 

yield and selectivity, and the direct aldolisation is highly 

promising. These recent results on both fields, allowing a direct 

access to the key intermediate for the tandem RCM and for the 

first total synthesis of some lycorine type alkaloids, will be 

presented. 

Keywords: total synthesis; ynol ether; sulfinylimidate; 

metathesis; 



s1011 

chem. Listy 106, s587–s1425 (2012) 


P - 0 2 9 9 

noveL, CLiCKABLe fAr red – nir MeGA-StoKeS 

fLuoroPhoreS for BioorthoGonAL 

LABeLinG, BioiMAGinG And fret SySteMS 

G. B. CSereP 1 , P. KeLe 2 

1 Eotvos Lorand University, Department of Organic Chemistry, 


2 Eotvos Lorand University, Institute of Chemistry, Budapest, 

Hungary 

Chemical labeling of biopolymers are key tools to many 

applications in biotechnology and medicine. The most convenient 

and efficient way towards fluorescent labeling of biological 

targets is bioorthogonal ligation. Among various techniques and 

reactions, the copper catalyzed azide-alkyne cycloaddition 

(CuAAC) is the most frequently used one due to the high 

selectivity and reaction rate of this reaction. Fluorescent labeling 

is common technique in biological experiments due to its 

relatively cheap and very sensitive detection. The most-frequently 

used fluorescent dyes, however, often suffer from drawbacks. 

Their so-called Stokes-shifts (ea. the difference between the 

excitation and emission maxima) are only 20-30 nm giving rise 

to relatively large self-absorption and high background 

fluorescence, both contributing to lowered detection efficiency. 

As a possible solution to overcome these limitations, so-called 

mega-Stokes fluorophores are used with Stokes-shifts larger then 

100 nm. The use of fluorescent tags in biological applications 

often requires emission wavelengths in the far-red – NIR spectral 

window where the transparency of living cells is the highest and 

autofluorescence of biological matter is negligible. 

With these aims in mind a set of new, azide or alkyne 

bearing lepidinium-based fluorophores were designed and 

synthesized for bioorthogonal labeling schemes. These fluorescent 

dyes all possess large Stokes-shifts with emission maxima in the 

far-red – NIR regime and can be excited by commonly used laser 

sources. The in vivo applicability and toxicity of these fluorescent 

dyes were tested in cell labeling experiments with CHO-cells. 

Furthermore, the applicability of these dyes in the construction of 

energy transfer (FRET) systems was also tested using one of these 

new fluorescent tags with daunorubicin, an anticancer drug with 

fluorescent features. This FRET labeled model system can be used 

to follow the uptake and the possible release of daunorubicin 

within cells. 

Keywords: Click chemistry; Fluorescence; Fret; Azides; 

Alkynes; 


P - 0 3 0 0 

nuCLeoSide ProBeS for deteCtinG 

o6-ALKyL-2'-deoxyGuAnoSine in dnA 

h. A. dAhLMAnn 1 , h. L. GAhLon 1 , S. J. SturLA 1 

1 ETH Zürich, Health Sciences and Technology, Zürich, 

Switzerland 

Alkylation of DNA to form nucleoside adducts is an 

important transformation leading to mutagenesis and 

carcinogenesis. A possible means for detecting DNA adducts are 

hybridization probes, which are oligonucleotides containing 

nucleoside analogs designed to pair opposite specific adducts, 

such as O6-alkyl-2'-deoxyguanosine (O6-alkyl-dG). Alternatively, 

polymerase-mediated amplification of adducted DNA to facilitate 

detection would be desirable. We have evaluated a series of 

nucleoside analogs for utilization in both hybridization probes and 

for polymerase-mediated incorporation opposite O6-alkyl-dG adducts. Results indicate that nucleoside analog size, shape, 

pi-stacking ability, and hydrogen bonding capacity influence 

selectivity and effectiveness in hybridization and DNA synthesis. 

Keywords: Alkylation; DNA damage; DNA recognition; 

Nucleosides; Noncovalent interactions; 



s1012 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 0 1 

hiGhLy enAntioSeLeCtive 

CArBoCyCLizAtionS By CoMBinAtion of AMine 

And heteroGeneouS MetAL CAtALyStS 

L. deiAnA 1 , A. CordovA 1 , e. JohnSton 1 , 

S. AfewerKi 1 , o. verho 1 


The first examples of one-pot highly enantioselective 

dynamic kinetic asymmetric transformations involving 

α,β-unsaturated aldehydes, propargylated nucleophiles and Pd (II) 

nanocatalyst. These DYKATs, which proceed by a combination 

of catalytic iminium activation, enamine activation and Pd (II) 

nanoparticles supported on aminopropyl-modified siliceous 

mesocellular foam (MCF) catalyzed carbocyclizations, gives 

access to functionalized cyclopentanes, dihydrofurans and 

2,5 –dihydropyrroles with up to 98% ee. The Pd (II) nanocatalyst 

was found to be remarkably stable and could be recycled several 

times with no leaching of the metal into solution or any change in 

activity. 

Keywords: asymmetric catalysis; organocatalysis; 

heterogeneous catalysis; palladium; cyclization; 


P - 0 3 0 2 

StruCture-ProPerty reLAtionShiPS of 

Low-MoLeCuLAr weiGht orGAnoGeLAtorS 

BASed on BiS[n-(P-AryL)-CArBAMoyLoxy]ALKAneS 

o. deMir-ordu 1 , K. ALPer 2 , h. SiMSir 2 

1 Abant Izzet Baysal University, Chemistry Department, Bolu, 

Turkey 

2 Karabuk University, Chemistry Department, Karabuk, Turkey 

The organogelation phenomenon exhibited by low-molecular 

weight organic compounds is the subject of increasing attention 

owing to their striking self-assembling properties, their responsive 

behavior and their applicability. [1, 2] Most organogels immobilizing 

various organic solvents at relatively small concentrations 

(≤5% wt) consist of long nanofibers self-assembled through 

non-covalent interactions. The search for the tuning of mechanical 

or thermal properties of the gels, the scope of gelated solvents and 

morphology of the gels is elementary in the field of gel chemistry. 

It is believed that structural variations provide a basis for a better 

understanding of the structure-property relationships. 

With this aim, we synthesized a class of Bis[N-(p-aryl)- 

-carbamoyloxy]alkanes and investigated their organogelation 

properties. 

These compounds have been synthesized by the reaction of 

p-aryl isocyanates with diols and their structures have been 

determined by 1H and 13C NMR. The sol-gel transition 

temperatures (T ) were determined by the dropping-ball method 

gel 

and differential scanning calorimeter. The morphology of the 

organogelators was investigated by scanning electron microscopy. 

The compounds were designed on the basis that they have 

two urethane units capable of forming hydrogen bonds, an aryl 

moiety substituted by electron-donating groups which increase 

the strength of p-p stacking and a hydrophobic unit that can be 

involved in hydrophobic interactions. It has been observed that 

the synthesized compounds favored the formation of 

supramolecular gels in alcohols, esters, toluene, xylene, 

dichloromethane. Infrared spectroscopy indicated that the 

organogelation occurred through hydrogen bonding. Crosslinked 

network was observed in the electron micrographs. Different 

gelation behavior was observed in different solvents by varying 

the alkyl chain length and the nature of para-substituents. In most 

of the cases, para-alkoxy derivatives promote gelation at lower 

gelator concentration compared to para-alkyl substituted 

compounds. 

references: 

1. Abdallah, D. J.; Weiss, R. G. Adv. Mater. 2000, 12, No.17, 

1237-1246. 

2. Terech, P.; Weiss, R. G. Chem.Rev. 1997, 97, 3133-3159. 

Keywords: Gels; Hydrogen bonds; Supramolecular chemistry; 

Pi interactions; Self-assembly; 



s1013 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 0 3 

SyntheSiS of new C-PrenyLAted And 

o-PrenyLAted CoMPoundS: MoLeCuLeS with 

PotentiAL BioLoGiCAL ACtivity 

M. A. dettori 1 , d. fABBri 1 , G. deLoGu 1 

1 CNR, Institute of Biomolecular Chemistry, Sassari, Italy 

Email: a.dettori@icb.cnr.it 

Magnolol and honokiol, are significant bioactive 

constituents isolated from the bark of Magnolia officinalis which 

posses potent anti-oxidative, anti-inflammatory and anti-cancer 

activities [1] . The chemical structure of magnolol is a C -symmetry 

2 

C-C dimer of 4-allyl-phenol which forms a biphenyl skeleton, 

whereas honokiol is its structural isomer (congener). It is known 

that the presence of a prenyl or geranyl group in natural 

polyphenols can lead to a remarkable increase in bioactivity due 

to an increment of lipophilicity through interaction with cellular 

membranes. 

With the aim to prepare compounds similar to magnolol 

and honokiol and some polyphenols, commercially available 

4,4'--dihydroxy biphenyl, 2,2'-dihydroxy biphenyl, 5,5'-diallyl- 

2,2'-dihydroxy biphenyl, 4-(4-hydroxy-3-methoxyphenyl)-butan- 

-2-one (zingerone), 4-hydroxy-3-methoxybenzaldehyde 

(vanillin), 1-(4-hydroxy-3-methoxyphenyl)-ethanone (apocynin), 

1-(2-hydroxy-4-methoxyphenyl)-ethanone and 3,4-dimethoxy - 

benzaldehyde (veratraldehyde) were used as starting materials. 

Claisen-Schmidt condensation of aryl aldehyde with the 

appropriate ketone in the presence of base [2] , allowed us to 

achieve α,β-unsatured ketons and calchones endowed with a free- 

OH phenolic group in 60-70% yield. Each phenol was treated with 

three different unsaturated alkyl halogens (allyl bromide, geranyl 

bromide, 1-bromine-3-methyl butene-2) in acetone, in the 

presence of K CO to give the corresponding O-prenylated 

2 3 

derivatives in 70-80% yield. 

In order to achieve C-prenylated phenols, the compounds 

were further subjected to Claisen rearrangement under both 

thermal condition and microwave irradiation. 

We were able to prepare directly C-prenylated biphenol by 

Heck reaction of linalool with 3,3' dibromo- 4,4'-dihydroxy-1,1'- 

-biphenyl, the latter obtained by bromination of 4,4'-dihydroxy 

biphenyl in the presence of Br and AcOH. 

2 

All synthesized compounds were obtained as air stable 

solids and easily purified by flash chromatography. 

Acknowledgement: This work has been supported by Sardinia 

Autonomous Region (L.R., August 7th 2007, n. 7) 

references: 

1. Kong Z. L. et al. Bioorganic & Medicinal Chemistry 

Letters 2005, 15, 163. 

2. Tatsuzaki J. et al. J. Nat. Prod. 2006, 69, 1445. 

Keywords: magnolol; prenylated compund; phenol; 


P - 0 3 0 4 

BifunCtionAL MeSoPorouS SiLiCA 

nAnoPArtiCLeS viA CLiCK-CheMiStry 

– CooPerAtive CAtALySiS At SurfACe 

A. diCKSChAt 1 , f. BehrendS 2 , h. eCKert 2 , 

A. Studer 1 

1 Chemisches Institut, Organische Chemie, Münster, Germany 

2 Chemisches Institut, Physikalische Chemie, Münster, Germany 

Mesoporous materials with size-tunable mesopores have 

been widely used in the past few years. Among these 

multifunctional catalytic systems have attracted a great deal of 

interest. Inorganic-organic hybrid-materials like MCM-41 

combine both flexibility and ease in synthesis of the organic 

component as well as rigidity and thermal stability of the 

inorganic framework. 

A precise attachment of organic functionalities onto 

mesoporous silica nanoparticles (MSNs) can be achieved either 

by post grafting of an organosilicon compound or by the 

co-condensation method. 

Several examples are known wherein the concept of a dual 

activation of nucleophiles and electrophiles by acids and bases 

respectively lead to synergistic catalytic enhancements. Herein 

we present the synthesis of acid-base bifunctional MSNs via 

co-condensation of tetraethoxyorthosilicate (TEOS) and various 

triethoxysilanes bearing orthogonal and therefore subsequently 

addressable functionalities. Their catalytic performance has been 

tested in the Henry-reaction. 

Via this approach we were also able to bring on ligands at 

surface and immobilize transitionmetals into the mesoporous 

particles in order to catalyze cross-coupling reactions. 

Keywords: binfuctional catalysis; mesoporous silica 

nanoparticles; heterogeneous catalysis; cooperativity; 



s1014 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 0 5 

rutheniuM-CAtALyzed direCt C–h Bond 

AryLAtionS of AreneS BeArinG reMovABLe 

direCtinG GrouPS 

e. dierS 1 , L. ACKerMAnn 1 

1 Georg-August Universität Göttingen, Institut für Organische 


Transition-metal-catalyzed direct arylation reactions via 

C–H bond cleavages constitute an economically and ecologically 

benign alternative to conventional cross-coupling reactions. [1] 

In recent years, we have reported on generally applicable, 

site-selective direct arylations of various arenes using aryl 

bromides, chlorides, tosylates and phenols as (pre)electrophiles. [2] 

We disclosed the beneficial effect of carboxylic acids as additives 

in ruthenium-catalyzed direct arylations [3] or direct alkylations 

with unactivated alkyl halides. [4] This catalytic system showed a 

broad scope, and the key C–H bond metalation was proposed to 

proceed through a carboxylate-assisted mechanism. [3] 

However, ruthenium-catalyzed C–H bond arylations of 

arenes with aryl halides continue to lack generality, as illustrated 

by their limitation to substrates that form five-membered 

ruthenacycles. [1–3] 

Recently, we devised first ruthenium-catalyzed direct 

arylations of arenes via six-membered ruthenacycles that set the 

stage for a removable directing group strategy. [5] 

Herein, we present the development, and scope of this 

transition-metal-catalyzed C–H bond functionalizations. 

references: 

1. a) L. Ackermann, Modern Arylation Methods, Wiley-VCH, 

Weinheim, 2009; 

b) L. Ackermann, R. Vicente, A. R. Kapdi, Angew. Chem., 

Int. Ed. 2009, 48, 9792–9826; 

c) X. Chen, K. M. Engle, D.-H. Wang,J.-Q. Yu, Angew. 

Chem. Int. Ed. 2009, 48, 5094; d) D. Alberico, M. Scott, 

M. Lautens, Chem. Rev. 2007, 107, 174-238. 

2. a) L. Ackermann, A. Althammer, S. Fenner, Angew. Chem. 

Int. Ed. 2009, 48, 201–204. 

b) L. Ackermann, S. Fenner, Chem. Commun. 2011, 47, 

430–432. 

c) L. Ackermann, A. V. Lygin, Org. Lett. 2011, 13, 

3332–3335. 

d) L. Ackermann, J. Pospech, H. K. Potukuchi, Org. Lett. 

2012, 14, 2146–2149. 

3. L. Ackermann, R. Vicente, A. Althammer, Org. Lett. 2008, 

10, 2299–2302. 

4. a) L. Ackermann, P. Novák, R. Vicente, N. Hofmann, 

Angew. Chem. Int. Ed. 2009, 48, 6045–6048. 

b) L. Ackermann, N. Hofmann, R. Vicente, Org. Lett. 

2011, 13, 1845–1877. 

5. L. Ackermann, E. Diers, A. Manvar, Org. Lett. 2012, 14, 

1154–1157. 

Keywords: C-H activation; Homogeneous catalysis; 

Ruthenium; Sustainable Chemistry; Arenes; 


P - 0 3 0 6 

SyntheSiS of A PhotoSenSitizer for 

PhotodynAMiC therAPy 

L. donAhue 1 

1 Loyola University Chicago, Chemistry, Chicago IL, USA 

A phenothiazine trimer (N-benzyl-3,7-diphenothiazinyl - 

phenothiazine) was synthesized for use as a photosensitizer (PS) 

in photodynamic therapy (PDT). Buchwald-Hartwig chemistry 

utilizing a Pd catalyst and XPhos ligand resulted in the formation 

of two new C-N bonds on the benzyl protected phenothiazine 

base. PDT involves the use of a PS, light, and singlet oxygen to 

destroy cancer cells. A PS can be administered to a patient, and 

light of a specific wavelength directed to the cancer site using 

optical fibers. The light excites the PS and energy is transferred 

to oxygen to produce singlet oxygen or to nearby molecules to 

produce radical species. The singlet oxygen and radicals damage 

vital cellular organelles, and subsequently destroy cancer cells. 

Highly conjugated photosensitizers will absorb longer 

wavelengths (600 – 900 nm), and have the potential to destroy 

cells of deeper tissue tumors. 

Future work involves the deprotection of the phenothiazine 

trimer, and subsequent attachment of a polyethylene glycol (PEG) 

linker so that the PS is more soluble in aqueous media. The linker 

will also allow attachment of a folic acid molecule to increase 

selectivity to cancer cells. Receptor mediated endocytosis will 

allow preferential uptake of the PS complex into cancer cells. 

Cross-linked hemoglobin will also be complexed to the PS. 

The final phase of the research involves testing the PS 

complex to assess the killing potential using HeLa and 

neuroblastoma cell cultures. A colorimetric MTT assay as well as 

confocal microscopy will be utilized to confirm cell death. The 

hypothesis is that the cells that have been folate restricted will 

show the most uptake of PS-folate complex and the greatest 

amount of cell death. 

Keywords: Cross-coupling; Medicinal chemistry; Palladium; 

P ligands; Singlet oxygen; 



s1015 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 0 7 

new PoLyMeriC MAteriALS froM reCyCLed 

therMoSetS 

d. ChriStiAn 1 , d. SÖthJe 1 , M. BAuer 1 

1 Fraunhofer Institution for Polymeric Materials and 

Composites, PYCO, Teltow, Germany 

Polycyanurate ester resins are a relatively new class of high 

performance polymers developed in the late 1960 as base 

materials for printed circuit boards. The thermosets obtained via 

a cyclotrimerization reaction from at least difunctional cyanate 

monomers, show high glass transition temperatures (up to 

400 °C), low dielectric constants, high thermostability, high 

mechanical strength and good stability against most chemicals. 

This property-profile makes them useful for fibre-reinforced 

polymers for applications in the aeronautic field, for outer space 

and also for the automotive area. 

A unique feature of the crosslinked polycyanurate ester 

resins is, that they can be decomposed easily under defined 

conditions into small molecules be breaking the chemical bonds, 

using a class of specific chemical agents. Depending on the 

particular recycling agent and on the recycling conditions, the 

composition and the kind of products can be influenced 

significantly. 

The resulting recycling-products, containing - besides other 

structures - phenoles and triazines can be transformed into new 

thermosets via simple chemical reactions. The authors obtained 

bulk and foamed materials from the recycled polycyanurates 

containing up to 30 mass-% of recycled material. In combination 

with monomers resp. oligomers from renewable resources, new 

thermosets with 22 mass-% of recycling- and 22 mass-% of 

renewable material were synthesized. The new polymers show 

glass transition temperatures of up to 130°C. Further 

investigations regarding the characterization of the new 

recycling-polymers are in progress. For the foamed polymers 

applicability in the automotive and aeronautic field, e.g. as core 

materials for sandwich-panels are under test. The non-foamed 

polymers might be used as impregnation- or coating material. 

Keywords: Polymer; recycling; renewable; thermoset; 

polycyanurate; 


P - 0 3 0 8 

P-ChiroGeniC SeCondAry PhoSPhine oxideS: 

new StereoSeLeCtive SyntheSiS And 

AroMAtiC CouPLinG owinG to the Aryne 

CheMiStry 

M. dutArtre 1 , J. BAyArdon 1 , S. JuGe 1 

1Universite de Bourgogne, Chemistry, Dijon Cedex, France 

The stereoselective synthesis of chiral organophosphorus 

compounds interests numerous fields: biological compounds, 

coordinating chemistry, asymmetric catalyzed reactions by 

transition metal complexes or organocatalysis. [1] 

Among the numerous chiral phosphorus compounds 

described, the P-chirogenic phosphine derivatives are of particular 

interest, because the chirality is closed to the metal center. 

The stereoselective synthesis of P-chirogenic phosphorus 

compounds was usually achieved in phosphoryled serie [2] or via 

their borane-complex precursors. [3] In continuation of our work 

on the stereoselective synthesis of new P-chirogenic building 

blocks, [3b] we investigated herein the synthesis and the use of 

secondary phosphine oxides. 

We report on one hand, a new stereoselective synthesis of 

P-chirogenic secondary phosphine oxides, via the formation of 

phosphinous acid borane, previously prepared using the ephedrine 

methodology. [3b] On the other hand, we also report the use of these 

compounds for the first stereoselective synthesis of P-chirogenic 

phosphine oxides bearing an o-bromoaryl substituent. [4] The key 

step of this synthesis is based on the secondary phosphine oxide 

reaction with an aryne species, in situ generated by reaction of 

1,2-dibromoarene with the n-butyl lithium, then metal-halide 

exchange. 

references: 

1. a) Phosphorous Ligands in Asymmetric Catalysis, Börner, 

A. (Ed.), Wiley-VCH, Weinheim, 2008, Vol. 3. 

b) Dalko, P. I.; Moisan, L. Angew. Chem. Int. Ed. 2001, 

40, 3726. 

2. a) Korpium, O.; Lewis, R.A.; Chickos, J.; Mislow, K. J. 

Am. Chem. Soc. 1968, 90, 4842. 

b) Leyris, A.; Bigeault, J.; Nuel, D.; Giordano, L.; Buono, G. 

Tetrahedron Lett. 2007, 48, 5247. 

c) Xu, Q.; Zhao, C-.Q.; Han, L-.B. J. Am. Chem. Soc. 

2008, 130, 12648. 

3. a) Crépy, K. V. L.; Imamoto, T. Top. Curr. Chem 2003, 229, 1. 

b) Jugé, S. Phosphorus Sulfur and Silicon & Related 

Compds 2008, 183 (2-3), 233. 

4. Bayardon, J.; Laureano, H.; Diemer,V.;Dutartre, M.; Das, U.; 

Rousselin, Y.; Henry, J.C.; Colobert, F.; Leroux, F.R.; 

Jugé, S. J. Org. Chem. submitted 

Keywords: P-chiral secondary phosphine oxides; aryne 




s1016 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 0 9 

SyntheSiS And PreLiMinAry StudieS of 

PorPhyrin-dotA LiGAndS And reLAted 

heteroBiMetALLiC CoMPLexeS for irM/Pet 

iMAGinG. 

A. eGGenSPiLLer 1 , n. deSBoiS 1 , J. M. BArBe 1 , 

f. denAt 1 , C. GroS 1 

1 Universite de Bourgogne, ICMUB, Dijon Cedex, France 

Last few years, the multimodal probe concept, that aims to 

use the same molecule as contrast agent of several imaging 

facilities, has grown significantly [1] . The project we develop 

concerns new heterobimetallic complexes for applications to the 

multimodal imaging field. The scaffold of ligand we propose, 

consists of two different chelators able to strongly bind metal 

centers of interest; on one hand a porphyrin derivative, which 

displays well-known properties, such as fluorescence or metal 

centers complexation, on the other hand a DOTA derivative, 

which is already used as Magnetic Resonance Imaging (IRM) 

contrast agent. One of the main interests of multimodal probes is 

the same biodistribution of the tracers and the combination of 

advantages from each technique. The series of ligands that we 

work on, allow the incorporation of gadolinium(III) into the 

tetraazamacrocycle cavity, and copper into the porphyrinic cavity [2] . 

The relaxivity of gadolinium(III) complexes was measured at 

different fields and temperature. The heterobimetallic complexes 

obtained are potentially useful for IRM/PET combination, if the 

radioactive 64Cu is chelated into the porphyrin moiety. Moreover 

the ligands are designed such as to include an activable function 

to graft them onto biological vectors [3] 

references: 

1. H. Kobayashi, M. R. Longmire, M. Ogawa, P. L. Chotke, 

Chem Soc Rev, 2011, 40, 4626-4648. 

2. C. P. Gros, A. Eggenspiller, A. Nonat, J.-M. Barbe, 

F. Denat, Med. Chem. Comm., 2011, 2, 119-125. 

3. M. Sibirian-Vasquez, T. J. Jensen, F. R. Fronczek, 

R. P. Hammer, M. G. H. Vicente, Bioconjugate Chem, 

2005,16, 852-863. 

Keywords: Porphyrinoids; Heterometallic complexes; 

Macrocyclic ligands; N ligands; Synthesis design; 


P - 0 3 1 0 

[3+2] CyCLoAddition reACtionS of ethyL 

(z)-3- And MethyL (e)-3-fLuoroProPenoAte 

with AzoMethine iMine 

n. ehterAMi 1 , t. PAtriCK 1 

1 Southern Illinois University Edwardsville, Chemistry, 

Edwardsville, USA 

Compounds with one or more fluorine atoms have become 

important in medicinal chemistry, due to fluorine unique 

electronic properties (the most electronegative atom) and its 

similar atom radius to hydrogen provides specific properties. The 

special nature of fluorine imparts a variety of properties in 

medicine including: enhanced binding interactions, metabolic 

stability by blocking metabolically sites, and change in 

physicochemical properties, such as lipophilicity or basicity. 

Fluorine also improves the molecules lipophilicity which 

facilitates bioavailability, hence higher benefit at lower dosage. 

In the other hand, Pyrazolidine, this is the building block for 

the compound that we have synthesized, received considerable 

attention in biological studies, and have been used as antibacterial, 

antifungal, and ectc. In that respect, there is growing demand for 

synthetic methods for the preparation of selectivity fluorinated 

hetrocyclic compounds for use in pharmaceutical and 

agrochemicals. Introducing of fluorine into 5 membered ring can 

significantly boosted activity of useful range. Introduction of 

fluorine into a certain position of a bioactive compound improves 

the efficiency of medicine by reducing the toxicity of the 

compound. 

The main objective of our research is to synthesis bioactive 

fluoro heterocyclic systems. Ethyl (Z)-3-fluoropropenoate has 

been prepared in a pure state in 68% yield by a Wittig procedure 

and methyl (E)-3-fluoropropenoate was prepared in 38% yield, 

and 1- benzylidene-3-oxopyrazolidine-1-ium-2-ide has been 

prepared in a pure state at 59 % yield. 

[3+2] cycloaddition reaction occurs to combine 

1-benzylidene-3-oxopyrazolidine-1-ium-2-ide and fluoropropeonate 

to yield fluorohetrocycles. 

Keywords: Fluorine; Pyrazolidine; [3+2] Cycloaddiotn 

reaction; 



s1017 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 1 1 

funCtionALizAtion of PoLyMer CoAted 

MAGnetiC nAnoBeAdS By MiCrowAve 

irrAdiAtion 

C. M. eiChenSeer 1 , q.M. KAinz 1 , o. reiSer 1 



Numerous studies demonstrate that heating by microwave 

irradiation in sealed vessels can reduce reaction times 

significantly. Additionally, compared to traditional heating higher 

product yields are often obtained because of fewer side reactions. 

The solvent employed plays a decisive role in the effectiveness 

of the heating by absorbing the microwave irradiation. Many 

nonpolar solvents, however, absorb little microwave energy. To 

circumvent this problem strongly absorbing passive heating 

elements (PHEs) can be added to the reaction mixture, e.g. 

cylinders made out of silicon carbide. [1] We investigated here if 

highly magnetic metal nanobeads can act as PHEs. The 

nanoparticles (Fe/C or Co/C) used in these experiments combine 

a metal core for rapid microwave absorption and magnetic 

separation and a shell of carbon for higher stability under basic 

and acidic conditions, while the high surface area and the good 

dispersion in the reaction mixture are advantageous in the heat 

distribution over massive PHEs. Surface functionalization was 

achieved via radical polymerization leading to a high loading of 

benzyl chloride moieties (> 3 mmol/g). [2] Starting from these 

polymer coated nanobeads a recyclable magnetic Wang aldehyde 

scavenger was prepared by substitution of the benzyl chloride 

moieties with 4-hydroxybenzaldehyde under microwave 

irradiation. Similarly, a magnetic borohydride resin was prepared 

by heating with triethylamine in ethanol and subsequent exchange 

of the chloride counterion with borohydride. Both substitution 

reactions proceeded quantitative within minutes under microwave 

irradiation while conventional heating led to incomplete 

conversion despite considerably prolonged reaction times 

(3 days). Building on these results, furan or maleimide moieties 

could be immobilized as anchors for a thermally triggered and 

reversible Diels Alder – Retro Diels Alder pathway for the 

immobilization of fluorescent dyes or even catalysts. 

references: 

1. Kremsner, J. M.; Kappe, C. O. J. Org. Chem. 2006, 71, 

4651-4658 

2. Schätz et al. Chem. Eur. J. 2011, 17, 10566-10573 

Keywords: Nanoparticles; Microwave irradiation; 


P - 0 3 1 2 

SyntheSiS, AntioxidAnt And AntituMor 

ACtivitieS of SoMe new PyrAzoLoPyridineS 

under MiCrowAve irrAdiAtion And 

ConventionAL heAtinG PArt ii 

M. eL-BorAi 1 , h. rizK 1 , d. eL-BeLtAGy 2 

1 Faculty of Science, Chemistry department, Tanta, Egypt 

2 Faculty of Science, Chemistry department, Damanhour, Egypt 

The reaction of DMF-DMA with 1-phenyl-3-(pyridin-3-yl)- 

-1H-pyrazol-5-(4H)-one (1) gave the corresponding 4- 

-(dimethylaminomethylene)-1-phenyl-3-(pyridin-3-yl)-1H-pyrazol- 

-5(4H)-one (enaminone) (2). The chemical behavior of (2) with 

active methylene reagents namely as β-ketonitriles, malononitrile, 

cyanoacetamide, cyanothioacetamide and ethyl nicotinoyl acetate 

was examined. Also, the reaction of (2) with some 

3-substituted-5-amino-1H-pyrazoles was prepared to give 

bis-pyrazolopyrimidine derivatives. All the prepared compounds 

were carried out by conventional heating and microwave 

irradiation technique to give the same products. The results of 

both methods were compared including yield and time of 

the reactions. The antioxidant activity of the prepared compounds 

was studied. Also, some of the prepared compounds were tested 

for antitumor activity against liver and breast cell lines. 



s1018 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 1 3 

CoMPuter-Aided deSiGn, SyntheSiS, And 

BioLoGiCAL evALuAtion of noveL 

2-SuBStituted AMinoMethyLenePyriMidine- 

-2,4,6-trioneS AS h1 AntihiStAMiniC AGentS 

(PArt 2) 

r. eLBAyAA 1 , r. eLBAyAA 1 

1 Faculty of Pharmacy, Pharmaceutical chemistry, Alexandria, 

Egypt 

As a part of a research project pertaining to the synthesis of 

novel candidates as nonsedating, nonclassic histaminergic (H ) 1 

blockers with low toxicity profiles, some new 2-substituted 

aminomethylenepyrimidine-2,4,6-triones were designed based on 

the H histaminic receptor pharmacophore model. The interactions 

1 

between the designed compounds and the H receptor were 

1 

studied using molecular docking on the homology model of H1 receptor. The designed compounds were synthesized and 

biologically evaluated for H -blocking activity; using isolated 

1 

segments from guinea pig ileum. Some compounds exhibited 

comparable activities to acrivastine as reference nonsedating drug. 

The C log P of designed compounds revealed lower values in 

relevance to acrivastine which might indicate decreased tendency 

for crossing the blood brain barrier. 

Keywords: histaminic receptor; pharmacophore model; 

histaminergic blockers; 


P - 0 3 1 4 

SeLeCtive Arene funCtionALizAtion 

throuGh SequentiAL oxidAtive And 

non-oxidAtive heCK reACtionS 

n. eLizArov 1 , B. SChMidt 1 

1 University of Potsdam, Organic Chemistry, Potsdam-Golm, 

Germany 

The oxidative Heck reaction, so-called Fujiwara-Moritani 

reaction, is an environmentally and economically attractive 

process for C-C bond formation between olefins and arenes. 

Compared to the classical Mizoroki Heck reaction there is no 

necessity for prehalogenation of the substrate. The bond formation 

is realized by an oxidative Pd-catalyzed cross-coupling reaction 

via direct C-H-activation. [1] 

This type of reaction allows regioselective functionalizations 

of arenes in the presence of electron donating and catalyst 

directing groups e.g. the acetamide group. The Lewis-basic 

character of the acetamide group facilitates the coordination to 

the transition-metal catalyst, which enables an intramolecular 

insertion of palladium into the C-H-bond selectively in 

ortho-position to the directing group. [2] 

Furthermore the acetamide group can be used in the 

previously investigated deacetylation-diazotation sequence: an 

operationally simple one-flask procedure which leads to isolable 

diazonium salts. Arene diazonium salts in turn are powerful 

reagents for Pd- catalyzed coupling and cross-coupling 

reactions. [3] Via a non-oxidative Heck reaction traceless removal 

of the acetamide and regioselective synthesis is achieved 

simultaneously. The described properties of the acetamide group 

open up an opportunity to combine oxidative and non-oxidative 

Heck reactions. 

The dual exploitation of the acetamide group as an arene 

activating and catalyst directing group in oxidative Heck reactions 

as well as a leaving group in a deacetylation/diazotation/ Heck 

coupling enables a regioselective synthesis of dialkenylated 

arenes from acetanilides. [4] 

references: 

1. M. Oestreich, The Mizoroki Heck Reaction, 2009, 

John Wiley & Sons. 

2. L. Ackermann, R. Vincente, A.Kapdi, Angew. Chem. Int. 

Ed. 2009, 48, 9792. 

3. B. Schmidt, R. Berger, F. Hölter, Org. Biomol. Chem. 

2010, 8, 1406. B. Schmidt, F. Hölter, R. Berger, 

S. Jessel Adv. Synth. Catal. 2010,352, 2463-2473. 

4. B. Schmidt, N. Elizarov, Chem. Commun., 48, 4350. 

Keywords: C-H activation; Heck reaction; Palladium; Diazo 

compounds; 



s1019 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 1 5 

oLiGothioPheneS with nAPhthALene 

BridGinG Moiety: reLAtionShiP Between 

StruCture And SeMiConduCtinG ProPertieS 

J. fiLo 1 , M. PutALA 1 , M. weiS 2 , J. JAKABoviC 2 

1 Comenius University, Department of Organic Chemistry, 


2 Slovak University of Technology, Institute of Electronics and 

Photonics, Bratislava, Slovak Republic 

Organic semiconducting materials offer an attractive 

alternative to conventional inorganic technology because they 

require less complex fabrication processes [1] . π-Conjugated 

organic semiconductors are, therefore, attracting considerable 

attention for application such as organic light-emitting diodes 

(OLEDs), organic field-effect transistors (OFETs), and 

photovoltaic cells. Their properties can be easily tuned by 

modification of the structure. 

Novel oligothiophenes were prepared via microwave 

assisted Suzuki cross-coupling reaction between 

hexylbithienylboronate and corresponding dihalonaphthalenes. 

Electrochemical properties of each derivative were characterized. 

OFET-s, prepared by tilt-casting on Si-substrates, exhibit thin film 

mobilities up to 3.6 × 10-2cm2V-1s-1 . Comparison of the functional 

properties and their relationship to the molecular structure of 

prepared derivatives will be presented. 

references: 

1. J. L. Brusso, O. D. Hirst, A. Dadvand, S. Ganesan, 

F. Cicoira, C. M. Robertson, R. T. Oakley, F. Rosei, 

D. F. Perepichka, Chem. Mater. 2008, 20, 2484-2494. 

And citations reported therein 

Keywords: oligothiophene; organic semiconductors; mobility; 

organic field-effect transistor; 


P - 0 3 1 6 

BridGe-Modified CALix[4]AreneS AS Potent 

hoSt CoMPoundS with CheMoSenSinG 

feAtureS 

C. fiSCher 1 , e. weBer 1 

1 Institut für Organische Chemie, TU Bergakademie Freiberg, 


Calixarenes demonstrate one of the most famous 

supramolecular hosts, available for inclusion of ionic and neutral 

guests as well as larger biomolecules depending on chemical 

modification. Besides the synthetical adaptation of the 

longitudinal axis of the chalice various approaches have been 

presented during the last two decades including the modification 

of the methylene bridge of calix[4]arenes. This horizontal 

expansion seems beneficial both for the direct incorporation of 

chemosensing units as well as anchoring of the calixarenes by 

means of the attachment of sticky- or spacer groups. [1–3] 

Synthetical attempts and sensing properties of novel bridge 

functionalized calixarenes are presented. 

references: 

1. C. Fischer, P. Bombicz, W. Seichter, F. Katzsch, E. Weber, 

Cryst. Growth & Design 2012, 12, 2445-2454. 

2. C. Fischer, G. Lin, W. Seichter, E. Weber, Tetrahedron 

2011, 67, 5656-5662. 

3. C. Fischer, T. Gruber, W. Seichter, E. Weber, Org. & 

Biomol. Chem. 2011, 9, 4347-4352. 

Keywords: calixarene; supramolecular chemistry; lateral 

substitution; fluorescence sensor; molecular recognition; 



s1020 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 1 7 

SyntheSiS And AntiProLiferAtive ACtivity of 

new iodine Goniofufurone AnALoGueS 

J. frAnCuz 1 , M. PoPSAvin 1 , v. KoJiC 2 , 

G. BoGdAnoviC 2 , v. PoPSAvin 1 

1 University of Novi Sad, Faculty of Sciences Department of 

Chemistry Biochemistry and Environmental Protection, 21000 

Novi Sad, Serbia 

2 Oncology Institute of Vojvodina, Oncology Institute of 

Vojvodina, 21204 Sremska Kamenica, Serbia 

Goniofufurone is a naturally occurring styryl lactone that 

exhibits a potent antitumour activity. Herein we want to report 

preparation of novel goniofufurone analogues (4 and 5) having 

an iodo-deoxy function at the C-7 position and a lipophylic 

5-O-benzyl function. 3-O-benzyl-1,2-O-isopropylidene-5-C- 

-phenyl-α-d-gluco-pentofuranose (1) that was readily available 

from d-glucose in four steps was conveniently used as a starting 

material in this work. Hydrolytic removal of isopropylidene 

protective group in 1gave the expected lactol 2, which was 

converted to the lactone 3 after treatment with Meldrum’s acid. 

Finally, direct substitution of benzylic alcohol function in lactone 

3 with iodo isostere was achieved under the Garegg-Samuelsson 

conditions. The synthesized analogues were evaluated for their in 

vitro cytotoxicity against several human tumour cell lines, as well 

as normal foetal lung fibroblasts (MRC-5). The preliminary 

results of their antiproliferative activity will be presented and 

discussed. 

Keywords: Antitumor agents; Medicinal chemistry; Synthetic 

methods; 


P - 0 3 1 8 

tAddoL-derived PhASe-trAnSfer CAtALyStS 

for the ASyMMetriC A-ALKyLAtion of 

GLyCine SChiff BASeS 

K. GrAtzer 1 , M. wASer 1 



Recently, the range of reactions that can be catalysed by 

phase-transfer catalysts (PTCs) has increased significantly. 

Besides privileged catalysts [1] , like Maruoka’s C -symmetric 

2 

BINOL-derived PTCs and cinchona PTCs, no other such powerful 

compounds have been reported. Although, tartaric acid is one of 

the most important chiral natural substances, it’s use in 

asymmetric phase-transfer catalysis has to our knowledge been 

limited to a few examples only. [2] 

With the before mentioned structures in mind and as both 

tartaric acid enantiomers are easily available, we envisioned the 

design of novel TADDOL [3] -derived chiral spiro ammonium salts 

as potent compounds for asymmetric reactions. [4] 

An overview of our research group’s investigations to 

successfully synthesize a series of new PTCs and to identify the 

most potent key-structural motives will be given. Ongoing 

structure modifications and their influence on the catalytic 

potential for the stereoselective α-alkylation of glycine Schiff 

bases will be reported. 

references: 

1. Asymmetric Phase Transfer Catalysis; Maruoka, K., Ed.; 

Wiley-VCH: Weinheim, 2008. 

2. a) Shibasaki, M.; Ohshima, T. In Asymmetric Phase 

Transfer Catalysis; Maruoka, K., Ed.; Wiley-VCH: 

Weinheim, 2008; 115-134. 

b) Arai, S.; Tsuji, R.; Nishida, A. Tetrahedron Lett. 2002, 

43, 9535-9537. 

c) Belokon, Y. N.; Kochetkov, K. A.; Churkina, T. D.; 

Ikonnikov, N. S.; Chesnokov, A. A.; Larionov, O. V.; 

Singh, I.; Parmar, V. S.; Vyskocil, S.; Kagan, H. B. 

J. Org. Chem. 2000, 65, 7041-7048. 

3. Seebach, D.; Beck, A. K.; Heckel, A. Angew. Chem. Int. 

Ed. 2001, 40, 92-138. 

4. Waser, M.; Gratzer, K.; Herchl, R.; Müller, N. Org. 

Biomol. Chem. 2002, 10, 251-254. 

Keywords: Asymmetric catalysis; phase-transfer catalysis; 

organocatalysis; alkylation; amino acids; 



s1021 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 1 9 

SS-CyCLodextrin BASed duPLexeS ConneCted 

with two diSuLfide BridGeS: SyntheSiS, 

StruCture And inCLuSion CoMPLexeS 

A. GriShinA 1 , t. KrAuS 2 , L. ruLiSeK 3 , 

M. BudeSinSKy 4 , i. KrizovA 5 , M. duSeK 6 

1 Charles University in Prague Faculty of Science, Organic and 

nuclear chemistry, Prague, Czech Republic 

2 Institute of organic chemistry and biochemistry AS CR v.v.i., 

Organic Synthesis, Prague, Czech Republic 


Computational Chemistry, Prague, Czech Republic 


NMR Spectroscopy, Prague, Czech Republic 


Biochemistry and Molecular Biology, Prague, Czech Republic 

6 Institute of Physics AS CR v.v.i., Department of Structure 

Analysis, Prague, Czech Republic 

Cyclodextrins (CD) attract attention of researchers from 

different fields because of their unique hydrophobic cavities 

which can host a range of organic compounds in aqueous media. 

Various derivatives of CDs were synthesized to improve their 

binding affinity. In our group, we are interested in the 

development of a new type of rigid tubular receptors composed 

of two CD macrocycles connected with two or three flexible 

disulfide bonds [1, 2] . 

Recently we have prepared a new β-cyclodextrin duplex and 

studied its binding properties. The synthesis of the new host 

compound consisting of two β-CD macrocycles connected with 

two disulfide bonds in a “head to head” manner was achieved in 

six steps starting from perbezylated β-CD. In the last oxidation 

step the predominance of formation of two isomers of the dimer 

can be attained under conditions of thermodynamic control. 

Binding affinities to various guests, including clinically used 

drugs, in the range Ka=10 5-108 M-1 was determined by isothermal 

titration calorimetry, demonstrating thus a great potential of 

ββ-duplexes as a new host system, which could find a broad 

application in medicine and other areas of research. 

references: 

1. Kumprecht L., Bude‰ínský M., Vondrá‰ek J., Vymetal J., 

Cerný J., Císarová I., Brynda J., Herzig V., Koutník P., 

Závada J., Kraus T., J. Org. Chem.2009, 74, 1082-1092. 

2. Krejcí L., Bude‰ínský M., Císarová I., Kraus T., Chem. 

Commun.2009, 3557-3559. 

Keywords: Cyclodextrins; Water chemistry; Host-guest 

systems; 


P - 0 3 2 0 

totAL SyntheSeS And BioLoGiCAL evALuAtion 

of noveL fLAvonoid derivAtiveS AS 

PotentiAL Cox-2 inhiBitorS 

r. Gueye 1 , C. PouGet 1 , L. BertrAnd 1 , d. LéGer 1 , 

y. ChAMPAvier 2 , J. L. duroux 1 , C. fAGnere 1 

1 EA 1069 “Laboratoire de Chimie des Substances Naturelles”, 

Faculté de Pharmacie, Limoges, France 

2 Service Commun de Recherche et d’Analyse de Biomolécules 

de Limoges, Université de Limoges, Limoges, France 

Cyclooxygenase-2 (COX-2) catalyses the production of 

prostaglandin E2 which is a key mediator of pain and 

inflammation [1, 2] . Thus, COX-2 enzyme is the molecular target for 

the therapeutic effect of non steroidal anti-inflammatory drugs [3] . 

In addition, numerous reports demonstrate that flavonoids, 

a wide family of natural compounds, inhibit COX-2 activity [4] . 

We are interested in the pharmacomodulation of flavonoids 

in order to develop novel COX-2 inhibitors. Therefore, 

pharmacophores associated with COX-2 inhibition and other 

functional groups, that seem to improve the expected biological 

activity, have been introduced on the flavonoid skeleton. 

2'-hydroxychalcones were synthesized through 

Claisen-Schmidt condensation between an acetophenone and a 

benzaldehyde both bearing a pharmacologically active 

substituent [5] . These chalcones are key compounds from which 

other flavonoids, such as flavanones, flavones and flavonols, were 

obtained. 

The synthetic methodologies and the biological results of 

these molecules will be presented. 

references: 

1. Liu, M.-L. et al. Neurosci. Lett. 2012, 508 (1), 31–36. 

2. Rukwied, R. et al. The Journal of Pain 2007, 8 (5), 

443–451. 

3. Marnett, L. J. Annu. Rev. Pharmacol. Toxicol. 2009, 49, 

265–290. 

4. O’Leary K.A. et al. Mutation Research 2004, 551 (1-2), 

245–254. 

5. Yahiaoui, S. et al. Eur. J. Med. Chem. 2011, 46 (6), 

2541–2545. 



s1022 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 2 1 

ChLoroStyreneS in iron-CAtALyzed 

CroSS-CouPLinG reACtionS 

S. GüLAK 1 , A. JACoBi von wAnGeLin 1 

1 Institute of Organic Chemistry, Chemistry and Pharmacy, 


Email: sguelak@gmx.de 

Metal-catalyzed cross-coupling reactions have matured to 

an indispensable tool for the functionalization of aromatic 

molecules. While the majority of protocols utilize electrophilic 

aryl bromides and aryl iodides, reactions with economically more 

attractive aryl chlorides remain a challenge for which only a 

handful of catalyst system exhibit satisfactory activity. [1] We wish 

to report on our efforts to design a cross-coupling reaction that 

takes advantage of the activation of aryl chlorides by vinyl 

substituents. Highly chemoselective iron-catalyzed cross-coupling 

has been observed under conditions commonly unsuitable for the 

consumption of deactivated aryl chlorides. [2] The mechanism is 

believed to involve initial coordination of the vinyl group to the 

iron catalyst, haptotropic migration along the conjugated p-system 

to the site of C-Cl bond cleavage. [3] 

references: 

1. A. C. Frisch, M. Beller, Angew. Chem. Int. Ed. 2005, 44, 

674. 

2. A. Fürstner, A. Leitner, M. Méndez, H. Krause, J. Am. 

Chem. Soc. 2002, 124, 13856. 

3. S. Gülak, A. Jacobi von Wangelin, Angew. Chem. Int. Ed. 

2012, 51, 1357. 

Keywords: Iron-Catalysis; Biaryls; Aryl-Chlorides; Substituted 

Styrenes; Cross-Coupling; 


P - 0 3 2 2 

new PhoSPhorouS LiGAndS derived froM 

BenzoxAntheneS 

B. GuLer 1 , e. zenGin 2 , v. KuMBArACi 1 , n. tALinLi 1 

1 Science and Technology, Chemistry, Istanbul, Turkey 

2 Science and Technology, Chemistry, Mugla, Turkey 

Aryl-14H-dibenzo[aj]xanthene derivatives have significant 

biological activities as antibacterials, antivirals, anti inflammatory 

agents in photodinamic therapy. Xanthene-based compounds have 

also been investigated for agricultural bactericide activity and 

some other benzoxanthenes also used in industries such as dyes 

in laser technology and fluorescent materials for visualization of 

biomolecules.[ 1] Moreover, interesting scaffold of dibenzoxanthene 

structure bring its’ possible catalytic activity to mind according 

to have resemblance to chiral phosphine ligands. These ligands 

have common applications in enantioselective organic reactions 

reactions. [2] In the present study, because of potentitial catalytic 

activity, effective synthesis of dibenzoxanthene compounds 

containing phosphorous ester moiety and analysing their catalytic 

activity have aimed. 

The synthesis of dibenzoxanthenes by the reaction of 

aldehydes with 2-naphthol in the presence of various acid catalyst 

is the most convenient method. In the present study, In order to 

prepare phosphorus ligand of benzoxanthenes, hydroxyaldehydes 

and dihydroxynaphthols were reacted in presence of different 

catalyst, i.e strongly acid catalyst Amberlyst-15, or P O . 2 5 [3] Then, 

phosphoros ester of dibenzoxanthene derivatives synthesized by 

the reaction of dichlorophenyl phosphine oxide and 

dibenzoxanthene derivatives. 

In the next step phosphine oxide containing 

dibenzoxanthene compounds will be attempted in organic 

reactions and their enantioselectivity will be examined. 

references: 

1. Selvam, N. P.; Shanthi, G.; Perumal, P. T.; Can. J. Chem. 

2007, 85, 989. 

2. Hatano, M.; Miyamoto, T.; Ishihara, K.; J. Org. Chem. 

2006, 71, 6474. 

. Karimi-Jaberi, Z.; Keshavarzi, M.; Chinese Chemical Lett. 

2010, 21, 547. 

Keywords: Benzoxanthene; Phosphorous ligands; Catalyst; 



s1023 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 2 3 

AMBerLySt-15 CAtALyzed SyntheSiS 

And reArrAnGeMent reACtionS of 

2-tetrAhydrofurAnyL etherS 

h. Gunduz 1 , v. KuMBArACi 1 , n. tALinLi 1 


The conversion to tetrahydropyranyl (THP) or 

tetrahydrofuranyl (THF) ethers are a part of an important method 

for protecting alcohol functional groups. It is well known that, in 

comparison with THP ethers, THF ethers have the advantage that 

they can be hydrolyzed under even milder acidic conditions and 

also they can be selectively cleaved in the presence of THP 

ethers. 1 

There are mainly two methods for the preparation of 

tetrahydrofuranyl ethers; the first one is using 2,3-dihydrofuran 

(DHF) in the presence of various acid catalysts, including 

Al(OTf) [1] , or pyridinium p-toluenesulfonate (PPTS) [2] . The second 

3 

is based on the use of tetrahydrofuran, THF, in the presence of 

one-electron oxidants like CrCl -CCl [3] etc. progressing in 

2 4 

radicalic pathway. 

In our study, a simple and one step method for the 

conversion of naphthols and phenols into corresponding 

2-aryltetrahydrofurans using Amberlyst-15 in THF is reported. 

This is the first example of the acid mediated formation and 

rearrangement reactions of tetrahydrofuranyl ether prepared from 

tetrahydrofuran and aromatic hydroxyl compounds. 

Corresponding THF ether of 2-naphthol was formed in 3% yield 

but it was accompanied by the rearrangement product in the yield 

of 40 %. Treatment of various aromatic compounds which have a 

free OH group gave o-substituted rearrangement products 

accompanied by a small amount of tetrahydrofuranyl ethers. 

Reaction can proceed in two steps: In the first step,THF 

was oxidized to 4-hydroxybutyraldehyde and it reacted with 

2-naphthol to form tetrahydrofuranyl ether, then in the presence 

of strong acid catalyst, Amberlyst-15, Fries rearrangement 

reaction occurred. 

references: 

1. Williams,G. B. D.; Simelane, S. B.; Lawton, M.; Kinfe, H. H. 

Tetrahedron 2010, 66, 4573. 

2. Kometani,T.; Kondo, H.; Fujimori, Y. Synthesis. 1988, 

1005. 

3. Baati, R.; Valleix,A.; Mioskowski, C.; Barma, D. K.; 

Falck, J. R. Org. Lett. 2000, 2, 485. 

Keywords: 2-aryltetrahydrofurans; tetrahydrofuranyl ethers; 

Amberlyst-15; rearrangement reactions; 


P - 0 3 2 4 

new tAndeM MetAtheSiS-iSoMerizAtion 

SequenCeS And their APPLiCAtion for 

nAturAL ProduCt SyntheSiS 

S. hAuKe 1 , B. SChMidt 1 


Germany 

During the last decade the ruthenium-catalyzed metathesis 

reaction was established as an important C-C-bond formation in 

organic synthesis. [1] Especially the development of tandem 

metathesis reactions has attracted a lot of attention, e.g. the 

metathesis-isomerization [2] sequence. Thereby, after completion 

of the metathesis step the metathesis-active ruthenium carbene 

species is converted in situ to an isomerization-active ruthenium 

hydride species by adding an additive. 

We developed two new tandem metathesis-isomerization 

sequences: [3] cross metathesis-isomerization/tautomerization of 

allylic alcohols and the ring-closing metathesis-isomerization of 

protected nitrogen precursor to isomerized tetrahydropyridine. 

Cross metathesis of allylic alcohol is performed with either acrylate 

or styrene to obtain the enol as an intermediate, which tautomerizes 

to 1,4-dicarbonyl compound or dihydrochalcone, a class of natural 

products. The N-ring-closing metathesis-isomerization allows a 

new access of imino sugars. 

references: 

1. a) Fürstner, A. Angew. Chem. Int. Ed. 2000, 39, 3012. 

b) Nicolaou, K.C.; Bulger, P.G.; Sarlah, D. Angew. Chem. 

Int. Ed. 2005, 44, 4490. 

2. Schmidt, B. J. Org. Chem. 2004, 69, 7672. 

3. Schmidt, B.; Hauke, S. manuscript in preparation. 

Keywords: Homogeneous catalysis; Ruthenium; Metathesis; 

Isomerization; Azasugars; 



s1024 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 2 5 

inSiGhtS into ASyMMetriC 

orGAnoAutoCAtALytiC MAnniCh reACtionS 

f. heLd 1 , A. finGerhut 1 , S. B. tSoGoevA 1 


Department of Chemistry and Pharmacy Chair of Organic 

Chemistry I, Erlangen, Germany 

Asymmetric autocatalytic reactions are among the most 

fascinating processes in catalysis. Several examples are known, 

the most prominent of which is the Soai reaction for its ability to 

amplify a tiny initial enantiomeric excess of a chiral pyrimidyl 

alkanol in the presence of i-Pr Zn to almost enantiomeric purity. 

2 

In 2007, the Tsogoeva group demonstrated for the first time 

that even in quite ordinary and reversible asymmetric and fully 

organic reactions, the chiral product alone could act as a catalyst 

with high stereoselectivity. Realising further that chiral 

autocatalysis is key to spontaneous mirror symmetry breaking, we 

have demonstrated for the first time that spontaneous random 

generation of enantiomeric excess is possible in common 

asymmetric and fully organic reactions - the aldol and Mannich 

reactions, even if they are run under essentially achiral conditions 

and in a system closed to matter flow. 

Very recently we have gained further insights on the 

Mannich reaction, carried out without external catalyst, 

reconfirming our earlier observations, while the mechanism to 

explain the emergent product enantiomeric excesses observed 

could still not be elucidated. Based on ESI-MS measurements and 

time-resolved 1H-NMR studies we proposed the in situ formation 

of several side products, which could assist in enolate formation 

from the ketone, and, hence, promote the reaction. Our most 

recent results on reaction kinetics of this transformation using 1H NMR studies, which are evidence of an induction period of 

product formation, indicating involvement of an autoinductive or 

autocatalytic process, will also be discussed in this presentation. 

Keywords: Autocatalysis; Organocatalysis; Kinetics; Mannich 

bases; Reaction mechanisms; 

P - 0 3 2 6 

SyntheSiS of CyCLoProPAneS viA 

PhASe-trAnSfer CAtALySiS 

r. herChL 1 , M. wASer 1 




Three-membered ring systems like epoxides, aziridines, and 

cyclopropanes have attracted considerable interest in the scientific 

community over a long time. Their syntheses are usually either 

achieved starting from olefins or carbonyl compounds, 

respectively imines. Surprisingly, the phase-transfer catalyzed 

synthesis of (chiral) cyclopropanes has so far been described only 

occasionally, thus leaving space for further improvements. [1] 

Combining our recent research interests into the synthesis 

of three-membered ring systems [2] and the development of new 

chiral phase-transfer catalysts [3] we have started investigations 

concerning the synthesis of chiral cyclopropanes by reacting 

α-halo carbonyl nucleophiles with Michael acceptors in the 

presence of chiral phase-transfer catalysts. 

Initial attempts show promising results. A detailed discussion 

will be provided on the poster. 

references: 

1. a) Arai, K. Nakayama, T. Ishida and T. Shioiri, 

Tetrahedron Lett., 1999, 40, 4215-4218; 

b) S.I. Kozhushov, A. Leonov and A. de Meijere, 

Synthesis, 2003, 6, 956-958; 

c) C. Del Fiandra, L. Piras, F. Fini, P. Disetti, M. Moccia 

and M. Adamo, Chem. Commun., 2012, 48, 3863-3865. 

2. R. Herchl, M. Stiftinger and M. Waser, Org. Biomol. 

Chem., 2011, 9, 7023-7027. 

3. M. Waser, K. Gratzer, R. Herchl and N. Müller, Org. 

Biomol. Chem., 2012, 10, 251-254. 

Keywords: Phase-transfer catalysis; Asymmetric synthesis; 

Chirality; Michael addition; Cyclization; 



s1025 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 2 7 

SyntheSiS of ruSCozePine A And B, noveL 

nAturAL ProduCtS iSoLAted froM ButCher’S 

BrooM 

J. herrMAnn 1 , G. JürGenLieMK 2 , J. heiLMAnn 2 , 

B. KÖniG 1 



2 Institute of Pharmacy, Department of Chemistry and 


The novel natural products, Ruscozepine A and B, have been 

isolated from Ruscus aculeatus L., also called Butcher’s Broom. [1] 

An extract from the roots of this shrub is already used for the 

treatment of various diseases, including chronic venous 

insufficiency [2] and hemorrhoids. [3] The pharmacological activity 

is mostly ascribed to the steroidal saponins and ruscinogens, being 

the main constituents of the Rusci rhizoma extract. However, 

nothing is known about the influence on the pharmacological 

effects of the novel found Benzoxepines. Because of the low 

availability of these compounds by isolation, a synthetic approach 

was needed to guarantee the supply for extensive pharmacological 

testing. Beside the synthesis of the isolated compounds a few 

analogues substances, e. g. Benzazepines, are synthesized to 

create a small substance library. 

references: 

1. Barbic, M., Schmidt, T. J., Jürgenliemk, G., Novel 

Phenyl-1-benzoxepinols from Butcher’s Broom 

(Rusci rhizoma). Chemistry & Biodiversity in press, doi: 

10.1002/cbdv.201100158 

2. Abascal, K.; Yarnell, E., Botanicals for Chronic Venous 

Insufficiency. Alternative and Complementary Therapies 

2007, 13 (6), 304 - 311. 

3. MacKay, D., Hemorrhoids and varicose veins: a review of 

treatment options. Altern Med Rev 2001, 6 (2), 126-40. 

Keywords: Natural products; Enantioselectivity; Biological 

activity; Synthetic methods; 


P - 0 3 2 8 

ControLLed SyntheSiS of SMArt druG 

deLivery SySteM froM veGetABLe oiL 

L. heSPeL 1 , G. MorAndi 1 , L. LeCAMP 1 , f. BureL 1 

1 Institut national des sciences appliquée de Rouen, 

Seine-Maritime, Saint Etienne du Rouvray, France 

Email: louise.hespel@insa-rouen.fr 

Since liposomes were first described in the 1960s and 

proposed as carriers of proteins and drugs for disease treatment, 

they have been extensively studied and their efficiency as drug 

delivery systems has been demonstrated. [1] However liposomology 

still faces major deficiencies, partly due to their large size. [2] 

Developing new vectorisation systems of smaller size, typically 

micelles, but having the same affinity with cells membrane is then 

of great interest and our group is consequently interested in 

synthesis of amphiphilic block copolymers containing a 

hydrophobic block based on a lipid chain. In that purpose, an 

original synthetic pathway in two main steps was chosen: (1) the 

vegetable oil is first chemically modified to introduce an initiating 

site for Atom Transfer Radical Polymerization (ATRP) leading to 

a lipoinitiator and (2) a synthetic hydrophilic block is added to 

the lipid block using ATRP. 

The final amphiphilic copolymers are soluble in water, 

leading to uncolored and foaming solutions. The properties and 

structure of this innovating micellar system are studied. The 

micelles present low critical micelle concentrations with a strong 

dependence to the pH value and a linear dependence to the 

hydrophilic block length. The micelles ability to encapsulate 

hydrophobic molecules has been demonstrated and their release 

properties are currently under investigation as well the 

polymerization of other monomers to access “intelligent” systems. 

references: 

1. D. Lasic & D. Papahadjopoulos, Medical applications of 

liposomes, Amsterdam, 1998. 

2. Y. Barenholz Curr. Opin. Colloid Interface Sci. 2001, 6, 

66-77. 

Keywords: Drug delivery; amphiphiles; lipid; renewable 

resources; Polymers; 



s1026 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 2 9 

towArdS A LiGht driven Proton PuMP 

B. heSSeLer 1 , M. zindLer 1 , u. LüninG 1 

1 Otto-Diels-Institut, Organische Chemie, Kiel, Germany 

Light driven uphill transport of protons is an essential 

process in nature. In the photosynthetic apparatus, light energy is 

used to pump protons across a cell membrane. 

In our model system, the proton transfer is realized by a 

photo-switchable acid, such as 2-(2,4-dinitrobenzyl)pyridine 

(DNBP), attached to a [2]rotaxane. Upon irradiation, the 

photo-switchable acid tautomerizes to a more acidic form and 

protonates the macrocycle. Due to electrostatic repulsion with a 

permanent positive charge on the axle, the macrocycle moves 

along the axle. After the release of the proton, the macrocycle 

returns to the starting position. 

For the realization of this model system, several novel 

DNBP derivatives were successfully synthesized including the 

development of a new method to obtain di- and trinitrobenzyl 

substituted pyridine derivatives. [1] Furthermore, several axles 

and macrocycles [2] were synthesized and assembled to yield a 

[2]rotaxane. 

references: 

1. A. Frej, C. Goeschen, C. Näther, U. Lüning, R. Herges, 

J. Phys. Org. Chem. 2010, 23, 1093-1098. 

2. U. Lüning, E. Mak, M. Zindler, B. Hartkopf, R. Herges, 

Eur. J. Org. Chem. 2010, 4932-4940. 

Keywords: Supramolecular chemistry; Rotaxanes; Proton 

transport; 


P - 0 3 3 0 

SyntheSiS And ChArACteriSAtion of Proved 

And PotentiAL MetABoLiteS of MePhedrone 

M. hiML 1 , i. LinhArt 1 

1 Institute of Chemical Technology Prague, Department of 

Organic Chemistry, Prague 6, Czech Republic 

In recent years, a new class of designer drugs has appeared 

on the drug of abuse market in many countries. Global increase 

in the abuse of 4'-methylmethcathinone (mephedrone) and 

related compounds created a requirement for full chemical 

characterisation of these products and their metabolites. [1, 2] In this 

work we present full synthetic and chemical characterisation data 

for proved and potential metabolites of mephedrone. 

Starting from 1-(p-tolyl)propan-1-one [3,4] several 

mephedrone derivatives, mainly, 1-(4-(hydroxymethyl)phenyl)- 

-2-(methylamino)propan-1-one, 2-amino-1-(p-tolyl)propan-1-one, 

2-amino-1-(4-(hydroxymethyl)phenyl)propan-1-one, 2-amino-1- 

-(p-tolyl)propan-1-ol, 4-(1-hydroxy-2-(methylamino)propyl)benzoic 

acid and some others were prepared by step-by-step syntheses. 

All the above mentioned mephedrone metabolites were 

synthesised as hydrochloride salts and will be used as synthetic 

standards for metabolism studies. Reaction conditions as well as 

various possible synthetic approaches to mephedrone metabolites 


Acknowledgement: Financial support by grant VG2VS/200 

from the Ministry of Interior of the Czech Republic is gratefully 

acknowledged. 

references: 

1. Anal. Bioanal. Chem. (2010), 397, 1225–1233 

2. J. Pharmaceut. Biomed. Anal. (2011), 56, 246–255 

3. Tetrahedron: Asymmetry (2001), 12, 719–724 

4. Tetrahedron: Asymmetry (2001), 12, 3417–3422 

Keywords: mephedrone; metabolism; 



s1027 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 3 1 

MutinuCLeAr nMr StudieS of PoLyGLutAMiC 

ACid CoMPLexeS with MetAL ionS 

t. hirAoKi 1 , M. fuJie 1 

1 Hokkaido University Graduate School of Engineering, 

Department of Applied Physics, Sapporo, Japan 

The structures of poly(α-D-glutamic acid)(PGA) complexes 

with mono-, di- and tri-valent metal ions in solid state were 

characterized with multinuclear( 1H, 13C, 23Na, 25Mg, 27Al) NMR 

spectroscopy. Most of PGA complexes with di- and tri-valent 

metal ions take an α-helical conformation as judged from the 

chemical shift values of the main-chain carbon resonances in 

13C CPMAS NMR spectra, while PGA-Na shows the disordered 

state. Their helical content of the complexes, which were 

estimated from the line shapes of their resonances, was found to 

remarkably depend on their ionic radius used. The chemical shift 

value of the carboxylate carbon in the side chain participated in 

the complex depends on the ionic radius as well, suggesting the 

diversity of the distance between the carboxylate and the metal 

ion. 

13 1 C- H HETCOR NMR spectra were obtained to ensure the 

spatial information of the complexes through 1H spin-diffusion. 

The direct C-H correlation signals of the complex were observed 

for a short CP time, and further two- and three-bonds correlation 

signals were observed as well for longer CP time. The two bond 

correlation signal between NH and Cα in the main chain was 

observed at CP of 100us for helical complexes, while it was 

observed at longer CP of 500us for disordered PGA-Na, showing 

the structural difference between ordered(helical) and disordered 

conformation of polymers. 

A single and almost symmetrical resonance with the half 

width of 3.4 kHz was observed at -13.1 ppm in 25Mg MAS NMR 

spectrum for PGA-Mg. The main signal of the isotropic chemical 

shift of -3.8ppm and the quadrupole product of 1.6 MHz was 

appeared in 25Mg 3Q MAS NMR spectrum, as well as the minor 

signal of -0.2 ppm and 2.8 MHz, showing two distinct Mg 

bindings. Other results will be presented in the poster. 

Keywords: polyglutamic acid; metal complex; NMR; 


P - 0 3 3 2 

SyntheSiS of P-nitroPhenyL SS-d-GLyCoSideS 

of diSACChAride of hoMoxyLAn tyPe And 

triSACChAride of 4-o-MethyL- 

-GLuCuronoxyLAn tyPe 

J. hirSCh 1 , M. BAráth 1 , M. KooS 1 , P. BieLy 1 

1 Slovak Academy of Sciences, Institute of Chemistry, Bratislava, 


Synthesis of oligosaccharides related to hemicelluloses of 

xylan type has been developed mainly for characterization of the 

structural features, physicochemical and various functional 

properties of these natural polysaccharides. 

This contribution describes the synthesis of two model 

di- and trisaccharides of xylan type, namely p-nitrophenyl 

4-O-(2-O-benzyl-β-D-xylopyranosyl)-β-D-xylopyranoside (1) 

and p-nitrophenyl 4-O-[2-O-(methyl 4-O-methyl-α-D-gluco pyrano - 

syluronate)-β-D-xylo-pyranosyl]-β-D-xylopyranoside (2) in order 

to serve as the chromogenetic substrates for testing of xylanase 

belongs to the GH5 family. 

The starting point in the synthesis of disaccharide 1 was 

nucleophile p-nitrophenyl 2,3-di-O-benzoyl-β-D-xylopyranoside [1] 

which was coupled with 3,4-di-O-acetyl-2-O-benzyl- 

-α,β-D-xylopyranosyl acetimidate (prepared from 1,3,4-tri-O- 

-acetyl-2-O-benzyl-D-xylopyranose [2] ). The final disaccharide 1 

was obtained by deacylation of the isolated blocked disaccharide 

from the reaction mixture in a good yield. For preparation of 

model trisaccharide 2, related to 4-O-methylglucuronoxylan, the 

3,4-di-O-acetyl-2-O-(methyl 2,3-di-O-acetyl-4-O-methyl-α-D- 

-glucopyranosyluronate)-α,β-D-xylopyranosyl acetimidate [3] 

was used as a glycosylating agent in a coupling reaction 

with p-nitrophenyl 2,3-di-O-benzoyl-β-D-xylopyranoside. The 

protected trisaccharide isolated by chromatography after 

deacylation gave aimed 2 in a satisfactory yield. The structure of 

both model oligosaccharides 1 and 2 and also their precursors was 

confirmed by NMR spectroscopy. 

Acknowledgments: This work was supported by the grants 

VEGA No. 2/0101/11 and 1/0962/12; Centre of Excellence- 

GLYCOMED and Centre of Excellence for Glycomics ITMS 

26240120031, supported by the Research&Development 

Operational Programme funded by the ERDF 

references: 

1. Takeo, K.; Ohguchi, Y.; Hasegawa, R.; Kitamura, S.: 

Carbohydr. Res. 1995, 277, 231 

2. Kovác, P.; Palovcík, R.: Chem. Zvesti 1977, 31, 98 

3. Hirsch, J.; Koó‰, M.; Kovác, P.: Carbohydr. Res. 1998, 

310, 145 

Keywords: oligosaccharides; synthesis; p-nitrophenyl 

glycoside; chromogenetic substrate; 



s1028 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 3 3 

CoMBinAtoriAL SyntheSiS, SCreeninG And 

PhotodeGrAdAtion of PhoSPhoreSCent 

MetAL CoMPLexeS for oLedS. 

A. hohenLeutner 1 , S. SChMidBAuer 1 , r. vASoLd 1 , 

B. KÖniG 1 



While there have been thousands of reported transition metal 

complexes for OLED applications in the last decade, an accurate 

prediction of their photophysical properties and especially their 

device stabilities/degradation mechanisms is not yet feasible. 

Therefore the laborious synthesis, purification characterization 

and testing of a larger number of compounds is still inevitable for 

the development of new phosphorescent emitters with improved 

performances. 

We report the combinatorial synthesis and screening of 

phosphorescent iridium complexes as solution processable 

emitters for OLEDs. Our approach allows for the rapid library 

synthesis, as well as the isolation, spectroscopic characterization 

and identification of the compounds based on chromatographic 

methods. Subsequent analysis of the irradiation induced 

degradation provides insight on the stability of the complexes 

under continuous excitation. Utilizing the developed screening 

methodology we purified and characterized a larger number of 

potential emitters. We examined the photophysical properties of 

the compounds by obtaining absorption and emission spectra 

directly from the chromatographic separation. Important trends in 

the dual emission behavior of selected heteroleptic complexes 

were observed that upon further studies might lead to the 

development of promising new compounds for white OLEDs. By 

investigating the photodegradation of the libraries in solution, we 

found surprising trends and could identify compounds with 

increased stabilities compared to the rest of the libraries. Further 

studies into degradation mechanisms and to elucidate possible 

connections between the device- and photo-stabilities are in 

progress. The gained insight into degradation mechanisms and 

structure property relationships will help in the design of 

phosphorescent dopants with improved performances. The 

reported chromatography based screening of organo-transition 

metal complexes is by no means restricted to the development of 

new OLED emitters but may be easily applied for the accelerated 

discovery of other metal complexes or organic dyes for various 

applications, e.g. in electroluminescence, photovoltaics and 

sensing. 

Keywords: Phosphorescence; combinatorial synthesis; Iridium 

Complexes; Screening; Oled; 


P - 0 3 3 4 

Photoswitchable Monolayers: A dynamic Control over Cell 

Adhesion 

M. hoLz 1 

1 Otto-Diels-Institut für Organische Chemie, 

Organic Chemistry, Kiel, Germany 

Photoswitchable monolayers of azobenzene derivatives 

mounted on glass, quartz or silicon surfaces offer an effective 

control over cell adhesion. The light induced reversible 

cis-/trans-isomerization of azobenzenes permits a precise 

temporal and spatial control of surface properties. 

We employed three strategies: 

1. Switching of wettability 

Upon isomerization of the azobenzene derivative, the 

surface wettability changes due to different dipole moments of 

the azobenzene isomers. This is especially the case when using 

polar head groups. 

2. fast oscillations 

Upon irradiation with white light, azobenzenes with 

push/pull substitution patterns are known to undergo a fast 

continuous switching between their cis- and trans-isomers. [1] 

We intend to utilize this effect to create a fast oscillating 

monolayer on surfaces. 

3. integrin mediated adhesion 

The establishment of an arginine-glycine-aspartate (RGD) 

tripeptide squence cell binding domain on surfaces offers the 

opportunity to target specific integrins of cells. We have chosen 

the c(-RGDfK-) peptide [2] as our future head group for this 

purpose, due to its specific binding to α β integrin. 

v 3 

references: 

1. T. Asano J. Am. Chem. Soc. 1980, 102, 1205; S. Hvilsted 

et al. J. Mater. Chem. 2009, 19, 6641; B. Schmidt et al. 

J. Phys. Chem. A. 2004, 108, 4399. 

2. R. Haubner et al. J. Am. Chem. Soc. 1996, 118, 7461. 

Keywords: Cell Adhesion; azobenzene; monolayers on glass; 

photoswitchable monolayers; 



s1029 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 3 5 

SyntheSiS of tri- And tetrASuBStituAted 

Benzene derivAtiveS orGAnoCAtALytiCALLy 

d. v. horvAth 1 , r. ferenCzi-PALKo 1 , t. SooS 1 

1 Research Centre for Natural Sciences Hungarian Academy of 

Sciences, Institute of Organic Chemistry, Budapest, Hungary 

Organocatalysis is a new, environmentally friendly synthetic 

approach in organic chemistry. In this method, small organic 

molecules are utilized to realize selective reactions. A frequent 

application is the use of different organic basis in Michael-type 

additions. 

Recently, we have initiated a program to tandem reaction 

between appropriate dielectrophiles and dinucleophiles to 

synthesize even highly substituated aromatic molecules, which 

difficult to obtain. 

Therefore the dimethylglutaconate, as a dinucleophile, was 

reacted with different α,β-unsaturated aldehydes and ketons. The 

first step is a Michael-addition, subsequently followed by a 

condensation. The formed cyclohexadienes could be easily 

oxidized to the desired benzene derivatives. 

We have examined whether this synthesis route is possible 

without any transition metal, from simple and cheap starting 

materials using also easily prepared, cost effective catalysts under 

mild conditions. 

We would like to present on the poster the development of 

the organocatalytic process, the optimalization of the conditions 

and some possible applications. 

Keywords: organocatalysis; Michael addition; cyclization; 

oxidation; 


P - 0 3 3 6 

SyntheSiS And BioLoGiCAL evALuAtion of 

ferroCenyL-iMonuSuGArS AS fuCoSidASe 

inhiBitorS for AntiCAnCer therAPy 

A. hottin 1 , J. B. Behr 1 

1 Institut de Chimie Moléculaire de Reims, UMR 7312, Reims, 

France 

Glycosylation affects many properties of glycoproteins, 

including their conformation, flexibility and hydrophobicity. As 

a result, it regulates proteins sorting, stability and protein-host 

interactions. Fucosylation of glycoconjugates in mammalian 

organisms is related to a variety of biological processes including 

cell adhesion, blood antigens and severe diseases like cancer 

metastasis. [1] Fucosylation of glycoproteins is mainly assumed by 

two classes of enzymes, fucosidases and fucosyltransferases, the 

activities of which are markedly enhanced in several types of 

cancer cell lines. [2] 

New drugs aimed at controlling the processing of fucose 

(fucosidase inhibitors) could selectively target abnormal cells. 

Moreover, the structural combination with a covalently linked 

cytotoxic moiety (ie ferrocene) could induce a strong antitumoral 

activity. [3] Iminosugars (nitrogen-containing sugar analogues) are 

potent inhibitors of fucosidase with Ki’s in the nM range. [4] These 

alkaloids compare favourably with the natural substrate of 

enzyme in terms of conformation and hydroxyl distribution. 

Thus, we targeted unprecedented ferrocenyl-iminosugars as first 

models for our study. The synthesis, the biologic results and the 

structure / activity relationships of a series of such compounds 


references: 

1. R. G. Spiro Glycobiology 2002, 12, 43R–56R. 

2. D. Ayude, J. Fernandez-Rodriguez, F ; J. Rodriguez-Berrocal, 

V. S. Martinez-Zorzano, A. de Carlos, E. Gil, 

M. P. de la Cadena Oncology 2000, 59, 310–316. 

3. a) M. F. R. Fouda, M. M. Abd-Elzaher, R. A. Abdelsamaia, 

A. A. Labib Applied Organomet. Chem. 2007, 21, 

613–625. 

b) G. Jaouen et coll. Chem. Commun. 2010, 5145–5147. 

4. A. Kotland, F. Accadbled, K. Robeyns, J.-B. Behr J. Org. 

Chem. 2011, 76, 4094–4098. 

Keywords: cancer; inhibitors; carbohydrate; 



s1030 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 3 7 

ACtivAtion of A CArBon-BroMine Bond By 

hALoGen-Bond donorS 

S. huBer 1 , S. wALter 1 , f. KnieP 1 , e. herdtweCK 1 

1 Technische Universität München, Department Chemie, 

Garching bei Muenchen, Germany 

Halogen bonds are attractive non-covalent interactions 

between terminal halogen atoms in compounds of type R-X 

(X =Cl, Br, I) and Lewis bases. [1] Strong halogen bonds are only 

obtained for very electronegative rests R. The interaction has 

mostly been studied in the solid state, and in contrast to the 

ubiquitous and much more common hydrogen bonds, very few 

applications in solution have been reported. More specifically, 

despite the various analogies between hydrogen bonds and 

halogen bonds, use of the latter in organocatalysis has only been 

reported for one case, namely the reduction of quinoline 

derivatives. [2] 

The aim of our investigations is to develop applications for 

halogen bonds in organic synthesis and organocatalysis. A special 

focus of our research efforts is on the rational design of novel 

multidentate halogen bond donors (i.e., Lewis acids) R-X. 

Since it is well known that halides as Lewis bases form 

strong halogen bonds in the solid state, we sought to use strong 

halogen bond donors for the abstraction of halide leaving groups 

from organic substrates. Recently we could demonstrate that 

certain dicationic halogen bond donors are able to activate the 

carbon-bromine bond of benzhydryl bromide and related 

substrates. [3] The bidentate halogen bond donors employed are 

based on iodoimidazolium groups and can be prepared easily and 

in high yield. In comparative experiments with non-iodinated 

reference compounds as well as with Broensted acids, strong 

indications were obtained that the activation of the carbon-bromine 

bond can indeed be ascribed to halogen bonding. 

references: 

1. Review: P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, 

G. Terraneo, Angew. Chem. Int. Ed. 2008, 47, 6114. 

2. A. Bruckmann, M. A. Pena, C. Bolm, Synlett 2008, 900. 

3. S. M. Walter, F. Kniep, E. Herdtweck, S. M. Huber, 


Keywords: Halogens; Noncovalent interactions; Solvolysis; 

Synthetic methods; 


P - 0 3 3 8 

SeLf-ASSeMBLy of PoLynuCLeAr 

SuPrAMoLeCuLAr MetAL-CoMPLexeS 

ContAininG Pyridine-LiGAndS 

S. hytteBALLe 1 , t. PiehLer 1 , r. hovorKA 1 , 

A. Lützen 1 

1 Kekulé Institute, Kekulé Institute, Bonn, Germany 

Self-assembly, a concept often seen in nature has become a 

useful strategy to form metallosupramolecular assemblies, ranging 

from simple helices to large ball-shaped cavities. These 

complexes can even find application as molecular reaction 

vessels. [1] 

Through several synthetic steps we have synthesized ligands 

with pyridine as the metal-binding unit, e.g. 9,9'-spirobifluorene- 

-based ligands [2] and ligands containing two different metal-binding 

units, which are able to form discrete complexes with different 

metal-ions through self-assembly. These form homonuclear 

helices or heteronuclear trigonal bipyramids, respectively, when 

combined with suitable metal-ions. 

references: 

1. a) F. Hof, S.L. Craig, C. Nuckolls, J. Rebek, Jr., Angew. 

Chem. 2002, 114, 1556-1578; 

b) M. Yoshizawa, J. K. Klosterman, M. Fujita, Angew. 

Chem. 2009, 121, 1370-1390. 

2. T. Piehler, A. Lützen, Z. Naturforsch. 2010, 65b, 329-336, 

F. Thiemann, T. Piehler, W. Saak, D. Haase, A. Lützen, 

Eur. J. Org. Chem. 2005, 1991-2001 

Keywords: supramolecular chemistry; self-assembly; 

metal-organic frameworks; 



s1031 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 3 9 

hiGhLy fLuoreSCent PentACyCLiC 

frAMeworK throuGh A CASCAde ProCeSS 

z. e. A. ChAMAS 1 , v. MAMAne 1 , y. fort 1 

1 Universite De Lorraine, Organic Chemistry, Vandoeuvre les 

Nancy, France 

This presentation describes the synthesis of a new family of 

pentacyclic chromophore whose fluorescence properties can be 

modulated according to the functional groups present in the 

molecule. These chromophores were obtained through 

a cascade reaction between 2-formylbenzene boronic acid and 

2,5-dihalopyridines. The cascade process was initiated by a 

palladium-catalyzed cross-coupling reaction and was followed by 

two successive nucleophilic cyclizations; the first cyclization 

performed on the pyridine nitrogen and the second occurred 

regioselectively on the adjacent carbon atom. This new cascade 

reaction allowed the formation of a pentacycle as a single 

regioisomer with four new bonds and two contiguous 

stereocenters with trans relationships. In addition, preliminary 

studies have shown that these polycyclic compounds have 

excellent fluorescence properties that should enable us to extend 

the scope of these new chromophores to the medical field and 

molecular electronics. 

Keywords: Chromophores; Diastereoselectivity; Fluorescence; 

Nitrogen heterocycles; Fused-ring systems; 

P - 0 3 4 0 

heteroGeneouS PhotoCAtALySiS in orGAniC 

SyntheSiS. 

M. CherevAtSKAyA 1 , M. neuMAnn 1 , S. fueLdner 1 , 

C. hArLAnder 1 , S. KueMMeL 1 , S. dAnKeSreiter 2 , 

A. Pfitzner 2 , K. zeitLer 1 , B. KoeniG 1 

1 University of Regensburg, Organic Chemistry, Regensburg, 

Germany 

2 University of Regensburg, Inorganic Chemistry, Regensburg, 

Germany 

Visible light photocatalysis is a topic of increasing interest 

for many applications. One way of utilizing the visible range of 

the solar spectra is the combination of organo- an photoredox 

catalysis as pioneered by MacMillan [1a] . Using MacMillan’s 

catalyst in conjunction with inorganic semiconductors as 

sensitizers, we have investigated the asymmetric C-C coupling of 

octanal with different bromo-substrates [1] . 

The range of investigated semiconductors includes the 

well-known blank TiO (P25), dye-sensitized TiO (1) as well as 

2 2 

novel PbBiO Br semiconductors. The PbBiO Br semiconductor 

2 2 

was used in two modifications – nanoparticles and bulk material, 

which have band gaps of 2.56 eV and 2.47 eV, respectively and 

can be irradiated with 440 nm LEDs. TiO was sensitized by the 

2 

Phos-Texas Red dye, which was immobilized on the surface and 

showed an absorption maximum at 560 nm. 

The products could be obtained in good to very good yields 

of up to 84 % (PbBiO Br nano/2-bromodiethylmalonate) and 

2 

with excellent enantioselectivities of up to 96% (PbBiO Br 2 

nano/bromoacetophenon) [2] . 

Other C-C bond formation reactions are under investigations 

in our group. 

Acknowledgement: Financial support: DFG: 

GRK 1626 – Chemical Photocatalysis. 


references: 

1. a) D. A. Nicewicz; D. W. C. MacMillan, Science 2008, 

322, 77; 

b) H. Shih, M. N. Vander Wal, R. L. Grange, 

D. W. C. MacMillan, J. Am. Chem. Soc. 2010, 132, 13600; 

2. M. Cherevatskaya, M. Neumann, S. Fueldner, C. Harlander, 

S. Kuemmel, S. Dankesreiter, A. Pfitzner, K. Zeitler, 

B. Koenig, Angew. Chemie Int. Ed., 2012, in press. 

Keywords: heterogeneous photocatalysis; visible-light 

photocatalysis; 



s1032 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 4 1 

ContinuouS MetAtheSiS under 

Liquid-Liquid ConditionS uSinG A diCAtioniC 

ru-ALKyLidene in MonoLith-SuPPorted ioniC 

LiquidS 

B. Autenrieth 1 , w. frey 2 , M. r. BuChMeiSer 1 

1 Stuttgart University, Institute of Polymer Chemistry, Stuttgart, 

Germany 

2 Stuttgart University, Institute of Organic Chemistry, Stuttgart, 

Germany 

Supported ionic liquid phase (SILP) catalysis has proven 

valid for various reactions7 [1] . There, the catalyst is immobilized 

within a thin layer of an ionic liquid, which is coating a highly 

porous support material. We have developed a catalytic system 

for continuous metathesis-reactions, based on porous ROMPderived 

polymeric monoliths, whose structures can be varied 

precisely with high reproducibility [2] . Following, the monoliths` 

surface was functionalized by grafting an ammonium-based 

monomer. Hereupon thin layers of the ionic liquid [BDMIM + BF4- ] were immobilized which contained the novel dicationic 

Ru-alkylidene complex [Ru(DMF) (IMesH )(=CH-2-(2-PrO)- 

3 2 

-C H )] 6 4 2+ (BF4- ) ]. Beside the primary objective to gain 

2 

catalyst-free products, our concept enables continuous product 

formation using two liquid phases, i.e. one supported and a second 

continuous one, simply by cycling reactants through a monolithic 

support containing a suitable catalyst dissolved in an ionic liquid. 

Our catalytic system has proven valid for several biphasic (l-l), 

continuous metathesis reactions at a multitude of different flow 

rates and temperatures. For instance, the ring-closing-metathesis 

(RCM) of neat 1,7-octadiene as well as the RCM of N,N-diallyl 

trifluoroacetamide and diethyl diallyl malonate where heptane 

served as non-polar mobile phase, have been investigated in 

detail. Furthermore, the system was applied to the self-metathesis 

of methyl oleate. High turnover numbers and an exceptionally low 

catalyst leaching (≤ 0.1% with respect to the initial amount of 

catalyst present in the IL phase) were observed. The fact, that a 

biphasic liquid/liquid system is used definitely widens the range 

of potentially accessible substrates. Moreover, the facile recycling 

of the monolithic support by flushing with, e.g., methanol, 

represents an additional advantage [3] . 

references: 

1. P. Wasserscheid, W. Keim, Angew. Chem. 2000, 112, 3926; 

A. Riisager, R. Fehrmann, M. Haumann, P. Wasserscheid, 

Topics Catal. 2006, 40, 91. 

2. E. B. Anderson, M. R. Buchmeiser, ChemCatChem. 2012, 

4, 30-44. 

3. B. Autenrieth, W. Frey, M. R. Buchmeiser, submitted 2012. 

Keywords: Metathesis; Ruthenium; Immobilization; 

Mesoporous materials; Ionic liquids; 


P - 0 3 4 2 

ShAPe-PerSiStent LineAr, KinKed, 

And CyCLiC oLiGo(PhenyLene-ethynyLene- 

-ButAdiynyLene)S: SeLf-ASSeMBLed 

MonoLAyerS 

A. ideLSon 1 , S. S. JeSter 1 , d. SChMitz 1 , 

f. eBerhAGen 1 , S. hÖGer 1 

1 Rheinische Friedrich-Wilhelms-Universität Bonn, Kekulé- 

Institut für Organische Chemie und Biochemie, Bonn, 

Germany 

Self-assembled monolayers (SAMs) of rigid oligomers, 

particularly phenylene-ethynylene-butadiynylenes at the 

HOPG/TCB interface, are studied by scanning tunneling 

microscopy (STM) with submolecular resolution. Substitution of 

the terminating acetylene functions of the linear oligomers with 

polar 3-cyanopropyl dimethyl silyl groups leads to a 2D phase 

separation and defined rod-rod interactions, which determine the 

packing distances between the rigid rods. The results stimulated 

the connection of rigid rods via septiarylene clamp units. They 

covalently link two rigid rod units and define the intramolecular 

rod-rod distance that matches the alkoxy substituent chain lengths. 

The systems can be described as half-ring structures of two rigid 

rods that are connected via a rotatable joint unit. These 

acetylene-terminated half-ring structures are also oligomerized 

under Cu and Pd catalysis to yield defined acyclic and cyclic 

oligomers. Detailed STM studies decode the molecular origin of 

the surface patterning of such systems. The dodecyloxy side 

chains are adsorbed along the HOPG main axes and, together with 

the alkoxy backbone angle, determine the adsorption direction of 

the adlayers. 

references: 

1. S.-S. Jester, A. Idelson, D. Schmitz, F. Eberhagen, S. Höger, 

Langmuir 2011, 27, 8205. 

2. S.-S. Jester, N. Shabelina, S. M. Le Blanc, S. Höger, 


Keywords: self-assembled monolayers; scanning tunneling 

microscopy; shape-persistent molecules; solid/liquid interface; 

freely rotating chains; 



s1033 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 4 3 

new diMerS of Benzene triAMide for hiGh 

orGAnizAtion in Liquid CryStAL MeSoPhASeS 

C. invernizzi 1 , r. neier 1 

1 University of Neuchatel, Department of Chemistry, Neuchatel, 

Switzerland 

Discotic Liquid Crystals (DLc’s) are well known in the field 

of organic materials [1] , due to their interesting properties like 1D 

charge transport [2, 3] . Reducing the degree of freedom by making 

dimers has been shown to increase the conductivity [4] . Our aim is 

to use an aromatic linker as a probe to study the intermolecular 

self-assembly. The synthesis of the discogenic monomeric 

precursor was completed, showing mesomorphic proprieties. 

Our attention is now focused on the design and screening of 

different types of aromatic linkers, in order to provide a rational 

understanding of the self-assembly in a discotic liquid crystal 

systems. 

references: 

1. Müllen. K., Science, 2001, 293, 1119 

2. Destrade, C.; Mondom, M.C.; Malthete, J.;J. de Physique, 

1979, C3 ; 17 

3. Laschat, S., et al., Angew. Chem. Int. Ed. 2007, 46, 4832 

4. Kumar, S., Liq. Cryst., 2005, 32, 108 

Keywords: Liquid Crystals; Materials scienc; Self-assembl; 

Dimerization; Hydrogen bond; 


P - 0 3 4 4 

red LiGht eMittinG SySteM BASed on 

AGGreGAtion of donor-ACCePtor dyeS in 

PoLAr wAter MediA 

t. iShi-i 1 

1 Kurume National College of Technology, Department of 

Biochemistry and Applied Chemistry, Kurume, Japan 

Red light emitting dyes have been of interest in view of their 

application as biological materials such as bioprobes and 

biosensors, because the red light emision is visible to the naked 

eye in an optical window. One of the simple strategies for the 

creation of the red light emitting dyes is based on a combination 

of electron-donor and electron-acceptor moieties. However, in a 

polar water system, the red light emission is quenched 

significantly by solvation of the polar water molecules. We have 

thought that the solvation-induced quenching can be restricted by 

the self-assembled aggregation of the donor-acceptor molecules. 

In this study, we have demonstrated that the strategy actually 

worked for a series of triphenylamine-benzothiadiazole 

donor-acceptor molecules. In a THF/water mixture solution, the 

red light emission was quenched by the solvation in a low water 

volume. In contrast, in a high water volume, the red light emission 

was recovered and enhanced upon the aggregate formation of the 

donor-acceptor molecules; a high quantum yield up to 0.8 was 

achieved. The present emissive aggregate system worked even at 

the low concentration of 1 × 10-10 M. The strong red light emission 

is attributed to the restriction of the solvation-induced quenching, 

because the inside of the formed aggregates is less polar than that 

of the outside. The red light emitting aggregates were 

characterized by absorption and fluorescence spectroscopy, 

dynamic light scattering, atomic force microscopy, and X-ray 

diffraction analyses. The present result will provide a new strategy 

for the creation of a red light emitting aggregate system based on 

the simple combination of an electron-accepting core and 

electron-donating amino moieties. 

Keywords: emission; aggregation; donor-acceptor; 



s1034 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 4 5 


Side-ChAin oxAzoLine-Styrene CoPoLyMerS 

BeArinG PhotoreSPonSive Azo-dye 

f. A. JerCA 1 , M. C. SPiridon 2 , v. v. JerCA 2 , 

d. M. vuLuGA 2 , G. StinGA 3 , d. f. AnGheL 3 , 

d. S. vASiLeSCu 4 

1 “Ilie Murgulescu” Institute of Physical Chemistry, Colloid 

Department, 060021 Bucharest, Romania 

2 Centre for Organic Chemistry Costin D. Nenitescu, Polymer 




4 University “POLITEHNICA” of Bucharest, Department of 

Polymer Science, 010072 Bucharest, Romania 

The importance given to azo-polymers, in the last two 

decades or so, it is mainly because of azobenzene reversible 

trans-cis photoisomerization that enables to control changes over 

a variety of properties by means of light as an external stimulus [1] . 

Therefore, azo-polymers can be used in many interesting 

applications, varying from optical components and lithography to 

sensors and smart materials [2] . Each application asks for specific 

requirements. Hence, the type of polymer matrix and azo-dye, 

chromophore load and nature of bonding to the polymer matrix 

must be well-chosen and optimized [3] . 

This paper depicts the synthesis and characterization of new 

polymeric structures, in which a side-chain azo-moiety was 

attached on poly(oxazoline) and poly(oxazoline-co-styrene)s by 

ring-opening addition of dye’s carboxyl group to the oxazoline 

cycle. The UV spectroscopy confirmed the quantitative addition 

of 4-((4(diethylamino)phenyl) diazenyl) benzoic acid to the 

oxazoline rings. The composition of products was controlled 

through co-monomers feed ratio, and estimated by means of 

1H-NMR spectroscopy and elemental analysis. Furthermore, a 

kinetic treatment using an integral method, revealed statistical 

copolymerization tendency of 2-isopropenyl-2-oxazoline with 

styrene in dichlorobenzene at 65°C. Both the substrates and 

azo-polymers exhibited good thermal stabilities and glass 

transition temperatures. 

Aknowledgements: This work was supported by a grant 

of Romanian National Authority for Scientific Research, 

CNCS–UEFISCDI, project number PN-II-RU-PD-2011-3-0063; 

and by Sectoral Operational Programme Human Resources 

Development 2007-2013 of Romanian Ministry of Labour, Family 

and Social Protection through the Financial Agreement 

POSDRU/107/1.5/S/76903. 

references: 

1. Zhao Y., Ikeda T., Smart Light-Responsive Materials, 

2009, John Wiley & Sons, Hoboken. 

2. Yesodha S.K., Pillai C.K.S., Tsutsumi N., Progress in 

Polymer Science, 2004, 29:45-74. 

3. Jerca V.V., Nicolescu F.A., Baran A., Anghel D.F., 

Vasilescu D.S., Vuluga D.M., React.&Funct. Polymers, 

2010, 70:827-835. 

Keywords: 2-oxazolines; azobenzene; polymer; cis-trans 

isomerization; photoresponsive behavior; 


P - 0 3 4 6 

iSoMerizAtion KinetiCS 

of 2,4-SuBStituted AzoBenzeneS 

And reLAted Azo-PoLyMethACryLAteS 

f. A. JerCA 1 , v. v. JerCA 2 , d. M. vuLuGA 2 , G. StinGA 3 , 

d. f. AnGheL 3 



2 Centre for Organic Chemistry Costin D. Nenitescu, Polymer 




The trans-cis-trans photo-isomerization of azobenzenes 

containing-polymers allows fine-tuning of the optical response 

for holographic memories [1] , optical storage data [2] , or actuators [3] . 

Considerable research has gone into elongating the cis lifetime, 

with the goal of creating bistable photoswitchable systems. 

Depending on the substitution pattern and local environment, the 

electronic push and pull structures, such as pseudo-stilbenes and 

aminoazobenzenes can isomerize from cis configuration back into 

transconfiguration very quickly at room temperature. However, 

the thermal cis-trans isomerization in azobenzene-type molecules 

is relatively slow, and it is even possible to elongate the cis isomer 

lifetime to years, if bulky substituents are introduced to hinder the 

thermal relaxation [4] . Understanding the relationship between 

molecular structure and photo-responsive behavior represents one 

of the most important issues in order to gain control over the 

response time. 

In this paper, the trans-cis-trans isomerization kinetics of 

four 2,4-nitro/cyan substituted azobenzenes and related 

poly(methyl methacrylate) copolymers (having the azobenzene 

moiety in the side-chain) [5] , is carried out through UV-Vis and 1H NMR spectroscopy. Different isomerization behaviour is 

evidenced due to particular substitution pattern of each 

azobenzene derivative. 

Aknowledgements: The present work was supported by a 

grant of the Romanian National Authority for Scientific Research, 

CNCS–UEFISCDI, project number PN-II-RU-PD-2011-3-0063. 

references: 

1. T. Endo, H. K. Kim, X. S. Wang, Y. Fujita, A. Sudo, 

H. Nishida, M. Fujii, Macromol. Chem. Phys. 2005, 206, 

2106. 

2. M. Hackel, L. Kador, D. Kropp, H. W. Schmidt, Adv. 

Mater. 2007, 19, 227–231. 

3. S. Kurihara, M. Z. Alam, T. Ohmachi, T. Ogata, T. Nonaka, 

Opt. Mater. 2006, 29, 365. 

4. Y. Zhao, T. Ikeda, Smart Light-Responsive Materials, 

John Wiley & Sons, Hoboken, 2009. 

5. F. A. Nicolescu, V. V. Jerca, D. M. Vuluga, D. S. Vasilescu, 

Polym. Bull. (Berlin) 2010, 65, 905. 

Keywords: azobenzene; isomerization; polymers; NLO; 



s1035 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 4 7 

SyntheSiS of Steroid-triLoBoLide CLiCKAteS 

for BioLoGiCAL StudieS 

M. JuráSeK 1 , P. drASAr 1 , J. hArMAthA 2 

1 Institute of Chemical Technology in Prague, Chemistry of 

Natural Compounds, Prague 6, Czech Republic 

2 Institute of Organic Chemistry and Biochemistry, Chemistry of 


In this contribution synthesis of short series of conjugated 

natural products concerned to steroids and trilobolide (TB) is 

described. Trilobolide is a sesquiterpene lactone which was 

previously found to have an inhibition activity of 

sarco/endoplasmic reticulum Ca2+ -ATPase (SERCA). Also, it 

has been demonstrated that TB can serve as an 

immunostimulatory agent. Estradiol, testosterone, pregnendiol 

and dihydroxyandrosten were used as motive of steroidal 

moiety. These steroids as relatively lipophilic compounds may 

modify its biological availability and transport, moreover, 

fundamental steroidal skeletons are recognized by nuclear 

receptors in the nucleus of the cell. In this work TB is transformed 

at C-6 position to 5-azidovalerate. This structure serve as a 

building block for successive click reaction with ethynylated 

steroids. For comparison, steroids were also clicked with 

5-azidovaleric acid to give corresponding trilobolide attached 

moieties. These compounds are now given for biological screens 

and tests to give new information about general behavior of such 

compounds. 

Keywords: trilobolide; steroids; click chemistry; 


P - 0 3 4 8 

Anion BindinG ProPertieS of A SALoPhen zinC 

CheLAte / BiLe ACid ConJuGAte inCorPorAted 

into CtABr MiCeLLeS 

o. JurCeK 1 , M. CAMetti 2 , e. KoLehMAinen 1 , 

K. riSSAnen 1 


Finland 

2 Politecnico di Milano, Department of Chemistry, Milano, Italy 

Metal complexes are excellent Lewis acidic binding sites for 

anions. In particular, Salophen-Metal complexes are extensively 

studied species, which have been successfully employed as 

receptors, catalysts, and carriers. [1] Bile acids are amphiphilic 

molecules found in the bile of mammals. They play many 

important biological functions, as in the metabolism of lipids for 

their ability to form mixed micelles, which interact with lipid 

bilayers of biological membranes and mediate transport of 

lipophilic compounds through the intestinal membrane. [2] 

We envisaged that, by combining the above described two 

structural units into one single entity, we could obtain 

a Metal-Salophen / Bile Acid conjugate possessing novel 

properties in terms of anion binding and transport. 1H NMR and 

UV-vis studies demonstrate that the Zn-chelate, 1, binds anions 

in DMSO, but the addition of 10% water severely hampers the 

binding. More importantly, the bile acid moieties in 1 render it 

capable of being incorporated into CTAB micelles. Using CTABr 

micelles as carriers for anion receptors is indeed a convenient way 

to test their anion binding properties in water. [3] Under such 

conditions, 1 is able to bind phosphate with a relatively high 

affinity (K ca. 500 M-1 ). TEM microscopy and Dynamic Light 

Scattering studies highlight the influence that 1 and anions have 

on the size and shape of the CTABr micelles. These are important 

aspects that must be considered to fully evaluate the binding 

properties of the Zn-chelate / CTABr supramolecular system 

which resulted in being an efficient anion binder in the highly 

competitive water medium. 

references: 

1. Dalla Cort A., Bernardin De P., Forte G., Mihan Yefteh F., 

Chem. Soc. Rev. 2010, 39, 3863. 

2. Virtanen E., Kolehmainen E., Eur. J. Org. Chem. 2004, 16, 

3385. 

3. Cametti M., Dalla Cort A., Bartik K., ChemPhysChem 

2008, 15, 2168. 

Keywords: micelles; click chemistry; anions; UV/Vis 

spectroscopy; Steroids; 



s1036 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 4 9 

reCyCLABLe PoLyMer-CoAted MAGnetiC 

nAnoBeAdS 

q. M. KAinz 1 , w. J. StArK 2 , P. r. hAnSon 3 , o. reiSer 1 



2 Institute for Chemical and Bioengineering, Department of 

Chemistry and Applied Biosciences, Zürich, Switzerland 


Lawrence, USA 

Chromatographic purification often is the limiting part of 

library syntheses and industrial high throughput processes due to 

high consumption of time and solvents. In order to avoid this 

bottleneck, polymer based reagents and scavengers have been 

developed, which enable easier purification through filtration. [1] 

However, filtration systems often suffer from membrane fouling 

and require energy-intensive pumping. As an alternative, highly 

magnetic nanoparticles combine high surface area with the benefit 

of agitation and separation via an external magnetic field. [2] 

Carbon coated cobalt and iron nanobeads were functionalized 

with norbornene tags followed by activation with Grubbs 

2nd generation catalyst and subsequent grafting of 

N-hydroxysuccinimide ROMPgels on the surface. [3] This approach 

allowed an easy tuning of the polymer by variation of the amount 

of monomer. The high loading hybrid magnetic material 

(2–3 mmol/g) was then applied in the acylation of various amines. 

Rapid and operationally simple magnetic decantation resulted in 

pure products with high yields. The nanoparticles were efficiently 

reused in more than five consecutive cycles. 

Alternatively, Co/C and Fe/C nanoparticles with a high 

loading of benzylchloride moieties were synthesized via radical 

polymerization on the surface of the nanomagnets. 

A “click”-reaction was utilized to tether cyclen azamacrocycles 

to the polymer coated nanobeads followed by complexation with 

zinc(II). Complete extraction of riboflavin (vitamin B2) from 

aqueous solutions and a commercial vitamin tablet at pH 7.4 and 

subsequent release at pH 3.6 was achieved for more than five 

consecutive cycles without considerable loss of activity. 

references: 

1. Kirschning, A.; Monenschein, H.; Wittenberg, R. 


2. Grass, R. N.; Athanassiou, E. K.; Stark, W. J. 

Angew. Chem. 2007, 119, 4996-4999. 

3. Maity, P. K.; Kainz, Q. M.; Faisal, S.; Rolfe, A.; 

Samarakoon, T. B.; Basha, F. Z.; Reiser, O.; Hanson, P. R. 

Chem. Commun. 2011, 47, 12524-12526. 

Keywords: Nanoparticles; Magnetic properties; Polymers; 

Acylation; Analytical methods; 


P - 0 3 5 0 

SyntheSiS of iLS with Boron-ContAininG 

Counter-ionS 

M. KALiner 1 , t. SChuLz 1 , t. StrASSner 1 

1 Technische Universität Dresden, Physikalische Organische 

Chemie, Dresden, Germany 

Ionic Liquids (ILs) have found wide spread and steadily 

expanding application, as solvents, in catalysis, as extraction material 

or as electrolyte in batteries. Most of them require ILs which are 

liquid at room temperature. We describe in our study TAAILs 

(Tuneable Aryl Alkyl Ionic Liquids) with novel counter-ions. 

TAAILs are imidazolium-based cations with variable alkyl chain 

lengths or substituents on the aryl ring. In comparison to the 

frequently used Bis(trifluoromethanesulfonimide) we investigate 

boron-containing non-coordinating counter-ions. 

Keywords: Ionic liquids; Boron; 



s1037 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 5 1 

reverSiBLy SwitChABLe wettABiLity 

throuGh ModuLAtinG SurfACe 

ChArACteriStiCS 

S. K. KAnG 1 

1 Soongsil University, Organic Materials and Fiber 

Engineering, Seoul, Republic of Korea 

Polyeletrolytes are negatively or positively charged 

polymers with repeating units that combine with an individual 

counterion and experience potentially strong electrostatic 

interactions due to their multiple charges. In particular, charged 

polymers exhibit diverse physicochemical properties depending 

on the natures of their counterions. The exchange of counterions 

connected with charged units induces significant changes in the 

chemical architectures and properties of polyelectrolytes as well 

as in their unique functions. Moreover, since ion-exchange 

reactions enable the collection of specific salts from electrolyte 

solutions through the trapping and releasing reactions between the 

ions, polyelectrolytes have been widely used in a number of 

industrial fields, such as the desalination of sew water, 

demineralization, water softening, polymer electrolyte fuel cells 

(PEFCs), pharmaceutics, sensors, and carbohydrate refining. In 

particular, by adsorbing ion-exchangeable polymers onto 

nanostructures surfaces, the ion-paring interaction leads to 

changes in surface characteristics through the capture of specific 

ions with various polarities and hydration energies by selection 

of the appropriate counterions, and thus plays a pivotal role in the 

development of intelligent devices such as smart windows, 

humidity sensors, oil separators. Multi-scale surface 

nanostructures with a large surface-to-volume ratio are an 

essential prerequisite for maximizing the performance of such 

smart devices and systems, because the rate of the ion exchange 

process depends intrinsically on the specific surface area. In this 

study, we developed a multifunctional electrospun polymeric 

nanofiber web with switchable superhydrophobicity as well as 

oleophobicity via clicking counterions. To produce this smart 

fabric, we used a strategy that combines electrospinning to 

fabricate nanofibrous templates with nanopores a d a simple 

coating of the polyelectrolyte that can exchange counterions with 

various hydration energies. 

Keywords: Exchange interactions; polymers; Surface 

chemistry; Nanostructures; Hydrophobic effect; 


P - 0 3 5 2 

SyntheSiS of new AntituBerCuLotiCS 

derived froM 

BenzyLSuLfAnyLheteroAroMAteS 

K. GALinA 1 , J. roh 1 , K. vAvrovA 1 , J. StoLAriKovA 2 , 

v. KLiMeSovA 1 , A. hrABALeK 1 

1 Charles University in Prague, Department of Inorganic and 

Organic Chemistry, Hradec Kralove, Czech Republic 

2 Regional Institute of Public Health, Department for Diagnostic 

of Mycobacteria, Ostrava, Czech Republic 

The search for effective antituberculotics remains current 

and very important topic because a lot of patients are infected by 

Mycobacterium tuberculosis and their number is increasing. 

It was showed that benzylsulfanyl derivatives of 

benzimidazoles, benzothiazoles and benzoxazoles possessed the 

highest in vitro antitubercular activity when the benzylsulfanyl 

moiety carries the electron-withdrawing substituents [1, 2] . 

Our work focused on the synthesis of new potential 

antituberculotics based on benzylsulfanylheteroaromates. 

A series of 1-alkyl/aryl-5-benzylsulfanyl-1H-tetrazole with 

electron-withdrawing substituents on the benzylsulfanyl moiety 

was prepared. We found that substituents in the position 1 have 

only low influence on the antimycobacterial activities. 

The series of selenium, oxygen, sulfinyl and sulfonyl 

isosteric analogues of 1-alkyl/aryl-5-benzylsulfanyl-1H-tetrazole 

were synthesized. The oxygen and selenium derivatives showed 

the activities like the sulfanyltetrazoles, while sulfinyl and 

sulfonyl analogues had lower activities. 

We also synthesized the series of 2,5-disubstituted 

1,3,4-oxa- and 1,3,4-thiadiazoles with substituted benzylsulfanyl 

moiety. These compounds showed higher activities than tetrazole 

analogues. 

It is necessary to note that some of the selected compounds 

showed only low toxicity against isolated human hepatocytes as 

well as JEG3 cells. 

Acknowledgement: This project was supported by the Grant 

Agency of Charles University (Project no. 55610/2010) and by 

the Charles University in Prague (SVV 265 001) 

references: 

1. Koci, J.; Klimesova, V.; Waisser, K.; Kaustova, J.; Dahse, 

H.-M.; Mollmann, U. Bioorg. Med. Chem. Lett. 2002, 12, 

3275-3278 

2. Klimesova, V.; Koci, J.; Waisser, K.; Kaustova, J.; 

Mollmann, U. Eur. J. Med. Chem. 2009, 44, 2286-2293 

Keywords: Medicinal chemistry; Heterocycles; 



s1038 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 5 3 

A new APProACh to PrePArAtion of 

ConduCtive CoMPoSiteS BASed on 

PoLyAniLine 

G. KArPAChevA 1 , A. orLov 1 , S. KiSeLevA 1 

1 A.V.Topchiev Institute of Petrochemical Synthesis, Chemistry 

of polyconjugated systems, Moscow, Russia 

Polyaniline takes a special position among conducting 

materials due to the simplicity of its synthesis, ease of carrying 

out reversible processes of doping – dedoping and a range of 

excellent properties. However, the rigidity of the polymer chain 

and, consequently, infusibility and insolubility in most organic 

solvents, as well as the lack of stability in the operating conditions 

are the serious obstacles to its practical application. The solution 

to this problem is the creation of polymeric composite materials 

based on PANI, characterized by good electrical and mechanical 

properties. 

The goal of this research work is the development of a new 

original method of preparation polymer-polymer composites, in 

which microlayers of PANI are distributed in the inert matrix of 

polystyrene (PS), which provides high mechanical properties and 

stability of electrophysical characteristics. PANI-PS composites 

were prepared by border-line polymerization of aniline at the 

interface of immiscible liquid phases – aqueous solution of aniline 

and oxidant and organic solution of PS. Under intensive stirring 

the forming PANI microlayers encapsulate drops of PS solution. 

After the separation of the aqueous phase, as a result of 

destruction of the microcapsules, a new composite material, in 

which microlayers of PANI with length 1-3 μm and thickness 

~0,2 μm are dispersed in the volume of solid inert PS matrix, is 

being formed. PANI microlayers are characterized by a high 

degree of homogeneity both in terms of morphology and chemical 

structure as follows from electron microscopy and FTIR surface 

reflection data. Electrophysical properties of the obtained 

composites were studied. Depending on preparation conditions 

conductivity falls insite the limits of 10-3-10 Sm/cm. 

Obtained polymer-polymer composites are of advantage for 

application in organic electronics, electrochromic systems, as 

antistatic coatings and protecting shields from electromagnetic 

and radioactive emission. 

Keywords: conducting materials; polymerization; electron 

microscopy; 


P - 0 3 5 4 

ordered hyBrid thin fiLMS froM 

PoLy(3-hexyLthioPhene) BLoCK CoPoLyMerS 

for PhotovoLtAiC APPLiCAtionS 

M. Kern 1 , S. BoyeS 1 

1 Colorado School of Mines, Department of Chemistry and 

Geochemistry, Golden CO, USA 

Thin film hybrid photovoltaics, which include organic donor 

and inorganic acceptor components, are attractive due to higher 

adsorption coefficients, more desirable mechanical properties and 

less expensive processing. Despite these advantages, hybrid thin 

film devices have shown limited efficiency due to poor charge 

separation and extensive charge recombination. Control of film 

morphology at the nanoscale and of the organic/inorganic 

interface is essential for further improvements in device 

efficiency. The present work seeks to yield well-defined film 

architectures by taking advantage of the phase separation of block 

copolymer films. Block copolymers of poly(3-hexyl thiophene) 

P3HT were prepared via reversible addition-fragmentation chain 

transfer (RAFT) polymerization. A novel P3HT macroRAFT 

agent was designed to maintain a trithiocarbonate end group after 

the preparation of a block copolymer. The P3HT macroRAFT 

agent was utilized to prepare rod-coil block copolymers with 

poly(styrene) and poly(tert-butylacrlyate). The trithiocarbonate 

end group was subsequently used for attachment of the P3HT 

homopolymer and the block copolymers to inorganic surfaces. 

This utility was demonstrated by attaching P3HT polymer to gold 

nanorods, which were then incorporated into polymer films. The 

location of the nanoparticles in the thin films can be controlled 

by the polymer on the nanoparticle surface. 

Keywords: Block Copolymers; Self assembly; Nanostructures; 



s1039 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 5 5 

trAnSient And SwitChABLe ProteCtion of 

dnA AGAinSt CLeAvAGe By reStriCtion 

endonuCLeASeS 

P. KieLKowSKi 1 , h. MACíCKová-CAhová 2 , 

M. hoCeK 2 


of Organic Chemistry, Prague, Czech Republic 

2 Institute of Organic Chemistry and Biochemistry AS CR, 

Bioorganic & Medicinal Chemistry, Prague, Czech Republic 

The restriction endonucleases type II (REs) are very 

important in the manipulation of DNA. [1] In previous studies was 

found that several of these showed a high tolerance to the presence 

of alkynyl group but not to more bulky groups at position 7 of 

7-deazaadenine. [2] 

Our method utilises the trialkylsilyl protected 7-ethynyl-7- 

-deazaadenine as a bulky substitution of 7-deazaA which protects 

the DNA against cleavage by REs and after removal of 

trialkylsilyl group the afforded 7-ethynyl-7-deazaadenine is 

tolerated by REs and thus, DNA could be cleaved. [3] 

.We tested three trialkylsilyl protective groups: 

trimethylsilyl, triethylsilyl (TES) and triisopropylsilyl. 

According to the experimental results the most suitable protecting 

group of 7-ethynyl-7-deazaadenine for our method is TES. The 

modified nucleoside triphosphate dAteSetP is very good 

substrate for DNA polymerases in primer extension experiment 

and the construction of large DNA by PCR. The resulting 

modified DNA is fully protected against cleavage by REs. 

Another key advantage of using the TES protecting group is the 

ease at which it can be removed by the treatment with aqueous 

ammonia, which is simply evaporated and without any further 

purification DNA could be cleaved by REs. 

This approach may find applications in manipulation of 

DNA sequences, where target sequences for some REs must be 

distinguished. 

Acknowledgement: This work is a part of the research 

projects Z4 055 0506 supported by the Academy of Sciences 

of the Czech Republic. It was specifically supported by Czech 

Science Foundation (203/09/0317) and by Gilead Sciences, Inc. 

(Foster City, CA, U. S. A.). 

references: 

1. Pingoud, A.; Jeltsch, A. Nucleic Acids Res. 2001, 29, 

3705–3727. 

2. Macícková-Cahová, H.; Hocek, M. Nucleic Acids Res. 

2009, 37, 7612–7622. 

3. Kielkowski, P.; Macícková-Cahová, H.; Pohl, R.; Hocek, 

M. Angew. Chem. Int. Ed. 2011, 50, 8727–8730. 

Keywords: DNA cleavage; Nucleic acids; 


P - 0 3 5 6 

Study on the PhySiCAL ProPertieS And 

CryStALLizAtion KinetiCS of Modified PP 

CoMPoSiteS with nAnofiLLer 

y. C. KiM 1 , K. h. yun 1 , P. dAhAL 1 

1 Kongju National University, Polymer Science & Engineering, 

Cheonan, Republic of Korea 

Commercial Polypropylene (PP) exhibits low melt and 

impact strengths, which limit its use in foaming and automotive 

applications. The melt strength of PP can be improved by 

controlling the molecular weight property and introducing 

long-chain branches (LCBs). Control of the crystal growth rate is 

crucial for the preparation of modified PP (m-PP) with LCB 

because the crystallization kinetics affect the polymer processing. 

The objective of this study is to determine the effects of LCB 

and loading nano-filler on the physical properties and the 

crystallization kinetics of m-PP. 

M-PPs were prepared by melt grafting and electron beam 

irradiation, and m-PP composites with nano-filler were fabricated 

by adding 1–7 wt% filler using a mini-compounder at 200 °C. 

Layered silicate, carbon nano-tube (CNT), and graphene were 

used as the nano filler. There was no difference in the spectra of 

m-PP and pure PP whcih were measured by FT-IR and 1H-NMR. To check branch reaction, the branching level was calculated by 

zero-shear viscosity and molecular property. The rheological 

properties were monitored using an oscillatory viscometer (Anton 

Paar, MCR 301). The crystallization behavior of m-PP and the 

nanocomposites were analyzed using the isothermal and 

non-isothermal kinetic process proposed by Avrami and Ozawa, 

respectively. The enhanced melt strength can be interpreted from 

the observation that the loading of nano-filler and introducing 

LCB into PP enhances its solid-like properties in the PP melts. 

The dispersion of nano-filler was verified by transmission electron 

microscope (TEM) and X-ray diffraction (XRD). The melt 

stregnths of PP were measured by Instron capillary rheometer with 

tensiometer. 

Keywords: polypropylene; long-chain branch; nano-filler; 

nanocomposite; crystallization; 



s1040 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 5 7 

teMPLAte-direCted SyntheSiS, StruCture, 

And SuPrAMoLeCuLAr CheMiStry of 

ConJuGAted PorPhyrin nAnorinGS 

C. e. i. KnAPPKe 1 , d.v. KondrAtuK 1 , 

h. L. AnderSon 1 



Fully π-conjugated porphyrin nanorings combine an end-free 

π-system with well-defined size and shape. They provide models 

for testing our understanding of light harvesting in natural 

photosynthetic systems, and they may lead to the creation of new 

functional materials. Here we report on such systems consisting 

of 6, 8, 12, 18 and 24 porphyrin units, respectively, that are linked 

by butadiyne-bridges. These structures have been approached by 

template-directed synthesis. The formation of the larger rings 

illustrates the scope for Vernier templating as an efficient tool for 

the synthesis of monodisperse molecules of unprecedented sizes. 

Investigations of the structure and supramolecular chemistry of 

the nanorings are presented. 

references: 

1. M. Hoffmann, C.J. Wilson, B. Odell, and H.L. Anderson, 


2. J. K. Sprafke, D. V. Kondratuk, M. Wykes, A. L. Thompson, 

M. Hoffmann, R. Drevinskas, W.-H. Chen, C. K Yong, 

J. Karnbratt, J. E. Bullock, M. Malfois, M. R. Wasielewski, 

B. Albinsson, L. M. Herz, D. Zigmantas, D. Beljonne, 

H. L. Anderson, J. Am Chem. Soc. 2011, 133, 17262. 

3. M. C. O’Sullivan, J. K. Sprafke, D. V. Kondratuk, C. Rinfray, 

T. D. W. Claridge, A. Saywell, M. O. Blunt, J. N. O’Shea, 

P. H. Beton, M. Malfois, and H. L. Anderson, Nature 2011, 

469, 72. 

Keywords: Conjugation; Nanostructures; Porphyrinoids; 

Supramolecular Chemistry; Template Synthesis; 


P - 0 3 5 8 

4,4'-Azo-BiS(hALoPyridiniuM) derivAtiveS: 

StronG MuLtidentAte hALoGen-Bond donorS 

with A redox-ACtive Core 

f. KnieP 1 , S. M. wALter 1 , e. herdtweCK 1 

, 

S. M. huBer 1 

1 Technische Universität München, Organic Chemistry 1, 


Recently, a growing number of studies describe applications 

of halogen bonds (XBs), which are non-covalent interactions 

between lewis-acidic halogen atoms in compounds R-X (X =Cl, 

Br, I) and a Lewis base, [1] in solution (e.g. for anion recognition 

and organocatalysis [2] ). 

For these applications, the formation of strong XBs is a 

necessity, which can be achieved by making the rest R sufficiently 

electronegative. The usage of cationic moieties attached to the 

halogen atom provides this electron withdrawal. In the course of 

our investigations, we recently reported the activation of the 

carbon-bromine bond in benzhydryl bromide by imidazolium-based 

halogen bond donors (XB-donors). [3] Based on X-ray structural 

analyses of halopyridiniummoieties, which also form 

strong XBs with halides, [4] we synthesized new azo-bridged 

bis(halopyridinium) compounds, firstly to extend the XB-based 

activation of carbon-heteroatom bonds to further multidentate 

XB-donors and secondly to investigate their activation potential 

in the mentioned benchmark reaction by comparing it to the 

activation potential of the imidazolium-based XB-donors. The azo 

bridge, which also constitutes a built-in redox option, was chosen 

as a short and easy to install junction for the connection of two 

halopyridinium fragments. Several X-ray structural analyses of 

these new XB-donors could be obtained and NMR titration 

experiments showed a higher efficiency of these activators in our 

benchmark reaction. [5] 

references: 

1. P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, G. Terraneo, 

Angew. Chem. Int. Ed. 2008,47, 6114. 

2. A. Bruckmann, C. A. Pena, C. Bolm, Synlett, 2008, 900. 

3. S. M. Walter, F. Kniep, E. Herdtweck, S. M. Huber, 


4. T. A. Logothetis, F. Meyer, P. Metrangolo, T. Pilati, 

G. Resnati, New J. Chem. 2004, 28, 760. 

5. F. Kniep, S. M. Walter, E. Herdtweck, S. M. Huber, 

Chem. Eur. J 2012, 18, 1306. 

Keywords: Halogens; Solvolysis; Noncovalent interactions; 

Azo compounds; 



s1041 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 5 9 

MoLeCuLAr SwitCheS for AfM 

MeASureMentS 

i. KÖhL 1 , P. of. dr. uLriCh LüninG 1 

1 Christian-Albrechts-Universität zu Kiel, Otto-Diels-Institut für 

Organische Chemie, Kiel, Germany 

Azobenzenes are the prototype of switchable molecules. [1] 

Therefore, the mechanical work of their photoisomerization shall 

be determined quantitatively. Azobenzene derivatives shall be 

attached covalently between a glass surface and a cantilever in an 

atomic force microscope (AFM). 

New azobiphenyl molecules to amplify the effective 

distance change during the E,Z-isomerization will be presented. 

This shall lead to a better signal-to-noise ratio due to increased 

change of length. [2] The azobiphenyls are substituted with 

methylgroups to improve solubility. All synthesis were done by 

an oxidative copper(II)-catalyzed coupling reaction in 

combination with a Suzuki reaction. 

In solution, the switching behavior of azobenzenes and 

azobiphenyles was examined by NMR and UV/Vis spectroscopy. 

The amount of cis isomer was determined by NMR spectroscopy. 

The reversibility of switching was investigated by 

UV/Vis spectroscopy. All investigated molecules showed 

E,Z-isomerization and sufficiently long half-life times. 

references: 

1. G. S. Hartley, Nature 1937, 140, 281. 

2. C. Glockner, Dissertation 2011, CAU Kiel. 

Keywords: Azo compounds; Photochemistry; Oxidation; 


P - 0 3 6 0 

viSiBLe LiGht Photoredox CAtALySiS with 

n-A-rAdiCALS AS interMediAteS 

P. KohLS 1 , d. JAdhAv 2 , G. PAndey 2 , o. reiSer 1 

1 Institute of Organic Chemistry, Chemie und Pharmazie, 


2 Organic Chemistry, NCL, Pune, India 

In recent years many discoveries were made in the field of 

photochemistry mediated by visible light. Light is inexpensive 

and readily available worldwide. It is not polluting the 

environment and can transfer energy under mild reaction 

conditions. Applying the concept of photoredox catalysis with 

visible light, ruthenium(II) and iridium(III) complexes proved to 

be versatile catalysts due to their good charge separation abilities 

and redox properties. [1] The transition metal complex acts hereby 

as an electron shuttle which transfers electrons from a donor to 

an acceptor or vice versa. 

Due to our progress in the field of photocatalytical 

debromination reactions we started to investigate photocatalytical 

conjugate addition reactions. [2] In the course of our studies, we 

discovered that tert. amines can be oxidized by photoredox 

catalysts to an amine located radical cation which rearranges to a 

N-α-radical under loss of an proton. This radical than attacks an 

enone system and forms the conjugate addition product 

subsequently. [3] N-Phenyltetrahydroisoquinoline species proofed 

to be the most suitable tert. amine. On the other hand, most enone 

systems are applicable in this reaction and lead to the expected 

conjugate addition products in moderate to good yields. 

Our current studies focus on expanding the scope and 

increasing the yield of the reaction. Especially the 

functionalization of different tert. amines would be of interest due 

to their regular appearance in natural products and pharmaceutical 

drugs. We are also concentrated on the development of a selective 

photocatalytic conjugate addition. 

references: 

1. a)Teplý, F. Collect. Czech.Chem. Commun.2011, 76, 859; 

b) K. Zeitler, Angew. Chem. Int. Ed. 2009, 48, 9785–9789. 

2. Maji, T.; Karmakar, A.; Reiser, O. J. Org. Chem.2011, 76, 

736. 

3. Kohls, P.; Jadhav, D.; Pandey, G.; Reiser, O. Org. Lett. 

2012, 14, 672. 

Keywords: photocatalysis; conjugate addition; photoredox 

catalysis; 



s1042 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 6 1 

PALLAdiuM-CAtALyzed direCt C–h Bond 

funCtionALizAtionS 

C. KornhAASS 1 , L. ACKerMAnn 1 



Heteroatom-substituted secondary phosphine oxides 

(HASPO) have emerged as efficient preligands for transition 

metal-catalyzed cross-coupling reactions. [1, 2] Recently, we 

synthesized well-defined air-stable palladium complexes derived 

from (HA)SPO-preligands, which turned out to be versatile 

catalysts for efficient Kumada-Corriu cross-coupling reactions of 

unactivated (hetero)aryl- and alkenyl tosylates with an improved 

catalytic activity as compared to the corresponding in-situ 

generated catalysts. [3] 

These complexes were found to be highly active catalysts 

in environmentally benign direct C–H bond arylations and 

benzylations of various azoles. [5, 6] Moreover, direct C–H bond 

alkynylations of heteroarenes were accomplished with 

inexpensive gem-dichloroalkenes as user-friendly electrophiles. [7] 

references: 

1. L. Ackermann, Synlett 2007, 507–526. 

2. L. Ackermann, Isr. J. Chem. 2010, 50, 652–663. 

3. a) L. Ackermann, A. Althammer, Org. Lett. 2006, 8, 

3457–3460; 

b) L. Ackermann, H. K. Potukuchi, A. R. Kapdi, 

C. Schulzke, Chem. Eur. J. 2010, 16, 3300–3303. 

4. L. Ackermann, A. R. Kapdi, S. Fenner, C. Kornhaaß, 

C. Schulzke, Chem. Eur. J. 2011, 17, 2965–2971. 

5. L. Ackermann, S. Barfüßer, C. Kornhaaß, A. R. Kapdi, 

Org. Lett. 2011, 13, 3082–3085. 

6. selected reviews: 

a) D. Alberico, M. E. Scott, M. Lautens, Chem. Rev. 2007, 

107, 174–238; 

b) X. Chen, K. M. Engle, D.-H. Wang, J.-Q. Yu, Angew. 

Chem. Int. Ed. 2009, 48, 5094–5115; 

c) L. Ackermann, R. Vincente, A. R. Kapdi, Angew. Chem. 

Int. Ed. 2009, 48, 9792–9826. 

7. L. Ackermann, C. Kornhaaß, Y. Zhu, Org. Lett. 2012, 14, 

1824–1826. 

Keywords: Cross-coupling; C-H activation; Heterocycles; 

Homogeneous catalysis; Palladium; 


P - 0 3 6 2 

SyntheSiS And Anti-infLuenzA viruS ACtivity 

of n-AryLAted BetA-AMidoAMidineS 

StruCturALLy reLAted to nAturAL 

AntiBiotiC AMidinoMyCin 

e. KorShin 1 , L. zAKhArovA 2 , y. Levin 2 , 

o. Pozdeev 3 

1 Weizmann Institute of Science, Organic Chemistry, Rehovot, 

Israel 

2 Arbuzov Institute of Organic and Physical Chemistry, Organic 

Synthesis, Kazan, Russia 

3 Medical University, Microbiology, Kazan, Russia 

Influenza infections are responsible for many million cases 

of illness and up to a half of million deaths per year. Despite of 

availability of antiviral drugs against influenza infections, the 

emergence of viral resistance to existing antiviral drugs 

emphasizes the demand for development of new antiviral drugs 

against influenza. Naturally occurring Amidinomycin and 

Noformycyn represent a b-amidoamidine type of antibiotics, 

which is of considerable chemotherapeutic interest due to a wide 

range of antibacterial and antiviral activity. However these 

compounds and their close derivatives appeared to possess high 

level of toxicity. 

In this work, we report an efficient 3-step synthesis of 

racemic N-arylated b-amidoamidines 4, which being non-toxic 

revealed an antiviral potency against influenza virus A (H3N2) in 

vitro. Indeed, reactions of methacryloyl anilides 1 with PCl at rt 5 

smoothly afforded the imidoyl chlorides 2, which upon treatment 

with 2 equiv of the same aniline gave the corresponding 

N-arylated b-aminoamidines 3 as hydrochlorides. The salts 3 were 

converted to free bases, the latter were mono-acylated with acyl 

chlorides at the less nucleophilic b-amino-group to give the 

b-amidoamidines 4. A plausible mechanism for this 

mono-functionalization of the less reactive reaction center through 

the acyl-group migration will be briefly discussed. 

The b-aminoamidines 3 and the b-amidoamidines 4, being 

tested in vitro against influenza virus A/St.Peterburg/34/72 

(H3N2) exhibited different level of antiviral activity and 

cytotoxicity. For example, while N-phenyl-substituted 

b-aminoamidine 3 (HCl-salt) is totally inactive and extensively 

cytotoxic (MCC 85 mmol), it’s b-N-acetyl derivative 4a is twice 

50 

less toxic and considerably active (IC 68 mmol). An elongation 

50 

of the alkyl chain in 4c (R = n-C H ) resulted in significant 

8 17 

antiviral potency ((IC 0.95 mmol) accompanied by a modest 

50 

toxicity (MCC 250 mmol). A considerable in vivo protective 

50 

activity of long alkyl chain 4 against experimental influenza virus 

A/Aichi/68 (H3N2) infection was also observed. 

Keywords: amination; Michael addition; acylation; 

cyclization; antiviral agents; 



s1043 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 6 3 

SyntheSiS of new xAnthene derivAtiveS for 

LABeLinG of BioMoLeCuLeS 

M. KotASKovA 1 , M. heLM 1 

1 Joh. Gutenberg University, Institute of Pharmacy and 

Biochemistry, Mainz, Germany 

Xanthene dyes, particularly fluorescein are a well known 

class of fluorescent dyes, which have widespread applications in 

natural sciences. The synthesis of xanthene derivatives via acid 

catalyzed condensation of substituted phenols with phthalic 

anhydride, to afford the required derivatives, is well established. 

The high temperature, harsh reaction conditions and often lower 

yields make this method less convenient. The synthesis of 

xanthene dyes by direct modification of the fluorophore moiety 

is a great option to avoid the standard procedure. Our new 

synthetic strategy for preparation of novel asymmetric xanthene 

dyes via direct conversion of hydroxyl groups on 3'- and 

6'-positions into leaving groups by mesylation is reported. It was 

discovered that 3',6'-dimesylated fluorescein undergo catalyst free 

nucleophilic aromatic substitution with sulfur nucleophiles. 

Additional this type of alteration of the fluorophore structure 

improved significantly its photostability. Not only 3',6'-mesylated 

fluorescein, but also 3',6'-mesylated 2',7'-dichloro, 4',5'-dibromo 

or 4',5',7'-tribromo derivatives of fluorescein are used as 

starting materials for preparation of these new fluorescent dyes. 

This strategy provides novel fluorescent probes with the 

linker suitable to further modifications. The modifications of the 

linker enable to prepare fluorescein derivatives that can be used 

as fluorescent labels in peptides, oligonucleotides and for cell 

imaging. Especially new azido fluorescein derivatives are 

reported. They could be used for a “click” reaction with acetylene 

modified nucleosides and be incorporated into live cells during 

cellular transcription and translation. 

Keywords: Fluorescent probes; Sulfur; Synthesis design; 

Azides; Aromatic substitution; 


P - 0 3 6 4 

PrePArAtion of new PuSh-PuLL 

ChroMoPhoreS with ferroCene Moiety 

J. KouSALovA 1 , J. KuLhAneK 1 

1 University of Pardubice, Faculty of Chemical Technology, 

Pardubice, Czech Republic 

Objective of this work was the synthesis of new push-pull 

chromophores, whose preparation has not yet been published. 

Ferrocene was used as donor group and N-methylimidazole-4,5- 

-dicarbonitrile was used as acceptor group. Thiophene ring in 

combination with one or more multiple bonds was used as a 

p-linkage between donor and acceptor unit. 

Target chromophores were synthesized by three to five step 

synthesis using mainly Heck, Sonogashira and Suzuki-Miyaura 

cross-coupling reactions and some others. Overall it was prepared 

twenty five intermediate products. It was ten final products 

obtained in high purity. 

Structures and purity of the prepared compounds have been 

verified by basic analytical methods - GC/MS or LC/MS, 1H and 

13C NMR, infrared spectroscopy and elemental analysis. 


Agency of the Czech Republic (P106/12/0392) and by the 

Ministry of Education, Youth and Sport of the Czech Republic. 

Keywords: Push-pull chromphores; ferrocene; thiophene; 

N-methylimidazole-4,5-dicarbonitrile; 



s1044 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 6 5 

MotionAL And ConStitutionAL dynAMiCS of 

iMineS 

P. KovAriCeK 1 , J. M. Lehn 1 

1 Institut de Science et d’Ingenierie Supramoleculaire, 

Laboratoire de Chimie Supramoleculaire, Strasbourg, France 

The imine double bond possesses many interesting features: 

it can form reversibly from an aldehyde and amine eliminating a 

molecule of water, it is susceptible to attack with nucleophiles 

such as amines, performing imine exchange, and it responds to 

certain chemical stimuli such as pH, coordinating metals, etc. 

These properties provide a good background for applications 

in Dynamic Covalent Chemistry (DCC). General demands in this 

field comprise of fast formation of dynamically interconverting 

species and rapid response towards physical and chemical stimuli 

which can occur in a vast range of applicable solvents, with a 

particular interest for aqueous solutions. 

Salicylaldehyde and pyridine-2-carboxaldehyde have been 

identified as the most promising aldehydes for imine-based DCC. 

They form imines with high conversion and rate even in aqueous 

media and readily exchange with their amine counterparts. 

Amines bearing more than one amino-group undergo both 

intermolecular and intramolecular exchange, wherein the rate of 

the former depends on concentration and the latter on distance 

between the two amino-groups. 

The condensation of salicylaldehyde and ethylenediamine 

strongly prefers imine formation over the aminal form, making 

the aldehyde end-to-end displacement observable and quantifiable 

by VT-NMR. The rate of such displacement decreases rapidly 

with increasing chain length. Thus for a molecule of cadaverine, 

intramolecular exchange is not observed. 

Extending the simplest aliphatic diamines to complex linear 

polyamines such as diethylenetriamine and triethylenetetramine, 

the very same behaviour is observed. Imine formation is 

predominant in solution and intramolecular end-to-end exchange 

is observed by 2D-EXSY. This exchange proceeds in a stepwise 

fashion by participation of the secondary nitrogens, giving rise to 

aminal intermediates, which is confirmed by kinetic studies, 2D 

NMR and molecular modeling of analogues without secondary 

nitrogens. 

This interesting behaviour can be considered to be nondirectional 

small molecule walking along a track, a remarkable 

observation found for first time with imines. 

Keywords: imine exchange; dynamic covalent chemistry; 

molecular dynamics; molecular motors; 


P - 0 3 6 6 

SyntheSiS of the triCyCLiC Core unit of 

diSCoderMide 

M. KreBS 1 , S. LASChAt 1 

1 Stuttgart University, Institut für Organische Chemie, Stuttgart, 

Germany 

The marine natural product discodermide was isolated for 

the first time in 1991 by Gunasekera and co-workers from the 

Caribbean marine sponge Discodermia dissoluta. [1] Discodermide 

belongs to the class of tetramic acid lactams and displays 

remarkable biological characteristics. It inhibits the in vitro 

proliferation of cultured murine P388 leukemia cells with an ICM 

of 0.3 µg/mL as well as the growth of C. albicans with an MIC of 

12.5 µg/mL. Other members of this class are cylindramide, 

isolated from the Okinawan sponge Halichondria cylindrata, [2] or 

geodine A, recently isolated from the southern australian marine 

sponge Geodia. [3] Characteristic structural features of these 

compounds are the tetramic acid moiety and the substituted 

bicyclo[3.3.0]octane unit. In the case of discodermide the 

bicyclo[3.3.0]octane is replaced by the tricyclic 

dodecahydrocyclopent[a]indene unit. Compared to cylindramide, 

which was synthesized by Cramer in 2005, [4] discodermide is 

currently neither available by synthesis nor fermentation. 

In the course of a total synthesis of discodermide, the 

tricyclic core unit, the dodecahydrocyclopent[a]indene, is 

synthesized in diastereomerically pure form prepared from readily 

available 1,5-cyclooctadiene. After cyclisomerization the 

obtained bicyclo[3.3.0]octane-2,6-dione is functionalized by 

copper-mediated 1,4- or magnesium-mediated 1,2-addition. The 

key step is an intramolecular aldol reaction to obtain the tricyclic 

core unit, which is then further functionalized. 

references: 

1. S. P. Gunasekera, M. Gunasekera, P. McCarthy, J. Org. 

Chem. 1991, 56, 4830-4833. 

2. S. Kanazawa, N. Fusetani, S. Matsunaga, Tetrahedron 

Lett. 1993, 34, 1065-1068. 

3. R. J. Capon, C. Skene, E. Lacey, J. H. Gill, D. Wadsworth, 

T. Friedel, J. Nat. Prod. 1999, 62, 1256-1259. 

4. a) N. Cramer, M. Buchweitz, S. Laschat, W. Frey, A. Baro, 

D. Mathieu, C. Richter, H. Schwalbe, Chem. Eur. J. 2006, 

12, 2488-2503; 

b) N. Cramer, S. Laschat, A. Baro, H. Schwalbe, 

C. Richter, Angew. Chem. Int. Ed. 2005, 44, 820-822. 

Keywords: Natural products; Asymmetric synthesis; Grignard 

reaction; 



s1045 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 6 7 

totAL SyntheSiS of ArteLudoviCinoLide A 

A. Kreuzer 1 , o. reiSer 1 



The total synthesis of natural products is of increasing 

interest since such molecules inherit a huge potential for 

biologically active compounds. Therefore, many plant extracts 

have been investigated to find new lead structures for novel 

effective drugs. Several members of the genus Artemisia have 

been widely used in traditional medicine in the northern 

hemisphere. Among the numerous sesquiterpene lactones 

discovered in Artemisia ludoviciana, the guaianolide 

Arteludovicinolide A was found. [1] It was shown that this 

compound exhibits significant antiinflammatory activity. [2] 

The key step of the synthesis toward the γ-butyrolactone 

utilized a recently discovered synthetic intermediate, an α/β-chiral 

aldehyde which could be accessed in four simple steps from 

readily available starting materials: The enantio- and 

diastereoselective synthesis of the natural product started from 

furan-2-carboxylic ester by asymmetric cyclopropanation 

followed by ozonolysis and successive, highly diastereoselective 

Sakurai-allylation. [3] After some further synthetic manipulations, 

the α/β-chiral aldehyde was obtained in high yield. By reacting a 

lithiumorganyl with this aldehyde, the key structural element, a 

trans-substituted γ-butyrolactone was obtained. After introduction 

of the exo-methylene group via Eschenmoser`s salt followed by 

chemoselective Wacker oxidation the natural product was 

obtained in 10 linear steps and 2.9% overall yield. 

The scope of the α/β-chiral aldehyde for the construction of 

diverse trans-substituted γ-butyrolactones has also been 

investigated. Thus, various substructures can be introduced in the 

lactone moiety by applying organometallic reagents. 

references: 

1. Jakupovic, J., Tan, R. X., Bohlmann, F., Boldt, P. E., 

Jia, Z. J., Phytochemistry, 1991, 30, 5, 1573. 

2. Abdel-Lateff, A., Hegazi; M-E. F., Gamal-Eldeen, A., 

Nat. Prod. Comm. 2008, 3, 6, 851. 

3. Nosse, B., Chhor, R. B., Jeong, W. B., Böhm, C., Reiser, 

O., Org. Lett. 2003, 5, 941. 

Keywords: total synthesis; natural products; enantioselectivity; 

ketones; ozonolysis; 


P - 0 3 6 8 

A GenerAL reGioSeLeCtive 

APProACh to 2,4-diSuBStituted 

PyriMidine-5-yL C-2-deoxyriBonuCLeoSideS 

t. KuBeLKA 1 , M. hoCeK 1 



C-nucleosides bearing hydrophobic aryl groups as 

nucleobase are interesting compounds with wide range of 

applications in chemical biology, for example in extension of the 

genetic alphabet. [1] There are several synthetic approaches to 

C-nucleosides, but none of them is truly general and many of them 

suffer from poor selectivity and low yields. [2] 

A new modular synthesis of diverse 2,4-disubstituted 

pyrimidin-5-yl C-2'-deoxyribonucleosides by sequential 

regioselective reactions of 2,6-dichloropyrimidin-5-yl 

C-nucleoside was developed. [3, 4] The intermediate was prepared 

by the Heck coupling of 2,6-dichloro-5-iodopyrimidine with 

glycal followed by desilylation and reduction. Its mild 

nucleophilic substitutions, Fe-catalyzed cross-coupling with 

MeMgCl or Pd-catalyzed amination proceeded regioselectively 

at position 4. In second step position 2 was functionalised to 

prepare four series of diversely substitued derivatives. 

In conclusion two-dimensional library of 2,4-disubstituted 

pyrimidine C-deoxyribonucleosides bearing two different 

substituents was prepared. Some of these nucleosides will be 

transformed to triphosphates and tested as substrates of DNA 

polymerases. These studies are now under way in our laboratory. 

references: 

1. Henry, A. A.; Romesberg, F. E. Curr. Opin. Chem. Biol. 

2003, 7, 727-733. 

2. Stambasky, J.; Hocek, M.; Kocovsky, P. Chem. Rev. 2009, 

109, 6729–6764. 

3. Kubelka, T.; Slavetinska, L.; Klepetarova, B.; Hocek, M. 

Eur. J. Org. Chem. 2010, 2666-2669. 

4. Kubelka, T.; Slavetínská, L.; Hocek, M. Synthesis 2012, 

44, 953-965. 

Keywords: nucleosides; cross-coupling; Heck reaction; 

nucleophilic aromatic substitution; regioselectivity; 



s1046 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 6 9 

ConverSionS of PhoSPhonoMethionine And 

reLAted CoMPoundS 

M. Kudzin 1 , z. Kudzin 2 , P. urBAniAK 2 , 

J. drABowiCz 3 

1 Textile Research Institute, Laboratory of Chemical Testing and 

Instrumental Analyses, Lodz, Poland 

2 University of Lodz, Faculty of Chemistry, Lodz, Poland 

3 Jan Dlugosz University in Czestochowa, Department of 

Chemistry Enviromental Protection and Biotechnology, 

Czestochowa, Poland 

1-Aminoalkylphosphonic acids are structural analogs of 

natural amino acids, obtained by an isosteric substitution of the 

planar carboxylic group [C(O)OH] by the tetrahedral phosphonic 

function [P(O)(OH) ]. In this class of amino acids the group 

2 

of special interest present so called, the proteinogenic 

1-aminoalkylphosphonic acids, in this phosphonomethionine 

(MetP ) and related compounds [1]. 

Phosphonomethionine – originally synthesized in 1980 [2], 

and its analogs - phosphonohomocysteine (HcysP ) [2, 4] and 

phosphonocysteine (CysP ) [3, 4], present the interesting subject 

for chemical [5–8] and biological [9] explorations. 

In this communication, we present our results on the further 

sulfur functionalisation of this type of aminophosphonic acids, 

especially their N-methyl, and N,N-dimethyl derivatives. 

references: 

1. Kudzin Z.H., Kudzin M.H., Drabowicz J., Stevens Ch.: 

Aminophosphonic Acids - Phosphorus Analogues of Natural 

Amino Acids. Part 1: Syntheses of α-Aminophosphonic 

Acids. Curr. Org. Chem. 15 [2011] 2015-2071. 

2. Kudzin Z.H., Stec W.J.: Phosphohomocysteine 

derivatives. Synthesis 1980, 1032-1034. 

3. Kudzin Z.H. Phosphocysteine derivatives. 

Thioureidoalkanephos-phonates via acetals. 

Synthesis 1981, 643-645. 

4. Kudzin Z.H., Stec W.J.: Phosphocysteine and 

phosphohomocysteine. Synthesis and isolation. 

Synthesis: 1983, 812-814. 

5. Kudzin Z.H., Andrijewski G., Drabowicz J.: 

1-Aminothiaalkane-phosphonic acids – sulphinyl and 

sulphonyl derivatives. Synthesis and acidic properties. 

Heteroatom Chem. 5 [1994] 1-6. 

6. Kudzin Z.H., Mokrzan J., Skowronski R.: Long chain 

aminothiaalkane-phosphonates, their sulphinyl and 

sulphonyl derivatives. A new class of complexane type 

surfactants. Phosphorus & Sulfur 42[1982] 41-46. 

7. Kudzin Z.H., Saganiak M., Andrijewski G., Drabowicz J.: 

Oxidation of phosphonocysteine and 

phosphono-homocysteine. Synthesis of phosphonocysteic 

and phosphonohomocysteic acids. Pol. J. Chem. 79 [2005] 

529-539. 

8. Tam C.C., Mattocks K., Tishler M.: Synthesis of 

phosphono-methionine and related compounds. Synthesis 

1982, 188-191. 

9. Kudzin M.H., Kudzin Z.H., Drabowicz J.: Derivatives of 

aminoalkylphosphonic acids and glycylaminoalkylphosphonic 

acids as antibacterial additives in biopolymers. European 

Polymer Congress EPF-2011; Grenada 26.06-1.07.2011. 

Keywords: Aminoalkylphosphonic acids; 

Phosphonomethionine; Amino acids; 


P - 0 3 7 0 

CritiCAL ASSeSSMent of the effiCienCy of 

ChitoSAn-BASed MAteriALS AS PotentiAL 

orGAnoCAtALyStS for C-C Bond forMAtion 

d. KuehBeCK 1 , G. SAiduLu 2 , K. r. reddy 2 , 

d. diAz diAz 3 

1Institute of Organic Chemistry, University of Regensburg, 


2 Indian Institute of Chemical Technology, Inorganic and 

Physical Chemistry Division, Hyderabad, India 

3 ISQHC, Universidad de Zaragoza-CSIC, Zaragoza, Spain 

Since petrochemical-based feedstocks will be limited in 

future and are getting therefore much more expensive, cheap 

alternative sustainable resources like polysaccharides (e.g. 

chitosan, alginates, hyoluronic acid, carrageenan, cellulose, etc.) 

already play and will play a more important role in high-tech 

applications and industrial processes. [1] Beside such key 

advantages like biodegradability, biocompatibility and 

antibacterial activity, these materials are wide abundant on earth, 

offer a variety of functional groups and own in most cases chiral 

backbones. [2] Latter benefits qualify these compounds as potential 

organocatalysts in different organic transformations. 

In this study the effectiveness of commercial available 

chitosan powder (CSP), air-dried chitosan hydrogel beads 

(ADCSHB) and neutral pH chitosan hydrogel beads (CSHB) as a 

green organocatalyst for different C-C bond forming reactions 

(i.e. aldol reaction, Knoevenagel condensation, nitroaldol (Henry) 

reaction and Michael addition) has been comprehensively 

evaluated. Reaction rates, conversions and selectivities were 

investigated in dependence of different input variables including 

size, pH and reactive surface of the beads, catalyst loading, 

temperature, molecular weight of the biopolymer, concentration, 

solvent system and molar ratio of reactants. Moreover, the 

chitosan-based materials were characterized by a variety of 

techniques including, among others, SEM, FT-IR, TGA and 

DSC. [3] 

references: 

1. R. Höfer and J. Bigorra, Green Chem., 2007, 9, 203-212. 

2. M. Elnashar (Ed.), Biopolymers, InTech, 2010. 

3. D. Kühbeck, G. Saidulu, K. R. Reddy, D. D. Díaz, Green 

Chem., 2012, 14, 378-392. 

Keywords: chitosan; hydrogel; C-C bond formation; 

organocatalysis; 



s1047 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 7 1 

viSiBLe LiGht PhotoCAtALySiS – fLAvinS AS 

CAtALyStS in orGAniC reACtionS 

S. KueMMeL 1 , r. LeChner 1 , B. KoeniG 1 



Flavins are nature’s beloved redox co-factors. [1] When 

irradiated by blue light, their ability to oxidize is dramatically 

increased and thus they can be used in photocatalysis. [2] They are 

easily accessible by synthesis and their properties can be tuned 

by substitution pattern. [3] 

Recently we reported different organic reactions with 

vitamin B 2 derivatives as efficient photocatalysts. [4,5] The key step 

of the photocatalytic cycle is the formation of the triplet state of 

the flavin. [6] Based on the conclusions of these investigations we 

are now able to present some improved derivatives of this catalyst 

that yield higher triplet state populations due to heavy atom effect. 

These new photocatalysts accelerate the oxidation reactions and 

improve quantum yields. 

Acknowledgement: Research supports: Deutsche 

Bundesumweltstiftung (DBU), DFG: GRK 1626 – Chemical 

Photocatalysis. 

references: 

1. V. Massey, Biochem. Soc. Trans. 2000, 28, 283-296. 

2. a) B. J. Fritz, S. Kasai, K. Matsui, Photochem. Photobiol. 

1987, 45, 113-117; 

b) A. Bowd, P. Byrom, J. B. Hudson, J. H. Turnbull, 

Photochem. Photobiol. 1968, 8, 1. 

3. Chemistry and Biochemistry of Flavoenzymes; 

F. Müller, Ed., CRC Boca Raton, Fl, 1991. 

4. R. Lechner, B. König, Synthesis 2010, 10, 1712. 

5. R. Lechner, S. Kümmel, B. König, Photochem. Photobiol. 

Sci. 2010, 9, 1367-1377. 

6. U. Megerle, M. Wenninger, R.-J. Kutta, R. Lechner, 

B. König, B. Dick, E. Riedle, Phys. Chem. Chem. Phys. 

2011, 13, 8869-8880. 

Keywords: Photochemistry; Homogeneous Catalysis; Green 

Chemistry; 


P - 0 3 7 2 

orGAnoCAtALySiS of dynAMiC iMine Bond 

exChAnGe 

S. KuLChAt 1 , K. MeGueLLAti 1 , n. ALLendÖrfer 1 , 

J. M. Lehn 1 


Chemistry, Strasbourg, France 

Oganocatalysis by primary and secondary amines via 

enamine and iminium intermediates has been actively pursued in 

recent years to facilitate carbonyl condensation reactions. [1] 

Reversible covalent bond formation and exchange of imines are 

fundamental reactions in organic chemistry. [2, 3] Recently, the 

imine bond exchange has been given considerable attention with 

the development of dynamic covalent chemistry. [2] In this study, 

we describe the component exchange of imines using L-proline 

as an organocatalyst to significantly accelerate the exchange 

reaction, in some cases, up to a 10-fold rate increase. 

references: 

1. a) B. List, Chem. Rev. 2007, 107, 5413. 

b) D.A. Bock, C.W. Lehnmann, B. List, Proc. Natl. Acad. 

Sci. U.S.A. 2010, 107, 20636. 

2. a) J.-M. Lehn, Chem. Eur. J. 1999, 5, 2455. 

b) P.T. Corbett, J. Leclaire, L. Vial, K. R. West, 

J.-L. Wietor, J.K.M. Sanders, and S. Otto, Chem. Rev. 

2006, 106, 3652. 

3. M.E. Belowich and J.F. Stoddart, Chem. Soc. Rev. 2012, 

41, 2003. 

Keywords: Combinatorial chemistry; Organocatalysis; 

Supramolecular chemistry; 



s1048 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 7 3 

rCM–eLeCtroCyCLiC rinG oPeninG And 

rCM-iSoMerizAtion SequenCe for the 

SyntheSiS of (z, e)-dienoiC ACidS And 

A,B-unSAturAted d-vALeroLACtoneS 

o. Kunz 1 , B. SChMidt 1 

1 University of Potsdam, Organische Synthesechemie, Potsdam, 

Germany 

(Z, E)-Dienoic acids and their derivates are lead structures 

in many natural products. The dienoic acid building block is either 

part of a ring system, e. g. a macrolactone, or in the side chain of 

the natural product. Examples are the antiviral and cytotoxic 

macrolactins [1] or the cleorodane diterpenes [2] . α,β-Unsaturated 

δ-valerolactones are also found in numerous natural products, 

such as the well known fostriecin. [3] 

Both RCM sequences starts with the same starting materials, 

but the product depends on the use of the chemical trigger. 

We developed a new synthetic strategy to (Z, E) dienoic 

acids. [4] The key step is a one-pot ring closing metathesis/ base 

induced rearrangement sequence, which proceeds in high yields 

and very high (E/Z)-selectivity. 

The key step for the synthesis of δ-lactones is a one-pot ring 

closing metathesis/ isomerization sequence with triethylsilane as 

chemical trigger, which proceeds in high yields. [5] 

references: 

1. Gustafson, K.; Roman, M.;Fenical, W. J. Am. Chem. Soc. 

1989, 11, 7519; 

2. Whitson,E.; Thomas, C.; Henrich, C.; Sayers, T.; 

McMahon, J.; McKee, T. J. Nat. Prod. 2010, 73,2013; 

3. Hokanson, G. C.; French, J. C. J. Org. Chem. 1985, 

50,462; 

4. Schmidt, B.; Kunz, O. Eur. J. Org. Chem. 2012, 1008; 

5. Schmidt, B.; Kunz, O. Synlett 2012, 23, 851. 

Keywords: ring closing metathesis; 


P - 0 3 7 4 

PuLSed nMr eLuCidAtion of CurinG ProCeSS 

of ePoxy reSin 

t. KurotSu 1 , A. ASAno 1 , h. KiMoto 1 , 

C. nAKAzAwA 1 

1 National Defense Academy, Applied Chemistry, Yokosuka, 

Japan 

introduction: Pulsed NMR method is generally used to 

elucidate certain aspects of polymer structure and molecular 

motion. Spin-lattice relaxation time, T and spin-spin relaxation 

1 

time, T are parameters sensitive to the behavior of molecular 

2 

motion, such as a chain entanglement or the permanent cross-links 

of polymers. The curing process of epoxy resin forms a network 

structure and restricts its chain mobility. We, therefore, applied 

this method to study a curing process of epoxy resin in terms of 

mobility of spin. 

Method: The same volumes (0.2ml) of epoxy resin and 

curing agent was mixed in a glass tube (6mmΦ) for 1min and then 

put into NMR tube (10mmΦ). The reaction was carried out in the 

probe and then solid echo signals were recorded for T . T was 

2 1 

obtained by saturation recovery method. 

results and Conclusions: As the curing reaction proceeds, 

three kinds of T (T ; long,T ; short,T ; intermediate) were 

2 2L 2S 2M 

obtained from the observed solid echo signals. A short T (T ) 2 2S 

below 20us suggests an existence of a motion restricted polymer 

chains, that is, cured element of resin and its fraction (F ) S 

increased sigmoidally with its reaction time.On the other hand, 

F decreased reciprocally against the reaction time, suggesting the 

L 

disappearance of highly mobile molecules arose from pre-cured 

resin. F showed the behavior of transition between the above two 

M 

fractions, that is, F gives birth to F , via F . The time course of 

L S M 

T linearly increased with the reaction, which is reasonably 

1 

explained by the BBP theory. DSC measurement on the process 

was also carried out. Heat-flow rate curves against reaction time 

are parallel to that of F , which means that reaction heat is closely 

S 

related to the appearance of F . These results explain that the 

S 

curing process reflects on the time course of relaxation times and 

their fractions obtained by pulsed NMR method. 

Keywords: NMR Spectroscopy; Polymerization; 



s1049 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 7 5 

PhotoSwitChABLe KinASe inhiBitorS 

n. KuzMAnoviC 1 , n. tSChAMMer 2 , M. GrÖtLi 3 , 

B. KÖniG 1 



2 Emil Fischer Center, Department of Chemistry and Pharmacy, 

Erlangen, Germany 

3 Medicinal Chemistry, Department of Chemistry, Göteborg, 

Sweden 

Remote-controlling kinase activity is a convenient tool to 

investigate cell signaling pathways in anticancer research. 

Photoresponsive kinase inhibitors were designed which can be 

turned on and off by light of a certain wavelength allowing 

reversible control of the activity of Erk1/2 kinase in a living cell. 

Dithienylethenes (DTEs) are a well-established class of 

photochromic molecules. [1] By modifying the substituents of the 

thiophenes, ATP competitive kinase inhibitors were synthesized 

and their photochromic as well as biological activities were 

investigated. 

Irradiating a methanol solution of all target compounds as 

ring-open photoisomers with UV light (312 nm) resulted in an 

immediate conversion to obtain the appropriate ring-closed 

photoisomers. Upon exposure to visible light (λ > 420 nm) the 

reverse process was observed. The ring-closing/-opening cycles 

could be repeated at least seven times without any major signs of 

degradation. 

OHG cells were treated with the target compounds and their 

ability to inhibit Erk1/2 kinase activity was evaluated by an 

ELISA. The regulation of enzyme activity by irradiation with 

visible and ultraviolet light was confirmed. 

references: 

1. M. Irie, Chem. Rev. (Washington, DC, U. S.) 2000, 100, 

1685-1716. 

Keywords: Inhibitors; Isomerization; Medicinal chemistry; 



P - 0 3 7 6 

CovALent GrAftinG of BioCidAL CoPoLyMerS 

onto PvC SurfACeS 

J. LAfArGe 1 , n. KeBir 1 , f. BureL 1 

1 Institut national des sciences appliquée de Rouen, Chimie, 

Saint Etienne du Rouvray, France 

Email: jerome.lafarge@insa-rouen.fr 

Polyvinyl chloride (PVC) is known as a highly versatile 

polymer with an excellent balance of properties particularly 

adapted to biomedical devices. In fact, more than 5% of PVC is 

employed in biomedical applications. However, their applications 

are limited by the phenomenon of bacterial infection. 

In order to overcome this problem, some strategies have 

been investigated such as antibiotics impregnation of biomaterials 

or surface modification by grafting bioactive molecules. Within 

this last strategy grafting bioactive copolymers onto biomaterials 

surfaces is now considered as a long term option. [1, 2] 

In this work, four new biocidal copolymers containing 

quaternary ammoniums or phosphoniums groups were 

synthesized, purified and characterized by spectroscopic (FTIR 

and NMR) and thermal (TGA and DSC) analysis. 

Their bactericidal activity was probed against Escherichia 

Coli (Gram-negative bacteria) and Staphylococcus Epidermidis 

(Gram-negative bacteria) by evaluating their Minimum Inhibitory 

Concentration (MIC). 

These hydrophilic copolymers were covalently grafted onto 

PVC-N surfaces using a metal catalyzed azide/alkyne ‘click’ 

3 

reaction. 

The surface modification of the PVC-N was evidenced by 

3 

contact angle measurements and the surface charge density was 

evaluated by a fluorimetric method. 

At last, the assessment of bactericidal efficiency was 

performed using the “live and dead” test by fluorescence 

microscopy. 

references: 

1. Pavon-Djavid G, Hélary G, Migonney V, ITBM-RBM 

2005; 26:183-191 

2. Arnt L, Nüsslein K, Tew GN, Journal of Polymer Science: 

Part A: Polymer chemistry 2004; 42:3860-3864. 

Keywords: polymers; biological activity; click chemistry; 

Fluorescence; 



s1050 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 7 7 

BorAte eSter MediAted AMidAtion And 

trAnSAMidAtion reACtionS 

r. LAniGAn 1 , t. ShePPArd 1 

1 University College London, Chemistry, London, 


The formation of an amide bond is an essential 

transformation in organic chemistry, the amide bond is found in 

25% of known drugs. [1] It is a condensation reaction between a 

carboxylic acid and an amine with the elimination of one molecule 

of water. Amidation reactions typically require preactivation of 

the carboxylic acid as an acid chloride or anhydride, or the use of 

coupling reagents, which reduces the efficiency of the reaction. 

We have previously shown that tris-(2,2,2-trifluoroethyl) borate 

[B(OCH CF ) ] can be used to amidate unactivated carboxylic 

2 3 3 

acids. [2] We have recently developed a cheaper and more 

convenient procedure for the synthesis of B(OCH CF ) from 

2 3 3 

boric anhydride (£27/kg) instead of boron tribromide (£765/kg) [3] 

. 

Unlike previous work involving stoichiometric boron 

reagents for amidation B(OCH CF ) does not require anhydrous 

2 3 3 

conditions or an excess of the carboxylic acid or amine for the 

reaction to proceed efficiently. A wide range of amides can be 

synthesised containing aliphatic, aromatic and heteroaromatic 

substituents on both the acid and amine partner. [3] The synthesis 

of paracetamol has also been carried out using this methodology. 

The products are purified via simple aqueous or solid phase work 

up. This method is also useful for the amidation of N-protected 

amino acids with both primary and secondary amines. [3] 

A formylation method using DMF in the presence of 

B(OCH CF ) has also been developed. 2 3 3 3 Trimethoxyboroxine was 

investigated as an amidation reagent and displayed similar utility 

to B(OCH CF ) . We have carried out an NMR study to elucidate 

2 3 3 

the reaction mechanism. 

references: 

1.. C. A. G. N. Montalbetti and V. Falque, V. Tetrahedron, 

2005, 61, 10827-10852. 

2. P. Starkov and T. D. Sheppard, Org. Biomol. Chem., 2011, 

9, 1320-1323. 

3. R. M. Lanigan, P. Starkov and T. D. Sheppard, Manuscript 

in preparation. 

Keywords: Amides; Borates; Boron; Carboxylic acids; 

Amines; 


P - 0 3 7 8 

fLuoroALKyLideneS SyntheSiS froM 

BenzothiAzoLyL derivAtiveS 

f. LArnAud 1 , e. Pfund 1 , A. GAneSAn 2 , B. LinCLAu 3 , 

t. Lequeux 1 

1 Laboratoire de Chimie Moléculaire et Thioorganique, UMR 

6507, Caen, France 

2 University of East Anglia, School of Pharmacy, Norwich, 


3 University of Southampton, School of Chemistry, Southampton, 


The fluorovinylic moiety has been introduced onto several 

bio-active compounds such as vitamins, prostaglandins, 

hormones, pheromones and peptide isosteres. However, access to 

fluoroalkylidenes is not straightforward and required numerous 

steps including functionalization of fluoroacrylates easily obtained 

by HWE reaction. 

In 2002, our group described the first one step synthesis of 

fluoroalkylidene via the modified Julia reaction. Since this report, 

our main research deals with the preparation of various alkylated 

fluorobenzothiazolylsulfones as new building blocks for the 

expeditive synthesis of fluoroalkenes. 

For the preparation of alkylfluorosulfones, our strategy is 

based on alkylation reactions under Barbier conditions of 

benzothiazolylsufonyl fluoroacrylate using alkyl iodides and 

alcohols, followed by a decarboxylation process carried out under 

Krapcho conditions. 

Currently, this approach is applied for on the developement 

of new peptidomimetics. Indeed, we already reported the 

expeditive synthesis of fluorinated dipeptide analogues using the 

modified Julia reaction. Our recent results will be presented. 

Keywords: Julia reaction; fluorine; olefination; 

Peptidomimetics; alkenes; 



s1051 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 7 9 

the infLuenCe of PerfLuorinAted 

SuBStituentS on the nuCLeoPhiLiC 

reACtivity of SiLyL enoL etherS 

h. LAuB 1 , d. GLAdow 2 , h. u. reiSSiG 2 , h. MAyr 1 

1 Ludwig-Maximilians-Universität, Department Chemie, 

München, Germany 

2 Freie Universität Berlin, Institut für Chemie und Biochemie, 


Introducing fluorine into organic molecules can alter the 

properties of these substances substantially, especially concerning 

their biological activity. [1] Therefore, fluorinated compounds are 

of interest for pharmaceutical and agricultural industry. Intrigued 

by their unique properties we have employed the benzhydrylium 

methodology to investigate the effect of perfluorinated alkyl and 

aryl groups on the reactivities of silyl enol ethers, which are 

important building blocks in organic synthesis. [2] 

As benzhydrylium ions with variable p- and m-substituents 

cover a broad range of reactivity while the steric shielding of the 

reaction center is kept constant, they have been used as reference 

electrophiles for the construction of a comprehensive 

nucleophilicity scale based on eq 1, in which electrophiles are 

characterized by one parameter (E) and nucleophiles are 

characterized by the solvent-dependent parameters s (sensitivity) 

N 

and N (nucleophilicity). [3] 

log k(20 °C) = s (N + E) (1) 

N 

We now studied the kinetics of the reactions of fluorinated 

silyl enol ethers with benzhydrylium ions by UV–Vis 

spectroscopy in dichloromethane in order to quantify the 

deactivating effects of perfluorinated groups. Comparison of 

previously reported nucleophilicity parameters of silyl enol 

ethers [3] with those of their fluorinated analogues shows that 

fluorination decreases the nucleophilic reactivity tremendously. 

Thus, H C=C(CF )OSiMe is 10 2 3 3 6 times less reactive than 

H C=C(CH )OSiMe and H C=C(C F )OSiMe is 10 2 3 3 2 6 5 3 4 times less 

reactive than H C=C(C H )OSiMe . These fluorinated enol ethers 

2 6 5 3 

thus have similar nucleophilicities as ordinary alkenes. 3 

references: 

1. Müller, K.; Fäh, C.; Diederich, F. Science 2007, 317, 

1881–1886. 

2. Kobayashi, S.; Manabe, K.; Ishitani, H.; Matsuo, J. I. Sci. 

Synth. 2002, 4, 317–369. 

3. a) Mayr, H.; Bug, T.; Gotta, M. F.; Hering, N.; Irrgang, B.; 

Janker, B.; Kempf, B.; Loos, R.; Ofial, A. R.; 

Remennikov, G.; Schimmel, H. J. Am. Chem. Soc. 2001, 

123, 9500–9512; 

b) For a comprehensive listing of nucleophilicity 

parameters N and electrophilicity parameters E, see: 

http://www.cup.uni-muenchen.de/oc/mayr/DBintro.html. 

Keywords: Silanes; Substituent effects; Kinetics; Linear free 

energy relationships; Fluorine; 

P - 0 3 8 0 

eSi-MS StudieS of oxidAtive 

PALLAdo-CAtALyzed reACtionS 

J. Le BrAS 1 


1 Institut de Chimie Moléculaire de Reims, UMR CNRS 7312, 

Reims, France 

Comprehensive mechanistic investigations usually require 

kinetic data, identification of catalytic species and a global 

reaction law. For processes based on combination of different 

parameters, such as catalytic reactions, the proposition of a 

mechanism and the selection of the active species for the 

determination of the rate law may not be accurate. ESI-MS has 

rapidly become a major tool in identifying reactive intermediates 

and has achieved great success in mechanistic investigations. [1] 

Most of the examples of palladium catalysis consist of 

nonoxidative methods, especially cross-coupling reactions. 

Oxidative reactions tend to be more challenging; they require the 

use of an external oxidant, and the conditions are incompatible 

with air-sensitive phosphine ligands, which have been critical to 

the success of the Pd0-catalysed cross-couplings. As a result, 

palladium-catalyzed oxidative reactions have received less 

attention than their nonoxidative counterparts and their 

mechanisms are less known. 

We will present the mechanistic studies developed by 

ESI-MS in our laboratories over the past years on various palladocatalyzed 

reactions. [2] We have for examples shown that dinuclear 

palladium complexes are more involved as active catalytic 

intermediates than mononuclear species in the Wacker oxidation 

of alkenes. A cascade reaction from allylphenols leading to 

2-(1,2-dihydroxypropyl)phenol derivatives will be presented. The 

nature of the catalytic species involved in dehydrogenative Heck 

reactions and in the formation of diarylalkanes, through 

C-H activation, will be also discussed. 

references: 

1. L. S. Santos Reactive Intermediates: MS Investigations in 

Solution, Wiley-VCH, Weinheim, 2010. 

2. E. Thiery, C. Chevrin, J. Le Bras, D. Harakat, J. Muzart 

J. Org. Chem. 2007, 72, 1859. E. Thiery, D. Harakat, J. Le 

Bras, J. Muzart Organometallics 2008, 27, 3996. 

E. Thiery, C. Aouf, J. Belloy, D. Harakat, J. Le Bras, 

J. Muzart J. Org. Chem. 2010,75, 1771. 

D. Harakat, J. Muzart, J. Le Bras, RSC Adv. 2012, 2, 3094. 

Keywords: Mass spectrometry; C-H activation; Homogeneous 

catalysis; Reaction mechanisms; Palladium; 



s1052 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 8 1 

AnALySiS of therMAL deGrAdAtion BehAviorS 

of PoLyKetone/PoLyAMide-6 BLendS 

C. S. Lee 1 , C. yiM 1 , S. KiM 1 , C. dreyer 2 , J. AhLerS 2 , 

h. J. GLAeSeL 2 , S. K. yoon 3 , J. y. Jho 4 

1 Hyundai Motor Group Automotive R&D Division, Polymeric 

Materials Research Team, Whasung city, Republic of Korea 

2 Fraunhofer Institution Polymeric Materials and Composites, 

PYCO, Teltow, Germany 

3 Hyosung, Technology Commercialization Center, Anyang city, 


4 Seoul National University, School of Chemical and Biological 


An aliphatic polyketone (PK) terpolymer consisting of 

carbon monoxide, ethylene, and propylene has excellent 

properties such as low water absorption, superb chemical 

resistance, low gas permeability, and high heat distortion 

temperature. Polyketone is well miscible with polyamide-6 due 

to H-bonding between –C=O in polyketone and –NH- in 

polyamide-6, and the mechanical properties of polyketone are to 

be easily controlled through blending with polyamide-6. So the 

blends are thought to be the promising materials for the 

automotive parts, especially under the hood. During the residence 

at the processing temperatures, however, the blends have a 

chance to degrade easily. The thermal degradation behaviors of 

the blends with additives were observed. After long time 

residence for more than 60 min at 250 °C (the upper limit 

temperature recommended for injection molding of the blends), 

the initial single melting peak split into two peaks corresponding 

to polyketone and polyamide-6 moiety, respectively. With 

increasing content of polyamide-6 in the blends, the melting 

points of polyketone moiety in the blends showed the tendency 

of significant decrease with increasing content of polyamide-6 in 

the blend, but the melting points of polyamide-6 moiety were 

almost constant. TGA isothermal measurement at 250 °C for 

60 min showed the weight reduction was enlarged with increasing 

content of polyamide-6 in the blends. Inorganic particles were 

compounded in the blends in order to improve the thermal 

stability at the processing temperature. With decreasing the size 

of the particles, the thermal stability of the materials was more 

improved, especially in tens of nano size. In conclusion, 

polyamide-6 tends to accelerate the thermal degradation of 

polyketone in the blends, but polyamide-6 itself will not degrade 

at high processing temperature. Nano inorganic particles are good 

additives for the improvement of thermal stability of polyketone 

and its blends with polyamide-6. 

Keywords: Polymers; Amides; Ketones; 


P - 0 3 8 2 

GoLd-CAtALyzed SyntheSiS of fLuorinAted 

2,5-dihydrofurAnS And 3,4-dihydroPyrAnS 

L. LeMPKe 1 , n. KrAuSe 1 

1 TU Dortmund, Organic Chemistry, Dortmund, Germany 

The enormous potential of fluorine-substituted molecules in 

organic chemistry is reflected in a special interest of new synthetic 

strategies. Based on the significant change of chemical and 

physiological properties there exist many pharmaceutical and 

industrial applications. [1] These include solubility, lipophilicity, 

metabolic stability and bioavailability by replacement of hydrogen 

with fluorine. [2–3] 

In terms of heterocyclic structures several methods for 

C-F-bond formation have been developed using electrophilic and 

nucleophilic fluorination reagents. Examples to form 

fluorinated precursors as well as fluorination of the heterocyclic 

products are known. [4–5] Particularly interesting are 

tandem-fluorination-cyclization reactions using Selectfluor or 

NFSI (N-Fluorobenzenesulfonmide) as fluorelectrophiles. [6–7] 

The gold-catalyzed cycloisomerization of α- and 

β-hydroxyallenes forming 2,5-dihydrofurans and 

3,4-dihydropyrans, respectively, is a well-known reaction. [8] 

Using this selective formation to prepare fluorinated 

cycloisomerization products is of particular value for the total 

synthesis of natural compounds and their derivatives. 

In this project, the gold-catalyzed cycloisomerization of 

α- and β-hydroxyallenes forming fluorinated cyclization products 

is pursued. First results of our investigations and their perspectives 

are reported. 

references: 

1. Dolbier Jr., W. R.; J. Fluorine Chem. 2005, 126, 157–163. 

2. O’Hagan, D.; Chem. Soc. Rev. 2008, 37, 308–319. 

3. Fluorine in Bioorganic Chemistry (Eds.: J.T. Welch, 

S. Eswarakrishman); Plenum, New York, 1991. 

4. Li, Y.; Wheeler, K. A.; Dembinski, R.; Adv. Synth. Catal. 

2010, 352, 2761–2766. 

5. Coe, P. L.; Taleker, R. R.; Walker, R. T.; J. Fluorine Chem. 

1994, 69, 19-24. 

6. Qian, J.; Liu Y.; Zhu, J.; Jiang, B.; Xu, Z.; Org. Lett. 2011, 

13, 4220–4223. 

7. Xu, T.; Mu, X.; Peng, H.; Liu, G.; Angew. Chem. 2011, 

113, 8326–8329. 

8. Winter, C.; Krause, N.;.Chem. Rev. 2011, 111, 1994-–2009. 

Keywords: Gold; Allenes; Cyclization; Fluorine; Heterocycles; 



s1053 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 8 3 

AdAPtoMerS: enhAnCinG trAnSPort 

ProPertieS throuGh MoLeCuLAr 

AdAPtABiLity 

K. LinG 1 , S. SMith 1 , J. CLouGh 1 

1 Syngenta, Herbicide Chemistry, Bracknell, United Kingdom 

The bioavailability of an agrochemical or drug molecule at 

the target site requires the successful balance of physicochemical 

properties such as aqueous solubility and membrane 

permeability. 1 Such properties are often inversely related and so 

designing the optimum molecule generally requires a compromise 

in one or both properties. An alternative strategy is to design 

molecules that can adapt their physical properties to match their 

environment, allowing, for example, simultaneously high aqueous 

solubility and membrane permeability. 2 The authors present a 

systematic study into the use of intramolecular hydrogen-bonding 

as a tool for molecular adaptability in a series of heteroaryl ureas. 

The relationship between the intramolecular hydrogen-bonding 

equilibrium constant (K ) and a number of measured and 

i 

calculated physicochemical properties will be discussed. 


P - 0 3 8 4 

A hiGhLy SeLeCtive diAryLProLinoL SiLyL 

ether CAtALySt iMMoBiLized on 

PhoSPhorouS dendriMerS And MAGnetiC 

nAnoBeAdS 

r. LinhArdt 1 , M. KeLLer 2 , J. P. MAJorAL 2 , 

A. M. CAMinAde 2 , o. reiSer 1 

1 Institute of Organic Chemistry, Faculty for Chemistry and 


2 Laboratoire de Chimie de Coordination, CNRS, Toulouse, 

France 

Over the last years the immobilization of catalysts on solid 

supports became of increasing interest with regard to recycling 

and protection of environmental resources. [1] The choice of the 

support mainly depends on its physical, thermal and chemical 

stabilities. Furthermore, the decision is also dependent on the ease 

of recovery of the supported catalyst. Classic heterogeneous 

catalysts were recovered by filtration or extraction techniques, 

however, they often suffer from the drawback of a low activity 

in comparison to homogeneous catalysts. In contrast, 

semi-heterogeneous catalysts combine the benefits of 

heterogeneous and homogeneous catalysis by linking a 

homogeneous catalyst to readily dispersible nanoparticles [2] 

or soluble macromolecules (e.g. polymers, PEG or dendritic 

structures) [3] which can be precipitated at the end of the reaction. 

Here, we report the immobilization of a diarylprolinol silyl 

ether catalyst on phosphorous dendrimers and polymer-coated 

magnetic nanobeads as semi-heterogeneous spherical supports. 

The catalysts were successfully used in the enantioselective 

Michael addition of propanal to (E)-b-nitrostyrene. The reactions 

showed good to excellent yields, diastereoselectivities and 

enantioselectivities. Furthermore, a positive dendritic effect was 

observed. Recycling was achieved by precipitation and filtration 

in the case of dendrimers and magnetic decantation in the case of 

magnetic nanobeads. 

references: 

1. A. F. Trindade, P. M. P. Gois, C. A. M. Afonso, Chem. Rev. 

2009, 109, 418-514. 

2. a) D. Astruc, F. Lu, J. R. Aranzaes, Angew. Chem. Int. 

Ed. 2005, 44, 7852-7872; 

b) S. Shylesh, V. Schünemann, W. R. Thiel, Angew. Chem. 

Int. Ed. 2010, 49, 3428-3459; 

c) A. Schätz, O. Reiser, W. J. Stark, Chem. Eur. 

J. 2010, 16, 8950-8967. 

3. a) D. E. Bergbreiter, Catal. Today 1998, 42, 389-397; 

b) D. Astruc, F. Chardac, Chem. Rev. 2001, 101, 2991- 

3024. 

Keywords: Michael addition; Nanoparticles; Dendrimers; 



s1054 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 8 5 

CheMoSeLeCtive CroSS-CouPLinG reACtionS 

with differentiAtion Between two 

nuCLeoPhiLiC SiteS on A SinGLe thioPhene 

BuiLdinG BLoCK 

J. LinShoeft 1 , A. C. J. heinriCh 1 , S. A. w. SeGLer 1 , 

A. StAuBitz 1 

1 Otto-Diels-Institut für Organische Chemie, Christian- 

Albrechts-University, Kiel, Germany 

Transition metal catalyzed cross-coupling reactions are 

among the most powerful tools in synthesis. [1] In contrast to the 

well-established electrophile-selective cross-coupling reactions, 

nucleophile-selective cross-coupling reactions are barely 

described in synthetic organic chemistry. We have systematically 

developed a nucleophile-selective cross-coupling method with 

excellent isolated yields, using the different reactivities of the 

Stille reaction and Suzuki-Miyaura cross-coupling reaction. [2] For 

this purpose, we synthesized a thiophene building block, bearing 

a stannyl group and boronic ester in 2- and 5-position, which can 

undergo a selective Stille coupling with a wide range of 

electrophiles. The remaining boronic ester can be used for a 

separate Suzuki coupling, which may be performed in an efficient 

one-pot approach. 

references: 

1. a) A. Suzuki, Angew. Chem. 2011, 123, 6854; Angew. 

Chem. Int. Ed. 2011, 50, 6722; 

b) A. d. Meijere, P. J. Stang, Metal-Catalyzed Cross-Coupling 

Reactions, 2nd ed., Wiley-VCH, Weinheim, 2004. 

2. J. Linshoeft, A. C. J. Heinrich, S. A. W. Segler, P. J. Gates, 

A. Staubitz, submitted. 

Keywords: Cross-coupling; Chemoselectivity; Heterocycles; 



P - 0 3 8 6 

effeCtS of the nAno zno Powder in SoMe 

therMAL And PhySiCAL ProPerty of riGid 

PoLyurethAne foAMS 

S. Lotfi 1 , A. MirMohSeni 1 , L. MohAMMAd 2 

1 University of Tabriz, Applied Chemistry, Tabriz, Iran 

2 University of Tehran, Agriculture, Tabriz, Iran 

Development of rigid polyurethane foams (RPUF) in the 

industrial insulation, and saving energy was cased the importance 

of thermal conductivity and isolation property of RPUF. The 

properties of rigid polyurethane foams can be modified over a 

wide range depending on the raw materials used for its synthesis. 

The objective of this study is to investigate an appropriate 

process to fabricate the polyurethane Nanocomposites. In 

nanocomposites, nano powders were used as nucleating agent to 

decrease a cell size of the RPUFs as well as improve the thermal 

insulating properties of rigid polyurethane foams. Rigid 

polyurethane foams Nanocomposites (R PUFs) that contain up to 

0.93% Zinc oxid were successfully fabricated from polymeric 

4,4-diphenylmethane diisocyanate, polyether polyols, nano ZnO 

powder, silicone surfactant, hydrochlorofluorocarbon (HCFC) 

141B, and distilled water. This Nanocomposite 30% decreased 

amount of thermal conductivity in 0.93% (w/w) Zinc oxid than 

reference. 

Keywords: rigid polyurethane foam; thermal conductivity; 

Nanocomposit; Nucleating agents; ZnO; 



s1055 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 8 7 

AtroPiSoMeriC ChirAL 4,4'-BiPyridineS 

v. MAMAne 1 , e. AuBert 2 , P. PeLuSo 3 , S. CoSSu 4 

1 Universite de Lorraine, Organic Chemsitry, Vandoeuvre les 

Nancy, France 

2 Universite de Lorraine, Physical Chemsitry, Vandoeuvre les 

Nancy, France 

3 CNR, Istituto di Chimica Biomolecolare, Sassari, Italy 

4 Universita Ca’ Foscari di Venezia, Scienze Molecolari e 

Nanosistemi, Venezia, Italy 

4,4'-Bipyridine is one of the most famous ligand used in 

supramolecular chemistry due to the presence of two donor atoms 

along a rigid structure. Considering the importance of chiral 

supramolecular networks in many applications such as 

asymmetric catalysis, it was surprising to find limited examples 

of chiral 4,4'-bipyridines in the literature. Based on our recent 

synthesis of polyhalogenated 4,4'-bipyridines [1] , we report herein 

two methods for the preparation of enantiomerically pure 

4,4'-bipyridines. The first method is based on the synthesis of a 

chiral tetrahalogenated 4,4'-bipyridine (substituted in 3,3',5,5') 

which after selective cross-couplings yields several atropisomeric 

derivatives. The enantiomers are separated by chiral HPLC and 

their absolute configurations are determined by X-ray diffraction 

(XRD) and electronic circular dichroism (ECD). Alternatively, 

the chiral tetrahalogenated 4,4'-bipyridine can be first 

enantioseparated and then involved in cross-coupling reactions 

without racemization [2, 3] . The second method concerns the 

direct functionalization in 3-position of an achiral 

tetrahalogenated 4,4'-bipyridine (substituted in 2,2',5,5') to 

generate atropisomeric chiral 4,4'-bipyridines; this second method 

allows for asymmetric synthesis. Chiral HPLC allows easy 

enantioseparation due to a butressing effect of substituent in 

2-position [3] and the absolute configurations of the separated 

atropisomers are determined by XRD and ECD. In order to show 

the potential interest of these new chiral ligands for Metal Organic 

Frameworks (MOFs) synthesis and applications, some metal 

complexes including tetrahalogenated 4,4'-bipyridines and 

derivatives will be presented. 

references: 

1. M. Abboud, V. Mamane, E. Aubert, C. Lecomte, Y. Fort, 

J. Org. Chem. 2010, 75, 3224. 

2. V. Mamane, E. Aubert, P. Peluso, S. Cossu, J. Org. Chem. 

2012, 77, 2579. 

3. P. Peluso, V. Mamane, E. Aubert, S. Cossu, J. Chromat. 

A, Accepted 

Keywords: Atropisomerism; Biaryls; Circular dichroism; 

Configuration determination; Chiral resolution; 


P - 0 3 8 8 

hiGh-PerforMAnCe Liquid ChroMAtoGrAPhy 

enAntioSePArAtion of AtroPiSoMeriC 

4,4'-BiPyridineS on iMMoBiLized 

PoLySACChAride-BASed ChirALPAK iA And 

ChirALPAK iC: iMPACt of SuBStituentS And 

eLeCtroniC ProPertieS 

P. PeLuSo 1 , v. MAMAne 2 , e. AuBert 3 , S. CoSSu 4 

1 CNR - Consiglio Nazionale delle Ricerche, Istituto di Chimica 

Biomolecolare, Sassari, Italy 

2 Universite de Lorraine, Organic Chemistry, Vandoeuvre les 

Nancy, France 

3 Universite de Lorraine, Physical Chemistry, Vandoeuvre les 

Nancy, France 

4 Universita Ca Foscari di Venezia, Scienze Molecolari e 

Nanosistemi, Venezia, Italy 

More than other techniques [1] , high-performance liquid 

chromatography (HPLC) on chiral stationary phases (CSPs) is the 

most used for the enantioseparation of chiral compounds. 

Recently, this technique has been successfully applied to 

the preparation of pure enantiomers of new atropisomeric 

4,4'-bipyridines [2–3] . Due to the novelty of the field, asymmetric 

procedures devoted to the preparation of optically pure 

4,4'-bipyridines are not available yet in the literature. The 

4,4'-bipyridyl system is one of the most used connectors between 

transition metal atoms for building metal organic frameworks 

(MOFs) due to its structural and topological characteristics. Chiral 

MOFs are of great interest in asymmetric catalysis and the access 

to enantiopure 4,4'-bipyridines is therefore highly required. Based 

on the chromatographic methods recently developed by us for the 

enantioseparation of atropisomeric 4,4'-bipyridines by using 

coated polysaccharide-based CSPs [4], we report herein 

new and efficient methods for the direct enantioseparation 

of 3,3',5,5'-tetrahalogenated, 2,2',3,3',5-pentahalogenated, 3,3'- 

-dibromo-5,5'-disubstituted and 2,2',3,3'-tetrahalo-5-substituted 

4,4'-bipyridines on two immobilized polysaccharide-based CSPs, 

Chiralpak IA and Chiralpak IC. The impact of structural 

modifications inside the bipyridyl skeleton on the separation 

behavior was investigated through a parallel evaluation of 

experimental data, such as retention (k) and separation factors (α), 

resolution (R ) and density functional theory (DFT) computed 

s 

molecular properties of the analytes. The semipreparative 

recoveries of optically pure atropisomers of the examined 

4,4'-bipyridines provide valuable starting materials for the future 

preparation of homochiral MOFs. 

references: 

1. T. J. Ward, K. D. Ward, Anal. Chem. 2010, 82, 4712. 

2. A. Rang, M. Engeser, N. M. Maier, M. Nieger, W. 

Lindner, C. A. Schalley, Chem. Eur. J. 2008, 14, 3855. 

3. V. Mamane, E. Aubert, P. Peluso, S. Cossu, 

J. Org. Chem. 2012, 77, 2579. 

4. P. Peluso, V. Mamane, E. Aubert, S. Cossu, 

J. Chromatogr. A 2012, accepted. 

Keywords: Biaryls; Molecular recognition; Enantioselectivity; 

Analytical Methods; Atropisomerism; 



s1056 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 8 9 

SyntheSiS of AnALoGueS of Azt with 

triAzoLe Moiety 

e. MAouGAL 1 , M. MAthé-ALLAinMAt 1 , 

d. duBreuiL 1 , J. LeBreton 1 

1 Universite de Nantes, Loire atlantique, Nantes, France 

Currently, AidS (Acquired Immune Deficiency Syndrome) 

is considered as a pandemic, causing about 1.8 million deaths 

between 1981 (date on which the first case of AIDS was 

identified) and 2009. Azt or 3'-azido-3'-deoxythymidine was the 

first antiretroviral approved for the treatment of AIDS. This 

compound, due to the absence of the hydroxyl group in position 

3', inhibits reverse transcriptase, and prevents the extension of the 

viral DNA chain and finally viral replication of the RNA. 

Herpes is a viral disease caused by both Herpes Simplex 

Virus type 1 (HSV-1) and type 2 (HSV-2). This pathogen, in its 

various forms, affects more than 90% of the population 

worldwide. Acyclovir or 9-[{2-hydroxyethoxy}-methyl]- 

-guanosine (ACV) is an acyclic analogue of the natural nucleoside 

2'-deoxyguanosine, considered as the first choice of treatment for 

herpes simplex virus types 1 and 2. ACV is also deprived of this 

3’-OH function present in the natural nucleosides, inhibits herpes 

DNA polymerase, and behaves as a “suicide inhibitor” 

As part of the discovery of new molecules to complete the 

therapeutic arsenal directed to these two viral diseases, we are 

interested in the synthesis of a new family of antiretroviral of the 

AZT type with a 1,2,3-triazole-1,4-disubstituted moiety. These 

compounds were tested against HIV in collaboration with the 

group of Professor Raymond F. Schinazi (Emory University 

School of Medecine/Veterans Affair Medical Center, Atlanta, 

Georgia 30033, USA) and against herpes in collaboration with 

Professor Nathalie Bourgougnon (University of Bretagne Sud, 

Laboratory of Biotechnology and Marine Chemistry, Vannes). 

Keywords: Click Chemistry; Drug discovery; 


P - 0 3 9 0 

triBenzotriquinACene – A new And verSAtiLe 

SyntheSiS 

G. MArKoPouLoS 1 , L. henneiCKe 1 , J. Shen 2 , 

y. oKAMoto 2 , P. G. JoneS 3 , h. hoPf 1 

1 Institut für Organische Chemie, Technische Universität 

Braunschweig, Braunschweig, Germany 

2 Polymer Materials Research Center, Harbin Engineering 

University, Harbin, China 

3 Institut für Anorganische und Analytische Chemie, Technische 

Universität Braunschweig, Braunschweig, Germany 

Tribenzotriquinacene is a rigid bowl-shaped hydrocarbon 

that was first synthesized by Kuck and co-workers. We have 

developed a new synthesis of this intriguing molecule which 

affords the parent compound in higher yield. In addition, our 

synthetic scheme allows easy preparation of ortho-functionalized 

and C -chiral derivatives that have so far only been poorly 

3 

accessible. These derivatives are interesting for asymmetric 

catalysis and supramolecular chemistry and their chiral resolution 

by HPLC is reported. 

Keywords: hydrocarbon chemistry; bowl-shaped molecules; 

chiral resolution; 



s1057 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 9 1 

quAntitAtive PrePArAtion of 3,4-di(Methy - 

Lene)tetrAhydrothioPhene-1,1-dioxide By 

zn-induCed 1,4-eLiMinAtion. A 6-C Synthon 

for the PrePArAtion of A Short-ChAin [4+2] C60 

MonoAdduCt. 

M. MArKouLideS 1 , C. ioAnnou 1 , M. MAnoS 1 , 

n. ChronAKiS 1 

1 University of Cyprus, Department of Chemistry, Nicosia, 

Cyprus 

Our interest in the synthesis of [60]fullerene derivatives 

derived from the Diels-Alder reaction in combination with the 

limitations posed by the current methods which utilize 

2,2'-bisallyl-diradical prompted us to investigate the 

optimum reaction conditions for the preparation of 

3,4-di(methylene)tetrahydrothiophene-1,1-dioxide and the 

subsequent efficient synthesis of a short-chain [4+2] C60 monoadduct bearing a reactive site for further functionalization. 

In summary, we have demonstrated a practical 

and efficient preparation of the highly reactive 

3,4-di(methylene)tetrahydrothiophene-1,1-dioxide. Optimization 

of the reaction parameters allow the quantitative preparation of 

the diene-sulfone via a zinc-induced 1,4-elimination of 

3,4-bis(bromomethyl)-2,5-dihydrothiophene-1,1-dioxide with 

no signs of polymerization. In particular, acetone was the solvent 

of choice at a concentration of 6 mg/mL. Activated Zn-dust 

promoted efficiently the 1,4-elimination step while, the shortest 

reaction time was achieved with microwave irradiation. The 

diene-sulfone can be employed in Diels–Alder reactions with 

dienophiles either in acetone or after exchanging the solvent with 

dry benzene where the diene remains stable for several weeks 

at -20 °C. The overall yield of the one-pot procedure 

(1,4-elimination/Diels-Alder reaction) when DMAD was utilized 

as a dienophile was more than 90%. Zinc incompatible 

dienophiles can be treated with acetone solutions of diene-sulfone 

by simply filtration of the zinc salts prior to the Diels-Alder 

cycloaddition. The diene-sulfone synthesized under the 

aforementioned optimum conditions was utilized for the synthesis 

of a [4+2] C monoadduct bearing a masked-diene moiety. The 

60 

applied method led to the successful preparation of the C60 cycloadduct isolated in 56% yield. [1] 

Dienophiles with a wide range of chemical functionalities 

could be employed to provide a novel post-synthetic modification 

strategy via cheletropic extrusion of SO targeting novel C 2 60 

derivatives for various applications in materials science. 

references: 

1. Markoulides, M. S.; Ioannou, C. P.; Manos, M. J.; 

Chronakis, N. J. Org. Chem. 2012, submitted. 

Keywords: 3,4-di(methylene)tetrahydrothiophene-1,1-dioxide; 

[60]fullerene; [4+2] monoadducts; six carbon (6-C) synthon; 

2,2'-bisallyl diradical; chemoselective one-pot 1,4elimination/[4+2] 

cycloaddition/aromatization; 


P - 0 3 9 2 

SyntheSiS And StruCturAL eLuCidAtion 

of noveL 2-[(1e,3e)-4-AryLButA-1,3- 

-dienyL]quinoLin-4(1h)-oneS 

v. L. M. SiLvA 1 , A. M. S. SiLvA 1 , J. A. S. CAvALeiro 1 

1 University of Aveiro, Chemistry Department, Aveiro, Portugal 

Quinolin-4(1H)-ones are well known heterocyclic 

compounds due to their significant biological properties. A wide 

variety of clinical applications have been approved for these 

compounds including the treatment of respiratory, gastrointestinal, 

and gynaecologic infections, sexually transmitted diseases, 

prostatitis and some skin, bone and tissues infections. [1] 

Quinolin-4(1H)-ones are a class of drugs that target the bacterial 

type II DNA topoisomerases and could also inhibit mammalian 

topoisomerase activity and tubulin polymerization thus acting as 

potent antitumor agents. [2] They are also cytotoxic agents and 

cardiovascular protectors. [3, 4] 

Following our previous studies on (E)-2-styrylquinolin- 

-4(1H)-ones, 5,6 now we report the synthesis of their highly 

conjugated analogues 2-[(1E,3E)-4-arylbuta-1,3-dienyl]quinolin- 

-4(1H)-ones, which are very important scaffolds for the synthesis 

of new 1-arylacridin-9(10H)-ones. The developed synthetic 

methodology involves the condensation of 2'-aminoacetophenone 

with (2E,4E)-5-arylpenta-2,4-dienoic acid derivatives in the 

presence of DCC and 4-pyrrolidino-pyridine to give the (2E,4E)- 

-N-(2-acetylphenyl)-5-arylpenta-2,4-dienamides in moderate 

yields. Finally the base-induced cyclization of these dienamides 

afforded the desired 2-[(1E,3E)-4-arylbuta-1,3-dienyl]quinolin- 

-4(1H)-ones in good yields. To the best of our knowledge, the 

synthesis of these quinolin-4(1H)-ones or their N-substituted 

derivatives is not reported as well as their structural elucidation 

which was accomplished by 1D and 2D NMR spectroscopic 

studies. 

Acknowledgement: Thanks are due to the University of Aveiro, 


Unit and the Project (POCI/QUI/58835/2004). Vera Silva also 

thanks FCT for the grant (SFRH/BPD/27098/2006). 

references: 

1. Livermore, D.M. (2012), Antimicrob. Agents, 283. 

2. Mitscher, L.A. (2005), Chem. Rev., 105, 559. 

3. Xia, Y., Yang, Z.-Y., Xia, P., Bastow, K.F., Nakanishi, Y., 

Nampoothiri, P., Hamkel, E., Brossi, A., Lee, K.-H. 

(2003), Bioorg. Med. Chem. Lett., 13, 2891. 

4. Lee, H.-Z., Lin, W.-C., Yeh, F.-T., Wu, C.-H. (1998), 

Eur. J. Pharmacol., 354, 205. 

5. Almeida, A.I.S, Silva, V.L.M., Silva, A.M.S., Pinto, 

D.C.G.A., Cavaleiro, J.A.S. (2008), Synlett, 17, 2593. 

6. Silva, V.L.M., Silva, A.M.S., Cavaleiro, J.A.S., (2010), 

Synlett, 17, 2565. 

Keywords: Nitrogen heterocycles; Conjugation; Alkylation; 

Cyclization; NMR spectroscopy; 



s1058 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 9 3 

PoLyMer BLendinG AS MACroSCoPiC 

exPreSSion of MoLeCuLAr reCoGnition 

d. MASSeroni 1 , M. dioniSio 1 , L. riCCi 2 , 

G. ruGGeri 2 , e. dALCAnALe 1 

1 University of Parma, Dipartimento di Chimica Organica e 

Industriale, Parma, Italy 

2 University of Pisa, Dipartimento di Chimica e Chimica 

Industriale, Pisa, Italy 

Polymer blends are widespread materials used in modern 

industry and represent one of the most rapidly growing areas in 

polymer science. [1] Numerous attempts have been made to 

minimize interfacial energy and reduce the propensity for phase 

segregation of the polymers. One of the most appealing 

approaches has been the use of non covalent interactions such as 

hydrogen bonding. [2] Recently, our research group has developed 

tetraphosphonate cavitands as monomers for supramolecular 

polymers. They present outstanding molecular recognition 

properties towards positively charged species such as 

N-methylammonium and N-methylpyridinium moieties. [3] Herein 

we present our recent results on molecular level mixing of two 

immiscible polymers, such as polystyrene (PS) and 

poly(butyl)methacrylate (PBMA), [4] through host-guest 

interactions. Specifically, we embedded a tetraphosphonate 

cavitand along the backbone of PS as host (PS-Host) and a 

N-methylpyridinium derivative in the skeleton of PBMA as guest 

motif (PBMA-Guest). The formation of a supramolecular polymer 

architecture was demonstrated in solution by 31 P-NMR and in 

solid state by atomic force microscopy and differential scanning 

calorimetry. The AFM image of 50% PS-Host:50% PBMA-Guest 

mixture shows no phase separation in accordance with the 

formation of supramolecular network. A DSC study of the blend 

shows a single T g at temperature intermediate between the T g of 

the two starting polymers. Moreover chemically induced 

segregation has been triggered by addition of a competitive guest 

(N-methylbutylammonium chloride) which replaced the 

N-methylpyridinium moiety in cavitand binding. 

references: 

1. Lipatov Y. S., Prog. Polym. Sci., 2002, 27, 1721–1801; 

2. Zimmerman S. C. et al., J. Am. Chem. Soc., 2006, 128, 

11582–11590; 

3. Dalcanale E. et al., Angew. Chem. Int. Ed., 2008, 47, 

4504–4508; 

4. Raczkowska J. et al., Macromolecules,2004, 37, 

7308–7315. 

Keywords: Host-guest systems; Polymers; Supramolecular 

chemistry; Molecular recognition; Cavitands; 


P - 0 3 9 4 

SyntheSiS of MoLeCuLeS for the 

ControLLed funCtionALizAtion of 

GrAPhene SurfACeS 

C. MAttioLi 1 , A. Gourdon 1 

1 Cemes, 31, Toulouse, France 

Graphene, a monolayer of carbon atoms packed in a 

two-dimensional honeycomb lattice, has lately become a very 

interesting material, being endowed with exceptional physical 

properties. [1] In particular, electronic properties constitute one of 

the most investigated aspects of graphene, which is considered a 

zero band gap semiconductor. Chemical functionalization 

represents a promising approach for opening a band gap into its 

energetic levels, but, if many ways have been suggested to 

functionalize the surface in a non-covalent [2] or covalent [3] 

“random” fashion, controlled functionalization (i. e. only at 

selected sites) has not yet been described. The innovative 

approach we suggest to get precise control on the sites of 

chemisorption of the molecules is to switch from “chemistry in 

solution” to “on-surface chemistry”: it has been envisaged to 

design molecules self-organizing on graphene surfaces and 

control their chemisorption at an atomic scale precision resorting 

to STM techniques. Here we present the synthesis of molecules 

characterized by the presence of groups potentially reactive under 

the STM tip and long alkyl chains to enlarge the stability of the 

assemblies [4] and allow a control of their geometry [3a] , as well as 

the first results of the STM studies. 

references: 

1. Novoselov, K. S., Angew. Chem. Int. Ed., 2011, 50, 

6986–7002. 

2. Pollard, A. J.; Perkins, E. W., Smith, N. A.; Saywell, 

A., Goretski, G.; Phillips, A. G.; Argent, S. P.; Sachdev, H.; 

Müller, F.; Hüfner, S.; Gsell, S.; Fisher, M., Schreck, M., 

Osterwalder J.; Greber, T.; Berner, S.; Champness, N. R.; 

Beton, P. H.,Angew. Chem. Int. Ed., 2010, 49, 1838–1843. 

3. a) Sarkar, S., Bekyarova, E., Niyogi, S., Haddon, R. C., 

J. Am. Chem. Soc., 2011, 133, 3324–3327; 

b) Hossain, M. Z., Walsh, M. A., Hersam, M. C., 

J. Am. Chem. Soc., 2010, 132, 15399-15403. 

4. Groszek, A. J., Proc. Roy. Soc. Lond. A., 1970, 314, 

473–498. 

Keywords: Scanning probe microscopy; graphene; 




s1059 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 9 5 

APPLiCAtionS of hyPervALent iodine 

reAGentS in the PrePArAtion of SynthetiC 

quinoidS 

B. Meier 1 , G. LAiner 1 , A. PreSSer 1 

1 Karl-Franzens-Universität Graz, Pharmaceutical 

Sciences /Pharmaceutical Chemistry, Graz, Austria 

Naturally occurring quinones and quinols are very 

interesting chemical leads with several biological activities [1] . To 

prepare these promising compounds a number of procedures were 

found in the literature [2] , but all of them have some restrictions. 

As part of a program directed at the discovery of new 

antiprotozoal agents, we were interested in the facile construction 

of the p-quinol skeleton. Hypervalent iodine reagents 

(phenyliodine(III) diacetate, phenyliodine(III) bis-trifluoroacetate, 

etc.) are a versatile oxidation tool meeting the concept of green 

chemistry because of their low toxicity, easy handling, safety and 

ready availability [3] . 

Here we report a practical and general method to prepare a 

series of quinol-derivatives using hypervalent iodine reagents. 

Commercial available para-substituted phenols and their briefly 

modified derivatives acted as starting material. 

references: 

1. Wang WS, Lu P, Duan CH, Feng JC. Nat Prod Res 24, 

370-4 (2010). 

2. a) Fischer A, Henderson GN. Tetrahedron Letters 24, 

131–4 (1983); 

b) Araki S, Katsumura N, Kawasaki K, Butsugan Y. 

J Chem Soc Perk Trans 1 3, 499-500 (1991); 

c) Wells G, Berry JM, Bradshaw TD, Burger AM, Seaton 

A, Wang B, Westwell AD, Stevens MFG. J Med Chem 

46, 532-41 (2003); 

d) Kawakami J, Nakamoto K, Nuwa S, Handa S, Miki S. 

Tetrahedron Letters 47, 1201–3 (2006); 

e) Clive DLJ, Sunasee R, Chen Z. Org Biomol Chem 6, 

2434-41 (2008). 

3. Encyclopedia of Reagents for Organic Synthesis 

Copyright © 2005 John Wiley & Sons, Ltd. 

Keywords: Hypervalent iodine; dearomatization; p-quinol; 

antiprotozoal; 


P - 0 3 9 6 

hiGhLy diAStereoSeLeCtive Method 

for the PrePArAtion of 1,2-ALKenyL dioLS 

t. MeJuCh 1 , i. MAreK 1 



The development of new and highly diastereoselective 

processes for the creation of carbon-carbon and carbon-heteroatom 

bonds is one of the major targets in chemical synthesis. In contrast 

to tertiary stereocenters, the construction of quaternary 

stereocenters, that are carbon centers bearing four different 

non-hydrogen substituents, represents one of the most challenging 

and dynamic areas in organic synthesis. The state-of-the-art is the 

asymmetric construction of such quaternary stereocenters in 

non-cyclic systems (more complicated due to the number of 

degrees of freedom associated with these structures). Most of the 

current methods produce only one carbon-carbon bond per 

chemical step and, therefore, may suffer from low efficiency. 

Recently, we have developed highly diastereoselective and 

efficient process for the construction of 1,2-alkenyl diol moiety 

from simple alkynyl ethers through the formation of several 

carbon-carbon bonds in one chemical step (T. Mejuch, M. 

Botoshansky, I. Marek, Org. Lett. 2011, 13, 3604; T. Mejuch, B. 

Dutta, M. Botoshansky, I. Marek, Org. Biomol. Chem. 2012, 

Advance Article doi: 10.1039/C2OB25121C). The 

stereochemistry was rationalized through a Zimmerman-Traxler 

transition state, in which the bulky group of the carbonyl occupies 

a pseudo-axial position to avoid one gauche interaction (N. 

Gilboa, H. Wang, K. H. Houk, I. Marek, Chem. Eur. J. 2011, 17, 

8000). 

Keywords: allylation; carbonyl compounds; diastereoselective 

synthesis; 



s1060 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 9 7 

SyntheSiS of nAno-CLiP And nAno-Box 

CoMPoundS hAvinG free BASe PorPhyrinS AS 

wALL 

P. Mineo 1 , e. SCAMPorrino 1 , f. SPitALeri 1 

1 University of Catania, Department of Chemical Sciences, 

Catania, Italy 

There is interest in developing smart nanostructures for 

applications in many different fields, from environmental 

monitoring to biological, medical and industrial chemistry. For 

some specific properties, porphyrin-derivatives are among the 

most studied compounds and some applications like chemical 

and/or biological receptors, artificial sensors for drug 

determinations, mimesis of biological systems, etc., are already 

well-defined. Recently, several 3D cyclic oligo-porphyrins with 

different architectures have been studied. The properties of these 

molecules may depend on the size and the hydrophobic nature of 

cavities inside their 3D structure (e.g. suitable to accommodate 

hydrophobic chemicals). 

In this work, the synthesis and characterization of some novel 

water soluble macromolecular cyclic ethers, constituted by two or 

four porphyrin units and spaced with methylene bridges, are 

reported. These compounds, obtained by reaction between 

dibromomethane and 5,15-di[p-(9-methoxytriethylenenoxy)phenyl]- 

-10,20-di[p-hydroxyphenyl] porphyrin, have a co-facial (nano-clip) 

or a four wall-box (nano-box) architecture. 

The aim of these syntheses was to obtain molecular systems 

for recognition and/or carriage of bio-molecules. In particular, 

UV-vis titration showed the easy and reversible protonation of the 

pyrrolic cores with modification of the spatial distance between 

the two co-facial porphyrins and, therefore, the cavity size. This 

reversible modification could be used to change dimer molecule 

status from Open to Closed, and facilitate the accommodation or 

release of suitable chemical species, acting then as a drug carrier. 

Tetrameric porphyrin molecule (a Nano-box) could also be 

used as a drug-carrier, forming inclusion complexes with 

macromolecular drugs or as a nano-reactor for the peculiar 

conditions inside the box. In this last case, 1H-NMR spectroscopic 

analysis showed a high-field shift of aromatic and ether protons 

present in the upper and lower box rims as a specific characteristic 

of this molecular structure. These compounds differ from previous 

analogous porphyrinic systems in their totally covalent structure 

that makes them more versatile potential macromolecular tools. 

Keywords: Porphyrinoids; Synthesis design; UV/Vis 

spectroscopy; NMR spectroscopy; 


P - 0 3 9 8 

GrAftinG C -fuLLerene on AMino ACid Side 

60 

ChAin uSinG PhoSPhine BorAne: new Method 

And eLeCtroCheMiCAL BehAvior 

P. MinoiS 1 , J. BAyArdon 1 , M. J. ondeL eyMin 1 , 

r. Meunier PreSt 1 , S. JuGe 1 

1 Universite de Bourgogne, Molecular Chemistry, Dijon Cedex, 

France 

Recently, amino acid fullerene derivatives received growing 

interest in biological field, [1] for their inhibition properties of the 

hepatitis C virus RP and human immunodeficiency virus-RT. [2] 

Moreover, these unusual amino acids could be used as markers, 

due to the specific spectroscopic and electrochemical properties 

involving the fullerene moiety. [3] 

Recently, we synthesized the first amino acid derivatives 

bearing a secondary phosphine borane, starting from L-aspartic 

acid. Here, we reported the use of these amino acid derivatives to 

link the C -fullerene by P-C bond formation, under phase transfer 

60 

conditions. The electrochemical behavior of these new fullerene 

amino acids is described. 

references: 

1. L.A. Watanabe, M.P.I. Bhuiyan, B. Jose, T. Kato, N. Nishino, 

Tetrahedron Lett. 2004, 45, 7137-7140 

2. T. Mashino, K. Shimotohno, N. Ikegami, D. Nishikawa, 

K. Okuda, K. Takahashi, S. Nakamura, M. Mochizuki, 

Bioorg. & Med. Chem. Lett. 2005, 15, 1107–1109 

3. A. Bianco, T. Da Ros, M. Prato, C. Toniolo, J. Peptide Sci. 

2001, 7, 208–219 

Keywords: amino acids; fullerene; phosphine borane; 



s1061 

chem. Listy 106, s587–s1425 (2012) 


P - 0 3 9 9 

SyntheSiS of 4h-ChroMene derivAtiveS By 

reACtion Between ALKyL iSoCyAnideS And 

diALKyL ACetyLenediCArBoxyLAte in the 

PreSenCe of 7-hydroxyCuMArine 

B. MohtAt 1 , S. fArSiJAni 1 

1 Islamic Azad University Karaj Branch-, Chemistry, Karaj, Iran 

Chromenes constitute a major class of naturally occurring 

compounds, and interest in their chemistry continues unabated 

because of their usefulness as biologically active agents. 

Substituted 4H-chromenes are a new class of anti-cancer 

compounds. 2-amino-4Hchromenes have been of interest because 

of their biological activity and some methods have been reported 

for their synthesis. We now report an efficient synthetic route to 

2-amino-4H-chromenes using alkyl isocyanides and dialkyl 

acetylenedicarboxylate in the presence of 7-hydroxycumarine. 

The structures were deduced from IR, 1H NMR, 13C NMR spectra. 

The present method carries the advantage that not only is 

the reaction performed under neutral conditions, but also the 

starting materials and reagents can be mixed without any 

activation or modification.. 

Keywords: 2-amino-4H-chromene; 7-hydroxycumarine; alkyl 

isocyanides; 


P - 0 4 0 0 

towArdS the deveLoPMent of SuStAinABLe 

P-ConJuGAted MAteriALS: SyntheSiS of new 

donor-ACCePtor SySteMS BASed on extended 

BenzodifurAn derivAtiveS 

C. MouSSALLeM 1 , f. Gohier 1 , P. frere 1 

1 MOLTECH-Angers, Pays de la Loire, Angers, France 

New materials are required to meet the stringent 

requirements of new generation of consumer electronics such as 

cell phone displays, computer and television screens, and solar 

cells. The synthetic pathways of organic semiconductors (OSC) 

are mainly based on coupling reactions involving metal catalysts. 

The electronic properties of these materials are strongly dependent 

on their purity and they must be extensively purified prior to being 

used in an electronic device. A new challenge for the development 

of OSC is to target materials that: 1) are easily prepared, 2) do not 

need to be purified, and 3) have tunable properties. 

The project aims to develop new conjugated systems that 

are compatible for developing organic electronic devices, by using 

green chemistry processes as condensation reactions which give 

only water as byproduct during different stages of the syntheses. 

In this context we have developed a new series of donoracceptor 

materials based on benzodifuran units. The rational of 

this design relies on the easy access to diamino-benzodifuran 

derivative bearing a pentafluorophenyl group by condensation of 

1,4-benzoquinone with pentafluorophenylacetonitrile. Then, the 

lengthening of the conjugation was performed by azomethine 

bonds (isoelectronic of ethylenic bond) obtained by reaction of 

the diamino compound with aldehyde derivatives carrying short 

oligothiophene units. Synthesis, electronic properties and the first 

examples of electronic devices will be discussed; the role of the 

pentafluorophenyl groups on the supramolecular organization will 

be also evidenced. 

Keywords: diamino-benzodifuran; semiconductors; green 

chemistry; devices; azomethine; 



s1062 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 0 1 

ChirAL BifunCtionAL CAtALyStS BASedM on 

C(SP3)-MetALAted PinCer CoMPLexeS 

S. MuSA 1 , d. GeLMAn 1 

1 The Hebrew University of Jerusalem, Organic Chemistry, 


Cooperating ligands are non-innocent ligands that actively 

participate in reversible structural transformations of catalytic 

species over the course of a catalytic cycle. The ligand-metal 

cooperation often brings about unusual and exciting reactivity and 

plays very important role in natural and artificial systems. Among 

others, this concept is of great interest for the design of new 

catalytic bond-breaking/-forming processes, as it offers a 

non-oxidative mechanistic alternative to the classical oxidative 

addition/reductive elimination sequence. 

Recently [1] , we describe the design and synthesis of a new 

bifunctional dibenzobarrelene-based PC(sp3)P pincer ligand, and 

its excellent performance in acceptorless dehydrogenation of 

alcohols. The mechanism of the reaction involving intramolecular 

cooperation between the structurally remote functionality and 

the metal center originates from a unique topology of the 

barrelene-based PC(sp3)Ps. 

We wish now to describe the synthesis of new chiral 

nonracemic dibenzobarrelene based PC(sp3 )P pincer ligand. 

references: 

Musa, S.; Shaposhnikov, I.; Cohen, S.; Gelman, D. Angew. 

Chem., Int. Ed. 2011, 50, 3533. 


P - 0 4 0 2 

CoLLoid-CheMiCAL APProACheS to Crude oiL 

PrePArAtion 

B. MutALiyevA 1 , G. MAdyBeKovA 2 , S. AidArovA 3 

1 South-Kazakhstan State university, Biotechnology, Shymkent, 

Kazakhstan 

2 South-Kazakhstan State pedagogical institute, Chemistry, 

Shymkent, Kazakhstan 

3 Kazakh National Technical university, “Excellence Polytech” 

International Postgraduate Institute, Almaty, Kazakhstan 

Formation of emulsion at an oil recovery is one of the basic 

problems of a petroleum industry which lead to large oil losses at 

preparation for processing. Therefore there is a necessity of the 

decision of the important practical problems, such as clearing of 

oil from salts and waters which is reached by use of various 

deemulgators. 

Researches of colloid-chemical properties of 

polyacrylonitrile derivatives compositions with surfactants have 

allowed to predict their application as deemulgators. Results of 

researches have shown, that deemulsifier action of polymeric 

compositions substantially depends on the macromolecules 

conformation condition defined by a degree of polymer functional 

groups ionization. It is established, that deemulgation depends 

also on superficial activation of polyelectrolits compositions with 

surfactants on the interface. 

From the calculated values of superficial activity of 

polyacrylonitril derivatives compositions with sodium salts of 

oleic acid follows, that formation of a composition leads to 

increase in superficial activity and reduction of standard free 

energy of polymers adsorption. 

Increase of ?? with growth of polymer concentration in a 

mix testifies about interaction between sodium salts of oleic acid 

with polymers by hydrogen communications formation that leads 

to change of macromolecules adsorbtion parameters in mixes. In 

result occurs the shielding of SAS and polymer polar groups, that 

will lead to increase of macromolecules hydrophobility and 

strengthening of intra-and intermacromolecular hydrophobic 

interactions in compositions. Reduction of standard free energy 

of macromolecules adsorption during of complex formation 

testifies about macromolecules hydrophobization during 

formation of the compositions, leading to increase in their 

superficial activity and ability to adsorbtion on border of phases 

section. 

it is established, that at n =0,25 the deemulsifier action of 

polymeric composition is shown most full, that is explained 

by conformation condition, influencing on surface activity. 

Keywords: Polyacrilonitrile derivatives; Surfactants; 

Deemulgation; adsorption; conformation condition; 



s1063 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 0 3 

SyntheSiS of 1-MethyL-3,5-dinitro-1,2,4- 

-triAzoLe(dnMt) uSinG MiCroreACtor 

K. nAKAyAMA 1 , t. ohtA 1 

1 NOF Corp., Aichi Work, Taketoyo, Japan 

1-methyl-3,5-dinitro-1,2,4-triazole(DNMT) has excellent 

IM(Insensitive munitions) capabilities and is used in 

gas-generating agents. DNMT can be synthesized by nitration of 

a nitrate salt of 1-methylguanazole(DAMT) with nitrating 

agents(H SO and NaNO ). Attempting to scale up in an usual 

2 4 2 

batch method, we assume that the reaction efficiency is decreased, 

due to emission of NOx which is a possible nitro source in large 

quantities out of the system. Therefore we constructed a 

consecutive reaction process to react NOx efficiently by means 

of microreactors. In order to establish a reaction process that can 

accommodate a wide range of compounds, we also studied 

nitration of DAMT under neutral conditions with Nafion, known 

as a solid superacid, instead of sulfuric acid. 

Keywords: Microreactors; Nitrogen heterocycles; 


P - 0 4 0 4 

CoLd PuLPinG of BAGASSe 

M. nASSAr 1 , M. eLSAKhAwy 2 , S. MohAMed 1 

1 National Research Center, Packaging and Packing, Cairo, 

Egypt 

2 National Research Center, Cellulose and Paper, Cairo, Egypt 

Amongst the common non-wood fibers, bagasse pulp mills 

are typically one of the largest non-wood mills which have been 

built because large volumes of bagasse are available in one spot 

– the sugar mill. Typically, bagasse pulp is produced in integrated 

pulp and paper mills, and softwood kraft or sulfite pulp is added 

to provide the strength requirements to the paper. However, 

non-wood pulp in particular may be used instead of softwood kraft 

or sulfite pulp, thus producing a 100% non-wood paper. Since 

chemical pulping is a high- temperature ( ~170°C) heat energy 

intensive process, bagasse was cooked in this study in 

polyethylene bags regarded as containers at 75 °C to produce 

bagasse pulp. The pulping was carried out in two stages, 

pretreatment by hot water at 100 °C for 1 hour and chemical pulp 

by NaOH for 3,4,5 hours. Active alkali charge was 20% based on 

pre-extracted raw material. Increasing the time of pulping to 

5 hours has no effect on pulp yield. In general, beating time of the 

produced pulp was long. This pulp was characterized by good 

yield, low tensile strength but high tear strength ( 1, 2). The 

mechanical strengths of pulp were improved by adding a blend of 

starch and borax (1:1) to the pulp before making paper sheets 

references: 

1. M. Sarwar Jahana,*, M. Shamsuzzamana, 

M. Mostafizur Rahmana, S.M. Iqbal Moeizb, Y. Nic Effect 

of pre-extraction on soda-anthraquinone (AQ) pulping of 

rice straw. Industrial Crops and Products 37 (2012) 

164–169 

2. S.L. Walton, D. Hutto, J. M. Genco, J.P.V Walsum, 

A. R. P. van Heiningen, Pre- Extraction of Hemicelluloses 

from Hardwood Chips Using an Alkaline Wood Pulping 

Solution Followed by Kraft Pulping of the Extracted Wood 

Chips. Ind. Eng. Chem. Res.,49 (24), (2010), 

12638–12645. 

Keywords: Carbohydrates; mechanical properties; Industrial 

Chemistry; 



s1064 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 0 5 

heteroGeneouS orGAnoCAtALytiC SySteMS 

And their APPLiCAtionS 

S. nAtour 1 

1 The Hebrew University of Jerusalem, Organic Chemistry, 


In the last decade, organocatalysis has emerged as an 

attractive new field in catalysis [1] . Many organocatalysts were 

developed and applied specifically in asymmetric organic 

transformations. However, in order to have efficient 

organocatalytic reactions, there is a crucial requirement for 

applying high loading of catalysts; therefore complicated 

procedures for the isolation of the desired products are needed. In 

order to cope and minimize such difficulties, a great deal of 

attention has been invested in developing methods for the 

heterogenization of homogeneous organocatalysts. In our 

research, we focus on developing new heterogeneous catalytic 

systems based on encapsulation of organocatalysts in the cores of 

chiral and achiral poly-urea microcapsules. Such systems are 

prepared by emulsification of the organocatalyst in water or apolar 

organic solvents followed by interfacial polymerization of 

isocyanate monomers with diamines in O/O and W/O emulsions. 

Applications of the heterogenized catalytic systems in Michael 

addition reactions will be shown and the effect of the shell type 

on the catalytic performance of the encapsulated organocatalyst 

in asymmetric transformations will be presented. 

references: 

1. a) P. I. Dalko, L. Moisan, Angew. Chem. Int. Ed., 2001, 

40, 3726. 

b) P. I. Dalko, L. Moisan, Angew. Chem. Int. Ed., 2004, 

43, 5138. c) A. Berkessel, H. Gröger, Asymmetric 

Organocatalysis; Wiley-VCH: Weinheim, 2005. 

Keywords: Organocatalysis; Heterogeneous catalysis; 

Chirality; 


P - 0 4 0 6 

SyntheSiS of noveL PotentiAL 

AntituBerCuLotiCS BASed on 5-SuBStituted 

BenzyLSuLfAnyL heteroAroMAteS 

J. neMeCeK 1 , G. KArABAnoviCh 1 , J. roh 1 , 

K. vAvrovA 1 , J. StoLAriKovA 2 , v. KLiMeSovA 1 , 

A. hrABALeK 1 

1 Charles University in Prague Faculty of Pharmacy, 

Department of Organic and Inorganic Chemistry, Hradec 

Kralove, Czech Republic 

2 Regional Institute of Public Health, Department for Diagnostic 

of Mycobacteria, Ostrava, Czech Republic 

Tuberculosis (TBC) is a widespread infectious disease. 

About one third of world population is infected with TBC. About 

8.8 mil new cases of TBC were found and 1.7 mil people died in 

2010. Another major problem is the presence of strains resistant 

to the conventional treatment. Therefore, the search for new 

antitubercular drugs, active also against these resistant strains, is 

highly important. 

A lot of works dealing with the synthesis of new 

antitubercular drugs have been published to date. Many 

substances were prepared and evaluated, but in fact no one was 

implemented to the clinical practice. Nevertheless it was 

discovered that some substances containing benzylsulfanyl group 

bound on the heteroaromates (benzoxazole, benzothiazole, 

benzimidazole) had the same or comparable activity as standard 

isoniazide. Also it was found that antitubercular activity was 

increased by the addition of electron-withdrawing substituents to 

the benzylsulfanyl moiety. These substances seem to be 

perspective and it is necessary to carry out more structure-activity 

relationship studies. 

In our work, the methylenesulfanyl linker between 

substituted phenyl group and heteroaromates has been modified. 

Selected compounds with methylenesulfanyl, methyleneoxy and 

sulfanyl linker and one type without linker were synthesized. 

Antimycobacterial activity of these compounds as well as 

their cytotoxicity on the isolated hepatocytes will be evaluated. 

Acknowledgement: This project was supported by the Grant 

Agency of Charles University (Project no. 55610/2010) and by 

the Charles University in Prague (SVV 265 001) 

Keywords: Medicinal chemistry; Heterocycles; Antibiotics; 



s1065 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 0 7 

inveStiGAtion of different orGAniC 

reACtionS CAtALySed By MetALS on 

heteroGeneouS SuPPortS 

J. neMeth 1 , A. KiSS 1 , z. heLL 1 



Hungary 

In the last decades one of the main targets of the organic 

chemical research is to find new catalysts, which are more active, 

more selective, reusable, can be treated simply, and are 

environmentally more friendly than the most common catalysts. 

In the last years the use of different mineral based catalysts 

became more and more important. Also, these substance are often 

used as support of different metal catalysts. 

At the Department of Organic Chemistry and Technology 

of BUTE experiments have been made for the use of solid acids 

and bases in organic syntheses since years. Joining in this research 

group, my first task was to investigate the applicability of 

palladium on magnesium-lanthanum mixed oxide support, 

developed in the group earlier, as catalyst in dehalogenation of 

aromatic halogenides. 

I investigated the reaction with aryl iodides in the presence 

of sodium hydroxide in ethanol. In most cases I obtained the 

desired products with acceptable yields. In the case of 

halonitrobenzenes, in ethanol, in the presence of sodium 

hydroxide we observed the reduction of the nitro group. Further 

investigation of this reduction verified a transfer hydrogenation 

mechanism, the solvent alcohol oxidised to the corresponding 

acid. Changing the support and the reaction conditions we could 

also prepare the intermediates (azoxybenzene, azobenzene) 

selectively, in an environmentally friendly way. 

Earlier this palladium catalyst were used succesfully in the 

Heck-, Sonogashira- and Suzuki-coupling. I examined the 

possibility of replacing this catalyst with newly improved 

supported palladium catalysts. The examined model reaction was 

the Heck-coupling of iodobenzene and styrene. 

Based on earlier results of the research group, we also 

investigated the use of copper on 4A molecular sieve support in 

the coupling reaction between aryl halogenides and ethyl 

acetoacetate. Only aryl iodides gave results, under the applied 

reaction conditions aryl bromides did not react. 

Keywords: Heterogeneous catalysis; palladium; copper; 


P - 0 4 0 8 

the effeCtS of AProtiC SoLventS And 

StruCture on the eLeCtroniC ABSorPtion 

SPeCtrA of the iSoMeriC Pyridine 

CArBoxyLiC ACidS 

J. niKoLiC 1 , S. drMAniC 1 , B. JovAnoviC 2 

1 University of Belgrade, Faculty of Technology and Metallurgy, 


2 University of Belgrade, 2Institute of Chemistry Technology 

and Metallurgy, Belgrade, Serbia 

The ultraviolet absorption spectra of the carboxyl group of 

three isomeric pyridine carboxylic acids (picolinic acid, nicotinic 

acid and isonicotinic acid) were determined in a set of aprotic 

solvents in the wavelength range from 200 to 400 nm. In order to 

to analyze the aprotic solvent effect on the obtained absorption 

maxima, the ultraviolet absorption frequencies of the electronic 

transitions in the carboxylic group of the examined acids were 

correlated using a total solvatochromic equation of the form 

ν =v +sπ* + bβ, where ν is the absorption frequency (1/λ ), 

max 0 max max 

π* is a measure of the solvent polarity and β represents the scale 

of solvent hydrogen bond acceptor basicities, the property 

characteristic for aprotic solvents. The correlation of the 

spectroscopic data was carried out by means of multiple linear 

regression analysis. The solvent effects on the ultraviolet 

absorption maximums of the examined acids were discussed. 

Keywords: picolinic acid; nicotinic acid; isonicotinic acid; 

ultraviolet absorption maximum; aprotic solvents; 



s1066 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 0 9 

heteroAroMAtiC-Steroid ConJuGAteS 

z. novAKovA 1 , e. KoLehMAinen 2 , P. drASAr 3 

1 Institute of Chemical Technology Prague, Chemistry of 

Natural Compounds, Prague, Czech Republic 

2 University of Jyväskylä, Organic Chemistry, Jyväskylä, 

Finland 

3 Institute of Chemical Technology Prague, Chemistry of 


Bile acids are important natural substances that are final 

products of cholesterol metabolism. They are characterised by 

typically amphiphilic structure and due to a very special 

combination of both hydrophilic and hydrophobic side they could 

be used as lipid emulsifiers or surfactants [1] . Biologically, they 

have many different biological functions in human body [2, 3] . 

Aromatic compounds with heterocyclic electro-donors 

atoms can be used for metal complexations [4] . Firstly, we aimed 

to preparation of different heterocyclic mono- and di-amines. Next 

step was reaction of those heterocycles with bile acids giving 

steroid-aromatic compounds. In dependence on excess of 

activated acid in reaction with di-amine we observed mono or 

bisubstitution 

For those compounds we expected some self-stacking 

potential-for that UV/VIS spectra were measured. Also in-vitro 

biological activity tests were done for chosen substrates. 

Acknowledgment: This work was supported by 

MSM6046137305 (MSMT). 

references: 

1. Dukh, M.; ·aman, D.; Kroulík, J.; Cerný, I.; Pouzar, V.; 

Král, V.; Dra‰ar, P. Tetrahedron, 2003, 59, 4069. 

2. Jenkins, G.; Hardie, L. J. Bile Acids: Toxicology and 

Bioactivity, 2008, 6. 

3. Virtanen E.; Kolehmainen E. Eur. J. Org. Chem., 2004, 16, 

3385. 

4. Li Y., Shi L., Qin L. X., Qu L. L., Jing C., Lan M., James 

T. D., Long Y. T.: Chem. Commun. 2011, 47, 4361; 

Belcher, R. Pure Appl. Chem., 1973, 34, 13. 

Keywords: steroid; bile acid; heterocycles; UV measurements; 


P - 0 4 1 0 

SeLeCtivity ControL of ALKyne [2+2+2] 

CyCLoAddition reACtion And itS APPLiCAtion 

to ChAin-Growth CyCLoAddition 

PoLyMerizAtion reACtionS 

S. oKAMoto 1 

1 Kanagawa University, Department of Material and Life 

Chemistry, Yokohama, Japan 

We demonstrate that the alkyne [2 + 2 + 2] cycloaddition 

reaction catalyzed by dipimp (2-iminomethylpyridine 

ligand)/CoCl -6H O/Zn is applicable to polymerization, yielding 

2 2 

linear polymers via a selective cross-cyclotrimerization reaction, 

which occurs in a chain-growth manner. 

For controlled polymerizations by partially intramolecular 

cycloaddition that produce linear polymers via the reaction of 

AB-type monomers comprising monoalkyne and diyne moieties, 

directing alkyne reactivities towards selective cross-coupling over 

homo-cycloaddition is important. The selective cross-coupling 

between monoalkyne and diyne parts yields linear polymers. 

Alternatively, polymerization involving a self-coupling reaction 

forms linear and branched structures in a non-controlled manner. 

We have succeeded in nearly complete control by 

substitutents of substrates for cross-cycloaddition, and applied it 

to design an AB-type monomer for the cycloaddition 

polymerization. The polymerization of such AB-type monomers 

catalyzed by the cobalt catalyst proceeded smoothly in a chaingrowth 

fashion to provide linear polymers, achieving control over 

molecular weights and the polydispersity of the resultant 

polymers. The utilization of this method to the one-shot 

spontaneous block copolymerization of a mixture of two 

monomers has also been demonstrated. Currently, we propose a 

catalyst transfer mechanism for this polymerization, although the 

immortal polymerization mechanism cannot be ruled out. Further 

investigation on the reaction mechanism and application is 

underway. 

Based on a high functional group compatibility with the 

catalysis, this method may be useful in preparing diverse 

functionalized polymers in a controlled manner. 

Keywords: Alkynes; Cycloaddition; Copolymerization; 

Homogeneous catalysis; Polymerization; 



s1067 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 1 1 

PrePArAtion of PoLyCArBonAte with 

AnthrACene And Azido PendAnt GrouPS And 

itS GrAftinG viA CLiCK CheMiStry 

P. S. oMurtAG 1 , A. dAG 1 , h. durMAz 1 , u. S. GunAy 1 , 

G. hizAL 1 , u. tunCA 1 


This study deals with the synthesis of anthracene- and azidefunctional 

cyclic carbonate monomers, anthracen-9-ylmethyl 

5-methyl-2-oxo-1,3-dioxane-5-carboxylate and 2-azidoethyl 

5-methyl-2-oxo-1,3-dioxane-5-carboxylate, by the reaction 

of anthracen-9-ylmethyl 3-hydroxy-2-(hydroxymethyl)-2methylpropanoate 

and 2-azidoethyl 3-hydroxy-2- 

-(hydroxymethyl)-2-methylpropanoate with ethyl chloroformate 

in tetrahydrofuran at room temperature, respectively [1] . The 

copolymerization of these anthracene- and azide-functional cyclic 

carbonate monomers was carried out successfully via 

ring-opening polymerization (ROP) using benzyl alcohol as 

initiator, 1,8-diazabicyclo[5.4.0]undec-7-ene and 

1-(3,5-bis(trifluorometh1-(3,5-bis(trifluoromethyl))-3-cyclohexyl- 

-2-thiourea, as catalyst system [2] . In addition, side chains were 

synthesized via atom transfer radical polymerization and ROP. 

The grafting reaction of these side chains with the anthraceneand 

azidefunctional polycarbonate as a main chain was 

accomplished under facile conditions via click reactions (CuAAC 

and Diels-Alder). 

The composition and molecular weight of the 

polycarbonates were characterized by 1H NMR and GPC. 

Thermogravimetric analysis and differential scanning calorimetry 

measurements were used to investigate the thermal properties of 

the resulting polymers. 

references: 

1. Zhang X, Zhong Z, Zhuo R, Macromolecules, 44: 

1755–1759, 2011. 

2. Sanders DP, Fukushima K, Coady DJ, Nelson A, 

Fujiwara M, Yasumoto M, Hedrick LJ, J. Am. Chem. Soc., 

132: 14724–14726, 2010. 

Keywords: Polymers; Polymerization; 


P - 0 4 1 2 

AryLSuLfinAteS AS rePLACeMent of 

orGAnoMetALLiC reAGentS in 

PALLAdiuM-CAtALyzed CouPLinG reACtionS 

d. ortGieS 1 , A. BArtheLMe 1 , S. ALy 1 , P. forGione 1, 

B. deShArnAiS 1 , M. de CiCCo 1 , S. rioux 1 , f. Chen 1 , 

1 Concordia University, Chemistry and Biochemistry, Montréal 


Substituted biaryls are an important motif in a variety of 

pharmacophores, pesticides and chiral ligands. Palladium-catalyzed 

cross-coupling reactions employing stoichiometric amounts of 

organometallic reagents as nucleophiles are generally utilized for 

their synthesis. Therefore multi-step, expensive, moisture-sensitive 

and potentially toxic transformations are often needed to access 

these coupling partners. Decarboxylative cross-couplings have 

recently emerged as an alternative method to overcome these 

limitations. We successfully advanced this principle to the use of 

aromatic sulfinates salts as analogues of benzoic acids. Our efforts 

involving this desulfinylative coupling of substituted 

benzenesulfinates with aryl-bromides also led to the development 

of a catalytic homo-coupling of aryl-sulfinates under oxidative 

conditions. The scope of these reactions will be presented. 

Furthermore, their reactivity in aqueous media as a way to develop 

a more environmentally benign reaction will be highlighted. 

Keywords: Palladium; C-C coupling; Green chemistry; Sulfur; 



s1068 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 1 3 

SyntheSiS And inveStiGAtionS of MuLtiPLe 

hydroGen Bonded SuPrAMoLeCuLAr hoSt – 

GueSt CoMPLexeS 

P. otte 1 , u. LüninG 1 


In supramolecular chemistry, molecular recognition via noncovalent 

binding sites such as hydrogen bonds is common. It is 

necessary to have complementary hydrogen bond acceptor (A) 

and hydrogen donor (d) patterns. A single hydrogen bond is 

relatively weak, but the combination of multiple hydrogen bonds 

can lead to stable host - guest complexes. [1] 

Due to the existence of attractive and repulsive secondary 

hydrogen bonds, binding patterns with as many attractive 

secondary hydrogen bonds as possible are the target. An example 

with a DDDD-AAAA pattern shows an association constant of 

105-106M-1 . [2] 

It is reasonable to synthesize molecules whose preferred 

conformation is the one which can form the highest number of 

hydrogen bonds. If an intramolecular bond has to be broken to get 

the needed binding pattern, a loss of energy at the expense of the 

complex stability would be the consequence. [3] Therefore, the aim 

should be to stabilize the preferred conformation by using, for 

example, intramolecular hydrogen bonds. [4] 

Due to the orthogonality of the binding sites, highly specific 

dendrimeric systems could be generated. [5] 

references: 

1. J. Taubitz, U. Lüning, Eur. J. Org. Chem. 2008, 

5922–5927. 

2. B. A. Blight, C. A. Hunter, D.A.Leigh, H. McNab, 

P. I. T. Thomson, Nature Chemistry, 2011, 3, 244–248. 

3. S. Brammer, U. Lüning, C. Kühl, Eur. J. Org. Chem. 2002, 

4054–4062. 

4. E.W. Meijer et al. Science 1997, 278, 1601–1604. 

5. J. Eckelmann, C. Dethlefs, S. Brammer, A. Dogan, 

A. Uphoff, U. Lüning, Chem. Eur. J. 2012, DOI: 

10.1002/chem.201200181 

Keywords: Hydrogen bonds; Host-guest systems; Molecular 

recognition; Supramolecular chemistry; 


P - 0 4 1 4 

in Situ CLiCK CheMiStry for huMAn 

ACetyLChoLineSterASe inhiBitorS 

diSCovery 

e. oueiS 1 , C. ronCo 1 , G. rASteLLi 2 , A. roMieu 1 , 

v. toGnetti 3 , L. JouBert 3 , f. nAChon 2 , L. JeAn 1 , 

C. SABot 1 , P. y. renArd 1 

1 Université de Rouen UMR 6014 CNRS COBRA, Equipe de 

Chimie Bioorgnanique, Mont-Saint-Aignan, France 

2 Institut de Recherche Biomédicale des Armées, Cellule 

Enzymologie Département de Toxicologie, La tronche, France 

3 Université de Rouen UMR 6014 CNRS COBRA, Equipe 

analyse et modélisation, Mont-Saint-Aignan, France 

In situ click chemistry is a new approach (K.B. sharpless 

and coll. Angew. Chem. Int. Ed. 2002, 41, 1053-1057) to lead 

discovery applied to target guided synthesis (TGS) that allows a 

biological target to assemble its own inhibitors. Indeed, in the 

presence of the targeted multisite enzyme and a series of building 

blocks bearing complementary reactive functions, ligands with 

the best affinities would react to form an irreversible bond. The 

enzyme serves as a template for the reaction. 

Being implicated in the pathogenesis of the Alzheimer’s 

disease, recombinant human (rh) strain of Acetylcholinesterase 

(AChE) is our enzyme of choice for the application of this 

concept. New Huprine (Hup) derivatives were found to be very 

potent AChE inhibitors, presenting IC values in the 

50 

subnanomolar range (P.Y. Renard and coll. ChemMedChem, 2011, 

8, 876-888). These acylation site inhibitors were tested for in situ 

click chemistry with known peripheral site ligands 

(tetrahydroisoquinoline, PIQ) in the presence of rh and mouse 

AChE. The in situ Huisgen reaction was successful, allowing the 

formation of two new potent heterodimeric inhibitors using for 

the first time human AChE. In addition, the click reaction 

occurred unprecedentedly in the gorge of the enzyme far from the 

acylation active site inducing different regioselectivities than 

those already described in the literature. 

Furthermore, new click reactions are being explored such 

as the hetero Diels Alder reaction. Polysubstituted 

3-hydroxypyridines scaffolds are obtained from the corresponding 

5-alkoxyoxazoles and dienophiles. The reaction needs activation 

(thermal or catalytic) to form an irreversible bond, what makes it 

a very interesting target for in situ click chemistry since it should 

not proceed without the enzyme. Huprine derivatives bearing 

a terminal electron-poor olefin and PIQ derivatives a 

5-alkoxyoxazole ring are being investigated for the in situ click 

chemistry approach with AChE as the target. 

Keywords: click chemistry; host-guest systems; inhibitors; 

enzymes; regioselectivity; 



s1069 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 1 5 

SyntheSiS And ABSorPtion ChArACterizAtion 

of new Mixed derivAtiveS of 

P-ChLorodiAzALine CALix[4]AreneS 

ContAininG ACryLoyL GrouPS 

S. ÖzKinALi 1 

1 Science, Chemistry, Corum, Turkey 

Calixarene are macrocyclic molecules made up of 

p-substituted phenolic units linked by methylene bridges ortho to 

the OH functions. [1–3] They are known to provide useful building 

blocks for hollow molecular scaffolds with easily functionalizable 

hydrophilic and hydrophobic lower and upper rims, respectively. [4, 5] 

A series of acryloyl derivatives of calix[4]arene [6, 7] which is 

including the first examples of mixed p-chlorodiazaline esters. In 

the first step, p-tert-butylcalix[4]arene have been obtained by 

condenzation of p-tert-butylphenol and formaldehyde. In the 

second step calix[4]arene have been prepared by removing the 

tert-butyl group by the reaction of p-tert-butylcalix[4]arene with 

AlCl according to reverse Friedel-Crafts reaction. The 

3 

calix[4]arene compounds containing azo groups have been 

prepared by the reaction of diazotized p-chloroaniline with 

calix[4]arene in dry condition in order to 1:1, and 1:2 molar ratio. 

Acryloyl derivatives of azo calix[4]arene compounds have been 

synthesised by the reaction of azo calix[4]arene with metallic 

sodium and then acryloyl chloride in N atmosphere in order to 

2 

1:1, 1:2, 1:3 and 1:4 molar ratio. The structures of these 

compounds have been characterized by elementel analysis, IR, 

UV-VIS, 1H-NMR and 13C-NMR. references: 

1. Gutsche, C.D. Calixarenes. In Monographs in Supramolecular 

Chemistry. 1989, 223. 

2. Gutsche, C. D. Iqbal, M.; Organic Syntheses. 1990, 68, 

234-23. 

3. Böhmer,V. Angew. Chem., Int. Ed. Engl. 1995, 34,713. 

4. Hana, T. A; Liu L.; Zakharov, L. N.; Reingold, A. L.; 

Watson, W.H.; Gutsche,C.D. Tetrahedron, 2002, 58, 

9751-9757. 

5. Chawla, M. H.; Singh, S. P.; Upreti, S. Tetrahedron, 2006, 

62, 2901-2911 

6. S. Özkinali.; I. Utar.; H.kocaokutgen.; and A.Bulut.; 

Acta Crystallographica Section E63, 2007, 03396. 

7. S. Özkinali.; I. Utar.; H.Kocaokutgen and A Bulut.; 

Acta Crystallographica Section E63, 2007, 03378. 

Keywords: calix[4]arene; diazenyl; acryloyl chloride; 


P - 0 4 1 6 

inveStiGAtion of inoSitoL-PyroPhoSPhAte 

MediAted Protein PyroPhoSPhoryLAtion 

A. PABSt 1 , h. J. JeSSen 1 

1 University of Zurich, Organic Chemistry Institute, Zürich, 

Switzerland 

Inositol-pyrophosphates (PP -InsP ) as secondary messenger 

y x 

are in sharp focus of biochemical research due to their importance 

in different cellular processes like apoptosis, telomere length 

regulation or cytoskeleton dynamics. [1] Furthermore, recent 

investigations showed nonenzymatic transfer of a phosphate 

moiety from a PP -InsP on a phosphoserine residue generating a 

y x 

protein pyrophosphate. [2] The function of this post-translational 

modification is still unclear. One possibility to investigate this 

phenomenon would be the identification of a selective 

electrophilic trap for pyrophosphates. The design of probes for 

the tagging of sulfhydryl or thiophosphate groups with 

electrophilic traps has already contributed much to our 

understanding of cellular processes. [3] Based on this rationale, the 

development of strategies to tag pyro- or thiopyrophosphates will 

provide information about the targets and functions of this novel 

post-translational modification. We will present the synthesis of 

pyro- and thiopyrophosphorylated derivatives of e.g. serine and 

threonine. The reactivity of these compounds will be screened 

against different electrophiles to evaluate the specificity of the 

tagging in the presence of other nucleophiles. The knowledge 

obtained from these experiments will help us to develop selective 

tagging strategies for target proteins of PP -InsP mediated 

y x 

phosphorylation in cellular extracts. 

references: 

1. R.I. Irvine, M. J. Schell, Nat. Rev. Mol. Cell Biol. 2001, 2, 

327-338. 

2. A. Saiardi, R. Bhandari, A. C. Resnick, A. M. Snowman, 

S. H. Snyder, Science 2004, 306, 2101-2105. 

3. a) F. Eckstein, Annu. Rev. Biochem. 1985, 54, 367-402. 

b) J. J. Allen, S. E. Lazerwith, K. M. Shokat, J. Am. Chem. 

Soc. 2005, 127, 5288-5289. 

Keywords: Phosphorylation; Proteins; amino acids; 

Bioorganic chemistry; 



s1070 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 1 7 

SyntheSiS of 1h-PyrAzoLo[1,2-A][1,2,4]- 

-triAzoL-8-iuM ionS froM A one Pot reACtion 

uSinG A diPhoSPhoruS triCAtion SynPhoS 

reAGent 

r. PAnzer 1 , J. J. weiGAnd 1 

1 WWU Münster, Institut für Anorganische und Analytische 



Highly charged main group element centered cations can 

possess unusual reactivities. [1] We are especially interested in using 

cationic, highly-reactive PIII centered compounds (synPhos) as 

reagents for unusual transformation reactions. The high 

oxophilicity of PIII-compounds allows deoxygenation and 

condensation reactions, which represents important 

transformations in organic synthesis. Recently, we developed the 

Janus-head type diphosphorus trication [2] [pyr P ] 3 2 3+ (pyr = 1,3- 

-dimethylpyrazole) and used it for the deoxygenation of 

phosphanoxides. [3] This reaction was accompanied with 

the transfer of a pyrazole moiety to yield novel 

pyrazolylphosphonium salts. [3] In this contribution, we present a 

novel access to 1H-pyrazolo[1,2-a][1,2,4]-triazol-8-ium ions 

using trication [pyr P ] 3 2 3+ in condensation reactions of aldehydes 

and nitriles. 

references: 

1. a) Martin, C. D.; Ragogna, P. J. Inorg. Chem. 2010, 49, 

8164; 

b) Martin, C. D.; Le, C. M.; Ragogna, P. J. J. Am. Chem. 

Soc. 2009, 131, 15126. 


Ehlers, A. Lammertsma, K. Angew. Chem. Int. Ed. 2010, 

49, 6178. 

3. Feldmann, K.-O.; Schulz, S.; Klotter, F.; Weigand; J. J: 

ChemSusChem 2011, 4, 1805 

Keywords: Aldehydes; Phosphorus; Green chemistry; 

Synthesis design; 


P - 0 4 1 8 

noveL BiSPhoSPhineS for the AMidAtion of 

SteriCALLy deMAndinG AryL ChLorideS 

J. PArAdieS 1 , f. C. fALK 1 

1 Karlsruhe Institute of Technology, Institute of Organic 


The palladium-catalyzed amidation of sterically hindered, 

deactivated aryl chlorides with bulky aryl amides was achieved. 

This highly challenging transformation was accomplished 

using the novel [2.2]paracyclophane-derived unsymmetrical 

bisphosphine GemPhos in combination with a palladium(0) 

source. [1] 

The catalyst system was exceptionally active for sterically 

demanding coupling partners. The ligand was further optimized 

featuring an electron rich and an electron deficient phosphino 

group. Those electronically reversed phosphine groups displayed 

synergistic behavior as evidenced from kinetic investigations. 

The transmetallation and the reductive elimination were identified 

as rate determining steps. [2] 

references: 

1. F. C. Falk, R. Fröhlich, J. Paradies, Chem. Commun. 2011, 

47, 11095-11097. 

2. F. C. Falk, R. Fröhlich, J. Paradies, 2012, submitted. 

Keywords: Phosphines; Amides; Cross-coupling; Palladium; 



s1071 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 1 9 

noveL reACtivity of fruStrAted LewiS PAirS: 

Low teMPerAture hydroGen ACtivAtion And 

hydroGenAtion of unfunCtionALized 

douBLe BondS 

J. PArAdieS 1 , L. GreB 1 



The hydrogenation of unsaturated compounds is 

traditionally accomplished by transition metal catalysts. The 

activation of hydrogen by frustrated Lewis pairs (FLP) has 

emerged to a powerful tool as an transition metal-free 

alternative. [1] Despite the tremendous advances in this field, so 

that even for complex organic transformations [2] could be realized, 

the hydrogenation of unfunctionalized double bonds remained a 

challenge. 

However, we succeeded in the low temperature hydrogen 

activation by electron deficient phosphines in combination with 

the Lewis acid tris(pentafluorophenyl)borane (1). The high 

reactivity of the frustrated Lewis pair was exploited in the 

hydrogenation of unfunctionalized double bonds even at room 

temperature. [3] Aliphatic as well as aromatic olefins and dienes 

were hydrogenated in excellent yields. 

references: 

1. a) G. C. Welch, R. R. S. Juan, J. D. Masuda, D. W. Stephan, 

Science 2006, 314, 1124; 

b) D. W. Stephan and G. Erker, Angew. Chem., 2010, 122, 

50; Angew. Chem. Int. Ed., 2010, 49, 46. 

2. a) T. Mahdi, Z. M. Heiden, S. Grimme, D. W. Stephan, 

J. Am. Chem. Soc. 2012, 134, 4088; 

b) L. Greb, P. Ota-Burgos, A. Kubas, F. C. Falk, F. Breher, 

K. Fink, J. Paradies Dalton Trans., 2012, DOI: 

10.1039/C2DT30374D. 

3. L. Greb, P. Ona-Burgos, B. Schirmer, F. Breher, S. Grimme, 

D. W. Stephan, J. Paradies, 2012, submitted. 

Keywords: Alkenes; Boranes; Hydrogenation; Phosphines; 


P - 0 4 2 0 

funCtionALizAtion of BiCyCLo[3.3.0]oCtAneS 

AS Key BuiLdinG BLoCKS in nAturAL ProduCtS 

And SyntheSiS of noveL hyBrid MoLeCuLeS 

n. PArK 1 , S. LASChAt 1 

1 Stuttgart University, Institut für Organische Chemie, Stuttgart, 

Germany 

Bicyclo[3.3.0]octane is a common building block in a 

variety of natural products and pharmaceuticals, for example in 

the macrolactams cylindramide [1] or geodin A. [2] Cylindramide has 

been isolated from the marine sponge Halichondria cylindrata. 

It is a macrocyclic lactam including an acyltetramic acid and a 

trisubstituted bicyclo[3.3.0]octene. This lactam shows significant 

cytotoxicity against B16 melanoma cells with an IC of 50 

0.8 μg/mL. The total synthesis of cylindramide has been published 

by Cramer [1] in our research group in 2005. Geodin A is also a 

tetramic acid macrocycle isolated from the marine sponge Geodia 

sp. Unlike cylindramide it could only be isolated as geodin A Mg 

salt and it bears a methylene group instead of a methyl group. 

Previous work on cylindramide A revealed that the 

bicyclo[3.3.0]octane unit as well as the tetramic acid macrocycle 

are essential for the biological activity of tetramic acid 

macrolactams. [3] Starting from readily available cyclooctadiene 

bicyclo[3.3.0]octane systems have been synthesised and further 

functionalized towards new hybrid molecules. Key step is a 

diastereoslective Shi-epoxidation followed by a selective epoxide 

opening. Biological essays will reveal if these compounds exhibit 

comparable or even increased biological activities. 

references: 

1. a) S. Kanazawa, N. Fusetani, S. Matsunaga, Tetrahedron 

Lett. 1993, 34, 1065-1068. 

b) N. Cramer, M. Buchweitz, S. Laschat, W. Frey, A. Baro, 

D. Mathieu, C. Richter, H. Schwalbe, Chem. Eur. J. 

2006, 12, 2488-2503. 

c) N. Cramer, S. Laschat, A. Baro, H. Schwalbe, 

C. Richter, Angew. Chem. Int. Ed. 2005, 44, 820-822. 

2. R. J. Capon, C. Skene, E. Lacey, D. Wadsworth, T. Friedel, 

J. Nat. Prod. 1999, 62, 1256-1259. 

3. N. Cramer; S. Helbig, A. Baro, S. Laschat, D. Mathieu, 

C. Richter, G. Kummerloewe, B. Luy, H. Schwalbe, 

ChemBioChem 2008, 9, 2474–2486. 

Keywords: Natural Products; Asymmetric synthesis; Biological 

activity; 



s1072 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 2 1 

3-PyrAnone dioxACorroLe - An 

extrAordinAry trAnSforMAtion 

of 21,23-dioxAPorPhyrin 

M. PAwLiCKi 1 , d. ByKowSKi 1 , L. SzterenBerG 1 , 

L. LAtoS GrAzynSKi 1 

1 University of Wroclaw, Chemistry, Wroclaw, Poland 

A ubiquitous nature of furan places this heterocycle in a row 

of significant players involved in several widely explored aspects 

of current research in the organic chemistry, starting from the total 

synthesis of natural products ending on formation of extended 

π-systems responsible for an optoelectronic behaviour. Within 

these paths a reactivity of furan stays in the central point of 

investigation as that heterocycle takes a crucial role in the 

formation of other systems (oxidative reactions) but also a 

cycloaddition observed on a post-synthetic level and widely used 

in the total synthesis. Similarly, the reactivity observed with a 

support of Al O is an example of derivatization on a surface of 

2 3 

the solid used in the wide range of environment concerning 

reactions. 

While comparing the modifiability of furan, a transformation 

of such heterocycle with subtly changed electronic structure i.e. as 

an integral part of oxaporphyrin(s) stays in opposite side of 

mentioned rules as this building block remains unreactive in such 

systems as the demands of macrocycle take control over the 

subunit independence. Nevertheless an application of alumina to 

dioxaporphyrin led to an extraordinary transformations observed 

for the first time in the porphyrin-like skeleton. Here we present 

an unprecedented example of the Achmatowicz reaction observed 

for 21,23-dioxaporphyrin giving a 3-pyranone dioxacorrole 

skeleton. The new macrocycle presents features characteristic for 

a non aromatic molecule, and formally is a product of addition of 

a water molecule followed by a sequence of transformation leading 

to formation of presented molecule. The coordination of 

palladium(II) forces the formation of an unstable tautomer 

obtained by a creation of a palladium(II)-carbon bond within the 

coordination cavity. Characteristic features observed for the 

macrocycle and its behaviour will be discussed based on the 

spectroscopic premises (NMR, UV-Vis) along with a single 

crystal analysis. 

Keywords: Macrocycles; Oxidation; Porphyrinoids; 


P - 0 4 2 2 

fABriCAtion And ChArACterizAtion of 

LLdPe-Modified nAnoSiLiCA/LdPe/LLdPe fiLM: 

MiCrowAvABLe PACKAGinG APPLiCAtion 

C. PeChyen 1 , S. thAnAKKASArAnee 1 , t. JinKArn 1 

1 Kasetsart University, Packaging and Materials Technology, 

Bangkok, Thailand 

LDPE and LLDPE are popular applied in the flexible food 

packaging. Because there are strong, tough, clear, good moisture 

barrier and can be sealed with heat. However, they are poor gas 

barrier or moisture resistances are not enough to be able to 

preserve food. Therefore, the concept of this work was used the 

nanosilica applied in preparing LLDPE/nanosilica as a outer layer 

film for LLDPE reinforced nanosilica/LDPE/LLDPE multilayer 

film for microwavable packaging materials in future work. 

Therefore, the objective of this work was to study the optimal 

conditions for preparing linear low density polyethylene film 

reinforced with uncoated and coated nanosilica and LLDPE 

reinforced nanosilica/LDPE/LLDPE multilayer film on 

mechanical properties, Thermal properties, barrier properties and 

physical properties. The experiment of this work was divided into 

4 main steps. First, coating nanosilica with vinyltriethoxysilane 

by internal mixer. Preparation of linear low density polyethylene 

film reinforced with uncoated and coated nanosilica which 

different silica quantities are 1, 3, and 5 phr by blown film 

extruder. Preparation of LLDPE/nanosilica as a outer layer film 

for LLDPE reinforced nanosilica/LDPE/LLDPE multilayer film 

And then the surface morphology of film was examined by SEM 

and contact angle of film was measure by optical contact angle 

measurement systems. The properties of the film were analyzed; 

oxygen permeability by OTR and water vapor permeability by 

WVTR. Tensile properties of film were examined by universal 

testing machine and thermal properties of film was characterized 

by TGA. Results indicated that addition at 1 phr of treated 

nanosilica into LLDPE matrix (LLDPE-nano-SiO 1 phr) 

2 

presented the highest tensile strength, modulus and elongation of 

these films. LLDPE treated nano-SiO /LDPE/LLDPE multilayer 

2 

film presented the lowest of water vapor permeability but 

presented the highest of oxygen permeability. However, LLDPE 

treated nano-SiO /LDPE/LLDPE multilayer film presented the 

2 

highest of degradation temperature. 

Keywords: LLDPE film; Nanosilica; Vinyltriethoxysilane; 

Barrier properties; Mechanical properties; 



s1073 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 2 3 

GoLd And SiLver CAtALySed reACtionS of 

ProPArGyLiC ALCohoLS 

M. PenneLL 1 , t. ShePPArd 1 , P. turner 2 

1 University College London, Chemistry, London, United 

Kingdom 

2 GlaxoSmithKline, Chemistry, Stevenage, United Kingdom 

The 1,3-isomerisation of propargylic alcohols to enones is 

known as the Meyer-Schuster rearrangement. We have 

demonstrated efficient room temperature reaction conditions for 

the gold-catalysed Meyer-Schuster rearrangement (>30 examples) 

of a wide array of secondary and tertiary propargylic alcohols to 

the corresponding enones in generally excellent yields and with 

high E-selectivity. [2, 3] The methodology has also successfully been 

applied to the synthesis of two small natural products, 

Isoegomaketone (anti-inflammatory properties) and Daphenone 

(cytotoxicity against five human tumour cell lines). [3] 

Primary propargylic alcohols rearrange to give highly 

reactive terminal enones, which can undergo conjugate addition 

reactions with nucleophiles to access β-substituted products 

through convenient one-pot procedures. [2, 3] The use of silver 

as a catalyst, instead of gold, promotes substitution of the 

electron-rich propargylic alcohol with various oxygen, carbon and 

nitrogen nucleophiles. [3] β-Hydroxyketones can be accessed via a 

gold-catalysed hydration, employing phenols as the reaction 

additive. [2, 4] This methodology has been developed for the synthesis 

of enantiomerically enriched β-hydroxyketones and the synthesis 

of a natural nonadecenetriol (antiprotozoal agent against 

Tyransome parasites). [4] The gold catalysed hydration offers an 

alternative to traditional aldol procedures with the benefit of 

tolerating the presence of other enolisable centres. 

The full scope of the Meyer-Schuster rearrangement and the 

investigation into the role of protic additives in the gold and silver 

catalysed reactions of propargylic alcohols will be described in 

the presentation. 

references: 

1. Meyer, H. K.; Schuster, K. Chem. Ber. 1922, 55, 819-823. 

2. Pennell, M. N.; Unthank, M.; Turner, P.; Sheppard, T. D. 

J. Org. Chem. 2011, 76, 1479-1482. 

3. Pennell, M. N.; Turner, P. G.; Sheppard, T. D. Chem. Eur. 

J. 2012, DOI: 10.1002/chem.201102830. 

4. Pennell, M. N.; Turner, P. G.; Sheppard, T. D. Manuscript 

in preparation. 

Keywords: Gold; Homogeneous cataylsis; Meyer-Schuster 

rearrangement; Propargylic alcohols; Silver; 


P - 0 4 2 4 

SyntheSiS of fLuorinAted AnALoGueS of 

6-hetAryL-7-deAzAPurine nuCLeoSideS 

P. PerLiKovA 1 



Analogues of nucleosides are an important class of 

anti-tumor and anti-viral therapeutics. Recently, nanomolar 

cytostatic activity against a panel of cancer cell lines was shown 

in 6-hetaryl-7-deazapurine ribonucleosides. [1] The aims of this 

project were: a) further modification of the lead structure by 

replacement of the 2'-hydroxy group by isosteric fluorine; 

b) comparison of cytostatic activities of ribonucleosides and their 

fluorinated analogues. A synthetic route to 6-hetaryl-7- 

-deazapurine 2'-fluoro-2'-deoxyribonucleosides was developed. 

A key intermediate 6-chloro-7-deazapurine 2'-fluoro-2'- 

-deoxyribonucleoside 1 was synthesized starting from 6-chloro- 

-7-deazapurine ribonucleoside 3 in 9 steps in 18 % overall yield. 

The synthesis started with silyl protection of 3'- and 5'-hydroxy 

group followed by oxidation of 2'-hydroxy group and 

stereoselective reduction to obtain silylated arabinonucleoside 2. [2] 

Then, several protection and deprotection steps as well as 

fluorination of the 2'-hydroxy group with DAST were used to 

synthesize 2'-fluoro-2'-deoxyribonucleoside 3. Fluoroderivative 

3 was used as a starting material for Suzuki cross-coupling 

reactions with hetarylboronic acids under aqueous conditions. 

6-Hetaryl-7-deazapurine 2'-fluoro-2'-deoxyribonucleosides were 

obtained in 37–88% yield. All 6 target compounds were tested for 

their cytostatic activity against cancer cell lines. None of the 

fluorinated analogues showed any cytostatic activity. The results 

lead to conclusion that 2'-hydroxy group is esential for cytostatic 

activity of 6-hetaryl-7-deazapurine ribonucleosides. 

Acknowledgement: This work is a part of the research project 

Z4 055 0506 from the Academy of Sciences of the Czech 

Republic. It was supported by the Czech Science Foundation 

(P207/11/0344) and by Gilead Sciences, Inc. 

references: 

1. Naus P., Pohl R., Votruba I., Dubák P., Hajdúch M., 

Ameral R., Birkus G., Wang T., Ray A.S., Mackman R., 

Cihlar T., Hocek M.: J. Med. Chem. 53, 460 (2010) 

2. Naus P., Perlíková P., Pohl R., Hocek M.: Collect. Czech. 

Chem Comm. 79, 957 (2011) 

Keywords: nucleosides; fluorination; 



s1074 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 2 5 

CoPPer-CAtALyzed enAntioSeLeCtive 

CyCLoProPAnAtionS of heteroCyCLiC 

CoMPoundS uSinG diAzoACetAteS 

L. PiLSL 1 , B. LoPez-SAnChez 1 , K. hArrAr 1 , 

o. reiSer 1 



A broad variety of biologically active natural products contain 

a cyclopropane moiety within their structure. It has been shown that 

this three-membered ring system can play a significant role for the 

activity of potential drugs. While the asymmetric cyclopropanation 

of simple olefins like styrene has been well developed, electronrich 

heterocyclic substrates like N-protected pyrroles and furan 

derivatives proved to be a challenging task. [1, 2, 3] Herein we report 

highly enantioselective cyclopropanation reactions of 

aromatic, heterocyclic substrates using diazoacetates toward 

multiple functionalized bicyclic compounds, which proved 

to be versatile building blocks for natural product synthesis 

approaches, [4] as well as for the synthesis of 

β-aminocyclopropanecarboxylic acids (β-ACCs) toward 

foldamers. [5, 6] In order to gain mechanistic insight into this 

important type of reaction computational calculations with QM 

methods are under investigation at the moment. 

references: 

1. C. Böhm, M. Schinnerl, C. Bubert, M. Zabel, T. Labahn, 

E. Parisini, O. Reiser, Eur. J. Org. Chem. 2000, 2955. 

2. M. Schinnerl, C. Böhm, M. Seitz, O. Reiser, Tetrahedron 

Asymmetry 2003, 14, 765. 

3. R. B. Chhor, B. Nosse, S. Sörgel, C. Böhm, M. Seitz, 

O. Reiser, Chem. Eur. J. 2003, 9, 260. 

4. K. Harrar, O. Reiser, Chem. Commun. 2012, 48, 3457. 

5. L. Pilsl, O. Reiser, Amino Acids 2011, 41, 709. 

6. S. De Pol, C. Zorn, C. D. Klein, O. Zerbe, O. Reiser, 


Keywords: asymmetric cyclopropanation; diazoacetates; azabisoxazoline 

ligands; heterocycles; 


P - 0 4 2 6 

Cu(dAP)2CL AS effiCient viSiBLe LiGht 

MediAted Photoredox CAtALySt 

M. PirtSCh 1 , S. PAriA 1 , o. reiSer 1 , t. MAtSuno 2 , 

h. iSoBe 2 

1 University Regensburg, Institute of Organic Chemistry, 


2 Tohoku University, Department of Chemistry, Sendai, Japan 

Photochemistry has become an attractive field of research 

as well as an interesting tool in organic synthesis. As most of the 

recently reported reactions are employing photoredox catalysts 

which contain worthy transition metals such as ruthenium or 

iridium, more inexpensive alternatives are desirable. 

Sauvage et. al. reported in 1987 the photodimerisation of 

para-nitrobenzylbromide using Cu(dap) Cl. Inspired by this work 

2 

we further explored the catalytic scope of this catalyst. Upon 

irradiation with green light (LED 530 nm) the ATRA-reaction 

of various activated organobromides (tetrabromocarbon, 

diethylbromomalonate, α-bromoacetophenone) and organoiodines 

(perfluoro-iodo-alkanes) with olefins as well as the allylation of 

α-keto-bromides and –chlorides was successfully developed. The 

obtained halogenated photoadducts can be further converted to 

precursors that appear to be useful for cross coupling reactions 

such as Heck-coupling, Suzuki-coupling or Tsuji-Trost allylations. 

Keywords: Photochemistry; Copper; atom-transfer radical 

addition; allylation; redox chemistry; 



s1075 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 2 7 

tetrAhALoGeno-diPhenyLGLyCoLuriLS 

verSuS n-hALoSuCCiniMideS: 

MethyL-AroMAtiCS free rAdiCAL 

hALoGenAtion BehAvior. 

G. PoiSSon 1 , d. n. trAn 1 , v. BuLACh 2 , n. eL hASSAn 3 , 

S. dAhAoui 4 , J. M. GiLLet 5 , n. e. GherMAni 3 , 

A. MArSurA 6 

1 Nancy Universite, UMR 7565 SRSMC, Vandoeuvre-les-Nancy, 

France 

2 Strasbourg univertsité, Laboratoire de Chimie de Coordination 

Organique Institut Le Bel – UDS 4, Strasbourg, France 

3 Université Paris Sud 11, Laboratoire de Physique 

Pharmaceutique UMR CNRS 8612, Chatenay-Malabry, 

France 

4 Nancy Université, CRM2 UMR CNRS 7036, Vandoeuvre-les- 

Nancy, France 

5 Ecole Centrale Paris, Laboratoire Structures Propriétés et 

Modélisation des Solides (SPMS) UMR CNRS 8580, 

Chatenay-Malabry, France 

6 Nancy Université, UMR 7565 SRSMC, Vandoeuvre-les-Nancy, 

France 

It is obvious that efforts to find efficient and selective 

methods to functionnalise organic compounds remain of high 

priority. In this sense, free radical reactions represent an important 

field of valuable methods. Nevertheless, in recent years we 

already observed a dramatic failure of bromination of some 

essential nitrogen heterocycles and bis-heterocycles 

building blocks often involved in the synthesis of 

metallo-supramolecular structures. In this sense, 1,3,4,6-tetrachloro 

and 1,3,4,6-tetrabromo-3α,6α-diphenylglycolurils smooth 

halogen-oxidizers have been exploited in a new direction 

as reagents for free radical substitution towards some 

N-halosuccinimides non-reactive bis-heterocycles. An unexpected 

selectivity and reactivity were observed with methyl-benzenes, 

methyl-heterocycles and methyl-bis-heterocycles of interest. 

Crystal structure of 1,3,4,6-tetrachloro-3α,6α-diphenylglycoluril 

was accurately determined from high resolution X-ray diffraction 

data at 100 K. Ab initio calculations were also performed in order 

to reveal the halogen ... halogen interaction properties in this last 

compound. Electron and electrostatic features were carefully 

analyzed. 

Keywords: halogenation; heterocycles; Density functional 

calculations; radical reactions; charge transfer; 


P - 0 4 2 8 

Short SyntheSiS of diLACtAMS-LinKed 

SuCroSe MACroCyCLeS 

M. PotoPnyK 1 , SLAwoMir JAroSz 1 

1 Institute of Organic Chemistry, Polish Academy of Sciences, 


Sucrose, an inexpensive natural optically pure compound, 

is a promising building block for the preparation of chiral 

macrocyclic receptors. [1, 2] In the present communication the 

synthesis of optically pure macrocyclic derivatives with sucrose 

scaffold is presented. 

The synthesis was initiated from 1',2,3,3',4,4'-hexa-O- 

-methylsucrose (readily obtained from free sucrose by sililation- 

-methylation-desililation) in which the secondary and 

1'-OH hydroxyl groups were protected as methyl ethers. 

1',2,3,3',4,4'-Hexa-O-methylsucrose was converted into 

1',2,3,3',4,4'-hexa-O-methyl-6,6'-di-O-(methylsulfonyl)sucrose. 

Its condensation with 2 equiv. of the proper nitro- or 

cyanophenoles (o-, m-, p- respectively) provided the expected 

6,6'-di-O-nitrophenyl-1',2,3,3',4,4'-hexa-O-methylsucroses and 

6,6'-di-O-cyanophenyl-1',2,3,3',4,4'-hexa-O-methylsucroses, 

re duction of which afforded the corresponding 

di-amines. Condensation of these compounds with isophthaloyl 

or 2,6-pyridinedicarbonyl dichloride furnished the 

desiredmacrocyclic bis-lactams. 

Acknowledgement: The support from Grant: POIG.01.01.02- 

14-102/09 (part-financed by the European Union within the 

European Regional Development Fund) is acknowledged. 

references: 

1. B. Lewandowski, S. Jarosz ChemCommun., 2008, 

6399–6401. 

2. B. Lewandowski, S. Jarosz Org. Lett., 2010, 12, 

2532–2535. 

Keywords: sucrose; macrocycle; dilactams; isophthaloyl 

dichloride; 



s1076 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 2 9 

MiCrowAve-ASSiSted SeLeCtive oxidAtion of 

deoxyChoLiC ACid 

B. PreKodrAvAC 1 , n. niKoLiC 1 , M. SAKAC 1 , 

J. CAnAdi 1 

1 University of Novi Sad Faculty of Sciences, Department of 

chemistry biochemistry and enviromental protection, 

21000 Novi Sad, Serbia 

Promotive action of bile acids on the transport of some drugs 

through the cell membrane attracted huge attention in 

pharmaceutical sciences. Such promotive action of bile acids was 

further increased by replacing hydroxyl groups with oxo groups 

yielding derivatives with lower hydrophobicity [1] . 

Synthesis of such bile acid derivatives with conventional 

experiments is generally time consuming giving low or moderate 

yield2 . The aim of this work is in applying microwave technology 

in some reactions for selective oxidation of deoxycholic acid. 

Reactions have been performed in Discover Bench Mate 

microwave reactor (CEM, maximum output power 300 W, 

Synergy software) in closed-vessel system. Microwave process 

vials, with operating filling volume from 2-5 mL, have been used 

as reaction vessel. 

Pure product of 3α,12α-diformyloxy-5β-cholanoic acid was 

obtained in quantitative yield from 3α,12α-dihydroxy-5β- 

-cholanoic acid (deoxycholic acid) by dissolving it in methanoic 

acid and heating at 55ºC in microwave reactor for 30 minutes. 

Compared to the conventional heating experiments the presence 

of an acidic catalyst, like perchloric acid, was unnecessary. In the 

next phase, a partial deformylation of 3α,12α-diformyloxy-5β- 

-cholanoic acid with sodium-hydroxide in acetone was achieved 

at 60 ºC during 5 minutes. Microwave-assisted selective oxidation 

with N-bromosuccinimide in terc-butanol and further 

deformylation gave 12α-hydroxy-3-oxo-5β-cholanoic acid in high 

yield and purity. Compared to the conventional protocol a 

remarkable reduction in overall processing time from hours to a 

few minutes was achieved. Structures of synthesized bile acids 

have been confirmed by 1H- and 13C- NMR spectroscopic data. 

Acknowledgments: This work was supported by a research 

grant from the Ministry of Education and Science of the 

Republic of Serbia (Grant No. 172021). 

references: 

1. M. Posa, S. Kevresan, M. Mikov, V. Cirin-Novta, 

C. Sarbu, K. Kuhajda, Colloids Surf. B: Biointerf. 59 

(2007) 179. 

2. K.-Y. Tserng, P.D. Klein, Steroids 29 (5) 1977. 

Keywords: Oxidation; steroids; 


P - 0 4 3 0 

SyntheSiS of 15-SuBStituted eStrone 

derivAtiveS 

e. PrChALovA 1 , d. SedLAK 2 , P. BArtuneK 2 , 

M. KotorA 1 



2 Institute of Molecular Genetics AS CR, Laboratory of Cell 

Differentiation, Prague 4, Czech Republic 

Study of the estrogen receptors ERα and ERβ has been 

recently of considerable interest, because both receptors play a 

crucial role in female and male reproductive systems, regulate 

some key processes during development, and are important 

factors in certain types of cancer. ERα mediates the action of 

estrogens in classical tissues like uterus and mammary gland and 

it is also a traditional target for therapy of breast cancer as it 

promotes proliferation of certain healthy and cancerous tissues. 

On the contrary, ERβ is found in the ovary, brain, cardiovascular 

system, prostate and blood cells. In this respect, development of 

new ligands capable of selective binding to these receptors is of 

general interest. The preferential attention has been devoted to 

17-substituted estradiol derivatives. [1, 2] In this respect 

15-substituted estradiols or estrones constitute an interesting but 

hitherto mostly unexplored3 class of compounds that might serve 

as potential ligands for the estrogenic receptors. 

Our approach to the 15-substituted estrone derivatives 

started with the synthesis of 15β-vinylestrone that was greatly 

improved in comparison with the original procedure. The presence 

of the terminal double bond makes this compound an ideal 

substrate for cross-metathesis reaction with other terminal olefins 

as means for the attachment of variously substituted side-chains. 

As olefins were used alkenes or fluorinated alkenes, styrenes and 

their substituted congeners. In this manner we were capable 

generating a series of variously substituted 15β-estrone 

derivatives in good yields. Some of the prepared compounds were 

subjected for binding testing to ERα, ERβ, and other steroidal 

receptors. 

references: 

1. Sedlák, D.; Novák, P.; Kotora, M.; Bartunek, P. 

J. Med. Chem. 2010, 53, 4290. 

2. Eignerova, B.; Sedlák, D.; Dracínský, M.; Bartunek, P.; 

Kotora, M. J. Med. Chem. 2010, 53, 6947. 

3. Kirschning, A.; Harmrolfs, K.; Mennecke, K.; Messinger, 

J.; Schön, U.; Grela, K. Tetrahedron Lett. 2009, 49, 3019. 

Keywords: metathesis; steroids; 



s1077 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 3 1 

AntioxidAtive ACtivity of SuBStituted 

5-AMinoPyriMidineS And their oxidAtive 

SeLf-CondenSAtion in diMethyL SuLfoxide 

e. ProCházKová 1 , A. BrezinovA 2 , P. JAnSA 2 , 

A. hoLy 2 , h. MertLiKovA-KAiSerovA 2 , 

M. drACinSKy 2 

1 Charles University of Prague Faculty of Science, Department 

of Physical and Macromolecular Chemistry, Prague, Czech 

Republic 

2 Institute of Organic Chemistry and Biochemistry AS CR, NMR, 


Pyrimidine heterocyclic nucleobases are the basic building 

blocks of nucleic acids, but they also work as coenzymes or highenergy 

molecules. Modified pyrimidines display a wide range of 

biological properties such as antiviral, cytostatic or antimicrobial 

activities. In this work we have observed the antioxidative effects 

of a series of substituted 5-aminopyrimidines using in vitro 

(TEAC, LPO) and cell-based assays. 2,4,6-trisubstituted 

5-aminopyrimidines have been discovered as the most active in 

the TEAC (direct scavenging of long-lived radical) and LPO 

(compounds ability to protect rat liver microsomes against the 

Fe2+ /O -induced lipid peroxidation) assays but not in cell-based 

2 

assay probably because of lower cell membrane permeability. 

Hence, the compounds which contained “protected” 

5-aminogroup by a lipophilic substituent actually acted like a 

potential prodrugs, and the oxidative stress of Hep G2 cells was 

decreased. On the other hand, in cell-free assays the antioxidative 

activity of potential prodrugs was not found which is in agreement 

with the fact that the presence of “free” aminogroup in position 5 

on pyrimidine skeleton is necessary for the antioxidative ability 

of the studied compound. Surprisingly, the active compounds 

were decomposed in dimethyl sulfoxide (DMSO) to deeply 

coloured and highly insoluble products. DMSO can act as an 

oxidation agent, but the ability of DMSO to oxidize 

5-aminopyrimidines has not been described till now. We 

determined the structures of the products obtained by the DMSO 

oxidation of 5-aminopyrimidines. The 5-aminogroup can be 

oxidized to a keto group and a subsequent condensation with 

another molecule of an aminopyrimidine leads to tricyclic 

pyrimidinopteridines condensation products. The reaction rate of 

the oxidation-condensation reaction correlates well with the 

antioxidant activities of the 5-aminopyrimidines. 

Keywords: 5-aminopyrimidines; antioxidants; lipid 

peroxidation; DMSO oxidation; pyrimidopteridines; 


P - 0 4 3 2 

A reinveStiGAtion of the reGioSeLeCtive 

SyntheSiS of triMethoxyiSLAndiCin 

S. quevA 1 , M. SorMAz 1 , C. vALLA 1 , e. urBAn 1 , 

B. LAChMAnn 1 , C. r. noe 1 

1 University of Vienna Faculty of Life Science, Medicinal 


The mould metabolite islandicin [1] represents a key 

substructure of anthracycline tumour antibiotics. Thus it is not 

surprising that the total synthesis of this compound has been 

extensively investigated, resulting in several described synthetic 

methods for unsymmetrical anthraquinones. Nevertheless, there 

is still a controversy [2] about reaction regiospecificity, which is 

required to obtain unambiguous relative positions of the methoxy 

group on the one side of the ring system and the methyl group on 

the other. Our interest in an efficient industrial synthesis of 

anthracyclines prompted us to reinvestigate the synthesis of 

trimethoxyislandicin. 

Our synthetic sequence started with 2,3-dimethylanisole, 

which prove to be a superior source for 3-methoxyphthalic 

anhydride. The key step of the reaction was a Friedel-Crafts 

acylation of the anhydride with 2,5-dimethoxytoluene. This 

reaction was studied carefully both with respect to overall 

regioselectivity and yield of the desired regioisomer. 

A modification of the anthraquinone ring closure was worked out, 

which allowed carrying out the ring closure reaction and the 

preceding reduction in one pot, followed by oxidation to yield the 

title product. 

references: 

1. Howard B. H., Raistrick H., Biochem. J., 44, 227 (1949) 

2. Smith W. C., Ambler J. S., Steggles J. D., Tetrahedron. 

Lett., 34 (46), 7747-77450 (1993); 

Kim K. S., Spatz M. W., Johnson F., Tetrahedron Lett., 4, 

331-334 (1979); 

deSilva S. O., Watanabe M., Snieckius V., J. Org. Chem., 

44 (26), 4802-4808 (1979); 

Kende A. S., Belletire J. L., Herrmann J. L., Romanet R. F., 

Hume E. L., Schlessinger R. H., Syn. Commun., 3 (6), 

387-392, (1973) 

Keywords: Regioselectivity; 



s1078 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 3 3 

SyntheSiS of oLiGoPhenyLeneethynyLeneS 

with terMinAL thioeSter GrouPS for SinGLe 

MoLeCuLe SPeCtroSCoPy 

G. rAuCh 1 , G. GAefKe 1 , w. honG 2 , S. hÖGer 1 , 

t. wAndLowSKi 2 

1 Kekulé Institute, AK Höger, Bonn, Germany 

2 Department of Chemistry & Biochemistry, AK Wandlowski, 

Bern, Switzerland 

The variation of the length of oligomers with 

phenyleneethynylene units (OPEs) presents an excellent 

possibility to analyze the changes of the physical properties as a 

function of molecule length. Using single molecule spectroscopy, 

we want to study the charge transport properties of OPEs 

connected to two gold electrodes using a mechanically controlled 

break junction method. [1] For the synthesis of such defined 

oligomers, a stepwise building is necessary. That includes 

Pd-catalyzed coupling reactions and acetylene deprotecting 

reactions. 

To analyze the OPEs using single molecule spectroscopy we 

designed OPEs with terminal thioester groups able to bind to gold 

surfaces. The purification of these OPEs is of highest importance, 

and best performed by recycling gel permeation chromatography 

(rec. GPC). 

references: 

1. V. Kaliginedi, P. Moreno Garcia, H. Valkenier, W. Hong, 

V. Garcia-Suarez, P. Buiter, J. L. H.Otten, J. C. Hummelen, 

C. J. Lambert, T. Wandlowski, J. Am. Chem. Soc., 2012, 

134, 5262–5275. 

Keywords: Single-molecule studies; Conducting materials; 

electron transport; Alkynes; 


P - 0 4 3 4 

AxiAL-ChirAL ConCAve 1,10-PhenAnthroLineS 

L. reCK 1 , u. LüninG 1 


The three-dimensional concave environment of the active 

centre of enzymes is to a large extent responsible for their high 

selectivity. That is why this concept was imitated for the design 

of concave reagents. [1] These concave macrocyclic, mostly 

bimacrocyclic, compounds can be compared to a “lamp” with the 

concave environment as the “lampshade” and the active centre as 

the “light bulb”. Structurally, these concave reagents are much 

less demanding than enzymes, but they are also much more stable 

concerning different influences like pH or temperature. 

Concave 1,10-phenanthrolines are one group of concave 

reagents. Their concave shape is realized by phenyl bridgeheads 

in the 2- and 9-position of the 1,10-phenanthroline which are 

connected by ethylene glycol or methylene chains. 

Achiral variants of concave 1,10-phenanthrolines were 

successfully used as ligands for diastereoselective metal 

catalysis. [2, 3] 

It is our new aim to enable enantioselective catalysis. 

Therefore, it is necessary to build an axial-chiral cavity, which 

can be realized by the introduction of one naphthyl bridgehead. 

references: 

1. U. Lüning, Concave Reagents, in U. H. Brinker, 

J.-L. Mieusset, Molecular Encapsulation, John Wiley & 

Sons 2010, 175–199. 

2. F. Löffler, M. Hagen, U. Lüning, Synlett. 1999, 1826–1828. 

3. M. Gelbert, U. Lüning, Supramol. Chem. 2001, 12, 435–444. 

Keywords: Supramolecular chemistry; Macrocycles; 

Enantioselectivity; 



s1079 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 3 5 

noveL ArteSuniC ACid hoModiMerS AS Potent 

Anti-LeuKeMiA AGentS 

C. reiter 1 , A. herrMAnn 1 , A. CAPCi 1 , 

S. B. tSoGoevA 1 , t. efferth 2 


Department of Chemistry and Pharmacy Chair of Organic 

Chemistry 1, Erlangen, Germany 

2 University of Mainz, Department of Pharmaceutical Biology 

Institute of Pharmacy and Biochemistry, Mainz, Germany 

Cancer claims the lives of many people every year, hence 

great effort is put into the development of effective drugs against 

these diseases and therefore new lead structures of active 

compounds are of significant value. Representatives of the 

1,2,4-trioxane family, like artemisinin and its semi-synthetic 

analogue artesunic acid (or artesunate), are impressive examples 

for compounds known to be highly active against cancer. The 

innovative concept of hybridization, meaning the connection of 

bioactive natural products (fragments) by at least one carboncarbon 

bond, can be applied to artesunic acid. It has been shown 

by the Tsogoeva group in 2010, that dimers of artesunic acid are 

more effective against leukemia cells than artesunic acid itself and 

that they evade the problem of multidrug resistance of leukemia 

cells in contrast to some known anti-cancer agents. As a 

follow-up, we decided to synthesize three new homodimers of 

artesunic acid, connected by three different linkers (aliphatic, 

aromatic and alcoholic),to gain knowledge about the linker’s 

contribution to the anti-cancer activity. 

To obtain these molecules, artesunic acid was coupled with 

the corresponding diamine linkers, applying amide-bond-coupling 

conditions, and the three desired homodimers could be obtained 

in good yields (83 – 88%). After biological activity tests against 

thehuman leukemia cells CCRF-CEM and the multidrug resistant 

one CEM/ADR5000, we realized, that the shorter the linker, the 

more active the homodimer is against the two cell types. This 

insight and the successful application of the hybridization concept 

on artesunic acid takes us a significant step forward in the design 

of aforementioned new lead structures against cancer. 

Keywords: Artesunic acid; homodimers; anti-cancer agents; 

P - 0 4 3 6 

SyntheSiS of ChirAL th-SyMMetriCAL 

hexAKiS AdduCtS of C 60 

M. riALA 1 , n. ChronAKiS 1 



Cyprus 

Hexakis adducts of C with an octahedral addition pattern, 

60 

a motif which is unique in organic chemistry, represent attractive 

3D building blocks for the construction of Covalent Organic 

Frameworks (COFs). [1] The combination of these highly 

symmetrical hexakis adducts with a rigid linear spacer can lead 

to the formation of extended organic frameworks with a cubic 

topology while the formation of other possible structures will be 

suppressed. Furthermore, if the addends of the building blocks 

bear stereogenic centers and are optically pure then the 

corresponding COF will be equipped with this element of 

chirality. 

Our target is the synthesis of hexakis adducts of C bearing 

60 

functional groups with well-defined geometry. For this purpose, 

we designed three novel optically pure cyclo-[1]-malonate esters 

bearing C8, C12 and C14 spacers. The malonate esters were 

synthesized via the condensation reaction of malonyl chloride 

with the appropriate optically pure diols. 2 

Subsequently, a six-fold Bingel reaction with C was 60 

performed, leading to the corresponding T -symmetrical hexakis 

h 

adducts. Their acetal deprotection under acidic conditions will 

lead to the fully deprotected fullerene adducts, where the 1,2-diol 

moieties will be arranged in an octahedral well defined geometry. 

references: 

1. A. P. Côté, A. I. Benin, N. W. Ockwig, M. O’Keeffe, 

A. J. Matzger, O. M. Yaghi, Science, 2005, 310, 1166. 

2. N. Chronakis, T. Brandmüller, C. Kovacs, U. Reuther, 

W. Donaubauer, F. Hampel, F. Fischer, F. Diederich, 

A. Hirsch, Eur. J. Org. Chem., 2006, 2296. 

Keywords: [60]fullerene; Hexakis-adduct; Chiral; COF; 



s1080 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 3 7 

SyntheSiS of BiPhenoLS throuGh 

SuzuKi-MiyAurA-reACtionuSinG Pd/C in wAter 

M. rieMer 1 , B. SChMidt 1 


Germany 

Biphenols and their derivativesare lead structures in many 

natural products, drugs (e.g. vancomycin) andprecursor of many 

ligands. [1] 

A good method to synthesise biarylsis the Pd-mediated 

Suzuki-Miyaura-reaction.It has been shown that electron-rich 

arylhalides are less reactive, especiallyphenolates under the 

basic conditions of the Suzuki-Miyaura-reaction.In the majority 

of reactions the phenolic hydrogen was masked by 

a protecting-group,followed by the aryl-aryl-coupling and the 

deprotection of the phenol (3steps). In the case of biphenols 

actually only a few examples of a direct onestep coupling are 

known, avoiding the protection/deprotection-steps. [2] 

We report an efficient methodfor the synthesis of biphenols 

in one step and in good to excellent yields,inspired by the green 

protocol of Hirao,a ligandless Suzuki-Miyaura-reactionusing 

simple Pd on charcoal (heterogenous, easy to remove) in 

water. [3] Thereby the basic conditions (K CO ) enhance the 

2 3 

solubilityof the phenolic substrates. 

references: 

1. Bringmann, G.; Gulder, T.; Gulder, T. A. M.; Breuning, M; 

Chem. Rev. 2011, 111, 563; Brückner, R. 

Reaktionsmechanismen,Spektrum: Berlin; Vol. 3 

2. Freundlich, J. S.; Landis, H. E. Tetrahedron Lett. 2006, 47, 

4275 

3. Hirao, T.; Sakurai, H. J. Org. Chem. 2002,67, 2721 

Keywords: Palladium; Borates; Water chemistry; 

Heterogeneous catalysis; Biaryls; 


P - 0 4 3 8 

evALuAtion And oPtiMizAtion of vAriouS 

APPLiCABLe CroSSLinKerS on GeLAtion tiMe 

of PoLyACryLAMide GeL 

M. ABedi LenJi 1 , M. vAfAie Sefti 1 , 

A. MouSAvi MoGhAdAM 1 , M. BAGhBAn SALehi 1 , 

h. nAderi 2 , z. SArreShteh dAri 1 

1 Tarbiat Modares University, Chemical engineering, Tehran, 

Iran 

2 Research Institute of Petroleum Industry, Center for 

Exploration and Production Studies and Research Division, 

Tehran, Iran 

In this work, various polymer gels were prepared by 

crosslinking of aqueous solutions of polymer and crosslinker for 

the purpose of water shut off treatment in oil fields. A co-polymer 

of 2-acrylamido-2methyl-propanesulfonic-acid sodium salt 

(AMPS) and acrylamide (PAMPS) was used as polymer and 

chromium triacetate, polyethyleneimine (PEI) and 

hexamethylenetetramine (HMTA) were used as a metallic 

crosslinker and organic crosslinkers, respectively. In order to 

predict the gelation time of these three polymer gels, central 

composite design (CCD), the most popular form of Response 

Surface Methodology (RSM), was applied for the experimental 

plan. Three quadratic models were presented for the three polymer 

gels which was highly significant. Therefore, the main effects and 

the interactions between the factors were also identified. The 

results showed that the polymer concentration was the main effect 

in all polymer gels. The interaction between the two factors 

(polymer concentration and crosslinker/polymer ratio) had the 

most effect on the gelation time of chromium triacetate polymer 

gel, while it had less effect on the gelation time of PEI polymer 

gel and negligible effect on the gelation time of HMTA polymer 

gel. It was also found that increase of polymer concentration and 

crosslinker/polymer ratio caused a decrease in the gelation time 

of HMTA polymer gel. However, selecting a suitable ratio for the 

factors of PEI and chromium triacetate polymer gels was essential 

for obtaining the optimum gelation time with a purpose of 

maximizing it. According to the optimization of polymer gels 

separately, the 13172 ppm concentration of polymer and 0.44 ratio 

of chromium triacetate/polymer resulted to the gelation time of 

34 hr. Moreover, the 13208 ppm concentration of polymer and 

0.16 ratio of PEI/polymer and the 13190 ppm concentration of 

polymer and 0.17 ratio of HMTA/polymer resulted to the gelation 

time of 8.3 hr and 25 hr, respectively. 

Keywords: Polymer Gel; Gelation Time; Chromium Triacetate; 

Polyethyleneimine; Hexamethylenetetramine; 



s1081 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 3 9 

SeLf-ASSeMBLy of A SuPrAMoLeCuLAr 

hexAMeriC entity: forMAtion, StruCture 

And ProPertieS 

G. SChAeffer 1 , o. fuhr 2 , d. fenSKe 2 , J. M. Lehn 1 

1 Institut de Science et d’Ingenierie Supramoleculaires, 

Laboratoire de Chimie Supramoleculaire, Strasbourg, France 

2 Karlsruhe Institute of Technologie, Institut für Anorganische 

Chemie, Karlsruhe, Germany 

Molecular self-assembly is a powerful tool to generate order 

by using various types of interactions, such as hydrogen bonds, 

donor-acceptor or coordination interactions. It is a multistep 

process that is driven by the formation of selective, spontaneous 

and reversible association between the individual molecular 

components. [1] 

We have discovered a case whereby a multisite hydrogen 

bonding molecular component L forms a well-defined hexameric 

species L in a strongly selective process. We describe here the 

6 

assembly, the structure and the features of this entity, 

self-assembled from two variants 3L and 9L differing only by the 

length of the four hydrocarbon chains attached to the core, propyl 

and nonyl respectively. 

The compounds 3L and 9L have been described earlier and 

are known to form supramolecular polymers in solution [2] or on 

surfaces [3] when combined with an equimolar amount of a ditopic 

monomer capable of establishing six hydrogen bonds with one of 

their terminal subunits. The two molecules have been fully 

characterised in polar solvents as well as in the solid state after 

crystallisation from such solvents. Nevertheless, their full 

potential is yet to be realised, as indicated by their ability to 

self-assemble into a well-defined hexameric species 3L and 6 9L6 under other conditions. 

In the work presented here, we discuss the nature of this new 

and complex hexameric assembly, paying particular attention to 

its stability as a function of temperature and other chemical 

stimuli. 

references: 

1. J.-M. Lehn, Supramolecular Chemistry - Scopes and 

Perspectives, Wiley-VCH ed., Weinheim, 1995. 

2. a) V. Berl, M. Schmutz, M. J. Krische, R. G. Khoury, 

J.-M. Lehn, Chem. Eur. J. 2002, 8, 1227-1244; 

b) E. Kolomiets, E. Buhler, S. J. Candau, J.-M. Lehn, 

Macromolecules 2006, 39, 1173-1181. 

3. A. Ciesielski, G. Schaeffer, A. Petitjean, J.-M. Lehn, 

P. Samori, Angew. Chem. Int. Ed. 2009, 48, 2039-2043. 

Keywords: Supramolecular chemistry; Self-assembly; 


P - 0 4 4 0 

MuLtiPLy twiSted (LK > 1) MÖBiuS MoLeCuLeS 

G. SChALLer 1 , r. herGeS 1 

1 Otto-Diels-Institut für Organische Chemie, Chemistry, Kiel, 

Germany 

The credit of introducing the Möbius topology to chemistry 

goes to Heilbronner. As a consequence of his theoretical 

predictions, [1] the original Hückel rule is reversed for Möbius 

annulenes. Or more precisely, cyclic conjugated systems with 

Lk=odd are aromatic with 4n and antiaromatic with 

4n+2 π-electrons. A number of theoretical articles followed, but 

not before 2003 a synthesis of the first aromatic Möbius molecule 

(Lk=1) could be accomplished. [2] Initiated by this breakthrough 

the concept of Möbius topology has gained further attention. 

Recently, a number of Möbius porphyrins were published by 

Latos-Grazynski [3] and Osuka [4] . However, multiply twisted 

(Lk > 1) Möbius molecules are still elusive, and therefore they are 

challenging synthetically targets. Starting from the topology of 

the “Boy surface” we developed an instruction guide to assemble 

a triply twisted (Lk=3) Möbius molecule. 

references: 

1. Heilbronner Tetrahedron Lett. 1964, 5, 1923–1928. 

2. Herges et al. Nature 2003, 426, 819-821. 

3. Latos-Grazynski et al. Angew. Chem. 2007, 119, 8015–8019. 

4. Osuka et al. J. Am. Chem. Soc. 2008, 130, 13568–13579. 

Keywords: Macrocycles; 



s1082 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 4 1 

A PotentiAL MeChAniSM for 

5-MethyLCytidine deMethyLAtion in dnA 

S. SChieSSer 1 , B. hACKner 1 , t. PfAffeneder 1 , 

M. MüLLer 1 , C. hAGeMeier 2 , M. truSS 2 , 

t. CAreLL 1 

1 Ludwig-Maximilians-Universität, Chemistry, Munich, 

Germany 

2 Charite Universitätsklinikum, Centrum für Kinder und 

Jugendmedizin Klinik für Allgemeine Pädiatrie Labor für 

Pädiatrische Molekularbiologie, Berlin, Germany 

C5-Methylation of 2'-deoxycytidine (dC) in DNA to form 

methyl-2'-deoxycytidine (mC) is a well-known process, which is 

involved in gene expression and genomic imprinting. [1] By way 

of contrast the active removal of this methyl group to erase 

epigenetic marks is barely understood. One possible mechanism 

involves base excision repair, which could cut out mC and replace 

it by dC. However, this includes generation of strand breaks and 

therefore could lead to genomic instability. One also more 

atom-economic pathway would be the conversion of the methyl- 

-residue into a good leaving group. Consequently the elimination 

of non-toxic CO was put into focus after the discovery that 

2 

TET-enzymes oxidize mC to 2'-deoxycarboxycytidine (caC) via 

[2, 3, 4] 

the hydroxymethyl- and formyl derivatives. 

To prove the existence of such a decarboxylation pathway 

in biological systems a [ 15N ]-labeled caC phosphoramidite was 

2 

synthesized in 14 steps and incorporated into oligonucleotides. 

These strands were incubated with mouse embryonic stem cell 

(mESC) extract (or non-mESC extract as control), re-isolated via 

a clicked biotin-label and digested. The resulting nucleoside 

mixture was analyzed by a HR-HPLC-MS based isotope tracing 

method. Whereas in the negative control no 15N-labeled dC was 

detectable, incubation with mESC extract resulted in [ 15N ]-dC 2 

which can only be formed by decarboxylation of [ 15N ]-caC. 2 

To gain deeper insight into a potential reaction mechanism, 

chemical studies with a caC nucleoside and DNA were performed. 

Without saturation of the C5-C6 double bond of caC no 

decarboxylation could be observed in these experiments. 

The saturation can be obtained transiently by C6 addition of 

a thiol (for example cysteine), which re-eliminates after 

decarboxylation. Furthermore the presence of imidazole (as in 

histidine) or an amine (as in lysine) is essential, which suggests a 

proton catalyzed mechanism. [5] Consequently the active center of 

the postulated decarboxylase should contain a nucleophilic center 

and residues capable of proton catalysis. 

references: 

1. H. Cedar, Y. Bergman, Nat. Rev. Genet. 2009, 10, 295–304. 

2. T. Pfaffeneder, B. Hackner, M. Truss, M. Münzel, 

M. Müller, C. A. Deiml, C. Hagemeier, T. Carell, Angew. 

Chem. Int. Ed. 2011, 50, 7008–7012. 

3. Y. F. He, B. Z. Li, Z. Li, P. Liu, Y. Wang, Q. Tang, J. Ding, 

Y. Jia, Z. Chen, L. Li, Y. Sun, X. Li, Q. Dai, C. X. Song, 

K. Zhang, C. He, G.L. Xu, Science 2011, 333, 1303–1307. 

4. S. Ito, L. Shen, Q. Dai, S. C. Wu, L. B. Collins, J. A. 

Swenberg, C. He, Y. Zhang, Science 2011, 333, 1300–1303. 

5. S. Schiesser, B. Hackner, T. Pfaffeneder, M. Müller, 

C. Hagemeier, M. Truss, T. Carell, Angew. Chem Int. Ed. 

2012 accepted. 

Keywords: DNA methylation; Bioorganic chemistry; 

Imprinting; isotopic labeling; mass spectrometry; 


P - 0 4 4 2 

CArBoxyLAte-ASSiSted rutheniuM-CAtALyzed 

hydroAryLAtion of unACtivAted ALKeneS By 

C-h Bond funCtionALizAtion 

M. SChinKeL 1 , L. ACKerMAnn 1 



Chelation-assisted catalytic C-H bond functionalizations 

have emerged as a powerful tool for direct arene derivatization. [1] 

Whereas direct C-H bond alkylations [2] has been developed as a 

sustainable alternative to traditional transition-metal-catalyzed 

cross-coupling reactions between organometallic reagents and 

alkyl halides, C-H bond additions to multiple C-C bonds by 

hydroarylations represents one of the most atom-economical 

approaches to alkylated arenes. [1] 

Since the seminal work on ruthenium-catalyzed 

hydroarylations by Lewis and Murai [3] various catalytic systems 

have been devised for this challenging transferreaction [4] . Despite 

this progress the hydroarylation of unactivated alkenes continues 

to require harsh reaction conditions, while electronically activated 

alkenes have successfully been utilized under milder reaction 

conditions. 

Herein we present a ruthenium catalyst for the 

hydroarylation of unactivated alkenes, which operates under mild 

reaction conditions and displays a broad functional group 

tolerance. Thus, several electron-rich and electron-deficient arenes 

were alkylated in a highly chemo-selective fashion. Furthermore, 

valuable functional groups, such as ethers, ketones, esters and 

halides now were tolerated. 

references: 

1. a) L. Ackermann, Modern Arylation Methods, Wiley-VCH, 

Weinheim, 2009; 

b) Ritleng, C. Sirlin, M. Pfeffer, Chem. Rev. 2002, 102, 

1731–1769; 

c) F. Kakiuchi, T. Kochi, Synthesis 2008, 3013–3039; d) 

F. Kakiuchi, N. Chatani, Adv. Synth. Catal.2003, 345, 

1077-1101; 

2. a) L. Ackermann, Chem. Commun. 2010, 46, 4866–4877; 

b) L. Ackermann, N. Hofmann, R. Vicente, Org. Lett. 

2011, 1875–1877; 

c) L. Ackermann, P. Novák, R. Vicente, N. Hofmann, 

Angew. Chem. Int. Ed. 2009, 48, 6045–6048; 

3. a) L. N. Lewis, J. F. Smith, J. Am. Chem. Soc. 1986, 108, 

2728—2735; 

b) S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, 

M. Sonoda, N. Chatani, Nature 1993, 366, 529–531; 

4. a) M.-O. Simon, J.-P. Genet, S. Darses, Org. Lett. 2010, 

12, 3038–3041; 

b) R. Martinez, M.-O. Simon, R. Chevalier, C. Pautigny, 

J.-P. Genet, S. Darses, J. Am. Chem. Soc. 2009, 131, 

7887–7895. 

Keywords: C-H activation; Ruthenium; Homogeneous 

catalysis; Sustainable Chemistry; Alkenes; 



s1083 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 4 3 

ChroMAtoGrAPhiC inveStiGAtionS on the 

PhotodeGrAdAtion BehAvior of iridiuM 

BASed triPLet eMitterS 

S. SChMidBAuer 1 , A. hohenLeutner 1 , r. vASoLd 1 , 

B. KÖniG 1 



In the last few years, the choice of products using 

OLED-technology increased rapidly: from mobile phones, TVs 

and digital cameras to lighting devices and diverse car equipment. 

But to become a competitive technology on the world market, it 

is an imperative to overcome the still remaining problems 

concerning the operational lifetimes of OLEDs. Many attempts 

have been made so far, to shed light on the degradation 

mechanisms, studying the physical and chemical changes in the 

device. 

Regarding emitter degradation, two different mechanisms 

attracted attention: the degradation via the excited state and the 

chemical degradation caused by highly reactive species like in 

situ formed radicals or singlet oxygen. To gain some insight into 

the correlations between the degradation types and the compound 

structures, we established a chromatography based screening 

setup to analyze the degradation behavior of emitter complexes 

under different conditions. We used well known iridium 

complexes of different emission energies for the screening in a 

variety of solvents under inert as well as ambient conditions. After 

irradiation, the dissolved samples were subjected to our screening 

setup where the complexes were chromatographically separated 

from degradation products (HPLC). Analysis of the degradation 

rate and products were performed via DAD detection and Q-TOF 

mass spectrometry. The obtained data enables us to draw 

conclusions regarding the mechanisms and processes responsible 

for the emitter degradation and may help in future to predict 

emitter stabilities in a reliable way. 

Keywords: iridium; analytical method; mass spectrometry; 


P - 0 4 4 4 

SyntheSiS And ProPertieS of 

BiChroMoPhoriC MACroCyCLeS 

d. SChMitz 1 , S. JeSter 1 , S. Liu 2 , n. BoryS 2 , 

J. LuPton 3 , S. hÖGer 1 

1 Kekulé Institut, AK Höger, Bonn, Germany 

2 Department of Physics & Astronomy, AK Lupton, Salt Lake 

City, USA 

3 Institut für Experimentelle und Angewandte Physik, AK 

Lupton, Regensburg, Germany 

Conjugated polymers have attracted increased attention in 

the last decades due to interesting optical and electronic 

properties. Although these compounds are applied in OLEDs and 

photovoltaics nowadays, some of the fundamental physics like 

the interchain interaction in highly-concentrated solutions or in 

films still remains controversial. [1] 

We have synthesized and investigated model dimers 

of conjugated oligomers, linked in a macrocyclic scaffold. 

Two monodisperse conjugated oligomers, based on 

phenylene-ethynylene-butadiynylene entities are intramolecularly 

fixed by rigid clamp units, providing a defined distance. The size 

and distance of the chromophores can be defined synthetically. [2] 

The final ring closure towards the target structures is 

achieved by an intramolecular oxidative coupling of rigid 

bisacetylenes in a Pd-mediated coupling reaction. The 

bichromophoric systems and linear model compounds are purified 

by recycling GPC and fully characterized and visualized by means 

of NMR, MALDI-TOF-MS, GPC and STM. 

All bichromophoric systems and linear model compounds 

are investigated by optical spectroscopy in detail, using both time 

resolved and single molecule luminescence techniques. The most 

closely spaced chromophores show a slight red shift and a slowing 

of fluorescence lifetime, indicating the formation of a weak 

intramolecular excimer or H-aggregate. Intramolecular energy 

transfer is monitored for the acyclic bichromophoric system by a 

rapid fluorescence depolarization. Energy transfer is also detected 

for the cyclic bichromophores by low temperature single molecule 

fluorescence spectroscopy. [3] 

references: 

1. B. J. Schwartz, Rev. Phys. Chem. 2003, 54, 141. 

2. S.-S. Jester, N. Shabelina, S.M. Le Blanc, S. Höger, 


S.-S. Jester, A. Idelson, D. Schmitz, F. Eberhagen, 

S. Höger, Langmuir 2011, 27, 8205; 

S.-S. Jester, D. Schmitz, F. Eberhagen, S. Höger, Chem. 

Commun. 2011, 47, 8838. 

3. S. Liu, D. Schmitz, S.-S. Jester, N. J. Borys, S. Höger, 

J. M. Lupton, J. Phys. Chem. B, DOI: 10.1021/jp301903u. 

Keywords: macrocycle; conjugated oligomers; Pd catalyzed 

reaction; optical spectroscopy; 



s1084 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 4 5 

nitroALdoL reACtion AS A Key SteP in the 

SyntheSiS of rAre diAMino SuGArS 

C. SChMÖLzer 1 , w. SChMid 1 

1 University of Vienna, Institute of Organic Chemistry, Vienna, 

Austria 

Host-pathogen interactions are mediated by biopolymers 

attached to the cell membrane of bacteria. These complex 

molecules consist of different carbohydrates and fatty acids with 

a variety of linkage types. [1] Among the involved carbohydrates 

polydeoxy-polyamino sugars play an important role. Since their 

isolation from natural sources is usually demanding and 

purification of these rare molecules often fails due to 

non-separable impurities, chemical synthesis has to supply 

appropriate glycopolymers. [2] The synthesis of these targets is still 

a challenge for synthetic chemists. Herein we present a 

straightforward route towards diamino trideoxy sugars using a 

nitro aldol reaction. We synthesized the L-threonine derived 

aldehyde by applying the Garner protocol [3] which was further 

converted into the target molecule using 2-nitroacetaldehyde 

diethylacetal under basic conditions to establish the carbon 

backbone. The reduction of the nitro group with Raney-nickel 

and subsequent peracetylation led to a fully protected derivative 

of 2,4-diamino-2,4,6-trideoxy-D-galactose. The D-galacto 

configuration was assigned by NMR-spectroscopy. After a 

deprotection step the free di-N-acetylated carbohydrate as well as 

the corresponding ethylglycosides were isolated, depending on 

the reaction conditions applied. 

references: 

1. Kohler, T.; Xia, G.; Kulauzovic, E.; Peschel, A. In: 

Microbial Glycobiology 1st ed.; Moran, A.P.; Holst, O.; 

Brennan, P.; von Itzstein, M.; Academic Press: London, 

UK, 2009, pp 75-91. 

2. Schmidt, R.R.; Pederson, C.M.; Quia, Y.; Zähringer, U. 

Org. Biomol. Chem., 2011, 9, 2040-2052. 

3. Garner, P.; Park, J.M. Org. Synth., 1991, 70, 18. 

Keywords: Carbohydrates; Amino acids; Aldol reaction; 


P - 0 4 4 6 

PhotoCAtALytiC AryLAtion of ALKeneS, 

ALKyneS And enoneS with diAzoniuM SALtS 

P. SChroLL 1 , d. P. hAri 1 , B. KÖniG 1 

1 Institute of Organic Chemistry, University of Regensburg, 


An efficient visible-light-mediated radical arylation of 

unsaturated compounds in presence of aryl diazonium salts and 

[Ru(bpy) ] 3 2+ (“bpy” is 2,2'-bipyridine) or eosin Y as photocatalysts 

under irradiation with blue or green light is reported. An aryl 

diazonium salt is reduced by the photoexcited state of the 

photocatalyst giving an aryl radical which can subsequently add 

to olefins, acetylenes and enones. Reoxidation of the intermediary 

formed radical by the catalyst followed by deprotonation of the 

carbenium ion gives the arylated product. Alkenes and enones 

undergo sp2-sp2 , alkynes undergo sp2-sp cross-coupling. The 

reaction of phenyldiazonium salt with styrene gives stilbene, for 

example. The coupling of unsaturated compounds and aryl 

diazonium salts is an experimentally simple procedure which is 

characterized by high yields, low catalyst loadings and mild 

conditions using visible light and ambient temperature. The oneelectron 

oxidation and reduction photoredox process improves a 

classic Meerwein arylation protocol significantly. 

Keywords: photocatalysis; arylation; diazonium salts; 

radicals; visible light; 



s1085 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 4 7 

in Situ GenerAted dioxirAne 

orGAnoCAtALyStS in 

enAntioSeLeCtiveePoxidAtion reACtionS 

S. M. M. SChuLer 1 , P. r. SChreiner 1 

1 Institute of Organic Chemistry, Justus-Liebig University, 


Organocatalysis has become a viable strategy for the 

preparation of epoxides. [1] Using carbonyl groups and Oxone 

generating the corresponding dioxiranes in situ provides an 

effective organocatalytic access. [2] We could identify a new 

catalytic moiety (4-(trifluoroacetyl)benzoic acid) based on this 

concept. In our efforts to develop multicatalysis approaches, [1c,3] 

a peptide-like catalyst was synthesized to optimize the reaction 

conditions for the epoxidation of 1-phenyl-1-cyclohexene 

(20 mol% catalyst, 20 mol% TBABr, Oxone (3 equiv), NaHCO3 (4.6 equiv.), DCM/H O (1:1), 5 h, r.t., 95% conversion). In an 

2 

attempt to improve enantioselectivity, both functionalized peptide 

catalysts containing a non-natural adamantane amino acid and 

C -symmetric difunctionalized diamine catalysts have been 

2 

synthesized. 

references: 

1. a) K. M. Weiß, S. B. Tsogoeva, Chem. Rec. 2011, 11, 18; 

b) C. E. Jakobsche, G. Peris, S. J. Miller, Angew. Chem. 

Int. Ed. 2008, 47, 6707; 

c) R. Hrdina, C. E. Müller, R. C. Wende, L. Wanka, 

P. R. Schreiner, Chem. Commun. 2012, 48, 2498. 

2. a) O. A. Wong, Y. Shi, in Asymmetric Organocatalysis, 

Vol. 291 (Ed.: B. List), 2010, pp. 201; 

b) D. K. Romney, S. J. Miller, Org. Lett. 2012, 14, 1138. 

3. a) C. E. Müller, R. Hrdina, R. C. Wende, 

P. R. Schreiner, Chem. Eur. J. 2011, 17, 6309; 

b) R. C. Wende, P. R. Schreiner, Green Chem. 2012, 

in press. 

Keywords: Epoxidation; Organocatalysis; Peptides; 

Enantioselectivity; 


P - 0 4 4 8 

SyntheSiS of interLoCKed MoLeCuLeS 

ContAininG ShAPe-PerSiStent MACroCyCLeS: 

A CovALent teMPLAte APProACh towArdS 

rotAxAneS 

C. SChweez 1 , S. S. JeSter 1 , S. hÖGer 1 


Interlocked molecules like rotaxanes or catenanes have been 

attracting chemists’ interests since their discovery due to their 

extraordinary shape, the synthetical challenge, and promising 

chemical-physical properties, particularly in the context of 

artificial devices like molecular machines. A lot of template 

directed syntheses using weak interactions e.g. metal coordination 

or hydrogen bonding, were established, whereas routes using 

covalently bonded templates were mostly rejected. Recently, a 

renaissance of this pioneer approach arose and the capability of 

this method was confirmed by several published applications. 

Our group employed covalently bonded templates 

successfully for various purposes, particularly in syntheses 

towards shape-persistent macrocycles or macrocycle encapsuled 

polymers. [1] Based on this earlier work, now we used covalently 

bonded templates in the synthesis of a novel [2]rotaxane 

containing rigid macrocycles. A centered phenylene–ethynylene 

macrocycle is threaded onto a phenylene-ethynylene rod axis and 

macrocyclic stopper units prevent a slippage effectively. The 

synthetic approach relies on the centered macrocycle being 

connected via phenolic ester bonds to the axis and subsequently 

a selective bond cleavage by nucleophilic substitution at the 

carbonyl group leads from the prerotaxane to the rotaxane. 

The formation of the rotaxane was confirmed by 

MALDI-TOF-MS, 1H NMR and GPC. Additionally, we 

visualized the [2]rotaxane by scanning tunneling microscopy at 

the solid/liquid interface of 1,2,4-trichlorobenzene and highly 

oriented pyrolytic graphite. 

references: 

1. a) K. Becker, P. G. Lagoudakis, G. Gaefke, S. Höger, 

J. M. Lupton, Angew. Chem. 2007, 119, 3520-3525. 

b) K. Becker, G. Gaefke, J. Rolffs, S. Höger, J. M. Lupton, 

Chem. Commun. 2010, 46, 4686-4688. 

Keywords: Rotaxanes; Macrocycles; Template synthesis; 

Conjugation; 



s1086 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 4 9 

SyntheSiS of new fLuoreSCent BuiLdinG 

BLoCK BASed on ChoLeSteroL, 

PhenyLALAnine And CouMArine 

L. SKorPiLovA 1 , M. JurASeK 1 , P. drASAr 1 , 

z. wiMMer 2 


Natural compounds, Prague 6, Czech Republic 

2 Institute of Experimental Botany AS CR v.v.i., Isotope 

Laboratory, Prague 4, Czech Republic 

Cholesterol as a fundamental steroidal unit remains in 

interest of both organic chemists and biochemists. It is known, 

that cholesterol derivatives represent model and emerging class 

of chiral liquid crystals. Moreover, this highly lipophilic 

compound may serve as molecule which helps to deliver certain 

pharmacophore to targeting tissue. In this labor as a central linker 

4-azido or 4-iodo L-phenylalanine were used. The α-amino group 

of L-Ala was derived in both cases by fluorescent coumarine 

marker, aromatic azide was introduced into Huisgen 

1,3-dipolar cycloaddition and iodo derivative into Sonogashira 

cross-coupling reaction with propargylated cholesterol. These 

compounds themselves may well be interesting from both, the 

supramolecular point of view, as well as, subsequent 

derivatization which is enabled due to the carboxylic acid 

functionality remains the only non-derived unit in the molecule. 

Acknowledgment: Grant P503/11/0616 (GACR) and 

MSM6046137305 (MSMT). 

Keywords: cholesterol; fluoprescence; click chemistry; cross 

coupling; 


P - 0 4 5 0 

effiCient SyntheSiS of new 

PoLyhydroxyLAted fLAvon-3-oLS 

J. L. C. SouSA 1 , A. M. S. SiLvA 1 

1 University of Aveiro, Department of Chemistry & QOPNA, 

3810-193 Aveiro, Portugal 

The flavonoids are prominent components of citrus fruits, 

seeds, olive oil, tea, red wine and other food sources. They are 

part of the human diet and can show important beneficial effects 

on human health [1] . The flavonols are a subclass of this 

family of low molecular weight compounds, which have a 

3-hydroxyflavone backbone. These oxygen heterocyclic 

compounds have been identified as fulfilling most of the 

necessary criteria to present a strong antioxidant activity, because 

they present a C2 = C3 double bond conjugated with the 4-keto 

group, an ortho-dihydroxy-substitution on ring B and free 

OH groups at the C-3 and C-5 positions [2] . Examples of some 

well-known naturally occurring flavonols are quercetin, 

kaempferol, myricetin, among others. 

In the present work, 3-hydroxyflavones were prepared 

through a two-step synthetic route, namely an aldol condensation 

of appropriate 2'-hydroxyacetophenones and benzaldehydes [3] and 

an Algar-Flynn-Oyamada reaction [4] , ending with the cleavage of 

the protecting groups. The experimental procedures and results of 

this study as well as the structural characterization of the new 

compounds will be presented and discussed in this 

communication. 

Acknowledgements: Thanks are due to the University of Aveiro, 

Fundacio para a Ciencia e a Tecnologia (FCT, Portugal) and 

FEDER for funding the Organic Chemistry Research Unit 

(project PEst-C/QUI/UI0062/2011) and the Portuguese 

National NMR Network. J.L.C. Sousa is also grateful to FCT for 

her PhD grant (SFRH/BD/76407/2011). 

references: 

1. Middleton Jr., E.; Kandaswami, C.; Theoharides, T.C., 

Pharmacol. Rev. 2000, 52, 673-751. 

2. Gomes, A.; Neuwirth, O.; Freitas, M.; Couto, D.; Ribeiro, 

D.; Figueiredo, A.G.P.R.; Silva, A.M.S.; Seixas, R.S.G.R.; 

Pinto, D.C.G.A.; Tomé, A.C.; Cavaleiro, J.A.S.; 

Fernandes, E.; Lima, J.L.F.C., Bioorg. Med. Chem. 2009, 

17, 7218-7226. 

3. De la Torre, M.D.L.; Rodrigues, A.G.P.; Tomé, A.C.; 

Silva, A.M.S.; Cavaleiro, J.A.S., Tetrahedron 2004, 60, 

3581-3592. 

4. Dahlén, K.; Wallén, E.A.A.; Gr?tli, M.; Luthman, K., 

J. Org. Chem. 2006, 71, 6863-6871. 

Keywords: Antioxidants; Cyclization; NMR spectroscopy; 

Oxygen heterocycles; Protecting groups; 



s1087 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 5 1 

PhotoCAtALySiS with fLAvinS: 

hiGh-Power-reduCtionS 

C. StAnGLMAir 1 

1 Institut für Organische Chemie, Prof. König, Regensburg, 

Germany 

One of the most famous photoreceptor dyes is riboflavin, 

also known as vitamin B , which takes part in a lot of biochemical 

2 

reactions as coenzyme. [1] Upon irradiation with blue light 

(440 nm) their redox power is dramatically increased: 

The reduction potential for the two electron reduction is 

about -200 mV. [2] This can be used for oxidative chemistry: [3] The 

reduced flavin is simply reoxidized by air. 

When air is excluded new reduction pathways are enabled: 

The reduced flavin can be excited via UV-light which raises the 

reduction power enormously. We present our first results 

investigating organic reactions with reduced flavins. 

Research supports: DFG: GRK 1626 – Chemical 

Photocatalysis. 

references: 

1. A. M. Edwards, in Flavins Photochemistry and 

Photobiology, Vol. 6 (Eds.: E. Silva, A. M. Edwards), 

The Royal Society of Chemistry, Cambdrige, 2006, pp. 1–11. 

2. S. Ghisla, W. C. Kenney, W. R. Knappe, W. McIntire, 

T. P. Singer, Biochemistry 1980, 19, 2537–2544. 

3. a) R. Lechner, S. Kummel, B. Konig, Photochemical & 

photobiological sciences: Official journal of the European 

Photochemistry Association and the European Society for 

Photobiology 2010, 9, 1367–1377; 

b) R. Lechner, B. König, Synthesis2010, 2010, 1712–1718. 

Keywords: Photocatalysis; Flavin; Reduction; 


P - 0 4 5 2 

new C-BridGed n-heteroCyCLeS AS ChirAL 

LiGAndS And for CoPPer dioxyGen 

CoMPLexeS 

M. SteinBACh 1 , r. GÖttLiCh 1 , S. SChindLer 2 

1 Justus-Liebig-Universität Gießen, Organische Chemie, 


2 Justus-Liebig-Universität Gießen, Anorganische Chemie, 


new C-bridged N-heterocycles as chiral ligands: The 

concept of C2-symmetry has proved to be invaluable for 

asymmetric catalysis. Among the vast number of ligands known, 

the most successful ones such as the binaphthyls or the 

bisoxazolines contain a C2-symmetry axis, and only a few notable 

exceptions such as phosphinooxazolines or ferrocenyl ligands are 

equally effective chiral inductors. 

As the fact that C2-symmetrical bisoxazolines are excellent 

ligands, we were interested in similar methylene-bridged 

N-heterocycles like bispiperidine or bistetrahydroquinoline as new 

chiral ligands. In comparison to the bisoxazoline nitrogen the 

bispiperidine-analogue nitrogen is electronic different due to its 

hybridization from which some differences in complexation 

properties can be expected. To study these new ligands we 

synthesized them, analyzed them and use them to prepare different 

complexes. After this they will test as asymmetric catalyst. Results 

of these studies will be presented on the poster. 

Copper dioxygen complexes with some of these ligands: 

Copper is known as active centre of several redox active 

metalloproteins. Because of the ability of many copper enzymes 

to catalyse selective oxidations with air, one of the goals in 

bioinorganic chemistry currently is to model this functionality and 

to use such small molecular synthetic copper complexes as 

catalysts for selective oxidation reactions in the laboratory and in 

industry. To get such a model complex, oxygen is allowed to react 

under controlled conditions with a copper(I)-complex of the 

N-heterocyclic ligands. To study a couple of these model 

complexes, they were synthesized and characterized by using in 

this case some similar methylene-bridged N-heterocyclic ligands 

like bispiperidine or bisquinoline. Results of these studies will be 

presented on the poster. 

Keywords: N ligands; Asymmetric catalysis; copper; 

O-O activation; 



s1088 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 5 3 

SyntheSiS And oPtiCAL ProPertieS of 

BiS(terPyridine)oLiGothioPheneS And 

reLAted MetALLo-SuPrAMoLeCuLAr 

dynAMerS 

P. StenCLovA 1 , J. zedniK 1 , J. vohLidAL 1 , 

J. SvoBodA 1 


of Physical and Macromolecular Chemistry, Prague 2, Czech 

Republic 

Reversible linking of α,ω-functionalized oligomer 

molecules by noncovalent interactions or appropriately labile 

covalent or coordination bonds transforms the oligomers into 

constitutional-dynamic polymers, co called dynamers. Main 

advantages of dynamers are possibilities of additional 

modification (in order to tune or tailor their properties) or 

self-healing of the main chains by an exchange or reshuffling of 

their components. Ideal systems of this constitution can be 

repeatedly switched, in contrast to classical permanent polymers 

composed of irreversible macromolecules. 

Novel, fully π-conjugated ditopic oligomers: α,ωbis(terpyridine)oligothiophenes 

(bithiophenes and terthiophenes, 

unsubstituted, methyl- or hexyl- substituted), were synthesized 

via Pd-catalyzed organic cross-coupling reactions from 

monoterpyridine compounds. The obtained products were fully 

characterised and their optical properties (absorption and emission 

maxima, lifetimes of excited states and photoluminescence 

efficiency) are presented as function of their structure. Interaction 

of soluble compounds with Zn2+ ions were studied with 

absorption and emission spectroscopy. Metallo-supramolecular 

dynamers were obtained from the reaction of 

bis(terpyridine)oligothiophenes with Zn2+ salts and additional 

exchange of counterions. 

On the basis of our results, we can draw several principal 

conclusions: (i) the wavelength of the longer-wavelength 

maximum of the oligomer absorption increases with 

oligothiophene linker prolongation and (ii) decreases with 

introduction of alkyl group onto thiophene ring, (iii) the emission 

maximum in photoluminescence spectra increases with 

conjugated chain prolongation. The lifetimes of excited states are 

relatively short (0.55–0.77 ns) and the photoluminescence 

emission quantum yields are 33–43% for bis-terpyridines with 

non-substituted oligothiophene linker and 12–23% for compounds 

with alkyl-substituted oligothiophene linker. Detailed 

characterization of metallo-supramolecular dynamers is currently 

underway in our laboratory. 

Both π-conjugated oligomers as well as related 

supramolecular dynamers might be, after additional detailed study 

of their electronic properties in solution and solid phase suitable 

materials for light emitting devices or dye-sensitized solar cells. 

Keywords: C-C coupling; N-ligands; supramolecular 

chemistry; UV/Vis spectroscopy; fluorescence; 


P - 0 4 5 4 

ASyMMetriC dieLS-ALder reACtion witn 

nitroACryLAte 

o. StePAneK 1 , M. KotorA 1 



Diels-Alder reaction of nitropropenoates with various dienes 

constitutes one of the approaches to regioselectively substituted 

cyclohexenes. Interestingly, its enantioselective variant that would 

open a route to asymmetrically substituted cyclohexenes remains 

hitherto a rather unexplored area. Since there are numerous 

interesting compounds possessing chiral cyclohexene scaffold 

(e.g. Tamiflu, [1] carbasugars, etc), this method is of considerable 

synthetic interest. We focused on asymmetric Diels–Alder 

reaction of the nitroacrylate bearing chiral ester auxiliary group 

with 1-alkoxydienes. Although the formation up to eight possible 

stereoisomers could be expected as the result of the Diels-Alder 

reaction, only two of them were preferentially formed owing to 

structural features (steric and electronic) of both reactants [2] . 

Influence of reaction conditions on the stereoisomer ratio, and 

asymmetric induction will be discussed. In addition, further 

transformation of the obtained products into advanced synthetic 

building blocks and their application in organic synthesis will be 

presented as well. 

references: 

1. Farina, V.; Brown, J. D. Angew. Chem. Int. Ed. 2006, 45, 

7330. 

2. Kakushima, M.; Scott, D. J. Can. J. Chem. 1979, 57, 1399. 

Keywords: Asymmetric synthesis; Cycloaddition; Chiral 

auxiliaries; 



s1089 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 5 5 

MiChAeL AdditionS uSinG nitro derviAteS 

– A Key SteP for the SyntheSiS of indoLe 

ALKALoidS And reLAted n-ContAininG 

heteroCyCLeS 

B. StreifinGer 1 , A. PoPP 1 , K. ziereiS 1 , 

S. MAhBooBi 1 

1 University of Regensburg, Pharmaceutical and Medicinal 

Chemistry I, Regensburg, Germany 

The addition of compounds with an activated C-H bond to 

α,β-unsaturated molecules like esters, ketones or nitro-derivatives, 

e.g. the so called Michael acceptors, is a well known method for 

the formation of C-C single bonds. [1] Michael started in 1887 to 

describe the base catalyzed reaction of malonates with enones 

within a couple of publications. [2] Nowadays, nearly every 

1,4-addition of a nucleophile to an activated double bond is called 

Michael addition. 

Nitroalkenes are often used for the synthesis of 

functionalized amines by Michael addition and subsequent 

reduction of the nitro group. This way can be used for a broad 

variety of products, e. g. amino sugars, amino alkohols and 

diamines. 3 Thus, nitroolefines are excellent Michael acceptors 

with only a neglectable tendency towards 1,2-addition and a 

strong anion stabilizing property of the nitro group. [2] The 

asymmetric Michael addition enables high enantioselectivities 

using simple, protonated triamine and diamine catalysts for the 

enantioselective addition of cyclic ketones to nitroalkenes. [4] 

Furthermore the cascade intermolecular Michael addition 

facilitates a salient feature using a Lewis acid catalyzed 

intermolecular Michael addition followed by a thermal induced 

intramolecular azide/internal alkyne 1,3-dipolar cycloaddition 

reaction in one pot. [5] 

references: 

1. Bergman, E. D.; Ginsburg, D.; Pappo, R. Org. React. 

1959, 10, 179–555. 

2. Komnenos, T. Liebigs Ann. Chem. 1883, 218, 145–169. 

3. Morris, M. L.; Sturgess, M. A. Tetrahedron Lett. 1993, 34, 

43–46. 

4. Panscare S.V., Pandaya K., J. Am. Chem. Soc. 2006, 128, 

9624–9625. 

5. Arigela R. K., Mandadapu A. K., Kumar B., Kundu B., 

Org. Lett. 2012, 14, 1804–1807. 


P - 0 4 5 6 

SeLf-ASSeMBLinG unitS BASed on 

PhytoSteroLS 

J. SuSteKovA 1, 2 , z. wiMMer 1, 2 , P. drASAr 1 


Chemistry of Natural Compounds, Praha 6, Czech Republic 

2 Institute of Experimental Botany, Isotope laboratory, Praha 4, 


In past, bile acids have often been used in designing 

supramolecular structures. Recently, we have used selected 

phytosterols as elementary units for designing self-assembling 

systems. The first step of my investigation consisted in 

synthesizing hemiesters of sterols (e.g., stigmasterol, sitosterol or 

ergosterol), which were prepared by reacting anhydrides of 

dicarboxylic acids with appropriate phytosterols in dry pyridine 

and in a presence of the catalytic amount of DMAP. The yields of 

these esterification reactions varied from 49 % (branched 

anhydrides) to 93 %. These intermediate hemiesters were used for 

subsequent synthesis of conjugates with nitrogen containing 

compounds (e.g., esters of selected amino acids or other 

heterocyclic substances). Reactions were made in the dry 

dichloromethane, and DCC and DMAP were used as catalysts. 

The required amides were obtained with the yields exceeding 

90 %. 

Physico-chemical characteristics of the prepared conjugates 

were subjected to investigation. Their UV spectra were measured 

either in acetonitrile / water or ethanol/water (from 100% solvent 

to 100% water) systems. Only the solvent ratios changed, while 

the concentrations of the studied conjugates were always constant 

during the investigation. Changes in the intensity and/or position 

of the maximum absorbance in the UV spectra were recorded and 

evaluated. Self-assembly behavior of the studied compounds was 

indicated by non-linear dependence of the UV maximum 

absorbance on time and solvent ratios. Several substances have 

been proven to form gels reversibly in selected solvents, and at a 

given temperature. 

Acknowledgment: A financial support from specific university 

research (MSMT No. 21/2012), project P503/11/0616 (GACR) 

and the research program MSM6046137305 (MSMT) is 


Keywords: Steroids; Self-assembly; Amides; UV/Vis 

spectroscopy; 



s1090 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 5 7 

Mixed MAtrix MAteriALS BASed on 

hyPerBrAnChed PoLyiMide And SiLiCA 

P. SySeL 1 , e. MinKo 1 , K. frieSS 2 , v. hyneK 2 , 

M. SiPeK 2 , M. zGAzAr 2 , o. voPiCKA 2 , K. PiLnACeK 2 


Polymers, Prague 6, Czech Republic 


Physical Chemistry, Prague 6, Czech Republic 

Linear aromatic polyimides show a very good overall 

stability from – 150 to 250 °C. In recent years, an increasing 

attention has been devoted to hyperbranched polyimides due to a 

possible connection of the advantages of polyimides with those 

of hyperbranched polymers. The important structural features of 

hyperbranched polymers are a highly branched structure, absence 

of chain entanglements and large number of terminal groups. 

Polyimides are especially employed in electronics, aircraft 

industry and as membranes in gas separations. They show high 

selectivity in gas separation but traditionally low gas fluxes. It has 

been reported that the permeability coefficients of some gases in the 

membrane prepared from a hyperbranched polyimide were 2 – 3.5 

higher than those in the membrane prepared from a linear polyimide 

having similar chemical composition at the comparable selectivities. 

The incorporation of microporous/mesoporous materials into 

polyimides may further increase their permeability [1] . 

In this work, the mixed matrix materials based on the 

hyperbranched polyimide bearing amino end-groups 

(prepared from 4,4'-oxydiphthalic anhydride and 

4,4',4''-triaminotriphenylmethane) and silica (up to 20 wt% 

of nano- or mesoporous particles) were prepared. 

3-Glycidyloxypropyltrimethoxysilane was used as a coupling 

agent (its epoxy groups react with amino end-groups of the 

hyperbranched polyimide and alkoxy groups with silanol groups 

of the silica). The thickness of self-standing films was about 

50 microns. The composition – (thermal, mechanical) property 

relationships of these materials were evaluated. The permeability 

coefficients of some gases were also determined. Their analysis 

has brought some fruitful results (e. g. a membrane containing 

20 wt% of mesoporous silica bound to the polymer matrix shows 

about 150% increase in the oxygen flux in comparison with a pure 

hyperbranched polyimide membrane and the selectivity 

oxygen/nitrogen reaches up to 9). 

Acknowledgement: GA CR P106/12/0569 

references: 

1. P. Sysel, et al.: Desalination and Water Treatment 34, 211 

(2011). 

Keywords: hyperbranched polyimide; silica; coupling agent; 

mixed matrix material; 


P - 0 4 5 8 

BioACtive heteroCyCLeS – interMediAteS of 

A nAturAL ProduCt inSPired SyntheSiS AS 

PotentiAL AntiBACteriAL LeAd CoMPoundS 

S. w. B. tAn 1 , C. L. L. ChAi 2 , M. G. MoLoney 1 

1 University of Oxford, Chemistry, Oxford, United Kingdom 

2 Institute of Chemical and Engineering Sciences ASTAR 

National University of Singapore, Pharmacy, Singapore, 

Singapore 

Since penicillin was introduced into the clinical setting in 

the 1940s, antibiotic resistance has emerged very rapidly. As 

subsequent generations of this class of antibiotics contained a 

similar molecular scaffold which act upon similar cellular targets 

within the bacteria, the development of further resistance have 

been accelerated. [1] 

In recent drug discovery processes, early combinatorial 

approaches have not delivered the expected results, and no new 

chemical entities from de novo combinatorial chemistry for 

antibacterial compounds have been reported; it is now thought 

that the diversity of the libraries was too limited, having been 

prepared from narrowly focused commercially available starting 

materials, principally coupled by amide bond formation. The 

library thus formed is inadequate to populate a sufficiently large 

area of chemical space to provide the required hits. [2, 3] 

We are interested in the development of novel antibacterial 

compounds, and have used biologically active natural products as 

starting points for potential lead compounds in the drug discovery 

process, since they are evolutionarily selected for binding to 

specific protein domains, possibly providing a ‘privileged’ 

structural framework. [4] 

Herein, we describe the synthesis of heterocycles based on 

the natural product (-)-Pramanicin, starting from known 

enantiopure compounds derived from pyroglutamic acid 

and -Serine. These analogues have been assessed by bioassay, 

L 

and activities have been correlated with physicochemical 

parameters calculated using a software (MARVIN 5.3.8), in order 

to assess their potential for application as lead compounds. 

references: 

1. G. Taubes, Science, 2008, 321, 356-361. 

2. G. M. Cragg, P. G. Grothaus and D. J. Newman, 

Chemical Reviews, 2009, 109, 3012-3043. 

3. D. P. Walsh and Y. T. Chang, Chemical Reviews, 2006, 

106, 2476-2530. 

4. D. Brohm, S. Metzger, A. Bhargava, O. Muller, F. Lieb 

and H. Waldmann, Angewandte Chemie-International 

Edition, 2002, 41, 307-311. 

Keywords: Drug discovery; Heterocycles; Antibiotics; 



s1091 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 5 9 

ASyMMetriC direCt ALdoL reACtion in wAter 

orGAnoCAtALySed By reCyCLABLe And 

heteroGeneouS ChitoSAn AeroGeLS 

n. tAnChoux 1 , C. GioiA 2 , A. riCCi 2 , L. BernArdi 2 , 

K. BourAhLA 1 , M. roBitzer 1 , f. quiGnArd 1 

1 ICGM - UMR5253, MACS, Montpellier Cedex 5, France 

2 University of Bologna, Department of Organic Chemistry 

“A. Mangini”, Bologna, Italy 

The development of heterogeneous catalytic systems for fine 

chemical synthesis has become a major area of research. The 

ability to use heterogeneous catalysts in the liquid phase can aid 

considerably in the separation, recovery and reuse of catalysts. It 

can afford clean separation of products from the crude thus 

making a major impact on the environment performance of a 

synthesis. Chitosan derived by deacetylation of chitin (biopolymer 

obtained from sea crustaceans) can be considered as a natural 

polyamine. 

The lack of literature reports dealing with the heterogeneous 

asymmetric organocatalysis displayed by polysaccharides 

prompted us to undertake a detailed study of the chitosan potential 

in this new frontier area of organocatalytic reactions. Accordingly, 

to evaluate the putative chitosan catalytic activity, the direct aldol 

reaction, one of the most important carbon-carbon bond forming 

reactions, was investigated in water without any organic co 

solvent, by using supercritical CO dried chitosan as the catalyst. 

2 

Indeed aerogel formulation of chitosan affords high surface area 

materials (up to 350 m2 .g-1 ) with high accessibility to the 

functional groups (up to 5.2 mmol.g-1 NH ). 2 [1] Initial tests were 

performed in the reaction between p-nitrobenzaldehyde and 

cyclohexanone aimed at establishing the optimized reaction 

conditions. Then, aerogel microspheres of chitosan have 

successfully catalyzed the asymmetric aldol reaction in water, 

providing the products in high yields, with good stereoselectivity 

(up to 93 % ee) and recyclability (up to 4 runs). Yields were 

favourably affected by additives such as 2,4-dinitrophenol and 

stearic acid. We have developed the first direct asymmetric aldol 

reaction that can be performed in water using chitosan as 

heterogeneous organocatalyst. [2] The simple and environmental 

friendly experimental procedure and the recycling of the catalytic 

systems highlight good assets of this protocol. 

references: 

1. F. Quignard et al. NJC, 2008, 32, 1300 

2. A. Ricci, et al. Chem. Commun. 2010, 46, 6288 

Keywords: Natural Products; Biomass; Enantioselectivity; 

Green chemistry; 


P - 0 4 6 0 

fLuorinAted orGAnoCAtALyStS for the 

enAntioSeLeCtive ePoxidAtion of enALS: 

MoLeCuLAr Pre-orGAniSAtion By the 

fLuorine-iMiniuM ion GAuChe effeCt 

e. M. tAnzer 1 , r. GiLMour 1 

1 ETH Zurich, Laboratory for Organic Chemistry, Zürich, 

Switzerland 

The fluorine-iminium ion gauche effect, [1, 2] and its strategic 

use in the design of small molecule organo-catalysts that undergo 

conformational changes in response to substrate binding will be 

described. The condensation of a secondary β-fluoroamine 

with an α,β-unsaturated aldehyde reversibly generates a 

β-fluoroiminium salt as a consequence of stabilizing 

hyperconjugative interactions (e.g. σ ?σ* ) C-H C-F [1] as well as 

electrostatic/charge dipole interactions [3] with the electropositive 

center (e.g. Fδ--C -C -N β α + ). Introducing additional structural 

features leading to stabilizing (e.g. π-stacking or 

C-H-π interactions) or destabilizing interactions helps 

discriminate between the two possible gauche conformations. 

Consequently, substituents attached to the fluorine-bearing carbon 

can be predictably positioned in an area of molecular space and, 

in the case of enantioselective organocatalysis, exploited as 

shielding groups to direct incoming nucleophiles to one 

of two faces of a planar electrophile. The β-fluoroamine 

(S)-2-(fluoro diphenylmethyl)-pyrrolidine [4] is an effective catalyst 

for the Weitz-Scheffer epoxidation of alpha-beta-unsaturated 

aldehydes. A process of structural editing [5] has revealed that the 

efficiency of this catalyst is due to the (fluorodiphenyl)methyl 

group when it is embedded in a β-fluoroiminium motif. 

Furthermore the epoxidation of challenging cyclic 

α,β-disubstituted, β,β-disubstituted and α,β,β-trisubstituted enals [5] 

catalysed by (S)-2-(fluoro diphenylmethyl)-pyrrolidine proceeded 

with excellent levels of enantiocontrol (up to 98% ee). 

references: 

1. D. O’Hagan, Chem. Soc. Rev. 2008, 37, 308-319 

2. L. E. Zimmer, C. Sparr, R. Gilmour, Angew. Chem. 2011, 

123, 12062-12064; Angew. Chem. Int. Ed. 2011, 50, 

11860-11871. 

3. D. Y. Buissonneaud, T. van Mourik, D. O’Hagan, 

Tetrahedron 2010, 66, 2196-2202. 

4. a) C. Sparr, W. B. Schweizer, H. M. Senn, R. Gilmour, 

Angew. Chem. 2009, 121, 3111-3114; Angew. Chem. Int. 

Ed. 2009, 48, 3065-3068. 

b) C. Sparr, E.-M. Tanzer, J. Bachmann, R. Gilmour, 

Synthesis 2010, 1394-1397. 

5. E.-M. Tanzer, L. E. Zimmer, W. B. Schweizer, R. Gilmour, 

unpublished results. 

Keywords: Conformation analysis; Enantioselectivity; 

Fluorine; 



s1092 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 6 1 

CoMPArAtive Study of enoLetherS with 

r-hydrAzineS in exPeriMentS And KinetiCS 

d. tArABová 1 , v. MiLAtA 1 , J. hAnuSeK 2 

1 Faculty of chemical and food technology STU Bratislava, 

Department of organic chemistry, Bratislava, Slovak Republic 

2 Faculty of chemical technology Pardubice, Department of 

organic chemistry and technology, Pardubice, Czech Republic 

Selected enolethers [1, 2] provided with R-hydrazines as 

binucleophiles (R=H, methyl, acetyl, phenyl) products of vinylic 

nucleohilic substitution reaction at room temperature by using of 

appropriate solvents. There were observed cyclization products 

by addition-elimination step at higher temperature opposite to the 

room tepmperature. On these sytems were realized kinetic studies 

for same conditions as for experiments. Reactions took place in 

ultra rapidly, reaction run by pseudo – first order. These fact gave 

us valuable results in the kinetic study of these isoelectronic 

systems [3]. 

The authors are greatful to Grant Agency for Science 

No. 1/0660/11 and Slovak Research and Development Agency 

No. APVV-0339-10 for financial support. 

references: 

1. Milata, V., Ilavský, D., Goljer, I., Lesko, J., Chahinian, M., 

Henry-Bash, E.: Coll. Czech. Chem. Commun. 1990, 55, 

1038. 

2. Salon, J., Milata, V., Prónayová, N., Lesko, J.: Monatsch. 

Chem. 2000, 131, 293. 

3. Dyachenko V. D., Tkachev, R. P.: Russ. J. Org. Chem. 

2003, 39(6), 757. 

Keywords: enolethers; vinylic nucleophilic substitution 

reaction; pseudo-first order; 


P - 0 4 6 2 

MG/AL hydrotALCiteS: StruCturAL And 

CAtALytiC BehAviour in heteroGeneouS 

CyAnoethyLAtion 

f. teodoreSCu 1 , o. d. PAveL 1 , v. PArvuLeSCu 1 

1 University of Bucharest Faculty of Chemistry, Department of 

Organic Chemistry Biochemistry and Catalysis, Bucharest, 

Romania 

The preparation, characterization and catalytic behavior of 

hydrotalcites (LDH), mixed oxides obtained via LDH thermally 

decomposition and reconstructed LDH by means of memory 

effect were extensively reported in the literature [1–3] . LDH is 

considered an ionic lamellar class of base solid catalysts and there 

are many evidences on their efficiency in various heterogeneous 

basic reactions. 

In this study we report the preparation of Mg/Al LDH with 

molar ratio 3, by co-precipitation of Mg and Al nitrated solutions 

with Na CO and NaOH at pH = 10. The solids were thermally 

2 3 

decomposed at 460°C in air atmosphere in order to obtain mixed 

oxides which were then hydrated with bi-distilated water for the 

reconstruction of the LDH structure. The solids obtained were 

characterized using in- / ex-situ techniques such as: XRD, 

DRIFTS, CO -TPD, N adsorption-desorption isotherms. The 

2 2 

catalytic activity of the solids was evaluated in cyanoethylation 

reaction between different alcohols (methanol, ethanol, propanol) 

and nitriles (acrylonitrile, crotonitrile, cinnamyl nitrile). All these 

reactions arising with a higher selectivity in the desired product. 

No by-products were detected by means of GS-MS 

chromatography and 1H-NMR. As an example, the conversion of 

nitrile with ethanol was 98% with acrylonitrile and around 30% 

with crotonitrile and cinnamyl nitrile using reconstructed samples. 

Acknowledgement: This work was supported by the strategic 

grant POSDRU/89/1.5/S/58852, Project “Postdoctoral 

programme for training scientific researchers” cofinanced by 

the European Social Found within the Sectoral Operational 

Programme Human Resources Development 2007-2013. 

references: 

1. F. Cavani, F. Trifir?, A.Vaccari, Catal. Today 11 (1991) 

173. 

2. A. Vaccari, Appl. Clay Sci. 14 (1999) 161. 

3. G. Centi, S. Perathoner, Micropor. Mesopor. Mat. 107 

(2008) 3. 

Keywords: base; solid catalysts; cyanoethylation; 



s1093 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 6 3 

SyntheSiS of PyriMido[4,5-B]indoLe 

riBonuCLeoSideS BeArinG (het)AryL GrouPS 

At PoSitionS 4 And 6 

M. tiChy 1 , M. hoCeK 1 


Of Organic And Nuclear Chemistry, Prague 2, Czech Republic 

introduction: 7-Deazapurine nucleosides bearing hetaryl 

group in position 6 and H, F or Cl atom at position 7 showed 

cytostatic activity against multiple cell lines. Furyl and thienyl 

derivatives were the most active compounds. [1] Based on previous 

results, goal of this work was the synthesis of new type of 

annulated deazapurine derivatives bearing hetaryl group for 

biological testing. 

results and discussion: The synthesis of 4,6-dichloro-9H- 

-pyrimido[4,5-b]indole and its ribosylation to protected 

ribonucleoside intermediate has been developed starting from 

2,4-dichloronitrobenzene. This five-step synthesis (nucleofilic 

substitution, reduction, heterocyclization, substitution and 

glycosylation) has been optimized for tens gram scale with only 

one final column chromatography and excellent overall yield 30 %. 

A series of target ribonucleosides bearing aryl or hetaryl 

group at position 4 of pyrimidine ring has been prepared by 

regioselective Pd-catalyzed Suzuki or Stille cross-coupling 

reactions1 of protected nucleoside in good yields. Final 

deprotection under the Zemplen conditions using NaOMe in 

methanol led to free nucleosides in 70 - 90 % yields. Further 

arylation at position 6 is possible only under modified conditions 

using Buchwald ligands in good yields (62-79 %). Final 

deprotection furnished desired free nucleosides in 90 % yields. 

Title 4,6-disubstituted derivatives were tested for biological 

activities. 

Acknowledgements: This work was supported by the Academy 

of Sciences of the Czech Republic, Czech Science Foundation 

(P207/11/0344) and by Gilead Sciences, Inc. 

references: 

1. Nau‰ P., Pohl R., Votruba I., DÏubák P., Hajdúch M., 

Ameral R., Birku‰ G., Wang T., Ray A. S., Mackman R., 

Cihlar T., Hocek M.: J. Med. Chem. 2010, 53, 460. 

Keywords: pyrimido[4,5-b]indole ribonucleosides; palladium 

cytalysed cross-coupling; 


P - 0 4 6 4 

froM BifunCtionAL LiGAndS to A diverSity of 

hoMo- And heteroMetALLiC CoMPLexeS 

r. w. troff 1 , f. toPiC 1 , C. A. SChALLey 2 , 

K. riSSAnen 1 





In metallo-supramolecular self-assembly, ligands containing 

different coordination motifs are interesting building blocks which 

can be used for a large variety of different purposes like 

hierarchical self-assembly or self-sorting. Inspired by these 

possibilities, a series of four ligands was designed, which contain 

one 2,2'-bipyridine coordination site that is substituted in 4,4'- or 

5,5'-position, respectively, with two pyridine binding moieties. 

Additionally, the position of the nitrogen atoms in the pyridine 

moieties is varied. 

The combination of these ligands with suitable metal centers 

with different coordination numbers and coordination geometries 

results in the formation of different metallo-supramolecular 

structures. Discrete metallo-supramolecular complexes are 

obtainable as well as metal-organic frameworks. When the ligands 

are combined with a suitable combination of two or more different 

metal centers also the formation of heterometallic structures is 

observed. 

For example, the combination of the ligands under study 

with two equivalents of cis-blocked square-planar [Pd(en)](NO ) 3 2 

results in the formation of M L complexes using the 

2 

4,4'-substituted ligands or M L complexes for the 5,5'-substituted 

4 2 

ligands (M = metal center; L = ligand), respectively. 

When the 4,4'-substituted ligands are combined 

with square-planar [Pd(CH CN) ](BF ) , the formation of 

3 4 4 2 

metallo-supramolecular macrocycles is observed. For example, 

the ligand containing two 3-pyridine moieties results in the 

exclusive formation of M L macrocycles, wherein one Pd(II) ion 

4 4 

is coordinated by one 2,2'-bipyridine unit and two pyridine units 

of the next ligand. Thus, the M L complexes are unidirectional, 

4 4 

which would result in chiral complexes, when those complexes 

are adsorbed on a proper surface. 

By a combination of the ligands with 1/3 eq. of an iron(II) 

salt ML complexes can be achieved, which are interesting 

3 

precursors for further self-assembly reactions. Mixing these ML3 complexes with other metal centers leads for example to the 

formation of heterometallic metal-organic frameworks. 

On the poster we present some of the structures described 

above. 

Keywords: supramolecular chemistry; metal complexes; 

heterometallic complexes; self-assembly; functional ligands; 



s1094 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 6 5 

ASyMMetriC reduCtion of ProChirAL 

KetoneS with BorAne uSinG ChirAL 

BetA-hydroxAMideS derived froM 

nAPhthoiC ACid And ChirAL AMino 

ALCohoLS AS CAtALyStS 

y. turGut 1 , M. AzizoGLu 1 , A. erdoGAn 1 , 

n. ArSLAn 1 , i. StiBor 2 

1 Dicle University, Chemistry, Diyarbakir, Turkey 

2 Institute for Nanomaterials Advanced Technologies and 

Innovation Technical University, Katedra chemie, Liberec, 


Enantiopure oxazaborolidine-catalyzed borane reduction of 

prochiral ketones is one of the most important methods to prepare 

optically pure secondary alcohols [1, 2] . Such alcohols are important 

intermediates for the synthesis of various organic compounds 

including liquid crystalline materials as well as biologically active 

compounds [3] . The pioneering work of Itsuno and coworkers was 

developed by Corey and Link, and called as CBS (named after 

Corey, Bakshi, and Shibata) reduction. The study of catalysts 

derived from chiral oxazaborolidine has become one of the most 

active research fields [4] . 

A series of β-hydroxyamides were synthesized from 

3-hydroxy-2-naphthoic acid and chiral amino alcohols. Their 

catalytic activity in asymmetric borane reduction of prochiral 

ketones was investigated. After the fine optimization of solvent, 

temperature, amount of borane complex, and the length of catalyst 

generation period, good to excellent yields (up to 99 %) and 

enantioselectivity ( up to 96 %) has been achieved. 

Acknowledgement: Financial support from TUBITAK (Project 

number: 110T 809) is gratefully acknowledged 

references: 

1. Deloux, L.; Srebnik, M. Chem Rev, 93, 763,1993; 

Corey, E. J.; Helal, C. J., Angew Chem Int Ed Engl, 37, 

1986, 1998. 

2. Zhou, Y.; Wang, Y-W.; Dou, W.; Zhang, D.; LIU, W-S., 

Chirality 21,657-662,2009. 

3. Togni, A.; Venanzi, L. M., Angew. Chem., Int. Ed. Engl., 

33, 497–526, 1994. 

4. Hirao, A.; Itsuno, S.; Nakahama, S.; Yamazaki, N.; 

J. Chem. Soc. Comm. 1981, 315-317; Corey, E. J.; Link, 

J.O., Tetrahedron Lett., 31, 601-604, 1990. 

Keywords: beta-hydroxamides; asymmetric reduction; borane 

reduction; prochiral ketone; 


P - 0 4 6 6 

KinetiC reSoLution of 

4-hydroxy-2-CyCLoPentenone derivAtiveS By 

Pd-CAtALyzed ALLyLiC ALKyLAtion And 

APPLiCAtion in SyntheSiS of CArBoCyCLiC 

nuCLeoSideS 

K. uLBriCh 1 , v. tirAyut 2 , r. oLiver 1 

1 University Regensburg, Institute of Organic Chemistry, 


2 Chulalongkorn University, Department of Chemistry, Bangkok, 

Thailand 

Today there is an increasing interest in methods applying 

renewable materials as the source of chemical building blocks. 

Furan derivatives like furfuryl alcohol are mainly produced from 

agricultural waste and consequently come not into conflict with 

food production. [1] They offer interesting possibilities for chemical 

transformations like the rearrangement of furfuryl alcohol to 

4-hydroxy-2-cyclopentenone. For this reaction a continuous flow 

process was developed in our group giving the racemic product 

in high yield. [2] As this substance was inexpensively available in 

our group, different enantiomerically pure 4-substituted 

2-cyclopentenones, which are useful chiral building blocks for 

synthesis of many important compounds, [3] have been synthesized. 

This was accomplished by kinetic resolution of 

4-(tert-butoxycarbonyloxy)-2-cyclopentenone, which was 

obtained from the free alcohol by simple Boc-protection, with 

Pd-catalyzed asymmetric allylic alkylation using a chiral ligand. 

Various oxygen-, nitrogen- and sulfur-nucleophiles have been 

employed in this reaction giving excellent yields and selectivities. 

An application for the kinetic resolution was found in the 

synthesis of carbocyclic nucleosides, which show interesting 

biological activity. One main obstacle in their synthesis is the use 

of expensive enantiomerically pure starting materials or the 

introduction of the stereochemical information when using 

racemic compounds. [4] Our method overcomes this problem 

by starting from racemic 4-(tert-butoxycarbonyloxy)-2- 

-cyclopentenone and 6-chloropurine as nucleophile in the kinetic 

resolution, which gives the 4-substituted product in high yields 

and with excellent enantiomeric excesses. This product presents 

an important intermediate in the synthesis of certain carbocyclic 

nucleosides. [5] 

references: 

1. Biorefineries-Industrial Processes and Products; Kamm 

B., Gruber P., Kamm M., Eds.; Wiley-VCH: Weinheim, 

2007. 

2. Ulbrich K., Kreitmeier P., Reiser O. Synlett 2010, 13, 

2037. 

3. Aitken D. J. Eur. J. Org. Chem. 2010, 5339–5358. 

4. Medicinal Chemistry of Nucleic Acids; Zhang L.-H., Xi Z., 

Chattopadhyaya J., Eds.; John Wiley & Sons, Inc., 

Hoboken, 2011. 

5. Mackman R. L. Bioorganic & Medicinal Chemistry 2009, 

17, 1739–1746. 

Keywords: Asymmetric catalysis; Enantioselectivity; Kinetic 

resolution; Palladium; Renewable Resources; 



s1095 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 6 7 

SwitChinG MoLeCuLeS on 

SurfACeS – A PLAtforM APProACh 

S. uLriCh 1 

1 Otto-Diels-Institut, Organic Chemistry, Kiel, Germany 

Azobenzenes and other photochromic molecules have 

gained great attention as molecular switches. In this project we 

are developing methods to attach azobenzene derivatives to single 

crystalline Au(111) surfaces. 

To minimize the electronic coupling of the azobenzene with 

the gold surface and to prevent steric interaction with 

neighbouring molecules the azobenzene units have to be anchored 

in an upright position with a well defined orientation and distance 

to the surface and to each other. This approach should provide 

higher quantum yields for photochemical switching (trans to cis 

and cis to trans) then azobenzenes physisorbed flat on the surface. 

Moreover with polarized light it should be possible to control the 

switching direction. 

A promising method to achieve the above mentioned 

properties is the use of TATA (triazatriangulenium) and TOTA 

(trioxatriangulenium) as platforms. Azobenzene molecules can be 

covalently attached to the central carbon atom and are therefore 

perpendicular to the plane of the platform. [1] 

Both the unfunctionalized and functionalized platforms form 

hexagonally ordered self assembled monolayers on Au(111) 

[2, 3, 4] 

surfaces. 

More advanced lateral structures will be attempted by 

substitution of the platforms with hydrogen-bond donor and 

acceptor domains. Via supramolecular interactions the platforms 

should form well-defined and highly ordered mixed monolayers. 

Using functionalized platforms with different functional groups 

attached to the central carbon atom, also control of vertical growth 

could be possible. 

references: 

1. J. Kubitschke, C. Näther, R. Herges, Eur. J. Org. Chem. 

2010, 5041-5055. 

2. S. Kuhn, B. Baisch, U. Jung, T. Johannsen, J. Kubitschke, 

R. Herges, O. Magnussen, Phys. Chem. Chem. Phys. 2010, 

12, 4481-4487. 

3. B. Baisch, D. Raffa, U. Jung, O. M. Magnussen, C. Nicolas, 

J. Lacour, J. Kubitschke, R. Herges, J. Am. Chem. Soc. 

2009, 131, 442-443. 

4. S. Kuhn, U. Jung, S. Ulrich, R. Herges, O.Magnussen, 

Chem. Commun. 2011, 47, 8880-8882. 

Keywords: platform; gold surface; functionalized adlayers; 


P - 0 4 6 8 

reGioSeLeCtive CyCLoPoLyMerizAtion of 

1,7-oCtAdiyneS 

J. unoLd 1 , M. r. BuChMeiSer 1 

1 Stuttgart University, Chemistry, Stuttgart, Germany 

The cyclopolymerization of 1,6-heptadiynes via olefin 

metathesis is a powerful method for synthesizing soluble, 

conjugated polyacetylene-type polymers [1] . Using designed 

Schrock-type initiators, the regioselective cyclopolymerization of 

1,6-heptadiynes provides either five- or six-membered repeat units 

via a- or b- addition, respectively [2] . With 1,6-heptadiynes, 

b- addition leads to the formation of six-membered repeat units 

and few examples for selective b- addition have been reported [3] . 

Here we report on the regioselective cyclopolymerization of 

1,7-octadiynes [4] . In order to elucidate on the structure of the 

resulting polymers, we synthesized the diastereomeric 

4,5-diethoxycarbonyl-1,7-octadiynes from which the pure 

diastereomers were obtained by Soxhlet extraction in CHCl . 3 

Using the concept of “small alkoxides” developed by Schrock et 

al. [5] , all monomers were cyclopolymerized with a series of 

different Schrock-type initiators, varying the size of the alkoxide 

ligands. As a result, poly(1,7-octadiyne)s with a high content of 

six-membered repeat units (> 90 %) were obtained. Both the 

structure of the polymers and the regioselectivity of insertion were 

confirmed by comparing the 13C-NMR shifts of model compounds 

with those of the corresponding polymer. The living character of 

the polymerization was demonstrated by kinetic studies and end 

group analysis via MALDI-ToF MS. Finally, diblock copolymers 

were prepared from an 1,7-octadiyne and a 1,6-heptadiyne. 

references: 

1. Buchmeiser, M. R. Adv. Polym. Sci. 2005, 176, 89. 

2. Anders, U.; Nuyken, O.; Buchmeiser, M. R.; Wurst K.; 


3. Schattenmann, F. J., Schrock, R. R. and Davis, W. M.; 

J. Am. Chem. Soc., 1996, 111, 3295. 

4. Naumann, S., Unold, J, Frey, W, Buchmeiser, M. R.; 

Macromolecules, 2011, 44, 8380; 

highlighted in SYNFACTS, 8 (2), 0150, 2012 by. Swager, 

T. M and Cox, J. R.; 

5. Schrock R. R., Luo S, Zanetti N. C., Fox H. H.; 

Organometallics; 1994; 13; 3396. 

Keywords: Metathesis; Polymerization; Catalysis; 

Molybdenum; Kinetics; 



s1096 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 6 9 

MetALLo- And Photo- SwitChed dynAMiC 

networKS 

G. vAntoMMe 1 , S. JiAnG 1 , J. M. Lehn 1 


chemistry, Strasbourg, France 

Hydrazones may be considered as tools, used in 

constitutional dynamic chemistry (CDC), to control the 

constitution of dynamic networks. They exhibit double-dynamic 

properties [1] : a) constitutional dynamics, by exchange of 

hydrazone bounds; b) configurational dynamics, by metal 

coordination and photochemical cis-trans isomerization. 

A dynamic network based on hydrazones has been designed 

to respond differently to two types of stimulation: physical (light 

irradiation) and chemical (addition of a metal cation) thereby 

undergoing adaptation of their constituents via component 

exchange and selection. These switched dynamic networks offer 

the prospect of long term information storage, training of the 

system to recognize different effectors and formation of an 

ecological niche. 

references: 

1. M.N. Chaur, D. Collado, J.-M. Lehn, Chem. Eur. J. 2011, 

17, 248-258. 

Keywords: Combinatorial Chemistry; Supramolecular 

Chemistry; Hydrazones; 


P - 0 4 7 0 

AzoniA CAtionS By rinG-CLoSinG MetAtheSiS 

J. J. vAquero 1 , B. ABArCA 1 , A. nunez 1 , 

A. M. CuAdro 1 , J. ALvArez-BuiLLA 1 

1 Universidad de Alcala, Química Orgánica, Alcalá de Henares 

(Madrid), Spain 

Quinolizinium derivatives [1] have proven useful in some 

applications such as cyanine dyes and highly fluorescent 

compounds used as probes for the detection of biomolecules. 

These compounds also show some relevant biological activities 

and the quinolizinium system is present in a variety of natural 

alkaloids such as coralyne and the family of berberines. Other 

significant alkaloids such as sempervirine, flavopereirine, 

neooxygambirtannine and afrocurarine inter alia are based on an 

indolo[2,3-a]quinolizinium heterocyclic system. 

Recently, our group reported the ring–closing metathesis 

(RCM) reaction of a new type of azinium azadiene, which allowed 

a novel approach to dihydroquinolizinium and quinolizinium 

cations from pyridinium salts in good overall yields under mild 

reaction conditions. [2, 3] The success of the RCM reactions 

involving this class of charged diene, particularly those based on 

2-alkenyl- 

-1-vinylpyridinium substrates, led us to explore the synthesis of 

systems from the appropriate azinium salts. 

In this communication we will report our results 

to access to benzo-, dibenzo-, naphtho-, aza- and 

indolo[2,3-a]quinolizinium derivatives using different 

approaches based on a RCM as key reaction. 

Acknowledgments: Spanish Ministerio de Economía y 

Competitividad (CTQ2011/24715) and Instituto de Salud Carlos 

III (REDinREN, RD06/0016/0016). 

references: 

1. J. J. Vaquero; J. Alvarez-Builla Heterocycles Containing a 

Ring-Junction Nitrogen in Modern Heterocyclic Chemistry. 

J. Alvarez-Builla, J. J. Vaquero and J. Barluenga Eds. 2011, 

Wiley-VCH Verlag, vol. 4, p. 1989-2070 

2. W. A. L. van Otterlo, C. B. de Koning, Chem. Rev. 2009, 

109, 3743–3782. 

3. A. Núnez, B. Abarca, A. M. Cuadro, J. Alvarez-Builla, 

J. J. Vaquero, J. Org. Chem. 2009, 74, 4166–4176 

Keywords: Hetocycles; Cations; Metathesis; synthetic 

methods; 



s1097 

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P - 0 4 7 1 

KinetiC inveStiGAtion of A CinChonA BASed 

orGAnoCAtALytiC MiChAeL Addition 

e. vArGA 1 , L. t. MiKA 2 , G. KArdoS 3 , t. SooS 3 



2 Eotvos Lorand University Faculty of Science, Institute of 

Chemistry, Budapest, Hungary 



Organocatalysts represent a powerful tool for creation of 

C-C bond, in particular, many new bifunctional organocatalysts 

were described for enantioselective Michael addition, in the past 

decade. Most of these researches target new substrate applications. 

On the other hand, we focus herein on the kinetics of an 

organocatalized Michael addition. 

We studied the addition of acetylacetone and β-nitrostyrene 

using a cinchona based squaramide catalyst in order to understand 

better the mechanism of the catalytic reaction and to determine 

the rate-limiting steps. Kinetic studies were carried out under 

synthetically relevant conditions and the reactions were followed 

by in situ IR measurement, and were confirmed with 1H-NMR spectroscopy. 

Based on kinetic analysis we conclude, that the reaction rate 

shows linear dependence on the catalyst concentration. The order 

of β-nitrostyrene was found to be around one at low initial 

concentration (up to 0.6 mol/dm3 ), while at higher initial 

concentration, we found high reaction rate and product inhibition. 

The significant product inhibition was also confirmed by addition 

of the product at the beginning of the reaction: we observed a 

dramatic rate decrease. Surprisingly, the reaction rate does not 

clearly correlate with acetylacetone concentration, the order in 

this reactant is lower than one. We suggest competitive binding 

of acetylacetone and product to the active site of the catalyst. 

We also confirmed this assumption by investigation of 

catalyst-substrate complexes by NMR spectroscopy. Additionally, 

the effect of temperature was also studied, and the activation 

energy of the reaction was calculated. 

On the poster we shall present all the detailed kinetic studies 

and the proposed catalytic cycle describing the reaction 

mechanism. 

Keywords: Organocatalysis; Kinetics; Michael addition; 


P - 0 4 7 2 

nAno-PALLAdiuM on AMino-funCtionALized 

MeSoCeLLuLAr foAM: An effiCient CAtALySt 

for trAnSfer hydroGenAtionS And SuzuKi 

reACtionS 

o. verho 1 , A. nAGendirAn 1 , e. JohnSton 1 , 

C. w. tAi 2 , J. e. BäCKvALL 1 


2 Stockholm University, Materials and Environmental 

Chemistry, Stockholm, Sweden 

Nanoparticles have recently attracted an increasing interest 

because of their unique properties and numerous applications in 

a variety of fields, including electronics, energy technology, 

optics, magnetism, and chemistry. In chemistry, heterogenous 

catalysts based on transition-metal nanoparticles have shown to 

be efficient and selective for a wide range of organic 

transformations under mild conditions. Furthermore, 

heterogeneous catalysts allow for simpler separation and recycling 

of catalyst compared to homogeneous counterparts. This solves 

many practical problems associated with industrial-scale 

production of chemicals and pharmaceuticals, where metal 

impurities in the final products can possess an issue of major 

concern. 

Among the many types of heterogeneous catalysts 

developed so far, those based on palladium have in general 

exhibited highest activity and selectivity. In our group, we have 

recently developed a heterogeneous catalyst based on Pd 

nanoparticles immobilized on siliceous mesocellular foam (MCF). 

Here we report on the applications of the Pd nanocatalyst in 

Suzuki cross-coupling reactions and transfer hydrogenations of 

alkenes are described. The catalyst showed to be highly efficient 

for both transformations, resulting in (i) facile coupling of a wide 

range of aryl halides with various boronic acids in high yields and 

(ii) chemoselective reduction of variety alkenes employing 

1-methyl-1,4-cyclohexadiene as hydrogen donor. Moreover, the 

catalyst can be recycled several times without any significant 

decrease in activity or leaching of metal into solution. 

Keywords: Heterogeneous Catalysis; Cross-coupling; 

Hydrogenation; Green Chemistry; Nanoparticles; 



s1098 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 7 3 

reCent deveLoPMentS in hoMoGeneouS 

GoLd(i) CAtALySiS 

M. h. viLheLMSen 1 , A. S. K. hAShMi 1 

1 University of Heidelberg, Institute of Organic Chemistry, 


For more than two decades gold(I) has been used to activate 

carbon-carbon multi-bonds towards nucleophilic attack and thus 

has induced the formation of carbon-hetero atom bond. [1] The role 

normally ascribed to gold(I) in such reactions is that of an 

activator of carbon-carbon multi-bonds by pi-coordination. 

However, recently a new type of homogeneous gold catalysis has 

been added to the repertoire – namely that of gold participating 

in two distinct roles through dual sigma/pi activation. [2, 3] This 

presentation will focus on some of the newest developments 

within the field of homogeneous gold-catalyzed reactions forming 

carbon-carbon bonds or carbon-heteroatom bonds. 

references: 

1. a) M. Rudolph et al., Chem Commun., 2011, 47, 

6536–6544; 

b) M. Rudolph et al., Chem. Soc. Rev., 2012, 41, 

2448–2462. 

2. L. Ye, et.al, J. Am. Chem. Soc., 2012, 134, 31–34. 

3. a) A.S.K. Hashmi, et.al, Organometallics, 2012, 31, 

644–661; 

b) A.S.K. Hashmi, et.al., Adv. Synth. Catal., 2012, 354, 

555–562; 

c) A.S.K. Hashmi, et.al, Angew. Chem. Int. Ed., 2012, 

early view (DOI: 10.1002/anie.201109183). 

Keywords: Gold; Catalysis; Alkynes; Polycycles; 

Heterocycles; 


P - 0 4 7 4 

A GoLd-CAtALyzed entry to heteroCyCLiC 

SPiro CoMPoundS 

B. wAGner 1 , v. BeLtinG 1 , n. KrAuSe 1 


Many natural products contain spiroacetals as 

characteristicstructure element. Synthesis methods for the most 

common [O,O]-spiroacetals arewell known, e.g. under Lewis- or 

Bronsted-acid catalysis. [1, 2] Otherheterocyclic spiro compounds 

have been relegated to a niche existence. 

As a carbophilic Lewis-acid, gold has the ability toactivate 

alkenes and alkynes for nucleophilic attack to form C-C-, C-O-, 

C-N-or C-S-bonds. [3] The obvious advantages of gold catalysis 

are mildreaction conditions at oftentimes room temperature, 

tolerance against differentfunctional groups and its low toxicity, 

which is useful for the application inthe synthesis of drugs. 

Previously, we have shown that tetrahydrofuranylethers are 

accessible by gold-catalyzed tandemcycloisomerization- 

-hydroalkoxylation of homopropargylic alcohols. [4] We now 

disclose a new access to [N,O]-spiroacetals by cyclization 

ofaminoalkynols in the presence of a gold catalyst. [5] This 

methodtolerates various substituents and protecting groups and 

can be used to accessspiroacetals with five- or six-membered 

rings. By changing the nucleophilicpositions (eg. thiols or esters), 

this method provides a new access to a widerange of interesting 

heterocyclic spiro compounds. 

references: 

1. H. Stetter, M. M.Rauhut Chem. Ber. 1958, 91, 2543–2547. 

2. B. Liu, J. K. DeBrabander Org. Lett. 2006, 8, 4907–4910. 

3. Review: A. S. K. Hashmi Chem. Rev. 2007, 107, 

3180–3211; A. S. K. Hashmi, G. J. Hutchings 


4. V. Belting, N. Krause Org. Lett. 2006, 8, 4489–4492. 

5. B. Wagner, V. Belting, N. Krause manuscript in preparation. 

Keywords: Spiro compounds; Gold; Cyclization; Heterocycles; 




s1099 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 7 5 

iSotherMAL CALoriMetriC titrAtionS on 

ChArGe-ASSiSted hALoGen BondS: roLe of 

entroPy, CounterionS, SoLvent And 

teMPerAture 

S. wALter 1 , f. KnieP 1 , f. SChMidtChen 1 , 

e. herdtweCK 2 , S. huBer 1 

1 Technische Universität München, Organic Chemistry 1, 


2 Technische Universität München, Inorganic Chemistry, 


Halogen bonds (XBs) are non-covalent interactions between 

terminal halogen bonds in compounds R-X (X =Cl, Br, I) and a 

Lewis base (LB), analogous to hydrogen bonds (HBs). [1] Due to 

their high directionality, the main application of XBs so far has 

been in crystal engineering, and as a consequence, most 

determinations of the interaction strength of halogen bonds have 

been carried out in the solid state. [2] 

Though well-established in solution (and in the gas phase), 

systematic studies of XB-strengths in liquids have been rare. 

Using isothermal titration calorimetry (ITC), we have carried out 

extensive investigations on the interaction between cationic 

bidentate halogen bond donors (R-X) and halides (LBs) in 

different solvents and at different temperatures in order to gain 

insight into the role of various factors on halogen bond strength 

in solution. [3] Several derivatives of bis(haloimidazolium) 

compounds were used as XB-donors. The data collected in these 

experiments is intended to aid the rational design of halogen bond 

donors as well as the development of XB-based applications in 

solution. In all cases examined, the entropic contribution to the 

overall free energy was found to be of major significance. 

The binding affinities became slightly stronger with higher 

temperatures, while showing little dependency on the 

weakly-coordinating counter-anions of the halogen-bond donors. 

We also noted a marked influence of different solvents on the 

interaction strength. 

references: 

1. P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, G. Terraneo, 


2. See, for example: M. Formigué, Curr. Opin. Solid State 

Mater. Sci. 2009, 13, 36-45. 

3. S. M. Walter, F. Kniep, L. Rout, F. P. Schmidtchen, 

E. Herdtweck, S. M. Huber, J. Am. Chem. Soc. 2012, 

in print. 

Keywords: halogens; non-covalent interactions; 

thermodynamics; 


P - 0 4 7 6 

ALiPhAtiC PoLyKetoneS oBtAined froM 

diMethyLKetene And ethyLKetene 

h. wAnG 1 , n. deSiLLeS 1 , f. BureL 1 

1 Institut National des Sciences Appliquées de Rouen, Seine- 

Maritime, Saint Etienne du Rouvray, France 

Email: Hanbin.wang@insa-rouen.fr 

Ketenes are derivatives of carboxylic acids which contains 

two consecutive double bonds (C=C=O). [1, 2] By ionic 

polymerization, and assuming a suitable choice of initiator and 

solvent, ketenes can lead to polyketone, polyester or polyacetal. 

Previous works in our laboratory showed that a film made of the 

dimethylketene-based polyketone present excellent gas barrier 

properties (ex: oxygen, water vapor and carbon dioxide) even in 

the presence of humidity, enabling this material to compete with 

the compounds currently used in the food packaging industry. 

The purpose of my thesis is to elaborate new ketene-based 

aliphatic polyketones, using the several years experience gained 

in this field by the laboratory. Indeed, a major drawback of 

aliphatic polyketones is their poor processability. The introduction 

of defects in the macromolecular chains should decrease the 

crystallinity of the polymer and thus make easier its moulding. 

Firstly, the copolymerization involving dimethylketene and 

ethylketene in different proportions was carried out in toluene 

at –78°C, by using AlBr as Lewis acid initiator, aiming at 

3 

obtaining a statistical copolymer. Secondly, the polymerization of 

dimethylketene was tested using carbocation initiators, generated 

in situ by reacting chlorinated or brominated reactants or polymers 

with a Lewis acid in a Friedel-Craft process, to target block or 

star-shaped polyketones. 

The composition of all the obtained polymers was 

determined by 1H, 13C NMR and FTIR, and the thermal properties 

were more particularly analyzed (RX, TGA, DSC). 

references: 

1. Egret H., Couvercelle J.P., Belleney J., Bunel C., 

Eur.Polym.J., 2002, 38 (10). 

2. Hayki N., Desilles N., Burel F., Polym.Chem., 2011, 2, 

2350-2355. 

Keywords: Carbocations; Polymerization; Polymers; 



s1100 

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P - 0 4 7 7 

CAtALytiC CyCLizAtion And AnnuLAtion 

reACtionS of AMinoCyCLoProPAneS 

J. wASer 1 , f. de SiMone 1 , f. de nAnteuiL 1 , 

f. BenfAtti 1 

1 Ecole Polytechnique Fédérale de Lausanne, ISIC, Lausanne, 

Switzerland 

Carbo- and hetero-cycles are omnipresent in bioactive 

natural and synthetic compounds. Consequently, the development 

of new cyclization or annulation methods for their synthesis is an 

important field of research in organic chemistry. In this context, 

donor acceptor-substituted cyclopropanes have been extensively 

used as precursors of reactive intermediates in cyclization and 

annulation reactions. [1–2] 

Nevertheless, the use of aminocyclopropanes is still 

underdeveloped, despite the importance of nitrogen-based 

functional groups in bioactive molecules. In 2010, we have 

reported the first highly regioselective cyclizations of 

aminocyclopropanes onto indole heterocycles for the synthesis of 

natural alkaloids. [3] 

Herein, we report the first Lewis acid-catalyzed [3+2] 

annulation reactions of aminocyclopropanes. [4–6] The reaction 

worked for olefins, aldehydes and ketones as partners. Key for 

success was the modulation of the push-pull properties of the 

substituents on the aminocyclopropane, with the optimum being 

met for phthalimide as donor and a diester as acceptor. In the case 

of olefins, the reaction is both stereospecific in relation to the 

configuration of the double bond and enantiospecific, giving 

access to enantiopure cyclopentylamines in high yields. [4] On the 

other hand, the reaction with aldehydes and ketones gives access 

to aminotetrahydrofurans, which constitute the core of DNA and 

RNA. [5–6] Current efforts in our laboratory focus on the 

transformation of the obtained products into bioactive 

compounds, as well as in the development of catalytic asymmetric 

methods. 

references: 

1. H. U. Reissig, R. Zimmer, Chem. Rev. 2003, 103, 1151. 

2. F. De Simone, J. Waser, Synthesis 2009, 3353. 

3. F. De Simone, J. Gertsch, J. Waser, Angew. Chem., Int. Ed. 

2010, 49, 5767. 

4. F. de Nanteuil, J. Waser, Angew. Chem., Int. Ed. 2011,50, 

12075. 

5. F. Benfatti, F. de Nanteuil, J. Waser, Org. Lett. 2012, 14, 

386. 

6. F. Benfatti, F. de Nanteuil, J. Waser, Chem. Eur. J. 2012, 

18, 4844. 

Keywords: Annulation; Cyclization; Synthetic methods; 

Asymmetric synthesis; Alkaloids; 


P - 0 4 7 8 

hydroGenAtion of ALKeneS And ALKyneS 

with CAtALytiC iron(0) PArtiCLeS 

A. weLther 1 

1 Institute of Organic Chemistry, Chemistry, Regensburg, 

Germany 

Transition metal-catalyzed hydrogenations of alkenes and 

alkynes are among the most important synthetic transformations 

with numerous lab-scale and technical applications to the 

synthesis of fine chemicals, pharmaceuticals, natural products, the 

processing of vegetable oils and fatty acids, and in petrochemical 

conversions. 

Over the past decades, iron catalysts have evolved as an 

attractive alternative to precious and toxic catalyst systems. 

Recently, several groups reported on nanoparticulate iron catalysts 

in reductions of carbonyl compounds, olefins, and alkynes. [1] As 

part of our program directed at the utilization of cheap iron 

catalysts for the synthesis and manipulation of fine chemicals, [2] 

we also became interested in the development of a practical and 

sustainable alternative to established Raney-Nickel-type catalysts. 

We wish to report on a hydrogenation protocol that 

combines the economical and environmental benefits of iron as 

cheap and non-toxic catalyst metal with the operational simplicity 

of a heterogeneous process. 

references: 

1. a) C. Rangheard, C. de Julián Fernandez, P.-H. Phua, 

J. Hoorn, L. Lefort, J. G. de Vries, Dalton Trans. 2010, 

8464; 

b) M. Stein, J. Wieland, P. Streurer, F. Tölle, R. Mülhaupt, 

B. Breit, Adv. Synth. Catal. 2011, 353, 523; 

c) R. Hudson, A. Riviere, C. M. Cirtiu, K. L. Luska, 

A. Moores, Chem. Commun. 2012, 48, 3360; 

d) J. F. Sonnenberg, N. Coombs, P. A. Dube, R. Morris, 

J. Am. Chem. Soc. 2012, 134, 5893. 

2. a) W. M. Czaplik, M. Mayer, A. Jacobi von Wangelin, 

Angew. Chem. 2009, 121, 616; Angew. Chem. Int. Ed. 

2009, 48, 607; 

b) W. M. Czaplik, M. Mayer, A. Jacobi von Wangelin, 

ChemCatChem 2011, 3, 135-138; 

c) M. Mayer, W. M. Czaplik, A. Jacobi von Wangelin, Adv. 

Synth. Catal. 2010, 352, 2147. 

Keywords: Hydrogenation; Catalysis; Iron; 



s1101 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 7 9 

the SyntheSiS of SuBStituted triAzineS AS 

PotentiAL SynthetiC Auxin herBiCideS 

w. whittinGhAM 1 , J. BLAnC 1 , C. winn 1 

1 Syngenta, Research Chemistry, Bracknell, United Kingdom 

Herbicides that act by mimicking the plant hormone auxin 

(indole acetic acid) have been known and used for 70 years. 

However, only in the last decade has the molecular mechanism of 

action of these compounds begun to be understood. In parallel 

with this increased knowledge a number of new herbicides of this 

class have been launched or entered development. These 

compounds have structures based on a pyridine and pyrimidine 

core, but there are no reports of synthetic auxins based on 

triazines. 

We will describe our work to explore the potential of 

compounds with a 1,3,5-triazine core to act as synthetic auxins. 

Aspects of the design of the compounds will be discussed, as will 

a number of synthetic approaches to the desired targets and the 

biological results obtained. 

Keywords: triazine; herbicide; auxin; 


P - 0 4 8 0 

PoLyAMine ConJuGAteS of SeLeCted SteroLS: 

froM deSiGn to AntiMiCroBiAL And 

CytotoxiCity teStS 

z. wiMMer 1 , n. vidA 2 , L. rArovA 3 , P. drASAr 2 , 

S. forCzeK 1 

1 Institute of Experimental Botany CAS, Isotope Laboratory, 




3 Centre of the Region Hana of the Palacky University, Growth 

Regulators, Olomouc, Czech Republic 

Several new polyamine conjugates with stigmasterol and 

sitosterol were synthesized and subjected to basic antimicrobial 

and cytotoxicity tests. Selected sterols were transformed into their 

hemiesters with short-chained dicarboxylic acid anhydrides. The 

free carboxylic functionality of the sterol hemiesters was activated 

and then allowed to react with N-protected polyamines to form 

their amide conjugates. Finally, the N-protecting groups were 

removed affording the target products, for which their 

physico-chemical characteristics were calculated and compared 

with the Lipinski [1] and Ghose [2] rules. The conjugates derived 

from spermine displayed considerable antimicrobial activity on 

Staphylococcus aureus, a gram-positive bacterium at low 

concentration (50 mg.mL-1 ), while these compounds were inactive 

towards several gram-negative bacteria. The cytotoxic activity 

was tested on cells of human T-lymphoblastic leukemia, breast 

adenocarcinoma, cervical cancer, and also on normal human 

fibroblasts, and the results will be presented in the IC-50 values 

indicating the lethal effect of the tested compound to 50 % of the 

tumor cells. 

Acknowledgment: Thanks are due to the grants P503/11/0616 

(GACR), MSM6046137305 (MSMT) and OC10001 (MSMT), a 

part of the COST Action CM0804. 

references: 

1. C. A. Lipinski, F. Lombardo, B. W. Dominy, P. J. Feeney, 

Adv. Drug Deliv. Rev. 46 (2001) 3-26. 

2. A. K. Ghose, V. N. Viswanadhan, J. J. Wendoloski, 

J. Combin. Chem. 1 (1999) 55-68. 

Keywords: conjugation; steroids; amides; antifungal agents; 

antitumor agents; 



s1102 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 8 1 

A GLyCoPoLyMeriC Pt(ii) CArrier: SyntheSiS 

And it’S induCtion of APoPtoSiS in reSiStAnt 

CAnCer CeLLS 

A. winter 1 , A. wiLd 1 , K. BABiuCh 1 , M. KoeniG 2 , 

M. d. hAGer 1 , M. GottSChALdt 1 , A. ProKoP 2 , 

u. S. SChuBert 1 



2 Children’s Hospital of Cologne, Department of Pediatric 

Oncology, Cologne, Germany 

The development of anti-cancer drugs overcoming 

resistance towards common cytostatics is one challenge in cancer 

research, in particular for Pt-based drugs. [1] Compounds that 

actively accumulate inside afflicted tissues and organs can be 

obtained by introduction of targeting moieties that specifically 

interact with cells or the usage of polymer vehicles, taking 

advantage of the enhanced permeability and retention effect in 

tumor vasculature. [2] Platinum-polymer complexes, dendrimers, 

micelles and micro-particulates are discussed in the current 

literature. [3] The therapeutic efficacy of the drug is increased, 

mechanisms of resistance are circumvented and the overall toxic 

side-effects reduced. 

We present the synthesis of the first PtII-carrying glycopolymer with promising anti-cancer activities against 

resistant leukemia cells. 

The materials synergizes the properties of glycopolymers 

and square-planar PtII complexes: Glycopolymers have found, for 

instance, applications in clinical diagnostics, targeted drug 

delivery, for affinity separations and bioassays. [4] Sugar moieties 

on polymeric backbones may act as cell-type specific ligands for 

a broad spectrum of protein receptors, providing macromolecules 

with targeting properties. [5] Terpyridine ligands are effective 

complexing units for transition metal ions leading to therapeutic 

agents or diagnostic tracers. [6] Since square-planar PtII-terpyridine complexes show high cytotoxicities due to DNA-intercalation, [7] 

they were choosen to prepare the glycopolymer with potential 

antitumor activity. 

references: 

1. L. Kelland, Nat. Rev. Cancer 2007, 7, 573–584. 

2. S. Kaida, H. Cabral, M. Kumagai, A. Kishimura, 

Y. Terada, M. Sekino, I. Aoki, N. Nishiyama, T. Tani, 

K. Kataoka, Cancer Res. 2010, 70, 7031–7041. 

3. K. J. Haxton, H. M. Burt, J. Pharm. Sci. 2009, 98, 

2299–2316. 

4. S. G. Spain, N. R. Cameron, Polym. Chem. 2011, 2, 60–68. 

5. S. R. S. Ting, G. Chen, M. H. Stenzel, Polym. Chem. 

2010, 1, 1392–1412. 

6. M. Gottschaldt, U. S. Schubert, Chem. Eur. J. 2009, 15, 

1548–1557. 

7. I. Eryazici, C. N. Moorefield, G. R. Newkome, Chem. 

Rev. 2008, 108, 1834–1895. 

Keywords: Polymerization; Platinum; Cancer; 

Supramolecular Chemistry; Glycoconjugates; 


P - 0 4 8 2 

induCed ChArGe effeCt of Co(ii) ionS on the 

ConforMAtion of A LiGAnd-funCtionLized 

CoPoLyMer 

A. winter 1 , B. hAPP 1 , G. M. PAvLov 1 , 

i. PerevyAzKo 1 , M. d. hAGer 1 , u. S. SChuBert 1 



Poly(alkyl methacrylate) copolymers embedding bidentate 

2-(1H-1,2,3-triazol-4-yl)pyridine (trzpy) chelating units as 

comonomer in the side chains were synthesized by controlled 

radical addition-fragmentation transfer (RAFT) polymerization. 

The RAFT polymerization technique led to well-defined 

copolymers as confirmed by 1H NMR spectroscopy, size 

exclusion chromatography coupled with a photodiode array 

detector (SEC-PDA) and UV/vis titration experiments. The free 

trzpy units were complexed by FeII and CoII ions, and the 

coordination behavior in solution was studied extensively by 

utilizing UV-vis and viscosity titration experiments as well as 

detailed analytical ultracentrifugation (AUC) investigations. Both 

metal salts showed a cross-linking ability in concentrated solution 

(c > 10 mg?mL-1 ), whereby in the case of CoII a highly viscous 

fluid was observed. Complexation of the polymer chains was 

observed, which resulted in characteristic UV-vis absorption 

bands and an increase in the solution viscosity. Addition of a solid 

coordinating ligand, such as N-(2-hydroxyethyl)-ethylenediamine 

triacetate (HEEDTA), resulted in a quantitative decomplexation. 

In a concentrated polymer acetone solution an exponential 

increase of the dynamic viscosity was observed after adding CoII ions upon intermolecular cross-linking of the macromolecule 

chains. Furthermore, the intramolecular complexation with CoII ions was studied in highly diluted acetone solution of the 

trzpy-containing copolymer by means of different analytical 

ultracentrifugation experiments. By the addition of a small amount 

of CoII ions a significant decrease of the intrinsic sedimentation 

coefficient was observed, which could be explained by the 

elongation of the individual polymer coils upon the electrostatic 

repulsion of the coordinated CoII ions. 

Keywords: Copolymerization; Supramolecular Chemistry; 

Analytical methods; Conformation analysis; 



s1103 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 8 3 

forMAtion of 1,3-dioxoLAneS froM ePoxideS 

And KetoneS/ALdehydeS uSinG zn(otf) AS A 2 

CAtALySt 

L. xie 1 , w. wAnG 1 , y. KAnG 2 , S. zhAo 1 , y. tiAn 1 , 

h. fenG 2 

1 Beijing Research Institute of Chemical Industry SINOPEC, 

Fine Chemicals Department, Beijing 100013, China 


Department of Catalysis, Beijing 100013, China 

Email: xielj.bjhy@sinopec.com 

1,3-dioxolanes are important chemical raw materials, which 

can be used to synthesize steroids and carbohydrates, serve as the 

intermediates to protect carbonyl groups or diols. Besides, some 

1,3-dioxolanes are used as solvent in chemical reactions. In the 

recent year, some 1,3-dioxolanes are found to have special flavor 

and are used in food and tobacco industry. Some catalysts like 

[1] [2] anhydrous Cu(SO ) , montmorillonite, Lewis acids and etc are 

4 2 

used to synthesize 1,3-dioxolanes from epoxides and 

ketone/saldehydes. Among these catalysts, anhydrous Cu(SO ) 4 2 

was found to have low yield and long reacting time, 

montmorillonite shows bad result while applying larger epoxide 

molecular, some Lewis acids show poor selectivity and yield 

isomerized products [3] .Anhydrous zinc and magnesium halides 

afforded the rearranged products [4] . By applying Zn(OTf) we 2 

obtained relatively good result. 

Epoxides, ketones/aldehydes and Zn(OTf) were added in a 

2 

sealed reaction kettle under magnetic stiring, at certain reacting 

temperature and time. Reactants were cooled and analyzed by 

GC-MS. Conversion and yields are calculated based on GC-MS 

results. After separation and purification of the product, 

1,3-dioxolane, was obtained and analyzed through MS, 1H NMR 

and IR to assure the structure. 

Zn(OTf) showed good catalytic performance in the reaction 

2 

of 1,3-dioxolanes fromation with yields of 76–98% from various 

epoxides and ketones/aldehydes. So we can see Zn(OTf) is an 2 

effective catalyst for this reaction. Compared with Cu(SO ) , 4 2 

Cu(OTf) , ZnX , and montmorillonite, better results were 

2 2 

achieved by Zn(OTf) nearly without rearrangement of epoxides 

2 

to aldehydes or ketones as side products. 

references: 

1. Hanzlik, R.P., Leinwetter, M. J. Org. Chem., 43, 438 

(1978). 

2. Daniel, S.T., John, J.F., William, J.S. J. Org.Chem., 58, 

7274-7276 (1993). 

3. Lee, S-H., Lee, J-C., Li, M-X., Kim, N-S. Bull. Korean 

Chem. Soc., 26, 221-222 (2005) 

4. I. Mohammadpoor-Baltork, A. R. Khosrppour, H. Aliyan. 

Synthetic Communications, 31(22. 31(22), 3411-3416 

(2001). 

Keywords: ketones; Synthetic methods; Aldehydes; 

Cyclization; Lewis acids; 


P - 0 4 8 4 

PrePArAtion of A 2, 3-diALKyL-2- 

-CyAnoSuCCinAte CoMPound And itS 

APPLiCAtion for ProPyLene PoLyMerizAtion 

L. xie 1 , y. tiAn 1 , y. LinG 2 , z. fenG 1 , S. zhAo 1 , 

z. Sun 1 


Fine Chemicals Department, Beijing 100013, China 


Propylene Polymerization Department, Beijing 100013, China 

Email: xielj.bjhy@sinopec.com 

A 2,3-dialkysuccinate compound, especially 

2,3-diisopropylsuccinate compound, is known as an internal donor 

in a solid catalyst component for olefin polymerization [1] . But the 

2,3-dialkysuccinate compound is difficult to be synthesized in 

industrial scale [1] and diethyl 2,3-diisopropylsuccinate compound 

was prepared at reaction temperature of -78 oC with only 

20% yield. [2] Therefore we design a process for preparing 

2,3-di(non-linear–alky)-2-cyanosuccinate compounds, especially 

2,3-diisopropyl-2-cynanosuccinate compound, and processes for 

preparing 2,3-diisopropylsuccinic acid and esters thereof by using 

the 2,3-diisopropyl-2-cyanosuccinate compound as an 

intermediate. [3] 

A facile synthesis of diethyl 2,3-diisopropyl-2- 

-cyanosuccinate was obtained with 75% yield by treatment of 

ethyl 2-cyano-3-methylbutyrate with potassium ethoxide followed 

by condensation the potassium salt of ethyl 2-cyano-3- 

- methylbutyrate with 2-bromo-3-methylbutyrate at temperature 

from room temperature to reflux in an aprotic solvent. The 

structure of obtained diethyl 2,3-diisopropyl-2-cyanosuccinate is 

confirmed by instrument analyses of IR, 1H NMR, MS(EI) and 

high resolution mass spectrometry of electro spray ionization 

(ESI). 

The diethyl 2,3-diisopropyl-2-cyanosuccinate is used for the 

first time as an internal electron donor of a solid catalyst 

component for propylene polymerization. When a catalyst 

comprising the catalyst component is used in propylene 

polymerization, the catalyst exhibits good catalytic activity, and 

the resulting polymer has a good isotacticity and a broad 

molecular weight distribution. [4] 

In conclusion diethyl 2,3-diisopropyl-2-cyanosuccinate is as 

good internal electron donor as diethyl 2,3-diisopropylsuccinate 

for propylene polymerization and is much better in manufacture 

than diethyl 2,3-diisopropylsuccinate. 

references: 

1. Giampiero Morini, Giulio Balbontin, Yuri V. Gulevich, 

Remco T. Kelder, Henricus P. B. Duughuisen, 

Peter A. A. Klusener, Franciscus Korndorffer, 

WO0063261,2000-10-26. 

2. Michael W. Rathke, Andreas Lindert, J. Am. Chem. Soc., 

1971, 93, 4605-4606. 

3. Lunjia Xie, Yu Tian, Zaixing Feng, Siyuan Zhao et al., 

WO2010094211, 2010-08-26. 

4. Lunjia Xie, Yongtai Ling, Yu Tian, Zaixing Feng, 

Siyuan Zhao et al., EP 2287208, 2010-08-13 

Keywords: Heterogeneous catalysis; Synthesis design; 

Polymerization; Synthetic methods; Industrial Chemistry; 



s1104 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 8 5 

PoLy(ethyLene)-GrAft-PoLy(tert-ButyL 

ACryLAte) viA AtoM trAnSfer rAdiCAL 

PoLyMerizAtion: funCtionAL PoLyoLefinS 

froM PoLyBroMinAted ALKAneS 

G. xu 1 , d. wAnG 1 , M. BuChMeiSer 1 


Germany 

Over the last decade, polyolefin-based materials have 

experienced outstanding growth - not only because of the ease of 

their manufacture, but also because polyolefin-based 

thermoplastics can be recycled or combusted with good 

preservation of energy. Furthermore, since they are solely 

composed of carbon and hydrogen, the only combustion products 

are merely carbon dioxide and water1 . Unfortunately, polyolefins 

are highly non-polar, which strongly limits their compatibility 

with other polymers as well as dying and coating applications. 

Over the last decades, with the development of controlled radical 

polymerizations techniques, atom transfer radical polymerization 

(ATRP) has been introduced. ATRP offers access to the synthesis 

of macromolecules with controlled molecular weights and narrow 

molecular weight distributions. ATRP is also characterized by a 

great tolerance for the copolymerization of various functional 

monomers. Meanwhile, brush- as well as graft-copolymers have 

been prepared via ‘grafting to’ and ‘grafting from methods, the 

‘grafting from’ method certainly being the best approach in terms 

of brush density. 

What all ATRP-based methods have in common is the use 

of activated alkyl halides, e.g., of a-bromocarboxylic esters. Such 

activated halogen-alkyl bonds are weaker than standard alkyl 

halide bonds and thus more susceptible to homolytic cleavage by 

the Cu (I) complex. Vice versa, to the best of our knowledge, there 

are no reports on the ATRP involving non-activated alkyl halides. 

Starting from poly-halogenated polyethylene, such an approach 

would offer a highly useful access to functionalized polyolefins. 

Starting from Poly-brominated linear PE, we successfully 

developed an ATRP-based synthesis of a series of novel 

well-defined functional poly(ethylene) graft copolymers with 

different graft densities and graft lengths thereby developing a 

straight-forward access to functional polyolefins2 . 

references: 

1. Walter Kaminsky, J. Chem. Soc., Dalton Trans., 1998, 

1413. 

2. G. Xu, D. Wang, M. R. Buchmeiser, Macromol. Rapid 

Commun. 2012, 33, 75-79. 

Keywords: Poly(ethylene); Atom transfer radical 

polymerization; comb-copolymer; 


P - 0 4 8 6 

Study of AntifunGAL And 

AntiBiotiC druGS LoAded MiCroSPhereS 

BASed on PoLy(dL-LACtide) And 

PoLy(dL-LACtide-Co-CAProLACtone) 

P. yAMMine 1 , r. KASSAB 1 , d. MouSSA 1 

1 University of Balamand, Chemistry, Tripoli, Lebanon 

In an effort to develop a new way of Drug Delivery Systems, 

two biodegradable polymers, poly(DL-lactide) (PLA) and 

poly(DL-lactide-co-caprolactone) (PLC) were used for the 

formulation of microspheres loaded with antifungal drugs 

(Nystatin and Amphotericin B) and antibiotics (Tetracycline and 

Doxycycline) respectively. 

Microspheres were prepared using the solvent evaporation 

technique by changing the masses of drugs introduced. They were 

then evaluated for percentage yield, drug entrapment, particle size, 

morphology, drug-polymer interaction, stability and in vitro 

drugrelease. 

The particle size analyzer showed a homogeneous size 

distribution for the microspheres, ranging between 80 to 110 μm. 

The maximum drug entrapment reached 20% and 81% for 

PLC microspheres loaded with Nystatin and Amphotericin B 

respectively. As for Tetracycline and Doxycycline, the drug 

entrapment was 30% and 18% respectively. Scanning Electron 

Microscopy (SEM) and Optical Microscopy revealed that the 

microspheres have a spherical shape with a porous surface. 

Fourier Transform-Infrared (FT-IR) study confirmed the absence 

of chemical interaction between the drug and the polymer. 

Stability study indicated no appreciable difference concerning the 

degradation of the microspheres after 3 months of storage at 

different temperatures. The in vitrorelease study was carried out 

for the formulations with the highest percentage of encapsulation. 

For Nystatin and Amphotericin B, the drug release needed few 

days in comparison with Tetracycline and Doxycycline, which 

required only several hours to go to completion. 



s1105 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 8 7 

the SyntheSiS And ChArACterizAtion of 

PoLyALPhAoLefin By uSinG ALuMinuM BASed 

LewiS ACid CAtALySt 

J. J. ChA 1 , J. h. yiM 1 

1 Kongju National University, Division of Advanced Materials 

Engineering, Cheonan, Republic of Korea 

Polyalphaolefin (PAO) is the synthesis lubricant that 

superior to petroleum-based and mineral-based lubricant in the 

terms of physical, chemical characteristics such as low pour point, 

high viscosity index (VI), thermal stability. We have synthesized 

a several kinds of PAOs using 1-pentene, 1-hexene, 1-octene, 

1-dodecene as monomer and different types of aluminum based 

lewis acids as cationic polymerization catalyst. The control of 

polymerization performance (yield, activity) and physical 

properties of PAO (molecular weight, kinetic viscosity, pour point, 

viscosity index) could be achieved by changing polymerization 

parameters such as polymerization time and temperature, the type 

and concentration of monomer and catalysts. In view 

of polymerization yield and molecular weight of PAO, 

Et Al Cl /t-butylchloride catalyst system was superior to another 

3 2 3 

used aluminum based catalysts. Microstructure of PAO was 

investigated by means of TOF-MS (Time of Flight-Mass 

Spectroscopy) studies. The important parameters for lubricant 

such as VI and pour point were strongly depended on 

microstructure of PAO i.e. branch length. In other words, 

the VI value of PAO increased with increasing the branch 

length of PAO. 

Keywords: Polyalphaolefin; Aluminum; Catalyst; 

Polymerization; Lubricant; 


P - 0 4 8 8 

the Study of infLuenCe of MiCro AdditiveS 

of SinGLe-wALL CArBon nAnotuBeS on 

StreSS-StrAin ProPertieS And StruCture of 

noveL PoLyurethAne BLoCK CoPoLyMerS 

M. zAverKinA 1 , v. KoMrAtovA 1 , A. GriShChuK 1 , 

v. LeSniChAyA 1 , y. eStrin 1 , e. BAdAMShinA 1 

1 Institute of Problem of Chemical Physics RAS, plastic binder 

laboratory, Chernogolovka, Russia 

Carbon nanotubes are capable to change properties of 

polymers, such as mechanical strength, the Young modulus, the 

tensile strain, optical properties etc. However, the insufficient 

attention is given to studying of influence of micro additives of 

single-wall carbon nanotubes (SWCNT) on the polymers 

structure. 

Polyurethane block copolymers (PUBCP) were synthesized 

for the first time in the present work by interaction of 

oligodiethylenglycol adipate (ODGA, crystallization temperature 

T = 60 °T), of the mixture of symmetric with asymmetric 

c 

diisocyanates and of agents of chains extension in solution at 

room temperature. The influence of micro additives of SWCNT 

on stress-strain properties and structure of PUBCP was studied. 

PUBCP possess quite high Young modulus (about 450 MPa) 

up to T . It undergo orientation deformations up to 900 % with 

c 

forming of the strong rigid films (rupture strength ~ 45 MPa) at 

stretching after achievement of the limit of forced rubberlike 

elasticity. The oriented samples completely restore their initial 

sizes at the heating above T . c 

Introduction of SWCNT in PUBCP (0.002 – 0.008 wt. %) 

leads to various changes of stress-strain properties and structural 

parameters. Changes of supramolecular structure of polymer 

under the influence of SUNT consist in increase in the Young 

modulus and tensile strain for 20-30 %. At the same time, tensile 

strength of the filled and unfilled samples does not change 

practically. The SWCNT additives influence noticeably on 

relaxation behavior of polymer. Thus, recovery of the initial sizes 

of the samples, containing up to 0.008 wt. % of SWCNT, after 

deformation requires more high temperatures and prolonged time 

in comparison with unfilled samples. 

Data of DSC and analysis of X-ray diffraction patterns of 

PUBCP, containing SCNT, testify considerable structural changes 

in comparison with unfilled polymer. The reasons of influence of 

SCNT on structure and, therefore, properties of synthesized 

PUBCP are discussed. 

Keywords: single-wall carbon nanotubes; stress-strain 

properties and structural parameters; Polyurethane block 

copolymers; 



s1106 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 8 9 

SyntheSiS of nonAPePtide (B22-B30) of inSuLin 

B-ChAin uSinG Modified SoLid PhASe MethodS 

with And without MiCrowAve teChnique 

M. zewAiL 1 , A. nAGLAh 1 , S. ABdeL rAhMAn 2 

1 National Research Center, Peptide Chemistry, Cairo, Egypt 

2 Faculty of Science Zagazig University, Chemistry, Zagazig, 

Egypt 

The biological activity of Insulin is known to be closely 

related to the C-terminal nonapeptide (B -B ) fragment of its 

22 30 

B-chain. This does not necessarily mean, however, that each of 

the amino acid residues of the nonapeptide fragment is essential 

for its activity. 

Keywords: Insulin; Peptide; Amino Acids; Modified Solid 

Phase and Microwave.; 


P - 0 4 9 0 

eLeCtroCheMiCAL ChArACterizAtion of 

Pvdf BASed PoLyMer eLeCtroLyteS for 

SeCondAry BAtterieS 

e. zeytuni 1 , M. h. uGur 1 , e. CAKMAKCi 1 , 

A. GunGor 1 

1 Institute of Science, Chemistry, Istanbul, Turkey 

PVDF-based polymer electrolytes have many different uses 

according to the intended use. For example; also being used as 

electrolyte in rechargeable batteries [1] , they can also be used in 

fuel batteries (electrolyte), [2] besides, they can be used as a binder 

for the preparation of cathode material in rechargeable batteries, [4] 

as an electrolyte for supercapacitor applications [5] and as polymer 

electrolytes in solar batteries. [6] 

The chemical and the thermal stability that the PVDF-based 

gel polymers show, make such type of materials attractive for 

battery and fuel cell applications. Being among the cheapest 

fluoropolymers and having a wide melting point range 

(115 °C–175 °C), PVDF is a processable polymer which also has 

properties such as low surface tension [referans] 

In this study; the electrochemical stability window of the 

membrane has been evaluated with the recyclable voltametry 

technique using the 3 (triple) electrode system. All 

electrochemical measurements have been performed within glove 

box (argon gas cabin). Ac conductivity values of the membranes 

containing with Li salts have been found within the range of 

10-5 –10-6 S/cm. In this study lithium salts such as LiClO , LiPF 4 6 

and LiBF were used by dissolving them in solvents like 

4 

PC(propylene carbonate), EC (ethylene carbonate), 

DEC(diethylene carbonate). The obtained polymer electrolyte 

membrane has been characterized in Li (anode)?Polymer 

electrolyte?LiCoO2(cathode) battery assembly. 

references: 

1. M-K. Song, Y-T. Kim, B. W. Cho, B. N. Popov and 

Hee-Woo Rhee,Thermally Stable Gel Polymer 

Electrolytes, Journal of The Electrochemical Society, 

Vol. 150, Issue 4, pp. A439–A444,2003 

2. B. Ameduri, From Vinylidene Fluoride (VDF) to the 

Applications of VDF-Containing Polymers and 

Copolymers, Recent Developments and Future Trends, 

Chemical Reviews, 109, 6632–6686, 2009 

3. Dong-Min Im, Young-Min Choi, Gue-Sung Kim, 

Hyo-Sugtee, Jung-Jong Park,Cathode Active Material for 

Lithium Rechargeable Battery and Lithium Rechargeable 

Battery Using The Same, United States Patent, US7, 601, 

462 B2, 2009 

4. Ionic liquid incorporated polymer electrolytes for 

supercapacitor application, G. P. Pandey, Y. Kumar, 

S. A. Hashmi; Indian Journal of Chemistry, Vol. 49A, pp. 

743–751, 2010 

5. YW Chen-Yang *; YT Chen; CC Lia; HC Yu; YC Chuang; 

CH Su, YT Lin,Preparation of UV-filter Encapsulated 

Mesoporous Silica with High Sunscreen Ability, Mater. 

Lett., Vol.65, No.6 p.1060–1062, 2011 

Keywords: rechargeable battery; ionic conductivity; gel 

polymer electrolyte; 



s1107 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 9 1 

eLeCtroCheMiCAL ChArACterizAtion of 

Pvdf BASed PoLyMer eLeCtroLyteS for 

SeCondAry BAtterieS 

e. zeytuni 1 , M. h. uGur 1 , e. CAKMAKCi 1 , 

A. GunGor 1 

1 Institute of Science, Chemistry, Istanbul, Turkey 

PVDF-based polymer electrolytes have many different uses 

according to the intended use. For example; also being used as 

electrolyte in rechargeable batteries [1] , they can also be used in 

fuel batteries (electrolyte) [2] , besides, they can be used as a binder 

for the preparation of cathode material in rechargeable batteries [3] , 

as an electrolyte for supercapacitor applications [4] and as polymer 

electrolytes in solar batteries [5] . 

The chemical and the thermal stability that the PVDF-based 

gel polymers show, make such type of materials attractive for 

battery and fuel cell applications. Being among the cheapest 

fluoropolymers and having a wide melting point range 

(115°C–175°C), PVDF is a processable polymer which also has 

properties such as low surface tension. 

In this study; the electrochemical stability window of the 

membrane has been evaluated with the recyclable voltametry 

technique using the 3 (triple) electrode system. All 

electrochemical measurements have been performed within glove 

box (argon gas cabin). Ac conductivity values of the membranes 

containing with Li salts have been found within the range of 

10-5 –10-6 S/cm. In this study lithium salts such as LiClO , LiPF 4 6 

and LiBF were used by dissolving them in solvents like PC 

4 

(propylene carbonate), EC (ethylene carbonate), DEC (diethylene 

carbonate). The obtained polymer electrolyte membrane has been 

characterized in Li (anode)?Polymer electrolyte?LiCoO 2 

(cathode) battery assembly. 

references: 

1. M-K. Song, Y-T. Kim, B. W. Cho, B. N. Popov and 

Hee-Woo Rhee,m Thermally Stable Gel Polymer 

Electrolytes, Journal of The Electrochemical Society, 

Vol. 150, Issue 4, pp. A439–A444, 2003 

2. B. Ameduri, From Vinylidene Fluoride (VDF) 

to the Applications of VDF-Containing Polymers and 

Copolymers, Recent Developments and Future Trends, 

Chemical Reviews, 109, 6632–6686, 2009 

3. Dong-Min Im, Young-Min Choi, Gue-Sung Kim, 

Hyo-Sugtee, Jung-Jong Park,Cathode Active Material for 

Lithium Rechargeable Battery and Lithium Rechargeable 

Battery Using The Same, United States Patent, US7, 601, 

462 B2, 2009 

4. Ionic liquid incorporated polymer electrolytes for 

supercapacitor application, G. P. Pandey, Y. Kumar, 

S. A. Hashmi; Indian Journal of Chemistry, Vol. 49A, 

pp. 743–751, 2010 

5. YW Chen-Yang *; YT Chen; CC Lia; HC Yu; YC Chuang; 

CH Su, YT Lin, Preparation of UV-filter Encapsulated 

Mesoporous Silica with High Sunscreen Ability, 

Mater. Lett., Vol.65, No.6 p.1060–1062, 2011 

Keywords: secondary batteries; gel polymer electrolyte; ionic 

conductivity; 


P - 0 4 9 2 

SyntheSiS of the Side ChAin deuterAted 

BrASSinoSteroidS 

v. zhABinSKii 1 , y. erMoLoviCh 1 , A. hurSKi 1 , 

o. GuLyAKeviCh 1 , v. KhiPACh 1 

1 Institute of Bioorganic Chemistry National Academy of 

Sciences of Belarus, Laboratory of Steroids, Minsk, Belarus 

Since the discovery of brassinolide in 1979, about 70 related 

compounds called as brassinosteroids (BS) have been identified 

in plants. Because of a very low content of BS in natural sources, 

only few of them have been isolated as individual compounds. In 

most cases, their presence in plant sources has been proven by 

instrumental methods. The necessary prerequisite for such 

investigation is elaboration of appropriate biochemical hypothesis 

and the presence of a set of compounds which are expected to be 

found. These compounds have to meet some requirements. At 

least three deuterium atoms should be present in the molecule to 

avoid possible interferences with the peaks [M+1] and [M+2] 

belonging to natural 13C and 18O containing species. 

The identification procedure implies feeding of plants with 

labeled precursors followed by analysis of plant extracts by 

instrumental methods (GC/MS or LC/MS). The success of search 

is very much influenced by the proper choice of labeled 

compounds. The label should be located in a metabolically inert 

position and not be subjected to spontaneous isotopic exchange. 

In the present work, new results concerning the preparation 

of BS and their biosynthetic precursors with three deuterium 

atoms in the side chain will de discussed. 

Keywords: Brassinosteroids; Labeling; Brassinolide; 

Epibrassinolide; 



s1108 

chem. Listy 106, s587–s1425 (2012) 


P - 0 4 9 3 

triLoBoLide PhArMACoPhore ModifiCAtionS 

t. ziMMerMAnn 1 , M. JurASeK 1 , P. drASAr 1 , 

J. hArMAthA 2 

1 Institute of Chemical Technology in Prague, 


2 Institute of Organic Chemistry and Biochemistry, 


Trilobolide is a sesquiterpene lactone isolated from Laser 

trilobum. This compound was previously found to play a role as 

inhibitor of sarco/endoplasmic reticulum Ca2+ -ATPase activity 

(SERCA) [1] . Moreover, the farmacophores of this unique 

compound are known and this contribution is coming with view 

on “vicinal diol” farmacophore at positions 7 and 11 of the 

guaianolide skeleton. It was previously demonstrated, that the 

similar diol of the structurally related compound thapsigargin can 

be easily transformed to epoxide [2] . Trilobolide was transformed 

to 7,11-epoxide which was used as the starting material for further 

syntheses. The modifications of epoxide may well be done by 

nucleophilic opening of epoxide giving corresponding hydrines. 

In this work, the primary results from epoxide opening reactions 

are described. It is expected that such synthetic modifications may 

change the biological behaviour of such trilobolide hybrids. 

Acknowledgement: This work was supported by grant number 

MSM 6046137305. 

references: 

1. E. Kmonickova, J. Harmatha, K. Vokac, P. Kostecká, 

H. Farghali and Z. Zidek, Fitoterapia 2010, 81, 1213–1219. 

2. S. Broegger Christensen, I. Kjoeller Larsen, U. Rasmussen 

and C. Christophersen, The Journal of Organic Chemistry 

1982, 47, 649–652. 

Keywords: Terpenoids; Biological activity; Synthetic design; 




s1109 

chem. Listy 106, s257–s1425 (2012) 

Poster session 2 - Analytical Chemistry 

P - 0 4 9 4 

deterMinAtion of CAdMiuM By AdSorPtive 

StriPPinG voLtAMMetry uSinG PyroCAteChoL 

vioLet CheLAtinG AGent 

A. AhMAd 1 , A. ALdABAh 1 , A. ALMAiuf 1 

1 King Saud University, Chemistry, AlRiyadh, Saudi Arabia 

The adsorptive collection of Cd (II) complex with 

pyrocatechol violet ligand, coupled with the square wave 

voltammetric technique, yields a very sensitive electroanalytical 

procedure for the determination of cadmium in various industrial 

samples. The optimized experimental conditions include: 

supporting electrolyte (carbonate buffer), pH (9.5), pyrocatechol 

violet concentration (1.5?10-5 moll-1 ), accumulation time (30 s), 

accumulation potential (0.0 V), scan rate (200 mV s-1 ), pulse 

amplitude (0.05 V) and SW frequency (50 Hz). The monitored 

stripping voltammetric current was linear over the range of 

7.5?10-8 –1.75?10-7 moll-1 and the detection limit was 0.66 ppb. 

The relative standard deviation was calculated as 1.02% (n =10) 

for 1?10-7 mol l-1 Cd(II) and the obtained electrochemical signal 

was stabile for up to 120 minutes. Possible interferences by either 

co-existing metal ions or other chelating agents were also 

investigated. The applicability of the developed method for the 

determination of Cd element was assessed by the analysis of 

various industrial and environmental samples. The accuracy of 

the obtained voltammetric analytical results was validated by 

comparing with that obtained by atomic absorption spectrometry 

and conducting the necessary statistical evaluation. 

Keywords: Electrochemistry; Voltammetry; Cadmium; 


P - 0 4 9 5 

deterMinAtion of PKA vALue of irinoteCAn 

uSed for treAtMent of CoLoreCtAL CAnCer 

By reverSed PhASe Liquid ChroMAtoGrAPhy 

B. AKMeSe 1 , S. SAnLi 2 , n. SAnLi 2 

1 Hitit University Faculty of Science and Arts, Chemistry, 

Corum, Turkey 

2 Usak University Faculty of Science and Arts, Chemistry, Usak, 

Turkey 

Email: bdhylcn@hotmail.com 

Colorectal cancer, also called coloncancer or large bowel 

cancerincludes cancerous growths in the colon, rectum and 

appendix. It is the thirdmost common form of cancer and the second 

leading cause of cancer-related deathin the Western world [1] . 

Colorectal cancer is the third mostcommon form of cancer appears 

in our country and it can also occur in everyage, but above the 

90% of the patients are more than 40 years old [2] . Recently, 

combined active drugs in the treatment of colorectal cancer was 

usedbecause of more efficiently destroy the tumor cells in the 

standard therapy forpatients. Irinotecanwhich is one of the drugs 

for this purpose, an antineoplastic drug usedintravenously in the 

treatment of advanced colorectal cancer. It is isolatedfrom 

Camptotheca acuminata which issitotiksik a tree that grows in 

China [3] . 

The ionization constant is an importantphysico-chemical 

parameter of a drug and the knowledge of this parameter is 

offundamental importance in a wide range of applications and 

research areas. Inthis study pK values of irinotecan were 

a 

determined and the effectof the mobile phase composition on the 

ionization constant was studied bymeasuring the pK at different 

a 

acetonitrile-water mixtures, 35,40,45, 50 % (v/v) using LC-UV 

method. 

references: 

1. A. S. Sameer, S. Abdullah, M. Z. Banday, N. Syeed, 

M. A. Siddiqi,International Journal of Genetics 

andMolecular Biology, 2010, 2(6), 101–111. 

2. C. Smith and J. A. Butler, Diseases ofthe Colon & Rectum, 

1989, 32, 843–846. 

3. W. Zhang, G. E. Dutschman, X. Li, M. Ye, Y.C. Cheng, 

Journal of Chromatography B,2009, 877, 3038–3044. 



s1110 

chem. Listy 106, s257–s1425 (2012) 


P - 0 4 9 6 

SuPrAMoLeCuLAr CoMPLexeS forMAtion. 

PoSSiBiLitieS of MASS SPeCtroMetriC StudieS 

f. AMAto 1 , e. M. PenA-Mendez 2 , t. PivettA 3 , 

n. r. PAnyALA 1 , J. hAveL 1 

1 Masaryk University Kampus Bohunice Kamenice 5/A14, 

Department of Chemistry Faculty of Science, 62500 Brno, 


2 University of La Laguna Faculty of Chemistry Campus de 

Anchieta, Department of Analytical Chemistry Nutrition and 

Food Science, 38071 La Laguna, Spain 

3 University of Cagliari, Department of Chemical and 

Geological Sciences, 09042 Monserrato, Italy 

In supramolecular complexes the molecules or ions are held 

together by non-covalent interactions: Host + Guest < => {Host, 

Guest}. Usually, compounds like cyclic ethers, cyclodextrines, or 

other macrocycles might act as hosts while various 

organic/inorganic cations, anions, neutral molecules etc. are 

playing the role of guests. 

The paper deals with the application of mass spectrometry 

(MS) for fast screening of variour host-guests combinations in 

order to find out the formation of supramolecular complexes 

and/or to search for new potential drug carriers or to decrease their 

toxicity. 

MS was done using either matrices, laser desorption 

ionization (LDI) or surface assisted LDI. Mass spectrometric 

analysis was used because the reactions can also be done directly 

on the MS target and several combinations can be examined with 

the minimum amount of often scarce and expensive reagents. 

Several examples of supramolecular complex formation 

using different types of macrocycles (cyclodextrins, 

cucurbit[n]urils, etc.) as hosts, and either drugs like antivirals, 

cancerostatics or inorganics including nanoparticles as guests, will 

be given and discussed. 

The proposed application of mass spectrometry represents 

fast, efficient and economic way to search for the formation of 

new supramolecular complexes. The results might find application 

in medicine. 

Keywords: Mass Spectrometry; Supramolecular complexes; 


P - 0 4 9 7 

eLeCtroCheMiCAL oxidAtion of AqueouS 

ProPyLene GLyCoL wASte 

v. AnAnev 1 , v. AnAnevA 1 , n. SherinA 1 

1 Kemerovo State University, Analitycal Chemistry, Kemerovo, 

Russia 

Advanced oxidation processes are currently used to treat 

industrial effluents. However, they have some major drawbacks 

if wastewater contents the large amount of inorganic chlorides. In 

this context, oxidative electrochemical technologies offer an 

alternative solution to purification of wastewater formed under 

oxide propylene production. The electrochemical oxidation of this 

wastewater contents propylene glycol and the chloride ions in 

strong basic media has been studied. 

Chemical oxygen demand (COD) and concentration of the 

chloride ions were determined using a chemical analysis. The 

concentrations of propylene glycol and products of their 

electrochemical oxidation were determined by optical 

spectroscopy, IR-spectroscopy, and chemical analysis. The optical 

absorption spectra were registered on Shimadzu UV-2450 

spectrophotometer. The diffuse reflectance IR-spectra were 

registered by the FTIR spectrometer “System-2000” by Perkin 

Elmer. The oxidation of propylene glycol was carried out in a 

single compartment electrochemical cell. Stainless steel 

electrodes were used. The composition of the wastewater 

used in the experiments was, 32800±500 mg/dm3 (Cl- ), 

1500-2500 mg/dm3 (COD), and pH 11-12. The current density 

used was 75 mA cm-2 . Voltage used was 4.3 V. 

The main by-products of propylene glycol decay under 

electrochemical oxidation are established. Maximum of the 

organic waste mineralization is ~80%. Time of the treatment 

increases from 10 to 30 min with increasing COD from 1500 to 

2500 mg/dm3 for this degree of mineralization. The concentration 

of the chloride ions remains unchanged. 

Keywords: Electrochemical oxidation; Propylene glycol; 

Wastewater; 



s1111 

chem. Listy 106, s257–s1425 (2012) 


P - 0 4 9 8 

fLuoreSCenCe deteCtion of nuCLeotideS 

under PhySioLoGiCAL ConditionS uSinG 

CoPPer(ii)-CoMPLexeS 

r. ArnoLd 1 , n. BACKMAnn 1 , e. KAtAev 1 

1 Chemnitz University of Technology, Organic Chemistry, 

Chemnitz, Germany 

Detecting anionic species of biological importance like 

phosphates with the help of chemosensors has attracted 

considerable attention in recent years. [1] Especially high selective 

receptors for adenine containing nucleotides are of particular 

interest. [2] 

Herein we present a novel approach for fluorescent sensing 

of nucleotides based on designing the ligands that not only contain 

fluorescent dyes but also a recognition site for metal ions like 

copper(II) which are known for strong interactions with 

phosphates. Together with analytes these ligands can form ternary 

copper(II)-complexes in aqueous solution. 

The ligand works as key component that determines the 

selectivity and generate an analytical signal. We synthesized 

ligands 1-4 which in the presence of copper(II)-salts showed 

moderate selectivity for ATP and GTP according to fluorescence 

measurements. The recognition mechanism for each ligand was 

investigated. It was shown that selectivity can be achieved using 

a combination of several ligands with copper(II)-salts. 

references: 

1. a) A. E. Hargrove, S. Nieto, T. Z. Zhang, J. L. Sessler, E. 

V. Anslyn, Chem. Rev., 2011, 111, 6603–6782; 

b) M. Wenzel, J. R. Hiscock, P. A. Gale, Chem. Soc. Rev., 

2012, 41, 480–520. 

2. D. C. Liemburg-Apers, H. Imamura, M. Forkink, M. 

Nooteboom, H. G. Swarts, R. Brock, J. A. M. Smeitink, P. 

H. G. M. Willems, W. J. H. Koopman, Pharm. Res-Dord., 

2011, 28,2745 – 2757. 

Keywords: Fluorescence; copper; nucleotides; sensor; 


P - 0 4 9 9 

oPtiMizAtion of SodiuM BiCArBonAte 

ProduCtion froM BorAx By tAGuChi Method 

A. M. ASLAndAS 1 , M. CoPur 2 , y. onGAner 1 

1 Atatürk University, Chemistry, Erzurum, Turkey 

2 Atatürk University, Chemical Engineering, Erzurum, Turkey 

The demand for boron products of industrial companies in 

the world are increasing every passing day. Turkey has about 72 % 

of the known boron reserves of the world. An important part of 

Turkey’s boron reserves is occurred colemanite, tincal and ulexite 

minerals. It is of great importance that variety of boron 

compounds produced from boron minerals have increased and 

that compounds have produced in minimum cost. Tincal is 

dissolved in hot water and is separated from impurities by 

filtration and is obtained as borax decahydrate (borax). Although 

there are many studies concerned with the production of different 

boron chemicals from borax, the studies with regard to sodium 

bicarbonate from borax are scarcely available. 

In this study, the sodium bicarbonate production from borax 

decahydrate in ammonia solutions saturated by carbon dioxide 

gas in pressure reactor was studied and the effects of relevant 

parameters, namely; reaction temperature, solid-to-liquid ratio, 

reaction time, pressure and ammonia concentration have been 

investigated on the sodium bicarbonate production from borax by 

using the Taguchi method. The chosen experimental parameters 

were as follows: reaction temperature, 45–60 °C; solid-to-liquid 

ratio, 0.69-0.92 g/mL; reaction time, 30- 60 min; pressure, 

5-20 bar; ammonia concentration, 2,82-5,65 M. Steering speed 

was stable at 500 rpm. The optimum conditions have been 

determined between the sodium bicarbonate production efficiency 

from borax and relevant parameters by means of variance analysis 

by using the statistical computer software. The optimum 

conditions were found to be as follows: reaction temperature, 

60°C; solid-to-liquid ratio, 0.77 g/mL; reaction time, 50 min; 

pressure 20 bar; ammonia concentration 3.7634 M. In these 

conditions, produced sodium bicarbonate has approximately to 

70% efficiency and 98% purity. 

Keywords: Boron; High-pressure chemistry; Industrial 

chemistry; Solid-phase synthesis; Carbon dioxide; 



s1112 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 0 0 

inveStiGAtion of SodiuM BiCArBonAte 

ProduCtion froM BorAx in AMMoniA 

SoLutionS SAturAted with CArBon dioxide 

GAS under PreSSure 

A. M. ASLAndAS 1 , M. CoPur 2 , y. onGAner 1 


2 Atatürk University, Chemical Engineering, Erzurum, Turkey 

The most important mine that Turkey has got approximately 

72% of the world reserves is the boron minerals. Boron products 

such as borax decahydrate, borax pentahydrate, boron nitride, zinc 

borate, boric acid, sodium pentahydrate, boron oxide, disodium 

octaborate tetrahydrate, anhydrous borax are produced from boron 

minerals. In this study, sodium bicarbonate which is an important 

industrial input is aimed to be produced by using borax 

decahydrate and CO as raw materials for both the highest yield 

2 

and purity. In addition, it is expected to be contributed positively 

to the reduction of CO causing global warming. 

2 

In this study, the optimum conditions of sodium bicarbonate 

production from sodium tetraborate decahydrate 

(Na B O .10H O) in ammonia solutions saturated with carbon 

2 4 7 2 

dioxide gas under pressure is investigated. Experiments were 

carried out by using the experimentation method with change of 

one factor at a time (OFAT). The chosen experimental parameters 

were as follows: reaction temperature (45-65°C), solid-liquid ratio 

(0.69-0.92 g/mL), reaction time (30-60 min), pressure (5-30 bar), 

ammonia concentration (2,82-5,65 M) and crystallization 

temperature (0-50°C). As the target of optimization was both the 

highest yield and purity, solid amount(g) / B O % was chosen as 

2 3 

the optimization criterion. The value of optimization criterion 

(solid amount(g)/%B O ) had increased, NaHCO purity and yield 

2 3 3 

increased, indicating B O % decreases and solid amount 

2 3 

increases. As a result, the criterion of optimization observed to 

increase up to a certain point with increasing reaction temperature, 

solid-liquid ratio, reaction time, pressure, ammonia concentration 

and crystalization temperature. The optimum conditions were 

found to be as reaction temperature, 60°C; solid-to-liquid ratio, 

0.77 g/mL; reaction time, 50 min; pressure, 20 bar; ammonia 

concentration, 4.7043 M. In these conditions, produced sodium 

bicarbonate has solid amount(g) / %B O = 10.04 and 97.75% 

2 3 

purity. 

Keywords: Borates; High-pressure chemistry; Solid-phase 

synthesis; Carbon dioxide; Industrial chemistry; 


P - 0 5 0 1 

dye-SurfACtAnt interACtion Studied By 

PhotodynAMiC PArAMeterS 

B. M. Aydin 1 , M. toPrAK 2 , M. AriK 3 , y. onGAner 3 

1 Erzincan University, Chemistry, Erzincan, Turkey 

2 Bingöl University, Chemistry, Bingöl, Turkey 


Pyronine Y (PyY) which is a positively charged dye 

compound is a xanthene derivative dye compound used in this 

study. Xanthene derivatives are very efficient laser dyes and 

fluorescent probes that offer outstanding photophysical and 

photodynamic properties. Therefore, PyY is used in model 

biologic systems and laser spectroscopy widely. Photophysical 

and photodynamic properties of this kind of dyes depend on the 

media. Thus, it is important to determine behavior of PyY in 

different media. 

In this study, the photodynamic of PyY compound in the 

negatively charged sodium dodecyl sulfate (SDS) surfactant 

medium has been examined. Pyronin Y concentration was kept 

constant and experiments were carried out as a function of 

temperature in SDS surfactant solutions prepared at different 

concentrations. Photodynamic parameters were fluorescence 

anisotropy, rotational diffusion times and microviscosity of the 

probe environment. Experimental temperature range was 10 to 

60°C and the effect of temperature on surfactant-dye interactions 

has been observed via photodynamic parameters. 

Fluorescence anisotropy is a reflection of rotational 

diffusion and used in molecular biology studies such as proteinligand 

interactions, protein denaturation, and membrane activity. 

As a result, steady-state fluorescence anisotropy values 

obtained with surfactants below the critical micelle concentration 

were low. This observation is due to the probe environment that 

permits probe molecules move freely without any restriction. The 

decrease of anisotropy values at higher temperatures is also an 

indication of the deformation of the micelle structure with 

temperature increase. It has been observed that the steady-state 

fluorescence anisotropy values calculated for PyY at 10oC in 

20 mM SDS surfactant solution was equal to the limiting 

anisotropy value of 0.373±0.002 for xanthene family dye 

compounds. Moreover, the largest value of microviscosity value 

was determined at the critical micelle concentration of SDS. It 

stated that the micro environment of PyY is more rigid in this 

condition. 

Keywords: Dye-surfactant interaction; Pyronine Y; 

Photodynamic; 



s1113 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 0 2 

inveStiGAtion of MoLeCuLAr interACtionS 

Between CouMArin 35 And Bovine SeruM 

ALBuMin: fLuoreSCenCe reSonAnCe enerGy 

trAnSfer (fret) 

t. BAyrAKtutAn 1 , y. onGAner 1 


Coumarin 35 (C35) is also named 7-dietil amino-4-trifloro 

methyl coumarin or coumarin 481. It is dye compound derived 

from 7-amino coumarins. 7-amino coumarins are the important 

groups used as analgesics, anticoagulants, fluorescence probes 

and sensitizer in photo processes. 1 Serum albumin is the abundant 

protein in plasma and plays a major role to the distribution of 

various biologically active compounds such as metabolites, drugs 

and other organic compounds. 2 Bovine serum albumin (BSA) was 

selected as a model protein to study interactions with C35. 

In this study, the molecular interaction mechanism between 

C35 and BSA were studied by using fluorescence spectroscopy 

techniques. The fluorescence properties of dye in the free state 

and interacted with BSA were investigated. The distance r 

between BSA (donor) and C35 (acceptor) was calculated using 

by Förster’s theory in different temperatures. Förster’s theory 

known as Fluorescence Resonance Energy Transfer Method 

(FRET) is often used for measuring molecular distances in various 

systems as biological, macromolecular systems. 3 Accordingly, the 

efficiency of energy transfer between the donor (BSA) and the 

acceptor (C35), molecular distances; R (Förster radius) and r (the 

0 

binding distance) in between C35 and BSA were determined in 

different temperatures. Synchronous fluorescence spectra supplied 

information about the conformational changes in BSA. 

Synchronous fluorescence spectra indicated that the interaction 

of BSA with C35 was affected from the conformation of tyrosine 

residues micro-environment. It was revealed that C35 is more 

accessible to the tyrosine residues than to tryptophan residues. 

Keywords: Bovine Serum Albümin (BSA); Coumarin 35 (C35); 

Fluorescence Resonance Energy Transfer Method (FRET); 

Fluorescence spectroscopy; 


P - 0 5 0 3 

BindinG ProPertieS of Bovine SeruM ALBuMin 

to the CouMArin 35: SCAtChArd PLot And 

douBLe LoGArithMiC PLot. 

t. BAyrAKtutAn 1 , y. onGAner 1 


The interaction between coumarin 35 (C35) and bovine 

serum albumin (BSA) were studied by using UV-Vis. absorption 

and fluorescence spectroscopy techniques. In our different study, 

the binding distance, the conformational changes and the energy 

transfer between BSA and C35 were determined. In this paper, 

the binding equilibrium between BSA and C35 was studied by 

using two different methods. There are many methods for the 

determination of binding constants. Because determination of 

binding constants is useful tool for both to understand and 

characterize the protein – ligand interactions, 1 The most common 

methods, scatchard and double logarithmic plots, were exploited 

for investigation. In this study, the binding constants from 

scatchard and double logarithmic plots for the C35-BSA systems 

were calculated for different temperatures. It was determined that 

there is a decrease in binding constant values with increasing 

temperature for both methods. The high linearity was obtained for 

the plots. It was concluded that the presence of a single class of 

binding sites is valid. 2 

Keywords: Bovine Serum Albümin (BSA); Coumarin 35 (C35); 

Fluorescence spectroscopy; Scatchard Plot; Double 

Logarithmic Plot; 



s1114 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 0 4 

A two diMenSionAL SePArAtion for the 

enAntioSeLeCtive deterMinAtion of 

hexABroMoCyCLododeCAne (hBCd) froM 

environMentAL SAMPLeS 

K. BeSter 1 , K. vorKAMP 1 

1 Department of Environmental Science, Aarhus University, 

Frederiksborgsvej 399, 4000 Roskilde 

Email: kb@dmu.dk 

A new method has been developed to determine the 

enantiomers of the α-,β- and γ-isomers of the brominated flame 

retardant Hexabromocyclododecane (HBCD) undisturbed from 

each other. While often (+) α HBCD tends to coelute with (+) βand 

(+) γ-HBCD in the enantio-selective HBCD analysis, we use 

a two dimensional high performance liquid chromatography 

(HPLC) approach to separate the non labelled isomers and their 

13C-labelled analogues on a conventional column and transfer the 

isomers separately by heart cuts to an enantio-selective column. 

The enantio-selective column thus acts as a real second 

dimension. For this approach the first separation is set to stop flow 

after the first isomer is transferred to the secondary 

enantio-selective column. Only when the secondary column is 

reconditioned the primary chromatogram is developed further and 

the other two isomers are transferred to the enantio-selective 

column. 13C-labelled isomers are separated in the same way and 

allow enantio-specific quantification by isotope dilution. 

Detection is performed by tandem mass spectrometry utilizing 

electrospray in negative mode. 

The result is a completely undisturbed enantio-selective 

separation for α-HBCD, the predominating isomer in high trophic 

level biota. Different data treatment methods (using area values, 

area values referred to the corresponding internal standard area 

and full internal standard calibration) are discussed. The 

performance of the system has been tested by repeated analysis 

of fish oil and a multitude of environmental samples. 


P - 0 5 0 5 

the interACtion in SuLPhAniLAMideS – Azo 

dyeS SySteMS And their AnALytiCAL 

APPLiCAtion 

M. BoiKo 1 , t. vruBLevSKA 1 , o. KorKunA 1 , 

G. teSLyAr 2 

1 Ivan Franko Lviv National University, Chemistry, Lviv, 

Ukraine 

2 State Scientific Research Control Institute of Veterinary 

Preparations and Fodder Additives, Laboratory of 

Instrumental Methods of Control, Lviv, Ukraine 

Spectrophotometry is used for sulphanilamides (SA) 

quantity control in antibacterial preparations. However, it is not 

suitable for complex medicines analysis because of insufficient 

selectivity of known spectrophotometric reagents. 

It was established that diazotized sulphanilamides interact 

with acid monoazo dye Tropaeolin O (Tr O), 

heterocyclic azoreagents 4-(2-pyridylazo)resorcinol (PAR) and 

4-(2-thiazolylazo)-resorcinol (TAR) and o,o , -dihydroxo 

substituted azo dyes eriochrome black T, eriochrome blue-black 

R and eriochrome blue SE forming coloured compounds. 

Optimum conditions for SA interaction with azo reagents were 

studied: pH at the presence of proper buffer solution (neutral or 

basic media depending on the reagent) and corresponding reagents 

excess (1.5-6-fold). Effective molar absorptivities for SA-azo 

reagents systems approximately are 103-104 M-1 cm-1 . Developed 

methods are suitable for SA microgram amounts determination in 

complex mixtures. 

Diazotized sulphanilamides azocouple with Tr O, PAR and 

TAR forming disazo dyes, which is confirmed by new absorbance 

maximum appearance at 590-615 nm for product solutions. This 

assumption is confirmed by voltammetric studies. We observed 

two peaks of azo-groups reduction on products polarogramms. 

Potentiometric titration and spectrophotometric study in 

atmospheric oxygen presence and in oxygen free media verified 

that in SA–azo reagents systems redox interaction did not take 

place. 

Decrease of azo dyes absorbance maxima and appearance 

of other maximum are observed on UV-Vis absorbance spectra of 

products of diazotized SA interaction with o,o , -dihydroxo 

substituted azo dyes. Voltammetric studies also showed that due 

to SA diazonium salt azo-groups reduction peak is decreased and 

a new shoulder appears for all products. Potentiometric redox 

titration confirmed the redox nature of interaction in diazotized 

SA-o,o , -dihydroxo substituted azo dyes systems (azo dyes are 

oxidized), because significant changes of systems redox potentials 

were observed on titration curves. UV-Vis spectra of obtained 

compounds showed that O does not react with azo dye. 

2 

Keywords: Azo compounds; Analytical Methods; Oxidation; 

Sulfonamides; UV/Vis spectroscopy; 



s1115 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 0 6 

MoLeCuLAr BehAvior of CouMArin 120 in 

reverSe MiCeLLe ContAininG PoLyMer 

e. BozKurt 1 , M. ACAr 1 , y. onGAner 1 

1 Ataturk University Science Faculty, Chemistry, Erzurum, 

Turkey 

7-amino-coumarin derivatives are used as solvation probes 

in various micro-environments. When amino-coumarin dyes were 

excited with electromagnetic radiation, intramolecular charge 

transfer (ICT) takes place from the electron donating amino group 

to the electron withdrawing carbonyl group of the coumarin ring. 

This process causes a large change in the excited state dipole 

moment. Due to difference in dipole moments, ICT occurs 

gradually with increasing solvent polarity. In addition, depending 

on the solvent-solute interactions, energy gap between the ground 

and the lowest excited singlet state reduced. This causes a Stokes’ 

shift of fluorescence emission. 

Reverse micelles consist of surfactant molecules dispersed 

in a non-polar organic solvent and polar solvent (usually water), 

forming water pool. The size of water pool is determined by W0 (water/surfactant molar ratio). W


s1116 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 0 8 

identifiCAtion And deterMinAtion of 

GentAMyCin And itS MetABoLiteS froM 

huMAn PLASMA And CeLL CuLture MediA By 

SPMe-LC/MS n 

B. BuSzewSKi 1 , S. MALGorzAtA 1 

1 Department of Environmental Chemistry and Bioanalytics, 

Chair of Environmental Chemistry & Bionanalytics, Torun, 

Poland 

Determination of biologically active compounds from 

various matrices, including environmental and biological samples 

is a serious problem in a modern analytical chemistry. The most 

relevant matrices to be analyzed for this purpose are plasma or 

blood, due to providing a good correlation between their 

concentration and pharmacological effects. One of the major tool 

is the combination of high-performance liquid chromatography 

and mass spectrometry (LC/MSn ). The main aim of this 

investigation was to apply a fast and sensitive extraction technique 

using electrochemically prepared a new polymeric coatings as 

sorbents for solid phase microextraction (SPME). Polypyrrole 

(PPy), polythiophene (PTh) and poly(3-alikilothiopenes) SPME 

coatings were used and evaluated their ability to extract 

gentamycin from human plasma samples and cell culture media 

as well. Mass spectrometric parameters were optimized for target 

compound in positive ion mode over the m/z 100–500 range. 

Quantitation was done using multiple reaction monitoring (MRM) 

mode to monitor precursor ion at [M+H] + to product ion transition 

of 478 ? 322 for gentamycin (GEN). Validation data for accuracy 

and precision for intra- and inter-day were good and satisfied 

FDA’s guidance: CV between 0.39% and 9.83% and accuracy 

between 95.7% and 111.3% for all compounds. Developed 

method can be used for the quantitative analysis of selected 

biologically active compound, and provide a potential application 

to study the metabolism and pharmacokinetics of other drugs from 

different medical classes from the biological matrices. In 

conclusion, although various LC-MS/MS methods have been 

developed and reported in the literature for the measurement of 

gentamicin, the described method by us appears to be particularly 

promising. It is rapid and accurate, and can be applied as a 

routinely used in clinical laboratories. 

Acknowledgement: This work was supported by National 

Science Center (Cracow, Poland), no. 2011/01/N/ST4/03178. 

Keywords: gentamycin; human plasma; cell culture media; 

SPME-LC/MSn; 


P - 0 5 0 9 

oPtiCAL ProPertieS of Mno thin fiLMS in 

2 

non-AqueouS eLeCtroLyteS 

C. A. CAStro ruiz 1 , G. ruiz SierrA 1 , 

d. roChefort 1 , d. BéLAnGer 2 

1 Université de Montréal, Chemistry, Montréal (Québec), 

Canada 

2 Université du Québec Montréal, Chemistry, Montréal 


In recent years, supercapacitors (SCs) have attracted much 

attention for their power enhancement compared to batteries and 

fuel cells, and higher energy densities than common capacitors 

[1]. Among several transition metal oxides (RuO , IrO , NiO, 

2 2 

CoO , SnO and MnO ) tested as electrode materials for 

x 2 2 

pseudocapacitors [1, 2, 3, 4] , MnO due to its low cost, satisfactory 

2 

electrochemical performance and natural abundance is considered 

as one of the most promising materials for SCs in many 

technological applications ranging from mobile devices to electric 

vehicles [2, 5] . 

In this contribution, we will report on the electrochemical 

behaviour of MnO in protic ionic liquid (PIL) electrolytes 

2 

obtained by a mixture of a base like 2-methoxy-pyridine 

(2-MeOPy) and an acid (trifluoroacetic) that were shown to 

sustain pseudocapacitance in this oxide. Thus, the MnO films 2 

electrochemically deposited onto ITO substrates were studied and 

characterized. Further information about synthesis, 

characterization by SEM, XRD, CV and UV-vis spectroscopy and 

stability performance will be reported. Spectroelectrochemical 

experiments have been carried out to study the changes in the 

optical properties of the MnO films which are linked to the 

2 

oxidation state of the material. Further developments on 

task-specific ionic liquids for electrolytes in metal-oxide based 

supercapacitors are expected to increase their charge storage 

properties. 

references: 

1. C. Ye, Z. Lin, S. Hui, J. Electrochem. Soc. 152(6) (2005) 

A1272. 

2. M. Winter, R. Brodd, Chem. Rev., 104 (2004) 4245. 

3. V. Subramanian, H. Zhu, R. Vajtai, P. Ajayan, B. Wei, 

J. Phys. Chem. B, 109 (2005) 20207. 

4. L. Mayrand-Provencher, D. Rochefort, J. Phys.Chem. C, 

113 (2009) 1632. 

5. M. Jayalakshmi, K. Balasubramanian, Int. J.Electrochem. 

Sci., 3 (2008) 1296. 

Keywords: Ionic liquids; UV/Vis spectroscopy; Manganese; 



s1117 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 1 0 

ChAnGeS in LiPid ProfiLeS of PAtientS with 

CArdivASCuLAr diSeASeS 

B. CervenA 1 , e. CifKovA 1 , M. LiSA 1 , M. hoLCAPeK 1 , 

J. znALezionA 2 , J. voStALovA 2 , J. GALuSzKA 3 

1 University of Pardubice, Department of Analytical Chemistry, 


2 Palacký University Olomouc, Medical Faculty, Olomouc, 


3 Faculty Hospital Olomouc, Faculty Hospital Olomouc, 


Cardiovascular diseases (CVDs) are one of the most 

common cause of death in the world. It is strongly connected with 

the change of the lipidome. Differences between samples of 

healthy volunteers and patients are studied in our project. The 

group of 50 men contained 5 subgroups (healthy volunteers, obese 

and 3 types of CVDs). Each sample was divided into erythrocytes, 

plasma and 3 lipoproteins fraction (VLDL, LDL, HDL). Samples 

were extracted using Folch method [1] . The total lipid extract was 

separated using HILIC-LC/ESI-MS into individual polar classes 

of lipids [2] . Non-polar lipid extracts were prepared using 

hexane/methanol/water and analyzed by NP-HPLC/APCI-MS. 

Fatty acid methylesters (FAMEs) were prepared using the 

transesterification with sodium methoxide and quantified by 

GC/FID. There are differences in profiles of lipids and FAMEs 

between each type of samples. Changed levels of polar class lipids 

between healthy control and patients were observed in our 

chromatograms. An increase of relative percents of some FAMEs 

for patients was observed in GC/FID chromatograms. These 

changes have will be important for CVDs biomarker discovery in 

our future studies. 

Acknowledgement: This work was supported by the grant 

project No. 206/11/0022 (Czech Science Foundation). 

references: 

1. J. Folch, M. Lees, G. H. S. Stanley, J. Biol. Chem. 226 

(1957) 497. 

2. M. Lísa, E. Cífková, M. Holcapek, J. Chromatogr. A 1218 

(2011) 5146. 

Keywords: lipid; cardiovascular diseases; mass spectrometry; 


P - 0 5 1 1 

deterMinAtion of SuLfAMethizoLe uSinG 

CArBon PASte eLeCtrode 

h. deJMKovA 1 , M. MiKeS 1 , J. ziMA 1 , J. BAreK 1 

1 Charles University Faculty of Science, Department of 


Two new methods were developed for the electrochemical 

determination of sulfamethizole, sulfonamide antibiotic used for 

the treatment of urinary tract, using carbon paste electrode. The 

first method employs differential pulse voltammetry (DPV) and 

is aimed to the determination of sulfamethizole in samples of 

pharmaceutical formulations; the other method uses HPLC with 

amperometric detection and is aimed to the determination in 

biological samples. Optimization of the determination conditions 

was performed. In the case of DPV, Britton-Robinson buffer pH 

7 was selected as the supporting electrolyte. In case of HPLC, 

mobile phase consisted of buffer pH 3:methanol (7:3, v/v); 

amperometric detection was performed in a wall-jet arrangement 

at +1.3 V detection potential. Determination limits of the methods 

are 1.3 μmol L –1 and 0.14 μmol L –1 for DPV and HPLC, 

respectively. The applicability of the methods was tested on the 

real tablet samples and model urine samples, in the latter case after 

the preliminary separation by the solid phase extraction. 

Keywords: Pharmaceutical; Voltammetry; Amperometry; 



s1118 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 1 2 

SuPrAMoLeCuLAr reCoGnition of 

BioAnALyteS 

A. J. devAdoSS 1 , M. eLStner 1 , A. SChiLLer 1 


Selective recognitions of biological important analytes under 

physiological conditions is a challenging task in supramolecular 

chemistry. Synthetic receptors that can achieve such tasks are 

important as diagnostic tools in medicinal chemistry and 

molecular biology. Molecular receptors for biologically important 

analytes like pyrophosphate (PPi), Adenosine-5'-triphosphate 

(ATP) and saccharides were investigated. Zn(II)-based 

coordination complex with a pendant azo-functionality as the 

reporter group [1] and self-assembled polydiacetylene (PDA) based 

vesicular receptors [2] have been prepared for the selective 

recognition of the ATP and PPi in aqueous solution. This receptor 

could be used as a staining agent and could even be capable of 

distinguishing the Gram +ve, Gram -ve bacteria and yeast cells. [1b] 

A two-component glucose sensing concept based on anionic 

fluorescent dye and boronic acid-appended bipyridinium salt was 

already formulated. [3] Boronic acid-appended new photo 

switchable azopyridinium and bis-viologen based receptors have 

been prepared for improved carbohydrate recognition in water. 

Many different classes of enzymes, including phosphatases, 

phosphorylases, mutases, transferases, hydrolases and isomerases 

are involved in carbohydrate transformation. Thus, going beyond 

saccharide sensing, our current focus is to develop new assays for 

carbohydrate-active enzymes in a non-destructive, continuous 

manner for an industrial application. [4] 

references: 

1. a) Amilan Jose, D.; Mishra, S.; Ghosh, A.; Mishra, S. K.; 

Srivastava, A. and Das. A. Org. Lett. 2007, 9, 

1979–1982. 

b) Ghosh, A.; Shrivastav, A.; Amilan Jose, D.; Mishra, S.; 

Chandrakanth, C. K.; Mishra, S. and Das, A. Anal. 

Chem. 2008, 80, 5312-5319. 

2. Amilan Jose, D.; Stadlbauer, S. and Köenig, B. Chem. Eur. 

J. 2009,15, 7404 – 7412. 

3. a) A. Schiller, B. Vilozny, R. A. Wessling, B. Singaram, 

in Reviews in Fluorescence 2009, Springer, 2011. 

b) A. Schiller, in Molecules at Work. Selfassembly, 

Nanomaterials, Molecular Machinery 

(Ed.: B. Pignataro), Wiley-VCH, Weinheim,2012, 315. 

4. www.novosides.eu. 

Keywords: Supramolecular chemistry; Enzymes; 

Carbohydrates; Sensors; Fluorescent probes; 


P - 0 5 1 3 

the CorroSion BehAvior of iron Powder 

PieCeS in SALt SPrAy environMent 

A. didu 1 , A. SAMide 1 , h. verMeSAn 2 

1 University of Craiova- Facullty of Exact Sciences, Chemistry, 

Craiova, Romania 

2 Technical University of Cluj-Faculty of Materials Science and 

Engineering, Surface Engineering and Environmental 

Protection, Cluj-Napoca, Romania 

This paper presents studies on the corrosion behavior in 

saline medium of iron powder samples, obtained by powder 

metallurgy. They have parallelopipedic shape with dimensions of 

10x10x55 mm and 5x10x55 mm and were pressed at 200 MPa, 

300 MPa and 400 MPa. The samples of iron powder, reinforced 

and not reinforced with alloyed steel yarns were subjected to 

corrosion in salt spray environment, observing their behavior for 

about 100 hours. 

Some of the specimens tested were electrolytic galvanized 

with zinc-as anticorrosive protection method, this way it was 

possible to make a comparison between the behaviors of two types 

of pieces. Verifications were made for observing the appearance 

and corrosion manifestation during the time the samples were kept 

in salt spray enclosure, this was captured in images. There have 

been tried other types of metallic coatings, as they will be 

subjected to corrosion in salt spray. 

Acknowledgement: This work was partially supported by the 

strategic grant POSDRU/88/1.5/S/49516, Project ID 59516 

(2009), co-financed by the European Social Fund – Investing in 

People, within the Sectorial Operational Programme Human 

Resources Development 2007-2013. 

Keywords: Corrosion; salt spray environment; 



s1119 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 1 4 

CorroSion BehAvior of Sintered iron PM 

PArtS 

A. didu 1 , A. SAMide 1 , M. didu 2 

1 University of Craiova- Facullty of Exact Sciences, Chemistry, 

Craiova, Romania 

2 University of Craiova- Facullty of Mecanics, Automotive 

Engineering Transport and Industrial Engineering, Craiova, 

Romania 

This paper presents some preliminary research on corrosion 

behavior in acidic pollutant medium for some sintered composite 

materials based on iron. This composite material can be used in 

carrying car component parts (gear wheels, levers). For testing 

we used cylindrical specimens pressed at 200 MPa, 300 MPa and 

400 MPa, having the matrix from powder named ANCORSTEEL 

1000B, reinforced with alloyed steel yarns 

Experimental samples were subjected to chemical and 

electrochemical corrosion in aqueous solutions of de H SO 1M 

2 4 

and HCl 0.5 M, 1 M, 1.5 M, 2 M, 2.5 M. The experimental results 

regarding the corrosion rate for electrochemical tests were 

represented by Tafel curves, using a potentiostat VOLTALAB 40; 

chemical tests were obtained by calculation of gravimetric 

parameters and corrosion parameters. Tests showed that material 

to analyze is strongly corroded in weak acid environments, as 

factors that influence this process being specified: temperature, 

porosity of samples (ranging from 15-20%) and concentration of 

used solutions. For this reason, this new composite material 

cannot be utilized without using anticorrosion protection methods. 

Acknowledgement: This work was partially supported by the 

strategic grant POSDRU/88/1.5/S/49516, Project ID 59516 

(2009), co-financed by the European Social Fund – Investing in 

People, within the Sectorial Operational Programme Human 

Resources Development 2007-2013. 


P - 0 5 1 5 

AntioxidAnt ACtivity of wAter extrACtS in 7 

SeLeCted herBS 

P. diniSová 1 , z. StenCLová 1 , L. CeSLová 1 , 

P. CeSLA 1 , J. fiSCher 1 



Email: petra.dinisova@student.upce.cz 

Herbs are used in many domains, including medicine, 

nutrition, flavouring, beverages, dyeing, repellents, fragrances, 

cosmetics and they are a rich source of polyphenols. Polyphenolic 

compounds are commonly found in both edible and inedible 

plants, and they have been reported to have multiple biological 

effects, including antioxidant activity. Typical phenolics that 

possess antioxidant activity are known to be mainly phenolic acids 

and flavonoids. Phenolic acids are a major class of phenolic 

compounds, widely occurring in the plant kingdom especially in 

fruits and vegetables. 

Total equivalent antioxidant capacities (TEAC) and phenolic 

contents of 7 spices herbs grown in Czech republic were 

investigated. The total antioxidant capacity was estimated by the 

following methods: ABTS (2,2-azinobis-(3-ethylbenzthiazoline- 

-6-sulfonic acid)), DPPH (1,1-diphenyl-2-picrylhydrazyl radical) 

and ferric reducing/antioxidant power (FRAP) expressedas 

TEAC. The influence of season, location of harvest and treatment 

of selected herbs was investigated. 

Keywords: phenolic compounds; herbs; antioxidant activity; 



s1120 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 1 6 

the deteCtion of new AntiBiotiCS And their 

trAnSforMAtion ProduCtS ProduCed By 

AdvAnCed oxidAtion ProCeSSeS in Modern 

wASte wAter treAtMent in CoMPAriSon to 

BioLoGiCAL deGrAdAtion 

J. BruenSinG 1 , M. MoeLLer 1 , w. dott 1 

1 RWTH – Hygiene and Environmental Medicine, University 

Hospital Aachen, Aachen, Germany 

Environmental studies focus on researching and assessing 

today’s most common pharmaceuticals. Modern and last resort 

antibiotics used for the treatment of bacterial infections caused by 

multi resistant bacteria are not subject to recent environmental 

risk assessments since they are rarely used and not detected today. 

The goal of this study is to evaluate the effects of advanced 

oxidation processes techniques to the recent last resort-antibiotics 

Tigecycline, Linezolide, Daptomycine and the modern agents 

Rifaximin, Piperacillin and Doripenem. For the detection of the 

new substances and their transformation products UPLC-MS 

(Synapt) was used. 

As an exemplary result of two different transformation 

products of one origin substance we found with the treatment of 

Piperacillin with UV-radiation and the combination of H O and 

2 2 

Ozone. The usage of UV-radiation caused a specific breaking 

point and the production of a dioxopiperazine, whereas another 

method produced a thiazol carbocyclic acid. 

The treatment of Daptomycin demonstrated the different 

efficiency of the advanced oxidation processes: The UV-radiation 

was unable to break down the target compound within the 

30 minutes treatment, whereas the UV+H O -treament showed a 

2 2 

complete degradation in the 10 minutes sample. Ozone seems to 

be strongest oxidizing agent since no original substance is 

present in the 5 minutes sample in all methods containing 

ozone-treatment. 

Another exemplary result is of great concern showing a very 

stable transformation product. Linezolid was completely degraded 

after a few minutes, but the generated transformation product was 

insensitive to the selected treatment and is still present in the 

30-minutes sample. Until now we were not able to identify the 

molecule, in addition no information is known about its possible 

(eco-) toxicity or biodegradability in aqueous systems. 

Currently the structures of some metabolites of the aerobic 

biodegradation are subject of research and will be presented. 


P - 0 5 1 7 

fLuoreSCenCe-BASed oPtiCAL fiBer AnALyzer 

for deterMinAtion of CAteChoLAMineS 

A. duArte 1 , L. SiLvA 1 , K. duArte 2 , C. JuStino 3 , 

A. C. freitAS 4 , t. PAnteLeitChouK 2 , 

t. roChA-SAntoS 4 


Portugal 

2 Instituto Piaget, ISEIT, Viseu, Portugal 





This work proposes an optical fibre (OF) analyzer for 

sensitive determination of catecholamines (dopamine, 

norepinephrine and epinephrine) in biological samples by induced 

fluorescence. The analytical set-up includes a chromatographic 

column for catecholamine separation, and a fluorescence-based 

OF detection (FOF-analyzer). The proposed methodology showed 

an adequate analytical performance for the determination of the 

above mentioned catecholamines in actual samples of human 

urine. The analytical performance of the FOF-analyzer 

was investigated against the high performance liquid 

chromatography – electrochemical detection (HPLC-ED) method. 

The FOF-analyzer showed lower detection limits and larger 

linear ranges for determination of dopamine, norepinephrine and 

epinephrine than the HPLC-ED and other methodologies 

such as HPLC-fluorescence. These advantages combined with the 

compact design, low-scale instrumentation, and effective cost 

of analysis makes this system a viable alternative to the 

existing methodologies for the determination of catecholamines 

in clinical samples. 


for Competitiveness Factors – COMPETE and by national 

funds via FCT (Fundacio para a Ciencia e a Tecnologia, 

Portugal) within the framework of the research project 

CATSENSOR (references FCOMP-01-0124-FEDER-010896 

and PTDC/QUI/70970/2006). This work was also funded 

through scholarships - references SFRH/BD/60429/2009, 

SFRH/BPD/65410/2009, and SFRH/BPD/73781/2010 under 

QREN-POPH funds, co-financed by the European Social Fund 

and Portuguese National Funds from MCTES. 

Keywords: fluorescence; biosensors; liquid chromatography; 



s1121 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 1 8 

deterMinAtion of CAdMiuM And LeAd in the 

PPB rAnGe By AtoMiC ABSorPtion 

M. eL-rAiS 1 , A. etorKi 1 

1 Tripoli University, chemistry, Tripoli, Libyan Arab Jamahiriya 

Great Socia 

In this study, a method is developed for the determination 

of cadmium and lead from fresh waters by flame atomic 

absorption spectroscopy (FAAS) after preconcentration by 

solvent extraction using Dithizone-ammonium pyrrolidine 

dithiocarbamate (APDC)-chloroform and compared to two other 

systems: APPC-chloroform and Dithizone-chloroform. Recovery 

values obtained in the preliminary studies after 20 fold 

preconcentration for lead and cadmium showed that the 

APDC-Dithizone system was in the same level or better when 

compared with the other two systems. The APDC-Dithizone 

system was then applied to ground waters. The Pb concentration 

was high enough to be determined by FAAS, but for Cd it was 

too low to be determined and GFAAS was tried for the 

determination of Cd. However, because of the poor condition of 

the instrument it became necessary to abandon the use of GFFAS 

and instead to increase the concentration factor. A 100 fold 

concentration factor was tested, combined with FAAS, with 

different concentration of Pb and Cd. The minimum measurable 

concentration for Cd was 0.2 ppb with average % recovery 

99.1 ± 5.7 and the minimum measurable concentration for Pb 

was 1 ppb with average % recovery 102 ± 10.2. 

Atom Trapping, slotted quartz tube (SQT) for increasing the 

sensitivity, was investigated for direct determination of analyte 

for FAAS. The sensitivity increased by 3 folds for Cd and Pb. 


P - 0 5 1 9 

non-AqueouS CAPiLLAry eLeCtroPhoreSiS 

APPLied to deterMinAtion of ACid BASe 

diSSoCiAtion ConStAntS of AzAheLiCeneS 

M. eLiAS 1 , A. AndronovA 2 , A. JAnCAriK 3 , 

J. KLivAr 2 , M. SAMAL 2 , J. zAdny 2 , i. StArA 2 , 

i. StAry 2 , v. KASiCKA 1 


Electromigration Methods, Prague 6, Czech Republic 


Ivo Stary, Prague 6, Czech Republic 



Azahelicenes represent unique helically chiral polyaromatic 

heterocycles [1] , which are sparingly soluble or insoluble in water. 

Non-aqueous capillary electrophoresis (NACE) in methanolic 

background electrolytes (BGEs) with UV-absorption detection has 

been employed to determine acid-base dissociation constants 

(pKa) of ionogenic groups of selected azahelicenes. Acid-base 

dissociation constants of azahelicenes were calculated from the 

dependence of their effective electrophoretic mobilities on pH by 

nonlinear regression analysis. The effective mobilities were 

determined by NACE in methanolic BGEs within a wide pH 

range 2.1 – 11.2. NACE separations were performed in a 

home-made CE device equipped with UV-absorption detector 

operating at 206 nm and on a P/ACE MDQ instrument equipped 

with photodiode-array detector (Beckman Coulter, Fullerton, CA, 

USA) set at 206 nm. Experimental data were collected by 

chromatography station Clarity (Data-Apex, Prague, CR) and by 

software P/ACE MDQ System, version 32 Karat (Beckman 

Coulter), respectively. All results were handled by program Origin 

6.1 (OriginLab, Northampton, MA, USA). Separations were 

performed in fused silica capillary (id/od = 50/375 µm, 

effective/total length 201/306 mm, outer polyimide coating, 

internally untreated). Applied voltage for separations was 12 kV 

(anode at the injection capillary end). Dimethyl sulfoxide was 

used as electroosmotic flow (EOF) marker [2, 3] . 

Acknowledgement: The work was supported by the GACR 

(grant Nos. 203/08/1428, P206/12/0453, P207/10/2207 and 

203/09/1766), GA ASCR (grant No. IAA400550916 and 

IAA400550916) and by the ASCR, Research Project 

RVO61388963. 

references: 

1. a) Misek J., Teply F., Stara I. G., Tichy M., Saman D., 

Cisarova I., Vojtisek P., Stary I., Angew. Chem. Int. Ed. 

2008, 47, 3188–3191; 

b) I. Stary, I. G. Stara in Strained Hydrocarbons 

(Ed.: H. Dodziuk), Wiley-VCH, Weinheim, 2009, 

pp. 166–176. 

2. Ehala S., Misek M, Stara I. G., Stary I., Kasicka V., 

J. Sep. Sci. 2008, 31, 2686–2693. 

3. Psurek A., Scriba G. K. E., Electrophoresis 2003, 24, 

765–773. 

Keywords: Non-aqueous capillary electrophoresis; acid-base 

dissociation constants; azahelicenes; 



s1122 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 2 0 

SACChAride SenSinG And MoLeCuLAr LoGiC At 

the few MoLeCuLe LeveL of the rePortinG 

dye 

M. eLStner 1 , A. SChiLLer 1 


The allosteric indicator displacement assay of a boronic acid 

appended viologen (BBV) and a fluorescent dye can detect 

saccharides in physiological conditions [1–4] . 

We investigated the interaction of the saccharide receptor 

and the reporter molecule with fluorescence correlation 

spectroscopy (FCS). This sensitive technique allows the detection 

of fluorescence signals from single/few molecules. FCS analyzes 

fluorescence intensity fluctuations with a confocal microscope 

mainly caused by local changes in concentration of the fluorescent 

dye. 

On the basis of a nanomolar dye solution we showed the 

step-wise quenching of a fluorescent perylene diimide (PDI) with 

different BBV concentrations, followed by the fluorescence 

recovery with fructose (0 – 2 mM). Fluorescence transients were 

further used to calculate autocorrelation curves. 

This switchable system allows to turn off the PDI 

fluorescence by adding the BBV-quencher and turn it on again via 

addition of fructose. The sensor forms a gate with the material 

implication (IMP) logic function, working with chemical input 

and generates a fluorescence output. The autocorrelation function 

yields the complementary notimplication function simultaneously. 

IMP is an extraordinary logic function from which all other 

Boolean-operators can be constructed, including only a trivial 

FALSE-operation [5] . Thus, IMP and FALSE operations are able 

to form adder and multiplicator logic circuits, based on the 

saccharide probe and fructose. 

references: 

1. A. Schiller, R. Wessling, B. Singaram, Angew. Chem. Int. 

Ed. 2007, 46, 6457. 




3. A. Schiller, B. Vilozny, R. A. Wessling, B. Singaram, 

in Reviews in Fluorescence 2009, Springer, 2011, 155. 

4. B. Vilozny, A. Schiller, R. Wessling, B. Singaram, 

Anal. Chim. Acta 2009, 649, 246. 

5. M. Elstner, K. Weisshart, K. Müllen, A. Schiller, 

J. Am. Chem. Soc. 2012, DOI: 10.1021/ja303214r. 

Keywords: Fluorescence spectroscopy; Sensors; fret; 

Carbohydrates; 


P - 0 5 2 1 

AdSorPtion Study of MetAL ionS on 

eLeCtroCheMiCALLy SyntheSized 

PoLyAniLine 

A. etorKi 1 , M. ABuein 1 

1 Tripoli University, chemistry, Tripoli, Libyan Arab Jamahiriya 

Great Socia 

The present work deals with the study of uptake behavior of 

Hg(II), Pb(II), Cd(II) and Zn(II) ions by Electrochemically 

synthesized Polyaniline using batch equilibration technique with 

both single and binary mixtures. The effect of the various 

parameters such as electrochemically synthesis method, physical 

oxidation state of the polymer, polymer thickness, solution pH 

and metal ion concentration on the adsorption, kinetics and 

efficiency were investigated. 

The results showed avary broad concentration range of the 

metal ions from (0.2 to 10 mg/L) can be adsorbed on the polymer 

at pH = 5.8 (efficiently >98%). The adsorption capacity of the 

polymer to different concentrations of metal ions was evaluated 

as the milligram of metal ions by one gram of various forms of 

the polymer. The DC conductivity measurements were also 

employed on the solid polymer before and after adsorption of 

metal ions. The experimental adsorption date was fitted to 

different mathematical isotherms to estimate the binding constant 

of metal ions with the polymer in both single and mixed ion 

solutions. 



s1123 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 2 2 

deterMinAtion of iron (ii), iron (iii) And 

totAL iron in SoMe SS-thALASSeMiA PAtientS 

uSinG different AnALytiCAL teChniqueS 

n. fAKhre 1 , d. ALi 1 

1 Univ. of Salahaddin, Chemistry, Erbil, Iraq 

Iron as an essential element for living organisms, is oxygen 

transport and its role in oxidative-reductive reaction that utilize 

its alternative ferrous-ferric states. The biological importance of 

iron is widely attributed to its chemical properties, there are two 

oxidative forms, ferrous (Fe2+) and ferric (Fe3+) iron. Failure in 

this control result in anemia or iron overload. Thalassemia is a 

pediatric inherited disease, it is a type of chronic, microcytic 

anemia. It is gene-linked disease that can cause serious health 

problems because it can lead to the destruction of red blood cells. 

There are many well-known analytical methods for determination 

of iron (II) and iron (III). A mong these methods: gravimetric, 

titrimetric, potentiometric, conductometric, batch and flow 

– injection spectrophotometric methods. In the present study, two 

batch spectrophotometric, atomic absorption spectrometric and 

biolabo kit methods have been used for determination of iron (II), 

iron (III) and total iron. The present methods have the advantages 

of high sensitivity, low cost reagent, low operation cost, 

simplicity, speed and their applications for determination of iron 

(II) and iron (III) in some serum samples of normal human and 

β-thallasemia patients in Erbil city. 

For the first time especially in Erbil city attempts were made 

to use zero, first and second derivative spectra to identify the 

serum samples of some β-thallasemia patients from the normal 

human serum samples due to the appearance and resolution of 

peaks in both cases. 

Keywords: Determination; Iron; ß-Thalassemia Patients; 

Analytical Techniques; 


P - 0 5 2 3 

deveLoPMent of new CoLoriMetriC redox 

indiCAtorS for nAdh viSuALizAtion 

M. foMin 1 , n. SteinKe 1 , B. KÖniG 2 , C. horn 1 

1 Roche Diagnostics GmbH, Diabetes Care, Mannheim, 

Germany 

2 Universität Regensburg, Institut für Organische Chemie, 


Nicotinamide adenine dinucleotide/reduced nicotinamide 

adenine dinucleotide (NAD+/NADH) plays an important role as 

cofactor in numerous biocatalized processes, including energy 

metabolism, mitochondrial responses, immunological functions, 

aging and cell death. Particularly, the NAD+/NADH couple acts 

as the cofactor taking part in more than 300 dehydrogenase 

enzymatic reactions. Intracellular NADH also can serve as a 

natural biomarker for cellular redox reactions, a myriad of 

metabolic activities, and mitochondrial anomalies under different 

pathophysiological conditions. Consequently, numerous strategies 

have been proposed for NADH detection, including fluorescence 

imaging, enzymatic assay, high-performance liquid 

chromatography, electrospray ionization mass spectrometry, 

capillary electrophoresis, and electrochemical assay. [1] Under 

certain conditions, a colorimetric methodology may be preferred. 

For example, colorimetric assays are not sensitive to 

autofluorescence background, do not require complex instruments 

and demonstrate high sensitivities. [2] However existing redox 

indicators have multiple disadvantages: limits in UV and green 

range of light, poor solubility in water, low reactivity, lability to 

UV-light, water and oxygen. 

Quinones have been known as representative organic 

electron acceptors for NADH oxidation due to their strong 

oxidizing ability as well as stability of the reduced species. It was 

found that UV-vis spectrum of quinone derivatives after NADH 

reduction exhibit absorptions in the longer-wavelength region. [3] 

With these in mind, we have decided to design new derivatives 

and analogues of quinones and test them for NADH visualization. 

The NADH reduction of new quinone-type electron 

acceptors was seen by naked eye and monitored by UV-vis 

extinction spectra. Design, synthesis and UV-vis properties of 

several new indicators for NADH detection will be discussed. 

references: 

1. Liu, S.; Du, Z.; Li, P.; Li, F. Biosensors and Bioelectronics 

2012, (in press). 

2. Zhu, A.; Romero, R.; Petty, H. R. Analytical Biochemistry 

2011, 419, 266. 

3. Heindl, D.; Herrmann, D.; Hönes, D.; Josel, D.; 

Junius-Comer, D.; Merdes, D.; Schmidt, D.; 

Selbertinger, D.; U. S. Patent 6,057,120: May 2, 2000. 

Keywords: Redox chemistry; Biosensors; Dyes/Pigments; 

Cofactors; Quinones; 



s1124 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 2 4 

SiMuLtAneouS AnALySiS of CirCuLAtinG 

25-hydroxy-vitAMin d3, 25-hydroxy-vitAMin 

d2, CArotenoidS, retinoidS, toCoPheroLS, 

And oxidized And reduCed CoenzyMe q10 By 

hPLC with Photo diode-ArrAy deteCtion 

uSinG C18 And C30 CoLuMnS ALone or in 

CoMBinAtion 

A. frAnKe 1 , C. MorriSon 1 , L. CuSter 1 , x. Li 1 , 

J. LAi 1 

1 University of Hawaii Cancer Center, Cancer Biology, 

Honolulu, USA 

Modern epidemiological and clinical studies commonly 

require high-throughput analyses that provide multiple biomarkers 

from a small volume, single blood specimen. Essential circulating 

lipid-soluble compounds play important roles in health and 

disease prevention and can, therefore, serve as useful biomarkers. 

We sought to develop a simple, fast, affordable, and highly 

accurate HPLC assay with diode array detection (DAD) that 

simultaneously measured all circulating lipid-soluble compounds. 

In our study, 25-hydroxy vitamin D and D , retinol, alpha- 

2 3 

, beta-, gamma-, and delta-tocopherol, all major carotenoids 

including their isomers, and ubiquinol-10 and ubiquinone-10 were 

accurately quantitated in a single chromatographic run using 

a) a C18 column alone; b) a C30 column alone; or c) C18 and 

C30 columns connected in series. After several modifications, we 

refined our methods to resolve all analytes within 45–90 minutes 

or fewer analytes within 10 minutes. 

The C18 alone excellently separated all major analytes but 

insufficiently resolved the vitamin D metabolites, lycopene 

isomers, and resulted in co-elution of lutein with zeaxanthin and 

beta- with gamma-tocopherol. The C30 alone was superior 

at separating the carotenoid isomers and beta- from 

gamma-tocopherol, but failed to resolve carotenoids from Q10 

compounds. Connecting C18 and C30 in series with a DAD 

between and after the columns resulted in accurate quantitation 

of all analytes, however, was unacceptably long (90 minutes) due 

to the very low flow rate requirement imposed by back pressure 

limitations. Connecting C18 and C30 in series with only one DAD 

after the C30 column also resulted in carotenoid- Q10 

interferences, but was remedied by adding a 6-port valve between 

the columns, which permitted resolution of all analytes in 

45 minutes with a possible shortening of 15–20 minutes 

depending on the analytes included. In summary, our proposed 

methods can be custom designed to meet the needs of individual 

projects depending on analyte requirements. 

Keywords: Analytical Methods; Liquid Chromatography; 

UV/Vis Spectroscopy; 


P - 0 5 2 5 

utiLizAtion And oPtiMizAtion of extrACtion 

By uLtrASoniC ProBe for GAS 

ChroMAtoGrAPhiC/MASS SPeCtroMetriC 

AnALySiS of ProPeLLAnt CoMPonentS 

o. fryS 1 , P. CeSLA 1 , P. BAJerovA 1 , K. venturA 1 



Analysis of explosives, mainly smokeless powders and 

explosives mixtures, is an integral part of the production of 

explosives, fulminating compounds or propellants. Nowadays, 

chromatographic methods are used for these analyses, for example 

high performance liquid chromatography with ultraviolet 

detection (HPLC/UV). Modern methods and classical methods of 

propellant analysis (titration, gravimetry) require sample 

preparation to analysis. It means that target analytes have to be 

isolated from sample for their analysis. Isolation step of propellant 

analysis includes extraction methods usually. The extraction 

method is always selected according to the matrix of a sample and 

kind of sample. Conventional method for preparation of 

propellant samples and explosives samples is Soxhlet extraction 

with dichloromethane or diethyl ether as extraction agent. 

A method for ultrasonic extraction by ultrasonic probe of 

nitroglycerin, triphenyl amine and acetyl tributhyl citrate 

presented in double-base propellant samples following by the gas 

chromatography/mass spectrometry analysis was developed. 

A central composite design of the experiments and response 

surface modeling was used for optimization of the time, amplitude 

and sample amount. The dichloromethane was used as the 

extractant solvent. The optimal extraction conditions with respect 

to the maximum yield of the lowest abundant compound triphenyl 

amine were found at the 20 min extraction time, 35 % amplitude 

of ultrasonic waves and 2.5 g of the propellant sample. The results 

obtained under optimal conditions were compared with the results 

achieved with validated Soxhlet extraction method. The extraction 

yield for acetyl tributhyl citrate using both extraction methods was 

comparable; however, the yield of extraction by ultrasonic probe 

of nitroglycerin and triphenyl amine was lower than using Soxhlet 

extraction. 

Keywords: smokeless powder; extraction by ultrasonic probe; 

optimization; Soxhlet extraction; gas chromatography/mass 

spectrometry; 



s1125 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 2 6 

inveStiGAtion wAter-SoLuBLe And 

LiPoSoLuBLe AntioxidAntS uSinG MetAL 

CoMPLexeS 

e. GerASiMovA 1 , i. KrAvetS 1 , A. ivAnovA 1 , 

A. MAtern 1 

1 Ural Federal University named after the first President of 

Russia B.N.Yeltsin, Institute of Chemistry and Technology, 

Yekaterinburg, Russia 

Currently, the great attention is given to development of 

methods for determination of antioxidant activity (AOA). The 

most accessible and express method for determining of AOA are 

electrochemical methods. 

The simple potentiometric method determination of AOA 

has been proposed. It is based on the interaction of antioxidants 

of the sample with the mediator system 

K [Fe(CN) ]/K [Fe(CN) ] 3 6 4 6 [1-2] . However, the using of 

water-soluble complexes does impossible to use this method in 

organic solvents for the study of liposoluble compounds with 

antioxidant properties, which are the most important class of 

antioxidants. The approach which based on the using of 

metal-organic compounds in organic solvents as a redoxmediators 

was offered. Ferrocene and hetaryl-ferrocenes systems 

and their oxygenized salts have been investigated. The using of 

these systems is limited to a small stability of salts ferrocenium 

in organic solvents. 

A new approach based on measurement of the electrode 

potential after the chemical reaction between the antioxidants of 

the sample and the oxidized form of the metal complex. It is leads 

to reducing of number of measurement steps. The use of singular 

form of the reagent can significantly increase the number of 

reagents used and the range of the objects in different solvents. 

The validity of the proposed approach is confirmed by the 

“introduced-found” method in the case the well-known 

interactions model of K [Fe(CN) ] and of water-soluble 

3 6 

antioxidants. Diketonates of metals, particularly iron (III), showed 

the greatest perspective in use in organic solvents. Experiments 

with this complex were carried out on models of phenolic 

antioxidants in acetonitrile and ethyl alcohol. 

references: 

1. Kh.Z. Brainina, L.V. Alyoshina, E.L. Gerasimova et al. 

// Electroanalysis, 2009, V.21, P. 618-624. 

2. Kh.Z. Brainina, A.V. Ivanova, E.N. Sharafutdinova et al. 

// Talanta, 2007, V. 71, P. 13–18. 

Keywords: Antioxidant; Metal complexes; Potentiometry; 


P - 0 5 2 7 

A new Method for A CoMPLete 3-d AnALySiS 

of orGAnoMetALLiCS in A few hourS 

A. GeriSCh 1 , M. AdAM 1 , J. MizerA 2 , B. SChuMM 3 , 

B. Beyer 4 

1 Bruker AXS GmbH, SC-XRD, Karlsruhe, Germany 

2 Koordinationschemie, TU Dresden, Dresden, Germany 

3 Inorganic Chemistry I, TU Dresden, Dresden, Germany 

4 Fraunhofer Institute, Photonic Microsystems, Dresden, 

Germany 

Single crystal X-ray diffraction (SC-XRD) is a powerful tool 

for synthetic chemists. It is the most unambiguous method to 

accomplish a ‘3D analysis’ in the course of one single experiment. 

This complements and extends information obtained using other 

methods, such as NMR, IR, UV, MS, ORD and many more. The 

‘3D analysis’ obtained using SC-XRD reveals constitution, 

configuration and conformation, with accurate information about 

bond lengths, bond angles and the arrangement of the molecules 

within the sample. Unfortunately, synthetic chemists often had 

limited access to SC-XRD since they had to send their samples 

to external X-ray facilities. These instruments require trained 

specialists, already for collecting the required data. This made the 

3D analysis a time consuming tedious undertaking in the past. 

Now, the SMART X2S greatly simplifies the availability of 

SC-XRD in your laboratory. The SMART X2S desktop system 

helps controlling your synthesis by true walk away automation. 

Recently solved structures (UC H N O ; IrC H N Cl) will be 

45 22 2 5 30 20 2 

discussed to highlight the system’s main features. 

Keywords: Bruker; SMART X2S; single crystal diffraction; 



s1126 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 2 8 

ACtivity of diSinfeCtAnt SoLutionS 

B. GJorGJeSKA 1 

1 University Goce Delcev Stip, Faculty of Medical Science, Stip, 

Macedonia 

Knowing antiseptic activity of chemical disinfectant 

substances has a great practical value. It is evidential that there is 

the need for defining standard technique for quantitative 

determination of bactericidal activity of chemical disinfectant 

substances. Solution of phenol (5%) was considered as referent 

standard for evaluation of efficacy of disinfectant aqueous 

solutions. On the other side the methods for evaluation of 

antiseptic activity of disinfectant aqueous solutions are 

microbiological. 

The aim of this study is to develop a new empirical 

coefficient which is capable to express the various 

physicochemical properties of disinfectant solutions on 

bactericidal activity. This parameter (Disinfection Activity 

Coefficient of Solution - DACS) has to express capability for 

comparison and prediction of disinfectant activity. The DACS 

index, which is the sum of four terms (fluidity, surface tension, 

redox potential and osmolality) is in good correlation with the 

activity at different disinfectant aqueous solutions. The DACS 

index can be calculated using additive and statistical models. 

Statistical model is adequate for evaluation of different 

disinfectant solutions because of better expressing the bactericidal 

activity then additive model. For analyze of various dilutions of 

one disinfectant there is no significant difference between this two 

models. The usefulness of DACS is demonstrated for analyze of 

bactericidal activities on different disinfectant solutions 

containing boric acid, chlorhexidne, chlorhexidine with cetrimide, 

chloroxylenol, chlorophen, eosin, hydrogen peroxide, phenyl 

mercury borate, povidon-iodine, thiomersal, tosilchloramide and 

phenol. Results for bactericidal activities obtained from 

microbiological tests on Staphylococcus aureus were compared 

with activities predicted by DACS. As the conclusion, it is 

considered good correlation between experimental and calculated 

values for bactericidal activity. 

Keywords: disinfectant; bactericidal activity; 


P - 0 5 2 9 

eLeCtroCheMiCAL ProPertieS of 

CuPPer(ii)-GLyCine CoMPLex 

e. GoKMeSe 1 , e. ÖLzer 1 , A. KASArCi 1 

1 Hitit University, Chemistry, Corum, Turkey 

The diversity of inorganic compounds and their applications 

in medicine encompass cancer chemotherapy, arthritis, 

antimicrobial agents, and many others. Metal complexes of 

biologically important ligands are sometimes more effective than 

the free ligands. Cu(II), Ni(II), Co(II) and Zn(II) metal cations are 

recognized as essential elements that are distributed in biological 

systems including cells and body fluids. Also, copper exists in 

nuclei and plays a key role in determining DNA quaternary 

structure. There are a few studies on the electrochemical 

investigation of glcyinato complexes of metal cations. In this 

study Cupper(II)-Glycine complex was synthesized and 

characterized firstly and then the electrochemical behaviour of 

this complex hes been investigated by the use of several 

electrochemical methods in DMSO on glassy carbon electrode. 

The number of electron transferred (n) and diffusion coefficient 

(D) in the reduction of the complex were calculated by cyclic 

voltammetric and chronoamperometric results for both the 

complex and ferrocene with ultramicro electrode. The mechanism 

confirmed by comparing experimental cyclic voltammogram to 

the theoretical one drawn with simulation software. On the other 

hand the standard rate constant (k ) and transfer coefficient (a) of 

s 

the electrochemical reaction were also calculated from this 

simulation study. 

Keywords: Cupper(II)-Glycine complex; Transititon metal 

complexes; Electroanalytical chemistry; ultramicroelectrode; 

cyclic voltammetry; 



s1127 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 3 0 

eLeCtroCheMiCAL BehAviour of 

CoBALt(ii)-GLyCine CoMPLex 

f. GÖKMeSe 1 , G. KurSun 1 , d. A. KÖSe 1 


The electrochemical properties of Cobalt(II)-Glycine 

complex has been investigated by the use of several 

electrochemical methods in DMSO on glassy carbon electrode. 

Metal complexes of biologically important ligands are sometimes 

more effective than the free ligands. Co (II), Ni(II), Cu(II) and 

Zn(II) metal cations are recognized as essential elements that are 

distributed in biological systems including cells and body fluids. 

It is well documented that heterocyclic compounds play a 

significant role in many biological systems, especially N-donor 

ligand systems being a component of several vitamins and drugs. 

The metal-binding properties of carbohydrates have been shown 

to be of fundamental importance in many biochemical processes 

such as the transport and storage of metals, the function and 

regulation of metalloenzymes, the mechanism of action of metal 

–containing pharmaceuticals, and toxic metal metabolism. There 

are a few studies on the electrochemical investigation of glcyinato 

complexes of metal cations. In this study Cobalt(II)-Glycine 

complex was synthesized and characterized firstly and then the 

electrochemical reduction of this complex was investigated by 

several techniques. The number of electron transferred was 

calculated by the use of ultramicro electrode. The reversibility 

tests were applied to elucidate the reaction mechanism. The 

mechanism also confirmed by simulation studies. k and a values 

s 

were calculated from simulation studies. 

Keywords: Cobalt(II)-Glycine complex; Transititon metal 

complexes; Chronoamperometry; Electroanalytical chemistry; 

Electrochemical simulation; 


P - 0 5 3 1 

LABeL-free eLeCtroCheMiCAL APtASenSorS 

with SuB-feMtoMoLAr deteCtion LiMit 

towArdS throMBin 

h. w. Gu 1 , J. Lee 1 , G. S. ChA 1 , h. nAM 1 , J. h. Shin 1 

1 Kwangwoon University, Department of Chemistry, Seoul, 


Immunosensors based on aptamers as a new molecular 

recognition element have received great attention due to aptamer’s 

specific binding to a wide range of target molecules including 

proteins, enzymes, and even small organic molecules. To achieve 

more robust utility for aptamer sensors, it is particularly important 

to develop label-free detection methods. Several strategies of 

label-free immunoassay have been demonstrated by employing 

electrochemical impedance spectroscopy (EIS), quartz crystal 

microbalance (QCM), surface plasmon resonance (SPR) 

spectroscopy, and atomic force microscope (AFM) cantilever. 

Herein, we report on a new approach to design an electrochemical 

aptamer sensor for a simple, label-free detection of thrombin as a 

model target protein. The thiolated thrombin-binding aptamer 

(TBA) is immobilized on the gold electrode surface based on 

well-known gold-thiol chemistry, followed by immobilization of 

1-mercapto-6-hexanol on the electrode to prevent non-specific 

binding of thrombin and other proteins. The specific binding of 

thrombin with TBA leads to changes in the interfacial electron 

transfer of electrochemically active probes (e.g., ferrocene and 

ferricyanide). Indeed, the surface coverage with thrombin 

prohibits the access of electrochemically active probes to the 

electrode surface. To amplify such a blocking effect associated 

with thrombin-TBA complex formation, we employ silica 

nanoparticles as a scaffold to design “macromolecular 

electroactive probes.” The ferrocene-modified silica nanoparticles 

are synthesized by carbodiimide coupling chemistry between 

ferrocene-carboxylic acid and amines functionalized on the silica 

surface. The effects of particle size (7 to 14 nm), surface charge, 

and density of ferrocene on the silica surface on sensor 

performance (e.g., sensitivity and detection limit) will be 

discussed. 

Keywords: Aptasensor; Label-free; Ferrocene-modified silica 

nanoparticle; Electrochemical sensing; Thrombin; 



s1128 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 3 2 

quAntitAtive deterMinAtion of 

LAnSoPrAzoLe And itS iMPuritieS By hPLC 

n. Gunden GoGer 1 , C. SACinti 1 , 

S. yAriMKAyA BAS 1 

1 Gazi University Faculty of Pharmacy, Analytical Chemistry, 

Ankara, Turkey 

Lansoprazole, 2-[(3-methyl-4-(2,2,2-trifluoroethoxy) 

pyridin-2-yl) methylsulfinyl] -1H-benzoimidazole, is a 

proton-pump inhibitor (PPI) which prevents the stomach from 

producing gastric acid. The aim of the study is to seperate and 

determine Lansoprazole and its impurities, Lansoprazole sulphide, 

Lansoprazole sulphone, Lansoprazole N-oxide, by HPLC. 

A precise, accurate, sensitive and fast model is described for 

quantitative determination of these compounds in pharmaceutical 

forms. A reversed phase C18 column (5 µm, 150 mm x 4.60 mm, 

i.d.) and o-phosphoric acid: water: methanol, 5:245:750, v/v, 

mobile phase were used. The flow rate was 1.0 mL/min and 255 

nm was selected for UV detection wavelength. The recoveries 

were in the range of 98.7-100.6% for Lansoprazole. The results 

for Lansoprazole in tablets were in agreement with the labeled 

quantities. 

Keywords: Analytical Methods; Liquid Chromatography; 


P - 0 5 3 3 

CyCLiC voLtAMMetriC Study of diffuSion 

CoeffiCientS of rAdiCAL ionS And the 

CorreSPondinG neutrAL MoLeCuLeS in rooM 

teMPerAture ioniC LiquidS 

y. hA thi hAi 1 , G. GrAMPP 1 , S. LAndGrAf 1 

1 Graz University of Technology, Physical and Theoretical 

Chemistry, Graz, Austria 

The ratio D /D , where D and D are the diffusion 

ox red ox red 

coefficients of the electrogenerated radical anion and of the 

corresponding neutral molecule, respectively, is commonly found 

to be one in organic solvents. Sometimes, this is not the case in ionic 

liquids, as shown by Compton et al [1, 2] who reported that the 

diffusion coefficients of ferrocenium cation, cobaltocenium cation 

and TMPPD +. (TMPPD: N,N,N',N'-tetramethyl-pphenylenediamine) 

are smaller than those of the reduced forms. 

Similar results have been obtained by Hapiot et al for aromatic 

nitro compounds [3] and ferrocene derivative [4] . Therefore, an 

incorrect assumption about the ratio D /D leads to errors in 

ox red 

calculation of the heterogeneous electron transfer rate constant. 

In this work, diffusion coefficients of an electroactive 

neutral substance, tetracyanoethylene (TCNE) and of the 

potassium salt of the corresponding radical anion have been 

measured by cyclic voltammetry in five different room 

temperature ionic liquids: emim + - + - + - BF , bmim PF6 , bmim BF4 , 

4 

omim + - + - PF , omim BF4 . The values of the diffusion coefficients 

6 

depend on the inverse viscosity for all ionic liquids. The diffusion 

coefficients of TCNE-. are lower than those of TCNE whichever 

the medium. The results found for the diffusion coefficients in 

these ionic liquids are used to determine the heterogeneous 

electron transfer rate constants. 

references: 

1. E. I. Rogers, D. S. Silvester, D. L. Poole, L. Aldous, 

C. Hardacre, and R. G. Compton; J. Phys. Chem. C 2008; 

112; 2729-2735. 

2. E. I. Rogers, D. S. Silvester, S. E. Ward Jones, L. Aldous, 

C. Hardacre, A. J. Russell, S. G. Davies and R. G. Compton; 

J. Phys. Chem. C 2007; 111; 13957-13966. 

3. D. Zigah, J. Ghilane, C. Lagrost, and P. Hapiot; 

J. Phys. Chem. B 2008; 112; 14952-14958. 

4. O. Fontaine, C. Lagrost, J. Ghilane, P. Martin, G. Trippé, 

C. Fave, J.-C. Lacroix, P. Hapiot, H. N. Randriamahazaka; 

Journal of Electroanalytical Chemistry; 632; 2009; 88-96. 

Keywords: Cyclic voltammetry; Ionic liquids; 

Electrochemistry; Electron transfer; 



s1129 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 3 4 

Study of ionizAtion of oPiAteS in urine 

SAMPLeS for MASS SPeCtroMetriC AnALySiS 

L. hArtMAnovA 1 , L. BorovCovA 1 , L. KAreL 1 

1 RCPTM Palacky University in Olomouc, Department of 

Analytical Chemistry, Olomouc, Czech Republic 

Opiates are substances which are naturally occurring in 

opium or semi-synthetic substances. They exhibit narcotic effects 

and relieve the pain but also create psychological a physical 

dependence. They cause mood swings (euphoria, sedation), 

tremor, insomnia etc. In this study, ionization of three opiate 

representative (morphine, 6-acetylmorphine and morphine-3b-D- 

-glucuronide) using electrospray and nanoelectrospray was 

studied. 

Experiments were performed using LCQDUO Ion Trap 

(Thermo Finnigan USA) equipped with two ion sources 

– electrospray (ESI) and nanoelectrospray (nanoESI). Their 

tolerance to salt in samples was evaluated. Nanoelectrospray 

showed a higher tolerance and was used for urine sample analysis. 

Human urine was spiked by standards; deuterated substances were 

used as internal standards. Solid phase extraction was used for 

sample purification and analyte preconcentration. SPE columns 

Waters OASIS MCX Cartridge were used. Phosphate buffer 

(pH = 8,5) for conditioning, acetate buffer (pH = 4) elution of 

impurities and methanol:water 98:2 for analyte elution. Eluates 

were evaporated to dryness and dissolved in 100ul of 

methanol:water:HCOOH 50:49:1 (v/v). These samples were 

analyzed by nanoESI without chromatographic separation. 

Morphine and 6-acetylmorphine can be detected in urine at level 

0,2 mg/l. 


P - 0 5 3 5 

A BioMiMetiC SenSor SurfACe to deteCt 

Anti-BetA2-GLyCoProtein-i AntiBodieS AS A 

MArKer for AntiPhoSPhoLiPid SyndroMe 

u. hiLBiG 1 , o. BLeher 1 , A. Le BLAnC 1 , 

G. GAuGLitz 1 

1 University of Tuebingen, Institut für physikalische und 

theoretische Chemie Arbeitskreis Prog. Gauglitz, Tuebingen, 

Germany 

A biomimetic sensor has been developed, that allows for 

quantification of autoantibodies related to the antiphospholipid 

syndrome (APS). Autoantibodies directed against the 

β2-glycoprotein-I (β2GP-I) are known as the best markers for 

diagnosis of APS, however, detection of such antibodies is still a 

challenge. The epitopes of β2GP-I are exposed upon binding to 

negatively charged membranes. The surface of the sensor chips 

was therefore modified with such type of membranes, on which 

β2GP-I molecules were subsequently immobilized as recognition 

elements. Using the label-free method, reflectometric interference 

spectroscopy, it was possible to quantify anti-β2GPI antibodies 

and to calibrate the sensor chip in buffer. A mild regeneration 

procedure allows for many consecutive measurements without 

stripping off the membrane in between. 

Keywords: Reflectometric interference spectroscopy (RIfS); 

Biosensors; Antibodies; Membranes; Liposomes; 



s1130 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 3 6 

A CoMPAriSon of MALdi MAtriCeS BASed on 

LithiuM SALtS for AnALySiS of 

hydroCArBonS And wAx eSterS 

P. horKA 1 , v. vrKoSLAv 2 , K. PeCKovA 1 , J. CvACKA 2 

1 Faculty of Science Charles University in Prague, Analytical 


2 Institute of Organic Chemistry and Biochemistry v.v.i. 

Academy of Sciences of the Czech Republic, Mass 

Spectrometry, Prague 6, Czech Republic 

Matrix assisted laser desorption/ionization (MALDI) is an 

effective method for a rapid characterization of lipid mixtures. 

Data obtained from MALDI spectra are useful for quick 

comparison of the samples composition or chemotaxonomic 

purposes. MALDI is a suitable method for analysis of all classes 

of lipids from complex polar lipids to simple and completely nonpolar 

lipids. The processes taking place in MALDI are rather 

complicated and have not been fully understood yet. The choice 

of MALDI matrix depends on the analyte structure. For neutral 

lipids only few effective matrices have been described. In this 

work several new matrices based on lithium salts of organic 

aromatic acids (lithium 2,5-dihydroxytereftalate, lithium 

2,5-dimethoxybenzoate, lithium α-cyano-4-hydroxycinnamate, 

lithium sinapate, lithium benzoate, lithium salicylate, lithium 

vanillate) were tested as potential matrices for MALDI-MS 

analysis of hydrocarbons (HCs) and wax esters (WEs). As shown 

previously, the ionization of neutral lipids occurs via attachment 

of lithium cation, which yields [M + Li] + adducts. The new 

matrices were evaluated and compared with lithium 

2,5-dihydroxybenzoate, which is a proven matrix for MALDI 

analysis of lipids. Several parameters, including laser power, 

sample deposition protocols and matrix to analyte ratio were 

optimized for each matrix. The signal intensity and repeatability 

was compared using standards (stearyl behenate, n-triacontane). 

In addition, the nature of matrix ions and their range on m/z scale, 

absorbance at laser wavelength 337 nm and solubility in various 

solvents were studied. The morphology of the sample deposits 

were discussed based on images taken from a scanning electron 

microscope. The applicability of the matrices was tested on 

natural samples (WEs from bees wax and plant waxes, insect 

cuticular HCs). The best results were achieved with lithium 

vanillate. It was found that effective matrices contain hydroxyl 

group. A correlation between efficiency and a content of crystal 

water in the matrix crystals was also observed. 

Acknowledgement: This work was supported by Czech Science 

Foundation GACR (Project No. 203/09/0139) and the Academy 

of Sciences of the Czech Republic (Project RVO: 61388963). 

Keywords: MALDI matrices; wax esters; hydrocarbons; 


P - 0 5 3 7 

vCd Study of 

1-PhenyLethyL-n,n-diMethyL-n-ALKyL 

AMMoniuM BroMide 

t. hruBy 1 , K. zuCeK 2 , v. SetniCKA 1 




Chemical Engineering, Prague 6, Czech Republic 

The chiral derivatives of 1-phenylethyl-N,N-dimethyl- 

-N-alkyl ammonium bromide are agents from group of 

α-phenylethylamine, which is a well known and often used chiral 

auxiliary, e.g. in chiral ligands for asymmetric catalysis, resolving 

agent or in organocatalysts. Ammonium bromides are potentiall 

agents for accelerated penetration of chiral drugs through the skin. 

The compounds were investigated using vibrational circular 

dichroism (VCD) spectroscopy. Experimental spectra of alkyl 

ammonium bromides (alkyl R = 0, 8, 10, 12, 14, 16, 18 carbon 

atoms) were measured in deuterated methanol in spectral region 

of 1800 – 1200 cm-1 . Spectra were interpreted using a combination 

with ab initio calculations based on density functional theory. 

Results relevant to the conformation and absolute 

configuration will be discussed. 

Acknowledgement: The work was supported by the Ministry 

of Education, Youth, and Sports of the Czech Republic 

(Grant No MSM6046137307); the Czech Science Foundation 

(Grant No P208/11/0105) and the Specific University Research 

MSMT No 21/2012 - A1_FCHI_2012_003 and 

A2_FCHI_2012_045. 

The access to computing and storage facilities owned by parties 

and projects contributing to the National Grid Infrastructure 

MetaCentrum, provided under the programme “Projects of 

Large Infrastructure for Research, Development, and 

Innovations” (LM2010005) is highly acknowledged. 

Keywords: Circular dichroism; Conformation analysis; Ab 

initio calculations; Chiral auxiliaries; 



s1131 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 3 8 

PreSSurized hot wAter extrACtion of 

CAPSAiCin And dihydroCAPSAiCin froM ChiLLi 

PePPerS 

P. Chárová 1 , P. BAJerová 1 , A. eiSner 1 , 

K. venturA 1 



Pressurised hot water extraction (PHWE) use water as an 

extraction medium and belongs to one of the field called „green 

chemistry’. Water is non-flammable, non-toxic, readily available 

and cheap and as solvent environmentally benign. The change in 

its physic-chemical properties at elevated temperatures and 

pressures enhances its usefulness. Pressurized hot water has been 

used to replace conventional organic solvents in extraction 

process. Optimized parameters are in particular temperature, 

pressure, extraction time and amount of sample. PHWE was used 

for extraction of capsaicin (CPA) and dihydrocapsaicin (DHC) in 

seasoning (chilli peppers). Like reference method to PHWE was 

chosen ultrasonication extraction. HPLC/UV/MS was used for 

determination of target analytes. 

Keywords: PHWE; capsaicin; dihydrocapsaicin; 

HPLC/UV/MS; 


P - 0 5 3 9 

the effeCt of o-SuBStituent on MASS 

SPeCtruMS of SChiff BASeS PrePAred froM 

SALiCyALdehyde 

e. K. inAL 1 , G. denizLi 1 , u. erGun 2 , M. A. AKAy 1 , 

o. AtAKoL 1 , e. erGun 1 

1 Ankara University Faculty of Science, Chemistry, Ankara, 

Turkey 

2 Düzce University Faculty of Science and Arts, Chemistry, 

Düzce, Turkey 

As is known, Schiff bases are ligands used in coordination 

chemistry by P.Pfeiffer in early 1930s [1] . Despite the old age of 

the material class, there has not been many studies on the mass 

spectra of schiff bases reported in the literature [2] . In this study 

asymmetric and symmetric salicylaldymines were ionized by 20, 

40, 60, 100, 120 and 140 eV electrons using Direct Inlet and 

obtained m/z values were evaluated. The schiff bases that were 

used are o, m, p-substituted N-phenyl salicylaldimines and 

Bis-N-N'(salicylidene)-diamino alkanes. Especially in mass 

spectra of o-substituted Schiff bases, the formation of H O, HF, 

2 

HCl, HBr, HI or CH OH by phenolic hydrogen and o-substituent 

3 

was observed and the remaining mass was noted as the main peak 

subsequent to the leaving of these groups. It was also seen that 

HBr and HI species, formed by bromine and iodine substituents, 

get attached to the molecule. At this point, it is clear that the 

additions of HBr and HI do not occur by an acid-base reaction 

mechanism because the found mass values are equal to the sum 

of the mass of the Schiff base molecule injected to the DI probe 

and the mass of one HBr or HI molecule. 

references: 

1. a) A. G. Martell, M. Calvin, Die Chemie der Metallchelat 

Verbindungen, translated by H. Specker Verlag Chemie, 

200-265, 1958. 

b) Jr. D. M. Kurtz, Oxo-and Hydroxo-Bridged diiron 

complexes: A chemical perspective on a biological unit 

Chem. Rev. 90, 585-606, 1990. 

2. a) A. S. Eduardo Espinoza, E. Stashenko, J. Martinez, 

U. Mora, V. Kouznetsov, J. Mass Spectr. 42, 1496-1503, 

2007. 

b G. Holzman, H.W.Rothkoff, D. Wöhrle, Org. Mass. 

Spectr., 13, 371-378, 1978 

Keywords: Schiff base; DI; Mass spectrum; o- effect; 



s1132 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 4 0 

ChArACterizAtion of iverMeCtin And itS 

MetABoLiteS uSinG uhPLC/MS/MS 

v. JedLiCKovA 1 , r. JirASKo 1 , i. voKrAL 2 , 

L. SKALovA 2 , M. hoLCAPeK 2 



2 Charles University, Department of Biochemical Sciences, 

Hradec Kralove, Czech Republic 

Ivermectin (IVE) is an anti-parasitic drug with a broadspectrum 

of usage in the veterinary and human medicine. It 

belongs to a macrocyclic lacton drug group called avermectins 

that is effectively applied in cases of nematode, arthropod and 

especially onchocerciasis infections. In mammals, IVE is 

metabolized mainly in liver, where hydroxylated and 

demethylated metabolites and sulphate conjugates are formed, but 

these processes are not extensive. The elimination of the parent 

form and its metabolites is ensured in 90% by the fecal and 

bilinary system. In our work, IVE was incubated with rat 

hepatocytes and microsomes. Subsequently, the solid-phase 

extraction of microsomal and hepatocyte incubation mixtures was 

performed. Moreover, human microsomal samples were obtained 

from in vitro experiments. The comparison of incubated samples 

with placebo experiments simplified the identification of 

metabolites. Studied samples were analyzed using optimized 

ultra-high performance liquid chromatography with electrospray 

ionization tandem mass spectrometry providing the information 

about IVE microsomal and hepatic biotransformation pathways. 

Structural changes of particular phase I and II metabolites were 

suggested based on high mass accuracy measurements in the full 

scan and tandem mass spectrometry modes using QqTOF 

analyzer. 

Acknowledgement: This work was supported by grant project 

P502/10/0217 (Czech Science Foundation). 

Keywords: anthelmintic drug; ivermectin; tandem mass 

spectrometry; ultra high performance liquid chromatography; 


P - 0 5 4 1 

CorreLAtion of x-rAy fLuoreSenCe SPeCtrA, 

SCAnninG eLeCtron MiCroSCoPe iMAGeS And 

BAtCh reMovAL effiCienCy of Low CoSt 

AdSorBerS in the reMovAL PB(ii)froM 

wAStewAterS 

f. JuMeAn 1 , L. PAPPALArdo 1 

1 American University of Sharjah, Biology Chemistry & 

Environmental Sciences, Sharjah, United Arab Emirates 

X-ray fluorescence (XRF) spectra and scanning electron 

microscope images (SEM) of low cost adsorbers were collected 

and correlated with their Pb(II) removal efficiencies. Adsorbers 

employed included white, red and yellow sands (United Arab 

Emirates), Hannon, Micawer and Aritain zeolites (Jordan), 

activated silica (Jordan) and commercial bentonite. Removal 

efficiencies of Pb(II) on the above surfaces were investigated at 

25.0oC as a function of Pb(II) concentration and adsorbent dosage 

using the batch equilibrium method. These results were compared 

to those obtained with commercial silica and alumina. 

Bentonite was found to be the most efficient adsorber, 1.0 g of 

which being sufficient to completely remove Pb(II) ions 

from 0.100 dm3 of a 100 ppm aqueous solution. Bentonite was 

followed by zeolites whose removal efficiency order was: 

Hannon > Aritain > Micawer. These were followed by UAE sand 

which followed the order: yellow > white > red. Finally, on the 

lower efficiency scale, the order observed was: activated 

silica > kaolin> silica~alumina. The removal efficiency of 

bentonite was nearly ten-fold that for the least efficient remover, 

silica or alumina. XRF spectra suggest that the high content in 

zeolites of the oxides of magnesium, iron and aluminum enhance 

their removal efficiency. SEM images allow for the correlation of 

the adsorber morphology to its adsorptive efficiency. 

Keywords: X-ray fluorescence; 



s1133 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 4 2 

SyntheSiS of ConduCtinG PoLyMer/Pt 

CoMPoSiteS – Pt dePoSition And MorPhoLoGy 

Study 

M. KAMrAdeK 1 , P. hoLzhAuSer 1 


Inorganic Chemistry, Prague 6, Czech Republic 

Conducting polymer/Pt (CP/Pt) composites are nowadays 

widely used for many applications. For example in 

microelectronics, catalysis and in chemical sensors. These 

composites found significant application in the field of fuel cells 

where they are considered to be an alternative catalyst support. 

There are different ways of platinum particles deposition. In 

almost all published cases Pt is deposited from chloride ions 

containing precursors – H [PtCl ], K [PtCl ], H [PtCl ], K [PtCl ], 

2 6 2 6 2 4 2 4 

PtCl . It is well known that chloride ions adsorb on platinum 

4 

surface and the electrocatalytic activities of such particles can be 

influenced. 

The aims of this study are: (i) to find suitable, chloride free 

and commercially available platinum compounds which can be 

used for CP/Pt composites synthesis, (ii) to study the influence of 

the precursor and deposition method on platinum particles 

morphology and (iii) to compare electrocatalytic activities of 

composites prepared from chloro- and nonchloro-precursors. 

Composites based on polyaniline (PAni) and polypyrrole 

(PPy) were studied. The films were prepared electrochemically. 

Glassy carbon rotating disc electrode, area 0,196 cm2 , served as a 

support. PAni was synthesized using cycling voltammetry, PPy 

was prepared potentiostatically at the potential 1 V vs. SHE. 

Platinum particles were deposited galvanostatically and 

potentiostatically under different conditions from K [PtCl ], 

2 4 

K [Pt(ox) ], [Pt(NH ) ](NO ) and Pt(NO ) . The samples with 

2 2 3 4 3 2 3 2 

different amounts of platinum were characterized by scanning 

electron microscopy and by means of image analysis. 

Subsequently the electrocatalytic activities of prepared samples 

for methanol oxidation reaction using cycling voltammetry were 

determined. 

It was found that the only compounds from which the 

platinum can be deposited on the PAni and PPy films are K [PtCl ] 2 4 

and K [Pt(ox) ]. The morphology of obtained Pt particles differs 

2 2 

strongly. The precursors [Pt(NH ) ](NO ) and Pt(NO ) are not 

3 4 3 2 3 2 

suitable for Pt depositin on CP films. 

Keywords: conducting polymer/platinum composites; platinum 

deposition; 


P - 0 5 4 3 

infLuenCe of ChLoride ionS on 

eLeCtroCAtALytiC ACtivity of ConduCtinG 

PoLyMer/Pt CoMPoSiteS 

M. KAMrAdeK 1 , P. hoLzhAuSer 1 


Inorganic Chemistry, Prague 6, Czech Republic 

Conducting polymer/Pt (CP/Pt) composites can be used in 

the fuel cells as an alternative electrode material. Platinum serves 

as an electrocatalyst and poisoning of its surface can lead to 

decrease of the fuel cell efficiency. 

Despite the chloride ions sorption on platinum surface is 

well known effect, practically only the chlorocomplexes of 

platinum are used for CP/Pt synthesis. Together with fact that 

chlorides are common impurity in drinking water there is a risk 

of decrease of electrocatalytic activities of composites in FC 

applications. Yet the systematic study of this effect has not been 

done. 

The aims of this study are to measure electrocatalytic 

activities of CP/Pt composites for methanol oxidation reaction 

(MOR) and for hydrogen oxidation reaction (HOR) and determine 

the influence of chloride ions on these activities. 

Composites based on polyaniline (PAni) and polypyrrole 

(PPy) were studied. The films were prepared electrochemically. 

Glassy carbon rotating disc electrode, area 0,196 cm2 , served as a 

support. Platinum particles were deposited potenciostatically at 

the potential 0,1 V vs. SHE from K [Pt(ox) ], Pt loading 

2 2 

100 μg cm-2 . Subsequently the electrocatalytic activities for MOR 

and HOR under different chloride concentration were measured. 

The activities for MOR were measured using cyclic voltammetry, 

activities for HOR were obtained by Koutecky-Levich analysis 

of polarization curves. 

It was found that chloride ions strongly decrease the 

electrocatalytic activity. Concentration of chloride anions 

10-2 mol dm-3 leads to decrease of activity for HOR of about 

50–70%. It was also found that the influence of the chloride ions 

on the HOR on the PPy/Pt composites is dependent on the 

electrode potential. The influence of the chloride ions on the MOR 

is even more pronounced, in the presence of above stated chloride 

ions concentration the platinum surface is almost completely 

blocked and the MOR doesn’t take place. 

Keywords: conducting polymer/platinum composites; chloride 

poisoning; 



s1134 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 4 4 

APPLiCAtion of iCP-AeS Method for 

CoMPoSition deterMinAtion of niCKeL 

SuPerALLoyS 

f. KArAChevtSev 1 , t. zAGvozdKinA 1 , 

r. dvoretSKov 1 

1 All-Russian Scientific Research Institute of Aviation Materials, 

Laboratory “Spectrum chemico-analytical researches and 

standard specimens”, Moscow, Russia 

To control quality and composition of new Nickel 

superalloys we have developed test methods for the analysis of 

doping elements (Al, Co, Re, Ru, Ta, W, Cr, Mo, Ti, Nb) and 

impurities (La, B, Si, Ce, Y, Fe, Cu, Mn, P) by using ICP-AES 

method. 

To choose acids for Ni alloys dissolving we have taken into 

account chemical properties of analysing elements: 

• Si with HF forms volatile SiF , SiH ; in mixture of HCl 

4 4 

and HNO silicon is precipitated into silica sol (H SiO ) ; 

3 2 3 n 

silicon is washed away from the glass spray system of 

spectrometer; silicon is adsorbed on the teflon spray 

system; 

• at dissolving in mixture of acids HCl, HNO and HF 

3 

without water aluminum forms poorly soluble fluoride 

AlF at Al content more than 4 % wt; 

3 

• if Cr content is more than 15 %, Cr is passivated in HNO ; 3 

• at dissolving of carbon-bearing alloys chromium carbide 

solved completely only in HF; 

• Ru forms volatile compounds; 

• boron is washed away from the glass spray system; 

• W, Nb, Ta, Mo is dissolved completely only in present of 

HF. 

Therefore analysing elements were devided in two groups. 

For dissolving of La, B, Ce, Y, Fe, Cu, Mn, Si (up to 3 % wt) we 

chose mixture of chlorazotic acid and water in the ratio 1:2,5. Re, 

Ru, Ta, W, Mo, Ti, Nb, P, Cr, Al, Co, Si (more than 0,1 % wt) was 

dissolved in mixture of acid HCl, HNO and HF. Alloy samples 

3 

were dissolved by using microwave digestion system MARS5 for 

excluding losses. Investigations were carried out by using 

ICP-AES spectrometer Varian 730ES with axial system. 

The wavelengths were chosen for elements’ analysis without 

interference. 

Thus developed test methods considering abovementioned 

properties allow to determine elements with error 3 % in 

concentration ranges from 0,01 to 20 % wt. 

Keywords: Ni alloys; ICP-AES; test method; 


P - 0 5 4 5 

AMPeroMetriC nitriC oxide And oxyGen GAS 

MiCroSenSorS for MonitorinG MyoCArdiAL 

iSCheMiA And rePerfuSion inJury in rAt 

heArt 

S. K. KiM 1 , B. Seo 1 , G. J. Lee 2 , h. K. PArK 2 , J. h. Shin 1 

1 Kwangwoon University, Department of Chemistry, Seoul, 


2 Kyung Hee University, Department of Biomedical 


Endogenously produced nitric oxide (NO) has been studied 

extensively. It has a number of important physiological actions in 

the cardiovascular system. The heart generates NO from 

L-arginine and oxygen (O ) by nitric oxide synthases (NOSs) 

2 

which is present in the coronary endothelium, endocardial 

endothelium, and cardiac myocytes. Since NO endogenously 

generated has been implicated in the control of O consumption, 

2 

it may be essential to monitor O levels during NO measurement 

2 

in physiological milieu. Electrochemical gas sensors possess 

several major advantages, including high sensitivity, high spatial 

and temporal resolution, and simple miniaturization for in vivo 

measurement. Recently, amperometric NO and O gas sensors 

2 

have been extensively employed to determine NO and 

O concentrations in biological systems. However, the 

2 

electrooxidation of NO requires a comparatively high working 

potential (+0.8 V vs. Ag/AgCl); thus, selective detection of NO 

is difficult due to other readily oxidizable interfering species 

(e.g., nitrite, ascorbic acid, uric acid, and acetaminophen). Another 

problem associated with biological measurements is biofouling 

(initiated by protein adsorption) at the electrode surface. To 

improve both the selectivity and protein adsorption, the working 

electrode surface is modified with a xerogel membrane. It is wellknown 

that amorphous, hydrophobic perfluoropolymers 

(e.g., Teflon) are highly permeable to various gaseous species 

including NO and O . Herein we devlop amperometric NO and 

2 

O microsensors modified with perfluorinated xerogel-derived gas 

2 

permeable membrane, exhibiting dramatically improved 

selectivity and biocompatibility, while maintaining high 

permeability toward NO and O . Furthermore, we demonstrate 

2 

the utility of the perfluorinated xerogel-modified microsensor to 

monitor NO and O concentrations in myocardial ischemia and 

2 

reperfusion injury in a rat model in vivo. The measurement reflects 

co-dynamic relationships between NO and O contents in rat 

2 

heart. 

Keywords: Amperometric gas sensor; Nitric oxide; Oxygen; 

Myocardial ischemia/reperfusion injury; Rat heart model; 



s1135 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 4 6 

Study of SySteMS ContAininG SiLver 

nAnoPArtiCLeS Modified By CySteine 

enAntioMerS 

J. KoKtAn 1 , P. rezAnKA 1 , v. KrAL 1 

1 Institute of Chemical Technology in Prague, Analytical 


In this study we report a behavior of systems containing 

silver nanoparticles and L- or D-cysteine. Silver nanoparticles, 

approximately 45 nm in diameter, were prepared by citrate 

reduction of silver nitrate solution. Optical activity was induced 

via post-synthetic modification of nanoparticles surface with 

L- or D-cysteine. Influence of cysteine concentration, pH, and 

time on these systems was studied. Mixtures were mainly 

characterized by electronic circular dichroism (ECD), but UV-Vis 

absorption spectroscopy and surface enhanced Raman scattering 

(SERS) measurements were also used. Results of SERS showed 

that cysteine was bonded on surface of nanoparticles and we were 

able to detect it in concentration up to 5.10 –9 mol L –1 . Also ECD 

spectroscopy revealed the influence of cysteine concentration on 

ECD spectra. 

Keywords: Circular dichroism; Silver nanoparticles; Chirality; 


P - 0 5 4 7 

voLtAMMetriC deterMinAtion of 

ornidAzoLe By MeAnS of A MerCury MeniSCuS 

Modified SiLver SoLid AMALGAM eLeCtrode 

z. KreJCovA 1 , L. SKvorovA 1 , v. vySKoCiL 1 , 

J. BAreK 1 



In therapeutic research, nitro compounds have become an 

important group of drugs with multiple pharmacological activities 

and, on the other hand, a nitro group is frequently associated with 

increased mutagenicity and carcinogenicity of the substance. 

Ornidazole, a derivative of nitroimidazole, is used as an 

antibacterial and antiprotozoal drug. 

This work is focused on optimization and application of 

voltammetric techniques (direct current voltammetry (DCV) and 

differential pulse voltammetry (DPV)) for the determination of 

ornidazole using a mercury meniscus modified silver solid 

amalgam electrode (m-AgSAE). This electrode offers good 

repeatability and renewability of its surface, it represents cheaper, 

more user- and environmental-friendly alternative to the hanging 

mercury drop electrode (HMDE). The optimum conditions for the 

determination of ornidazole in the concentration range from 

2·10-7 mol/L to 1·10-4 mol/L were found in the medium of 

Britton–Robinson buffer of pH 8.0; the limits of quantification 

(L s) were found to be 1.5·10 Q -7 mol/L for DCV and 2.3·10-7 mol/L 

for DPV. 

The practical applicability of the newly developed DPV 

methodology was verified for the direct determination of 

ornidazole in model samples of drinking and river water, with 

L s ≈ 2.4·10 Q -7 mol/L and 2.0·10-7 mol/L reached in drinking a river 

water, respectively. 

Acknowledgement: This research was financially supported 

by The Ministry of Education, Youth and Sports of the Czech 

Republic (Project MSM0021620857), by the Charles University 

in Prague (Projects UNCE 2012/44 and SVV 2012-265201) and 

by The Grant Agency of the Czech Republic (Project 

P206/12/G151). 

Keywords: Electrochemistry; Voltammetry; Analytical 

methods; Amalgams; 



s1136 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 4 8 

CAPiLLAry eLeCtroPhoreSiS 

ASSAy for deterMinAtion of 

BetA-n-ACetyLhexoSAMinidASe ACtivity 

t. KrizeK 1 , v. douBnerovA 2 , h. rySLAvA 2 , 

P. CoufAL 1 

1 Charles University Faculty of Science, Deparment of 


2 Charles University Faculty of Science, Deparment of 

Biochemistry, Prague 2, Czech Republic 

Determination of enzyme activity is vital for basic and 

applied research in biochemistry and molecular biology. Apart 

from that, it can be used for the diagnosis of serious diseases, such 

as cancer, that causes changes in the enzyme activity in body 

fluids. This work focuses on the development of capillary 

electrophoresis methods for determination of substrates and 

products of the β-N-acetylhexosaminidase enzyme. The enzyme 

in question plays an important role in the cell regeneration, 

hyphenation and septa formation in fungi and, therefore, it is of a 

great research interest. β-N-acetylhexosaminidase is also present 

in human, where it is involved in degradation processes. 

Mutations of this enzyme can cause fatal inborn errors known as 

Tay-Sachs and Sandhoff disease. 

A reliable capillary electrophoresis method enabling the 

monitoring of hydrolysis of N,N’,N’’-triacetylchitotriose and 

N,N’-diacetylchitobiose by β-N-acetylhexosaminidase has been 

developed and statistically evaluated. The method works with a 

borate-based background electrolyte that gives an electric charge 

to the neutral analytes and enables their separation. Using this 

method, the pH optimum, substrate specificity and 

further characteristics, have been investigated for the 

β-N-acetylhexosaminidase fromAspergillus oryzae. The work also 

reports on the development of an online enzyme assay. In this 

case, the mixing of substrate and enzyme, reaction and analytical 

separation occur directly in the capillary using so called 

“Transverse Diffusion of Laminar Flow Profiles” methodology. 

This approach offers a high degree of automation, enhanced 

repeatability and very low danger of sample loss or contamination. 

Acknowledgement: Financial support by Charles University in 

Prague (project SVV 2012-26520), GAUK (project 710) and 

M·MT CR (project MSM0021620857) is gratefully 

acknowledged. 

Keywords: electrophoresis; enzymes; kinetics; 


P - 0 5 4 9 

rP-hPLC And Cze AS PowerfuL tooLS for 

MonitorinG of reACtion interMediAteS in 

SyntheSiS of MAGnetiC reSonAnCe ContrASt 

AGentS 

A. KuBiCKovA 1 , t. KrizeK 1 , P. CoufAL 1 


of Analytical Chemistry, Prague, Czech Republic 

Magnetic resonance imaging (MRI) is one of the most 

powerful noninvasive methods in clinical diagnostics. To improve 

the contrast of the image, contrast agents are utilized. The contrast 

agents are often based on a transition metal or lathanide ion such 

as Gd3+ . In order to reduce their toxicity and prevent their 

accumulation in body tissues, the metal ions must be applied in 

form of highly stable complexes. For this purpose, the best ligands 

were found among cyclene (1,4,7,10-tetraazacyclododecane) 

derivatives containing carboxylate pendant arms. 

In the development of new contrast agents, carboxyl groups 

are very often protected with tert-butyl ester groups. Among these 

derivatives, tBu DO3A is of the highest importance. Therefore, 

3 

reverse phase high performance liquid chromatography 

(RP-HPLC) and non-aqueous capillary zone electrophoresis 

(CZE) methods were evaluated for qualitative and quantitative 

analysis of tBu DO3A, i.e. 1,4,7,10-tetraazacyclododecan-1,4,7- 

3 

-tris(tert-butylacetate) and two typical reaction by-products, i.e. 

tBu DOTA (1,4,7,10-tetraazacyclododecan-1,4,7,10-tetrakis(tert- 

4 

-butylacetate) and tBu DO2A (1,4,7,10-tetraazacyclododecan-1,4- 

2 

-is(tert-butylacetate). Both methods exhibited satisfactory 

efficiencies, good reproducibility and short analysis time. The 

optimized methods were successfully applied to monitoring of 

real reaction mixtures during synthesis of a new MRI contrast 

agent. No further sample pretreatment was necessary. 

Acknowledgement: Authors thank to the Charles University in 

Prague (projects SVV 2012-265201 a UNCE 2012/44) and the 

Ministry of Education, Youth and Sports (project MSM 

0021620857) for the financial support. 

Keywords: Electrophoresis; Liquid chromatography; Imaging 

agents; Macrocyclic ligands; 



s1137 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 5 0 

Study of the eLeCtroCheMiCAL reMovAL of 

CAdMiuM froM SiMuLAted LeAChAte diLute 

SoLutionS 

M. e. LoPeS 1 , e. MeStrinho 2 , A. P. Pinto 3 , 

M. i. SiLvA PereirA 4 

1 School of Sciences and Technology of the University of Évora, 

Chemistry CQE, Evora, Portugal 


Chemistry, Evora, Portugal 


ICAAM, Evora, Portugal 

4 Faculty of Sciences University of Lisbon, CCMM Chemistry 

and Biochemistry, Lisboa, Portugal 

In this work the electrodeposition of Cd from aqueous 

solutions with low concentration of the ion is studied, having in 

view the removal of this heavy metal via an electrochemical 

process. The metal was deposited on stainless steel electrodes. 

Deposits formed under different conditions were studied by linear 

and cyclic voltammetry techniques, X-ray powder diffraction, 

scanning electron microscopy and EDS surface analysis. 

Chronoamperometry was used to evaluate kinetic data of the 

deposition process. The effect of several ions concentration, pH 

and potential applied is evaluated in the electrodeposition 

efficiency. Model solutions prepared with multiple salts were 

tested in order to simulate an average composition of a leachate 

and to understand the influence of different electrolytes on the 

mechanism of electrodeposition. It was possible to recover 

electrodeposited Cd from solutions as dilute as 100 mg/l. The 

studies indicate that chloride, nitrate and sulfate have distinct 

influence on the voltammetric peak potential of electrodeposition 

and on the process. The studies also indicate the occurrence of 

simultaneous reducing processes that may be attributed to 

hydrogen evolution and nitrate reduction. Some morphological 

differences in the deposits may also be observed. 

Keywords: Cadmium; Electrochemistry; Kinetics; 

Environmental chemistry; X-ray diffraction; 


P - 0 5 5 1 

eLeCtroCheMiCAL BehAvior of rifAMPin 

druG And itS deterMinAtion inthe 

PhArMACeutiCAL SAMPLeS uSinG CArBon 

CerAMiC eLeCtrode 

S. Lotfi 1 , n. heriSi 2 , M. MAJidi 2 

1 University of Tabriz, Applied Chemistry, Tabriz, Iran 

2 University of Tabriz, Analytical Chemistry, Tabriz, Iran 

In this work, the electrochemical behavior of RIF on 

carbon-ceramic electrode was investigateied by using cyclic 

voltametry at acetate-acetic acid buffer pH = 4. Sol-gel 

trechnology and using of silicated matrix that finally was 

crystallized as glassical crystals, was used for analytical 

investigation since former century. Sol-gel electrochemistry has 

provided extensive research range in analytical chemistry in last 

fifty years. 

Sol-gel process was done on the base of hydrolysis and 

condensation of organometallic alkoxides following the gel 

formation process by forming polymeric bonds with M 

(OR)X.Carbon-ceramic electrode prepared in equeous solution 

contains rifampin has been used for investigation of 

electrochemical its behavior.Also, Electrocatalytic activities of 

proposed electrode were compared with other electrode substrates 

by cyclic voltammetry. Effective parameters such as solution pH, 

supporting electrolyte kind and its concentration, scan rate, 

applying frequency of square wave voltammetry, stirring speed 

and time of solution in the adsorption cell for RIF determination. 

RIF antibiotic adsorpted on carbon-ceramic electrode was 

determined by using cyclic voltammetry and square wave 

voltammetry and separation of adsorption cell from determination 

cell. Calibration curves was drawn for both methods and 

calculated detection limits 1.9 and 0.1 µM for cyclic voltammetry 

and square wave voltammetry, respectively. Calibration curves 

obtained from square wave voltammograms show two linear 

ranges from 0.010–0.168 µM and 0.49–56.6 µM.The CCE shows 

catalytic ability for the oxidation of RIF. The results show good 

stability for electrode and high sensivity in determination of low 

concentrations of RIF. Electrode efficiency as a voltammetric 

sensor was utilized for the determination of RIF in pharmaceutical 

samples involving 300 mg capsule and 150 mg/ml oral solution 

with satisfactory results. 

Keywords: Carbon ceramic electrode; Rifampin; Square wave 

voltammetry; Sol-gel; isoniazide; 



s1138 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 5 2 

effeCt of ALKALinity And the nAture of the 

BASiC SoLution (CA(oh) And BA(oh) ) on the 

2 2 

eLeCtroKinetiC StABiLity And rheoLoGy of 

the driLLinG Mud 

M. MAALeM 1 , B. SAfi 2 , M. SAidi 2 

1 Boumerdes University, Process Engineering, Boumerdes, 

Algeria 

2 Boumerdes University, Materials Engineering, Boumerdes, 

Algeria 

The fall recurrently in alkalinity and pH of the drilling mud 

was observed during the use of local barite towards higher salt 

saturated mud for the drilling phase of 8" 1 /2 of oil well at Hassi 

Messaoud in Algiers. This finding was confirmed on site oil, despite 

treatment with hydrated lime. This drop is due to alkalinity of the 

fine fraction of barite which tends to agglomerate easily. This results 

in the increase in rheological properties (the yield value and plastic 

viscosity) of mud during the drilling phase in question. 

To overcome the difficulties associated with limitations in 

current understanding of such rheological behavior of the mud 

system studied, it is necessary to study the structure and stability 

of this system. 

Drilling muds are dispersed colloidal systems, the 

dimensions and particle properties are important factors that 

determine the aggregative stability of disperse systems. Indeed, 

this stability is very sensitive to different factors governing the 

electrical phenomena and especially the physicochemical 

properties of the interfacial layer mineral solution. Among the 

physicochemical properties of this layer include: adsorption at the 

mineral interface, the orientation of the ions, the ionization of 

particles therein and the electrokinetic phenomenon appears. This 

can be a means to better understand the stability of suspensions. 

For this purpose, this work aims to study the influence of 

the alkalinity of the mud and the nature of basic solution (Ca(OH) 2 

and Ba(OH) ) on the rheological parameters (plastic viscosity and 

2 

yield value). And secondly, to give a microscopic approach to the 

stability of these parameters based on physical or chemical 

interactions existing between suspended particles, and the concept 

of zeta potential. 

Keywords: Zeta potentiel; Alkalinity; electrical double layer; 

drilling mud; barite; 


P - 0 5 5 3 

oPtiMizAtion of MerCury CoLd vAPor 

GenerAtion for on-Line AnALySiS of MerCury 

SPeCieS 

K. MALiSovA 1 , o. MeSteK 1 

1 Institute of Chemical Technology in Prague, Analytical 

chemistry, Prague 6, Czech Republic 

Mercury is one of the most dangerous elements in terms of 

its impact on the human body. Because the toxicity of mercury 

varies depending on its chemical species, it is very important to 

determine the exact amount of each species. 

To determine the amount of each mercury species, 

speciation analysis is used. Speciation analysis combines a 

suitable separation method, such as gas or liquid chromatography 

with the appropriate detection method, such as inductively 

coupled plasma mass spectrometry (ICP-MS). Improved detection 

limits can be achieved using the mercury cold vapor generation 

(CVG) method. Cold vapor generation can be achieved using 

various compounds, but not all of them can be used in conjunction 

with high pressure liquid chromatography (HPLC) and ICP-MS 

detection. 

In this work the mercury CVG method was optimized 

to determine the amount of mercury species using on-line 

HPLC-ICP-MS. We optimized the composition of the reagents 

required for CVG: the HCl concentration for the acidification of 

the effluent; the NaOH concentration for the stabilization of the 

NaBH solution; the concentration of NaBH . In addition, the 

4 4 

internal standard and flow rates were also optimized. 

Our optimization resulted in reduced limits of detection 

(LOD) for methyl mercury species and inorganic mercury species. 

Methyl mercury LOD was reduced by almost a factor two to 0.021 

ng/g and inorganic mercury by a factor of ten to 0.013 ng/g. There 

results suggest that our optimized method of CVG is useful for 

the speciation analysis of mercury in samples with low mercury 

content. 

Acknowledgement: Financial support from specific university 

research MSMT No 21/2012 - A1_FCHI_2012_003 and 

A2_FCHI_2012_001 

Keywords: Mercury; Liquid chromatography; Analytical 

Methods; Mass spectrometry; Trace analysis; 



s1139 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 5 4 

deterMinAtion of BroMhexine on CArBon 

PASte eLeCtrode uSinG differentiAL PuLSe 

voLtAMMetry And fiA with AMPeroMetriC 

deteCtion 

J. MiKA 1 , A. neMeCKovA 1 , J. ziMA 1 , J. BAreK 1 , 

h. deJMKovA 1 



Bromhexine is frequentlyused mucolytic agent and 

therefore, there is a demand for its fast and reliabledetermination. 

Thanks to its chemical structure, bromhexine is a suitablecandidate 

for electrochemical determination. 

This fact was used for the development of new methods of 

determinationbased on differential pulse voltammetry (DPV) and 

flow injection analysis (FIA)with amperometric detection on 

glassy carbon paste electrode (GCPE) in a wall-jetarrangement. 

Optimum determination conditions of analysis were found. 

Incase of DPV, the optimum supporting electrolyteconsists of 

methanol and Britton-Robinson (B-R) buffer pH 9.0 (80:20, v/v). 

Theoptimum conditions for the FIA determination are: carrier 

solutionconsisting of methanol and ten times diluted B-R buffer 

pH 9.0 (80:20, v/v),detection potential +1.1 V, flow rate 

1.5 mL min –1 ,the injected volume 100 μL, The possibility to 

increase sensitivity of DPV by preliminary adsorptionstep was 

tested with 5 min accumulation time, but significant decrease of 

detectionlimit was not obtained. The limit of detection for FIA 

was 0.9×10 –8 mol L –1and for DPV 5.8×10 –7 mol L –1 . Applicability 

of the methods was tested by determination of realsamples of 

pharmaceutical preparations. 

Acknowledgement: The researchwas supported by the Ministry 

of Education, Youth and Sports of the Czech Republic (Project 

MSM 0021620857), Charles University in Prague (Project SVV 

2012-265201) and Grant Agencyof the Czech Republic(Project 

P206/12/G151). 

Keywords: Bromhexine; Glassy carbon paste electrode; 

Differential pulse voltammetry; Flow injection analysis; 

Amperometric detection; 


P - 0 5 5 5 

hPLC/uv Method for deterMinAtion of 

SeLeCted BenzodiAzePineS 

M. MuChA 1 , J. KALinA 1 , P. KurKA 2 

1 University of Ostrava Faculty of Science, Chemistry, Ostrava, 


2 University Hospital Ostrava, Department of Forensic 

Medicine, Ostrava, Czech Republic 

introduction: Benzodiazepines are the most popular 

psychotropic drugs by doctors and drug addicts in the present. They 

are used mainly as sedatives, anxiolytics or as premedication before 

elective surgery due to its depressant effects on central nervous 

system. The side effects are mainly fatigue and sleepiness [1, 2] . The 

aim of this work was to developed HPLC/UV method for 

determination of six benzodiazepines (Alprazolam, Bromazepam, 

Clonazepam, Diazepam, Chlordiazepoxide and Oxazepam). 

experimental part: It was used ammonium acetate and 

formic acid for the preparation of mobile phase A. Acetonitrile 

was used as mobile phase B. Six powder standards of 

benzodiazepines, which were dissolved in methanol, was used 

further. The method was developed on the instrument Agilent 

1200, which was equipped with a column Gemini 5μ C18 110A. 

The developed method was tested (its limits of detection (LOD) 

and quantification (LOQ), linearity, reproducibility, repeatability, 

precision and accuracy were determined). 

results: The developed method had following parameters: 

mobile phase A – 0.01M ammonium acetate + 0.1% (v/v) 

formic acid, mobile phase B – acetonitrile, total flow of mobile 

phase – 0,34 – 0,17 μl/min, mobile phase B gradient – 15 – 90% 

(0 – 17 min), column temperature – 20°C and spray – 20 μl. 

The parameters of method were following: LOD – 0,1 μl/min, 

LOQ – 0,2 μl/min, correlation linearity coefficients higher than 

0,985, deviation of reproducibility and repeatability better 

than ±7% and deviation in precision and accuracy better 

than ±7%. 

Conclusion: The obtained HPLC/UV method for 

determination of six benzodiazepines is suitable for introduction 

into practical usage in hospital laboratories. 

references: 

1. Lüllmann, Heinz, Klaus Mohr a Martin Wehling. 

Farmakologie a toxikologie. Praha: Grada Publishing, a.s., 

2004. ISBN 80-247-0836-1. 

2. Rasková, Helena, Jirí Vanecek, Zdenek Votava a Max 

Wenke. Farmakologie: učebnice pro lékařské fakulty. 

2. edition. Praha: Avicenum, 1970. 

Keywords: Liquid chromatography; Medicinal chemistry; 



s1140 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 5 6 

direCt voLtAMMetriC deterMinAtion of 

ACifLuorfen, nitrofen And oxyfLuorfen in 

drinKinG And river wAter. 

v. novotny 1 , J. BAreK 1 

1 Charles University Faculty of Science, Analytical Chemistry, 


The herbicides Acifluorfen, Nitrofen and Oxyfluorfen were 

developed for the protection of various crops against weeds. They 

are toxic to aquatic organisms, interfere with blood formation, 

and are endocrine disruptors. Many methods have been developed 

for their determination [1, 2] . Voltammetric techniques offer 

inexpensive, reliable and sensitive alternative to spectrometric 

determination of electroactive pollutants [3, 4] . This work is a 

continuation of our previous work on the same topic [3, 5] . This 

presentation is devoted to the determination of tested substances 

in model samples of drinking and river water, both alone and, if 

possible, in a mixture using a meniscus modified silver solid 

amalgam electrode (m-AgSAE). Acifluorfen was determined by 

DPV at m-AgSAE in 1 mL 1 mol?L-1 phosphoric acid and 9 mL 

of model sample of AF drinking/river water. Nitrofen and 

Oxyfluorfen were determined by DPV at m-AgSAE in a mixture 

of 1 mL 1 mol?L-1 NaOH, 3 mL of methanol and 6 mL of model 

sample of Nitrofen or Oxyfluorfen in drinking/river water. 

The calibration dependences were linear in the concentration 

range 1·10-5 - 2·10-7 mol·L-1 and the detection limit was around 

2·10-7 mol·L-1 in drinking and river water, respectively. 

Acknowledgement: The financial support of M·MT CR (MSM 

0021620857), TACR (TA01020565), and UK Prague (SVV 

2012-265201) is gratefully acknowledged. 

references: 

1. A. Lagana, G. Fago, L. Fasciani, A. Marino, M. Mosso, 

Anal. Chim. Acta, 414 (2000) 79. 

2. H.-L. Sheu, Y.-H. Sung, M.B. Melwanki, S.-D. Huang, 

J. Sep. Sci., 29 (2006) 2647. 

3. B. Yosypchuk, J. Barek, Crit. Rev. Anal. Chem., 39 (2009) 

189. 

4. J. Barek, J. Cvacka, A. Muck, V. Quaiserová, J. Zima, 

Fresenius. J. Anal. Chem., 369 (2001) 556. 

5. V. Novotný, J. Barek, Chem. Listy, 103 (2009) 217. 

Keywords: Voltammetry; River water; Drinking Water; 

Herbicide; Determination; 


P - 0 5 5 7 

deterMinAtion of PAtuLin in CoMMerCiAL 

BABy foodS froM turKiSh MArKetS By hPLC 

n. SAnLi 1 , A. KArAKoSe 2 , S. SAnLi 1 

1 Usak University, Chemistry, Usak, Turkey 


Patulin is present globally in a wide range of fruit and 

vegetables. It has been identified in different types of fruits but 

was found more in apples, pears, peaches, and in their processed 

products like juices and puree [1, 2] . PAT is toxic for animals; it 

induces intestinal injuries, including epithelial cell degeneration, 

inflammation, ulceration; it has also been shown to be mutagenic, 

carcinogenic and teratogenic [3] . The EC Regulation 1881/2006 

which indicates maximum levels for certain contaminants in food, 

sets the maximum limit of patulin equal to 10 μg/kg (or 10 μg/L) 

in baby food samples. 

In this study, a fast, reliable, sensitive, and effective method 

with DAD detection for the quantitative analysis of PAT is 

described and evaluated according to the ICH guidelines. HMF 

was used as internal standard. These compounds are well separated 

on a Phenomenex Gemini C18 (110 A°, 250 x 4,6 x 3mm) column 

by using the mobile phase consisting of a mixture of acetonitrile 

(15:85; v/v, 15 mM CH COOH- pH = 4.0) at a flow rate 

3 

of 1.0 mL/min and 40 °C. Good sensitivity for all analytes was 

observed. The LOD and LOQ values were 5.02x10-4 mg L-1 and 

1.52x10-3 mg L-1 , respectively. 

In view of their wide use, both because they supply the 

nutritional needs for children, and because they consent easiness 

and rapidity in preparing meals, several samples of 

fruit-homogenized baby food were collected from Turkish 

markets to analyze and assess the patulin presence and their 

compliance with the limits provided by the law. 

references: 

1. A. Ritieni, J. Agric. Food Chem. 2003, 51, 6086–6090. 

2. World Health Organization (WHO), 1996. Available from: 

www.inchem.org/documents/jecfa/jecmono/v35je16.htm. 

3. R.Mahfoud, M. Maresca, N. Garmy, J. Fantini, Toxicol. 

Appl. Pharmacol. 2002, 181, 209–218. 

4. Commission Regulation (EC) No 1425/2003 of 11 August 

2003 amending Regulation (EC) No 466/2001 as regards 

patulin. Official J. Eur. Union L 203/1–L 203/3. 

Keywords: Patulin; Baby Foods; Liquid Chromatography; 

Determination; 



s1141 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 5 8 

deterMinAtion PKA vALueS of AntifunGAL 

druGS By uv SPeCtroSCoPiC Method 

n. SAnLi 1 , f. BASArAn 2 , S. SAnLi 1 , n. CoLAK 2 

1 Usak University, Chemistry, Usak, Turkey 


Email: nurullahsanli@gmail.com 

Dissociation constants (pK values) are useful 

a 

physicochemical parameters describing the extent of ionization 

of functional groups with respect to pH. The knowledge of pK is a 

important in drug discovery and development since the 

pharmacokinetic and pharmacodynamic properties of different 

protonation/ionization forms of the drug molecules may vary 

considerably [1] . 

In this study, the acidity constants of eight antifungal drugs 

(fenticonazole, isocanozole, itracanozole, ketocanozole, 

mikanozole, ornidazole, tinidazole, tiocanozole) have been 

determined in water and 10–20 % (v/v) MeCN-water mixtures at 

(25.0 ± 0.1) °C and in 0.1 mol L-1 KCl by UV spectroscopic 

method. Datas were processed using the program STAR (Stability 

Constants by Absorbance Readings) which calculates stability 

constants and molar absorptivities of the pure species by multi 

linear regression [2] . 

references: 

1. P. J. Taylor, “Hydrophobic Properties of Drugs”. 

In C. Hansch, P.G. Sammes, J.B. Taylor, (Eds.), 

Comprehensive Medicinal Chemistry, Vol. IV; 

Pregamon Press: Oxford, 1990; pp. 241-294. 

2. J. L. Beltran, R. Codony, M. D. Prat, Anal Chim Acta 

1993, 276, 441–454. 

Keywords: Analytical methods; Antiviral agents; Drug design; 

Solvent effect; UV/Vis spectroscopy; 


P - 0 5 5 9 

iMPortAnCe of evALuAtinG the fALSe 

non-CoMPLiAnCe And fALSe CoMPLiAnCe in 

the deterMinAtion of the MiniMuM 

ContentS of Protein, dry MAtter And the 

rAtio fAt dry MAtter in zAMorAno CheeSe 

when A nir-PLS ProCedure iS uSed 

M. L. oCA 1 , M. C. ortiz 1 , L. SArABiA 2 

1 University of Burgos (Faculty of Sciences)), Analytical 

Chemistry, Burgos, Spain 

2 University of Burgos (Faculty of Sciences)), Mathematics and 

Computation, Burgos, Spain 

Nowadays, near-infrared (NIR) spectroscopy means a useful 

methodology in process monitoring, determination of quality, 

geographical origin and adulteration of dairy products. However, 

because of the changes in spectra caused by various physical 

properties, a calibration against a reference method for the 

constituent of interest is required. Generally, a Partial Least 

Squares (PLS) regression is applied. The compliance of a 

maximum or a minimum limit for the quantity of a substance in 

food is mandatory in many of these determinations. So assessing 

the efficiency of NIR-PLS procedures in terms of detection 

capability (CDβ) evaluating the probabilities of false 

non-compliance (α) and false compliance (β) is needed. 

This work was aimed to develop a rapid analytical tool for 

monitoring simultaneously the contents of fat, dry matter, protein 

and the ratio fat/dry matter in Zamorano cheese samples by NIR 

spectroscopy. Zamorano cheese is protected with a Designation 

of Origin and registered as Protected Designation of Origin, which 

represent the system of recognition of a distinctive quality within 

the European framework. Calibration models based on a PLS 

regression of the percentage in weight of every constituent on the 

spectra recorded were estimated. Therefore, values of the 

explained variance of the response between 92.54 and 96.57% 

were obtained, and the mean and the standard deviation of the 

absolute value of the relative error in calibration ranged 

from 0.66 to 1.05% and from 0.43 to 0.87%, respectively. 

The trueness of every method was also ensured, and the minimum 

contents of protein, dry matter and the ratio fat/dry matter 

according to specific regulations were calculated. 

Experimental values of CDβ equal to 24.57% for protein, 

53.28% for dry matter and 43.78% for the ratio fat/dry matter 

were obtained (α=β=0.05) 

Acknowledgements: financial support through projects 

CTQ2011-26022 and BU108A11-2. M.L. Oca thanks to 

University of Burgos for her FPI grant. 

Keywords: NIR; Partial Least Squares; Cheese; False 

compliance; Capability of detection; 



s1142 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 6 0 

inveStiGAtion of SodiuM Borohydride 

eLeCtrooxidAtion MeChAniSM on SiLver 

eLeCtrode in BASiC MediuM 

A. orBAy 1 , G. yiLdiz 1 


As fossil fuel sources come to an end and problems due to 

pollution rises, fuel cells with environment friendly reagents (like 

hydrogen) become more important. Hydrogen is one of the 

preferred energy sources, which can be hard to store due to limited 

area capacity and exploding hazards. At this point a suitable 

energy carrier compound, sodium borohydride (NaBH ), steps 

4 

in and conducts in-situ hydrogen generation through 

hydrolysis reaction within its superior characteristics such as 

non-flammability, stability and recyclability. 

In this study, the electrochemical oxidation mechanism of 

NaBH on silver electrode in sodium hydroxide support electrolyte 

4 

was investigated. The effect of sodium hydroxide concentration 

and optimum conditions to obtain maximum oxidation in presence 

of oxidative reagent like potassium permanganate were also 

investigated. 

references: 

1. Santos D. M. F., Sequetra C. A. C., Renewable and 

Sustainable Energy Reviews, 2011, 15, 3980-4001 

2. Santos D. M. F., Sequeira C. A. C., 

Int. Journal of Hydrogen Energy, 2010, 35, 9851-9861 

3. Sanli E., Uysal B. Z., Aksu M. L., 

Int. Journal of Hydrogen Energy, 2008, 33, 2097-2104 


P - 0 5 6 1 

exPeriMentAL And CoMPutAtionAL StudieS 

on the therMAL deCoMPoSition of 

nitroAzidoBenzeneS 

S. Öz 1 , e. ÖzKArAMete 2 , e. K. inAL 2 , i. SvoBodA 3 , 

o. AtAKoL 2 , M. A. AKAy 2 

1 Ahi Evran University, Chemistry, Kirsehir, Turkey 


3 TU-Darmstadt, Strukturforschung FB Materialwissenschaft, 

Darmstadt, Germany 

In this combined experimental and theoretical study 

the thermal decomposition of 2-nitroazidobenzene (i), 

2,4-dinitroazidobenzene (ii) and 2,4,6-trinitroazidobenzene (iii) 

to yield benzofuroxan (iv), 4-nitrobenzofuroxan (v) and 

4,6-dinitrobenzofuroxan (vi) were investigated by thermoanalytical 

(TG, DSC) and computational methods. Interestingly, furoxan 

formation was not observed for 4-nitroazidobenzene (vii) under 

heating due to the para position of the nitro group in the benzene 

ring. All compounds were characterized by elemental analysis, 

vibrational (IR) spectroscopy and mass spectrometry. The crystal 

structure of compound iii was determined by single crystal 

X-ray diffraction [1a, b] . All calculations were carried out using the 

Gaussian G09W (revision B.01 [2a] . DFT-based structure 

optimizations and frequency analyses were performed at the 

B3LYP/cc-pVDZ level of theory [2b] . The structural parameters of 

the fully optimized compound iii was in good agreement with 

the single-crystal X-ray data. The enthalpies of formation for 

compounds i, ii, iii, iv, v and vi were calculated using the 


in order to obtain accurate energy values [2c] . The enthalpies of 

decomposition for compounds i, iiand iii were obtained from 

calculated enthalpies of formation according to Hess Law and 

were compared with the experimental values which were available 

from DSC analysis and were also found to be in very good 

agreement. 

references: 

1. a) Oxford Diffraction (2002) CCD and CrysAlis RED. 

Version 1. 170. 14. Oxford Diffraction, Oxfordshire, 

England. 

b) Sheldrick GM SHELXS97 and SHEXL97 Program for 

Crystal Structure Solution and Refinement (1997) 

University of Gottingen, Germany. 

2. a) Gaussian 09 Software, Revision B01.2009 

b) A. D. Becke, J. Chem. Phys., 88, 1053-1062, 1988 

c) Jr. A. J. Montgomery, M. J. Frisch, J. W. Ochterski, 


Keywords: Thermal Decomposition; CBS-4M; 

Nitroazidobenzene; IR; TG; 



s1143 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 6 2 

nitroMethAne eLeCtroCheMiCAL SenSinG 

Method for An exPLoSive trACe deteCtor By 

ConCentrAtion in Liquid MediA 

e. PASquinet 1 , S. deLiLe 1 , t. MAiLLou 1 , P. PALMAS 1 , 

M. BouSquet 1 , S. BeAuGrAnd 1 , v. LAir 2 , M. CASSir 2 

1 Cea Le Ripault, DXPL, Monts, France 

2 Chimie ParisTech, ENSCP, Paris, France 

During the past ten years, the terrorism menace has 

increased and the development of efficient explosive detection 

devices has become an urgent worldwide necessity. In this 

context, the CEA (Commissariat l’Energie Atomique et aux 

Energies Alternatives) started several projects aimed at developing 

detectors of explosives traces. Nebulex is a patented device which 

solubilises vapors or particles of explosive (or precursor) in a tank 

via a spray formation. The solubilised molecules can be detected 

in-situ using an adapted reagent to a technique of detection. First, 

colorimetric and fluorescent methods were used in associate with 

specific reagents developed for peroxides detection. In this study, 

we evaluated electrochemistry as a new method for the detection 

of a nitro compound, the nitromethane. 

Whereas aromatic nitro compounds such as trinitrotoluene 

(TNT) have already been widely studied, nitromethane doesn’t 

seem to have attracted much interest. Nitromethane is a 

constituent of artisanal explosive compositions, and like the other 

nitro compounds, it can be detected by the electrochemical 

reduction of the NO group. The objective of this study is to define 

2 

and optimize conditions for the detection with a simple and robust 

system of electrodes. 

The higher intensity of reduction was obtained in neutral 

media and by using a gold electrode with a simple system. In these 

conditions, a limit of detection (LOD) of 3 µmol/L of 

nitromethane was achieved in the absence of dissolved oxygen. 

In air environment, which is more representative of real condition 

encountered with Nebulex device, the LOD grows to 12 µmol/L 

due to increase of noise. 

An important constraint imposed by the project is to 

minimize the system for a portable application in the Nebulex 

device. For this, a portable potentiostat and a screen-printed 

electrodes system were evaluated and compared with laboratory 

equipment. 

Keywords: electrochemistry; sensors; trace analysis; 


P - 0 5 6 3 

MASS SPeCtroMetriC APProACh to 

evALuAtion of hiStoriCAL PAintinGS By 

identifiCAtion of PruSSiAn BLue And indiGo 

v. PAuK 1 , B. PAPouSKovA 1 , P. SuLovSKy 2 , K. LeMr 1 


Chemistry RCPTM, Olomouc, Czech Republic 

2 Palacky University in Olomouc, Department of Geology, 


Prussian blue and indigo are very famous and widely used 

blue pigments. They often exhibit similar properties in paintings 

and they are highly insoluble in water and common organic 

solvents. Prussian blue is the synthetic pigment discovered at the 

beginning of the 18th century in Berlin, natural indigo was 

produced from plant material since ancient times and used up to 

the end of the 19th century when it was replaced by the synthetic 

dye. 

The aim of this work was to develop a fast and sensitive 

method for analysis of both pigments of high historical 

importance. 

The experiments were performed using a Q-TOF Premier 

mass spectrometer (Waters, Manchester, UK) by flow injection 

analysis with negative electrospray ionization. The compounds 

were subsequently detected after simple sample preparation based 

on two chemical reactions in alkaline solution: decomposition of 

Prussian blue and reduction of indigo with dithionite to soluble 

leucoindigo. 

The main advantage of the developed procedure is that no 

chromatographic separation is required. The proposed method is 

fast (2 minutes runtime), very sensitive (LODs for Prussian blue 

and indigo are 47 pg and 59 pg in injection, respectively) and has 

a wide dynamic range (linear calibration was observed from 10 

to 5000 ng/mL, injection volume 5µL). 

The method was successfully applied for identification of 

Prussian blue in samples taken from the painting of ‘Crucifixion’, 

St. Sebestian church on St. Hill in Mikulov, Czech Republic, and 

results were confirmed by Raman spectroscopy. This technique 

can be used for fast screening of two blue pigments in small 

samples of historical and art objects. 

Acknowledgement: The support by the Ministry of Education, 

Youth and Sports of the Czech Republic (ME10013), 

Operational Program Research and Development for 

Innovations - European Regional Development Fund (project 

CZ.1.05/2.1.00/03.0058) and by Palacky University 

(PrF_2012_020) is gratefully acknowledged. 

Keywords: Mass spectrometry; Dyes/Pigments; 



s1144 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 6 4 

PotentioMetriC deterMinAtion of 

PiroxiCAM in Pure And PhArMACeutiCAL 

doSAGe forMS 

n. PeJiC 1 , n. SArAP 2 , J. MAKSiMoviC 3 , 

S. BLAGoJeviC 1 , L. KoLAr-AniC 3 , S. AniC 4 


Physical Chemistry and Instrumental Methods, Belgrade, 

Serbia 

2 Institute of Nuclear Science Vinca, Radiation and 

Environmental Protection Department, Belgrade, Serbia 

3 University of Belgrade Faculty of Physical Chemistry, 

Department of Dynamic and Structure of Matter, Belgrade, 

Serbia 

4 University of Belgrade Institute of Chemistry Technology and 

Metallurgy, Department of Catalysis and Chemical 

Engineering, Belgrade, Serbia 

Different analytical methods for determination of piroxicam 

(PX) in various real samples were summarized in [1] . However, 

some new methods based on relatively simple and inexpensive 

equipment were desirable. Regarding that, the method based on 

employing the analyte pulse perturbation technique to the 

Bray-Liebhafsky (BL) oscillatory reaction as very nonlinear 

system, as well as using the potentiometric monitoring of analyte 

perturbation, promise the alternative to some instrumental 

methods due to its low cost instrumentation and relatively rapid 

detection procedure. 

For quantitative determination of PX [2] , the BL matrix in a 

stable non-equilibrium stationary state that was generated in 

continuously fed well stirred tank reactor, was used. The BL matrix 

response to perturbations by different concentrations of PX is 

followed by a Pt electrode. The method relies on the linear 

relationship between maximal potential shift, ΔE m , and the added 

PX concentration in the range of 6.8 x 10 –5 –1.9 x 10 –3 mol L –1 . Under 

the optimized conditions (T=64.0°C, [H 2 SO 4 ] 0 =8.55x10 -2 mol L -1 , 

[KIO 3 ] 0 = 5.90x 10 -2 mol L -1 , [H 2 O 2 ] 0 = 1.50 x10 -1 mol L -1 

and j 0 =2.95x10 -2 min -1 ), the regression equation of the standard 

series calibration curve is ΔE m =-5.9 - 14671.9 x c PX . The method 

has a rather good sample throughput of 30 samples h -1 with the limit 

of detection LOD =6.3x 10 –5 mol L –1 , precision RSD =4.2 %, as 

well as recoveries RCV ≤ 104.7 %. Applicatibility of the proposed 

method to the direct determination of PX in different 

pharmaceutical formulations (tablets, ampoules and gel) was 

demonstrated. 

references: 

1. M. Starek, J. Krzek, Talanta, 2009, 77, 925. 

2. V. Vukojevic, N. Pejic, D. Stanisavljev, S. Anic, 

Lj. Kolar-Anic, Analyst, 1999, 124, 147. 

Keywords: piroxicam; potentiometric; oscillatory reaction; 


P - 0 5 6 5 

deterMinAtion of diffuSion CoeffiCientS By 

tAyLor diSPerSion AnALySiS uSinG CAPiLLAry 

eLeCtroPhoreSiS inStruMentAtion with 

vAriouS deteCtorS 

J. Petr 1 , P. GinterovA 1 , r. KnoB 2 , J. znALezionA 1 , 

v. MAier 1 , J. SevCiK 2 


– Palacky University in Olomouc, Department of Analytical 




Determination of diffusion coefficient represents an 

important task for many branches of the research ranging from 

pure physical chemistry to medicine where the diffusion of 

pharmaceutical active substances has an impact on the physiologic 

state of organism. There a plenty of methods used for such 

measurements. A special place is hold by capillary electrophoresis 

(CE). CE represents a fast, low cost, easy operation technique that 

needs only a few microliters of samples. On the basis of the Taylor 

and Aris theory, CE can be utilized for the measurements of the 

rate of the diffusion during the flow of compounds through the 

capillary. The aim of our work was to apply this methodology, 

called Taylor dispersion analysis (TDA), for measurements of the 

diffusion coefficient of model compounds employing various 

detectors that have an additional power (e.g. can be applied for 

UV non-absorbing compounds, provides structural information). 

In our study, three types of detectors were used: (i) contactless 

conductivity detector for analysis of some saccharides, 

(ii) laser-induced fluorescence detector for analysis of carbogenic 

quantum dots, and (iii) single quadrupole mass spectrometer for 

analysis of a mixture of aminoacids. We observed that the 

utilization of such detectors can be very profitable for the 

determination of diffusion coefficients. 

Acknowledgement: The financial support by the 

KONTAKT project LH11018, the Operational Program 

Research and Development for Innovations – ERDF 

(project CZ.1.05/2.1.00/03.0058), and the Operational 

Program Education for Competitiveness – ESF (project 

CZ.1.07/2.3.00/20.0018) is gratefully acknowledged. 

Keywords: diffusion coefficient; capillary electrophoresis; 



s1145 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 6 6 

the ProtoeLeCtriC PotentiAL MAP (PPM).A 

uniforM enerGy SCALe of the CheMiCAL 

PotentiAL of the Proton And eLeCtron in 

different MediA 

K. Puetz 1 , v. rAdtKe 1 , d. hiMMeL 1 , i. KroSSinG 1 

1 Albert-Ludwigs-Uni. of Freiburg, Anorganische und 

Analytische Chemie, Freiburg, Germany 

We recently introduced a unified Bronsted acidity scale on 

the basis of the chemical potential of the proton in any medium 

allowing the comparison of pH values of different media. We 

defined the reference state of maximum acidity as the standard 

chemical potential of the proton in the gas phase (ideal H + gas, 

1 bar, 298.15 K), arbitrarily set to 0 kJ mol –1 . The acidity and 

hence the chemical potential of the gaseous proton is lowered by 

the interaction with any type of a medium i.e. complexation of H + 

in the gas phase, solution, or in the solid state. [1] 

The definition and determination of absolute standard 

reduction potentials is under discussion since a long time. From a 

theoretical point of view as well as for many applications reduction 

potentials comparable between different solvents are of great interest 

and may lead to completely new insights and applications. [2] 

We define the absolute reduction potential scale totally analogous 

to the absolute pH scale setting the chemical potential of the 

electron in the gas phase (ideal e- gas, 1 bar, 298.15 K) 

to 0 kJ mol-1 . 

The Hydrogen Evolution Reaction (HER) correlates the pH 

scale with the redox scale. Our intention is to establish a novel 

uniform scale for the chemical potential of the proton as well as 

for the electron leading to the Protoelectric Potential Map (PPM). 

Once a suitable absolute redox scale pe is adopted the PPM as 

abs 

a 2D plot of pe versus pH allows one to determine the optimal 

abs abs 

solvent for a given redox reaction. The Poster will present our 

recent ongoing efforts to establish the PPM in liquid media with 

the help of electrochemical measurements and supported by 

quantum chemical thermodynamic calculations. [3] 

references: 

1. a) D. Himmel, S.K. Goll, I. Leito, I. Krossing, 

Angew. Chem., Int. Ed. Engl. 2010, 49, 6885-6888. 

b) viP-Paper: D. Himmel, S.K. Goll, I. Leito, 

I. Krossing, Chem. Eur. J. 2011, 17, 5808 – 5826. 

2. a) O. Popovych, R.G. Bates, Crit. Rev. Anal. Chem. 1970, 

1, 73. 

b) A.A. Isse, A. Gennaro, J. Phys. Chem. B 2010, 114, 

7894–7899. 

3. In preparation. 


P - 0 5 6 7 

KinetiC SPeCtroPhotoMetriC 

deterMinAtion of n-ACetyL-L-CySteine BASed 

on the reduCtion of CoPPer(ii)-neoCuProine 

reAGent 

n. rAdiC 1 , L. KuKoC-Modun 1 , M. BioCiC 1 

1 Faculty of Chemistry and Technology, Department of 

Analytical Chemistry, Split, Croatia 

Novel simple kinetic spectrophotometric method for the 

determination of N-acetyl-L-cysteine (NAC) has been developed 

and validated. NAC is a synthetic aminothiol antioxidant that has 

been in clinical use for more than 40 years, primarily as a 

mucolytic agent and in the management of paracetamol 

(acetaminophen) poisoning. 

The proposed method is based on the reduction of Cu(II)neocuproine 

reagent to Cu(I)-neocuproine with the analyte, in a 

Britton-Robinson buffer solution (Acetic/Boric/Phosphoric acid 

buffer solution, pH = 3.0). The non-stable absorbance of the 

formed Cu(I)-neocuproine chelate is measured at 458 nm. 

The proposed redox reaction is very fast, but the coloured 

product of the reaction is unstable probably due to oxidation with 

the oxygen from the air. Therefore is very important to measure 

the signal in kinetic part of the reaction (under dynamic conditions 

in which the concentrations of reactants and products are changing 

as a function of time). 

The initial rate and fixed time (at 1 min) methods were 

utilized for constructing the calibration graphs. Initial reaction 

rates were determined from the slopes of the absorbance-time 

curves. The logarithms of the reaction rates were plotted as a 

function of logarithms of NAC concentrations. The graph was 

linear in concentration range from 6.0 x 10-7 to 8.0 x 10-5 mol L-1 with the regression equation y=1.0181 x + 2.9927 (R2 =0.9998). 

The slope of the calibration curve (1.0181) confirmed the first 

order reaction. 

The graph of the fixed time method was linear in 

concentration range from 6.0 x 10-7 to 8.0 x 10-5 mol L-1 with the 

regression equation y = 7111 x - 0.0027 (R2 = 0.9999), and the 

limit of detection 1.7 x 10-7 mol L-1 . 

The proposed methods were successfully applied for the 

determination of NAC in its commercial pharmaceutical 

formulations and compared to the official iodimetric method. 

Keywords: kinetics; analytical methods; UV/vis spectroscopy; 

reduction; redox chemistry; 



s1146 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 6 8 

deteCtion And quAntifiCAtion of 

diCLofenAC in wAter 

S. rAu 1 , G. GAuGLitz 1 

1 University of Tuebingen, IPTC AK Gauglitz, Tuebingen, 

Germany 

Nonsteroidal anti-inflammatory drugs such as diclofenac are 

one of the most widely used drugs in human and veterinary 

medicine at present. Because the rate of elimination of diclofenac 

in communal sewage treatment plants is low [1] , diclofenac is 

ubiquitously present in the aquatic environment. Although, 

diclofenac was not found in surface waters at concentrations that 

were high enough to cause acute toxic effects [2] , its presence can 

lead to long-term effects due to bioaccumulation or additive and 

synergistic effects by mixing it with different pharmaceutically 

active compounds. 

To protect both the environment and human health, it is vital 

to develop reliable tools for detecting and monitoring diclofenac 

in water. The most common analytical techniques used to 

determine pharmacologically active substances in water at present 

are gas or liquid chromatography combined with mass 

spectrometry [3, 4] . Those methods are very sensitive, but have the 

disadvantage of requiring sample preparation and cleanup. 

Optical biosensors fulfill the requirements to be sensitive, 

simple, cost-effective and quick to perform. Furthermore they do 

not require extensive sample preparation. 

In this work Reflectometric Interference Spectroscopy 

(RIfS) [5] has been used as optical detection method to detect and 

quantify diclofenac in water samples. RIfS is a label-free and time 

resolved method, also ideal for optimizing surface chemistry, 

understanding matrix effects and calibrating the sensor. 

references: 

1. Hartmann J. et al., 2008. Chemosphere 70, 453-461. 

2. Fent K., Weston AA., Caminada D., 2006. Aquatic Toxicol 

76, 122–159. 

3. Noche GG. Et al., 2011. J Chromatogr A 1218(52), 

9390–9396. 

4. Baranowska I., Kowalski B., 2011. Pol J Environ Stud 

20(1), 21–28. 

5. Rau S., Gauglitz G., 2012. Anal Bioanal Chem 402(1), 

529–536. 

6. Tschmelak J. et al., 2005. Anal Bioanal Chem 382(8), 

1895–1903. 

Keywords: biosensors; immunoassays; 


P - 0 5 6 9 


MetronidAzoLe By MeAnS of A MerCury 

MeniSCuS Modified SiLver SoLid AMALGAM 

eLeCtrode 

t. ruMLovA 1 , L. SKvorovA 1 , v. vySKoCiL 1 , 

J. BAreK 1 



Metronidazole (2-(2-methyl-5-nitro-1H-imidazol-1-yl)ethanol) 

belongs to the group of antibiotics, amebicids and antiprotozoal 

medicaments, and it is known as a cancerogenic compound. This 

contribution is focused on the determination of metronidazole 

using modern voltammetric techniques, namely direct current 

voltammetry (DCV) and differential pulse voltammetry (DPV) at 

a mercury meniscus modified silver solid amalgam electrode 

(m-AgSAE), in drinking and river water model samples and on the 

determination of its content in selected pharmaceutical 

formulations. The main advantages of m-AgSAE are: Its wide 

potential window in cathodic region (cca 1,8 V span), easily 

renewable surface of the electrode and also non-toxicity as 

compared to mercury electrodes. It was confirmed in this work that 

it is possible to determine metronidazole in the concentration range 

of 0.2 to 100 μmol.l-1 in the medium of Britton–Robinson buffer 

of pH 8.0 with the limit of quantification (LOQ) 0.32 μmol.l-1 and 

0.19 μmol.l-1reached using DCV and DPV, respectively. Moreover, 

the practical applicability of the newly developed methods was 

verified upon the direct determination of metronidazole in model 

samples of drinking and river water in the concentration range of 

0.2 to 10 μmol.l-1 with LOQ ≈ 0.2 μmol.l-1 (for all the applications 

tested). The contents of metronidazole in pharmaceutical 

formulations Efloran ® (Krka) and Entizol ® (Polpharma) was 

successfully determined by the standard addition method and by 

the calibration curve method using both voltammetric methods 

developed. 

Acknowledgement: This research was financially supported by 

The Ministry of Education, Youth and Sports of the Czech 




P206/12/G151). 

Keywords: Electrochemistry; Analytical chemistry; 

Voltammetry; Amalgams; 



s1147 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 7 0 

PhotoCheMiCAL voLAtiLe forMS GenerAtion 

for deterMinAtion of SeLeniuM By quArtz 

furnACe AtoMiC ABSorPtion SPeCtroMetry 

M. ryBinovA 1 , d. dvorAKovA 1 , A. KoLoroSovA 1 , 

v. Cerveny 1 , J. hrAniCeK 1 , P. ryChLovSKy 1 

1 Faculty of Science Charles University in Prague, Analytical 


This work is focused on the determination of selenium in 

aqueous samples using photochemical generation of its volatile 

forms coupled with atomic absorption spectrometry. This 

emerging approach of sample introduction is a useful alternative 

to conventional chemical and electrochemical generation due to 

its simplicity, versatility and cost effectiveness. Method is based 

on the fact, that in the presence of a low molecular weight organic 

acid (formic, acetic, propionic or malonic), inorganic 

selenium(IV) is converted by the effect of UV radiation into 

volatile species (selenium hydride, selenium carbonyl, dimethyl 

selenide, diethyl selenide, respectively). In this approach of 

sample introduction, a flow-through photoreactor consisting of 

PTFE tubing (1.0 i.d. / 2.0 o.d.) wrapped around the low-pressure 

Hg vapor UV lamp was first constructed. Optimum experimental 

conditions for photochemical vapor generation using formic or 

acetic acid were then found. Attention was paid to optimize the 

carrier gas flow rate as well as the auxiliary hydrogen flow required 

for complete atomization of generated volatile selenium form in 

externally heated quartz furnace. Further key parameters were also 

optimized: effects of additives and acid concentration or the time 

of irradiation of the analyte (it depends on the length of PTFE 

tubing and sample flow rate). A detection limit of 1.0 µg L-1 Se(IV) 

with a repeatability of 3.4 % (RSD, n = 10, formic acid) was 

obtained using this coupled technique. Consequently, the 

generation efficiency was investigated. Except of classical 

methods (comparing of slope of calibration curves of 

photochemical and reference chemical generation; determination 

of residual analyte in waste), radiotracer 75Se was used. Similarly, 

interference study and verification of proposed method on real 

samples were realized. 

Acknowledgments: This work was supported by M·MT 

(project No. MSM0021620857), Charles University in Prague 

(project SVV 2012-265201 and project UNCE 204025/2012). 

Keywords: UV photochemical generation; volatile form; 

atomic absorption spectrometry; selenium; 


P - 0 5 7 1 

Study of CoLuMnS MACroCAPiLLAry thiCK 

fiLM in GAS ChroMAtoGrAPhy: effiCieny And 

CAPACity of inJeCtion 

M. SAidi 1 

1 University of M’hamed BOUGARA of Boumerdes, Department 

of Materials Engineering, Boumerdes, Algeria 

As part of a study columns macrocapillary a film thick and 

grafted in gas chromatography, recently developed as a friendly 

columns, we calculate an efficiency criterion impregnation has 

adapted the kinetic of these columns. 

However we show that for this, it does not involve the 

resistance to the transfer of liquid matter, considered negligible 

usual columns with a thin film. We must also take into account 

the interfacial resistance, expected by the theory of Khan and not 

by the equations of classical GOLAY. This work contributes to 

end a controversy thirty years old on a life of the term interfacial 

resistance. 

However we show that it is possible to preserve the full 

effectiveness of these columns within easy injection of the kind 

of columns, except for the rigor of solutes apolar, priced at a high 

dilution in the solvent. But these injections are perfectly possible 

if consent is a significant loss of efficiency, thanks to a high 

dilution and at a rate well above the optimum. It remains then 

these columns substantial benefits compared to packed columns. 

Keywords: Gas chromatography; Macrocapillary columns; 

Thick Film; Efficiency of impregnation; Quantity injection; 



s1148 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 7 2 

deveLoPMent of rP-hPLC Method for 

vinCriStine SuLfAte, dAunoruBiCin And 

doxoruBiCin 

S. SAnLi 1 , A. BedihA 2 , S. nuruLLAh 1 

1 Usak University, Chemistry Department, Usak, Turkey 

2 Hitit University, Chemistry Department, Corum, Turkey 

Email: senemkamacisanli@gmail.com 

Daunorubicin (DAU) and doxorubicin (DOX) are the most 

commonly used anthracycline anticancer antibiotics. Their 

molecules consist of a tetracyclic quinoid aglycone and an amino 

sugar–daunosamine, which are linked by a glycoside bond [1] . 

Vincristine sulfate (VCR) is a natural vinca alkaloid derived from 

the periwinkel plant Catharantus roseus G. Don. It has been used 

in variety of human neoplatic disorders for nearly 40 years. 

In this study, simple, reliable, and rapid RP-HPLC method 

has been developed for the determination of these drugs and this 

method has been succesfully applied human urine samples. These 

compounds are well separated on a C18 column by using the 

mobile phase consist of a mixture of acetonitrile (50:50; v/v, 

20 mM H PO - pH = 9.5) at a flow rate of 1.5 mL/min. Good 

3 4 

sensitivity for all analytes was observed with DAD detection. 

For each compound, the calibration curves were linear over 

a concentration range of 1–12 μg.mL-1 . Limits of detection (LOD) 

and the limits of quantification (LOQ) were found for VCR 0.2145 

and 0.6542 μg.mL-1 ; for DAU 0.045 and 0.1226 μg.mL-1 ; 

for DOX 0.0901 and 0.2731 μg.mL-1 . 

references: 

1. F. Arcamone, A.G. Franceshi, S. Pencom, S. Selva, 

Tetrahedron Lett. 1969, 1007–1010. 

Sparreboom, Anal. Biochem. 1999, 266, 216–221. 

Keywords: Analytical Methods; Liquid chromatography; 

Cancer; Drug delivery; Acidity; 


P - 0 5 7 3 

rAPid deteCtion of eSCheriChiA CoLi uSinG 

MiCroAnALyzer BASed on the PreSenCe of 

o-nitroPhenoL 

L. G. SAPtALenA 1 , u. teLGheder 1 

1 University Duisburg-Essen, Instrumental Analytical Chemistry, 

Essen, Germany 

With persistent occurrence of water- and food-borne 

diseases outbreaks such as those caused by pathogenic 

Escherichia coli, there is an urgent need for a (bio) analytical 

sensor that can rapidly detect and identify the source of 

contamination in a timely manner. Standard methods usually 

involve culturing which needs at least 18 h. In this work, an 

analytical method for rapid detection of E. coli in water sample 

was developed. E. coli was incubated in a lactose-rich nutrient 

containing Ortho-Nitrophenyl-β-galactoside (ONPG) substrate to 

induce the activity of β-galactosidase enzyme in E. coli. In a 

controlled environment, β-galactosidase enzyme can break 

β-galactoside bond in lactose, releasing o-nitrophenol. To allow 

the accumulation of the o-nitrophenol in the sample vials, the 

bacteria were incubated under anaerobic condition. To investigate 

the minimum period required for the production of the 

o-nitrophenol, the bacteria were incubated in different sample vials 

under different incubation periods. The incubation periods were 

varied from 0 to 4 h with 30 min intervals. To detect the 

o-nitrophenol, headspace analysis of o-nitrophenol were done using 

microAnalyzer, a miniaturized gas chromatography – differential 

mobility spectrometry (GC-DMS) system. It was found that the 

o-nitrophenol was able to be detected by microAnalyzer within 

200 s. It was also found that the minimum incubation period was 

2.5 h, whereas the optimum incubation period was 3 h. To our 

knowledge, our method offers the most rapid incubation and 

detection of E. coli and the first application of microAnalyzer in this 

field. With the microAnalyzer being portable, could be operated 

using ambient air, does not need oven, and has a low-energy 

requirement, to mention few, this method is very attractive to be 

applied for an on-site detection of E. coli, providing a better 

approach in the E. coli outbreak risk management. 

Keywords: Escherichia coli; microAnalyzer; microbial water 

quality monitoring; 



s1149 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 7 4 

dynAMiC extrACtion of oiL ProduCtS froM 

ContAMinAted SoiLS 

e. SAvoninA 1 , P. fedotov 1 , A. Soin 1 , 

t. MAryutinA 1 

1 Vernadsky Institute of Geochemistry and Analytical Chemistry 

RAS, Department of Analytical Chemistry, Moscow, Russia 

Control of oil content in contaminated soils is a very actual 

task because of increasing development of oil industry. Existing 

methods used for the determination of oil hydrocarbons in soils 

are routine and time-consuming due to the necessity of laborious 

sample pretreatment prior to instrumentation analysis. Hence, the 

development of new methods for organic analysis of soils is 

required. 

The use of flow-through extraction systems (FTES) for 

dynamic extraction of hydrocarbons from soils is very promising. 

Microcolumns (MC) packed with a particulate sample are wellknow 

FTES [1] . In the present work cylindrical MC were applied 

to the analysis of spiked with oil hydrocarbons (OH) and 

contaminated soil samples. Tetrachlormethane was used as solvent 

for MC extraction of OH prior to the detection by 

IR-spectrometry. The dependence of extraction efficiency on soil 

type, eluent volume and extraction time was systematically 

studied. Elution curves show that the eluent volume of 20–30 mL 

is enough for extraction in MC. Results on OH content obtained 

using extraction in MC, Soxhlet extraction and batch extraction 

were comprared. It has been showm that the recovery of OH after 

extraction using MC is 70–94%. No filtration step is required 

before the determination of OH in the MC effluent. The technique 

enables the extraction to be performed within 20–30 minutes 

only.The proposed approach to the sample pretreatment in organic 

soil analysis opens a new door into the development of new 

analytical methods for the control of oil contaminated soils. 

references: 

1. M. Rosende, M. Miró, V. Cerda Analytica Chim Acta, 

2008, 619, 192 

Keywords: extraction; oil products; soil; 


P - 0 5 7 5 

the inveStiGAtion of therMAL deCoMPoSition 

of nitro-ChLoro-AzidoBenzeneS with 

therMoAnALytiCAL And CoMPutAtionAL 

MethodS 

n. SenoCAK 1 , n. yiLMAz 2 , S. Öz 3 , i. SvoBodA 4 , 

o. AtAKoL 2 

1 Police Criminal Labratory, Chemistry, Ankara, Turkey 


3 Ahi Evran University, Chemistry, Kirsehir, Turkey 

4 TU- Darmstadt, FB Materialwissenschaft, Darmstadt, 

Germany 

1,2-dichlorobenzene and 1,2,3-trichlorobenzene were 

nitrated with HNO /H SO . The obtained mixtures were 

3 2 4 

converged into azido-chloro-nitrobenzenes via nucleophilic 

subtitution reaction with NaN as described in the literature 3 [1] . 

The components in the precipitate were seperated by fractional 

crystallization and were investigated by TG. Benzofuroxan 

formation after elimination of N at 100–120°C was observed from 

2 

IR, MS, and XRD results in case of nitro and azide groups are 

next to each other in the aromatic ring (Fig.1). Additionally, the 

released energies for exothermic reaction of o-nitroazidobenzenes 

were measured by DSC. On the other hand an obvious detonation 

reaction was observed for dinitrodiazidobenzenes at 130–150 °C. 

All theoretical calculations were carried out using the 

Gaussian G09W (revision B.01) program package. [2] DFT-based 

structure optimizations and frequency analyses were performed 

at the B3LYP/cc-pVDZ level of theory. [3] The enthalpies of 

formation of both reactants and products were calculated using 


in order to obtain accurate energies. [4] From the calculated heat of 

formations the enthalpies of decomposition were calculated 

according to Hess’s Law and were compared with the 

experimental values which were available from DSC analysis. 

The good agreement between the experimentally observed 

enthalpies of decomposition and the CBS-4M calculated values 

gives credence to the accuracy of the applied CBS-4M method. 

references: 

1. A. S. Bailey, J.R. Case, Tetrahedron, 3, 113-131,1958 

2. Gaussian 09 Software, Revision B01.2009 

3. A. D. Becke, J. Chem. Phys., 88, 1053-1062, 1988 

4. Jr. A. J. Montgomery, M. J. Frisch, J. W. Ochterski, 


Keywords: Benzofuroxan; CBS-4M; DFT; Nitroazidobenzene; 

Thermal analysis; 



s1150 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 7 6 

An uLtrASenSitive BioSenSor for C-erBB-3 

deteCtion BASed on eLeCtroCheMiCAL 

iMPedAnCe SPeCtroSCoPy 

C. SAyiKLi 1 , C. CAnBAz 1 

1 Namik Kemal University Faculty of Sciences and Arts, 

ChemistryBiochemistry Division, Tekirdag, Turkey 

Breast cancer is one of the most common cancers in women. 

Becouse of the aggresive behaviour, and can be diagnosed early, 

breast cancer is one of the most cancer type that is studied in the 

relation between diagnostic and treatment methods. [1, 2] 

The c-erB3 gene, which takes part on chromosome 12q13 

and codes for glycoprotein and is 180 000 molecular weight, is a 

declared member of the type I family of growth factor receptors. [3] 

C-erB3 protein is attended in normal human fatal and adult 

tissues [4] , and also known as expressed at protein levels and 

mRNA in tumor cells and primary tumor material [4, 5]. 

An electrochemical bio-sensor system based on 

electrochemical impedance spectroscopy is developed to detect 

c-erB3 by anti-c-erB3. AntiCerB was immobilized through 

covalent coupling with cysteamine which formed a self-assembled 

monolayer on gold electrodes covered with heksenditiol and 

AuNP. Electrochemical impedance spectroscopy(EIS) and cyclic 

voltammetry (CV) techniques were used to detect c-erB3 and to 

characterize the immobilization process. Kramers–Kronig 

Transform was performed on the experimental impedance data. 

To provide the biosensor’s currency, experimental parameters 

were optimized. The obtained results provided a linear response 

range from 0,2 pg to 1,4 pg c-erB3. 

references: 

1. R.A Oldenburg, H. Meijers-Heijboer, C.J. Cornelisse, 

P. Devilee, Crit. Rev. Oncol. Hemat. 2007, 63, 125. 

2. V.V. Levenson, Biochim. Biophys. Acta. 2007, 1770, 847. 

3. A Travis’, SE Pinder, JFR Robertson, JA Bell, P Wencyk, 

WJ Gullick, RI Nicholson, DN Poller, RW Blamey, 

CW Elston and IO Ellis Britsh Journal of Cancer 1996, 

74, 229–233 

4. N. R. Lemoine, D. M. Barnes, D. P. Hollywood, 

C. M. Hughes, P. Smith, E. Dublin, S. A. Prigent, 

W. J. Gullick, and H. C. Hurst Br J Cancer. 1992, 66(6): 

1116–1121. 

5. T. Rajkumar, W.J. Gullick. Br. J. Cancer 1994. 

70:459–465. 

Keywords: Breast cancer; biomarker c-erbB-3; biosensor; 

Electrochemical impedance spectroscopy; 


P - 0 5 7 7 

A noveL, uLtrA SenSiBLe BioSenSor BuiLt By 

LAyer-By-LAyer CovALent AttAChMent of A 

reCePtor for diAGnoSiS of tuMor Growth 

M. K. SezGintürK 1 , o. uyGun 1 

1 Namik Kemal University Faculty of Sciences and Arts, 

ChemistryBiochemistry Division, Tekirdag, Turkey 

In the presented research, a novel, ultra sensible biosensor 

for the impedimetric detection of vascular endothelial growth 

factor (VEGF) is introduced. The human vascular endothelial 

growth factor receptor 1 (VEGFR1, Flt-1) was used as a 

biorecognition element for the first time in the literature. The 

immobilization of VEGF-R1 on glassy carbon electrodes was 

carried out by layer-by-layer covalent attachment of VEGF-R1. 

The electrochemical properties of the layers constructed on the 

electrodes were characterized by electrochemical impedance 

spectroscopy (EIS) and cyclic voltammetry (CV). The differences 

in electron transfer resistance (R ) between the working solution 

et 

and the biosensor surface, recorded by the redox probe 

K [Fe(CN) ]/K [Fe(CN) ], confirmed the binding of VEGF to 

3 6 4 6 

VEGF-R1. The new biosensor allowed a detection limit of 

100 fg/mL with a linear range of 100 fg/mL to 600 fg/mL to be 

obtained. The biosensor also exhibited good repeatability (with a 

correlation coefficient of 1.95 %) and reproducibility. 

Keywords: Tumor growth; Vegf; Vegf-R1; Biosensor; 

Electrochemical impedance spectroscopy; 



s1151 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 7 8 

CoMPAriSon of direCt infuSion MASS 

SPeCtroMetry, hPLC/MS And ion MoBiLity/MS 

in AnALySiS of PoLyACryLiC ACidS 

K. SLovAKovA 1 , d. roBertS 2 , t. f. JorGe 3 , M. 

h. fLorenCio 3 , K. LeMr 1 

1 Palacky University Faculty of Science, Analytical chemistry, 


2 Waters, Atlas Park Simonsway, Manchester, United Kingdom 

3 Faculty of Sciences of the University of Lisbon, Chemistry and 

Biochemistry Centre, Lisbon, Portugal 

Polyacrylic acids (PAA) belong to potential environmental 

pollutants due to their extensive use and solubility in water 

contributing to their distribution in environment. 

The direct infusion and chromatographic experiments were 

performed using an LCQ DUO ion trap mass spectrometer 

equipped with electrospray ion source (Thermo Finnigan, San 

Jose, USA) and an HPLC Agilent 1100 Series chromatograph 

(Agilent, USA) with Gemini column (5μm C18, 110 A; 

Phenomenex, Torrance, USA). Ion mobility mass spectrometric 

experiments were carried out using a SYNAPT G2-S spectrometer 

(Waters, Manchester, UK) by flow injection analysis with 

negative electrospray ionization. 

Direct infusion mass spectrometry using electrospray 

ionization in negative ion mode allowed fast detection of several 

oligomeric series, but the detail polymer characterization required 

time consuming inspection and interpretation of spectra. 

Chromatographic separation (LC/MS) is more timeconsuming 

but allowed obvious differentiation of oligomeric 

series with different end groups. Subsequent LC/MS/MS analysis 

contributed to the identification of the end group. 

Ion mobility mass spectrometric experiments were used to 

provide further structural information by separation of the 

individual charge series. It allowed fast characterization of PAA 

samples and drift time vs m/z plots can be used as fingerprints for 

the differentiation of samples. It is evident that some separation 

(ion mobility or chromatographic) is very useful for complicated 

PAA mixture analysis. Hyphenation of chromatography, ion 

mobility and mass spectrometry can offer a very useful tool for 

PAA analysis. Evaluation of orthogonality of chromatographic 

and ion mobility is under study. 

Acknowledgement: The authors gratefully acknowledge 

the support by Palacky University (PrF 2012 020) and by the 


(ME10013) and Operational Program Research and Development 

for Innovations - European Regional Development Fund 

(project CZ.1.05/2.1.00/03.0058), and Fundacio para a Ciencia 

e a Tecnologia for financial support (PEst- 

OE/QUI/UI0612/2011). 

Keywords: Mass spectrometry; Liquid chromatography; 

Polymers; 


P - 0 5 7 9 

SuBStitution of wAter By MethAnoL in 

AqueouS norMAL PhASe Liquid 

ChroMAtoGrAPhy 

J. SouKuP 1 , P. JAnderA 1 



The effects of mobile phase composition on the separation 

of phenolic acids on four types of hydrosilated silica columns 

(hydrosilated silica, diamond hydride, cholesterol and bidentate 

column) in acetonitrile/water and acetonitrile/methanol mobile 

phases, both in the ANP and RP modes in the full mobile phase 

composition range including both aqueous normal phase (ANP) 

and reversed-phase (RP) HPLC modes were investigated. In case 

of ANP, the analyte is distributed between a water rich stationary 

layer and the bulk mobile phase with a lower water 

concentartions, probably by a combination of partition and 

adsorption mechanisms. Phenolic acids elute in the order of 

increasing polarities i.e. with increasing number of polar groups 

(OH, -COOH, etc.) opposite to the reversed-phase mechanism. 

The typical mobile phase for ANP chromatography includes 

acetonitrile containing 1-15% of buffered or acidified water. We 

have found that methanol in buffered mobile phase can substitute 

water in the ANP mode. In both types of mobile phases, the 

elution order of selected phenolic acids in the ANP mode is 

identical and their retention decreases as the concentration of 

water or methanol in mobile phase increases. Phenolic acids are 

more strongly retained in ACN/methanol on hydrosilated silica 

column in comparison to their retention on the same column in 

ACN/water mobile phase, whereas the retention of phenolic acids 

on cholesterol and diamond column is slightly higher in 

ACN/water than in ACN/MeOH. The retention of phenolic acids 

on bidentate column is comparable in both mobile phases. Slightly 

impaired resolution and selectivity was observed in ACN/MeOH 

as the mobile phase in comparison to the ACN/water on all 

columns tested. 

Acknowledgement: This work was supported by the by the 

Grant Agency of the Czech Republic, project P206/12/0398. 

Keywords: aqueous normal phase LC; phenolic acids; silica 

hydride material; 



s1152 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 8 0 

exPeriMentAL deSiGn APPLied on 

PyrohydroLytiC extrACtion of fLuorine 

And ChLorine froM CoAL 

i. SredoviC 1 , d. CoKeSA 2 , A. onJiA 2 , 

L. rAJAKoviC 3 

1 Faculty of Agriculture, Chemistry and Biochemistry, 

Belgrade-Zemun, Serbia 

2 Vinca Institute, Chemical Dynamics, Belgrade, Serbia 

3 Faculty of Technology and Metalurgy, Analytical Chemistry, 


This research has been focused on the determination of 

fluorine and chlorine content in the lignite coal by applying a 

experimental design approach. A pyrohydrolysis (Phy) apparatus 

system was constructed, and the pyrohydrolytic parameters were 

evaluated and optimized by two statistical methods: 

Plackett-Burman (PB) design and response surface methodology 

(RSM). Halogen content in the absorption solution was measured 

by ion selective electrode (ISE) and by ion chromatography (IC). 

Results of PB designed experiments indicated that the most 

important parameters on Phy-ISE determination of fluorine in coal 

were time, temperature and oxidation atmosphere, while the 

Phy-IC determination of chlorine was strongly influenced by 

absorption solution and temperature. These screening experiments 

signified that during the pyrohydroytic extraction and within the 

range of investigated parameters, in some degree the chlorine in 

coal could volatilizied as molecular chlorine. 

The RSM is a statistical modeling technique employed for 

multiple regression analysis using the data obtained from designed 

experiments. The statistical models applied were suitable for 

predicting and optimizing of fluorine determination within the 

range of variables used. 

It was concluded that optimal conditions for Phy-ISE 

determination of fluorine in coal were: 0.25 g of coal sample, 

0.30 mL min-1 of oxygen flux, a temperature of 1100 °C, 15 min 

of pyrohydrolysis and Na CO (2 mmol L 2 3 -1 ) as adsorption 

solution. The limit of detection of the proposed method was 

20 μg g-1 , with good recovery (95 %) and relative standard 

deviation value less than 5 %. According to the applied 

experimental design, the pyrohydrolytic extraction was unsuitable 

for chlorine in coal determination. 


P - 0 5 8 1 

effeCtS of Liquid MAnure AMendMent on 

ACCuMuLAtion of heAvy MetALS in wheAt And 

BArLey 

S. StAniSiC 1 , L. iGnJAtoviC 1 , S. PoPov 2 , 

S. SKrivAnJ 3 

1 Faculty of Physical Chemistry, Environmental Chemistry, 


2 Oenological Laboratory, Environmental Chemistry, Vrsac, 

Serbia 

3 Faculty of Chemistry, Environmental Chemistry, Belgrade, 

Serbia 

An experiment was carried out to evaluate uptake of heavy 

metals by wheat and barley in the presence of liquid manure 

amendment. Wheat and barley seedlings were grown on a filter 

paper in a 12-cm diameter Petri dish. Additionally, wheat 

seedlings were grown in pots containing unpolluted agricultural 

soil. All the seedlings were irrigated three times per week with 

prepared solutions: first solution with composition similar to rain 

water, second solution containing Cd, Cu, Zn, Pb, Ni, Fe, Mn, Hg 

and As, and the third solution of liquid manure containing the 

same heavy metals as the second one. After 10 days the plants 

were weighed and 1 g of plant tissue was prepared for ICP-OES 

analysis by microwave digestion with mixture of HNO and H O . 

3 2 2 

The results have shown that the uptake of arsenic and mercury 

was highest for both plants grown in Petri dish. Beside high 

arsenic content, the pot grown wheat contained a high amounts 

of iron and manganese, probably due to the adsorption of nickel, 

cadmium, cooper and mercury on soil phases. On the other hand, 

the wheat grown without soil had higher content of nickel, 

cadmium and cooper, while the uptake of manganese and iron was 

lowered. The lower uptake of all heavy metals was observed by 

amendment of liquid manure, with exception of manganese in pot 

grown wheat and mercury in all plants. 

Keywords: analytical chemistry; environmental chemistry; 

arsenic; mercury; 



s1153 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 8 2 


MonoLithiC StAtionAry PhASeS for the 

SePArAtion of SMALL MoLeCuLeS 

M. StAnKovA 1 , P. JAnderA 1 , J. urBAn 1 , 

v. SKeriKovA 1 



Monolithic stationary phases are composed of one piece of 

porous material which fills the whole space of capillary column. 

Organic polymer monoliths are prepared by radical 

polymerization inside the silica capillary. Polymerization mixture 

contains functional and crosslinking monomers, porogenic 

solvents and initiator of polymerization reaction. Optimization of 

the composition of the polymerization mixture allows easy control 

of separation and hydrodynamic properties such as porosity, 

efficiency and selectivity. 

To increase efficiency of isocratic separation of lowmolecular 

compounds the effect of applied crosslinking monomer 

in polymetacrylate monolithic columns was studied. 

Polymetacrylate monolithic columns containing lauryl 

metacrylate as functional monomer were prepared using 

crosslinking monomers with different lengths of methylene 

and oxyethylene chains between two metacrylate units. 

Generally used ethylene dimetacrylate crosslinker was replaced 

by tetramethylene, hexamethylene, dioxyethylene, trioxyethylene 

and tetraoxyethylene dimetacrylate. For example, substitution of 

ethylen dimetacrylate by tetraethylene dimethacrylate led to a 

significant increase in efficiency up to 71 000 plates/meter for 

benzene. 

In order to increase the application range lauryl metacrylate 

was replaced by N, N-dimethyl-N-metacryloxyethyl-N-(3-sulfopropyl) 

ammonium betaine. Columns prepared with this functional 

monomer are suitable for application in hydrophilic interaction 

chromatography. Column prepared with zwitterionic functional 

monomer and dioxyethylene dimetacrylate as a crosslinking 

monomer provided efficiency of 69 000 plates/meter for thiourea 

and again confirmed the significant effect of chain length in 

crosslinking monomer to efficiency of monolithic capillary 

columns. 

The optimized columns have been tested for reversed-phase 

and hydrophilic interaction separations of complex mixture of 

flavones and phenolic acids in one-dimensional and 

comprehensive two-dimensional liquid chromatography. 

Acknowledgement: The financial support of GACR project 

P206/12/0398 is gratefully acknowledged. 

Keywords: liquid chromatography; polymers; 


P - 0 5 8 3 

quAntitAtion of SertrALine And itS 

MetABoLite By hPLC in PLASMA 

S. Suzen 1 , n. yuCe 1 , z. uCKun 1 

1 Ankara University Faculty of Pharmacy, Toxicology, Ankara, 

Turkey 

High rates of poor compliance and clinical heterogeneity of 

depression are main problems for the practical application of 

selective serotonin reuptake inhibitors (SSRIs). Main targets for 

the use of therapeutic drug monitoring (TDM) in depression 

pharmacotherapy are achievement of therapeutic ranges, 

confirmation of subtherapeutic concentrations in treatment 

non-responsive patients [1, 2] . Sertraline is a widely used 

antidepressant belonging to the SSRIs class. 

The purpose of this study was to provide a fast and 

economic analytical method to determine sertraline (S) and its 

metabolite desmethylsertraline (DS) in plasma for the use of TDM 

applications. 

Isolation of S and DS from plasma was carried out by solid 

phase extraction method with usage C-18 extraction cartridges 

(50 mg, 1 ml). These elutes were injected to Eclipse XDB-C18, 

4.6 mm × 150 mm column. The column was eluted at 50 °C with 

a mobile phase of 45% acetonitrile and 55% NaH PO , pH 3,8 at 

2 4 

a flow rate of 0.4 ml/min. Four different wave-length 

(200-205-210-215 nm) UV detection was applied. 

The chromatogram of a drug-free sample showed stable 

base-line and only a few extraneous peaks, even at 200 nm. 

Calibration curves were linear in the range of 5-500 ng/ml for S 

and 10-750 for DS, all of them with coefficients of determination 

(r2 values) ≥ 0.9500. High percent recovery values of S and DS 

were obtained. The optimal retention time for determining S and 

its metabolite DS in plasma were 8.5 min and 7.5 min, 

respectively. This method was successfully validated and applied 

to the determination of S and DS in plasma. 

Acknowledgement: This study is supported by The Scientific 

and Technological Research Council of Turkey, Project No: 

109S147) 

references: 

1. Mitchell PB. Br J Clin Pharmacol. 49, 303-312, 2000. 

2. Bosch ME, Sanchez AJ, Rojas FS, Ojeda CB. J Pharm 

Biomed Anal. 15;48(5):1290-302, 2008. 



s1154 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 8 4 

utiLizAtion of ChiroPtiCAL SPeCtroSCoPy in 

the CLiniCAL diAGnoSiS of ALzheiMer’S 

diSeASe 

M. tAtArKoviC 1 , t. voStrACKA 1 , z. fiSAr 2 , 

r. JirAK 2 , J. rABoCh 2 , v. SetniCKA 1 


Analytical Chemistry, Prague, Czech Republic 

2 Charles University in Prague and General University Hospital 

in Prague, Department of Psychiatry First Faculty of 

Medicine, Prague, Czech Republic 

The number of people who have Alzheimer’s disease is 

expected to grow as the population becomes older. Unfortunately, 

there is no reliable and non-invasive method for clinical diagnosis. 

As an improvement on molecular spectroscopy, we used 

chiroptical methods [ECD (electronic circular dichroism) and 

ROA (Raman Optical Activity)] to investigate the blood plasma [1] 

of healthy elderly controls and patients with Alzheimer’s disease. 

The aim was to find specific spectral markers and develop a new 

method for early clinical diagnosis. 

The ECD spectra were measured directly after thawing 

frozen samples and also after dilution them by a phosphate buffer 

in 0.01 mm quartz cuvette. Unfortunately, the blood plasma had 

a very strong fluorescence background in ROA; therefore, we 

tried to suppress it by the three different procedures: i) filtration 

by a 0.45 μm membrane filter, ii) addition of solid sodium iodide 

as a kinetic quencher, iii) sample blanching by a laser beam before 

the measurement. By using a combination of these procedures, 

fluorescence background was reduced ten times. Finally, the 

spectral baselines were improved by correction using of Fourier 

filtering. 

Multidimensional statistical methods were used to evaluate 

the ECD and ROA spectra. After evaluation we got 4 groups of 

samples: healthy controls, mild dementia, moderate dementia and 

severe dementia. 

Our preliminary results suggest that the human blood plasma 

can be successfully measured by both the ECD and ROA methods 

and these methods could be potentially useful for the clinical 

diagnosis of Alzheimer’s disease. 

Acknowledgement: The work was supported by the Prague 

Operational Programme for Competitiveness (Grant No 

CZ.2.16/3.1.00/22197); the Ministry of Education, Youth, 

and Sports of the Czech Republic (Grant No MSM6046137307); 

the Czech Science Foundation (Grant No P208/11/0105); 

Specific University Research MSMT No 21/2012 - 

A1_FCHI_2012_003, A2_FCHI_2012_015. 

references: 

1. Michal Tatarkovic, Zdenek Fisar, Jiri Raboch, Roman Jirak, 

Vladimir Setnicka, Chirality, 2012, in press 

Keywords: Raman spectroscopy; Circular dichroism; 

Analytical Methods; Medicinal chemistry; 


P - 0 5 8 5 

ChiroPtiCAL SPeCtroSCoPy of huMAn BLood 

PLASMA for PotentiAL diAGnoSiS of CoLon 

CAnCer 

M. tAtArKoviC 1 , A. SynytSyA 1 , M. MiSKoviCovA 2 , 

L. PetruzeLKA 2 , S. vLAdiMir 1 


Analytical Chemistry, Prague, Czech Republic 

2 Charles University in Prague and General University Hospital 

in Prague, Department of Oncology First Faculty of Medicine, 


Colon cancer is after the breast cancer the most abundant 

cause of the cancer death in the world. The reason of high 

mortality is the fact that almost half of the colon cancers are 

detected at an advanced stage. Unfortunately, well-established 

clinical procedures as fecal occult blood test (FOBT) and the 

colon endoscopic examination have low reliability and sensitivity 

at an early-stage of the disease. Therefore, we used chiroptical 

methods – electronic circular dichroism (ECD) and Raman optical 

activity (ROA) – combined with Raman spectroscopy to 

investigate the human blood plasma [1] with the aim to find new 

specific spectral markers for minimally-invasive clinical diagnosis 

of the disease. 

The ECD spectra of blood plasma samples from healthy 

controls and the colon cancer patients were measured after the 

dilution of plasma by a phosphate buffer (pH =7.4). In the cases 

of ROA/Raman experiments, the undesirable fluorescence 

background of the plasma was suppressed by the combination of 

three different procedures: filtration by a 0.45 μm membrane filter, 

addition of solid sodium iodide as a kinetic quencher and sample 

blanching by a laser beam before the measurement. 

The obtained spectra were evaluated by multidimensional 

statistical methods, which allowed distinguishing the blood 

samples of healthy controls and the colon cancer patients. 

Acknowledgement: The work was supported by 

the Prague Operational Programme for Competitiveness 

(Grant No CZ.2.16/3.1.00/22197); the Ministry of Health 

of the Czech Republic (Grant No NT13259); the Ministry of 

Education, Youth, and Sports of the Czech Republic 

(Grant No MSM6046137307); the Czech Science Foundation 

(Grant No P208/11/0105) and Specific University Research 

MSMT No 21/2012 - A1_FCHI_2012_003 and 

A2_FCHI_2012_015. 

references: 

1. Michal Tatarkovic, Zdenek Fisar, Jiri Raboch, Roman Jirak 

and Vladimir Setnicka, Chirality, 2012, in press 

Keywords: Analytical Methods; Cancer; Circular dichroism; 

Medicinal chemistry; Raman spectroscopy; 



s1155 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 8 6 

eSi-MS inveStiGAtion of the CoMPLexAtion 

BehAvior of MACroCyCLiC thiACrown 

etherS And BivALent trAnSition MetALS 

A. tSyBizovA 1 , d. SChrÖder 2 , J. tArABeK 2 , 

P. hoLý 3 , M. BuChtA 3 

1 Charles University, Department of Organic Chemistry Faculty 

of Science, Prague 2, Czech Republic 

2 Institute of Organic Chemistry and Biochemistry, Physical 

organic chemistry, Prague 6, Czech Republic 

3 Institute of Organic Chemistry and Biochemistry, Organic 

Synthesis, Prague 6, Czech Republic 

Electrospray ionization mass spectrometry (ESI-MS) was 

used to study the complexation behaviour of three newly 

synthetized [1] thia-macrocycles with different 3d metal chlorides 

(i.e. CuCl , CoCl , NiCl , and ZnCl ). 

2 2 2 2 

The study demonstrates that the thiacrown ethers 

preferentially bind traces of copper even in the excess of other 

metal ions. The binding process is accompanied by a reduction 

from CuII to CuI and the formation of [(thiacrown)Cu] + species. 

By use of 18-crown-6 as a reference the absolute association 

constants are evaluated. 

The reduction process was also studied with EPR 

spectroscopy. EPR data in solution show evidence for the ligand 

oxidation (CuII + L CuI + L +• ), moreover an interaction of the 

oxidized ligand with solvent molecules was observed. 

references: 

1. P. Holý; M. Buchta; J. Rybácek; J. Hodacová; I. Císarová, 

Synthesis, 2010, 24, 4169. 

Keywords: Copper; Electrospray ionization; Mass 

spectrometry; Macrocyclic ligands; Sulfur heterocycles; 


P - 0 5 8 7 

deveLoPMent of CArBonAte SenSor BASed on 

Ln(iii) CoMPLexeS of MACroCyCLiC LiGAndS 

J. vAneK 1 , P. LuBAL 1 , P. herMAnn 2 , 

P. AnzenBACher Jr. 3 


Chemistry / CEITEC, Brno, Czech Republic 

2 Charles University Faculty of Science, Department of 

Inorganic Chemistry, Prague, Czech Republic 

3 Bowling Green State University, Department of Chemistry and 

Center for Photophysical Sciences, Bowling Green (OH), USA 

The Ln(III) complexes of macrocyclic ligands (mostly 

DOTA derivatives) are often employed in medicinal chemistry as 

MRI agents (Gd) and luminescent probes 

(Eu, Tb, Yb, Nd in VIS/NIR range). DO2A (1,4,7,10- 

-tetraazacyclododecane-1,7-diacetate) and DO3A (1,4,7,10- 

-tetraazacyclododecane-1,4,7-triacetate) are hexa- and heptadentate 

macrocyclic ligands forming very stable complexes with 

lanthanide(III) ions where two and three, respectively, 

coordination sites are occupied by water molecules. These 

complexes form ternary species with small mono- and bidentate 

ligands (e.g. fluoride, acetate, phosphate, carbonate) and, 

therefore, these complexes are suggested as sensors for sensitive 

luminescence-based determination of above mentioned anions. In 

this contribution, the thermodynamics of association of 

[Ln(H O) (DO3A)]/[Ln(H O) (DO2A)] (Ln = Eu, Tb) with 

2 2 2 3 

chosen bidentate anionic ligands using luminescence spectroscopy 

was studied. The ternary [Ln(DO3A)(L)] and [Ln(DO2A)(L)] 

complexes (Ln = Eu, Tb, L = picolinate, isoquinoline-3- 

-carboxylate) show improved photophysical properties due to the 

antenna effect of the these anions. High quenching effect of 

carbonate anion and, to a lesser extent also oxalate, enables 

construction of a linear calibration plot utilizing optimized 

experimental conditions for carbonate determination in solution. 

Both “on-off” sensors show a comparable sensitivity and the 

detection limit. The analysis of commercial samples of European 

mineral waters was carried out and confirmed no systematic error 

to the present analysis. The present analytical method is simple 

and rapid, and it is useful for sensitive determination of 

bicarbonate/carbonate concentration in water samples under 

aerobic conditions. Using organic ligands having similar spectral 

properties, this approach was modified and tested to get new 

“off-on” sensors operating in VIS region and the results will be 

presented. 

Acknowledgement: This work was supported by 

Ministry of Education of the Czech Republic (ME09065, 

MUNI/A/0992/2009 and MSM0021620857) and performed in 

framework of CM1006 and CEITEC CZ.1.05/1.1.0/02.0068 EU 

programs. 

Keywords: luminescent probe; anions; lanthanide complexes; 



s1156 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 8 8 


5-nitroBenziMidAzoLe At A BiSMuth 

fiLM-Modified GoLd eLeCtrode 

v. vySKoCiL 1 , B. ChLAdKovA 1 , d. deyLovA 1 , 

J. BAreK 1 

1 Charles University in Prague (Faculty of Science), Department 


Bismuth film electrodes have become an attractive new 

subject of electroanalytical research as a potential replacement for 

mercury electrodes. In this work, the voltammetric behavior of 

the genotoxic compound 5-nitrobenzimidazole was investigated 

using direct current voltammetry (DCV) and differential pulse 

voltammetry (DPV) at a bismuth film-modified gold electrode 

(BiF-AuE). The bismuth film was deposited ex situ at a constant 

potential of –1.2 V (vs. Ag/AgCl (3 mol L –1KCl)) for 300 s in a 

plating solution (1.0 g L –1 Bi(III) solution in 0.1 mol L –1 acetate 

buffer of pH 4.5) under stirring. The optimum conditions for the 

determination of 5-nitrobenzimidazole in the concentration range 

from 1 to 100 µmol L –1 were found in the medium of 

Britton–Robinson buffer of pH 9.0; the limits of quantification 

(L s) were found to be 0.54 µmol L Q –1 (for DCV) and 2.0 µmol L –1 

(for DPV). An attempt to increase the sensitivity using adsorptive 

stripping voltammetry at the BiF-AuE was not successful. The 

practical applicability of the newly developed methodology was 

verified for the direct determination of 5-nitrobenzimidazole in 

drinking and river water model samples, with L s≈10 Q -6 mol L-1 . 

Acknowledgement: This research was financially supported by 

The Ministry of Education, Youth and Sports of the Czech 




P206/12/G151). 

Keywords: Analytical methods; Electrochemistry; 

Voltammetry; Bismuth; Thin films; 


P - 0 5 8 9 

fuLLy deLoCALized 

(ethynyL)(vinyL)PhenyLene BridGed 

trirutheniuM CoMPLexeS in uP to five 

different oxidAtion StAteS 

e. wuttKe 1 

1 University of Konstanz, Chemistry, Konstanz, Germany 

Within the field of organometallic mixed-valent chemistry, 

1,4-diethynylphenylene has gained particular popularity as a 

bridging ligand because of the ready availability of the parent 

alkyne, its good ability to electronically couple the bridged sites 

and the stability it conveys to the oxidized forms. At the same 

time, the 1,4-diethynylphenylene ligand has turned out as an 

excellent example of Janus-headed behaviour with respect to 

Jorgensens original definition of a non-innocent ligand. [1] 

Spectroscopic and cyclovoltammetric investigations on the 

triruthenium complex [(dppe) 2 Ru{-C=C-1,4-C 6 H 4 -CH=CH- 

-RuCl(CO)(P i Pr 3 ) 2 } 2 ] n+ suggest that this carbon-rich complex is 

an intriguing case of extended metal-organic p-systems exhibiting 

complete electron delocalization over three redox-active subunits 

in five well-separated redox states (n = 0-4). The carbon rich 

ethynyl(vinyl)phenylene bridges are non-innocent redox-active 

ligands which actively participate in every redox process. Given 

the rather strong interest in understanding molecular wires [2] , it 

seemed worthwhile to add gold-binding functional groups on the 

terminal moieties in order to gain valuable insight into the 

structure-property relationships of molecular wires with holeconducting 

properties and low turn-on voltage. [3] 

Herein we report the synthesis and our findings on the 

bis(ethynylvinyl)phenylene bridged trinuclear complexestrans- 

-[{Ru(dppe) }{-C=C-1,4-C H -CH=CH-RuCl (CO)(P 2 6 4 iPr ) } ], 3 2 2 

trans -[{Ru(dppe) }{-C=C-1,4-C H -2,5-(OMe) - 

2 6 2 2 

- C H = C H -RuCl(CO) (P iPr ) } ] and its corresponding 

3 2 2 

derivative trans-[{Ru(dppe) }{-C=C-1,4-C H -CH=CH-Ru(η 2 6 4 2- -O CC H SAc)(CO)(P 2 6 4 iPr ) } ] with respect to charge and spin 

3 2 2 

delocalization. The terminal 4-mercaptobenzoate ligands of 

trans-[{Ru(dppe) }{-C=C-1,4-C H -CH=CH-Ru(η 2 6 4 2- -O CC H SAc)(CO)(P 2 6 4 iPr ) } ] bind to gold electrodes 

3 2 2 

and should allow for measuring molecular conductivities. 

references: 

1. C. K. Jorgensen, Coord. Chem. Rev., 1966, 1, 164-178. 

2. D. Astruc Electron-Transfer Processes in Transition Metal 

Chemistry; VCH: New York, 1995. 

3. E. Wuttke, F. Pevny, Y.-M. Hervault, L. Norel, 

M. Drescher, R. Winter and S. Rigaut 

Inorganic Chemistry 2012, 51, 1902. 

Keywords: cyclovoltammetry; spectroelectrochemistry; 

molecular wires; organometallic mixed-valent chemistry; 

Ruthenium; 



s1157 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 9 0 

SiLiCon deterMinAtion in niCKeL 

SuPerALLoyS By iCP-AeS Method 

M. yAKiMovA 1 , f. KArAChevtSev 1 , 

t. zAGvozdKinA 1 , r. dvoretSKov 1 

1 All-Russian Scientific Research Institute of Aviation Materials, 

Laboratory “Spectrum chemico-analytical researches and 

standard specimens”, Moscow, Russia 

Silicon is impurity in heat-resistant Ni alloys such as Inconel 

and determinate in ranges from 0,001 to 0,2 % wt, whereas at Si 

content from 0,5 to 2 % wt silicon reduce erosion. In nickel 

brazing (Solbraz, Nicrobraz, Colmonoy) silicon exclude erosion 

of brazed alloy at Si content more than 5 % wt. 

This work deals with of method of sample preparation and 

test method of Si analysis from 0,001 to 10 % wt in Ni alloy by 

using ICP-AES method. 

It’s known Si with HF forms volatile compound SiF ; under 

4 

the influence of HF Si is washed away from glass spray system 

of spectrometer; Si is adsorbed on plastic spray system of 

spectrometer; in mixture of HCl and HNO3 silicon precipitate into 

silica sol (H SiO ) . Therefore two ways of a sample preparation 

2 3 n 

and determination of silicon were offered. 

The first way consists in alloy dissolution in the minimum 

quantity of chlorazotic acid diluted with water in ratio 1:10. The 

second way consists in alloy dissolution in the minimum quantity 

of a mixture of H O, HCl, HNO , HF (in ratio 10:3:1:1). Alloy 

2 3 

samples are dissolved by using microwave digestion system 

MARS5. Measurements of Si content carried out on ICP-AES 

spectrometer VARIAN 730 ES in reference materials. At first way 

quartz spray system was used, at second - fluoroplastic spray 

system, a plastic spray. 

It’s shown that this way allows to determinate silicon in a 

range from 0,001 to 3 % wt with error no more than 3 % relative 

by using first way and in a range from 0,1 to 10 % wt with an 

error of no more than 5 % relative by second one. 

The proposed ways of Si analysis can be successfully 

applied in the silicon determination in alloys based on iron, cobalt, 

titanium, copper, etc. 

Keywords: silicon analysis; ICP-AES; test method; Ni alloys; 


P - 0 5 9 1 

SeLeCtive deteCtion of ProteinS in SdS-PAGe 

AnALySiS 

t. zAnni 1 , B. KÖniG 1 



SDS-PAGE is a widely used technique when dealing with 

biomacromolecules. The most used proteins detection techniques 

nowadays in SDS PAGE analysis are Coomassie brilliant blue 

stain and silver stain; both techniques allow to detect proteins in 

gels with good sensitivity and reasonable time consumption. 

When analysing complex mixture of proteins selectivity is often 

desired. Even if well-established techniques are available for this 

purpose (such as western blotting and post-translational 

modifications selective probes), the development of new, cheaper 

and faster methods to selectively detect proteins is of great 

interest. 

Several compounds showing affinity towards different kind 

of functional groups which are present in amino-acids side chains 

(e.g. phosphorylated sites [1] , imidazole ring [2] , carboxylates [3] ) 

have been reported in literature.The structure of such compounds 

consists of Zn(II) or Cu(II) coordination complexes as recognition 

moiety combined with a reporting fluorophore. Binding activity 

leads to changes in fluorescence, such as variation of intensity or 

emission wavelength shift, allowing detection. 

By mean of the same strategy, we designed different 

potential probes consisting of Zn(II) – cyclen complex covalently 

linked to fluorescent dyes such as nile blue, hodamine B and eosin 

Y. We are currently synthesizing such compounds, which will be 

tested as probes for selective recognition of consecutive 

negatively charged aminoacids sequences (e.g EE, DD, EED etc.) 

in model proteins. 

As different approach, we are going to use known specific 

interactions between metal cations and given amino acid 

sequences, followed by detection of bound cations (e.g by 

colorimetric indicators). The detection of polihistidine-tagged 

proteins by using the interaction with copper(II) cations is 

currently under investigation. 

references: 

1. Riechers, A. et al. ; Bioconjugate Chemistry, 20, 804-807 

(2009). 

2. Stadlbauer, S. et al.; Chemistry-A European Journal 14, 

2536-2541 (2008). 

3. Bhuyan, M. et al. ;. European Journal of Organic 

Chemistry 2011, 2807-2817 (2011). 

Keywords: molecular recognition; electrophoresis; fluorescent 

probes; 



s1158 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 9 2 

eLeCtrooxidAtion of nA+/K+-AtPASe After 

SoLuBiLizAtion By oCtAethyLene GLyCoL 

MonododeCyL ether 

M. zAtLouKALovA 1 , M. KuBALA 2 , J. vACeK 1 

1 Palacky University, Department of Medical Chemistry and 


2 Palacky University, Department of Biophysics, Olomouc, 


The present study is focused on oxidation and adsorption 

behaviour of full-length transmembrane protein Na+/K+-ATPase 

(NK) and its water-soluble isolated cytoplasmic loop connecting 

transmembrane helices 4 and 5 (C45) using voltammetric 

methods. Membrane proteins are substances that are poorly 

soluble or insoluble in aqueous solution. The C45 is soluble in 

water, the nonionic surfactant octaethylene glycol monododecyl 

ether was used for NK solubilization [1] . Both proteins, NK and 

C45, were studied using adsorptive transfer cyclic voltammetry 

and square-wave voltammetry on basal-plane pyrolytic graphite 

electrode. While NK gives two oxidation peaks (peak Y: +0.55 V 

and peak W: +0.7 V) related to tyrosine (Y) and tryptophan (W) 

oxidation, C45 is characterized by substantially lower anodic 

responses (peak Y&W: +0.65 V). High anodic currents of Y and 

W of NK are related to its transmembrane part, which are very 

rich in Y and W residues. These experimental procedures allow 

studying oxidation of NK and C45 at femtomole level without the 

necessity to use derivatization, labeling by electroactive markers 

or techniques based on protein immobilization within lipid bilayer 

attached to the electrode surface. 

Acknowledgments: The research was support by the internal 

grant LF UP (LF_2012_010), MZ CR (NT11071) and GA CR 

(303/09/H048). 

references: 

1. M. Huliciak et al., Biochem. Pharmacol., 83, 1507-1513, 

2012. 


P - 0 5 9 3 

the APPLiCAtion of hPLC with 

eLeCtroCheMiCAL deteCtion for the 

deterMinAtion of PeStiCide ChLorotoLuron 

J. zAvAzALovA 1 , L. houSKovA 1 , J. ziMA 1 , J. BAreK 1 , 

h. deJMKovA 1 


of Analytical Chemistry UNESCO Laboratory of 

Environmental Electrochemistry, Prague, Czech Republic 

Many herbicides are used in agriculture all over the world. 

Despite their benefits in increasing agricultural production, 

herbicides can have a negative impact on the environment and can 

pose a risk to animals and humans. For these reasons, there is a 

growing demand for fast and reliable pesticide monitoring in 

agriculture. 

A method for the determination of phenylurea herbicide 

chlorotoluron was developed using reversed-phase HPLC with 

amperometric detection on carbon paste electrode in wall-jet 

arrangement. Separation and detection conditions for the 

determination were optimized, namely pH of mobile phase and 

detection potential. The optimum conditions for the determination 

are: LiChroCART ® 125-4 Purospher ® RP-18 (5 μm) column, 

mobile phase consisting of methanol and ten times diluted 

Britton-Robinson buffer pH 4.0 (60:40, v/v), and detection 

potential +1.3 V. Concentration dependences are linear in the 

range from 1.0·10 –7 mol L –1 to 1.0·10 –4 mol L –1 and the limit of 

determination reaches value of 1.1·10 –7 mol L –1 . The method was 

applied on model samples of river water, with the limit of 

determination for amperometric detection 1.9·10 –7 mol L –1 . 

Acknowledgement: The research was supported by 

the Ministry of Education, Youth and Sports of the Czech 

Republic (Project MSM 0021620857 and KONTAKT (AMVIS) 

Project ME10004), Charles University in Prague (Project SVV 

2012-265201), Grant Agency of the Czech Republic (Project 

P206/12/G151), and Technology Agency of the Czech Republic 

(project TA01020565). J. Zavazalova thanks to the Faculty of 

Science, Charles University in Prague (project STARS) for 

financial support. 

Keywords: Electrochemistry; Environmental chemistry; Liquid 

chromatography; 



s1159 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 9 4 

GoLd And SiLver nAnoPArtiCLeS Modified By 

reCePtorS for AnionS reCoGnition 

P. zvAtorA 1 , J. KoKtAn 1 , L. veverKovA 1 , t. BrizA 1 , 

v. KrAL 1 



Development of receptors which are designed foranoint 

recognition is an important branch of chemistry. The design of 

syntheticreceptors for selective sulfate over phosphate recognition 

in aqueous media hasbeen a significant challenge. Many of these 

compounds are not soluble in water.This problem can be solved 

by immobilization on the nanoparticles surface. 

Nanoparticles were prepared by methodbased on the 

reduction of noble metals salts by reduction agents. The 

immobilizationsof polymethinium salt and two porphyrin-brucine 

derivatives were carried outby two different ways of ionic 

interaction. First, direct immobilization of selectormolecules on 

nanoparticles, second, immobilization of selector molecules on 

3-mercaptopropionicacid premodified nanoparticles. Such 

prepared nanoparticles were characterizedby UV-Vis 

spectroscopy. This method was used for study of interactions of 

anionswith the modified nanoparticles in water. 

Immobilization on nanoparticles, insome cases, prevents the 

selector molecules from aggregation in water. Variousspectral 

changes were observed in experiments with free versus 

immobilizedselectors in water depending on a type of used system 

and selected anions. The resultsshowed that type of used 

nanoparticles have positive or negative affected to stabilityof these 

systems in water and have a strong influence on their interactions. 

Acknowledgements: Thefinancial support from 

the Grant Agency of the Czech Republic no. 203/09/1311, 

the Grant Agency of the Czech Republic no. P303/11/1291, 

Grant Agency of theAcademy of Sciences of the Czech Republic 

KAN200100801 and Institute ofChemical Technology internal 

grant A1 FCHI 2012 003 is gratefully acknowledged. 

Keywords: Anions; Nanoparticles; UV/Vis spectroscopy; 


P - 0 5 9 5 

CheMiCAL CoMPoSition of different 

oreGAno (oriGAnuM vuLGAre L.) eSSentiAL 

oiLS: reLevAnCe for the ACtivity AGAinSt 

foodBorne And SPoiLAGe BACteriA 

J. S. AMArAL 1 , A. e. riBeiro 2 , S. ALveS 3 , 

A. GonCALveS 4 , P. PoetA 4 

1 REQUIMTE/Pharmacy Faculty of Porto, and 

ESTiG/Polytechnic Institute of Braganca, Braganca, Portugal 

2 LSRE/IPB, Polytechnic Institute of Braganca, Braganca, 

Portugal 

3 University of Trás-os-Montes and Alto Douro, Veterinary 

Science Department, Vila Real, Portugal 

4 University of Trás-os-Montes and Alto Douro, Veterinary 

Science Department and Center of Studies of Animal and 

Veterinary Sciences, Vila Real, Portugal 

Herbs and spices have been used for centuries in culinary 

for seasoning and flavouring purposes. More recently, there has 

been a growing interest regarding the use of some plants and its 

essential oils (EO) for their activity against foodborne pathogens 

and foodspoilage bacteria. Due to its potential in extending the 

self-life of foods and its better acceptability by consumers who 

demand more “natural” foods, the use of EO can be an interesting 

alternative to substitute, at least partially, synthetic preservatives. 

Oregano EO has been reported to possess a broad 

antimicrobial activity spectrum. Nevertheless, its activity is 

strongly dependent on the chemical composition which is known 

to differ with plant genotype, geographical origin and 

environmental conditions. Considering that most works focus on 

wild oregano but nowadays most is cultivated and sold in 

supermarkets, in this study we evaluated the chemical 

composition and antibacterial activity of commercially available 

oregano EO (EO1) and the EO extracted by hydrodistillation from 

oregano purchased from an aromatic plants supplier (EO2). The 

chemical profile of the essential oils, determined by gas 

chromatography-mass spectrometry (GC-MS), was very different 

with EO1 presenting carvacrol (68.3%), p-cymene (4.2%), thymol 

(3.8%) and gamma-terpinene (3.7%) as main compounds, while 

terpinen-4-ol (24.8%), p-menth-2-en-1-ol (13.9%), p-cymene 

(8.8%) and gamma-terpinene (7.4%) were the major ones in EO2. 

The antibacterial activity was determined against 7 Gram-positive 

and 3 Gram-negative bacterial strains by agar-diffusion method. 

Both oils inhibited all tested strains but the antibacterial activity 

was stronger for commercial EO with some strains presenting 

inhibition halos two times higher. This can be mainly ascribed to 

the higher content of phenolic derivatives, such as carvacrol and 

thymol, in EO1. These results demonstrate that oregano EO can 

be used for its antimicrobial effect against foodborne pathogens. 

Nevertheless, for this purpose it should be carefully chosen 

regarding its chemical composition. 

Keywords: Gas chromatography; Biological activity; Mass 

spectrometry; Natural products; 



s1160 

chem. Listy 106, s257–s1425 (2012) 

Poster session 2 - food chemistry 

P - 0 5 9 6 

Study of heAvy MetAL And eSSentiAL oiL 

Content in vAriouS SPiCeS 

S. BLAGoJeviC 1 , S. BLAGoJeviC 2 , n. PeJiC 2 

1 Institute of general and Physical Chemistry, Electrochemistry, 


2 Faculty of Pharmacy, Physical Chemistry and Instrumental 

Methods, Belgrade, Serbia 

A spice is a dried seed, fruit, root, bark, or vegetative 

substance primarily used for flavoring, coloring or preserving 

food. Sometimes a spice is used to hide other flavors.A spice may 

be available in several forms: fresh, whole dried, or pre-ground 

dried. Generally, spices are dried. A whole dried spice has the 

longest shelf life and small seeds, such as fennel and mustard 

seeds, are used both whole and in powder form. 

The flavor of a spice is derived in part from compounds that 

oxidize or evaporate when exposed to air. Grinding a spice greatly 

increases its surface area and so increases the rates of oxidation 

and evaporation. Thus, flavor is maximized by storing a spice 

whole and grinding when needed. The shelf life of a whole spice 

is roughly two years; of a ground spice roughly six months. The 

“flavor life” of a ground spice can be much shorter. Ground spices 

are better stored away from light. 

In this study we analyse concentration of As, Hg, Pb and Cd 

and oil content in five spieces (origano, red and black pepper, 

coriander and anis) from three producer from serbian market. 

Analysis of hazardous metals were done by grafite furance AAS 

technique for Pb and Cd and by hydride techique for As and cold 

vapor for Hg, and essential oil content was determined by ethanole 

extraction. Amount of hazardous metals was bellow concentration 

estimated by serbian regulation. 

Keywords: Analytical Methods; 


P - 0 5 9 7 

AuthentiCAtion of roMAniAn riPened Brine 

CheeSe And yeLLow CheeSe uSinG 1h-nMr 

SPeCtroSCoPy And GC-MS teChnique 

A. BrAtu 1 , M. MihALAChe 1 , A. hAnGAnu 2 , 

C. todASCA 1 , n. ChirA 1 , S. roSCA 1 

1 Politehnica University, Organic Chemistry, Bucharest, 

Romania 

2 Center of Organic Chemistry C.D.Nenitescu, Organic 

Chemistry, Bucharest, Romania 

Romanian ripened brine cheese, traditionally called 

“Teleme” cheese, represents 60% of all kinds of cheese produced 

in Romania [1] . Teleme cheese is a soft white-brined cheese with 

many similarities with Feta cheese. [2] 

The aim of this work was to establish whether fatty acids 

composition data obtained by 1H-NMR and GC-MS can be used 

in the discrimination of traditionally Romanian ripened brine 

cheese as well as yellow cheese according to variety (goat, sheep 

and cow). [3, 4] 

Characterizations of the lipid fraction of Romanian varieties 

of cheese samples were performed by 1H-NMR spectroscopy and 

GC-MS methods. Based on the integral values of the signals from 

the 1H-NMR, the fatty acid composition of traditionally romanian 

cheese samples was calculated5 . Statistical analyses of the spectral 

data by mean of Principal Component Analysis (PCA) allowed 

that varieties of cheese to be discriminated. 

references: 

1. G. Rotaru, D. Mocanu, M. Ulescu, D. Andonoiu, 

Innovative Romanian Food Biotechnology, 2008, 2, 30-39. 

2. E.C. Pappa, I.Kandarakis, E.M.Anifantakis, Food Control, 

2006, 17, 570-581. 

3. E.Hilma, D.Mierlita, G.Rotaru, Analele Universitatii din 

Oradea, 2011, 14, 85-92. 

4. M.A. Brescia, V.Mazzilli, A.Sgaramella, S.Ghelli, JAOCS, 

2004, 81, 431–436. 

5. N.A.Chira, M.C. Todasca, A. Nicolescu, A. Rosu, 

M. Nicolae, S.I. Rosca, Revista de Chimie, 2011,62 (1), 

42-46. 

Keywords: white-brined cheese; Teleme; Principal Component 

Analysis; 1H-RMN; GC-MS; 



s1161 

chem. Listy 106, s257–s1425 (2012) 


P - 0 5 9 8 

Ph effeCtS on the PhytoCheMiCAL 

CoMPoSition And AntioxidAnt ACtivity of 

ProCeSSed PeACh 

M. CoeLho 1 , A. oLiveirA 1 , h. GoMeS 1 , 

e. ALexAndre 1 , d. P. f. ALMeidA 2, 3 , M. PintAdo 1 

1 CBQF, Escola Superior de Biotecnologia, Rua Dr. António 

Bernardino de Almeida, 4200-072 Porto, Portugal 

2 Faculdade de Ciencias, Universidade do Porto, Rua do 

Campo Alegre, 687, 4169-007, Porto, Portugal 

3 Frulact, S.A., Rua do Outeiro, 589, 4475-150 Gemunde, Maia, 

Portugal 

Adjustment of pH is often made in processed fruit products 

to assure food safety or the stability or functionality of ingredients 

or additives (e.g. pectins or sorbate). The objective of the work 

was to assess the effect of pH on relevant markers of functional 

and nutritional properties (antioxidant activity, phenolics and 

carotenoids) of processed peach puree. Clingstone peach [Prunus 

persica (L.) Batsch ‘Catherine’] fruits were reduced to puree and 

the pH adjusted to 2.5; 3.0; 3.5; 4.0 and 4.5 with citric acid and 

sodium phosphate. Purees were then heated in water-bath at 

90 ºC for 10 minutes and subsequently stored during 90 days at 

4.5 ºC and at 23 ºC. Hydrophilic extracts were obtained with 

80% methanol and carotenoids were extracted as described by 

Lavelli et al. (2009). Total antioxidant activity was assessed by 

the ABTS method, total phenolics by Folin Ciocalteu’s method, 

and total carotenoids by spectrophotometery. Individual phenolics 

and carotenoids were separated and indentified by HPLC-DAD. 

After 90 days storage the total antioxidant activity, total phenolics 

and total carotenoids decreased, by 45%, 30%, and 47%, 

respectively (average of both temperatures). The decline was 

faster at 23 ºC than at 4.5 ºC, but the rate was not affected by pH. 

Levels of neochlorogenic and chlorogenic acid (7 and 

11 µg/ g fw respectively) were lower at pH 4.0 or 4.5 than at lower 

pH values. Zeaxanthin, β-cryptoxanthin and β-carotene levels 

decreased more during storage at pH 2.5 and 4.5 (70%, 47%, and 

45%, respectively), than at the intermediate pH values. In 

conclusion, puree pH, in the range 2.5 to 4.5 does not affect the 

overall antioxidant activity, but the kinetics of changes in the 

extractability of chlorogenic and neochlorogenic acids and 

zeaxanthin 

references: 

1. Lavelli V., Pompei C., Casadei M. A., (2009), “Quality of 

nectarine and peach nectars as affected by lye-peeling and 

storage”, Food Chemistry, 115: 1291–1298 

Keywords: Antioxidant activity; Carotenoids; Peach 

processing; Phenolics; 


P - 0 5 9 9 

enCAPSuLAtion of querCetin with Protein 

And Protein-SteAriC ACid Mixture CoAtinG 

MAteriALS And deterMinAtion of totAL 

AntioxidAnt CAPACity uSinG CuPrAC Method 

J. hizAL 1 , S. deMirCi CeKiC 2 , o. i. SAhin 1 , r. APAK 2 

1 Yalova University, Chemical and Process Eng., Yalova, Turkey 

2 Istanbul University, Chemistry, Istanbul, Turkey 

Microencapsulation method has been widely used in food 

industry in recent years. Retarding degradation of food additives, 

it causes expanded shelf life and controlled releasing of core 

materials through gastrointestinal system. Coating of surface takes 

place via secondary interaction between internal and external 

phase. Frequently encountered coating materials are cellulose 

derivatives, starch derivatives, and algynates etc. Coating 

antioxidant core with protein causes enhancing antioxidant 

efficient. Proteins have two important roles: They reduce surface 

tension at interface during emulsification and form 

macromolecular layer. Gelatin is a protein used widely in 

encapsulation process because of its excellent film-forming 

properties. 

At the first step in this study, quercetin was used as internal 

phase and gelatin was used as external phase. After wall and core 

material was reacted each other at fixed wall/core ratio, formed 

microcapsules were powdered using freeze dryer. The minimum 

mixing time and optimal wall/core ratio was found as 4 h and 1:1 

respectively. At the second step, gelatin and stearic acid mixture 

will be used as external phase. 

After DSC analysis and cold-stage microscopy 

determination and particle size measurement, surface 

characterization of microcapsules will be achieved. And also, 

encapsulation efficient and shelf life analyses and invitro digestion 

experiments in synthetic saliva, stomach, and intestine liquids will 

be performed. Antioxidant capacity will be quantitatively 

determined using CUPRAC method in all experiments. In this 

way, optimal wall matrix, wall/core phase ratio and shelf life will 

be designated for microcapsules which core retention is 

accomplished without reducing in their total antioxidant capacity. 

Keywords: antioxidants; polymers; UV/Vis spectroscopy; 

Analytical methods; 



s1162 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 0 0 

MonitorinG of funGiCideS effeCt on the 

ProduCtion of t-2 toxin 

d. hruBoSovA 1 , J. vytrASovA 2 



2 University of Pardubice, Department of Biological and 

Biochemical Sciences, Pardubice, Czech Republic 

The aim of the work was monitoring of fungicides effect on 

the production of T-2 toxin. Detection of toxigenic fungi was 

performed in malt houses and on barley seeds. Fusarium fungi 

are producers of a wide range of mycotoxins e. g. T-2 toxin, 

deoxynivalenol and zearalenone. T-2 toxin is trichothecene 

mycotoxin. The intoxication are especially in people with lowered 

immune system or weakened animals after ingestion of 

contaminated cereals. For this reason, set the limits that 

determined the maximum level of mycotoxins in cereals. The 

PCR method for confirmation of Tri5 gene which encodes the 

production of trichothecene mycotoxins were performed for all 

tested strains of Fusarium. PCR were performed for 172 strains 

of Fusarium isolated from real samples. The gene was proved for 

44 strains of Fusarium. Nutritive media were preparate with 

different concentration of tested fungicides (Polyversum, Horizon 

250 EW, Falcon 460 EC and Bioan) and inoculated with Fusarium 

fungi, then incubated under various conditions. The content of 

T-2 toxin was determined by Agra Quant ® T-2 toxin Test kit and 

HPLC. Our experiment showed that low concentration of 

fungicedes resulted in the increased production of T-2 toxin. 

Acknowledgements: This work was supported by MSM 

0021627502 and project of University of Pardubice 

No. SGFChT07/2012. 

Keywords: Fusarium; T2 toxin; ELISA method; fungicide; 


P - 0 6 0 1 

AnALySiS of MuShrooM toxinS By Liquid 

ChroMAtoGrAPhy – MASS SPeCtroMetry 

(LC-MS/MS) 

S. t. C. CheunG 1 , y. C. wonG 2 , f. w. Lee 1 , d. w. M. Sin 3 

1 Government Laboratory (HKSAR), Food Section, Hong Kong, 

Hong Kong 

2 Government Laboratory (HKSAR), Pharmaceutical Chemistry 

Section, Hong Kong, Hong Kong 

3 Government Laboratory (HKSAR), Food Safety and Quality 

Group, Hong Kong, Hong Kong 

Background: Mushroom poisoning usually results from the 

consumption of wild poisonous species, which were misidentified 

and consumed because of their resemblance in colour and general 

morphology with edible mushrooms. Some common symptoms 

of mushroom poisoning include gastrointestinal upset such as 

vomiting and diarrhea. However, there are a number of known 

mushroom toxins which may cause death to victims if no proper 

or delay in treatment is given. For example, consumption of a 

single piece of mushroom containing high level of amanitins 

toxins may cause death of an adult [1, 2] . Poisonous mushrooms 

accidentally leaked into the food markets may induce multiple 

outbreaks of food poisoning cases. With early identification of the 

toxins presented in the questioned food items could not only be 

useful for stopping the spreading of further cases, but also help 

physicians in finding suitable treatment for the victims. 

Method of Analysis: In this work, a quick and reliable 

analytical method for analyzing 5 mushroom toxins including the 

α, β, γ-amanitin, phallacidin and phalloidin using Liquid 

Chromatography – Mass Spectrometry (LC-MS/MS) is 

developed. A simple extraction and clean-up procedure is 

employed. The extract can be analyzed directly by LC-MS/MS in 

the Multiple Reaction Monitoring (MRM) mode. The method is 

capable of measuring mushroom toxins in food remnants down 

to 250μg/kg. Quantification and confirmation criteria are based 

on EC Directive 2002/657/EC. The mean spike recoveries of the 

5 toxins fall within 88 to 109% with RSD ranging from 2.6 to 

13%. The method is validated using a genuine dried specimen of 

Amanite exitialis, which is also known as the Guangzhou 

Destroying Angel. The cap and stipe of the specimen are found 

to contain high levels of α, β-amanitin and phallacidin. 

Application to Practice: The method has been used to assist 

the World Health Organization (WHO) in the investigation of a 

fatal mushroom poisoning case occurred in Laos in May 2011. 

The results revealed that one of the samples contained lethal levels 

of α, β, γ-Amanitin and Phallacidin, indicating that the item was 

not suitable for human consumption. 

references: 

1. Y. Bidnychenko. Detecting Mushroom Peptide Toxins in 

Body Fluids by Capillary Electrophoresis LCGC 19(9) 

(2001). 

2. A. Bresinsky and H. Besl. A Colour Atlas of Poisonous 

Fungi. Wolf Publishing Ltd., London, UK, 1990, pp 18-34. 

Keywords: Liquid chromatography; Mass spectrometry; 



s1163 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 0 2 

SiMuLtAneouS SCreeninG And deterMinAtion 

of PhthALAteS, SuCh AS di (2-ethyLhexyL) 

PhthALAte (dehP), diButyL PhthALAte (dBP), 

ButyL BenzyL PhthALAte (BBP) in food 

CirCuLAted At KoreAn MArKet uSe By GC/MS 

M. Cho 1 , J. KiM 1 , K. Lee 1 , S. PArK 1 

1 Korea Food and Drug Administration, Hazardous Substances 

Analysis Division, Seoul, Republic of Korea 

Known as environmental contaminants phthalates have been 

detected in various types of retail foods. Consumer’s exposure to 

phthalates is common so that are concerned about chemicals in 

food. This study has been conducted to determine 3 kinds of 

phthalates, such as di (2-ethylhexyl) phthalate (DEHP), dibutyl 

phthalate (DBP), butyl benzyl phthalate (BBP) which are 

extracted from processed food groups(sugar, soybean oil, red 

pepper paste etc). We first established validated methods. 

Standard phthalates were analyzed with hexane or acetonitrile and 

quantification was carried out using Gas-Chromatography in 

combination with Mass spectrometry detector(GC/MS) in 

electronic ionisation mode(EI) with selected ion 

monitoring(SIM). The base peak of all three phthalates was 

identified as m/z = 149 while characteristic ions, 223, 205 for 

DBP; 206, 91 for BBP; 167, 279 for DEHP were identified. Base 

peak will be used for screening and specific ions for quantitative 

studies. Limits of detection range for DEHP, DBP, and BBP was 

2 ~ 10 ng/mL, repectively. The calibration curves for 3 phthalates 

showed linearity in the range 0.990 ~ 0.999. Currently, we are 

applying this method to the processed foods for monitoring 

project. The results should provide useful information to 

guarantee food safety. 

Keywords: Phthalates; monitoring; DBP; BBP; DEHP; GC- 

MS(EI-SIM); 


P - 0 6 0 3 

tin And ALuMiniuM LeveLS in infAnt 

forMuLAS 

y. M. ChunG 1 , C. y. Lee 1 , J. w. PArK 1 , J. h. KuK 1 , 

S. K. Suh 1 

1 Gwangju Regional Koreal Food & Drug Administration, 

Hazardous substances analysis division, Gwangju, Republic of 

Korea 

Infant formula serve as substitutes for human milk and play 

a particular role in diets. Unlikely breast milk, artificial formula 

can contain several contaminants with toxic heavy metals and 

pesticides that carry potential health problems to infants. Infants 

are particularly sensitive to the effects of ingested toxicants as 

food consumption is greater on a body-weight basis. 

At the present, the Korean standards of tin and aluminium 

in infant formula are not established. 

This research was carried out to monitor the levels of tin and 

aluminium in infant formula distributed in Korean markets. The 

infant foumulas were analysed by ICP-MS after microwaveassisted 

digestion. The performance characteristics of ICP-MS 

were determined in terms of linearity, precision, recovery, limit 

of detection(LOD) and limit of quatification(LOQ). As a result, 

LOD and LOQ of powdered infant formula were 0.2ppb, 0.6ppb 

for tin and 2.8ppb, 9.2ppb for aluminium. The recoveries by 

standard addition were 88.4~110.0% for tin and 93.1~112.7% for 

aluminium. These results will be used as a fundamental database 

to set up the Korean standards of tin and aluminium in infant 

formula. 

Keywords: Tin; Aluminium; Infant formula; 



s1164 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 0 4 

PrePArAtion of Soy SAuCe Low in SodiuM 

ChLoride 

r. KurAMitSu 1 

1 Akashi National College of Technology, General Education, 

Akashi, Japan 

These days, people’s interest forcuses on health, and 

particularly the exsessive intake of table salt has received 

tremendous attention resulting in an increased demand for low 

NaCl-containing foods. Soy sauce, which is the Japanese 

representative seasoning, has a large amount of NaCl. In this study 

I attempted to decrease the NaCl content of the soy sauce whithout 

spoiling the flavor. Soy sauce contains 15-18% NaCl and 1-2% 

monosodium glutamate and is a traditional seasoning with salty 

and umami tastes as the core of the tasting characteristics. The 

low NaCl-containg soy sauce used in this study was prepareed by 

using a pre-soy sauce with an NaCl content 0.5 time the NaCl 

content of conventional soy sauce obtained by the short term 

fermentation method developed by Muramatsu et al. as the base 

material, and by adding a variety of amino acids and peptidic 

saltiness-enhancing substances such as Lys/HCl, Gly-OEt/HCl, 

and Orn-Tau/HCl which were developed by our laboratory. Based 

on the respective threshold values, intensities of salty and umami 

tastes were represented quantitatively in scores for sensory 

analysis. By using the scores the tasting characteristics of low 

NaCl-containing soy sauces to which were added various 

saltiness-enhancing substances were compared. The results 

revealed that commercial soy sauce was an ideal food in that it 

possessed well balanced intensities of salty and umami tastes. The 

balance of salty and umami tastes in the Orn-Tau/HCl added low 

NaCl-containing soy sauce was close to that of the commercial 

soy sauce. The low NaCl-containing soy sauce to which KCl, a 

long used substitute of NaCl, was added showed too strong of a 

umami taste that killed the effect of salty taste. 

Keywords: bioorganic chemistry; material science; peptides; 

salt effect; sodium; 


P - 0 6 0 5 

MonitorinG Anti-iMPotenCe druGS And itS 

AnALoGueS in foodS 

h. Lee 1 , J. KiM 1 , h. Lee 1 , S. won 1 , y. KAnG 1 , M. Jin 1 , 

h. ChAnG 1 , e. KiM 1 , r. SeonG 1 , K. Kwon 1 

1 Busan Regional Korea Food & Drug Administration, Center 

for Food & Drug Analysis, Busan, Republic of Korea 

Illegal compounds such as drugs and its synthetic analogues 

have been detected in foods until a recent date in Korea. 

Especially, unknown compounds that have the modified chemical 

structure of anti-impotence drugs such as sildenafil, tadalafil and 

vardenafil were frequently detected in various foodstuffs. Illegal 

compounds(benzylsildenafil, aminotadalafil, hydroxyvardenafil 

etc) that have modified chemical structure of the drugs have been 

used to avoid the government inspection. The adulteration of 

foods with drug analogues is potentially dangerous for human 

health because it is not proved their safety at all. In order to ensure 

food safety, we investigated the actual condition of the suspected 

samples and monitored about 40 retail foods. Three simultaneous 

analytical methods were established using LC/PDA and 

confirmed with LC/MS for 35 analogues and 5 anti-impotence 

drugs. Anti-impotence drugs and its analogues were detected in 

5 samples. Tadalafil was detected in an sample. Icariin was 

detected in 3 samples. Yohimbine was detected in 3 samples. 

Keywords: Illegal compounds; Anti-impotence drugs; 

monitoring; LC/MS; LC/PDA; 



s1165 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 0 6 

deterMininG 4-MethyLiMidAzoLe in CArAMeL 

CoLor By CAPiLLAry GAS ChroMAtoGrAPhy 

M. Lee 1 , K. hAn 1 , S. Choi 1 , S. h. KiM 2 , S. K. PArK 2 , 

h. S. LiM 2 

1 Korea Health Industry Instititute, Qulity Improvement, 

Chungju, Republic of Korea 

2 Korea Food & Drug Administration, Food additive & 

packaging, Osong, Republic of Korea 

As a color additive, Caramel color is the world’s most 

widely consumed food coloring ingredient. Caramel color 

contains 2-methylimidazole and 4-methylimidazole, both of 

which may cause cancer in laboratory animals. For such reason, 

the 4-methylimidazole content of caramel color, a food additive, 

is controlled in the EU, US(FCC), Japan, and Korea. 

The quantitative analysis of the 4-methylimidazole used in 

Korea’s Food Additive Code and US’s FCC (Food Chemical 

Codex) is a somewhat old-fashioned gas chromatography using 

column packing of 7.5% Carbowax 20M +2% KOH. 

For the aforesaid reason, a method of determining 

4-methylimidazole in caramel color via capillary gas 

chromatography was studied. The method consisted of methylene 

chloride extraction of the sample followed by concentration and 

GC analysis. 

GC analysis was performed using HP-20M, Carbox 20M, 

HP-5 capillary column (0.32?, ID?25M), and hydrogen 

flame-ionization detector. As internal standard material, 

2-methylimidazole was used. 

The linear range was 0.08~1.6?/L, and the limit of detection 

was 0.04 ?/L. The average recoveries were 90.4~98.0%, and the 

relative standard deviations were 0.8 ~2.5%. Consequently, 

4-methylimidazole contained in caramel color was analyzed using 

the capillary column, which is currently used widely. 

Keywords: 4-methylimidazole; Caramel; Gas 

Chromatography; Capillary; 


P - 0 6 0 7 

direCt MonitorinG of MyoGLoBin-CAtALyzed 

LinoLeAte PeroxidAtion By fourier 

trAnSforM infrAred SPeCtroSCoPy 

A. LouLLiS 1 , e. PinAKouLAKi 1 


Cyprus 

Lipid peroxidation reactions are a major concern in Food 

Science. These reactions represent a main part of the degrading 

processes taking place in food products resulting in changes in 

flavor, color, texture and producing cytotoxic and genotoxic 

compounds. Myoglobin has been demonstrated to catalyze lipid 

peroxidation in biological tissues and muscle-based foods. In this 

work we have employed UV/Vis and Fourier transform infrared 

spectroscopies to study the mechanism of myoglobin-catalyzed 

linoleate per oxidation. The UV/Vis spectra of the reaction of 

linoleate with met-myoglobin and with ferry-myoglobin show 

characteristic transitions at 235 nm and 285 nm indicating the 

formation of primary and secondary oxidation products. 

Ferryl-myoglobin is potent in inducing linoleate peroxidation 

independent of the linoleate/Mb ratio, while met-myoglobin has 

been found to be an effective catalyst only in high ratios (1:300). 

We have also monitored the reactions using Fourier Transform 

Infrared spectroscopy. During the reactions the decreasing 

intensity of marker linoleate vibrations and appearance of new 

vibrations in the 1700–1600 cm-1 and 1500–900 cm-1 regions that 

can be attributed to linoleate primary and secondary oxidation 

products have allowed us to directly monitor the process of 

linoleate peroxidation. Concurrent changes in the secondary 

structure of myoglobin are observed through amide I and amide 

II modes. The antioxidant activity of vitamin C has been 

investigated and will be discussed. 

Keywords: Oxidation; Proteins; Lipids; IR spectroscopy; 

UV/Vis spectroscopy; 



s1166 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 0 8 

MetABonoMiCS of tABLe GrAPeS: froM 

MetABoLiC ProfiLeS MonitorinG to 

CLASSifiCAtion of GrAPeS By exPert 

inforMAtiC SySteMS 

P. MAStroriLLi 1 , i. CAfAGnA 1 , v. GALLo 1 , 

M. LAtroniCo 1 , v. BeviLACquA 2 , M. triGGiAni 2 , 

G. ferrArA 3 

1 Polytechnic of Bari, DIAC, Bari, Italy 

2 Polytechnic of Bari, DEE, Bari, Italy 

3 University of Bari, DSAAT, Bari, Italy 

Table grapes are food products of considerable commercial 

value for several countries (USA, Brazil, Italy, South Africa, 

China, Chile, India and Australia are the most important 

producers). In Europe, Italy ranks first place for table grape 

production with more than eight million tons per year (ISTAT, 

2011). 

Recently, we developed an innovative analytical method for 

the characterization of various table grape cultivars. In our study, 

multivariate statistical analysis applied to 1H NMR data of table 

grapes, revealed that the inter-vineyard variability of the metabolic 

profile has a greater discriminating effect over the intra-vineyard 

one. [1] 

This presentation deals with the effects of several 

agronomical practices on the metabolic profile of the table grapes 

during different production stages. The variation of the metabolic 

features of the grapes was followed by 1H NMR spectroscopy. 

Moreover, 1H NMR spectra of ripe table grapes were processed 

to be used as input for expert classification systems based on three 

different algorithms: J48, Random Forest and an Artificial Neural 

Network performed with the Error Back Propagation procedure. 

The performances of the three algorithms in the discrimination of 

grapes on the bases of some common features (variety, vintage, 

use of plant growth regulators, trunk girdling, vineyard location) 

will be shown. 

references: 

1. V. Gallo, P. Mastrorilli, I. Cafagna, G. I. Nitti, 

M. Latronico, V. A. Romito, A. P. Minoja, C. Napoli, 

F. Longobardi, H. Schäfer, B. Schütz, M. Spraul, J. Agric. 

Food Chem. (2012), submitted. 

Keywords: NMR spectroscopy; metabolism; 


P - 0 6 0 9 

AuthentiCAtion of fourteen roMAniAn 

GrAPe Seed oiL vArietieS uSinG 

SPeCtroSCoPiC MethodS 

M. L. MihALAChe 1 , C. todASCA 1 , A. hAnGAnu 2 , 

n. ChirA 1 , A. rAnCA 3 , S. roSCA 1 

1 Politehnica University of Bucharest, Organic Chemistry, 

Bucharest, Romania 

2 Center of Organic Chemistry C.D.Nenitescu, Organic 


3 Research Center for Viticulture and Enology, Viticulture and 

Enology, Murfatlar, Romania 

Grape seed oil proved to be a much appreciated ingredient 

in food as well as in cosmetics [1] . Its specific composition in 

polyunsaturated fatty acids and the content of tochopherols and 

polyphenols makes the grape seed oil a nutraceutical product [2] . 

In this study 1H-NMR spectroscopy and systems of 

chemometrical equations were used to determine the composition 

of grape seed oils on four classes of fatty acids [3] . Using Principal 

Component Analysis (PCA) applied to the spectral information, 

grape seed oils were discriminated based on their variety and 

harvest time. 

1H-NMR spectral information was used to determine the 

composition of grape seed oils obtained from 14th different 

varieties of Romanian grapes (Burgundy, Cabernet Sauvignon, 

Muscat Ottonel, Feteasca Neagra, Feteasca Regala, Pinot Noir, 

Pinot Gris, Columna, Cristina, Chardonnay, Mamaia, Merlot, 

Riesling Italian collected from Murfatlar vineyard). Several 

compositional differences have been noticed. The compositional 

differences among the grape seed oils varieties becomes important 

when decision about the field of application is made. 

PCA statistical processing of the data obtained by NMR and 

IR spectroscopy applied directly on the triglycerides, allowed a 

better discrimination of grape seed oils on the bases of variety [4] . 

All triglycerides from the grape seed oil samples were 

subjected to esterification reaction and the resulted FAME were 

analysed by means of GC-MS standard method. 

references: 

1. O. Gurbuz, J.M.Rouseff, & R.L. Rouseff, Journal of 

Agriculture Food Chemistry, 2006, 54 (11), 3990-3996. 

2. S. Bail, G. Stuebiger, S. Krist, H. Unterweger, 

& G. Buchbauer, Food Chemistry, 2008, 108, 1122–1132. 

3. N.A.Chira, M.C. Todasca, A. Nicolescu, A. Rosu, 

M. Nicolae, S.I. Rosca, Revista de Chimie, 2011, 62 (1), 

42-46. 

4. A. Hanganu, M.C. Todasca, N.A.Chira, M. Maganu, 

S.I. Rosca, Food Chemistry, 2012, in press. 

Keywords: Grape seed oil; Principal Component Analysis; 

1H-NMR; GC-MS; Composition; 



s1167 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 1 0 

PoSt CoLuMn derivAtizAtion MethodS for 

the deterMinAtion of MyCotoxinS in food 

ProduCtS And feed MAteriALS By Liquid 

ChroMAtoGrAPhy with fLuoreSCenCe 

deteCtion 

M. MuSCAreLLA 1 , A. ArMentAno 1 , S. Lo MAGro 1 , 

M. iAMMArino 1 , C. PALerMo 2 

1 Istituto Zooprofilattico Sperimentale della Puglia e della 

Basilicata, Chemistry, Foggia, Italy 

2 Universita degli Studi di Foggia, Dipartimento di Scienze 

Agro-Ambientali Chimica e Difesa Vegetale, Foggia, Italy 

Mycotoxins are a group of toxic compounds, produced as 

secondary metabolites by organisms of the fungus kingdom. Some 

of the health effects found in animals and humans include 

mutagenic, carcinogenic and teratogenic effects, kidney and liver 

damage, neurotoxicity, gastrointestinal hemorrhage, immuno 

suppression and even death. In Europe maximum residue limits 

of the most toxic mycotoxins have been set, based on their toxicity 

and on the frequency of potentially contaminated foodstuffs. In 

the last decade liquid chromatography coupled with tandem mass 

spectrometric detection has gained more importance for 

multi-analyte mycotoxin determination, assuring accurate and 

sensitive determinations. Anyway, as underlined in European 

Decision 2002/657, chromatographic methods based on 

fluorescence detection represent a valid alternative as 

confirmatory methods in official control analyses, providing good 

results in terms of selectivity, sensitivity, instrumental costs and 

simplicity. 

Only a limited number of mycotoxins have natural 

fluorescence on their own; however most of mycotoxins lack of 

any significant chromophores, hence for a sensitive detection a 

derivatization step is required to convert them into fluorescent 

derivatives. Thus, liquid chromatography methods for the 

determination of mycotoxins are based on reverse-phase 

separations and fluorescence detection, coupled with pre- or 

post-column derivatization. 

The chemical post-column derivatization allows to 

overcome drawbacks and disadvantages due to pre-column 

techniques, such as low sensitivity, matrix-related limitations, use 

of toxic reagents, instability of fluorescent derivatives and slow 

reaction kinetics. 

In this study analytical methods based on post-column 

derivatization for the determination of aflatoxins (B , B , G and 

1 2 1 

G ), fumonisins (B and B ) and trichotecenes deoxynivalenol 

2 1 2 

(DON) and nivalenol (NIV) in foods and feed materials are 

presented. Separation experimental conditions, the sample 

extraction and clean-up and validation performances were 

carefully evaluated, shooting for developing fast and selective 

methods for high throughput applications in risk-assessment 

studies and control analyses. 

Keywords: liquid chromatography; 


P - 0 6 1 1 

the APPLiCAtion of different deteCtion 

MethodS for irrAdiAted foodS By tL, PSL, eSr 

And GC/MS 

h. y. PArK 1 , M. o. eoM 1 , y. M. JAnG 1 , S. S. Choi 1 

1 Korea Food and Drug Administration, Center for Food and 

Drug Analysis, Incheon, Republic of Korea 

Food irradiation, treatment of foods with ionizing radiations 

such as gamma rays, X rays and electron beams, is technique that 

do not modify nutritional properties of irradiated food, do not 

produce toxical effects and do not induce radioactivity in food 

itself. It can be used to prevent food contamination and to extend 

its shelf life. 

To set up applicability for foods which are not allowed to 

be irradiated in Korea, we have investigated 6 food groups 

including dried fruits and seeds. Samples were analysed by 

thermoluminescence(TL), photostimulated luminescence(PSL), 

electron spin resonance(ESR) method before and after gamma 

irradiation. And in case of seeds were applied by gas 

chromatography/mass spectrometry(GC/MS) method. 

The present work showed that TL method was a sensitive to 

identify irradiated foods and PSL was a suitable method for 

screening of irradiated foods. ESR was a very useful qualitative 

method, because of small sample size and no solvent 

consumption. Detection of hydrocarbons by GC/MS was 

applicable for identifying post-irradiation of samples. As a result, 

this study may help that consumers is able to make their own 

choices between irradiated and non-irradiated foods. 

Keywords: Irradiated foods; Thermoluminescence; 

Photostimulated luminescence; Electron spin resonance; Gas 

chromatography/Mass spectrometry; 



s1168 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 1 2 

Study on AnALytiCAL Method of Liquid 

PArAffin in foodS 

S. J. PArK 1 , J. C. Choi 1 , d. w. Shin 1 , h. S. LiM 1 , 

J. M. oh 1 , S. J. JAnG 1 , S. h. KiM 1 

1 Korea Food and Drug Administration, Food additives and 

Packages Division, Cheongwon-gun Chungcheongbuk-, 


Liquid paraffin is a mixture of heavier alkanes derived from 

petroleum. Liquid paraffin can be used as a lubricant in processing 

machinery, a coating agent for fruits and a releasing agent. There 

is a growing interest in food contaminated with liquid paraffin. 

The purpose of this study is to develop the analytical method of 

liquid paraffin in foods. To develop the time and cost effective 

method, gravimetric analysis and gas chromatography-flame 

ionized detector(GC-FID) were compared. Recovery tests were 

performed in cakes, capsules and dried fruits. Liquid paraffin was 

extracted by hexane and purified by alkaline permanganate 

oxidation and passing through a silica cartridge. GC-FID method 

was validated for liquid paraffin by measuring the limit of 

detection(LOD), the limit of quantification(LOQ) and the linearity 

of calibration curve. The amount of liquid paraffin in foods was 

determined by using the optimized analytical method. 

Keywords: Food additive; Liquid paraffin; Anayltical method; 


P - 0 6 1 3 

non ProteoLytiC AMinoACyL derivAtiveS in 

CheeSeS 

S. SforzA 1 , C. BotteSini 1 , e. SGArBi 2 , 

G. GALAvernA 1 , M. GAtti 2 , t. tedeSChi 1 , 

A. doSSenA 1 , r. MArCheLLi 1 

1 University of Parma, Organic and Industrial Chemistry, 

Parma, Italy 

2 University of Parma, Genetics Biology of Microorganisms 

Anthropolgy Evolution, Parma, Italy 

Cheeses are complex mixtures of amino acids, peptides and 

proteins, mostly derived from the proteolysis of the caseinic 

fraction precipitated in the curd during cheese production. In the 

last years several studies have demostrated that small aminoacyl 

dipeptide-like derivatives of non proteolytic origins are present 

in not negligible amount in several cheeses, like 

Parmigiano-Reggiano, Grana Padano and Asiago [1, 2] . These 

compounds were identified as gamma-glutamyl-amino acids, 

lactoyl-lamino acids and pyroglutamyl-amino acids, and 

collectively named Non Proteolytic Aminoacyl Derivatives 

(NPAD). NPADs were found to be only formed by L-glutamic, 

lactic and pyroglutamic acids (although in cheese their 

D-counterparts are abundant) linked to lipohylic amino acids 

(mostly Phe, Leu, Ile), suggesting a common enzymatic origin, 

and their amount was found to increase with the ageing time. By 

using LC/MS technologies, a deep investigation on their origin 

was undertaken. The cheeses where their amount was found to be 

higher (up to 50 mg /100 g of cheese) were those with a long 

ageing time and a consistent presence of lactic acid bacteria. 

Several strains of lactic acid bacteria, both starters and non 

starters, isolated from Parmigiano-Reggiano cheese, were found 

to have the ability to produce gamma-Glu-Phe e Lac-Phe. 

Experiments with Parmigiano-Reggiano extracts and isotopically 

labelled precursors indicated the presence in the cheese of an 

enzymatic activity able to produce these compounds starting from 

glutamic and lactic acid. Further investigations are now in 

progress in order to identify and isolate the producing enzyme(s). 

These compounds demonstrate that the peptidic fraction of 

Parmigiano-Reggiano is more complex than usually thought, and 

that enzymatic activities on proteins are not only reponsible for 

their hydrolysis, but starting from free amino acids can also form 

new unusual aminoacyl derivatives. 

references: 

1. Sforza et al., 2009, Int. Dairy J., 19, 582-587. 

2. Toelstede et al., 2009, J. Agr. Food Chem., 56, 2795-2804. 

Keywords: Peptides; Liquid chromatography; Mass 

spectrometry; Amino acids; 



s1169 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 1 4 

new SPin ProBeS for oLive oiL 

ChArACterizAtion with ePr SPeCtroSCoPy 

M. StyLiAnou 1 , C. drouzA 1 


Sciences, Lemesos, Cyprus 

The development of new methodologies utilizing fast and 

non destructive spectroscopic techniques, such as EPR 

spectroscopy, in food analysis and characterization has attracted 

great interest. Despite EPR is a very sensitive and quantifying 

technique up to date the number of applications developed in Food 

Science is limited. The current applications are oriented to the 

determination of the antioxidant activity of foods and the 

measurement of radical damage after γ-irradiation applied for 

conservation of food. The absence of naturally spin probes in 

foods makes difficult the utilization of the EPR spectroscopy, 

since EPR requires the presence of unpaired electrons. In this 

study, we develop: (a) new probes based on amphiphilic 

paramagnetic metal species active in the EPR spectroscopy and 

(b) selective oxidative reagents for the endogenous radical 

generation. The new methods were applied for the analysis of 

editable oils, in particular for the olive oil. The new methodologies 

target to utilize EPR towards the determination of olive oil 

adulteration, and its geographical and botanical discrimination. 

The main aspects mentioned above have been applied for the 

authentication of Cypriot olive oils and their classification 

according to their origin. The probes include amphiphilic 

molecules incorporating transition metal ion such as V(IV) or 

Cu(II) as active spin probes, synthesized by the reaction of metal 

ion salts with the amphiphilic chelators. The oils were titrated with 

the spin probes, the EPR spectra were recorded at the X-band, and 

the EPR parameters were determined. In the case of the 

endogenous radical generation the total antioxidant activity was 

quantified and the dynamics of radical decay were determined. 

All the above parameters show that be applied for the 

discrimination between oils of different botanical origin. 

Acknowledgement: Funding from Research Promotion 

Foundation and the European Structural Funds program: 

ANABAΘMIΣH/ΠAΓIO/0308/32 

Keywords: EPR spectroscopy; Amphiphiles; Radicals; 



P - 0 6 1 5 

ChArACterizAtion of the PhenoLiC Content 

And AroMA of the CyPriot wineS froM 

indiGenouS GrAPe vArietieS 

K. tSAouSi 1 , C. drouzA 1 


Sciences Biotechnology and Food Science, Limassol, Cyprus 

An important field of research today is the control of the 

“redox” status with the properties of food and food components. 

Natural antioxidants present in the diet increase the resistance 

towards oxidative damage and they may have a substantial impact 

on human health. In this aspect, wine has attracted great attention 

because it contains flavonoids which exhibit antioxidant and free 

radical scavenging activity in foods. There is accumulating 

evidence that flavonoids inhibit oxidation of low-density 

lipoprotein, reduce platelet aggregation, and their consumption 

always assure a reduced risk of cancer and cardiovascular disease. 

In Cyprus, indigenous vines varieties are cultivated, survived since 

the ancient years. Cypriot wines exhibit distinctive flavor and aroma 

profile, and a rich profile in antioxidants. So far, no records exist in 

the literature for antioxidant content and the chemical composition 

of aroma of wines from varieties indigenous to Cyprus. In this 

study, we demonstrate (a) the flavonoids content of and (b) their 

aroma profile of Cypriot wines using chromatographic techniques. 

The individual polyphenolic constituents were determined by 

High-Performance-Liquid-Chromatography coupled with diode 

array detector, utilizing a reverse phase column. Prototypes 

flavonoids solutions were used as external standards. Volatile 

compounds were isolated using a Solid-Phase-Micro-Extraction 

Head space technique and then separated and semi-quantified on 

a polar capillary column using a Gas-Chromatograph with a Mass 

Spectrometer detector. Identification of the volatiles was 

performed by using standards, the Kovat’s Index, and the MS 

library, while quantification was done using an internal standard. 

Determination of the flavonoids composition and the chemical 

composition of volatiles were performed for the indigenous and 

European varieties cultivated in Cyprus. The results showed that 

the Cypriot wines derived from the indigenous varieties have a 

rich aroma and high content of antioxidant compounds. 

Acknowledgement: Funding from Research Promotion 

Foundation and the European Structural Funds, program: 

ANABAΘMI∑H/ΠAΓIO/0308/32 

Keywords: Antioxidants; Aromaticity; Liquid chromatography; 

Gas chromatography; Mass spectrometry; 



s1170 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 1 6 

CheMiCAL StruCture And MeMBrAne 

interACtivity reLAtionShiP of 

nutrACeutiCAL fLAvonoidS in foodS And 

BeverAGeS: their AntiProLiferAtive effeCtS 

ASSoCiAted with the ChArACterized 

reLAtionShiP 

h. tSuChiyA 1 

1 Asahi University School of Dentistry, Dental Basic Education, 

Mizuho, Japan 

introduction: Flavonoids are referred to as nutraceuticals 

which provide plant-derived foods and beverages with disease 

preventive and therapeutic potentials. However, beneficial effects 

are significantly influenced by their chemical structures. Apart 

from acting on proteinous target enzymes and receptors, 

flavonoids also mechanistically interact with lipid bilayer 

membranes. We characterized the structure and membrane 

interactivity relationship of nutraceutical flavonoids, and verified 

their antiproliferative effects associated with the relationship. 

Methods: Biomimetic membranes were prepared with 

phospholipids and cholesterol, and they were reacted with 

32 structurally-relating flavonoids (flavones, flavonols, 

flavanones, flavanonols, anthocyanidins, flavanols and 

isoflavones) of 0.1–10 μM. The membrane interactivities of 

flavonoids were compared using the potencies to modify 

membrane fluidity by measuring fluorescence polarization with 

different probes. Their antiproliferative effects were determined 

by assaying the growth inhibition of mouse myeloma cells. 

results: Flavonoids structure-dependently acted on the 

deeper hydrophobic regions of lipid bilayers to decrease 

membrane fluidity. The characterized relationship between 

structure and membrane interactivity indicated that 

3-hydroxylation of the C ring, a double bond between 2-carbon 

and 3-carbon of the C ring, 3',4'-dihydroxylation of or no 

substituents on the B ring, and 5,7-dihydroxylation of the A ring 

are important for flavonoids to show greater membrane 

interactions. As the basic structure, flavonoids were far preferable 

to isoflavonoids. Aglycones were much more effective in 

rigidifying biomimetic membranes than glycosides. Quercetin, 

galangin, cyanidin and (–)-epigallocatechin gallate, meeting these 

structural requirements, inhibited the growth of tumor cells at 

10–100 μM. These antiproliferative flavonoids decreased the 

fluidity of tumor cell membranes with the potency correlating to 

the relative cell growth-inhibitory activity. 

Conclusion: Membrane-interacting anti-tumor flavonoids 

are contributable to the medical health benefits of plant-derived 

foods and beverages. However, attention should be paid to the 

possibility that nutraceutical flavonoids may exert adverse effects 

by interacting with membrane-active drugs in the combination 

therapy. 

Keywords: Structure-activity relationships; Membranes; 

Lipids; Natural products; Antiproliferation; 


P - 0 6 1 7 

deterMinAtion of StiLBeneS And 

2,4,6-trihydroxyPhenAnthrene-2-o- 

-GLuCoSide in GrAPevine LeAveS infeCted 

By PLASMoPArA vitiCoLA 

n. vrChotovA 1 , J. triSKA 1 , J. oLeJniCKovA 2 , 

r. JiLeK 1 , d. SeBeLA 2 , r. SotoLAr 3 

1 Global Change Research Centre AS CR v.v.i., Division on 

Impact Studies and Physiological Analyses, Ceske Budejovice, 


2 Global Change Research Centre AS CR v.v.i., Division on 

Impact Studies and Physiological Analyses, Nove Hrady, 


3 Mendel University in Brno, Faculty of Horticulture, Lednice, 


Plasmopara viticola stimulates the synthesis of stilbenes and 

2,4,6-trihydroxyphenanthrene-2- O-glucoside in grapevine leaves 

(Tríska et al. 2012), where 2,4,6-trihydroxyphenanthrene-2-O- 

-glucoside arises from cis-piceid by cyclization. Infected leaves 

of Pinot blanc, Pinot gris and Cabernet sauvignon were 

lyophilized, grounded and than extracted with 70% methanol. 

Extracts were analysed by reverse phase liquid chromatography 

using Hewlett Packard instrument and columnn Phenomenex 

Luna C18 (2) in gradient acetonitril-water-phosphoric acid. 

Compounds were detected by DAD and FLD detectors (Agilent). 

Phenanthrene derivative was confirmed also LC/MS 

measurements. LC/MS were carried out using the Thermo Accela, 

LCQ Fleet ion trap LC-MS instrument and APCI ionization 

technique in the positive mode. 

Values of trans-resveratrol were in ranges of 7-17mg/kg, 

trans-pterostilbene 0.3-1 mg/kg, cis-piceid 54-108 mg/kg and 

2,4,6-trihydroxyphenanthrene-2- O-glucoside 34-60 mg/kg. 

Acknowledgements: This study was funded by the Grant 

Agency of the Czech Republic, grant number 525/09/0365, and 

by CzechGlobe - Centre for Global Climate Change Impacts 

Studies, Reg. No. CZ.1.05/1.1.00/02.0073. 

references: 

1. Tríska J., Vrchotová N., Olejnícková J., Jílek R., Sotolár 

R.: Separation and identification of highly fluorescent 

compounds derived from trans-resveratrol in the leaves of 

Vitis vinifera infected by Plasmopara viticola. Molecules 

(2012) 17(3) 2773-2783. 

Keywords: Phytochemistry; UV/Vis spectroscopy; Mass 

spectroscopy; Biological activity; 



s1171 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 1 8 

LC-eSi-MS/MS Study of ChLorAMPheniCoL 

diStriBution on CheeSe MAKinG 

d. yAnovyCh 1 , o. KoroBovA 1 , M. rydChuK 1 

1 State Scientific Research Control Institute of Veterinary 

Preparations, Laboratory of Instrumental Methods of Control, 

Lviv, Ukraine 

Chloramphenicol (CAP) is effective antibiotic, which use is 

prohibited in food-producing animals. EU defined MRPL for CAP 

in food of animal origin - 0.3 μg/kg. Chloramphenicol control in 

raw milk is obligatory for cheesemakers. Since on manufacturing 

CAP may concentrate in cheese, then there is possibility to obtain 

contaminated product from allowable milk. Therefore, we 

developed LC-ESI-MS/MS method for CAP residues 

determination in cheese. Sample preparation was as follows: CAP 

extraction with ethyl acetate from grated cheese, evaporation, 

defatting and SPE clean-up. HPLC conditions: C column; 

18 

mobile phase - water - methanol. Analyte was quantified by 

negative ion mode LC-ESI-MS/MS (MRM of m/z 321≥152 and 

321≥257). LOQ =0.02 μg/kg. 

Since cheese sample matrix is complex, then minced cheese 

fortifying with internal or external CAP standard may not 

represent adequate recovery of analyte, present in initial milk. 

Therefore, we prepared cheese reference matrix to estimate the 

elaborated method’s recovery. Cheese was made in laboratory 

according to general procedure using blank cow’s milk, divided 

into two equal parts, one of which was spiked with 0.5 μg/kg CAP. 

Milk, whey, cheese and salt solution were sampled during cheese 

preparation and ripening. 

It was ascertained, that on cheese making 78% of 

chloramphenicol, added into initial milk, accumulates in whey, 

while 20% in cheese and 2% in salt solution. If milk contains 

0.5 μg/kg CAP, then CAP concentration in cheese and whey will 

equal 0.8 and 0.45 μg/kg, respectively. Hence, irregular 

chloramphenicol distribution occurs in main and by-products, 

therewith CAP concentration in cheese is 1.5-2-times higher than 

in utilized milk. Thus, even when making cheese from milk 

containing CAP level lower than MRPL, there is a possibility to 

obtain contaminated cheese. 

It was established, that chloramphenicol recovery from 

cheese with developed method is ~90%. Also, techniques for CAP 

determination in whey and salt solution were elaborated. 

Keywords: Mass spectrometry; Liquid chromatography; 

Antibiotics; 


P - 0 6 1 9 

Low teMPerAture of the MethAne CouPLinG 

with uv-ACtivAtion in the MeMBrAne 

reACtor 

n. BASov 1 , i. oreShKin 2 , n. oreKhovA 1 , 

M. erMiLovA 1 , A. yAroSLAvtSev 1 

1 A.V.Topchiev Institute of Petrochemical Synthesis RAS, 

Laboratory of Catalysis on Membranes, Moscow, Russia 


Laboratory of Metalllorganic Catalysis, Moscow, Russia 

The basic methods to produce hydrocarbon C and above 

2 

from methane is a thermal activation of the CH molecules that 

4 

breaks C-H bonds that often caused an uncontrolled breakup of 

these bonds with free carbon formation. To use the ultraviolet 

activation allows conducting the process under low temperature, 

but because of the reaction reversibility the methane conversion 

remains low. The membrane reactor makes to shift equilibrium 

possible by hydrogen removing from the reaction space and 

therefore to increase the methane conversion. 

The experiments were provided under atmospheric pressure 

of the pure methane (99.99%) in the temperature interval 

200–270°C with a mercury lamp. The membranes in the form of 

Pd-Ru alloy tubes (diameter 1 mm, wall thickness 50 mkm, 1 or 

1.7 m lengths) were placed inside the quartz glass reactor filled 

with CH . Any gas flow inside the tube allowed moving off the 

4 

hydrogen that penetrated through the membrane from the reaction 

space outside this tube. The mane products analysed by GC were 

propane and ethane with small quantity of the ethylene. 

The methane conversion with 1 m tube at 215°C was four 

times higher (5.2 %) when hydrogen was removed through a 

membrane than without hydrogen removing off at the same 

temperature. The highest obtained conversion was 14.3 % at 

265°C with hydrogen removing off from the reaction space. 

Probable products formation mechanism 

CH -> CH · + H· 

4 3 

CH -> CH : + H 4 2 2 

2CH · -> CH -CH 3 3 3 

CH : + CH -CH -> CH -CH -CH 2 3 3 3 2 3 

2CH : -> CH =CH 2 2 2 

2H· -> H2 The methane molecules’ activation by the UV-radiation 

allows providing their coupling under comparatively low 

temperature that reduces power inputs and a deep 

dehydrogenation with free carbon formation. To use a palladium 

alloy membrane reactor allows increasing the methane conversion 

due to hydrogen removing from the reaction space. 



s1172 

chem. Listy 106, s257–s1425 (2012) 

Poster session 2 - Energy and Carbon Dioxide 

P - 0 6 2 0 

KinetiCS of dye LoAdinG ProCeSS in dye 

SenSitized SoLAr CeLLS By MeAnS of reAL 

tiMe dye uPtAKe MonitorinG 

i. ConCinA 1 , e. friSon 2 , S. SiLveStrin 2 , 

M. MAGGini 2 , G. SBerveGLieri 1 , A. voMiero 1 , 

t. CArofiGLio 2 

1 CNR-IDASC, SENSOR Laboratory, Brescia, Italy 

2 Padova University, Dept. of Chemistry Sciences, Padova, Italy 

Since their set up, dye sensitized solar cells (DSCs) have 

attracted a remarkable interest as promising alternative devices to 

silicon-based photovoltaic technology [1] . However, device 

fabrication is an “artisanal” multi-step procedure still lacking of 

rationalisation. Dyeing process holds a relevant impact on both 

cell performances and scale-up perspective [2] . Indeed, DSCs are 

currently sensitized by means of a static impregnation process 

lasting about 20 hours, which would be time expensive in view 

of an industrial scale up. 

Herein we present a study on the real-time monitoring of 

dye loading process by means of UV-vis spectrophotometry 

allowing to rationalize the kinetics of dye uptake in both static 

and dynamic condition for the classical Ru-based N719 and 

N3 dyes at different concentrations on nanoparticulate TiO2 

photoanode [3] . 

Dynamic dye uptake was found to follow a two-step process, 

composed of a first faster contribution indicating a pseudo-first 

order kinetics (tens to hundreds of seconds) followed by a slower 

absorption according to a zero-order kinetics (hours). 

The choice between dynamic and static sensitization 

approaches turned out to heavily affect the final dye loading. 

Although the same mechanism was operating in both cases, 

dynamic uptake was found to provide for a lower dye loading, 

which is reflected in poorer DSC performances (a decrease of 

about 20% was found as for photoconversion efficiency). 

Although a prudential attitude should be adopted when 

comparing the two approaches, dynamic sensitization could be a 

powerful tool towards a reproducible and fully controllable 

fabrication of DSCs. 

references: 

1. B. O’Regan and M. Gratzel, Nature, 1991, 353, 737 

2. F. Sauvage et al., J. Am. Chem. Soc., 2011, 133, 9304 

3. I. Concina et al., Chem. Comm., 2011, 47, 11656 

Keywords: dye sensitized solar cells; dye loading kinetics; 


P - 0 6 2 1 

effeCtS of Cr o ModifiCAtion on the 

2 3 

PerforMAnCe of Sno eLeCtrode in 

2 

dye-SenSitized SoLAr CeLLS 

S. y. Choi 1 , A. h. Kwon 2 , y. u. Kwon 2 

1 Sungkyunkwan University, SKKU advanced institute of 

nanotechnology, Suwon, Republic of Korea 


Korea 

We demonstrate that Cr O , a visible absorbing insulator, 

2 3 

can be used as an efficient blocking layer material for the anode 

of dye-sensitized solar cells (DSSCs). We prepared SnO2 electrodes surface-modified with Cr O with various Cr/Sn ratios 

2 3 

and studied the effect of the modification on the performance of 

DSSCs. DSSCs with Cr/Sn ratios 0.02, 0.05, and 0.10 showed 

increased overall photon-to-electricity conversion efficiency from 

that of pure SnO . When Cr/Sn ratio was 0.02, 55%-improved 

2 

overall conversion efficiency was measured and the ratio 0.05, 

40% compared with pure SnO cell. The physical properties of 

2 

Cr O -modified SnO were studied by X-ray diffraction, 

2 3 2 

transmission electron microscopy, N adsorption studies and 

2 

UV-Vis diffuse reflectance spectroscopy. The electrochemical 

properties of Cr O -modified SnO were studied by Mott-Schottky 

2 3 2 

plots and electrochemical impedance spectroscopy. 

Keywords: Dye-sensitized solar cell; blocking layer; 



s1173 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 2 2 

ABSorPtion of Co into AqueouS PotASSiuM 

2 

SALt SoLutionS of AMino ACidS 

S. K. JeonG 1 , J. A. LiM 1 , y. yoon 1 , S. C. nAM 1 , 

i. h. BAeK 1 

1 Korea Institute Of Energy Research, Greenhouse Gas 

Research Center, Daejeon, Republic of Korea 

Since the industrial revolution, fossil fuel consumption has 

drastically increased. Carbon dioxide discharged from combustion 

processes is now believed responsible for global warming and an 

increase in the earth’s average temperature. The development of 

CO capture technologies is critical for reducing greenhouse gases 

2 

and coping with the climate change problem at its root. 

Monoethanolamine (MEA) is the leading alkanolamine absorbent. 

Although it features a fast absorption rate and a high alkalinity, it 

has the drawbacks of loss of absorbent due to degradation and 

corrosion of the equipment as well as the high amounts of energy 

required for absorbent regeneration. To solve these problems, the 

absorption of CO using an amino acid salt solution as an 

2 

alternative absorbent was studied. In this study, the CO2 absorption capacity and absorption heat of the aqueous potassium 

salts of L-alanine and L-proline were investigated using a semibatch 

absorption system and a differential reaction calorimeter 

(DRC). The speciation in the CO -loaded absorbents was 

2 

investigated using NMR spectroscopy. The results were compared 

with primary amine, MEA and secondary amine, diethanolamine 

(DEA). The CO loading capacities were found to be 0.50 and 

2 

0.68 mol CO /mol solute for aqueous MEA and potassium salt of 

2 

L-alanine at 298 K, respectively. The CO absorption heats of the 

2 

potassium salt of L-alanine and potassium salt of L-proline were 

lower than those of MEA. The absorption heats were found to be 

81.77, 67.06, 53.26 and 90.20 kJ/mol-CO for aqueous MEA 

2 

DEA, potassium salt of L-alanine, and potassium salt of L-proline, 

respectively. It was found that the potassium salt of L-alanine had 

an excellent for CO capture. Therefore, the potassium salts of 

2 

L-alanine and L-proline are deemed to be the potential CO2 absorbent to replace the existing amines. 

Keywords: CO Capture; Amino Acids; Amine; 

2 


P - 0 6 2 3 

wAter oxidAtion By SinGLe-Site rutheniuM 

CoMPLexeS – uSinG LiGAndS AS redox And 

Proton trAnSfer MediAtorS 

M. KärKäS 1 , t. AKerMArK 2 , e. JohnSton 1 , 

S. KAriM 1 , t. LAine 1 , B. L. Lee 1 , t. PrivALov 1 , 

B. AKerMArK 1 

1 Stockholm University, Department of Organic Chemistry, 

Stockholm, Sweden 

2 Stockholm University, Department of Materials and 

Environmental Chemistry, Stockholm, Sweden 

The splitting of water into molecular oxygen and hydrogen 

gas is an attractive option for the production of sustainable energy, 

where mastering the process of oxidizing water is the key step for 

the utilization of this potential. The possibilities are enormous, 

where the later can be used as a fuel, stored for future demands, 

or even to be used for the production of more complex fuels and 

chemicals. 

A serious problem is that most of the catalysts developed so 

far require a powerful sacrificial oxidant, i.e. CeIV , to be able to 

oxidize water. In a sustainable system, the oxidant needs to be a 

light-absorbing component, a photosensitizer, which can be 

regenerated. A major obstacle in light-driven water oxidation is 

frequently the mismatch between the relatively high redox 

potential at which a catalyst assumes its active state and the lower 

potential attainable with a photosensitizer. 

Comprising a redox and proton transfer mediator motif into 

the WOC would facilitate the simultaneous transfer of electrons 

and protons, thus avoiding high-energy intermediates and give 

access to new reaction pathways. In order to both decrease the 

redox potentials and permit coupled proton-electron transfer, 

imidazole and carboxylate were introduced as mediators into the 

ligands. Therefore the meridionally coordinating benzimidazole 

based ligands 1 and 2 and their related single-site ruthenium 

complexes 3 and4 were synthesized. Indeed, by introducing the 

redox and proton transfer mediator motif (imidazole) the WOCs 

were able to catalyze water oxidation, under neutral conditions, 

both by pre-generated and photogenerated [Ru(bpy) ] 3 3+ . 

Keywords: Water splitting; Sustainable chemistry; Ruthenium; 

Photochemistry; Electrochemistry; 



s1174 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 2 4 

PhotoCheMiCAL wAter oxidAtion – inSPired 

By nAture 

M. KärKäS 1 , e. KArLSSon 1 , B. L. Lee 1 , t. AKerMArK 2 , 

e. JohnSton 1 , J. Sun 2 , o. hAnSSon 3 , J. e. BäCKvALL 1 , 

B. AKerMArK 1 

1 Stockholm University, Department of Organic Chemistry, 

Stockholm, Sweden 

2 Stockholm University, Department of Materials and 

Environmental Chemistry, Stockholm, Sweden 

3 University of Gothenburg, Biophysics Group Department of 

Chemistry, Gothenburg, Sweden 

The direct conversion of solar energy into energy by the 

splitting of water into molecular oxygen and hydrogen gas, or 

even more complex fuels holds high potential in realizing a 

sustainable energy production for our future demands. Water 

oxidation is currently restricting the development of solar-energy 

devices and is considered to be essential to fully utilize this 

potential. 

The development of environmentally benign, abundant and 

thus inexpensive first row transition metal catalysts is of utmost 

importance for the incorporation into molecular light-harvesting 

devices on a large scale. To date, there are only a handful of 

homogeneous water oxidation catalysts which are capable of 

managing the difficult task of oxidizing water. 

Herein we report that the dinuclear manganese complex 1 

is capable of mediating the four electron oxidation of water, both 

by using a chemical oxidant and photochemically. Complex 1 is 

based upon a bioinspired ligand containing imidazole and 

carboxylate functionalities, which are both important components 

in the natural system. To the best of our knowledge this is the first 

example of a homogeneous manganese based water oxidation 

catalyst. 

Keywords: Water splitting; Manganese; Photochemistry; 

Sustainable chemistry; 


P - 0 6 2 5 

CLyStAL Growth of SeMiCLAthrAte hydrAte 

forMed with tetrA-n-ButyL AMMoniuM 

BroMide And CArBon dioxide 

S. KoyAnAGi 1 , r. ohMurA 1 

1 Keio University, Department of Mechanical Engineering, 

Yokohama, Japan 

This paper reports a visual crystal growth study concerning 

the separation of carbon dioxide utilizing formation and 

dissociation of clathrate hydrate. The obstacle to realize this 

hydrate technology is high pressure required for the hydrate 

formation. The high equilibrium pressure of CO hydrate may be 

2 

moderated with the addition of a second guest substance such as 

tetra-n-butyl ammonium bromide (TBAB).Visual observations 

were carried out on the formation and growth of semiclathrate 

hydrate crystals in the system of CO + TBAB + water. The 

2 

experimental thermodynamic conditions are (i) at pressure 

of 2.3 and 3.4 MPa and temperature range of 286 to 290 K for 

w = 0.40, (ii) at pressure of 2.3 and 3.4 MPa and in the 

TBAB 

temperature range of 282 to 288 K at w = 0.10 where w TBAB TBAB 

denotes the mass fraction of TBAB in the aqueous liquid. 

A hydrate crystal first formed in aqueous liquid or to intervene 

between the gas and aqueous liquid phases. Then hydrate crystals 

grew into aqueous liquid phase. The morphology of hydrate 

crystals grown in aqueous liquid varied distinctly depending on 

the system subcooling ΔT . (ΔT ΞT -T , where T is the 

sub sub eq ex eq 

equilibrium temperature of the hydrate at each mass fraction and 

T is the system temperature).When ΔT is smaller than ~ 2.0 K, 

ex sub 

hydrate crystals with planar morphology were observed. At the 

range of ~3.1 K > ΔT > ~2.0 K, the planar crystals were replaced 

sub 

by columnar and sword shaped crystals. At ΔT > ~3.1 K, hydrate 

sub 

crystals with needle morphology were observed. Pressure 

dependence of hydrate crystal morphology was not observed. 

The size of the individual hydrate crystals decreased with 

increasing ΔT . We also observed the crystals floating in aqueous 

sub 

liquid at ΔT > ~3.1 K 

sub 

Keywords: Clathrates; Hydrates; Crystal engineering; Crystal 

growth; Carbon dioxide fixation; 



s1175 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 2 6 

Pt/n-CodoPed tio nAnotuBe ArrAyS for 

2 

PhotoCAtALytiC hydroGen evoLution 

h. r. LiAo 1 , r. A. doonG 1 

1 National Tsing Hua University, Biomedical Engineering and 

Environmental sciences, Hsin-Chu, Taiwan 

In this study, The Pt/N-codoped TiO composites were 

2 

synthesized using TiO nanotube arrays as a support. The TiO 2 2 

nanotube arrays were electrochemically fabricated using 

20 × 20mm titanium and Pt foils as the anode and cathode, 

respectively. In addition, Pt ions and ammonia were loaded onto 

the TiO nanotube arrays to from Pt/N-codoped TiO composites 

2 2 

for enhanced photocatalytic reaction. The microstructures of TiO2 nanotubes including morphology, optical property, and 

crystallinity were determined. In addition, effect of operational 

parameters including catalyst loading, solution pH, and anneal 

temperature on the production of hydrogen gas were examined 

and optimized. The TiO nanotubes have several nm in diameter 

2 

and tens of μm in length after 5 h of anodization. The TEM images 

showed that Pt nanoparticles were well-dispersed on the surface 

of TiO nanotubes with diameter of 5-10 nm. In addition, TiO 2 2 

and Pt/N-codoped TiO nanotube arrays were used for 

2 

photocatalytic hydrogen generation. The hydrogen production rate 

from water by Pt/N-codoped TiO nanotube arrays was higher 

2 

than that of pure TiO nanotube arrays. Results show that 

2 

photocatalyst with optimal operational conditions could lead to 

enhanced hydrogen production rate. 

Keywords: TiO2 nanotube arrays; Codoping; Photocatalytic 

Hydrogen Evolution; 


P - 0 6 2 7 

identifiCAtion of GASoLine AduLterAtion By 

the Addition of SoLventS, tAGGed with 

trACerS, in A ProGrAM CreAted By the 

BrAziLiAn GovernMent 

P. PiveSSo 1 , A. LiMA 2 

1 Agencia Nacional do Petróleo Gás Natural e Biocombustíveis, 

Centro de Pesquisas e Análises Tecnológicas, Brasília, Brazil 

2 Agencia Nacional do Petróleo Gás Natural e Biocombustíveis, 

Superintendancia de Biocombustíveis e Qualidade de 

Produtos, Rio de Janeiro, Brazil 

Email: ppivesso@anp.gov.br 

Gasoline adulteration, through the addition of unauthorised 

solvents or kerosene, is a serious problem facing many national 

governments and producers today. The principal of tracer 

technology is that a material not found naturally within the fuel 

is added at ultra low levels to potential adulterants. An analysis 

of suspect fuel showing the tracer confirms adulteration. In many 

instances where a tracer material is added to potential adulterants, 

there is an incentive for the illicit removal of the taggant, often 

termed ‘laundering’. Therefore it is essential that the tracer is 

highly resistant to laundering by the methods likely to be used by 

those adulterating the gasoline. This system is adopted in Brazil, 

where the solvents are tagged to prevent and detect the 

adulteration of gasoline by the addition of these products. The 

Brazilian Program was a pioneer worldwide, since we decided to 

tag the adulterant instead of the gasoline. The chemical tracer used 

in the Program is detected by Gas Chromatography/Mass 

Spectrometry with NCI source employing suitable detection 

methods. The method allows the detection of the tracer at very 

low concentration (ppb), providing great reliability in identifying 

gasoline adulteration by the addition of solvents, even at very low 

concentrations. This paper describes the application of the GC/MS 

based system, and demonstrates why it is the analytical technique 

of choice for measuring ‘launder’ resistant taggants. It also 

highlights the positive results achieved in the last 10 years during 

use in the Brazilian Program to counter the adulteration of 

gasoline by the addition of solvents. 

Keywords: gasoline adulteration; identifying tracers in 

gasoline by GC/MS; energy; fuels; brazilian program; 



s1176 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 2 8 

Study of CyAno-SuBStituted hydrAziniuM 

SALtS for enerGetiC APPLiCAtionS 

C. Miro SABAte 1 , h. deLALu 1 



1,1-Dimethylhydrazine can be readily alkylated 

with bromoacetonitrile to form 1-cyanomethyl-1,1- 

-dimethylhydrazinium bromide ([(CH ) N(CH CN)NH ]Br, 1). 

3 2 2 2 

Metathesis of the bromide anion in 1 with an energetic anion 

transfer reagent lead to the formation of a new family of salts 

based on the [(CH ) N(CH CN)NH ] 3 2 2 2 + cation and nitrate (2), 

perchlorate (3), azide (4), 5-aminotetrazolate ([H N–CN ] 2 4 – , 5), 

5,5’-azobistetrazolate ([N C–N=N–CN ] 4 4 2– , 7) and picrate (8) 

anions. The new materials were characterized by elemental 

analysis, mass spectrometry and (multinuclear) NMR and 

vibrational (infrared and Raman) spectroscopies. Additionally, the 

molecular structure of the [(CH ) N(CH CN)NH ] 3 2 2 2 + cation in 

compounds 1, 3 and 8 and that of sodium 5,5’-azobistetrazolate 

octahydrate (NaZT*8H O) were solved by X-ray diffraction 

2 

techniques. The hydrogen-bonding networks found in the 

structure of salts 1, 3, 8 and NaZT*8H O is described using 

2 

graph-set analysis. The melting and decomposition points of the 

new compounds was determined by differential scanning 

calorimetry and all materials were submitted to standard tests to 

gain insight into their sensitivity towards impact, friction and 

electrostatics. Furthermore, we estimated some performance 

parameters of interest and we predicted the decomposition gases 

formed upon decomposition of the materials in this study and of 

their mixtures with an oxidizer. The interesting thermal, sensitivity 

and performance properties of some of the compounds make them 

attractive candidates towards a prospective energetic application. 

Keywords: Nitrogen; Ion exchange; NMR spectroscopy; 

Quantum Chemistry; X-ray diffraction; 


P - 0 6 2 9 

Co ABSorPtion ChArACteriStiCS of AqueouS 

2 

AMino SiLAne 

S. C. nAM 1 , y. JunG 1 , y. yoon 1 , S. JeonG 1 , K. PArK 1 

1 Korea Institute Of Energy Research, High Efficiency and 

Clean Energy Research Division, Daejeon, Republic of Korea 

There are many ways to reduce CO emission such as pre- 

2 

and post-combustion capture technologies these days. Also lots 

of studies have been conducted about this area. One of them is 

absorbent for CO capture. Moreover, the study on the 

2 

applications of absorbents for pilot plant is performed using 

absorbent such as commercial MEA. In this study, we investigated 

the possibility of amino-silane series as an absorbent for CO2 absorption. CO absorption capacity and characteristics of 

2 

amino-silane series were examined at the following conditions; 

temperatures (30, 50, 70?), pressure (1~30 bar). In addition, we 

investigated CO absorption capacity and characteristics of 

2 

amino-silane series with different ratios of amino-silane to 

distilled water. Based on the results, we compared amino-silane 

with MEA. In order to evaluate CO absorption capacity and 

2 

characteristics, we prepared equipments at constant temperature 

and pressure conditions. We removed water and other impurity 

gases in the equipment cells before experiments. High purity CO2 gas (99.9%, Dukyang energen gas corporation, Korea) was used 

for experiments. As the experiment was performed, CO2 absorption into absorbent was started and maintained for enough 

time until equilibrium condition between absorbent and CO . At 2 

that time, we calculated CO absorption rate and absorption 

2 

amount of the amino silane series. As the result of the 

experiments, CO absorption capacity and absorption rate 

2 

increased together with increasing the amount of amino silane in 

the mixture. We observed that all experiments were reached at 

equilibrium within 3 hr, although each equilibrium times are a 

little different. In this work, we confirmed CO absorption 

2 

capacity and characteristics of amino silane series. 

Keywords: carbon dioxide; capture; amino silane; greenhouse 

gas; global warming; 



s1177 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 3 0 

GLyCeroL CoMPound uSed AS A Green 

CoMPonent for dieSeL fueL 

e. e. oPreSCu 1 , e. StePAn 2 , P. roSCA 1 , A. rAdu 2 , 

C. enASCutA 2 

1 Petroleum-Gas University of Ploiesti, 

Petroleum engineering and petrochemistry, Ploiesti, Romania 

2 INCDCP ICECHIM, Bioresources, Bucharest, Romania 

Biodiesel is a good alternative for diesel fuel. Each tonne of 

produced biodiesel, generates more than 100 kg of crude glycerine 

which can be converted into useful products. An important 

direction for crude glycerine valorization is transformation into 

glycerol acetals/ketals that can be used as additives and/or 

components of classic diesel fuels. 

This paper presents the synthesis of 4-methylpentan-2-one 

glycerol ketal obtained from condensation of 4-methylpentan-2-one 

with glycerol, catalyzed by a solid superacid. The obtained 

glycerol compound was tested as diesel fuel component, focusing 

our interest in cold flow properties, viscosity and flash point. 

The catalytic ketalization of glycerol was made in presence 

2- of SO /TiO2-ZrO . The catalyst was prepared by coprecipitation 

4 

2 

followed by vacuum sonicated impregnation and characterized by 

X-ray diffraction, thermogravimetric analysis, FT-IR spectroscopy 

and elemental analysis. To determinate the optimal parameters, 

five impact factors were investigated in the experiments: molar 

ratio glycerol/4-methylpentan-2-one, catalyst calcination 

temperature, reaction time, catalyst amount and molar ratio of 

Ti/Zr. Synthesized ketal was analyzed by GC–MS/MS. 

The experimental results shows the maximum yield in 

4-methylpentan-2-one glycerol ketal of 92% was reached at molar 

ratio ketone to glycerol 1.1:1, mass ratio of the catalyst 1.5 wt % 

with respect to glycerol, reaction time 6.5 h, catalyst calcination 

temperature 550oC for 3 h and molar ratio Ti/Zr=4:1. 

The influence of viscosity, pour point and flash point on the 

quality parameters of diesel fuel blends with 2, 5, 7 and 10% of 

oxygenated compound were studied. The data obtained shows that 

of 4-methylpentan-2-one glycerol ketal slightly changes 

the flash point (from 61.1 to 62.1oC), but improves the pour point 

(from -13 to -23oC) and viscosity (from 2.7 to 2.59 mm2 /s ). 

Keywords: glycerol; solid superacid; ketal; diesel component; 

4-methylpentan-2-one; 


P - 0 6 3 1 

hydroGen PerMeAtion ProPertieS of 

vAnAdiuM-Boron ALLoy MeMBrAneS for 

Pre-CoMBuStion CArBon dioxide CAPture 

ProCeSS 

J. h. PArK 1 , h. J. KiM 2 , S. i. Jeon 1 , y. J. KiM 1 , J. G. KiM 2 

1 Korea Institute Of Energy Research, Greenhouse Gas 

Department, Daejeon, Republic of Korea 

2 Korea Institute Of Energy Research, Clean Fuel Department, 

Daejeon, Republic of Korea 

Novel membranes composed of the vanadium-boron alloys 

have been developed for the hydrogen separation in 

pre-combustion CO capture process. Group 5A metals, such as 

2 

vanadium are promising candidates for hydrogen permeation 

alloys because of their high hydrogen permeability values, 

however these metals alloys suffer from severe hydrogen 

embrittlement. In this work, a small amount of boron was added 

into vanadium base metal to enhance the stability of membrane 

during hydrogen separation. The hydrogen permeation 

experiments have been conducted to investigate the hydrogen 

transport property through the Pd-coated vanadium-boron alloy 

membrane under simulated gas feeding condition such as pure 

hydrogen and hydrogen-carbon dioxide gas mixture. Pressure was 

controlled with back pressure regulator in the region of 1.0~3.0 

bar at 400 °C. Hydrogen fluxes agreed with Sievert’s law 

irrespective of feeding condition. The maximum hydrogen flux 

of a 0.5 mm thick membrane was 48.5 ml/min•cm2 at 400 °C 

under pure hydrogen feeding condition. 

Keywords: vanadium; boron; metal alloy membrane; hydrogen 

separation; carbon dioxide capture; 



s1178 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 3 2 

extrACtion of LiPidS froM ALGAe with 

SwitChABLe SoLventS 

C. SAMori 1 , r. wet 2 , w. BriLMAn 2 , P. GALLetti 1 , 

d. LoPez BArreiro 3 , L. PezzoLeSi 1 , G. SAMori 1 , 

e. tAGLiAvini 1 

1 Centro Interdipartimentale di Ricerca Industriale (CIRI), 

University of Bologna, Ravenna, Italy 

2 Thermo-Chemical Conversion of Biomass Group, Faculty of 

Science and Technology, University of Twente, Enschede, The 

Netherlands 

3 Department of Biosystems Engineering, University of Ghent, 

Belgium 

Microalgae represent a very promising source of third 

generation biofuels. Benefits rising from the utilisation of aquatic 

over terrestrial biomasses are varied, however lipid extraction is 

currently a critical step in the industrial development of these 

biofuels. Here we propose a new green procedure based on 

switchable-polarity solvents (SPS) for the extraction of algal lipids 

from both dried samples and concentrated cultures. SPS are capable 

to turn from a non-ionic form, suitable for lipid extraction, to an 

ionic liquid, suitable for a recovery step, by simply bubbling CO , 2 

and to be reconverted in the non-ionic form by bubbling N or by 2 

heating [1] . We present the results obtained with different classes of 

SPS: i) one based on 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) 

and alcohols (ROH), switchable in alkylcarbonate 

salts; ii) the second based on alkyl amines 

(as N,N-dimethylcyclohexylamine, DMCHA) and water, 

switchable in hydrogencarbonate salts. 

The SPS were tested for the extraction of lipids from freezedried 

samples and directly from aqueous growth medium of 

several microalgae, as Botryococcus braunii, rich in unsaturated 

hydrocarbons [2] , and other freshwater and marine species 

(e.g. Chlorella sp., Nannochloropsis sp. and Desmodesmus sp.) 

and compared with the efficiency of traditional organic solvents 

(e.g. n-hexane and chloroform/methanol mixture). 

The use of a green technology suitable for extracting lipids 

from both dried microalgal biomass and directly from aqueous 

growth medium is an important issue considering that the harvest 

and the dewatering of algal biomass have a large impact on overall 

costs and energy balance. Besides the efficiency in lipid 

extraction, SPS have the great advantage to be recyclable 

non-volatile/non-inflammable systems, therefore suitable for 

non-hazardous small plants for biofuel production located nearby 

algal cultivation sites. 

references: 

1. Jessop, P. et al., 2005. Nature, 436, 1102 

2. Samori C. et al., 2010. Bioresource Technology, 101, 3274. 

Keywords: algae; switchable solvents; biofuels; 


P - 0 6 3 3 

CoMPAriSon of CheMiCAL AvAiLABiLity, 

PoLLutAnt And Co eMiSSionS froM 

2 

hydroGen, ethAnoL And nAturAL GAS AS 

enGine fueLS 

J. r. Sodre 1 , r. Brito 1 , G. LuBen 1 , L. ALMeidA 2 , 

S. LuiS CArLoS 2 

1 Pontifical Catholic University of Minas Gerais, Department of 

Mechanical Engineering, Belo Horizonte, Brazil 

2 FIAT Automobiles SA, Powertrain Technologies, Betim, Brazil 

The chemical availability of green fuels hydrogen and 

ethanol has been calculated and compared with common engine 

fossil fuels gasoline and natural gas. Other parameters evaluated 

were the concentrations of carbon monoxide (CO), nitric oxide 

(NO) and carbon dioxide (CO ) as combustion products. The 

2 

analysis has been carried out through an engine cycle simulation 

model developed using Engineering Equation Solver software. 

The results show that hydrogen present superior exergetic 

efficiency in comparison with gasoline and natural gas. Ethanol 

produced lower exergetic efficiency than the fossil fuels. CO and 

CO concentrations are significantly reduced with the use of the 

2 

green fuels, while NO concentration showed less accentuated 

reduction. 

Keywords: Hydrogen; Biomass; Energy Conversion; 

Renewable Resources; Thermochemistry; 



s1179 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 3 4 

A SiMPLe didACtiC ModeL of Mhd Power 

GenerAtor for the StudentS LABorAtory 

M. SynowieCKi 1 

1 WAT Military University of Technology, Faculty of New 

Technologies and Chemistry, Warsaw, Poland 

MHD (magnetohydrodynamic) generator is a heat engine 

that operates by passing a high velocity jet of partially ionized gas 

through a magnetic field to produce electricity. In effect, the solid 

rotor of conventional generator replaced with a plasma “rotor”. 

The advantages of such system are obvious. The plasma 

rotor can not melt in a high temperatures, so higher input 

temperatures and higher power producing efficiencies are 

possible. This rotor has little mechanical inertia, so the start-up 

time can be quite short. 

In order to achieve high efficiency of the MHD generator, 

the electrical conductivity of the plasma jet must be as high as 

possible. In my project, the flame is seeded with easily-ionized 

potassium (EI = 4,34 eV), and is highly conducting even at 

relatively low temperatures. In addition, thermal ionization of the 

exhaust gas takes place. 

A simple demonstration model MHD generator based on a 

small solid-fuel rocket motor (with black powder propellant) as a 

power source. The motor is exhausting between the poles of a two 

neodymium magnets. Steel electrodes placed at the edges of the 

gas jet detect the generated voltage for display on a digital 

multimeter (voltmeter). A rocket motor provides about five 

seconds of running time. 

Both the open-circuit voltage (several volts) and the 

short-circuit current (several miliamperes) can be calculated, 

giving students an excellent insight into the properties of this 

power system. 

In this study, basic assumptions and requirements to be taken 

into account in designing and building a model MHD generator 

are presented. In addition, modelling of a composite propellant 

including potassium is described. The parameters such as 

ionization ratio, electrical conductivity, chemical composition of 

exhaust gas and open-circuit voltage were also evaluated. 

Keywords: energy conversion; environmental chemistry; 

plasma chemistry; thermodynamics; 


P - 0 6 3 5 

the direCt SyntheSiS of hydroGen Peroxide 

BASed on MiCroreACtor teChnoLoGy 

t. inoue 1 , M. Lu 1 , K. ohtAKi 1 , J. AdAChi 1 , 

S. MurAKAMi 1 , S. MAtSuMoto 1 

1 AIST, UMEMSME, Tsukuba Ibaraki, Japan 

We successfully conducted the direct syntheisis of hydrogen 

peroxide using applying microreactor technology to produce 

aqueous solution of 10 wt%, under rather ambient condition 

(1 MPa, no cooling effort). The microreactor design was 

mandatory to proceed the reaction safely and efficiently. For the 

direct synthesis reaction is three phase reaction (gas, liquid and 

solid i.e. catalyst), proper distribution of both gas and liquid phase 

over catalyst is mandatory, which has been realized by our reactor 

design. Heat removal nature also worked favorable to maintain 

the reaction not only operatable but also productive for hydrogen 

peroxide. Also, proper choice of the catalyst promoted the 

concentration of hydrogen peroxide we provided. Our kinetics 

analysis indicated that hydrogen and oxygen reaction is a cascade 

reaction, whose primary product was hydrogen peroxide and 

water was subsequently produced. The second step was 

unfavorable to achieve high concentration of hydrogen peroxide. 

Details of the kinetics analysis will be presented on site. 

Keywords: hydrogen peroxide; direct synthesis; 



s1180 

chem. Listy 106, s257–s1425 (2012) 

Poster session 2 - Green Chemistry 

P - 0 6 3 6 

SynteSiS of BioLoGyCAL ACtive CoMPoundS 

froM veGetABLe rAw MAteriALS hAS 

AntioxidAnt ProPertieS 

n. dzhAKiPBeKovA 1 , G. tureBeKovA 1 , 

d. dzhAKiPBeKovA 1 

1 South-Kazakhstan State university, Chemistry, Shymkent, 

Kazakhstan 

Email: dzhakipbekova@mail.ru, g.tyre@mail.ru, 

The Republic of Kazakhstan has little of its pharmaceutical 

industry. Almost 90% of medicines are imported from far and near 

abroad, on a national scale spent huge sums in foreign currency. 

Drugs made from plant material, are especially effective in the 

treatment of diseases caused by unfavorable environmental 

conditions (Baikonur Spaceport, the Semipalatinsk nuclear test 

site) and the high background radiation do not cause side effects 

when they are used and are not toxic than drugs obtained by 

synthesis. In Kazakhstan, there are over 20,000 species of plants, 

6,000 of them contain biologically active substances. Of the six 

thousand six hundred species can be used as an intermediate 

product for the production of drugs, and from more than 

500 species can be ready to receive drugs. But the existing 

technology of medicines are very complicated and many-stage, 

energy-intensive and costly process. In addition, the purity of the 

products is poor, so they are not competitive on the world market. 

In Shymkent chemical-pharmaceutical plant from plant material 

obtained by extraction of drugs: morphine, codeine, papaverine, 

etc., and related alkaloids are in the blade, as some of them exhibit 

the toxicity, while others are ineffective, and some do not possess 

physiological activity. But the structure of these alkaloids can get 

from them is already known or new biologically active 

compounds by modifying their structure, by introducing new 

functional groups-OH, -OCH , -OC H , -NO , etc. These 

3 2 5 2 

biologically active agents are effective in the treatment of cancer 

and have antioxidant properties. To determine the molecular 

formula of compound chromatographically pure samples of the 

final products were subjected to qualitative and quantitative 

elemental analysis for carbon, hydrogen, nitrogen, bromine, 

according to the method. Belonging to a class of products com 

tions revealed the following way. Quantitative analysis on the 

methoxy group was carried out by the modified method 

Tseyzelya-Fibeka. 

Keywords: Alkaloids; Biological activity; Antioxidants; 

Electrochemistry; Biomass; 


P - 0 6 3 7 

PhotoinduCed deCArBoxyLAtion of AMino 

ACidS BeArinG furAn Moiety 

C. fAderL 1 , G. KAChKovSKyi 1 , o. reiSer 1 

1 Institute of Organic Chemistry, Universität Regensburg, 


Photochemistry and photocatalysis have found wide 

applications in organic chemistry. Light is an abundant and 

renewable energy source for new reactions and chemical 

transformations under mild and green conditions. [1] Okada and 

coworkers demonstrated redox photodecarboxylation of 

phthalimide esters using visible light. [2] 

We applied Okada’s approach to a sustainable chemistry 

using furans and amino acids as renewable resources. As a model 

compound we synthesized N-Furoyl-β-amino acid activated by a 

phthalimide moiety. Visible light (455 nm LED) mediated and 

[Ir(ppy) (dtbbpy)]PF catalyzed decarboxylation leads to a 

2 6 

primary alkyl radical. This radical undergoes an 5-exo-trig 

intramolecular cyclisation to an allylic cation and the spirolactol 

7-tert-butyl-2-hydroxy-1-oxa-7-azaspiro[4.4]non-3-en-6-one. 

The reaction scope was demonstrated on 10 examples. 

An acid catalyzed vinylogus semi-pinacol rearrangement 

into Furo[2,3-c]pyridinone was discovered for the photoreaction 

product. The plausible mechanism includes as an intermediate the 

same allylic cation which was proposed for phototransformation. 

Thus a cascade process could be developed. 

As an application of this chemistry we envisage a total 

synthesis of (-)-Stemoamide. Results may be expected in due 

course. 

references: 

1. J. M. R. Narayanam, C. R. Stephenson, J. Chem. Soc. Rev. 

2011, 40, 102. 

2. K. Okada, K. Okubo, N. Morita, M. Oda, Chem. Lett. 

1993, 2021 and references therein. 

Keywords: Photocatalysis; Decarboxylation; Cyclisation; 



s1181 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 3 8 

MeMBrAne interACtionS of ioniC LiquidS 

P. GALLetti 1 , d. MALferrAri 2 , n. GAL 3 , 

S. KoLuShevA 3 , e. tAGLiAvini 1 , r. JeLineK 3 

1 University of Bologna, Dep. of Chemistry “G. Ciamician” and 

CIRSA (Interdepartmental Centre for Environemental 

Sciences), Bologna, Italy 

2 University of Bologna, CIRSA (Interdepartmental Centre for 

Environemental Sciences), Ravenna, Italy 

3 Ben Gurion University, Department of Chemistry, Beer Sheva, 

Israel 

Ionic liquids (ILs) are organic salts with relatively low 

melting points and unique properties dependent upon the 

constituent cation and anion which can be separately modified. 

ILs have attracted great interest as an environmentally-benign 

source for alternative solvents, however, their broad solvation 

properties and their high solubility in water present health risks, 

since many ILs have proven to be cytotoxic. 

The mechanisms of ILs toxicity, however, are not well 

understood. Most studies have correlated the lipophilicity of ILs 

ion-pairs with their biological effects [1] , suggesting that disruption 

of the plasma membrane plays a major role in ILs toxicity [2] . We 

present here a comprehensive biophysical and microscopy study 

of membrane interactions of a series of ILs containing 

imidazolium and pyrrolidinium head groups with long, short and 

diethoxylated alkyl chain. The bio-analytical tests include vesicles 

dye release assay, confocal fluorescence microscopy, FRET 

analysis with small unilamellar vesicles, and lipid/polydiacetylene 

assay. 

Results point to group the compounds tested according to 

bilayer interactions. Specifically, IL with long alkyl chain 

exhibited the most pronounced binding and disruption effect of 

membrane bilayers, ILs with short alkyl chains also appeared 

fairly membrane-active whereas imidazolium oxygenated ILs 

featured the lowest bilayer activity among the compounds studied. 

This trend is in general agreement with previous studies on ILs 

cytotoxicity [3] and will be helpful for the design of new classes of 

ILs exhibiting benign environment profiles. 

references: 

1. J. Ranke, S. Stolte, R. Störmann, J. Arning, B. Jastorff, 

Chem. Rev, 2007, 107, 2183–2206. 

2. K. Evans, Colloids and Surfaces A: Physicochemical and 

engineering aspects, 2006, 274, 11–17. 

3. C. Samori, D. Malferrari, P. Valbonesi, A. Montecavalli, 

F. Moretti, P. Galletti, G. Sartor, E. Tagliavini, E. Fabbri, 

A. Pasteris, Ecotoxicol. Environ. Safety 2010, 73, 

1456–1464. 

Keywords: Ionic Liquids; membranes; cytotoxicity; 


P - 0 6 3 9 

eLeCtroCheMiCAL oxidAtion of MethAnoL 

By CArBon SuPPorted PLAtinuM 

nAnoPArtiCLeS PrePAred By new 

SurfACtAntS 

G. GÖKAGAC 1 , f. Sen 1 , S. Sen 1 

1 Middle East Technical University, Chemistry Department, 


In this study, platinum nanoparticle catalysts have been 

prepared using PtCl as starting material, and 1-hexylamine, 

4 

methylhexylamine and dimethylhexylamine as surfactants. All of 

those surfactants were used for the first time to see the effect of 

surfactants on the size of platinum nanoparticles and catalytic 

performances towards methanol oxidation reaction. X-ray 

photoelectron spectroscopy (XPS), X-ray diffraction (XRD), 

atomic force microscopy (AFM), transmission electron 

microscopy (TEM), cyclic voltammetry (CV) and 

chronoamperometry (CA) were used to characterize the prepared 

catalysts. XRD and TEM results indicated that all prepared 

catalysts have a face centered cubic structure and are 

homogeneously dispersed on the carbon support with a narrow 

size distribution. XPS studies of the catalysts indicated the 

existence of two types of platinum (Pt (0) and Pt (IV)). 

Electrochemical measurements demonstrated that the highest 

electrocatalytic activity was observed for Pt nanocatalysts 

stabilized by dimethylhexylamine. The main reasons for this result 

could be due to an increase in electrochemical surface area, 

Pt(0)/Pt(IV) ratio, percent platinum utility of this catalyst. 

Keywords: methanol oxidation; platinum nanoparticles; fuel 

cells; 



s1182 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 4 0 

MiCrowAveS, MAteriALS, SoLventS And 

CAtALySiS Green CheMiStry At the 

univerSity of yorK 

M. Gronnow 1 , J. CLArK 1 , d. MACquArrie 1 , 

A. MArthAru 1 , S. Breeden 1 , v. BudArin 1 , A. hunt 1 

1 University of York, Department of Chemistry, York, 


www.york.ac.uk/greenchemistry 

The Green Chemistry Centre of Excellence (GCC) at the 

University of York for many years has worked hard to establish a 

leading position internationally in green and sustainable 

chemistry. Some 70 people are based in the GCC including, MSc 

and PhD students, postdoctoral fellows, core academics, senior 

researchers, technical staff, core management, administrative staff 

and network personnel. In order to manage the large and diversely 

funded number of projects and people, four technology platforms 

(TPs), an education platform and a networks platform facilitate 

the delivery of our research, education, networking and industrial 

liaison activities. The TPs include “Renewable Materials” in 

particular the physical and chemical modification of naturally 

abundant materials, especially polysaccharides. “Clean Synthesis 

and Platform Molecules” covering the use of heterogeneous 

catalysts, elemental sustainability and alternative platform 

molecules. The “Natural Solvents” has specific interest in 

non-petrochemical, supercritical and liquid carbon dioxide as an 

extraction, fractionation and reaction medium. Projects include 

wax extraction from agricultural and food waste for personal care 

applications, the synthesis of flavour and aroma molecules using 

in-situ biocatalysis and modelling of “drop-in” bio-derived 

replacement solvents. The microwave chemistry platform 

incorporating the new “Biorefinery Microwave Demonstrator” 

brings together our interest in microwave-assisted chemistry with 

the conversion of biomass (e.g. forestry and agricultural wastes, 

food waste, etc) to useful products in addition to a long standing 

interest in microwave assisted synthesis. The Biorenewables 

Development Centre, a joint venture between Green Chemistry 

and the Centre for Novel Agricultural products, launched in 

Spring 2012, allows the work of the green chemistry centre to be 

scaled up to multi-kilo scale. The centre contains a range of scale 

up equipment including scCO2, fermentations, AFEX, microwave 

pyrolysis and distillation at demonstrator scale. 

Keywords: Microwave; Renewable; Green Chemistry; Clean 

synthesis; alternative solvents; 


P - 0 6 4 1 

rinG-oPeninG MetAtheSiS PoLyMer BASed on 

diCyLCoPentAdiene And 

tetrACyCLododeCene 

h. Lee 1 , v. t. widyAyA 1 , h. t. vo 1 , w. S. hwAnG 2 , 

B. S. Ahn 1 

1 Korea Institute of Science & Technology, Clean energy center, 


2 Kolon industries, HCR Reserch Institute, Incheon, Republic of 

Korea 

Cyclopentadiene (CPD) or its dimer, dicyclopentadiene 

(DCPD), is one of the major component in the C5 stream of 

naphtha creaking. However, until now, most C5 streams have been 

incinerated as fuels instead have been used as chemical sources. 

An approach for the increase the value of CPD/DCPD is the 

synthesis of tetracyclododecene from CPD with olefin and uses 

it for the production of high value polymer products. In this study, 

we synthesized cycloolefin polymers (COPs) composed of 

tetracyclododecene (TCD) and DCPD using W-based ROMP 

catalyst and Ni-based hydrogenation catalyst and characterized 

their structures and some chemical properties using FTIR, 

13C-NMR, GPC, DSC and UV. 

Keywords: Polymerization; Metathesis; Hydrogenation; NMR 

spectroscopy; CPD/DCPD; 



s1183 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 4 2 

An effiCient viSiBLe-LiGht-SenSitive 

Cu-GrAfted tio PhotoCAtALySt 

2 

L. ChiAnG 1 , r. doonG 1 

1 National Tsing Hua University, Department of Biomedical 

Engineering and Environmental Sciences, Hsinchu City, 

Taiwan 

Titanium dioxide (TiO ) is one of the most used 

2 

photocatalysts for the degradation of environmental pollutants. 

However, the main drawback of TiO is lacking of visible light 

2 

utilization which limits its practical application. Recently, metal 

ions (Cu, Fe, Cr and Ce) grafted TiO has found to be an efficient 

2 

way to solve the problem because they are visible light sensitive. 

In this study, the microwave-assisted impregnation method for 

preparation of Cu-grafted TiO photocatalysts was reported. 

2 

Parameters including reaction time and temperature were 

discussed in synthesized photocatalyst. In addition, UV-Vis 

diffuse reflectance absorption spectra and ICP-OES were used for 

the characterization of band-gap and for determination of weight 

percentage of as-synthesized Cu/TiO , respectively. The optimal 

2 

condition for preparation of microwave-assisted Cu/TiO is the 2 

dispersion of 250 mg P25 into 5 mL CuCl solution and heated at 

2 

120 degree C for 0.2 min. From UV-Vis diffuse reflectance spectra 

results, the absorption intensity of TiO starts to increase at 

2 

385 nm which is corresponding to the interband transition 

of P25 (3.2eV). In addition, another absorption region of Cu/TiO2 around 700-800 nm which indicates the Cu d-d transition, is 

observed. It can be ascribed to the direct interfacial charge transfer 

from the valence band of TiO to Cu. The ICP-OES result shows 

2 

that the weight ratio of Cu/TiO is in the range 0.005~0.008%. 

2 

Moreover, the photoactivity of the visible light activated Cu/TiO2 photocatalyst was studied by the photo-decomposition of 

sulfamethoxazole (SMX). The synthesized Cu/TiO have the 

2 

better photocatalytic activity toward SMX than that of Degussa 

P25, and the pseudo-first-order constant for SMX 

photodegradation by Cu/TiO is 14 times higher than that of P25 

2 

under illumination of 465 nm visible light, clearly showing the 

excellent visible-light-driven ability of the Cu-grafted TiO . 2 

Keywords: Cu; TiO ; visible light; sulfamethoxazole; 

2 


P - 0 6 4 3 

SyntheSiS of GLyCidoL froM GLyCeroL 

CArBonAte uSinG ioniC LiquidS 

J. S. Choi 1 , K. i. Lee 1 , S. d. Lee 1 , h. Lee 1 

1 Korea Institute of Science & Technology, Clean energy center, 


Glycidol, 2,3-epoxy-1-propanol, is used to a considerable 

extent in the textile, plastics, pharmaceutical, cosmetics, and 

photochemical industries. Conventionally, glycidol has been 

produced industrially by oxidizing allyl alcohol in the presence 

of an oxidizing agent and a catalyst. Recently, focus has also been 

paid to the synthesis of glycidol from glycerol carbonate which 

is one of the value added material based on glycerol. In this study, 

we conducted thermal decarboxylation of glycerol carbonate for 

the synthesis of glycidol. We found that some kinds of ionic 

liquids showed high catalystic activities for this reaction and 

elucidated the catalytic activities of ILs were closely related to 

the hydrogen bond basicity of the anions of ILs. 



s1184 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 4 4 

infLuenCe of SiLiCA-SuPPorted iMidAzoLiuM 

SALt on ConduCtinG BehAviorS of PoLyMer 

CoMPoSite eLeCtroLyteS BASed on 

PoLy(ethyLene oxide) 

S. KiM 1 , L. Lee 1 , M. KiM 1 

1 Pusan National University, Chemical Engineering, Busan, 


Polymer composite electrolytes (PCEs) are an alternative to 

liquid combustible systems because they possess superior voltage, 

temperature and mechanical stability. In this study, PEO/PMMA 

polymer matrix containing modified fillers were studied in order 

to enhance an ionic conductivity and interfacial properties. The 

fillers were modified by attaching an ionic liquid (IL) functional 

group. The fillers were the immobilized 1-propyl-3-n-butyl- 

-imidazolium bromide with amorphous silica (PBIm-AS). The 

addition of PBIm-AS fillers in polymer electrolytes has resulted 

in high ionic conductivity at room temperature. The crystallinity 

structure and morphology of the polymer composite electrolytes 

were measured using differential scanning calorimetry 

(DSC) / X-ray diffraction (XRD) and scanning electron 

microscope (SEM). Ionic conductivity was measured by an 

AC impedance method. The enhanced ionic conductivity was 

dependent on the decreased crystallinity and the changed 

morphologies. 

Keywords: Conducting materials; Electrochemistry; Energy 

conversion; Electron transport; Polymers; 


P - 0 6 4 5 

exfoLiAtion And reduCtion of GrAPhite 

oxide By eLeCtroStAtiC Method And their 

eLeCtroCheMiCAL BehAviorS 

S. KiM 1 , S. PArK 1 , J. KiM 1 

1 Pusan National University, Chemical Engineering, Busan, 


Carbon materials including graphene can meet the request 

of EDLC electrodes. Graphene nanosheets (GNS) are predicted 

as an excellent support material due to high surface area and 

remarkable conductivity. Graphite oxide is electrically insulating 

and various reduction methods have been developed to restore its 

electrical conductivity. Chemical reduction using agents such as 

hydrazine, NaBH4 and ethylene glycol have been used to reduce 

GO (Graphite oxide) or graphene oxide exfoliated from GO. Also, 

researchers reported microwave exfoliated GO (MEGO) and 

thermally exfoliated GO (TEGO) to get highly reduced GO 

having high surface area structures. A flash-assisted reduction of 

films composed of graphene oxide platelets and their polymer 

composites has been reported. Herein, we report preparation of 

exfoliated and reduced GO by treating an electrostatic method. 

GO precursor changed black fluffy reduced GO powder by simple 

electrostatic force. As-prepared powder showed specific surface 

area of 516m2 /g, higher than the value (464m2 /g) of MEGO 

powder. Using the exfoliated graphite oxide, we studied 

electrochemical behaviors for an application of supercapacitors. 

Keywords: Conducting materials; Electrochemistry; Energy 

conversion; Electron transport; Graphene; 



s1185 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 4 6 

SyntheSiS of SuCCiniC ACid derivAtiveS 

under MiCrowAve irrAdiAtion 

y. J. KiM 1 , J. h. SonG 2 

1 Chungnam National University, Chemistry, Daejeon, Republic 

of Korea 

2 Sunchon National University, Chemistry, Sunchon, Republic of 

Korea 

Dioctyl succinates and succinic anhydride were synthesized 

from succinic acid in the presence of a cation exchange resin, 

Amberlite IR-120. The synthesis of dioctyl succinate from 

succinic acid and octanol was perfomed in 18 h reflux condition 

with Amberlite IR-120 and the isolated yield of product was over 

90 %. For the synthesis of succinic anhydride, succinic acid was 

refluxed in isopropenyl acetate for 18 h with Amberlite IR-120 as 

a catalyst. The long reaction time was significantly reduced to less 

than 10 min under microwave irradiation. We will discuss the 

chemical transformation using microwave irradiation method and 

the reusability of catalyst. 

Keywords: Catalyst Reuseability; Microwave Irradiation; 


P - 0 6 4 7 

wAter-SoLuBLe tin(iv) PorPhyrinS AS 

PhotoSenSitiSerS for ArtifiCiAL 

PhotoSyntheSiS 

A. M. MAnKe 1 , P. Kurz 1 , K. GeiSeL 2 


Kiel, Germany 

2 Institut für Phys. Chem., RWTH Aachen Universität, Aachen, 

Germany 

Light-driven water-splitting into hydrogen and oxygen is a 

concept for sustainable energy generation. This concept is inspired 

by basic principles of photosynthesis, the process where solar 

energy is converted into chemically stored energy in nature. 

In vivo, chlorophyll molecules act as light absorbing molecules 

and electron transfer agents. They generate both the high oxidising 

potentials for water-oxidation and the strong reducing agents for 

NADP + -reduction. 

We study the water-soluble tin(IV) porphyrins dichlorido- 

-5,10,15,20-tetrakis(p-carboxyphenyl)-porphyrinato-tin(IV) 

(SnTPPC) and dichlorido-5,10,15,20-tetrakis(p-sulfophenyl)- 

-porphyrinato-tin(IV) (SnTPPS) as possible mimics for 

chlorophyll dyes. The compounds show favourable redox 

potentials to act as photosensitisers in an artificial system for 

light-driven water-splitting. We tested the ability of these synthetic 

porphyrins to act as photosensitisers in photocatalytic model 

systems and especially detected promising rates for light-induced 

H formation in a photocatalytic system developed by Krüger and 

2 

Fuhrhop. [1] Details on possible mechanisms, the reaction kinetics, 

photosensitiser stability and the use of different electron donors 


references: 

1. W. Krüger, J. H. Fuhrhop, Angew. Chem. Int. Ed. 21, 131 

(1982). 

Keywords: Bioinorganic chemistry; energy conversion; 

homogeneous catalysis; porphyrinoids; water splitting; 



s1186 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 4 8 

MoLyBdenuM-infLuenCed PoroSity in rf 

xeroGeLS 

B. nAGy 1 , K. LASzLo 1 , e. GeiSSLer 2 


Department of Physical Chemistry and Materials Science, 


2 Université J. Fourier de Grenoble, Laboratoire 

Interdisciplinaire de Physique CNRS UMR 5588, Grenoble, 

France 

Carbon aerogels that are simultaneously macro- and 

mesoporous offer advantages over other forms of adsorbents for 

applications that demand rapid access to the internal surface. 

Such carbons can be synthesized from resorcinol and 

formaldehyde under controlled conditions, like concentration, 

stoichiometric ratio, catalyst, pH, etc. The porosity of dried 

esorcinol-formaldehyde (RF) gels is conserved during the 

conversion to carbon. Due to their sol-gel preparation method 

these RF gels they can be easily doped with metals, which can 

enhance their catalytic and adsorption properties. Moreover, they 

provide an additional means of tuning the porosity of the system. 

In this work we focus on the effect of molybdenum, which is 

widely used as catalyst, e.g., in hydrocarbon industry. 

Molybdenum was added as aqueous ammonium- 

-heptamolybdate solution to the RF hydrogel prepared in a glass 

cylinder after a 1-week ageing process. After 24 hours diffusion 

the hydrogel rods were cut into 10 mm long pieces and air-dried 

to obtain Mo-doped xerogels. Low temperature nitrogen 

adsorption and scanning electron microscopy supported 

energy-dispersive X-ray spectroscopy (SEM/EDX) were used to 

characterize the morphology and the molybdenum content of the 

samples. 

Increasing the amount of Mo reduces the porosity 

(all class of pores) but the typical size of the mesopores is 

conserved. 


P - 0 6 4 9 

the iMPACt of the reConStruCtion effeCt 

on the StruCturAL ProPertieS of MGxALLdh 

MAteriALS And their CAtALytiC ACtivity in 

the oxidAtion of CyCLohexene 

o. d. PAveL 1 , r. zAvoiAnu 1 

1 University of Bucharest, Department of Organic Chemistry 

Biochemistry and Catalysis, Bucharest, Romania 

Many papers concerning the preparation, characterization 

and utilization of layered double hydroxides in different 

applications have been published [1, 2] . One of the goals has been 

to provide new insights on the role played by the LDH-like phase 

and the impact of the reconstruction through “memory effect” 

presented by LDH-like materials on the selectivity to cyclohexane 

epoxide during the oxidation of cyclohexene. The catalytic 

activities of parent Mg Al-LDH materials (x = 1,3,5,10), have 

x 

been compared with those of the corresponding mixed oxides and 

the corresponding reconstructed LDH-structures. The parent LDH 

were obtained by co-precipitation of Mg and Al nitrates with a 

base solution at pH = 10 under low supersaturation conditions; 

Mg Al-MO by thermal decomposition at 460 °C under air 

x 

atmosphere; Mg Al-RLDH by hydration with bi-distillate water 

x 

at room temperature. All catalysts were characterized by XRD, 

DRIFTS, BET and determination of base sites. The oxidation of 

cyclohexene was performed using two different oxidation agents: 

i) H O in a reaction mixture containing cyclohexene, acetonitrile 

2 2 

and acetone and ii) molecular O in a reaction mixture containing 

2 

cyclohexene, isobutyraldehyde, and acetonitrile. It has been found 

that LDH-like materials were poor catalysts for the oxidation of 

cyclohexene with H O while they exhibited higher catalytic 

2 2 

activity in the oxidation of cyclohexene with molecular O . This 2 

behaviour may be a consequence of the different reaction 

mechanisms involved, depending on the oxidation agent and the 

reaction mixture employed. The solids having Mg/Al = 3 were 

better reconstructed and higher catalytic activities. The variation 

order of the catalytic activity could be related to the variation of 

the basicity and surface areas of the solids. 

Acknowledgement: This work was supported by a grant of the 

Romanian National Authority for Scientific Research, 

CNCS – UEFISCDI, project number PN-II-RU-TE-2011-3-0026. 

references: 

1. F. Cavani, F. Trifir, A.Vaccari, Catal. Today 11 (1991) 173. 

2. A. Vaccari, Appl. Clay Sci. 14 (1999) 161. 

Keywords: layered double hydroxides; hydrotalcites; base 

materials; oxidation; 



s1187 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 5 0 

SeLeCtive reCyCLinG of MoLyBdenuM froM 

SPent hydrodeSuLfurizAtion CAtALyStS 

uSinG environMentAL-friendLy APProACheS 

i. S. S. Pinto 1 , h. M. v. M. SoAreS 1 

1 Faculdade de Engenharia da Universidade do Porto, 

REQUIMTE Department of Chemical Engineering, Porto, 

Portugal 

Recovery of valuable metals from spent 

hydrodesulfurization (HDS) catalysts avoids their disposal in the 

environment and permits the production of metal values from 

secondary resources. 

The goal of this work was to study the selective leaching of 

Mo from HDS spent catalysts, under mild alkaline conditions 

using microwave- or ultrasound- assisted conditions, and to 

recover it through an environmental and economically attractive 

process. 

Spent catalyst, containing Ni, Mo and Al, was roasted and 

its metal content was determined. Mo leaching was performed 

using aqueous NaOH at constant solid-liquid ratio under the 

following conditions: (i) microwave-assisted leaching by varying 

[NaOH] and number of cycles (30 seconds/cycle) and 

(ii) ultrasound-assisted leaching; for comparative purposes, 

(iii) conventional approach using a thermostatic bath, where 

temperature, time and [NaOH] were varied. 

Experiments in the bath at 80ºC, 120 minutes, showed that 

Mo dissolution increases with [NaOH], however Al extraction is 

also enhanced: 92% Mo, 19% Al, using 20g/l NaOH. Lower 

[NaOH] (10g/l) leads to a more selective leaching of Mo, though 

the yield is affected: 77% Mo, 7% Al. Applying microwave 

energy (4 cycles), at the same [NaOH], Mo leaching is improved 

with no enhancement in Al removal (89% Mo, 6% Al) which 

increases Mo selective leaching. Mo and Al leaching results, 

obtained under ultrasound-assisted conditions, were similar to the 

conventional ones, obtained at room temperature, but with shorter 

processing times. 

Al present in solution was precipitated at pH 8 and 

separated. Mo was recovered as SrMoO , a promising product in 

4 

the field of optical devices and lasers, with high yield (96%) and 

purity (>99%). 

These results show that microwave-assisted leaching, using 

mild alkaline conditions, may be an interesting alternative in the 

Mo leaching from spent catalysts; moreover, SrMoO can be 

4 

produced at high purity from secondary resources using a 

low-cost process. 

Keywords: Molybdenum; Microwave chemistry; Ultrasound; 

Strontium; Spent catalysts; 


P - 0 6 5 1 

ALGinAte-SuPPorted PALLAdiuM 

nAnoPArtiCLeS: A Green And reCyCLABLe 

heteroGeneouS CAtALySt with reMArKABLe 

ACtivity for the SuzuKi-MiyAurA reACtion 

f. quiGnArd 1 , L. yi 1 , M. roBitzer 2 , K. ouChAou 3 , 

M. ChAuMontet 3 , f. tArAn 3 

1 CNRS, ICGM, Montpellier Cedex 5, France 

2 ENSCM, ICGM, Montpellier Cedex 5, France 

3 CEA, Service de Chimie Bioorganique et de Marquage, Saclay, 

France 

Alginates are polysaccharides produced by brown algae 

mainly, constituted of (1-> 4) linked b-d-mannuronic (M) and 

a-l-guluronic (G) residues, they form ionotropic gel by 

complexation of divalent cations. Drying the gel under CO2 supercritical conditions afford highly dispersed materials. [1] This 

aerogel formulation is particularly adapted for supporting metal 

particles. Indeed, the gelling cations in a M-alginate gel can be 

exchanged by palladium cations. Palladium is easily reduced by 

ethanol; therefore, in situ formation of palladium particles 

supported on M-alginate occurs during the process leading to the 

aerogel. The process affords a double homogeneity in bead size 

and metal distribution inside the bead. This strategy applied to 

many gelling metals Mn+ allows the straightforward preparation 

of a panel Mn+ /PdNP/alginate gels [2] . The resulting bimetallic 

hybrid catalysts combine the textural properties of alginate, the 

high catalytic activity of palladium nanoparticles and the presence 

of a second metal species that might serve to co-catalysis. Indeed, 

only 10 ppm of Pd (< 0.01% w/w) in EtOH at 70°C were required 

to undergo complete conversion of reactants to biaryl product in 

only 3 hours. In same conditions but with 1 ppm PdNP, TurnOver 

Number is close to one Million (910 000) and the TurnOver 

Frequency is close to 10 reactions by second (TOF 35 000 h-1 ). 

references: 

1. F. Quignard, R. Valentin, F. Di Renzo, New. J.Chem. 2008, 

32, 1300 

2. M. Chtchigrovsky, Y. Lin, K. Ouchaou, M. Chaumontet, 

M. Robitzer, F. Quignard, and F. Taran, Chem Mater. 

2012, asap 

Keywords: Natural products; Cooperative effects; 



s1188 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 5 2 

CArBon Monoxide oxidAtion over Sno2 20wt%-Ceo Mixed oxide 

2 

A. redey 1 , t. yuzhAKovA 1 , J. KovACS 1 , z. KovACS 1 , 

A. vASiLe 2 , C. hornoiu 2 , i. rAduLy 3 , L. rAduLy 3 , 

e. doMoKoS 1 , v. SoMoGyi 1 

1 University of Pannonia, Institute of Environmental 

Engineering, Veszprem, Hungary 

2 Romanian Academy, Ilie Murgulescu Institute of Physical 


3 Babes-Bolyai University, Faculty of Economics and Business 

Managementsical Chemistry, Sfantu Gheorghe, Romania 

Ceria with appropriate dopants (e.g. SnO , CuO) has been 

2 

widely used as catalyst for heterogeneous oxidation processes 

such as CO oxidation to CO . The aim of this work was to prepare 

2 

the SnO -CeO catalysts in order to increase the oxygen 

2 2 

storage/release capacity of single oxides. Moreover it was aimed 

to investigate the redox properties of the mixed oxide and its 

catalytic activity with respect to their potential application for 

environmental oxidation processes. The adsorption properties of 

the surface layer with CO probe molecule was studied by 

electrical conductivity measurements in operando condition. CO 

oxidation was carried out in a mixture of CO and O (1:1) diluted 

2 

with helium. The experiments were carried out in the temperature 

range of 25°C up to 400°C. 

The obtained data showed that in the presence of oxygen the 

conversion of CO to CO was 99% over tin oxide-containing 

2 

sample at 400 °C in comparison with pure ceria and tin dioxide 

samples in which case the CO conversion was about 88 and 84 % 

respectively. It is to be noted that CO is also converted even in 

the absence of oxygen, however, obviously the obtained amount 

of CO was smaller; (less than 40%) over SnO 20wt%-CeO , 

2 2 2 

about 3% over CeO and about 4% over SnO . It indicates that 

2 2 

the lattice oxygen is involved in the CO conversion which was 

also supported by electrical conductivity measurements. 

Acknowledgments: This research was carried out in the 

frame of Agreement for Scientific and Educational Cooperation 

between the University of Pannonia, Veszprém, Hungary and 

the “Ilie Murgulescu” Institute of Physical Chemistry, Romanian 

Academy, Bucharest, Romania. This work was made under the 

projects TÁMOP-4.2.1/B-09/1/KONV-2010-0003 and TÁMOP- 

4.2.2/B-10/1-2010-0025. These projects are supported by the 

European Union and co-financed by the European Social Fund. 

Keywords: Heterogeneous catalysis; Oxidation; Redox 



P - 0 6 5 3 

ProduCtion of LiGhtweiGht AGGreGAte 

BASed on nAturAL PozzoLAniC And wASte 

MAteriALS 

o. rudiC 1 , d. zoriC 1 , J. rAnoGAJeC 1 , M. rAdeKA 1 , 

n. MiLenKoviC 1 

1 University od Novi Sad Faculty of Technology, Materials 

Engineering, Novi Sad, Serbia 

The physical and chemical properties of the lightweight 

aggregates (LWA) obtained by the thermal treatment of raw 

composition based on natural pozzolanic material, waste glass, 

suitable polymer and wooden dust are presented. The production 

process of LWA was consisted of raw material preparation, plastic 

shaping - extrusion, granulation and thermal treatment at the final 

firing temperature. The final temperature (T=1020 oC) was chosen 

based on the appropriate mechanical and physical properties of 

the designed LWA pellets. Properties of raw natural pozzolanic 

material were examined by using, DSC/TG, dilatometry, while 

waste glass was characterized by chemical analysis and XRF. 

The particle size distribution of the LWAs was unimodal 

(d ≈ 5 mm). Textural and mechanical properties of LWA pellets 

were examined by water absorption, mercury porosimetry and 

compressive strength. The microstructure of LWA pellets was 

characterized by SEM analysis while phase composition during 

thermal treatment was studied by using high temperature XRD 

analysis. Thermal conductivity of unbound, fired LWA pellets was 

determined by measuring the amount of axially transferred heat 

in the stationary state. 

The obtained value of the LWA thermal conductivity is 

suitable for the production of structural concrete blocks with 

improved thermal insulating properties. Due to their high porosity 

and appropriate compressive strength values, the designed LWA 

could be used in the production of concrete blocks. 

Keywords: Materials science; Ceramics; Electron microscopy; 

X-ray diffraction; Thermal conductivty; 



s1189 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 5 4 

froM LAyered BASiC zinC SALtS to zno 

hoLLow SPhereS By An eCo-friendLy 

SonoCheMiCAL ProCedure 

G. M. SoCoteAnu 1 , M. tudoSe 1 , 

J. M. CALderón-Moreno 2 , r. BirJeGA 3 , o. CArP 1 

1 “Ilie Murgulescu” Institute of Physical Chemistry Romanian 

Academy, Coordination and Supramolecular Chemistry, 


2 “Ilie Murgulescu” Institute of Physical Chemistry Romanian 

Academy, Surface Chemistry and Catalysis, Bucharest, 

Romania 

3 National Institute for Lasers Plasma and Radiation Physics, 

Plasma and Radiation Physics, Magurele Bucharest, Romania 

The attractive and unique characteristics of ZnO, a bio-safe 

and bio-compatible semiconductor, besides its huge variety of 

morphologies, made it a key functional material for applications 

in different fields. Among its structures, ZnO hollow spheres have 

shown a great potential for use in the delivery of drugs, catalysis, 

chemical storage, photoelectric materials and so on. 

Layered basic zinc hydroxide compound (LBZS) that 

contain both carbonate and acetate as intercalated anions have 

been obtained and deposited on starch-derived carbonaceous 

template by a new eco-friendly sonochemical procedure with a 

low power sonicator, using nonbasic zinc acetate aqueous 

solution. The synthetic route involves the hydrolysis and 

polymerization of the in situ formed complexes. Calcination 

treatments (600oC, 1h) of the LBZS and core/shell materials 

afforded ZnO porous sheets and hollow spheres respectively. The 

morphology, composition and phase structure of the precursors 

and their decomposition products were characterized by infrared 

spectroscopy, thermal analysis, scanning electron microscopy 

(SEM) and X-ray diffraction (XRD). The LBZS consists of 

lamellar structure with two interlayer distances (13.70 and 

19.34 ?), poorly ordered, both the XRD pattern and SEM images 

being characteristic for turbostratic materials. The acetate anions 

are intercalated as free anion and monodentate ligand, while the 

carbonate ones behave as bidentate ligand. The obtained ZnO 

preserves the sheet-like morphology of the layered precursors, 

presenting uniform pores and pore density while the core/shell 

materials attained after deposition represent efficient precursors 

for hollow ZnO spheres, allowing high heating rates treatments 

without altering the hollow sphere morphology. The obtained 

hollow spheres are composed by sintered ZnO nanocrystallites 

with mean crystallite sizes values strongly depending on the used 

heating rate. 

Acknowledgements: This work was supported by a grant of the 

Romanian National Authority for Scientific Research, CNCS - 

UEFISCDI, project number PN-II-ID-PCE-2011-3-0473/2011 

Keywords: environmental chemistry; layered compounds; 

green chemistry; 


P - 0 6 5 5 

SuBCritiCALLy dried CeLLuLoSe – BASed 

CArBon AeroGeLS with hiGh SurfACe AreA 

J. StefeLová 1 , v. SLováK 1 

1 University of Ostrava Faculty of Science, Department of 

Chemistry, Ostrava, Czech Republic 

Carbon aerogels are fascinating materials with large open 

pores, high values of specific surface area and low densities. 

Generally these materials are prepared from appropriate 

precursors by their condensation to small polymer particles 

followed by gelation. Spongelike network is obtained and the 

pores are filled usually with water or with alcohol [1]. Drying of 

wet gels is critical operation, because capillary effect causes 

collapse of nanostructure porous network. That is the reason for 

usage supercritical drying or freeze – drying methods [2]. 

Aim of our work was to replace established but difficult 

drying methods in the cellulose based carbon aerogels preparation 

with simple drying under atmospheric conditions. Aerogels from 

cellulose or cellulose acetate were prepared by dissolving these 

polymers in suitable solvents such as aqueous calcium thiocyanate 

[3] or mixture of sodium hydroxide with urea and water [4]. 

Prepared materials were either dried by freeze-drying or left to 

dry at laboratory conditions. This simple attempt lead to expected 

results – surface area of freeze dried samples was significantly 

higher (up to 460 m2 g-1 ) then surface area of samples dried on air 

(below 20 m2 g-1 ). We tried to use another ionic liquid 

N-methyl-morpholine-N-oxide [3] but obtained materials showed 

similar results after drying (25 - 270 m2 g-1 ). In another case of 

preparation of these materials, cross – linking agent PMDI 

(polymethylene polyphenylpolyisocyanate) [5] was used and 

obtained materials were freeze – dried and dried under ambient 

conditions. In both cases, values of surface area were higher than 

600 m2 g-1 . In this work, it was found that we can make these 

cellulose – based materials without supercritical or freeze – drying 

due to use of cross – linking agent PMDI. Usage of this compound 

sufficiently strengthens structure of these materials, which do not 

collapse during drying under ambient condition. 

Keywords: Cellulose - based carbon aerogels; cross - linking; 

subcritical drying; 



s1190 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 5 6 

enzyMe-CAtALySed reSoLution 

of n-BoC-3-hydroxy-4-PhenyLPyrroLidine in 

SuPerCritiCAL CArBon-dioxide 

A. SzeCSenyi 1 , M. utCzAS 1 , d. BALoGh 2 , 

e. KovACS 2 , e. SzeKeLy 1 , f. fAiGL 2 , B. SiMAndi 1 


Department of Chemical and Environmental Process 

Engineering, Budapest, Hungary 



Hungary 

The preparation of enantiopure drug intermediates is a topic 

of great importance in research. While there are numerous 

chemical methods for producing pure enantiomers, using enzymes 

has many advantages compared to other processes. The enzymes 

most commonly used for kinetic resolution are lipases, some of 

which could be active in supercritical media as well. Supercritical 

carbon-dioxide (scCO ) is a solvent with industrial applications. 

2 

Among its many advantages is the fact that its properties (density, 

viscosity) can be modified in a wide range by changing the 

pressure and temperature. Due to its relatively mild critical 

parameters, the decomposition of the product and substrate can 

be avoided. After depressurization, carbon-dioxide becomes 

gaseous, thus potentially yielding a solvent-free product. 

The kinetic resolution of N-Boc-3- hydroxy-4-phenylpyrrolidine 

was investigated by CALB-catalysed (lipase B from Candida 

Antarctica) acylation with vinyl acetate in scCO in a batch 

2 

reactor. The substrate:CALB mass ratio was 2:1. Vinyl acetate 

was used in excess. The samples were analyzed by chiral gas 

chromatography. The reaction progress was examined at different 

pressures (10–20 MPa) and temperatures (35–65°C) according to 

a 32 experimental design. 

In this reaction at 15 MPa and 50 °C, enantiopure 

(3R,4S)-N-Boc-3-hydroxy-4-phenylpyrrolidine (ee≥99.9 %) was 

achieved with good yield (Y~60 %) and moderate 

enantioselectivity (E~50). Increasing the temperature increases 

both the enzyme activity and the enantioselectivity, while 

enantioselectivity has an optimal pressure range around 15 MPa. 

Increasing the pressure has a negative effect on the reaction rate 

in the examined range. 

Acknowledgement: Our research was supported by the 

Hungarian Scientific Research Fund (OTKA 72861) and 

TAMOP-4.2.1/B-09/1/KMR-2010-0002. 

Keywords: kinetic resolution; supercritical fluids; enzyme 

catalysis; 


P - 0 6 5 7 

MetAheSiS reACtionS PerforMed in Pure 

wAter, uSinG CoMMerCiAL CAtALyStS 

J. toMASeK 1 , M. SeSSLer 1 , 

P. of. dr. JuerGen SChAtz 1 



Olefin metathesis is an interesting, atom-efficient, and very 

valuable synthetic transformation, mainly performed in organic 

solvent. Subsequently, fewer studies on metathesis reactions in 

pure water as solvent were done. 

We showed that olefin metathesis can be performed very 

efficiently in pure water without exclusion of air, using standard 

Grubbs-type catalyst. Beside activity, also stability tests were 

determined by standard RCM reactions. 

Addition of host molecules such as calix[n]arenes can boost 

the reactivity by a supramolecular interaction with in water 

protonated Cy3P which is released in the activation step of the 

catalysts. 

Keywords: Metathesis; water chemistry; supramolecular 

chemistry; ion pair; 



s1191 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 5 8 

one-Pot SyntheSiS of PArACetAMoL viA 

the CAtALytiC reduCtive CArBonyLAtion of 

P-nitroBenzene in ACetiC ACid-wAter AS A 

SoLvent 

A. vAvASori 1 , M. CAPPoni 1 , L. ronChin 1 

1 Universita Ca’ Foscari, Molecular Sciences and Nanosystems, 

Venezia, Italy 

Paracetamol (N-(4-hydroxyphenyl)acetamide) is a major 

ingredient in numerous cold and flu medications due to its 

analgesic and antipyretic properties. A number of commercial 

methods of paracetamol manufacture are currently in use around 

the world. Some commonly used processes start from 

chlorobenzene, phenol or nitrobenzene. All the industrial 

processes actually used, however, show several drawbacks. For 

instance, they are based on multistep routes which sometimes lead 

to poor overall yield, or show serious effluent problems. The 

increasingly stringent environmental legislation has generated a 

pressing need for cleaner methods of chemical production, for 

instance introducing technologies that reduce or, preferably, 

eliminate the generation of waste and avoid the use of toxic and/or 

hazardous reagents and solvents. According with this, we propose 

a new approach for the synthesis of paracetamol: by using 

Pd(II)-diphosphine catalyst precursors, in acetic acid-water as a 

solvent, we obtain paracetamol with high selectivity from 

nitrobenzene in one-pot. At 140 °C and under 45 atm of CO, 

p-nitrobenzene is completely converted to paracetamol and 

N-phenylacetamide. The latter is the major by-product of the 

reaction (ca. 15 molar %, under such reaction conditions) and also 

an interesting target for the pharmaceutical industry. The 

selectivity is influenced by several variables such as solvent 

composition (H O-acetic acid ratio), temperature and batch time. 

2 

The high temperature and the increase of reaction time favor the 

acetylation reaction, which occurs in-situ when p-aminophenol 

and aniline readily form from p-nitrobenzene/CO/H O. Such 

2 

reaction is proposed as a new sustainable alternative to the 

synthesis of paracetamol. The absence of chlorobenzene 

(chlorine-free chemistry), the use of efficient catalysts and the 

possibility to realize a single step process, make this reaction 

interesting to be evaluated as a possible alternative to the multisteps 

industrial processes actually used. 

Keywords: Carbonylation; Reduction; Homogeneous catalysis; 



P - 0 6 5 9 

CAtALytiC dePoLyMerizAtion of LiGnin 

under uLtrASoundS ConditionS 

M. verziu 1 , A. riCheL 2 , r. M. riChArdS 3 , 

v. i. PArvuLeSCu 1 

1 University of Bucharest Faculty of Chemistry, Department of 

Organic Chemistry Biochemistry and Catalysis, Bucharest, 

Romania 

2 University of Liege – Gembloux Agro-Bio Tech, Unit of 

Biological and Industrial Chemistry, Gembloux, Belgium 

3 Colorado School of Mines, Department of Chemistry and 

Geochemistry, Golden, USA 

Lignin is an aromatic polymer including three main 

phenylpropane units, namely p-coumaril, coniferyl and sinapyl 

alcohol which are linked by C-C or C-O-C. Recently Lavoie et 

all have reported depolymerisation of lignin in the presence of 

NaOH [1] . However, using homogenous catalysts is necessary a 

purification step of the reactions products that is a non-friendly 

environmental process producing high amounts of waste waters. 

A solution to this problem can be the use of heterogeneous 

catalysts because they can be recovered at the end of the reaction 

by centrifugation providing green, recyclable catalytic systems. 

In this study we investigated the influence of the 

crystallographic phase of Ru (RuNi, RuNiO and Ru/Al O ) in 2 3 

conversion of lignin to low molecular weight compounds under 

ultrasounds conditions. RuNi and RuNiO were prepared by 

replacement reaction between nickel or nickel oxide and RuCl3 in aqueous solution [2] while Ru/Al O was prepared by wet 

2 3 

impregnation of mesoporous alumina with a RuCl aqueous 

3 

solution. These materials were characterized by several techniques 

like: XRD,BET,XPS,etc. Lignin tested in this study was extracted 

from mischantus plants under both acid and basic conditions [3] 

and was characterised by DRIFT and TGA/DTA. 

Depolymerisation of lignin was carried out under bubling 

hydrogen in special designed ultrasound reactor. The reaction 

products analyzed by LC-MS had molecular weights with m/z 

below 1000 g/mol, that confirmed the depolymerization of 

lignin.Among the investigated catalysts RuNi led to an advanced 

depolymerisation of lignin. 

Acknowledgement: “This work was supported by the 

strategic grant PO SDRU/89/1.5/S/58852, Project ‘Postdoctoral 

programme for training scientific researchers’ co-financed 

by the European Social Foundation within the Sectorial 

Operational Program Human Resources Development 

2007–2013” 

references: 

1. Lavoie J.M.,Baré W.,Bilodeau M., Bioresource 

Technology 102 (2011) 4917. 

2. Zhao Z.F.,Wu Z.J.,Zhou L.X,Zhang M.H.,Li W.,Tao K.Y., 

Catalysis Communications 9 (2008) 2191. 

3. Vanderghem C.,Richel A.,Jacquet N.,Blecker C.,Paquot M., 

Polymer Degradation and Stability 

doi:10.1016/j.polymdegradstab.2011.07.022. 

Keywords: lignin; ultrasounds; heterogeneous catalysts; 



s1192 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 6 0 

iMMoBiLizAtion MeChAniSMS of PB(ii) 

AdSorPtion onto CoALS, CArBonS And 

CArBon AeroGeLS 

P. veSeLA 1 , B. tArABA 1 , v. SLovAK 1 



Removal of heavy metal ions from aqueous solutions is 

essential in terms of environmental and human health protection. 

One of the most used techniques is adsorption onto different 

carbon materials. 

The aim of this contribution is to point out different 

immobilization mechanisms of Pb(II) adsorption onto various 

types of carbon materials (coals, carbons and carbon aerogels). 

Two types of natural coals were used - oxidative altered 

bituminous coal (A) from the Upper Silesian Coal Basin and 

subbituminous coal (H) from the North Bohemian Coal Basin. 

Also commercial activated carbon (AC) from Hru‰ovské závody 

(Czech Republic) was tested. Carbon aerogels (CA) were 

prepared by sol-gel polycondensation, subcritical drying and 

pyrolysis of resorcinol and formaldehyde with or without addition 

of nitrogen containing precursor. Batch adsorption experiments 

and also pH solution measurements before and after adsorption 

were conducted in order to study immobilization mechanisms of 

Pb(II) on these materials. 

It was noticed that decisive (majority) role in adsorption of 

Pb(II) on the sample A has mineral composition when the crucial 

elements were found to be magnesium and calcium. As minority 

mechanisms for sample A are expected to be complexation and 

ion-exchange. Adsorption onto H can be described by different 

adsorption mechanisms - ion-exchange and complexation. Also 

mineral composition can be taken into account in the case of 

sample H. Immobilization of Pb(II) onto HS occurs on the 

graphene structures without releasing of hydrogenous ions. 

Basic mechanism connected with CA is expected to be ion 

exchange, but there is probably some additional mechanism 

(e.g. complexation) for N-doped CA which increase the 

adsorption capacity for Pb(II) in comparison with non-doped 

samples. 

It can be concluded that immobilization mechanism of 

Pb(II) is dependent on the carbonaceous material used for 

adsorption. 

Keywords: immobilization mechanism; Pb(II) adsorption; 

carbon material; 


P - 0 6 6 1 

ControLLed BioPoLyMer ASSiSted SynthetiC 

route of zinC oxide with different 

MorPhoLoGieS 

r. vodA 1 , J. CALderon-Moreno 2 , S. BArJeGA 3 , 

o. CArP 2 

1 University Politehnica of Timisoara, Faculty for Industrial 

Chemistry and Environmental Engineering Piata Victoriei 

No. 2, Timisoara 300006, Romania 

2 Institute of Physical Chemistry Ilie Murgulescu, Romanian 

Academy Spl. Independentei 202, Bucharest 060021, Romania 

3 National Institute for Lasers Plasma and Radiation Physics, 

P.O. BOX Mg - 27, Bucharest-Magurele, Romania 

Recently, the synthetic procedures that control the size, 

shape and dimensionality of inorganic nanocrystals materials has 

rapidly expanded into a promising topic of materials chemistry, 

due to materials unique size- and shape-dependent properties. 

A special place is occupied by ZnO a bio-safe and biocompatible 

n-type semiconductor which tendency to grow into a variety of 

aesthetic morphologies has induced great interest to explore 

simple methodologies of developing such nanoarchitectures. On 

the other hand, over the past years, the great concern on 

environment protection determined the development of green 

strategies for nanomaterials’ designing and synthesis. 

Polysaccharides thanks to their unique combination of 

environmentally friendly features and functional versatility 

represent an appropriate choice, with great potential as additives 

in materials synthesis. 

Herein we report an original, green and low temperature 

(


s1193 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 6 2 

SyntheSiS of new Mono And dinuCLeAr 

iMidAzoLiuM SALtS 

n. wunderLiCh 1 , S. doMMer 1 , J. vÖLKL 2 , w. ArLt 2 , 

J. SChAtz 1 




Separation Science and Technology, Erlangen, Germany 

Imidazolium salts are an important class of organic 

compounds with a plethora of modern applications in e.g. as 

solvent, catalysts or as precursors for N-heterocyclic carbens 

(NHC’s). [1-3] Such uses of these heterocycles are facilitated by the 

fact that they are easily synthesized and their properties can be 

fine-tuned by changing the substituents on the heterocyclic 

skeleton or changing the counter anion. 

First we want to present the synthesis of some imidazolium 

salts varying the number of imidazolium moieties included, and 

substituent at the ring nitrogen. A special focus lies on the 

influence of the anion and cation on the physical and chemical 

properties. 

Second we present the synthesis of different 

imidazoliumcarboxylates. The imidazolium salts where 

deprotonated with a strong base and afterwards carbon dioxide 

was bubbled through the solution. The formed imidazolium 

carboxylates were characterized by NMR, mass, IR and, to 

determine the thermal stability, by TGA/DSC. 

references: 

1. R. Giernoth, Angew. Chem. 2010, 122, 2896–2901. 

2. S. S. Khan, J. Liebscher, Synthesis 2010, 15, 2609–2615. 

3. S.-G. Lee, Chem. Commun. 2006, 1049–1063. 

Keywords: Ionic liquids; carbon dioxide fixation; 


P - 0 6 6 3 

iMProvinG the wAterProofinG MAteriAL’S 

PerforMAnCe ProPertieS By uSinG nAturAL 

fiLLerS And induStriAL reSidueS 

o. yASAr 1 , M. KiLiC 2 , A. e. Putun 2 , e. Putun 3 

1 Anadolu University, Graduate School of Science, Eskisehir, 

Turkey 

2 Anadolu University, Department of Chemical Engineering, 

Eskisehir, Turkey 

3 Anadolu University, Department of Materials Science and 

Engineering, Eskisehir, Turkey 

Background: Water in the form of vapor,liquids and solids 

presents below-grade construction with many unique 

problems.Water causes damage by water transmission through 

porous surface, by direct leakage in a liquid state and by spalling 

of concrete floors in a frozen or solid form. In construction, a 

structure needs waterproofing since concrete itself will not be 

watertight on its own. 

objectives: Solutions to the economic and environmental 

impacts of the construction industry have largely focused on 

choosing replacement materials at the level of products. The sole 

aim of this study focuses on the possible system improvements of 

the already advantageous cement based waterproofing material. 

Method: This study looks at the effectiveness of six 

powdered natural fillers and industrial waste materials after 28 

days of curing at: 5.0%, 25%, 50%, 75% and 100% w/w on the 

whole composition. 

In this study, utilization of natural pozzolanic fillers and 

industrial waste materials in the production of cement based 

waterproofing materials was investigated. For this purpose, 

Karakaya bentonite (B) ; Seyitgazi volcanic tuff (V) and Karaman 

diatomite (D) were used as natural puzzolanic fillers ; waste tire 

rubber from tire factory (R), tile powder from tile factory (T), 

waste marble powder from marble factory(M) were used as a 

industrial waste materials. Three types of pozzolans (B+V+D) and 

three type of waste materials (R+T+M) were added to cement 

pastes in. 

results and Conclussion/Application to practice: It was 

observed that, a comparison with the common fillers, waste tire 

rubber and marble powder using as a filler enhance tensile and 

compressive strengths at the age of 7 and 28 days, capillary 

absorption and permeability to water ability. Economically,new 

product with produce with marblr powder and waste tire rubber 

at the same ratio provide approximately % 27 per kg.(Prices may 

show variation due to the market conditions.) 

Keywords: industrial residues; waterproofing; natural fillers; 

green materials; 



s1194 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 6 4 

deveLoPMent And APPLiCAtion of noveL 

BioinSPired ioniC LiquidS 

K. zALewSKA 1 , L. BrAnCo 1 


Lisboa, Departamento de Química, Caparica Lisbon, Portugal 

Biological molecules are considered as building blocks of 

life. The understanding and use of their chemistry represents a 

crucial role in modern research science [1] . In last decades, Ionic 

Liquids (ILs) have emerged as a possible environmentally benign 

alternative to common organic solvents, due to use in a variety of 

areas [2] . In this context, Novel Functional Bioinspired ILs (FBILs) 

based on the incorporation of relevant biological molecules by 

simple dissolution (e.g. ILs and cyclodextrins) or by sustainable 

synthetic combinations (e.g. chiral ILs based on aminoacids such 

as L-cysteine derivatives) have been developed. 

The main goal is related with the development of novel 

Chiral biomaterials based on the interaction of biocompatible ILs 

and cyclodextrins as well as the preparation of L-cysteine 

derivatives as chiral ILs. Applications of this novel Chiral ILs 

include their use for chiral recognition processes and chiral media 

for asymmetric catalysis [3] . 

Two different approaches have been investigated: 

(i) dissolution and interaction studies of α-, β- and γ- cyclodextrins 

(CDs) with several ILs. Their dissolution performance and 

interaction behavior have been studied. Novel biomaterials based 

on simple combination of ILs and CDs can be applied for hostguest 

and drug delivery processes [4] ; (ii) preparation and 

characterization of novel chiral ILs based on L-cysteine 

derivatives such as S-methyl-L-cysteine and S-carboxymethyl-L- 

-cysteine combined with appropriate counter-ions. The most 

promising chiral ILs has been applied for enantiomeric resolution 

and asymmetric catalytic reactions. 

Novel biocompatible materials based on the combination of 

ILs and CDs can be explored for relevant chiral discrimination or 

separation processes. Novel L-cysteine ILs have been tested for 

resolution of racemates as well as chiral media for asymmetric 

aldol and Michael reactions [5] . Their efficiency should be 

dependent of the combination of L-cysteine as cation or anion 

with appropriate counter-ions. 

references: 

1. W. Chuanlong, F. Xiangkai, L. Shi, Eur. J. Org. Chem.; 7, 

(2011), 1291–1299. 

2. Wasserscheid P., Welton T., Ionic Liquids in Synthesis, 

VCH-Wiley, Weinheim, 2002. 

3. K. Bica, P. Gaertner, Eur. J. Org. Chem.; 19, (2008), 3235. 

4. N. Zhong, H. S. Byun, R. Bittrnan, Tetr. Lett; 39, 1998, 

2919–2920. 

5. W. Chuanlong, F. Xiangkai, L. Shi, Eur. J. Org. Chem.; 

2011, 7, 1291–1299. 

Keywords: Amino acids; Ionic liquids; Green chemistry; 

Asymmetric catalysis; Chirality; 


P - 0 6 6 5 

ProPertieS of LiGhtweiGht AGGreGAte 

BASed on CoAL fLy ASh 

d. zoriC 1 , d. LAzAr 2 , o. rudiC 1 , M. rAdeKA 3 , 

J. rAnoGAJeC 1 , h. hirSenBerGer 4 

1 University of Novi Sad Faculty of Technology, Materials 

Engineering, Novi Sad, Serbia 

2 University of Novi Sad Faculty of Sciences, Physics, Novi Sad, 

Serbia 

3 University of Novi Sad Faculty of Technical Science, Civil 

Engineering and Geodesy, Novi Sad, Serbia 

4 University of Novi Sad Faculty of Technical Science, Industrial 

Engineering and Engineering Management, Novi Sad, Serbia 

The paper presents the results of physical and chemical 

properties of lightweight aggregates (LWA) obtained by the 

thermal treatment of raw composition based on fly ash, supplied 

by electric plants from Serbia. The final temperature (T=1140 oC) was chosen based on the appropriate mechanical and physical 

properties of the designed pellets. 

The particle size distribution of the LWAs was unimodal 

(d ≈ 16 mm). Their textural and mechanical properties were 

examined by water absorption, mercury porosimetry and 

compressive strength. Leaching of mineral salts of the LWAs after 

24h of immersion was performed with an intensive stirring. Wide 

range of the elements in the LWAs aqueous extract was 

determined by using mass spectrometry. The thermal conductivity 

of unbound, fired LWA pellets, is determined by measuring the 

amount of axially transferred heat in the stationary state. 

Radioactivity of dried and fired LWA pellets was examined too. 

The obtained value of the LWA thermal conductivity 

(λ=0.0862 W/mK, T=1140oC) is suitable for the production of 

structural concrete blocks with improved thermal insulating 

properties. Radionuclide reducing after thermal treatment of LWA 

was noticed. Due to their high porosity and high compressive 

strength values, the designed LWA could be used instead of the 

conventional aggregates in the production of concrete blocks. 

Consequently, a real valorization of the waste material such as fly 

ash in Serbia was established. 

Keywords: Materials science; Ceramics; Waste prevention; 

Thermal conductivty; 



s1195 

chem. Listy 106, s257–s1425 (2012) 

SyntheSiS And therMAL treAtMent 

infLuenCe on zno nAnoPArtiCLeS 

LuMineSCenCe 

o. oPreA 1 , e. AndroneSCu 2 , B. vASiLe 2 , G. voiCu 2 


P - 1 0 1 3 

1 Politehnica University of Bucharest, Inorganic Chemistry, 


2Politehnica University of Bucharest, SIMONa, Bucharest, 

Romania 

The potential application of ZnO requires a good control of 

its optical properties. The photoluminescence spectra of ZnO 

powders usually present two emission peaks in the UV and visible 

ranges. The UV emission corresponds to the near band-edge 

emission and the visible emission is commonly referred to as a 

deep-level or trap-state emission. Some specific application 

requires that only one luminescence peak should be present so is 

of great importance that one can control the luminescence 

properties of ZnO nanoparticles. 

The magnitude and the relative intensity of these two bands 

are sensible tot the synthesis method and thermal treatment 

applied to the ZnO nanoparticles. In this paper, we present a study 

of a new non-basic, non-aqueous synthesis method of ZnO 

nanoparticles. We found that the nature of the alcohol used in the 

force solvolysis of zinc acetate influences the magnitude of the 

UV luminescence, and only marginal the intensity of the bluegreen 

one. A correlation could be made with the molecular mass 

of the alcohol, and length of the carbon chain, the fluorescence 

intensity increasing from methanol to 1-pentanol. 

The influence of the thermal treatment on the ZnO 

luminescence is also discussed. Both temperature and annealing 

time influences the magnitude and relative intensity of 

luminescence peaks. By increasing both parameters, we manage 

to increase the overall magnitude of fluorescence in ZnO 

nanoparticles, but we also increase the UV/Vis intensity ratio, up 

to 10/1. 

This study provides a simple method to control the 

luminescence properties of ZnO nanoparticles. 

Keywords: ZnO; luminescence; thermal treatment; 


P - 0 6 6 6 

MoLeCuLAr rotorS in MeSoPorouS 

MAteriALS 

M. BerettA 1 , S. BrACCo 1 , A. CoMotti 1 , P. SozzAni 1 

1 University of Milan Bicocca, Materials Science, Milano, Italy 

Molecular rotor systems have been one of most challenging 

topics in the last years. Inspiring to biological molecular machines 

based on rotor systems, such as ATP-synthase, chemists have tried 

to reproduce functional nanodevices based on molecular rotors. 

One of the main targets in this research field was the attainment 

of materials wherein molecular rotors are organized in such a way 

that the free space around them is maximized and the rotational 

barrier is as low as possible. 

In this work we present a first example of highly-ordered 

materials wherein molecular rotors are linked to the framework 

through robust covalent bonds, which confer both thermal and 

chemical stability to the final material. 

We have chosen Periodic Mesoporous Organosilica (PMO) 

systems with crystal-like pore walls, such as p-phenyl, 

diphenylene and p-divinylphenylensilica, to study the rotational 

properties of the organic linkers pivoted between two siloxane 

layers. In these materials, organic moieties are organized at 

molecular level in the pore walls with the adjacent organic linkers 

posed at a distance greater than the sum of van der Waals 

radii. We have explored the dynamics of the molecular rotors by 

2H NMR spectroscopy on the deuterated aromatic moieties. 

In fact, 2H NMR spectroscopy is a method of choice to determine 

the mechanism of motion. Rotational frequencies as fast as 108 Hz 

were estimated at room temperature and energy activation barriers 

of about 10 kcal/mol were calculated. Interestingly, we 

demonstrated for the first time that the rotational motion could be 

controlled by the presence of guest molecules diffused-in the 

mesopores and the materials change from a 2D rotational glass to 

a 2D rotational fluid behavior by increasing the temperature. In 

conclusion, these materials could find applications as gas-sensor 

systems or carriers for controlled release of stored molecules. 

Keywords: Mesoporous materials; Molecular devices; Hybrid 

materials; 



s1196 

chem. Listy 106, s257–s1425 (2012) 

Poster session 2 - solid state chemistry 

P - 0 6 6 7 

StudieS on uLtrASound-ASSiSted SyntheSiS of 

hiGhLy diSPerSed MAnGAneSe doPed zinC 

SuLPhide PowderS 

A. i. CAdiS 1 , e. J. PoPoviCi 1 , i. PerhAitA 1 , 

L. BArBu-tudorAn 2 , L. e. MureSAn 1 

1 Babes-Bolyai University, “Raluca Ripan” Institute for 

Research in Chemistry, Cluj-Napoca, Romania 

2 Babes-Bolyai University, Electronic Microscopy Center, 


Due to their special properties, the highly dispersed II-VI 

semiconductors account for the most investigated materials. Zinc 

sulphide-based materials have attracted increasing interest with respect 

to their applications in various domains i.e. optoelectronics [1] . 

Through controlling the size and the doping of zinc sulphide 

(ZnS) particles with manganese [2] , a different material with new 

properties and uses could be obtained. 

Because of strongly dependence of powders properties by 

synthesis method, a various methods have been developed for the 

preparation of un-doped or doped ZnS powders, methods such 

chemical precipitation [1] and ultrasound [3] assisted synthesis 

routes. 

Herein we report the ultra-sound assisted synthesis of highly 

dispersed Mn-doped zinc sulphide powders (ZnS:Mn) with 

luminescent properties. Synthesis was performed from 

zinc-manganese acetate and thioacetamide, in aqueous medium 

with controlled pH. Variable manganese concentrations and 

different organic additives were used in order to control the 

morphostructural and photoluminescence properties.. 

ZnS:Mn samples were characterized by photoluminescence 

spectroscopy (PL), transmission and scanning electron 

microscopy (TEM, SEM), X-ray diffraction (XRD) and 

inductively coupled plasma optical emission spectroscopy 

(ICP-OES). 

A correlation between the preparation conditions and 

powders characteristics was established. 

references: 

1. X.J. Zheng, Y.Q. Chen, T. Zhang, C.B. Jiang, B. Yang, 

B. Yuan, S.X. Mao, W. Li, Scr. Mater. 62, 520 (2010). 

2. A.-I. Cadis, E.-J. Popovici, E. Bica, I. Perhaita, 

L. Barbu-Tudoran, E. Indrea Chalcogenide Lett. 7, 631 

(2010). 

3. A.-R. Tomsa, E.-J. Popovici, A.-I. Cadis, M. Stefan, 

L. Barbu-Tudoran, S. Astilean, J. Optoelectron. 

Adv. Mater. 10, 2342 (2008). 

Keywords: Luminescence; Chalcogens; Doping; Manganese; 

Nanoparticles; 


P - 0 6 6 8 

ControLLinG the diSPerSion of 

MonoMetALLiC nAnoPArtiCLeS PrePAred By 

wAter-hexAne iMPreGnAtion on the 

MeSoPorouS SBA-15 SiLiCA 

B. drAGoi 1 , C. CiotoneA 1 , A. ChirieAC 1 , 

A. unGureAnu 1 , S. royer 2 , d. duPrez 2 , 

e. duMitriu 3 

1 “Gheorghe Asachi” Technical University of Iasi, Organic 

Biochemical and Food Engineering Department, Iasi, 

Romania 

2 Université de Poitiers, LACCO UMR 6503 CNRS, Poitiers, 

France 



Romania 

The purpose of this study is to prepare highly dispersed 

monometallic nanoparticles by impregnation of the mesoporous 

SBA-15 with nitrate precursors of copper, nickel and cobalt, and 

using water - hexane mixture as solvent. Three monometallic 

samples with 5 wt % metal loading were prepared. The calcined 

samples were characterized by ICP-OES, FT-IR, XRD at high and 

low angles, nitrogen physisorption, and TPR. Preliminary, all the 

catalysts were tested in the hydrogenation of cinnamaldehyde 

(CNA) to cinnamyl alcohol (CNOL). High angles XRD and TPR 

analyses displayed very high dispersion and high reducibility 

(T =230 °C), respectively of the supported copper oxide. These 

red 

results were reflected by the catalytic behavior, after reduction at 

350 °C under H flow, that shown a quite active and selective 

2 

catalyst. Therefore a X =20 mole % and S =40 mole % at 

CNA CNOL 

X = 10 mole % were obtained for this catalyst. For Co/ and 

CNA 

Ni/SBA-15 samples XRD and TPR investigations indicated two 

types of metal precursors. Therefore, the majority crystalline 

phase consisted in the corresponding oxides; typical reflections 

of the NiO and Co O were identified in the XRD patterns while 

3 4 

the TPR profiles display a first reduction peak at 480 °C for highly 

dispersed NiO and in low interaction with the support, and 

300 °C for Co O . Also, nickel and cobalt (phyllo)silicates phases, 

3 4 

respectively were observed in both samples and considered as 

additional factor which contributes to the good dispersion of metal 

nanoparticles. Additional information was provided by FT-IR 

spectroscopy which indicated a vibration band at 960 cm-1 attributed to Si-O vibration in 1:1 phyllosilicate. Preliminary tests 

in CNA hydrogenation shown active Ni/SBA-15 and inactive 

Co/SBA-15 catalysts. 

Acknowledgement: B. Dragoi acknowledges the project 

PERFORM-ERA “Postdoctoral Performance for Integration in 

the European Research Area” (ID-57649), financed by the 

European Social Fund-Romanian Government. 

Keywords: monometallic supported nanoparticles; waterhexane 

impregnation; hydrogenation; 



s1197 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 6 9 

hiGhLy diSPerSed CuCo (Bi)MetALLiC 

CAtALyStS PrePAred By 

dePoSition-PreCiPitAtion on MeSoPorouS 

SBA-15 SuPPort for the CinnAMALdehyde 

hydroGenAtion 

B. drAGoi 1 , A. unGureAnu 1 , A. ChirieAC 1 , 

C. CiotoneA 1 , S. royer 2 , d. duPrez 2 , 

e. duMitriu 1 



Romania 


France 

Highly dispersed copper-cobalt nanoparticles with 5 wt % 

metal loading and Cu:Co weight ratio of 4:1 were prepared by 

deposition-precipitation (DP), using urea as precipitating agent, 

into the channels of a mesoporous SBA-15 support. The 

monometallic Cu/ and Co/SBA-15 (5 wt. %) were also prepared 

by DP and used as references. The resulted materials either asmade 

or calcined were characterized in relation to their chemical, 

structural, textural and reducible properties by chemical analysis, 

XRD, N physisorption, TEM/EDX, FT-IR spectroscopy, ATG and 

2 

TPR. The catalytic performance of the copper-cobalt containing 

materials was evaluated in the hydrogenation of cinnamaladehyde 

(CNA) in liquid phase. The high-angle XRD patterns of 

mono- and bimetallic catalysts besides FT-IR spectra and ATG 

curves indicate the formation of phyllosilicates with very high 

dispersion and thermal stability as precursors of the metallic active 

phases. Moreover, the TPR analysis displayed reduction 

temperatures very close to those corresponding to phyllosilicates. 

However, the synthesis of such materials by DP led to partial 

alteration of the support mesostructure, which was shown by 

nitrogen physisorption and TEM. The EDX analysis carried out 

in various points of the catalysts shows a homogeneous 

distribution of the metal precursors at micrometric scale. 

Generally, the catalytic activity of the monometallic catalysts is 

in line with the characterization results. Therefore, for 

Cu/SBA-15, the very high dispersion of Cu0 precursor generate 

an active (conversion of CNA = 40 mole % after 360 min of 

reaction) and selective catalyst for cinamyl alcohol (CNOL, 

40 mole % at iso-conversion of 40 mole %). Due to their hardly 

reducible cobalt precursors, the cobalt based catalysts were less 

performing in the hydrogenation of CNA. However, the 

Co/SBA-15 displayed improved selectivity to CNOL (50 mole % 

at iso-conversion of 18 mole %). 

Acknowledgement: The authors acknowledge the project PNII- 

Idei No.264/2011 financed by UEFISCDI. 

Keywords: metal supported catalysts; copper; cobalt; 

cinnamadehyde hydrogenation; 


P - 0 6 7 0 

MiLd dryinG iMPreGnAtion Method uSed for 

the PrePArAtion of MeSoStruCtured 

CAtALytiC MAteriALS ContAininG Cu, ni And 

Co AS ACtive PhASeS in the hydroGenAtion 

of CinnAMALdehyde 

e. duMitriu 1 , B. drAGoi 1 , A. unGureAnu 1 , 

A. ChirieAC 1 , C. CiotoneA 1 , S. royer 2 , d. duPrez 2 


Biochemical and Food Engineering, Iasi, Romania 


France 

This study deals with the preparation of monometallic 

catalysts by an upgraded version of the conventional wetness 

impregnation method, named mild drying impregnation (MDI). 

Therefore, Cu, Co and Ni monometallic catalysts with 5 wt % 

metal loading on support were prepared by MDI on SBA-15, 

followed by calcination, reduction and then by characterization 

and testing in the hydrogenation of cinnamaldehyde (CNA) to 

obtain cinnamylalcohol (CNOL). For a good dispersion of the 

metal precursors, all impregnated samples were subjected to 

drying for two weeks at controlled temperature. All samples were 

preliminary characterized by XRD at high and low angles, 

nitrogen physisorption, TPR, FT-IR and ICP-OES. High angles 

XRD patterns mainly reveals the formation of the corresponding 

oxides and, in a less extent, of the (phyllo)silicates for all 

monometallic samples. The (phyllo)silicates are responsible for 

the dispersion and stabilization of the resulted metallic active 

phases but also for the high reduction temperatures as observed 

in TPR curves. The TPR profiles display two maxima, the first 

one corresponding to the reduction of the metallic cation from 

oxides while the second one is attributed to the reduction of 

cations from (phyllo)silicates. The textural properties of the 

calcined catalysts are similar to those of the mesoporous SBA-15 

support showing a narrow pore size distribution of the cylindrical 

pores. A new porous system is observed for Ni/ and Co/SBA-15 

samples. The catalytic evaluation of the monometallic samples 

revealed a very active Ni/SBA-15 catalyst but less selective for 

CNOL. Co/SBA-15 converted only 18 mole % of CNA in 

360 min of reaction but the selectivity to CNOL was much 

improved (60 mole % at X =20 mole %). Cu/SBA-15 displayed 

CNA 

no activity in the CNA hydrogenation. 

Acknowledgement: PNII-Idei, 264/2011 financed by 

UEFISCDI. 

Keywords: mild drying impregnation; metal supported 

catalysts; hydrogenation; cinnamaldehyde; 



s1198 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 7 1 

BinoL And SynthetiC BinoL derivAtiveS AS 

PotentiAL ChirAL reSoLvinG AGentS 

e. euSeBio 1 , t. M. r. MAriA 1 , J. CAnotiLho 2 , 

r. M. B . CArriLho 2 , A. r. ABreu 2 , M. M. PereirA 2 

1 University of Coimbra, Chemistry, Coimbra, Portugal 

2 University of Coimbra, Faculdade de Farmácia, Coimbra, 

Portugal 

BINOL was synthesized for the first time in 1926, but its 

ongoing interest as chiral inducer was only recognized after 

Noyori (Nobel Prize, 2001) discovered its application as ligand 

in the asymmetric catalytic reduction of aldehydes, in 1979 [1] . 

Since then, the synthetic chemical modifications on BINOL 

molecule received enormous attention, mainly to obtain new 

chiral ligands for several asymmetric catalytic reactions [2] . 

BINOL was also recently described as an useful co-former 

for resolution of racemic mixtures by co-crystallization [3] . The use 

of stereoselective co-crystals represents an alternative strategy for 

chiral resolution, which is of particular relevance for substances 

which do not have the appropriate functional group to readily give 

rise to salts. 

In this communication results on the investigation of the 

potential of BINOL and some synthetic BINOL derivatives as 

chiral resolving agents for selected chiral active pharmaceutical 

ingredients and diols are presented. Mixtures of the solid 

components, in different molar ratios, are submitted to 

mechanochemical methods which have proven to be an efficient 

method of co-crystal synthesis [4] . The outcomes of this process 

are evaluated by differential scanning calorimetry, polarized light 

thermomicroscopy and infrared spectroscopy. 

Acknowledgments: The authors thank for financial support to 

Programa Compete and QREN/FEDER/FCT (PTDC/QUI- 

QUI/112913/2009). 

references: 

1. R. Noyori, I. Tomino, Y. Tanimoto J. Am. Chem. Soc., 101 

(1979) 3129. 

2. A. R. Abreu, M. Lourenco, D. Peral, M. T. S. Rosado, 

M. E. S. Eusébio, Palacios, J. C. Bayón, M. M. Pereira, J. 

Mol. Catal. A: Chem.325 (2010) 91. 

3. B. N. Roy, G. P. Singh, D. Srivastava, H. S. Jadhav, 

M. B. Saini, U. P. Aher, Org. Process Res. Dev., 13 (2009) 

450. 

4. R. A. E. Castro, J. D. B. Ribeiro, T. M. R. Maria, 

M. Ramos Silva, C. Yuste-Vivas, J. Canotilho, 

M. E. S. Eusébio, Cryst. Growth Des., 11 (2011) 5396. 

Keywords: Binol; Co-crystal; 


P - 0 6 7 2 

rotAtionAL eCho douBLe reSonAnCe A 

vALuABLe tooL to inveStiGAte the SurfACe 

CheMiStry of MetAL nAnoPArtiCLeS 

t. GutMAnn 1 , e. BonnefiLLe 1 , h. BreitzKe 2 , 

P. J. deBouttiere 1 , K. PhiLiPPot 1 , 

G. BuntKowSKy 2 , B. ChAudret 3 

1 CNRS-LCC, Universite de Toulouse, Toulouse Cedex 4, 

France 

2 TU Darmstadt, Physical Chemistry, Darmstadt, Germany 

3 CNRS INSA LPCNO, Universite de Toulouse, Toulouse 

Cedex 4, France 

In the last decade the attention devoted to metal 

nanoparticles (MNPs) has been growing up rapidly, particularly 

due to their high application potential in colloidal and 

heterogeneous catalysis, i.e. hydrogenation, C-C coupling and 

oxidation reactions. The investigation of their surface chemistry 

is a crucial topic to understand the catalytic properties and to tune 

them up for technical reactions, as for example for 

Fischer-Tropsch, watergas-shift reaction, arene hydrogenation etc. 

To characterize ligands, probe molecules or intermediates 

on the surface of MNPs solid-state NMR has been demonstrated 

to be one method of choice. It allows getting information about 

their location and dynamics which is important to understand their 

organization on the surface. In the present work the distance 

measurement between stabilizing ligands and carbon monoxide 

(CO) reactive molecules at the surface of phosphine-stabilized 

ruthenium nanoparticles (RuNPs) is demonstrated employing 

Rotational Echo Double Resonance (REDOR) experiments. The 

studied model systems are RuNPs in the size range 1-2 nm 

stabilized with 1,3,5-triaza-7-phosphaadamantane (PTA) or 

triphenylphosphine (PPh ) ligands after exposure under CO 

3 

atmosphere. This REDOR study sheds more light on interactions 

between reactive probe molecules and ligands as well as on their 

binding geometries at the surface and helps the interpretation of 

complex solid-state MAS NMR spectra of ligand stabilized 

RuNPs. Further, this study builds up the basis for advanced 

mechanistic investigations of complex MNPs systems. 

Keywords: NMR spectroscopy; Nanoparticles; Phosphane 

ligands; Surface Chemistry; Ruthenium; 



s1199 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 7 3 

orGAniC SuPerConduCtinG MAteriALS – 

reCent reSuLtS 

h. MueLLer 1 , S. Brun 2 , M. hAnfLAnd 2 

1 European Synchrotron Radiation Facility, Chemistry & Micro- 

Imaging Laboratories, Grenoble cedex 9, France 

2 European Synchrotron Radiation Facility, Beamline ID09 A, 

Grenoble cedex 9, France 

This work addresses the chemistry and selected physical 

properties of organic, super-conducting radical cation salts derived 

from bis(ethylenedithiolo)tetrathiafulvalene (BEDT-TTF or ET). 

The following topics of general and recent interest will be 

highlighted in more detail: 

Use of X-ray microcrystal diffraction and high resolution 

powder diffraction techniques for a better understanding of the 

properties of organic superconducting materials. 

Organic superconductors under high pressure – crystallographic 

evidence for the existence of a new polymorphic phase 

of α-(ET) I at high pressure. 

2 3 

Keywords: superconductors; 


P - 0 6 7 4 

enthALPy-entroPy CoMPenSAtion for n o 2 

And Co AdSorPtion on zSM-5 ContAininG 

trAnSition MetAL ionS 

r. herCiGonJA 1 , v. rAKiC 2 , v. rAC 2 , A. Auroux 3 

1 Faculty of Physical Chemistry University of Belgrade, Faculty 

of Physical Chemistry, Belgrade, Serbia 

2 Faculty of Agriculture University of Belgrade, Faculty of 

Agriculture, Belgrade, Serbia 

3 Institut de recherches sur la catalyse et l’environnement de 

Lyon Université Lyon, Institut de recherches sur la catalyse et 

l’environnement de Lyon, Lyon, France 

The “enthalpy-entropy compensation” phenomenon refers 

to the linear scaling between enthalpy (ΔH) and entropy (ΔS) for 

a set of related reactions. At the “compensation temperature” any 

variation in enthalpy is balanced by such variation in entropy so 

that the total change in free energy remains constant [1] . 

There is a growing interest in manganese incorporation in 

zeolite lattices, mainly because of the role of this metal in 

numerous metallo-enzymes. Also, Mn2+ is a very active catalyst 

for SO oxidation in aqueous phase. 

2 

In this work, thermodynamic parameters and the existence 

of enthalpy-entropy compensatory behaviour in adsorption of N O 2 

and CO on Mn2+ exchanged ZSM-5 zeolites, and bi-metallic 

FeMnZSM-5 and CuMnZSM-5 were investigated. The changes 

of entropy caused by N O and CO adsorption were calculated 

2 

from differential heats [1]. 

The N O and CO adsorption was investigated by 

2 

microcalorimetry and FTIR spectroscopy. Heats of adsorption 

were measured at 303 K in a heat-flow microcalorimeter 

(C80 Setaram) linked to a glass volumetric line. FTIR spectra 

were recorded using FTIR Brucker spectrometer with OPUS 22 

software. 

Existence of enthalpy-entropy compensation effect was 

evidenced by the linearity of –ΔH vs. –ΔS plots with the 

correlation coefficients 0.99, characteristic for all investigated 

zeolites, expect for CO adsorption on CuMnZSM-5. It was found 

that compensation effect depends on the type of charge-balancing 

cation. The compensation effect is governed by electrostatic 

interactions between highly polarizing cationic centres in zeolite 

and N O and CO molecules (depending of the size and charge of 

2 

the cation) and by specific interactions (depending of the electron 

configuration of the cation). 

Existence of the compensation effect is of interest for the 

possibility of predicting adsorption behaviour of the system and 

providing data for the zeolite as a catalyst. 

references: 

1. R. Hercigonja, V. Rac, V. Rakic, A. Auroux, J. Chem. 

Therm. 48 (2012) 112-117. 

Keywords: Adsorption; Zeolites; Thermodynamics; 



s1200 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 7 5 

StruCture PrediCtion viA AB initio enerGy 

LAndSCAPeS exPLorAtion of Gef , A SySteM 

2 

feAturinG Lone PAir StruCture CAndidAteS 

M. JAnSen 1 , K. doLL 1 

1 Max Planck Institute for Solid State Research, Chemistry, 


Predicting which crystalline modifications can exist in a 

chemical system requires the global exploration of its energy 

landscape. [1] However, the large computational effort involved in 

such global searches has required the use of a variety of empirical 

potentials and cost functions followed by a local optimization on 

the ab initio level. But this approach fails when systems are 

studied that exhibit unusual bonding situations such as mixed 

covalent-ionic bonding or sterically active inert electron pairs. In 

order to address this problem, one must employ ab initio energy 

functions already during the global optimization phase of the 

structure prediction. [2] 

Germanium difluoride being such a system, we have studied 

its ab initio energy landscape using simulated annealing as a 

global exploration tool. [3] Most of the minimum configurations 

found during the global search exhibit structures with first 

coordination spheres that are characteristically unsymmetric, 

indicating a stereochemically active lone pair. Furthermore, many 

display covalently bonded substructures that are held together by 

interchain van-der-Waals interactions and F-Ge donor-acceptor 

bonds. Among the structures found are the known experimentally 

observed one (α-GeF ), and, furthermore, one which turned out 

2 

to be the correct solution for the (at the time of this study) not-yet 

solved structure of the high-temperature phase β-GeF . Detailed 

2 

studies of the electronic and structural properties on ab initio level 

show that the experimentally observed spectrum of distances 

could be qualitatively reproduced without any heuristic input. 

references: 

1. J. C. Schön, M. Jansen, Angew. Chem. Int. Ed., 1996, 

35:1286; 

M. Jansen, Angew. Chem. Int. Ed., 2002, 41:3746. 

2. J. C. Schön, K. Doll, M. Jansen, Phys. Stat. Sol. b, 2010, 

247:23. 

3. K. Doll, M. Jansen, Angew. Chem. Int. Ed., 2011, 

50:4627. 

Keywords: GeF2; ab initio energy landscape; 

stereochemically; active lone pairs; 


P - 0 6 7 6 

PhotoLuMineSCenCe ProPertieS of noveL 

ioniC SiLiCA nAnoPArtiCLe networKS 

M. KronStein 1 , M. A. neouze 1 



Novel hybrid materials ionic silica nanoparticle networks 

(ISNN) were synthesized. The efficient formation of this novel 

hybrid material allowed to process the material into monolithic 

gels or transparent films. The ISNN presented very interesting 

photoluminescence properties. 

For the synthesis of those hybrid materials, silica 

nanoparticles with an average diameter of 16 nm were modified 

with N-(3-propyltrimethoxysilane)imidazole. These imidazole 

modified silica nanoparticles reacted with halogen functionalized 

linkers. The coupling reaction, between the modified 

nanoparticles and the linker molecules, is a nucleophilic 

substitution. This substitution can be considered as a “clickchemistry-like” 

reaction. The molecules used as linkers consists 

in aromatic or condensed aromatic compounds containing two 

opposite-standing CH Cl-groups, such as p-Dichloroxylene or 

2 

4,4'-Bis(chloromethyl)-1,1' biphenyl. 

The photoluminescence measurements performed on the 

ISNN hybrid materials showed emission bands over a broad range 

in the visible region. The silica nanoparticles, as well as the 

imidazole or chloroalkyl modified silica nanoparticles are non 

luminescent. In the specific cases where the pure dichloro linkers 

were photoluminescent, their emission maximum occured at a 

different wavelength than for the corresponding hybrid material. 

SAXS measurements (Small Angle X-Ray Scattering) 

indicated a short range order which was assumed of being the 

origin for the photoluminescence properties of these hybrid 

materials. The short range order in form of strong π-π stacking 

interactions in the hybrid material was investigated when 

observing emission wavelength shifts by changing the linker. 

The measured quantum yields up to 80% making this ISNN 

extremely promising for photoluminescence applications. 

Keywords: Green chemistry; Ionic liquids; Luminescence; 

Silicates; Sol-Gel processes; 



s1201 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 7 7 

effeCt of hydroxyL denSity on 

CondenSAtion BehAviorS of SeLf-ASSeMBLed 

MonoLAyerS And PerforMAnCe of 

PentACene-BASe orGAniC thin-fiLM 

trAnSiStorS 

M. y. Kuo 1 , h. C. tiAo 1 

1 National Chi Nan University, Applied Chemistry, Nantou, 

Taiwan 

A series of self-assembled monolayers (SAMs), comprising 

octadecyltrichlorosilane (ODTS), dodecyltrichlorosilane (DDTS), 

and hexamethyldisilazane (HMDS), were prepared to examine the 

effects of phase states and condensation behaviors of SAMs on 

the morphologies and performance of pentacene-based organic 

field-effect transistors (OFETs) by means of Fourier Transform 

Infrared (FT-IR) spectrometer, atomic force microscope (AFM), 

X-ray diffraction (XRD), and semiconductor parameter analyzer. 

Experimental results reveal that the treatment of SiO substrates 

2 

with O plasma (denoted as O -SiO ) and the preparation 

2 2 2 

temperature of SAMs dramatically influence the morphologies of 

SAMs and the performance of corresponding pentacene-based (no 

purification) OFETs. When the SAMs were prepared at 30 °C, the 

OFET based on ODTS-treated O -SiO substrate had the highest 

2 2 

hole mobility, reaching as large as 1.15 cm2V-1s-1 , and an on/off 

current ratio in excess of 105 ; these values are both much larger 

than those of a device based on ODTS-modified SiO substrates 

2 

without O plasma treatment and O -SiO substrates modified by 

2 2 2 

ODTS SAMs prepared at other temperatures. OFETs based on 

O -SiO substrates that were modified by DDTS and HMDS 

2 2 

SAMs prepared at 4 °C performed best. 

Keywords: Organic field-effect transistors; self-assembled 

monolayer; pentacene; O2 plasma; preparing temperature; 


P - 0 6 7 8 

deveLoPMent of wAter-BASed SoL-GeL 

CoAtinGS AS AdheSion Pre-treAtMent for 

ALuMiniuM SheetS 

S. Meyer 1 , u. SChuBert 1 



Since 2000, as the chromate conversion coatings were 

forbidden in the automotive and aircraft sector, much research has 

been done to find a follow-up system for corrosion protection of 

aluminium. Sol-gel coatings are very promising because the 

precursors can be modified easily and the coatings can be tailored 

for different requirements. 

This work deals with the development of water-based 

coatings providing a good pre-treatment for adhesive bonding as 

well a good corrosion protection, even after aging under corrosive 

conditions. 

Based on a coating system which consists of zirconia 

nanoparticles embedded in a silica network [1] made of tetraethyl 

orthosilicate (TEOS) and glycidoxypropyltrimethoxysilane 

(GLYMO), a water-based coating was developed. Furthermore 

the replacement of zirconium by titanium was tested. This new 

system was varied with regard to the aging time of the sol, ratio 

of transition metal precursor and water proportion. The suitability 

as adhesion pre-treatment was tested by tensile shear strength 

measurements. Additionally, the aging resistance was investigated 

by storing the bonded specimens in a salt spray chamber for 

480 hours and testing them after this treatment. Morphological 

characterization was done by SEM and the composition was 

investigated by XPS. 

references: 

1. M.L. Zheludkevich, R. Serra, M.F. Montemor, I.M. Miranda 

Salvado, M.G.S. Ferreira Surface and Coatings Technology 

200 (2006) 3084–3094 

Keywords: Aluminum; Sol-gel processes; Water chemistry; 



s1202 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 7 9 

inverSe GAS ChroMAtoGrAPhy AS 

A verSAtiLe tooL for the deterMinAtion of 

PhySiCo-CheMiCAL PArAMeterS of the 

MetAL-orGAniC frAMeworK hKuSt-1 

A. MünCh 1 , S. GLAnte 1 , f. MertenS 1 

1 TU Bergakademie Freiberg, Institute of Physical Chemistry, 


Metal organic frameworks (MOF) are highly porous hybrid 

compounds consisting of inorganic and organic building blocks, 

called secondary building units (SBU) and linker molecules. Since 

1999, the year of the discovery of HKUST-1 and MOF-5, this 

field of research has constantly grown and very different fields of 

application, such as catalysis and gas storage, are explored. 

In recent years several studies in the field of MOF-based gas 

chromatography demonstrated the potential of MOFs as stationary 

phases for so-called PLOT (porous layer open tubular) columns. 1 

Beside its function as an analytical tool, MOF based stationary 

phases in gas chromatography offer a convenient tool to determine 

fundamental thermokinetic data for the interaction of a large 

number of volatile compounds with the respective MOF structure. 

Furthermore the investigation of kinetic and thermodynamic 

phenomena is one of the prerequisites in order to find new and 

optimized practical applications and to understand the specific 

properties of the MOF-materials in question. 

Based on the analyses by Cremer, van Deemter, and Golay, 

adsorption enthalpies, entropies, diffusion constants and other 

parameters can simply be gained by retention time and peak shape 

measurements. Beside the interaction with simple hydrocarbons, 

we investigated the interaction of electron donating analytes, such 

as aromatic and free electron pair possessing compounds with 

HKUST-1 as a representative of MOFs with open metal sites by 

inverse gas chromatography. 

In this contribution a new method preparing the 

corresponding MOF based PLOT capillary columns is also 

presented, called the cyclic CSA (Controlled SBU Approach) 

coating procedure. 

references: 

1. a) Z.-Y. Gu, X.-P. Yan, Angew. Chem., Int. Ed. 2010, 49, 

1477; 

b) A. S. Münch, F. O. R. L. Mertens, J. Mater. Chem. 

2012, 22, 10228; 

c) A. S. Münch, J. Seidel, A. Obst, E. Weber, 

F. O. R. L. Mertens Chem.-Eur. J. 2011, 17, 10958. 

Keywords: Metal-organic frameworks; Gas chromatography; 

Kinetics; Thermodynamics; Synthetic methods; 


P - 0 6 8 0 

viSiBLe LiGht reACtive PhotoCAtALySt 

n-doPed tio SyntheSized At A Low 

2 

teMPerAture 

K. MurAi 1 , K. JofuKu 2 , t. MoriGA 1 

1 The University of Tokushima, Institute of Technology and 

Science, Tokushima, Japan 

2 The University of Tokushima, Graduate School of Advanced 

Technology and Science, Tokushima, Japan 

It is said that photocatalyst N-doped TiO which is sintered 

2 

at 400–500 °C has a highest catalytic activity. However, it is also 

said that in this temperature, reoxidation of catalyst causes the 

deterioration of activities. In this study, we attempted to synthesize 

N-doped TiO at a lower temperature and evaluated the properties. 

2 

The samples were prepared in the sol-gel method and fired at 300, 

400 or 500 °C after mixed with urea. These samples were 

characterized by X-ray diffraction (XRD), X-ray photoelectron 

spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy 

(UV-vis DRS). The photocatalytic activity of the samples was 

determined in the methylene blue decomposition with 470 nm 

wave-length visible light. All samples had an anatase-type 

structure. The sample sintered at 500 °C had a highest crystalline. 

The sample prepared at 400 °C had a highest absorption of visible 

light. However, the sample which adsorbed and decomposed the 

methylene blue most efficiently was that one prepared at 300 °C. 

In the catalytic activity test of the gel precursor before calcination 

and non-doped TiO , it was observed that non-doped TiO did not 

2 2 

adsorb the methylene blue but gel precursor adsorbed it. 

Moreover, the adsorption of methylene blue of the sample after 

N-doping increased materially. These results mean that the sample 

which is doped nitrogen and has a low crystalline adsorbs the 

methylene blue efficiently. The most nitrogen was doped in the 

sample fired at 300 °C. The catalytic activity of this sample was 

about twice as high as that of one commercial available TiO2 catalyst. It is believed that N2p orbitals were hybridized to the 

valence band in the catalyst and this caused the improvement of 

the hole mobility and quantum efficiency. 

Keywords: Solid-state structures; Synthetic methods; 



s1203 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 8 1 

two iSoeStruCturAL hyBrid CoMPoundS 

BASed on KeGGin-tyPe PoLyoxoMetALAteS 

And CoPPer-PiCoLinAte CoMPLexeS 

A. PAChe 1 , B. Artetxe 1 , A. iturroSPe 1 , 

L. SAn feLiCeS 1 , S. reinoSo 1 , 

J. M. Gutiérrez-zorriLLA 1 

1 Universidad del País Vasco., Inorganic Chemistry, 


Polyoxometalate chemistry is one of the many areas in 

inorganic chemistry that is developing most rapidly today driven 

by their versatile nature in terms of structure, size, redox 

chemistry, photochemistry, and charge distribution [1] . One of the 

most remarkable approaches in POM chemistry is the design of 

functionalized materials based on POMs and different transitionmetal 

complexes [2] . Incorporation of metalorganic moieties into 

inorganic oxide clusters provides a powerful method for structural 

modification and synthesis of novel metalorganic-inorganic 

hybrid materials that combine the features of both substructures 

resulting in large numbers of one-, two- and three-dimensional 

compounds [3] . 

In this work we report the synthesis, chemical and 

spectroscopic characterization, X-ray structure and magnetic 

properties of two hybrid inorganic-metalorganic compounds 

based on Keggin type polyoxometalates as inorganic building 

block, which are decorated with a copper-picolinate metalorganic 

complex and guanidinium cations; [C(NH ) ] [{SiW O } 

2 3 4 12 40 

{Cu(pic) }].nH O and [C(NH ) ] [{GeW O }{Cu(pic) }].nH O. 

2 2 2 3 4 12 40 2 2 

These compounds were both prepared by open air methods. 

The structure of these compounds can be described as 

double layers of keggin-type polyanions joined together through 

hydrogen bonds involving guanidinium cations. These layers are 

joined together by π-π interactions of the picolinate rings creating 

a hydrophobic area. These layers are stacked along the z direction, 

following the sequence: Cu(pic) -[POM- Gua –POM] -Cu(pic) . 

2 2 

references: 

1. D.L Long, E.Burkholder, and L. Cronin, Chem.Soc.Rev., 

2007, 105, 121; 

L. Lisnard, A. Dolbecq, and P. Mialane, Dalton Trans., 

2005, 3913. 

2. T. Arumuganathan, A. Srinivasa Rao, and S. K. Das, 

Crystal Growth & Design, 10, No. 10, 2010; 

E.Antonova, C. Näther, P. Kögerler, and W.Bensch, Inorg. 

Chem. 2012, 51, 2311-2317 

3. H. Jin, Y. Qi, E. Wang, Y. Li, Xinlong Wang, C. Qin, and 

S. Chang, Crystal Growth & Design, Vol. 6, No. 12, 2006;. 

A. Dolbecq, E. Dumas, C. R. Mayer, and Pierre Mialane, 

Chem. Rev. 2010, 110, 6009–6048. 

Keywords: polyoxometalate; keggin; copper-picolinate; 


P - 0 6 8 2 

CorroSion-reSiStAnt CerAMiC CoAtinGS for 

SoLid oxide fueL CeLL interConneCtS 

M. PALCut 1 , L. MiKKeLSen 2 , K. neufeLd 2 , 

M. Chen 2 , r. KniBBe 2 , P. v. hendriKSen 2 

1 University of Oslo, Department of Chemistry, Oslo, Norway 

2 Technical University of Denmark, Department of Energy 

Conversion and Storage, Roskilde, Denmark 

Solid oxide fuel cells (SOFC) are environmentally friendly 

electrochemical devices, used to produce the electricity from 

gaseous fuels, such as hydrogen or methane. Each cell operates 

at high temperatures and uses a dense layer of solid oxide 

electrolyte to transport oxide ions between electrodes. 

Interconnects are current conductors that connect each cell in 

series. These materials separate the neighboring anode and 

cathode compartments of two adjacent cells. Interconnects need 

to be stable and corrosion-resistant at elevated temperatures. 

Candidate interconnect materials are ferritic steels since metals 

are less brittle, cheaper and easier to shape compared to traditional 

LaCrO -based materials. Nevertheless, metallic materials react 

3 

with corrosive gases and form poorly conducting surface oxide 

layers. Corrosion resistance can be greatly improved by ceramic 

coating. The coating is an oxygen transport barrier. Furthermore, 

the coating material can be a source of metal cations, such as 

Mn3+ , Ti3+ and La3+ , which may improve the oxide scale 

conductivity and/or adhesion to the metal surface. In the present 

work, the corrosion resistance of candidate steels for SOFC 

interconnects is studied. The steel sheets were cut, ground and 

coated by a single and double layer ceramic coatings based on 

lanthanum strontium manganese oxide (LSM) and cobalt oxide. 

The samples were annealed for 140 – 1000 h at 1123 K in different 

oxidizing atmospheres. The corrosion kinetics was followed by 

measuring the mass increase of the samples over time. The oxide 

scale phase composition and microstructure are studied by XRD 

and SEM/EDS. The mass gain of the samples follows a parabolic 

rate law. The parabolic rate constant decreases with increasing 

chromium concentration in the steel. Furthermore, dense LSM 

and Co O coating layers significantly reduce the oxidation rate. 

3 4 

The reaction mechanism is proposed. The results are discussed in 

relation to the proper interconnect functioning in a working SOFC 

stack. 

Keywords: Fuel cells; Ceramics; Oxidation; Kinetics; 



s1204 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 8 3 

PoLyMorPhiSM of 

trAnS-1,4-CyCLohexAnediMethAnoL 

t. roSeiro 1 , M. t. S. roSAdo 1 , A. M. C. MeireLeS 1 , 

S. S. BeBiAno 1 , r. A. e. CAStro 2 , M. r. SiLvA 3 , 

J. CAnotiLho 2 , M. e. S. euSéBio 1 

1 University of Coimbra, Chemistry Department, Coimbra, 

Portugal 

2 University of Coimbra, Faculty of Pharmacy, Coimbra, 

Portugal 

3 University of Coimbra, Department of Physics, Coimbra, 

Portugal 

Cyclohexane derivatives, despite the simplicity of their molecular 

structures, show a complex solid state phase behaviour [1, 2] . 

One of the dihydroxylated derivatives, trans-1,4-cyclohexanediol, 

has the particularity of presenting in the crystal lattice of the 

two known polymorphs bi-equatorial conformers as well as 

conformers in which the hydroxyl groups have the 

axial-axial orientation [3, 4] . 1,4-cyclohexanedimethanol differs from 

1,4-cyclohexanediol only in two methylene groups placed 

between a cyclohexane carbon atom and the OH group, which 

may confer more flexibility to the molecule. 

This study aims to investigate the polymorphism of 

1,4-cyclohexanedimethanol and to evaluate the influence of the 

substituent group in the stabilization of the axial conformers. 

Trans-1,4-cyclohexanedimethanol polymorphic forms were 

generated by crystallization from solutions, and by cooling the 

melt. A combined approach using differential scanning 

calorimetry, polarized light thermomicroscopy and X-ray 

diffraction has been employed in the results interpretation. Two 

polymorphs were isolated and their crystal structures were solved 

by single crystal X-ray diffraction, at room temperature. 

The conformational space of trans-1,4-cyclohexanedimethanol 

was studied by computational calculations at the MP2 level of 

theory, investigating the relative stability of the different 

equatorial and axial conformers. The comparison of the most 

stable structures for the isolated molecules and in the crystal will 

permit to draw insight on the relative importance of the molecular 

stability and intermolecular association in order to explain the 

conformational preferences of trans-1,4-cyclohexanedimethanol. 

references: 

1. Maria, T.M.R.; Costa, F.S.; Leitao, M.L.P.; Redinha, 

J. S. Thermochim. Acta 269 (1995) 405–413. 

2. Leitao, M.L.P.; Castro, R.A.E.; Costa, F.S.; Redinha, 

J.S. Thermochim. Acta 378 (2001) 117–124. 

3. Steiner, T.; Saenger, W. J., Chem. Soc., Perkin Trans. 2 

(1998) 371–377. 

4. Maria, T. M. R.,Castro, R. A. E., Bebiano, S. S., Silva, 

M. R., Beja, A. M., Canotilho, J., Eusébio, M. E., 

Cryst. Growth Des., 2010, 10 (2010) 1194-1200. 

Keywords: Polymorphism; Crystal growth; Calorimetry; 

Conformation analysis; X-ray diffraction; 


P - 0 6 8 4 

therMAL BehAvior of CAndeSArtAn 

CiLexetiL CoMPLexeS 

L. SeiLerová 1 , B. KrAtoChvíL 1 , h. BruSová 2 , 

L. KreJCíK 2 

1 Institute of Chemical Technology, Department of Solid State 


2 Zentiva k.s., R&D, Prague, Czech Republic 

A lot of newly developed pharmaceuticals are poorly soluble 

drugs. [1] This project deals with improvement of candesartan 

cilexetil solubility. Candesartan cilexetil is very poorly soluble 

antihypertensive drug. It is a prodrug of candesartan exactly, 

which selectively affects secreting of angiotensin II, the main 

generator of hypertension. 

The major goal of this project is to test improvement of 

candesartan cilexetil solubility using different types of 

cyclodextrin (β-cyclodextrin, hydroxyl-propyl-β-cyclodextrin, 

sulphated-β-cyclodextrin and carboxy-methyl-β-cyclodextrin) and 

porous starch. [2-3] 

We have used thermal analysis as a great tool to characterize 

complexes of candesartan cilexetil with cyclodextrins and systems 

with porous starch. This both groups are bonded with candesartan 

thanks to weak interactions, which effect synthesis of complexes 

and better soluble systems with candesartan cilexetil. Those are 

hard to characterize using other solid state analysis methods. By 

using DSC it is possible to distinguish complexes from simple 

mixtures of candesartan cilexetil with cyclodextrins and starch. 

Characterization of such complexes via thermal analysis and 

contribution to the candesartan solubility will be discussed. 

Acknowledgement: Financial Support from specific university 

research (MSMT No. 21/2012 and 6046137302). 

references: 

1. Kane, R.; Kuchekar, B. Preparation, physicochemical 

characterization, dissolution and formulation studies of 

telmisartan cyclodextrin inclusion complexes. 

Asian. J. Pharm. [serial online] 4 (2010) 52-9. 

2. Al Omari, A.; Al Omari, M.; Badwan, A.; Khaldoun, A. 

Effect of cyclodextrins on the solubility and stability of 

candesartan cilexetil in solution and solid state. 

J. Pharm. Biomed. Anal. 54 (2011) 503–509. 

3. Deveswaran, R. et al.: Devlopment of modified porous 

starch as a carrier to improve solubility. 

Adv. Appl. Sci. Res. 3(1) 2012 162-170. 

Keywords: Cyclodextrins; Calorimetry; Drug delivery; 



s1205 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 8 5 

nAnoenGineerinG BioMiMetiC tio -BASed 

2 

PhotoCAtALyStS for PoLLution ControL 

froM A detAiLed StruCturAL/MeChAniStiC 

underStAndinG 

P. SerMon 1 , M. worSLey 1 

1 Brunel University, Wolfson Materials Centre, Uxbridge, 


Biomimetic chemistry started in the realm of organic 

chemistry but has progressed to benefit materials design and 

now catalytic chemistry. With evolution many living plant 

and animal species have constructed species-specific 

biominerals/biocomposites that have nano-architectures that are 

the envy of materials scientists. Here we show how one can learn 

from and overcoat some of nature’s 8.7 million biotemplates 

available on Earth with TiO -based phases to form novel hybrid 

2 

nanostructures and then remove the biotemplate to produce novel 

intricate TiO -based replicas that show novel green photocatalytic 

2 

properties in pollutant control. 

TiO is a well known effective photocatalyst. It can be 

2 

improved by an adsorbed dye sensitizer, Pt, ion-doping, lowering 

its particle size or changing the anatse:rutile ratio, but 100-120 nm 

thick anatase overlayers grown on rutile produce hetero-junctions 

exhibited even higher pseudo-first-order rate constants and rates 

of photocatalysed dye decoloration. Since TiO photocatalytic 

2 

properties are structure-dependent, new and interesting properties 

were expected from the unusual and complex biomimetic 

TiO -based replica structures. This is the focus of the present 

2 

work. 

The photocatalytic activities and selectivities of the 

biomimetic TiO –based material coatings in the control air 

2 

pollutant (toluene, HCHO, NO ) and water pollutant 

x 

(0.1mM methyl orange, benzene, toluene, phenol, alkyl phenol 

and alkyl phenol ethoxylates) levels per unit area were found to 

be much higher than those of commercial TiO nanoparticulate 

2 

coatings using a 0.5kW photon source. The modes of action of 

these biomimetic photocatalysts were investigated in-situ by 

FTIR-UV-vis-RGA analysis. Doping (e.g. Eu3+ ) allows the 

biomimetic catalyst fine-tuning. 

The potential of this approach for improved green catalysts 

in general (and TiO photoanodes in DSSCs [30], photocatalysts 

2 

for CO reduction and water splitting and metal fuel cell 

2 

electrodes and antibacterial coatings) is considered in detail. 


P - 0 6 8 6 

infLuenCe of heAt treAtMent on StruCture 

of eLeCtroPLAted Pd-ni-P MetALLiC GLASS 

fiLMS 

M. ShiBAtA 1 , C. MoChizuKi 1 , y. KiMurA 1 

1 University of Yamanashi, Applied Chemistry, Kofu, Japan 

The metallic glass is amorphous alloy with a glass transition 

temperature and supercooled liquid region. It is possible to give 

the material the new function, when various material surfaces are 

coated with such metallic glass film. Though the producing of the 

amorphous alloy by the electrodeposition is well known, the 

report on the electrodeposition of metallic glass film is not found 

except our papers. We have investigated the formation of Pd-Ni- 

P metallic glass films using the electrodeposition method from the 

view point of the bulk Pd based metal glass studied in great 

numbers as a basic research material. 

In this study, the influence of heat treatments at the 

temperatures of supercooled liquid region on the crystal growth 

was examined in the electroplated Pd-Ni-P metallic glass film 

having various composition. 

The substrates were sheets of Cu and Ti with dimensions of 

15 x 67 x 0.20 mm. The base composition of electrolyte for 

Pd-Ni-P electroplating was PdCl , NiSO , H PO , 

2 4 3 4 

NH CH CH NH and NaCl. Heat treatments of the electroplated 

2 2 2 2 

films were carried out using an infrared gold image furnace 

(MILA-3000, ULVAC) under Ar gas atmosphere. The films were 

characterized by X-ray fluorescence analysis (XRF), X-ray 

diffraction (XRD) and differential scanning calorimetry (DSC). 

The glass transition temperature and crystallization 

temperature of the electroplated Pd Ni P metallic glass film 

44 38 18 

were 571 K and 646 K, respectively. XRD examination for 

Pd Ni P metallic glass film shows that the pattern consists only 

44 38 18 

of one broad peak and no distinct crystalline peaks can be seen 

from the films formed by electrodeposition, indicating that there 

exists an amorphous metal. After annealing at the temperature 

over 603 K for 30 min, some crystalline peaks, which are 

attributed to Pd, Pd P , Ni P and Ni Pd P, were observed at the 

5 2 3 2 2 

XRD patterns. 

Keywords: Heat treatment; Electroplating; Pd-Ni-P; Metallic 

glass; Crystallization; 



s1206 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 8 7 

Ge-GA-SB-S AMorPhouS ChALCoGenideS doPed 

with rAre-eArth eLeMentS 

L. StriziK 1 , t. wAGner 1 , J. heo 2 , C. Liu 2 , 

M. PAvLiStA 3 , J. PriKryL 1 , B. fruMArovA 4 , 

M. fruMAr 1 

1 University of Pardubice, Department of General and Inorganic 

Chemistry, Pardubice, Czech Republic 

2 Pohang University of Science and Technology, Center for 

Information Materials Department of Materials Science and 

Engineering, Pohang, Republic of Korea 

3 University of Pardubice, Department of Physics, Pardubice, 


4 University of Pardubice and the Institute of Macromolecular 

Chemistry AS CR, Joint Laboratory of Solid State Chemistry of 

the University of Pardubice and the Institute of 

Macromolecular Chemistry AS CR, Pardubice, Czech Republic 

Amorphous chalcogenides are very promising materials for 

various applications in infrared spectral region because they have 

a broad optical window from visible to mid-infrared spectral 

range, a high refractive index, low phonon energy and some of 

them are photosensitive. These properties predetermine them for 

using as host matrix materials for doping with rare-earths 

elements [1, 2] . 

Nowadays the renewable energy sources are in the spotlight. 

Our work is focused for preparation of photon up-converters 

which can be used for enhancement of silicon solar cell efficiency 

as well as for telecommunications. 

Various compositions of Ge-Ga-Sb-S amorphous 

chalcogenides were prepared by the conventional meltingquenching 

technique in sealed silica tubes from pure elements. 

Some of these materials were used for deposition of films onto 

microscopic glassy substrates by pulsed laser deposition and flash 

thermal evaporation techniques. The chemical composition of 

prepared samples was investigated by EDX spectroscopy, their 

crystallinity by XRD analysis. Variable angle spectroscopic 

ellipsometry was used for determination of the optical band gap 

energy, dispersion of the refractive index, thickness and roughness 

of films and for study of optical homogeneity. Up-conversion and 

photoluminescent spectra were studied via photoluminescence 

spectroscopy with using of tunable Ti:sapphire laser as excitation 

source. The results are discussed. 

Acknowledgement: The authors would like to thank the MSMT, 

LH KONTAKT II, project LH11101 and to ESF and MSMT for 

financial support from CZ.1.07/2.3.00/20.0254 project 

“ReAdMat-Research team for advanced non-crystalline 

materials”. 

references: 

1. J. Troles, Y. Niu, C. Duverger-Arfuso, F. Smektala, 

L. Brilland, V. Nazabal, V. Mozain, F. Desevedavy, 

P. Houizot, Synthesis and characterization of chalcogenide 

glasses from the system Ga-Ge-Sb-S and preparation of 

single-mode fiber at 1.55 μm, Mater. Res. Bull., 43 (2008) 

976-982. 

2. A. Zakery and S.R. Elliott, Optical properties and 

applications of chalcogenide glasses: a review, 

J. Non-Cryst. Solids, 330 (2003) 1-12. 

Keywords: chalcogenides; rare earths; up-conversion; 

luminescence; Ga-Ge-Sb-S; 


P - 0 6 8 8 

exPLorinG the StruCturAL enerGy 

LAndSCAPe of uLtrA MiCroPorouS 

frAMeworK MAteriALS 

A. trewin 1 , K. JeLfS 1 , A. CooPer 1 

1 University of Liverpool, Chemistry, Liverpool, United 

Kingdom 

Materials with molecular-scale porosity are important in 

wide range of applications such as gas storage, molecular 

separation, and heterogeneous catalysis. Framework materials 

offer scope for ultra high porosities and hence high gas uptake 

values. 

The structural properties of a polymer can have a direct 

influence over its ability to pack efficiently and hence direct void 

formation and connectivity. For example, the series of conjugated 

microporous polymers (CMPs) show statistical control over the 

pore dimensions and surface area by systematically changing the 

length of the strut and the node topology. [1] Porous aromatic 

frameworks (PAFs) were recently discovered and showed ultra 

high surface areas (SA 5600 m BET 2 /g). A highly crystalline 

diamondoid topology was suggested as a structural model. 

However, the PXRD suggests an amorphous structure and an 

alternative structure based on the amorphous structure of silica 

has been suggested. [2] However, the calculated surface area for 

this model does not exhibit the ultra high surface areas observed 

experimentally. 

The energy landscape of the range of possible structural 

models available has been explored by mapping the PAF-1 

node-strut structure onto a series of amorphous and crystalline 

silica topologies. Gaining a structural understanding of the 

PAF-1 system may open pathways to designing novel ultra porous 

materials. 

references: 

1. a) J.-X. Jiang et al, Journal of the American Chemical 

Society 2008, 130, 7710–7720; 

b) J.-X. Jiang et al, Macromolecules 2009, 42, 2658–2666; 

c) J. Jiang et al, Angew. Chem. Int. Ed. 2007, 46, 1–5. 

2. A. Trewin, A. I. Cooper, Angewandte Chemie 

International Edition 2010, 49, 1533–1535. 

Keywords: Microporous materials; Amorphous materials; 

Solid state structures; Computational Chemistry; 



s1207 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 8 9 

BiMetALLiC niCu nAnoPArtiCLeS Confined in 

the MeSoPoreS of SBA-15 AS effeCtive 

CAtALyStS in the hydroGenAtion of 

CinnAMALdehyde 

A. unGureAnu 1 , A. ChirieAC 1 , B. drAGoi 1 , 

S. royer 2 , d. duPrez 2 , e. duMitriu 1 


Biochemical and Food Engineering, Iasi, Romania 


France 

Bimetallic nanoparticles (NPs) confined within mesoporous 

host structures are emerging as very interesting materials for 

catalysis because: (i) as compared with the corresponding 

monometallic NPs, they have improved catalytic performances 

due to a synergy between the two metals, and (ii) they are highly 

sintering-resistant due to the geometric stabilization of NPs inside 

the host mesochannels. A novel mild drying impregnation 

approach was developed to successfully prepare bimetallic NiCu 

rod-like NPs confined within the mesopores of SBA-15 silica (S) 

(constant metal loading: 5 wt. %, variable Ni/Cu weight ratios: 

4/1, 3/2, 2/3 and 1/4), as shown by low- and high-angle XRD, 

nitrogen adsorption/desorption and TEM-EDX. It was observed 

that at similar particle size, the composition of bimetallic NPs 

determines to a large extent both the reducibility and catalytic 

performance in the hydrogenation of cinnamaldehyde (CNA). 

Hence, characterization by H -TPR revealed an optimal 

2 

reducibility at Ni/Cu ratios of 3/2 and 2/3(T ~ 180-240 °C), 

red 

which is much improved when compared with monometallic Ni/S 

and Cu/S reference samples (T ~ 510 and 345 °C, respectively). 

red 

This is best explained through the existence of strong Ni?Cu 

interactions in the bimetallic nanoparticles. The catalytic results 

showed an outstanding catalytic activity of the bimetallic 

NiCu/S-4/1 catalyst when compared with either Ni/S or Cu/S 

-1 -1 (initial reaction rates of 3.212, 1.909 and 0.008 µmol .g .s , 

CNA cat 

respectively). As a general trend, the gradual decrease of the 

Ni/Cu ratio is followed by a decrease in the catalytic activity of 

bimetallic catalysts. Interestingly, the selectivity to cinnamyl 

alcohol (measured at X of 20 mol %) continuously increased 

CNA 

from 1-2 mol % (Ni/S) up to 15-16 mol % (NiCu/S-1/4), 

suggesting that the gradual addition of inert Cu to active Ni causes 

changes of its geometric and/or electronic properties, which 

finally results in enhanced chemoselectivity of NiCu/SBA-15 

catalysts. 

Acknowledgement: PNII-Idei, 264/2011 financed by 

UEFISCDI. 

Keywords: Supported catalysts; Nanoparticles; Metals; 

Mesoporous materials; Hydrogenation; 


P - 0 6 9 0 

ChArACterizAtion of CoBALt BASed tPP-BiPy 

CoordinAtion PoLyMer 

M. K. urtiAGA 1 , A. fidALGo-MAiJuAn 1 , 

G. BArAndiKA 2 , B. BAzán 1 , M. i. ArriortuA 1 

1 Universidad del País Vasco (UPV/EHU), Mineralogía y 

Petrología, Leioa-Bizkaia, Spain 

2 Universidad del País Vasco (UPV/EHU), Química Inorgánica, 

Vitoria-Gasteiz, Spain 

Metalloporphyrin systems are one of the cornerstones on 

which the existence of life is based, as major biochemical, 

enzymatic and photochemical functions depend on the special 

properties of the tetrapyrrolic macrocycle. [1] The possibility of 

introducing porphyrin units into MOFs (metal-organic 

frameworks) increases the variety of new materials based on these 

macrocycles. During the last years, cobalt porphyrins are 

well-known to be prominent catalysts for oxygen reduction 

reactions (ORR) [2] and in order to obtain materials which provide 

new properties our research group is working with different 

combinations of metalloporphyrins and organic ligands . [3] 

The work herein presented aims to the characterization of 

[CoTPP(bipy)]·[CoTPP] ·TPP (TPP= meso-tetraphenylporphyrin 

0.22 0.78 

and bipy=4,4'-bipyridine) compound in order to know the thermal, 

electronic and catalytic properties of these new porphyrin-based 

coordination polymer. 

Acknowledgements. This work has been financially supported 

by the Ministerio de Ciencia e Innovación (MAT2010-15375) 

and the Gobierno Vasco (Basque University System Research 

Groups, IT-177-07), which we gratefully acknowledge. SGIker 

(UPV/EHU) technical support (MEC, GV/EJ, European Social 

Fund) is gratefully acknowledged. A. Fidalgo-Marijuan thanks 

the UPV/EHU fellowships. 

references: 

1. I. Beletskaya, V.S. Tyurin, A.Y. Tsivadze, R. Guilard, 

C. Stern, Chem. Rev., 2009, 109, 1659-1713. 

2. C. J. Chang, Y. Deng, C. Shi, C.K. Chang, F.C. Anson, 

D.G. Nocera, Chem. Commun., 2000, 1355-1356. 

3. A. Fidalgo-Marijuan, G. Barandika, B. Bazán, 

M. K. Urtiaga, M. I. Arriortua, Polyhedron, 2011, 30, 

2711-2716. 

Keywords: Porphyrin; Metal-organic frameworks; 



s1208 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 9 1 

MoLeCuLAr interACtionS in CoMPLexeS 

of 4,4'-dinitroBiPhenyL 

P. vAn rooyen 1 , d. LiLeS 1 , e. ModAu 1 


Africa 

The focus of this study was to investigate the nature of 

molecular donor-acceptor interactions in the solid state, using 

spectroscopic techniques such as IR, Raman, NMR and 

X-ray crystallography. Complexes of para disubstituted and 

4-monosubstituted biphenyl formed with 4,4'-dinitrobiphenyl 

(DNBP), demonstrate intense colours upon formation, dissimilar 

to the colour combination of the parent compounds. Typical 

interactions observed in such molecular complexes include pi-pi 

interactions, hydrogen bonding, charge transfer and van der Waals 

interactions. Complexes of DNBP, as the host molecule, included 

a variety of mono- and disubstituted biphenyl donors or guests, 

such as dihalo, diamino, di- and monohydroxy groups [1] , as well 

as urea with a 1:1 host:guest ratio [2] and thiourea with a 7:6 

ratio. Molecular complexes formed between DNBP with 

difluorobiphenyl with a 3:1 ratio and DNBP with 

dibromobiphenyl and diiodobiphenyl with 4:1 ratios. The crystal 

structures of these complexes showed retention of the non-planar 

conformation of DNBP with a dihedral angle between the phenyl 

rings of around 35° [3] . 

The conformation for DNBP has also been studied using 

density functional theory (Guassian03) calculations that showed 

good agreement between the theoretically calculated and 

experimentally observed IR and Raman spectra in the solid state. 

The packing of the complexes in the solid state is directed mainly 

by the similar packing of DNBP units in these complexes. Some 

of the molecular ratios for these complexes that vary, depending 

on the electronic properties of the donor molecules, were 

determined using NMR spectroscopy. 

references: 

1. Brock, C.P.; Haller, K.L., Acta Crystallogr. Sect.C: Cryst. 

Struct Commun., 1984, 40, 1387. 

2. Thaimattam R.; Reddy, D.S.; Feng Xue; Mak, T.C.W.; 

Nangia, A.; Desiraju, G.R. J. Chem. Soc.,Perkin Trans.2, 

1998, 1783. 

3. Boonstra, E.G, Acta Cryst. 1963, 16, 816. 

Keywords: Host-guess systems; X-ray diffraction; 

computational chemistry; Density functional calculations; 

Charge transfer; 


P - 0 6 9 2 

infLuenCe of wAter/ethAnoL rAtio in 

SyntheSiS of n, S doPed tio2 on 

PhotoCAtALytiC ACtivity 

A. yAMAhAtA 1 , t. nAKAGAwA 1 , K. MurAi 2 , 

t. MoriGA 2 

1 The University of Tokushima, Graduate School of Advanced 

Technology and Science, Tokushima, Japan 

2 The University of Tokushima, Institute of Technology and 

Science, Tokushima, Japan 

In this study, visible light reactive N-doped and N, S 

co-doped TiO sample were prepared in the sol-gel method and 

2 

sintered after mixed with urea or thiourea. These samples were 

characterized by X-ray diffraction (XRD), X-ray photoelectron 

spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy 

(UV-vis DRS). The photocatalytic activity of the samples was 

determined in the methylene blue decomposition. In the synthesis 

of N-doped TiO , the specific surface area of precursor was 

2 

increased with decreasing the water/alcohol ratio in the hydrolysis 

reaction. However, the samples prepared by the higher alcohol 

quantity had the lower visible light absorption because of the 

reoxidation in the calcination. The sample with sulfuric acid 

treatment before recalcination could be controlled the absorption 

of visible light because of the restraint of reoxidation by sulfuric 

acid on the surface of the sample. On the other hand, in XPS result 

of the sample prepared by thiourea, the peak identified as S6+ which was derived from sulfuric acid was observed on the surface 

of the sample. The peak intensity of N3+ was increased and that 

of S2- was decreased in the bulk of sample with increasing the 

quantity of water. The absorption of visible light was decreased 

with increasing the water supply. The case that N3- is doped in O2 site needs oxygen defect in order to compensate the electric 

charge. These defects increase the recombination center. However 

the dopes of S2- do not cause the oxygen defects. This means that 

TiO photocatalyst doped S 2 2- is more effectual than that doped N3 on the methylene blue decomposition and it is possible to control 

of dopant quantity by the water addition ratio. In this study, we 

could not confirm the effect of co-dope. 

Keywords: Titaniumu dioxide photocatalyst; N, S co-doping; 

water-adding quantity; 



s1209 

chem. Listy 106, s257–s1425 (2012) 

Poster session 2 - Nanochemistry, Nanotechnology 

P - 0 6 9 3 

hydrotherMALLy SyntheSized nAno-Ce Sn o 2 2 7 

viA [BMiM][CL] And dtAB with PhotoCAtALytiC 

ProPerty 

f. AdhAMi 1 , M. r. MotAKef GhoMi 1 

1 Islamic Azad University Shahr-Ray Branch, Chemistry, 

Tehran, Iran 

In recent years, a lot of research has been extensively 

investigated to manufacture nanoscaled materials in order to 

create numerous properties in them. These are of interest for 

potential technological and medical applications. Today the 

hydrothermal technique is easy and effective, method with high 

reproducibility and good control over the composition and 

morphology of nanocompounds. One kind of these 

nanocompounds is nanosize semiconductors. A variety of 

semiconductor materials such as oxides and sulfides act as 

photocatalysts and degrade toxic organic compounds, dyes and 

others contaminants in wastewater [1] . 

In current research, synthesis of Ce Sn O nanocomposite 

2 2 7 

has been discussed by SnCl .5H O and Ce(NO ) (1:1). pH of the 

4 2 3 3 

media was gradually adjusted with sodium hydroxide. Then, 

addition of [bmim] [Cl] and DTAB was separately carried out to 

the previous solution. All of the reactions were done under N2 

gas. Two homogeneous solutions were transferred into autoclaves 

and heated at 180–200 ºC in different times. Two obtained 

precipitates were separated by centrifuge, washed with water and 

dried in vacuum oven. Surfactant and ionic liquid were eliminated 

by calcination and washing respectively. The final products were 

characterized by XRD, FT-IR, SEM and EDX. The obtained 

results comparison of two methods showed figure of the 

nanocomposites are different within two methods. Therefore 

surfactant and ionic liquid are important and give effect to figure 

of the nanocomposites. 

Also, these products were used to remove different kinds of 

textile dyes from industrial wastewater. Photocatalytic 

degradation experiments were investigated under sun light and 

ultraviolet irradiations for both of the products and the results 

were compared to gather. 

references: 

1. X. Ji, et al., Journal of Alloys and Compounds 503 (2010) 

L21. 

Keywords: nanocomposite; hydrothermal synthesis; 

photocatalytic property; 


P - 0 6 9 4 

ControLLed forMinG of AGCL 

nAnoStruCtureS on AGBr nAnoCryStAL 

SurfACe 

v. AnAnev 1 , J. SPirinA 2 

1 Kemerovo State University, Analitycal Chemistry, Kemerovo, 

Russia 

2 Kemerovo State University, Inorganic Chemistry, Kemerovo, 

Russia 

Ag-containing nanomaterials are used in many catalysis 

areas. Their creation may be based on the photographic processes, 

for example, by means of the formation of AgBr nanocrystals 

having a desirable form and size. For this purpose the controllable 

two-jet crystallization method is used, it consists in simultaneous 

addition of KBr and AgNO with certain concentrations at a 

3 

constant rate into the solution whose temperature is kept constant. 

It enables us to prepare the substrate which contains homogeneous 

tabular AgBr nanocrystals with the thicknesses ~100 nm. 

The catalysis properties of the initial nanocrystals may be 

changed by means of the formation of the heterocontact structures 

on the surface of the initial AgBr nanocrystals. These structures 

are AgCl nanocrystals, i.e. epitaxial particles. They was 

synthesized in two ways: by adding KCl and AgNO solutions 

3 

into the initial substrate under certain conditions (Method I), or, 

by adding the substrate containing previously synthesized AgCl 

nanocrystals into the initial substrate (Method II). The resulting 

epitaxial particles are located along the entire surface of the initial 

AgBr crystals. 

The surfaces of the initial AgBr nanocrystals were varied by 

adding the surface modification agent KJ into the initial substrate. 

In this case the number and the location of epitaxial particles on 

the surfaces of AgBr nanocrystals depend on the concentration of 

the iodide ions. It is established that at a certain concentration of 

the surface modification agent, the epitaxial particles are formed 

only onto the corners of the modified AgBr nanocrystals 

(Method I) and onto their sides (Method II). 

Photolysis and next chemical treatment of the substrate with 

the initial and modified AgBr nanocrystals results in the Agcontaining 

nanocrystals with different surface structures. 

Keywords: Silver bromide nanocrystal; Epitaxy; Nanostructure; 



s1210 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 9 5 

SteAM reforMinG of MethAne over niCKeL 

CAtALyStS SuPPorted on nAnoCryStALLine 

MAGneSiuM oxide 

A. MAhMood 1 , M. rezAei 2 

1 Islamic Azad University Omidiye Unit, Chemistry, Tehran, 

Iran 

2 University of Kashan, Chemical Engineering Department, 

Tehran, Iran 

The conversion of methane to valuable chemicals is very 

important. In the past decades, the most studied technology for 

syngas production was steam-methane reforming (SMR), in 

which methane reacts with steam to produce a mixture of 

hydrogen, carbon dioxide, and carbon monoxide. In order to 

obtain acceptable reaction rates, a catalyst is required to accelerate 

the process. In this study, Ni catalysts supported on 

nanocrystalline magnesium oxide with high surface area and 

various Ni loadings (5, 7, 10, 15 wt%) have been employed in 

steam reforming of methane (SMR) and the effect of Ni loadings 

on the catalytic activity was investigated. 

The preparation of MgO via surfactant-assisted precipitation 

method led to the formation of a nanocrystalline carrier for nickel 

catalysts. The synthesized samples were characterized by XRD, 

BET, and TPH techniques. The results showed that the prepared 

catalyst with 7 % Ni loading indicated high activity and good 

stability in steam reforming reaction. It could be attributed to high 

dispersion of reduced Ni species and basicity of support surface. 

Methane conversions of 4 catalysts with different Ni loading 

were shown that the catalyst with 7% Ni loading has higher 

conversion at all temperatures. Specially, at higher temperatures, 

higher activity of 7%Ni/MgO catalyst is more distinguishable. 

However, if the Ni content is higher than 7 wt%, there is a 

negative effect on the catalytic activity of SRM over reduced 

Ni/MgO catalyst. 

Keywords: Nickel; nanostructures; Magnesium; 


P - 0 6 9 6 

the CheMiStry of diSuLfide-deCorAted 

MonoLAyer SurfACeS 

v. ArteL 1 , C. SuKeniK 1 

1 Bar-Ilan University, Bar-Ilan Institute of Nanotechnology and 

Advanced Materials, Ramat-Gan, Israel 

The attachment of bio-molecules to surfaces is of 

considerable importance both in the study of their fundamental 

properties and mode of action and in the creation of devices based 

on molecular arrays for screening and sensing. Thiol-bearing 

SAMs provide a platform for a stable (covalent) anchoring of 

biomolecule in a well-defined orientation. 

A possible surface anchoring strategy is to create disulfide 

linkages between surface thiols and those of the molecules to be 

immobilized. Surprisingly, disulfide anchoring is relatively 

uncommon and seems not to be able to achieve a high degree of 

loading of immobilized molecules on the surface. 

The work reported herein describes the creation of uniform 

thiol-functionalized siloxane-anchored SAMs and their 

transformation into intra-monolayer (bridging) disulfides. These 

disulfides provide for the efficient immobilization of biomolecules 

bearing pendant thiols, with no need for added oxidant. 

A fundamental problem in developing this surface chemistry was 

the lack of analytical methods that distinguish between thiol and 

disulfide moieties on a surface. They have similar XPS binding 

energies and similar surface wetting properties, with no distinctive 

features in the routine FTIR window (4000-1500 cm-1 ). Therefore, 

we also developed (and report herein) a method for distinguishing 

and quantifying thiol and disulfide surface functionality on a 

monolayer array. Our analysis is based on the reaction with 

2,4-dinitrofluorobenzene (DNFB, Sanger’s reagent). This reagent 

readily reacts with thiol-SAMs (but does not react with disulfides) 

to form stable derivatives with distinctive IR, UV, and XPS 

signatures. 



s1211 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 9 7 

SeLf-ASSeMBLed CoMPLexeS of quAntuM dotS 

And AnthrACene derivAteS 

t. AveLLini 1 , M. AMeLiA 1 , S. SiLvi 1 , A. Credi 1 



Inorganic semiconductor nanocrystals known as quantum 

dots (QDs), owing to their peculiar photophysical properties, are 

emerging nanostructured materials that could find applications 

ranging from solar energy conversion to diagnostics and medicine. 

The particular property of these nanomaterials is their narrow 

emission band whose maximum wavelength can be precisely 

tuned by controlling the size of the nanocrystal. [1] Moreover, the 

broad absorption band in the UV-visible region, high absorption 

coefficient and high luminescence quantum yield, enable 

measurements of luminescence signal in extreme dilute 

conditions. 

In this study we investigate the possibility of controlling and 

implementing specific physico-chemical properties by chemical 

functionalization of the QD surface. The surface of the 

nanocrystals can be decorated with organic molecules, via either 

covalent or non-covalent interactions. Based on previous work [2] 

we studied the association process of CdSe/ZnS core/shell QDs 

with an aminoanthracene derivative and with the corresponding 

ammonium species, which can be obtained by protonation of the 

former with an acid in solution. Our results show that both the 

QD luminescence and the anthracene fluorescence are quenched; 

moreover the emission intensity of the QD can be modulated by 

controlling the protonation state of the molecular species. This 

system could therefore be used as a luminescent pH sensor. 

references: 

1. Semiconductor Nanocrystal Quantum Dot-Synthesis, 

Assembly, Spectroscopy and Applications, A. L. Rogach, 

Ed. Springer-Verlag, Wien, 2008. 

2. Gadenne B., Yildiz I., Amelia M., Ciesa F., Secchi A., 

Arduini A., Credi A., Raymo F. M. J. Mater. Chem., 2008, 

18, 2022. 

Keywords: Nanotechnology; Self-assembly; Luminescence; 

Quantum dots; 


P - 0 6 9 8 

PhotoinduCed MeMory effeCt in A redox 

ControLLABLe BiStABLe MeChAniCAL 

MoLeCuLAr SwitCh 

t. AveLLini 1 , A. CoSKun 2 , A. Credi 1 , S. SiLvi 1 , 

J. f. StoddArt 2 , M. venturi 1 



2 Northwestern University, Department of Chemistry, Evanston, 

USA 

A controllable molecular shuttle is a rotaxane that bears in 

the thread-like molecule (dumbbell) two or more units, whose 

affinity for the macrocycle can be tuned using external stimuli [1] . 

As result, the macrocycle can shuttle along the dumbbell. 

In this work we present a study on a bistable molecular 

shuttle composed of cyclobis(paraquat-p-phenylene) (CBPQT, the 

ring) and a dumbbell-shaped molecule containing three functional 

unit: 1) a tetrathiafulvalene (TTF), 2) a dioxynaphtalene moiety 

(DNP) and 3) an azobenzene unit (AZO). TTF and DNP are two 

electron-donor units, that interact with the electron-acceptor 

CBPQT. AZO is a photocromic molecule that can be reversibly 

photoisomerized from its stable trans form to the metastable cis 

form. Initially the CBPQT is positioned on the TTF unit. After 

oxidation of the TTF unit, the CBPQT shuttles from TTF to the 

DNP unit across the trans-AZO. Upon UV irradiation, the AZO 

unit isomerizes from trans to cis. Reduction of the TTF + unit 

restores the initial situation under the electronic viewpoint but not 

for the conformational aspect: the rotaxane is locked in a 

metastable state where the CBPQT is forced to interact with DNP. 

The initial conformation is restored upon the thermal or 

photochemical trans to cisconversion of the AZO unit. Here we 

demonstrate the possibility to lock more than 50% of the rotaxane 

molecule in the metastable state [2] . This rotaxane is an example of 

flash memory where the written information is not erased after 

the removal of the writing stimulus. 

references: 

1. Balzani, V.; Credi, A.; Venturi M. Molecular Devices and 

Machines – Concepts and Perspectives for the Nano 

World, Wiley-VCH, Weinheim, 2008. 

2. Avellini, T.; Li H., Coskun, A., Barin, G.; Trabolsi, A.; 

Basuray, A.N.; Dey, S.K.; Credi, A.; Silvi, S.; Stoddart, J.F.; 

Venturi, M., Angew. Chem. Int. Ed, 2012, 51, 1611–1615 

Keywords: Rotaxanes; Molecular devices; Azo compounds; 

Nanotechnology; Supramolecular chemistry; 



s1212 

chem. Listy 106, s257–s1425 (2012) 


P - 0 6 9 9 

donor-ACCePtor PAirS inCorPorAted in new 

hyBrid MeSoPorouS SiLiCA nAnoPArtiCLeS 

for SoLAr CeLLS 

C. BALeizAo 1 , M. SouSA 1 , M. de MiGueL 2 , 

h. GArCiA 2 

1 Instituto Superior Técnico, Centro de Química-Física 

Molecular, LISBOA, Portugal 

2 Universidad Politecnica de Valencia, Chemistry Department 

and ITQ-CSIC, Valencia, Spain 

The morphology of the active layer in organic solar cells 

based on conjugated and small molecules (fullerenes or 

perylenediimides) plays a crucial role on the overall efficiency of 

the device. The poor compatibility between the two components, 

the nature of the solvent, and the conditions of wet-processing 

deposition lead to phase segregation with concomitant losses of 

energy, reductions on charge mobility transport and increase of 

the recombination process [1] . 

Mesoporous silica nanoparticles (MSNs) [2] with well-defined 

and controllable particle morphology are exceptional supports for 

molecules and polymers that have a tendency to aggregate or 

forming dimers with less desirable properties. Molecules with two 

or more trialkoxysilane groups can be incorporated in the silica 

framework during the synthesis of the nanoparticles, and the pore 

(after template removal) can accommodate polymers or other 

molecules. 

The use of MSNs to incorporate donors and acceptors 

entities will maximize the interfacial area and the donor:acceptor 

contact increasing the active volume, and isolate the polymer 

chains into nanoscale domains leading to a confinement effect. 

This will control the phase segregation and minimize the 

recombination process, and improving charge separation and 

increase carrier’s mobility. 

Herein we present the preparation and photochemical 

characterization of hybrid MSNs incorporating perylenediimide 

derivatives in the walls and conjugated polymers on the pores. 

The photochemical and photophysical properties of these 

materials will give an indication about the most promising 

material for solar cells. 

Acknowledgements: This work was supported by Fundacio 

para a Ciencia e a Tecnologia (FCT-Portugal) and COMPETE 

(FEDER) within project PTDC/CTM/101627/2008. 

references: 

1. G. Dennler, N. S. Sariciftci, C. J. Brabec, in Semiconducting 

Polymers: Chemistry, Physics and Engineering, 

G. Hadziioannou, G. G. Malliaras (Eds.), Weinheim, 

Wiley-VCH, 2006, 455. 

2. I. I. Slowing, J. L. Vivero-Escoto, B. G. Trewyn, 

V. S.-Y. Lin, J. Mater. Chem., 2010, 20, 7924. 

Keywords: perylenediimides; Mesoporous silica nanoparticles; 

Pedot; solar cells; Donor-Acceptor pairs; 


P - 0 7 0 0 

dynAMiC AnALyte reCoGnition By ArtifiCiAL 

SynthetiC veSiCLeS 

S. BALK 1 

1 Institute of Organic Chemistry, Prof. Dr. Burkhard Koenig, 


Mimicking recognition processes at natural cell membranes 

we recently reported synthetic vesicles with multi-receptor 

surfaces as chemo sensors for small biomolecules. [1] Functional 

phospholipid-based membranes are used for optical sensing by 

fluorescent labelling of embedded molecules. [2] 

To understand the physical interactions of vesicular 

anchored receptors we developed a simple model system for the 

dynamic recognition: multivalent target molecules spatially 

rearrange multiple membrane-embedded receptors equipped with 

FRET labels. These liposomal tethered amphiphiles are assumed 

to form patches and approximate with the addition of a binding 

partner to give a typical FRET response. 

The influence of analyte binding towards the FRET signal 

was investigated by emission titrations. The investigation of these 

dynamic interactions is part of an approach towards imprinted 

vesicles as soft nanoparticles with ordered surfaces that perfectly 

match a templating target molecule. 

references: 

1. B. Gruber, S. Stadlbauer, K. Woinaroschy, B. König, Org. 

Biomol. Chem., 2010, 8, 3704-3714. 

2. B. Gruber, S. Stadlbauer, A. Späth, S. Weiss, M. Kalinina, 

B. König, Ang. Chem. Int. Ed. 2010, 49, 7125. 



s1213 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 0 1 

CMoS-CoMPAtiBLe LoCALized Growth And 

inteGrAtion of SeMiConduCtinG nAnowireS 

S. BArth 1 , r. JiMenez-diAz 2 , J. SAMA 2 , 

A. roMAno-rodriGuez 2 



2 University of Barcelona, Departament d’Electronica, 


In recent years, one-dimensional semiconductor 

nanostructures with tunable morphologies, dimensions, 

crystallographic phases, and orientations have gained tremendous 

attention due to their vast number of applications, including 

electronics, sensing, energy harvesting, etc... Several techniques 

have been successfully employed for the growth of high quality 

semiconducting nanowires [1] ; however, most of the processes 

using metal supported methodologies require high temperatures 

of an entire substrate for an effective formation of single 

crystalline nanowires. 

In this study, we used micromembranes and microhotplates 

for the localized growth of high quality semiconducting 

nanowires, including Ge, SnO and In O , via LPCVD techniques 

2 2 3 

employing molecular sources. The heated areas were the range of 

several hundreds of square microns allowing a site-specific 

formation of nanowires. Key features of such microsystems are 

extremely fast cooling and heating processes due to their low mass 

and low power consumption. The growing nanowire bundles 

bridge the gap between a set of interdigital electrodes located on 

top of the heated membranes und thus leading to in situ contact 

formation. This approach allows us to perform heating and 

measuring operations independently, which is mandatory for 

thermally supported devices such as metal oxide gas sensors. [2] 

To the best of our knowledge, this is the first report for the growth 

of these materials using such a technique. Additional advantages 

include the possibility to grow various types of nanowires on the 

same chip using multiple micromembranes or microhotplates and 

the in situ contact formation replacing cost and time consuming 

procedures. The presented data will demonstrate the enormous 

potential of this approach for the fabrication of novel 

nanostructure-based devices. 

references: 

1. S. Barth, F. Hernandez-Ramirez, J. D. Holmes, A. 

Romano-Rodriguez. Prog. Mater. Sci. 2010, 55, 563. 

2. S. Barth, R. Jimenez-Diaz, J. Sama, J. D. Prades, I. Gracia, 

J. Santander, C. Cane, A. Romano-Rodriguez. 

Chem. Commun. 2012, 48, 4734. 

Keywords: Chemical vapor deposition; Nanostructures; 

Nanotechnology; Sensors; 


P - 0 7 0 2 


Sio -SuPPorted fe/Co nAnoPArtiCLeS 

2 

S. BehnAM 1 , M. feyzi 1 , S. nAdri 1 , M. JoShAGhAni 1 , 

e. rAfiee 1 


Introduction of cheap, efficient and selective catalysts for 

production of fuels and heavier hydrocarbons from lighter ones 

is of great challenge in refineries and petrochemical industries [1] . 

Both Fe- and Co-based catalysts individually have advantages and 

disadvantages properties [2] . Therefore effort to couple them in the 

hope to bring forth a more efficient catalyst having parents’ 

advantages is of great importance. Herein, a series of cobalt-iron 

nanocatalysts were prepared using some wet chemically methods 

and were characterized using thermal analysis (TGA/DSC), N2 physisorption measurements such as BET, BJH, DH methods and 

X-ray diffraction (XRD) techniques. The average sizes of 

crystallites were determined below 100 nm from the half-width 

of the most intense peak of the diffraction pattern using the 

Scherrer equation. The crystallite sizes of catalysts were decreased 

with increasing SiO content which clearly confirm. The 

2 

Brunauer-Emmett-Teller surface area (BET SA) measures of the 

products show also that the increase of SiO ratio results in an 

2 

increase in the catalyst surface area linearly In the other hand, the 

pore volume increases with increasing of SiO ratio to reach a 

2 

maximum at 50% SiO , and then decreases with further increasing 

2 

of SiO ratio. 2 

references: 

1. A. Y. Khodakov, W. Chu, P. Fongarland, Chem. Rev. 107 

(2007) 1692. 

2. R. M. Malek Abbaslou, A. Tavassoli, J. Soltan, 

A. K. Dalai, Appl. Catal. A: Gen 367 (2009) 47. 

Keywords: X-ray diffraction; Iron; Cobalt; Sol-Gel Process; 



s1214 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 0 3 

ru(ii) CoMPLexeS enCAPSuLAtion in 

BioCoMPAtiBLe PLGA nAnoPArtiCLeS 

– ChArACterizAtionS And PotentiALitieS in 

two-Photon-PhotodynAMiC therAPy 

G. Boeuf 1 , J. MoreAu 1 , G. rouLLin 1 , S. duKiC 2 , 

L. vAn GuLiCK 2 , C. terryn 3 , v. GAfA 4 , f. ChuBuru 5 , 

M. MoLinAri 6 , G. LeMerCier 5 

1 ICMR UMR 7312, Chemistry, Reims, France 

2 UMR 6237, Pharmacology, Reims, France 

3 IFR53, Imaging platform, Reims, France 

4 EA4303, Immunology, Reims, France 

5 ICMR UMR 7312, Chemistry, Reims, France 

6 LRN EA4682, Physics, Reims, France 

Interest for nanoparticles in medicine (nanomedicine) was 

increasing the last ten years and especially as multifonctionnal 

compounds for imaging, diagnosis, and therapy. In this field, our 

team is engaged in the encapsulation of new coordination complex 

within biocompatible and biodegradable nanoparticles based on 

a co-polymer (PLGA) for applications in imaging, such as 

magnetic resonance imaging (MRI), or luminescence, and 

photodynamic therapy (PDT). In this context, the development of 

new Ru(II) complexes involving 1,10-phenanthroline-based 

ligands are developed. These compounds possess a wide 1MLCTtype 

absorption band around 450 nm, which makes them good 

candidates as sensitizers for the local photo-generation of 

cytotoxic singlet dioxygen1O2. Moreover, their third order 

nonlinear optical properties can be used in a two-photon 

absorption process. The optical properties and the potential in 

PDT (and two-photon-PDT, TP-PDT) of two ruthenium 

complexes (with different hydrophilic characteristics) and the 

related metalled nanoparticles [Ru]@PLGA are described and 

commented. 

Keywords: Ru(II) complexes; photodynamic therapy; 

nanoparticles; two-photon absorption; plga; 


P - 0 7 0 4 

dendritiC PoLyAriLSiLAneS AS effeCtive 

nAnoStruCtured LuMinoPhoreS 

o. BorShChev 1 , y. LuPonoSov 1 , M. PoLinSKAyA 1 , 

n. Surin 2 , S. PonoMArenKo 1 

1 Institute of Synthetic Polymeric Materials Russian Academy of 

Sciences, Laboratory of Functional Materials for Organic 

Electronics and Photonics, Moscow, Russia 


Sciences, Laboratory of termostable plastics, Moscow, Russia 

During the last years the number of light-harvesting 

luminescent dendrimers has increased rapidly. One of the most 

interesting features of dendrimers is a possibility of incorporation 

of different chromophores within one dendritic molecule that can 

lead to an intramolecular directional energy transfer from their 

peripheries to the centre (a molecular antenna effect). It allows 

tuning the emission color of the core across the entire visible 

spectrum, which provides an efficient tool for controlling a 

wavelength of light emission in organic photonic and electronic 

devices. Light-harvesting antennas are essential for natural 

photosynthetic processes and currently attracting much attention. 

Up to now different organic dendritic structures have been 

reported to show the antenna effect, but there are no organosilicon 

molecules among them, that is, containing thiophene and silicon 

units. It was recently shown that silicon atoms break the 

conjugation as well as increase the luminescence efficiency in 

bithiophenesilane dendrimers. In this work we report the synthesis 

and investigation of the organosilicone molecular antennas based 

on new oligoarylsilane compounds with different branching 

topology: dendrimers and “butterfly”-like molecules. 

Photoluminescence study of the new molecules has shown an 

intramolecular energy transfer with the efficiency up to 99% and 

luminescence quantum yield up to 87%. 

We applied these molecular antennas as spectral shifters in 

new highly effective plastic scintillators (radiation detectors). 

Since two different luminophores are fixed properly on the 

nanoscale distance at the same branching molecule, both the light 

output and the attenuation length of the plastic scintillators 

significantly increase. This lead to a new type of scintillating 

devices with nanostructured luminophores. 

Acknowledgement: This work was supported by Foundation of 

President of the Russian Federation (project MK 1528.2011.3) 

and Presidium of Russian Academy of Sciences 

(Program No. 24) 

Keywords: Dendrimers; Luminescence; Energy transfer; 

Nanostructures; Sensors; 



s1215 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 0 5 

nAnoAdheSion And nAnofriCtion SurfACe 

ProPertieS of BioPoLyMerS fiLMS 

M. BroGLy 1 , A. fAhS 1 , S. BiStAC 1 

1 Université de Haute Alsace, LPIM - Equipe CPCP, Mulhouse 

cedex, France 

Hydroxypropyl methylcellulose (HPMC) constitutes one of 

the most dedicated polymers used in the production of film 

coatings for pharmaceutical applications (capsules, tablets, … 

).This study represents an attempt to assess adhesion and friction 

properties of such biopolymers at the nanoscale using the atomic 

force microscopy (AFM). Hydroxypropyl methylcellulose 

(HPMC) is a very important hydrophilic biopolymer for the 

preparation of oral controlled drug delivery systems due to its high 

swellability characteristic and film forming properties. Additives 

such as plasticizers, surfactants, lipids, colorants or other filmforming 

polymers are frequently incorporated into biopolymer 

matrices to produce high quality drug protective films and to 

control the surface sliding and adhesion properties. However, 

these additives do not affect only the bulk physicochemical 

properties of films, they also affect the surface properties. We 

point out the advantage of AFM and chemical force microscopy 

(CFM), based on force curve experiments, in the quantitative 

determination of the surface thermodynamic properties of 

biopolymer films, such as surface energy and thermodynamic 

work of adhesion. The study also concerns the interplay between 

nanoadhesion and nanofriction. The study investigates the 

influence of an hydrophilic plasticizer (polyol) and an 

hydrophobic excipient (fatty acid) on the surface properties of 

hydroxypropylmethylcellulose (HPMC) films. On the basis of 

original atomic force microscopy (AFM) experiments, interplay 

between nanoadhesion and nanofriction are detailed. The results 

clearly underline the strong dependence of film properties on 

additive nature, concentration or water sensitivity and the 

interplay with additive-biopolymer matrix compatibility. It also 

shows that first the HPMC-additive compatibility seems to be an 

interesting factor behind the variation of surface properties of 

HPMC formulated films, and second that formulation is an 

effective way to tune surface and nanoscale properties of HPMC 

biopolymer films. 

Keywords: Biopolymer; Atomic force microscopy (AFM); 

Nano-adhesion; Nano-friction; Cellulose-based polymer; 


P - 0 7 0 6 

the reLAtionShiP Between the Ph induCed 

CoLor And ConforMAtionAL ChAnGeS in 

yeASt CytoChroMe C CoAted GoLd 

nAnoPArtiCLeS 

C. e. Brown 1 , S. BAi 1 , A. donG 1 

1 University of Northern Colorado, Chemistry and Biochemistry, 

Greeley, USA 

The uses of protein-coated metallic nanoparticles including 

gold as potential colorimetric biosensors and drug delivery 

vehicles have been studied extensively. A potential biosensor 

application for detecting protein folding/unfolding is yeast 

cytochrome c-coated gold nanoparticles. It was reported (Chah et 

al., Chem. Biol., 12, 323-328, 2005) cytochrome c-coated gold 

nanoparticles can be potentially used as a colorimetric biosensor 

for detecting acid-induced unfolding of cytochrome c, based on 

the observation of color changes associated with changes in pH, 

from neutral to acidic during this pH change; the color of a 

cytochrome c-coated gold nanoparticle suspension changes from 

red to blue and to clear. 

In the present study, we comparatively analyzed the 

secondary structure of cytochrome c coated on different sizes of 

gold nanoparticles (13 nm and 19nm), and the unfolding at 

various pH conditions by FT-IR spectroscopy. The results of 

secondary structural analysis revealed that although the color 

changes coincided with the decrease in pH, as reported previously, 

this event is unrelated to the true acid-induced unfolding of the 

protein. The binding of cytochrome c to gold nanoparticles 

induces partial unfolding of the protein event at neutral pH 

condition. However, the unfolding of the protein does increase as 

pH decreases. The color changes are more related to the changes 

in sizes of gold nanoparticles due to aggregation than the 

acid-induced unfolding. By inserting a short linker molecule 

thiopropanonic (HOOC(CH ) SH) between cytochrome c and 

2 2 

gold nanoparticles (13 nm), the secondary structure of cytochrome 

c remains native at similar acidic conditions. 

Keywords: nanoparticles; cytochrome c; pH induced changes; 



s1216 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 0 7 

AMino funCtionALized iMidAzoLiuM SALtS: 

duAL roLe PLAyerS in orGAnoMetALLiC 

CheMiStry And nAnoSCienCe 

M. C. CASSAni 1 , B. BALLArin 1 , S. orLAnduCCi 2 

1 Universita di Bologna, Chimica Fisica ed Inorganica, 


2 Universita di Roma Tor Vergata, Scienze e Tecnologie 

Chimiche, Roma, Italy 

Imidazolium salts incorporating functional groups on the 

cation and/or anion, represent a class of compounds having great 

versatility due to their applications as ionic liquids (ILs) or 

N-heterocyclic carbene precursors (NHCs). Our research in this 

field has been dealing with the synthesis of (Boc)-protected and 

deprotected amino-functionalized imidazolium cations 

[NHR1CH CH imR 2 2 2 ] + ([1] + , R1 = Boc, H; R2 = Me, Bz, Trit) and 

related NHC-Ag(I) and Rh(I) complexes. 1 We have also 

demonstrated that [NH CH CH imMe] 2 2 2 + plays a dual role in gold 

chemistry: i) can give the gold(III)-aminoethyl imidazolium 

aurate salt [Cl AuNH (CH ) imMe)][AuCl ] (2) used in the 

3 2 2 2 4 

preparation of catalytically active gold nanoparticle-containing 

polycarbonate membranes or ITO glasses; 2 ii) can act as a primary 

amino-functionalized NHC precursor to give the dimeric, 

photoluminescent complex [Au (NH (CH ) imMe) ][NO ] (3). 2 2 2 2 2 3 2 3 

We now present some very recent results of a research 

focused on the preparation of detonation nanodiamond(ND)/AuNPs hybrid materials. Two different experimental routes are followed 

for the decoration of ND by Au , that are in turn prepared by an 

NPs 

innovative electroless approach using the gold complex 2. 

Structure and morphology at the nanoscale level of the 

Au -on-ND deposits have been deeply investigated by electron 

NPs 

microscopy (FE-SEM, HR-TEM) and diffraction (XRD) 

techniques. The optical properties of these systems have been 

determined by performing scattering and UV-Vis absorption 

measurements and by comparing the experimental data with 

simulated extinction spectra. The preliminary results of the 

present research establish the first rules for future designs of more 

complex Au /ND systems. 

NPs 

references: 

1. L. Busetto, M. C. Cassani, C. Femoni, M. Mancinelli, 

A. Mazzanti, R. Mazzoni, G. Solinas, Organometallics, 

30, 2011, 5258. 

2. B. Ballarin, M.C. Cassani, D. Tonelli, E. Boanini, 

S. Albonetti, M. Blosi, M. Gazzano, J. Phys. Chem. C, 

114, 2010,9693. 

3. B. Ballarin, L. Busetto, M. C. Cassani, C. Femoni, 

A. M. Ferrari, I. Miletto, G. Caputo, Dalton, 41, 2012, 2445. 

Keywords: Ionic liquids; Carbene ligands; Gold; Carbon; 

Nanostructures; 


P - 0 7 0 8 

ChirAL PorPhyrin J-AGGreGAteS induCed By 

tArtAriC ACid 

M. A. CAStriCiAno 1 , A. roMeo 2 , r. zAGAMi 2 , 

i. oCChiuto 2 , n. MiCALi 3 , L. MonSu SCoLAro 2 

1 CNR, ISMN, Messina, Italy 

2 University of Messina, Dipartimento di Chimica Inorganica 

Chimica Analitica e Chimica Fisica, Messina, Italy 

3 CNR, IPCF, Messina, Italy 

Chirality expression in supramolecular assemblies is a very 

fascinating topic due to its close relationship with biological 

systems and the origin of life itself. Organization at higher levels 

is extremely intriguing in the case of achiral molecules that 

self-assemble in the presence of a chiral bias to afford chiral 

supramolecular complex structures. Chiral J-aggregates of the 

achiral TPPS porphyrin represent a nice example that recently is 

4 

gaining attention for their peculiar optical and structural features. 

The use of optically active tartaric acid as chiral inducer has been 

reported as the first example of organic aggregates showing 

magneto-chiral dichroism. [1] As part of our interest, we have also 

shown an interesting structural transition from fractal to rod-like 

aggregates, that depends on the porphyrin concentration and the 

ionic strength and that is responsible for a peculiar inversion of 

the circular dichroism spectra with the same templating 

enantiomer. [2] Chiral porphyrin nanoaggregates have been 

confined into microemulsions water pools achieving a remarkable 

scaling of the quality of the circular dichroism signal on the 

dimension from the nano- up to mesoscopic regime. [3] Here we 

report on the chiral induction mediated by D- and L- tartaric acid 

in bulk aqueous solutions. The kinetics of growth for chiral TPPS4 J-aggregates induced by tartaric acid have been investigated under 

different experimental conditions. [4] We anticipate that, depending 

on the overall rate of the process, a distinctive kinetic difference, 

together with a variance in the extent of the chiral transfer, is 

clearly evident for the two enantiomeric. 

references: 

1. Y. Kitagawa, et a. Angew. Chem. Int. Ed. 2011, 50, 9133. 

2. N. Micali, et al. J.Phys. Chem. B 2006, 110, 8289. 

3. M. A. Castriciano, et al. J. Am. Chem. Soc. 2011, 133, 765. 

4. M. A. Castriciano, et al. Chem. Commun. 2012, 48, 4872. 

Keywords: Aggregation; Kinetics; self-assembly; 

supramolecular chemistry; circular dichroism; 



s1217 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 0 9 

PoLyoxoMetALAte riCh thin fiLMS with 

ControLLed StruCture And funCtion for 

deSiGner eLeCtroniCS 

S. CAtALdo 1 , v. fiGo 1 , B. PiGnAtAro 1 , 

P. MoLinA SAnChez 2 , L. Cronin 2 

1 University of Palermo, Department of Chemistry “S. Cannizzaro”, 

Palermo, Italy 


Kingdom 

During the last two decades, polyoxometalates (POMs) have 

attracted growing attention due to their potential application as 

functional materials potentially enabling new device design and 

opening new areas of technology. POMs are metal-oxide clusters 

of early transition metals Mo, W, V, etc with a diverse range of 

structures and properties, such as reversible electrical 

capacitance, [1] programmable surface 0D, 2D or 3D structure [2] 

which could together be of potential application in 

ultra-high-density data storage, [3, 5] catalysis [4] and also in 

medicine as antiviral drugs. [5] In the present work, we show 

that it is possible to assemble structured thin-films by the 

self-assembly/organization of different POMs (Mo96- and 

V16-clusters, TRIS-Mn-Anderson and Mn-Dawson types) onto 

solid supports via electrochemical co-deposition or by preparing 

multi-planar heterojunction structures with polymers via 

Langmuir-Schaefer deposition. In the framework of nanoscale 

organic/hybrid electronics we show here the relationships between 

the thin film structure and electrochromic or smart dielectric 

properties. 

references: 

1. C. Musumeci, M. H. Rosnes, F. Giannazzo, M. D. Symes, 

L. Cronin and B. Pignataro, Acs Nano 2011, 5, 9992-9999. 

2. a) C. Musumeci, A. Luzio, C. P. Pradeep, H. N. Miras, 

M. H. Rosnes, Y.-F. Song, D.-L. Long, L. Cronin and 

B. Pignataro, Journal of Physical Chemistry C 2011, 

115, 4446-4455; 

b) M. H. Rosnes, C. Musumeci, C. P. Pradeep, 

J. S. Mathieson, D.-L. Long, Y.-F. Song, B. Pignataro, 

R. Cogdell and L. Cronin, Journal of the American 


3. A. Müller, F. Peters, M. T. Pope and D. Gatteschi, 

Chemical Reviews 1998, 98, 239-272. 

4. Y. V. Geletii, B. Botar, P. Kögerler, D. A. Hillesheim, 

D. G. Musaev and C. L. Hill, Angewandte Chemie 

International Edition 2008, 47, 3896-3899. 

5. J. T. Rhule, C. L. Hill, D. A. Judd and R. F. Schinazi, 

Chemical Reviews 1998, 98, 327-358. 

Keywords: Nanotechnolgy; Thin Films; Electrochemistry; 

Material Science; Self-Assembly; 

P - 0 7 1 0 

SyntheSiS of MonodiSPerSe CuSio3 hierArChiCAL hoLLow SPhereS (hhSS) And 

their SuBSequent ConverSion to Cu n/Sio 3 2 

And CuS/Sio hyBrid hhSS 

2 

r. deShMuKh 1 , u. SChuBert 1 



Monodisperse hollow spheres are of great interest due to 

their characteristic shape, well-controlled size, high surface area 

and large void space, which makes them potential candidate for 

various technological applications. Inorganic silica-based 

composite materials having structural features in the nanometer 

regime are an important class of hybrid materials. The chemical 

inertness, high temperature stability and biocompatibility are 

important features of silica which makes them ideal constituent 

of nanocomposites. Exploring new morphologies of metal nitride 

and metal sulphide based nanomaterials, may deliver new or 

improved physical and chemical properties to meet the demands 

of future advanced functional materials. 

CuSiO HHSs were synthesized under hydrothermal 

3 

conditions using monodispersed Stöber silica spheres as a 

chemical template [1] . A subsequent thermal treatment under 

ammonia atmosphere allowed formation of Cu N/SiO hybrid 

3 2 

HHSs. Furthermore, room temperature sulphidation reaction of 

CuSiO 3 


. H2 O HHSs with aqueous (NH 4 ) 2 S gave CuS/SiO 2 hybrid 

HHSs. The Cu N/SiO and CuS/SiO hybrid HHSs were 

3 2 2 

characterized by X-ray diffraction, transmission electron 

microscopy and energy-dispersive X-ray spectroscopy analysis. 

. The morphology of CuSiO H2O HHSs is well kept after 

3 

nitridation and sulphidation reactions. The use of Stöber silica 

spheres as a chemical template appears to be a simple way to 

accomplish synthesis of monodisperse Cu N/SiO and CuS/SiO 3 2 2 

hybrid HHSs. 

references: 

1. Y. Wang, G. Wang, H. Wang, W. Cai and L. Zhang, Chem. 

Comm., 2008, 48, 6555-6557. 

Keywords: Nanostructures; Silicates; Nitrides; 



s1218 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 1 1 

PrePArAtion of SuPrAMoLeCuLAr networKS 

uSinG LAnGMuir-BLodGett teChniqueS 

M. dudiC 1 , J. PerMAn 1 , M. CiPoLLoni 1 , J. MiChL 1 


Organic Chemistry and Biochemistry, Prague 6, 


The liquid-air interface is an ideal environment for the 

preparation of monolayer regular grids using supramolecular 

(non-covalent) interactions that permit self-correction of errors. 

Connector molecules with polygonal shapes are deposited 

on the liquid surface and compressed to a desired area per 

molecule using a Langmuir-Blodgett trough, permitting 

hydrogen-bonding or metal ion-ligand interactions to occur. 

Hydrogen-bonded monolayers of the annulene derivative 

2,2',2''-(1,3,8,10,15,17-Hexaoxo-5,6,12,13,19,20-hexadehydro- 

-8,10,15,17-tetrahydro-1H-cyclododeca[1,12-f:4,5-f’:8,9-f’’]- 

-triisoindole-2,9,16(3H)-triyl)triacetic Acid [1] were formed 

spontaneously and were subsequently transferred onto various 

substrates and examined using UV/Vis, IR and STM techniques. 





supported by the Academy of Sciences of the Czech Republic 

RVO: 61388963. 

references: 

1. Dudic, M.; Císarová, I.; Michl, J. J. Org. Chem. 2012, 77, 68. 

Keywords: Supramolecular; Monolayer; Langmuir-Blodgett; 


P - 0 7 1 2 

inveStiGAtionS of nAnoSCALe CArBAzoLe 

BASed ArChiteCtureS 

t. eAton 1 , M. MAyor 1 


Switzerland 

Massive fully conjugated cyclic π-systems are expected to 

show unique optical and magnetic properties, especially when the 

induced electronic coupling through the cycle is particularly 

strong. [1] Cyclic forms of linear chains can show marked 

differences in their photo-physical properties. [2] Carbazoles in 

particular are highly luminescent and as they are strong hole 

transporters, they are widely applied in opto-electronic devices 

and as such should prove ideal candidates for study. However 

carbazole based macrocycles reported to date lack efficient 

π-conjugation throughout their entire backbone. 

Here we present the synthesis and physical investigations of 

model systems that maximise the conjugation in carbazole 

oligo-phenyl-ethylene rods and cycles. After establishing new 

synthetic routes towards carbazole based oligomers, we present a 

26 step, template directed synthesis of a fully conjugated 7 nm 

diameter carbazole based macrocycle. A range of polar, 

orthogonal acetylene protecting groups were employed to 

assemble the macrocyclic structure via palladium catalysed crosscoupling 

reactions. [3] The carbazole moieties allow insertion of a 

semi-rigid template, facilitating an efficient cyclisation. 

While studying the effect of substituent architecture and 

push-pull substituents in carbazoles we confirmed that 

2,7-substituted carbazoles show considerably enhanced 

conjugation over other substitution patterns. Photo-luminescent 

studies showed that a bathochromic shift in absorption of the 

carbazole band of over 100 nm could be achieved in the monomer 

unit. Aggregation of short chain 9-substiuted carbazole could be 

studied by NMR, while further altering the 9-position lead to 

liquid crystalline behaviour. 

references: 

1. M. Mayor and C. Didschies, Angew. Chem. Int. Ed., 2003, 

42, 3176–3179. 

2. J. K. Sprafke et al., J. Am. Chem. Soc., 2011, 133, 

17262–17273. 

3. N. Jenny, M. Mayor, T. R. Eaton, Eur. J. Org. Chem., 

2011, 4965–4983. 

Keywords: Alkynes; C-C Coupling; Donor-acceptor systems; 

Macrocycles; Supramolecular chemistry; 



s1219 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 1 3 

the PeCuLiAritieS of Me/nAnodiAMond 

CAtALyStS in ethAnoL SteAM reforMinG for 

Co-free hydroGen ProduCtion 

M. erMiLovA 1 , e. MironovA 1 , n. oreKhovA 1 , 

A. yAroSLAvtSev 1 , M. efiMov 2 , L. zeMtSov 2 , 

G. KArPAChevA 2 


Laboratory of Membrane Catalysis, Moscow, Russia 


Laboratory of Polyconjugated Systems, Moscow, Russia 

The study of ethanol steam reforming (ESR) in catalytic 

membrane reactors now attracts a great interest due to the 

possibility of manufacture of ultra pure hydrogen from accessible 

and renewable sources. The variety of heterogeneous catalysts of 

this process was offered, e.g., Rh, Ru, Pd, Pt and Ni on oxide 

supports. The problem of such systems is the catalyst deactivation 

because of carbon deposit formation during the process. The new 

carbon materials as catalyst’s support may solve this problem due 

to their resistance to carbonization, high specific area and stability. 

Thus, nanodiamonds, produced by detonation synthesis (DND), 

are promising supports for platinum group catalysts due to similar 

lattice types of diamond and platinum metals and facilitated 

adhesion of the active metal to the surface of DND particles. 

In this study the new catalysts of ESR were developed 

presenting Pt, Ru, Ni, Pt-Ni and Pt-Ru nanoparticles, supported 

on DND and prepared by IR-pyrolysis of precursors, based on 

metal salts and DND particles. The structure, phase content and 

morphology of obtained catalysts were determined by XRD, 

IR-spectroscopy and TEM. 

ESR on powder metal-DND catalysts was carried out in 

conventional tube reactor (TR) at the temperatures from 300 to 

550°C and the various water/alcohol ratios. The catalysts studied 

demonstrated high hydrogen productivity and stable activity 

during experimental tests. The individual Pt-, Ru- and Ni/DND 

catalysts had shown lower activity than bimetallic Pt-Ru/DND 

and Pt-Ni/DND catalysts. The highest hydrogen productivity and 

the lowest CO yield were observed on the Pt-Ru/DND catalyst. 

ESR was carried out also in a plug flow membrane reactor 

with catalyst’s fixed bed (MR) and membrane of Pd-Ru foil. 

Up to 18.2 mmol/g cat·h of ultra pure hydrogen was produced in 

MR with Pt-Ru /DND catalyst at the hydrogen recovery of 60%. 

Keywords: nanodiamond; catalyst; ethanol; reforming; 

membrane reactor; 


P - 0 7 1 4 

PrePArAtion of re-CryStALLized SiLver 

nAnoPArtiCLeS viA hiGhLy ConCentrAted 

nACL SoLution for SurfACe enhAnCed rAMAn 

SPeCtroSCoPy 

A. fArGASovA 1 , r. PruCeK 1 , A. PAnACeK 1 , v. rAnC 2 , 

v. MASeK 3 , L. KviteK 1 , r. zBoriL 1 

1 Palacky University in Olomouc, Regional Centre of Advanced 

Technologies and Materials and Department of Physical 




3 Palacky University in Olomouc, Department of Pharmacology, 


Since Fleishman’s discovery in 1974 and Creighton 

rediscovery in 1977, surface enhanced Raman spectroscopy 

(SERS) technique has gained broad focus from scientists. SERS 

is a powerful tool for the study of single molecules in 

concentrations reached up 8 x 10-14 M. It is known that silver 

nanoparticles due to their unique optical properties served as the 

commonly used enhancers of Raman signal. An enhancement 

effect depends on the size and morphology of silver nanoparticles. 

For the ordinarily used argon laser with an excitation wavelength 

of 514.5 nm was observed to the ‘hot particle size’ ranging from 

80 nm to 100 nm [1, 2] . 

This work presents the activation of silver nanoparticles for 

SERS measurements with excitation wavelengths both in the 

visible (488 nm) and near infrared region (1064 nm). The silver 

nanoparticles with an average particle size of 28 nm were 

synthesized by a reduction of silver ammonia complex by 

D-maltose and as activation agent of primary silver nanoparticles 

were used chloride anions with final concentrations of 400 mM. 

Particle size distribution measurements discover rapid 

recrystallization of primarily prepared silver nanoparticles to oneorder 

larger crystallites (400 nm) appearing during 15 minutes 

from the moment of NaCl addition. It was proved, that 

recrystallized silver nanoparticles are efficient enhancers of 

Raman signal of both visible (488 nm) and near infrared laser 

excitation (1064 nm) as was observed in the representative spectra 

of adenine. 

Acknowledgements: This work has been supported 

by the Operational Program Research and Development for 

Innovations - European Social Fund (CZ.1.05/2.1.00/03.0058), 

Czech Science Foundation (Project No. GAP304/10/1316), 

Operational Program Education for Competitiveness— 

European Social Fund (CZ.1.07/2.3.00/20.0056) and by 

internal grant of Palacky University in Olomouc 

(PrF_2012_028). 

references: 

1. Kneipp, K., Wang Y., Dasari R. R., Feld M. S.: Applied 

Spectroscopy 49, 780 (1995). 

2. Garrell R. L.: Analytical Chemistry 61, A401 (1989). 

Keywords: silver nanoparticles; Raman spectroscopy; 

aggregation; 



s1220 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 1 5 

StrAiGhtforwArd SyntheSiS of GoLd 

nAnoPArtiCLeS SuPPorted on CoMMerCiAL 

SiLiCA-PoLyetiLeniMine BeAdS And their 

CAtALytiC ACtivity 

S. fAzzini 1 , B. BALLArin 2 , M. C. CASSAni 2 , d. nAnni 3 , 

M. GiorGetti 2 , C. MACCAto 4 

1 Universita di Bologna, Chimica Organica A. Mangini, 


2 Universita di Bologna, Dipartimento Chimica Fisica ed 


3 Universita di Bologna, Dipartimento Chimica Organica A. 

Mangini, Bologna, Italy 

4 Universita di Padova, Dipartimento Scienze Chimiche, 

Padova, Italy 

Nanoscience and nanotechnology play an important role in 

the design of novel heterogeneous catalysts. [1] When the sizes of 

supported or unsupported metal particles are decreased down to 

a few nanometers, those metal nanoparticles (M ) may exhibit 

NPs 

unprecedented physicochemical and catalytic properties, not 

observed in bulk materials or large-sized particles. The 

nanoparticle sizes influence the surface-to-volume ratio and the 

surface energy of these materials, enabling to make them very 

active species in catalysis but, on the other hand, their stability 

decreases when they become prone to aggregation. To overcome 

this drawback, catalytic nanoparticles are hence usually 

immobilized on a suitable support material that also facilitates 

catalyst recycling. [2] 

This study entails the synthesis and characterization of 

supported gold nanoparticles (Au ) adsorbed on commercial 

NPs 

polyetilenimine-functionalized silica beads (SiO -PEI) exploitable 

2 

for heterogeneous catalysis. The Au /SiO -PEI catalysts were 

NPs 2 

prepared by in situ postdepositon reduction of HAuCl to Au(0) 

4 

by the PEI itself, without the need of neither external reducing 

nor stabilizing agents. [3] 

Six different types of Au /SiO -PEI were obtained and 

NPs 2 

fully characterized by UV-Vis-DRS, XRF, SEM-FEG, XANES 

and EXAFS, more over the catalytic activity was evaluated for 

the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) 

obtaining results in line with literature data. [4] 

references: 

1. a) D. Astruc, F. Lu, J. R. Aranzaes, Angew. Chem., Int. Ed. 

2005, 44, 7852; 

b) J. H. Graham, Chem. Commun., 2008, 1148; 

2. a) A. Corma, H. Garcia, Chem. Soc. Rev., 2008, 37, 2096; 

b) Ballarin B.; Cassani M.C; Tonelli, D.; Boanini E.; 

Albonetti S.; Blosi M.; Gazzano M. J. Phys. Chem, 

2010, 114, 9693. 

3. S. Fazzini, D. Nanni, B. Ballarin, M. C. Cassani, 

M. Giorgetti, C. Maccato, manuscript in preparation. 

4. K. Kuroda, T. Ishidaa, M. Haruta, J. Mol. Catal. A: 

Chemical, 2009, 298, 7. 

Keywords: gold; Nanoparticles; Heterogeneous catalysis; 

EXAFS spectroscopy; X-ray absorption spectroscopy; 


P - 0 7 1 6 

fLuorinAted orMoSiL nAnoCAPSuLeS AS 

veCtorS to AntituMor rutheniuM 

CoMPLexeS 

L. M. f. LoPeS 1 , L. M. iLhArCo 1 

1 Instituto Superior Técnico, Centro de Química-Física 


In the past decade, silica nanoparticles have attracted 

considerable attention for their potential biomedical applications, 

owing to their biocompatibility, good water solubility and easy 

surface chemical functionalization. Given the soft conditions and 

control of the porous structure offered by some fabrication 

methods, these particles have been explored as effective drug 

delivery systems for a variety of therapeutic agents and diagnosis 

probes, in particular for those involved on the fight against cancer. 

In this work, we report the fabrication of narrow dispersity 

organically modified hollow silica nanoparticles (nanocapsules) 

of ~60 nm of diameter and variable cavity size, synthesized at 

room temperature by combination of the sol-gel process and the 

water-in-oil emulsion technique, following different approaches. 

The nanocapsules were functionalized with a fluorinated silica 

precursor, in order to enhance their cellular uptake and to enable 

their use as contrast agent for 19F NMR imaging. 

The influence of some parameters related to the micellar 

system (water to surfactant ratio) and sol-gel reaction (nature and 

ratio of precursors and surface modifiers, pH, reaction time) on 

the morphology, chemical and porous structure of the 

nanoparticles were tested and assessed by complementary results 

obtained by transmission electron microscopy, diffuse reflectance 

infrared spectroscopy and nitrogen adsorption/desorption 

isotherms. Among those parameters, the pH of the mixture and 

the ratio of aminated surface modifiers, proved to account for the 

most significant changes. 

The hollow particles were tested as nanocarriers 

for the azole-based antitumor ruthenium complex (H trz)[trans- 

2 

-RuCl (N 4 2-Htrz) ], which belongs to the hottest family of non- 

2 

platinium anticancer drugs. The complex was loaded into the 

nanocapsules during their synthesis stage, by dissolution in the 

aqueous phase of the micellar system. Different chemical 

structures of the drug were stabilized by adjustment of the 

aqueous phase pH, and their nature and interactions with the silica 

matrix were analysed by diffuse reflectance UV-Vis and infrared 

spectroscopies. 

Keywords: Nanoparticles; Sol-gel processes; Antitumor 

agents; Ruthenium; 



s1221 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 1 7 

APPLiCAtion of A ntfet iMMunoSenSor to the 

deteCtion of C-reACtive Protein 

A. C. freitAS 2 , C. JuStino 1 , t. roChA-SAntoS 2 , 

J. P. AMArAL 3 , S. CArdoSo 3 , A. duArte 1 





3 INESC-MN, INESC-MN, Lisbon, Portugal 

Due to their enhanced structural and electronic properties [1] , 

the single-walled carbon nanotubes (SWCNT) have been used as 

the building blocks of biosensing/electronic devices. The 

fabrication of field effect transistors (FET) based on SWCNT 

(NTFET devices) represents a promising approach for 

applications on the electronic detection of biomolecules [2] . In 

this study, we report a NTFET device for the detection of 

C-reactive protein (CRP) by immunoreaction. Such acute-phase 

protein is considered as the current better validated inflammatory 

biomarker, being an indicator of the risk of cardiovascular 

diseases [3] . The antibodies specific for CRP (anti-CRP) were 

firstly immobilized by direct adsorption onto SWCNT. The 

analytical signal is calculated as the normalized drain current (I ) D 

after the exposure of various concentrations of CRP in relation to 

the I obtained after the immobilization of anti-CRP and SWCNT. 

D 

The label-free biosensor is capable to detect various 

concentrations of CRP, which include the normal levels of CRP 

in serum, it requires small volume of sample, and it is portable 

with fast and simple analysis of CRP. In this work, we also present 

the microfabrication steps to the definition of FET devices which 

are in the origin of the applied biosensors to CRP. 


for Competitiveness Factors – COMPETE, FCT (Fundacao 

para a Ciencia e a Tecnologia, Portugal) within the framework 

of research project CARDIOSENSOR (references FCOMP-01- 

0124-FEDER-010902 and PTDC/SAU-BEB/099042/2008). 

This work was also funded through scholarships - references 

SFRH/BD/60429/2009, SFRH/BPD/65410/2009, and 

SFRH/BPD/73781/2010 under QREN-POPH funds, co-financed 

by the European Social Fund and Portuguese National Funds 

from MCTES. 

references: 

1. I. Heller, A.M. Janssens, J. Männik, E.D. Minot, 

S.G. Lemay, C. Dekker. Nano Letters 8, 591-595 (2008). 

2. P.D. Kichambare, A. Star, In: Nanomaterials for 

biosensors, C.S.S.R. Kumar (ed.), pp. 1-26, Wiley-VCH 

(2007). 

3. R.R. Packard, P. Libby. Clinical Chemistry 54, 24-38 

(2008). 

Keywords: nanotubes; biosensors; immunochemistry; 


P - 0 7 1 8 

dePoSition of SiLiCon nAnoStruCtureS By 

AfM-LithoGrAPhy 

r. fritzSChe 1 , M. toAder 2 , f. SeideL 2 , 

M. hietSChoLd 2 , h. LAnG 1 , d. r. t. zAhn 2 , 

M. MehrinG 1 


Germany 

2 Chemnitz University of Technology, Physic, Chemnitz, 

Germany 

The recent development of semiconductor devices and the 

ongoing miniaturization in all process steps led to an increasing 

demand for techniques to fabricate nanostructures. Among these 

techniques atomic force microscopy offers a precise control of 

nanostructure formation. [1-3] Furthermore, it has been shown that 

AFM-lithography offers a possible technique to produce 

electronic devices on the micro and nanometer scale. [2] AFM also 

provides a tool to operate and control chemical reactions in a 

defined area and to analyze the results simultaneously. [3, 4] Selected 

examples are electrochemical reactions [3] which make use of a 

bias voltage or thermally induced reactions which make use of a 

heated tip. [5, 6] Noteworthy, the reactions take place in a small area 

around the tip. This provides the possibility to carry out novel 

reactions and processes and to develop novel applications. A 

recent example is the decomposition of commercially available 

liquid diphenylgermane and diphenylsilane using AFM to provide 

germanium and silicon nanostructures with potential for 

microelectronic applications. [7] Herein we report our results on the 

use of diverse silanes of the type R SiH and RSiH for the 

2 2 3 

deposition of silicon nanostructures using AFM-lithography from 

solution under atmospheric pressure. 

references: 

1. M. Rolandi,C.F. Quate,H. Dai, Adv. Mater. 2002, 14, 191. 

2. L. Pellegrino,Y. Yanagisawa,M. Ishikawa,T. Matsumoto, 

H. Tanaka,T. Kawai, Adv. Mater. 2006, 18, 3099. 

3. J.D. Torrey,S.E. Vasko,A. Kapetanovic,Z. Zhu, 

A. Scholl,M. Rolandi, Adv. Mater. 2010, 22, 4639. 

4. S.E. Vasko,W. Jiang,R. Chen,R. Hanlen,J.D. Torrey, 

S. Dunham,M. Rolandi, Phys. Chem. Chem. Phys. 2011, 

13, 4842. 

5. A.W. Knoll,D. Pires,O. Coulembier,P. Dubois,J.L. Hedrick, 

J. Frommer,U. Duerig, Adv. Mater. 2010, 22, 3361. 

6. B. Gotsman,U. Duerig,J. Frommer, C.J. Hawker, 

Adv. Funct. Mater. 2006, 16, 1499. 

7. S.E. Vasko,A. Kapetanovic,V. Talla,M.D. Brasino, 

Z. Zhu,A. Scholl,J.D. Torrey, M.Rolandi, Nano Let. 2011, 

11, 2386. 

Keywords: silicon; silanes; lithography; deposition; 

nanostructures; 



s1222 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 1 9 

SPrAy-iLGAr ® dePoSition of ControLLABLe 

znS nAnodotS And APPLiCAtion for hiGhLy 

effiCient thin fiLM SoLAr CeLLS 

y. fu 1 , t. KoehLer 1 , M. KrueGer 1 , r. SAez ArAoz 1 , 

M. Ch. Lux-Steiner 1 , d. ABou-rAS 1 , C. h. fiSCher 1 

1 Helmholtz-Zentrum Berlin, Institute for Heterogeneous 

Materials Systems, Berlin, Germany 

The spray ion layer gas reaction (Spray-ILGAR) technique 

produces homogeneous, compact metal chalcogenide films used 

as buffer layers for thin film solar cells with high efficiencies. It 

was a great challenge to elaborate this method for the deposition 

of nanodots. Now we show that high quality ZnS nanodots can 

be synthesized at low temperature by this sequential, cyclic and 

low cost method, which can be scaled up for industrial in-line 

production. 

The choice of the process parameters allows the control of 

particle density and size. The unique sequential process results in 

the formation of the nanodot film with good properties. The dots 

are rather homogeneous in size, shape and composition, and tend 

to keep maximum distance from each other. In contrast, ZnS 

nanodots deposited by a continuous spray chemical vapor 

deposition (Spray-CVD) are larger and irregular in shape with 

inclusions of ZnO. By interpretation of the SEM, TEM, XPS and 

mass spectrometry results, the decomposition mechanism of Zn 

precursor and the self-limiting growth of ZnS nanodots are 

studied. 

In addition, a passivation layer/point contact buffer 

composed of the ZnS nanodots covered by a homogenous In S 2 3 

layer is produced consecutively by the Spray-ILGAR process. The 

ZnS reduces the recombination of the charge carriers at the 

absorber/buffer heterointerface which is one important position 

for performance loss in the chalcopyrite cells. The In S 2 3 

in-between and on top of the ZnS dots is necessary for the charge 

carrier transport as ZnS has poor conductivity. The optimal ZnS 

dot density, In S thickness and process temperature with respect 

2 3 

to optimum solar cell performance are investigated. Moreover, 

different In precursor solutions and different ZnS nanodot 

deposition methods are studied and compared. As compared to a 

pure In S buffered cell, the solar cell efficiency with 

2 3 

nano-ZnS/In S buffer layer could be improved by about 1% 

2 3 

absolutely upto 15.7%. 

Keywords: ZnS nanodots; Spray-ILGAR; buffer layer; thin film 

solar cells; passivation; 


P - 0 7 2 0 

SeLf-ASSeMBLed tetrAGonAL PriSMAtiC 

nAnoCAGe CAPABLe of SeLeCtiveLy interACt 

with Pi-AnioniC SuBStrAteS 

C. GArCiA-SiMon 1 , L. GóMez 1 , i. GArCiA-BoSCh 1 , 

x. riBAS 1 , M. CoStAS 1 

1 University of Girona, Departament de Química Inorganica, 

Girona, Spain 

The development of functional nanosized molecules has 

gained relevance thanks to the straightforward nature of the 

metal-directed supramolecular synthetic approach. In previous 

work we reported the use of macrocyclic dicopper(II) complexes 

as metal-organic molecular clips capable of self-assembling at 

room temperature with different di- tri- and tetracarboxylate 

linkers to yield nanomolecular 2D rectangles, and polyfunctional 

3D trigonal prisms. [1, 2, 3] Among the various systems developed 

so far, discrete nanosized cage-like molecules are of particular 

interest for the implementation of specific functions because they 

provide an inner cavity that can be filled with functional guest 

molecules when brought together in solution. [4] 

In this work we report the preparation of a new nanocapsule 

with A B tetragonal prismatic geometry (where A corresponds to 

4 2 

dipalladium macrocyclic complexes, and B corresponds 

to the tetraanionic form of palladium 5,10,15,20-tetrakis(4- 

-carboxyphenyl)-porphyrin). The large inner void space of the 

obtained structure and the supramolecular affinity for guest 

molecules towards porphyrin-based hosts converts this 

nanomolecular 3D structure in a good candidate for host-guest 

chemistry. The interaction between the nanocage and different 

guest molecules has been studied by means of NMR, UV-vis, 

ESI-MS and DOSY experiments. Selective molecular recognition 

has been found for anionic, planar-shaped p-guests, in contrast to 

the absence of interaction for neutral aromatic or cationic 

substrates. Moreover using macrocycles of different lengths, we 

are able to tune the cage dimensions to accommodate guests of 

different sizes. [5] 

The simplicity in the synthesis developed for the obtention 

of these complex architectures represents a step forward for the 

development of polyfunctional supramolecular nanovessels, with 

multiple applications. 

references: 

1. A. Company et al., Inorg. Chem. 2006, 45, 2501–2508 

2. L. Gómez,et al., Chem. Commun. 2007, 4410-4412 

3. A. Company et al., Dalton Trans., 2008, 1679–1682 

4. Guido H. Clever et al., Inorg Chem. 2011, 50, 4689-4691 

5. M. Fujita et al., Acc. Chem. Res. 2005, 38, 371-380 

Keywords: supramolecular chemistry; Nanostructures; 

Receptors; Anions; Palladium; 



s1223 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 2 1 

new LuMineSCent hyBrid MeSoPorouS 

CoPPer-SiLiCA MAteriALS 

M. riCo 1 , A. e. SePúLvedA 2 , e. SerrAno 1 , 

J. r. BerenGuer 2 , e. LALinde 2 , 

J. GArCiA-MArtinez 1 

1 Laboratorio de Nanotecnología Molecular, Departamento de 

Química Inorgánica, Universidad de Alicante, Carretera San 

Vicente s/n 

2 Departamento de Química-Grupo de Síntesis Química de La 

Rioja, UA-CSIC, Universidad de La Rioja, E-26006 

Luminescent mesoporous organosilicas (PMOs) are usually 

prepared by total or partial co-condensation of organic 

chromophores bearing alkoxysilyl groups [1] . This method has 

several advantages like good pore volume values or absence of 

leaching, but the materials lacks of the tunability that coordination 

complexes possesses. Recently, we have reported the 

incorporation of various Pd(II) complexes bearing ligands with 

triethoxysilyl terminal groups into the framework of mesoporous 

silica and organosilica materials, using a facile solvent-free 

one-pot method [2] . In order to extend this synthetic method to the 

obtention of luminescent siliceous materials, and taking into 

account the growing interest that luminescent polynuclear 

d10 metal complexes are attracting [3] we firstly synthesize a new 

tetrametallic alkynyl copper(I) chromophore for its further 

co-condensation with tetraethoxysylane (TEOS), in the presence 

of a neutral surfactant. The new mesoporous hybrid luminescent 

metal complex-silica materials present a remarkable hydrothermal 

stability, considerably higher than those synthesized by the 

traditional post-synthetic routes, showing emissive properties that 

have been easily achieved by co-condensation of a strong emitter 

tetra-nuclear alkynyl copper cluster with TEOS; thus, opening the 

possibility of the synthesis of new materials with a great 

applicability potential [4] . 

references: 

1. N. Mizoshita, T. Tani, S. Inagaki, Chem. Soc. Rev. 2011, 

40, 789. 

2. a) N. Linares, A. E. Sepúlveda, M. C. Pacheco, 

J. Berenguer, E. Lalinde, C. Nájera, J. García-Martínez, 

New J. Chem. 2011, 35, 225; 

b) N. Linares, A. E. Sepúlveda, J. R. Berenguer, E. Lalinde 

and J. García-Martínez, Micropor. Mesopor. Mater., 2012, 

http://dx.doi.org/10.1016/j.micromeso.2012.03.0363; 

c) N. Linares, E. Serrano, M. Rico, A.M. Balu, E. Losada, 

R. Luque, J. García-Martínez, Chem. Commun. 2011, 

47, 9024. 

3. X. He, N. Zhu, V. W. W. Yam, Dalton Trans. 2011, 40, 

9703. 

4. M. Rico, A.E. Sepúlveda, S. Ruiz, E. Serrano, 

J.R. Berenguer, E. Lalinde, J. Garcia-Martinez, 

Chem. Commun. 2012 (sent). 

Keywords: mesoporous materials; luminiscent; copper; 

chromophore; hydrothermal stability; 


P - 0 7 2 2 

nAnoCoMPoSiteS BASed on PhyLLoSiLiCAte 

And MetALLoSuPrAMoLeCuLAr 

PoLyeLeCtroLyteS: ModuLAr CoMPoundS for 

eLeCtrorheoLoGiCAL fLuidS 

M. GeiSt 1 , d. G. Kurth 1 

1 University of Würzburg, Chemical Technology of Advanced 

Materials, Wuerzburg, Germany 

Particles dispersed in a non-conductive oil can respond to 

an electric field. If the particles get polarized they form column 

like structures, which affect the viscosity. Those dispersions are 

called electrorheological fluids (ERF). For such an ERF we 

prepared a new nanocomposite based on the phyllosilicate clay 

Montmorillonite (MMT) and metallo-supramolecular 

polyelectrolytes (MEPE). To examine the electrorheological 

properties, we tested the rheological response of different 

nanocomposite/silicone oil dispersions to an electric field. The 

examined samples show a distinctive ER effect with only small 

active substance necessary. Furthermore the observed currents are 

very small, which is essential for a potential application. 

Metallo-supramolecular polyelectrolyts based on a ditopic 

bisterpyridine ligand and different metal ions are intercalated into 

MMT. The intercalation is verified by powder X-ray diffraction, 

thermal analysis and IR spectroscopy. The powder diffraction 

pattern shows a shifted (001) reflection indicating a widening of 

the interlayer spacing and the differential thermal analysis display 

an increased decomposition temperature. These results indicate 

an inclusion of the MEPE rods into the interlayer of MMT. IR 

spectroscopy confirms the intercalation. 

The storage and the loss moduli of the dispersed 

nanocomposites are measured with an oscillating rheometer as a 

function of the potential within a range from 0 to 2 kV/mm. The 

nanocomposite shows an electrorheological (ER) effect depending 

on concentration (2, 3, 5 and 10 wt %). With a content of 10 wt % 

the storage modulus G’ of a nanocomposite dispersion increases 

from 20 to 2700 Pa. We were able to examine the structure of the 

polarized particles under the microscope and an applied electric 

field. The effect is accompanied by small currents 

(0.01 mA/mm²). Pure MMT shows under the tested conditions 

only a small ER-effect, indicating the contribution of the MEPE 

to the effect. 

Keywords: Supramolecular chemistry; Clay; 

Electrorheological Fluid; Intercalations; 



s1224 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 2 3 


nAnoMetriC oxide CoAtinGS with tunABLe 

StiffneSS 

K. GotLiB-vAinShtein 1 , o. GirShevitz 1 , 

C. n. SuKeniK 1 , d. BArLAM 2 , e. KALfon-Cohen 3 , 

S. r. Cohen 3 

1 Bar-Ilan University, Department of Chemistry and Institute of 

Nanotechnology & Advanced Materials, Ramat-Gan, Israel 

2 Ben-Gurion University, Department of Mechanical 

Engineering, Beer-Sheva, Israel 

3 Weizmann Institute of Science, Department of Chemical 

Research Support, Rehovot, Israel 

The design of surfaces with controlled stiffness is attractive 

for applications ranging from controlling biological cell growth 

to mechanical and electrical engineering design. We report the 

creation of layered composites with tunable surface stiffness 

achieved by coating a soft PDMS polymer (~10 microns) with a 

stiff film of amorphous titania (2 - 50 nm). The oxide layer is 

smooth (6 nm rms roughness at 2 µm2 image size), and crack-free. 

Air plasma pre-treatment of the PDMS was used to promote 

adhesion of the titania overlayer. 

Nanomechanical characterization of the layered structure 

has been done by a number of different experimental approaches 

and the results have been modeled. The surface mechanical 

properties of the samples have been probed using both 

instrumented nanoindentation and atomic force microscopy-based 

nanomechanical characterization. The results have been compared 

to finite element analysis (FEA) simulations. 

By fitting the FEA simulations with the experimental AFM 

curves it is shown that the hard titania film and the soft PDMS 

substrate individually maintain their characteristic elastic moduli, 

while the stiffness of the vertical nanocomposite can be 

controllably modified by changing the thickness of the stiff layer. 

Liquid phase deposition of the oxide allows control of its 

thickness at the nm level. 

This synthetic approach can be quite versatile, and can, in 

principle, be extended to different oxides and a wide range of 

thicknesses. It allows variation in mechanical properties of the 

surface while maintaining a constant surface chemistry. This 

exploratory work is a first step towards defining the range of 

surface stiffnesses that can be achieved in this way, as well as 

developing general methodologies for their characterization. 


P - 0 7 2 4 

funCtionAL SynthetiC veSiCLeS: BioMiMetiC 

SenSinG & CAtALySiS 

B. GruBer 1 , B. KÖniG 1 



Cell membranes play a key role for the function of living 

organisms. Thus the development of artificial membranes is of 

great interest – not only as biological mimics but also to open up 

ways to new functional materials. 

We have developed synthetic vesicles based on natural 

phospholipids which were doped with artificial functional 

amphiphiles. Amongst these membrane-embedded compounds 

are artificial receptors for biomolecule recognition, [1] fluorescent 

dyes for optical sensing [2] and transition metal catalysts for 

catalytic transformations at the membrane-water interface. [3] This 

way we have established a novel approach towards modular 

luminescent chemosensors and highly-active supramolecular 

catalysts. 

Characterization of our soft nanoparticles includes methods 

like DLS, AFM, Cryo-TEM, DSC, SPR, ITC and optical 

spectroscopy. The embedded functional amphiphiles are assumed 

to form domains within the phospholipid membranes and under 

certain conditions respond to external stimuli by spatial 

rearrangements. Currently we pursue the development of 

multi-receptor surfaces which respond to specific analytes by 

defined emission patterns like FRET-signatures and 

photopolymerized particles as molecularly imprinted materials. 

references: 

1. B. Gruber, S. Stadlbauer, K. Woinaroschy, B. König, 

Org. Biomol. Chem., 2010, 8, 3704-3714. 


B. König, Angew. Chem. Int. Ed., 2010, 49, 7125-7128. 

3. B. Gruber, E. Kataev, J. Aschenbrenner, S. Stadlbauer, 

B. König, J. Am. Chem. Soc., 2011, 133, 20704-20707. 

Keywords: Vesicles; Sensors; Fluorescence; Self-assembly; 

Heterogeneous catalysis; 



s1225 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 2 5 

PhotoACtive ion exChAnGe PoLyStyrene 

nAnofiBer textiLeS 

P. henKe 1 , P. KuBAt 2 , J. MoSinGer 1 


of Inorganic Chemistry, Prague, Czech Republic 

2 Academy of Sciences of the Czech Republic J. Heyrovsky 

Institute of Physical Chemistry, Department of Spectroscopy, 


The nanofiber textiles prepared by electrospinning with an 

encapsulated photosensitizer efficiently photogenerate singlet 

oxygen, which is able to oxidize external chemical and biological 

substrates/targets [1–3] . Herein we present sulfonated elektrospun 

polystyrene (PS) nanofiber textiles with externally bound 

cationic photosensitizers and/or encapsulated nonpolar 

meso-tetraphenylporphyrin or aluminum phthalocyanine chloride. 

We used two diferent types of cationic photosensitizers, 

namely 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin tetra(p- 

-toluenesulfonate) and methylene blue. The materials were studied 

by microscopic methods, steady state and time-resolved 

absorption and fluorescence spectroscopy. All nanofiber materials 

exhibited photogeneration of singlet oxygen and singlet oxygen 

mediated delayed fluorescence (SODF). Prompt and SODF was 

used as a sensitive tool for estimation of an optimal amount of 

externally bond photosensitizer for maximum generation of 

singlet oxygen. Doped sulfonated PS nanofibers exhibit the 

oxidation of an external substrate and antibacterial activity against 

E. coli. when activated by visible light. Ever moderate sulfonation 

strongly increase the wettability of hydrophobic PS nanofibers 

yielding to increase of antibacterial activity of nanofibers with an 

encapsulated photosensitizer. Extensive sulfonation of nanofibers 

is associated with postpolymerization crosslinking effect 

increasing the resistence of nanofiber material to nonpolar media 

but decrease oxygen diffusion in polymer. 

Acknowledgement: The research was supported by the Czech 

Science Foundation (P207/10/1447 and P208/10/1678) 

references: 

1. Mosinger J.; Jirsak O.; Kubat P.; Lang K.; Mosinger B., Jr; 

J. Mater. Chem., 2007, 17, 164. 

2. Mosinger J.; Lang K.; Kubat P.; Sykora J.; Hof M.; Plistil L.; 

Mosinger B., Jr.; J. Fluoresc. 2009, 19, 705. 

3. Jesenska S.; Plistil L.; Kubat P.;Lang K.;Brozova L.; 

Popelka S.; Szatmary L.; Mosinger J.; J. Biomed. Mater. 

Res. Part A 2011, 99A, 676. 

Keywords: Photochemistry; Photophysics; Singlet oxygen; 

Porphyrinoids; Phthalocyanines; 

P - 0 7 2 6 

Photo-ACtive SPiroPyrAn-BASed 

interLoCKed SySteMS 

d. hernAndez MeLo 1 , J. tiBurCio 1 


1 Cinvestav, Chemistry, Mexico. D.F., Mexico 

Interlocked molecules, such as catenanes and rotaxanes, are 

considered models of artificial molecular machines since they can 

transform an energy input (chemical, electrochemical or optical) 

into a mechanical motion of their components without 

dissociation. [1] 

An important precursor for the synthesis of rotaxanes and 

catenanes are pseudorotaxanes. In a previous work we have 

shown that 1,2-bis(pyridinium)ethane axles and macrocyclic 

ethers, like dibenzo-24-crown-8 ether [dB24C8] and 

disulfonated-dibenzo-24-crown-8 ether [dSdB24C8] 2– , are 

capable of assembling into [2]pseudorotaxanes, which then can 

be transformed into [2]rotaxane type complexes. [2] 

Now, we have developed a new [2]pseudorotaxane motif by 

substitution of one pyridinium unit on the axle by a spyropiran 

moiety (SP), which can be isomerized into a monocationic 

merocyanine fragment (ME) by an optical or chemical stimulus. [3] 

Isomerization of SP into ME changes the crown ether affinity 

towards the axle. Here, we will discuss the behaviour of the axle 

in presence of [dB24C8] or [dSdB24C8] 2– , in several different 

solvents. Also, we will present our progress on the development 

of [2]rotaxane systems where the motion can be controlled by 

reversible structural changes on the axle. 

In summary, we have designed a new spiropyran-based 

interlocked molecule where the photo-isomerisation of the SP 

fragment triggers the motion of the components. 

references: 

1. Coskun A., Banaszak M., Astumian R. D., Stoddart J. F., 

Grzybowski B. A. Chem. Soc. Rev. 2012, 41, 19-30. 

2. Hoffart D. J., Tiburcio J., De la Torre A., Knight L. K., 

Loeb S. J. Angew. Chem. Int. Ed. 2008, 47, 97-101; 

Mercer D. J., Vella S. J., Guertin L., Suhan N. D., 

Tiburcio J., Vukotic N., Wisner J. A., Loeb S. J. Eur. J. 

Org. Chem. 2011, 1763-1770. 

3. Raymo F. M., Giordani S. J., J. Am. Chem. Soc. 2001, 123, 

451. 

Keywords: Supramolecular chemistry; Rotaxanes; 

Photochromism; 



s1226 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 2 7 

intrAMoLeCuLAr fLuoreSCenCe quenChinG 

in 2,6-SuLfAnyL-Core-SuBStituted 

nAPthALenediiMide 

P. heSS 1 , M. MAyor 1 


Switzerland 

Herein we report the successful synthesis of a tailor-made 

2,6-sulfanyl-core-substituted naphthalenediimide (NDI) with an 

efficient intramolecular fluorescence quenching. 

Core-substituted NDIs have tunable photoluminescent 

properties based upon the substitution pattern at their core and are 

easily functionalizable organic n-semiconductors, which belong 

to the class of fluorophores. By varying the core substitution of a 

particular NDI very low or high fluorescence quantum yields can 

be obtained. According to literature those yields are not only 

depending on the core substitution, but also on conformational 

changes and the involved electron transfer processes. 

Recently, Pugliesi et al. [1] published the first time-resolved 

study on the charge transfer rate from a core substituent to the 

NDI unit. In particular, they compared different model compounds 

with three different moieties (alkyl, benzyl and phenyl), which 

were directly attached to a 2,6-sulfanyl-core-substituted NDI, by 

investigation of their fluorescence quenching behavior. Only if an 

electron donor such as a phenyl unit was linked in plane with the 

core substituent an ultrafast and efficient fluorescence quenching 

was detected. 

Inspired by these results a tailor-made model compound has 

been designed and synthesized which consists of a symmetrical 

2,6-sulfanyl-core substitution. Reliable synthetic procedures have 

been subsequently developed to isolate the desired target structure 

only after 6 linear steps. The phenylsulfanyl substituents are fixed 

in such way that the fluorescence quenching could be drastically 

increased. This has been proven by measuring the absorption and 

fluorescence spectra of the model compound. 

references: 

1. I. Pugliesi, P. Krok, S. Lochbrunner, A. Blaszczyk, 

C. von Hänisch, M. Mayor and E. Riedle, 

J. Phys. Chem. A 2010, 48, 12556. 

Keywords: Fluorescence; Fluorescence spectroscopy; 

Nanostructures; Napthalenediimide; Ab initio calculations; 


P - 0 7 2 8 

inveStiGAtion of Pd And Pdo BASed CAtALyStS 

in the oxidAtion of PriMAry And SeCondAry 

ALCohoLS 

n. A. heutz 1 , M. hoLz 2 , K. tÖLLe 2 , A. BirKner 3 , 

K. Merz 1 , M. MuhLer 2 

1 Ruhr-University Bochum, Department of Inorganic Chemistry 

I, Bochum, Germany 

2 Ruhr-University Bochum, Laboratory of Industrial Chemistry, 


3 Ruhr-University Bochum, Department of Physical Chemistry I, 


Oxidation of primary and secondary alcohols plays a 

fundamental role to produce carbonyl compounds as building 

blocks in organic synthesis, for example in the fragrance and 

pharmaceutical industries [1] . In our work we focus on the usage 

of palladium based catalysts in alcohol oxidation. It is still under 

debate whether Pd0 or PdO, is the active site for oxidation 

processes [2] . Our investigations show, that Pd/TiO and PdO/TiO 2 2 

show similar activity in the gaseous phase oxidation of 

2-propanol. In order to understand this finding we used 

comparative experiments to investigate the formation of the active 

material. The samples were prepared by colloidal deposition on 

titania [3] using PdCl as precursor. Information about the catalyst 

2 

material was obtained from PXRD, TEM and XPS. 

Detailed investigation on the temperature dependents 

(RT-160°C) in methanol oxidation over Pd/TiO and PdO/TiO 2 2 

(followed by on-line QMS) show, that PdO is inactive below 

100 °C, while Pd/TiO is already active at room temperature. 

2 

Multiple cycle experiments show that PdO gets activated in the 

presence of gaseous alcohols, reaching high conversion in 

methanol oxidation, comparable to Pd/TiO suggesting the 

2 

formation of metallic palladium as active species in alcohol 

oxidation. To prove this change of PdO to Pd, near ambient 

pressure XPS is performed at different temperatures. 

references: 

1. T. Mallat and A. Baiker et al, Chem. Rev., 2004, 104 

2. A. Baiker et al, J. Phys. Chem. B, 2006, 110 

3. M. Comotti, W.-C. Li, B. Spliethoff and F. Schueth, 

J. Am. Chem. Soc., 2006, 128 

Keywords: Palladium; Nanoparticles; Gas-phase reactions; 

Oxidation; Alcohols; 



s1227 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 2 9 

GerMAniuM nAnoPArtiCLe forMAtion froM 

differentLy SuBStituted MoLeCuLAr 

PreCurSorS 

– whAt iS the roLe of hydride? 

M. hoffMAn 1 , J. G. C. veinot 1 

1 University of Alberta, Department of Chemistry, Edmonton 

AB, Canada 

One route to germanium nanoparticle formation utilizes high 

temperature decomposition of organogermanium precursors. We 

have previously investigated the influence of organic substitution 

on germanium-rich oxide formation for solid-state synthesis of 

germanium nanocrystals, and found that the elimination 

mechanism of the organic group plays an important role in the 

formation temperature. [1] In this talk, we will present the findings 

from investigating different substitution patterns of the molecular 

precursor n-butylgermane. 

Tetra-n-butylgermane has been found to decompose at 

285 °C to give elemental germanium and various organic 

byproducts. We will discuss the impact that hydride-substitution 

has on this decomposition process and the subsequent formation 

of germanium nanoparticles as we progress from tetra- to tri-, diand 

mono-n-butyl-substitution. 

references: 

1. M Hoffman, JGC Veinot Chemistry of Materials 2012 24, 

1283-1291. 

Keywords: Germanium; Nanoparticles; 


P - 0 7 3 0 

MeSoPorouS GALLiuM oxide thin fiLMS 

And the ConverSion of the wALL MAteriAL 

into non-oxideS By SuPerCritiCAL fLuid 

treAtMent 

J. e. honG 1 , y. S. Ko 1 , y. u. Kwon 1 


Korea 

We develop the synthesis method of mesoporous gallium 

oxide (Ga O ) thin films by using a non ionic surfactant (F-127) 

2 3 

as a structure directing agent. None of the previously reported the 

mesoporous Ga O has a thin film structure. The mesorporous 

2 3 

Ga O thin films are expected to utilize as acid-catalysts or other 

2 3 

functional materials. Furthermore the mesoporous Ga O thin 

2 3 

films can be converted to Ga S films, which are semiconductor 

2 3 

materials, by supercritical fluid reaction. All films have wormlike 

structure and about 10nm pore sizes. Also we can control the film 

thickness in the range of 40–340nm depending on the composition 

of gallium source (GaN O ) and F127 of the coating solution. The 

3 9 

mesostructure of the films was characterized by transmission 

electron microscopy (TEM) and scanning electron microscopy 

(SEM). The elemental composition was determined by energy 

dispersive spectroscopy (EDS) and X-ray photoelectron 

spectroscopy (XPS). 

Keywords: Gallium oxide; Mesoporous; Supercritical fluid; 

Gallium sulfide; 



s1228 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 3 1 

trAnSverSe reLAxivity inveStiGAtionS of 

MAGnetiC MeSoPorouS SiLiCA nAnoPArtiCLeS 

K. hurLey 1 , y. S. Lin 1 , J. zhAnG 1 , M. GArwood 1 , 

C. hAyneS 1 

1 University of Minnesota Twin Cities, Chemistry, Minneapolis, 

USA 

Mesoporous silica nanoparticles (MS NPs) have attracted 

much interest in recent years due to their potential as effective 

nanotherapeutic devices. Their large pore volume provides 

excellent drug delivery abilities, and well-understood silica 

chemistry presents many opportunities for the incorporation of 

multiple functionalities. Especially important for both clinical 

trials and subsequent personalized patient care is the incorporation 

of contrast agents such as Fe O nanoparticles for T magnetic 

3 4 2 

resonance imaging (MRI). These magnetic core/shell 

nanoparticles have been developed by several research groups, 

but none have investigated the effect of synthetic conditions on 

magnetic relaxivity (r ), the indicator of contrast agent quality. In 

2 

addition, while many of the literature MS NP systems have 

provided in vivo contrast post-injection, personalized medicine 

will require high-quality imaging hours or days after 

administration. To this end, MS NPs with imaging capabilities 

must retain particle stability in biological environments, and the 

effectiveness of the contrast agent must be maintained. To our 

knowledge, no long term studies on magnetic MS NP image 

contrast have been previously reported. Studies on parameters 

affecting r , both on short and long time scales, are called for. In 

2 

this work, we probe the effects of silica shell thickness, iron oxide 

core synthesis, and hydrothermal treatment on the r of magnetic 

2 

MS NPs. In addition, we examine short- and long-term stability 

of r in water, phosphate buffered saline, and acidic media to 

2 

mimic biological environments. We show that a simple 

hydrothermal treatment proves particularly effective in 

maintaining colloidal and r stability and in providing resistance 

2 

against acid degradation in biological environments. 

Keywords: Mesoporous Materials; Magnetic Properties; 

Nanoparticles; Imaging Agents; Drug Delivery; 


P - 0 7 3 2 

nitroGen-doPed GrAPhene CreAted with 

different PreCurSorS 

y. ito 1 , h. SAChdev 1 , K. MüLLen 1 

1 Max-Planck-Institute for Polymer Research, Synthetic polymer, 

Mainz, Germany 

Nitrogen-doped graphene is of general interest for electronic 

devices. We try to include nitrogen into the graphene lattice by 

CVD methods and successfully fabricated high quality nitrogendoped 

graphene from CVD method of simple molecular 

precursors like pyridine. 

The graphene quality is related to the molecular precursor 

and the decomposition parameters. For example, the temperature 

dependence was studied in detail in the range from 600–1000 °C. 

As the temperature increased, the graphene formation was 

improved and well-separated D, G and 2D peaks were generated. 

It is considered that the decomposition and the following graphene 

growth are promoted at higher temperatures. The optical and 

morphological properties of nitrogen-doped CVD graphene were 

characterized and compared for understanding the graphene 

formation. 

Keywords: Chemical vapor deposition; Nitrogen-doped 

graphene; Raman spectroscopy; 



s1229 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 3 3 

SuPrAMoLeCuLAr heLiCAL nAnofiBer 

forMAtion froM the SeLf-ASSeMBLy of 

CytidyLiC ACid-APPended BoLAAMPhiPhiLe 

with di- And tri-CArBoxyLiC ACid 

r. iwAurA 1 , M. ohniShi-KAMeyAMA 1 

1 National Agriculture and Food Research Organization, 

National Food Research Institute, Tsukuba Ibaraki, Japan 

Bottom-up approach, which refers to the build-up of 

materials from molecular components, has attracted much 

attention to many researchers in the field of nanotechnology. In 

particular, combination of self-assembly and molecular 

recognition, as often seen in biomolecules, is one of the elegant 

strategies to make well-defined nanostructures. We chose DNA 

as a motif because the excellent property of self-assembly with 

molecular recognition ability is already incorporated into DNA 

molecules. [1–2] In addition, the production of materials using 

renewable bioresources is now a challenging theme in the field of 

bottom-up nanotechnology. Herein, the binary self-assembly of 

1, 18-cytidylic acid-appended bolaamphiphile (C18C) [3] in which 

a 3'-phospholylated cytidine moiety is connected to both ends of 

an octadecamethylene chain, and di- or tricarboxylic acids is 

reported. Atomic force microscopy (AFM), circular dichroism 

(CD), UV absorption, and Fourier-transform infrared (FT-IR) 

spectroscopy, and electrospray ionization-Fourier-transform ion 

cyclotron resonance (ESI-FTICR) mass spectrometry experiments 

revealed the binary self-assembly of C18C and malonic, succinic, 

glutaric, or citric acids formed nanofibers through molecular 

recognition. Moreover, left-handed helicity was observed in the 

nanofiber obtained from the binary self-assembly of C18C and 

citric acid (CA) with diameters, lengths, and pitches ca. 6 – 7 nm, 

several hundred nm to 5 μm, and ca. 30 – 40 nm, respectively. 

Based on the observations, we performed the self-assembly of 

C18C in lemon juice containing citric acids, and succeeded in the 

formation of the left-handed helical nanofiber by the fusion of 

supramolecular chemistry and renewable biomaterials. [4] 

references: 

1. R. Iwaura et al, Angew. Chem. Int. Ed., 2003, 42, 1009. 

2. R. Iwaura et al, Chem. Eur. J., 2009, 15, 3729. 

3. R. Iwaura et al, Small, 2010, 6, 1131. 

4. R. Iwaura et al, Chem. Commun., accepted. 

Keywords: Self-assembly; Nanofibers; Supramolecular 

Chemistry; Bolaamphiphiles; Nucleotides; 


P - 0 7 3 4 

ALiGned Growth of GoLd nAnorodS in PMMA 

ChAnneLS: PArALLeL PrePArAtion of 

nAnoGAPS 

t. JAin 1 , S. LArA-AviLA 2 , y. KervenniC 2 , 

K. Moth-PouLSen 3 , K. norGAArd 1 , S. KuBAtKin 2 , 

t. BJornhoLM 1 



2 Chalmers University of Technology, Department of 

Microtechnology and Nanoscience, Gothenburg, Sweden 

3 Chalmers University of Technology, Department of Chemical 

and Biological Engineering, Gothenburg, Sweden 

The fabrication of electrode pairs separated by a few 

nanometers is a fundamental challenge in nanotechnology. [1, 2] 

Nanogaps between metallic electrodes or nanoparticles are 

applied within diverse areas such as single-molecule electronics, 

plasmonics and spectroscopy. In single-molecule electronics the 

goal is to utilize single molecules as electrical components by 

understanding how electron transport through molecules is 

governed by the chemical structure of a molecule in order to be 

able to tailor its specific function. Here, we demonstrate alignment 

and positional control of gold nanorods grown in situ on substrates 

using a seed-mediated synthetic approach. Alignment control is 

obtained by directing the growth of spherical nanoparticle seeds 

into nanorods in well-defined poly(methyl methacrylate) 

nanochannels. Substrates with prepatterned metallic electrodes 

provide an additional handle for the position of the gold nanorods 

and yield nanometer-sized gaps between the electrode and 

nanorod. The nanogaps are electrically characterized, and to 

test the stability of the nanogaps, electronically active 

oligo(phenylenevinylene) (OPV) molecules are inserted into a 

nanogap junction by solution deposition, which results in an 

increase in the electrical conductance of several orders of 

magnitude compared to the empty nanogap. 

The presented approach is a novel demonstration of 

bottom-up device fabrication of multiple nanogap junctions on a 

single chip mediated via in situ growth of gold nanorods acting 

as nanoelectrodes. 3 

references: 

1. Jain, T.; Roodbeen, R.; Reeler, N. E. A.; Vosch, T.; Jensen, 

K. J.; Bjornholm, T.; Norgaard, K. J. Colloid Interface Sci. 

2012, 376, 83-90. 

2. Jain, T.; Westerlund, F.; Johnson, E.; Moth-Poulsen, K.; 

Bjornholm, T. ACS Nano 2009, 3, 828-34. 

3. Jain, T.; Lara-Avila, S.; Kervennic, Y.-V.; Moth-Poulsen, K.; 

Norgaard, K.; Kubatkin, S.; Bjornholm, T. ACS Nano 

2012, DOI: 10.1021/nn204986y. 

Keywords: Nanoparticles; Nanostructures; Molecular 

electronics; 



s1230 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 3 5 

SiLiCA CAPSuLe with AdJuStABLe SheLL 

MorPhoLoGy 

q. Ji 1 , J. P. hiLL 1 , K. AriGA 1 

1 National Institute for Materials Science, MANA supermolecules 

Group, Tsukuba, Japan 

Hollow spheres or capsules are some of the most actively 

investigated structures due to their potential applications in areas 

including biology, synthesis, photonics and catalysis. Various 

practical applications often require robustness and flexibility in 

microcapsule-based materials. Structure-adjustable capsules have 

been fabricated from inorganic components by using a 

self-template method. The resulted microcapsules possess flake 

shell which is composed by silica sheet with several nanomenter 

thickness. The capsules shrink under thermal stimulus and their 

structures can be adjusted by treatment at different pH. The flake 

shell capsules were shown high loading efficiency on drug 

molecules and DNA. In addition, the structrual flexibility in 

tuning of shell pore diameters leads to tailored drug release over 

prolonged periods. 


P - 0 7 3 6 

effiCient uLLMAnn CroSS-CouPLinGS uSinG Pd 

nAnoPArtiCLeS 

M. JoShAGhAni 1 , e. rAfiee 1 , e. AzAdi 1 


The Ullmann cross-coupling of aryl halides is an old but 

very important rout for synthesis of dissymmetric biaryls specially 

since introducing the palladium compounds as catalyst. [1] In the 

other hand, palladium nanoparticles have unique applications as 

catalyst in a wide variety of reactions. [2] Therefore, in continuation 

of our previous study on cross-coupling reactions [3–4] , we 

synthesized Pd nanoparticles via a simple method using 

polyethyleneglycol as both reducing agent and stabilizer. The 

efficiency of these palladium nanoparticles was investigated in 

the cross coupling reaction of aryl halides. A wide variety of 

substrates bearing different functional groups (electron 

withdrawing and electron donating groups) in para position were 

sufficiently coupled to yield the desired functionalized biaryls. 

references: 

1. M. Kotora, T. Takahashi, in “Handbook of 

Organopalladium Chemistry for Organic Synthesis”, 

E.-I. Negishi (Ed.), Wiley Interscience, NY, 2002. 

2. C. Yang, H. Wustefeld, M. Kalwei, F. Schiith, “Studies in 

Surface Science and Catalysis”, Vol. 154, Part C, 2004, 

Pages 2574-2580. 

3. Sh. Nadri, E. Azadi, A. Ataei, M. Joshaghani, E. Rafiee, 

J. Organomet. Chem. 2011, 696, 2966-2970. 

4. Sh. Nadri, M. Joshaghani, E. Rafiee, Organometallics 

2009, 28, 6281–6287. 

Keywords: Cross-Couplings; Nanoparticles; Palladium; 



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chem. Listy 106, s257–s1425 (2012) 


P - 0 7 3 7 


znfe o @tio SuBMiCron PArtiCLeS for 

2 4 2 

MAGnetiC PhotoCAtALySt 

J. S. JunG 1 , w. P. BAiK 2 

1 Gangneung-Wonju National University, Chemistry, 

Gangneung, Republic of Korea 

2 Myongji University, Chemistry, Yongin, Republic of Korea 

In recent years, superparamagnetic submicron materials 

have become particularly crucial in research area for biomedical 

application such as drug delivery, biosensor, and photocatalyst. 

In order for magnetic submicron materials to be applied in this 

kind of application, it needs to be soluble in water solution and 

has to have high saturated magnetization in mild magnetic field 

at room temperature. Among the reported photocatalysts, titanium 

dioxide(TiO ) is one of the most studied semiconductors for 

2 

photocatalytic reactions because of its high activity, chemical 

stability, robustness against photocorrosion, low toxicity and 

availability at low cost, especially for the detoxification of water 

and air. However, practical applications of photocatalysis are 

limited because of several problems arising from using fine TiO2 powders in photochemical process such as separating and 

recycling of the photocatalyst. In order to avoid these technical 

problems, several approaches have been taken. For example, 

powder type photo-catalysts have been immobilized on various 

supports, including glasses, silica, polymers, and film type 

photocatalysts have been prepared through sol-gel, CVD, 

oxidation of Ti plate etc. In this study, we synthesized 

monodispersed superparamgnetic ZnFe O submicron particles 

2 4 

by using a one-step solvothermal method. To induce the 

photocatalytic function, we coated TiO on ZnFe O nanoparticles 

2 2 4 

by atomic layer deposition(ALD). The submicron particles of 

ZnFe O and ZnFe O @TiO was analyzed by using X-ray 

2 4 2 4 2 

diffraction(XRD), field emission scanning electron 

microscopy(FE-SEM), and transmission electron 

microscopy(TEM). The diameter of prepared ZnFe O @TiO 2 4 2 

shows a monodispersed size distribution of 200±10 nm and 10nm 

in shell thickness. The magnetization was measured by a vibrating 

sample magnetometry(VSM). The magnetization curve of two 

samples have superparamagnetic behavior showing no hysteresis. 

The recyclable ZnFe O @TiO demonstrated an excellent 

2 4 2 

catalytic ability to degrade 2,4,6-tricholorophenol(2,4,6-TCP) in 

aqueous solution. 

Keywords: photochemistry; magnetism; nanoparticles; 

nanostructures; Spinel phases; 


P - 0 7 3 8 

PrePArAtion And CAtALytiC ACtivity of 

nAnoAG@MontMoriLLonite CoMPoSite 

MAteriALS 

M. KArLiKovA 1 , L. KviteK 1 , A. PAnACeK 1 , J. fiLiP 2 

1 Palacky University, Physical chemistry, Olomouc, Czech 

Republic 

2 Regional Centre of Advanced Technologies and Materials, 

Physical chemistry, Olomouc, Czech Republic 

In recent years, silver nanoparticles (Ag NPs) have belonged 

to intensively studied nanomaterials particularly due to their 

unique electrical, optical, catalytic or biologic properties. The 

increase of application potential of Ag NPs can bring their 

anchoring on a solid substrate. As a suitable materials for 

anchoring of Ag NPs clay minerals can be used especially due to 

their large surface area and good economic accessibility [1] . 

This work is aimed on the preparation and catalytic activity 

of composite materials containing silver nanoparticles (Ag NPs) 

anchored onto solid surfaces of the two types of clay minerals 

– calcium and sodium form of montmorillonite. The aqueous 

dispersion of silver NPs was prepared by reduction of [Ag(NH ) ] 3 2 + 

complex cation by maltose disaccharide [2] . The average size of 

the prepared particles was about 30 nm with narrow size 

distribution. Nanocomposite materials were prepared using simple 

adsorption of the silver NPs from their aqueous dispersion on the 

afore mentioned types of clay minerals. 

Catalytic activities of nanoAg@CaMMT and nanoAg@NaMMT 

composite materials were studied on a model reduction reaction 

of 4-nitrophenol to 4-aminophenol by sodium borohydride in 

aqueous solution. The rate constant of the reaction was obtained 

from the spectral changes of absorption peak of 

4-nitrophenolate ions at 400 nm with time. 

Acknowledgements: This work has been supported by 

the Operational Program Research and Development for 

Innovations - European Social Fund (CZ.1.05/2.1.00/03.0058), 

Czech Science Foundation (Project No. GAP304/10/1316), 


European Social Fund (CZ.1.07/2.3.00/20.0056) and also by 

internal grant of Palacký University in Olomouc 

(PrF_2012_028). 

references: 

1. Praus P., Turicova M., Machovic V., Studentov S.: 

Appl. Clay Sci. 49, 341-345, 2010. 

2. Panacek A., Kvitek L., Prucek R., Kolar M., Vecerova R., 

Pizurova N., Sharma V.K., Nevecna T., Zboril R.: 

J. Phys. Chem. B 110, 16248, 2006. 

Keywords: Adsorption; Nanoparticles; Silver; 



s1232 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 3 9 

interMetALLiC Cu-zn nAnoPArtiCLeS in 

StruCture of ir-PyroLyzed 

PoLyACryLinitriLe 

G. KArPAChevA 1 , d. MurAtov 1 , e. dzidziGury 2 , 

L. zeMtSov 1 

1 A.V.Topchiev Institute of Petrochemical Synthesis, Chemistry 

of Polyconjugated Systems, Moscow, Russia 

2 Nathional University of Science and Technology “MISIS”, 

Novel Materials and Nanotechnologies, Moscow, Russia 

Metal-carbon nanomaterials are of great interest for 

researchers due to wide spectrum of their practical application. 

The investigation of phase content, structure and morphology of 

metal-carbon nanocomposites as a function of preparation 

conditions opens up possibilities for regulation of their properties. 

The goal of research work is development of preparation 

method of metal-carbon nanocomposites based on IR-pyrolized 

polyacrylonitrile (IR-PAN) and bimetallic Cu-Zn nanoparticles 

and investigation of their structural characteristics. 

Metal-carbon composites were firstly prepared under the 

conditions of IR-pyrolysis of a precursor based on common 

solution of PAN, copper and zinc acetates in dimethylformamide. 

Pyrolysis was performed in an IR-chamber of a setup for pulse 

photon annealing. The carbonization of PAN and metals reduction 

in the presence of hydrogen which is released during 

dehydrogenation of backbone polymer chain of PAN took place 

simultaneously. In the obtained nanocomposites nanoparticles of 

intermetallic compounds are finely dispersed in graphite-like 

structure of IR-PAN. 

According to the X-ray difraction data for nanocomposites 

prepared at 300–500 °C there was one intensive peak 

corresponding to CuZn intermetallic compound reflection angles. 

5 

At 500


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chem. Listy 106, s257–s1425 (2012) 


P - 0 7 4 1 

funCtionALized MuLtiwALLed CArBon 

nAnotuBeS for the deLivery of therAPeutiC 

AntiSenSe oLiGodeoxynuCLeotideS AGAinSt 

non-MuSCLe-invASive BLAdder CAnCer 

A. KAufMAnn 1 , d. KunhArdt 2 , S. hAMPeL 2 , 

B. SChwenzer 1 

1 TU Dresden, Biochemistry, Dresden, Germany 

2 Leibniz Institute for Solid State and Materials Research 

Dresden, Institute for Solid State Research, Dresden, Germany 

Antisense oligodeoxynucleotides (AS-ODNs) are able to 

specifically down-regulate the expression of tumor-related genes 

like VEGF and survivin. Hence, they have a great potential as 

anticancer agent. In case of non-muscle-invasive bladder cancer 

the biggest challenge is an effective delivery of AS-ODNs and 

other drugs to the bladder wall before they can be excreted. 

Multiwalled carbon nanotubes (MWCNTs) are known to 

easily enter cells. Additionally, the surface of MWCNTs can be 

functionalized for different purposes like drug delivery and for 

increased mucoadhesive properties. In this way, they can enhance 

the local drug concentration at the mucous membrane of the 

bladder wall. For the delivery of AS-ODNs a DNA anchoring 

strand was coupled to MWCNTs and the complementary 

AS-ODNs can hybridize with these DNA-MWCNTs. Since 

hybridization of complementary DNA strands is a reversible 

process the AS-ODNs can be easily released from the carrier after 

the delivery to the bladder wall. Furthermore, the releasing 

behaviour of AS-ODNs can be controlled by adjusting the hybrid 

stability. For this reason, functionalized MWCNTs have a great 

potential as carriers for AS-ODNs. 

MWCNTs were produced by chemical vapour deposition. 

By washing the MWCNTs with nitric acid they were 

simultaneously oxidized. Afterwards, they were functionalized by 

a 1,3-dipolar cycloaddition reaction to insert hydroxyl groups for 

an improved stability of dispersion in aqueous solutions. DNA 

was coupled to these functionalized MWCNTs by covalent 

binding or helical wrapping. Afterwards AS-ODNs could 

hybridize with DNA-MWCNTs. Since the AS-ODNs were 

fluorescence-labelled subsequent desorption was investigated by 

fluorescence spectroscopy at different buffers and temperatures 

as well as under physiological conditions in urine and as function 

of varied anchoring strand sequences. 

The delivery of AS-ODNs by MWCNTs demonstrates a 

novel strategy to improve the therapy for non-muscle-invasive 

bladder cancer. In this way, the high recurrence and progression 

rates should be decreased. 

Keywords: Nanotechnology; Nanotubes; Oligonucleotides; 

Drug delivery; Cancer; 


P - 0 7 4 2 

MACroCyCLeS AS orGAnoCAtALySt – A new 

StrAteGy for rotAxAne SyntheSiS 

L. KAufMAnn 1 , A. A. Senf 1 , C. A. SChALLey 1 

1 Freie Universität Berlin, Chemistry and Biochemistry, Berlin, 

Germany 

Mechanically interlocked supramolecules such as rotaxanes 

and catenanes are of current interest not only because of their 

molecular topology but also as basis for the development of 

artificial molecular machines. One well-known example for such 

host molecules and rotaxane wheels are tetralactam macrocycles 

(TLM). They provide four converging hydrogen bonds to interact 

with suitable axle molecules and therefore have been frequently 

applied in templated rotaxane synthesis. As we report herein, the 

TLM may not only function as a host molecule but may also 

activate guest molecules. Several reactions like Diels-Alder 

reactions, Michael additions, electrophilic bromination can thus 

be organocatalytically accelerated. Basic requirement is the choice 

of a suitable reactant that fits geometrically into the cavity of the 

wheel and thus is activated by hydrogen bonding to the four amide 

protons. 

As rotaxane synthesis is often assisted by the templatedirected 

preorganization of the individual building blocks “via” 

metal-coordination, hydrogen bonding or donor-acceptor 

interactions, we combined the old template strategy with the 

observed catalytic effect into a new one: In addition to the 

preorganization of axles with suitable binding motifs within the 

macrocycle the following rotaxane formation is accelerated by the 

host. Our results suggest the interplay of organocatalysis and 

templates to become a powerful synthetic strategy for functional 

molecules. 

Keywords: Rotaxane; Organocatalysis; Diels-Alder reaction; 

Michael addition; 



s1234 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 4 3 

hoSt-GueSt CoMPLexeS: how SMALL 

StruCturAL ChAnGeS And MuLtivALent 

effeCtS CAn hAve A LArGe iMPACt on BindinG 

ProPertieS 

L. KAufMAnn 1 , n. L. LÖw 1 , h. SChrÖder 1 , 

n. f. KÖniG 1 , J. huuSKonen 2 , K. riSSAnen 2 , 

C. A. SChALLey 1 

1 Freie Universität Berlin, Chemistry and Biochemistry, Berlin, 

Germany 

2 University of Jyväskylä, Chemistry, Jyväskylä, Finland 

The binding behavior of differently substituted diamide axle 

molecules to Hunter/Vögtle tetralactam macrocycles was studied 

with a combination of NMR titration, ITC experiments, crystal 

structures, and density functional calculations. Therefore, it could 

be shown that substituents have a decisive effect on the binding 

situation: guests with alkyl or alkenyl chains attached to the 

diamide carbonyl groups have a significantly higher binding 

affinity to the macrocycle than guests with benzoyl amides and 

their substituted analoga. In these cases, the electronic effects of 

para-substituents at the benzoyl moieties determine the binding 

affinities. Electron donating substituents increase, while electronwithdrawing 

substituents decrease the binding energies until 

nearly no binding could be observed anymore. 

These results not only have an impact on the design of 

template effects for rotaxane synthesis, but all the more they are 

the basis for our synthesis of multivalent host-guest complexes 

based on pseudorotaxane structure, which are formed through an 

interplay of self-organization, self-sorting, template effects and 

multivalent interaction. 

The synthetic accessibility of these components allows the 

design of analogous series of pseudorotaxanes with different 

number of binding sites and thus a systematic evaluation of 

multivalent binding situations can be realized. 

Keywords: Pseudorotaxanes; Host-guest complexes; 

Multivalency; NMR titration; 


P - 0 7 4 4 

SyntheSiS And SuBSequent uSe of iron oxide 

nAnoPArtiCLeS And SiLver nAnoPArtiCLeS 

M. KiLiAnovA 1 , r. PruCeK 1 , J. tuCeK 1 , 

A. PAnACeK 1 , L. KviteK 1 , M. KoLAr 2 




2 Palacky University in Olomouc, Department of Microbiology, 


Nanoparticles of magnetic iron oxides, magnetite and 

maghemite, present materials, which are due to their specific 

properties used as biological sensors, catalysts, adsorbents, 

carriers of drugs, contrast agents in magnetic resonance and in 

many other applications. Nanoparticles of silver are regarded to 

be another interesting nanomaterial, they are commercially used 

because of their high antibacterial activity. By combining these 

nanoparticles, we gain nanocomposites of iron oxide nanoparticles 

and silver nanoparticles - Ag@Fe O and γ-Fe O @Ag. Magnetic 

3 4 2 3 

nanocomposites present one of the remarkable developed 

materials of nanotechnology research. Thanks to their magnetic 

properties, they can be efficiently transported to the required place 

of the human body by external magnetic field. 

We prepared these nanocomposites by the chemical 

reduction of silver ions in the presence of magnetic iron oxides, 

polyacrylic acid sodium salt and D-maltose. The prepared 

nanocomposites were characterized by transmission electron 

microscopy, SQUID magnetometry, X-ray powder diffraction, 

atomic absorption spectroscopy and Mössbauer spectroscopy. 

Both nanocomposites were tested for their antibacterial activity 

and cytotoxicity. For tested bacteria species there was obtained 

minimal inhibition concentration (MIC) ranges from 15.6 mg/L 

to 125 mg/L and for tested candida species the MIC levels range 

from 1.9 mg/L to 31.3 mg/L. To the contrary, acute cytotoxicity 

against mice embryonal fibroblasts was observed at 

concentrations of higher than 292 mg/L for γ-Fe O @Ag 

2 3 

nanocomposite and 430 mg/L for nanocomposite Ag@Fe O . 3 4 

Keywords: nanoparticles; iron; silver; magnetic properties; 



s1235 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 4 5 

SoLvent free PrintinG of eLeCtroniC 

CirCuitS with SiLver nAnoPArtiCLeS 

PrePAred By A Green And ControLLed 

SyntheSiS 

r. KLAAS 1 , r. dr. SChneider 1 , 

M. Prof. BuChMeiSer 1 


Germany 

Progresses in the fabrication of printed electronics have 

opened the door for the production of portable, flexible and very 

low-cost electric circuits. Concrete examples for printable 

electronics are photovoltaics, antennas, flexible displays and 

batteries, sensors, RFID tags, lighting devices, resistive heaters 

and transistors. It is known from literature that recent 

investigations focused on the integration of conductive tracks on 

[1, 2, 3] 

flexible polymer foils, paper and textile fabrics. 

For the fabrication of printed electronic devices different 

printing technologies can be used such as screen printing, gravure, 

offset lithography, flexography or inkjet printing. Inkjet printing 

offers a number of advantages compared to the other printing 

techniques. It is a digital printing technology and therefore no 

special templates have to be fabricated and it is a nonimpact 

printing procedure with inks of low viscosity. 

Since the end oft the 20th century, special fabric printers 

using colour ink-jet technology by digital printing are 

inexpensively available on the market. Investigations were made 

to use these standard commercial printers for the fabrication of 

highly conductive patterns on textile fabrics. Therefore special 

water-based, non-toxic, solvent-free, ‘green‘ inks had to be 

prepared. 

Silver was chosen as conductive material because it has the 

highest electrical conductivity of all metals. During the last years, 

the synthesis of silver nanoparticles has attracted tremendous 

interest. Different synthetic methods have been developed and in 

few cases details on mechanism of formation are known. [4, 5] Here, 

we present a new synthesis that allows for controlling the 

nanoparticle size and thus preparing water-based silver inks for 

textile printers. The particles were characterized using different 

techniques like DLS, UV/Vis spectroscopy and SEM micrographs. 

An overview of ink preparation will be given on the poster. 

references: 

1. A. Bok, D. Lorang, J. Lewis, J. Nanoscale 2011, 3, 

2700–2702 

2. L. Hu, M. Pasta, F. La Mantia, L. Cui, S. Jeong, H. 

Deshazer, J. Choi, S. Han, Y. Cui Nano Lett. 2010, 10, 

708–714 

3. A. Dennulin, A. Blayo, C. Neumann, J. Bras J. Nano. Res. 

2011, 13, 3815–3823 

4. Y. Li, Y. Wu, B.S. Ong, J. Am. Chem. Soc. 2005, 127, 

3266–3267. 

5. A. Karakoti, S. Das, S. Thevuthasan, S. Seal, Angew. 

Chem. Int. Ed. 2011, 50, 1980–1994. 

Keywords: Nanotechnology; Silver; Sustainable Chemistry; 


P - 0 7 4 6 

toPoCheMiCAL reACtionS in fuLLerene 

BASed CryStALS 

e. KovAtS 1 , G. BorteL 1 , S. PeKKer 1 

1 Institute for Solid State Physics and Optics Wigner Research 

Centre for Physics, Experimental Solid State Physics, 


Topochemical reactions in fullerene-based crystals can be 

originated from crystal- and molecular structural features. 

Fullerenes are the 3D analogues of planar aromatic systems, their 

reactivity comes from reactive double bonds. The basic material, 

C has various solid phase reactions in pure crystals and in 

60 

cocrystals too. 

In pure fullerene crystals photopolymerization can occur by 

the effect of light resulting small sized cycloadduct fullerene 

homo-oligomers. We worked out a new method to produce C60 photopolymer in gram scale [1] , and we detected several small 

sized oligomers, and obtained solvent-free photo-dimer crystals. 

Based on the relatively big size of the fullerenes big cavities 

can be found in the crystal structure with different symmetries. 

Small guest molecules can be built into these voids. We showed 

that with reactive guest molecules, like piperylene or small azides 

topochemical reactions can be carried out with high selectivity 

and good yield. 

Several high symmetry cocrystals arise with the 

combination of fullerenes and cubanes [2] . These supramolecular 

crystals have unusual dynamics based on the match of molecular 

surfaces of the rotating and static components, that we called 

‘rotor-stator property’. We showed that rotor-stator systems can 

be formed with C and higher fullerenes too and also with 

60 

disubstituted cubane derivatives. At elevated temperature a single 

phase copolymerization occurs induced by the thermal 

decomposition of cubanes. 

Acknowledgement: This work has been supported by the grant 

OTKA T072954. G. B. and É. K. acknowledge support of the 

Bolyai János Scholarship of the Hungarian Academy of 

Sciences. 

references: 

1. É. Kováts, G. Oszlányi and S. Pekker, 

J. Phys. Chem. B, 2005, 109, 11913-11917. 

2. S. Pekker, É. Kováts, G. Oszlányi, G. Bényei, G. Klupp, 

G. Bortel, I. Jalsovszky, E. Jakab, F. Borondics, K. Kamarás, 

M. Bokor, G. Kriza, K. Tompa, G. Faigel, 

Nature Materials, 2005, 4, 464-467. 

Keywords: fullerenes; topochemistry; cocrystals; 



s1236 

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P - 0 7 4 7 

SyntheSiS And StruCture of A 

SuLfonAto-BridGed ti-oxo CLuSter 

J. Kreutzer 1 , C. Artner 1 , u. SChuBert 1 

1 Vienna University of Technology, Materials Chemistry, Vienna, 

Austria 

Transition metal -oxo clusters find increasing interest in 

material science as nanosized building blocks, especially for 

inorganic-organic hybrid materials [1] . When polymerizable 

ligands are attached to the cluster surface, the inorganic building 

blocks can be incorporated in polymers by covalent bonding [2] . 

Numerous transition metal-oxo clusters with polymerizable 

ligands were synthesized and used to obtain polymers with 

tailored properties. 

A versatile route to such clusters is by reactions of transition 

metal alkoxides with carboxylic acids, whereby cluster size and 

shape is determined by the alkoxide/acid ratio, the kind of 

carboxylic acid and the kind of alkoxo groups. 

During the last decade mainly carboxylic acids were used 

for cluster synthesis. The change from bidentate carboxylic acids 

to potentially tridentate ligands for the cluster synthesis can widen 

the range of structural possibilities. 

In this work we present the synthesis and structure of a new 

type of Titanium-oxo cluster based on phenylsulfonic acid. 

references: 

1. C. Sanchez, G. J. de Soler-Illia, F. Ribot, T. Lalot, 

C. R. Mayer, V. Cabuil, Chem. Mater. 13, 3061 (2001). 

2. U. Schubert, Chem. Mater. 13, 3487 (2001). L. Rozes, 

N. Stenou, G. Fornasieri, C. Sanchez, Monatsh. Chem. 137, 

501 (2006). 

Keywords: Oxo Cluster; Hybrid materials; 


P - 0 7 4 8 


CAdMiuM teLLuride nAnoPArtiCLeS 

v. KuBAt 1 , A. StySKALiK 1 , J. novoSAd 1 



Cadmium telluride is an attractive semiconducting material. 

Its unique properties are making it an ideal candidate for 

applications in optoelectronical devices (mainly solar cells). In 

this work we present a new method of synthesis of cadmium 

telluride using bis(diphenylphosphino)amine, cadmium carbonate 

and tellurium as starting materials. 

In our system, all three reactants are suspended in toluene 

and heated in an autoclave to 160 – 180 °C. Under these mild 

conditions acidic H + from NH group of Ph PNHPPh protolyses 

2 2 

cadmium carbonate releasing cadmium(2+) ions. In addition 

P(III) atoms of Ph PNHPPh also act as reducing agents reducing 

2 2 

tellurium to telluride. That means that cadmium telluride is 

directly formed in the reaction mixture and no other interventions 

into the system are necessary. 

Formation of CdTe was confirmed by PXRD analysis. 

Product morphology was investigated by SEM imaging. Particle 

size of prepared CdTe is about 102 nm, however, particle size 

distribution is not narrow and formed particles are aggregated. We 

are studying this problem intensively. 

To conclude, we offer a new method of synthesis of 

cadmium telluride using Ph PNHPPh , CdCO and Te as starting 

2 2 3 

materials. Main advantage of presented system is that the whole 

reaction takes place in one reaction step. 

Keywords: Nanoparticles; Cadmium telluride; 



s1237 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 4 9 


PorouS ALuMinA SoL-GeL CoAtinGS 

d. Kun 1 , z. horvoLGyi 1 


Department of Physical Chemistry and Materials Science, 


Nowadays there is a growing interest in sol-gel coatings 

since sol-gel process provides a relatively cheap, simple and 

robust method to create thin films on solid substrates giving them 

special features (antireflexion, self-cleaning etc.). 

Our aim was to determine experimentally the optimum 

conditions (precursor sol composition, rate of film transfer) for 

preparing γ-Al O coatings with maximum porosity via a sol-gel 

2 3 

process applying surfactant templates. Thickness and refractive 

index of the coatings were characterized by UV-Vis 

spectrophotometry and scanning angle reflectometry analyzing 

the data with different optical models [1–3] . Porosity was estimated 

with the Lorentz-Lorenz formula. 

A modified recipe [4] was used for the precursor sols which 

were prepared via the hydrolysis of aluminium-triisopropoxide, 

the acidic peptization of the boehmite formed and the addition of 

cetyl-trimethyl-ammonium-bromide (CTAB) as template. Thin 

films were prepared on microscope glass slides by dip-coating. 

The coated substrates were dried and annealed at 500 °C for 

90 minutes. The analysis of differential scanning calorimetry, 

thermogravimetry, infrared spectroscopy and wide-angle X-ray 

scattering proved that this annealing process results in γ-Al O 2 3 

powder. 

An optimum CTAB concentration was established at which 

porosity of ca. 40 % was reached. The highly porous samples can 

be good candidates for sensor applications in the future. 

Acknowledgement: Help of E. Hild, E. Volentiru, Á. Detrich, J. 

Madarász, A. Menyhárd and G. Pénzes is gratefully 

acknowledged. This work was supported by the Hungarian 

Scientific Research Fund (OTKA CK 78629) and the New 

Széchenyi Plan (TÁMOP-4.2.1/B-09/1/KMR-2010-0002). 

references: 

1. E. Hild, Per. Pol., Chem. Eng. 19 (1975) 295-305 

2. E. Hild, A. Deák, L. Naszályi, Ö. Sepsi, N. Ábrahám, 

Z. Hórvölgyi, J. Opt. A: Pure Appl. Opt. 9 (2007) 920-930 

3. E. Hild, T. Seszták, D. Völgyes, Z. Hórvölgyi, Prog. 

Colloid Polym. Sci. 125 (2004), 61-67 

4. Y-C. Chen, X. Al, C-Z. Huang, Mat. Sci. Eng. B77 (2000) 

221-228 

Keywords: sol-gel processes; thin films; UV-Vis spectroscopy; 

nanotechnology; 


P - 0 7 5 0 

SoLution-ProCeSSed uLtrAthin CheMiCALLy 

derived GrAPhene fiLMS AS Soft toP 

ContACtS for SoLid-StAte MoLeCuLAr 

eLeCtroniC JunCtionS 

t. Li 1 , J. hAuPtMAnn 1 , z. wei 1 , B. LAurSen 1 , 

K. norGAArd 1 , t. BJornhoLM 1 

1 University of Copenhagen, Nano-Science Center, Copenhagen, 

Denmark 

A major goal of molecular electronics is to understand 

charge-transport properties of single molecules and their 

ensembles. Ultimately this will pave the way for electronic 

components made of molecular building blocks that can overcome 

[1, 2] 

the limits of conventional semiconductor technology. 

Compared with the junctions built on a very limited number of 

molecules, self-assembled monolayers (SAMs) offer a more 

reproducible way for the fabrication of molecular electronic 

devices, and are more amenable to mass production and 

integration. However, direct in situ evaporation of metals onto 

SAMs has proven to be too invasive and damaging. Filamentary 

paths of metals or damages to the molecules can very easily cause 

short-circuits. 

Here, we report the use of solution-processed chemically 

derived graphene (CDG) films for non-destructive fabrication of 

molecular electronic junctions. [3] Wafer-scale continuous films 

with sub-10 nm thicknesses can be uniformly delaminated from 

the substrate and transferred without polymer supports onto SAMs 

to function as soft electrical top-contacts. Two types of molecular 

junctions are developed demonstrating a versatile application of 

the CDG thin-films. We believe this protocol will greatly enrich 

the test beds for molecular electronics due to its low-cost, 

easy-processing and flexible nature. 

references: 

1. K. Moth-Poulsen, T. Bjornholm, Nat. Nanotechnol. 4 

(2009) 551. 

2. T. Li, W. P. Hu, D. B. Zhu, Adv. Mater. 22 (2010) 286. 

3. T. Li, J. Hauptmann, Z. Wei, S. Petersen, N. Bovet, 

T. Vosch, J. Nygard, W. P. Hu, Y. Q. Liu, T. Bjornholm, 

K. Norgaard, B. W. Laursen, Adv. Mater. 24 (2012) 1333. 

Keywords: Molecular electronics; Graphene; 



s1238 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 5 1 

orGAniC nAnotuBeS for druG LoAdinG And 

CeLLuLAr deLivery 

y. MAitAni 1 , A. wAKASuGi 1 , M. ASAKAwA 2 , 

M. KoGiSo 2 , t. ShiMizu 2 

1 Hoshi University, Medicinal Chemistry, Tokyo, Japan 

2 National Institute of Advanced Industrial Science and 

Technology, Nanotube Research Center, Tsukuba, Japan 

Background: Organic nanotubes made of synthetic 

amphiphilic molecules are novel materials that form by selfassembly. 

objectives: Organic nanotubes were expected to apply a 

drug carrier in drug delivery system. 

Methods: Organic nanotubes with a carboxyl group (ONTs) 

at the surface were used as a carrier for the anticancer drug 

doxorubicin, which has a weak amine group. Drug loading into 

ONT and cellular delivery of them was investigated, using 

cytotoxicity and transmission electron microscope. 

results: The IC(50) values of ONT for cells were higher 

than that of conventional liposomes, suggesting that ONTs are 

safe. The results showed that the drug loading of ONTs was 

susceptible to the effect of ionic strength and H(+) concentration 

in the medium, and drug release from ONTs was promoted at 

lower pH, which is favorable for the release of drugs in the 

endosome after cellular uptake. ONTs loaded with the drug were 

internalized, and the drug was released quickly in the cells, as 

demonstrated on transmission electron microscopy images of 

ONTs and the detection of a 0.05% dose of ONT chelating 

gadolinium in the cells. Moreover, ONT could be modified 

chemically with folate by simply mixing with a folate-conjugate 

lipid. 

Conclusion: These novel, biodegradable organic nanotubes 

have the potential to be used as drug carriers for controlled and 

targeting drug delivery. 

Keywords: nanotube; cellular uptake; drug load; doxorubicin; 


P - 0 7 5 2 

dnA-nAnoCuBeS hyBridS for BioMoLeCuLAr 

reCoGnition 

C. MArtini 1 , C. AiMe 1 , t. CorAdin 1 

1 University Pierre and Marie Curie, Laboratoire de Chimie de 

la Matiere Condensée, Paris, France 

Biomolecules recognition is a very important area of 

research for medical diagnostic improvement. Among existing 

methods, the specific disassembling of network based on 

“aptamer” – DNA interactions appears to be one of the most 

promising strategy. Aptamers are oligonucleic acids or peptides 

selected through repeated rounds of in vitro selection (SELEX: 

systematic evolution of ligands by exponential enrichment) to 

bind strongly to various molecular targets such as proteins, nucleic 

acids and even whole cells. Combined with a complementary 

sequence, oligonucleotide aptamers are able to assemble owing 

to Watson-Crick DNA base pairing. The obtained double strands 

disassemble as the target molecule is introduced, aptamer-target 

interactions being higher than that of aptamer-complementary 

sequence. While aptamers are bonded to nanoparticles, 

self-assembled networks of nanoobjects can be obtained. Their 

disassembling in the presence of the target molecule can strongly 

disturb the physical properties such as plasmonic or magnetism, 

depending on the chemical nature and the organization of 

nanoparticles. Such physical disturbing can be easily exploited 

for biomolecular detection. In this context, we develop 

nanohybrids composed of DNA associated with platinum, 

iron-platinum or iron oxide nanocubes. Since they own planar 

faces, nanocubes represent unique shapes for self-assembly. The 

poster will present all aspects of this work: the chemical synthesis 

of nanocubes, the ligands exchange to confer water solubility and 

to further introduce specific functions, and the peptidic coupling 

between DNA and functionalized nanocubes. 



s1239 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 5 3 

PoLyMer nAnoPArtiCLeS for the 

ControLLed reLeASe of SinGLet oxyGen 

S. MArtinS 1 , J. S. fArinhA 1 , C. BALeizAo 1 , 

M. n. BerBerAn-SAntoS 1 

1 Instituto Superior Técnico, Centro Química Física Molecular, 

Lisboa, Portugal 

Singlet oxygen ( 1O ) is a reactive form of O that plays an 

2 2 

important role in many oxidation processes, e.g. photooxidation, 

DNA damage, and photodynamic therapy [1] . Due to its short 

lifetime and often low local concentration of ground state O , a 2 

controlled production and release of 1O is difficult to achieve. In 

2 

this work we describe a new strategy for producing singlet 

oxygen, using the thermolysis of 9,10-diphenylanthracene (DPA) 

endoperoxides incorporated within polymer nanoparticles. DPA 

can react reversibly with singlet oxygen, forming an endoperoxide 

that can regenerate the initial aromatic compound by thermolysis, 

releasing singlet oxygen [2] . 

Nanoparticles of polybutylmethacrylate were prepared by a 

two-step, starved feed emulsion polymerization technique, using 

a DPA-acrylate co-monomer. The nanoparticles were then 

irradiated in the presence of a photosensitizer to obtain the 

endoperoxides. Subsequent thermolysis of the nanoparticles 

triggers the controlled released of singlet oxygen. We will present 

the preparation and characterization of the nanoparticles as well 

as the comprehensive fluorescence spectroscopy study of 

endoperoxide formation and thermolysis in the nanoparticles. 

Acknowledgement: SM was supported by a Ph. D. grant from 

FCT- Fundacio para a Ciencia e Tecnologia 

(SFRH/BD/47660/2008). 

references: 

1. DeRosa, M. C., Crutchley, R. J., Coord. Chem. Rev. 233 

(2002) 351 

2. Turro, N. J., Chow, M. F., Rigaudy, J., J. Am. Chem. Soc. 

103 (1981) 7218 

Keywords: Singlet Oxygen; Nanoparticles; Polymers; 


P - 0 7 5 4 

CovALent PoLyoxoMetALAte hyBridS for the 

eLABorAtion of funCtionAL deviCeS 

B. MAtt 1 , G. izzet 1 , C. rinfrAy 1 , S. renAudineAu 1 , 

M. MenAnd 1 , M. SoLLoGouB 1 , A. ProuSt 1 

1 University Pierre and Marie Curie, Institut Parisien de Chimie 

Moléculaire, Paris, France 

Polyoxometalates (POMs) are molecular oxides offering a 

wide range of applications in catalysis, medicine and materials 

science. The modularity of their structural and electronic 

properties associated with their ability to accept electrons or the 

diversity of their functionalization ways, make them attractive 

candidates for the elaboration of multifunctional molecular 

materials. The Polyoxometalates group in Paris has a long 

tradition in the synthesis and functionalization of 

organic/inorganic hybrids based on POMs, especially by 

anchoring a covalent link between the polyanion and the organic 

tether. [1] This covalent approach allows us to initiate new 

applications for POMs by integrating them into functional devices 

and strengthening the interaction between the organic and the 

inorganic part. Based on recent examples, [2, 3] we will herein 

present the synthetic approach towards various functionalized 

POMs and the applications of the resulting hybrids in different 

fields such as artificial photosynthesis, [4] molecular nanosciences [5] 

or self-organized materials. [6] 

references: 

1. A. Proust, R. Thouvenot, P. Gouzerh Chem. Commun. 

2008, 1837-1852. 

2. V. Duffort, R. Thouvenot, C. Afonso, G. Izzet, A. Proust 

Chem. Commun. 2009, 6062-6064. 

3. B. Matt, C. Coudret, C. Viala, D. Jouvenot, F. Loiseau, 

G. Izzet, A. Proust Inorg. Chem. 2011, 50, 7761–7768. 

4. B. Matt, J. Moussa, L-M. Chamoreau, C. Afonso, 

A. Proust, H. Amouri, G. Izzet Organometallics., 2012, 

31, 35-38. 

5. N. Joo, S. Renaudineau, G. Delapierre, G. Bidan, 

L. M. Chamoreau, R. Thouvenot, P. Gouzerh, A. Proust 

Chem. Eur. J., 2010, 16, 5043-5051. 

6. G. Izzet, M. Menand, B. Matt, S. Renaudineau, 

L. M. Chamoreau, M. Sollogoub, A. Proust Angew. Chem. 

Int. Edit., 2012, 51, 487-490. 

Keywords: Polyoxometalate; Molecular electronics; 




s1240 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 5 5 

A SAMPLe CheMiCAL route towArd 

MonodiSPerSe iron CArBide nAnoPArtiCLeS 

diSPLAyinG tunABLe MAGnetiC And 

unPreCedented hyPertherMiA ProPertieS 

A. Meffre 1 , B. MehdAoui 1 , v. KeLSen 1 , 

P. f. fAzzini 1 , J. CArrey 1 , S. LAChAize 1 , 

M. reSPAud 1 , B. ChAudret 1 

1 INSA, GP, Toulouse, France 

Monodisperse and air stable magnetic nanoparticles 

displaying high magnetization and tunable anisotropy are highly 

desirable for several nanotechnology applications1 . However, 

among the various magnetic nanoparticles previously described, 

no one fills of these properties. A recent study in our group reveals 

that iron(0) nanoparticles could be good candidates for 

hyperthermia but lack the air-stability criteria2 . In contrast, 

iron/iron oxide core-shell and iron oxide nanoparticles display a 

good air-stability but a low magnetization. An improvement of 

these behaviors requires either coating iron(0) nanoparticles with 

a protective shell or changing the chemical nature of the particles3 . 

In this respect, iron carbides nanoparticles are particularly 

attractive since combining high magnetization, air stability and 

the possibility to modulate the magnetic properties as function of 

carbon content. But up to now no wet chemical methods for their 

synthesis were described. 

Here, we report the first chemical synthesis sample and 

reproducible for the preparation of monodisperse iron carbides 

and iron/iron carbides nanocrystals with controlled sizes and 

compositions4 . The synthesis deriving from the Fischer Tropsch 

mechanism is original and is based on decomposition of Fe(CO) 5 

on different mild conditions on a colloidal solution of iron(0) NPs 

stabilized by hexadecylammonium chloride and hexadecylamine5 . 

Under dihydrogen atmosphere, we were able to enlarge the 

particle size and activate the carbon diffusion inside the iron 

nanoparticle. Their mean size is well controlled by adjusting the 

seeds one and/or the Fe(CO) concentration. All these 

5 

nanoparticles display excellent magnetic properties and airstability. 

More, by tunning the experimental conditions, as 

temperature and reducing agent, we can control the amount of 

carbon diffused inside and therefore their magnetic anisotropy. 

However, these nanoobjects have no precedent and some of 

them display the highest efficiency so far reported for magnetic 

hyperthermia in the current operating treatment conditions. 

Keywords: nanoparticles; magnetic properties; 


P - 0 7 5 6 

PrePArAtion of PerovSKite oxide thin fiLM 

eLeCtrodeS By rf MAGnetron SPutterinG 

for environMentAL APPLiCAtionS 

M. e. MeLo JorGe 1 , M. i. SivA PereirA 1 , A. roviSCo 2 , 

J. S. MArtinS 2 , y. nuneS 2 , S. Sério 2 

1 CCMM, Departamento de Química e Bioquímica Faculdade 

de Ciencias da Universidade de Lisboa, Lisboa, Portugal 

2 CEFITEC, Departamento de Física Faculdade de Ciencias e 

Tecnologia da Universidade Nova de Lisboa, Lisboa, Portugal 

The search of new and more efficient methods for the 

treatment of effluents containing several persistent pollutants 

species is a very important issue. Electrochemical technology 

offers an efficient and environmental friendly approach for the 

elimination of different kinds of pollutants. The removal of 

metallic ions from solution by electrochemical reduction is a well 

known process. Depending on the cathode material and applied 

potential, a selective recovery of metals from solution can be 

performed. 

Perovskite type structure oxides are potential materials for 

this application. However, special attention must be given to the 

electrode construction, in particular its mechanical stability. The 

sputtering technique presents several advantages on electrodes 

preparation [1] such as high deposition rates, high-purity films and 

extremely high adhesion film/support. 

The main objective of this work was to optimize the growth 

conditions for obtaining crystalline Ca Sm MnO thin films 

1-x x 3 

prepared by an innovative approach using the magnetron 

sputtering technique. The films were prepared by radio frequency 

magnetron sputtering under various deposition conditions using 

nanosized powder compacted targets. The polycrystalline samples 

Ca Sm MnO used as targets were previously prepared by 

1-x x 3 

self-combustion method using citric acid [2] . The plasma medium 

was characterized using optical emission spectroscopy. 

The characterization of the bulk and the thin films were 

performed using different tools. The structural and morphological 

characterization was carried out by X-ray diffraction (XRD), 

scanning electron microscopy (SEM) and atomic force 

microscopy (AFM). 

Acknowledgements: Financial support from FEDER, 

through Programa Operacional Factores de Competitividade– 

COMPETE, and Fundacio para a Ciencia e a Tecnologia–FCT, 

for the projects PTDC/AAC-AMB/103112/2008. 

references: 

1. S. Sério, M. E. Melo Jorge, M. J. P. Maneira, Y. Nunes, 

Mat. Chem. Phys., 126 (2011) 73-81. 

2. I. Matos, S. Sério, M. E. Lopes, M. R. Nunes, 

M. E. Melo Jorge, J.Alloys Compds, 509 (2011) 9617–9626. 

Keywords: Perovskite phases; Thin films; Nanotechnology; 

Surface analysis; X-ray diffraction; 



s1241 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 5 7 

CoAtinG Pt(o) nAnoPArtiCLeS with MethyLS: 

the reACtion Between MethyL rAdiCALS And 

Pt(o)- nP(S) SuSPended in AqueouS SoLutionS 

d. MeyerStein 1 , r. BAr-ziv 2 , i. ziLBerMAnn 2 , 

t. zidKi 3 , G. yArdeni 4 

1 Ariel University center of samaria, Biological Chemistry, 

Ariel, Israel 

2 Nuclear Research Center Negev and Ben-Gurion University of 

the Negev, Chemistry, Beer-Sheva, Israel 

3 Ben-Gurion University of the Negev and Brookhaven National 

Laboratory, Chemistry, Beer-Sheva and Upton, Israel 

4 Nuclear Research Centre Negev and Ben-Gurion University of 

the Negev, Chemistry, Beer-Sheva, Israel 

Methyl radicals react with Pto-NPs suspended in aqueous 

solutions in fast reactions. The major product is stable methyl 

coated Pto-NPs, (Pto-NPs)-(CH ) . C H , C H and some 

3 n 2 6 2 4 

polymerization products are also formed. These results differ 

significantly from those reported for the analogous reactions with 

Ago and Auo NPs. The source of the differences is discussed in 

detail. 

Keywords: Pt(0); ; Nanoparticles; ; Methyl Radicals; 


P - 0 7 5 8 

end-to-end diStAnCe deterMinAtion in A 

CuCurBit[6]uriL-BASed rotAxAne By PuLSed 

eLeCtron-eLeCtron douBLe reSonAnCe 

SPeCtroSCoPy 

e. MezzinA 1 , r. Pievo 2 , M. BennAti 2 , C. CASAti 1 , 

P. frAnChi 1 , M. LuCArini 1 

1 University of Bologna, Department of Organic Chemistry 

‘A. Mangini’ Via San Giacomo 11 40126, Bologna, Italy 

2 Max Planck Institute for Biophysical Chemistry, Research 

Group Electron Paramagnetic Resonance am Faßberg 11 

37077, Göttingen, Germany 

The development of molecular machines is one of the most 

attractive and challenging fields of supramolecular chemistry. In 

particular, there is a great interest in their potential use for 

nanoelecronics and nanotechnology. [1] 

For an efficient design of such nanostructures, it is required 

a quantitative knowledge about the structure, features and 

properties of each of its molecular components, as well as for 

understanding of the mechanical and dynamic properties once 

these nanoobjects are assembled together in a supramolecular 

architecture. The access to the information regarding the intrinsic, 

structural and conformational flexibility of these molecular 

machines can be gained from the distance distribution among their 

constituting objects. 

In 2011, we have reported the synthesis and the 

characterization of a series of paramagnetic cucurbituril-based 

rotaxanes, in which the thread end-units were constituted by 

2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) radicals. [2] 

Here we report the use of pulsed electron-electron double 

resonance (PELDOR) spectroscopy for the determination of the 

distance distribution among the nitroxidic end units of a 

paramagnetic cucurbit[6]uril-based [3]rotaxane (1). [3] 

PELDOR measurements on rotaxane (1) have revealed a 

very sharp distances distribution, centered at 3.07 (± 0.14) nm that 

can be attributed to the elongated conformation inferred by the 

cucurbit[6]uril macrocyclic units. In the absence of the latters, the 

free thread exhibited a broader and more complex distance 

distribution underlining a higher conformational freedom. 

These experimental data have been also strongly supported 

by molecular dynamic simulations. [3] 

references: 

1. A. Coskun, M. Banaszak, R. D. Astumian, J. F. Stoddart, 

B. A. Grzybowski, Chem. Soc. Rev. 2012, 41 (1), 19. 

2. E. Mileo, C. Casati, P. Franchi, E. Mezzina, 

and M. Lucarini, Org. Biomol. Chem. 2011, 9 (8), 2920. 

3. R. Pievo, C. Casati, P. Franchi, E. Mezzina, M. Bennati, 

M. Lucarini, ChemPhysChem, DOI: 

10.1002/cphc.201200103. 

Keywords: EPR spectroscopy; Radicals; Rotaxanes; 

Supramolecular Chemistry; 



s1242 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 5 9 

hierArChiCAL SeLf-ASSeMBLy of LuMineSCent 

LAnthAnide CoMPLexeS on SiLiCon 

K. MiSztAL 1 , J. MALiCKA 2 , n. ArMAroLi 2 , 

e. dALCAnALe 1 



2 Instituto per la Sintesi Organica e la Fotoreattivita - CNR, 

Molecular Photoscience Group, Bologna, Italy 

An innovative approach for surface functionalization with 

Lanthanide complexes via molecular recognition is presented. 

Silicon wafers were decorated with tetraphosphonate cavitands 

using photochemical grafting protocol to obtain a functional 

surface presenting specific molecular recognition properties. [1] 

This kind of cavitands are known as versatile synthetic receptors 

which can complex neutral molecules like alcohols [2] as well as 

positively charged species like ammonium salts. [3] Based on this 

premise, we decided to functionalize the phenanthroline ligand of 

luminescent Eu complex with a suitable substituent bearing a 

methyl ammonium unit. Ternary complex formation in solution 

was confirmed by NMR and MS experiments. Photophysical 

studies revealed good luminescence properties of complex 

(quantum yield 20%) and also confirm complexation. A slightly 

modified protocol has been used for solid state transfer. 

Deposition of ternary complex on silicon wafers consists of two 

steps: host-guest complexation of phenanthroline-sarcosine ligand 

followed by coordination of Eu(hfac) . Each step was monitored 

3 

by XPS technique and physisorption has been excluded. The 

resulting hybrid material presents good luminescent properties 

without luminescence quenching caused by the silicon surface. 

references: 

1. Biavardi, E. et al., J. Am. Chem. Soc., 2009, 131, 

7447–7455 

2. Maffei, F. et al., Angew. Chem., Int. Ed., 2011, 50, 

4654–4657 

3. Biavardi, E. et al., Chem. Commun., 2008, 1638–1640 

Keywords: Lanthanides; Supramolecular chemistry; Molecular 

recognition; Cavitands; Silicon; 


P - 0 7 6 0 

PSeudorotAxAneS AS PrototiPeS of 

MoLeCuLAr MAChineS worKinG on GrAPhite 

SurfACeS 

P. MonteLLAno 1 , A. roMero 1 , J. tiBurCio 2 , 

f. PAeSAni 3 , f. GonzALez 2 

1 Centro de Investigación y de Estudios Avanzados del IPN, 

Materials, Queretaro, Mexico 

2 Centro de Investigación y de Estudios Avanzados del IPN, 

Chemistry, Mexico D.F., Mexico 

3 University of California at San Diego, Chemistry & Biochemistry, 

La Jolla, USA 

Nanoscience is rapidly expanding its influence on our daily 

life; this is probably due to the advantages of new technologies 

based on the molecular behavior of nano-sized systems. 

Supramolecular self-assembled systems as rotaxanes, 

pseudorotaxanes and catenanes, are depicted as some of the most 

promising molecular structures in the development of 

nanosciencies, because they are good prospects for building 

molecular machines. In this work, we deal with pseudorotaxanes, 

which are systems composed of two interpenetrated molecules 

-axle and wheel-, attached to graphite surfaces. The axles we have 

synthesized and characterized are viologen derivatives; they were 

designed to have a recognition site for a disulfo-dibenzo-24- 

-crown-8 ether and also a carboxilate group, that can be used to 

electrochemically attach the axle to a graphene surface. The axles 

and its dynamical behavior in solution with the wheel have been 

characterized by several techniques such as nuclear magnetic 

resonance, electronic spectroscopy and mass spectrometry. In this 

work, we will present our results on Molecular Dynamics 

simulations using AMBER 11 and also Potential of Mean Force 

(PMF) calculations. The simulations have shown that two coconformations 

are possible for the associated components in 

solution, one is the traditional threaded co-conformation and the 

other one is the exo-associated co-conformation, better known as 

the taco co-conformation. The PMF results prove that a 

recognition site for the wheel is present in the axle, that is located 

close to the cationic nitrogen on the axle. The linkage between 

the axles and a graphene sheet was studied from first principles 

calculations using the Density Functional Theory. This results 

show that a covalent bond between the axle and the graphene 

surface can be formed. 

Keywords: Supramolecular chemistry; Nanotechnology; 

Electrochemistry; Ab initio calculations; Molecular Dynamics; 



s1243 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 6 1 

deveLoPMent of veSiCLe-BASed 

CheMoSenSorS: direCted funCtionALizAtion 

of veSiCLe SurfACeS 

A. MueLLer 1 , B. KoeniG 1 



For the development of highly specific vesicle-based 

chemosensors, a well defined two-dimensional assembly of 

different binding sites on the spherical vesicle surface is necessary. 

However, simple addition of the desired receptors to the 

phospholipid mixture during vesicle preparation is subject to 

restrictions: Firstly, suitable artificial amphiphilic receptor 

molecules are needed – often only accessible by a tedious 

synthesis. Secondly, based on previous works from our group, the 

embedded binding sites are supposed to gather in tightly packed 

patches due to phase separation. [1] This makes a directed receptor 

assembly on the surface difficult. In order to overcome those 

limitations, our approach relies on a subsequent controlled 

attachment of receptors on unfunctionalized liposome 

membranes, which are only modified with special binding 

anchors. As a fast and reliable reaction for covalent fixation, the 

UV light induced thiol–ene click reaction is used. This reaction 

fulfills the essential requirement of water and oxygen tolerance 

and exhibits biocompatibility. Here, we present preliminary results 

from our investigations towards a defined receptor structuring on 

vesicle surfaces. 

references: 


B. König, Angew. Chem. Int. Ed. 2010, 49, 7125–7128. 


Vesicles; Sensors; Click chemistry; 


P - 0 7 6 2 

‘MoLeCuLAr CLiP’ reCePtorS for 

dihydroxyBenzeneS with SuitABLe BindinG 

SiteS for enhAnCed CoPPer CoMPLexAtion 

B. MurrAy 1 , J. MorAn 1 , J. MCGinLey 2 

1 Institute of Technology Tallaght, Science, Dublin 24, Ireland 

2 National University of Ireland Maynooth, Chemistry, 

Maynooth Co. Kildare, Ireland 

Email: brian.murray@ittdublin.ie 

Urea-based Molecular Clips mimic natural receptors, with 

an upper organic-cavity that binds to dihydroxybenzene (DHB) 

molecules. [1] Many neurotransmitters such as dopamine contain a 

DHB moiety. 

The locking phenyl groups of the Molecular Clip hold it in 

a convergent conformation for binding a DHB, but these groups 

– with suitable modification can also serve as a binding site for 

metals. The addition of nitrogen-containing groups here are ideal 

for copper complexation [2] , whose ions play a large role in neural 

functions. Elevated Cu2+ levels have been implicated in the 

formation of protein plaques that are found in the neural tissue of 

Alzheimer’s patients. [3] Such clips may act a model for the binding 

and control of the redox states of copper, and protection of 

DHB-type neurotransmitters. 

Current work involves the addition of bipyridine moieties 

to the lower locking phenyl ring system, and synthesis of new 

benzil molecules which can be further functionalised to enhance 

copper complexation. 

references: 

1. B. A. Murray and G. S. Whelan, Pure & Appl. Chem. 

1996, 68, 1561-1567. 

2. M. Kozien, PhD. Thesis, ITT Dublin, 2009. 

3. A. Binolfi, G. R. Lamberto, R. Duran, L. Quintanar, 

C. W. Bertoncini, J. M. Souza, C. Cervenansky, 

M. Zweckstetter, C. Griesinger and C. O. Fernández, 

J. Am. Chem. Soc., 2008, 130, 11801-11812. 


Dopamines; Copper; Allosterism; 



s1244 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 6 3 

hiGh-LeveL GeoMetriC ControL of new 

rotAMeriC MoLeCuLAr CLiP reCePtorS: nMr 

StudieS of rotAMer interConverSion And 

BindinG to dihydroxyBenzene GueStS 

B. MurrAy 1 , B. CreAven 1 , M. Kozien 1 , J. MorAn 1 , 

z. yeASMin 1 

1 Institute of Technology Tallaght, Science, Dublin 24, Ireland 

Molecular clips, originally introduced by Nolte [1] , are 

well-known artificial receptors for dihydroxyaromatics, e.g. 

resorcinol, catechol, catecholamines, and other biomolecules 

bearing a dihydroxyaromatic unit. Two xylylene walls and two 

carbonyl groups, making a pre-organized cavity, are the key 

features which bind the substrate via two aryl-stacking & two 

hydrogen-bonding interactions. [1] 

We have prepared new clips which exist as rotamers: 

isomers interconverted by rotation about a single bond. [2] The 

rotameric site is incorporated into two phenyl substituents which 

control the convergent conformation of the receptor, but do not 

directly disturb the binding site. 

VT-NMR allows us to interconvert these rotamers, and 

measure the energy barrier; the latter is also accessible via free 

energy calculations. Surprisingly, the energy barrier was found to 

be independent of the nature of the substituent in the 

3,3'-positions, but this has now allowed us rationalize the 

mechanism of interconversion. 

We have now moved on to a more hindered 

2,2'-disubstituted series, where variation of the substituent now 

allows a significant biasing towards the trans-rotamer being more 

stable (up to 100%), and also leads to higher interconversion 

barriers. 

NMR titration yields binding constants to guests such as 

resorcinol. 

The new rotameric clips show considerable promise for 

high-level control of receptor geometry and of associated binding 

of guests to each rotamer. 

references: 

1. a) Sijbesma, R. P.; Wijmenga, S. S.; Nolte, R. J. M. J. Am. 

Chem. Soc. 1992, 114, 9807; 

b) Sijbesma, R. P.; Bosman, W. P.; Nolte, R. J. M. J. Org. 

Chem. 1991, 56, 3199; 

c) Smeets, J. W. H.; van Dalen, L.; Kaats-Richter, 

V. E. M.; Nolte, R. J. M. J. Org. Chem. 1990, 55, 454. 

2. Kozien, M. PhD Thesis, ITT Dublin, 2009. 

Keywords: Molecular recognition; NMR spectroscopy; 

Isomerization; Atropisomerism; Host-guest systems; 


P - 0 7 6 4 

nAnoPArtiCuLAte AeroSoL MAnufACturinG 

ProCeSS 

f. nALBAntoGLu 1 , M. ozBeK 2 , e. er 2 , o. KArBAn 2 , 

G. KAynAr 2 , M. KArABuLut 2 , t. ozden 1 

1 Gazi University Faculty of Pharmacy, Pharmaceutical 


2 World Medicine pharmaceuticals, R&D, Istanbul, Turkey 

Micronised drug particles for MDI products of aerosol 

asthma drugs on the market tends to be acculumated on the inner 

surface of containers, or valve components during their shelf lifes. 

These micronised particles can also undergo moisture initiated 

instability where water can promote chemical instability and 

particle adhesion/cohesion differences in these formulations. 

While we were devoloping a new aerosol formulation, 

suprisingly, we founded that if the formulation have specific 

parameters in terms of particles size distribution rate or 

morphology which affects obtainable surface area and moisture 

absorbtion profiles, the resulted formulation have greater 

suspension stability in its life-time use while comparing its former 

specifications. 

The formulation must be a nanoparticulate pharmaceutical 

composition -solid concentration between 0.1 % – 0.5 %- at least 

one active pharmaceutical ingredient or salt or solvate, at least 

one propellant or propellant mixture, at least one polymer or 

polymer combination which has moleculer weight of 

190-70000 g/mol. 

Formulation trials have been done for these nanoparticulate 

aerosol formulations in order to obtain desired particle size and 

morphology which are < 0.5 μm and spherical, respectively. 

Sample concentrations were used in 2.5 % – 5 % (as weight basis). 

Solution or suspension were prepared in water and mixed by 

mechanical mixer before spraying through the nozzles. Nano 

spray-drying method encapsulates successfully active ingredient 

with polymer/ polymer combinations which increases the 

moisture and gas barrier properties while increasing surface area 

of dispersed particles in liquefied gas. This leads to improvements 

on the chemical instability resulted from the moisture in the 

structure and more cohesive forces which enhances the uniformity 

of the composition. Active ingredient were mixed with polymer 

or polymer combinations in different ratios. A yield of 70-75% is 

attained with the use of spheric particles with the size between 

0,6 and 4 micron. 

Keywords: nanoparticles; Drug delivery; Polymers; 

Nanotechnology; 



s1245 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 6 5 

eLeCtron And Phonon Size-quAntizAtion 

effeCtS in nAnoStruCtured zinC SeLenide 

thin fiLMS. oPtiCAL ABSorPtion And rAMAn 

SCAtterinG Study 

i. nAStovA 1 , B. PeJovA 1 

1 Faculty of Natural Sciences and Mathematics, Institute of 

Chemistry, Skopje, Macedonia 

Nanostructured thin films composed by close packed zinc 

selenide quantum dots of sphalerite structural type were 

synthesized by our recently developed template-free chemical 

route. Structural and compositional characteristics of the films 

were studied by X-ray diffraction. Average crystal size, lattice 

constants, lattice strain and dislocation densities were computed 

by analysis of the XRD data for as-deposited and thermally 

annealed films. Electronic quantum confinement effects in the 

synthesized quantum dot solids were investigated by optical 

absorption spectroscopy. On the basis of the measured spectral 

dependencies of absorption coefficients of the films, band gap 

energies were calculated with a combined interpolationextrapolation 

technique, employing the parabolic approximation 

for the dispersion relation. The experimentally measured 

dependence of the band gap energy of the films on the average 

crystal size was compared to the predictions of various theoretical 

models. To study the phonon-confinement effects in the 

synthesized low-dimensional semiconductors, Raman scattering 

technique was employed. Raman spectra were recorded using 

micro-Raman spectrometer, Horiba Jobin-Yvon LabRam 300, 

equipped with double-frequency Nd:YAG laser line operating at 

532 nm. The band due to the LO phonon mode in the Raman 

spectra of the synthesized quantum dot solids was found to exhibit 

a notable red shift in comparison to the value characteristic for 

the bulk material. The half-width of this band was found to be 

significantly larger in the case of the studied low-dimensional 

solid as compared to the bulk sample, and its low-frequency side 

exhibited a pronounced asymmetry. These effects were attributed 

to the relaxation of the k = 0 selection rule, due to the finite 

dimensions of the quantum dots. The low-frequency shoulder of 

the one-phonon LO band could be attributed to the surface optical 

phonon (SO) or zone-edge (ZE) modes. Aside from the onephonon 

LO mode, also several replicas thereof have been detected 

in the Raman spectrum. 

Keywords: zinc selenide; quantum dots; phonon confinement 

effects; 


P - 0 7 6 6 

hydroGen in LiGht-MetAL CLuSter-CAGe 

ASSeMBLieS: towArdS A nAnofoAM StorAGe 

f. nAuMKin 1 , d. wALeS 2 

1 UOIT, Faculty of Science, Oshawa, Canada 

2 University of Cambridge, Department of Chemistry, 

Cambridge, United Kingdom 

Potential high-capacity storage of hydrogen in 

metal-hydride solids is problematic due to hydrogen strongly 

binding to metal atoms, with its release requiring unacceptably 

high temperatures. Adsorption of hydrogen on metal-cluster 

surfaces impose similar limitations, while hydrogen absorption 

into cluster cages may enable its relatively easy withdrawal due 

to predicted lower stability of the systems. 

This work presents results of ab initio calculations for maingroup 

light-metal clusters M (n≤18) with up to two endohedral 

n 

H molecules [J.Phys.Chem.A 115 (2011) 12105]. Of primary 

2 

interest are the systems structure and stability relative to separate 

cage and H molecule(s), including energy barriers to hydrogen 

2 

escape from the cage. The origin of the reduced stability is 

explored, involving cage-molecule charge-transfer and Coulomb 

explosion of the molecules confined inside the surrounding cage. 

Related potential direct energy storage is also discussed. 

Preservation of the cage integrity and hydrogen confinement 

are investigated for these core-shell units merging together into 

larger aggregates. Such cluster assemblies structurally resemble 

fragments of hydrogen-filled metal nanofoams, possible isomeric 

forms of metal-hydride solid, nonfilled (pure-metal) nanofoams 

being already feasible experimentally. With H molecules 

2 

undergoing metal-cage induced (endohedrally catalyzed) 

dissociation, different “nanofoam” isomers are composed of either 

pairs or single H atoms suspended electrostatically inside the 

metal cage units (“nanobubbles”). Interesting features include 

simultaneous exit of two H atoms, unexpected stabilization of the 

systems in specific geometries, higher stability of assembly 

isomers formed by less stable isomers of units. Preliminary 

structural extrapolations estimate potential hydrogen storage 

capacity of up to ~10 weight-%. 

Also of interest is the alteration of the metal-cage structure 

and related properties via inserting hydrogen, including induced 

polarity. Non-covalent interactions of the molecular core and the 

metal shell can facilitate metal-cluster shape and property design 

and tuning. Relevant parameters characterize charge distribution, 

electronic excitation, ionization, and electron attachment. 

Keywords: Hydrogen; Cluster compounds; Cage compounds; 

Main group elements; Computational chemistry; 



s1246 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 6 7 


SeLeCtive SenSor nAnoPArtiCLeS for 

MAGnetiC reSonAnCe iMAGinG 

d. nordMeyer 1 , P. StuMPf 1 , d. GrÖGer 2 , f. PAuLuS 2 , 

r. hAAG 2 , A. SeMiSCh 3 , C. riChter 3 , A. hArtwiG 3 , 

J. dernedde 4 , r. MALz 5 , u. rAuCh-KrÖhnert 5 , 

J. SChnorr 6 , i. GeMeinhArdt 6 , M. tAuPitz 6 , 

C. GrAf 1 , e. rühL 1 

1 Freie Universität Berlin, Biology Chemistry and Pharmacy 

Institute of Chemistry and Biochemistry Physical and 

Theoretical Chemistry, Berlin, Germany 

2 Freie Universität Berlin, Biology Chemistry and Pharmacy 

Institute of Chemistry and Biochemistry Organic Chemistry, 


3 Technische Universität Berlin, Institute of Food Technology 

and Food Chemistry, Berlin, Germany 

4 Charité – Universitätsmedizin Berlin, Institute of Laboratory 

Medicine Clinical Chemistry Pathobiochemistry, Berlin, 

Germany 

5 Charité – Universitätsmedizin Berlin, Cardiovascular 

Diseases, Berlin, Germany 

6 Charité – Campus Mitte, Institute of Radiology, Berlin, 

Germany 

The aim of the present study is the synthesis of iron oxide 

nanoparticles functionalized by hyperbranched sulfated 

polyglycerols (a heparin analogue) on their surface. This leads to 

antiinflamatory, antimetastatic, antiathereosclerotic, and 

antiproliferativ effects in organisms and can accumulate in 

infected biological tissue. These hyperbranched sulfated 

polyglyceroles functionalized iron oxide nanoparticles might be 

used as contrast agents in the magnetic resonance imaging. It is 

found that the number of functionalizing groups in the 

hyperbranched sulfated polyglycerol determines the stability of 

the iron oxide nanoparticles. Measurements are performed in 

different biological media, such as Dulbecco`s Modified 

Minimum Medium (DMEM) and isotonic saline, where the 

stability of the nanoparticles and aggregation is probed. 

Additionally, cell viability studies are reported using human colon 

cancer cells. These are incubated with hyperbranched sulfated 

polyglycerol functionalized iron oxide nanoparticles, indicating 

that the viability of the cells is increased. Surface plasmon 

resonance (SPR) studies indicate that the hyperbranched sulfated 

polyglyceroles functionalized iron oxide nanoparticles lead to an 

inhibition of L-selectin binding. Finally, the binding of 

hyperbranched sulfated polyglycerol functionalized iron oxide 

nanoparticles to infected tissue is tested using a mice-model, 

which is infected with viral induced myocarditis. 

These results indicate that hyperbranched sulfated 

polyglycerol functionalized iron oxide nanoparticles may be 

suitable for being used as a contrast agent in the magnetic 

resonance imaging. 

Keywords: Nanoparticles; Inflammation; Inhibitors; 


P - 0 7 6 8 

MoLeCuLAr eLeCtroniCS in SeLf-ASSeMBLed 

And SoLid-StAte deviCeS 

K. norGAArd 1 , t. Li 1 , t. JAin 1 , t. BJornhoLM 1 



Molecular nanogap junctions have been the subject of 

intense study for the last decade, and include a variety of 

approaches, such as mechanically controlled break junctions, 

electromigration and scanning probe techniques. Herein, we 

report recent progress towards the fabrication of novel 

self-assembled molecular electronics systems, including solidstate 

devices [1, 2] and chemically prepared nanogap junctions [1] . 

Self-assembled solid-state monolayer devices containing a 

range of conjugated organic molecules have been realized 

employing chemically derived graphene as a soft, transparent 

top-contact. Additionally, the graphene can serve as a protecting 

layer against monolayer degradation from evaporating a metallic 

top electrode [1] . Finally, chemically prepared nanogaps between 

gold nanostructures have been achieved in solution [3] and on 

surfaces [4] with a variety of molecules trapped in the gaps, 

providing a possible route towards large-scale fabrication of 

(single) molecular devices. 

references: 

1. T. Li et al., Adv Mater 24 1333-1339 (2012) 

2. Z. Wei et al, Langmuir 28 4016-4023 (2012) 

3. T. Jain et al., J. Colloid Interface Sci T, 376, 83-90 (2012) 

4. T. Jain et al., ACS Nano, DOI: 10.1021/nn204986y (2012) 

Keywords: Molecular electronics; Self-assembly; 

Nanostructures; Graphene; 



s1247 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 6 9 

qCM Study of SAM forMAtion on SiLver 

nAnorod LAyerS 

z. novAKovA 1 , r. orinAKovA 2 

1 Faculty of Science Comenius University, Department of 

Physical and Theoretical Chemistry, Bratislava, Slovak 

Republic 

2 Pavol Jozef Safarik University, Department of Physical 

Chemistry, Kosice, Slovak Republic 

Self assembled monolayers (SAM) of thiols and disulfides 

have been studied for their potential application, since their 

discovery in 1983 by Nuzzo and Allara. SAM formation provides 

one easy route towards surface functionalization by organic 

molecules (both aliphatic and aromatic) containing suitable functional 

groups like –SH, –CN, –COOH, –NH and silanes on selected 

2 

metallic (Au, Cu, Ag, Pd, Pt, Hg and C) as well as semiconducting 

surfaces (Si, GaAs, indium coated tin oxide, etc.) [1] . 

Electron transfer through nanometer-thick organic films is 

of fundamental importance in the development of nanometer-scale 

electronic materials. Knowledge of how chemical compositions 

and chemical structures affect electron transfer between a solid 

substrate and a redox-active molecule is central to the study of 

molecular-level electron transfer [2] . 

The adsorption of SAM was monitored using a quartz 

crystal microbalance (QCM). QCM measurements confirmed the 

inhibition of molecules adsorption on substrate surface [3] . 

The aim of this study was modification of silver nanorod 

layers electrochemically deposited on stainless steel substrate with 

SAM. The effect of time and concentration of 1-hexadecanethiol 

in chloroform solution on the formation of SAM adsorbed on 

silver nanorod layers was studied using QCM. It was found that 

the prolonged time of adsorption step resulted in the SAM 

molecular weight increase. 


VEGA 1/0211/12 of the Slovak Scientific Grant Agency and the 

Project APVV SK-CZ-0113-11 of the Slovak Research and 

Development Agency. 

references: 

1. Ciftci H., Tamer U.: Reactive & Functional Polymers 72 

(2012) 127-132 

2. Raoof J. B., Ojani R., Rashid-Nadimi S.: Electrochimica 

Acta 53 (2008) 7261-7265 

3. Yuyama J., Masuhara H.: Applied Surface Science 255 

(2009) 7647-7651 

Keywords: nanostructures; self-assembly; monolayers; silver; 

electrochemistry; 


P - 0 7 7 0 

ACtuAtinG ProPertieS of CoMPoSiteS 

ContAininG CArBon nAnotuBeS 

M. oMAStovA 1 , K. CzAniKovA 1 , P. KASAK 2 , 

d. ChorvAt Jr. 3 , i. KruPA 1 

1 Polymer Institute, Department of Composite Materials, 


2 Polymer Institute, Department for biomaterials research, 


3 International Laser Center, Department of Biophotonics, 


The composites with elastomeric matrix are highly 

developing, because of various interesting applications. Carbon 

nanotubes (CNT) have been widely used as filler for different 

kinds of polymers for the preparation of high performance 

composite materials. Recently, nanotube-enriched elastomeric 

polymers have shown photo-actuating properties. Photo- and 

thermo-mechanical actuation is preferred to electromechanical 

transduction because of some advantages including wireless 

connection, a producing low noise, fast response, etc. However, 

only few materials actually exhibit photo or thermal-actuation. 

This presentation will contribute to solving basic aim of 7 RP 

project NOMS (Nano-Optical Mechanical Systems) which is the 

processing of photoactuating elastomeric composites containing 

well dispersed carbon nanotubes. The purpose of the project is to 

build a visual-aid tablet for visually impaired people. 

For preparation of the composites ethylene vinyl acetate 

copolymer – EVA was used as polymeric matrix. Two different 

types of CNT, multiwall CNT, and singlewall CNT were use as 

fillers. Non-covalent modification of CNT was carried out with 

the surfactant based on pyrene molecules. The nanocomposites 

were prepared by casting from solution. The actuation of two 

forms of the nanocomposites, strips and specifically designed 

samples prepared using so called punch and die system was study. 

The dispersion of CNT in the polymeric matrix has been 

investigated by scanning electron microscopy and transition 

electron microscopy. In order to characterize the deformation 

changes of material under light irradiation, Nanoindenter TI-750 

(Hysitron, USA), and SEM technique combined with camera were 

applied for study of light inducted photo and thermo-actuation of 

prepared nanocomposites. 

In the presentation we will show results of photo-actuating 

behaviour of new photo-actuating materials based on the 

commercial elastomers such as ethylene-vinylacetate copolymer 

filled with carbon nanotubes. 

Acknowledgements: This work was supported by project NOMS 

which is funded by the European Commission under contract 

no. 228916, and by project VEGA 2/0064/10. 

Keywords: actuator; polymeric nanocomposite; carbon 

nanotubes; 



s1248 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 7 1 

nAnoteChnoLoGy of MoLeCuLAr LAyerinG 

for PrePArAtion of trAditionAL And 

MeMBrAne CAtALyStS 

n. oreKhovA 1 , M. erMiLovA 1 , A. MALyGin 2 , 

A. MALKov 2 , S. MiKhAiLovSKy 2 


Laboratory of Membrane Catalysis, Moscow, Russia 

2 St.Petersburg Technical University, Department of 

Nanotechnology, St.Petersburg, Russia 

Molecular layering method (ML) is based on the irreversible 

interaction between of low-molecular reagents and functional 

groups of a surface of solid substrate under the conditions of 

continuous reagent input and removing the formed gaseous 

products. In this multistage process, a number of physical and 

chemical stages are separated; as a result of these stages, a 

monomolecular layer of new structural units is formed on the 

matrix surface. The thickness of the deposited coating is 

controlled by the number of ML cycles rather than the exposure 

time. In this case the precision in determining the composition is 

achieved on the atomic–molecular level. 

In the present study the series of nanostructured catalysts 

was prepared by ML deposition of Ti, V oxides structures on the 

alumina powders. The other application of ML was the 

optimization of the selectivity of gas permeability of alumina 

membranes by modification of their porous structure with ML 

deposition of titania into pores of initial membrane at a variation 

of number of cycles ML. The following insertion by ML method 

of the vanadium - and vanadium-phosphorus oxide nanostructures 

gave the composite membranes catalytically active in oxidative 

dehydrogenation of methanol to formaldehyde. It was shown that 

methanol conversion and selectivity of formation of formaldehyde 

on traditional and membrane catalysts depend on the nature of the 

catalytically active components on a surface of modified catalyst 

and on the number of ML cycles. 

It is shown that the nanotechnology of ML gives a 

possibility to prepare on the surface of porous support in the 

united chemical-technological cycle the assembly of 

nanostructures of various functional purpose: for providing the 

system with the desired catalytic properties and for the regulating 

of the pores size of substrates. 

Keywords: molecular layering; membrane; catalyst; oxidative 

dehydrogenation; 


P - 0 7 7 2 

effeCtS of MontMoriLLonite-SorBitoL on 

CryStALLizAtion BehAviorS And iMPACt 

reSiStAnCe of PoLyProPyLene 

nAnoCoMPoSiteS 

C. PeChyen 1 , S. ChuAyJuLJit 2 , 

A. uSSAwAdiLoKrit 2 

1 Kasetsart University, Packaging and Materials Technology, 

Bangkok, Thailand 

2 Chulalongkorn University, Materials Science, Bangkok, 

Thailand 

Effects of sorbitol-modified montmorillonite 

(MMT-sorbitol) on crystallization behaviors and impact strength 

of polypropylene (PP) nanocomposites were studied. The 

modification process included mixing MMT and sorbitol at a 

MMT/sorbitol weight ratio of 1/2 using a high speed mixer. 

Results from X-ray diffraction (XRD) indicated that sorbitol was 

intercalated between MMT layers along the 001 direction. PP 

resin was mixed with MMT-sorbitol powder at 1 to 7 parts per 

hundred of resin (phr) by means of melt blending on a two-roll 

mill, and pressed into specimens. XRD patterns indicated that PP 

chains could intercalate into the gallery of MMT-sorbitol to form 

exfoliated PP nanocomposites. The crystal obtained from this 

process was the α-monoclinic PP form. Compared to the neat PP, 

higher amounts and smaller sizes of spherulites were observed in 

the nanocomposites. Specimens of the nanocomposite with a 

MMT-sorbitol concentration of 1 phr exhibited the highest impact 

strength: 3.4, 3.2 and 2.7 kJ/mm2 when the specimens were at 

room temperature (25 °C), 0 °C and -30 °C, respectively. 

Keywords: Crystallization behaviors; Impact resistance; 

Montmorillonite-sorbitol; Polypropylene; 



s1249 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 7 3 

rotor-StAtor CoCryStALS of fuLLereneS 

with CuBiC And oCtAhedrAL MoLeCuLeS 

S. PeKKer 1 , e. KovAtS 1 , G. BorteL 1 , e. JAKAB 2 , 

G. durKo 3 , i. JALSovSzKy 3 

1 Wigner Research Centre for Physics, Institute for Solid State 

Physics and Optics, Budapest, Hungary 

2 Research Centre for Natural Sciences, Institute of Materials 

and Environmental Chemistry, Budapest, Hungary 

3 Eötvös Loránd University, Institute of Chemistry, Budapest, 

Hungary 

Fullerenes form cocrystals with a great variety of organic 

molecules. The majority of these materials belongs to various 

host-guest systems, depending on the shape and size of the counter 

molecules. Fullerene-cubane cocrystals represent a special family: 

none of the components form a host framework, they rather form 

separated sublattices [1] . The major stabilizing factor of such 

structures is the almost perfect mach of the molecular surfaces of 

convex fullerenes and concave cubanes. The expanded fullerene 

sublattice confines cubanes in static positions. On the other hand, 

the atomic arrangement of the fullerene surface is 

incommensurate with that of cubane, therefore, the rotation of 

fullerenes has no influence on the match. Thus, cubanes behave 

as a molecular bearing for the freely rotating fullerene, resulting 

in unusual dynamics. The alternating array of static and rotating 

components distincts this family of rotor-stator phases from both 

the orientationally ordered and plastic crystals. Rotor-stator 

properties slightly depend on the size and symmetry of the 

fullerenes and the substituents of cubane, but the major properties 

are characteristic of the whole family. We present here a new 

member of this family, the rotor-stator cocrystal of the endohedral 

Sc N@C with cubane. In this material the rotor-stator properties 

3 80 

of the molecules are extended to the rotation of the endohedral 

Sc N units. Besides the cubic shaped cubane, octahedral and other 

3 

high-symmetry molecules may form similar cocrystals with 

fullerenes. In the absence of octahedral molecules of suitable size, 

we studied the fullerene cocrystals with the distorted octahedral 

pairs of mesitylene. We compare the influences of the cubic and 

octahedral shapes on the structures and properties. 

references: 

1. Pekker, S., Kováts, É., Oszlányi, G., Bényei, Gy., Klupp, 

G., Bortel, G., Jalsovszky, I. Jakab, E., Borondics F., 

Kamarás, K., Bokor, M., Kriza, G., Tompa, K., Faigel, G., 

Nature Materials, 2005, 4, 764. 

Keywords: fullerenes; cocrystals; supramolecular chemistry; 


P - 0 7 7 4 

inveStiGAtion of the SoL-GeL CheMiStry for 

the PrePArAtion of tio -zro And Pure tio 2 2 2 

nAnoStruCtured PowderS 

S. PfLeiderer 1 , d. LützenKirChen-heCht 1 , 

r. frAhM 1 

1 University of Wuppertal, Fachbereich C-Physik, Wuppertal, 

Germany 

Nanostructured titania materials can be used in a wide field 

of applications. The most popular application is maybe the use of 

TiO nanoparticles as photocatalyst. For this application, it is 

2 

important to have a look on the materials characteristics, which 

were found to influence the catalytic activity in a sensitive way. 

Desired characteristics for good catalysts are a small particle size 

and a large specific surface area, a high crystallinity and the 

anatase TiO polymorph. To prepare nanostructured materials with 

2 

tailored characteristics, the sol-gel process is very popular. It has 

been found by different research groups that the preparation of 

TiO -ZrO composite nanopowders is very interesting due to the 

2 2 

stabilization of the crystallite size and phase and an enhanced 

photocatalytic activity. 

Different possibilities are known to influence the sol-gel 

chemistry and by doing so the structure of the reaction products. 

Nevertheless, there are to our best knowledge no systematical 

investigations of the influence of sol-gel chemistry on the reaction 

products of TiO -ZrO composite samples, in contrast to the case 

2 2 

of pure TiO samples. 

2 

We studied the influence of the zirconia concentration on 

the composite powder structure and conducted further 

experiments concerning the influence of the chemical reaction 

path. The powders were prepared from titanium isopropoxide and 

zirconium n-propoxide precursors. Powder characterization was 

made with x-ray diffraction to determine the crystallite structure 

and size and x-ray absorption spectroscopy, which provides 

information about the crystallinity and the atomic environment of 

the absorbing species. 

We found that the possibility of crystallization of the titania 

to anatase particles is only given for small zirconia concentrations. 

The crystallite size stayed nearly constant in the composite 

samples with increasing annealing temperature and phase 

transformations can substantially/successfully be suppressed, 

which could be derived from comparison with pure titania 

powders. 

Keywords: Sol-gel processes; Nanoparticles; X-ray absorption 

spectroscopy; X-ray diffraction; 



s1250 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 7 5 


12-tunGStoPhoSPhoriC ACid iMMoBiLized on 

G-fe o @Sio Core-SheLL nAnoPArtiCLeS AS 

2 3 2 

SoLid ACid CAtALySt for BiGineLLi reACtion 

e. rAfiee 1 , S. eAvAni 1 , f. MAhMoodi 1 , 

M. JoShAGhAni 1 


In the field of heterogeneous catalysis, solid supported 

Keggin type heteropoly acids (HPAs), such as 

12-tungstophosphoric acid, H PW O (PW), arouse much 

3 12 40 

attention for they not only have strong Brönsted acidity, but they 

can also be recovered from reaction media and reused. Among the 

supports that can be used to immobilize HPAs, acidic or natural 

substance like SiO , TiO or active carbon are suitable and the 

2 2 

Keggin structure of HPAs is retained upon adsorption onto their 

surfaces over a broad range of loading. [1] However, although these 

solid supported HPAs can be recovered by filtration or 

precipitation, lower activity or selectivity compared to 

homogeneous ones are commonly detected due to steric and 

diffusion factors. In the attempt to resolve such problems, 

nanomagnetically-recoverable HPA-based catalyst, was 

synthesized and used as novel special heterogeneous HPAs in 

Biginelli reaction. [2] A simple ferric oxide, γ-Fe O , was used as the 

2 3 

magnetic material for its low price, simplicity and non-toxicity. 

It was coated with silica shell. After the surface coating by SiO , 2 

magnetic solid (designed as γ-Fe O @SiO ) was used as support 

2 3 2 

for immobilization of PW. The obtained catalyst (designed as 

γ-Fe O @SiO -PW) was collected by a permanent magnet and 

2 3 2 

dried. [3,4] It was found that the catalyst exhibits several attractive 

features for the synthesis of fine chemicals. 

references: 

1. E. Rafiee, H. Jafari; Bioorg. Med. Chem. Lett. 2006, 16, 

2463. 

2. Kozhevnikov, I. V. Chem. Rev 98, 1998, 171. 

3. M. Kotani, T. Koike, K. Yamaguchi, N. Mizuno, 

Green Chem. 2006, 8, 735. 

Keywords: Nanoparticle; Heterogeneous catalysis; Magnetic 

Properties; Polyoxometalate; Supported catalyst; 


P - 0 7 7 6 


h Cow o SuPPorted on nAno SiLiCA froM 

5 12 40 

riCe huSK ASh AS A Green BifunCtionAL nAno 

CAtALySt 

e. rAfiee 1 , M. KhodAyAri 1 , M. JoShAGhAni 1 


The recent emergence of nano catalysis has received a lot 

of attention because it opens new perspectives for the mild 

catalysis of important reactions with lower environmental impact. 

Catalysis based on heteropoly acids (HPAs) and related 

compounds especially those comprising the strongest Keggin-type 

HPAs is an important field in which new and promising 

developments are being carried out both at research and 

technological levels [1] . Most reactions have been carried out over 

HPA supported on different carriers. They have excellent catalytic 

activity and present a greater number of surface acid sites than 

their bulk components [2–3] . Nano silica has been prepared from 

rice husk (RH), which is an agricultural waste, with high surface 

area and in amorphous form. Formation of reactive nano scale 

silica from RH is a simple process compared to other conventional 

techniques for its production including vapor-phase reaction, 

sol-gel and etc [4] . 12- Tungestocobaltic acid (H CoW O , CoW) 

5 12 40 

has been supported on the silica from rice husk ash (RHA) to 

produce nano silica supported CoW (NCoW/SiO ) as a 

2 

bifunctional nano catalyst (as an electron transfer and strong 

Brönsted acid). NCoW/SiO was characterized by FT-IR, XRD 

2 

and TEM, also, acidic properties has been studied by 

potentiometric titration method. Catalytic activity of these 

nanocatalyst has been investigated in some organic reactions. 

references: 

1. Misono, M.; Okuhara, T. Chem. Technol. 23 (1993) 23. 

2. Rafiee, E.; Shahbazi, F.; Joshaghani, M.; Tork, 

F. J. Mol. Catal. A: Chem. 242 (2005) 129–134. 

3. Kozhevnikov, I.V. Catalysis by Polyoxometalates, 2, 

Wiley, Chichester, 2002. 

4. Tomozawa, M.; Kim, D.L.; Lou, V. J. Non-Cryst. Solids 

296 (2001) 102. 

Keywords: Nanocatalyst; Heterogenous catalysis; Supported 

catalyst; nanoparticles; Electron transfer; 



s1251 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 7 7 

MetAL oxide nAno-SheetS with (111) SurfACeS 

AS CAtALyStS And CAtALySt SuPPortS 

r. riChArdS 1 

1 Colorado School of Mines, Chemistry and Geochemistry, 

Golden, USA 

The interface of the fields of catalysis and nanoscale 

materials is one of the most exciting areas of modern science and 

is at the forefront of the quest for a “green” and sustainable future. 

Recent progress on new methods to control the size, shape and 

composition of nanoscale materials and their application in 

renewable energy technologies are particularly intriguing. 

Recently, the Richards’ research group has developed techniques 

to produce a number of new nanoscale materials that have 

demonstrated unique physical and chemical properties through 

controlled facetting. Here, recent highlights regarding these 

materials and their applications will be presented with a particular 

focus towards nanostructured metal oxides. MgO and NiO have 

a typical rocksalt structure and although the stoichiometry and 

crystallinity change little, the morphology can vary in shape, 

particle size and surface structure. The (100) facet of the rocksalt 

structure is unambiguously the most stable due to its low surface 

energy, therefore, it is unaminously the surface demonstrated by 

current wet chemical preparations. Numerous studies have 

demonstrated that the shape and size of crystalline MgO and NiO 

are highly influential on the adsorption properties. Furthermore, 

nanoscale MgO has been reported to be extremely effective for 

the destructive adsorption of numerous environmental toxins and 

several chemical warfare agents (VX, sarin, mustard gas). 

However, the (111) surface consists of alternating polar 

monolayers and thus, a strong electrostatic field perpendicular to 

the (111) surface is created. Such a surface has provided a 

prototype for the study of surface structure and surface reactions, 

which drew great attention for both experimental and theoretical 

studies. These studies imply the importance of size and shape 

control in metal oxide synthesis for their applications. 

Keywords: green chemistry; nanostructures; Heterogeneous 

catalysis; Supported catalysts; 


P - 0 7 7 8 

An effiCient And oPtiMized 

AMinoSiLAnizAtion of ti6AL4v ALLoy for 

BioMediCAL deviCeS 

A. rodríGuez-CAno 1 , M. C. fernández-CALderón 2 , 

M. A. PAChA-oLivenzA 3 , r. BABiAno 4 , P. CintAS 4 , 

M. L. GonzáLez-MArtín 3 

1 Universidad de Extremadura. Centro de Investigación 

Biomédica en Red en Bioingeniería Biomateriales y 

Biomedicina (CIBER-BBN), Química Orgánica e Inorgánica, 

Badajoz, Spain 



Biomedicina (CIBER-BBN), Ciencias Biomédicas, Badajoz, 

Spain 



Biomedicina (CIBER-BBN), Física Aplicada, Badajoz, Spain 

4 Universidad de Extremadura, Química Orgánica e Inorgánica, 


Titanium and titanium alloys are widely employed in biomedical 

implants due to their chemical inertia and biocompatibility. [1] The latter 

is generally improved by forming thin films of bioactive small molecules 

on the metal surface, thus preventing bacterial adhesion which 

represents a major concern. A common chemical functionalization of 

such alloys involves silanization with organosilanes such as 

(3-aminopropyl)triethoxysilane (APTES), thereby resulting in an 

aminated surface. Unfortunately, the amount of amino groups 

deposited and therefore available to further modification is not 

routinely evaluated. Moreover, there is confusion as to which reaction 

conditions will produce a stable and densely aminated film. [2] 

In this communication we report an efficient and 

reproducible methodology for coating Ti6Al4V alloy with 

(3-aminopropyl)trimethoxysilane (APTMS). The influence of 

reaction time, water concentration, reaction temperature, and 

cross-linking conditions on surface coverage was studied. 

Ninhydrin assays were systematically employed to assess the 

density of amino groups. XPS, FTIR-ATR, and SEM analyses 

helped us to determine changes in both surface composition and 

roughness. 

In addition, bacterial adhesion and biofilm formation of 

Staphylococcus ATCC35983 and S. epidermidis ATCC35984 

were also evaluated on both silanized disks according to the 

above-mentioned protocol and those exposed subsequently to 

degradation with PBS. Adhesion and biofilm formation decreased 

with respect to oxidized control disks. 

Acknowledgments. This work was supported by grants from the 

Ministry of Science and Innovation (MAT2009-14695-C04-01, 

MAT2009-14695-C04-03 and CTQ2010-18938), Gobierno de 

Extremadura (Ayudas a Grupos Consolidados: GR10049 and 

GR10149) and FEDER (Fondo Europeo de Desarrollo 

Regional, Una Manera de Hacer Europa). One of us (ARC) 

thanks the Ministry for a scholarship (BES-2010-033417). 

references: 

1. Geetha M, Singh AK, Asokamani R, Gogia AK. 

Prog Mater Sci 2009, 54, 397-425. 

2. Kingshott P, Andersson G, McArthur SL, Grieser HJ. 

Curr Op Chem Biol 2011, 15, 667-676. 

Keywords: titanium; alloys; material science; self-assembly; 

biological activity; 



s1252 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 7 9 

CheMiCAL ModifiCAtion And StruCturAL 

ChArACterizAtion of ti6AL4v ALLoy 

SurfACeS 

A. rodríGuez-CAno 1 , r. BABiAno 2 , P. CintAS 2 , 

M. L. GonzáLez-MArtín 3 



Nanomedicina (CIBER-BBN), Química Orgánica e 

Inorgánica, Badajoz, Spain 

2 Universidad de Extremadura, Química Orgánica e Inorgánica, 




Nanomedicina (CIBER-BBN), Física Aplicada, Badajoz, Spain 

Titanium-based medical implants are employed worldwide 

in bone repair. The success of this sort of regenerative medicine 

depends critically on appropriate chemical functionalization of 

the titanium surface that facilitates osseointegration, while 

decreasing bacterial adhesion and biofilm formation caused by 

quorum sensing mechanisms [1] . A common strategy involves the 

creation of siloxane chains attached to the metal surface and 

ending in halogen or amino functional groups, which further react 

with an organic partner that enhances the biocompatibility [2] . 

We report herein a robust amination of Ti6Al4V, an alloy 

of broad use in medical prostheses, via reaction with 

(3-aminopropyl)trimethoxysilane. The resulting polysiloxane 

network had a maximum coverage of amino groups, which 

underwent coupling with reactive organic molecules affording 

thin films on the alloy. Thus, alkyl and aryl isocyanates reacted 

smoothly to give the corresponding ureas. On the other hand, 

reaction with cinnamaldehyde gave rise to a more labile imino 

linkage, which can break under acidic conditions, thereby 

releasing this bioactive aldehyde. 

Structural characterization of these chemically-modified 

surfaces was accomplished by FTIR-ATR, XPS, and SEM 

analyses. Amino group densities were monitored through 

ninhydrin assays. Controlled liberation of cinnamaldehyde was 

also checked by UV-Vis spectrophotometry and results were 

compared with those obtained via XPS. Studies aimed at 

evaluating cell proliferation as well as resistance to bacterial 

adhesion and growth are currently under way. 

Acknowledgments. This work was supported by grants from the 

Ministry of Science and Innovation (MAT2009-14695-C04-01 

and CTQ2010-18938), Gobierno de Extremadura (Ayudas a 

Grupos Consolidados: GR10049 and GR10149) and FEDER 

(Fondo Europeo de Desarrollo Regional, Una Manera de 

Hacer Europa). One of us (ARC) thanks the Ministry for a 

scholarship (BES-2010-033417). 

references: 

1. Amara N, Krom BP, Kaufmann GF, Meijler MM. Chem 

Rev 2011, 111, 195-208. 

2. Silverman BM, Wieghaus KA, Schwartz J. Langmuir 

2005, 21, 225-228. 

Keywords: surface chemistry; material science; titanium; 

alloys; self-assembly; 


P - 0 7 8 0 

PorPhyrin BindinG And SeLf-AGGreGAtion 

MediAted By A PoLyeLeCtroLyte MAtrix 

A. roMeo 1 , M. A. CAStriCiAno 2 , 

L. MonSu SCoLAro 1 

1 University of Messina, Inorganic Analytical and Physical 

Chemistry, Messina, Italy 

2 ISMN, CNR, Messina, Italy 

Non-covalent self-assembly is an ubiquitous process in 

biology and it represents an effective tool in order to access to a 

large variety of structures with sizes spanning from nano- to 

mesoscopic scale showing different architectures and 

functionalities. Supramolecular species containing porphyrins are 

interesting from a fundamental viewpoint as they offer the 

possibility of mimicking photosynthetic centers and of accessing 

to supramolecular devices. In this respect, charged biopolymers, 

e.g. DNA, RNA, polypeptides and even filamentous 

bacteriophages [1] have been exploited to organize oppositely 

charged porphyrins in tailored assemblies. In this framework, the 

employment of simple polyelectrolyte templates allows to reduce 

the number of interaction modes of the porphyrin on the scaffold 

so affording i) to a larger stability in the formation of porphyrin 

aggregates in solution, as well as in the solid state and ii) to a 

better assessing of the interaction mechanism between the 

polymer scaffold and the chromophores. [2] Poly(sodium 

vinylsulfonate) (PVS), completely dissociated from its gegen ion 

in aqueous solution, represents an efficient and versatile highly 

charged polyanion template for binding various cationic species 

exclusively through Electrostatic Self-Assembly. Here we report 

on the interaction of this polymer with the tetracationic 

water soluble meso-tetrakis(N-methylpyridinium-4-yl)porphine 

(TMpyP) and some its metal derivatives (Cu(II), Zn(II), Mn(III), 

Au(III)) under different experimental conditions. We present 

evidence that, depending on pH, the high electrostatic field of 

PVS stabilizes the diprotonated form of the free base porphyrin 

at unusual pH values and causes the formation of H-type 

aggregates. 

references: 

1. L. M. Scolaro, M. A. Castriciano, A. Romeo, N. Micali, 

N. Angelini, C. Lo Passo, F. Felici, J. Am. Chem. Soc., 

2006, 128, 7446. 

2. L. M. Scolaro, A. Romeo, A. Terracina, Chem. Commun., 

1997, 1451. 

Keywords: porphyrin; aggregation; supramolecular chemistry; 

polyelectrolyte; spectroscopic investigation; 



s1253 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 8 1 

inteGrAted 3d-Printed reACtionwAre for 

CheMiCAL SyntheSiS And AnALySiS 

M. h. roSneS 1 , P. J. KitSon 1 , M. d. SyMeS 1 , 

v. drAGone 1 , L. Cronin 1 


Kingdom 

Email: Lee.Cronin@glasgow.ac.uk 

3D-printing has the potential to transform science and 

technology creating bespoke, low-cost appliances which have 

previously required dedicated facilities. An attractive but 

unexplored application is using the 3D-printer to initiate chemical 

reactions by printing the reagents directly into the 

3D-reactionware matrix, putting reactionware design, 

construction and operation under digital control. In this 

contribution, we desecribe how by using a low-cost 3D-printer 

and open-source design software, we produced reactionware for 

organic and inorganic synthesis, including printed-in catalysts, 

and other architectures with printed-in components for 

electrochemical and spectroscopic analysis. This allowed 

reactions to be monitored in situ so that different reactionware 

architectures could be screened for their efficacy for a given 

process, giving a digital feed-back mechanism for device 

optimisation. Furthermore, by solely modifying reactionware 

architecture, reaction outcomes could be drastically altered. Taken 

together, this approach constitutes a cheap, automated and 

reconfigurable chemical discovery platform that makes techniques 

from chemical engineering accessible to typical synthetic 

laboratories. [1] It is even conceivable that this approach could be 

used to undertake complex reactions and allow the reliable access 

to chemistry beyond the laboratory created in the ‘reactionware’ 

environment and the prospects for this will be discussed. 

references: 

1. M. D. Symes, P. J. Kitson, J. Yan, C. J. Richmond, 

G. J. T. Cooper, R. W. Bowman, T. Vilbrandt, L. Cronin, 

Nature Chem. 2012, 4, 349-354. 

Keywords: Inorganic Chemistry; Multicomponent reactions; 

Polymers; 


P - 0 7 8 2 

effeCt of the AL o And BAo Addition on the 

2 3 

therMAL And PhySiCAL ProPertieS of 

ternAry GLASS SySteM 

B. SAfi 1 , M. MAALeM 2 , d. ABoutALeB 1 , M. SAidi 1 

1 Boumerdes University, Materials Engineering, Boumerdes, 

Algeria 

2 Boumerdes University, Process Engineering, Boumerdes, 

Algeria 

In borate glasses, the main structural units are the [BO ] 3 

triangles and [BO ] tetradral which form different superstructural 

4 

units like; boroxol rings, metaborate rings and chains, pentaborate, 

diborate, triborate and pyroborate. In this work, the Barium 

aluminoborate glasses were prepared. Some of properties were 

investigated by measure like density and chemical durability and 

the other by calculs. The dilatometric curves were determined and 

they revealed that the temperature of transition (Tg) and softening 

(Ts) and the dilatation coefficient increase by addition of Al O 2 3 

and BaO content. 

Keywords: Barium aluminoborate glass; dilatometric curves; 

chemical durability; densiy; dilatation coefficient; 



s1254 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 8 3 

druG reLeASe BehAvior And 

AntituMor effiCienCy of 5-ASA LoAded 

ChitoSAn-LAyered SiLiCAte nAnoCoMPoSiteS 

n. SALAhuddin 1 , r. ABdeen 1 

1 Faculty of science, Chemistry department, Tanta, Egypt 

5-Amino salicylic acid (5-ASA) loaded chitosan- 

-montmorillonite nanocomposites were prepared by different 

methods and using different ratios of modified chitosan. Chitosan 

(CS) was modified first through chloroacetylation followed by 

formation of phosphonium salt. The intercalation occurred 

through ion exchange process between sodium cations in MMT 

and phosphonium ions in the modified chitosan. The structure of 

the resulting composites as determined by Infra red spectroscopy 

(IR), X-ray diffraction (XRD), consisted of the insertions of 

modified chitosan between lamellar layers. 

The modified chitosan is strongly fixed to layered silicate. 

The morphology of these materials was examined by transmission 

electron microscopy (TEM (. The thermal stability of the 

nanocomposite was investigated by thermogravimetry analysis 

(TGA). The release of 5-ASA behavior from nanocomposites at 

different pH (5.4 and 7.8) was assessed and compared with the 

release from sodium montmorillonite (Na-MMT) and CS. 

The dispersed layered silicate platelets encase the 5-ASA 

retarding the diffusion of the drug molecule in the nanocomposite. 

Furthermore, their use as antitumor agents for treatment of colon 

cancer is investigated. 

Keywords: 5-amino salicylic acid; Chitosan; nanocomposite; 

antitumor; 


P - 0 7 8 4 

ConfiGurABLe reACtor ArChiteCtureS for 

the dynAMiC ControL of the SeLf-ASSeMBLy 

of nAnoStruCtured MAteriALS 

v. SAnS SAnGorrin 1 , A. ruiz de LA oLivA 1 , 

C. riChMond 1 , L. ALexei 2 , L. Cronin 1 


Kingdom 

2 University of Warwick, School of Engineering, Coventry, 


Email: Lee.Cronin@chem.gla.ac.uk 

Self-assembly processes are increasingly gaining 

importance in bottom-up synthesis of advanced materials (metal 

nanoparticles, quantum dots, polyoxometalates, etc.), medicine 

(drug release), catalysis, etc. The difficulty to control and 

scale-up these processes limits potential industrial applications. 

Herein, we present a novel set of approaches aiming to bridge this 

gap. Two examples are selected, which show the potential of flow 

systems to synthesise nanostructured materials in a highly 

controlled and reproducible fashion. In both cases, a set of 

computer controlled pumps were programmed to obtain different 

flow configurations to produce nanoparticles and nanostructured 

molecules. 

The first set-up was designed to synthesise Au nanoparticles 

employing a continuous-flow reactor, non-conventional dielectric 

heating and two in-line characterisation techniques. Fine control 

over the properties of the nanoparticles was achieved by tuning 

the composition, flow rate and temperature of the reactor. 

A second configurable reaction system was employed to 

dynamically control the self-assembly of nanoscale 

polyoxometalates. The control was achieved by simultaneously 

tuning a single parameter in three interconnected reactors. This 

represents a revolution in flow based complex chemical discovery. 

Keywords: self-assembly; nanoparticles; flow; gold; 

polyoxometalates; 



s1255 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 8 5 

thin fiLM heteroJunCtionS By CArBon 

nAnotuBe derivAtiveS with enhAnCed 

SoLuBiLity And oPtiCAL ProPertieS 

C. SArtorio 1 , P. SALiCe 2 , S. CAtALdo 1 , A. BurLini 2 , 

A. PACe 2 , e. MennA 2 , B. PiGnAtAro 1 

1 Universita degli Studi di Palermo, Chimica, Palermo, Italy 

2 Universita di Padova, Scienze Chimiche, Padova, Italy 

The combination of single-walled carbon nanotubes 

(SWNTs), characterized by high electron mobility, with p-type 

semiconducting polymers could lead to an overall improvement 

in the exciton dissociation and carrier extraction efficiencies in 

practical devices. [1] However, one of the main concern in the use 

of SWNTs, relates to the their scarce solubility. Chemical 

modification has been widely employed to increase the solubility 

of SWNTs, but usual reaction conditions limit such syntheses to 

a small scale with low productivity. 

Here, we employ SWNTs which have been functionalized 

with aromatic and heteroaromatic moieties via 1,3-dipolar 

cycloaddition and through diazotization reaction under batch and 

continuous-flow conditions. This offers a safer, scalable 

processing and the opportunity to a rapid reaction screening using 

a relatively small amount of reagents. [2] 

Such systems in combination with P3HT have been used to 

fabricate bulk heterojunctions (BHJ) by Langmuir-Blodgett, 

which offers a simple method of producing ultrathin-films with 

fine control over thickness. Thanks to the improved solubility of 

SWNT derivatives we prepared multi-planar heterojunctions 

(MHJ) consisting of alternate layers of P3HT and SWCNTs, by 

horizontal lifting (Langmuir-Schaefer) technique. Then we 

induced a transition from MHJ to BHJ by thermal annealing to 

mix the layers. 

While the degree of functionalization ensured by 

diazotization, higher than 1,3-dipolar cycloaddition, improves 

processability, fluorescence quenching measurements have 

demonstrated that thienyl groups ensure a stronger interaction 

with P3HT and consequently a better electron transfer. Such 

properties have been modulated within the thin film by changing 

its internal morphology tuning the parameters of the mixing 

process. Thienyl derivatives obtained through controllable 

functionalization of SWNTs in flow conditions are promising 

candidates for the incorporation in the active layer of OPV cells. 

references: 

1. Cataldo, S.; Salice, P.; Menna, E.; Pignataro, B. Energy 

Environ. Sci. 2012, 5, 5919. 

2. Salice, P.; Maity, P.; Rossi, E.; Carofiglio, T.; Menna, E.; 

Maggini, M. Chem. Commun. 2011, 47, 9092. 

Keywords: Nanotubes; Langmuir-Blodgett films; Electron 

transfer; Thin films; Energy conversion; 


P - 0 7 8 6 

infLuenCe of oxyGen PArtiAL PreSSure on 

the Growth And PhotoCAtALytiC ACtivity 

of wo fiLMS PrePAred By MAGnetron 

3 

SPutterinG 

S. Sério 1 , B. BArroCAS 1 , L. C. SiLvA 1 , G. MArtinS 1 , 

y. nuneS 1 , o. C. Monteiro 2 , M. e. MeLo JorGe 3 

1 CEFITEC, Departamento de Física Faculdade de Ciencias e 

Tecnologia da Universidade Nova de Lisboa, Caparica, 

Portugal 

2 CQB, Departamento de Química e Bioquímica da Faculdade 

de Ciencias da Universidade de Lisboa, Lisboa, Portugal 

3 CCMM, Departamento de Química e Bioquímica da 

Faculdade de Ciencias da Universidade de Lisboa, Lisboa, 

Portugal 

Several semiconductor materials have been reported to offer 

high photocatalytic activity to degrade organic and inorganic 

pollutants. Among them TiO , has been employed extensively as 

2 

photocatalyst, however the drawback is the wide band gap 

(3.2 eV) limiting its use to the UV part of electromagnetic 

spectrum (2–3%) under sunlight. WO is also an important 

3 

photoactive material with a band gap energy of 2.5 eV and can 

absorb the blue part of solar spectrum up to ca. 500 nm. 

In this work, WO films were deposited on unheated glass 

3 

and conductor glass substrates by DC reactive magnetron 

sputtering using a tungsten target. The depositions were carried 

out in a mixture of Ar and O , at constant total sputtering gas 

2 

pressure (P ) of 0.8 and 1.6 Pa and sputtering power of 220 W. 

T 

The oxygen partial pressure (PO ) was changed between 10 and 

2 

100% of P . The as-sputtered films were thermal annealed in air 

T 

atmosphere at 400 ºC for 2 h. The films were characterized by 

X-ray diffraction, scanning electron microscope, atomic force 

microscopy and UV–Vis spectroscopy. 

It has been revealed that the PO is a key factor on the 

2 

structural, morphological and optical properties of WO films as 

3 

observed in similar study with TiO films 2 [1] . 

The films photocatalytic activity was tested, under visible 

irradiation, on the decolorization of Rhodamine 6G aqueous 

solutions. The dye photodecolorization process was studied 

considering the influence of the crystallinity and preferred 

orientation of growth of the prepared films. 

Acknowledgements: Financial support from FEDER, 

through Programa Operacional Factores de Competitividade– 

COMPETE, and Fundacio para a Ciencia e a Tecnologia–FCT, 

for the projects PTDC/AAC-AMB/103112/2008, S.Sério and 

O.C.Monteiro acknowledge FCT for the Programme Ciencia 

2007. 

references: 

1. S. Sério, M. E. Melo Jorge, M. J. P. Maneira, Y. Nunes, 

Mat. Chem. Phys., 126 (2011). 

Keywords: Thin films; Nanotechnology; Heterogeneous 

catalysis; Surface analysis; UV-Vis spectroscopy; 



s1256 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 8 7 

BiSMuth nAnoPArtiCLeS for 

therMoeLeCtriC MAteriALS GenerAted By 

LASer ABLAtion of BiSMuth oxide SuSPended 

in orGAniC LiquidS 

C. SChAuMBerG 1 , M. woLLGArten 2 , 

K. rAdeMAnn 1 


Germany 

2 Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 

Institut für Technologie, Berlin, Germany 

The ongoing search for sustainable sources of electric 

energy leads to great efforts to improve the efficiency of 

thermoelectric generators (TEG). The efficiency of TEG can 

be described by the figure of merit zT =(σ S T) / (κ + κ ) 

el ph 

with σ - electrical conductivity, S - Seebeck coefficient, 

T - temperature, κ - thermal conductivity caused by electrons and 

el 

κ - thermal conductivity caused by phonons. 

ph 

One attempt to get higher zT values is to decrease the 

thermal conductivity caused by phonons while keeping the other 

parameters nearly constant. [1] This is possible through phonon 

scattering at specific introduced grain boundaries. Thus 

nanostructured materials like nanoparticles can be used to 

improve the efficiency of TEG. 

We focus on the synthesis of bismuth based nanostructured 

materials by laser ablation. Laser ablation of solid targets is a well 

know method to get colloidal solutions of metal nanoparticles. [2] 

Unfortunately the production rates are relatively low. This 

drawback can be overcome by the usage of the corresponding 

metal oxide powder instead of the bulk metal targets. [3] We report 

the formation of bismuth nanoparticles by laser ablation of Bi O 2 3 

powder suspended in organic solvents. This approach will be 

extended to bismuth based semiconductors like Bi Te . 2 3 

The obtainted nanoparticles are characterized by atomic 

force microscopy and transmission electron microscopy. 

references: 

1. M. Scheele, N. Oeschler, K Meier, A. Kornowski, 

C. Klinke, H. Weller, Adv. Funct. Mater. 2009, 19, 

3476–3483. 

2. P.V. Kazakevich, A.V. Simakin, V.V. Voronov, 

G.A. Shafeev, Appl. Surf. Sci. 2006, 252, 4373–4380. 

3. M.-S. Yeh, Y.-S.Yang, Y.-P. Lee, H.-F. Lee, Y.-H. Yeh, 

C.-S. Yeh, J. Phys. Chem. B 1999, 103, 6851–6857. 

Keywords: bismuth nanoparticles; laser ablation; transmission 

electron microscopy; thermoelectric materials; 


P - 0 7 8 8 

the eLeCtroCAtALytiC ACtivity of 

nAnoStruCtured ni-CoAted SCreen-Printed 

CArBon eLeCtrodeS 

L. SKAntArovA 1 , A. MerKoCi 2 , 

A. de LA eSCoSurA Muniz 2 , A. orinAK 3 , 

r. orinAKovA 3 

1 Comenius University/Faculty of Sciences, Department of 

Analytical Chemistry, Bratislava, Slovak Republic 

2 Catalan Institute of Nanotechnology, Nanobioelectronics & 

Biosensors Group, Campus de la UAB -Edifici Q (ETSE) - 2 

planta Bellaterra (Barcelona), Spain 

3 P. J. Safarik University/Faculty of Science, Department of 

Physical Chemistry, Kosice, Slovak Republic 

The mass fabrication of useful thick film-electrodes is 

achieved by screen-printing technology, which is known as a 

simple and fast method. Its ability to produce inexpensive and 

reproducible substrate electrodes is one of their most attractive 

characteristics and designates screen-printed electrodes for further 

modifications. Screen-printed effective electrochemical sensors, 

in particular, those for the detection of glucose, hydrogen 

peroxide, cholesterol and phenolic compounds, are commercially 

avalaible. The way of performing routine electroanalysis has been 

revolutionized by these sensors and can be viewed as disposable 

single-use sensors onto which a droplet of the sample is directly 

deposited. It has been reliably accomplished that screen-printed 

electrodes can be certainly prepared and applied for the 

determination of a great variety of biomolecules and several 

inorganic species. In an effort to improve the performance of the 

screen-printed electrodes (SPEs), in terms of sensitivity and 

specificity, several bulk or surface modification routes have been 

adopted. Enzyme-modified SPEs are highly applicable in 

environmental analysis, while other SPEs are useful as 

immunosensors, or in genetic and drug testing [1, 2] . We present 

here screen-printed carbon-based electrodes (SPCEs), coated with 

Ni film as a novel alternative to the unmodified electrodes. In an 

effort to achieve reproducible film-modified SPCEs we used 

electrochemical deposition as a convenient and fast method for 

the preparation of Ni-SPCEs. In this way, these disposable 

substrate electrodes acquire very specific electrocatalytical 

properties even being re-useable. The morphology and 

homogeneity of nano-scaled surface Ni-modified SPCEs was 

studied by scanning electron microscopy. The electrocatalytical 

activity of Ni-coated SPCEs was evaluated by hydrogen evolution 

reaction (HER) opening the way to rapid ‘in-situ’ analyses. 

Acknowledgement: The authors wish to thank M· SR VEGA 

1/0211/12 for financial support. 

references: 

1. Lin, J., et al., in: Bioscience 10 (2005) 483–491. 

2. Domínguez Renedo, O., et al., in: Talanta 73 (2007) 

202–219. 

Keywords: Immunoassays; Nanoparticles; Nickel; Proteins; 

Sensors; 



s1257 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 8 9 

PrePArAtion And ChArACterizAtion of druG 

LoAded ChitoSAn nAnoPArtiCLeS 

A. SrinivASAn 1 , n. duCzAK 2 , S. ShoyeLe 1 

1 Thomas Jefferson University, Of Pharmaceutical Sciences, 

Philadelphia, USA 

2 Thermo Fisher Scientific, Thermo Scientific, New Jersey, USA 

The aim of the present study was to prepare drug loaded 

chitosan nanoparticles (NP) using trastuzumab as homing device. 

Trastuzumab is a monoclonal antibody directed against 

extracellular domain of the human HER-2 receptor, over 

expressed in non-small cell lung carcinomas. As HER-2 receptor 

is accessible on the cell surface, trastuzumab provides a promising 

target to cancer cells thus achieving cell type specific drug carrier 

system. 

Chitosan NP’s were obtained by inducing ionic gelation with 

TPP. The blank NP’s were loaded kinase inhibitor drugs. NP’s 

were concentrated by centrifugation and lyophilized. The 

supernatant was collected for unbound drug analysis. 

The antibody was thiolated and added thiol groups was 

quantified by Ellman’s test. The chitosan NP’s was decorated with 

thiolated trastuzumab by a linker. The antibody-NP binding 

efficiency was determined by using ITC. HER-2 expression in 

lung cancer cell lines was performed using western blotting and 

flow cytometer. in vitro cell specific binding efficiency of the 

trastuzumab decorated NP’s will be determined for the lung 

cancer cell lines. 

The formation of chitosan NP is dependent upon on the 

gelation procedure, which is controlled by the addition of TPP. 

The mean particle size for the lyophilized chitosan NP’s from 

DLS ranged from 60.66 ± 0.2, 84.81 ± 0.4 and 107.56 ± 5.0. The 

mass spectrometry data indicated 80% encapsulation of the drug 

with the chitosan NP’s. 

Thiolation of trastuzumab with 2-iminothiolane introduces 

additional thiol groups. The number of sulfhydryl groups 

introduced per trastuzumab was 0.91 ± 0.15. It is expected that 

chitosan NP’s decorated with trastuzumab will be produced and 

characterized. It is also expected that trastuzumab decorated NP’s 

will have enhanced cell penetration in comparison to the 

non-decorated NP’s using cancer cells. We also expect superior 

cytotoxic effect by the decorated NP’s when compared to the 

non-decorated chitosan and unprocessed drug. 

Keywords: analytical method; Mass Spectrometry; 

Nanoparticles; 


P - 0 7 9 0 

the PrePArAtion And AntiBACteriAL ACtivity 

of PoLyMer-StABiLized SiLver BroMide And 

SiLver nAnoPArtiCLeS 

P. SuChoMeL 1 , L. KviteK 1 , A. PAnACeK 1 , 

r. PruCeK 1 




The thesis presents the preparationof silver bromide 

nanoparticles and their subsequent reduction to 

metallicnanoparticles by the using of sodium borohydride as 

reducing agent. Thisproposed method using consecutive reactions 

enable efficient comparing ofproperties of silver bromide and 

silver nanoparticles. Clear colloiddispersions of silver 

nanoparticles and primarily of silver bromidenanoparticle are 

aggregately unstable and because of that, there were usedseveral 

polymers as stabilizers. The chosen polymers were also used as 

particlesize modifiers and their using enabled the preparation of 

silver bromide andsilver nanoparticles with the different sizes 

ranges between 55 and 112 nm forAgBr and between 39 and 

93 for Ag nanoparticles. Prepared dispersions of silverbromide 

and silver nanoparticles were tested for their antibacterial 

andantifungal activity. This was tested against several types of 

gram-positive andgram-negative bacteria and against several 

strains of candida. Finally,obtained results of biological activity 

of prepared silver bromide and silvercolloidal dispersions in the 

presence of various polymers were compared witheach other. 

Acknowledgements: This work has been supported by the 

OperationalProgram Research and Development for 

Innovations - European Social Fund(CZ.1.05/2.1.00/03.0058), 

Czech Science Foundation (Project No.GAP304/10/1316), 


EuropeanSocial Fund (CZ.1.07/2.3.00/20.0056) and also by 

internal grant of Palacky Universityin Olomouc 

(PrF_2012_028). 

Keywords: silver; nanoparticles; reduction; Biological 

activity; 



s1258 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 9 1 

orGAniC SeLf-ASSeMBLed MonoLAyerS AS A 

tooL for Low teMPerAture wAfer BondinG 

C. SuKeniK 1 , v. ArtAL 1 , M. ShuBeLy 1 , A. zAdoK 2 , 

i. BAKiSh 2 , t. iLovitSh 2 

1 Bar-Ilan University, Chemistry, Ramat-Gan, Israel 

2 Bar-Ilan University, Engineering, Ramat-Gan, Israel 

Silicon photonics is an important research field because of 

the promise of large scale integration of electro-optic devices 

alongside electronics. A potential approach to active 

silicon-photonic devices relies on the vertical integration of 

electro-optic materials, such as germanium or III-V 

semiconductors, alongside silicon for the making of hybrid 

devices. Such devices support propagating modes that overlap 

both materials, and bring together the guiding of light in silicon 

and its manipulation in other electro-optic materials. 

Hybrid devices that rely on wafer bonding processes 

between dissimilar materials pose numerous challenges. The 

direct bonding approach is typically a high temperature process. 

An alternative process uses a polymeric glue and typically results 

in a relatively thick (tens of nm or more) inter-phase. 

We report herein an alternative paradigm for the bonding of 

various electro-optic materials to silicon. The bonding procedure 

relies on the deposition of an organic self-assembled monolayer 

on the surface of one or both wafers, and their subsequent bonding 

through controlled surface chemistry between the monolayers on 

the surfaces of the wafers, or between one monolayer and the 

surface of the other wafer itself. Using variously functionalized 

monolayers, we report the bonding of two silicon wafers, as well 

as the bonding of silicon to optical materials such as InP and 

LiNbO . All processes were carried out at temperatures £ 150 °C 

3 

and the bonding interface has a thickness of only a few nm. We 

have also directly interrogated the integrity of the bonding 

interface and developed methodology for measuring the strength 

of the bond between the two substrates. 

The monolayer-based approach to wafer bonding should 

enhance the strength and yield of such device fabrication 

processes. It should reduce the thermal stresses and out-gassing 

often associated with current bonding approaches and should 

broaden the range of materials that can be bonded. 

Keywords: self-assembly; monolayers; surface chemistry; 


P - 0 7 9 2 

hoMoChirAL MetAL-orGAniC frAMeworK 

CryStALS for ASyMMetriC CAtALySiS And 

enAntioMer SePArAtion 

K. tAnAKA 1 

1 Kansai University, Department of Chemistry and Materials 

Engineering, Suita, Japan 

The field of metal-organic frameworks (MOFs) has grown 

explosively in recent years and numerous studies have been 

reported owing to their potential applications in gas storage, 

separation and heterogeneous catalysis. While a large numbers of 

MOF are being discovered so far, only a few examples of chiral 

MOF for enantioselective separations or heterogeneous 

asymmetric catalysis have been investigated. Here, we wish to 

report the synthesis of a novel chiral porous metal-organic 

framework (R)-MOF and its function as asymmetric 

heterogeneous catalyst for the alcoholytic kinetic resolution of 

styrene oxide during ring opening reaction to 2-methoxy-2- 

-phenylethanol. Chromatographic enantiomer separations of some 

sulfoxides over a chiral metal-organic framework in HPLC are 

also reported. 

Keywords: Asymmetric catalysis; Metal-organic frameworks; 

Kinetic resolution; Heterogeneous catalysis; Supramolecular 




s1259 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 9 3 

SyntheSiS of new Azo CoMPoundS in order 

to vAry SurfACe ProPertieS 

M. vALASeK 1 1, 2 

, M. MAyor 

1 Karlsruhe Institute of Technology, Institute of Nanotechnology, 

Eggenstein-Leopoldshafen, Germany 


Switzerland 

The immobilization of π-conjugated systems with 

electro-optical properties on gold surfaces by formation of 

self-assembled monolayers (SAMs) is a focus of high interest. [1] 

Reversible photoswitching devices were demonstrated with 

azobenzene and diarylethene derivatives and open the route for 

potential applications as optical switches in molecuar electronics, 

molecular machines, photoswitchable surface wettability, and 

biosensors. [2] Molecular rods incorporating azo units and 

organized in SAMs, undergo efficient photoisomerization 

producing cooperative molecular movements able to express 

mechanical work. [3, 4] The potential for manipulation and control 

inherent in molecule-based motors holds great scientific and 

technological promise. 

For this purpose, we have designed and prepared new rigid, 

rod-like azobenzenes comprising a terminal sulfur anchor group. 

These compounds might harness the force expressed by azo 

SAMs, in order to move vertically nano-particles sitting on the 

azo SAMs, and move laterally nano-particle, by sweeping across 

the surface patterns formed by alternating Z- and E- isomers. 

We have also developed syntheses of previously unknown 

azobenzenes carrying long brush-like hydrophilic resp. 

fluorophilic chains, which should display large differences in 

hydrophilicity resp. fluorophilicity between E- and Z- form upon 

immobilization on a surface. The synthetic methodology 

described here provides versatile synthetic pathways to 

azobenzene derivatives that might be used as potential 

photo-responsive nanoscale devices. 

references: 

1. Katsonis, N.; Lubomska, M.; Pollard, M. M.; Feringa, B.; 

Rudolf, P. Prog. Surf. Sci. 2007, 82, 407. 

2. Klajn, R. Pure Appl. Chem. 2010, 82, 2247. 

3. G. Pace, G.; Ferri, V.; Grave, C.; Elbing, M.; von Hänisch, C.; 

Zharkinov, M.; Mayor, M.; Rampi, A.; Samori, P. 

Proc. Natl. Acad. Sci. U. S. A., 2007, 104, 9937. 

4. Ferri, V.; Elbing, M.; Pace, G.; Dickey, M. D.; Zharnikov, M.; 

Samori, P.; Mayor, M.; Rampi, M. A. Angew. Chem., Int. 

Ed. 2008, 47, 3407. 


P - 0 7 9 4 

deSiGn And SyntheSiS of SwitChABLe 

MoLeCuLAr tweezerS 

G. viveS 1 , B. doiStAu 1 , B. hASenKnoPf 1 


Molecular recognition of substrates is an important 

challenge in supramolecular chemistry. Among host-guest 

molecular systems, molecular tweezers [1] have generated 

increasing interest during the past few years especially for the 

recognition of small organic molecules. At the frontier of dynamic 

supramolecular systems, the development of switchable molecular 

tweezers [2] has opened up a wide field of applications in molecular 

transport by complexation-release, drug delivery, magnetic or 

luminescent switches. 

We are interested in the design of molecular tweezers 

switchable by coordination [3] for reversible molecular recognition. 

Our system is based on a terpyridine ligand substituted in 6 and 

6" positions by two arms bearing molecular recognition moieties. 

The terpyridine unit can switch upon metal coordination between 

a “W” shaped open form and a “U” shaped closed form bringing 

the two recognition units in an optimal geometry for recognition 

of flat aromatic substrates. Upon decoordination the tweezers will 

reopen releasing the intercalated substrate. The recognitions units 

are based on salen complexes with magnetic or luminescent 

properties depending on the metallic center for sensing. 

The design and synthesis of a terpyridine(Ni-salen)2 based 

molecular tweezers will be presented as well as its reversible 

switching and molecular recognitions properties. 

references: 

1. M. Hardouin-Lerouge, P. Hudhomme, M. Salle, 

Chem Soc Rev 2011, 40, 30–43. 

2. J. Leblond, A. Petitjean, Chemphyschem 2011, 12, 

1043–1051. 

3. M. Linke-Schaetzel, C. E. Anson, A. K. Powell, G. Buth, 

E. Palomares, J. D. Durrant, T. S. Balaban, J. M. Lehn, 

Chemistry 2006, 12, 1931–1940. 

Keywords: Molecular tweezers; Molecular switch; 




s1260 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 9 5 

nAnoPArtiCLeS in two-PhASe SePArAtion 

MethodS 

v. vorotyntSev 1 


FTMCET department, Nizhny Novgorod, Russia 

One of the most important ways to raise the degree of purity 

of substances is to improve the methods of high purification for 

new type of impurities. These new impurities are impurities in the 

form of suspended particles of submicron size and recently named 

nanoparticles [V.M. Vorotynsev Nanoparticles in two-phase 

systems.- Moscow: Izvestiy.2010.-320 p]. 

The peculiarity of the current stage of technology 

development of high-purity substances is a merging of the size of 

a number of heterogeneous impurities with impurities in 

molecular form. Behavior of nanoscaled particles in the two-phase 

distillation and crystallization methods of separation requires new 

conceptual apparatus and new technological approaches. 

In this report are considered the concepts of nanoparticles 

as impurities in high-purity substances, the nature and method of 

its generation in gas, liquid and solid substances. Investigation of 

high purification of liquids from suspended nanoparticles 

including experimental determination of separation coefficient of 

nanoparticles between liquid and vapor, method for determining 

the content of nanoparticles, determination of its separation 

coefficient, dependence of nanoparticles separation on their size 

and the velocity of distillation. Also it is considered the high 

purification from nanoparticles by rectification. It was given 

the design of apparatus for new separation method 

– termodisstillation. It was shown the application of 

termoditillation method in silicon and germanium production, in 

epitaxial structures production and in optical fiber raw material 

production. It was considered the distribution of nanoparticles in 

the phase equilibrium in the crystallization process. The 

mechanism of capture of nanoparticles from melt by the growth 

crystal has been proposed. It was shown the transition of 

nanoparticles from melt to crystalduring the crystallization for 

electrolyte and nonelectrolite solutionsIt is considered the 

dependence of separation factor countercurrent crystallization 

column on the fraction of recrystallized solid phase and 

dependence of separation factor. 

Keywords: nanoparticles; distillation; crystallization; 

high-purity substances; silicon; 


P - 0 7 9 6 

fABriCAtion of GoLd MiCro-StruCtureS viA 

reACtion Between hydroxyLAMine And 

ChLoroAuriC ACid 

K. winKLer 1 , M. LiSzewSKA 2 , A. KAMinSKA 1 , 

t. woJCieChowSKi 3 , M. fiALKowSKi 1 

1 Institute of Physical Chemistry, Department of Soft Condensed 

Matter, Warsaw, Poland 

2 Military University of Technology, Department of Explosive 

Materials, Warsaw, Poland 

3 Institute of Physics, Department SL-3, Warsaw, Poland 

Reaction between chloroauric acid (HAuCl ) and 

4 

hydroxylamine hydrochloride (NH OH·HCl) is widely used in a 

2 

seed-mediated growth of gold nanoparticles. It is commonly 

believed that hydroxylamine can reduce Au3+ ions to Au0 only in 

the presence of metallic gold. The possibility of nucleation in the 

mixture of HAuCl and NH OH·HCl has never been confirmed 

4 2 

experimentally and, until now, has been remaining only a 

hypothesis. 

Here, for the first time, we demonstrate the evidence of 

nucleation in mixtures containing aqueous solutions of 

chloroauric acid and hydroxylamine. Moreover, we employ this 

reaction as a powerful tool in a fabrication of new metallic 

nano-materials. 

In our approach, gold micro-flowers (AuMFs)—metallic 

particles of expanded nano-structured surface—are formed in the 

bulk solution. In the process the AuMFs sediment and deposit 

onto solid substrate. The method offers easy control both over the 

AuMFs morphology and density of the gold coating, which is 

formed as a result of the deposition of the AuMFs. Also, by 

addition of halides or silver ions to the reaction mixture we can 

to a great extent modify the morphology of the resulting coating. 

In particular, for certain compositions of the reaction mixture, a 

porous metallic film can be obtained instead of the micro-flower 

coating. Both the thickness and the roughness of such films are 

controllable by the mixture composition. 

The metallic layers obtained with our method have been 

used as efficient platforms for chemical and biological sensing 

based on surface enhanced Raman spectroscopy (SERS). The 

obtained platforms have been proven to be mechanically stable 

and to have good SERS enhancement factors as well as excellent 

repeatability. 

Keywords: nanostructures; microporous materials; surface 

plasmon resonance; 



s1261 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 9 7 

the SyntheSiS of noveL nAnoPArtiCLeS in 

SuPerfLuid heLiuM nAnodroPLetS 

S. yAnG 1 

1 University of Leicester, Chemistry, Leicester, United Kingdom 

Email: sfy1@le.ac.uk 

Tel: +44-116 252 2127; Fax: +44-116 252 3789 

Helium nanodroplets are large helium clusters typically 

containing 103-106 helium atoms. [1] They are superfluid and have 

an exceptionally high thermal conductivity; as a result, foreign 

species, when captured by helium nanodroplets, can be cooled 

rapidly to the equilibrium temperature of helium nanodroplets, 

0.38 K, by evaporative loss of helium atoms. [2] Most atoms and 

all molecules enter helium nanodroplets rather than sit on the 

surface; when more than one dopant is picked up, agglomeration 

of dopants will occur. Consequently, the potential exists for 

growing not only small atomic and molecular clusters, but also 

much larger objects such as nanoparticles, inside helium 

nanodroplets. This capability has been demonstrated, for the first 

time, in Dr Yang’s research group at the University of Leicester, 

where core-shell molecular clusters with small water clusters as 

the core were synthesised. [3] 

In this presentation, we will briefly overview the 

fundamentals of helium nanodroplets as uniquely powerful but 

astonishingly versatile nano-reactors for synthesising 

nanoparticles, as well as new experimental results on core-shell 

structures and metal nanoparticles that have been obtained by 

Dr Yang’s research group at the University of Leicester. 

references: 

1. J. P. Toennies and A. F. Vilesov, Angew. Chemie Int. Ed. 

43 (2004) 2622. 

2. W. L. Lewis, B. E. Applegate, J. Sztáray, B. Sztáray, 

T. Baer, R. J. Bemish and R. E. Miller, J. Am. Chem. Soc. 

126 (2004) 11283. 

3. J. Liu, B Shepperson, A. M. Ellis and S. Yang, Phys. 

Chem. Chem. Phys. 13 (2011) 13920. 

Keywords: Helium nanodroplets; core-shell nanoparticles; 


P - 0 7 9 8 

SyntheSiS of A denSeLy PACKed CyLindriCAL 

dendronized PoLyMer of GenerAtion 6 

h. yu 1 

1 ETH Zürich, Materials Department, Zürich, Switzerland 

Dendronized polymers (DP) are a class of comb polymers 

to which a regularly branched unit (dendron) is attached to each 

repeat unit. [1] In recent years a divergent methodology has been 

developed by which a series of DP was synthesized up to the 

5th generation (PG5), which is the largest synthetic linear 

macromolecule. [2] The structure perfection for each generation 

was quantified by a UV labeling method. [3] The resulting DP show 

generation dependency in their thickness, persistence length and 

stretching elasticity. [1,4] 

Higher generations (≥ 6) are also of particular interest, 

because theoretical studies suggest that the 6th generation DP 

(PG6) is close to the highest possible generation (g , which is 

max 

6.1) that can accommodate all perfect dendrons. [5] At or above gmax all the atoms in the dendritic architecture will be packed densely 

with no “unused space” that would allow conformational change. 

These DP will be “molecular objects”, which do not change their 

cross-sectional size and shape irrespective of their environments. [6] 

Here we report the synthesis and characterization of the first 

homologous DP series that includes PG6, which is a densely 

packed organic cylinder. Its properties are currently being 

explored. 

references: 

1. Schlüter, A. D.; Rabe, J. P., Angew. Chem. Int. Ed., 2000, 

39, 864. 

2. Zhang, B.; Kröger, M.; Halperin, A.; Schlüter, A. D., 


3. Shu, L.; Gössl, I.; Rabe, J. P.; Schlüter, A. D., 

Macromol. Chem. Phys., 2002, 203, 2540. 

4. Popa, I.; Zhang, B.; Maroni, P.; Schlüter, A. D.; 

Borkovec, M., Angew. Chem., Int. Ed., 2010, 49, 4250. 

5. Zhang, B.; Wepf, R.; Kröger, M.; Halperin, A.; 

Schlüter, A. D., Macromolecules, 2011, 44, 6785; 

6. Stupp, S. I., et. al, J. Am. Chem. Soc. 1995, 117, 5212. 



s1262 

chem. Listy 106, s257–s1425 (2012) 


P - 0 7 9 9 

PhototherMAL ConverSion of GoLd 

nAnoPArtiCuLeS ProBed By LoCAL 

PoLyMerizAtion 

L. zAArour 1 , J. SAfi 1 , J. PLAin 1 

1 Université Technologie de Troyes, Laboratoire de 

Nanotechnologie et Instrumentations Optiques, Troyes, France 

Metallic nanoparticles have been playing a very important 

role in the development and applications of nanotechnology. For 

example iron, cobalt, and nickel magnetic nano-particles are used 

as contrast agents in magnetic resonance imaging. Silver 

nanoparticles are known to have antibacterial function and can be 

used in bio-physics and bio-medical applications. 

Optical properties of metallic nanoparticles are mainly 

dominated by the Localized Surface Plasmon Resonance (LSPR) 

at optical frequencies. At this specific frequency, nano-particles 

exhibit intense absorption and light scattering due to the LSPR. 

Moreover, metal nanoparticles are able to transform absorbed 

light into heat. This photothermal conversion effect has been used 

for many applications. In particular, it has been used in the 

development of photothermal therapies (hyperthermia) for cancer 

treatment, as well as laser ablation as a technique of malignant 

cell destruction. More recently, plasmonic heating has been used 

to promote drug release through polymer phase change, hybrid 

DNA cleavage, or enhanced diffusion. 

We propose here a new approach based on 

nanopolymerization thermally initiated to characterize the heat 

pattern in the vicinity of photoexcited gold nanoparticles (GNPs). 

For this we developed thermopolymerizable formulations that are 

characterized by a controlled threshold temperature (Tth) of 

polymerization. Below this threshold temperature, the 

polymerization cannot occur. This sharp control allows us to use 

such material as thermal nanoprobe to measure the local 

temperature around the particle as well as to print the heat 

distribution around the nanoparticule. 

Keywords: Nanotechnologie; Nanoparticles; Polymerization; 

Gold; polymers; 


P - 0 8 0 0 

dendronized PoLyMerS: orGAniC 

nAnoCyLinderS with tunABLe thiCKneSS 

B. zhAnG 1 , h. yu 1 , A. d. SChLüter 1 

1 ETH Zurich, Department of Materials, Zürich, Switzerland 

Dendronized polymers (DP) are a class of polymers, which 

carry dendrons on each backbone repeat unit. [1] By grafting 

dendritic groups from a polymer backbone in a divergent fashion, 

a series of cylindrical polymers with tunable thickness (~1-10 nm) 

has been synthesized with high precision (> 97% structure 

integrity) and efficiency (addition of 1×108 Da in one step). This 

powerful method using simple organic chemistry allows organic 

synthesis to enter the dimention of biology: at the 5th generation 

level the largest synthetic linear macromolecule was produced and 

compared with Tobacco Mosaic Virus. [2] 

Can the nano-construction go further? According to the 

theoretical predictions, the maximal generation (g ), beyond 

max 

which perfect dendritic structures cannot be obtained, is ~6.1. [3] 

However, the imperfect polymers above g can still be prepared 

max 

and will be densely packed cylindrical organic objects, with no 

“unused” internal space to mediate responsivity. DP of the 

6th generation (PG6), which is the last generation below g , has max 

been recently synthesized and characterized in our laboratory. 

Being close to g , PG6 outstands among the homologous series, 

max 

regarding the structure perfection, atomic mobility and 

deformability. This offers for the first time the chance of a true 

cylindrical “molecular object”. [4] 

references: 

1. A. D. Schlüter, J. P. Rabe, Angew. Chem. Int. Ed. 2000, 39, 

864; H. Frauenrath, Prog. Polym. Sci. 2005, 30, 325. 

2. B. Zhang, R. Wepf, K. Fischer, M. Schmidt, S. Besse, 

P. Lindner, B. T. King, R. Sigel, P. Schurtenberger, Y. 

Talmon, Y. Ding, M. Kröger, A. Halperin, A. D. Schlüter, 


3. B. Zhang, R. Wepf, M. Kröger, A. Halperin, 

A. D. Schlüter, Macromolecules 2011, 44, 6785. 

4. S. I. Stupp, S. Son, L. S. Li, H. C. Lin and M. Keser, 

J. Am. Chem. Soc. 1995, 117, 5212. 

Keywords: synthesis; shape persistence; dendrimers; 

dendronized polymers; molecular objects; 



s1263 

chem. Listy 106, s257–s1425 (2012) 


P - 1 0 1 4 

PoroSity of roBot LASer hArdeninG 

SPeCiMenS 

M. BABiC 1 , K. Peter 2 , M. MiLfeLner 3 

1 Emo orodjarna d.o.o., emo, Celje, Slovenia 

2 Faculty of Health Sciences Slovenia, Faculty of Health 

Sciences Slovenia, Maribor, Slovenia 

3 Tic-Lens d.o.o., celje, celje, Slovenia 

Porouse structure in material is one of important mechanical 

property which impact on hardness of materials. We study was 

limited on tool steel standard label DIN standard 1.7225. We can 

not apply Evclidian geometry to describe porouse of hardened 

specimens, thus we use very good method, fractal geometry. The 

specimen test section had a cylindrical form dimension 25×10mm 

(diameter×high). Speciment with the porosity about 19% to 50%, 

were prepared by laser technic, followed by hardening at T? [800, 

2000] °C and v?[2,5] mm/s. Also, we changed one parameter of 

robot laser cell, temperature T ? [1000, 1400] °C to 50 °C steps. 

Microstructure of specimens was observed with an field emission 

scanning electron microscope JSM-7600F JEOL company. 

To investigate the possibility of application of fractal analysis 

to heat-treated surface, we have examined the relation between 

surface porosity and fractal dimensions depending on various 

parameter of temperature of robot laser cell. Also we present 

temperature of robot laser cell impact on poruse specimens in 

process of robot laser hardening. We are interested to calculate 

relationship between fractal dimension and porosity in: 

• two-beam laser robot hardening (laser beam is divided into 

two parts), 

• areas of overlap (the laser beam covers the already 

hardened area), 

• robot laser hardening at different angles (the angles change 

depending on x and y axis). 


P - 0 8 0 1 

GoLd-CAtALyzed CyCLoiSoMerizAtion 

reACtionS of vinyLALLene derivAtiverS 

G. e. AKPinAr 1 


Email: eray.akpinar@tu-dortmund.de 

Allenes are present in many natural products and 

biologically active compounds. Over the years the use of catalytic 

reagents for the synthesis of allenes has highly developed. Several 

useful methods for synthesis of vinylallene derivatives have also 

been reported.Recently, vinylallenes were found to undergo goldcatalyzed 

cycloisomerization reaction to give cyclopentadiene 

derivatives.In this study, vinylallene derivatives which bear 

electron-donating or -withdrawing groups on the aryl moiety were 

subjected to the gold-catalyzed cycloisomerization reaction to 

examine the effect of the substituents on aryl moiety. Their 

gold-catalyzed cycloisomerization reactions afforded the 

formation of cyclopentadiene derivatives in high yields via C-C 

bond formation. Surprisingly, we found that an aryl shift took 

place to the central carbon atom of the allenic moiety. Moreover, 

the reaction was highly depending on the substituents at the aryl, 

allenyl, and alkenyl group. 

Keywords: vinylallene; gold; cycloisomerization; 



s1264 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 0 2 

SiLiCon tetrAChLoride MediAted 

orGAnoCAtALytiC ALdoL reACtion 

d. AKSAKAL 1 , o. doGAn 1 


Aldol addition reaction is one of the important and most 

studied carbon-carbon bond forming reactions in organic 

chemistry. The idea behind the catalysis of Aldol reactions 

emerged from the similarity between allylsilane addition and silyl 

enolether addition (C-Si bond cleavage and O-Si bond cleavage). 

In catalytic asymmetric aldol addition reactions, new stereogenic 

centers with controllable absolute configurations are formed 

which is also important in synthesis of natural products. 

Different from the Mukaiyama-type aldol reactions, 

recently, chiral lewis bases have been used as promoters and in 

the presence of SiCl , these reactions proceed through the 

4 

formation of a cyclic transition state leading to anti aldol product 

as a major product with moderate-to-good diastereoselectivities 

and enantioselectivities. Phosphoramide derivatives, BINAPO 

and its derivatives, and N,N-dioxides and N-oxides have been 

extensively used for this purpose. 

Recently, our group has designed new phosphineoxy 

aziridinyl phosphanates (POAP) as organocatalysts which can be 

synthesized easily starting from vinyl phosphonate by Gabriel- 

Cromwell reaction. These organocatalysts were used for the 

asymmetric aldol addition reaction. Cyclohexanone and different 

aldehydes were reacted in the presence of SiCl and POAP 

4 

organocatalyst to form aldol product. Although the optimization 

studies are still continuing, the results so far showed that aldol 

product can be obtained in good yield and reasonable 

enantioselectivity. At this conference the synthesis of POAP 

organocatalyst and the details of organocatalytic aldol reaction 


Keywords: Asymmetric synthesis; Aldol reaction; 

Organocatalysis; Silicon- based; 


P - 0 8 0 3 

PrePArAtion And Study of Liquid 

CryStALLine BehAviour And eLeCtriCAL 

ProPertieS of A different tyPeS of SChiff’S 

BASeS diMMerS And it iS CoMPLexeS 

A. AL-KhALAf 1 , S. hAddAwi 2 , o. yASSer 1 

1 Babylon University, Chemistry Department-Science College, 

Hilla City/ Babylon, Iraq 

2 Karbala University, Chemistry Department-Science College, 

Karbala, Iraq 

Preparation of three different series of the symmetrical twin 

dimmers (Schiff’s bases) are derived from benzidine. Besides, 

Preparation and study of the liquid crystalline behaviour was 

achieved for eight compounds of (I) series. 

These prepared compounds characterized by I.R, 

UV-spectroscopy, and 1HNMR technique. The liquid crystalline 

properties of this prepared compounds was verified by optical 

polarizing microscopy and differential scanning calorimeter 

(DSC) and thermal gravimetry analysis (TG). The mesomorhic 

behaviour of these compounds was found to be nematic 

(enantiotropic), while three compounds (Di-9-anthrylidene 

benzidine, Di-4-hydroxy benzylidene benzidine, and 

Di-3-methoxy-4-hydroxy benzylidene benzidine) did not show 

any liquid crystalline behaviour. It has been found the nematic 

range exhibited by these compounds follows the order: 

MeO > NO > H > Cl 

2 

In addition, preparation and characterization were achieved 

for four complexes of Schiff’s bases with ions of (Cu +2 , Ni +2 ): 

(DMeOBB-Cu +2 , DMeOBB-Ni +2 , NO2BB-Cu +2 , NO2BB-Ni +2 ) 

were found to be nematic (enantiotropic). It is found that the (D.C) 

electrical conductivity ranged from (10-12 ) to (10-9 ) (ohm. cm) -1 

lies in the usual range of organic semiconductors. 



s1265 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 0 4 

SyntheSiS And AntiMiCroBiAL ACtivitieS of 

SoMe new SyntheSized iMide And SChiff’S 

BASe derivAtiveS 

M. AL-oMAr 1 , n. M. SABry 2 , e. M. fLefeL 3 , A. e. AMr 4 

1 King Saud University, College of Pharmacy, AlRiyadh, Saudi 

Arabia 

2 King Khalid University, Chemistry Department, Abha, Saudi 

Arabia 

3 National Research Center, Photochemistry Department, Cairo, 

Egypt 

4 King Saud University, Drug Exploration & Development 

Chair, AlRiyadh, Saudi Arabia 

A series of macrocyclic imide and Schiff-base derivatives 2 

and 3 have been prepared from pyridine-N-amino derivatives 1 

as starting material according to the literature procedures [1–4] . 

A series of 2,6-bis(substituted thiazolopyrimi-dinyl) pyridine (2a, 

b) and corresponding Schiff’s bases (3a-j) were synthesized from 

2,6-bis-(3-amino-2-methyl-4-oxo-9-substituted-3,4-dihydropyrido- 

-[30,20:4,5]-thieno[3,2-d]pyrimidin-7-yl)pyridines (1a, b) as 

starting materials. The compounds 1a,b were reacted with 2,3,4,5- 

-tetrachlorophthalic anhydride in glacial acetic acid to give the 

corresponding bis-imides (2a, b). But, they are treated with 

aromatic aldehydes in refluxing ethanol to afford the Schiff’s base 

derivatives (3a-j). The antimicrobial screening showed that many 

of these newly synthesized compounds had good antimicrobial 

activities comparable to Streptomycin and Fusidic acid as positive 

controls. The detailed synthesis, spectroscopic data, and 

antimicrobial activities of the synthesized compounds will be 

reported. 

references: 

1. A. E. Amr, M. I. Hegab, A. A. Ibrahim, M. M. Abdulla, 

Monatsh Chem., 2003, 134, 1395-1409. 

2. A. E. Amr, Z. Naturforsch. 2005, 60b, 990. 

3. M. H. Abou-Ghalia, A. E. Amr, M.M. Abdalah, Z. 

Naturforsch. 2003, 58b, 903. 

4. M. A. Al-Omar, A. E. Amr, Molecules, 2010, 15, 4711. 

Keywords: macrocyclic imide; Schiff-base; Synthesis; 

Antimicrobial; 


P - 0 8 0 5 

(6-hydroxy-3-oxo-3h-xAnthen-9-yL)MethyL: 

A PhotoreMovABLe ProteCtinG GrouP 

ABSorBinG ABove 500 nM 

J. AL AnShori 1 , P. SeBeJ 2 , t. SLAninA 1 , 

L. A. P. Antony 1 , P. KLán 2 , P. MüLLer 3 , 

J. wintner 3 , J. wirz 3 

1 Masaryk University Fac Sci, Chemistry, Brno, Czech Republic 

2 Masaryk University Fac Sci, Chemistry and Research Centre 

for Toxic Compounds in the Environment, Brno, Czech 

Republic 

3 University of Basel, Chemistry, Basel, Switzerland 

Photoremovable protecting groups (PPGs) are a versatile 

synthetic tool which found many applications in caging of 

biomolecules. [1] Coumarin-based PPGs have strong absorption 

extended to the visible light and fast release rate from its excited 

singlet state, and they gained considerable attention, especially 

for their applications in biological chemistry [2] and caging of 

cyclic nucleotides, carboxylic acids, and phosphates. [3-6] To extend 

the wavelength range of coumarin PPGs, we synthesized and 

studied a structurally similar (6-hydroxy-3-oxo-3H-xanthen-9- 

-yl)methyl derivatives with three different leaving groups 

(OP(=O)OEt , OAc, and Br) in 7 steps with an overall chemical 

2 

yields of 20–25%. The formation of a CT complex of 1a-c with 

DDQ during synthesis was observed and investigated by 

comparative study with the interactions of DDQ with 

succinylfluorescein and its methyl ester. [7] All derivatives of 

release the leaving groups in aq buffer at pH =7 upon irradiation 

with a 546-nm green light. The quantum yields of photorelease 

were found in the range of 0.5–4.2%. The MO calculations 

suggested that the heterolytic release of a leaving group 

strategically attached to the xanthenyl chromophore occurs from 

[8, 9] 

the first excited singlet state. 

references: 

1. Goeldner, M.; Givens, R. S., Dynamic Studies in Biology. 

Wiley-VCH: Weinheim. Germany, 2006 

2. C. Schultz, HFSP J. 2007, 1, 230. 

3. Kim, H.C., et al., Chemical Physics Letters, 2003, 

372(5,6): p. 899-903. 

4. Furuta, T., et al., Proceedings of the National Academy of 

Sciences of the United States of America, 1999, 

96(4): 1193-200. 

5. Fedoryak, O.D. and T.M. Dore, Organic Letters, 2002, 

4(20): p. 3419-3422. 

6. Schade, B., et al., Journal of Organic Chemistry, 1999, 

64(25): p. 9109-9117. 

7. Amat-Guerri, F., et al., Journal of Chem. Research, 1988, 

1447-1465. 

8. Zimmerman, H. E.; Sandel, V. R., Journal of the American 


9. Seiler, P.; Wirz, Journal of Helv. Chim. Acta 1972, 55, 

2693-712. 

Keywords: Photoremovable protecting groups; Coumarin; CT 

complex; Xanthene; Chromophore; 



s1266 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 0 6 

PerSPeCtiveS in the deSiGn, SyntheSiS And 

ChArACterizAtion of PoLyMer MAteriALS 

with APPLiCAtionS in oPtiCAL fieLd 

A. M. ALBu 1 , i. GAvriLA 1 , L. trinCA 1 

1 University Politehnica of Bucharest, Department of 

Bioresources and Polymer Science, Bucharest, Romania 

The organic macromolecules with extended electronic 

sequences remain one of the most attractive points of start for 

implementation of the specialized device. Why the polymer 

systems? Because is relatively easy to process organic polymeric 

materials into practical devices. They are certainly remarkable 

materials through their flexibility, versatility and architectural 

accessibility, which allow their optimization for the desired 

applications. 

Since the discovery of the photorefractive effect in organic 

polymers, polymers containing carbazole have also attracted 

much attention for their photoconductivity. In this context, 

multicomponent polymers with structural units containing both 

photoconductive and electrooptic functionalities in the side chain 

can be regarded as potentially suitable materials for 

photorefractive applications. Indeed, polymers with the carbazolyl 

diazene side group prepared by polymerization of the 

corresponding functionalized monomers, or by azocoupling postreaction 

to carbazole containing polymers, proved to show 

photorefractive and NLO properties as well as photoinduced 

orientation and formation of surface relief gratings. Moreover, the 

helical configurations, particularly the ‘stacking’ of the carbazole 

pendant groups in the syndiotactic polymer, would allow for many 

of the interesting electronic and photoconductive properties 

associated with polyvinylcarbazole. The such materials can be 

characterized, in solution, by chiral conformations related to the 

combined effects of the strongly dipolar conjugated carbazole 

system with the conformational stiffness of optically active rings, 

favouring the instauration of a conformational arrangement with 

a prevailing handedness, at least for chain sections of the 

macromolecules. 

In this idea, we propose the synthesis and characterization 

of few new carbazole compounds, to foreshadowing, based theirs 

physical properties, the potential applications of polymer 

materials, with such sequences, in the nonlinear optical field. 

Structured in three sections, the aims is to highlight the most 

important peculiarities regarding the structural - constituent 

relationship to the polymer materials, based on the consacrated 

analytical techniques. 

Keywords: Azo compounds; polymers; 


P - 0 8 0 7 

Proton-CAtALyzed, SiLAne-fueLed 

intrAMoLeCuLAr friedeL–CrAftS AryL 

CouPLinG: fLuoroArene C–f ACtivAtion By 

SiLyL CAtionS 

o. ALLeMAnn 1 , K. BALdridGe 1 , J. SieGeL 1 

1 University of Zurich, OCI, Zürich, Switzerland 

Friedel–Crafts transformations are known for a long time 

and still present a very important class of chemical reactions. In 

terms of aryl-aryl couplings, the reaction is limited due to the 

thermodynamic instability of the phenyl cation. This fact gave rise 

to a large variety of coupling reactions using transition metal 

catalysts and activated arenes. Combining our group’s knowledge 

about silylium ions in general [1] and our findings on carbon 

fluorine bond activation, [2] we developed a method for an 

intramolecular Friedel–Crafts type coupling of an aryl fluoride 

with an unactivated aryl nucleophile without using a transition 

metal. [3] The transformation involves cleavage of the C–F bond 

using the very reactive silylium ion and attack by an adjacent 

arene moiety within the same molecule. In our example reaction, 

we use an iPr Si carborane to abstract fluoride from 

3 

1-(2-Fluorophenyl)naphthalene, which is transformed to 

fluoranthene by ring closure and subsequent elimination of a 

proton. Since the proton can be used to generate a silyl cation from 

a silane, only a catalytic amount of initiator (i.e. silylium ion) can 

be used. We applied this method to more complex systems 

towards larger polyaromatic hydrocarbons and are exploring the 

possibilities concerning substrate scope and adaptabilities of the 

reaction. 

references: 

1. a) S. Duttwyler, Q. Q. Do, A. Linden, K. Baldridge, J. 

Siegel, Angewandte Chemie International Edition 2008, 

47, 1719; 

b) P. Romanato, S. Duttwyler, A. Linden, K. K. Baldridge, 

J. S. Siegel, Journal of the American Chemical Society 

2010, 132, 7828. 

2. S. Duttwyler, C. Douvris, N. L. P. Fackler, F. S. Tham, 

C. A. Reed, K. K. Baldridge, J. S. Siegel, Angewandte 

Chemie International Edition 2010, 49, 7519. 

3. O. Allemann, S. Duttwyler, P. Romanato, K. K. Baldridge, 

J. S. Siegel, Science 2011, 332, 574. 

Keywords: silyl cations; C-F activation; Friedel–Crafts; 

polyaromatic hydrocarbons; proton-catalyzed; 



s1267 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 0 8 

MAniPuLAtion of the ALPhA,BetA-unSAturAted 

CArBonyL unit of ChALConeS AS tooL to 

fine-tune reACtivity And BioLoGiCAL 

ACtivity 

S. AMSLinGer 1 


Pharmacy University of Regensburg, Regensburg, Germany 

Michael acceptors are often referred to as being nonspecific 

and have widely been neglected in drug development. Gribble and 

Sporn et al. showed that a variation of the α-substituent of an 

α,β-unsaturated carbonyl system can directly influence biological 

activity. [1] We are interested to use new in α-position of the 

α,β-unsaturated carbonyl system modified enones [2] to address 

specifically thiols which are of great biological importance. 

To test this concept, we investigate the expression and 

activity of proteins such as heme oxygenase-1 (HO-1) and 

inducible NO-syn-thase (iNOS). These enzymes are important 

targets within inflammatory processes and are regulated by the 

transcription factors Nrf2 and NF-κB. In both regulation 

mechanisms sulfhydryl groups are essential for activation or 

inhibition, and therefore Michael acceptors could be applied. 

We were able to synthesize a library of α-substituted 

chalcones (1,3-diphenylpropenones), X-derivatives, and test their 

reactivity in kinetic measurements using thiols. Here, we could 

clearly demonstrate that the substituent X has a great influence 

on the second order rate constant k . Moreover, we tested their 

2 

influence on the activity and expression of the proteins HO-1 and 

iNOS. 

references: 

1. a) T. Honda, G. W. Gribble, N. Suh, H. J. Finlay, 

B. V. Rounds, L. Bore, F. G. Favaloro, Y. Wang, 

M. B. Sporn, J. Med. Chem. 2000, 43, 1866-1877; 

b) T. Honda, B. V. Rounds, L. Bore, H. J. Finlay, 

F. G. Favaloro, N. Suh, Y. P. Wang, M. B. Sporn, 

G. W. Gribble, J. Med. Chem. 2000, 43, 4233-4246. 

2. S. Amslinger, ChemMedChem 2010, 5, 351-356. 

Keywords: Synthesis design; Michael addition; Inflammation; 

Kinetics; Protein expression; 


P - 0 8 0 9 

MetAL CAtALyzed ASyMMetriC CASCAde 

1,3-diPoLAr CyCLoAddition reACtion of 

AzoMethine yLideS 

S. AyAn 1 , o. doGAn 1 

1 Arts and Sciences, Chemistry, Ankara, Turkey 

In recent years cascade reactions have been 

studiedsignificiantly by different groups. This reaction provides 

complex moleculesfrom very simple starting materials in a single 

step. For that reason, it is considered as atom economicalreaction 

and “green chemistry”. Asymmetric version of this reaction is 

alsobeing studies by organic groups for the synthesis of complex 

chiral compounds.In this respect, we have studied metal catalyzed 

cascade reaction of azomethineylides with electron defficient 

dipolarophiles by using chiral ligands with silvermetal. As the 

chiral ligands, amino alcohol based ferrocenyl aziridinyl 

methanol(FAM) and phosphorous based phosphino ferrocenyl 

aziridinyl methanol (PFAM)were used. These ligands have an 

advantage of being synthesized easily on agram scale starting 

from acryloyl ferrocene. Moreover, the yellow color offerrocene 

ease the purification by flash column chromatography. For the 

cascadereaction of azomethine ylides glycine methyl ester, 

aromatic aldehyde,dipolarophile, chiral ligand, and silversalt were 

mixed in the same reaction flask to form pyrrolidine derivatives. 

Although the optimization studies are stillgoing on and showed 

that, pyrrolidine derivatives can be obtained in goodyields and 

enantioselectivities. At this conference, synthesis of chiral 

ligandand pyrrolidine synthesis via azomethine ylide chemistry 


Keywords: azomethine ylides; ligand effects; cascade; 



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P - 0 8 1 0 

iSoMerizinG oLefine MetAtheSiS 

S. BAAder 1 , d. M. ohLMAnn 1 , L. J. GooSSen 1 

1 Technische Universität, Fachbereich Chemie, Kaiserslautern, 

Germany 

Combining a metathesis catalyst with an isomerization 

catalyst can lead to a process in which unsaturated compounds 

are continuously converted into equilibrium mixtures of double 

bond isomers, which are concurrently undergoing olefin 

metathesis. Using highly active catalyst systems, the isomerizing 

olefin metathesis becomes an effective way to access defined 

distributions of unsaturated compounds from olefinic substrates. 

When ethylene is the cross metathesis partner, this isomerizing 

ethenolysis can be used for the shortening of olefin chains via 

stepwise cooperative isomerization and ethenolysis. Following 

this process, terminal olefins of higher value are obtained, with 

propylene being the only side-product. This new catalytic 

transformation is a potentially powerful tool for the transformation 

of easy available allylic compounds to the corresponding vinylic 

products. This concept is even viable for 4-phenyl-1-butene, 

which is converted to styrene via two subsequent isomerizing 

ethenolysis steps. 

After systematic optimization of the reaction conditions 

using a Ru-catalyst, we explored the scope of this new 

transformation. Starting from low-price natural products, such as 

eugenol (16 € / 100 g), this method gives a direct access to 

valuable functionalized styrenes, such as 3-methoxyvinylphenol 

(500 € / 100 g), in very good yield and excellent selectivities. 

Under these reaction conditions, common functional groups, such 

as hydroxy groups, are tolerated. Phenolic substrates are 

challenging because of their tendency to polymerize. [1] 

Compared to the traditional waste intensive methods like 

Wittig reactions, the transition metal catalyzed isomerizing 

ethenolysis is an atom-economical and environmentally friendly 

alternative for the synthesis of functionalized styrenes. [2] 

references: 

1. a) R. C. Sovish, J. Org. Chem. 1959, 24, 1345–1347; 

b) L. A. Cohen, W. M. Jones, J. Am. Chem. Soc. 1960, 82, 

1907–1911. 

2. N. Bettach, Y. Le Bigot, Z. Mouloungui, M. Delmas, 

A. Gaset, Synthetic Comm. 1992, 22, 513–518. 

Keywords: Metathesis; Isomerization; Fatty acids; Sustainable 

Chemistry; 


P - 0 8 1 1 

CoMPArinG the SPeCtrAL ProPertieS of 

Pyrene ProBe, LABeL And derivAtive in the 

PreSenCe of A nonioniC SurfACtAnt 

A. BArAn 1 , G. StinGA 1 , d. f. AnGheL 1 , A. ioveSCu 1 , 

C. MihAiLeSCu 1 , M. tudoSe 2 , P. ionitA 3 


Chemistry Laboratory, Bucharest, Romania 

2 “Ilie Murgulescu” Institute of Physical Chemistry, 

Coordination and Supramolecular Chemistry Laboratory, 


3 University of Bucharest, Organic Chemistry Department, 


The behavior of pyrene as probe, label and derivative in 

octaethylene glycol mono n-dodecyl ether (C E ), with or without 

12 8 

polyacrylic acid (PAA), was mainly investigated by steady-state 

fluorescence spectroscopy. PAA was home labeled with pyrene 

(3% mol). As a probe, pyrene showed a typical behavior, 

irrespective of absence or presence of PAA; its emission spectrum 

presented five vibronic peaks for monomer and at higher 

wavelength and surfactant concentration, the peak corresponding 

to the sandwich excimer. As a label on PAA, the emission 

spectrum had higher intensity and the same shape, but 4 nm 

bathochromically shifted. The peak corresponding to the sandwich 

excimer appeared even in surfactant-free solution. The pyrene 

derivative was 4-(N',N'-diphenyl-hydrazine)-3,5-dinitrobenzoic 

acid 2-oxo-2-pyren-2-yl-ethyl ester. Its fluorescence emission 

spectrum had very low intensity, only two monomer peaks (I and 1 

I ), no sandwich excimer and a bathochromic shift of 9 nm. It was 

5 

unexpected that, at the highest surfactant concentration used in 

this study, the derivative spectrum presented a 17 nm 

bathochromic shift. The data revealed that as a probe, pyrene is 

located in free or polymer-bound micelle, close to the core. As a 

label, it was first solubilized in the hydrophobic domains (it might 

force the polymer to shrink the coil) and, with surfactant addition, 

it was solubilized in micelles, closer to the ethylene oxide chains. 

The low intensity of the derivative fluorescence spectrum is due 

to the self-quenching favored by its structure. The derivative is 

probably located even closer to the palisade layer or actually 

hanged on it, which may explain the large bathochromic shift. As 

the nonionic micelle changes its shape and size, the derivative 

may be expelled somehow from the palisade layer. This approach 

may be useful in investigating such multi-assembled systems with 

the adequate fluorophore. 

Keywords: Fluorescent probes; Micelles; Polymers; 



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chem. Listy 106, s257–s1425 (2012) 


P - 0 8 1 2 

BioPoLyMeriC MiCroPArtiCLeS SyntheSized 

By interACtion of ChitoSAn with AnioniC 

SurfACtAntS 

A. BArAn 1 , S. Peretz 1 , d. f. AnGheL 1 , 

M. fLoreA SPiroiu 2 , A. ioveSCu 1 , G. StinGA 1 , 

M. MAxiM 1 



2 University of Bucharest, Department of Physical Chemistry, 


Particles obtained by interaction of polymers with 

surfactants are important because they have multiple applications 

in environmental protection, pharmacy, medicine, etc. Among the 

candidates used to develop such particles a special attention was 

paid to chitosan (CS) biopolymer and sodium lauryl sulfate (SDS) 

surfactant. To extend the range of surfactants used to prepare 

polymer-surfactant (PS) particles we use in the present study the 

sodium laureth sulfate (SLES) and dioctylsodium sulfosuccinate 

(AOT) as anionic surfactants. Unlike SDS, SLES has ethylene 

oxide groups between the anionic group and the alkyl chain, 

which modify the hydrophobic character of the surfactant. 

Depending on the condition of synthesis two types of particles 

were obtained: a) microparticles – at atmospheric pressure, 

b) ultrafine particles – at high pressure. The microparticles are 

formed instantaneously at atmospheric pressure when drops of 

SLES come into contact with the CS solution. Depending on the 

weight ratio between chitosan and surfactant, the complex gel can 

take different forms: microcapsule that expels its content, stable 

microcapsule and deformed microcapsule. 

To obtain ultrafine particles the SLES or AOT solution in 

contact with high pressure CO were sprayed into chitosan 

2 

solution bath, through a stainless steel capillary nozzle forming 

the chitosan-surfactant complex. It was found that increasing the 

spaying pressure the average diameter of ultrafine particles 

decreases. 

The formation of CS-SLES and CS-AOT complexes was 

investigated by Fourier Transform Infrared (FTIR) Spectroscopy, 

whereas scanning electron microscopy was used to characterize 

the morphology, size and shape of particles. FTIR spectrum 

proves the interaction between the sulfate group of SLES or AOT 

and the ammonium group of CS. The microparticles are 

quasi-spherical but some of them can take the form of pellets. The 

study allowed us to understand the interaction between CS and 

SLES, and to suggest a scheme of molecular complex formation 

by cross linking. 

Keywords: Surfactants; Polymers; 


P - 0 8 1 3 

environMentALLy BeniGn MetAL-free 

deCArBoxyLAtive ALdoL And MAnniCh 

reACtionS 

J. BAudoux 1 

1 Laboratoire de Chimie Moléculaire et Thioorganique UMR 

CNRS 6507, Chimie, Caen Cedex, France 

Organocatalysis stands as an eco-friendly and cost-effective 

methodology for the creation of carbon-carbon, carbonheteroatom 

and carbon-hydrogen bonds. 

β-hydroxyester is a structural moiety frequently encountered 

in many bioactive compounds and natural products [1] . Most of the 

methods to synthesize β-hydroxyesters rely on organometallic 

chemistry and the use of metal complexes (Reformatsky [2] , 

aldol-type reactions [3] ) in particular when the control of the 

stereochemistry is needed. Therefore, in those conditions, 

anhydrous solvents, low temperature, and the presence of a strong 

base are often required. 

The aim of this work is to develop an efficient methodology 

affording β-hydroxyesters and β-aminoxyesters under metal-free 

conditions. We describe herein a detailed study of the 

decarboxylative aldol and mannich reactions between a 

non-substituted ester hemimalonic acid and aldehydes and imines, 

in the presence of an achiral amine. The methodology was 

extended to a-substituted hemimalonic acids giving access to 

α-substituted-β-hydroxy/aminoesters. 

references: 

1. a) Shen, R.; Lin, C. T.; Bowman, E. J.; Bowman, B. J.; 

Porco, A. A. J. Am. Chem. Soc. 2003,125, 7889-7901. 

b) Assa, C.; Riveiros, R.; Ragot, J.; Fürstner, A. 

J. Am. Chem. Soc. 2003, 125, 15512-15520. 

c) Ghosh, A. K.; Kulkarni, S. Org. Lett.2008, 10, 

3907–3909. 

2. Ocampo, R.; Dolbier, W. R. Tetrahedron 2004, 60, 

9325–9374. 

3. a) Oisaki, K.; Suto, Y.; Kanai, M.; Shibasaki, M. 

J. Am. Chem. Soc. 2003, 125, 5644–5645. 

b) Oisaki, K.; Zhao, D.; Kanai, M.; Shibasaki, M. 

J. Am. Chem. Soc. 2006, 128, 7164–7165. 

Keywords: Organocatalysis; Decarboxylation; Mannich; 

aminoacids; aldol reaction; 



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chem. Listy 106, s257–s1425 (2012) 


P - 0 8 1 4 

wAter SoLuBLe n-heteroCyCLiC CArBene 

GoLd CoMPLexeS 

K. BeLGer 1 , n. KrAuSe 1 


In 1991 Arduengo [1] isolated the first “free” N-heterocyclic 

carbene. Since then the interest in NHC transition metal 

complexes increased rapidly due to their σ-donating properties 

and their broad variation range in steric features which allow an 

excellent stabilization of the metal center and an enhancement of 

[2, 3] 

their catalytic activity. 

In our investigations, water soluble NHC gold catalysts will 

be synthesized. During the last two decades, water has gained 

great interest as a solvent. Low costs as well as environmental and 

safety aspects are the main advantages of water. Therefore, 

water-based catalysts are required. [4] The introduction of a water 

soluble residue at the NHC ligand like an ammonium salt or a 

sulfonate group is a potential approach. These residues are already 

known from phosphine ligands. [5] However, there are just a few 

water soluble NHC complexes so far. [6-9] 

references: 

1. A.J. Arduengo III, R. L. Harlow, M. Kline, J. Am. Chem. 

Soc. 1991, 113, 361. 

2. S. Díez-González, N. Marion, S. P. Nolan, Chem. Rev. 

2009, 109, 3612–3676. 

3. S. P. Nolan, Acc. Chem. Res. 2011, 44, 91. 

4. A. Azua, S. Sanz, E. Preis, Chem. Eur. J. 2011, 17, 

3963–3967. 

5. K. H. Shaughnessy, Chem. Rev. 2009, 109, 643-710. 

6. W. Wang, J. Wu, C. Xia, F. Li, Green Chem. 2011, 13, 

3440. 

7. S. Roy, H. Plenio, Adv. Synth. Catal. 2010, 352, 

1014–1022. 

8. A. Azua, S. Sanz, E. Peris, Organometallics, 2010, 29, 

3661–3664. 

9. S. H. Hong, R. H. Grubbs, J. Am. Chem. Soc. 2006, 128, 

3508–3509. 

Keywords: Carbene ligands; Gold; Nitrogen heterocycles; 

Ligand design; Water chemistry; 


P - 0 8 1 5 

Proton trAnSfer in CALCiuM-reGuLAted 

BioLuMineSCent reACtionS: PeCuLiAritieS of 

fLuoreSCenCe SPeCtrA 

n. BeLoGurovA 1 , n. KudryAShevA 1 

1 Institute of Biophysics SB RAS, Photobiology, Krasnoyarsk, 

Russia 

Calcium-regulated bioluminescent reactions catalyzed by 

photoproteins are responsible for bioluminescence of marine 

coelenterates. Photoprotein is a stable enzyme-substrate complex 

consisting of a single polypeptide chain and an oxygen “pre-activated” 

substrate, 2-hydroperoxycoelenterazine which is tightly but 

noncovalently bound within a hydrophobic cavity inside the protein. 

Addition of calcium ions to photoprotein triggers a bioluminescent 

reaction resulting in light emission with λ =485 nm. The product 

max 

of the bioluminescent reaction (enzyme-bound chromophore, 

coelenteramide) is a fluorescent protein; It is called ‘discharged’ 

photoprotein. Obelin isolated from hydroid Obelia longissima is 

one of the most studied among photoproteins. Obelin is stable and 

nontoxic natural complex; its spectra, and hence, color of 

luminescence, are variable. This is why it is considered as 

perspective bioluminescent and fluorescent marker for biological 

and medical investigations in vitro and in vivo. Therefore the 

fluorescent peculiarities of obelin are of high interest. 

Spectra of obelin bioluminescence and discharged obelin 

photoluminescence are wide and complex. Photoluminescence 

spectra depend on external physico-chemical conditions of obelin 

solution (pH, calcium concentration, and temperature), but 

bioluminescence spectra do not. 

The spectra were deconvolved into spectral components 

using Gauss distribution and method of second derivative. 

Spectral components were attributed to protonated and several 

deprotonated forms of coelenteramide with different acidity in its 

fluorescent states. Effectiveness of proton-transfer process 

depends on conformation of obelin active center - distance 

between coelenteramide and proton-accepting group of amino 

acid environment. We suggest that discharged obelin might form 

several conformations depending on physico-chemical conditions. 

For example, analysis of photoluminescent spectra of discharged 

obelin under different calcium concentration revealed 

considerable spectral changes at [Ca2+ ] ≈ 0.5 μM, this pointing to 

enzymatic conformational transition in discharged obelin. 

Meanwhile only one conformation of obelin is responsible for 

bioluminescence under different conditions. 

Keywords: Fluorescence spectroscopy; Proton transport; 

Photoprotein; 



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P - 0 8 1 6 

new SAMAriuM diiodide MediAted CASCAde 

reACtionS – APProACheS towArdS StryChnoS 

ALKALoidS 

C. Bentz 1 , C. BeeMeLMAnnS 1 , h. reiSSiG 1 

1 Freie Universität Berlin, Institut für Chemie und Biochemie – 

Organische Chemie, Berlin, Germany 

The indole ring system is probably the most ubiquitous 

heterocycle in nature and has become an important structural 

component in many pharmaceutical agents. [1] In our group indole 

derivatives are used in SmI - mediated reductive 6- to 8-exo-trig 

2 

cyclizations in order to build up highly functionalized 

polyheterocycles. [2] Recently, various substitution patterns of the 

indole moiety and different electrophiles as trapping reagents for 

the in situ generated samarium enolate have been investigated and 

the desired tricyclic compounds were obtained in high yields as 

single diastereomers. Now, we report a novel cascade reaction 

mediated by SmI which leads to synthetically interesting 

2 

tetracyclic indole derivatives and features the generation of two 

new rings and three stereogenic centers, including a new 

quarternary center. 

The tetracycle was an ideal candidate for a formal total 

synthesis of Strychnine. A total synthesis with the pentacyclic key 

building block was already described by Rawal in 1994. [3] Herein, 

we will describe our approach towards the key building block, 

finalizing a very short formal synthesis of Strychnine. [2f] 

references: 

1. a) J. Bonjoch, D. Solé, Chem. Rev. 2000, 100, 3455–3482; 

b) G. R. Humphrey, T. Kuethe, Chem. Rev. 2006, 106, 

2875-2911; 

c) K. Higuchi, T. Kawasaki, Nat. Prod. Rep. 2007, 24, 

843–868. 

2. a) S. Gross, H.-U Reissig, Org. Lett. 2004, 5, 4305; 

b) M. Berndt, S. Gross, A. Hölemann, H.-U. Reissig, 

Synlett 2004, 422–438; 

c) V. Blot, H.-U. Reissig, Eur. J. Org. Chem. 2006, 

4989–4992; 

d) C. Beemelmanns, H.-U. Reissig, Org. Biomol. Chem. 

2009, 7, 4475–4480; 

e) C. Beemelmanns, S. Gross, V. Blot, H.-U. Reissig, Eur. 

J. Org. Chem. 2010, 3635–3646; 

f) C. Beemelmanns, H.-U. Reissig, Angew. Chem. 2010, 

122, 8195-8199; Angew. Chem. Int. Ed. 2010, 49, 

8021–8025; C. Beemelmanns, H.-U. Reissig, Chem. 

Sov. Rev. 2011, 40, 2199-2210. 

3. V. H. Rawal, S. Iwasa, J. Org. Chem. 1994, 59, 

2685–2686. 

Keywords: Samarium; Radicals; Cyclization; Natural 

products; 


P - 0 8 1 7 

SyntheSiS of nitroGen-ContAininG GrAPhene 

nAnoriBBonS 

r. BerGer 1 , x. fenG 1 , K. MüLLen 1 


Chemistry Group, Mainz, Germany 

The replacement of one or multiple carbon atoms in a 

polyaromatic hydrocarbon (PAH) clearly changes its 

optoelectronic properties. This is not only a very interesting topic 

of heteroaromatic chemistry but also a challenging task in the field 

of materials science, regarding nitrogen-containing graphitic 

materials. For example such metal-free materials have proven to 

be promising candidates for oxygen reduction catalysts at 

cathodes of fuel cells. 

As a synthetic group the tools of organic chemistry allow us 

to create nanographenes, as well as longitudinally extended graphene 

nanoribbons (GNRs) in a variety of topologies. For the fabrication 

of GNRs we applied techniques of solution or surface-assisted 

polymerization of dihalogenated tetraphenyltriphenylene 

derivatives, followed by cyclodehydrogenation to give the 

planarized graphitic material. In this study, we utilized this method 

and introduced nitrogen atoms to GNRs at designed positions by 

designing appropriate precursors. All the nitrogen atoms were 

located at the periphery, which could be controlled to be uniform 

pyrimidine or pyridine type structure. This is in sharp contrast to 

other protocols such as pyrolysis of nitrogen enriched precursors 

and treatment of graphene with nitrogen sources like ammonia, 

which give structurally undefined nitrogen-containing graphenes. 

Furthermore, it is possible by this method to compare the nitrogen 

doped GNRs with their parent GNRs and to evaluate the effect of 

the nitrogen atoms on their properties. By statistical 

copolymerisation of doped and undoped monomers it is also 

possible to adjust the nitrogen content without changing the 

structure of the carbon framework. 

In summary we could extend our established method of 

bottom-up synthesis to a new class of nitrogen containing GNRs. 

Keywords: Graphene; Nitrogen; 



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P - 0 8 1 8 

redox ModuLAtion of the ShuttLinG Motion 

in A triStABLe [2]rotAxAne 

J. BernA 1 , M. ALAJArin 1 , C. MArin-rodriGuez 1 , 

C. frAnCo-PuJAnte 1 

1 Regional Campus of International Excellence “Campus Mare 

Nostrum” Universidad de Murcia, Deptartamento de Quimica 

Organica Facultad de Química, Murcia, Spain 

The investigation on mechanically interlocked architectures 

has produced a number of programmed systems for performing 

induced movements at will. [1] In this context, two-station 

[2]rotaxanes involve a privileged place due to their potential use 

as molecular devices. [2] In a previous work we proved that 

azodicarboxamide groups can act as efficient templates for the 

assembly of hydrogen-bonded rotaxanes and can be employed for 

the building of chemically-driven molecular shuttles. [3] Herein we 

describe the submolecular translational movement in novel 

hydrogen-bonded [2]rotaxanes containing benzylic amide 

macrocycles and two azo/hydrazodicarboxamide binding sites. [4] 

We disclosed that the modulation of the oxidation level of these 

systems give rise to interlocked molecular architectures featuring 

novel dynamics of significance for the tuning of distance and/or 

time dependent properties. 

Acknowledgement: This work was supported by the MICINN 

(Projects CTQ2008-05827/BQU and CTQ2009-12216/BQU), 

MINECO (Project CTQ2012-36158/BQU) and Fundación 

Séneca-CARM (Project 08661/PI/08). J.B. thanks to the 

MICINN for a Ramón y Cajal contract (RYC-2008-02647), cofinanced 

by the European Social Fund. 

references: 

1. E. R. Kay, D. A. Leigh, F. Zerbetto, Angew. Chem. Int. Ed. 

2007, 46, 72. 

2. E. Coronado, P. Gavina, S. Tatay, Chem. Soc. Rev., 2009, 

38, 1674. 

3. J. Berná, M. Alajarín, R.-A. Orenes, J. Am. Chem. Soc., 

2010, 132, 10741. 

4. J. Berná, M. Alajarín, C. Marín-Rodríguez, 

C. Franco-Pujante, Chem. Sci., 2012, 

DOI: 10.1039/C2SC20488F 

Keywords: Rotaxanes; Noncovalent interactions; Azo 

compounds; Molecular dynamics; Redox chemistry; 


P - 0 8 1 9 

non-CovALent interferenCe on the 

MACroCyCLe rotAtion of hydroGen Bonded 

[2]rotAxAneS 

J. BernA 1 , M. ALAJArin 1 , L. BurioL 2 , 

M. A. P. MArtinS 2 , J. S. MArtinez-eSPin 1 , 

r. A. oreneS 3 


Nostrum” Universidad de Murcia, Dept. de Quimica Organica 

F. de Química, Murcia, Spain 

2 Universidade Federal de Santa Maria, Departamento de 

Quimica, Santa Maria, Brazil 


Nostrum” Universidad de Murcia, Servicio de Apoyo la 

Investigacion (SAI), Murcia, Spain 

Controlling motion in interlocked molecular architectures 

has been a trending subject during the last years [1] for the scientific 

community and, mainly, for researchers interested on the 

modelling of the biological machinery and the development of 

stimuli-responsive molecular devices. [1c] 

In this communication we disclose that the incorporation of 

cyclohexylmethyl stoppers on the succinamide-based binding site 

of a [2]rotaxane has a clear effect over the macrocycle rotation [2] 

through the establishment of non-covalent interactions This study 

was supported by a dynamic 1H NMR study performed with a set 

of five hydrogen bonded [2]rotaxanes and the molecular structure 

in the solid state of one of these interlocked molecules. [3] 

Acknowledgement: This work was supported by the MICINN 

(Projects CTQ2008-05827/BQU and CTQ2009-12216/BQU), 

the MINECO (Project CTQ2012-36158/BQU) and the 

Fundación Séneca-CARM (Project 08661/PI/08). J.B. thanks to 

the MICINN for a Ramón y Cajal contract (RYC-2008-02647), 

co-financed by the European Social Fund. 

references: 

1. a) V. Balzani, A. Credi, M. Venturi, From Non-Covalent 

Assemblies to Molecular Machines, 2011, 159. 

b) J.F. Stoddart, Chem. Soc. Rev., 2009, 38, 1802. 

c) E.R. Kay, D.A. Leigh, F. Zerbetto, Angew. Chem., Int. 

Ed., 2007, 46, 72. 

d) A. Harada, Acc. Chem. Res., 2001, 34, 456. 

e) V. Balzani, A. Credi, F.M. Raymo, J.F. Stoddart, Angew. 

Chem., Int. Ed., 2000, 39, 3348. 

2. V. Bermúdez, N. Capron, T. Gase, F.G. Gatti, F. Kajzar, 

D.A. Leigh, F. Zerbetto, S. Zhang, Nature, 2000, 406, 

608–611. 

3. J. Berná, M. Alajarín, J.S. Martínez-Espín, L. Buriol, 

M.A.P. Martins, R.A. Orenes, Chem. Commun., 2012, 

DOI: 10.1039/C2CC32092D. 

Keywords: Rotaxanes; Self-assembly; Noncovalent 

interactions; Molecular dynamics; X-ray diffraction; 



s1273 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 2 0 

ChirAL iMidAte-PhoSPhAneS: ProGreSS in 

their SyntheSiS And APPLiCAtion AS 

n,P-LiGAndS 

K. Bert 1 , t. noeL 2 , P. JAnSSenS 1 , 

J. vAn der eyCKen 1 


2 Eindhoven University of technology, Chemical Engineering 

and Chemistry, Eindhoven, Netherlands 

Chiral imidate-phosphanes were recently developed in our 

lab as a new type of P,N-ligands, easily accessible via a one-step 

procedure starting from an imidate precursor and a commercially 

available chiral aminophosphane. [1] 

We wish to report here on the performance of these ligands 

in the Pd(0)-catalyzed allylic alkylation and amination and the 

Ir(I)-catalyzed asymmetric hydrogenation of unfunctionalized 

olefins. [2] 

The observed performance of our imidate-phosphane 

ligands with various carbon and amine nucleophiles in the 

Pd(0)-catalyzed allylic alkylation and amination appeared to be 

good to excellent (yields up to 99% and ee’s up to 99%). Moderate 

to very good results (yields up to 99.9% and ee’s up to >99%) 

were obtained with our imidate-phosphane ligands in the 

Ir(I)-catalyzed asymmetric hydrogenation of unfunctionalized 

olefins. 

references: 

1. Noel, T.; Bert, K.; Van der Eycken, E.; Van der Eycken, J. 

Eur. J. Org. Chem. (2010), 21, 4056-4061. 

2. Noel, T., Bert, K., Janssens, P. and Van der Eycken, J. 

(2012) Chiral Imidate Ligands: Synthesis and Applications 

in Asymmetric Catalysis, in Innovative Catalysis in 

Organic Synthesis: Oxidation, Hydrogenation, and C-X 

Bond Forming Reactions (ed P. G. Andersson), 

Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 

Germany. doi: 10.1002/9783527646586.ch14 

Keywords: Asymmetric catalysis; Asymmetric synthesis; 

Hydrogenation; Palladium; 


P - 0 8 2 1 

AroMAtiC CArBoxyLiC ACidS in 

deCArBoxyLAtive etherifiCAtion 

S. BhAdrA 1 , w. i. dziK 1 , L. J. GoSSen 1 

1 Technische Universität Kaiserslautern, FB Chemie – 

Organische Chemie, Kaiserslautern, Germany 

Transition metal-catalyzed decarboxylative coupling 

reactions have emerged as a powerful strategy to form carbon– 

carbon or carbon–heteroatom bonds starting from carboxylic 

acids. In these reactions, C–C bonds to carboxylate groups are 

cleaved, and in their place, new carbon–carbon bonds are formed. 

Decarboxylative cross-couplings constitute advantageous 

alternatives to traditional cross-coupling or addition reactions 

involving preformed organometallic reagents. While the 

overwhelming majority of decarboxylative couplings of aromatic 

carboxylates proceed with formation of C–C bonds, the only 

example of C–heteroatom bond forming reactions are restricted 

to C–S and C–Se bond formation. 

Here we present the decarboxylative C–O coupling as a 

practical access to alkyl-aryl and diaryl ethers avoiding the use of 

the often expensive organic halide and boronic acid precursors. 

Alkyl aryl- or diaryl ethers are synthesized starting from easily 

available aromatic carboxylic acids and alkoxysilanes or aryl 

boranes respectively. The reaction occurs under aerobic conditions 

in the presence of silver carbonate as the decarboxylation catalyst 

and copper acetate as the cross-coupling catalyst. Thus, aromatic 

carboxylates with various electron-withdrawing and –donating 

groups in the ortho position e.g. nitro, methoxy, dimethylamino, 

sulfonyl, chloro, fluoro, trifluoromethyl or phenyl groups, were 

successfully converted to the corresponding aryl ether. On the 

other hand, for carboxylates with a low tendency to extrude 

carbon dioxide, an alternative pathway consisting of ortho 

functionalization followed by protodecarboxylation has been 

shown to be functional, so that the ether group is installed in the 

ortho rather than theipso position of the former carboxylate group. 

This approach combines the key benefit of regiospecificity with 

the broad availability, low cost, and easy handling of carboxylate 

substrates and therefore serves as an attractive alternative to the 

traditional Buchwald-Hartwig and Chan-Evans-Lam reactions. 

Keywords: C-C activation; cross-coupling; regioselectivity; 

copper; silver; 



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P - 0 8 2 2 

dynAMiC KinetiC reSoLution of MethyL 

2,3-dihydroBenzo[B]furAn-3-CArBoxyLAte 

And ethyL 5-ChLoro-2,3-dihydroBenzo[B]furAn- 

-3-CArBoxyLAte 

P. BonGen 1 , J. PietruSzKA 1 , r. C. SiMon 2 

1 Institute of Bioorganic Chemistry, Juelich, Germany 

2 Chemie, Graz, Austria 

Enzymatic kinetic resolution is a powerful tool for 

separating enantiomers of a racemic mixture. A severe limitation 

is the maximum theoretical yield of 50% in all cases, unless 

racemisation of the substrate is possible. The dynamic enzymatic 

kinetic resolution could in these cases overcome the disadvantage 

and would thus furnish products with a very high enantiomeric 

excess and in high yield. Hydrolases such as lipases are still the 

preferred biocatalysts to establish dynamic enzymatic kinetic 

resolution since they are readily available and – concerning the 

reaction conditions – show considerable flexibility. [1] 

Herein we report a method for the kinetic resolution of 

racemic methyl 2,3-dihydrobenzo[b]furan-3-carboxylate and its 

chlorine derivative methyl 5-chloro-2,3-dihydrobenzo[b]furan-3- 

-carboxylate. After establishing a successful biocatalytic system 

with outstanding results concerning ee and yield, dynamic, 

enzymatic, kinetic resolutions were investigated to increase 

yields up to more than 50 %. The compounds of interest were 

known precursors for analgesic agent 7-benzoyl-5-chloro-2,3- 

-dihydrobenzo[b]furan-3-carboxylic acid (BRL 37959). [2] 

For improving enzyme screening, reversed phase HPLC 

with CD detector was used to determine ee during screening. This 

method allows high throughput screening because of its time 

advantage compared to normal phase chiral HPLC. Especially to 

find an enzyme that hydrolyses selectively ethyl 5-chloro-2,3- 

-dihydrobenzofuran-3-carboxylate which affords better 

yields than the corresponding methyl ester when carrying out 

Friedel-Crafts acylation to come to ethyl 7-benzoyl-5-chloro-2,3- 

-dihydrobenzo[b]furan-3-carboxylate, which can easily be 

hydrolysed under acidic conditions to afford analgesic agent 

BRL 37959. 

references: 

1. E.g. U. T. Bornscheuer and R. J. Kazlauskas, Hydrolases 

in Organic Synthesis - Regio- and Stereoselective 

Biotransformations, Wiley-VCH, Weinheim, 1999. 

2. E. A. Boyle, F. R. Mangan, R. E. Markwell, S. A. Smith, 

M. J. Thomson, R. W. Ward, P. A. Wyman, J. Med. Chem. 

1986, 29, 894. 

Keywords: dynamic kinetic resolution; chemoenzymatic; 

analgesic agent; 


P - 0 8 2 3 

diAStereoSeLeCtive SyntheSiS of 

new oPtiCALLy ACtive 1-(SuBStituted 

AryL)PyrroLe derivAtiveS 

e. B. BottKA 1 , A. thurner 2 , f. fAiGL 2 


Department of Organic Chemistry and Tecnology, Budapest, 

Hungary 

2 Budapest University of Technology and Economics, MTA-BME 

Organic Chemical Technology Research Group, Budapest, 

Hungary 

Multisubstituted 1-arylpyrroles are known intermediates of 

biologically active compounds (mytomycine analogs, 

pyrrolobenzoxazepines, neopyrolomycine). Synthesis of these 

compounds via classical methods usually results in low yields 

because of the acid sensitivity of the pyrrole ring. Application of 

organometallic reagents can help one to get rid of that problem if 

highly selective mono- and dimetallation methods were available 

for these types of compounds. 

First members of C symmetric atropisomeric 1-arylpyrrole 

1 

derivatives were prepared by our research group about 10 years 

ago [1] . Some of these derivatives can be applied as chiral ligands 

too. Later we prepared the optically pure atropisomeric 

1-(2-carboxymethyl-6-ethylphenyl)-1H-pyrrole-2-carboxylic acid 

by consecutive dimetalation of 1-(2-ethylphenyl)-1H-pyrrole with 

activated organometallic type base and solid carbondioxide to 

provide racemic derivative followed by the resolution of 

dicarboxylic acid with (S)-1-phenylethylamine [2] . Herein we 

report on the examination of the regioselective metalation and 

stereoselective derivative formation of the atropisomeric 

dicarboxylic acid. The new derivatives were obtained in a 

diastereoselective way and in good yields by consecutive 

monometalation of the acid with LiDA-KOR followed by the 

reactions with different reagents (for example iodomethane, 

benzaldehyde, dimethylformamide, isobutyl bromide, benzyl 

bromide, etc.). 

Absolute configurations of successfully prepared 

(+)-1-(2-(1-carboxyethyl)-6-ethylphenyl)-1H-pyrrole-2-carboxylic 

acid was determined using single crystal X-ray diffraction 

measurements. 

The substituted dicarboxylic acids were converted into 

monoesters in two different ways: selective hydrolysis of the 

diester, which was formed with an excess of thionyl chloride in 

ethanol or selective monoesterification. 

references: 

1. Fogassy, K., Harmat, V., Böcskei, Zs., Tárkányi, G., Toke, L., 

Faigl, F.: Tetrahedron: Asymmetry 11(23), 4771–4780 

(2000). 

2. Faigl, F.; Vas-Feldhoffer, B.; Kubinyi, M.; Pal, K.; 

Tarkanyi, G.; Czugler, M.: Tetrahedron: Asymmetry 20(1), 

98–103 (2009). 

Keywords: Regioselectivity; Diastereoselectivity; Metalation; 



s1275 

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P - 0 8 2 4 

BindinG Mode infLuenCe on GAS-PhASe 

frAGMentAtion of AdAMAntyLAted 

BiSiMidAzoLiuM@CuCurBit[7]uriL CoMPLexeS 

P. BrAnná 1 , M. rouChAL 1 , J. CernoChová 1 , 

r. víChA 1 

1 Tomas Bata University in Zlin Faculty of Technology, 

Department of Chemistry, Zlin, Czech Republic 

Within two past decades, the host-guest chemistry of 

cucurbit[n]urils (CBs) and various guests has been extensively 

studied in solution as well as in the gas phase. We prepared new 

adamantylated bisimidazolium (BIM) salts and examined their 

binding behavior towards CB7 in the gas phase using an ion trap 

instrument equipped with electrospray ion source. Two distinct 

binding modes may be supposed for our systems. In the first class 

of complexes, the adamantane moiety is arranged inside the 

interior cavity of CB7 and only one CB7 carbonyl portal is 

occupied by positively charged imidazolium ring. If it is sterically 

allowed, the CB7 unit may slip over the BIM scaffold to form the 

complex of the second class with both CB7 carbonyl portals 

occupied by imidazolium rings. Sole BIM dications decomposed 

in concert with electrostatic repulsion to produce two singly 

charged fragments upon collision induced dissociation (CID) 

conditions. Similarly, the complexes of BIM bearing bulky 

substituents dissociated to singly charged axel residue and 

aggregate of 1-adamantylmethyl cation with CB7. In contrast, 

some BIMs complexed to CB7 released neutral fragment 

(1-adamantylcarbene) to form doubly charged aggregate of CB7 

and axel residue. Furthermore, the subsequent releasing of the 

second 1-adamantylcarbene was observed. This unexpected 

fragmentation occurred only when the slippage of CB7 unit over 

the BIM axel is sterically allowed. This phenomenon may be 

employed as an efficient tool for binding mode clarification using 

mass spectrometry. 

Acknowledgement: The financial support of this work by the 

Internal Founding Agency of Tomas Bata University in Zlin 

(project No. IGA/FT/2012/016) is gratefully acknowledged. 

Keywords: gas-phase reactions; host-guest system; 


P - 0 8 2 5 

trACeLeSS toSyLhydrAzone-BASed triAzoLe 

forMAtion: towArdS A viABLe And roBuSt 

ALternAtive for the CovALent LABeLinG of 

vAriouS BioMoLeCuLeS 

S. BrAuCh 1 , S. S. vAn BerKeL 2 , B. weSterMAnn 1 

1 Leibniz Institute of Plant Biochemistry, Department of 

Bioorganic Chemistry, Halle (Saale), Germany 

2 University of Oxford, Department of Chemistry, Oxford, United 

Kingdom 

Traceless Tosylhydrazone-based Triazole formation (Sakai 

reaction) can be readily achieved by reacting primary amines with 

functional α,α-dichlorotosylhydrazones under ambient conditions. 

This fast and efficient alternative to the copper-assisted azidealkyne 

cycloaddition (CUAAC) and strain-promoted azide-alkyne 

cycloaddition (SPAAC) affords, exclusively, 1,4-substituted 

triazole “click-products” with high stereoretention. Moreover the 

observed versatility and chemoselectivity of the here presented 

metal-free triazole formation methodology led us to the 

conclusion that primary amines, inherent to many natural products 

and biomolecules, should be applicable as functional handles 

for further modifications (e.g. fluorescent labeling, 

biotinylation). Besides the synthesis of various functional 

α,α-dichlorotosylhydrazones, first attempts regarding the 

bioapplicability of the Sakai reaction will be discussed. 

references: 

1. K. Sakai, N. Hida, K. Kondo, Bull. Chem. Soc. Jpn. 1986, 

59, 179–183. 

2. S. S. van Berkel, S. Brauch, L. Gabriel, M. Henze, 

S. Stark, D. Vasilev, L. A. Wessjohann, M. Abbas 

B. Westermann, Angew. Chem. Int. Ed. 2012, in press, 

DOI: 10.1002/anie.201108850. 

Keywords: Click Chemistry; Heterocycles; Hydrazones; 



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P - 0 8 2 6 

A SeLeCtive ConverSion of BenzyLiC 

ALCohoLS to the CorreSPondinG CArBonyL 

CoMPoundS By MeAnS of An AG(iii) And Cu(iii) 

CoMPLexeS 

z. BuGArCiC 1 , n. JAnKoviC 1 , M. KoStiC 1 , v. divAC 1 

1 Faculty of Science, Department of Chemistry, Kragujevac, 

Serbia 

The oxidation of alcohols into aldehydes and ketones is a 

ubiquitous transformation in organic chemistry and numerous 

oxidizing agents are available to effect this key reaction. This 

reaction raises continuous interest, but most of these reactions 

have not been applied to sensitive natural polyfunctional products. 

In recent years investigators have been increasingly interested in 

studies of unusual oxidation states of transition metals such as 

Cu(III), Ni(III), Ni(IV), Ag(III). We now have looked more 

closely at the possibility of preparing carbonyl compounds with 

the aid of Ag(III) and Cu(III) complexes, partly because it is 

unusual for Ag and Cu species to have charge +3, which means it 

can easily change charge; partly because complex being easily 

made of inexpensive chemicals. [1, 2] 

Investigations have been carried out with some potentially 

oxidable substrates which contains different type of hydroxyl 

group in the molecule like D-(-)-threo-2-dichloroacetamido-1-(4- 

-nitrophenyl)-1,3-propanediol(chloramphenicol), (1R,2R)-(-)-2- 

-amino-1-(4-nitrophenyl)-1, 3 -propanediol, (S)-1-phenyl- 1, 3 - 

-propanediol and Ag(III) and Cu(III) complexes. The method 

gives the possibility of selective oxidation of benzylic hydroxyl 

groups in polyhydroxyl compounds in good yields. Such systems 

occur in nature and medicine and thus there is considerable 

interest in devising synthetic methods for their regioselective 

oxidation. 

references: 

1. Z. Bugarcic, S. Novokmet, Î. Senic, Î. Bugarcic, 

Monatshefte fur Chemie, 2000, 131, 799-802. 

2. Z. Bugarcic, S. Novokmet, V. Kostic, J. Serb. Chem. Soc. 

2005, 70, 681. 

Keywords: Alcohols; Aldehydes; Ketones; Oxidation; 


P - 0 8 2 7 

KiLoGrAM ProduCtion of CorAnnuLene: 

oPtiMizAtion And PotentiAL APPLiCAtionS 

A. ButterfieLd 1 , B. GiLoMen 2 , K. BALdridGe 1 , 

J. S. SieGeL 1 


Switzerland 

2 University of Zurich, Labor für Prozessforschung, Zürich, 

Switzerland 

Corannulene was first synthesized in 1966 in 16 steps with 

less than a 1% yield. [1] This synthesis on milligram-scale, albeit 

pioneering, was not suitable for preparing enough material for 

further application. Improvements in the synthesis of corannulene 

have opened the door for a series of mono-, di-, tetra-, penta-, 

hexa- and deca- substituted derivatives on gram scale. [2] These 

derivatives can be used as a template for a variety of higher order 

structures, such as graphite tubes/caps, liquid crystals, dendrimers, 

polymers, cruciforms, cyclophanes and molecular clefts. To 

exploit the materials chemistry of such derivatives, a chemical 

process for production of corannulene on kilo scale would be 

advantageous. 

An efficient entry process for the synthesis of corannulene 

has been demonstrated on kilogram scale. [3] Compared to the 

discovery and gram-scale syntheses, the amounts of solvents and 

reagents per gram of product were greatly reduced. Priority was 

given to implement the least toxic agents possible. Improvements 

in the purification of products obviated the need for column 

chromatography, alleviating four chromatographic operations. A 

new reduction method for the final step of the synthesis decreased 

reaction time from 6 to 0.5 days, and avoided the use of 100 equiv 

of zinc metal. The process now comprises nine steps, each of 

which runs smoothly at 100-L scale with a charging of 3–12 kg 

of educt. A total of 1.3 kg corannulene was isolated. This 

kilogram-scale process reduces material costs by over 2 orders of 

magnitude compared to that for the published gram-scale 

syntheses. 

references: 

1. Barth, W.E.; Lawton, R. G. J. Am. Chem. Soc. 1966, 88, 

380. 

2. Wu, Y.-T.; Siegel, J. S. Chem. Rev. 2006, 106, 4843. 

3. Butterfield, A. M.; Gilomen, B.; Siegel, J. S. Org. Process 

Res. Dev. 2012, 16, 664. 

Keywords: hydrocarbon; polycycles; 



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chem. Listy 106, s257–s1425 (2012) 


P - 0 8 2 8 

ASyMMetriC diethyLzinC Addition to 

n-SuLPhonyLiMine 

e. CAGLi 1 , o. doGAn 1 


Design of new chiral ligands for asymmetric synthesis is 

important. The ligand should be economical and efficient in 

enantioselective transformations. For the synthesis of some 

natural products and biologically active compounds optically 

active amines are used as important intermediates. For this reason, 

it is important to develop new catalyst system which can produce 

optically active amines in an economical and efficient way. Our 

group developed ferrocenyl aziridinyl methanol (FAM), 

phosphino ferrocenyl methanol (PFAM), and phosphineoxy 

aziridinyl phosphonate (POAP) ligands and used successfully for 

the enantioselective synthesis of organic compounds. These chiral 

ligands can also serve as organocatalysts for the synthesis of 

organic compounds. In this study, these ligands were tested as 

chiral catalysts for enantioselective synthesis of amines. For this 

purpose, diethylzinc was added to N-sulphonylimine synthesized 

from aromatic and aliphatic aldehydes in the presence of FAM 

and PFAM ligands. Although ligand screening and optimization 

studies are continuing, the results obtained so far showed that 

chiral amines can be obtained in good yields and acceptable 

enantioselectivities. During these studies, we have developed an 

excellent method for the synthesis of starting N-sulphonylimine. 

At this conference synthesis of N-sulphonylimine, chiral ligands 

and details of asymmetric diethylzinc addition to imines to form 

chiral amines will be presented. 

Keywords: Imines; Organometallic; Asymmetric synthesis; 


P - 0 8 2 9 

SyntheSiS And uSe of new PhoSPhineoxy 

AziridinyL PhoSPhonAteS (PoAP) AS 

orGAnoCAtALyStS in ASyMMetriC 

PhoSPhonyLAtion of ALdehydeS 

e. CAGLi 1 , M. iSCi 1 , o. doGAn 1 


α-Hydroxy phosphonates are biologically active 

compounds. [1] Enantioselective synthesis of these compounds is 

studied by a significant number of scientists by employing dialkyl 

phosphites known as Pudovik-type reaction. On the other hand, 

only one group studied the enantioselective synthesis of 

α-hydroxy phosphonates by employing trialkyl phosphites known 

as Abramov-type reaction in the presence of diphosphine oxy 

chiral Lewis bases. [2] In this respect, we tried newly synthesized 

phosphine oxy aziridinyl phosphonates (PoAP) as Lewis bases 

for the Arbuzov-type reaction. Reaction of trialkyl phosphite with 

aldehydes in the presence of SiCl and chiral Lewis base produced 

4 

desired α-hydroxy phosphonates in very good yields (up to 99%) 

but moderate enantioselectivities (highest 43%). Although the 

enantioselectivity is low, initial results are encouraging. Because, 

literature also reports similar enantioselectivities for the same 

reaction. We haven’t finished the optimization studies therefore 

more experiments are on the way for improving the 

enantioselectivy. The details of this study will be presented at this 

conference. 

references: 

1. Engel, R. Chem. Rev. 1977, 77, 349. 

2. Nakanishi, K.; Kotani, S.; Sugiura, M.; Nakajima, M. 

Tetrahedron 2008, 64, 6415. 

Keywords: Silicon based; Abramov-type phosphonylation; 

Organocatalyst; Hydroxy phosphonate; Asymmetric reaction; 



s1278 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 3 0 

totAL SyntheSiS of diPhoSPhoinoSitoL 

PoLyPhoSPhAteS (PP-inSP ) 5 

S. CAPoLiCChio 1 


Switzerland 

Secondary messengers permit the communication within 

and between cells and are crucial for the maintenance of life. 

Diphosphoinositol polyphosphates (PP-InsP ) belong to these 

5 

signaling molecules and are important in different cellular 

processes including signal transduction, vesicle trafficking, cell 

division and apoptosis. [1] Recently, pyrophosphorylation of proteins 

has been described, but the function of this post-translational 

modification is still unknown. [2] Therefore, an efficient synthesis 

of PP-InsP is necessary to study their unique mode of action. Due 

5 

to the structure of myo-inositol, many different phosphorylated 

derivatives are possible and those found in nature have distinct 

functions in cellular systems. Different syntheses of 

enantiomerically pure inositol polyphosphates have been reported3 and among these asymmetric phosphorylation is an outstanding 

way to introduce a phosphate group in a specific position in the 

structure of myo-inositol. We will report the synthesis and 

application of C symmetric phosphoramidites to desymmetrize 

2 

different inositol derivatives leading to diastereoisomeric 

mixtures. In some cases it was possible to separate the mixtures 

by simple column chromatography obtaining diastereomerically 

pure compounds. Also different phosphoramidite activators and 

solvents have been evaluated, demonstrating their importance in 

the selectivity of the phosphorylation. These results represent a 

new approach in the envisaged total syntheses of PP-InsP as well 

5 

as the starting point for the development of efficient reagents for 

asymmetric phosphorylation and pyrophosphorylation. 

references: 

1. a) C. J. Barker, C. Illies, G. C. Gaboardi, P.-O. Berggren, 

Cell. Mol. Life Sci. 2009, 66, 3851; 

b) A. Burton, X. Hu, A. Saiardi, J. Cell. Physiol. 2009, 

220, 8. 

2. A. Saiardi, R. Bhandari, A. C. Resnick, A. M. Snowman, 

S. H. Snyder, Science, 2004, 306, 2101. 

3. a) C. M. Longo, Y. Wei, M. F. Roberts, S. J. Miller, 


b) H. Zhang, J. Thompson, G. D. Prestwich, Org. Lett. 

2009, 11, 1551. 

Keywords: phosphorylation; synthetic methods; total synthesis; 

asymmetric synthesis; medicinal chemistry; 


P - 0 8 3 1 

SyntheSiS of PorPhyrin-Steroid ConJuGAteS 

L. CArdovA 1 , P. drASAr 1 

1 Institute of Chemical Technology, Department of Chemistry of 


The aim of this work was to synthesize and subsequently try 

on self-assembly properties of several porphyrin-steroid 

conjugates. Bile acids are a group of steroids with amphiphilic 

and detergent properties that are caused by a convex hydrophobic 

upper side, a concave hydrophilic α-side and a negatively charged 

side-chain [1] . Due to their large, rigid, curved steroidal skeletons 

and amphiphilicity, together with their availability and low cost 

are bile acids ideal building blocks for the design of novel 

molecular and supramolecular assemblies for molecular 

recognition [2] . Not only fluorescent activity is provided by 

porphyrin, these pyrrole macrocycles are recently studied for their 

use in photodynamic therapy [3] as well. 

Several porphyrin-steroid conjugates with ester, amide and 

ether bound were prepared and their properties are studied now. 

Resulting compounds show aggregation properties – extensively 

investigated nowadays because of their possible technological 

applications. Aggregation experiments were carried out according 

to known procedure [4] . Hence, using of DMSO/water solution 

solvent-promoted aggregation of amphiphilic porphyrin derivative 

was achieved. This composition induces efficient porphyrin 

self-aggregation process to form J-type aggregates, observed by 

the broadening and bathochromic shift of the Soret band. 

Acknowledgement: This work was supported by the Ministry of 

Education, Youth and Sports of the Czech Republic in a project 

No. MSM6046137305. 

references: 

1. Virtanen, E.; Kolehmainen, E. Eur J Org Chem 2004, 3385. 

2. Ropponen, J.; Tamminen, J.; Lahtinen, M.; Linnanto, J.; 

Rissanen, K.; Kolehmainen, E. Eur J Org Chem 2004, 73. 

3. Swamy, N.; James, D. A.; Mohr, S. C.; Hanson, R. N.; 

Ray, R. Bioorganic & medicinal chemistry 2002, 10, 3237. 

4. Monti, D.; Venanzi, M.; Stefanelli, M.; Sorrenti, A.; 

Mancini, G.; Di Natale, C.; Paolesse, R. J Am Chem Soc 

2007, 129, 6688. 

Keywords: Aggregation; Steroids; Porphyrinoids; 



s1279 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 3 2 

wAter-SoLuBLe PhthALoCyAnineS for 

PhotodynAMiC therAPy 

A. CidLinA 1 , P. ziMCiK 1 , v. novAKovA 2 

1 Charles University Faculty of Pharmacy, Department of 

Pharmaceutical Chemistry and Drug Control, Hradec 



Biophysics and Physical Chemistry, Hradec Kralove, Czech 

Republic 

Photodynamic therapy (PDT) is one of the alternative 

approaches for cancer treatment. PDT uses a combination of three 

essential components: photosensitizer, oxygen and light. 

Unsubstituted phthalocyanines (Pc) are completely waterinsoluble 

and they tend to aggregate in solution. These properties 

are limiting factors for use in PDT. Presence of cationic 

substituents on periphery of Pc macrocycle generally increases 

water solubility and limits the aggregation. In this study, cationic 

magnesium, zinc and metal free Pcs substituted in peripheral (β) 

or non-peripheral (α) positions on macrocycle were prepared. 

Pcs are usually synthesized by cyclotetramerization reaction 

from corresponding precursors, substituted phthalonitriles. Thus, 

4,5-bis[2-(diethylamino)ethylsulfanyl]phthalonitrile was prepared 

by nucleophilic substitution from 4,5-dichlorophthalonitrile. 

Similarly, 3,6- disubstituted phthalonitrile arose from 

3,6-dihydroxy phthalonitrile after conversion of hydroxyl groups 

to tosyl groups. Cyclotetramerization of these precursors was 

accomplished with magnesium butoxide as an initiator of the 

reaction. Magnesium Pcs prepared in this way were were 

converted to metal-free Pcs using 1% hydrochloric acid. 

Metal-free Pcs reacted with anhydrous zinc acetate in pyridine to 

form corresponding zinc complexes. Finally, peripheral tertiary 

amino groups of these complexes of Pcs containing were 

quarternized with ethyliodide. 

The Pcs substituted in α positions did not aggregate in water 

in wide range of concentrations. Moreover, cationic zinc Pc with 

substitution in α positions showed excellent absorption and 

photochemical properties (λ 756 nm and quantum yield of 

max 

singlet oxygen 0.91). Therefore this Pc could become a new 

potential photosensitizer for PDT. 

Keywords: Phthalocyanines; Singlet oxygen; Fluorescence; 

Cancer; 


P - 0 8 3 3 

inSiGhtS ABout the StruCture of 

A PoSSiBLe hiGh-enerGy interMediAte of the 

CheMiLuMineSCent PeroxyoxALAte 

reACtion 

L. f. CiSCAto 1 , e. BAStoS 2 


Humanas, Santo Andre, Brazil 

2 Universidade de Sao Paulo, Instituto de Quimica, Sao Paulo, 

Brazil 

The peroxyoxalate system is one of the most efficient 

nonenzymatic chemiluminescent reactions known, showing 

quantum efficiency of up to 50%. The bluish light, first observed 

by Chandross from the reaction between oxalyl chloride and 

hydrogen peroxide in the presence of 9,10-diphenylanthracene 

(DPA), has inspired generations of scientists to investigate the 

reaction mechanism and to search for new experimental 

conditions to improve emission efficiency. The exact mechanism 

of the chemiexcitation process has been determined, but the 

structure of the high-energy intermediate responsible for this 

chemiexcitation remains not fully determined. 

Bimolecular interaction of this HEI, accumulated in the 

reaction of oxalyl chloride with hydrogen peroxide, with an 

activator (highly fluorescent aromatic hydrocarbons with low 

oxidation potential) added in delay shows unequivocally that this 

intermediate is responsible for chemiexcitation of the activator. 

Activation parameters for the unimolecular decomposition of this 

intermediate (ΔH≠ = 11.2 kcal mol-1 ; ΔS≠ = –23.2 cal mol-1 K-1 ) 

and for its bimolecular reaction with 9,10-diphenylanthracene 

(ΔH≠ = 4.2 kcal mol-1 ; ΔS≠ = –26.9 cal mol-1 K-1 ) show that this 

intermediate is much less stable than typical 1,2-dioxetanones and 

demonstrate its highly favored interaction with the activator. 

Therefore, it can be inferred that structural characterization of the 

high-energy intermediate in the presence of an activator must be 

highly improbable. 

Kinetic studies of the imidazole catalyzed chemiluminescent 

reaction of a series of substituted peroxalic acids, postulated 

intermediates of the PO system, yielded a linear free-energy 

correlation of the catalytic rate constants with Hammett 

parameters (ρ=+2.0 ± 0.2 and β = –1.1 ± 0.1) which are 

LG 

compatible with a base-catalyzed concerted intramolecular 

substitution reaction in the chemiluminescent pathway of this 

transformation. Therefore, these data indicate the cyclic peroxydic 

carbon dioxide dimer 1,2-dioxetanedione as the most probable 

high-energy intermediate in the peroxyoxalate reaction. 

Keywords: organic peroxides; chemiluminescence; 

peroxyoxalate; 



s1280 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 3 4 

SoMe AqueouS CheMiStry of the 

thioPhoSPhoryL GrouP 

L. ConwAy 1 , M. trMCiC 1 , r. deLLey 1 , 

J. norCLiffe 1 , d. hodGSon 1 

1 Durham University, Chemistry, Durham, United Kingdom 

the Aqueous reduction of Azides using Sodium 

thiophosphate: We present a clean, aqueous method for the 

conversion of azides to amines with trisodium thiophosphate as 

the reducing agent. [1] The transformation is shown to be effective 

on a range of alkyl and aryl substrates. 

thiophosphoryl ‘Click’ Chemistry: Our group has 

developed a one-pot synthesis allowing two organic groups to be 

conjugated by a thiophosphoramidate linker. [2] The reaction has 

been tested on a range of substrates and has been found to be 

widely applicable. The method shows high levels of conversion 

and generates innocuous by-products. This chemistry has potential 

as a mimic of phosphate-containing biological systems, and as an 

example of this, we have applied the methodology to the synthesis 

of a thymidyl-(3'-5')-thymidine thiophosphoramidate analogue 

with a view to studying the hydrolytic properties of this system. 

references: 

1. J. L. Norcliffe, L. P. Conway, and D. R. W. Hodgson, 

Tetrahedron Lett., 2011, 52, 2730-2732 

2. M. Trmcic and D. R. W. Hodgson, Chem. Comm., 2011, 

47, 6156-6158 

Keywords: Aqueous; Azide; Phosphate; Thiophosphate; 


P - 0 8 3 5 

reACtivitieS of ethyL AryLACetAte AnionS 

f. CorrAL BAutiStA 1 , h. MAyr 1 


The anions of ethyl arylacetates are frequently used as 

nucleophiles in Michael additions and Claisen condensations. 

Furthermore, they can easily be alkylated or added to carbonyl 

groups, imines, or acetylenes leading to a wide variety of products 

of biological and medicinal interest. 

Kinetic investigations of the reactions of the anions of ethyl 

arylacetates with quinone methides and diethyl 

benzylidenemalonates in DMSO allowed us to quantify their 

nucleophilic reactivities according to the linear free energy 

relationship eq [1] , in which electrophiles are characterized by one 

parameter E and nucleophiles are characterized by 

the solvent-dependent parameters s (sensitivity) and 

N 

N (nucleophilicity). 1 

lg k (20 °C) =s (N + E) (1) 

2 N 

Our investigations show that the nucleophilic reactivities of 

these compounds are highly affected by the substitution pattern 

of the aromatic ring. Their nucleophilicities are comparable to 

those of the anions of phenyl acetonitriles. [2] The title compounds 

thus belong to the most reactive nucleophiles so far studied by 

our group and can be used to characterize very weak electrophiles. 

references: 

1. H. Mayr, T. Bug, M. F. Gotta, N. Hering, B. Irrgang, 

B. Janker, B. Kempf, R. Loos, A. R. Ofial, G. Remennikov, 

H. Schimmel, J. Am. Chem. Soc. 2001, 123, 9500–9512. 

2. For a comprehensive listing of nucleophilicity parameters 

N, s and electrophilicity parameters E, 

N 

see www.cup.uni-muenchen.de/oc/mayr/DBintro.html. 

Keywords: Kinetics; Carbanions; Linear free energy 

relationship; 



s1281 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 3 6 

SyntheSiS And evALuAtion of 

triAzoLe-LinKed CALix[4]Arene ionoPhoreS 

J. B. CziroK 1 , i. JuhASz 1 , P.d. Mezei 2 , A. SiMon 2 , 

G. JAGerSzKi 2 , e. r. GyurCSAnyi 2 , L. drAhoS 3 , 

K. toth 2 , i. Bitter 1 



Hungary 


Department of Inorganic and Analytical Chemistry, Budapest, 

Hungary 


Sciences, Institute of Molecular Pharmacology, Budapest, 

Hungary 

Over the past decade the Cu(I)-catalyzed dipolar azidealkyne 

cycloaddition (CuAAC) leading to 1,2,3-triazoles has 

attracted an enormous interest as one of the most useful and 

valuable example of click chemistry. In calixarene chemistry 

CuAAC has also been applied for the easy access to sophisticated 

large molecules such as triazole-linked calix[4]arene ionophores 

often supplied with chromo/fluorogenic moieties. Interstingly, the 

majority of these ligands has a common binding site comprised 

of two distal triazole- and two OH groups on the lower rim of the 

calixarene framework. 

So far only one type of the tetrasubstituted derivatives has 

been reported, therefore we aimed at increasing the choice of 

ionophores in this field by synthesizing a series of ligands either 

with the combination of triazole- and (thia)carboxamide/ester 

groups or with introducing four triazole ligating groups at the 

lower rim in order to find metal ion-selective molecules suitable 

for developing new potentiometric sensors. 

The majority of the new molecules were tested by 

competitive MS measurements in the presence of a series of 

mono- and divalent metal ions to estimate the relative 

complexation abilities. Subsequently, PVC membrane electrodes 

(ISE) were fabricated to determine the potentiometric 

ion-selectivity coefficients. 

Keywords: Click chemistry; Calixarenes; Ionophores; Mass 

spectroscopy; Molecular recognition; 


P - 0 8 3 7 

funCtionALizAtion of CorAnnuLene viA 

direCt iridiuM-CAtALyzed BoryLAtion 

S. dA roS 1 , M. n. eLiSeevA 2 , L. t. SCott 2 , J. S. SieGeL 1 

1 University of Zurich, Organic Chemistry Institute, Zurich, 

Switzerland 

2 Boston College, Chemistry Department, Boston, USA 

Over the past decade, significant effort has been invested in 

the derivatization of polyaromatic hydrocarbons, such as 

corannulene, in order to introduce functionality and thus provide 

building blocks for more complex architectures. [1] Due to its fivefold 

symmetry, corannulene is a suitable core element of 

higher-order supramolecular structures such as host-guest 

complexes [2] , dendrimers [3] , and liquid crystals [4] . The conventional 

method for functionalizing corannulene, while keeping the fivefold 

symmetry, has been to convert it to 

1,3,5,7,9-pentachlorocorannulene, which may then undergo 

further alkylation or arylation reactions. [5, 6] However, this 

approach suffers from several challenges including poor 

solubility, difficult purification, and low reactivity of aryl 

chlorides toward substitution. To overcome these problems, a new 

synthetic strategy has been established for the functionalization 

of corannulene using iridium-catalyzed borylation under basic 

conditions. [7, 8] The reaction proceeds via direct C-H activation, 

affording highly soluble 1,3,5,7,9-pentakis(Bpin)corannulene in 

65–70% yield. Optimization studies as well as the properties of 

the newly synthesized compound and its reactivity toward Suzuki 

cross-coupling reactions will be presented. 

references: 

1. Y.-T. Wu, J. S. Siegel, Chem. Rev. 2006, 106, 4843–4867. 

2. A. J. Olson, J. H. E. Hu, E. Keinan, PNAS 2007, 104, 

20731–20736. 

3. D. Pappo, T. Mejuch, O. Reany, E. Solel, M. Gurram, 

E. Keinan, Org. Lett. 2009, 11, 1063–1066. 

4. D. Miyajima, K. Tashiro, F. Araoka, H. Takezoe, J. Kim, 

K. Kato, M. Takata, T. Aida, J. Am. Chem. Soc., 2009, 131, 

44–45. 

5. M. Mattarella, J. S. Siegel, Org. Biomol. Chem. 2012, 

DOI: 10.1039/c2ob25503k. 

6. K. K. Baldridge, K. I. Hardcastle, T. J. Seiders, 

J. S. Siegel, Org. Biomol. Chem. 2010, 8, 53–55. 

7. D. N. Coventry, A. S. Batsanov, A. E. Goeta, 

J. A. K. Howard, T. B. Marder, R. N. Perutz, 2005, 

2172–2174. 

8. M. Eliseeva, L. T. Scott, submitted. 

Keywords: corannulene; functionalization; borylation; 

C-H activation; polyaromatic hydrocarbon; 



s1282 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 3 8 

funCtionAL LC eLAStoMerS: towArdS 

ArtifiCiAL ACtuAtorS 

J. C. diAz-CuAdroS 1 , B. heinriCh 1 , d. GuiLLon 1 , 

B. donnio 1 

1 Institut de Physique et Chimie des Matériaux de Strasbourg, 

DMO, Strasbourg, France 

Liquid crystal elastomers (LCEs) are materials with 

uncommon elastic properties that combine the orientational 

ordering properties of liquid crystalline systems with the rubbery 

elasticity of polymer networks. [1] The ability of these materials to 

change their shape and size reversibly by inducing disorder in the 

liquid crystalline structure at the nematic – isotropic phase 

transformation (triggered by temperature) makes them attractive 

for use as actuating materials like sensors, valves and electronics. 

However, the study of such reversible systems is limited by their 

difficult syntheses and new methodologies are required. In this 

work we have developed a new strategy based on the Cu catalyzed 

1,3 dipolar cycloaddition between azides and alkynes [2] in a one 

pot process for the preparation of a variety of liquid crystal 

polymers (LCPs) and LCEs. In the context of this approach, a 

collection of calamitic and bent core monomers bearing alkyne 

groups have been synthesised and reacted with diazide spacers 

and multivalent alkyne substituted cross linkers to form LCPs and 

LCEs. A series of copolymers has also been prepared by using 

monomeric blends composed of mesogens of different shapes in 

order to prepare systems exhibiting nematic phases over wide but 

accessible temperature ranges. [3] The results indicate that our 

strategy can be generally applied to the preparation of polymeric 

and elastomeric materials since it leads to high polymer 

conversions, short reaction times, and simple purification 

techniques. 

references: 

1. Finkelmann H., Angew. Chem., Int. Ed. Engl. 1987, 26, 

816–824. 

2. Hein J. E., Fokin V. V., Chem. Soc. Rev., 2010, 39, 

1302–1315 

3. Kirsch P., Bremer A., Angew. Chem., Int. Ed. 2000; 39, 

4216. 

Keywords: Click chemistry; Liquid crystals; Polymers; 

Elastomers; 


P - 0 8 3 9 

ASyMMetriC induCtion in the free rAdiCAL 

CoPoLyMerizAtion of ACryLiC SuBStituted 

AMide 

A. diBLA 1 , A. niCoLeSCu 2 , A. M. ALBu 3 

1 Politehnica University of Bucharest, Department of 


2 “P. Poni” Institute of Macromolecular Chemistry Iasi, 

Analysis, Iasi, Romania 

3 Politehnica University of Bucharest, Department of 


The chemical composition and micro organization, 

particularly called tacticity, are mainly determiner for final 

properties of materials. Very interesting aspects regard obtaining 

the stereoregulate structures by free radical polymerization. In this 

context, stereoregulation methods has been devised for the radical 

polymerization of several monomers including methacrylates and 

vinyl esters, and efficient stereoregulation has been attained for 

methacrylates and vinyl esters by utilizing solvent effects. Effect 

of monomer concentration was applied to alter the 

stereochemistry of methacrylate and acrylate polymerization. All 

these studies treat only the polymerization aspects without 

approach to the copolymerization process in free radical 

mechanism. 

In this idea, the aim of this study is underline the 

stereochemical implication of solvent in the polymerization 

process of two-substituted acrylic amide (N- acryloylmorpholyne 

and N-methyl-N-vinyl acetamide) recognized for 

theirs application in biological field. 

For now, the main purpose was to investigate the effect of 

the solvent and temperature amongst the structure and 

composition of the products. Furthermore, the isotactic properties 

had our interest too, so we studied the same influence on the 

polymer tacticity. 

The elemental analysis, 1H NMR, 13C NMR analysis allows 

quantitative assessment of the constituent sequences of the 

material. 

Keywords: Asymmetric synthesis; 



s1283 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 4 0 

KinetiC inveStiGAtion of 

PhenyLSeLenoetherifiCAtion of SoMe 

?4-ALKenoLS in PreSenCe of CAtALytiC 

AMount of CoCL 2 

v. divAC 1 , M. KoStiC 1 , z. BuGArCiC 1 


Serbia 

The phenylselenoetherification of unsaturated alcohols is the 

one of the most rapid and convenient methods for formation of 

THF and THP type of rings. The convenient position of a double 

bond and a hydroxyl group in an alkenol can easily lead to 

formation of corresponding cyclization product. The reaction of 

selenium electrophiles with alkenols is a stereospecific anti 

addition where the nucleophile (pendant hydroxyl group) attacks 

usually at higher substituted carbon atom (Markownikoff 

stereoselectivity). [1] Despite the established synthetic utility of 

these selenofunctionalization reactions, there is no many report 

on a detailed kinetic investigation of these transformations. [2] In 

previous work it was found that in the presence and absence of 

various additives these reactions follow the mechanism of 

bimolecular nucleophile substitution S 2 pathway. N [2c] 

In this work we reported the kinetic study of the cyclization 

of some Δ4-alkenols with PhSeX (X=Cl, Br) in presence of 

catalytic amount of CoCl . We investigated the influence of 

2 

olefinic and carbinol substitution pattern in some Δ4-alkenols on 

the rate constants of the cyclization under the pseudo-first order 

conditions, in the presence and absence of CoCl , by UV-VIS 

2 

spectrophotometry. Reactions were carried out in the THF as a 

solvent. The obtained values for rate constants have shown that 

the reactions with phenylselenenyl bromide are slower then with 

chloride. Reactions with CoCl present are faster then without one. 

2 

Values for rate constants strongly depend on a substitution pattern 

of used alkenol. 

references: 

1. N. Petragnani, H. A. Stefani, C. J. Valduga, Tetrahedron, 

2001, 57, 1411-1448. 

2. a) G. H. Schmid, D. G. Garratt, J. Org. Chem. 1983, 48, 

4169-4172. 

b) Z. M. Bugarcic, M. D. Rvovic, V. M. Divac, ARKIVOC, 

2009, 14, 135-145. 

c) M. D. Rvovic, V. M. Divac, R. Puchta, Z. M. Bugarcic, 

J. Mol. Model. 2011, 17, 1251-1257. 

Keywords: Alcohols; Heterocycles; Cyclization; Kinetics; 


P - 0 8 4 1 

2-(MethyLAMino)Pyridine AS 

A LiGAnd PreCurSor for the ti-CAtALyzed 

hydroAMinoALKyLAtion of ALKeneS And 

StyreneS 

J. doerfLer 1 , S. doye 1 

1 Institute of Pure and Applied Chemistry, Organic Chemistry, 

Oldenburg, Germany 

Due to its direct and highly atom-efficient conversion of 

simple starting materials into more complex molecules by C–C 

bond formation the hydroaminoalkylation of alkenes [1, 2] and 

styrenes [1c, 2b] must be regarded as a very promising alternative to 

the industrial synthesis of amines. While reactions of 1-alkenes 

performed with group 5 metal catalysts (Ta, Nb) exclusively 

deliver the branched hydroaminoalkylation product [1] mixtures of 

the branched and the linear product are obtained with 

Ti-catalysts. [2] However, in this context, it must be noted that even 

with Ti-catalysts, the branched product is always formed as the 

major product and successful hydroaminoalkylations of styrenes 

can only be achieved with N-methyl anilines. Herein, we report 

the first intermolecular hydroaminoalkylation reactions of 

styrenes with N-alkyl anilines and dialkyl amines. The reactions 

are catalyzed by a 2-aminopyridinato Ti-complex [3] that is 

generated in situ from Ti(NMe ) and the ligand precursor 

2 4 

2-(methylamino)pyridine. Most importantly, it is possible for the 

first time to obtain the industrially more interesting linear product 

as the major product of the reaction. 

references: 

1. a) S. B. Herzon, J. F. Hartwig, J. Am. Chem. Soc. 2007, 

129, 6690; 

b) P. Eisenberger, R. O. Ayinla, J. M. P. Lauzon, 

L. L. Schafer, Angew. Chem. Int. Ed. 2009, 48, 8361; 

c) A. L. Reznichenko, K. C. Hultzsch, J. Am. Chem. Soc. 

2012, 134, 3300. 

2. a) R. Kubiak, I. Prochnow, S. Doye, Angew. Chem. Int. Ed. 

2009, 48, 1153; 

b) R. Kubiak, I. Prochnow, S. Doye, Angew. Chem. Int. 

Ed. 2010, 49, 2626. 

3. a) R. Kempe, Eur. J. Inorg. Chem. 2003, 791; 

b) R. Kempe, Z. Anorg. Allg. Chem. 2010, 636, 2135; 

c) R. Kempe, P. Arndt, Inorg. Chem. 1996, 35, 2644; 

d) R. Kempe, Z. Kristallogr. NCS 1997, 212, 477. 



s1284 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 4 2 

MetAL CAtALyzed enAntioSeLeCtive 

SyntheSiS of orGAniC CoMPoundS uSinG fAM 

And PfAM ChirAL LiGAndS 

o. doGAn 1 

1 Middle East Technical University, Chemistry Department, 


Asymmetric synthesis of organic compounds is an important 

field of ornganic chemistry. As the method, metal catalyzed 

asymmetric synthesis has been developed and applied by 

significant number of researchers worldwide for the last two 

decades. In this respect we have synthesized new amino alcohol 

based ferrocenyl aziridinyl methanol (FAM) and phosphorous 

based phosphino ferrocenyl aziridinyl methanol (PFAM) chiral 

ligands and used for metal catalyzed asymmetric synthesis of 

organic compounds. These ligands can be synthesized easily on a 

gram scale starting from acryloyl ferrocene by applying 

Gabriel-Cromwell reaction. Among the metal-ligand catalyzed 

enantioselective reactions diethylzinc addition to aldehydes was 

carried out to form secondary alcohols in excellent 

enantioselectivity. Another reaction was alkynylzinc addition to 

aliphatic and aromatic aldehydes which formed propargylic 

alcohols also in excellent enantioselectivity. In another reaction 

1,3-dipolar cyloaddition of azomethine ylides was carried out to 

produce pyrrolidines in good yields and enantioselectivities. In 

the case of nitromethane addition (nitroaldol reaction) to aromatic, 

aliphatic, a,b-unsaturated, and heteroaromatic aldehydes and 

b-ketoesters corresponding b-nitroalcohols were obtained in very 

good yields and enantioselectivities. Diethylzinc addition to 

enones was also stied which formed b-ethylketones in good yields 

and enantioselectivities. 

Synthesis of chiral ligands and their application to metal 

catalyzed enantioselective synthesis of organic compounds will 

be presented at this conference. 

Keywords: metal catalyzed asymmetric synthesis; chiral 

ligands; 


P - 0 8 4 3 

new ChirAL PhoSPhine oxy AziridinyL 

PhoSPhonAteS (PoAP) AS orGAnoCAtALAyStS 

for enAntioSeLeCtive ALLyLAtion of 

ALdehydeS with ALLyLtriChLoroSiLAne 

o. doGAn 1 , M. A. teCiMer 2 , A. BuLut 2 

1 Middle East Technical University, Chmistry Department, 


2 Kirikkale University, Chmistry Department, Kirikkale, Turkey 

New class of chiral phosphine oxy aziridinyl phosphonates 

(POAP-A, POAP-B, PAPA, and PAPB) were synthisized and 

tested as organocatalysts for the enantioselective addition of 

allyltrichlorosilane to aldehydes. Of the four, the chiral catalayst 

POAP-B showed the highest catalytic activity at ambient 

temparature. The enantiomeric excesses are moderate to good (up 

to 81 ee). In addition, temparature, solvent, equivalency and bases 

were screened during the optimization reactions. Dichlorometane 

was found to be the best solvent while diisopropyl ethylamine 

(DIPEA) showed highest catalytic activity as a base. 

The chiral phosphine oxy aziridinyl phosphonates were 

prepared in 5 steps starting from diethyl vinylphosphonate with 

quantative yields and characterized by means of spectral 

analysises. Notably, the chiral aziridinyl type catalaysts were used 

for the first time in the enantioselective addition of 

allyltrichlorosilane to aldehydes. Details of this study will be 

presented at this conference. 

Keywords: organocatalyst; aziridinyl phosphonates; allylsilane 

addition; 



s1285 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 4 4 

SyntheSiS of SuBStituted BiPyridineS And 

terPyridineS By PALLAdiuM-CAtALyzed 

direCt C-h AryLAtion of Pyridine n-oxideS 

And BiPyridine n-oxideS 

S. duriC 1 , f. d. SyPASeuth 1 , S. hoof 1 , 

C. C. tzSChuCKe 1 

1 Freie Universität Berlin, Institut für Chemie und Biochemie 

– Organische Chemie, Berlin, Germany 

Bipyridines and terpyridines constitute an important class 

of heterocycles and numerous synthetic approaches have been 

described. [1] Cross coupling and ring assembly reactions are the 

most widely used. However, these synthetic routes make use of 

pyridyl organometallics and assembly precursor, which are 

frequently unstable and require multistep preparation procedures. 

Catalytic C-H-activation allows direct C-C-coupling and reduces 

the number of synthetic steps significantly. [2] In this context, we 

present a new versatile synthesis of functionalized bipyridines and 

terpyridines based on palladium-catalyzed C-H-functionalization 

of pyridine N-oxides. [3] Several examples of asymmetrically 

substituted 2,2'-, 2,3'- and 2,4'-bipyridine N-oxides, containing 

alkyl, methoxy, ester, nitrile, nitro, fluorine, and trifluoromethyl 

substituents, have been successfully synthesized. The 

2,2'-bipyridine N-oxides have been further used for the 

preparation of 2,2';6',2''-terpyridine N-oxides, with asymmetric 

substitution patterns that are not easily accessible by other 

methodologies. The final deoxygenation of the N-oxides to the 

coressponding bipyridine or terpyridine is accomplished in high 

yield by either catalytic hydrogenation or reduction with PCl . 3 

references: 

1. Hapke, M.; Brandt, L.; Lützen, A., Chem. Soc. Rev. 2008, 

37, 2782. 

Newkome, G. R.; Patri, A. K.; Holder, E.; Schubert, U. S., 

Eur. J. Org. Chem. 2004, 235. 

Heller, M.; Schubert, U. S., Eur. J. Org. Chem. 2003, 947. 

2. Alberico, D.; Scott, M. E.; Lautens, M., Chem. Rev. 2007, 

107, 174. 

3. Duric, S.; Tzschucke, C. C., Org. Lett. 2011, 13, 2310. 

Campeau, L. C.; Rousseaux, S.; Fagnou, K., J. Am. Chem. 

Soc. 2005, 127, 18020. 

Keywords: C-H activation; Palladium; Heterocycles; C-C 

coupling; 


P - 0 8 4 5 

PotASSiuM 

(trifLuoroMethyL)triMethoxyBorAte – A 

SheLf-StABLe trifLuoroMethyLAtinG 

reAGent 

w. dziK 1 , t. KnAuBer 1 , A. BuBA 1 , B. KhAn 1 , 

L. GooSSen 1 

1 Technische Universität, Fachbereich Chemie – Organische 

Chemie, Kaiserslautern, Germany 

The introduction of a CF group has a profound effect on the 

3 

chemical and physical properties of a molecule. This is highly 

beneficial in many functional molecules spanning from 

pharmaceuticals or agrochemicals to high performance polymeric 

materials.Traditional methods for trifluoromethylations operate 

at harsh reaction conditions and use corrosive reagents like HF, 

SbF or SF . Therefore, substantial research has been devoted to 

5 4 

the development of milder reagents suitable for a selective 

late-stage trifluoromethylation of functionalized molecules. Stateof-the-art 

trifluoromethylation reactions use trifluoromethyl 

silanes, which are rather difficult to handle due to their volatility 

and moisture-sensitivity, as the sources of a CF nucleophiles. 

3 

Here, we introduce potassium (trifluoromethyl)trimethoxyborate 

as a new source of CF nucleophiles for trifluoromethylation 

3 

reactions. The crystalline salt is stable on storage, easy to handle, 

and can be obtained in near-quantitative yields simply by mixing 

B(OMe) , CF SiMe , and KF. This reagent is suitable for 

3 3 3 

trifluoromethylating both aryl electrophiles and nucleophiles 

under oxidative conditions. The scope of possible transformations 

includes the copper-catalyzed synthesis of trifluoromethyl 

(hetero)arenes from aryl iodides or boronates, and metal-free 

synthesis of trifluoromethyl alcohols from carbonyl compounds. 

Alkoxy, ester, amide, alkylamine, nitro, cyano and bromo 

substituents are tolerated and the reaction proceeds under very 

mild conditions. 

This new reagent is an attractive alternative, to 

trifluoromethyl silanes and allows a smooth conversion of a 

variety of compounds into their trifluoromethyl derivatives. 

Keywords: Borates; C-C coupling; Arenes; Homogeneous 

catalysis; Fluorine; 



s1286 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 4 6 

PrePArAtion of ALPhA-SuBStituted 

ALLyLBoronAteS And APPLiCAtion in nAturAL 

ProduCt SyntheSiS 

n. C. eiChenAuer 1 , M. BiSChoP 1 , J. PietruSzKA 1 

1 Heinrich-Heine-Universität Düsseldorf, Institut für 

Bioorganische Chemie im Forschungszentrum Juelich, Juelich, 

Germany 

Chiral α-substituted allylboronates are valuable tools for the 

stereoselective construction of homoallylic alcohols. [1,2] 

Diastereomerically pure allylboronates bearing (2R,3R)-1,4- 

-dimethoxy-1,1,4,4-tetraphenyl-butane-2,3-diol as protective 

group for the boronic acid moiety were shown to give 

predominantly (Z)-configured allylation products in high yield 

and excellent enantioselectivity. For this reason these reagents are 

of considerable interest regarding the synthesis of natural products 

containing a (Z)-configured homoallylic alcohol moiety as a 

structural motif. [3] 

Bench-stable α-substituted allylboronates were synthesised 

by [3,3]-sigmatropic rearrangements of the corresponding 

boron-containing allylic alcohols. [4] The extraordinary stability of 

the boronate moiety enabled further transformations yielding 

allylboronates suitably functionalised for application in envisaged 

syntheses of marine oxylipins. Allylic addition reactions to 

aldehydes furnished the desired (Z)-configured homoallylic 

alcohols in nearly enantiomerically pure form and very good 

yield. Furthermore, various functionalised α-substituted 

allylboronates were obtained by copper-mediated allylic 

substitution reaction of mesylated boron-containing allylic 

alcohols. Herein, the utilisation of organozinc halides and 

diorganozinc compounds allowed the introduction of side chains 

containing sensitive functional groups in α-position. 

We will present recent progress in stereoselective synthesis 

of marine natural products, therein making use of 

diastereomerically pure functionalised α-substituted 

allylboronates as advanced intermediates. 

references: 

1. S. R. Chemler, W. R. Roush, Modern Carbonyl Chemistry 

(Ed.: J. Otera); Wiley-VCH Weinheim, 2000, 403-490. 

2. S. E. Denmark, N. G. Almstead, Modern Carbonyl 

Chemistry (Ed.: J. Otera); Wiley-VCH Weinheim, 2000, 

299-401. 

3. C. A. Berg, N. C. Eichenauer, J. Pietruszka, Pure Appl. 

Chem. 2012, accepted manuscript. 

4. J. Pietruszka, N. Schöne, W. Frey, L. Grundl, Chem. Eur. 

J. 2008, 14, 517. 

Keywords: Asymmetric Synthesis; Natural Products; Boron; 

Protective Groups; 


P - 0 8 4 7 

viSiBLe LiGht-MediAted C-h 

funCtionALizAtion uSinG Pi-ConJuGAted 

orGAniC PhotoCAtALyStS 

A. eiSenhofer 1 , P. SChroLL 1 , C. MArtineLLi 2 , 

d. M. A. SAnChez 3 , A. f. SierrA rAMoS 3 , C. A. SierrA 3 , 

G. M. fArinoLA 2 , B. KÖniG 1 

1 University of Regensburg, Organic Chemistry, Regensburg, 

Germany 

2 University of Bari, Chemistry, Bari, Italy 

3 National University of Colombia, Organic Chemistry, Bogotá 

D.C, Columbia 

Activating chemical reactions by light is a challenging task 

for synthetic chemists. The idea of harnessing the energy of solar 

radiation to enable endothermic or kinetically hindered organic 

reactions already arises one century ago. Besides classical 

photochemical transformations, the field of photoredox catalysis 

emerged in the last decade as a powerful tool in organic synthesis 

initiating organic transformations with high selectivity under mild 

reaction conditions. Catalyst design with respect to 

electrochemical and photophysical properties is crucial for the 

photocatalytic performance. Applied from material science 

different large π-conjugated organic systems frequently used as 

electron transport materials were synthesized and investigated as 

photocatalysts. The structures were selected due to favorable 

redox potentials, visible light absorption and chemical stability. 

The possibility of processing these materials as films or layers 

provides additional access to heterogeneous applications. 

Dependent on the structure the photocatalytic activity was 

investigated in oxidative or reductive quenching cycle. Test 

reaction for investigations on the oxidative quenching cycle was 

the photoinduced C-H arylation of unsaturated compounds with 

diazonium salts. [1,2] The oxidative power of the photoexcited 

compounds was determined by the efficiency of α-C-H 

functionalization of tertiary amines. [3] 

references: 

1. D. P. Hari, P. Schroll, B. König, J. Am. Chem. Soc. 2012, 

134, 2958-2961. 

2. P. Schroll, D. P. Hari, B. König, ChemistryOpen 2012, 

DOI: 10.1002/open.201200011. 

3. A. Eisenhofer, M.Sc. thesis, University of Regensburg 

2011. 

Keywords: Photocatalysis; C-H functionalization; Crosscoupling; 



s1287 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 4 8 

AzoLe funCtionALized diACetyLeneS 

GrouPS:SyntheSiS, Studie of their 

PoLyMerizAtion, interACtion with 

MoLeCuLeS ABLe to forM hydroGen BondinG 

And CoMPLexAtion. 

K. fAhSi 1 , A. duArte 1 , L. viAu 1 , S. dutreMez 1 , 

A. vioux 1 

1 1Institut Charles Gerhardt UMR 5253 CNRS-UM2-ENSCM- 

UM1 Université de Montpellier 2 cc 1701 34095, Chimie, 


Diacetylenes are atypical molecules due to their ability to 

polymerize in the solid state. This topochemical polymerization 

is obtained under thermal or photochemical stimulus thus leading 

to the formation of conjugated diacetylenic polymers. Since their 

discovery in 1969 by Wegner [1] , polydiacetylenes have been the 

object of several researches. The main interests were to 

understand the polymerization mechanism and to study their 

diverse photophysical [2] , optical and electronic properties [3] . Here, 

we will describe in the first part the synthesis of new neutral 

diacetylenic molecules which are functionalized by azoles groups 

and we will study their polymerization in the solid state4 . Then, 

we will present the modification of the organization of these 

diacetylenes by interaction with molecules able to form hydrogen 

bonding and finally we will describe their use as ligands for the 

synthesis of Metal Organic Frameworks (MOFs). 

references: 

1. Wegner et al. G. Z. Naturforsch., Teil B. 1969, 24, 824. 

2. M. Schott et al. J. Phys. Chem. B. 2006, 110, 15864. 

3. M. Schott et al. “Photophysics of Molecular Materials. 

From Single Molecules to Single Crystals”, G.Lanzani 

et al. Ed., Wiley-VCH, Weinheim. 2006, pp. 49. 

4. S. Dutremez et al. Chem. Mater. 2010, 22, 3961. 

Keywords: diacetylene; polydiacetylene; topochemical 

polymerisation; Metal Organic framewords; hydrogen bonding; 


P - 0 8 4 9 

enAntioSeLeCtive SyntheSiS of 

ALPhA-CyCLoProPyLPhoSPhonAteS 

A. M. fAíSCA PhiLLiPS 1 , M. t. BArroS 1 


Lisboa, Chemistry, Caparica Lisbon, Portugal 

The cyclopropane ring is present in about 100 

pharmaceuticals and in more 4000 naturally occurring 

compounds, like chrysanthemic acid in the flowers of C. 

cinerariaefolium where it has a defensive role. Some synthetic 

derivatives are potent pesticides. This ring is often used in 

medicinal chemistry to increase conformational rigidity, to 

increase activity of a drug or reduce its side effects, and for lead 

optimization. There are a few cyclopropylphosphonates with 

proven biological activity: insecticidal, anti-malarial, anti-viral, 

enzyme inhibitors and glutamate metabotropic receptor agonists. 

Presently chiral α-cyclopropylphosphonates are otained mainly 

by resolution, with chiral auxiliaries, or from chiral reagents. [1] 

Catalytic enantioselective methods are more efficient, since only 

a small amount of chiral catalyst is needed and synthetic routes 

are short, but examples are scarce, and usually involve transition 

metal-induced carbene transfer reactions with Ru, Rh or Cu 

complexed to chiral ligands. [2] Although very high diastereo- and 

enantioselectivities may be obtained, the scope is limited, since 

only alkyl or aryl substituents are compatible with the conditions 

used. As a continuation of our interests in organocatalyzed 

reactions applied to phosphonate chemistry, [3] we have developed 

an organocatalyzed method to obtain these substances with good 

diastereoselectivities and high enantioselectivities. The reactions 

proceed under mild conditions and allow for the presence of a 

variety of functional groups, suitable for further synthetic 

elaboration. Relevant results showing the scope of the new 

methodology and its potential for target-oriented synthesis will 

be presented in this comunication. 

references: 

1. A. A. Al Quntar, V. M. Dembitsky, M. Srebnik, 

Org. Prep. Proceed. Int. 2008, 40, 505-542. 

2. H. Pellissier, Tetrahedron 2008, 64, 7041-7095. 

3. a) M. T. Barros and A. M. Faísca Phillips, Eur. J. Org. 

Chem., IYC Special Issue: Women in Chemistry 2011, 

4028-4036; 

b) A. M. Faísca Phillips and M. T. Barros, Org. Biomol. 

Chem. 2012, 10, 404-412. 

Keywords: asymmetric synthesis; organocatalysis; 

cyclopropylphosphonates; biological activity; 



s1288 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 5 0 

StudieS in the iodinAtion of 

3(5)-(2-hydroxyPhenyL)-5(3)-StyryL-1h- 

-PyrAzoLeS 

J. ferreirA 1 , v. SiLvA 1 , A. SiLvA 1 , J. CAvALeiro 1 


4-Iodopyrazoles are valuable starting materials in the 

synthesis of important biologically active substances. They have 

been used in transition-metal catalyzed cross-coupling reactions, 

such as Heck, Stille, Suzuki, Sonogashira and Negishi couplings 

and other important reactions. There are several methods reported 

for the iodination of pyrazoles, but they present rather complicated 

problems such as the use of large amounts of reactants and the 

lack of regioselectivity giving mixtures of iodinated compounds. 

So regioselective iodination of 4-pyrazolic position in order to 

obtain 4-functionalized derivatives is an important issue. 

Continuing our work on the search for biologically active 

pyrazoles, now we report our findings concerning the reactivity 

of 3(5)-(2-hydroxyphenyl)-5(3)-styryl-1H-pyrazole derivatives, 

containing electron donor and electron withdrawing substituents 

in the aromatic ring of the styryl group, in the oxidative iodination 

using molecular iodine and ceric(IV) ammoniun nitrate (CAN) as 

the in situ oxidant. We found that the reactivity of the C-4 position 

in the iodination reaction is sensitive to the electronic properties 

of its neighboring substituents. Electron donating groups promote 

the monoiodination in the activated orto and para positions of the 

2'-hydroxyphenyl group while electron withdrawing groups direct 

the iodination to the 4-position of the pyrazole ring. The structural 

elucidation of the obtained iodinated derivatives was 

accomplished by 1D and 2D NMR spectroscopic studies. 

Theoretical studies are underway to rationalize the 

obtained iodination results of 3(5)-(2-hydroxyphenyl)-5(3)-styryl- 

-1H-pyrazoles. 

Keywords: Nitrogen Heterocycles; Halogenation; Iodine; 

Substituents effects; NMR spectroscopy; 


P - 0 8 5 1 

direCt PrePArAtion of 

MononitroCALix[5]Arene uSinG [4+1] 

CondenSAtion 

K. fLidrovA 1 , P. LhotAK 1 


Organic Chemistry, Prague, Czech Republic 

Calix[5]arene is known as an effective receptor for 

fullerenes C and C . Despite its excelent complexation 

60 70 

behaviour,the utilization of calix[5]arene is limited by 

complicated synthesis and derivatization. The direct synthesis of 

calix[5]arene substituted in p-position significantly simplifies the 

process of the preparation of fullerene receptors. The commonly 

used methodology is a cyclization of linear dimer and trimer 

[2+3]. We chose another approach and optimized the cyclization 

of p-nitrosubstituted monomer and tetramer [1+4]. Surprisingly, 

the mass spectroscopy revealed presence of not only 

mononitrocalix[5]arene but also mononitrocalix[6]arene and 

mononitrocalix[7]arene in appreciable yield. 

We studied possibilities of the separation of these higher 

calixarenes and the influence of reaction condition and template 

effect on the relative abundance of these products. 

Acknowledgement: This work is supported by the Czech 

Science Foundation (203/09/0691). Financial support from 

specific university research (MSMT No 21/2012). 

Keywords: calixarene; 



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chem. Listy 106, s257–s1425 (2012) 


P - 0 8 5 2 

SuLfonAMide CArBAzoLeS AS verSAtiLe 

reAGentS in MoLeCuLAr reCoGnition And 

orGAnoCAtALySiS 

A. fuenteS de ArriBA 1 , o. hernAndez ruBio 1 , 

M. GArCiA turieL 1 , v. ALCAzAr Montero 2 , 

L. SiMon ruBio 3 , J. rodriGuez MorAn 1 

1 University of Salamanca, Organic Chemistry Department, 

Salamanca, Spain 

2 Polytechnic University of Madrid, Industrial Chemical 

Engineering and Environment Department, Madrid, Spain 

3 University of Salamanca, Engineering Chemistry Department, 

Salamanca, Spain 

Carbazole is a heterocyclic compound which has been 

widely used as building block in the synthesis of a large number 

of molecules due to its synthetic versatility and optical properties. 

The two benzene rings of carbazole can be easily functionalized 

in different ways, which allows its application in different fields 

like molecular recognition, organocatalysis and conducting 

polymers. 

In this work the synthesis of several 1,8-sulfonamide 

carbazoles is described. These compounds functionalized with 

hydrogen bond donors have shown excellent properties for 

molecular recognition and as organocatalysts. 

The synthesis of the compounds is straightforward from 

9H-carbazole, although positions 3 and 6 need to be blocked prior 

to sulfonation. Once 3 and 6 positions have been properly 

modified, sulfonation can take place simultaneously or 

sequentially in both positions 1 and 8. In the first case carbazole 

with two sulfonamide groups are easily obtained, which can be 

further functionalized to afford novel receptors. In the case of 

sequential sulfonation, the synthetic strategy provides direct 

access to bifunctional organocatalysts due to the introduction of 

different functional groups which can mimic the action 

mechanism of enzymes. Groups able to form H-bonds or charge 

transfer complexes with the substrate have been easily introduced. 

These compounds have shown excellent results in several 

reactions with industrial interest as well as in the molecular 

recognition field. 

Keywords: Organocatalysis; Molecular recognition; Charge 

transfer; Asymmetric catalysis; Hydrogen bonds; 


P - 0 8 5 3 

CAtALySt-free, one-Pot, three-CoMPonent 

StreCKer reACtion in wAter: A SiMPLe And 

effiCient ProtoCoL uSinG ACetone 

CyAnohydrin AS CyAnide SourCe 

d. GiACoMini 1 , P. GALLetti 1 , M. Pori 1 , r. SoLdAti 1 

1 University of Bologna, Dep. of Chemistry “G. Ciamician”, 


The Strecker reaction is a milestone in organic synthesis as 

the classical method to obtain α-amino nitriles, important 

precursors for aminoacids, aminols and diamines. The classical 

Strecker reaction is a three-component reaction between a 

carbonyl compound, ammonia and an alkaline cyanide in aqueous 

solution, and in terms of atom-economy it represents a model. 

Hydrogen cyanide is the most straightforward cyanating 

agent but its toxicity and volatility heavily limits widespread and 

practical applications in organic synthesis. To avoid the use of 

toxic HCN, a variety of cyanating agents were used. As an 

example TMSCN is widely used in the Strecker reaction, but 

Brönsted or Lewis acids or bases are often required as 

catalysts. Acetone cyanohydrin in water is frequently used 

in chemoenzymatic synthesis of cyanohydrines via 

transhydrocyanation, but surprisingly it found few applications in 

the Strecker reaction. 

Here we illustrate a simple, convenient, and practical 

method for the synthesis of α-aminonitriles through a one-pot 

three-component Strecker reaction of a carbonyl compound, 

amine, and acetone cyanohydrin in water. 1 Reactions proceed very 

efficiently without any catalyst at room temperature with high 

chemoselectivity and giving in some cases the expected 

α-aminonitrile pure just after direct separation from water. The 

protocol is particularly efficient on both aliphatic or aromatic 

aldehydes and cyclic ketones, in combination with primary and, 

interestingly, with secondary amines. The asymmetric version of 

the protocol by using amino esters and amino alcohols coming 

from natural chiral pool was also developed, in particular 

derivatives of phenylglycine, phenylalanine, tripthophane and 

proline were used as chiral auxiliary leading to some 

unprecedented chiral α-aminonitriles and related derivatives. 

references: 

1. Paola Galletti, Matteo Pori, Daria Giacomini Eu. J. Org. 

Chem. 2011, 3896-3903. 

Keywords: Multicomponent reactions; cyanides; aldehydes; 

ketones; amines; 



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chem. Listy 106, s257–s1425 (2012) 


P - 0 8 5 4 

SyntheSiS of noveL Anion reCoGnition unitS 

And eStiMAtion of their BindinG ABiLity 

M. GÖCKeL 1 , S. thuMAnn 1 , J. SChAtz 1 


chemistry and pharmacy, Erlangen, Germany 

Anion receptor chemistry is a fast growing field in modern 

chemistry. Urea, thiourea and amide based receptors have been 

well studied in their ability of binding anions [1, 2, 3, 4] but there are 

only view studies on sulfonamide groups as anion binding sites. 

As the sulfon group is very electron drawing, the amide proton is 

[5, 6] 

more acid and expected to be a better proton donator. 

Here, we want to present the synthesis of novel tripodal 

sulfonamide and thiourea anion receptors based on different 

benzole platforms, in order to investigate different steric influence 

and preorganisation of the anion affinity. 

Furthermore, we present the synthesis of a mono functional 

sulphonamide receptor which is attached to the same platform in 

order to examine the influence of the numbers of binding sites on 

anion recognition ability. Our focus lies in the complexation of 

different small spherical anions fluoride, bromide, chloride and 

iodide, as well as the trigonal planar nitrate. 

references: 

1. D.E.Gomez, L. Fabbrizzi, M. Licchelli, E. Monzani, 

Org. Biomol. Chem. 2005, 3, 31495-1500. 

2. S. Sasaki, D. Citterio, S. Ozawa, K. Suzuki, 

J. Chem. Soc. Perkin Trans 2, 2001, 2309-2313. 

3. P. A. Gale, S. E. Garcia-Garrido. J. Garric., 

Chem. Soc. Rev. 2008, 37, 151-190. 

4. P. A. Gale, Chem. Soc. Rev. 2010, 39, 3746-3771. 

5. K. Kavallieratos, C. M. Bertao, R. H.Crabtree, 

J. Org. Chem. 1999, 64, 1675-1683. 

6. V. Amendola, L. Fabrzzi, L. Mosca, F. P. Schmidtchen, 

Chem. Eur. J. 2011, 17, 5972-5981. 

Keywords: Anions; Sulfonamides; Receptors; 


P - 0 8 5 5 

iron CAtALyzed BenzyLiC oxidAtionS 

z. GondA 1 , f. SzABó 1 , B. Petho 1 , z. nováK 1 


Hungary 

Oxidation of benzylic carbon atoms is one of the most 

important synthetic transformations in organic chemistry. Besides 

the stoichiometric inorganic oxidants, several metal catalyzed 

transformations were developed and used in organic synthesis. 

Recently, iron proved to be an efficient, non-toxic catalyst for the 

oxidation in the presence of environmentally benign oxidants. [1] 

Herein, we present our results on the examination of iron 

catalyzed methylene oxidation. We developed new and efficient 

conditions for the iron catalyzed benzylic oxidation of organic 

compounds under mild and economic aqueous conditions. 

The transformation utilizes easily accessible iron sources, such 

as FeCl or Fe (SO ) and aqueous solution of tert- 

3 2 4 3 

butylhydroperoxide. We established the importance of ionic 

surfactant, sodium dodecyl sulfate in the catalytic transformation. 

This additive not only ensures micellar catalytic condition for the 

oxidation, but generates effective iron catalyst in situ. We also 

demonstrated the applicability and limitations of the developed 

conditions through the functionalization of different molecular 

architectures in order to obtain important compounds bearing 

carbonyl functional group. 

references: 

1) Nakanishi, M.; Bolm, C. Adv. Synth. Catal. 2007, 349, 

861–864. 

Keywords: Oxidation; Iron; Micelles; 



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chem. Listy 106, s257–s1425 (2012) 


P - 0 8 5 6 

A StereoControLLed APProACh towArdS 

triCyCLiC MArine ALKALoidS uSinG 

ene-yne-ene-rrM rCM CASCAde 

M. GrABowSKi 1 , S. BLeChert 1 

1 Technische Universität Berlin, Institut für Chemie, Berlin, 

Germany 

Ring-rearrangement metathesis has proven to be a powerful 

synthetic tool for the construction of carbo- and heterocycles and 

has been efficiently applied to various natural product syntheses 

of diverse polycyclic systems. A cascade reaction with 

adiastereoselective Ene-Yne-Ene-RRM RCM as a key step has 

been developed for the synthesis of tricyclic indolizines. 

Dienynes turned out to be challenging substrates for tandem 

metathesis processes, due to a lack of selectivity-controlling 

groups. A rational design for the desired pathway is shown within 

this work: a cyclic ene subunit with a triple bond in an 

appropriated distance for a favored RRM, and a R-group which 

is not diminishing the catalyst activity, for the post-RRM RCM, 

offer perfect reaction control and avoid undesired side pathways. 

This attractive and versatile concept can be easily applied 

for the synthesis of several lepadiformine/ cylindricine alkaloids. 

Keywords: Alkaloids; metathesis; natural products; synthetic 

methods; homogeneous catalysis; 


P - 0 8 5 7 

AMPhiPhiLiC PoLy(BetA-PePtoid)S viA 

rinG-oPeninG PoLyMeriSAtion (roP) 

A. GroSSMAnn 1 , r. Luxenhofer 1 

1 Technische Universität Dresden, Prof. für Makromolekulare 

Chemie, Dresden, Germany 

Poly(β-peptoid)s (β-POIs) are a group of peptidomimetic 

polymers, which comprise a β-alanine backbone and a substituent 

at the nitrogen atom. The missing hydrogen donating ability for 

hydrogen bonding [1] and their proteolytic stability in comparison 

to peptides [2] are properties, which make them interesting for a 

variety of applications. Although the poly(β-peptoid)s have great 

potential as new polymer class in different fields of research, they 

are not well studied until now. 

Reported routes for their preparation, like solid-phase 

synthesis [3] or the living alternating copolymerization of 

N-alkylaziridines and carbon monoxide, show limitations in the 

DP. [1] 

Another method for the synthesis of poly(β-peptoid)s is the 

ring-opening polymerization (ROP) of N-substituted β-amino acid 

N-carboxyanhydrides (β-NNCAs). Although living nucleophilic 

ROP of α-NNCAs offers excellent synthetic control and can be 

performed in a wider range of solvents, [4] publications about the 

β-analogs are rare. [5, 6] Here we present a route for the synthesis 

of β-NNCAs and their ROP under different conditions. We are 

able to show for the first time that ROP of β-NNCAs has a living 

character. [7] Thus, complex architectures and highly defined 

polymers should be accessible, which is currently investigated in 

our lab. 

references: 

1. Lin, S.; Zhang, B.; Skoumal, M. J.; Ramunno, B.; Li, X.; 

Wesdemiotis, C.; Liu, L.; Jia, L. Biomacromolecules 2011, 

7, 2573-2582. 

2. Shuey, S. W.; Delaney, W. J.; Shah, M. C.; Scialdone, M. A. 

US Pat. Appl. US20060160735, 2006. 

3. Hamper, B. C.; Kolodziej, S. A.; Scates, A. M.; Smith, R. G.; 

Cortez, E. J. Org. Chem. 1998, 3, 708-718. 

4. Fetsch, C.; Grossmann, A.; Holz, L.; Nawroth, J. F.; 

Luxenhofer, R. Macromolecules 2011, 17, 6746-6758. 

5. Birkofer, L.; Kachel, H. Naturwissenschaften 1954, 576. 

6. Zilkha, A.; Burstein, Y. Biopolymers 1964, 2, 147-161. 

7. Grossmann, A.; Luxenhofer, R. Macromol. Rapid Commun. 

in revision process. 

Keywords: peptidomimetics; ring-opening polymerization; 

polymers; block copolymers; 



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P - 0 8 5 8 

new CAtALytiC hALoGenAtion StrAteGieS 

for the GenerAtion of unuSuAL reACtivitieS 

t. GuLder 1 

1 RWTH Aachen university, Institute of Organic Chemistry, 

Aachen, Germany 

The halogenation of organic molecules is one of the most 

widespread techniques for the functionalization of substrates, 

which is often attributed to the good leaving group nature of 

halogen atoms in a multitude of substrates. Compounds bearing 

halogen atoms are thus versatile starting materials as well as 

intermediates in organic syntheses. Due to the intrinsic properties 

of the halogen substituents these molecules also play important 

roles in medicinal chemistry, material science, and as agro 

chemicals. Despite the broad application of halogenated 

compounds, common strategies for the formation of 

carbon-halogen bonds often suffer from severe drawbacks such 

as stereo- and regioselectivity issues, making the development of 

more selective and thus more atom economic and environmentally 

friendly methods a rewarding goal. 

Our research therefore addresses the problem of catalytic 

halogenations by developing mild, generally applicable, and 

selective catalytic methods for the directed oxidative formation 

of carbon-halogen bonds. One aspect within our research program 

tries to unlock hidden reactivities by catalytically activating 

common halogenation reagents in order to access new structures 

under mild conditions. Our recent advances in developing novel 

halogenation strategies will be discussed. 

Keywords: organocatalysis; halogenation; iodine(III); natural 

products; 


P - 0 8 5 9 

CheMo-enzyMAtiC ConCePtS for the 

SyntheSiS of CoMPLex BACteriAL nAturAL 

ProduCtS 

t. A. M. GuLder 1 , A. hüLyA 1 , r. riChArz 1 , h. honG 1 , 

f. SChAeferS 1 

1 University of Bonn, Kekulé Institute of Organic Chemistry and 

Biochemistry, Bonn, Germany 

The use of chemical entities isolated from natural sources 

has been of particular significance for human health. This can be 

rationalized by the often observed high selectivity and potency of 

such natural products towards a distinct target. Their chemical 

preparation is, however, often characterized by a high number of 

individual synthetic steps using seemingly superfluous protective 

groups, overall low chemical/optical yields, and the necessity of 

expensive and sometimes highly toxic reagents. Novel approaches 

towards the preparation of structurally complex metabolites by 

combining the strengths of total organic synthesis with the 

efficacy of nature’s strategies to generate molecular complexity 

have the potential to solve these problems. Our research is 

therefore focused on understanding and applying biosynthetic 

enzymes as biocatalysts for the preparation of biomedically 

relevant natural products in efficient biomimetic ways. Recent 

achievements towards the chemo-enzymatic preparation of 

synthetically challenging bacterial non-ribosomal peptides will be 

discussed. 

Keywords: Natural products; biosynthesis; Biomimetic 

synthesis; Biocatalysis; 



s1293 

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P - 0 8 6 0 

AdAPtAtion of iMine ConStituentS in 

dynAMiC CovALent SySteMS under 

reverSiBLe PhASe SePArAtion 

n. hAfezi 1 , J. M. Lehn 1 

1 Institut de Science et d’Ingenierie Supramoleculaires, 

Chemistry, Strasbourg, France 

The dynamic selection of interconverting imines has been 

achieved by the reversible separation of a homogeneous liquid 

phase into two non-miscible phases by the action of either a 

physical stimulus or by addition of a chemical effector. This 

results in the re-organization of a dynamic library based on the 

medium preference of the library members. Moreover, we 

demonstrate reversibility in the library re-organization by 

interconversion between the biphasic mixture and the 

homogeneous solution. Finally, we note that such processes 

provide access to dynamic non-equilibrium systems. 

Keywords: Exchange interactions; Molecular evolution; Schiff 

bases; Amines; Aldehydes; 


P - 0 8 6 1 

ConJuGAted donor-ACCePtor-CoPoLyMerS 

for PoLyMer SoLAr CeLLS 

M. d. hAGer 1 , d. SChMidt 1 , f. KretSChMer 1 , 

o. SynooKA 2 , h. hoPPe 2 , u. S. SChuBert 1 



2 Technical University Ilmenau, Institute for Physics, Ilmenau, 

Germany 

One of the most-promising donor materials for polymer 

solar cells (bulk heterojunction solar cells with polymer/fullerene 

blends) are donor-acceptor copolymers. Currently, there is a quest 

for new materials to achieve solar cells with higher efficiencies. 

More and more complex building blocks are synthesized and 

incorporated into polymeric materials. 

Another possibility for the optimization of the polymer 

structures is the combination of different building blocks within 

one polymer. Some examples, which are described in the 

literature, of random copolymers, which contain two or three 

different building blocks, showed promising performance in solar 

cells. They revealed higher efficiencies than both homopolymers. 

In this context, we report the systematic synthesis of three 

different donor-acceptor-copolymer libraries, which contain two 

different acceptor moieties. The optical and electronic properties 

of these copolymer libraries were investigated in detail. The 

absorption of these polymers is broadened due to the presence of 

two different acceptor moieties within the polymers. Moreover, 

the emission of these materials is governed by the acceptor 

moiety, which features the lower energy. 

The performance of the random copolymers in polymer 

solar cells was investigated in detail. Additionally the 

corresponding homopolymers and blends of two homopolymers 

have been studied in solar cell tests in order to investigate the 

influence of the copolymerization of two different acceptor 

moieties. Some of these copolymers featured higher efficiencies 

than the homopolymers and their mixtures. The influence of the 

polymer composition and of the combination of different acceptor 

moieties on the performance of random copolymers in solar cells 

will be discussed in detail. 

Keywords: Conducting materials; Polymers; Combinatorial 

chemistry; Donor-acceptor systems; 



s1294 

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P - 0 8 6 2 

SyntheSiS And AntivirAL evALuAtion 

of SoMe noveL PyrAzoLeS And 

PyrAzoLo[3,4-d]PyridAzineS BeArinG 

the 5,6,7,8-tetrhydronAPhthALene Moiety 

n. hAMdy 1 , w. eL- SenouSy 2 

1 National Research Centre, Applied Organic Chemistry, Cairo, 

Egypt 

2 National Research Centre, Enteric Viruses Laboratory, Cairo, 

Egypt 

objective: Synthesis of new series of 5,6,7,8- tetra - 

hydronaphthalene derivatives conjugated with pyrazole and 

pyrazolo[3,4-d]pyridazine functionalities hoping to produce 

antiviral activity against Adenovirus type 7 and human 

Rotaviruses. 

Background:Literature survey showed that many 

derivatives bearing tetrahydronaphthalene nucleus attached to 

different heterocyclic functionalities exhibit wide spectra of 

biological activities [1, 2] . Adenovirus infections cause pneumonia 

and disseminated disease in both immunocompromised and 

nonimmunocompromised hosts and Rotaviruses are the single 

most important cause of severe diarrhea illness in infants and 

young children in both developed and developing countries 

worldwide. [3, 4] 

Methodology: The enaminone 2 was reacted with 

hydrazonyl halides 3a-d to afford the corresponding pyrazole 

derivatives (6a-d) which reacted with hydrazine hydrate to afford 

the new pyrazolo[3,4-d]pyridazine derivatives 7a-d, respectively. 

In addition, compound 2 was reacted with some primary aromatic 

amines to give the corresponding secondary enaminones 10a-c 

and reacted with sulphapyridine or sulphapyrimidine to produce 

the corresponding sulphonamide derivative 12a and 12b. 

results: Evaluation of these new compounds against 

rotavirus Wa strain and adenovirus type 7 showed that (6c, 6d, 

7c, 7d, 10b, 10c, 12a, and 12b) exhibited high efficiency as 

antiviral agents. 

Conclusion: Some tested compounds of pyrazole, 

pyrazolo[3,4-d]pyridazine, secondary enaminones, and 

sulphonamides contributed to tetrahydronaphthalene moiety 

showed antiviral effect against adenovirus type 7 and human 

rotavirus Wa strain which may be considered as promising 

antiviral compounds. 

references: 

1. Hamdy N.A., Gamal-Eldeen A.M.: Eur. J. Med. Chem. 44, 

4547 (2009). 

2. Hamdy N.A., Gamal-Eldeen A.M., Abdel-Aziz H.A., 

Fakhr I.M.I.: Eur. J. Med. Chem. 45, 463 (2010). 

3. Carballal G., Videla C., Misirlian A., Requeijo P.V., 

Aguilar M., BMC Pediatr. 2, 6 (2002). 

4. Estes M., Kapikian A.: Rotaviruses, In D. M. Knipe, 

Howley P.M., Griffin D.E., Lamb R.A., Martin M.A., 

Roizman B., Straus S.E., Fields virology, 5th ed., vol. 2. 

Lippincott, Williams and Wilkins, Philadelphia, PA.: 

pp 1917(2007). 

Keywords: Enaminone; pyrazole; pyrazolo[3,4-d]pyridazine; 

sulphonamide; antiviral activity; 


P - 0 8 6 3 

SyntheSiS of A MoLeCuLAr MuSCLe for 

oPerAtion on A SurfACe 

M. hAMMeriCh 1 

1 Otto Diels-Institut, Organic Chemistry, Kiel, Germany 

The design and synthesis of molecular mashines is one of 

the most active fields in synthetic and supramolecular chemistry. 

Attention was given to the immobilization of functional molecules 

on surfaces, particularly Au(111). 

Among the known methods to attach functional molecules 

to gold, the platform concept developed by Herges et al. proved 

to be particularly successful. Triazatriangulenium (TATA) -ions 

are used as molecular platforms, which form self assembled 

monolayers (SAMs) on Au(111)-surfaces. [1] Molecules (e.g 

ethynyl or pheny) can be attached to the central carbon atom of 

these platforms that stand like poles with a pedestal on the 

surface. [2] In the present study a molecule was synthesized in 

which two “poles” were horizontally connected by an azobenzene 

(“laundry line molecule”). 

The photochemical switching of the azobenzene should lead 

to a shortening of the distance between the platforms. The 

movement resembles the contraction of a muscle so that the 

molecule was named “molecular muscle”. 

references: 

1. a) B. Baisch, D. Raffa, U.Jung, O. M. Magnussen, 

C. Nicolas, J. Lacour, J. Kubitschke, R. Herges, 

J. Am. Chem. Soc. 2009, 131, 442–443; 

b) S. Kuhn, B. Baisch, U. Jung, T. Johannsen, 

J. Kubitschke, R. Herges O. Magnussen, 

Phys. Chem. Chem. Phys. 2010, 12, 4481. 

2. J. Kubitschke, C. Näther, R. Herges, Eur. J. Org. Chem. 

2010, 26, 5041-5055. 

Keywords: molecular muscle; platform concept; gold surface; 



s1295 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 6 4 

A Boron CAtALyzed ALdoL reACtion 

u. hAnefeLd 1 , t. MueLLer 1 , K. dJAnAShviLi 1 , 

i. w. C. e. ArendS 1 

1 Delft University of Technology, BOC, Delft, Netherlands 

The aldol reaction plays an important role in the formation 

of C-C-bonds. A major challenge in the catalytic aldol reaction is 

selectivity, since the reaction is immediately followed by the 

elimination of water [1] . Boronic acid derivatives were 

demonstrated to be valuable catalysts for the aldol reaction; 

however they have to be dissolved in water [2, 3] . We developed a 

tetrahedral boronate salt, which is soluble in organic solvents. 

Therefore we are able to perform the reaction in the substrate, 

acetone. 

The aldol reactions were performed with our soluble 

catalyst, sodium (3,5-difluorophenyl) triisopropoxy boronate. 

The Aldol reaction is carried out in a short reaction time with 

a good conversion for an electron poor aromatic system. After 

20 min. 80 % conversion (38% aldol) was obtained with 

4-Methoxybenzaldehyde. Performing the reaction with 

benzaldehyde gave good selectivity. After 20 min. 73 % of the 

aldol product and 23 % of the elimination product were obtained. 

An extensive screening of substrates and reaction conditions will 

be presented. 

references: 

1. R. Mahrwald, Modern Aldol Reactions, Wiley-VCH (2004). 

2. Y. Mori, J. Kobayashi, K. Manabe, and S. Kobayashi, 

Tetrahedron, 58 (2002) 8263 – 8268. 

3. K. Aelvoet, A S. Batsanov, A. J. Blatch, C. Grosjean, 

L. G. F. Patrick, C. A. Smethurst and A. Whiting, 

Angew.Chem.Int.Ed., 47 (2008) 768 – 770. 

Keywords: Catalysis; Solvent free; boron; 


P - 0 8 6 5 

ProGreSS in the SeArCh for the C-Cn2 CArBene 

e. hAnzLovA 1 , t. MArtinu 1 , r. nAvrAtiL 1 , 

C. ShAffer 2 , d. SChrÖder 2 

1 Institute of Chemical Technology, Department of Organic 


2 Institute of Organic Chemistry and Biochemistry AS CR, 

Molecular Spectroscopy, Prague 6, Czech Republic 

Experimental evidence and computational results suggest 

that 3-bromodiazirine-3-carboxylic esters (1) undergo anionic 

fragmentation to the bromodiazirinyl anion (c-CN Br 2 – ), a weakly 

bound complex of the bromide ion and diazirinylidene (c-CN ), 2 

formally the simplest N-heterocyclic carbene (NHC) containing 

two nitrogen atoms. Esters 1 react with alkoxides to afford the 

corresponding carbonates via nucleophilic acyl substitution. The 

c-CN Br 2 – leaving group dissociates to the strongly electrophilic 

c-CN (cf.the classical nucleophilic NHCs), which is then 

2 

transformed in the presence of an alcohol to an alkoxymethylene 

(ROCH) via a 3-alkoxydiazirine. The ROCH carbene inserts into 

the O–H bond of the alcohol resulting in an isolable product, 

dialkoxymethane. Additionally, 2-oxabicyclo[4.1.0]heptanes are 

formed from the nucleophilic ROCH by an intramolecular 

cycloaddition when some 4-alken-1-ols are employed. The 

alkoxide cleavage of 1 is always accompanied by the evolution 

of N . When the reactions are performed in amidic solvents, 

2 

mixtures of N and CO result (even under oxygen-free 

2 

conditions). This observation can be explained by an oxygen atom 

transfer from the solvent to the c-CN followed by fragmentation. 

2 

In the gas phase, collision-induced dissociation (decarboxylation) 

of the 3-bromodiazirine-3-carboxylate ion generated from the 

ester 1 results in the appearance of a CN Br 2 – ion. The constitution 

of this species remains to be determined, however, its facile loss 

of the bromide ion agrees well with the proposed precursor of 

c-CN . 2 



s1296 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 6 6 

PoLy(thioPhene-PhenyLene-vinyLene)S By 

oxidAtive PoLyMerizAtion 

d. hAuSen 1 , G. wenz 1 

1 Saarland University, Organic Macromolecular Chemistry, 

Saarbrücken, Germany 

Electroluminescent conjugated polymers are of great interest 

for the electronic industry and academia. Different π-conjugated 

polymers are applied in several optoelectronic devices like lightemitting 

diodes, solar cells and field-effect transistors [1] . They 

have the advantages over the inorganic semiconductors such as 

low cost, thin size and good flexibility [2] . 

Our works concern of the synthesis of various organic 

materials for these electronic applications. The main structures of 

our π-conjugated compounds are substituted phenylene-vinylene 

units with terminal thiophene groups. They are synthesized in a 

four- or seven-step sequence based on hydrochinone and 

thiophenecarbaldehyde. The important step in our monomer route 

is the Horner-Emmons olefination with high (E,E) selectivity3 . On 

one hand the polymerization can be realized in solution by 

oxidation withLewis acids like antimony(V)chloride or by 

Grignard metathesis. We can monitor the oxidative 

polymerization by UV absorption. On the other hand the 

polymerization can be performed electrochemically 3 . 

Homogenous polymer films were produced this way. They were 

analyzed inter alia by nanoindentation or AFM. Alternative 

polymer films will be obtainable from our soluble polymers by 

spin coating. 

We attached various substituents like linear and branched 

alkyl groups, β-cyclodextrine, etc. to our monomers and the 

resulting oligomers and polymers. Some attachements were 

realized via Huisgen [2+3] click chemistry4 . One of our future 

targets is a water soluble π-conjugated polymer. 

Optical and electrochemical data of our substituted 

bis(thiophenyl-vinyl)-benzenes derivates demonstrate that they 

can be potential building blocks for optoelectronic materials. 

references: 

1. Kraft, A.; Grimsdale, A.C.; Holmes, A.B.; 

Angew. Chemie, Intern. Ed. 1998, 37, 402 

2. Roncali, J.; Chem. Rev. 1992, 711 

3. Hausen, D.; Wenz, G.; PMSE Preprints 2010, 

San Francisco National 239th ACS Meeting 

4. Mourer, M.; Hapiot, F.; Monflier, E.; Menuel, S.; 

Tetrahedron 2008, 64, 7159 

Keywords: polymers; click chemistry; electrochemistry; 

Grignard metathesis; 


P - 0 8 6 7 

BAMBuSuriL derivAtiveS And their 

SuPrAMoLeCuLAr ProPertieS 

v. hAveL 1 , v. SindeLAr 1 

1 Masaryk University Fac Sci, Chemistry, Brno, Czech Republic 

Bambusurils are a family of macrocycles based on glycoluril 

with interesting supramolecular properties. They are promising 

receptors for a variety of anions because of their selectivity and 

stability of resulting complexes. Supramolecular as well as 

physical properties could be tuned by the modification of the 

bambusuril structure or by the preparation of homologues with 

various number of glycoluril unit within the macrocycle. 

At this meeting we will demonstrate the differences in 

supramolecular behavior of selected bambusuril derivatives 

bearing various functional groups on their skeleton. 

Acknowledgement: Support for this work was provided 

by the Grant Agency of the Czech Republic (P207/10/0695), 

the project CETOCOEN (no. CZ.1.05/2.1.00/01.0001) from 

the European Regional Development Fund and the Brno Ph.D. 

Talent scholarship program sponsored by Brno City 

Municipality. 

Keywords: Anions; Heterocycles; Macrocycles; Receptors; 




s1297 

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P - 0 8 6 8 

SyntheSiS of new MonoMerS for ConduCtinG 

PoLyMerS 

A. heinriCh 1 , A. StAuBitz 1 



In organic synthesis, the formation of new carbon-carbon 

bonds is one of the most important reactions, enabling the 

construction of complex molecular structures from simple 

building blocks. A variety of structures can be linked to each other 

in the most efficient way by cross-coupling reactions. [1–2] 

Selective cross-coupling reactions which can distinguish 

between different halogens and pseudo halogens are well described 

[1, 3–4] 

and an important tool in the field of organic synthesis. 

Cross-coupling reactions which are selective with respect to 

nucleo-philes (RM) on the other hand offer great potential, but at 

present they are virtually unexplored.Therefore, new orthogonal 

metal-selective cross-coupling reactions between aromatic 

components were explored. The resulting compounds had both 

one metal and one halogen functional group. These functional 

groups are essential for the polymerization by a living 

polymerization process. 

references: 

1. A. d. Meijere, P. J. Stang, Wiley-VCH, 2nd ed. 2004, 

Weinheim. 

2. R. Chincilla, C. Nájera, Chem. Rev. 2007, 107, 874. 

3. T.-Y. Luh, M.-K. Leung, K.-T. Wong, Chem. Rev. 2000, 

100, 3187. 

4. M. Beller, C. Bolm, Wiley-VCH, 2n ed. 2004Weinheim. 

Keywords: Cross-coupling; Polymers; Polymerization; 



P - 0 8 6 9 

deveLoPMent of new CLiCKABLe turn-on 

tyPe fLuoreSCent dyeS 

A. herner 1 , P. KeLe 2 

1 Eotvos Lorand University, Department of Organic Chemistry, 



Hungary 

The importance of fluorescence labeling-based techniques 

is probably best demonstrated by the continuously increasing 

number of publications on the topic. Low detection limits, high 

sensitivity, good temporal and spatial resolution and the relatively 

cheap detection of the fluorescence signal all contribute to the 

popularity of fluorescence-based methods. 

Labeling of biomolecules by means of fluorescent tags is 

one of the most important topics within these techniques. The use 

of conventional fluorescent tags always requires the separation of 

unreacted dyes. Not only is there a need to omit this extra washing 

step is highly demanded in labeling schemes of biological matters, 

but the sensitivity is also further enhanced when so-called 

“turn-on” type of fluorescent tags are used. The unique nature of 

this fluorophore class is that it is virtually non-fluorescent in its 

unbound form, while it becomes highly fluorescent upon chemical 

ligation to its target biomolecule. Another case of turn-on type 

tags is presented by labels with emission maxima that are 

significantly shifted upon conjugation. 

Upon our continuing efforts to fabricate turn-on type labels 

it was also demanded to incorporate such functionalities that allow 

the use of these fluorogenic tags in bioorthogonal labeling 

schemes. Besides, the prospective use of these tags in energy 

transfer (FRET) systems further demanded complete separation 

of excitation and emission bands a feature present in so-called 

mega-Stokes dyes. In line with all these criteria we have set forth 

a study where we designed and synthesized turn-on type of 

fluorescent tags possessing large Stokes shifts and functionalities 

that allow incorporation of these tags by means of bioorthogonal 

labeling schemes. 

Keywords: Fluorescence; Fluorescent probes; Click chemistry; 

Azides; Bioconjugate chemistry; 



s1298 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 7 0 

StereoSeLeCtive oxidAtion of ALCohoLS 

uSinG teMPo-PePtide CAtALyStS 

C. hofMAnn 1 , P. r. SChreiner 1 

1 Institute of Organic Chemistry, Justus-Liebig-University 

Giessen, Giessen, Germany 

Oxidations of alcohols to obtain ketones, aldehydes or 

carboxylic acids are fundamental transformations in synthetic 

organic chemistry. A transition metal-free aerobic alcohol 

oxidation with TEMPO as a catalyst is feasible and useful for 

organocatalysis. [1] TEMPO could be easily attached in small 

peptides to achieve chiral nitroxide radical derivatives. 

Synthesized TEMPO-peptides [2] have been tested as chiral 

catalysts for the oxidative desymmetrization [3] and the oxidative 

kinetic resolution [4] of diols. 

The highest enantiomeric excesses were observed for 

catalysts including the rigid, cyclic amino acid TOAC 

(2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid). [5] 

Syntheses of other peptide derivatives bearing the TEMPO 

function are in progress. Our goal is to include the 

enantioselective oxidation process in a multicatalytic system. [6] 

references: 

1. R. Liu, X. Liang, C. Dong, X. Hu, J. Am. Chem. Soc. 

2004, 126, 4112. 

2. R. Formaggio, C. Toniolo, Chem. Eur. J. 2002, 8, 84. 

3. a) M. C. Willis, J. Chem. Soc. Perkin Trans. 1 1999, 1765; 

b) C. E. Müller, D. Zell, P. R. Schreiner, Chem. Eur. J. 

2009, 15, 9647. 

4. a) E. Vedejs, M. Jure, Angew. Chem. Int. Ed. 2005, 44, 

3974; 

b) M.Tomizawa, M. Shibuya, Y. Iwabuchi, Org. Lett. 

2009, 11, 1829. 

5. A. Rassat, P. Rey, Bull. Soc. Chim. Fr. 1967, 815. 

6. R. C. Wende, P. R. Schreiner, Green Chem. 2012, in press. 

Keywords: Organocatalysis; Oxidation; Peptides; 


P - 0 8 7 1 

tAndeM MiChAeL Addition/rAdiCAL 

CyCLizAtionS for the ConStruCtion of 

hiGhLy funCtionALized CyCLoPentAneS 

M. hoLAn 1 , r. PohL 1 , i. CíSArová 2 , u. JAhn 1 


Organic Chemistry and Biochemistry, Prague, Czech Republic 

2 Charles University in Prague, Department of Inorganic 


Tandem reactions are an effective tool in synthetic organic 

chemistry, since they allow the time- and resource-efficient access 

to complex structures from simple precursors. 1 

The methodology employs a diastereoselective Michael 

addition, where enolates of different carbonyl compound classes 

are successfully coupled with various Michael acceptors. The 

diasteroselectivity of the Michael addition can be switched using 

either Z- or E-enolates of esters. 2 This is pivotal steering element 

that controls diastereoselectivity of the subsequent radical 

cyclization. Those two aspects allowed to construct highly 

functionalized cyclopentanes diastereoselectively in a one pot 

procedure. The interconversion between anionic and radical stage 

is mediated either by ferrocenium hexafluorophosphate, a 

recyclable, less toxic single electron transfer oxidant or by 2,2,6,6- 

-tetramethyl-1-oxopiperidin-1-ium hexafluorophosphate, which 

enables catalytic tandem processes. The whole sequence is 

terminated by trapping with the TEMPO radical. 

references: 

1. a) H. Pellisier, Tetrahedron, 2006, 62, 1619. 

b) H. Pellisier, Tetrahedron, 2006, 62, 2143. 

2. a) U. Jahn, Chem. Commun., 2001, 1600. 

b) M. Holan, R. Pohl, I. Císarová, U. Jahn, Eur. J. Org. 

Chem., 2012, DOI: 10.1002/ejoc.201200077 

Keywords: Cyclization; Diastereoselectivity; Michael addition; 

Radical reactions; Domino reactions; 



s1299 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 7 2 

A hiGhLy ConverGent route towArdS 

4-AMino-4-deoxy-L-ArABinoSe Modified LiPid A 

r. hoLLAuS 1 , P. KoSMA 1 , A. zAMyAtinA 1 

1 University for Natural Resources and Applied Life Sciences, 


Lipid A of gram negative bacteria anchors the 

lipopolysaccharide chain to the outer cell membrane. It possess a 

rather conservered structure: To a β(1-6) diglucosamine backbone 

are phosphates attached at positions 1 and 4'. Different acylation 

pattern are possible for positions 2-N, 2'-N, 3, 3', were 

(R)-3-hydroxy or (R)-3-acyloxy fatty acids could be attached. 

Covalent modification of Lipid A by cationic β-L-Ara4N at 

either both 1- and 4'- phosphates or solely at the reducing 

phosphate, which is characteristic for Burkholderia strains, is 

associated with augmented bacterial virulence, resistance to 

antibiotic treatment and modulation of TLR4-MD-2-mediated 

innate immune response. Mono- and bis- β-L-Ara4N substituted 

Lipid A structures, corresponding to native Burkholderia Lipid A 

were synthesised. 

Starting from glucosamine, an orthogonally protected Glc2N 

key intermediate was assembled, carrying 2-N-Troc-, 

1-O-TBDMS- and 4,6-O-anisyliden protecting groups, position 3 

was acylated with (R)-3-(((allyloxy)car-bonyl)oxy)tetradecanoic 

acid. The compound was used for the synthesis of a glycosyl 

donor by regioselective reductive opening of 4,6-O-anisylidene 

acetal to furnisch 4-OPMB ether, followed by 6-O-Alloc 

protection, 1-O-desilylation and subsequent appel reaction to give 

a bromide donor. Glycosyl acceptor was prepared in a convergent 

manner using the same precursor by acetal opening to provide 

6-O-PMB ether, 4-O-Alloc protection, cleavage of 2N-Troc group 

followed by acylation with 3-oxyacyl lipid chain. Subsequent 

6-O-PMB deprotection and glycosylation of the liberated 6-OH 

by bromide donor, reductive cleavage of 2'-N-Troc protection and 

N-acylation afforded fully protected pentaacylated β(1-6) 

diglucosamine disaccharide. Regioselective deprotection of 

positions 4'-O-PMB and 1-O-TBMS allowed for selective 

coupling with either diallyl-N,N-diisopropylphosphoramidite 

or H-phosphonate of 2,3-di-O-Alloc-protected β-L-4-azido- 

-arabinose, respectively, leading, after global deprotection (Alloc 

deprotection followed by azide reduction), to target Burkholderia 

Lipid A structures. 

Keywords: Synthetic methods; Carbohydrates; 

Phosphorylation; Phospholipids; Azides; 


P - 0 8 7 3 

unuSuAL BehAviour of 

5-(2-PyridyL)SuLfinyL-tetrAProPoxy - 

CALix[4]Arene in Pd-CAtALyzed reACtion. 

J. hoLuB 1 , v. eiGner 1 , P. LhotáK 1 



Palladium catalyzed cross-coupling reactions using direct 

C-H bond activation is very attractive topic in modern synthetic 

organic chemistry. The presence of a directing group usually 

enables regioselective introduction of the coupling agent into a 

specific position. Among these groups, the 2-pyridylsulfinyl 

moiety possesses very strong C-H activating properties. We have 

introduced this directing group into the upper rim of calix[4]arene 

and attempted the direct arylation of calixarene skeleton into the 

meta position. This reaction should provide very interesting 

inherently chiral systems which could be useful in the design of 

novel chiral receptors. Surprisingly, we have found that the 

isolated product is not the expected aryl-substituted calixarene, 

but some unknown, meta substituted and inherently chiral 

calix[4]arene derivative. The NMR spectra of this compound were 

very complicated and did not lead to the structure elucidation. On 

the other hand, the single-crystal X-ray crystallography gave us 

the final solution. The activation of the neighbour C-H bond (next 

to the 2-pyridylsulfinyl directing group) led to the unexpected 

intramolecular bridging of two meta positions on the proximal 

phenolic subunits via a direct C-C bond. This kind of reaction has 

never been observed in calixarene chemistry. The application of 

this phenomenon for the synthesis of inherently chiral calixarenebased 

receptors is currently underway. 

Keywords: Calix[4]arene; 



s1300 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 7 4 

SyntheSiS of noveL ene-yne CoMPoundS 

derived froM SeLeniuM heteroCyCLeS 

B. hoLzer 1 , d. LuMPi 1 , e. horKeL 1 , C. hAMetner 1 , 

J. frÖhLiCh 1 

1 Technische Universität Wien, IAS, Vienna, Austria 

Organoselenium compounds have become attractive 

synthetic targets in material synthesis, ligand chemistry and 

biologically relevant processes. Among organoselenium 

compounds, selenophene derivatives are widely studied because 

of their potential application in organic electronics. [1] Despite 

structural similarities, however, sulfur and selenium compounds 

are often strikingly different with respect to their stability, 

properties, and ease of formation. 

The topic of this contribution will be the presentation of 

organoselenium-based functional organic materials. On the one 

hand the structural focus will be on novel annealed selenophene 

scaffolds; on the other hand an investigation of selenophene ringopening 

moieties towards ene-yne compounds will be presented. 

Based on various 2-bromoselenophene derivatives, bearing 

different substituents (H, alkyl, aryl) in α- respectively β-position, 

the Halogen-Dance (HD) reaction [2] proves to be a versatile 

synthetic route to multisubstituted selenophenes. Subsequent 

controlled selenophene ring fragmentation reaction selectively 

leads to the Z-isomer of ene-yne compounds. Further modification 

by microwave-assisted Cu-catalyzed Huisgen cycloaddition [3, 4] 

affords the corresponding triazoles as 1,4-adducts. The 

applicability of these triazoles in organic electronics 

references: 


1. Patra, A., Bendikov, M., J. Mater. Chem., 2010, 20, 422–433. 

2. Fröhlich, J., Prog. Heterocycl. Chem., 1994, 6, 1-35. 

3. Tornoe, C. W., Christensen, C., Meldal, M., J. Org. Chem., 

2002, 67, 3057. 

4. Rostovtsev, V. V., Green, L. G., Fokin, V. V., Sharpless, K. B., 


Keywords: Organic Electronics; Selenophene; Selenophene 

Ring Fragmentation; Halogen Dance Reaction; Huisgen 

cycloaddition; 


P - 0 8 7 5 

direCt CouPLinG of Cox with ePoxideS: 

CAtALytiC ProduCtion of BiodeGrAdABLe 

PoLyMerS 

z. hoStALeK 1 , J. MernA 1 


Polymers, Prague 6, Czech Republic 

The development of catalysts for activation and use of 

carbon oxides (CO and CO ) as a feed-stock for synthesis of new 

2 

materials is an attractive research target in last 20 years. One of 

the most promising strategies of carbon oxides utilization is direct 

coupling/copolymerization of CO and CO with epoxides. 

2 

Depending on catalytic system (catalyst/cocatalyst ratio) and 

experimental conditions either cyclic esters/carbonates or 

polymers susceptible towards biological or hydrolytical 

degradation can be obtained. 

The aim of this work is to develop effective catalytic system 

for direct conversion of carbon monoxide and carbon dioxide and 

epoxides to biodegradable polymers or to their cyclic esters 

precursors, which can be easily polymerized via metal-catalyzed 

ring-opening polymerization. For this purpose chromium and 

cobalt SALEN complexes were synthesized and tested as catalysts 

for direct high-pressure epoxide/CO copolymerization. The effect 

2 

of cocatalyst and experimental conditions (temperature, pressure 

of CO and epoxide/catalyst/cocatalyst ratio) was also 

x 

investigated. Similar catalytic complexes (combination of SALEN 

complexes with Co(CO) salt) were also tested for direct coupling 

4 

of epoxides with CO. 

Keywords: Polymerization; Chromium; Cobalt; 

Carbonylation; Carbon dioxide fixation; 



s1301 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 7 6 

noveL APProACh to SyntheSiS of 

CALix[4]Arene reCePtorS 

o. hudeCeK 1 , P. CurinovA 2 , J. BudKA 1 , v. eiGner 3 , 

P. LhotAK 1 



2 Institute of Chemical Process Fundamentals of the ASCR v. v. 

i, Department of Organic Synthesis and Analytical Chemistry, 


3 Institute of Chemical Technology Prague, Department of Solid 

State Chemistry, Prague 6, Czech Republic 

Calix[4]arenes are widely used as platforms for synthesis of 

receptors acting in host-guest chemistry. The structure of 

calixarene molecule allows interactions with all types of substrates 

(soft or hard metal cations, anions and even neutral molecules). [1] 

Due to various shapes of anions and their solvent-dependent 

stability, the most sophisticated design is required for their 

effective binding. [2] 

In this research, a novel regioselective derivatisation [3] of 

calix[4]arene skeleton has been developed and optimized. This 

multi-step synthetic procedure leads to interesting derivatives with 

so far almost inaccessible substitution pattern. A subsequent 

modification enables to prepare precursors for ureido-based anion 

receptors fixed in a cone and a partial cone conformation, and for 

versatile receptors which adopt a 1,2-alternate conformation. 

Some of them have been synthesized and used for the 

complexation experiment. The results as well as the synthetic 

approach will be presented. 

Acknowledgement: This research is supported by the Czech 

Science Foundation (P207/12/2027) and by financial support 

from specific university research (MSMT No 21/2012). 

references: 

1. Gutsche, C. D. Calixarenes An Introduction: Monographs 

in Supramolecular Chemistry. 

2. Stibor, I.; Budka, J.; Michlova, V.; Tkadlecova, M.; 

Pojarova, M.; Curinova, P.; Lhotak, P. New J. Chem., 

2008, 32, 1957-1607. 

3. a) Hudecek, O.; Curinova, P.; Budka, J.; Lhotak, P. 

Tetrahedron, 2011, 67, 5213-5218. 

b) Hudecek, O.; Budka, J.; Eigner, V.; Lhotak, P. 

Tetrahedron, 2012, 68, 4187-4193. 

Keywords: calix[4]arenes; host-guest chemistry; 


P - 0 8 7 7 

Steroid ProBeS for the Study of trAnSPort 

in A LivinG oBJeCtS 

h. ChodounSKá 1 , v. KAPrAS 2 , B. SLAvíKová 3 , 

e. Kudová 3 , L. rAMBouSeK 4 , K. vALeS 5 , 

v. vyKLiCKý 6 , L. Jr. vyKLiCKý 6 


Neuroprotectives, Praha 6, Czech Republic 


Chemistry of Natural Products, Praha 6, Czech Republic 


Neuroprotectives, Praha 6, Czech Republic 

4 ICT Prague, Dept. of Organic Technology, Praha 6, 


5 Institute of Physiology AS CR v.v.i., Dept. of Neurophysiology 

of Memory, Praha 4, Czech Republic 

6 Institute of Physiology AS CR v.v.i., Dept. of Cellular 

Neurophysiology, Praha 4, Czech Republic 

Steroids and steroid-like compounds are important 

molecules for many living organisms. They act as a building 

blocks of membranes, take part in the digestion, and in the 

signaling pathways. Although many of the steroid roles have been 

already understood; a lot of them are continuously being explored. 

One example of new and attractive avenues of investigation is the 

research of the synthesis and action of neurosteroids in the brain. 

Recent development in the methodologies of the biological 

processes allows revealing roles of neurosteroids more 

straightforward. However, these new methods demand effective 

molecular standards and probes. 

We have prepared steroid molecules labeled with isotopes, 

fluorescent, or photoactive moieties. These probes were used for 

the assessment of pharmacokinetics of steroidal neuroprotectives 

and for the study of their transport to the neurons. 

Keywords: steroids; isotopic labeling; fluorescent probes; 



s1302 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 7 8 

towArdS the SyntheSiS of APiCuLAren A: An 

APPLiCAtion of new MethodoLoGy to 

ConStruCt 2,6-Anti-tetrAhydroPyrAn rinGS 

S. S. ChuA 1 , A. ALni 1 , t. P. Loh 1 

1 Nanyang Technological University, Chemistry and Biological 

Chemistry, Singapore, Singapore 

Since the isolation [1] and the subsequent structural 

elucidation [2] of Apicularen A, 1, by Hofle and co-workers, the 

molecule has been an intriguing molecule to the chemical society. 

Its wondrous biological properties [3] place Apicularen A as a 

potential candidate for anticancer drug target and the delicate 

architecture of the molecule are two major factors that motivate 

many synthetic chemists to construct Apicularen A. The first total 

synthesis successfully reported by De Brabander and co-workers [4] 

and there are hitherto 11 total syntheses and numerous formal 

syntheses for this interesting molecule found in the literature. 

Our group also became interested and jumped onto the 

bandwagon in the attempt to construct the molecule. We embarked 

on our synthetic study with commercially available 

2,6-dihydroxybenzoic acid and effected a hetero-Diels-Alder to 

obtain intermediate 2. We then applied a new methodology 

recently developed in our group, [5] which involves 

Mukaiyama-Michael addition of silyl enol ether that is catalyzed 

by indium trichloride (InCl ), to dihydropyranone at ambient 

3 

temperature to yield the desired, 2,6-anti-tetrahydropyran 

intermediate 3 with high diastereoselectivity.In conclusion, we 

managed to demonstrate the applicability of the methodology 

developed and the total synthesis of Apicularen A is currently still 

underway. 

references: 

1. Kunze, B.; Jansen, R.; Sasse, F.; Hofle, G.; Reichenbach, 

H. J. Antibiot. 1998, 51, 1075. 

2. Jansen, R.; Kunze, B.; Reichenbach, H.; Hofle, G. 

Eur. J. Org. Chem. 2000, 6, 913. 

3. Boyd, M. R.; Farina, C.; Belfiore, P.; Gagliardi, S.; Kim, J. W.; 

Hayakawa, Y.; Beutler, J. A.; McKee, T. C.; Bowman, B. J.; 

Bowman, E. J. J. Pharmacol.Exp. Ther. 2001, 297, 114. 

4. a) Bhattacharjee, A.; Seguil, O. R.; De Brabander, J. K. 


b) Bhattacharjee, A.; De Brabander, J. K. Tetrahedron Lett. 

2001, 42, 1217. 

5. Chua, S.-S.; Alni, A.; Chan, L.-T. J.; Yamane, M.; Loh, T.-P. 

Tetrahedron 2011, 67, 5079. 

Keywords: Synthetic methods; Total synthesis; Michael 

addition; Indium; 

P - 0 8 7 9 

SynthetiC And MeChAniStiC StudieS on 

niCKeL-CAtALyzed C–C Bond forMAtionS 

APPLyinG weLL-defined niCKeL CoMPLexeS 

Modified By tridentAte o,n,o'-LiGAndS 

C. inoue 1 , S. enthALer 1 


1Technical University Berlin, Department of Chemistry, 


Nowadays nickel-catalyzed carbon–carbon bond formations 

have been extensively developed, and have been used in synthesis 

of fine chemicals and natural products. In contrast to well 

established sp2 –sp2 cross coupling reactions, sp3 –sp3 cross 

coupling reactions are more challenging tasks, because of the 

several problems, e.g., β–hydride elimination. [1] One option to 

overcome these problems is the design and fine-tuning of the 

catalyst, which has been demonstrated in a number of studies. 

Nevertheless, the development of novel ligands is still requested 

for improving the catalyst performance. Furthermore the 

understanding of the underlying reaction mechanism is also 

important to advance these reactions. 

Recently we studied the abilities of octahedral nickel 

complexes containing O,N,O?–ligands in coordination chemistry 

and catalysis. [2] Moreover, the octahedral nickel complexes were 

successfully applied as pre-catalyst in cross coupling reactions. 

Hence, we report herein the synthesis and characterization of 

square planar nickel complexes modified by tridentate O,N,O?– 

ligands and a phosphane as an additional ligand, which can be a 

useful probe (e.g., NMR). Moreover, the capability of the 

complexes were investigated in C(sp2 )–C(sp3 ) cross coupling 

reactions of aryl halides with zinc reagents and experiments to 

shed light on the underlying reaction mechanism were performed. 

references: 

1. a) R. Jana, T. P. Pathak, M. S. Sigman, Chem. Rev., 2011, 

111, 1417; 

b) X. Hu, Chem. Sci., 2011, 2, 1867. 

2. a) C. I. Someya, S. Inoue, E. Irran, S. Krackl, S. Enthaler, 

Eur. J. Inorg. Chem. 2011, 2691; 

b) C. I. Someya, S. Inoue, E. Irran, S. Krackl, S. Enthaler, 

Eur. J. Inorg. Chem. 2012, 1269. 

Keywords: Homogeneous catalysis; C-C coupling; Nickel; 

Tridentate ligands; Reaction mechanisms; 



s1303 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 8 0 

PoLy(CArBoSiLAzAne-B-Styrene) – noveL 

hyBrid BLoCK CoPoLyMerS viA SequentiAL 

AnioniC PoLyMerizAtion 

K. inzenhofer 1 , r. KeMPe 2 , G. Motz 1 

1 Universität Bayreuth, Ceramic Materials Engineering, 

Bayreuth, Germany 

2 Universität Bayreuth, Inorganic Chemistry II, Bayreuth, 

Germany 

Novel hybrid diblock copolymers of the type 

poly(carbosilazane-b-styrene) were synthesized via sequential 

anionic polymerization. N-trimethylsilyl-1,1,3,3-tetramethyl-1,3- 

-divinyldisilazane was polymerized in n-hexane using butyl 

lithium as initiator [1] . As obtained living polycarbosilazane chains 

were subsequently used as macroinitiators for the anionic 

polymerization of styrene in a mixture of n-hexane and toluene 

(1:1). Standard methods (IR, NMR, size exclusion 

chromatography (SEC)) were applied for the characterization of 

the obtained polymers. Absolute molecular weights were obtained 

by analysis of SEC eluents with an additional light scattering 

detector. The Flory-Huggins interaction parameter, χ, for the block 

copolymer system was calculated [2] from related homopolymer 

solubility parameters in order to make a theoretical prediction of 

the block copolymer microphase behavior. Polymer films were 

prepared from a variety of solvents and analyzed by microscopic 

methods (scanning electron microscopy, transmission electron 

microscopy, atomic force microscopy). Finally, the accuracy of 

theoretical predictions was assessed by comparison with 

experimental findings. 

references: 

1. Krska, S. W.; Ueno, K.; Seyferth, D. Macromolecules 

1998, 32, (1), 1-9. 

2. Lindvig, T.; Michelsen, M. L.; Kontogeorgis, G. M. Fluid 

Phase Equilibria 2002, 203, (1-2), 247-260. 

Keywords: Block copolymers; organic-inorganic hybrid 

composites; self-assembly; solvent effects; 


P - 0 8 8 1 

PrePArAtion of BiodeGrAdABLe PoLy(LACtiC 

ACid-Co-GLyCoLiC ACid) By LiPASe CAtALyzed 

CoPoLyMerizAtion ProCeSSeS 

i. irSAi 1 , C. MAJdiK 1 

1 Babes-Bolyai University, Chemistry and Engineering 

Chemistry, Cluj-Napoca, Romania 

Poly(lactic acid-co-glycolic acid) was obtained by lipase 

catalyzed copolymerization of L-lactic acid and glycolic acid. The 

structure of poly(lactic acid-co-glycolic acid) was characterized 

by IR, 1H NMR and MALDI-TOF spectrometry. The influence of 

the reaction conditions, such as solvent, temperature and the type 

of lipase was studied to optimize the synthetic procedure. Low 

molecular weight copolymers can be produced from lactic acid 

and glycolic acid by using enzyme lipase B from Candida 

Antarctica (Novozyme 435) at 50 °C in a 5-hour reaction. 

Keywords: biopolymers; enzymatic polymerization; 



s1304 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 8 2 

SeLeCtive ConverSion of KetoneS into 

hydroPeroxideS: froM CrieGee 

interMediAte to AntiMALAriAL tetrAoxAneS 

J. iSKrA 1 

1 Jozef Stefan Institute, Department of Physical and Organic 

Chemistry, Ljubljana, Slovenia 

One of the most famous conversion of ketones into 

hydroperoxide was found during the investigation of 

Baeyer-Villiger oxidation, where Criegee intermediate was 

postulated as an intermediate, although this intermediate in 

reactions with hydrogen peroxide was elusive. [1] Recent 

developments in the preparation of α-heteroatom substituted 

hydroperoxides (gem-dihydroperoxides...) are interesting due to 

their diverse bioactivity. [2] Furthermore they are synthetic 

intermediates for the preparation of various cyclic peroxides via 

cyclization reactions. The most notable example is antimalarial 

activity of cyclic peroxides that are active against the chloroquine 

resistant strains of malarial parasites. [3] 

The most general method for hydroperoxides is the 

ozonolysis of ketone enol ethers or a-olefins in the presence of 

either H 2 O 2 or alcohol, while alternative methods include 

acid-catalyzed peroxidation of ketones or ketals with H 2 O 2 

reaction. The drawbacks of these peroxidations include the need 

for the prior synthesis of the starting substrates, the use of highly 

concentrated H 2 O 2 , the need for excess acid, moderate yields and 

a restricted substrate range. Neutral conditions offers a solution, 

however reactivity of H 2 O 2 is weak – activation with MeReO 3 in 

fluorinated alcohols or with iodine. [4] 

We will present a study on the activation of peroxidation of 

carbonyl compounds by H O without any catalyst, where 

2 2 

activation of reaction occurs at the border between homogenous 

solution and the solvent-free reaction. Furthermore, conditions 

that enables selective mono- or di-hydroperoxidation were 

studied. The relevance of this reaction for the formation of cyclic 

peroxides, as well as connection with Baeyer-Villager oxidation 


references: 

1. Renz, M.; Meunier, B.; Eur. J. Org. Chem. 1999, 737. 

2. Zmitek, K.; Zupan, M.; Iskra, J. Org. Biomol. Chem. 2007, 

5, 3895. 

3. Jefford, C. W. Drug Discovery Today 2007, 12, 487. 

4. Zmitek, K.; Stavber, S.; Zupan, M.; Iskra, J. J. Org. Chem. 

2007, 72, 6534. 

Keywords: Peroxides; Green chemistry; Ketones; O-O 

activation; Solvent effects; 


P - 0 8 8 3 

dihALoiodAteS(i): SyntheSiS with hydroGen 

Peroxide And hALoGenAtinG ACtivity 

J. iSKrA 1 , L. BedrAC 1 

1 Jozef Stefan Institute, Department of Physical and Organic 

Chemistry, Ljubljana, Slovenia 

In organoiodine molecules iodine can be found in different 

oxidation states and forms. Most common are iodine (I) 

compounds, however, iodine is also capable to form stable 

hypervalent compounds, usually as iodine(III) and iodine(V) 

species. [1] Iodine(I) compounds differ in chemistry to iodine(III) 

and (V) compounds and serve mainly as electrophylic iodinating 

reagents (NIS, IPy BF , ICl). 

2 4 

Dichloroiodates(I) are less known analogues, although they 

were used for iodination of aromatics, alkenes, enaminones and 

flavones. Structural analogues of dichloroiodates(I) are 

dibromoiodates(I) and difluoroiodates(I). There is little known on 

chemistry of dihaloiodates(I). According to the literature, 

dichloroiodates(I) are prepared using strong and dangerous 

oxidants i.e. ICl, Cl or hypochlorite. 2 [2] Due to our interest on the 

use of “green” oxidants for oxidative halogenation, [3] we will 

present a study on the use of hydrogen peroxide for oxidation of 

- iodine into iodine(I) compounds (IX salts) with an emphasis on 

2 

a solvent-free method for the preparation of dihaloiodates(I) using 

different forms of hydrogen peroxide for oxidation of iodine in 

the presence of halide ions. In addition, a study on the activity of 

tetraalkylammonium and pyridinium dichloroiodates(I) 

(Alk N 4 + - ICl ) and dibromoiodates(I) (Alk4N 2 

+ - IBr ) as halogenating 

2 

reagents will be presented. 

references: 

1. in, V. V.; Stang, P. J., Chem. Rev. 2008, 108, 5299. 

2. Filimonov, V. D.; Semenischeva, N. I.; Krasnokutskaya, E. A.; 

Ho, Y. H.; Chi, K. W., Synthesis 2008, 401. 

Zefirov, N. S.; Sereda, G. A.; Sosonuk, S. E.; Zyk, N. V.; 

Likhomanova, T. I., Synthesis 1995, 1359. 

Hajipour, A. R.; Arbabian, M.; Ruoho, A. E., J. Org. 

Chem. 2002, 67, 8622. 

3. Podgorsek, A.; Zupan, M.; Iskra, J., Angew. Chem. Int. 

Edit. 2009, 48, 8424. 

Keywords: Halogenation; Iodine; Hypervalent compounds; 

Green chemistry; Oxidation; 



s1305 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 8 4 

new CAtALytiC oxidAtive And therMAL 

rAdiCAL CyCLizAtion APProACheS 

u. JAhn 1 , f. KAfKA 1 , t. AMAtov 1 , M. hoLAn 1 , 

M. GeBAuer 1 , P. JAGtAP 1 


Organic Chemistry and Biochemistry, Prague 6, 


For some time we have been working on oxidative tandem 

approaches combining polar organometallic processes with 

radical reactions. So far these reactions had to be performed using 

stoichiometric amounts of ferrocenium hexafluorophosphate. [1] 

Here we present the first approaches to perform these tandem 

reactions catalytically in the metal oxidant. 

Reactivity limitations of certain substrates in electron 

transfer-induced cyclizations are overcome by performing 

stoichiometric or catalytic oxygenations using TEMPO. The 

resulting alkoxyamines can be transformed subsequently to 

complex ring systems using thermal radical cyclizations 

employing the persistent radical effect. [2] 

references: 

1. Recent examples: 

a) U. Jahn, E. Dinca, Chem. Eur. J. 2009, 15, 58-62. 

b) U. Jahn, E. Dinca, J. Org. Chem. 2010, 75, 4480-4491. 

c) U. Jahn, F. Kafka, R. Pohl, P. G. Jones, Tetrahedron 

2009, 65, 10917-10929. 

2. Reviews: 

a) H. Fischer, Chem. Rev. 2001, 101, 3581-3610. 

b) A. Studer, Chem. Eur. J. 2001, 7, 1159-1164. 

c) L. Tebben, A. Studer, Angew. Chem. Int. Ed. 2011, 50, 

5034-5068. 

d) T. Vogler, A. Studer, Synthesis 2008, 1979-1993. 

Keywords: Radical reactions; Electron transfer; Cyclization; 

Domino reactions; 


P - 0 8 8 5 

PyrAzinAMide derivAtiveS MiCrowAve 

SyntheSiS And their BioLoGiCAL evALuAtion 

o. JAndoureK 1 , M. doLezAL 1 , M. KLeMentová 1 , 

M. veJSová 1 , K. KrALovA 2 


Pharmaceutical Chemistry and Drug Control, Hradec 


2 Comenius University Faculty of Natural Sciences, Institute of 

Chemistry, Bratislava, Slovak Republic 

According to WHO, the number of new tuberculosis cases 

is falling slowly during last years. But new problems have 

appeared with Mycobacterium tuberculosis strains which are 

becoming more resistant to standard treatment (first line drugs as 

well as second line drugs), and with HIV co-infection, which leads 

to quicker spreading of the TBC infection. These complications 

have become an epidemiological problem all over the world [1] . 

Pyrazinamide, which belongs to the first line 

antituberculotic drugs, is very applicable for chemical 

modification and becomes a template for compounds being 

prepared in this research project. 

3-chloropyrazine-2-carboxamide was chosen as a starting 

structure and was treated with a various group of aromatic amines 

(using a microwave reactor with focused field). This reaction 

yielded N-substituted 3-aminopyrazine-2-carboxamides. 

Prepared compounds were purified using flash 

chromatography and then were chemically characterized by 

melting points, IR and NMR spectra, logP, logK and elemental 

analysis. 

Biological tests in vitro were made afterwards. It means 

antimycobacterial screening (various Mycobacterium strains, 

using pyrazinamide and isoniazide as standard), antibacterial and 

antifungal screening (8 bacterial and 8 fungal stems, making use 

of neomycin, bacitracin, penicillin G, ciprofloxacine, 

phenoxymethyl penicillin, amphotericin B, voriconazole, nystatin, 

and fluconazole as standards) and testing for herbicidal activity 

(inhibition of the photosynthetic electron transport in spinach 

chloroplasts with DCMU (Diurone ® ) as a standard – IC ). 50 

A small group of prepared substances has shown herbicidal 

activity, but it has not reached as good activity as standard 

(IC for DCMU is 1.9 µmol/l). 

50 

Acknowledgement: This study was supported by the Grant Agency 

of Charles University (B-CH/710312), by Ministry of Health of 

Czech Republic (IGA NZ 13346) and by Ministry of Education, 

Youth and Sports of Czech Republic (SVV-2012-265-001). 

references: 

1. Progress, WHO Global tuberculosis control report 2011, 

WHO/HTM/TB/2011.16, 

Accessed at: http://www.who.int/tb/publications/ 

/global_report/2011/gtbr11_full.pdf, April 2nd, 2012 

Keywords: Pyrazinamide; Tuberculosis; Microwave; 

Mycobacterium; 



s1306 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 8 6 

SyntheSiS And evALuAtion of noveL fLexiBLe 

And PArtLy ConStrAined LonG-ChAin 

AryLPiPerAzine derivAtiveS of SALiCyLAMide 

AS Serotonin reCePtorS LiGAndS 

J. JASKowSKA 1 , P. KowALSKi 1 , A. BuCKi 2 , 

M. KoLACzKowSKi 2 

1 Cracow University of Technology, Faculty of Chemical 

Engineering and Technology, Kraków, Poland 

2 Jagiellonian University Collegium Medicum, Faculty of 

Pharmacy, Kraków, Poland 

Continuing our previous research concerning structureactivity 

relationship of serotonin receptor ligands representing the 

long-chain arylpiperazines, novel series of ligands was 

synthesized. Our present study concentrated on the influence of 

linker conformation on the in vitro activity in the group of 

synthesized ligands. Structural modifications involved 

replacement of the pentyl and hexyl chain by m-xylene and 

p-xylene moieties, while maintaining O-substituted salicylamide 

and 2-methoxyphenylpiperazine motifs on both sides of the 

modified linker. To check the impact of the modifications on the 

desired pharmacokinetic and pharmacodynamic properties of 

those putative CNS ligands, analysis of their physicochemical and 

structural properties (e.g. Lipinski’s Rule of Five) and probability 

prediction of psychotropic activity by PASS (Prediction of 

Activity Spectra for Substances) was performed. Binding affinity 

for serotonin 5-HT and 5-HT receptors was tested for all the 

1A 7 

synthesized compounds and was also compared with their affinity 

for dopamine D 2 

receptors. The potentially bioactive 

conformation was investigated for the chosen ligand by means of 

molecular modeling techniques. To this end, we selected the most 

preferred conformations by docking the ligands to the binding 

sites of homology models of the receptors of interest. On the basis 

of the results of our structure-activity research, new lead structures 

were identified providing guidelines for further pharmacological 


Keywords: Ligand design; Synthesis design; Molecular 

modeling; Amides; Drug design; 


P - 0 8 8 7 

dinuCLeAr titAniuM CoMPLexeS with 

SuLfAMide LiGAndS AS CAtALyStS for 

hydroAMinoALKyLAtion And 

hydroAMinAtion reACtionS 

d. JASPerS 1 , S. doye 1 

1 University of Oldenburg, Institute of Pure and Applied 

Chemistry, Oldenburg, Germany 

The hydroamination [1] as well as the hydroaminoalkylation [2] 

of alkenes must be regarded as environmentally friendly and 

ecologically desirable processes. For both reactions, 

group-IV-metal complexes have been found to be good catalysts 

but all of them are more or less limited in scope. For that reason, 

much effort has been spent on the identification of new kinds of 

catalysts that allow the efficient addition of N-H or N-C-H bonds 

across C-C double bonds. In search of new ligands for 

Ti-catalyzed hydroaminoalkylation and hydroamination reactions 

we recently focused our work on bis-sulfamide compounds like 

O S(NHR) . A promising synthetic approach towards this class of 

2 2 

ligand precursors was provided by a work from Boncella et al. [3] 

who introduced bis-sulfamides as precursors for chelating diamide 

ligands for the synthesis of tantalum complexes like 

Ta(NMe ) [O S(N-tert-Bu) ]. Herein, we describe the first 

2 3 2 2 

synthesis of a dinuclear Ti-sulfamido complex and its application 

as a catalyst in hydroaminoalkylation and hydroamination 

reactions. In the presence of the catalyst [Ti(NMe ) ] [O S(NPh) ], 

2 3 2 2 2 

various aminoalkenes are converted into the corresponding 

hydroamination products in excellent yields while 

hydroaminoalkylation reactions of alkenes with N-methylamines 

give the desired products only in poor to good yields. 

references: 

1. For a recent review on hydroamination, see: T. E. Müller, 

K. C. Hultzsch, M. Yus, F. Foubelo, M. Tada, Chem. Rev. 

2008, 108, 3795-3892. 

2. Examples of Ti-catalyzed hydroaminoalkylation reactions 

of alkenes can be found in: R. Kubiak, I. Prochnow, S. 

Doye, Angew. Chem. Int. Ed. 2009, 48, 1153-1156. 

3. R. C. Mills, P. Doufou, K. A. Abboud, J. M. Boncella, 

Polyhedron 2002, 21, 1051-1055. 

Keywords: Hydroamination; Hydroaminoalkylation; 

Sulfamide-Ligands; Titanium-catalyzed; 



s1307 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 8 9 

PALLAdiuM funCtionALiSed MiCroSPhereS 

for intrACeLLuLAr CheMiStry 

e. M. v. JohAnSSon 1 , r. M. yuSoP 1 , 

A. unCiti-BroCetA 1 , r. M. SAnChez-MArtin 1 

1 University of Edinburgh, EaStCHEM School of Chemistry, 

Edinburgh, United Kingdom 

Polymeric styrene microspheres have a great potential at the 

interface of chemistry, biology and medicine. Microspheres have 

previously been used in both cellular labelling and intracellular 

delivery of biomaterials. [1, 2] The use of palladium nanoparticles 

entrapped within cross-linked resin beads have been shown to 

operate in a truly heterogeneous catalysis manner. [3] 

In this study the combination of these technologies produced 

a catalyst shown to be both non-cytotoxic and rapidly taken up 

by cells. This provides the basis for the customisation of a 

heterogeneous unnatural catalyst as a tool to carry out chemistry 

never known before inside a cell. The studied reactions include a 

Suzuki-Miyaura cross-coupling reaction for the in situ generation 

of a mitochondria-localized fluorophore. This opens up a wide 

range of possible applications ranging from cellular labelling to 

in cellulo synthesis and specific activation of drugs at specific 

targets and inhibitors of cell function. [4] 

references: 

1. R. M. Sanchez-Martin, M. Cuttle, S. Mittoo, M. Bradley, 

Angew. Chem. Int. Ed., 2006, 45, 5472. 

2. L. M. Alexander, R.M. Sanchez-Martin, M. Bradley, 

Bioconjug. Chem., 2009, 20, 422. 

3. J. K. Cho, R. Najman, T. W. Dean, O. Ichihara, C. Muller, 

M. Bradley, J. Am. Chem. Soc., 2006, 128, 6276. 

4. R. M. Yusop, A. Unciti-Broceta, E. M. V. Johansson, 

R. M. Sánchez-Martín, M. Bradley, Nat. Chem. 2011, 3, 239. 

Keywords: palladium; cell delivery; Fluorescent probes; 


P - 0 8 9 0 

PoLyMorPhiSM of SuCCinoBuCoL And itS 

ConJuGAtion with SteroidS to ALter itS 

druG effeCt And BioAvAiLABiLity 

o. JurCeK 1, 2, 3 , S. iKonen 1 , M. LAhtinen 1 , 

L. BuriCovA 2, 3 , J. horniCeK 4 , A. GALAndAKovA 5 , 

J. uLriChovA 5 , M. wiMMerovA 2 , z. wiMMer 2, 3 , 

P. drASAr 2 , e. KoLehMAinen 1 

1 Laboratory of Organic Chemistry, Department of Chemistry, 

FI-40014 University of Jyvaskyla, Finland 

2 Institute of Chemical Technology, Prague, Technická 5, 16628, 


3 Institute of Experimental Botany, Academy of Sciences of the 

Czech Republic, Isotope Laboratory, Videnska 1083, 14220 


4 Department of Spectroscopy and Physical Organic Chemistry, 

Institute of Organic Chemistry and Biochemistry, Academy of 

Sciences of the Czech Republic, 16610, Prague 6, Czech 

Republic 

5 Palacky University in Olomouc, Institute of Translational and 

Molecular Medicine, Hnevotinska 3, 77515, Olomouc, Czech 

Republic 

Succinobucol, 1, was developed as a drug for treatment of 

atherosclerosis. Later, its range of activity was extended on 

diseases induced by oxidative and inflammatory stress with focus 

on type 2 diabetes. Nevertheless, clinical studies on the drug 

showed mixed results which later lead to the failure of the drug 

in the approval process. Knowing some of the drug’s weak points, 

as low ability to decrease the blood level of cholesterol and low 

bioavailability, we have designed a novel type of plant steroid / 1 

co-drug with the goal to alter its pharmacological profile. Plant 

steroids or their esters are clinically used as agents lowering blood 

level of cholesterol and are known to also have anti-inflammatory 

properties. Prepared conjugates were fully characterized on their 

molecular and submolecular level, [1] preliminarily tested on their 

toxicity, bioavailability and antioxidant activity and based on the 

results were found to be interesting compounds for further studies 

of their biological activity. [2] Furthermore, four different 

polymorphs and one phase mixture of two polymorphs of 1 were 

characterized by spectral and thermoanalytical methods, and a 

coarse estimate of their thermodynamic stability was deduced 

based on the analysis of fresh and aged polymorph samples. [3] We 

still believe that succinobucol possesses some undiscovered 

potential as drug and therefore further research is desirable. 

references: 

1. Ikonen S., Jurcek O., Wimmer Z., Drašar P., 

Kolehmainen E., J. Mol. Struct. 2012, 1011, 25. 

2. Jurcek O., Ikonen S., Buricová L., Wimmerová M., 

Wimmer Z., Drašar P., Hornícek J., Galandáková A., 

Ulrichová J., Kolehmainen E., Molecules 2011, 11, 9404. 

3. Jurcek O., Lahtinen M., Wimmer Z., Drašar P., 

Kolehmainen E., J. Pharm. Sci. 2012, 101, 1794. 

Keywords: Steroids; Antioxidants; Drug Design; 

Polymorphism; Crystal Growth; 



s1308 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 9 1 

wAter-SoLuBLe funCtionAL PorPhyrinS And 

PorPhyCeneS 

n. Jux 1 , w. Brenner 1 , J. MALiG 1 , d. GuLdi 1 


Chemistry & Pharmacy, Erlangen, Germany 

Porphyrins are Nature’s prime choice for electron and 

energy transfer purposes. To do this job properly, the dyes have 

to be embedded in matrices that allow for hierarchical order. 

Often, this ordering generates a redox gradient which increases 

the efficiency of electron transfer processes. Using highly charged 

synthetic porphyrins and dyes, it is possible to build layer-by-layer 

devices in water with alternatingly charged molecules with such 

a gradient. Water as solvent also offers the advantage of strong 

hydrophobic effects such as π-π-stacking for another way to order 

the dyes. Here, we present some of our recent results [1, 2] in this 

field including syntheses of novel functional water-soluble 

porphyrins and porphycenes. 

references: 

1. J. Malig V. Strauss N. Jux, D. M. Guldi, J. Porphyrins 

Phthalocyanines 2011, 15, 1317-1325. 

2. J. Malig, C. Romero-Nieto, N. Jux, D. M. Guldi, Adv. 

Materials 2012, 24, 800-805. 


P - 0 8 9 2 

ModuLAr SyntheSiS And CAtALytiC 

APPLiCAtionS of P-ChirAL Pn-, Pnn- And PnnP- 

PhoSPhine LiGAndS 

n. KAnn 1 , K. h. o. AnderSSon 1 , K. LundBerG 1 , 

M. J. JohAnSSon 1 

1 Chalmers University of Technology, Dept. of Chemical and 

Biological Engineering, Göteborg, Sweden 

Chiral phosphorous-containing ligands are useful tools in 

organometallic chemistry as they have the capability to interact 

with a wide variety of transition metals and can be tailored to 

provide the desired electronic and steric properties. The most 

common residency of chirality in such compounds is on the 

surrounding carbon framework. However, recently P-chirogenic 

phosphines have garnered increased attention as means to prepare 

them have improved. Among such P-chirogenic phosphines, 

mixed PN-type ligands have shown promise in catalysis. We here 

present methodology that provides ready access to different 

P-chirogenic PN, PNN and PNNP-phosphine boranes via a 

modular synthesis with the possibility of varying both the steric 

and electronic properties of the ligands. Applications in ruthenium 

catalyzed hydrogenation are also presented. 

Keywords: asymmetric synthesis; phosphane ligands; chirality; 

ruthenium; hydrogenation; 



s1309 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 9 3 

noveL hyPer And hiGhLyBrAnChed 

PoLy(urethAne-triAzoLe)S 

S. v. KArPov 1 , G. v. MALKov 1 , v. P. LodyGinA 1 , 

e. r. BAdAMShinA 1 

1 Institute of Problems of Chemical Physics RAS, Department of 

Polymers and Composite Materials, Chernogolovka, Russia 

Dendrimers with their unique molecular architecture and 

performances have attracted considerable interests, but processes 

of their synthesis are usually too complicated. Hyperbranched 

polymers (HBP) have similar structure and performances as well 

as dendrimers, but unlike the latter they could be synthesized 

easier. This circumstance is promoted to the development of 

methods of the synthesis of HBP with new combinations of 

functional groups. 

Earlier we have elaborated an approach to the synthesis of 

new urethane-triazole polymers with classic hyperbranched 

structure. It is implemented through two quantitative reaction viz. 

urethane formation and 1,3-dipolar cycloaddition azides and 

alkynes (1,3-DCA). This method consists of three stages. The first 

one is the synthesis of diazidourethaneisocyanate precursor via 

interaction between diazidopropan-2-ol (DAPOL) with an excess 

of diisocyanate to ensure a higher yield. Unreacted diisocyanate 

is separated from the precursor. On the second stage 

diazidoacetylene monomer is obtained by a reaction of a precursor 

with propargyl alcohol, and the third step is one pot synthesis of 

HBP. In such a way purification of monomer can be avoided. 

Inasmuch as synthesis of urethane-triazole HBP is 

complicated because of precursor purification, it is easier to 

synthesize partially cross-linked highlybranched polymers (HP) 

which are similar in their properties to HBP. Urethane-triazol HP 

was obtained by 1,3-DCA from A +B monomers without extra 

2 4 

purification, with diurethanediacetylene as A and 

2 

tetraazidodiurethane as B . The ratio of azide and acetylene groups 

4 

was varied from 2 to 3. 

All synthesized polymers were characterized by 1H-NMR, IR, DSC and SEC. The obtained urethane-triazol HBP and HP are 

yellow solids soluble in polar aprotic solvents. Owing to high 

adhesion to various materials they can be used as addition to 

coatings. Moreover a large number of terminal azide groups allow 

further modification of urethane-triazol HBP and HP; in 

particular, water soluble polymers can be produced. 

Keywords: hyperbranched polymers; highlybranched 

polymers; urethane formation; 1,3-dipolar cycloaddition; 

urethane-triazole; 


P - 0 8 9 4 

MAGnetiCALLy reCoverABLe Cufe o 2 4 

nAnoPArtiCLeS: A CAtALySt for the SyntheSiS 

of AryL AzideS And 1,4-diAryL 1,2,3-triAzoLeS 

froM BoroniC ACidS 

M. Knorn 1 , S. KuMAr 2 , B. SreedhAr 2 , o. reiSer 1 



2 Indian Institute of Chemical Technology, Inorganic and 

Physical Chemistry, Hyderabad, India 

In recent years, application of magnetic nanoparticles has 

attracted great attention in many different disciplines. 

Besides their use in the fields of magnetic fluids, 

biotechnology/biomedicine, magnetic resonance imaging, data 

storage and environmental remediation they are widely used as 

catalysts for organic transformations. Due to their magnetic 

properties they can be easily separated from the reaction mixture 

by applying a magnetic field. This is a practical and efficient 

alternative to filtration or centrifugation as it speeds up the 

isolation and prevents loss of catalyst. 

There are only few literature precedents on 1-aryl-1,2,3- 

-triazoles synthesis using aryl halides, sodium azide, and terminal 

alkynes. These protocols use long reaction times at elevated 

temperature and inert gas atmosphere because of the slow 

azidonation of aryl halides. [1] To overcome these drawbacks, Liu 

et al. developed a copper catalyzed one-pot synthesis of 1-aryl- 

-1,2,3-triazoles from boronic acids in order to replace the aryl 

halides as starting materials. [2] 

To broaden the scope of magnetite based nanoparticles as 

robust and readily available heterogeneous catalyst with high 

surface area, we report a simple, efficient and sustainable 

procedure for the synthesis of aryl azides and a one-pot synthesis 

of 1-aryl-1,2,3-triazoles using CuFe O as magnetically easily 

2 4 

recyclable catalyst. Notably, the reaction is performed under green 

conditions in water at room temperature affording the desired 

products in good to excellent yields. Convenient magnetic 

separation of the catalyst eliminates catalyst filtration after 

completion of the reaction. The high catalytic efficiency of the 

nanoparticles remained unaltered even after five consecutive 

cycles. 

references: 

1. a) Feldman, A. K.; Colasson B.; Fokin, V. V. Org. Lett. 

2004, 6, 3897; 

b) Andersen, J.; Bolvig, S.; Liang, X. Synlett 2005, 2941; 

c) Zhao, Y.-B.; Yan Z.-Y.; Liang, Y.-M. Tetrahedron Lett. 

2006, 47, 1545. 

2. Tao, C.-Z.; Cui, X.; Li, J.; Liu, A.-X.; Liu L.; Guo, Q.-X. 


Keywords: Magnetic Nanoparticles; Nanoparticles; Triazoles; 

Aryl azides; 



s1310 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 9 5 

SyntheSiS of LAte-trAnSition MetAL 

CAtALySt tethered on SiLiCAAnd itS 

L-LACtide PoLyMerizAtion 

y. S. Ko 1 , S. h. KiM 1 , J. S. Lee 1 , J. h. yiM 2 

1 Kongju National University, Department of Chemical 

Engineering, Cheonan, Republic of Korea 

2 Kongju National University, Department of Advanced 

Materials, Cheonan, Republic of Korea 

Plastics are used almost everywhere in the world and more 

environment-friendly plastics are requested from many 

application areas. Polylactide(PLA) is a biodegradable aliphatic 

polyester synthesized from renewable resources, such as corn or 

potato starch. PLA can be prepared by condensation of lactic acid 

and by the ring-opening polymerization(ROP) of the lactide. ROP 

is known to produce PLA with high-molecular weights. Many 

catalysts have been investigated for the polymerization of lactide 

including complexes of aluminum, zinc, tin. In this study, we 

constructed late-transition metal catalysts on the surface of 

nanoporous silica, and examined their performance in L-lactide 

polymerization. The resulting PLLA were characterized by 

FT-IR, DSC and GPC. 

Keywords: L-lactide; Polymerization; Late-transition metal; 

Nanoporous material; 


P - 0 8 9 6 

viSiBLe LiGht Photoredox CAtALySiS AS A 

verSAtiLe tooL for CroSS dehydroGenAtive 

CouPLinG reACtionS 

r. KoeniGS 1 , M. ruePinG 2 

1 Grunenthal GmbH, GI-P-D-MC1, Aachen, Germany 

2 RWTH Aachen, Institute of Organic Chemistry, Aachen, 

Germany 

In recent years, the application of visible light as a 

ubiquitous and renewable source of energy has attracted the 

interest of synthetic organic chemists. While photochemical 

reactions often need to be performed with high-energy UV light, 

the use of sunlight renders photochemical transformations highly 

attractive. [1] 

Inorganic metal poly-bipyridyl complexes possess 

well-known properties and emerged as a highly potent class of 

catalysts for photochemical transformations. In particular, the 

photoexcited states of ruthenium and iridium based polybipyridyl 

complexes were shown to be highly efficient for catalytic 

oxidations of tertiary amines. [2] 

Herein, we wish to present our latest findings on the 

photochemical oxidation of amines that can be efficiently coupled 

with further consecutive transformations for the efficient 

construction of C-C, C-P and C-N bonds. Further applications 

concentrated on the development of efficient dual catalytic 

transformations, relying on photochemical oxidations and 

catalytic C-C bond forming reactions for the convenient 

construction of functionalized amines. [3] 

references: 

1. A. Albini and M. Fagnoni, eds., Handbook of Synthetic 

Photochemistry, Wiley-VCH, Weinheim, 2010. 

2. a) K. Zeitler, Angew. Chem. Int. Ed., 2009, 48, 9785-9789; 

b) J. M. R. Narayanam, C. R. J. Stephenson, Chem. Soc. 

Rev., 2010, 39, 2011, 40, 102-113. 

3. a) M. Rueping, C. Vila, R. M. Koenigs, K. Poscharny and 

D. C. Fabry, Chem. Commun. 2011, 47, 2360-2362; 

b) M. Rueping, R. M. Koenigs, K. Poscharny, D. C. Fabry 

D. Leonori, C. Vila, Chem. Eur. J., 2012, 18, 5170-5174; 

c) M. Rueping, S. Zhu, R. M. Koenigs, Chem. Commun. 

2011, 47, 8679-8681; 

d) M. Rueping, S. Zhu, R. M. Koenigs, Chem. Commun. 

2011, 47, 12709-12711. 

Keywords: Photocatalysis; Organocatalysis; Cross 

Dehydrogenative Coupling; Visible Light; 



s1311 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 9 7 

C3v-SyMMetriC tetrAAMMoniuMtriPtyCene 

derivAtiveS AS verSAtiLe SynthetiC BuiLdinG 

BLoCK – towArdS GiAnt ShAPe-PerSiStent 

MACroCyCLeS And CAGe CoMPoundS 

B. KohL 1 , M. MAStALerz 1 

1 Ulm University, Organic Chemistry II & Advanced Materials, 

Ulm, Germany 

Aminotriptycenes are versatile precursor for the synthesis 

of shape-persistent molecules. For instant, triaminotriptycene is 

used for the synthesis of discrete organic cage compounds [1] , 

whereas the hexaaminotriptycene was used to form molecular 

crystals with extrinsic [2] and triptycene-based metal salphens with 

intrinsic [3] porosities. Beside the synthesis of cyclododeciptycene 

quinone by Hua et al. [4] , MacLachlan et al. [5] proposed a triptycene 

based macrocycle formed by multifold imine condensation 

reaction. However the macrocycle was synthetically not realized 

yet. 

With regard to the suggested macrocycle [5] we developed a 

versatile route for the synthesis of diverse C -symmetrical 

3v 

tetraammoniumtriptycene derivatives to overcome solubility 

issues. The synthesized triptycene derivatives are potential 

precursors for the synthesis of giant macrocycles or cage 

compounds. 

references: 

1. M. W. Schneider, I. M. Oppel, H. Ott, L. G. Lechner, 

H.-J. S. Hauswald, R. Stoll, M. Mastalerz, Chem. Eur. J. 

2012, 18, 836-847. 

2. M. Mastalerz, I. M. Oppel, Angew. Chem. 2012, DOI: 

10.1002/ange.201201174. 

3. J. H. Chong, S. J. Ardakani, K. J. Smith, M. J. MacLachlan, 

Chem. Eur. J. 2009, 15, 11824-11828. 

4. K. Lou, A. M. Prior, B. Wiredu, J. Desper, D. H. Hua, 

J. Am. Chem. Soc. 2010, 132, 17635-17641. 

5. J. H. Chong, M. J. MacLachlan, J. Org. Chem. 2007, 72, 

8683-8690. 

Keywords: macrocycles; 


P - 0 8 9 8 

the SyntheSiS And ProPertieS of new 

CArBAzoLe-ContAininG CoMPoundS 

t. KoMon 1 , z. fLorJAnCzyK 2 

1 Industrial Chemistry Research Institute, Department of 

Proecological Modernization of Technology, Warsaw, Poland 

2 Faculty of Chemistry of Warsaw University of Technology, 

Department of Polymer Chemistry and Technology, Warsaw, 

Poland 

A lot of interest in carbazole-containing compounds 

was caused by the discovery of photoconductivity in 

poly(N-vinylcarbazole) by H. Hoegl. In 1957, he has established 

that PVK sensitized with suitable electron acceptors showed high 

enough levels of photoconductivity to be useful in practical 

applications like electrophotography. As a result of the following 

activities, IBM introduced its Copier I series in 1970, in which an 

organic photoconductor, the charge transfer complex of PVK with 

2,4,7-trinitro fluorenone was used for the first time. 

The ongoing peak of interest in carbazole-containing 

compounds in connected mostly with the discovery of polymeric 

light emitting diodes and organic photorefractive materials. Apart 

from electrophotographic photoreceptors, light emitting diodes 

and photorefractive materials carbazole-containing compounds 

are studied as components of photovoltaic devices. In all these 

fields of application of their ability to transport positive charges 

(holes) are exploited. 

In this work, the reaction of carbazole with triethylaluminum 

has been studied and in the next step product of this reaction has 

been exposed to cyclic anhydrides and other heterocyclic 

compounds (esters, carbonates) in order to examine the direction 

of ring opening and to initiate polymerization. 

The reaction of carbazole with triethylaluminum formed 

diethyl(N-carbazolyl)aluminum, which undergoes aggregation 

and occurs in dimeric form. Monomer and dimer in solution 

are in equilibrium, and their proportion vary depending 

on temperature and concentration. The reaction of 

diethyl(N-carbazolyl)aluminum with cyclic anhydrides, esters or 

carbonates followed by ring opening and incorporation of 

compound between aluminum and nitrogen. Additionally, in an 

easily polymerization cyclic esters such as ε-caprolactone and 

lactide, followed by initiating polymerization. Acid hydrolysis of 

the reaction mixture can be obtained from the reaction of cyclic 

anhydrides - acids, and the reaction of cyclic esters or carbonates 

- alcohols, which in its structure contains carbazole. 

Keywords: carbazole; triethylaluminum; anhydrides; cyclic 

esters; 



s1312 

chem. Listy 106, s257–s1425 (2012) 


P - 0 8 9 9 

SyntheSiS of AroMAtiCS viA the C-C Bond 

ACtivAtion 

A. KorotviCKA1 , M. KotorA1 1 Charles University in Prague Faculty of Science, Department 


Whereas different methods for creation of new C–C bonds 

are basic elements in organic synthesis, procedures which use 

cleavage of such bonds are not very common. Synthetic approach 

based on the C–C bond cleavage can be conveniently applied on 

strained carbocycles such as cyclopropanes and cyclobutanes, 

because it is driven by release of the ring strain.. 

Biphenylene is a typical compound bearing the strained 

cyclobutane ring. Therefore it easily undergoes oxidative addition 

with many transition metal complexes (Ir, Rh, Ni, Co, Fe, Pd, Pt) 

forming metallacyclopentanes [1] . We focused on the catalytic 

cycloaddition of biphenylene with alkynes and nitriles in the 

presence of iridium and rhodium complexes. Through this 

method a large number of substituted phenanthrenes 

(including ferrocenylphenanthrenes) and phenanthridines (new 

methodology) were synthesized [2] . The reaction of biphenylene 

proceeded even with sterically hindered diferrocenylacetylene 

giving rise to the corresponding 9,10-diferrocenylphenanthrene 

in a good isolated yield (42%). Our alkyne insertion procedure 

was also applied on the more complexed system such angular 

[3]phenylene exclusive and unexpected selectivity of the course 

of the reaction was observed (addition from the sterically 

disfavoured side). 

references: 

1. T. Shibata, G. Nishizawa, K. Endo, Synlett 2008, 5, 

765–768. 

2. A. Korotvicka, I Císarová, J. Roithová, M. Kotora, Chem. 

Eur. J. 2012, in press. 

Keywords: iridium; Rhodium; C-C activation; 


P - 0 9 0 0 

SyntheSiS of PALLAdiuM(ii) CoMPLex with 

2-(PhenyLSeLenoMethyL)tetrAhydroPyrAn 

M. KoStiC 1 , v. divAC 1 , n. rAdenKoviC 1 , 

z. BuGArCiC 1 


Serbia 

The use of organoselenium compounds as ligands in 

transition metal coordination chemistry has deserved special 

attention, in part as a result of the recognition that they may confer 

significantly different properties on the resultant complexes [1] . 

In addition, many organoselenium compounds play important 

roles in biochemical processes, ranging from antioxidant, to 

anticancer and antiviral activities [2] . 

In order to study biological activity, Pd(II) complex with 

2-(phenylselenomethyl) tetrahydropyran as ligand was 

synthesized. It is noteworthy to mention that this kind of ligand 

compounds can be easily obtained in high yields via 

phenylselenoetherification of corresponding unsaturated alcohols 

in the presence of additives, such as pyridine [3] . For synthetic 

procedure, PdCl and ligand were used in ratio 1:1. Single crystals 

2 

were obtained after slow evaporation of complex compound from 

ethanol/methanol solvent system. The crystal and molecular 

structure of the complex [Pd(L) )]Cl has been determined by 

2 2 

X-ray diffraction. It turned out that two ligands are coordinated 

to the Pd via Se atom in trans-fashion and the other two trans 

position are occupied by Cl atoms. 

references: 

1. E.G. Hope, W. Levason, Coord. Chem. Rev. 1993, 122, 109. 

2. G. Mugesh, W. du Mont, H. Sies, Chem. Rev. 2001, 101, 2125. 

3. Z. M. Bugarcic, B. M. Mojsilovic, V. M. Divac, J. Mol. 

Cat. A: Chem. 2007, 272, 288. 

Keywords: selenium; heterocycles; palladium; 



s1313 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 0 1 

SynthetiC StudieS towArd SeLeCtive And 

StABLe inhiBitorS of dnA PoLyMerASe ALPhA: 

CArBoCyCLiC AnALoGS of dehydroALtenuSin 

S. KovACovA 1 , K. PAruCh 1 

1 Masaryk University, Department of Chemistry, Brno, Czech 

Republic 

DNA polymerases play a key role in replication and 

maintaining of genome stability and some of them can help cancer 

cells tolerate DNA damage. Their selective inhibition is therefore 

considered viable strategy for therapeutic intervention in 

oncology. [1] Accordingly, depletion of DNA polymerase alpha (pol 

alpha) combined with inhibition of CHK1 kinase afforded 

synthetic lethal phenotype in cancer cells. [2] 

Dehydroaltenusin is virtually the only known 

sub-micromolar selective inhibitor of pol alpha [3] that exhibited 

in vivo biological activity (include mice HeLa xenograft model). [4] 

However, the mechanism of action and potential usefulness of 

dehydroaltenusin are rather questionable as the compound is 

unstable and in polar solvents it exists as equilibrium mixture of 

two species: tricyclic lactone and its spirocyclic isomer. [5] 

We have prepared racemic carbocyclic analogs of both 

forms of dehydroaltenusin. The target structures as well as some 

of the key intermediates contain novel, potentially useful 

pharmacophores. As the compounds are chemically stable, they 

could serve as appropriately robust chemical biology probes and 

good starting points for further medicinal chemistry optimization. 

references: 

1. Lange, S. S.; Takata, K.; Wood R. D. Nat. Rev. Cancer 

2011, 11, 96. 

2. Parry, D. A.; Taricani, L. PCT Int. Appl.WO2008/063558. 

3. Ljungman M. Chem. Rev. 2009, 109, 2929. 

4. Naoki Maeda et al. Biochem. Biophys. Res. Commun. 

2007, 352, 390. 

5. Kamisuki S. et al. Bioorg.Med. Chem. 2004, 12, 5355. 

Keywords: Medicinal chemistry; Inhibitors; Spiro compounds; 


P - 0 9 0 2 

SuPerBASe ProMoted StereoSeLeCtive 

Azetidine SyntheSiS 

e. KovACS 1 , G. turCzeL 1 , f. ferenC 1 



Hungary 

Email: erkovacs@mail.bme.hu 

In the framework of an ongoing research project optically 

active 2-3-disubstituted oxetanes were prepared in our laboratory 

via superbase induced enantioselective rearrangements of chiral 

benzyloxymethyl oxiranes [1, 2] . From these oxetanes pyrrolidine 

derivative can be formed from in three steps [3] . 

Starting from that findings, our new aim was the further 

investigation of the stereoselective intramolecular rearrangement 

reaction with the intetntion to get azetidine derivatives. First we 

prepared oxirane derivatives which are substituted with 

benzylaminomethyl group instead of benzyloxymethyl function. 

These compounds were treated with LIDAKOR superbase. 

The reaction provided the desired new azetidine derivatives 

containing the ring substituents in trans position, exclusively. The 

1-methyl-2-phenyl-3-(1-(trimethylsilyloxy)-2-(trityloxy)ethyl)azetidine 

was prepared by TMSCl from the 1-(1-methyl-2-phenylazetidin- 

-3-yl)-2-(trityloxy)ethanol. Now we try to prepare pyrrolidine 

derivatives from this compound. 

The derivatives of the synthesized compounds can be 

valuable intermediates of drugs in pharmaceutical research [4] , and 

can be used as chiral ligands in enantioselective catalytic 

reactions. 

This work is connected to the scientific program of the 

“Development of quality-oriented and harmonized R+D+I 

strategy and functional model at BME” project. This project is 

supported by the New Hungary Development Plan (Project ID: 

TÁMOP-4.2.1/B-09/1/KMR-2010-0002) and was carried out in 

the framework of a bilateral scientific cooperation between the 

Hungarian Academy of Sciences and CNR Italy. 

references: 

1. A. Mordini, S. Bindi, S. Pecchi, A. Degl’Innocenti, 

G. Reginato, A. Serci: J.Org.Chem.,61, 4374 (1996) 

2. A. Thurner, F. Faigl, L. Toke, A. Mordini, M. Vallachi, 

G. Reginato, G. Czira: Tetrahedron, 57, 8173 (2001) 

3. E. Kovács, A. Thurner, F. Farkas, F. Faigl, L. Hegedus, 

Journal of Molecular Catalysis A, 339, 32 (2011) 

4. US4622327 patent 

Keywords: superbase; rearrangement; enantioselective 

synthesis; heterocycles; azetidines; 



s1314 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 0 3 

deSiGn And APPLiCAtion of new 

iMidAzoLyLSuLfonAte BASed Benzyne 

PreCurSor: An effiCient trifLAte 

ALternAtive 

S. KovACS 1 , A. i. CSinCSi 1 , t. z. nAGy 1 , i. BoroS 2 , 

G. tiMári 2 , z. nováK 1 


Hungary 

2 Sanofi, Chinoin Zrt, Budapest, Hungary 

Arynes are reactive intermediates due to their strained 

structure caused by the presence of distorted triple bond in the six 

membered carbacycle. This exotic compound class can be 

transformed efficiently in nucleophilic or electrophilic reactions, 

in pericyclic reactions and in transition metal catalyzed reactions. 

To exploit the advantages of imidazolylsulfonates over triflates 

we aimed to design new benzyne precursor family for organic 

syntheses. 

Several o-(trimethylsilyl)aryl imidazolylsulfonates were 

synthesized in a simple process and successfully applied in 

cycloadditions involving benzyne intermediates. The precursor 

offers an efficient alternative for generating benzynes compared 

to widely used ortho TMS triflates under similar reaction 

conditions. With the utilization of this new precursor, the 

formation of potentially genotoxic trifluoromethanesulfonate side 

product is eliminated. Applicability of the new benzyne precursor 

was demonstrated in different type of cycloaddition reactions to 

prepare heterocyclic molecules. 

references: 

1. Kovács, Sz.; Csincsi, I. Á.; Nagy, Zs. T.; Boros, S.; 

Timári, G.; Novák, Z. Org. Lett., 2012, 14, 2022-2025. 

Keywords: Arynes; Cycloaddition; 

P - 0 9 0 4 

SyntheSiS of 7-AryL- And 

7-(AMinoAryL)GuAnineS 

A. KrALiK 1 , i. LinhArt 1 




Position N7 at guanine is a prominent site of attack by 

electrophiles in the DNA. Various electrophilic compounds can 

bind to this position in vivo causing DNA damage. Therefore, 

7-alkyl- and 7-arylguanines are needed as analytical standards for 

studies on the DNA damage by mutagens and carcinogens. 

N2-(Dimethylaminomethylene)guanine has been described 

previously as a suitable guanine precursor affording 

predominantly 7-arylderivatives by reaction with arylboronic 

acids in the presence of copper(II) ions (Keder et al., 2009). 

We used this procedure for synthesis of 7-(3,4- 

-Dihydroxyphenyl)guanine, which was prepared by 

treating N2-(dimethylaminomethylene)guanine with 

3,4-dimethoxyphenylboronic acid and subsequent deprotection. 

The same substrate was used for synthesis of 

7-(2-aminophenyl)guanine and 7-(4-aminophenyl)guanine. 

In this case, N2-(dimethylaminomethylene)guanine was arylated 

by corresponding fluoronitrobenzene. Predominating N7-isomer 

was separated from its mixture with N9-isomer, amino group 

deprotected by hydrolysis and, finally, the nitro group was reduced 

with hydrogen on palladium to afford 7-(aminophenyl)guanine in 

moderate yield. 

Arylation of N2-(dimethylaminomethylene)guanine by 

fluoronitroarenes seems to be a promising synthetic route to 

7-(aminoaryl)guenines. 

references: 

1. Keder, R., H. Dvoráková, D. Dvorák, Eur. J. Org. Chem. 

2009, 2009, 1522-1531. 

Keywords: arylation; arylguanines; DNA adducts; 



s1315 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 0 5 

towArdS the totAL SyntheSiS of BetiCoLin 0 

C. KrAMer 1 , S. BräSe 1 



Background: Beticolins are mycotoxins produced by the 

phytopathogen Cercospora beticola and are responsible for the 

leaf spot disease (cercosporiosis) on sugar beet. Biological studies 

on Beticolins revealed a broad cytotoxic profile by the interaction 

with different cellular targets and the ability to dimerize to nonspecific 

ion channels. All Beticolins share the same unique 

polycyclic carbon skeleton consisting of a mono-chlorinated 

xanthone- and a tetrahydro-anthraquinone subunit. Both subunits 

are forming a hydrophobic bicyclo[3.2.2]nonane ring system what 

is a distinguished structural feature of this natural product class. 

results: In spite of their unique structure and their broad 

biological profile, any synthetic studies towards the synthesis of 

beticolins were not published yet. Preliminary experiments 

revealed that the anthraquinone moiety (A,B,C-ring-system) and 

the quarternary center of Beticolin can be constructed by a quinoid 

Diels–Alder reaction. This reaction can be enabled either by 

irradiation or by the use of organocatalysts. Using the latter, the 

asymmetric synthesis of the tricyclic unit is currently examined 

by the application of enantiopure catalysts. The formation of the 

unique bicyclo[3.2.2]nonane ring-system via a metal-catalyzed 

cross-coupling reaction is also under current investigation. The 

completion of the carbon skeleton of Beticolin 0 should be 

accomplished by the synthesis of the remaining tetrahydroxanthenone 

moiety with a domino-Oxa–Michael-aldol-reaction. 

Conclusion: Synthetic efforts provided access to 

the A,B,C-ring system of Beticolin. These results are also 

of importance for the synthesis of the biosynthetically 

related xanthoquinodins and acremoxanthones. 

Keywords: Natural Products; Cytotoxicity; 


P - 0 9 0 6 

SyntheSiS of 5-ALKyLidene-1,2,5,6- 

-tetrAhydroPyridin-2-oneS reLAted to 

GeLAStAtinS 

J. KrAtoChviL 1 , e. MAtouSovA 1 , o. KrenK 1 , 

J. KuneS 1 , M. Pour 1 

1 Charles University Faculty of Pharmacy, Inorganic and 

Organic Chemistry, Hradec Kralove, Czech Republic 

Email: kratj5aa@faf.cuni.cz 

Compounds with 5,6-dihydro-2H-pyran-2-one skeleton 

occur in nature and possess wide range of biological activities 

from antibacterial effects to cytotoxicity [1] . Given these interesting 

properties, our research in recent years was focused on gelastatins 

A and B [2] . These molecules (isolated from Westerdykella 

multispora) have shown the ability to inhibit gelatinase A, a 

metalloproteinase participating on degenerative inflammatory 

processes and penetration of tumour cells into healthy tissues [3] . 

Over the past few years, our group has synthesized 

3,5-disubstituted 5,6-dihydro-2H-pyran-2-ones with an alkylidene 

substituent at C5 [4] , which possess interesting cytostatic activity. 

Regrettably, these compounds suffer from low stability. The 

purpose of this work has been to develop the synthesis of 

analogous lactams, which should be more stable and also more 

water-soluble than their lactone counterparts and investigate their 

chemical properties as potential Michael acceptors. 

Acknowledgements: This work is generously supported by the 

Grant Agency of Charles University (No. 0255/2010) and the 

“Centre for New Antivirals and Antineoplastics” founded by the 


(1M0508). 

references: 

1. Herz, W. et al. Fortschritte Der Chemie Organischer 

Naturstoffe / Progress in the Chemistry of Organic 

Natural Products / Volume 75, Birkhäuser, 1998 

2. Lee H.-J. et al. Ann. NY Acad. Sci. 1999, 878, 635 

3. Kim E. J., Ko S. Y. Bioorg. Med. Chem. 2005, 13, 4103 

4. Pavlik J., Snajdr I., Kunes J., Spulak M., Pour M. J. Org. 

Chem. 2009, 74, 703 

Keywords: Lactams; Nucleophilic addition; Palladium; 



s1316 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 0 7 

SyntheSiS of ferroCene-BASed MoLeCuLAr 

wireS 

n. KrAuSSe 1 

1 Institut für Organische Chemie, Leibniz Universität Hannover, 

Hannover, Germany 

Email: holger.butenschoen@mbox.oci.uni-hannover.de 

Molecular wires of the oligo(phenylene ethynylene) (OPE) 

type have rigid structures with fixed molecular lengths. To 

introduce limited conformational flexibility we are interested in 

replacing some 1,4-phenylene units by 1,1'-ferrocenylidene 

groups. Different molecular wires with two or three ferrocene 

units with tert-butylsulfanyl groups as anchoring groups were 

obtained via Sonogashira coupling reaction or Negishi coupling 

[1, 2] reaction. 

In search for different anchoring groups we noted that 

Wandlowski reported about molecular wires with nitrile groups. [3] 

First examples for nitrile-terminated molecular wires based on 

ferrocene have recently been prepared. 

references: 

1. J. Ma, M. Vollmann, H. Menzel, S. Pohle, H. Butenschön, 

J. Inorg. Organomet. Polym. 2008, 18, 41–50. 

2. I. Baumgardt, H. Butenschön, Eur. J. Org. Chem. 2010, 

1076–1087. 

3. A. Mishchenko, L. Zotti, D. Vonlanthen, M. Bürkle, 

F. Pauly, J. Cuevas, M. Mayor, T. Wandlowski, 

J. Am. Chem. Soc. 2011, 133, 184–187. 

Keywords: Ferrocene; OPE; Molecular Wire; 


P - 0 9 0 8 

APPLiCAtion of ChirAL rutheniuM CAtALyStS 

in enAntioSeLeCtvie oLefinMetAtheSiS 

C. Kuhn 1 , C. huLot 1 , d. SChLeSiGer 1 , A. BerGer 1 , 

S. BLeChert 1 

1 Technical University Berlin, Institute of Chemistry, Berlin, 

Germany 

The development of chiral Ru-based olefin metathesis 

catalysts to obtain high enantioselectivities has been shown to be 

a challenge in the field of asymmetric olefin metathesis. Recently 

we reported the development of highly active and chiral Ru-based 

metathesis catalysts with high stability which show excellent 

results in asymmetric ring-opening cross metathesis (AROCM) 

as well as in enantioselective ring-rearrangement metathesis 

(eRRM). 

Various cross partners such as allylsilanes, allyl alcohol, 

allyl chloride and allyl tert-butyl carbonate can be used in the 

AROCM of norbornene derivatives providing products with high 

E-selectivity and excellent enantioselectivities up to 93%ee. The 

AROCM products with allyl silanes can further be transformed 

in a Sakurai reaction into highly enantiomerically enriched 

bicyclo[3.2.0]heptanones with 4 stereogenic centers which 

contain a new built 4-membered ring. 

Ring-rearrangement metathesis is a well-known and 

powerful method to construct complex carbo- and heterocycles in 

a domino process that has been used in several natural product 

syntheses. Nevertheless efficient enantioselective RRM still 

remain challenging. 

Here the first examples of asymmetric Ene-Yne-RRM based 

on chiral Ru-metathesis catalysts were performed providing 

excellent enantioselectivities up to 94%ee giving 

tetrahydropyridines selectively. 

Keywords: metathesis; domino reactions; ruthenium; 

enantioselectivity; regioselectivity; 



s1317 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 0 9 

SyntheSiS And ProPertieS of unique 

ArendiAzoniuM SALtS with LiPoPhiLiC 

nAture 

K. KutonovA 1 , P. Petunin 1 , M. truSovA 1 , 

P. PoStniKov 1 , v. fiLiMonov 1 

1 Tomsk Polytechnic University, Biotechnology and 

Organic Chemistry, Tomsk, Russia 

Arenediazonium salts are widely used in classical organic 

synthesis and in the preparation of modern organic 

nanocomposites and the grafting of organic molecules onto 

metallic or non-metallic surfaces. A new type of diazonium salts 

– arendiazonium dodecylsulfonates (ADDS) was firstly obtained 

by diazotization of aromatic amines in the presence of 

dodecylsulfonic acid at room temperature with 50-80 % yields. 

ADDS have unique solubility in both polar and nonpolar 

(benzene, hexane, tetrachloromethane) solvents and stability in 

dry state and in solutions. The lipophilic nature of ADDS can open 

new possibilities for usage of diazonium compounds in organic 

synthesis. 

ADDS have typical diazonium nature, giving the products 

of azo-coupling and aryliodides by the reaction with KI in 

quantitative yields. Also their high reactivity in C-C-coupling 

reaction was demonstrated. Thus, a new method of olefins 

arylation in water in the presence of palladium catalysts under 

microwave irradiation with excellent yields of target products was 

proposed. 

In conclusion, a new arenediazonium dodecylsulfonates as 

a previously-unknown class of diazonium salts was prepared in a 

pure, dry state. Due to their unique amphiphilic nature it is firstly 

possible to carry out diazonium reactions in nonpolar media in 

the absence of phase-transfer catalysts. Because of their stability, 

they can be stored safety for a long time. It is especially interesting 

that these salts reveal good solubility in nonpolar solvents and 

high reactivity in a typical reaction of diazonium salts and 

C-C-coupling reactions. 

Keywords: Diazo compounds; Amphiphiles; C-C coupling; 


P - 0 9 1 0 

SPeCtAtor ferroCenyL SuBStituent: PKAS of 

PLAnAr ChirAL Pyridine orGAnoCAtALyStS 

C. M. LAM1 , A. C. o’donoGhue1 1 Durham University, Department of Chemistry, Durham, 


Leading the advances in new asymmetric methodology, Fu 

and co-workers developed planar chiral organocatalysts derived 

from 4-(dimethylamino)pyridine. The coupling of a ferrocenyl 

group to a pyridine ring introduced asymmetry into the system 

and this has proved to be highly efficient, high yielding, and most 

importantly, highly enantioselective for a range of reactions. [1] 

As part of a mechanistic investigation of the role of these 

organocatalysts in several transformations routes to additional 

derivatives of the catalyst with varying substituents at the 

4-position of the pyridine ring were developed. These include the 

4-methoxy, 4-chloro and the unsubstituted parent catalyst. 

The pK values for the conjugate acids of the pyridine- 

a 

ferrocenyl catalyst and novel analogues in dry dimethyl sulfoxide 

and acetonitrile have been measured employing a UV-Vis 

spectrophotometric bracketing buffer method. [2] Due to rapid 

decomplexation of the conjugate acid forms of novel analogues 

the application of stopped-flow spectrophotometry was required 

to determine the pK s rather than conventional UV-Vis 

a 

spectrophotometry. 

pK values from 12.8 to 19.9 were recorded in acetonitrile 

a 

and 3.3 to 10.3 in dimethyl sulfoxide. A comparison of the 

measured pK s for the pyridine-ferrocenyl catalysts with 

a 

analogous achiral pyridinium ions revealed no significant effect, 

consistent with a spectator role for the ferrocenyl substituent on 

pK . The role of ion pairing and addition of up to 5 vol% H O on 

a 2 

the pK was also assessed. 

a 

These pK values may be used in a Bronsted analysis of 

a 

arylalkyl ketene-nucleophilic addition reactions catalysted by 

these planar chiral pyridine organocatalysts for the purpose of 

mechanistic evaluation. 

references: 

1. Fu, G. C. Acc. Chem. Res. 2004, 37, 542. 

2. P. Christ, A. G. Lindsay, S. S. Vormittag, J. Neudorfl, 

A. Berkessel, A. C. O’Donoghue. Chem. Eur. J. 2011, 17, 

8524–8528 

Keywords: Bronsted acid-base; Organocatalysis; Asymmetric 

catalysis; Reaction mechanisms; UV-Vis spectroscopy; 



s1318 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 1 1 

funCtionALized veSiCLeS in MoLeCuLAr 

reCoGnition - viSuALizAtion And BindinG 

AffinitieS 

t. LAnG 1 , B. KÖniG 1 

1 Institute of Organic Chemistry, Chemistry, Regensburg, 

Germany 

Non-covalent interactions of receptors and ligands at 

liposomal surfaces are very similar to recognition processes at 

biological membranes. Molecular recognition on such membranes 

is often governed by dynamic multivalent interactions. Based on 

previously reported vesicular chemosensors for the recognition of 

small biomolecules, [1] we currently focus on more complex 

liposomal systems with different artificial binding sites for the 

dynamic recognition of multivalent target molecules. 

The visualization and determination of binding affinities of 

such multi-receptor surfaces requires a lot of different methods 

and techniques. 

For the visualization of liposomes we use dynamic light 

scattering (DLS), fluorescence microscopy, atomic force 

microscopy (AFM) and cryogenic temperature transmission 

electron spectroscopy (Cryo-TEM). 

For the determination of binding affinities between doped 

liposomes and suitable analytes fluorescence based binding assays 

are already established very well. Besides we developed a surface 

plasmon resonance (SPR) based assay for the determination of 

binding constants for the interaction between functionalized 

surfaces and proteins, peptides and other analytes. 

references: 


B. König, Ang. Chem. Int. Ed. 2010, 49, 7125. 

Keywords: liposomes; molecular recognition; supramolecular 

chemistry; surface chemistry; metal complexes; 


P - 0 9 1 2 

the BioSyntheSiS of MurAyMyCinS: SyntheSiS 

of PotentiAL interMediAteS for StudieS on 

the ASSeMBLy of CoMPLex nAturAL ProduCtS 

A. LeMKe 1 , A. P. SPorK 1 , C. duCho 2 

1 Georg-August University Göttingen, Organic and 

Biomolecular Chemistry, Göttingen, Germany 

2 University Paderborn, Chemistry, Paderborn, Germany 

The Streptomyces-produced muraymycins (e.g. muraymycin 

A1), a subclass of nucleoside antibiotics, are potent inhibitors of 

bacterial cell wall biosynthesis. [1] Due to their structural 

complexity, the synthesis of new muraymycin analogues is 

challenging. Detailed investigations on the biosynthesis of this 

important family of natural products could provide access to new 

muraymycin derivatives through fermentation-based production 

of unusual building blocks, such as the non-proteinogenic amino 

acid epicapreomycidine, a cyclic arginine derivative. The 

biosynthesis of the 3-epimer of epicapreomycidine, 

capreomycidine, has been elucidated and utilises (3S)-3-hydroxy- 

-l-arginine as an intermediate. [2] Thus it is proposed that 

3-hydroxy-l-arginine also serves as an intermediate in the 

biosynthesis of epicapreomycidine and therefore also in the 

formation of muraymycins in Streptomyces. Both potential 

intermediates (3R)-3-hydroxy-l-arginine and (3S)-3-hydroxy-l- 

-arginine have been synthesised using a novel route suitable for 

multiple isotope labelling. [3] 

Recently, the gene cluster for muraymycin biosynthesis has 

been identified, sequenced and analysed by Cheng et al. 

Homology studies led to a proposed pathway for muraymycin 

biosynthesis. [4] Using both diastereomers of isotope-labelled 

3-hydroxy-l-arginineand other potential intermediates this outline 

proposal can be tested experimentally. 

references: 

1. L. A. McDonald, L. R. Barbieri, G. T. Carter, E. Lenoy, 

J. Lotvin, P. J. Petersen, M. Siegel, G. Singh, 

R. T. Williamson, J. Am. Chem. Soc. 2002, 124, 

10260–10261. 

2. J. Ju, S. G. Ozanick, B. Shen, M. G. Thomas, 

ChemBioChem 2004, 5, 1281-1285. 

3. A. Lemke, M. Büschleb, C. Ducho, Tetrahedron 2010, 66, 

208–214. 

4. L. Cheng, W. Chen, L. Zhai, D. Xu, T. Huang, S. Lin, 

X. Zhou, Z. Deng, Mol. BioSyst. 2011, 7, 920-927. 

Keywords: Antibiotics; Amino acids; Biosynthesis; Isotopic 

labeling; Nucleosides; 



s1319 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 1 3 

SyntheSiS of PoLyoxoMetALAte-PoLyMer 

hyBridS viA rAft PoLyMerizAtion 

J. LeSAGe de LA hAye 1 , J. rieGer 2 , L. ruhLMAnn 3 , 

B. hASenKnoPf 4 , e. LACôte 5 


2 University Pierre and Marie Curie, LCP, Ivry, France 

3 University Paris-Sud 11, LCP, Orsay, France 

4 University Pierre et Marie Curie, IPCM, Paris, France 

5 Institut de Chimie des Substances Naturelles, ICSN, Gif-sur- 

Yvette, France 

Organic hybrids of polyoxometalates (POMs) - molecularly 

defined, anionic nanosized metal oxygen clusters of highly 

oxidized early transition metal cations (W, Mo, V) – have attracted 

considerable interest over the past few years due to their specific 

properties. 

This work aims at the synthesis of POM-polymer conjugates 

which can be obtained by two strategies. In the first one, the 

« grafting to » approach, the polymer is firstly synthesized and 

then covalently linked to the POM (post-functionalization). [1, 2] 

The second approach, the « grafting from » one, is based on 

polymer growth from a POM-based initiator. [3] To date, there are 

three different POM-polymer hybrids reported, obtained by 

controlled radical polymerization. [1, 2, 3] 

Here, we focus on the synthesis of thermoresponsive 

polyoxometalate-polymer hybrids, via Reversible 

Addition-Fragmentation Chain Transfer (RAFT) polymerization 

using a « grafting from » approach (Scheme 1). We worked on 

Dawson-type polyoxometalates, which were functionalized with 

a trithiocarbonate reactive group. This precursor was used to 

synthesize conjugates containing different polymer lengths. The 

thermoresponsive properties of the conjugates in water were 

studied. 

references: 

1. S. Chakraborty, A. Keightley, V. Dusevich, Y. Wang, 

Z. Peng, Chem. Mater. 2010, 22, 3995. 

2. J. Rieger, T. Antoun, S-H. Lee, M. Chenal, G. Pembouong, 

J. Lesage de la Haye, I. Azcarate, B. Hasenknopf, 

E. Lacôte, Chem. Eur. J. 2012, 18, 3355. 

3. Y. Han, Y. Xiao, Z. Zhang, B. Liu, P. Zheng, S. He, 

W. Wang, Macromolecules 2009, 42, 6543. 

Keywords: Polyoxometalates; polymerization; aggregation; 

polymers; Organic-inorganic hybrid composites; 


P - 0 9 1 4 

totAL SyntheSiS of fuSAriSetin A 

A. Li 1 , J. denG 1 , B. zhu 1 , z. Lu 1 , h. yu 1 

1 Shanghai Institute of Organic Chemistry Chinese Academy 

of Sciences, State Key Laboratory of Bioorganic and Natural 

Products Chemistry, Shanghai, China 

The first total synthesis of (-)-fusarisetin A, the enantiomer 

of naturally occurring acinar morphogenesis inhibitor 

(+)-fusarisetin A, was accomplished, leading to the reassignment 

of the absolute configuration of the natural product. The synthesis 

featured a Lewis acid-promoted intramolecular Diels-Alder 

reaction, a Pd-catalyzed O?C allylic rearrangement, a 

chemoselective Wacker oxidation, and a Dieckmann 

condensation/hemiketalization cascade. 

Keywords: total synthesis; cell migration/invasion inhibitor; 

intramolecular Diels-Alder; Wacker oxidation; Pd-catalyzed 

O?C allylic rearrangement; 



s1320 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 1 5 

SoLid StAte PhotoPoLyMerizAtion of A 

ShAPe-PerSiStent MACroCyCLe with two 

1,8-diAzAAnthrACene unitS to A riGid-rod 

PoLyMer in the SinGLe CryStAL 

M. Li 1 , A. d. SChLüter 1 , J. SAKAMoto 1 

1 ETH Zurich, D-MATL, Zürich, Switzerland 

A shape-persistent macrocyclic monomer with two opposing 

1,8 diazaantharcene photoreactive units is polymerized in the 

single crystal by photochemically induced [4 + 4]-cycloaddition 

reaction between neighboring monomers in which the 

diazaanthracene units are face-to-face stacked at the critical 

Schmidt-distance. The severe structural changes associated with 

this are compensated by the monomer design whereby the linkers 

between the two opposing 1,8-diazaanthracenes are connected to 

the 1 and 8 positions of the latter. It is those sites whose spatial 

positioning suffers the least change during dimerization and thus 

helps keeping the monomer’s overall shape basically unchanged 

during polymerization. The resulting new rigid-rod polymer is 

soluble in its protonated form and can be depolymerized after 

counter ion exchange with a surfactant in an organic solvent upon 

relatively mild thermal treatment (120 °C) back into monomer. 

Keywords: Solid state photopolymerization; rigid-rod polymer; 

diazaanthracene; depolymerization; 


P - 0 9 1 6 

noveL BodiPy LABeLLed CyCLodextrin ProBe 

A. LiPPACh 1 , M. SChnABeL 1 , G. wenz 1 


Saarbrucken, Germany 

Fluorescence labels have nowadays a wide field of 

application, ranging from analytical chemistry, molecular biology 

and biotechnology to medical applications. Due to the high 

sensitivity, fluorescence phenomena are the methods of choice for 

studying processes such as release kinetics of agents in cells. 

Numerous different classes of fluorescent dyes have been 

established over the years. Among them 4,4-difluoro-4-bora- 

3a,4a-diaza-s-indacene (BODIPY) based dyes are widely used 

because of their chemical and physical stability, high molar 

extinction coefficients and fluorescence quantum yields, sharp 

absorption and emission bands. [1] One disadvantage is their poor 

solubility in water. 

Cyclodextrines are cyclic oligosaccharides, which possess 

a hydrophilic exterior and a hydrophobic cavity: They form easily 

inclusion complexes with appropriate hydrophobic guest 

molecules in aqueous media. [2] 

We report here on the synthesis, characterization and 

possible applications of a novel BODIPY labelled cyclodextrin 

derivative, with high solubility in water and very interesting 

fluorescence properties. The labelling reaction causes a 

considerable blue shift of both the absorption and emission 

maxima of the dye, which offers an easy method for observing 

the successfulness of the reaction. This new fluorescence probe 

can be used to study the properties and behaviour of inclusion 

complexes with optical inactive guest molecules in various 

environments. 

references: 

1. N. Boens, V. Leen, W. Dehaen, Chemical Society Reviews 

2012, 41, 1130-1172. 

2. G. Wenz, Angewandte Chemie International Edition in 

English 1994, 33, 803-822. 

Keywords: Cyclodextrin; Bodipy; Fluorescence; 



s1321 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 1 7 

noveL hiGhLy LuMineSCent PoLyMerS 

A. LiPPACh 1 , G. wenz 1 


Saarbrücken, Germany 

Luminescent polymers are of great scientific and industrial 

importance for example for the production and improvement of 

organic light emitting diodes (OLED). [1] 

We describe the synthesis and characterization of several 

new pi-conjugated, fluorescent polymers. The macromolecules 

contain electron rich arylether and/or electron poor aromatic 

N-hetereocycles such as pyrazine. Good solubility in common 

organic solvents is achieved by using long alkyl or 

oligoethylenglykol groups. The polymers are built up by a 

combination of Horner-Wadsworth-Emmons-, Sonogashira 

reaction and/or Glaser-coupling of several different 

buildingblocks. The macromolecules show interesting absorption 

and emission wavelengths and an overall good solubilities. 

Due to their centro-symmetrical structure and the presence 

of donor and acceptor groups these polymers are hopefully good 

candidates for two-photon exited fluorescence. 

references: 

1. A. C. Grimsdale, K. Leok Chan, R. E. Martin, P. G. Jokisz, 

A. B. Holmes, Chemical Reviews 2009, 109, 897-1091. 

Keywords: Oled; Polymers; Fluorescence; 


P - 0 9 1 8 

trAnSforMAtion of inorGAniC hALoGenS to 

ChLorinAted hydroCArBonS By enzyMeS 

S. LouKotovA 1 , S. t. forCzeK 1 , z. wiMMer 1 

1 Institute of Experimental Botany CAS, Isotope Laboratory, 


Biogeochemical cycle of chlorine, particularly formation of 

organically bound chlorine (Cl ), is still known only in outlines. 

org 

In continental ecosystems chloride acts as stress factor, and also 

as source of chlorine; it originates from precipitation, which 

comes from marine cloud masses. Cl are formed naturally by 

org 

biotical and abiotical way. The biological factors are 

microorganisms, soil enzymes, plants and even animals. 

Halogenation processes undergo in marine environment as well, 

the main difference is the presence of bromine besides chlorine, 

therefore the reaction and formation of brominated compounds. 

One group of Cl represents volatile chlorinated hydrocarbons 

org 

(VOCl). Several VOCl can react with atmospheric ozone, 

consequently causing its depletion. The best known sources of 

VOCl are soil, the microorganisms living in it, and their 

exoenzymes released into it. 

The heme peroxidases in the group EC 1.11.1 can perform 

halogenation of organic compounds. Hydrogen peroxide or 

organic peroxides are the substrates of this reaction in which 

hypochlorous acid is generated. The halogen in reactive form then 

carries chlorine onto the organic compound. 

To study enzymatic mediation of chlorination processes, we 

chose commercially available enzymes (chloroperoxidase from 

Caldariomyces fumago and horseradish peroxidase). To 

concentrate the formed analytes, we used solid-phase 

microextraction (SPME) method or cryofocusing method, 

followed by GC-ECD or GC-MS analysis. 

The formation of VOCl was confirmed in experiments, 

where enzyme, citric acid buffer, halogen ions (KBr, NaCl) and 

substrates (acetic acid, aceton) were present. Contrary to the 

literature, both enzymes formed chlorinated and brominated 

volatile compounds. The main volatile organic chlorinated 

compounds were chloroform, bromoform, trichloroethylene, 

tetrachloroethylene, halogenated methane derivatives and 

aliphatic compounds. The formation was dependent on the length 

of the enzyme reaction. 

Acknowledgement: We thank the endowment of Czech Science 

Foundation P503/11/0616. 

Keywords: chlorine; gas chromatography; halogenation; 

enzyme catalysis; bromine; 



s1322 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 1 9 

noveL 1,2,3-triAzoLe funCtionALized 

PentACene CoMPoundS: SyntheSiS And 

ChArACterizAtion 

d. LuMPi 1 , B. hoLzer 1 , e. horKeL 1 , C. hAMetner 1 , 

J. frÖhLiCh 1 



Organo-electronic materials have gained raising scientific 

and commercial interest in recent years due to various advantages 

compared to inorganic semi-conductors. [1] Outstanding electronic 

properties of acenes, relying on the topology of the π-systems, led 

to intense research efforts on this compound class. [2] In particular 

pentacene proved to be a benchmark p-type organic 

semiconductor for applications such as organic field effect 

transistors (OFETs) and organic photovoltaics (OPVs). [1] In the 

recent years Anthony et al. revealed that also the functionalization 

of acene derivatives results in highly efficient semi-conductive 

[1, 2] 

materials by improved molecular stacking. 

Typical drawbacks of acenes are the relatively low solubility 

(which is of great technological interest) and stability (e.g. 

oxidation and dimerization) of these compounds. [2, 3] Hence, it was 

shown that the attachment of electron withdrawing groups to the 

6- and 13-position of pentacene significantly improves the 

stability towards oxidative processes. [3] 

In this contribution we focus on the symmetric 

bis-functionalization of the pentacene moiety with 1,2,3-triazole 

moieties in the 6- and 13-positions. As previously described in the 

course of investigations on nonlinear optical (NLO) materials the 

1,2,3-triazole moiety exhibits interesting electron accepting 

properties. [4] Thus, the effects on stability, solubility and molecular 

arrangement (examined also in OFET devices) are content of this 


The synthetic concepts are based on the application of 

organo-lithium mediated procedures, SnCl assisted aromatization 

2 

and Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC), one of 

the most popular reactions in the click chemistry concept, [5] 

yielding the target compound starting form readily available 

6,13-pentacenequinone. 

references: 

1. J.E. Anthony, Functional Organic Materials Syntheses, 

Strategies and Applications, ed. T.J.J. Mueller, U.H.F. 

Bunz, Wiley-VCH,Weinheim, 2007, ch.14, 511–545. 

2. J.E. Anthony, Angew.Chem.,Int. Ed., 2008, 47, 452–483. 

3. K. Ono, et al., TetrahedronLett., 2007, 63, 9699–9704. 

4. D. Lumpi, et al., CrystEngComm., 2011, 13, 7194–7197. 

5. H.C. Kolb, M.G. Finn, K.B. Sharpless, 

Angew. Chem.,Int.Ed., 2001, 40, 2004–2021. 

Keywords: pentacene; triazole; ofet; click; 


P - 0 9 2 0 

A Modern APProACh towArdS the SyntheSiS 

of [18]AnnuLene 

d. LunGeriCh 1 , n. Jux 1 , P. v. r. SChLeyer 2 

1 Friedrich-Alexander-University Erlangen-Nuremberg, Institut 

für Organische Chemie, Erlangen, Germany 

2 University of Georgia, Center for Computational Chemistry, 

Athens, USA 

As of this writing, only two successful syntheses towards 

[18]annulene were reported. The first was reported in 1962 by 

Sondheimer and Wolovsky, starting from 1,5-hexadiyne in three 

steps and 0.6% overall yield. 

The second synthesis was reported in 1970 by Figeys and 

Gelbcke in five steps, starting from propargyl alcohol to yield 

0.42% [18]annulene. 

Although determined by X-ray structure, the structure of 

[18]annulene remains controversially discussed by many 

scientists. Therefore, we developed a new and efficient route 

towards [18]annulene. This three-step synthesis is not only more 

practical and safer in today’s laboratories, but also increases the 

yield by more than 700% compared to earlier published routes. 

Starting from cis-1,2-dichloroethene, we utilized the Sonogashira 

cross-coupling reaction to produce TMS-protected hexaenediyne, 

which is then deprotected and trimerized in one pot to 

hexadehydro[18]annulene. The reduction via Lindlar-catalyst 

gives the target molecule in 4.4% overall yield. Although we 

cannot show definite prove, we provide experimental and 

computational evidences that a lower symmetry, such as D or 3h 

C , appears more realistic for [18]annulene rather than 

2 

D -symmetry. 

6h 

Keywords: Annulenes; Aromaticity; Cross-coupling; 



s1323 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 2 1 

BithioPheneSiLAne-BASed dendritiC 

MACroMoLeCuLeS: SyntheSiS And ProPertieS 

y. LuPonoSov 1 , S. PonoMArenKo 1 , n. rASuLovA 1 , 

n. Surin 1 , e. MALtzev 2 , d. LuPenKo 2 , 

A. MuzAfArov 1 


Sciences, Laboratory of Functional Materials for Organic 

Electronics and Photonics, Moscow, Russia 

2 Institute of Physical Chemistry and Electrochemistry Russian 

Academy of Sciences, Laboratory, Moscow, Russia 

Dendrimers are unique organic materials, which combine 

highly branched regular arrangement of functional organic 

moieties within one macromolecule having typical dimensions of 

1 to 10 nm. Oligothiophenesilane dendrimers are known for their 

efficient molecular antenna effect [1] , as well as intensive 

photoluminescence in the violet-blue region, the quantum yields 

of which are significantly higher than those measured for their 

constituent luminophores themselves [2] . The main drawback of the 

high-molecular weight dendrimers is their multistage synthesis, 

which limits their practical applications. This problem may be 

solved by the synthesis of dendronized polymers. These unique 

materials combine the properties of both dendrimers and 

polymers. They are currently are under intense investigation with 

respect to various applications, including the synthesis of 

hierarchically structured materials, catalysis, applications in the 

biosciences, such as ion channel mimics and DNA 

compactization, as well as optoelectronic applications [3] . We report 

here the synthesis and investigation of several generations of 

bithiophenesilane-based dendrimers and dendronized polymers [4] 

as well as preliminary application of the most perspective 

molecules in organic light-emitting diodes. 

Acknowledgement: This work was supported by the Program of 

President of Russian Federation (grant MK-1567.2011.3) and 

by the Presidium of Russian Academy of Sciences 

(Program No. 24). 

references: 

1. Luponosov, Y.N., Ponomarenko, S.A., Surin, N.M., 

Borshchev, O.V., Shumilkina, E.A., Muzafarov, A.M. 

Chem. Mater. 2009, 21, 447. 

2. Luponosov, Y.N., Ponomarenko, S.A., Surin, N.M., 

Muzafarov. A.M. Org. Lett., 2008, 10, 2753. 

3. Frauenrath H. Prog. Polym. Sci. 2005, 30, 144-150. 

4. Ponomarenko, S. A., Rasulova, N. N., Luponosov, Y. N., 

Surin, N. M., Buzin, M. I., Leshchiner, I., Peregudova, S. M., 

Muzafarov. A. M. Macromolecules, 2012, 45, 2014. 

Keywords: dendronized polymers; dendrimer; luminescence; 


P - 0 9 2 2 

new CArBoCyCLiC nuCLeoSide AnALoGS 

L. MAier 1 , o. hyLSe 1 , K. PAruCh 1 

1 Masaryk University, Department of Chemistry, Brno, Czech 

Republic 

Nucleoside analogs encompass a variety of biologically 

active compounds, namely those with antiviral and anticancer 

properties. Significant efforts have been invested in order to 

prepare nucleoside analogs possessing new structural motifs [1] . 

Carbocyclic nucleoside analogs have been particularly attractive 

as the tetrahydrofuran moiety can often be replaced with more 

metabolically stable carbocycles without significant loss of 

activity [2] . Nevertheless, cyclopentane nucleoside analogs 

(especially those with the base attached via C-C linkage) are quite 

rare and most published syntheses produced only single target 

compounds [3] . 

Of biologically active carbocyclic nucleoside analogs, 

pseudoisocytidine proved active against cytarabine-resistant 

leukemias and showed resistance toward deamination mediated by 

cytidine deaminase [4] , but its hepatotoxicity (of unknown origin) 

in humans halted the clinical progression [5] . We have synthesized 

the direct carbocyclic analog of pseudoicytidine and additional 

compounds with differently substituted pyrimidine base parts. 

In addition, we have developed flexible synthesis of 

cyclopentane nucleoside analogs possessing tertiary OH at the 

1'-position. Unlike the tetrahydrofuran-containing analogs, the 

compounds are chemically robust. Our methodology enables 

selective manipulation of individual positions around the 

cyclopentane ring. 

references: 

1. Modified Nucleosides in Biochemistry, Biotechnology and 

Medicine; Herdewijn, P.; Ed.; Wiley-VCH, 2008. 

2. Lutz, S.; Benner, S. A. Nucleic Acids Res. 1999, 27, 2792. 

3. Zhu, X. F. Nucleosides Nucleotides and Nucleic acids, 

2000, 19, 651. 

4. Burchenal, J. H. et al. Cancer Res. 1976, 36, 1520. 

5. Woodcock, T. M. et al. Cancer Res. 1980, 40, 4243. 

Keywords: nucleosides; synthetic methods; drug design; 



s1324 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 2 3 

An oxidAtive CouPLinG route to 

MACroCyCLiC thioPheneS And itS 

APPLiCAtion in the SyntheSiS of A 

donor/ACCePtor hyBrid MoLeCuLe 

S. MAier 1 , S. S. JeSter 1 , S. hÖGer 1 

1 Kekulé Institute, Ak Höger, Bonn, Germany 

Thiophene-containing macrocycles are known for their 

unique optoelectronic properties and their ability to form 

supramolecular structures. [1] Yet, their synthesis is difficult, and 

ring closure is rarely performed at the thiophene sites themselves. 

Here we present a cyclooligomerization approach towards 

macrocyclic thiophenes via direct oxidative coupling of 

unfunctionalized thiophenes. [2] 

The synthetical concept was applied to prepare a thiophene 

macrocycle with covalently attached perylenbisimide units. In this 

donor/acceptor hybrid structure a highly efficient electron transfer 

can be induced by optical excitation of either one of the 

subunits. [3] The molecule forms supramolecular 2D assemblies at 

the solid/liquid interface that were investigated by scanning 

tunnelling microscopy. Chain-like structures were observed, 

consistent with strong stacking interaction of adjacent 

perylenebisimide units. 

references: 

1. M. Fritzsche, A. Bohle, D. Dudenko, U. Baumeister, 

D. Sebastiani, G. Richardt, H. W. Spiess, M. R. Hansen, 

S. Höger, Angew. Chem. Int. Ed. 2011, 50, 3030. 

2. S. K. Maier, S.-S. Jester, U. Müller, W. M. Müller, 

S. Höger, Chem. Commun. 2011, 47, 11023. 

3. A. Marchanka, S. K. Maier, S. Höger, M. van Gastel, 

J. Phys. Chem. B 2011, 115, 13526. 

Keywords: Cyclooligomerization; Donor-acceptor systems; 

Macrocycles; Electron Transfer; Self-assembly; 


P - 0 9 2 4 

SenSinG fLuoride with tren reCePtorS 

throuGh eLeCtroStAtiC interACtionS And 

hydroGen BondinG 

t. MäKeLä 1 , M. LAhtinen 2 , K. riSSAnen 1 




Finland 

Developing a receptor for fluoride anion is challenging task 

because of its high hydration energy, small ionic radius and 

hardness as Lewis base making fluoride sensing difficult 

particularly in aqueous environment. [1] Due to these still unresolved 

challenges scientific community is pursuing to develop more 

specific and stronger receptors for fluoride. 

In this study we have developed simple TREN 

[tris(2-aminoethyl)amine] based aromatic receptors having three 

amide groups and three nitro-functionalized aromatic rings. 

Receptors are synthesized with microwave-assisted method using 

previously reported tripodal molecules that has been shown to 

bear the ability to bind fluoride. [2] Binding is achieved via preorganization 

of the receptor, amide group mediated hydrogen 

bonds and electrostatic interactions. The binding process has been 

studied with variety of methods both in solvent and solid states. 

The interaction between the receptor and the fluoride anion is 

clearly seen for example by NMR measurements. 

Even though these receptor are demonstrated to bind 

fluoride in polar aprotic DMSO which is suitable media for anion 

recognition, similar kinds of receptors could possibly be used for 

fluoride recognition also in aqueous environment. There is 

ongoing study in our laboratory to develop this receptor-type 

further and to reach the ultimate goal in fluoride sensing, 

recognize it in water. 

references: 

1. Cametti, M.; Rissanen, K. Recognition and sensing of 

fluoride anion. Chem. Commun. 2009, 2809-2829. 

2. Ravikumar, I.; Lakshminarayanan, P. S.; Ghosh, P. Anion 

binding studies of tris(2-aminoethyl)amine based amide 

receptors with nitro functionalized aryl substitutions: 

A positional isomeric effect. Inorg. Chim. Acta 2010, 363, 

2886-2895. 

Keywords: Anion recognition; Fluoride; 



s1325 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 2 5 

AnioniC PoLyMerizAtion of 

ePSiLon-CAProLACtone initiAted By ethyL 

MAGneSiuM BroMide 

L. MALinovA 1 , J. BrozeK 1 

1 Institute of Chemical Technology, Department of Polymers, 


Poly(ε-caprolactone) is well-known biocompatible and 

biodegradable polymer which can be prepared by either of 

ring-opening polymerizations of ε-caprolactone using a variety of 

anionic, cationic and coordination initiators. The best known 

initiators of the ε-caprolactone polymerization are aluminum 

tri(isopropoxide) and tin(II) 2-ethylhexanoate with co-initiator 

(mostly an alcohol). Magnesium compounds are used as initiators 

in the ε-caprolactone polymerization like magnesium lactate, 

magnesium octoate, magnesium alkoxides etc. 

We have focused on the study of solution polymerization of 

ε-caprolactone initiated by ethyl magnesium bromide which is 

rather neglected in literature. The ε-caprolactone polymerization 

was carried out in dry toluene at 0 and 25 °C and at two 

monomer/initiator ratios (250 and 500) in order to describe 

polymerization course. For comparison, we also proceeded a 

reference solution polymerization of ε-caprolactone initiated by 

tin(II) 2-ethylhexanoate. Polymerizations initiated by ethyl 

magnesium bromide proceeded by a living fashion and, in the 

initial phase of the process molar mass was controlled by the 

monomer/initiator ratio. The polymer in the initial phase of the 

process has a narrow molar mass distribution. This is explained 

by the formation of the complex of magnesium initiator with 

carbonyl groups of ε-caprolactone and polyester formed which 

suppresses both intra- and intermolecular side reactions. The 

isolation and characterization of the magnesium/ε-caprolactone 

complex supports suggested mechanism of polymerization. 

Acknowledgement: This work was financially supported from 

specific university research (MSMT No. 21/2012) and grant 

No. 106/09/1378 of Grant agency Czech Republic. 

Keywords: polymerization; kinetics; magnesium; 


P - 0 9 2 6 

SyntheSiS of the erythrinA ALKALoid 

eryBidine By A PhotoCheMiCAL CyCLizAtion 

And itS StereoCheMiCAL AnALySiS 

M. MALter 1 , A. SPeiCher 1 

1 Saarland University, Organic Chemistry, Saarbrücken, 

Germany 

Biaryl natural compounds are a widespread substance class 

with numerous pharmacological applications. Furthermore, they 

often show axial chirality. These are reasons why these 

compounds become increasingly important. [1] 

Erythrina alkaloids are natural products found in the leaves 

of Erythrina bidwillii. Erybidine was shown to be 

5,6,8,9-tetrahydro-2,11,12-trimethoxy-7-methyl-dibenz[d,f]azonin- 

-3-ol. [2] This compound contains a biaryl axis, which offers the 

possibility of a non-obvious chirality. We investigated if the 

compound forms two atropoisomers due to inhibited rotation 

around the biaryl axis with only two ortho-substituents but 

additional ring strain. 

We improved the synthesis of Erybidine formerly described 

in the literature. [3] The amide-coupling-step is changed and a 

photochemical intramolecular coupling with a 100 W high 

pressure mercury lamp yielded three different products. One of 

them gave rise to Erybidine. 

The stereochemical behaviour of Erybidine at the biaryl axis 

was examined by racemization experiments and MD studies. Due 

to the two ortho-substituents and the cyclic structure of Erybidine 

free rotation around the biaryl axis is limited. Separation of the 

two atropoisomeres was effected by HPLC on a chiral column. 

Furthermore, the ring-size of the aza moiety plays an important 

role. 

references: 

1. G. Bringmann, C. Günther, M. Ochse, O. Schupp, 

S. Tasler, in: Progress in the Chemistry of Organic 

Natural Products 82, Springer, Wien, New York, 2001. 

2. K. Ito, H. Furukawa, H.Tanaka, T. Rai, Yakugaku Zasshi, 

1973, 94, 1617 

3. K. Ito, H. Tanaka, Chem. Pharm. Bull., 1974, 22, 2108 

Keywords: natural products; alkaloids; axial chirality; 



s1326 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 2 7 

Cu–vinyLPhoSPhonAte reveALinG 

SeMiConduCtor eLeCtriCAL BehAvior 

B. MArAneSCu 1 , A. viSA 1 , v. MArAneSCu 2 , G. iLiA 1 , 

M. MrACeC 3 

1 Institute of Chemistry Timisoara of Romanian Academy, 

Organic Chemistry, Timisoara, Romania 

2 University “Politehnica” of Timisoara Faculty of Electronics 

and Telecommunications, Applied Electronics, Timisoara, 

Romania 

3 Institute of Chemistry Timisoara of Romanian Academy, 

Computational Chemistry, Timisoara, Romania 

Starting from the X ray experimental data for 

Cu-vinylphosphonate (VP-Cu), a theoretical study was performed 

using cuanto-chemichal calculus using PM3 semiempirical 

method under Hyperchem 7. Strategy was based built models or 

extracted models from X ray data. From geometrical analysis, for 

VP-Cu it was observed that bonding lengths of C-C and Cu-O 

were all similar with the values found in literature [1] . Cu-Ow bonding lengths were slightly underestimated compared to X ray 

experimental data. From electronic properties of VP-nCu (n=2, 

3, 4, 8), structures used as models to build VP-Cu compound, it 

was observed that the lowest LUMO-HOMO energetic difference 

is 2.933eV for VP-3Cu, revealing a potential semiconductor 

behavior. 

For electrical conductivity measurements, a setup was built 

using a screw-nut type polyamide insulated fixture embedding 

two sliding conductive electrodes. The exact compound thickness 

between electrodes was confirmed by using an electronic 

microscope. For faster humidity and temperature settling of the 

compound, radial holes were practiced in electrodes area. 

Measurements conditions were provided by a climatic 

chamber, and performed after 1h settling time for each 

combination between temperatures in 25–90°C range and relative 

humidity in 50–95% range. For conductivity measurement it was 

used cyclic voltammetry at low and fast speed. As voltage current 

dependence was found to have a linear dependence, independent 

on voltammetry speed, it was concluded that conduction takes 

place using electrons. By representing Arrhenius plot for 

conductivity it was possible to extract activation energy which 

was close to the cuanto-chemical estimated value, thus proving 

semiconductor behavior of the compound. Increasing conductivity 

with relative humidity indicates also potential applications for 

humidity sensors, and further experiments will determine 

electrical conductivity settling time versus humidity variations. 

references: 

1. D.A. Knight, V. Kim, R.J. Butcher, B.A. Harper, 

T.L. Schull, J. Chem. Soc., Dalton Trans., 2002, 824 

Keywords: Metal-organic frameworks; Semiconductors; 


P - 0 9 2 8 

new extended PoLyCondenSed AroMAtiC 

hydroCArBon of the C60 CLASS 

S. MArtin CABA 1 , t. A. Jenny 1 

1 University of Fribourg, Chemistry, Fribourg, Switzerland 

Alkyl-substituted tribenzo[fg,ij,rst]pentaphenes (TBP) 

represent versatile polycondensed aromatic hydrocarbon building 

blocks exhibiting pronounced π-π stacking properties [1] . Best 

positions for placing the solubilizing alkyl side chains were 

determined by theoretical studies on the π-π stacking behavior. 

This investigations yielded exact geometries for minimum 

energies of stacked dimers. 

A convenient synthesis for a 15,16-disubstituted derivative 

involves a Diels-Alder reaction between phencyclone and 

8-hexadecyne followed by a classical Scholl oxidation under 

Kovacic conditions (FeCl /CH NO in CH Cl at r.t.) of the 

3 3 2 2 2 

resulting diheptyl-diphenyl-terphenylene [2] . We were surprised to 

find that in this specific case intermolecular oxidative 

dimerization predominates over intramolecular aryl-aryl coupling, 

since we observe a triply connected completely oxidized dimer 

as a major product even before complete consumption of the 

starting material. The observation of a singly linked starting 

molecule as well as a singly linked but otherwise fully oxidized 

dimer (for which a 5,5'-link could be deduced from the 1H-NMR spectrum), permitted us to propose a reaction sequence for this 

surprising transformation and to attribute a structure to the triply 

connected fully oxidized dimer, which otherwise failed to yield 

interpretable NMR spectra. Interestingly emission spectroscopy 

proved to be a sensitive tool since even slightest changes, 

e.g. concerning the location of side chains, were reflected in subtle 

changes of the emission spectra [3] . 

references: 

1. Grimme, S. Angew. Chem. Int. Ed. 2008, 47, 3430. 

2. Kovacic, P.; Koch, F. W. J. Org. Chem. 1963, 28, 1864. 

3. Alameddine, B.; Caba, S. M.; Schindler, M.; Jenny, T. A. 

Synthesis 2012, 44, 1928. 

Keywords: Polycycles; C-C coupling; Pi interactions; Fusedring 

systems; Dehydrogenation; 



s1327 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 2 9 

fLuoreSCenCe AniSotroPy of Bi - 

CyCLo[1.1.1]PentAne/oLiGoPhenyL-BASed rodS 

inCLuded in triS(o-PhenyLenedi oxy)CyCLo - 

triPhoSPhAzine 

M. MASAt 1 , M. CiPoLLoni 1 , J. KALetA 1 , J. MiChL 1 



Motion of rod-like molecules included into the channels of 

hexagonal (tris-o-phenylenedioxy)cyclotriphosphazine (TPP) 

have been examined in the past by NMR techniques. We now 

report an examination of this motion by fluorescence anisotropy 

measurements with time resolution in the fs range as a function 

of temperature, using suspensions of nanocrystals of TPP loaded 

with 0.02 - 2% of the guests. The included molecular rods, 

specially synthesized for the purpose, contained a fluorophore 

(such as quaterphenyl or pyridazine) held between two bulky 

groups (such as 1,3-disubstituted bicyclo[1.1.1]pentanes), which 

were found to fix the orientation of the long axis along the TPP 

channel direction. At high guest loadings, concentration 

depolarization interfered with the interpretation of the 

measurements, but in highly diluted samples this interference 

disappeared and the long molecular axis was found to exhibit no 

detectable motion, allowing us to focus on rotation around it. 





also supported by the Academy of Sciences of the Czech 

Republic RVO: 61388963. 

Keywords: UV/Vis spectroscopy; Molecular rotors; 

Fluorescence anisotropy; 


P - 0 9 3 0 

CoMBinAtoriAL SyntheSiS And evALuAtion of 

A-iMinoCArBoxAMide-niCKeL (ii) CAtALyStS 

for the CoPoLyMerizAtion of ethyLene And 

A PoLAr MonoMer 

h. MASui 1 , S. fuSe 1 , t. tAKAhAShi 1 

1 Tokyo Institute of Technology, Department of Applied 

Chemistry Graduate School of Science and Engineering, 

Tokyo, Japan 

α-Iminocarboxamide structure is found in a lot of functional 

molecules. In particular, α-iminocarboxamide-nickel (II) complex 

has attracted much attention in recent years as a catalyst for the 

copolymerization of ethylene with functionalized monomers. The 

polymerization activities of this catalyst vary from small 

differences of functional groups in α-iminocarboxamide. 

However, combinatorial optimization of substituents has not been 

reported. We anticipated that the highly active catalyst could be 

discovered through constructing a combinatorial library consisting 

of a-iminocarboxamides with systematically modified 

substituents. Herein we wish to report the development of the 

efficient synthetic method of α-iminocarboxamides, and the 

evaluation of the ethylene polymerization and copolymerization 

activities of a-iminocarboxamide-nickel (II) catalysts prepared 

from synthesized a-iminocarboxamides. 

We plan to synthesize α-iminocarboxamide by two routes. 

First route involves an amidation of the α-ketoacid chloride and a 

subsequent imination of the obtained ketone. Second route 

involves a three-component coupling of alkyl samarium (III) with 

isocyanide and isocyanate. 

The amidation and imination conditions were efficiently 

optimized by using parallel synthesizers. By utilizing 

the optimized conditions, 87-membered library of 

α-iminocarboxamide was successfully synthesized. Next, we 

have investigated one-pot three-component coupling approach. 

To our delight, the one-pot three-component coupling reaction 

of alkyl samarium (III) with isocyanide and isocyanate 

afforded α-iminocarboxamides in excellent yields. 

We also investigated ethylene polymerization and 

copolymerization activities of α-iminocarboxamide-nickel 

complexes by using the synthesized ligands. Nickel catalysts were 

prepared from synthesized a-iminocarboxamides according to a 

previously reported procedure, after some modification. The crude 

catalysts were used for the evaluation of polymerization activities 

of alkenes, without further purification for the sake of throughput 

improvement. Activities of the prepared catalysts for ethylene 

polymerization and copolymerization were efficiently evaluated 

by using a parallel synthesizer. 

Keywords: Combinatorial Chemistry; a-Iminocarboxamide- 

Nickel(II) Catalyst; Lab-Automation; Multi-component 

Reaction; 



s1328 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 3 1 

MonodiSPerSe LineAr oLiGoMerS of uP to 

38 nM LenGth 

r. MAy 1 , S. S. JeSter 1 , S. hÖGer 1 

1 Kekulé Institute, Ak Höger, Bonn, Germany 

Email: hoeger@uni-bonn.de 

Conjugated shape-persistent arylene-alkynylene oligomers 

are discussed as one-dimensional molecular wires and as 

building blocks for supramolecular materials as well as for 

two-dimensional adlayers on surfaces. [1] Dodecyl-substituted 

p-phenylene-butadiynylene tetramers are obtained via stepwise 

synthesis using the polar 3-cyanopropyl diisopropyl silyl 

protective group. Statistical oligomerization under Glaser 

coupling conditions of the deprotected tetramer and subsequent 

recycling gel permeation chromatography for separation of the 

crude products allow an efficient access to monodisperse 

oligomers of distinct oligomerization degree in sufficient 

quantities. 

Here we present an approach towards monodisperse 

shape-persistent oligo(phenylene-butadiynylene)s of up to 38 nm 

length. Self-assembled monolayers of these molecules at the 

liquid/solid interface (here: 1,2,4-trichlorobenzene/HOPG) are 

investigated by scanning tunneling microscopy. We also 

determined the conversion factors for GPC calibration (PS vs. 

OPB). The overestimation of molar masses of the dodecyl 

substituted oligomers is unexpectedly lower as compared to the 

previously investigated hexyl substituted analoga. [1] 

references: 

1. D. Mössinger, S.-S. Jester, E. Sigmund, U. Müller, 

S. Höger, Macromolecules 2009, 42, 7974-7978. 

Keywords: nanostructures; molecular electronics; 

oligomerization; interfaces; 

P - 0 9 3 2 

ShAPe-PerSiStent MACroCyCLeS 

C. MAzAL 1 , B. v. PhuLwALe 1 




The construction of nanostructured materials with advanced 

functions from well-designed molecular building blocks is one of 

the key topics in modern materials chemistry. The shape-persistent 

macrocycles attract a wide attention of many organic as well as 

materials chemists, particularly in the last decade, as the 

molecules, which can be used as building modules for 

construction of more complex molecular or supramolecular 

structures with high level of complexity. The “shape persistence” 

means that the macrocycles are constructed from parts that are 

rather rigid and connected in such a manner that prevents 

collapsing of the final structure. In other words, the rigid 

molecular backbone surrounds an internal cavity which diameter 

is approximately equal to the backbone length divided by π. 

One of the most popular backbones is the arylene ethynylene 

one, in which the arylene units are connected by ethynylene or 

diethynylene linkers. For this kind of backbones, many coupling 

reactions involving ethynyl group were adapted including 

Sonogashira, Negishi, Heck, Castro-Stephens, and Glaser 

coupling reactions as well as alkyne metathesis. The last one 

differs from the others in a possibility of the thermodynamic 

control of the ring closure reaction. Similarly, the thermodynamic 

control is possible in construction of the backbones involving 

annular heteroatoms by imine and amide condensation reactions. 

As the backbone consists mostly of π-conjugated segments 

the pi-pi stacking dominates the intermolecular interactions that 

result in a remarkable tendency of such molecules to self-organize 

in 1D, 2D or 3D scaffoldings. 

We would like to report on the new shape persistent 

macrocycles of arylene ethynylene type and of a triangular as well 

as rectangular shape. Their structure is based on phenanthrene and 

carbazole units grafted with alkyl chains for better solubility. Their 

dominant π stacking interaction is in some of them perturbated by 

incorporation of bulky σ non-congugated units of 

bicyclo[1.1.1]pentane cages. 

Keywords: Alkynes; Cross-coupling; Macrocycles; Pi 

interactions; 



s1329 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 3 3 

deSiGn of new BorAneS: BroAdeninG the 

SCoPe of fruStrAted LewiS PAirS 

h. Mehdi 1 , A. GyÖMÖre 1 , e. dorKó 1 , t. SoóS 1 

1 Hungarian Academy of Sciences, Research Centre for Natural 

Sciences, Budapest, Hungary 

Metal-free catalysis is one of the most developing topics in 

chemistry. The group of Stephan has recently introduced the 

concept of Frustrated Lewis Pair (FLP), which seems to be a 

powerful tool in the activation of small molecules, such as 

hydrogen. [1] Frustrated Lewis Pairs consist of a sterically crowded 

borane, as the Lewis acid component, and a phosphorous- or 

nitrogen-containing base that are unable to form stable, classical 

donor-acceptor adducts. Despite the steric hindrance it is proposed 

that these pairs associate giving the unique “frustrated 

complexes”. [2] 

The most common Lewis acid that is used for the FLP-based 

activation of hydrogen is tris(pentafluorophenyl)borane. Despite 

its availability the application of this borane is limited in the field 

of Frustrated Lewis Pairs due to its low selectivity. Because of the 

strong Lewis acidity and the steric accessibility of this boron 

compound only bulky substrates were capable for hydrogenation. 

Based on our previous results [3] we have started to design 

and synthesize new boranes that are sterically more crowded. We 

now present the synthesis of some new boron compounds that are 

promising prototypes of new catalysts. 

references: 

1. G. C. Welch, R. R. San Juan, J. D. Masuda, D.W. Stephan, 

Science 2006, 314, 1124 – 1126.; 

D. W. Stephan, G. Erker, Angew. Chem. Int. Ed. 2010, 49, 

46 – 76. 

2. T. A. Rokob, A. Hamza, A. Stirling, T. Soós, I. Pápai, 

Angew. Chem. Int. Ed. 2008, 47, 2435–2438. 

3. G. Eros, H. Mehdi, I. Pápai, T. A. Rokob, P. Király, 

G. Tárkányi, T. Soós, Angew. Chem. Int. Ed. 2010, 49, 

6556-6563.; 

Eros, G.; Nagy, K.; Mehdi, H.; Pápai, I.; Nagy, P.; Király, 

P.; Tárkányi, G.; Soós, T.; Chem. Eur. J., 2012, 18, 

574–585. 

Keywords: borane; 


P - 0 9 3 4 

ChirAL 4,12- And 4,15- diSuBStituted 

[2.2]PArACyCLoPhAneS 

G. Meyer-ePPLer 1 , A. Luetzen 1 

1 Kekulé Institute, AK Luetzen, Bonn, Germany 

Our group is interested in the stereoselective formation of 

supramolecular aggregates. One important element of these is a 

central dissymmetric unit. So far, BINOL and Tröger’s base 

derivatives [1] have been proven to be effective for this purpose. 

Now, we are looking for other types of molecules with uncommon 

stereogenic elements. One interesting class of compounds in this 

respect are planar chiral disubstituted [2.2]paracyclophanes [2] . Yet, 

we have been able to synthesize some disubstituted 

[2.2]paracyclophanes which can be used as precursor for 

supramolecular ligands. Most of these difunctionalized 

[2.2]paracyclophanes are already known [3, 4, 5] but we were able to 

improve some of the syntheses resulting in higher yields. The key 

step for the synthesis of enantiomerically pure ligands, however, 

is the resolution of the enantiomers. In fact, the separation of the 

paracyclophanes has only been achieved via formation and 

separation of diastereomeric derivatives obtained upon 

transformation with optically pure auxiliaries or by enzymatic 

separation [6, 7, 8] . We now present complimentary methods 

employing HPLC on a chiral stationary phase that allowed us to 

improve the resolution of the chiral [2.2]paracyclophanes with 

regard to yield and optical purity. 

references: 

1. J. Bunzen, U. Kiehne, C. Benkhauser-Schunk, A. Lutzen, 

Org. Lett. 2009, 11, 4786. 

2. F. Vögtle, Cyclophan-Chemie, Teubner Studienbücher, 

Stuttgart, 1990. 

3. L. Bondarenko, I. Dix, H. Hinrichs, H. Hopf, Synthesis 

2004, 2751. 

4. N. V. Vorontsova, V. I. Rozenberg, E. V. Sergeeva, 

E. V. Vorontsov, Z. A. Starikova, K. A. Lyssenko, H. Hopf, 

Chem. Eur. J. 2008, 14, 4600. 

5. D. Y. Antonov, E. V. Sergeeva, E. V. Vorontsov, 

V. I. Rozenberg, Russ. Chem. Bull. 1997, 46, 1897. 

6. D. C. Braddock, I. D. MacGilp, B. G. Perry, J. Org. Chem. 

2002, 67, 8679. 

7. Biao Jiang, Xiao-Long Zhao, Tetrahedron: Asymmetry 

2004, 15, 1141. 

8. Biao Jiang, Xiao-Long Zhao, Xiang-Ya Xu, Tetrahedron: 

Asymmetry 2005, 16, 1071. 



s1330 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 3 5 

MACroCyCLiC nAnoChAnneLS AS hoStS for 

fuLLerene derivAtiveS 

A. Meyer 1 , M. fritzSChe 1 , A. BohLe 2 , 

d. dudenKo 2 , u. BAuMeiSter 3 , d. SeBAStiAni 4 , 

G. riChArdt 1 , h. w. SPieSS 2 , M. r. hAnSen 2 , 

S. hÖGer 1 


2 Max Planck Institute, Polymer Research, Mainz, Germany 

3 Institute for Chemistry, Martin Luther University, Halle, 

Germany 

4 Department of Physics, Freie Universität Berlin, Berlin, 

Germany 

The formation of channels on a molecular scale is 

mandatory within living organism, like for example the 

connection of different compartments such as transmembrane 

proteins which function as ion channels, transporters or 

antibiotics. Inspired by the functionality of natural systems, the 

investigation of self-assembled channel-forming structures has 

been started to get applied, expanded and adapted. Macrocyclic 

systems offer the ability to form supramolecular channels if they 

are organized in a columnar mesophase with close-packing of 

successive rings. The possibility of inclusion and manipulation of 

nano-objects becomes feasible depending on the macrocycles’ 

functionalization. [1] 

Phenylene-ethynylene-butydiynylene macrocycles containing 

benzodithiophene units were obtained by the statistical Glaser 

coupling of the appropriate “half-rings” under Pd catalysis and 

subsequent purification by recycling gel permeation 

chromatography. The macrocycles include a nanoscale interior 

with a diameter of approximately 1.3 nm and exhibit liquid 

crystalline phases within a wide temperature range of more than 

100 K as studied by optical microscopy (crossed polarizers) and 

differential scanning calorimetry (DSC). 

We investigated the solubility of various fullerene 

derivatives in these liquid crystalline phases. Furthermore, 

self-assembled monolayers of the macrocycles and coadsorption 

with fullerenes on HOPG were investigated by scanning tunneling 

microscopy (STM) at the solid/liquid interface. 

references: 

1. M. Fritzsche, A. Bohle, D. Dudenko, U. Baumeister, 

D. Sebastiani, G. Richardt, H. W. Spiess, M. R. Hansen, 

S. Höger, Angew. Chem. 2011, 123, 3086-3089. 

Keywords: Fullerenes; Macrocycles; Liquid crystals; 


P - 0 9 3 6 

deSiGn, SyntheSiS, doCKinG StudieS, And 

evALuAtion of LoSArtAn derivAtiveS with 

PotentiAL duAL ACtivity At AnGiotenSin ii 

tyPe 1 reCePtor And PeroxiSoMe 

ProLiferAtor ACtivAted reCePtor GAMMA 

M. Meyer 1 , S. fouLquier 2 , G. MonArd 3 , f. duPuiS 2 , 

i. GriLLiez-vuiSSoz 4 , d. henrion 5 , S. fLAMent 4 , 

y. ChAPLeur 1 , i. LArtAud 2 , M. BoiSBrun 1 

1 Universite de Lorraine, Groupe SUCRES UMR 7565 SRSMC, 

Vandoeuvre-les-Nancy, France 

2 Universite de Lorraine, CITHEFOR EA 3452, Nancy, France 

3 Universite de Lorraine, Groupe CBT UMR 7565 SRSMC, 


4 Universite de Lorraine, SIGRETO EA 4421, 


5 Universite Angers, BNMI UMR 6214, Angers, France 

Hypertension, diabetes and metabolic syndrome are 

important risk factors for cardiovascular morbidity and mortality. 

Angiotensin II plays an important role in blood pressure 

regulation and angiotensin II type 1 receptors (AT1) blockers are 

widely used in the treatment of hypertension. Some, such as 

telmisartan, and at a lesser degree, losartan, also exhibit activity 

at the Peroxisome Proliferator Activated Receptor gamma 

(PPAR-gamma), a nuclear receptor involved in the control of 

glucose metabolism. This represents a new therapeutic approach 

for the treatment of hypertension and diabetes, which are often 

concomitant and difficult to treat by one-target molecules. 

In this context, instead of pharmacomodulations on 

telmisartan (already done by Mizuno et al.), we preferably choose 

to modify the structure of losartan, in order to build-up new 

PPAR-gamma/AT1 dual molecules. The losartan structure was 

linked to a 4'-hydroxy-5-benzilidenethizolidinedione moiety, 

which is found in many PPAR-gamma agonists. Many chemical 

modulations were done on the resulting molecule, in order to get 

structure-activity relationships to both targets. In parallel, we 

realized docking experiments, with the aim of predicting the 

activities of the compounds. 

The molecules were docked into the PPAR-gamma receptor 

by the Autodock software, using a set of various PPAR-gamma 

X-ray structures from the Protein Data Bank. In order to validate 

the method, we first applied this procedure for rosiglitazone, a 

well-known PPAR-gamma agonist. 

In vitro AT1 activity was evaluated by displacement of 

fluorescent angiotensin II in cells overexpressing AT1 receptors. 

In vivo AT1 antagonistic activity was evaluated in anesthetized 

normotensive Wistar rats via the blunted hypertensive response 

to acute angiotensin II (10-10 mol/kg; intravenously). In vitro 

PPAR-gamma activity was evaluated in MCF-7 cells by 

co-transfection of (PPRE) -TK-Luc and hPPAR-gamma vectors. 

3 

As a result, many molecules showed in vitro potency on AT1 

or PPAR-gamma receptors. Furthermore, some exhibited strong 

in vivo antihypertensive activity. 

Keywords: bioorganic chemistry; ligand design; structureactivity 

relationships; 



s1331 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 3 7 

nitroGen BridGed triAryLCArBeniuM SALtS 

AS PLAtforMS for Anion reCoGnition 

f. MiLdner 1 , P. reeh 1 , J. SChAtz 1 


& Pharmazie, Erlangen, Germany 

Anions play an important role in many biological and 

biochemical processes. Therefore, their recognition and sensing 

by artificial receptors is of great interest in the field of 

supramolecular chemistry. Despite the special intrinsic properties 

of anions, which hamper the design of efficient artificial hosts, a 

lot of novel receptors were presented during the last years. [1–3] 

Most of them consist of an aromatic platform and at least 

one side chain containing hydrogen bond donating functionalities 

such as urea and thiourea moieties. Previous results in our group 

show that benzene or calixarenes as core molecules for anion 

receptors are too small to host larger anions such as carboxylates. 

Therefore, larger aromatic platforms are desirable. Furthermore, 

the complexation can be improved by the introduction of charged 

and/ or electron deficient (poly)aromatics. [4] 

In our group these strategies were applied to design 

receptors based on nitrogen bridged stable organic 

triarylcarbenium ions for the recognition of different mono- and 

dicarboxylates. All of them are accessible in a few steps from 

tris(2,6-dimethoxyphenyl)carbeniumtetrafluoroborate by stepwise 

reaction with particular amines. Their binding affinities to several 

organic anions were studied by 1H-NMR titration experiments. [5] 

references: 

1. P. A. Gale, Chem. Soc. Rev. 2010, 39, 3746–3771. 

2. A.-F. Li, J.-H. Wang, F. Wang, Y.-B. Jiang, Chem. Soc. 

Rev. 2010, 39, 3729–3745. 

3. C. Caltagirone, P. A. Gale, Chem. Soc. Rev. 2009, 38, 

520–563. 

4. M. Frank, Diplomarbeit,Universität Ulm 2001. 

5. P. Reeh, Diplomarbeit, Universität Erlangen-Nürnberg 

2008. 

Keywords: Supramolecular chemistry; Receptors; Anions; 


P - 0 9 3 8 

SyntheSiS And ChArACteriSAtion 

of PyrAzoLidine By oxidAtion of 

1,3-diAMinoProPAne 

C. Miro SABAte 1 , A. J. BouGrine 1 , A. eL hAJJ 1 , 

h. deLALu 1 



This work presents a new method for the synthesis of 

pyrazolidine (PYRZ), hydrazine used in the pharmaceutical and 

cosmetic industries. The new method uses the Raschig process 

via oxidation of the amine (1,3-diaminopropane) with sodium 

hypochlorite. The advantages of this new protocol are: low 

toxicity, low associated cost, high reaction rates, high selectivity 

and high feasibility for a continuous transposition. A global 

process was developed involving the characterization of the 

reaction mechanisms, a kinetic study of all the reactions of 

formation and degradation, the modelling and finally, the 

optimization of the synthesis parameters. The synthesis part, 

which is resting on a kinetic approach, was studied in two steps: 

first, the identification of the products, their kinetic evolution 

versus time and the knowledge of the associated mechanisms 

(products were identified and quantified by UV, HPLC/MS and 

GC/MS methods); secondly, a detailed study of all formation and 

degradation rates of reactions in order to know the evolution of 

the pyrazolidine concentrations as function of the initial reagent 

concentrations, the pH and the temperature. 

Keywords: hydrazine; Raschig process; Pyrazolidine; kinetics; 



s1332 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 3 9 

SyntheSiS, StruCture oPtiMizAtion And 

AntifunGAL SCreeninG of noveL tetrAzoLe 

rinG BeArinG ACyL-hydrAzoneS 

M. MohMMAd younuS wAni 1 , 

M. MAnzoor AhMAd MALiK 2 , A. AiJAz AhMAd 3 , 

M. MAqSood AhMAd MALiK 4 

1 Jamia Millia Islamia, Centre for Interdisciplinary research in 

Basic Sciences, New Delhi, India 

2 Jamia Millia Islamia, Department of Chemistry, New Delhi, 

India 

3 Jamia Millia Islamia, Department of Biosciences, New Delhi, 

India 

4 King Abdul Aziz University, Department of Chemistry, Jeddah, 

Saudi Arabia 

Candida albicans is an opportunistic and often deadly 

pathogen that invades host tissues, undergoes a dimorphic shift, 

and then grows as a fungal mass in the kidney, heart or brain. It is 

the fourth leading cause of hospital-acquired infection in the 

United States and over 95% of AIDS patients suffer from 

infections by C. albicans. Existing antifungals can treat mucosal 

fungal infections but very few treatments are available for 

invasive diseases. The current antifungal therapy suffers from 

drug related toxicity, severe drug resistance, non-optimal 

pharmacokinetics, and serious drug-drug interactions. Because of 

all these striking problems, there is a pressing need to develop 

novel antifungal drugs with higher efficiency, broader spectrum, 

improved pharmacodynamic profiles and lower toxicity. Azoles 

are generally fungistatic, and resistance to fluconazole is emerging 

in several fungal pathogens. In an attempt to find novel azole 

antifungal agents with improved activity a series of tetrazole ring 

bearing acylhydrazone derivatives were synthesized and 

characterized by elemental analysis, IR, 1H NMR, 13C NMR, and 

mass spectral studies. The compounds were screened for their in 

vitro antifungal activity. The mechanism of their antifungal 

activity was assessed by studying their effect on the plasma 

membrane using flow cytometry and determination of the levels 

of ergosterol, a fungal-specific sterol. Propidium iodide rapidly 

penetrated a majority of yeast cells when they were treated with 

the synthesized compounds at concentrations just above MIC, 

implying that fungicidal activity resulted from extensive lesions 

of the plasma membrane. Target compounds also caused a 

considerable reduction in the amount of ergosterol. The results 

also showed that the presence and position of different 

substituents on the phenyl ring of the acylhydrazone pendant seem 

to play a role on the antifungal activity as well as in deciding the 

fungistatic and fungicidal nature of the compounds. 

Keywords: tetrazole; acylhydrazone; Candida albicans; flow 

cytometry; ergosterol; 


P - 0 9 4 0 

StruCture-BASed druG deSiGn exPLoitinG 

dynAMiC CoMBinAtoriAL CheMiStry to 

identify noveL inhiBitorS for 

endothiAPePSin 

M. MondAL 1 , A. PArK 2 , h. KÖSter 2 , G. KLeBe 2 , 

A. K. h. hirSCh 1 

1 University of Groningen, Stratingh Institute for Chemistry, 


2 Philipps-Universität Marburg, Institut für Pharmazeutische 

Chemie, Marburg, Germany 

Dynamic combinatorial chemistry (DCC) offers an efficient 

and innovative approach to accelerate identification of novel 

ligands for biological targets. In a dynamic combinatorial library 

(DCL) of acylhydrazones, the connection bonds between the 

building blocks (aldehydes and hydrazides) are reversible and 

continuously being made and broken. The composition of a DCL 

will respond to the addition of a target protein that selectively 

binds one or more library members and will extract such 

member(s) from the DCL. [1] 

2Using a protein–ligand co-crystal structure of 

endothiapepsin, a well-accepted model system for the pepsin-like 

aspartic proteases that are involved in numerous diseases such as 

hypertension, amyloid disease, malaria and AIDS, [2] we designed 

a library of potential inhibitors (acylhydrazones) by 

structure-based design. We have been using a DCC approach to 

identify the best binder(s) using a DCL generated from five 

aldehydes and five hydrazides in ammonium acetate buffer at pH 

4.5. Using the nucleophilic catalyst aniline (20 mM), the DCL 

equilibrated in one day. Upon addition of endothiapepsin, the 

library member(s) captured as potent protein binders are identified 

by HPLC and LC-MS. [3] After successful identification of the best 

ligands, these molecules are synthesized separately and tested for 

their biological activity using an enzyme-based fluorescence 

assay. 

references: 

1. Lehn, J.-M., Ramström, O. Nat. Rev. Drug Discovery 

2002, 1, 26–36. 

2. Cooper, J. B. Curr. Drug Targets 2002, 3, 155–174. 

3. Bhat, V. T.; Caniard, A. M.; Luksch, T.; Brenk, R.; 

Campopiano, D. J.; Greaney, M. F. Nat. Chem., 2010, 2, 

490–497. 

Keywords: Drug Design; Inhibitors; Enzymes; 



s1333 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 4 1 

CAtALytiC CArBonyLAtion reACtionS: 

verSAtiLe tooLS for the SyntheSiS of 

SteroidAL CArBoxAMide diMerS And AMino 

ACid derivAtiveS 

M. S. M. Moreno 1 , r. M. B. CArriLho 2 , 

A. r. ALMeidA 2 , r. d. S. diAS 2 , L. KoLLár 2 , 

M. M. PereirA 2 

1 University of Coimbra, Faculdade de Farmácia, Coimbra, 

Portugal 

2 University of Coimbra, Departamento de Química, Coimbra, 

Portugal 

Steroids are biologically active molecules widely found in 

both plant and animal kingdoms, and play significant roles in 

biological systems. Therefore, there is huge interest in promote 

structural modifications on steroidal molecules, since the 

introduction of different functionalities, such as formyl, amide or 

amino acid groups, into the steroid skeleton, can render marked 

changes in their biological activity. [1, 2] Particularly, dimeric 

steroids represent a class of compounds that have recently 

attracted attention for their rigid, predictable and inherently 

asymmetric architecture. Steroid dimers, such as natural 

cephalostatins, ritterazines and the respective analogues have 

found remarkable pharmaceutical properties, namely, antimalarial, 

antineoplastic and cholesterol lowering activities. [3] 

Since the early discovery of carbonylation reactions in the 

presence of O- and N-nucleophiles, iodoalkenes of various 

structures have been transformed into α, β-unsaturated 

carboxamides, through aminocarbonylations. [4] However, the use 

of diamines as N-nucleophiles in such reactions is rather limited 

and the preparation of dimeric molecules using this synthetic 

strategy has never been described. 

In this communication, we report the first Pd-catalyzed 

aminocarbonylation reactions involving steroids with 

iodo-functionality and several diamine nucleophiles, as an 

efficient tool for the preparation of steroidal carboxamide dimers 

with unprecedented structures. Herein, we also report the 

synthesis of formyl-steroid derivatives through Rh-catalyzed 

hydroformylation of unsaturated steroids, and the respective 

sequential one-pot derivatization into amino acids, via Strecker 

reaction, followed by acidic hydrolysis of the previous 

aminonitriles. 

Acknowledgments: The authors thank financial support 

from Programa Compete and QREN/FEDER/FCT 

(PTDC/QUI-QUI/112913/2009). 

references: 

1. R. Skoda-Foldes, L. Kollár, Chem. Rev. 2003, 103, 

4095–4129. 

2. A.F. Peixoto, M.M. Pereira, A.M.S. Silva, C.M. Foca, 

J.C. Bayón, M.J.S.M. Moreno, A.M. Beja, J.A. Paixo, 

M.R. Silva, J. Mol. Catal. A: Chem., 2007, 275, 121–129. 

3. L. Nahar, S.D. Sarker, A.B. Turner, Current Med. Chem., 

2007, 14, 1349-1370. 

4. R.M.B. Carrilho, M.M. Pereira, A. Takács, L. Kollár, 

Tetrahedron, 2012, 68, 204-207. 

Keywords: Aminocarbonylation; Steroids; Carboxamide 

dimers; Hydroformylation/Strecker reaction; Amino acids; 


P - 0 9 4 2 

BottoM-uP SyntheSiS of StruCturALLy 

defined And hundred-nAnoMeter-LonG 

GrAPhene nAnoriBBonS 

A. nAritA 1 , x. fenG 1 , K. MüLLen 1 

1 Max Planck Institute for Polymer Research, Synthetic 

Chemistry Group, Mainz, Germany 

Graphene nanoribbons (GNRs) are stripes of graphene and 

possess band gaps in contrast to zero-band-gap graphene. The 

electronic properties of GNRs depend on their width and edge 

structures, which make it highly important to fabricate GNRs with 

structural precision. Top-down approaches such as lithographic 

cutting of graphene and longitudinal unzipping of carbon 

nanotubes cannot produce GNRs of defined lateral structures. We 

have employed a bottom-up approach utilizing the intramolecular 

oxidative cyclodehydrogenation of highly twisted polyphenylene 

precursors, and achieved syntheses of structurally defined GNRs. 

However, it was hitherto impossible to synthesize GNRs with 

average length of more than 30 nm with this method. In this study, 

we aimed at the synthesis of structurally defined and 

longitudinally extended GNRs, and employed Diels-Alder 

polymerization, instead of previously used Suzuki and Yamamoto 

polymerization, for the synthesis of polyphenylene precursors. An 

AB-type monomer based on tetraphenylcyclopentadienone was 

thus designed and synthesized. Interestingly, the molecular weight 

of the polyphenylene polymers, resulting from the monomer, 

could be controlled by changing the concentration and the reaction 

time, and weight-average molecular weight of up to 600000 g/mol 

was achieved, corresponding to the resulting GNRs of ca. 600 nm. 

Subsequently, GNRs were synthesized from thus obtained 

polyphenylene precursors by cyclodehydrogenation. 

Characterization by IR and Raman spectroscopies as well as an 

investigation of a model dimer proved the efficiency of the 

cyclodehydrogenation in this system and the homogeneity of the 

GNRs. Thanks to the long alkyl chains attached to the periphery, 

the GNRs could be dispersed in standard organic solvents such as 

THF and chlorobenzene, which allowed UV-Vis absorption 

analysis, solution processing, and STM visualization of individual 

GNRs. In summary, we achieved the synthesis of structurally 

defined and hundred-nanometer-long GNRs via Diels-Alder 

polymerization, which also indicated the suitability of this method 

for the fabrication of highly homogeneous GNRs. 

Keywords: Graphene; Polycycles; Cycloaddition; Raman 

spectroscopy; UV/Vis spectroscopy; 



s1334 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 4 3 

APProACheS to the SyntheSiS of ACyCLiC And 

MACroCyCLiC MuLtiurACiLS 

A. niKoLAev 1 , v. SeMenov 1 , r. GiniyAtuLLin 1 , 

A. MiKhAyLov 1 , d. ShArAfutdinovA 1 , v. rezniK 1 

1 A.E. Arbuzov Institute of Organic and Physical Chemistry, 

Chemistry of Nucleotide Bases, Kazan, Russia 

Earlier we’ve shown that pyrimidinophanes (macrocycles 

containing pyrimidine units) do possess high biological activity, 

comparable with that of reference drugs, and demonstrate a wide 

spectrum of antimycobacterial activity. We suggested that a 

compound, consisting of several “monomeric” pyrimidinophanes 

linked together in some way, can demonstrate higher activity 

and/or selectivity. 

Herein we present the results of our investigations in the 

area. We’ve developed several routes to nanosized structures 

containing pyrimidinophanes. Among them we’ve chosen those 

with the highest yield - we used paraformaldehyde to cross-link 

the macrocycles containing 6-methyluracil. Another option is to 

link macrocycles through the functional substitutents in either 

uracil unit or at the heteroatom. Pyrimidinophanes containing 

propynyl substituents were cross-linked using azide-alkyne 

cycloaddition and coupling of acetylenes with copper acetate, in 

some cases the reactions proceed quantitatively. 

The same azide-alkyne cycloaddition was used to obtain 

another type of oligomeric macrocyclic and acyclic pyrimidine 

derivatives - dendrimers containing uracil units. Di- and 

oligoazides (i.e. 1,4-diazidomethylbenzene, 1,3,5-triazidomethyl- 

-2,4,6-triethylbenzene, 1,3-bis(5-azidopentyl)-6-methyluracil etc.) 

were introduced in the reactions with 1,3-bis(w-bromoalkyl)-5- 

-propynyl-6-methyluracil to obtain first generation dendrimers. 

Subsequent substitution of bromine atoms for azide groups and 

consecutive reiteration afforded higher generation dendrimers. 

Such synthetic approach gives us the possibility to introduce 

various groups and units into the dendrimer molecule by a simple 

nucleophilic substitution of terminal bromine atoms, another 

option for modification is again a “click” reaction of terminal 

azide groups with a wide range of acetylenes, including 

5-propynyluracils. 

Alkylation of the dimers and oligomers provided the onium 

salts which were tested towards a series of bacteria and fungi. 

We’ve discovered that the earlier found regularities for the 

monomers do not work for the dimers and higher molecular 

weight oligomers. 

Acknowledgement: Financial support of the Russian 

Foundation for Basic Research (project #10-03-00365-a) and 

the President’s grant for young Russian researchers (project 

MK-5936.2012.3) is acknowledged. 

Keywords: uracil; dendrimer; synthesis; pyrimidinophane; 

oligomeric macrocycles; 


P - 0 9 4 4 

the effeCtS of ProtiC SoLventS And 

StruCture on the eLeCtroniC ABSorPtion 

SPeCtrA of the iSoMeriC Pyridine 

CArBoxyLiC ACidS 

S. drMAniC 1 , J. niKoLiC 1 , B. JovAnoviC 2 

1 Faculty of Technology and Metallurgy University of Belgrade 

Karnegijeva 4 Belgrade Serbia, Organic Chemistry, Belgrade, 

Serbia 

2 2Institute of Chemistry Technology and Metallurgy University 

of Belgrade, Organic Chemistry, Belgrade, Serbia 

The ultraviolet absorption spectra of the carboxyl group of 

three isomeric pyridine carboxylic acids (picolinic acid, nicotinic 

acid and isonicotinic acid) were determined in a set of protic 

solvents in the wavelength range from 200 to 400 nm. In order to 

analyze the solvent effect on the obtained absorption maxima, the 

ultraviolet absorption frequencies of the electronic transitions in the 

carboxylic group of the examined acids were correlated using a total 

solvatochromic equation of the form ν =v +sπ* + aα+ bβ, where 

max 0 

n is the absorption frequency (1/λ ), π* is a measure of the 

max max 

solvent polarity, β represents the scale of solvent hydrogen bond 

acceptor basicities and α represents the scale of solvent hydrogen 

bond donor acidities. The correlation of the spectroscopic data 

was carried out by means of multiple linear regression analysis. 

The solvent effects on the ultraviolet absorption maximums of the 

examined acids were discussed. 

Keywords: picolinic acid; nicotinic acid; isonicotinic acid; 

ultraviolet absorption maximum; protic solvents; 



s1335 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 4 5 

PrePArAtion of SyndiotACtiC PoLy(vinyL 

ALCohoL) MiCroSPhereS with rAdioPACity 

viA SuSPenSion CoPoLyMerizAtion And 

SAPonifiCAtion 

t. oh 1 , J. ChA 1 , S. hAn 1 , y. Seo 1 

1 Yeungnam University, Nano Medical and Polymer Materials, 

Gyeongsan, Republic of Korea 

introduction: Poly(vinyl alcohol) (PVA) can be synthesized 

by the saponification of poly(vinyl ester) like poly(vinyl acetate) 

(PVAc) and poly(vinyl pivalate) (PVPi). There have been some 

reports on the preparation of monodisperse PVAc and PVPi as 

precursor for PVA via low temperature suspension polymerization 

of VAc and PVPi. Stable steady monomer droplets are necessary 

for obtaining polymer beads with narrow particle size distribution 

(PSD), and excessive coalescence should be excluded at growth 

stage. In this work, preparation conditions of syndiotactic PVA 

microspheres with radiopacity via suspension copolymerization 

and saponification were investigated. 

experimental: To prepare P(VPi/VAc) microspheres with 

radiopacity, the suspension copolymerization in the presence of 

aqueous radiopaque nanoparticles was utilized. Suspension agent 

was dissolved in water under a nitrogen atmosphere and with 

constant stirring, in a 500 ml three-neck round bottom flask fitted 

with a condenser. P(VPi/VAc)/nanoparticles microspheres were 

slowly added to flask during stirring under a nitrogen atmosphere 

at a fixed saponification temperature. After the reaction, the 

reaction mixture was poured into cold water and kept for 1 day to 

separate and to sink s-PVA/P(VPi/VAc)/nanoparticle 

microspheres of skin/core structure. 

results and Conclusion: P(VPi/VAc)/nanoparticles 

microspheres were saponified in heterogeneous system, and then 

the P(VPi/VAc)/ nanoparticles microspheres were converted to 

s-PVA/P(VPi/VAc) microspheres of skin/core structure via 

heterogeneous surface saponification. By increasing of 

saponification time, skin layer of s-PVA/(VPi/VAc)/nanoparticles 

microspheres got gradually thicker. Nanoparticles enters between 

high molecular weight polymer chains and thus the gap between 

chains widens, and hence alkali solution can permeate easily 

between polymer chains. P(VPi/VAc)/nanoparticles microspheres 

were converted into s-PVA/nanoparticles microspheres by 

heterogeneous surface saponification. Radiopacity of the 

s-PVA/nanoparticles microspheres was confirmed by CT. It 

showed that s-PVA/TiO and s-PVA/Ti microspheres have 

2 

excellent radiopacity. 

Acknowledgement: This work was supported by grant 

No. RTI04-01-04 from the Regional Technology Innovation 

Program of the Ministry of Knowledge Economy (MKE). 

Keywords: Poly(vinyl alcohol); Microspheres; 

Copolymerization; Nanoparticles; Radiopacity; 


P - 0 9 4 6 

SyntheSiS of MACroCyCLiC oLiGoPhenyLeneS 

G. ohLendorf 1 , S. S. JeSter 1 , G. SChnAKenBurG 1 , 

S. hÖGer 1 

1 Kekulé Institute, Arbeitskreis Höger, Bonn, Germany 

The spontaneous formation of self-assembled monolayers 

(SAMs) on solid surfaces is of high interest in the development 

of nanoscale organic electronic devices. Complex applications 

require a sufficiently large distance between the active molecular 

component and the surface enabling conformational changes and 

electronic decoupling of the functional units from the substrate. 

In this context, outstanding purpose is the design of anchor 

molecules affording a perpendicular functionalization of surfaces. 

Recently, our group reported on a convenient synthesis of 

complex phenyl substituted p-phenylene oligomers without the 

need of common transition metal catalyzed cross-coupling 

reactions requiring complex protective group strategies. Based on 

these oligophenylenes, bicyclic components are obtained in very 

good yields. Recycling gel permeation chromatography (GPC) is 

used for purification. The novel structure is confirmed by 1H and 

13C NMR spectroscopy, MALDI-TOF-MS and most notably by 

its X-ray determined crystal structure. The molecules have a 

planar bicyclic unit with a perpendicular center which seems to 

be a promising structural unit to reach the purpose of 

three-dimensional growth on surfaces. Self-assembled 

monolayers at the solid/liquid interface of phenyloctane (PHO) 

and highly orientated pyrolytic graphite (HOPG) are investigated 

by scanning tunneling microscopy (STM). The interaction 

between the bicyclic structure and the surface is further studied 

using a model host-guest system by means of 1H NMR 

spectroscopy titration experiments. 

Keywords: Aggregation; Pi interactions; Surface chemistry; 

Self assembly; Adsorption; 



s1336 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 4 7 

PrePArAtion And APPLiCAtionS of dendritiC 

CAtALySt 

A. ouALi 1 , M. KeLLer 1 , A. Perrier 1 , A. hAMeAu 1 , 

A. M. CAMinAde 1 , J. P. MAJorAL 1 

1 Laboratoire de Chimie de Coordination du CNRS, 

Organic Chemistry and Catalysis, Toulouse, France 

Dendrimers, hyperbranched and perfectly defined polymers, 

constitute appealing supports for catalysts. Indeed, they display 

at least two main potential advantages: the possible recovery and 

reuse of the nano-sized catalysts and, in some cases, a significant 

enhancement of the activity compared to the parent monomers. 

Here we report the preparation and applications of 

phosphorous dendrimers decorated either with organocatalysts or 

with metal-based catalysts. In a first example, diarylprolinol 

derivatives were grafted at the periphery and the activity of the 

resulting organocatalysts evaluated in Michael reactions. Besides, 

dendritic thiazolylphosphines were tested as ligands for palladium 

in Suzuki couplings and dendritic diketones were associated to 

copper in O-arylation reactions. In a last example, dendrimers 

decorated with terpyridines were used as ligands for rare-earth in 

Friedel-Crafts acylations. In each case, the recycling abilities of 

the dendritic catalysts were explored. 

Keywords: catalysis; dendrimers; organocatalysis; transition 

metals; rare earths; 


P - 0 9 4 8 

unexPeCted forMAtion of 

n-(1-(2-AroyLhydrAzono)iSoindoLin-2- 

-yL)BenzAMideS And their ConverSion 

into 1,3,4-oxAdiAzoLeS 

C. PArASChiveSCu 1 , M. MAtAChe 1 , n. d. hAdAde 2 , 

A. niCoLeSCu 3 , C. deLeAnu 3 , C. d. ene 1 

1 University of Bucharest, Department of Chemistry, Bucharest, 

Romania 

2 “Babes-Bolyai” University of Cluj-Napoca, Faculty of 

Chemistry and Chemical Engineering, Cluj-Napoca, Romania 

3 Institute of Organic Chemistry, NMR Department, Bucharest, 

Romania 

Reaction between aldehydes and carboxylic acids 

hydrazides constitutes the main pathway in the synthesis of 

N-acyl-N’-arylidene-hydrazines, which are precursors in 

preparation of heterocyclic compounds such as 1,3,4-oxadiazoles. [1, 2] 

1,3-phtaladehyde and 1,4-phthaldehyde react with 

carboxylic acid hydrazides and generates the corresponding 

bis-aroylhydrazones. [3, 4] However, 1,2-phthaldehyde was reported 

to behave differently in reaction with hydrazides. 4 

We describe here the condensation products between 

1,2-phthaldehyde and various hydrazides, using different reaction 

conditions as well as their transformation into 1,3,4-oxadiazoles. 

The isolated N-(1-(2-aroylhydrazono)isoindolin-2-yl)benzamides 

and 1,3,4-oxadiazoles were fully characterized by NMR 

spectroscopy and high resolution mass spectrometry, indicating 

that the compounds are present in solution as a mixture of isomers. 

The N-(1-(2-aroylhydrazono)isoindolin-2-yl)benzamide structure 

was confirmed by X-ray diffraction. 

references: 

1. M. Dabiri, P. Salehi, M. Baghbanzadeh, M. Bahramnejad 


2. C. Dobrota, C.C. Paraschivescu, I. Dumitru, M. Matache, 

I. Baciu, L.L. Ruta, Tetrahedron Lett., 2009, 50(17), 

1879–1881. 

3. S. Rekkas, N. Rodios, N.E. Alexandrou Synthesis 1986, 

411. 

4. A.H.M. Elwahy, M.M. Ahmed, M. El-sadek J. Chem. Res. 

(S) 2001, 175. 

Keywords: 1,3,4-oxadiazole; 1,2-phthaldehyde; 

N-acyl-N’-arylidene-hydrazines; 



s1337 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 4 9 

totAL SyntheSiS of PAndurAtin A, A denGue 

ProteASe inhiBitor 

L. PASfieLd 1 , d. L. C. LAurA 1 , o. Gottfried 1 , 

M. MCLeod 1 

1 Australian National University, Chemistry, Canberra ACT, 

Australia 

Email: pasfield@rsc.anu.edu.au 

In recent years dengue fever has become the most common 

mosquito-borne disease worldwide. It is reported that 40% of the 

world’s population or 2.5 billion people in over 100 countries are 

at risk of dengue fever. Currently no drugs are in clinical use and 

a vaccine is yet to be successfully developed. 

Panduratin A (1) and 4-hydroxypanduratin A (2) are 

cylcohexenyl chalcone derivatives of the panduratin family 

isolated from Bosenbergia rotunda, a member of the ginger 

family. [1] Both panduratin A (1) and 4-hydroxypanduratin A (2) 

have shown competitive inhibition of the dengue virus protease 

with K values of 25 ± 8 and 21 ± 6 µM respectively. i [2] Thus these 

compounds are desirable synthetic targets for further study and 

testing. 

Methodology has been developed enabling the synthesis 

panduratin A (1), 4-hydroxypanduratin A (2) and other family 

members. A regioselectivity study on the key high pressure Diels- 

Alder reaction has also been completed. 

references: 

1. Tuntiwachwuttikul, P.; Pancharoen, O.; Reutrakul, V.; 

Byrne, L. T. Aust. J. Chem. 1984, 37, 449–53. 

2. Kiat, T. S.; Pippen, R.; Yusof, R.; Ibrahim, H.; Khalid, N.; 

Rahman, N. A. Bioorg. Med. Chem. Lett. 2006, 16, 

3337–3340. 

Keywords: Natural Products; Cycloaddition; 


P - 0 9 5 0 

one-Pot rhodiuM CAtALySed 

hydroforMyLAtion-AryLAtion And 

SiLyLCyAnAtion reACtionS 

M. M. PereirA 1 , A. r. ALMeidA 1 , A. C. B. neveS 1 , 

A. r. ABreu 1 , L. d. diAS 1 , r. M. B. CArriLho 1 , 

A. d. M. A. BAPtiStA 1 , M. J. f. CALvete 1 

1 University of Coimbra, Departamento de Química, Coimbra, 

Portugal 

Enantiopure aryl alcohols are key structural elements in a 

large number of pharmacologically active compounds. [1] In this 

context, the addition of aryl organometallic reagents to aldehydes 

is an attractive synthetic route to prepare this type of molecules. 

Therefore, the catalytic hydroformylation reaction is a crucial 

process to prepare several type of new aldehydes, which can be 

sequentially transformed into high value products. [2] 

In this communication we present optimization studies for 

sequential rhodium/phosphorus or Rh/NHCs catalysed 

hydroformylation of olefins, [3] followed by in situ aldehyde 

arylation with boronic acids, using the same catalytic precursor. 

The effect of the reaction conditions and ligand structure on the 

activity and selectivity of the sequential transformations will be 

presented and discussed. 

Furthermore, the one pot sequential hydroformylation 

reaction of olefins catalysed by Rh/P metal complexes followed 

by transformation of the aldehydes into the chiral cianosilyl 

derivatives catalysed by new titanium/bis-BINOL derivatives 

complexes will be discussed. 

Acknowledgments: The authors thank for financial 

support to Programa Compete and QREN/FEDER/FCT 

(PTDC/QUI-QUI/112913/2009). 

references: 

1. Y. Bolshan, C.-Y. Chen, J. R. Chilenski, F. Gosselin, 

D. J. Mathre, P. D. O’Shea, A. Roy and R. D. Tillyer, Org. 

Lett., 2004, 6, 111. 

2. A. F. Peixoto, D. S. de Melo, T. F. Fernandes, Y. Fonseca, 

E. V. Gusevskaya, A. M.S. Silva, R. R. Contreras, M. 

Reyes, A. Usubillaga, E. N. dos Santos, M. M. Pereira, 

J. C. Bayón, Applied Catalysis A: General, 2008, 340, 212. 

A. F. Peixoto, M. M. Pereira, A. M. S. Silva, C. M. Foca, 

J. C. Báyon, M. J. S. M. Moreno, A. M. Beja, J. A. Paixo, 

M. R. Silva, Journal of Molecular Catalysis A: Chemical, 

2007, 275, 121. 

3. A. R. Almeida, A. F. Peixoto, M. J. F. Calvete, P. M. P. Gois, 

M. M. Pereira, Current Organic Synthesis, 2011, 8, 764. 

Keywords: Hydroformylation; Arylation; Cyanosilylation; 

Tandem reactions; 



s1338 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 5 1 

the PrePArAtion of thin PoLyAniLine fiLMS 

By MeAnS of SCreen PrintinG 

n. PerinKA 1 , M. KAPLAnovA 1 , t. Syrovy 1 , 

M. exnerovA 2 , J. SteJSKAL 2 

1 University of Pardubice, Department of Graphic Arts and 

Photophysics, Pardubice, Czech Republic 

2 Institute of Macromolecular Chemistry of Academy of Sciences 

of the Czech Republic, Department of Supramolecular 

Polymer Systems, Prague, Czech Republic 

Currently, the research of new materials attracts a large 

interest of many scientists and enables also new industrial 

applications. Very interesting area of these new materials are so 

called functional polymers. These polymers have some additional 

properties, which allow them to be applied not only as “plastics” 

in a form of some three dimensional objects, but also to provide 

more functions (e.g. electrical conductivity, sensitivity to other 

compounds, fluorescence, bioactivity, etc.). This work is focused 

on the study of polymers, which show the electrical conductivity. 

These polymers are usually called as conducting polymers. The 

phenomenon of the electrical conductivity by polymers was first 

reported in 1970’s, and was later awarded by Nobel Prize for 

Chemistry in 2000. The main groups of conducting polymers are 

derived from polyacetylene, poly(p-phenylene), polythiophene, 

polyaniline, polypyrrole and poly(p-phenylene vinylene). 

Nowadays, these polymers are considered to be applied especially 

in the form of thin (flexible) layers which then form electrical 

devices. These layers can be prepared by means of various 

techniques (spin-coating, printing, other coating methods). The 

main advantage of the printing techniques is the possibility of 

pattering, large area application and high throughput. In this study, 

the films of polyaniline were prepared by means of the screenprinting 

technique. The quality of the films was optimized by 

means of changing the formulation of the prepared 

colloidal poly(N-vinylpyrrolidone) [poly(1-vinylpyrrolidin-2-one)] 

stabilized polyaniline dispersions, and also by changing of the 

printing parameters and conditions. The films were prepared on 

flexible polyethylene terephthalate transparent foil. The prepared 

films were further investigated by means of the optical 

microscopy and electrical measurements and profilometry. The 

thin layers of the polyaniline were successfully prepared. The 

thickness of the layers ranged from several hundreds of 

nanometers to 2 µm. The observed physical effects and properties 

and morphology of the printed films are discussed. 

Keywords: Polymers; Conducting materials; Colloids; Thin 

films; 


P - 0 9 5 2 

orGAnoCAtALySiS: new ACCeSS to 

PhenyLALAnine derivAtiveS throuGh the 

enAntioSeLeCtive deCArBoxyLAtive 

ProtonAtion 

M. PiGeAux 1 , J. BAudoux 1 , J. rouden 1 

1 Laboratoire de Chimie Moléculaire et Thioorganique UMR 

CNRS 6507, UMR 6507, Caen Cedex, France 

The enantioselective synthesis of amino acids is a research 

area of great interest due to the ubiquity of these small molecules 

in biologically active products. Recently, our lab has developed an 

efficient methodology to control the formation of carbon-hydrogen 

bond by an asymmetric organocatalyzed protonation [1]. In this 

context, our project aims at developing a versatile access to 

enantioenriched non-proteogenic phenylalanine derivatives, using 

enantioselective decarboxylative protonation. 

This methodology required first the preparation of racemic 

functionalized hemimalonic acids using a minimum number of 

steps from readily availalble starting materials. Then, cinchona 

alkaloids derivatives as chiral bases triggered the asymmetric 

decarboxylative protonation of these substrates. Recently, the 

thioureas analogues of these alkaloids promoted the 

decarboxylation of cyclic a-aminomalonates [2]. However, a 

stochiometric amount of base and low temperature/long reaction 

time were necessary to achieve good enantioselectivivies. This 

presentation summarizes our efforts to obtain high enantiomeric 

excess of phenylalanine derivatives using a catalytic amount of a 

new catalyst family, the squaramides. A comparative (squaramides 

vs thioureas) and comprehensive study of reaction parameters 

including the nature of the N-protecting group (PG) is underway 

in the specific case of these acyclic substrates. 

Keywords: organocatalysis; decarboxylation; cinchona 

alkaloids; squaramide; amino acids; 



s1339 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 5 3 

ohMiC heAtinG: A new And hiGhLy effiCient 

ProCeSS for orGAniC SyntheSiS in wAter 

J. Pinto 1 , v. L. M. SiLvA 1 , A. M. G. SiLvA 2 , A. M. S. SiLvA 1 , 

L. M. n. B. f. SAntoS 3 , J. A. S. CAvALeiro 1 , 

A. A. viCente 4 , J. A. C. teixeirA 4 

1 University of Aveiro, Chemistry QOPNA, Aveiro, Portugal 

2 REQUIMTE University of Porto, Chemistry and Biochemistry 

Faculty of Sciences, Porto, Portugal 

3 University of Porto, Chemistry Faculty of Sciences CIQ, Porto, 

Portugal 

4 University of Minho, IBB-Institute for Biotechnology and 

Bioengineering Centre of Biological Engineering, Braga, 

Portugal 

Synthetic chemists are challenged to consider more ecofriendly 

and sustainable processes for the generation of the desired 

target molecules, with reduced energetic impact of 

transformations mainly for those employed at a production scale. 

Another challenge of current chemical industry is reducing the 

use of toxic organic solvents. In this context, chemical reactions 

in aqueous media arouse great interest because water is non-toxic, 

non-flammable and relatively available at low cost. 

Here we present a new, highly efficient and safe process for 

organic synthesis in water based on an ohmic heating reactor. 

Ohmic heating is an advanced thermal processing method where 

the reaction mixture, is heated by passing electricity through it. [1] 

Four representative organic reactions, including Diels-Alder 

cycloadditions, nucleophilic substitutions, N-alkylations and 

Suzuki reaction were performed using this process. The results 

pointed that ohmic heating allows faster and uniform heating, 

leading to substantial savings of time with higher yields. 

The simple design and cost of the reactor, its easy 

maintenance and handling, the low heat capacity and thermal 

inertia of the ohmic heating process, the fast and uniform heating, 

as well as the possibility of visual monitorization and addition of 

reagents during the reaction, make the use of this process a highly 

advantageous and versatile option for organic synthesis especially 

in water. Thus, the scaling of direct ohmic heating for the pilot 

scale or even industrial scale should not present the limitations 

and difficulties of microwave radiation. Therefore, we believe this 

process is economically viable and environmentally sustainable. 

Acknowledgement: Thanks are due to University of Aveiro, 


Unit (PEst-C/QUI/UI0062/2011) and the FCT Project 

(PTDC/Qui-Qui/102454/2008). Joana Pinto also thanks FCT 

for the PhD grant (SFRH/BD/77807/2011). 

references: 

1. A. A. Vicente, I. Castro, J. A. Teixeira, Da-Wen Sun (Ed.), 

CRC Press, New York (ISBN 1-57444-628-2), 2006, 419. 

Keywords: Sustainable Chemistry; Water Chemistry; 

Microwave Chemistry; Industrial Chemistry; 


P - 0 9 5 4 

identifiCAtion of new GABAA reCePtor 

LiGAndS derived froM vALereniC ACid 

G. PototSChniG 1 , M. hAider 1 , G. eCKer 2 , 

S. herinG 3 , M. MihoviLoviC 1 



2 University of Vienna, Department of Medicinal Chemistry, 


3 University of Vienna, Department of Pharmacology and 

Toxicology, Vienna, Austria 

Root extracts of Valeriana officinalis are long used in 

traditional medicine for inducing sleep and treatment of panic 

disorders. Valerenic acid, a chiral bicyclic sesquiterpenoidal 

structure, was found to act as a subtype selective positive 

allosteric modulator of GABA receptors bearing β2 or β3 

A 

subunits. [1] Therefore it is mainly responsible for the desirable 

activity of valerian. 

The synthesis of valerenic acid requires exact control of 3 

stereocenters and the use of the cost-intensive Crabtree’s catalyst. 

Thus, a simplified scaffold for the design of drugable compounds 

shall be identified. To this end, the activity related structural 

motifs need to be discovered by both chemical synthesis and 

computational methods 

We present a comprehensive 3D QSAR model based on a 

congeneric dataset of 42 valerenic acid derivatives. The atom 

based 3D QSAR function implemented in Phase/Schrödinger was 

used. Alignment of training- and test- set- compounds was done 

in MOE2011.10 based on the best fitting conformation found for 

the most active compounds. The diaxial arrangement of both 

onring substituents, found in the X-ray structure of valerenic acid, 

was chosen as a starting point. The original dataset was randomly 

divided into 80% training and 20% test set multiple times and the 

best performing model was chosen to make predictions within a 

small dataset of related structures. New derivatives were predicted 

with a R2 of 0.87 and a Q2 of 0.73. The quality of the model was 

tested via biological testing of synthesized compounds. 

Acknowledgement: This work is kindly financed 

by the FWF project Nr. W1232 Molecular Drug Targets 

references: 

1. P-0001 Khom, S.; Strommer, B.; Ramharter, J.; Schwarz, T.; 

Schwarzer, C.; Erker, T.; Ecker, G. F.; Mulzer, J.; Hering, S., 

Valerenic acid derivatives as novel subunit-selective 

GABAA receptor ligands - in vitro and in vivo 

characterization. Br J Pharmacol 2010,161 (1), 65–78. 

Keywords: Computational chemistry; Structure-activity 

realtionships; Ion channels; 



s1340 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 5 5 

A Study of 2-SuBStituted 3,1-BenzoxAzin-4-oneS 

K. ProiSL 1 , J. KoSMrLJ 2 , d. urAnKAr 2 , S. KAfKA 1 



2 University of Ljubljana, Faculty of Chemistry and Chemical 


Substituted 3,1-benzoxazin-4-ones possess interesting 

biochemical properties including antifungal [1] and serine protease 

inhibitory [2–4] effects. Some of them are used as ultraviolet 

absorbers [5] and as acylating reagents or precursors of various 

heterocycles in organic synthesis [6] . 

This paper describes our work concerning the preparation 

of novel benzoxazinones substituted with indole moiety or acyl 

in position 2. Their preparation is achieved by cyclodehydration 

of the appropriate N-acylanthranilic acids by means of acetic 

anhydride or thionyl chloride, which is consistent with the 

standard procedure. 

In addition, a new route to starting N-acylanthranilic acids 

has been established. Firstly, N-(α-ketoacyl)anthranilic acids were 

readily obtained from 4-hydroxyquinolin-2-ones by two-step 

oxidation including peracetic acid hydroxylation into the 

corresponding 3-hydroxyquinoline-2,4-diones and subsequent 

oxidative ring opening with periodic acid or sodium periodate. In 

the cases of the prepation of the mentioned indole derivatives, the 

appropriate transformations of α-ketoacyl chain were carried out 

by known chemistry. 

As a part of our continued interest in the reactivity of various 

heterocyclic systems, we have studied reactions of title 

compounds with some nucleophiles. All compounds under 

investigation were characterized by available methods of 

structural analysis including high resolution mass spectrometry 

and two-dimensional NMR techniques. 

Acknowledgement: This study was supported by the internal 

grant of TBU in Zlín No. IGA/FT/2012/043 funded from the 

resources of specific university research. 

references: 

1. Mayama, S. et al. Tetrahedron Lett. 22, 1981, 2103–2106. 

2. Gilmore, J. L. et al. Bioorg. Med. Chem. Lett. 6, 1996, 

679–682. 

3. Robinson, V. J. et al. Canad. J. Chem. 66, 1988, 416–419. 

4. Krantz, A. et al. J. Med. Chem. 30, 1987, 589–590. 

5. Amasaki, I. et al. U.S. Pat. Appl. Publ. US 2009/0239982. 

6. Santagati, N. A. et al. Il Farmaco 54, 1999, 780–784. 

Keywords: 1,3-benzoxazin-4-one; anthranilic acid; 

cyclodehydration; periodic acid; heterocyclic; 


P - 0 9 5 6 

PArA hydroGen induCed PoLArizAtion in 

fLuorouS And orGAniC PhASeS 

t. rAtAJCzyK 1 , S. diLLenBerGer 1 , 

n. AMAdeu de SouSA 1 , t. GutMAnn 2 , h. BreitzKe 1 , 

G. BuntKowSKy 1 

1 Darmstadt University of Technology, Chemistry, Darmstadt, 

Germany 

2 Laboratoire de Chimie de Coordination, CNRS, Toulouse, 

France 

Since the discoveryof the Para Hydrogen Induced 

Polarization (PHIP) method [1–3] a lotof efforts have been put to 

develop this technique for practical andcommercial applications 

in the medicine and the industry [4, 5] . However, there are still some 

problems which hamper the PHIPutilization. For example, the 

problem of fast product/catalystseparation is one of special 

concern [6, 7] . 

In thispresentation this problem is addressed. We 

demonstrate that the PHIPeffect can be observed in different 

fluorous solvents.Further, we present that the PHIP signal can be 

observed influorous/organic systems. These systems are 

homogenous at hightemperature and biphasic at low temperature. 

This temperaturebehavior of fluorous/organic phases can be of 

crucial importance forproduct/catalyst separation in PHIP. 

Acknowledgments: Tomasz Ratajczyk wishes to thank for The 

Marie-Curie Intra EuropeanFellowship within the 7 th European 

references: 

1. Bowers, C. R., Weitekamp, D. P., Phys. Rev. Lett., 

57,2645-2648 (1986). 

2. Eisenschmid, T. C., Kirss, R. U., Deutsch, P. P. 

Hommeltoft, S. I.,Eisenberg, R., Bargon, J., Lawler, R. G., 

Balch, A. L., J. Am.Chem. Soc., 109, 8089 (1987). 

3. Bowers, C. R., Weitekamp, D. P., J. Am. Chem.Soc., 109, 

5541-5542 (1987). 

4. Terreno, E., Castelli, D.D., Viale, A., Aime, S., Chem.Rev., 

110, 3019-3042 (2010). 

5. Lysova, A.A.; Koptyug, I.V. Chem. Soc. Rev., 

39,4585–4601 (2010). 

6. Kovtunov, K.V., Zhivonitko, V,V,, Kiwi-Minsker, L., 

Koptyug, I,V,, Chem. Commun.,46, 5764-5766 (2010). 

7. Gutmann, T., Sellin, M., Breitzke, H., Stark, A., 

Buntkowsky, G.,Phys. Chem. Chem. Phys. 11,9170-9175 

(2009). 

Keywords: Para hydrogen induced polarization; Para 

hydrogen; NMR; Signal enhancement; 



s1341 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 5 7 

wAter-SoLuBLe n-tyPe ConJuGAted 

PoLyMerS: SyntheSeS And APPLiCAtionS 

S. roChAt 1 , t. M. SwAGer 1 

1 Massachusetts Institute of Technology, Chemistry, Cambridge, 

USA 

N-type conjugated polymers with high electron affinities and 

high ionization potentials are avidly sought after in the field of 

organic electronics. In particular, polymer photovoltaic devices 

frequently comprise fullerene-based acceptor molecules, which 

are notoriously poor light absorbers in the visible range. Hence, 

there is a critical need for new n-type polymeric materials. 

Here we report the syntheses, characterizations and some 

potential applications of a series of aqueous-solution processable 

n-type conjugated polymers. First, the monomeric unit, based on 

a 1,4-bis(5-bromopyridin-2-yl)benzene skeleton, is conveniently 

obtained in two steps from commercially available starting 

materials. This monomer can polymerize under Yamamoto 

conditions to obtain a poly(pyridine phenylene) precursor, that 

can undergo post-polymerization conversion into a 

poly(pyridinium phenylene), water-soluble and electron-deficient 

polymer. A variety of co-polymers could be obtained following 

the same synthetic pathway, in order to modulate the optical and 

electronic properties of the compounds. These materials were 

found to be moderately soluble in aqueous solutions, and were 

characterized by 1H NMR, gel permeation chromatography, as 

well as optical and electrochemical methods. In addition to 

interesting solubility properties, the polymers were found to 

possess promising electronic properties, such as reversible redox 

behaviors, high electron affinities and useful ionization potentials. 

Taking advantage of these properties, a variety of 

applications were envisioned, such as solution-based sensing of 

electron-rich analytes or enzyme-based electrocatalyis for 

renewable energy purposes. 

In conclusion, we report promising, easily accessible n-type 

polymers. These materials can be processed in aqueous solutions, 

display high electron affinities and reversible redox behaviors. 

These properties make these compounds promising for 

applications in various fields such as electrocatalysis, sensing or 

organic photovoltaics, which are currently under investigation in 

our laboratory. 

Keywords: polymers; electron-deficient compounds; block 

copolymers; redox chemistry; sensors; 


P - 0 9 5 8 

SyntheSiS of An ArtifiCiAL C-nuCLeotide AS 

PreCurSor of todAy’S nuCLeotideS And the 

therModynAMiCS of itS MoLeCuLAr 

interACtionS 

C. rooSt 1 , J. SieGeL 1 

1 University of Zurich, OCI, Zurich, Switzerland 

DNA with its four building blocks A, C, G, and t is the 

carrier of genetic information in all known living organisms, no 

matter how different they are. From which precursor did these 

nucleotides develop? This is a fundamental question in origin of 

live science. 

A pre-biotic DNA alphabet consisting of only pyrimidine 

bases has been proposed. This alphabet contains the natural 

nucleosides C and u as well as a nucleoside (d) which is 

modelled on 2,4-diaminopyrimidine. d can easily form C and u 

by hydrolysis and could therefore be their prebiotic precursor. 

To investigate this hypothesis, C-nucleoside d has been 

synthesised and incorporated into oligonucleotides. Now, 

isothermal titration calorimetry (ITC) experiments are conducted 

to probe the thermodynamics of the molecular interactions 

between d and the natural nucleotides. 



s1342 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 5 9 

PrePArAtion of 3-thiourenido-2-indoLoneS 

And 2-thioxoiMidAzo[4,5-C]quinoLin-4-oneS 

froM 3-hydroxyquinoLine-2,4-dioneS 

o. rudoLf 1 , A. LyCKA 2 , z. CernoCh 1 , A. KLASeK 1 



2 Research Institute for Organic Syntheses (VUOS), Research 

Institute for Organic Syntheses (VUOS), Rybitvi Pardubice, 


3-Aminoquinoline-2,4-diones, accessible by amination of 

3-chloroquinoline-2,4-diones, [1] reacts with in situ generated 

isothiocyanic acid to give mainly 3-thiourenido-2-indolones. 

3-Benzyl derivatives of 3-aminoquinoline-2,4-diones yield 

2-thioxoimidazo[4,5-c]quinolin-4-ones. [2, 3] 

These interesting results gave us incentive to perform 

analogous reactions with 3-hydroxyquinoline-2,4-diones, which 

are obtainable by oxidation of 4-hydroxyquinoline-2-ones. [4] 

Our intention was to prepare oxa-analogues of 

thioxoimidazoquinolinones and thiourenidoindolones. However, 

no reaction was observed when a model compound 

1-methyl-3-hydroxy-3-phenylquinoline-2,4-dione was boiled with 

potassium thiocyanate. 

On the other hand, 3-(3'-benzoylthioureido)-1-methyl-2- 

-oxo-2,3-dihydro-1H-indole was isolated when KSCN was 

substituted by NH SCN. The same results were obtained with 

4 

another 3-hydroxyquinolinediones (R and R = Me, Bu, Ph). In 

1 2 

addition, using starting compound 3-hydroxyquinolinediones 

bearing a benzyl group in position 3, C-debenzylation under 

formation of thioxoimidazoquinolinones was observed. 

The exhaustive results will be discussed and the reaction 

mechanism will be proposed. 

Acknowledgement: This study was supported by the internal 

grant of TBU in Zlín No. IGA//FT/2012/015 funded from the 

resources of specific university research. 

references: 

1. Kafka S. et al., Heterocycles, 2002, 57, 1659; 

2. Mrkvicka et al., Tetrahedron, 2010, 66, 8441; 

3. Mrkvicka et al., Tetrahedron, 2011, 67, 2407; 

4. Kafka S. et al., J. Heterocyclic Chem., 1996, 33, 1977. 

Keywords: quinoline-2,4-diones; isothiocyanic acid; 

3-aminoquinoline-2,4-diones; 3-hydroxyquinoline-2,4-diones; 

C-debenzylation; 


P - 0 9 6 0 

ProduCtivity enhAnCeMent of C=C 

BioreduCtionS By CouPLinG the in Situ 

SuBStrAte feedinG ProduCt reMovAL 

teChnoLoGy with iSoLAted enzyMeS 

A. SACChetti 1 , G. frAnCeSCo G. 1 , B. eLiSABettA 1 , 

P. fABio 1 , M. dAnieLA 2 

1 Polytechinc of Milan, Department of Chemistry “G. Natta”, 

Milano, Italy 

2 CNR, Institute of Chemistry ICRM, Milano, Italy 

The bioreduction of C=C double bond of prochiral 

aldehydes is an important synthetic tool for the generation of 

optically pure synthones. The first examples of such a reaction 

were carried out using resting cells of Saccharomyces cerevisiae. [1] 

In the last decade, great improvement, in terms of conversion and 

simplicity of work-up, has been achieved using isolated enoate 

reductases (ERs), such as the Old Yellow Enzymes (OYEs), 

instead of the whole microorganism. However, the productivity 

of these reactions is generally low, mainly due to the low substrate 

concentration used in most experimental set-ups. In addition, the 

products of isolated ERs-catalyzed reactions are saturated 

aldehydes which are intrinsically unstable compounds. [2] Here 

we describe the combination of multienzymatic systems, 

comprising selected OYEs and alcohol dehydrogenases (ADHs), 

with the SFPR (in situ Substrate Feeding Product Removal) 

concept. When applied to the reduction of a set of different 

prochiral α,β-unsaturated aldehydes to the corresponding 

saturated products (e.g. some important synthons for the 

preparation of the bioactive molecules Robalzotan and 

Rotigotine), this strategy allows an average 

100-fold improvement of productivity and helps to preserve the 

optical purity of products and the chemical stability of reagents. 

We also observed a remarkable chemoselectivity of selected 

ADHs toward saturated aldehydes in the presence of α,βunsaturated 

aldehydes. [3] 

references: 

1. a) S. Servi, Synthesis 1990, 1; 

b) R. Csuk, B.I. Glänzer, Chem. Rev. 1991, 91, 49. 

2. C. Stueckler, N.J. Mueller, C.K.Winkler, S.M. Glueck, 

K. Gruber, G. Steinkeller, K. Faber Dalton Trans. 2010, 

39, 8472. 

3. a) M. Bechtold, E. Brenna, C. Femmer, F.G. Gatti, 

S. Panke, F. Parmeggiani, A. Sacchetti, Org. Process 

Res. Dev. 2012, 269 

b) E. Brenna, F.G. Gatti, D. Monti, F. Parmeggiani, 

A. Sacchetti, Chem. Comm. 2012, 79 

Keywords: Biocatalysis; Reduction; 



s1343 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 6 1 

tetrAhydro-SS-CArBoLine-BASed 

SPiroCyCLiC LACtAM AS PotentiAL tyPe ii' 

SS-turn SoMAtoStAtine MiMetiC 

A. SACChetti 1 , A. SiLvAni 2 , G. LeSMA 2 , 

M. MuSoLino 2 , r. CeCChi 3 

1 Polytechinc of Milan, Chemistry, Milano, Italy 

2 University of Milan, Chemistry, Milano, Italy 

3 Sanofi-Aventis, Chemistry, Milano, Italy 

The development of privileged molecular scaffolds 

efficiently mimicking reverse turn motifs has attracted remarkable 

interest when structural constraints are exploited to increase both 

binding and selectivity of model peptides. One of the successful 

approaches to restrict peptide conformation is the disubstitution 

in the a position of an a-amino acid, leading to a conformational 

constraint and a stereochemically stable quaternary carbon center. 

In particular, spirocyclic scaffolds are able to provide, upon the 

attachment of appropriate functional groups, useful high-affinity 

ligands, relevant to the field of drug discovery. [1] 

At present, we are interested to spirocyclic tryptophan (Trp) 

analogues, in order to develop new reverse turn nucleating 

moieties able to be inserted into pharmacologically relevant 

peptidomimetic compounds. Among peptides sharing a 

tryptophan-containing β-turn motif of which the Trp residue is 

critical for binding, we looked at the hormone peptide 

somatostatin, [2] acting in various organ systems as a 

neuromodulator and a neurotransmitter, as well as a potent 

inhibitor of various secretory processes and cell proliferation. [3] 

Somatostatin and its analogue octreotide (Sandostatin ® drug, 

clinically used for the treatment of endocrine tumors and 

acromegaly) are thought to interact with the sst1-5 receptors 

mainly by inserting a β-turn substructure, carrying a lysine (Lys) 

and a Trp side chain into a pocket of the G protein-coupled 

somatostatin receptor. 

We report here the preparation and structural 

characterization of a new 1,2,3,4-tetrahydro-β-carboline 

(THBC)-based spirocyclic lactam as type-II' β-turn model 

compound and the application of its core structure to the synthesis 

of a somatostatin mimetic, whose biological evaluation is under 

way. 

references: 

1. Van Rompaey, K. et al. D. Eur. J. Org. Chem. 2006, 

2899–2911. 

2. Janecka, A. et al. J. Pept.Res. 2001, 58, 91–107. 

3. Reubi, G. C. Endocrine Reviews 2003, 24, 389–427. 

Keywords: Conformation analysis; Peptidomimetics; Drug 

design; 


P - 0 9 6 2 

Sweet tASte inveStiGAtionS on ASPArtAMe 

And neotAMe uSinG nMr SPeCtroSCoPy And 

CoMPutAtionAL MethodS 

B. SAGLAM 1, 2 , n. tuzun 1 , S. BeKiroGLu 2 , G. oruC 2, 3 

1 Istanbul Technical University, Department of Chemistry, 34469, 


2 TUBITAK Marmara Research Centre, Food Institute, 41470 

Gebze-Kocaeli, Turkey 

3 Bogazici University, Department of Chemistry, 34342, Istanbul, 

Turkey 

Email: saglambi@itu.edu.tr 

Aspartame (N-(L-α-Aspartyl)-L-phenylalanine,1-methyl ester) 

is used as an artificial, non-saccharide sweetener in the 

pharmaceutical and food industry and it is a dipeptide of aspartic acid 

and phenylalanine. [1] Neotame ((3S)-3-(3,3-Dimethylbutylamino)- 

-4-[[(2S)-1-methoxy-1-oxo-3-phenylpropan-2-yl]amino]-4-oxobutanoic 

acid) is a nonnutritive sweetener which is a derivative of 

aspartame. It is a high-potency sweetener which is 

6000–10 000 times sweeter than sucrose and 30-60 times sweeter 

than aspartame. [2] 

The aim of this research is to determine the relationship 

between structure and taste for aspartame and neotame by using 

NMR spectroscopy. Assignment of molecules are done by using 

1D 1H and 13C, 2D homonuclear NOESY, TOCSY, and 2D 

heteronuclear HSQC NMR spectra. Molecular interactions of 

aspartame and neotame within cyclodextrin complexes are 

investigated and findings are compared with the results that are 

acquired from computational methods. Although aspartame and 

neotame have similar structures, they have different taste quality. 

3,3-dimethylbutyl group of neotame is the most efficient 

substituent that makes the difference in taste. 2 

references: 

1. Sohajda T., Beni S., Varga E., Ivanyi R., Racz A., Szente L., 

Noszal B., Characterization of aspartame–cyclodextrin 

complexation, Journal of Pharmaceutical and Biomedical 

Analysis, Vol. 50, 2009, 737–745. 

2. Nofre C., Tinti J. M., Neotame: discovery, properties, 

utility, Food Chemistry, Vol. 69, 2000, 245-257. 

Keywords: Nmr Spectroscopy; Cyclodextrin complexes; 

Computational methods; Aspartame; Neotame; 



s1344 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 6 3 

Study on therMAL deCoMPoSition 

of P-tert-ButyL CALix[6]Arene derivAtiveS 

with different donor GrouP At the “nArrow 

riM” for MetALLiC ionS extrACtion 

A. SAPonAr 1 , e. J. PoPoviCi 1 , i. PerhAitA 1 , 

A. i. CAdiS 1 , G. neMeS 2 

1 Babes-Bolyai University, Raluca Ripan Institute for Research 

in Chemistry, Cluj-Napoca, Romania 



Calix[n]arene are cyclic molecules made of some phenolic 

units meta linked by methylene bridges. Owing to their 

cavity-shaped architecture, they are useful building blocks in the 

synthesis of receptors for cations, anions and neutral molecules [1] . 

Calix[n]arene derivatives can be synthesized by modification at 

the phenol OH groups (narrow rim) and in the para-position of 

the phenyl rings (wide rim). 

Calix[n]arene derivatives with ionophoric functional groups 

at the “narrow rim” exhibit excellent extraction/co-ordination 

abilities for metallic ions of technological interest. In order to find 

efficient extracting reagents for precious or rare earth metals, 

calix[6]arene derivatives functionalized at the narrow rim with 

three ethylester, three N,N-diethylacetamido, three crotyl, three 

crotyl-three N,N-diethylacetamido and three crotyl-three 

ethylester groups were investigated. 

The purpose of this study is to investigate the thermal 

behaviour of the p-tert-butyl calix[6]arene derivatives with 

different donor group at the “narrow rim”. The thermal 

decomposition was investigated by means of the 

thermogravimetric (TG) and differential thermogravimetic (DTG) 

analysis, and differential scanning calorimetry (DSC) [2] . The 

thermal stability domains, the composition of the pyrolysis 

products and the thermal effects were determined, on the basis of 

TG, DTG and DSC plots registered in nitrogen flow. Attempts to 

analyze the evolved gases using TG-FTIR coupling were also 

performed. 

It was demonstrated that the stability of the p-tert-butyl 

calix[6]arene derivatives depends on both the type and the number 

of the substituting groups grafted on the calix[6]arene skeleton. 

The thermal stability data complete the characteristics tableau of 

the calixarene-based compounds synthesized for the metal 

sequestration. 

Acknowledgement: This work was possible with the financial 

support of POSDRU 89/1.5/S/60189 Programme. 

references: 

1. Atanassova M., Lachkova V., Vassilev N., Varbanov S., 

Dukov I., Polyhedron, 29, 2010, 655. 

2. Saponar A., Popovici E.-J., Perhaita I., Nemes G., Cadis 

A.-I., Journal of Thermal Analysis and Calorimetry, 2012, 

DOI 10.1007/s10973-012-2415-2. 

Keywords: p-tert-butyl calix[6]arene derivatives; thermal 

analysis; evolved gas analysis; 


P - 0 9 6 4 

eStiMAtion of KinetiCS PArAMeterS for 

ioniC GeLAtion of PoLyACryLAMide in 

different MediA 

M. BAGhBAn SALehi 1 , e. vASheGhAni-fArAhAni 1 , 

M. vAfAie Sefti 1 , A. MouSAvi MoGhAdAM 1 , 

z. SArreShteh dAri 1 

1 Tarbiat Modares University, Chemical Engineering, Tehran, 

Iran 

Polyacrylamide-based hydrogels are used in many water 

shut -off treatments. Gelation time has the most important effect 

on polymer gel injection as the controller of the gel placement in 

porous media. The viscosity of the gelling solution builds up, as 

the gel network starts forming. So gelation reaction could be 

studied with viscosity measurements. In this research, sulfonated 

polyacrylamide was crosslinked with chromium triacetate. The 

kinetics parameters of the gelation reaction in different media such 

as distilled water, sea water, formation water and water contained 

of 10,000 ppm NaCl solution were obtained by steady shear 

viscometry mesearments. Avrami equation was used to obtain the 

reaction rate constant and reaction order. The effect of temperature 

on reaction rate was also investigated the reaction constant which 

was found to be k=9.3E+15 exp (-10244/T) with an activation 

energy of 85.17 KJ/mol for distilled water. It was also found that 

the highest and the lowest order of the reaction was 4.79 and 1.96 

for distilled water and for sea water, respectively. This is due to 

the presence of monovalent and/or divalent ions in the gelant 

solution which reduced the reaction rate of the gelation with 

consequent increase of gelation time. 

Keywords: Hydrogels; Kinetics Parameters; Avrami Equation; 

Reaction Rate Constant; Reaction Order; 



s1345 

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P - 0 9 6 5 

BioConJuGAtion throuGh MiLd And 

SeLeCtive nuCLeoPhiLiC SuBStitution of 

ALCohoLS “on wAter” 

S. SAuLnier1 , v. LoPez-CArriLLo1 , P. G. Cozzi1 1 University of Bologna, Dipartimento di chimica G. Ciamician, 


Bioconjugation is an expanding field of research.Novel 

methods for the mild and site-specific derivatization of 

biomoleculeshave been developed for applications such as ligand 

discovery, diseasediagnosis, and high-throughput screening. 

These powerful methods owe theirexistence to the discovery of 

chemoselective reactions that enablebioconjugation under 

physiological conditions. A number of water-compatibleorganic 

transformations such as nucleophilic additions to carbonyl, 

1,3-dipolarcycloadditions, Diels-Alder reactions, olefin 

cross-metathesis and palladiumcatalysed cross-coupling reactions 

have been optimized for use withbiomolecular substrates in 

biological systems. From this perspective, thedirect nucleophilic 

substitution of an alcohol is attractive as it should yieldwater as 

the only by-product. However, the activation of alcohols in 

physiologicallyconditions is a fairly challenging topic. 

Wedescribe a particular class of alcohols that can generate 

stabilized carbocationsin aqueous media through “on water” 

catalysis and that way react with variousnucleophiles in mild 

conditions. The thiol group of cysteine residues can beeasily 

alkylated in these conditions and the reaction shows a 

completeselectivity in the case of competitive reactions between 

several amino acidsbearing nucleophilic side chains (tyrosine, 

tryptophan, serine, aspartic acid). 

Allthe alcohols described can be functionalized for further 

application withoutaffecting their reactivity; they are therefore 

suitable for bioconjugation.This bioconjugation method is the first 

one based on the direct S 1-typenucleophilic substitution of 

N 

alcohols in aqueous media without the requirementof additional 

catalysis. 

Keywords: Amino acids; Carbocations; Conjugation; 

Nucleophilic substitution; Water chemistry; 


P - 0 9 6 6 

new CovALent orGAniC frAMeworKS BASed 

in PeryLenediiMide derivAtiveS 

r. SeBAStiAn 1 , C. BALeizAo 1 

1 Instituto Superior Técnico, CQFM-Centro de Química-Física 


Design and synthesis of microporous materials such as 

conjugated microporous polymers (CMPs), metal-organic 

frameworks (MOFs) or covalent-organic frameworks (COFs) 

have gained momentum in recent years due to their applications 

such as gas storage, catalysis, or semiconductors [1–3] . In particular, 

COFs are an emerging class of nanostructured porous and 

crystalline materials composed by light elements linked by strong 

covalent bonds to form 2D or 3D architectures [4] . 

COFs have received remarkable attention as gas storage 

materials as a result of their high thermal stability, low density 

and high surface area. Up to now, the incorporation of photoactive 

molecules in COFs reticular structures is scarce. From this 

perspective, perylenediimide (PDI) derivatives are excellent 

candidates for ligands in COFs due to the unique properties 

(excellent chemical, thermal, and photo stability). 

Here in, we present the preparation and photophysical 

characterization of a new COF incorporating perylenediimide 

derivatives as ligands. These new materials will find application 

as imaging agent or solar cell active material. 

references: 

1. Jiang, J.; Su, F.; Trewin, A.; Wood, C. D.; Campbell, N. L.; 

Niu, H.; Dickinson, C.; Ganin, A. Y.; Rosseinsky, M. J.; 

Khimyak, Y. Z.; Cooper, A. I. Angew. Chem. Int. Ed. 2007, 

46, 8574. 

2. Li, H.; Eddaoudi, M.; O’Keeffe, M.; Yaghi, O. M. Nature 

1999, 402, 276. 

3. Côté, A. P.; Benin, A. I.; Ockwig, N. W.; O’Keeffe, M.; 

Matzger, A. J.; Yaghi, O. M. Science 2005, 310, 1166. 

4. Spitler, E. L.; Colson, J. W.; Uribe-Romo, F. J.; Woll, A. R.; 

Giovino, M. R.; Saldivar, A.; Dichtel, W. R. Angew. Chem. 

Int. Ed. 2012, 51, 2623. 

Keywords: Metal-organic frameworks; Solid-state structures; 

Dyes/Pigments; 



s1346 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 6 7 

ProPeLLer-ShAPed MonoMerS with 

AnthrACene BLAdeS for toPoCheMiCAL 

SyntheSiS of 2d PoLyMerS 

M. ServALLi 1 , d. SChLüter 1 , J. SAKAMoto 1 

1 ETH Zurich, Materials Science, Zürich, Switzerland 

We aim at the rational synthesis of 2D polymers, defined as 

“one monomer unit thick” covalent periodic networks. These new 

synthetic materials, in contrast to conventional polymers, are not 

easy to prepare due to the complex chemistry behind it. To achieve 

the goal, we are exploring a topochemical polymerization 

approach based on a rational monomer design. Here we present 

two propeller-shaped monomers bearing anthracene blades. We 

expect these monomers to form laminar single crystals in which 

the anthracenes stack face-to-face in each layer. After 

crystallization of the monomers, photo-irradiation of the laminar 

crystals can induce the [4+4]-cycloaddition reaction among the 

stacked anthracenes to directly convert the layers to the 

corresponding 2D polymers. These are then to be isolated as 

individual discrete entities by solvent-induced delamination as 

previously demonstrated in our group. Synthesis of the monomers 

was performed by employing Sonogashira cross-coupling 

reactions of readily accessible building blocks. 

Keywords: Crystal engineering; Cycloaddition; 

Photochemistry; Monolayers; 


P - 0 9 6 8 

SyntheSiS And AntiMyCoBACteriAL 

evALuAtion of n-BenzyLPyrAzine-2- 

-CArBoxAMideS 

B. ServuSovA 1 , M. doLezAL1 , M. KLeMentovA1 , 

K. KrALovA2 1 Charles University in Prague Faculty of Pharmacy in Hradec 

Kralove, Department of Pharmaceutical Chemistry and Drug 

Control, Hradec Kralove, Czech Republic 

2 Comenius University in Bratislava Faculty of Natural 

Sciences, Institute of Chemistry, Bratislava, Slovak Republic 

In spite of slowly reducing incidence, tuberculosis (TB) 

belongs to one of the major causes of bacterial infections and 

mortality in the world. However, the increasing incidence of 

resistant mycobacterial stems underlines the need to develop new 

efficient antituberculars. [10] Pyrazinamide (PZA), an essential 

component of short-course antituberculosis chemotherapy, is used 

as a model structure for substances referred in this research 

project. Various substituted N-benzylpyrazine-2-carboxamides 

were prepared as potential antimycobacterial and herbicidal 

agents by two step synthesis. Substitution of aromatic ring in 

benzylamines was based on the experience with analogously 

substituted N-phenylpyrazine-2-carboxamides (already proved to 

be active). [2] 

Prepared compounds were characterized by analytical data 

and screened for in vitro antimycobacterial activity against 

Mycobacterium tuberculosis H37Rv, M. kansasii and two 

different stems of M. avium. The compounds were also tested for 

their photosynthesis-inhibiting activity (PET – the inhibition of 

photosynthetic electron transport in spinach chloroplasts, Spinacia 

oleracea L.), DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea, 

IC = 1.9 µmol.l 50 -1 ) was used as standard. 

Several of prepared compounds exhibited relatively good 

antimycobacterial activity against M. tuberculosis H37Rv 

comparable with PZA, e.g. N-(3-trifluoromethylbenzyl)pyrazine- 

-2-carboxamide (MIC=25 µg.ml-1 ). Other compounds were also 

active against stems resistant to PZA. 

Photosynthesis-inhibiting activity of the studied 

compounds was moderate or low in comparison with DCMU, 

e.g. 5-tert-butyl-N-(3-trifluoromethylbenzyl)pyrazine-2-carboxamide 

(IC = 15.6 µmol.l 50 -1 ). 

Acknowledgement: This study was supported by the Grant 

Agency of the Charles University (B-CH/ 710312), by the 


and by the Ministry of Health of Czech Republic (IGA NZ 13346). 

references: 

1. Global tuberculosis control, 

WHO report 2011, WHO/HTM/TB/2011.16, 

Accessed at: www.who.int/tb/publications/global_report/ 

/2011/gtbr11_full.pdf, 

November 6th , 2011 

2. Dolezal, M.; Kesetovic, D.; Zitko, J. Curr. Pharm. Des. 

2011, Vol. 17, No. 32, pp 3506-3514 



s1347 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 6 9 

CoAxiAL MuLtiChroMoPhoriC PhotoSySteMS 

G. SforAzzini 1 , n. SAKAi 1 , S. MAtiLe 1 



The organization of chromophores is pivotal for the 

performance of optoelectronic devices. [1] Control of the dyes’ 

positioning offers the possibility to regulate the dye to dye 

interactions and to tune the optical and electronic properties of 

the chromophores. In the present work we report the preparation 

of well-organized multichromophoric coaxial charge-transport 

architectures consisting of phthalocyanine (Pc) and 

perylenediimide (PDI). Here, a rationally designed Pc, containing 

structurally supporting peptide side-chains, hydrazides, 

polymerizable disulfides and diphosphonate anchoring groups 

was covalently bound onto an ITO surface. Self-organizing 

surface-initiated polymerization (SOSIP) [2] was used to build 

vertically aligned Pc assemblies (p-type channel) covalently 

linked by disulfide bonds. An outer vertical electron-transporting 

pathway (n-type channel) was introduced by Pc hydrazide 

functionalization with PDI aldehydes. [3] The proposed bottom-up 

approach allows the preparation of highly organized coaxial 

double-charge transport architectures which could be used as 

potential active components in photovoltaic cells. 

references: 

1. Bhosale, R.; Misek, J.; Sakai, N.; Matile, S.; Chem. Soc. 

Rev., 2010, 39, 138–149. 

2. Sakai, N.; Lista, M.; Kel, O.; Sakurai, S.; Emery, D.; 

Mareda, J.; Vauthey, E.; Matile, S., J. Am. Chem. Soc. 

2011, 133, 15224–15227 

3. Sakai, N.; Matile, S. J. Am. Chem. Soc. 2011, 133, 

18542–18545. 


P - 0 9 7 0 

SyntheSiS of noveL BenziMidAzoLe 

hydrAzone derivAtiveS And itS 

C-nuCLeoSideS with AntituMer ACtivity 

K. ShAheen 1 , S. ABu-BAKr 1 , h. toKudA 2 

1 National research centre, Photochemistry Department, Cairo, 

Egypt 

2 Kyoto Prefectural University of Medicine, Molecular 

Biochemistry Department, Kyoto, Japan 

Email: khashaheen@hotmail.com 

2-Methylene (aryl) hydrazinobenzimidazole derivatives 

2a-e was obtained when compound 1 refluxed with 

each of p-methoxybenzadehyde, p-fluorobenzaldehyde, 

p-nitrobenzaldehyde 1 , acetaldehyde and formaldehyde in 

presence of ethanol and catalytic amount of piperidine. Also, the 

triazole derivatives 3a-e was obtained by stirring compounds 

2a-e with mixture of bromine, glacial acetic acid and acetic 

anhydride. Heating compound 1 under reflux with 

2-acetylthiophene and in the presence of ethanol, afforded 

compound 4. In the same way, compound 1 undergoes 

many consecutive reactions with some monosacharides as 

D (+)-glucose, D (+)-mannose and D (+)-xylose to afford new 

acyclic N-nucleosides. On other hand, 2-mercapto benzimidazol 

was reacted with α-bromo-2',3',4', 6'-tetra-O-acetyl-D-gulcose or 

galactose and furnish derivatives 10a,b. Also, 2-mercapto 

benzimidazol was reacted with sugar like as 2-chloroethanol or 

3-chloro-1,2-propandiol, it give 11a,b. All tested compounds have 

antitumor activity with different percentages. 

Keywords: Hydrazinobenzimidazole; 2-Acetylthiophene; 

Triazole derivatives; Acyclic N-nucleosides; Antitumor activity; 



s1348 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 7 1 

SuLfoxide AuxiLiAry ControLLed SuzuKi 

tyPe C–C-CroSS CouPLinG for the SyntheSiS 

of AxiALLy ChirAL BiAryL nAturAL ProduCtS 

P. SChMitz 1 , A. SPeiCher 1 , S. ChoPPin 2 , 

f. CoLoBert 2 


Germany 

2 Université de Strasbourg, Laboratoire de stéréochimie, 

Strasbourg, France 

Axially chiral compounds are very important not only as 

ligands in organic syntheses but also as natural products. There 

are many reports of protocols that provide access to biaryl 

compounds with a high degree of axial stereocontrol. [1] 

The natural products Isoplagiochin C and D are cyclic 

bis(bibenzyls) which have been isolated from liverworts and are 

showing remarkable antitumor, antibacterial and antifungal 

activities. Intriguingly, these compounds offer a non-obvious 

chirality due to the combination of two biaryl axes, a helical 

stilbene unit and the ring-strain of the entire molecule. [2] 

Therefore, the use of chiral conditions for the C–C-cross coupling 

reaction to construct the stereo-determining axis “A” should give 

raise to an enantioselective synthesis of the macrocyclic 

isoplagiochin framework. 

We refer syntheses of axially chiral biaryls which 

can be obtained by an asymmetric (diastereoselective) 

Suzuki–Miyaura-cross coupling between phenyl boronic esters 

and an aryl iodide tethered sulfoxide auxiliary in ortho-position. [3] 

These syntheses provide the desired axially chiral biaryls in yields 

ranging from 51-98%, and with diastereoselectivities in the range 

50-98% de employing an asymmetric Suzuki-Miyaura process 

with Pd(OAc) and SPhos or (R)-/(S)-BINAP as ligands. 

2 

The further synthesis to Isoplagiochin C or D is based on typical 

Suzuki, Wittig and McMurry protocols. [4,5] 

references: 

1. a) Bringmann, G. et al., Angew. Chem. Int. Ed. 2005, 44, 

5384. 

b) Baudoin, O., Eur. J. Org. Chem. 2005, 4223. 

2. Bringmann, G.; Speicher, A. et al., J. Am. Chem. Soc. 

2004, 126, 9283. 

3. Colobert, F. et al., Org. Lett. 2009, 11, 5130. 

4. Eicher, T.; Speicher, A. et al. Eur. J. Org. Chem. 1998, 

877. 

5. Speicher, A.; Kolz, J.; Sambanje, R. P. Synthesis 2002, 

2503. 

Keywords: Suzuki coupling; axial chirality; biaryls; chiral 

sulfoxide; natural products; 


P - 0 9 7 2 

nAnoPAtterninG By MoLeCuLAr PoLyGonS 

n. SChÖnfeLder 1 , e. SiGMund 1 , S. S. JeSter 1 , 

S. hÖGer 1 


Shape-persistent macrocycles are formed by 

cyclooligomerization of respective acetylene-terminated building 

blocks under oxidative coupling conditions and subsequently 

separated by recycling gel permeation chromatography. 

Self-assembled monolayers of the monodisperse compounds are 

investigated by scanning tunneling microscopy at the interface of 

1,2,4-trichlorobenzene and highly oriented pyrolytic graphite. The 

macrocycles (n>2) can be viewed as equilateral molecular 

polygons (triangles, squares, pentagons, hexagons) that consist of 

a rigid backbone and long flexible alkoxy side chains. We 

particularly focus on dithiophene corner units linked by 

p-phenylene-ethynlene-butadiynylene rods. The length of the 

latter can be systematically increased, and the related polygon 

dimensions define the pattern periodicities. Additionally, we 

investigated mixtures of the polygons and obtained well-ordered 

mixed monolayers at the graphite surface. 

references: 

1. S.-S. Jester, E. Sigmund, S. Höger, J. Am. Chem. Soc. 

2011, 133, 11062. 



s1349 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 7 3 

CoPPer CAtALyzed AryLAtion of 

AryLethynyL-PiviLAniLideS viC C-h 

ACtivAtion 

A. SinAi 1 , A. MeSzAroS 1 , z. novAK 1 


Hungary 

Transition metal catalyzed C-H activation is one of the most 

important synthetic tools in recent organic chemistry. 

Functionalization of aromatic systems bearing directing groups 

can be achieved most frequently with palladium or copper 

catalysts. Beside several coupling partners, diaryl iodonium salts 

are used as aryl transfer reagents. With the utilization of 

hypervalent iodine compounds anilides can be functionalized in 

orto or meta position depending on the applied catalyst. Recently 

Gaunt discovered the meta selective arylation of anilides with 

diaryl iodonium salts in the presence of copper. [1] 

The poster presentation will discuss our recent results on the 

functionalization of o-arylethynyl-anilides with diaryl iodonium 

salts in copper(II)-triflate catalyzed C-H functionalization. 

references: 

1. Phipps, R. J. Gaunt, M. J. Science, 2009, 323, 1593-1597. 

Keywords: C-H activation; copper; Iodine; Aromatic 

substitution; palladium; 


P - 0 9 7 4 

fLuoreSCenCe BASed MetAL ion deteCtion By 

ALKyL/AryL PyrenyL SuLfoxideS 

r. S. KAthAyAt 1 

1 Organic Chemistry Institute, Organic Chemistry, Zürich, 

Switzerland 

Chemosensors are molecules which respond to binding 

analytes of interest by changes in its colourimetric, photophysical, 

electrochemical properties. Fluorescence being a very sensitive 

and non-invasive technique is well suited for chemosensing. 

Fluorescent chemosensors for ions have been widely used to 

monitor ions’ concentrations in biological, environmental and 

biomedical assays. Most such fluorionophores are based on 

signaling mechanisms like photoinduced electron transfer (PET), 

intramolecular charge transfer(ICT) or binding-induced 

conformational restriction [1] . Prevention of photoinduced electron 

transfer by oxidation of sulfoxide to corresponding sulfone has 

been used to detect oxidant analytes e.g. Triacetone triperoxide 

(TATP) [2] . Interestingly, oxidation of sulfide to corresponding 

sulfoxide leads to decrease in fluorescence quantum yield, an 

observation which cannot be explained by PET quenching [3] . 

These less fluorescent sulfoxides provide an opportunity to 

develop fluorescent chemosensors based on fluorescence recovery 

upon ion binding by the sulfoxide. A series of alkyl/aryl pyrenyl 

sulfoxide were synthesized and found to exhibit fluorescence 

enhancement with Zn2+ and Li + , and reduction with Fe3+ metal 

ions. 

references: 

1. Sergey A. Malashikhin, Kim K. Baldridge, 

Nathaniel S. Finney, Org. Lett. 2010, 12, 940-943. 

2. Sergey A. Malashikhin, Nathaniel S. Finney, J. Am. Chem. 

Soc. 2008, 130, 12846-12847. 

3. a) Yushen Guo, William S. Jenks, J. Org. Chem. 1995, 60, 

5480-5486. 

b) Brian W. Vos, William S. Jenks, J. Am. Chem. Soc. 

2002, 124, 2544-2547. 

Keywords: Chemosensors; Fluorescence; alkyl/aryl pyrenyl 

sulfoxides; 



s1350 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 7 5 

LewiS ACid CAtALySed inverSe 

eLeCtron-deMAnd dieLS-ALder reACtion 

– A new SynthetiC entry to SteroidS 

M. SiSA 1 , w. herMAnn 1 

1 University of Basel, Organic Chemistry, Basel, Switzerland 

A highly functionalized cyclopropanated naphthalene is 

easily accessible in one step via a domino inverse 

electron-demand Diels-Alder (IEDDA)-cyclopropanation reaction 

catalysed by a bidentate Lewis acid [1] . This intermediate can be 

transformed [2] to a precursor ideally suited for a homo-Nazarov 

cyclization [3] yielding directly the 6-6-6-5-tertacyclic steroid ring 

system. This strategy provides a straightforward access to steroids, 

i.e. estrogens as potential anticancer agents, which are difficult to 

prepare by standard steroid functionalization procedures. 

references: 

1. S. N. Kessler, H. A. Wegner, in preparation. 

2. S. E. Denmark, R. Klix, Tetrahedron, 1988, 4043. 

3. F. De Simone, J. Andres, R. Torosantucci, J. Waser, Org. 

Lett., 2009, 11, 1023. 

Keywords: Synthetic methods; Total synthesis; Steroids; 


P - 0 9 7 6 

SyntheSiS of PorPhyrin eSterS with BiLe 

ACidS 

K. SKACh 1 , L. CArdovA 2 , P. drASAr 2 

1 Masaryk Secondary School of Chemistry, Student, Prague, 


2 Institute of Chemical Technology, Department of Chemistry of 


The goal of this project was to synthesize porphyrin with 

bile acid. Bile acids are acids derived from cholesterol. Basic bile 

acid is cholic acid and chenodeoxycholic acid. These acids are 

very important part of metabolism – they are in bile and make its 

largest organic ingredient. Bile acids have an important role in 

digestion of lipids [1] . The second part of synthesized molecules 

was porphyrin. Porphyrins are cyclic organic substances derived 

from tetrapyrrol of porphyn. They make basis of huge number of 

important substances like heme, vitamin B12 and chlorophyll [2] . 

Substances similar to these which we prepared may be used in 

pharmacy. 

We have prepared the derivate of porphyrin from 

commercially obtained meso-(tetrahydroxyphenyl)porphyrin by 

successful synthesis with lithocholic and cholic acid. 

Esterification proceeded in DMF with chemical reagent EDAC 

or HOBt. Porphyrin synthesized with cholic acid was thereafter 

metalized by ions of gadolinium, cooper, nickel or zinc. 

Every synthesized substance was characterized by NMR, 

mass, infrared and UV-VIS spectroscopy. Measurements proved 

successful synthesis of substances and pointed out to other 

different properties. 

Planed synthesis of six substances unknown to date and their 

characterization was successful. In case of substance 2, there were 

aggregation studies made in different proportion DMSO : H O 2 

which indicate the likely properties of heteroaggregation. [3] 

references: 

1. Lubanda H., et al.: Chem. Listy, 103, 40 – 51, (2009). 

2. Král V., et al.: Physiol. Res. 55, Suppl. 2 S3-S26, 2006. 

3. Monti D., et al.: Chiral amplification of chiral porfyrin 

derivates by templated heteroaggregation, Journal of 

American Chemical Society, 129(21):6688-9 (2007). 

Keywords: Porphyrinoids; Steroids; Metalation; 



s1351 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 7 7 

MASS SPeCtroMetriC inveStiGAtion of 

rutheniuM CAtALySed reACtionS 

A. SKriBA 1 , J. roithovA 1 

1 Faculty of Science Charles University in Prague, Organic and 

Nuclear Chemistry, Prague 2, Czech Republic 

Transition metal catalysts have occupied the central role in 

most carbon-carbon bond-formation reactions in context of 

selectivity (chemo-, regio-, diastereo and enantioselectivity) and 

atom economy. Compared to other transition metals, ruthenium 

has the widest scope of oxidation states (from -2 valent to 

octavalent) and various coordination geometries in each electron 

configuration. This led to an increased use of ruthenium catalysts 

in numbers of reactions. [1, 2] According to these universal properties 

there is a need to deeply explore the reaction mechanisms to 

discover and understand the great potential of this metal. 

Binding energies of ruthenium complex RuCp(CH CN) PF 3 3 6 

have been studied by mass spectrometry using collision induced 

dissociation with xenon and ligand exchange interactions with 

unsaturated hydrocarbons. Reaction intermediates have 

been investigated by spectroscopic measurements using 

infrared multiphoton dissociation spectroscopy. [3] Experimental 

measurements have been compared with quantum chemistry 

calculations using density functional theory methods. 

references: 

1. Murahashi, S.; Takaya, H.; Naota, T. Chem. Rev. 1998, 98, 

2599. 

2. Trost, B. M.; Frederiksen, M. U.; Rudd, M. T. Angew. 

Chem., Int. Ed. 2005, 44, 6630. 

3. Roithova, J. Chem. Soc. Rev. 2012, 41, 547. 

Keywords: Ruthenium; Mass spectrometry; IR spectroscopy; 

Density functional calculations; 


P - 0 9 7 8 

PrePArAtion of PorPhyrin-BASed hPLC 

CoLuMnS for the SePArAtion of fuLLereneS 

J. SLAvíCeK 1 , S. SABAtA 2 , K. LAnG 3 , P. LhotáK 1 


Organic Chemistry, Prague, Czech Republic 

2 Institute of Chemical Process Fundamentals of the ACSR v. v. 

i., Department of Organic Synthesis and Analytical Chemistry, 


3 Institute of Inorganic Chemistry of the ACSR v. v. i., 

Laboratory of Bioinorganic Chemistry, ReD, Czech Republic 

Because of their interesting properties fullerenes are very 

attractive compounds both for the industry and for the basic 

research. Their massive applications are still restricted due to their 

high price, which is a consequence of very complicated separation 

from the crude fullerite soot. It is known that fullerenes can 

interact with porphyrin moieties, especially if they are 

preorganised in suitable geometry. We prepared some HPLC 

columns based on 5,10,15,20-(p-aminophenyl)porhyrin and his 

metallated derivatives anchored on silica gel. These columns were 

used in the separation of fullerene mixtures by HPLC under 

different conditions and the results were compared with those of 

commercial columns designed for fullerene analysis.This research 

was supported by the Czech Science Foundation (GACR 

203/09/0691) and finacial support from specific university 

research (MSMT No 21/2012). 

Keywords: Fullerenes; Separation; Porphyrin; 

Chromatography; 



s1352 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 7 9 

unPreCedented MetA-SuBStitution of 

CALixArenS: direCt wAy to inherentLy 

ChirAL reCePtorS 

P. SLAviK 1 , M. dudiC 2 , K. fLidrovA 1 , J. SyKorA 3 , 

i. CiSArovA 4 , S. BÖhM 1 , P. LhotAK 1 


Organic Chemistry, Praha 6, Czech Republic 

2 Academy of Sciencies of Czech Republic, Institute of Organic 

Chemistry and Biochemistry, Praha 6, Czech Republic 

3 Academy of Sciencies of Czech Republic, Institute of Chemical 

Process Fundamentals, Praha 6, Czech Republic 

4 Charles University, Department of Inorganic Chemistry, Praha 2, 


The electrophilic aromatic substitution in calix[n]arene 

series is a well-established procedure leading exclusively to the 

para-substituted derivatives. Here, we describe an unprecedented 

regioselectivity of mercuration reaction leading to the 

meta-substituted calix[4]arenes. We have recently described 

similar unexpected regioselectivity during the nitration and 

formylation of thiacalix[4]arene [1] skeleton. 

These compounds represent a new type of substitution 

pattern in classical calixarene chemistry and open the door for the 

straightforward synthesis of inherently chiral receptors based on 

calixarenes. 

Acknowledgement: This research was supported by the Czech 

Science Foundation (P207/12/2027). 

references: 

1.. a) O. Kundrat, J. Kroupa, S. Böhm, J. Budka, V. Eigner, 

P. Lhotak, J. Org. Chem. 2010, 75, 8372-8375. 

b) O. Kundrat, I. Cisarova, S. Böhm, M. Pojarova, 

P. Lhotak, J. Org. Chem. 2009, 74, 4592-4596. 

c) O. Kundrat, H. Dvorakova, V. Eigner, P. Lhotak, J. Org. 

Chem. 2010, 75, 407-411. 

Keywords: Calix[4]arenes; 


P - 0 9 8 0 

BuiLdinG BLoCKS for SuPrAMoLeCuLAr 

PhotoCAtALySiS BASed on 

2,2'-BiBenziMidAzoLe 

d. SorSChe 1 , n. roCKStroh 2 , S. rAu 1 


Germany 

2 Leibniz Institut für Katalyse, Angewandte Homogenkatalyse, 

Rostock, Germany 

In natural photosynthesis, light driven electron transfer 

processes between an oxygen evolving manganese cluster and 

several reduction catalysts lead to efficient water splitting and 

fixation of CO . In green leafs, the process is powered by 

2 

light absorption through the porphyrin-moieties of the 

photosystems P680 and P700. In artificial photosynthesis, 

tris(bipyridyl)ruthenium(II) complexes have proven their ability 

to convert light as efficiently into electronic energy to drive 

chemical conversions. One of the most challenging aspects here 

is to establish the directional electron transfer between two 

catalytically active systems. Looking at the electron transfer chain 

of the z-scheme, guiding the intermolecular transport of an excited 

electron through supramolecular pre-orientation is an interesting 

route. [1] Several groups including ourselves have shown that 

ruthenium(II) chromophors containing a bibenzimidazole ligand 

establish defined supramolecular assemblies with anions as well 

as cations through hydrogen bonds. [2–4] Since such aggregation 

changes the luminescent properties of the complexes, the 

corresponding complexes can also be considered as luminescent 

sensors. Following the procedure presented by Siegel et al. [5] we 

synthesized several substituted bibenzimidazoles and their 

corresponding ruthenium(II) complexes and characterized them 

with respect to their photochemistry, also in the presence of 

several guest molecules. 

references: 

1. S. Rau, B. Schäfer, S. Schebesta, A. Grüßing, W. Poppitz, 

D. Walther, M. Duati, W.R. Browne, J.G. Vos, Eur. 

J. Inorg. Chem., 2003, 8, 1503–1506 

2. S. Rau, T. Büttner, C. Temme, M. Ruben, H. Görls, 

and D. Walther*, M. Duati, S. Fanni, and J.G. Vos*, 

Inorganic Chemistry 2000 39 (7), 1621–1624 

3. Y. Cui, Y-L. Niu, M-L. Cao, K. Wang, H-J. Mo, Y-R. Zhong, 

and B-H. Ye, Inorganic Chemistry, 2008, 47 (13), 

5616–562 

4. N. Rockstroh, K. Peuntinger, H. Görls, D. M. Guldi, 

F. W. Heinemann, B. Schäfer, and S. Rau*, Z. Naturforsch, 

2010, 65b, 281 

5. Y. Yasui, D.K. Frantz, and J.S. Siegel*, Organic Letters 

2006 8 (22), 4989-4992 

Keywords: Bibenzimidazole; Ruthenium; Photochemistry; 

Supramolecular; 



s1353 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 8 1 

SyntheSiS of tetrAhydroChroMenoindoLe 

viA AzACouMeStAneS 

A. SPeiCher 1 , L. deJon 1 


Germany 

Heterocyclic natural products, particularly indoles play a 

prominent role in biological systems. A multiplicity of 

biologically active natural products and agents derive from the 

indole nucleus, hence a selective synthesis of indole derivatives 

still is of high interest. [1] 

Recently, from the roots of Robinia pseudoacacia 

H. Mohammed isolated a new natural product of the 

tetrahydrochromenoindole[4,3-b] type, which can be considered 

as the “indole” analogue of the well-known medicarpine. Further 

research has showed the cytotoxic effect of the compound against 

human promyelocytical leukemia cells. [2] Therefore, because 

of its promising properties, a total synthesis of 

tetrahydrochromenoindoles is worthwhile. 

Here, we report on the regioselective synthesis of this 

heterocyclic structure through Suzuki-Miyaura-coupling between 

indole boronic esters and adequate substituted arylcarbamates [3] 

to appropriate indolecarbamates in 71–83% yield. Subsequent 

intermolecular cyclisation provides an azacoumestane as 

intermediate, which affords the desired natural product by 

reduction and subsequent hydrogenation. 

references: 

1. M. Nazaré et al., Angew. Chem. 2004, 116, 4626. 

2. H. Mohammed, Natural and synthetic flavonoid 

derivatives with potential antioxidant and anticancer 

activities, Dissertation 2009, Universität des Saarlandes. 

3. C. A. James et al., J. Org. Chem. 2009, 74, 4094. 

Keywords: heterocycles; indole; natural products; total 

synthesis; 


P - 0 9 8 3 

eLeCtriC-fieLd ASSiSted PhotoGenerAtion 

in PoLy(n-vinyLCArBAzoLe) doPed with 

2,4,7-trinitrofLuorenone 

A. StefAniuK 1 

1 Lodz University of Technology, Department 

of Molecular Physics, Lodz, Poland 

Email: anna.stefaniuk@hotmail.com 

Polymeric photoconductors have many positive 

characteristics such as wide spectral sensitivity, low cost, and 

architectural flexibility. Such materials can exhibit high 

photogeneration efficiency, though in general they show relatively 

low charge carrier mobility. The polymeric photoconductors 

known thus far are polymers with a saturated backbone containing 

active chromophores as pendant groups or molecularly dispersed 

dopands. Poly(N-vinylcarbazole) (PVK), sensitized by adding the 

electron acceptor 2,4,7-trinitrofluorenone (TNF), is the best 

known and most widely investigated polymeric charge-transfer 

(CT) complex system. [1–2] 

In this paper we present results of examination of surface 

voltage photodischarge in PVK+TNF CT system. The samples of 

PVK, and their CT complexes with TNF were prepared by 

dissolving them in dichloromethane and by casting them on 

chromium-plated metal supports at room temperature. For the 

PVK+TNF system, one can recognize the CT band at around 

450 nm. 

The photogeneration quantum yield in the obtained 

nanocomposites were determined by means of Surface Potential 

Decay method consisting in monitoring of speed of the surface 

potential decay induced by illumination of the film with different 

initial surface potential. An HBO-200 mercury lamp with 430 nm 

interference filter was used as a light source. PVK+TNF films 

show remarkably dark decay and photodecays of the doped PVK 

samples are initially very quick. The potential decay rate is 

proportional to the photogeneration quantum yield of PVK+TNF 

system. 

references: 

1. Meltz, P. J., J. Chem. Phys., 57, 1694, (1972) 

2. Borsenberger, P. M., Weiss D. S., Organic Photoreceptors 

for Imaging Systems, Marcel Dekker, Inc., New York, 

(1993) 

Keywords: Photophysics; Polymers; 



s1354 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 8 4 

CAtALytiC hydroGenoLySiS of CALixArene 

derivAtiveS 

f. SteJSKAL 1 , P. LhotAK 1 

1 Institute of Chemical Technology, Organic Chemistry, Prague 6, 


Tobisu et al. recently published work about selective 

hydrogenolysis of alkyl(aryl)ethers and arylpivalates using silane 

and nickel(0) as a catalyst. [1] Using this method on calix[4]arenes 

can lead to dehydroxylated derivatives in high yield. 

First step in the synthetic pathway is creation of derivatives 

suitable for hydrogenolysis. Due to the presence of silane, all free 

hydroxy groups have to be modified. Pivalate can be used as a 

reactive group and rest of the substituents should be unreactive 

propoxy group. This can lead to several derivatives differing in 

conformational isomerism, number of reactive pivalates and 

substituents on upper rim. 

These derivatives can undergo hydrogenolysis using the 

Ni(cod) /PCy catalytic system and dimethoxymethylsilane as a 

2 3 

hydrogenolytic agent. Preliminary results show creation of 

didehydroxydipropoxycalix[4]arene in low yield. 

Another method was recently published by Sergeev and 

Hartwig. [2] They used N-heterocyclic carbene ligands instead of 

relatively unstable PCy . Best results were achieved with 

3 

1,3-bis(2,6-diisopropylphenyl)imidazolidinium chloride activated 

by sodium terc-butoxide. Hydrogen was used as the 

hydrogenolytic agent although silanes can be used as well. Using 

this system on tetramethoxycalix[4]arene afforded partially 

hydrogenated products. Reaction optimization should lead to 

higher yields and afford selectively hydrogenolysed derivatives. 

references: 

1. Tobisu M., Yamakawa K., Shimasaki T., Chatani N.; 

Nickel-catalyzed reductive cleavage of aryl–oxygen bonds 

in alkoxy- and pivaloxyarenes using hydrosilanes as a 

mild reducing agent, Chem. Commun., 2011, 47, 

2946–2948 

2. Sergeev A. G., Hartwig J. F.; Selective, nickel-catalyzed 

hydrogenolysis of aryl ethers, Science, 2011, 332, 439-443 

Keywords: Calixarenes; Nickel; Carbene ligands; Silanes; 

Hydrogen; 


P - 0 9 8 5 

SyntheSiS And StruCturAL Study of SuGAr 

derivAtiveS of oLiGoPyrroLeS uSinG 

CirCuLAr diChroiSM 

P. StePAneK 1 ,J. KAMinSKý 2 , o. šiMáK 2 , P. drAšAr 1 

1 Institute of Chemical Technology Prague, Deaprtment of 


2 IOCB AS CR, Flemngovo nam. 2, Praha 6, Czech Republic 

Email: jakub.kaminsky@uochb.cas.cz 

Ultraviolet circular dichroism (CD) is a standard mean for 

determining average secondary structure of many systems. 

Empirical interpretations of the CD spectra are very often not 

reliable. Unfortunately, CD is quite a complex phenomenon, and 

its simulations are currently still restricted by limited computer 

power and methodology problems [1] . This is unfortunate as CD 

provides enhanced information not only about molecular 

structure, but also about molecular interactions comprising solvent 

or other molecules. 

Therefore, combined computational techniques were utilized 

to provide more reliable representation of the experimental data. 

The theory was applied for carbohydrate-oligopyrrole 

condensates. The cyclic oligopyrroles (e.g. calix[4]pyrroles), 

similarly as porphyrin–carbohydrate conjugates, were found 

important as sensitizers in the photodynamic therapy. They can 

also incorporate into cell membranes, and interact with DNA and 

nucleotides, and exhibit electrochemical properties suitable for 

catalysis or usage in analytical chemistry. Calix[4]pyrrols were 

described as anion and neutral binders, chromatic, fluorescent or 

optical sensors.(e.g. Schell, 1999 or Zhang, 2001). 

A single calix[4]pyrrole cycle has zero CD signal. But chiral 

molecules (even not absorbing in UV-VIS, such as saccharides) 

can induce measurable CD. The CD signatures were studied with 

mono- or disubstituted tetrapyrroles. Effect of their aggregation 

into bigger units were also tried to be studied by concentration 

dependence. 

We aimed our attention to the direct carbohydrate 

functionalisation of oligopyrrole core via stable C-glycosidic 

bound which mimics well normal O-glycosides. This area is very 

challenging because even when we elarge the scope, cyclic 

oligopyrroles with carbohydrate substitution the meso-like and 

β-pyrrolic are rather rare [3] . 

references: 

1. Kaminský J. et al. J. Phys. Chem. A, 2011, 115, 

1734–1742. 

2. Štepánek P.; Šimák O.; Nováková Z.; Wimmer Z.; Drašar P.: 

Org. Biomol. Chem., 2011, 9(3), 682-683. 

3. a) Rusin, O., Král,V., Escobedo J. O., Strogin R. M., Org. 

Lett., 2004, 6, 1373; 

b) Zelenka K., Trnka T., Tislerová I., Král V., Dukh M., 

Drašar P., Collect. Czech. Chemm. Commun., 2004, 69, 

1149. 

Keywords: Circular dichroism; C-Glycosides; Supramolecular 




s1355 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 8 6 

SALt-induCed effeCt uPon the ProxiMity 

Between the Pyrene LABeLed PoLy(ACryLiC 

ACid) And SdS MiCeLLe 

G. StinGA 1 , A. BArAn 1 , A. ioveSCu 1 , M. MAxiM 1 , 

d. f. AnGheL 1 



The effect of salt upon the proximity between the pyrene 

labeled poly(acrylic acid) (PAAPy) and SDS micelles was studied 

by steady-state and time-resolved fluorescence spectroscopy. The 

technique employed was the fluorescence energy resonance 

transfer (FRET) between naphthalene probe as donor and Py label 

used as acceptor. We explored the changes at the level of the 

micellar interface caused by the presence of polyelectrolyte. A 

significant change of FRET was observed increasing both salt and 

surfactant concentrations. The donor-acceptor distances were 

calculated using Förster theory. A minimum donor-acceptor 

distance was established for a critical salt concentration. The 

favored interactions that involve SDS binding to PAAPy result 

from a delicate charge screening effect of Na + counterions acting 

at the micellar interface. 

Keywords: fret; micelles; polymers; 


P - 0 9 8 7 

A new Method for the MetALAtion of 

AzoBenzeneS 

J. StrueBen 1 , A. StAuBitz 1 



The direct metalation of azobenzene often leads to a 

reduction of the azo group to give hydrazine derivatives as main 

products instead of the desired metalated azobenzene species. [1] 

As an example, the maximum yield for the lithiation of 

azobenzene by halogen metal exchange is around 42 %. [2] 

Therefore, in cross-coupling reactions with azobenzenes, these 

compounds always servs as electrophiles (for example the 

iodinated species) which greatly limits the scope of the reaction. 

To solve this problem, we have developed a new, fast and easy 

method to metalate and transmetalate azobenzenes selectively in 

para and meta position of their aromatic units in high yields. We 

show that these can be used as reactants in cross-coupling 

reactions. 

references: 

1. F. A. Garlichs-Zschoche, K. H. Dötz, Organometallics 

2007, 26, 4535-4540. 

2. T. Kozlecki, L. Syper, K. A. Wilk, Synthesis 1997, 681. 

Keywords: Azo compounds; Lithiation; Transition metals; 



s1356 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 8 8 

noveL heteroAreniuM CAtALyStS for 

SuLfoxidAtionS 

J. SturALA 1 , r. CiBuLKA 1 

1 Institute of Chemical Technology Prague, 

Department of Organic Chemistry, Prague, Czech Republic 

Chemoselective introduction of oxygen into an organic 

molecule represents one of the key transformations in organic 

synthesis. Many organocatalysts are capable to introduce oxygen 

(even stereoselectively) into an organic substrate, e.g. chiral 

ketones and iminium salts. Among them, flavinium salts seem to 

be the most promising mediators for sulfoxidations and 

Baeyer-Villiger oxidations. [1] These catalysts are inspired by 

natural enzymes, where flavin moiety is present in the active site. 

In the catalysis of oxidations with hydrogen peroxide, flavinium 

salts form flavin-hydroperoxide which is the oxidising agent for 

the substrate. Oxidations of sulfides promoted by flavinium salts 

are highly chemoselective – no overoxidation to sulfones occurs. 

Use of chiral flavinium salt results in stereoselective oxidation. [2] 

We have found that flavin moiety is not necessary 

– pyrazinium salts [3] bearing electron-withdrawing substituents 

form pyrazine-6-hydroperoxides and oxidise substrates in similar 

manner as flavin catalysts. Major advantage of these salts is easy 

availability. 

This work is focused on heteroarenium salts based on 

pyrimidine. Effect of both electron-withdrawing and 

electron-donating groups in position 2- and 4- is examined to 

determine influence of electronic effects on catalytic cycle. Also 

effect of alkyl chain length and counteranion was studied to 

optimize catalyst core for introduction of cyclodextrin moiety and 

to make oxidations stereoselective. 


Ministry of Youth, Sports and Education of the Czech Republic 

(specific university research no. A2_FCHT_2012_012) and the 

Czech Science Foundation (Grant No. P207/12/0447). 

references: 

1. Gelalcha, F. G. Chem. Rev. 2007, 107, 3338-3361. 

2. Mojr, V.; Budesinsky, M.; Cibulka, R.; Kraus, T. Org. 

Biomol. Chem. 2011, 9, 7318-7326. 

3. Ménová, P.; Kafka, F.; Dvoráková, H.; Gunnoo, S.; Šanda, 

M.; Cibulka, R. Adv. Synth. Catal. 2011, 353, 865-870. 

Keywords: organocatalysis; pyrimidine salts; sulfoxidation; 

organic peroxides; 


P - 0 9 8 9 

MoLeCuLAr SwitCh BASed on CuCurBituriL 

J. SveC 1 , v. SindeLár 1 

1 Masaryk University Fac Sci, Department of Chemistry, Brno, 


Macrocycles cucurbit[n]uriles (CBn) can create 

supramolecular complexes with some positivly charced guest. We 

used as a guest simple lutidine derivative with carboxyalkyl 

group. We will demonstrated that the lutidine derivative forms 

stable inclusion complexes with CB6 and CB7 at acidic water. 

Under the complex formation CB6 engulfs aliphatic part of the 

guest contrary to CB7 which bind lutidinium part. Affinity of 

lutidinium toward CB6 is weaker compared to CB7 also the 

exchange of the guest molecule within the macrocycle take place 

significantly slower in the former case. Under basic condition the 

lutidinium•CB6 complex dissociates while the formation of 

lutidinium•CB7 also with smaller value of association constant. 

Acknowledgements: Support for this work was provided by the 

project CETOCOEN (no. CZ.1.05/2.1.00/01.0001) from the 

European Regional Development Fund (V.S.) and 

AMVIS/KONTAKT II (LH11012; V.S.). 

Keywords: Receptors; Macrocycles; 



s1357 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 9 0 

SyntheSiS of diAryLKetoneS froM 

ALdehydeS And n-AryLACetAMideS viA 

PALLAdiuM CAtALyzed C-h ACtivAtion under 

MiLd AqueouS ConditionS 

f. SzABo 1 , t. nAGy 1 , d. SiMKo 1 , A. MeSzAroS 1 , 

J. dAru 2 , A. StirLinG 2 , z. novAK 1 

1 Eotvos Lorand University, Organic Chemistry, Budapest, 

Hungary 

2 Chemical Research Center, Theoretical Chemistry, Budapest, 

Hungary 

The importance of cross coupling reactions in synthetic 

organic chemistry is well known. Recently couplings via C-H 

activation came to the front due to its halogen free, 

environmentally benign way of create new carbon-carbon bonds. 

Herein, we present our results on the palladium catalyzed 

oxidative coupling of substituted N-arylacetamides and 

benzaldehyde derivatives. This orto directed palladium catalyzed 

coupling via C-H activation was discovered very recently, 

however the known procedures require high temperature and 

organic media. We developed a mild condition to prepare a wide 

range of N-(2-benzoylphenyl)-acetamides using water as a 

solvent, at room temperature. The presented conditions allow 

straightforward transformations in shorter reaction time, and the 

functionalization of more challenging substrates. Mechanistic 

investigations are also discussed. 

Keywords: C-H activation; Ketones; Cross-coupling; 

Palladium; Oxidation; 


P - 0 9 9 1 

twiSted ChirAL PAddLewheeL StruCture: 

SyntheSiS And StruCture deterMinAtion of 

dirhodiuM CoMPLexeS By ChiroPtiCAL 

SPeCtroSCoPy 

G. SziLvAGyi 1 , B. BreM2 , G. BAti1 , e. vASS1 , 

M. hoLLoSi1 , z. MAJer1 1 Eötvös Loránd University, Department of Organic Chemistry, 


2 Babes-Bolyai University, Department of Chemistry and 

Chemical Engineering, Cluj-Napoca, Romania 

Dinuclear rhodium complexes are versatile compounds, 

being currently used as effective catalysts, anticancer agents and 

building blocks for supramolecular chemistry [1] . We have 

developed methods for separation and synthesis of 

tetrakis(carboxylato)dirhodium(II) 

[Rh (µ-O CR) (µ-O CCH ) x:1-4] complexes, where the chiral 

2 2 x 2 3 4-x 

ligands were protected amino acids [2] . Based on our previous 

work [3] we found that vibrational and electronic circular dichroism 

spectroscopies are powerful tools for determining the steric 

structure of chiral complexes. This presentation deals with 

diastereoselective synthesis and structure elucidation of chiral 

rhodium complexes where the used ligands are natural and 

unnatural amino acids and other carboxylic acids. The synthesis 

is simple, without additional reagents, and water can be used as 

green solvent. These complexes have non-tipical, twisted 

paddlewheel structures, because the chiral ligands are coordinated 

to the Rh unit by bidentate chelating mode. Their steric structure 

2 

was determined by chiroptical (VCD, ECD) spectroscopy 

supported by theoretical calculations at ab initio (DFT) level of 

theory. Results of the theoretical calculations on the electronic 

structure of studied complexes indicate their applicability in 

catalytic reactions. 

Acknowledgements: OTKA K81175 (M. Hollósi), TÁMOP- 

4.2.2/B-10/1-2010-0030, KMOP-4.2.1/B-10-2011-0002, 

ERASMUS 

references: 

1. Cotton, F. A.; Murillo, C. A.; Walton, R. A. (Eds.) Multiple 

Bonds between Metal Atoms Originally published by John 

Wiley (1st ed.) and Oxford University Press (2nd ed.) 3rd ed., 2005 

2. Szilvágyi, G.; Hollósi, M.; Tölgyesi, L.; Frelek; J.; Majer, 

Zs. Tetrahedron: Asymmetry 2008, 19, 2594. 

3. Szilvágyi, G.; Majer, Zs.; Vass, E.; Hollósi, M.; Chirality, 

2011, 23(4), 294. 

Keywords: Chiroptical spectroscopy; ECD; VCD; chiral 

dirhodium complex; 



s1358 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 9 2 

ePiMerS vS. inverSe ePiMerS: the ABSoLute 

ConfiGurAtion of ALnuMyCinS 

P. tAhtinen 1 , t. oJA 2 , n. dreiACK 1 , P. MAntSALA 2 , 

J. nieMi 2 , M. MetSA-KeteLA 2 , K. KLiKA 1 

1 University of Turku, Department of Chemistry, Turku, Finland 

2 University of Turku, Department of Biochemistry and Food 

Chemistry, Turku, Finland 

Alnumycins are aromatic polyketides produced by 

Streptomyces bacteria. They are composed of an 

isochromanequinone aglycone which is directly linked via a C-C 

bond to a sugar or a sugar-like unit. The bacterial aromatic 

polyketides have a number of established medicinal applications 

including use as antibiotics. Alnumycin A was originally described 

as a single compound but it was recently found to consist of a set 

of six stereoisomeric compounds [1] . They were isolated as part of 

our work elucidating the biogenesis of these compounds [2] . 

The determination of whether two stereoisomers constitute 

an epimeric pair or if they differ in their configuration at all 

stereogenic centers bar one can be a formidable challenge and 

represent a problem of greater complexity than just determination 

of absolute configuration per se. The latter stereochemical 

relationship is hereby defined as a pair of inverse epimers and is 

exemplified by alnumycins A1–3 to introduce the concept [1, 3] . 

Of these three pairs of naturally occurring C-1 inverse epimers, 

for the two new ones, alnumycins A2 and A3, the assignment of 

relative configurations was assigned based on 1H NMR NOE 

contacts and molecular modeling using density functional theory 

(DFT). Absolute configurations and inverse epimeric relationships 

were determined by the use of NMR spectroscopy together with 

chiral derivatization (MTPA) and by experimental circular 

dichroism (CD) measurements in conjunction with theoretical 

calculations. 

references: 

1. Oja, T.; Tähtinen, P.; Dreiack, N.; Mäntsälä, P.; Niemi, J.; 

Metsä-Ketelä, M.; Klika, K. D. Tetrahedron: Asymm. 

2012, In press, DOI: 10.1016/j.tetasy.2012.05.001 

2. Oja, T.; Klika, K. D.; Appassamy, L.; Sinkkonen, J.; 

Mäntsälä, P.; Niemi, J.; Metsä-Ketelä, M. Proc. Natl. 

Acad. Sci. U. S. A. 109, 2012, 6024 

3. Tähtinen, P.; Oja, T.; Dreiack, N.; Mäntsälä, P.; Niemi, J.; 

Metsä-Ketelä, M.; Klika, K. D. RSC Adv. 2012, Published 

online, DOI: 10.1039/C2RA20537H 

Keywords: Enantioselectivity; Diastereoselectivity; 

Polyketides; Circular dichroism; NMR spectroscopy; 


P - 0 9 9 3 

BridGed AzoBenzeneS – A new GenerAtion of 

SwitCheS 

t. teLLKAMP 1 

1 Otto Diels-Institut, Organic Chemistry, Kiel, Germany 

Azobenzenes as photochromic switching unit have been 

used to achieve a number of dynamic molecular functions. 

Driving directed motion in molecular motors or on surfaces is not 

possible because the “mechanical” power stroke affected by the 

trans-cisisomerization can point in two directions leading to two 

enantiomeric cis isomers. Randomly directed power strokes 

would not lead to directed motion. 

We therefore designed molecules based on azobenzene units 

that would perform power strokes preferentially to one direction 

(leading to diastereomers of different energy). Diazocines 

(azobenzenes bridged by a CH -CH group in ortho position) are 

2 2 

a good starting point for molecular design because diazocines are 

superior to azobenzenes with respect to photoconversion and 

quantum yield. [1] Whereas the parent diazocine still performs 

isomerization in two directions steric hindrance can be introduced 

at the CH -CH bridge or at the ortho positions of the phenyl 

2 2 

groups to disfavor one direction. 

The final goal is to attach these modified diazocines 

covalently to molecular platforms [2] and to prepare self-assembled 

monolayers. Directed motion would be induced by a cilia like 

movement of the switchable units using polarized light. 

references: 

1. R. Siewertsen, H. Neumann, B. Buchheim-Stehn, 

R. Herges, C. Näther, F. Renth, F. Temps, 

J. Am. Chem. Soc. 2009, 131, 15594-15595. 

2. B. Baisch, D. Raffa, U. Jung, O. M. Magnussen, 

C. Nicolas, J. Lacour, J. Kubitschke, R. Herges, 

J. Am. Chem. Soc. 2009, 131, 442-443. 

Keywords: Azo compounds; Diazo compounds; Isomerization; 



s1359 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 9 4 

SuBStituted 

5,6-dihydro-4h-PyrroLo[1,2-B]PyrAzoLeS 

L. tenorA 1 , G. JurAJ 1 , M. StAniSLAv 1 , v. AnetA 1 , 

P. MiLAn 1 

1 Masaryk University Faculty of Science, Chemistry, Brno, 


The pyrazole based natural product - alkaloid withasomnine 

was isolated from the roots of Withania somnifera, Newbouldia 

laevis, the shrub Elytraria acaulis and from the stem bark of 

Discopodium penninervium. Beside its analgetic effects, 

withasomnine has both CNS and circulatory system depressant 

properties. There are few publications related to the synthesis of 

this compound. 

We report here two synthetic pathways leading to substituted 

5,6-dihydro-4H-pyrrolo[1,2-b] pyrazoles. The first procedure 

starts with g-butyrolactone, which is transformed to 

6-chlorohex-1-en-3-one alternatively in 3 or 5 steps and 

in following 4 steps we are able to prepare substituted 

bicyclic compounds. The last step is Suzuki coupling where we 

tested different conditions changing substituted boronic acids and 

various Pd-catalysts. The second route comprise thermally 

initiated intramolecular cyclizations of substituted homoallenyl 

azines prepared from homoallenyl aldehydes to desired 

2,4-disubstituted heterocycles. 

Keywords: withasomnine; pyrrolo[1; 2-b]pyrazoles; Suzuki 

coupling; homoallenyl azines; intramolecular cyclization; 


P - 0 9 9 5 

PyrroLidine iMinoSuGArS with BioLoGiCAL 

ACtivity 

f. teodoreSCu1 , C. StAvArAChe 1 , i. MAn1 , 

C. deLeAnu1 , L. tArKo1 , A. hirtoPeAnu1 1 “Costin D. Nenitzescu” Center of Organic Chemistry 

Romanian Academy, Organic Chemistry, Bucharest, Romania 

Pyrrolidine iminosugars are sugar analogs (furanoside form) 

with the endocyclic oxygen replaced by a nitrogen atom, initially 

known as potent glycosidase inhibitors. They have also been 

found to be inhibitors of other glycoprocessing enzymes widening 

the area of their medical applications (drugs for metabolic 

disorders, antiviral and anticancer agents). Iminosugars are 

therefore of growing interest as new therapeutic leads. 

Preparation of pyrrolidine iminosugars is challenging, 

involving multistep procedures with low yields and poor 

stereoselectivities and this is the reason why there are no 

systematic studies on the effect of stereochemistry change at the 

chiral centers in the iminosugar ring. So, new methods are 

required for fast access to a series of these valuable biologically 

active compounds with systematic structural or stereochemical 

changes in order to determine a structure – activity relationship. 

The synthesis of pyrrolidine iminosugars by green and more 

efficient methods involving the use of microwave and/or 

ultrasonic activation will be presented, as well as the 

characterization of the synthesized compounds. 

The most active iminosugars to be synthesized were 

identified with the in-house designed QSAR software: PRECLAV 

(Property Evaluation by Class Variables) based on a calibration 

set for which the biological activity was reported in literature. 

Keywords: pyrrolidine iminosugars; qsar software; 



s1360 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 9 6 

SyntheSiS And ProPertieS of noveL 

SeMiConduCtinG donor-ACCePtor MAteriALS 

C. teuSCh1 , M. ALt2 , n. MeChAu2 , u. Bunz1 , 

K. MüLLen1 , M. hAMBurGer1 1 University of Heidelberg, Organisch-Chemisches Institut, 


2 Karlsruher Institut für Technologie, Lichttechnisches Institut, 

Karlsruhe, Germany 

In Organic Electronics there is a permanent need for new 

electron-conducting materials. To that end, an entire series of 

different acceptors such as fullerenes, phthalocyanines and 

rylene-type dyes has already been successfully examined. [1] 

Nitrogen-containing acenes are a class of semiconducting 

materials which are highly interesting for their application in 

organic electronics. [2] An exciting extension of this topic is the 

connection of these acceptors to donor molecules to form 

π-conjugated oligomeric and polymeric compounds in order to 

adjust electronic properties and to induce intramolecular and 

intermolecular interaction, which enhances charge carrier 

transport. [3] 

Herein, we will report on the synthesis of symmetric 

donor-acceptor-donor systems which can be easily synthesized by 

Pd-catalyzed cross-coupling. According to DFT-calculations, 

these materials show a HOMO-LUMO gap that would make them 

candidates as absorber materials for organic solar cells. 

Furthermore, the energies of the frontier molecular orbitals seem 

to make the synthesized compounds capable of serving as 

semiconductors in OTFTs (organic thin film transistors). 

The opto-electronic properties of the oligomers will be 

examined both in solution and in thin films; their semiconducting 

properties will be studied in field-effect transistors. 

As one aspect of future studies will be printing of these 

materials, special focus will be on their solubility in nonchlorinated 

solvents. 

references: 

1. H. Hoppe, N. S. Sariciftci, J. Mater. Res. 2004, 19, 

1924–1945. 

2. U. H. F. Bunz, Pure Appl. Chem. 2010, 82, 953–968. 

3. Z.-G. Zhang, J. Wang, J. Mater. Chem. 2012, 22, 

4178–4187. 

Keywords: Organic Electronics; Donor-acceptor systems; 

Electron transport; 


P - 0 9 9 7 

MoLeCuLAr dyAdS with StronG PuSh-PuLL 

ChroMoPhoreS AS eLeCtron ACCePtorS: 

SyntheSiS And PhotoPhySiCAL ProPertieS 

L. urner 1 , K. howeS 1 , h. BeLBAKrA 2 , 

P. reutenAuer 1 , A. LiStorti 2 , n. ArMAroLi 2 , 

f. diederiCh 1 

1 ETH Zurich, Laboratory of Organic Chemistry, Zürich, 

Switzerland 

2 Instituto Per La Sintesi Organica E La Fotoreattivita, 

Consiglio Nazionale delle Ricerche, Bologna, Italy 

One of the approaches in the development of organic solar 

cells (OSCs) is the molecular one, wherein a donor (D) and an 

acceptor (A) are covalently attached to a bridging unit (B) in a 

molecular dyad. While impressive progress has been made in 

OSC development, one of the limiting factors, in particular of 

covalent D–B–A dyads, has been the restricted set of acceptors 

used so far, mainly comprising derivatives of fullerenes, perylene 

diimides, and quinones. 

As an alternative to the often used fullerenes, a new class of 

strong organic electron acceptors (push-pull chromophores) has 

been introduced by the Diederich group into covalently linked 

donor-acceptor systems for photoinduced electron transfer (PET). 

These “superacceptors” are accessible by a versatile [2+2] 

cycloaddition (CA), between electron-rich alkynes and 

electron-poor alkenes, e.g. tetracyanoethylene (TCNE), followed 

by a retro-electrocylization (RE). [1, 2] The superacceptors have 

been incorporated into covalently linked molecular dyads with a 

meso-trans-bis(3,5-di-tert-butylphenyl)-zinc-porphyrin as electron 

donor. The photophysical properties of these molecular dyads and, 

of according reference compounds have been studied using steady 

state and time-resolved absorption and luminescence 

spectroscopies, both as solutions in aerated and deaerated toluene 

and benzonitrile. 

As evidenced by nanosecond transient absorption 

spectroscopy, the main deactivation pathway for dyad 1 is energy 

transfer, and electron transfer in the case of dyads 2 and 3. In 

benzonitrile, dyad 2 exhibits a long-lived charge-separated state 

of 2.3 µs. Further studies with this new promising class of 

acceptors are under way to examine their potential for PET in rigid 

molecular dyads, and as novel materials for OSCs. 

references: 

1. T. Michinobu, C. Boudon, J.-P. Gisselbrecht, P. Seiler, 

B. Frank, N. N. P. Moonen, M. Gross, F. Diederich, Chem. 

Eur. J. 2006, 12, 1889. 

2. P. Reutenauer, M. Kivala, P. D. Jarowski, C. Boudon, 

J.-P. Gisselbrecht, M. Gross, F. Diederich, Chem. 

Commun. 2007, 46, 4898. 

Keywords: Molecular electronics; Electron transfer; Energy 

transfer; Supramolecular chemistry; Porphyrinoids; 



s1361 

chem. Listy 106, s257–s1425 (2012) 


P - 0 9 9 8 

SyntheSiS of triCyCLiC indoLe derivAtiveS 

viA ASyMMetriC orGAnoCAtALySiS 

S. vArGA 1 , K. ArAdi 1 , C. SzAntAy 1 , t. SooS 1 



Asymmetric organocatalysis is a powerful method to 

assemble chiral molecules without using transition metals or harsh 

reaction conditions. Most of the applied organocatalysts have been 

synthesized from renewable sources (e.g., amino acids, alkaloids) 

and used in enantio- and diastereoselective syntheses of complex 

chiral molecules, which are valuable building blocks. 

We have developed bifunctional cinchona based thiourea 

catalysts, which have been used in several asymmetric 

transformations with high enantioselectivities and yields [1, 2] . 

Recently, we have applied these bifunctional catalysts in an 

iterative Michael-Michael-Henry process to diastereoselectively 

construct chiral cyclohexanes. This unique selectivity and 

reactivity were explained with the double diastereocontrol 

phenomenon [3] . 

As part of our synthetic program, we wished to apply our 

catalysts in the synthesis of biologically active, natural products, 

namely, indole alkaloids. Thus, we selected 3,4-substituted indole 

compounds to transform them via efficient enantioselective 

organotandem procedures to ergot and secergoline type alkaloids. 

Our results in the asymmetric synthesis of various indole 

derivatives will be disclosed in the poster. 

Acknowledgement: Financial support provided by grants 

OTKA 75705, K-69086, NK-77784 are gratefully 

acknowledged. 

references: 

1. B. Vakulya, Sz. Varga, A. Csámpai, T. Soós Org. Lett. 

2005, 7, 1967-1969. 

2. B. Vakulya, Sz. Varga, T. Soós J. Org. Chem. 2008, 73, 

3475-3480. 

3. Sz. Varga, G. Jakab, L. Drahos, T. Holczbauer, 

M. Czugler, T. Soós Org.Lett. 2011, 13, 5416-5419. 

Keywords: Organocatalysis; Alkaloids; Enantioselectivity; 


P - 0 9 9 9 

dehydroGenAtive heCK reACtion of furAnS 

And thioPheneS with StyreneS under MiLd 

ConditionS 

A. vASSeur 1 , J. MuzArt 1 , J. Le BrAS 1 

1 Institut de Chimie Moléculaire de Reims, Méthodologie en 

Synthese Organique, Reims, France 

The Pd-catalyzed direct cross-couplings of arenes with 

alkenes through C-H activation, also called intermolecular 

Dehydrogenative Heck Reactions (DHRs), have drawn much 

attention in recent years. [1] 

Among the arenes used in DHRs, furans and thiophenes 

have received little attention because the former are acid sensitive 

and the latter require elevated temperatures, due to their higher 

aromatic resonance energy and stability. Moreover, styrenes are 

electron-rich compounds and are a notoriously difficult substrate 

class due to facile polymerization and cleavage under palladium 

oxidative conditions. 

In 2008, we have reported the synthesis of difurylalkanes 

through the bis-coupling of 2-alkylfurans with various alkenes, 

including styrenes. [2] Then, we reported a dehydrogenative 

coupling of furans and styrenes leading to Heck-type products 

which allowed the use of chlorinated and fluorinated substrates. [3] 

The previous transformation occured under mild conditions 

but nevertheless, brominated substrates were reluctant to react. 

Glorius et al. have recently shown that brominated compounds 

can be formed with no proto-debromination using Rh catalysts; 

however few examples have been reported and the scope of 

substrates remains to be developed. [4] We will present the DHRs, 

under mild conditions, of furans and thiophenes with styrenes, 

including brominated substrates. [5] The influence and the role of 

the oxidizing agent on the activity of the catalyst will be also 

discussed. 

references: 

1. Le Bras, J.; Muzart J. Chem. Rev. 2011, 111, 1170-1214. 

2. Thiery, E.; Harakat, D.; Le Bras, J.; Muzart, J. 

Organometallics 2008, 27, 3996-4004. 

3. Aouf, C.; Thiery, E.; Le Bras, J.; Muzart, J. Org Lett. 

2009, 11, 4096-4099. 

4. a) Rakshit, S.; Grohmann, C.; Besset, T.; Glorius, F. 

J. Am. Chem. Soc. 2011, 133, 2350-2353; 

b) Patureau, F. W.; Glorius, F. J. Am. Chem. Soc. 2010, 

132, 9982-9983. 

5. Vasseur, A.; Muzart J.; Le Bras, J. Chem. –Eur. J. 2011, 

17, 12556-12560. 

Keywords: C-H activation; Cross-coupling; Heck reaction; 

Palladium; Homogeneous catalysis; 



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chem. Listy 106, s257–s1425 (2012) 


P - 1 0 0 0 

fLuoreSCent Core dendriMerS – 

PhotoPhySiCAL ProPertieS Study 

P. vinS1 , P. drASAr1 , v. CeBoLLA2 , f. CoSSio3 1 Institute of Chemical Technology Prague, Department of 


2 Institute of Carbochemistry, High Council of Scientific 

Investigation, Zaragoza, Spain 

3 University of Basque Country, Department of Organic 

Chemistry I and Donostia International Physics Center, 

Donostia – San Sebastian, Spain 

Dendrimers are repeatedly branched macromolecules, which 

have been widely studied because of their intriguing properties as 

part of light-harvesting or charge-transport systems, catalysts or 

drug delivery systems. [1] 

In this work a set of dendrimers with Fréchet’s polyaromatic 

dendrons [2] and a fluorescent core consisting of natural dye 

apigenin was prepared. Convergent method of dendrimer 

synthesis was applied in order to gain sufficient control over final 

products structure, confirmation of which was provided mainly 

by NMR spectrometry and MALDI-TOF mass spectroscopy. The 

four new fluorescent dendrimers obtained, tri-O-methyl and 

tri-O-benzyl apigenin were used as subject compounds for 

photophysical properties comparison, with focus on fluorescence 

quantum yield and excitation state half-time as well as evolution 

of their ultraviolet absorption spectra. As the group of prepared 

compounds is possessing identical fluorescent core, progressive 

growth of number of aromatic layers in their dendritic branches 

enabled us to observe the influence of aromatic periphery on the 

dendrimer center. 

Interesting non-linear development of fluorescence quantum 

yield along with growing dendrimer generation number was 

observed as well as bathochromic shift in absorption spectra 

which was previously reported in case of metalloporphyrin cored 

polyaromatic dendrimers. [3] 

Acknowledgement: Ministry of Education, Youth and Sports of 

the Czech Republic in a project No. MSM6046137305. 

Donostia International Physics Center (DIPC). 

references: 

1. Lo, S.-C.; Burn, P., L.: Chem. Rev. 2007, 107, 1097. 

2. Hawker, C., J.; Fréchet, J., M., J.: J. Am. Chem. Soc. 1990, 

112, 7638. 

3. Matos, M., S.; Hofkens, J.; Verheien, W.; De Schryver, F.,C.; 

Hecht, S.; Pollak, K., W.; Fréchet, J., M., J.; Forier, B.; 

Dehaen, W.: Macromolecules 2000, 33, 2967. 

Keywords: Dendrimers; Fluorescence; 


P - 1 0 0 1 

PhoSPhonAte MetAL orGAniC frAMeworKS 

A. viSA1 , B. MArAneSCu1 , G. iLiA1 , M. MrACeC2 1 Institute of Chemitry Timisoara of Romanian Academy, 

Organic Chemistry, Timisoara, Romania 

2 Institute of Chemitry Timisoara of Romanian Academy, 

Computational Chemistry, Timisoara, Romania 

Phosphonates metal organic frameworks (MOF) are a very 

important class of compound with special properties, fascinating 

network topology and structural flexibility. Cobalt 

vinylphosphonate was obtained in our labs by the reaction of 

Co(NO ) 6H O, vinyl phosphonic acid in equimolecular ratio and 

3 2 2 

hydrothermal conditions. The synthesized compound was 

characterized by FTIR, elemental analysis, X-Ray 

crystallography, thermogravimetric analysis and quantochemical 

calculations. In order to compare the calculated and experimental 

geometric properties of the cobalt vinylphosphonate metal organic 

framework we performed a PM3 semi-empirical analysis of 

structural properties. For this reason five octahedral models were 

calculated: three arising from constructed geometries and two 

from experimental RX data [1, 2] . From the PM3 semi-empirical 

results the calculated bond lengths, bond angles and torsion angles 

are lower or comparable than the experimental ones. 

The LUMO-HOMO energetic difference decreases from the 

simplest to more complex model reaching to a value of 1.465 eV. 

Belonging to the same group of the periodic table of the elements 

cobalt and rhodium are expected to have the same electrical 

behavior. Using the same model, calculations were performed for 

rhodium vinylphosphonate. As is expected, in the case of rhodium 

vinylphosphonate, the LUMO-HOMO energetic difference 

decreases from the simplest to more complex model reaching to 

a value of 2.168 eV. This small difference allows one electron 

transition from the superior level into a conduction band and 

predicts the semiconductor properties of these compounds. 

references: 

1. R.M.P. Colodrero, A. Cabeza, P. Olivera-Pastor, D. 

Choquesillo-Lazarte,A. Turner, G. Ilia, B. Maranescu, 

K. E. Papathanasiou, G.B. Hix, K.D. Demadis, M.A.G. 

Aranda, 2011, Inorganic Chemistry, 50, 11202-112011 

2. B. Maranescu, A. Visa, M. Mracec, G. Ilia, V. Maranescu, 

Z. Simon and M. Mracec Rev. Roum. Chim, 2011, 56(5), 

473-482 

Keywords: metal phosphonate; semiempieical calculations; 

semiconductors; 



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chem. Listy 106, s257–s1425 (2012) 


P - 1 0 0 2 

MeMory of ChirALity of tertiAry AroMAtiC 

AMide:APPLiCAtion to the ASyMMetriC 

SyntheSiS of S ALPhA MethyLdoPA And 

nonProteinoGeniC AMino ACidS 

B. viSwAMBhArAn 1 , t. t. MAi 1 , d. Gori 1 , 

C. KouKLovSKy 1 , v. ALezrA 1 

1 Université Paris-Sud 11, Institut de Chimie Moléculaire et des 

Matériaux d’Orsay (ICMMO), Orsay Cedex, France 

Compounds possessing ‘axial chirality’ around a sigma 

bound are of great interest in asymmetric synthesis, especially in 

the field of chiral ligands (BINAP). Among these compounds, 

tertiary aromatic amides (eg. Benzamides, anilides), suitably 

substituted at the aromatic ring or at nitrogen, present ‘Dynamic 

Axial Chirality’, and have been less studied. Since 2005, 

Dr. V. Alezra and Pr. C. Kouklovsky have been developing some 

asymmetric synthesis of non proteinogenic quaternary/tertiary 

α-amino acids, based on ‘Dynamic Axial Chirality of tertiary 

aromatic amides’ and on the ‘Memory of Chirality’ (MOC)/ 

‘Frozen Chirality’ (FC) principle. [1–3] 

The objective is the application of this methodology for the 

synthesis of (S)-α-methylDOPA, a well-known quaternary amino 

acid, used in the treatment of hypertension, proceeding by the 

concept of ‘MOC-alkylation’, the only source of chirality being 

the starting D-alanine. The strategy involves i) the conversion of 

D-analine to its tertiary naphthamide, initial central chirality of 

the starting amino acid is transferred and induces an axial chirality 

to 1-naphthoyl oxazolidinone, ii) careful deprotonation/alkylation 

of the oxazolidinone, the axial chirality is retained while the 

central chirality is lost during enolization, iii) optimized 

deprotection of the oxazolidinone resulted (S)-α-methylDOPA 

with 98% ee after five steps. 

In continuation of our work, we envisaged the asymmetric 

synthesis of non proteinogenic β-hydroxy-α-amino acids by the 

above developed methodology and the real challenge is the 

diastereoselective creation of a second asymmetric center. We are 

able to extend this from MOC-alkylation to MOC-Aldol reaction. 

references: 

1. M. Branca, S. Pena, D. Gori, R. Guillot, V. Alezra, 

C. Kouklovsky, J. Am. Chem. Soc. 2009, 131, 

10711–10718; 

2. M. Branca, D. Gori, R. Guillot, V. Alezra, C. Kouklovsky, 

J. Am. Chem. Soc. 2008, 130, 5864–5865; 

3. T.T. Mai, M. Branca, D. Gori, R. Guillot, C. Kouklovsky, 

V. Alezra, Angew. Chem. Int. Ed. 2012, 51 doi 

10.1002/anie201200950. 

Keywords: Asymmetric synthesis; Amino acids; Aldol reaction; 

Chirality; 


P - 1 0 0 4 

the firSt CyCLoPentAdienyL niCKeL 

CoMPLexeS BeArinG A SiLyL SuBStituted 

PhoSPhine CheLAtinG SideChAin 

i. werner 1 , h. ButenSChoen 1 

1 Institut of Organic Chemistry, Leibniz Universitaet Hannover, 

Hannover, Germany 

Since the first report on a cyclopentadienyl complex with a 

transition metal bearing a pendant Lewis base functionalized 

ligand by Mathey et al. in 1978, this area has developed rapidly. 

This class of compounds exhibits a great potential in catalytic 

reactions in terms of catalyst improvement, stabilization of 

otherwise unstable intermediates and influence on stereochemical 

and stereoelectronic properties. 

In particular, complexes with a tertiary phosphine derivative 

in a sidechain have attracted much attention. A phosphine group 

acts as a soft electroneutral σ donor as well as a good π acceptor, 

capable at the same time of reversible coordination. 

The only known secondary phosphine pendant 

cyclopentadienyl complexes are those of zirconium and hafnium, 

reported by Ishiyama et al. in 2002. Since these complexes 

contained a reactive phosphorus-hydrogen bond, they were 

converted into the corresponding phosphide-substituted 

cyclopentadienyl chelate complexes. Both systems were 

successfully applied in catalytic ethylene and styrene 

polymerization reactions as well as in ethylene / styrene 

copolymerization reactions. 

To our knowledge, no analogous complexes of late transition 

metals containing a phosphorus-hydrogen or a phosphorus-silyl 

bond have so far been reported. We now report on the synthesis 

of the first cyclopentadienyl nickel complexes bearing a silyl 

substituted phosphine chelating sidechain. We intend in the future 

to cleave selectively the silyl substituent at phosphorus by 

treatment with a fluoride reagent, generating thus the first 

cyclopentadienyl nickel chelating phosphide complexes. 

Keywords: Cyclopentadienyl ligands; Phosphane ligands; 

Chelates; Nickel; 



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chem. Listy 106, s257–s1425 (2012) 


P - 1 0 0 5 

reCent AdvAnCeS towArdS the SyntheSiS of 

ruBroMyCinS 

M. wiLSdorf 1 , h. reiSSiG 1 



The rubromycin family is a class of natural products which 

is known for exhibiting antibiotic, cytostatic and antimicrobial 

activity. This type of natural products is characterized by a 

challenging molecular architecture whose basic structure consists 

of a highly functionalized naphthoquinone moiety which is linked 

[1, 2] 

to an isocoumarin unit by a 5,6-spiroketal core. 

In continuation of our long standing interest in the synthesis 

of rubromycin and heliquinomycin we here describe our recent 

results concerning a) the improved synthesis of model substrates, 

b) new insights into the process of the acid promoted ketalization 

of benzannuated precursors and c) the challenges and problems 

[3, 4] 

which still have to be solved. 

references: 

1. Review: M. Brasholz, S. Sörgel, C. Azap, H.-U. Reissig 

Eur. J. Org. Chem. 2007, 3801–3814. 

2. M. Chino, K. Nishikawa, T. Tsuchida, R. Sawa, 

H. Nakamura, K. Nakamura, Y. Muraoka, D. Ikeda, 

H. Naganawa, T. Sawa, T. Takeuchi, J. Antibiot. 1997, 50, 

143–146. 

3. S. Sörgel, C. Azap, H.-U. Reissig Org. Lett. 2006, 

4875–4878. 

4. C. Venkatesh, H.-U. Reissig Synlett 2008, 3605–3614. 

Keywords: Natural products; 


P - 1 0 0 6 

A CheMiCAL SyntheSiS of dAnSyLAted 

udP-MurnAC-PentAPePtidefor hiGh 

throuGhPut MrAy ASSAyS 

S. wohniG 1 , C. duCho 1 

1 University of Paderborn, Chemistry, Paderborn, Germany 

Because of the increase in bacterial resistance, the discovery 

of new antibiotics is of high relevance. The membrane-associated 

enzyme MraY, which catalyses the transfer of a 

glycosylphosphate-pentapeptide moiety onto a lipophilic 

membrane anchor in the course of bacterial peptidoglycan 

formation, represents an attractive target for the development of 

new antibacterial agents [1,2] . This enzyme is inhibited by the 

naturally occurring muraymycin nucleoside lipopeptide 

antibiotics [3] . The fluorescently labelled MraY substrate is required 

for high throughput MraY assays as reported by Stachyra et al., 

who used the dansylated derivative of UDP-MurNAcpentapeptide 

for an in vitro MraY assay [4] . A chemical synthesis 

of dansylated UDP-MurNAc-pentapeptide is desired in order to 

obtain an adequate amount, while the isolation from bacteria and 

subsequent dansylation of UDP-MurNAc-pentapeptide affords 

only a small amount of the desired product. 

Starting from commercially available N-acetylglucosamine, 

a protected glycosylphosphate precursor was prepared over seven 

steps in an overall yield of 30%. The peptide unit was synthesised 

using Cbz-protection of the amino function and different peptide 

coupling procedures. A novel convergent [4+1]-strategy for 

pentapeptide assembly gave the dansylated glycosylphosphate- 

-pentapeptide. Following debenzylation and diphosphate coupling 

with a reactive uridine derivative, the target compound was 

obtained after final global deprotection. Latest results on this 

synthetic approach will be presented. 

references: 

1. K. I. Kimura, T. D. H. Bugg, Nat. Prod. Rep. 2003, 20, 

252-273. 

2. M. Winn, R. J. M. Goss, K. I. Kimura, T. D. H. Bugg, 

Nat. Prod. Rep. 2010, 27, 279-304. 

3. L. A. McDonald, L. R. Barbieri, G. T. Carter, E. Lenoy, 

J. Lotvin, P. J. Petersen, M. M. Siegel, G. Singh, R. T. 

Williamson, J. Am. Chem. Soc. 2002, 124, 10260-10261. 

4. T. Stachyra, P. Ferari, A. Bouhss, J. van Heijenoort, 

D. Mengin-Lecreulx, D. Blanot, J. Bilton, D. LeBeller, 

Antimicrob. Agents Chemother. 2004, 48, 897-902. 

Keywords: Antibiotics; Carbohydrates; Fluorescence; 

Nucleotides; Peptides; 



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chem. Listy 106, s257–s1425 (2012) 


P - 1 0 0 7 

GrAftinG of PoLy(1-SuBStituted 

vinyLtriAzoLe) onto CoLLoidAL SiLiCA And 

SeLeCtive CoordinAtion to trAnSition 

MetAL ion 

K. yoShinAGA 1 , S. KAwASAKi 2 , S. MotoKuChou 1 , 

K. KoJio 1 

1 Nagasaki University, Chemistry and Materials Science, 

Nagasaki, Japan 

2 Kyushu Institute of Technology, Applied Chemistry, 

Kitakyushu, Japan 

Triazole compounds exhibit characteristic properties coming 

from π-conjugated five-membered ring with lone pair electrons 

for complex formation with transition metal ion. In this work, 

synthesis of poly(1-substituted-4-vinyl-1,2,3-triazole) and grafting 

of hydrophilic poly(vinyltriazole) to colloidal silica for application 

to selective extraction materials of transition metal ion. 

We examined two synthetic routes via (a) “One Pot” 

reaction and (b) polymerization of vinyltriazole, through “Click 

reaction”. In Route (a), poly(1-octyl-4-vinyl-1,2,3-triazole), 

1a, was obtained in 58% yield, but 2-(2-(2- 

-hydroxyethoxy)ethoxy)ethyl-substituted polymer, 2b, was given 

in low yield of 4%. Radical polymerization of vinyltriazoles in 

Rout (b) afforded polymer 1a of molecular weight 24,000 in high 

yield of 93%, and 2b and 1-(2-hydroxyethyl)-substituted polymer, 

2c, of molecular weight of 7,000 and 15,000 in relatively high 

yield, respectively. The reaction of colloidal silica, of 140 nm in 

diameter, with poly(4-vinyl-1,2,3-triazole)-trimethoxysilane with 

2-(2-(2-hydroxyethoxy)ethoxy)ethyl at 1-position gave high 

disperse polymer-grafted silica in aqueous solution. The hybrid 

particles selectively captured transition metal ion, Ni2+ , Cu2+ , Zn2+ , 

stability constants of which were in the range from 1.4 x 103 to 

3.6 x 103 , being 102 times higher than those of alkali earth metal 

ions, Zn2+ and Mg2+ . 

Keywords: Poly(vinyl triazole); Colloid; Grafting; 

Complexation; 


P - 1 0 0 8 

intrAMoLeCuLAr CyCLizAtion of 

6-hydroxyALKoxyPurineS 

K. zAChArovovA 1 , M. hiML 1 , i. LinhArt 1 



This work is aimed at the synthesis of tricyclic derivatives 

of guanine and hypoxanthine. The O6-Alkylguanines are 

recognized inhibitors of the O6-alkylguanin-DNA-alkyltransferase (AGT). Due to this inhibition, the derivatives are cytostatic by 

increasing the effect of O-alkylations on purine bases in tumor 

cells caused by alkylation agents. These derivatives are therefore 

potentially biologically active. 

The cyclization reactions were performed with 

6-hydroxyalkoxypurines bearing chains of various length, which 

were prepared by two-step synthesis via corresponding 

“DABCO-purines” and following alkoxylation with a diol 

(ethane-1,2-diol, propane-1,3-diol or butane-1,4-diol) in the 

presence of a base. 

The intramolecular cyclization proceeds via the terminal 

hydroxy-group transformation to a better leaving group. Appel 

reaction (Ph P/CBr ) was found to be the most fruitful method 

3 4 

leading to tricyclic derivatives by group transformation followed 

by immediate cyclization. The highest yield (64%) was achieved 

in the case of 2-amino-6-(3-hydroxypropoxy)purine as a starting 

material. Mitsunobu reaction (Ph P/DIAD) was found to give the 

3 

same products as well. These two methods were applied for the 

synthesis of derivatives with five- and six-membered rings. 

Formation of the seven-membered ring has not been achieved. 

All the intramolecular cyclizations of 6-hydroxyalkoxypurines 

proceed on the N1 site of the purine moiety as 

confirmed by two-dimensional NMR. 

Keywords: tricyclic analogues of purines; Appel reaction; 

Mitsunobu reaction; 



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chem. Listy 106, s257–s1425 (2012) 


P - 1 0 0 9 

the Study of infLuenCe of MiCro AdditiveS 

of SinGLe-wALL CArBon nAnotuBeS on 

StreSS-StrAin ProPertieS And StruCture of 

noveL PoLyurethAne BLoCK CoPoLyMerS 

M. zAverKinA 1 , v. KoMrAtovA 1 , A. GriShChuK 1 , 

v. LeSniChAyA 1 , y. eStrin 1 , e. BAdAMShinA 1 

1 Inst.of Problems of Chemical Physics RAS, 

Plastic Binder Laboratory, Chernogolovka, Russia 

Carbon nanotubes are capable to change properties of 

polymers, such as mechanical strength, the Young modulus, the 

tensile strain etc. However, the insufficient attention is given to 

studying of influence of micro additives of single-wall carbon 

nanotubes (SWCNT) on the polymers structure. 

Polyurethane block copolymers (PUBCP) were synthesized 

for the first time in the present work by interaction of 

oligodiethylenglycol adipate (ODGA, crystallization temperature 

T =60 °T), of the mixture of diisocyanates and of agents of chains 

c 

extension in solution at room temperature. The influence of micro 

additives of SWCNT on stress-strain properties and structure of 

PUBCP was studied. 

PUBCP possess quite high Young modulus (about 450 MPa) 

up to T . It undergo orientation deformations up to 900 % with 

c 

forming of the strong rigid films (rupture strength ~ 45 MPa) at 

stretching after achievement of the limit of forced rubberlike 

elasticity. The oriented samples completely restore their initial 

sizes at the heating above T . c 

Introduction of SWCNT in PUBCP (0.002–0.008 wt. %) 

leads to various changes of stress-strain properties and structural 

parameters. Changes of supramolecular structure of polymer 

under the influence of SUNT consist in increase in the Young 

modulus and tensile strain for 20-30 %. Thus, tensile strength of 

the filled and unfilled samples does not change practically. The 

SWCNT additives influence noticeably on relaxation behavior of 

polymer. Thus, recovery of the initial sizes of the samples, 

containing up to 0.008 wt. % of SWCNT, after deformation 

requires more high temperatures and prolonged time in 

comparison with unfilled samples. 

Data of DSC and analysis of X-ray diffraction patterns of 

PUBCP, containing SCNT, testify considerable structural changes 

in comparison with unfilled polymer. The reasons of influence of 

SCNT on structure and properties of synthesized PUBCP are 

discussed. 

Acknowledgement: Financial support by the Russian 

Foundation for Basic Research (the grant ? 12-03-00919-a) is 


Keywords: Polyurethane block copolymers; single-wall carbon 

nanotubes; stress-strain properties and structural parameters; 


P - 1 0 1 0 

effeCt of PyroLySiS ConditionS on the 

SPeCifiC SurfACe AreA of CArBon AeroGeLS 

t. zeLenKA 1 



Carbon aerogels are relatively novel carbon materials with 

unique properties. An aerogel is mainly mesoporous solid state 

material containing up to 95 vol. % of air [1] . These materials can 

be obtained by pyrolysis of organic aerogels, which are prepared 

by sol-gel polycondensation of certain organic monomers such as 

resorcinol and formaldehyde [2] . Due to the ability to control their 

pore texture via the synthesis, drying and pyrolysis operating 

variables, the properties of these materials can be adjusted to fit 

the application. Carbon aerogels has application such as 

supercapacitor, hydrogen electrostorage, adsorption medium or 

catalyst support [3] . Pyrolysis procedure is an important step in 

carbon aerogel preparation due to increase of their specific surface 

area. It was prepared acid and alkaline catalyzed organic aerogels 

and these were pyrolyzed under different conditions. Pyrolysis 

temperature (400–1000 °C) and time of this process (0.5–4 h) 

were studied with relation to their specific surface area. It was 

found that surface area of resulted fragile acid catalyzed carbon 

aerogels are depended on carbonization temperature. In this case 

the largest surface area (~900 m2 g-1 ) corresponds to temperature 

800 °C. Contrary resistant alkaline catalyzed carbon aerogels can 

maintain a relatively high specific surface area up to ~900 m2 g- 1 with no respect to the pyrolysis conditions (except 400 °C). 

Specific surface area of both types of aerogels is independent on 

the pyrolysis time in studied range. 

references: 

1. Hüsing N., Schubert U.: Aerogels-Airy Materials: 

Chemistry, Structure, and Properties. Angewandte Chemie. 

1998, 37, 22-45. 

2. Moreno-Castilla C., Maldorado-Hódar F.J.: Carbon 

aerogels for catalysis applications: An overview. Carbon. 

2005, 43, s. 455–465. 

3. Reuß M., Ratke L.: Subcritically dried RF-aerogels 

catalysed by hydrochloric acid. J Sol- Gel Sci Technol. 

2008, 47, s. 74–80. 

Keywords: Surface analysis; Sol-gel processes; Pyrolysis; 

Carbon aerogel; 



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chem. Listy 106, s257–s1425 (2012) 


P - 1 0 1 1 

A new APProACh to BrASSinoSteroid Side 

ChAin SyntheSiS viA nitriLe oxide 

CyCLoAdduCtS 

h. zhyLitSKAyA 1 , r. LitvinovSKAyA 1 , v. eiGner 2 , 

B. KrAtoChvíL 2 , P. drASAr 3 , v. KhriPACh 1 

1 Institute of Bioorganic Chemistry Has Belarus, Laboratory of 

Steroid Chemistry, Minsk, Belarus 

2 Institute of Chemical Technology, Department of Solid State 


3 Institute of Chemical Technology, Department of Natural 

Compounds, Prague, Czech Republic 

Being versatile tools for new C-C bond formation, nitrile 

oxides are successfully utilized in 1,3-dipolar cycloadditions with 

olefins for the synthesis of different types of compounds. The 

heterocyclic adducts, Δ2-isoxazolines, as the synthetic precursors 

of amino- and keto-alcohols are the convenient building blocks 

for natural products and related compounds. 

In continuation of our studies on application of nitrile oxide 

methodology for the synthesis of natural steroids and their 

modified analogs, here we present a new approach to 

brassinosteroid side chain synthesis via nitrile oxide cycloadducts 

with disubstituted steroidal Δ23-olefins. Steroidal isoxazolines were synthesized by the reaction of 

acetonitrile oxide with cis-, trans- and cyclic 22-hydroxy-Δ 23-olefins, where Δ23 double bond was activated with acceptor ester group. 

Surprisingly, the same set of products (four isoxazolines) was 

obtained both for cis- and trans- olefin substrates, and this result 

was not in the agreement with current opinion on the mechanism 

of 1,3-dipolar cycloaddition as the concerted synchronous one. It 

was shown that under diazabicycloundecene action the product 

set could be converted with a good yield into two isoxazolines 

with a ratio in favor of a product of the desirable (brassinolidelike) 

stereochemistry. 

The structure of new compounds was confirmed by NMR, 

MS, elemental, CD and X-ray analysis. 

The synthesized steroid isoxazolines could serve as the 

convenient precursors of natural brassinosteroids and their 

modified analogs, particularly amino and keto derivatives, and the 

corresponding synthetic routes will be reported. Taking into 

account unusual stereochemical course of the studied reactions of 

1,3-dipolar cycloaddition, asynchronous mechanism of these will 

be discussed. 

Keywords: Brassinosteroids; Nitrile oxides; 1,3-Dipolar 

cycloaddition; Steroids; 


P - 1 0 1 2 

CheMiCAL SyntheSiS of 

Protein-doMAin-ArrAyS 

r. zitterBArt 1 , f. Mende 1 , o. Seitz 1 

1 Humboldt-Universität zu Berlin, Chemistry, Berlin, Germany 

It is our goal to establish an elegant way to synthesize a 

variety of protein domains and small proteins by chemical means, 

to employ them in arrays for assay analysis. Fragment ligation is 

the method of choice for this total synthetic task. We use an 

α-peptide-thioester synthesis with a self-purifying effect, to avoid 

the time- and product-consuming HPLC-purification. We present 

an Fmoc-based solid-phase creation of peptide thioesters with 

self-purification, by the use of Kenner’s Safety Catch 

sulfonamide-linker. Self-purification is achieved consecutively by 

(a) N-terminal coupling of a cleavable cyclization linker, 

subsequent macro cyclization to a resin bound side chain, 

(b) activation of the sulfonamide linkage by alkylation, (c) 

thiolysis generates the side-chain bound thioester and detaches all 

truncation products, washing releases them, and (d) TFA cleavage 

yields the desired full length thioester in high purity. 

We are using this methodology to synthesize different SH3 

domains of yeast by Native Chemical Ligation. To establish the 

method we performed a cysteine scan of the SH3 domain SHO1 

and YSC84. Therefore 20-40 amino acid long peptide thioesters 

were synthesized in parallel with excellent purity. 

A consequent extension of the prior described method is the 

direct application of the generated peptide thioester in a Native 

Chemical Ligation on a solid support. With a tailored cyclization 

linker, the self-purified and deprotected thioester can be ligated 

on the resin with a crude mixture of cysteinyl peptides, since only 

the full length cysteinyl peptide reacts with the thioester; 

truncations might be washed off after ligation. The ligation 

product can whether be released from resin by basic treatment, or 

can be directly applied for usage in an assay, as a convenient 

on-bead immobilization. 

Keywords: peptides; Solid-phase synthesis; protein design; 

Bioorganic chemistry; Total synthesis; 


list of Authors 

s1368 

chem. Listy 106, s587–s1425 (2012) 


A 

Abarca B. s1096 

Abass h. s994 

Abdeen r. s1254 

Abdel Ghany A. s995 

Abdel rahman S. s1106 

Abdel-Salam r. A. s904 

Abdel-wahab B. s982 

Abedi Lenji M. s1080 

Abeyawarathan v. s950 

Abou-ras d. s1222 

Aboutaleb d. s1253 

Abouzid K. s721 

Abramczyk h. s604 

Abrams M. s983 

Abramson r. s859 

Abreu A. r. s1198, s1337 

Abu-Bakr S. s1347 

Abuein M. s1122 

Abuzeid h. s995 

Acar M. s1115 

Accetta A. s795 

Ackermann L. s1014, s1042, s1082, s696 

Adachi J. s1179 

Adam M. s1125 

Adanitsch f. s854 

Addadi L. s832 

Adhami f. s1209, s883 

Adriaan M. s763 

Afewerki S. s1012 

Afonso C. s783 

Agostinho M. s669 

Ahlers J. s1052 

Ahmad A. s1109 

Ahmed i. s650, s903 

Ahn B. S. s1182 

Aidarova S. s1062 

Aijaz Ahmad A. s1332 

Aime C. s1238 

Aimi f. s709 

Akay M. A. s1131, s1142, s610 

Akermark B. s1173, s1174 

Akermark t. s1173, s1174 

Akhmadullina n. s981, s984 

Akimov d. s864 

Akmese B. s1109 

Akpinar G. e. s1263 

Akram S. s608 

Aksakal d. s1264 

Al Anshori J. s1265 

Alajarin M. s1272, s1272 

Albericio f. s787 

Albler C. s998 

Albo y. s904 

Albov d. s991 

Albu A. M. s1266, s1282 

Alcazar Montero v. s1289 

Aldabah A. s1109 

Aldas Candan o. s998 

Aleksandrova G. s721 

Alexandre e. s1161 

Alexei L. s1254 

Alezra v. s1363 

Al-faifi S. s790 

Alghamdi A. s790 

Ali d. s1123 


Ali M. s982 

Aliev r. A. s928 

Al-Khalaf A. s1264 

Allemann o. s1266 

Allendörfer n. s1047 

Almaiuf A. s1109 

Almeida A. r. s1333, s1337 

Almeida d. P. f. s1161 

Almeida L. s1178 

Alni A. s1302 

Al-omar M. s1265 

Alonso doval d. s999 

Al-oweini r. s992 

Alper K. s1012 

Alt M. s1360 

Alvarez de Cienfuegos L. s740 

Alvarez r. s1002, s926 

Alvarez-Builla J. s1096 

Alves C. M. s791 

Alves S. s1159 

Aly S. s1067 

Alzina C. s793 

Alzoubi B. s883 

Alzoubi B. M. s686 

Amadeu de Sousa n. s1340 

Amadeu K. S. s818 

Amador C. s658 

Amaral J. P. s1221, s609 

Amaral J. S. s1159, s793 

Amato f. s1110 

Amatov t. s1305 

Amelia M. s1211 

Ammann M. s637 

Amodio M. s916 

Amouri h. s681 

Amr A. e. s1265 

Amslinger S. s1267, s897 

Anamimoghadam o. s999 

Ananev v. s1110, s1209 

Ananeva v. s1110 

Ananjaroenvong e. s1007 

Anderson h. s732 

Anderson h. L. s1040 

Andersson K. h. o. s1308 

Andrei-Selmer L. s896 

Andrejic M. s860 

Andrikopoulos P. C. s823 

Andrioletti B. s662 

Andronescu e. s1195 

Andronova A. s1121 

Aneta v. s1359 

Anghel d. f. s1034, s1034, s1268, s1269, s1355 

Anic S. s1144 

Antonio t. s860 

Antony L. A. P. s1265 

Anzenbacher Jr. P. s1155 

Aoun S. s1000 

Apak r. s1161 

Aphaiwong A. s1000 

Apotheker J. s620 

Appiani e. s649 

Apryshko G. s991 

Aradi K. s1361 

Archibald S. s607 

Ardizzone S. s849 

Arenas-valganón J. s811, s812 



s1369 

chem. Listy 106, s587–s1425 (2012) 


Arends i. w. C. e. s1295 

Aresta M. s692, s693 

Arico f. s661 

Ariga K. s1230 

Arik M. s1112 

Arikan S. s956, s957 

Arlt w. s1193 

Armaroli n. s1242, s1360 

Armentano A. s1167 

Arnold r. s1111 

Arrabito G. s712 

Arriortua M. s948 

Arriortua M. i. s1207, s953 

Arroyo M. s985 

Arsenijevic J. s600 

Arslan n. s1094 

Arslanoglu y. s956, s979 

Artal v. s1258 

Artel v. s1210 

Artetxe B. s1203, s961 

Artner C. s1236, s964, s979 

Asakawa M. s1238 

Asano A. s1048 

Ascencao C. s906 

Ashfold M. s807 

Ashfold M. n. r. s808 

Ashoka M. s763 

Aslandas A. M. s1111, s1112 

Assaf K. i. s869 

Assfeld x. s821 

Ataee A. s941 

Atakol A. s610 

Atakol o. s1131, s1142, s1149, s610 

Atanackovic n. s645 

Attia S. s958 

Atwood J. s836 

Aubé C. s1001 

Aubert e. s1055, s1055 

Aubrey A. s593 

Auer A. A. s963 

Auroux A. s1199 

Aurrecoechea J. s1002 

Autenrieth B. s1032 

Avellini t. s1211, s1211 

Aversa M. C. s940 

Axthelm J. s861 

Ayan S. s1267 

Aydin B. M. s1112 

Ayme J. f. s953 

Ayora C. s642, s642 

Azadi e. s1230 

Azizoglu M. s1094 

B 

Baader S. s1268 

Babiano r. s1251, s1252 

Babic M. s1263 

Babiuch K. s1102 

Babka o. s643 

Bacalum f. s905 

Bach t. s714, s769 

Bacher M. s896 

Bachl J. s1003 

Bachmann t. s964 

Backaert f. s1002 

Backmann n. s1111 


Bäckvall J. e. s1097, s1174, s806 

Badamshina e. s1105, s1366 

Badamshina e. r. s1309 

Badilita v. s905 

Baek i. h. s1173 

Baghban Salehi M. s1080, s1344 

Bai S. s1215 

Baik w. P. s1231 

Baiula M. s720 

Bajenaru i. G. s905 

Bajerova P. s1124 

Bajerová P. s1131 

Baker r. J. s924 

Bakish i. s1258 

Balali S. s870 

Balandier J. y. s798 

Balcar h. s976 

Bald A. s825, s867 

Baldridge K. s1266, s1276, s859, s862, s878 

Baleizao C. s1212, s1239, s1345 

Balintova J. s1003 

Balk S. s1212 

Balla C. s677 

Ballarin B. s1216, s1220 

Ballini r. s655 

Balogh d. s1004, s1190 

Balogh G. t. s894 

Balteanu d. s644 

Banach M. s877 

Banas P. s872 

Bang e. K. s1004 

Baptista A. d. M. A. s1337 

Bar L. s605 

Baran A. s1268, s1269, s1355 

Barandika G. s1207 

Barath M. s1027 

Barattucci A. s940 

Barbe J. M. s1016 

Barbera J. s628 

Barboiu M. s844 

Barbosa J. s916 

Barbu-tudoran L. s1196 

Barek J. s1117, s1135, s1139, s1140, 

s1146, s1156, s1158, s597 

Barjega S. s1192 

Barlam d. s1224 

Barnea z. s664 

Baroncini M. s734, s738 

Barreiro M. f. s793 

Barrocas B. s1255 

Barron L. s600 

Barros M. t. s1287 

Barroso J. M. s871 

Barrow r. s1005 

Barta J. s933 

Bartel C. s684 

Barth J. s745 

Barth S. s1213, s850 

Barthelme A. s1067 

Bartkowiak K. s1425 

Bartok A. s997 

Bartunek P. s1076 

Barzagli f. s665 

Bar-ziv r. s1241, s952 

Basaran f. s1141 

Basko M. s1005 



s1370 

chem. Listy 106, s587–s1425 (2012) 


Basov n. s1171 

Bassil B. s933, s985, s989, s992, s992, s993 

Bastien G. s782 

Bastl z. s1424 

Bastos e. s1279, s674, s861 

Batail P. s782 

Bati G. s1357 

Baudoux J. s1269, s1338 

Bauer M. s1015 

Bauer S. s884 

Bauer w. s695 

Baumeister u. s1330 

Baumgartner r. s652 

Bause M. s884 

Bay S. s699 

Bayardon J. s1015, s1060 

Bayraktutan t. s1113, s1113 

Bayramoglu M. B. s979 

Bazán B. s1207 

Bazzicalupi C. s679 

Beaugrand S. s1143 

Bebiano S. S. s1204 

Becker t. s957 

Bediha A. s1148 

Bednarek M. s1005 

Bednarova e. s768 

Bednarova L. s724, s886 

Bedrac L. s1304 

Beekman A. s1005 

Beemelmanns C. s1271 

Beer P. d. s863 

Begel S. s945 

Behnam S. s1213 

Behnke t. s903 

Behr J. B. s1029 

Behrends f. s1013 

Bélanger d. s1116, s594 

Belbakra h. s1360 

Belger K. s1270 

Belkhiri S. s919 

Bella M. s770 

Beller G. s688 

Beller M. s756 

Belogurova n. s1270 

Belting v. s1098 

Belvisi L. s720 

Ben t. s842 

Benaliouche f. s966 

Bencivenni M. s726 

Bendle M. s688 

Benfatti f. s1100 

Bennati M. s1241 

Benning L. s903 

Bentz C. s1271 

Berberan-Santos M. n. s1239 

Berenguer J. r. s1223, s682 

Beretta M. s1195, s834 

Bergamini G. s738, s938 

Berger A. s1316 

Berger r. s1271 

Berkessel A. s892 

Berna J. s1272, s1272 

Bernardes G. s796 

Bernardi L. s1091 

Bernhardt f. s656 

Bernhardt G. s884 


Berstis L. s862 

Bert K. s1273, s762 

Bertrand G. s700 

Bertrand L. s1021 

Bertrand M. P. s771 

Berzina M. s942 

Berzins A. s852 

Bester K. s1114, s648, s693, s905 

Bette M. s989 

Betz P. s740 

Beves J. e. s953 

Bevilacqua v. s1166 

Beyer B. s1125 

Bezuidenhout d. s700, s974 

Bhadra S. s1273, s765 

Bialek-Pietras M. s1006 

Bianchi n. s709 

Bichler B. s971 

Bickelhaupt f. M. s819 

Bidondo M. L. s906 

Biely P. s1027 

Bildziukevich u. s1006 

Bilge Kocak S. s991 

Billeter J. s611 

Biocic M. s1145 

Bird G. s644 

Birge r. r. s812 

Birjega r. s1189 

Birkner A. s1226 

Bischin C. s884 

Bischop M. s1286 

Bisio C. s843 

Bistac S. s1007, s1215, s786, s793 

Bitter i. s1281 

Bitto f. s970 

Bivaud S. s798 

Biyiklioglu z. s986, s987, s987, s988 

Bjornholm t. s1229, s1237, s1246, s743 

Black J. C. s885 

Blackstone v. s688 

Blagojevic S. s1144, s1160, s1160 

Bláha M. s881 

Blahova M. s768 

Blanc J. s1101 

Blanco A. s914 

Blanco Jaimes M. C. s1007 

Blanco Suarez v. s735 

Blanchard P. s773 

Blanford C. s740 

Blechert S. s1291, s1316 

Bleha t. s811 

Bleher o. s1129 

Bligh S. w. A. s943 

Blobner f. s830 

Bocarsly A. B. s693 

Bocian S. s1115 

Boeuf G. s1214 

Boey f. s814 

Bogdanovic G. s1020 

Bohac A. s898 

Bohle A. s1330 

Bohlender C. s946 

Böhm S. s1352 

Böhme u. s689, s967 

Boiko M. s1114 

Boisbrun M. s1330 



s1371 

chem. Listy 106, s587–s1425 (2012) 


Bollmann u. e. s648 

Bonacchi S. s749 

Bonaccorsi P. s940 

Bonacic-Koutecky v. s589, s817 

Bonakdarzadeh P. s1008 

Bongen P. s1274 

Bonifazi d. s731, s805 

Bonnefille e. s1198 

Bonnet S. s698 

Bonnot A. s936 

Bonvin d. s611 

Borcherding h. s612 

Borges S. s874 

Borghei G. s608 

Borisova A. s984 

Börner h. G. s749 

Bornscheuer u. s703 

Boros i. s1314 

Borovcova L. s1129 

Borovikova L. s721 

Borovska J. s778 

Borshchev o. s1214 

Bortel G. s1235, s1249 

Borys n. s1083 

Bosshak A. s995 

Botoshansky M. s797 

Bottesini C. s1168 

Bottger e. s1008 

Bottka e. B. s1274 

Boucheffa y. s919, s966 

Boudesocque S. s651 

Bouffier L. s595, s744 

Bougdour A. s714 

Bougrine A. J. s1331 

Bouhadid M. s802 

Bouhadja y. s980 

Bouit P. A. s739, s747 

Bourahla K. s1091 

Bousquet M. s1143 

Boutilier J. s613 

Boyd t. s697 

Boyes S. s1038 

Boyron o. s792 

Bozkurt e. s1115 

Bracco S. s1195, s834 

Braese S. s842 

Branco L. s665 

Branná P. s1275 

Bräse S. s1315 

Bratu A. s1160 

Brauch S. s1275 

Bräutigam M. s826, s830, s862 

Bredow t. s816 

Breeden S. s1182 

Bregadze v. s942 

Breitzke h. s1198, s1340 

Brem B. s1357 

Brendler e. s967, s970 

Brendler v. s640 

Brenner w. s1308 

Brett C. M. A. s595 

Brezinova A. s1077 

Brida d. s699 

Brilman w. s1178 

Brito r. s1178 


Briza t. s1159 

Brogly M. s1215, s793 

Broncova G. s742 

Brown C.e. s1215, s628 

Brown K. s828 

Broz B. s1009 

Brozek J. s1325 

Brozek-Pluska B. s604 

Bruensing J. s1120 

Bruhn C. s694 

Brumm S. s955 

Brun S. s1199 

Bruneel o. s924 

Bruns J. s932 

Bruns n. s792 

Brusová h. s1204 

Brust M. s751 

Bryant J. J. s784 

Brykalova x. o. s830 

Buba A. s1285 

Büchel G. s911 

Bucher G. s999 

Buchholz M. s729 

Buchmeiser M. s1104, s1235 

Buchmeiser M. r. s1032, s1095 

Buchta M. s1155 

Buchwald S. s801 

Bucki A. s1306 

Buckle t. s720 

Buckley d. M. s829 

Budarin v. s1182, s675 

Budesinsky M. s1021, s894 

Budka J. s1301 

Budnikov h. s597 

Bugar i. s827 

Bugarcic z. s1276, s1283, s1312 

Bujold K. s730 

Bulach v. s1075 

Bulut A. s1284 

Bunkan A. J. s863 

Buntkowsky G. s1198, s1340 

Bunuel e. s771 

Bunz u. s1360 

Bunz u. h. f. s784 

Buonerba A. s787 

Burel f. s1025, s1049, s1099 

Burford n. s946 

Bürgi t. s753 

Buricova L. s1307 

Buriol L. s1272 

Burke M. s728 

Burlini A. s1255 

Bury w. s690 

Burzuri Linares e. s736 

Buschauer A. s884 

Busche C. s666, s999 

Busetto L. s681 

Buszewski B. s1115, s1116, s601, s619, s857 

Butenschoen h. s1363 

Butterfield A. s1276 

Buydens L. s615 

Bykowski d. s1072 

Bytzek A. K. s684 

Byun J. y. s655 



s1372 

chem. Listy 106, s587–s1425 (2012) 


C 

Cadigan C. s660 

Cadiou C. s607 

Cadis A. i. s1196, s1344 

Cafagna i. s1166 

Cagli e. s1277, s1277 

Cai S. s704 

Cakir d. s987, s988 

Cakir v. s987 

Cakmakci e. s1106, s1107 

Calderon-Moreno J. s1192 

Calderón-Moreno J. M. s1189 

Calhorda M. J. s963 

Call A. s949 

Calle e. s811, s812, s831 

Calvete M. J. f. s1337 

Cametti M. s1035 

Caminade A. M. s1053, s1336 

Campana A. G. s771 

Campbell t. s885 

Campistron i. s1007 

Campolo d. s771 

Canadell e. s824 

Canadi J. s1076 

Canal-vila J. s925 

Canbaz C. s1150 

Candeias n. s783 

Canotilho J. s1198, s1204 

Canta M. s701 

Cao q. s845 

Capci A. s1079 

Capito f. s613 

Capolicchio S. s1278 

Cappa f. s1009 

Capponi M. s1191 

Caprioli f. s763 

Carbery d. s1010 

Cardenas d. J. s740 

Cárdenas d. J. s771 

Cardoso A. M. S. s791 

Cardoso do vale M. L. s879 

Cardoso S. s1221, s609 

Cardova L. s1278, s1350 

Carell t. s1082, s887 

Carey A. s985 

Carlone A. s735 

Carlson e. s716 

Carmeliet J. s648 

Caroen J. s1002 

Carofiglio t. s1172 

Caron t. s802 

Carp o. s1189, s1192 

Carreno M. C. s740 

Carret S. s1010 

Carrey J. s1240 

Carrilho r. M. B. s1198, s1333, s1337 

Carvalho f. s718 

Carvalho M. d. s978 

Carvalho S. s863 

Casado J. s811, s812, s831 

Casado M. A. s694 

Casati C. s1241 

Casiot C. s644, s924 

Casitas A. s701, s975 

Cassani M. C. s1216, s1220 

Cassir M. s1143 


Castriciano M. A. s1216, s1252 

Castro r. A. e. s1204 

Castro ruiz C. A. s1116, s594 

Cataldo S. s1217, s1255 

Cativiela C. s1003 

Cavaleiro J. s1288 

Cavaleiro J. A. S. s1001, s1057, s1339 

Cebolla v. s1362 

Ceccato d. s913 

Cecchi r. s1343 

Cejka J. s865, s976 

Celebi n. s908 

Ceoldo S. s913 

Cerisoli L. s767 

Cerkovnik J. s769 

Cermak J. s755 

Cernak J. s934 

Cernoch z. s1342 

Cernochová J. s1275 

Ceroni P. s738, s938 

Cerovsky v. s724, s886 

Cerullo G. s699 

Cervellati r. s722 

Cervena B. s1117 

Cerveny v. s1147, s605 

Cesla P. s1119, s1124 

Ceslová L. s1119 

Cespedes-Camacho i.f. s811, s812, s831 

Cetvati z. s870 

Cha G. S. s1127 

Cha J. s1335 

Cha J. J. s1105 

Chai C. L. L. s1090 

Chakravarty h. K. s815 

Chamas z. e. A. s1031 

Champavier y. s1021 

Chang C. s910 

Chang h. s1164 

Chang P. y. s959 

Chaniotakis n. s593 

Chapleur y. s1330 

Charleux B. s792 

Chárová P. s1131 

Chas M. s798 

Chatel G. s662 

Chatterton n. s943 

Chaturongakul S. s890 

Chaudret B. s1198, s1240 

Chaumontet M. s1187 

Cheah S. C. s954 

Chee C. s608 

Chekanova v. s882 

Chen f. s1067 

Chen G. s943 

Chen L. s660 

Chen M. s1203 

Chen x. s693, s905 

Cherevatskaya M. s1031 

Chergui M. s827 

Cheung S. t. C. s1162 

Chevreux S. s607 

Chiang L. s1183 

Chimowitz e. h. s666 

Chin P. s785 

Chira n. s1160, s1166 

Chirieac A. s1196, s1197, s1197, s1207 



s1373 

chem. Listy 106, s587–s1425 (2012) 


Chladkova B. s1156 

Chmelik J. s855 

Cho M. s1163 

Chodounská h. s778, s1301 

Choi J. s926 

Choi J. C. s1168 

Choi J. S. s1183 

Choi S. s1165 

Choi S. S. s1167 

Choi S. y. s1172, s609 

Choppin S. s1348 

Choquesillo-Lazarte d. s740 

Chorvat Jr. d. s1247 

Chou C. s660 

Chouzier S. s823 

Christian d. s1015 

Chronakis n. s1057, s1079, s799 

Chrysos M. s782 

Chtchigrovsky M. s658 

Chua S. S. s1302 

Chuayjuljit S. s1248 

Chuburu f. s1214, s607 

Chung y. M. s1163 

Churakov A. s981, s984 

Ciabatti i. s680 

Cibulka r. s1356 

Cidlina A. s1279 

Cielecka-Piontek J. s895 

Cieslak A. s690 

Cifkova e. s1117 

Cifra P. s811 

Cihaner S. S. s899 

Cik G. s827 

Cintas P. s1251, s1252 

Ciotonea C. s1196, s1197, s1197 

Cipolloni M. s1218, s1327 

Ciriaco L. s647, s906, s916 

Cirin d. s875, s875 

Císarová i. s1298, s1352 

Ciscato L. s861 

Ciscato L. f. s1279 

Civera M. s720 

Claeys M. s725 

Claridge t. d. w. s807 

Clark J. s1182, s675 

Clausen i. s689 

Clegg J. K. s733 

Clerici A. s767 

Clough J. s1053 

Co d. s828 

Coban t. s899 

Cocchi M. s617 

Cocuzza C. s722 

Codola z. s949 

Coelho J. s783 

Coelho M. s1161 

Cohen h. s904, s952 

Cohen S. r. s1224 

Cokesa d. s1152 

Colak n. s1141 

Collini e. s829 

Colobert f. s1348 

Coman C. s885 

Comba P. s889 

Comic L. s950 

Comotti A. s1195, s834 


Company A. s951, s955 

Concina i. s1172, s657 

Constable e. C. s996 

Conway L. s1280 

Cooper A. s1206, s820, s844, s848 

Cooper C. s884 

Cooper d. G. s656 

Copur M. s1111, s1112 

Coradin t. s1238 

Cordova A. s1012 

Corminboeuf C. s813 

Cornelissen J. s731 

Corradini r. s709, s795 

Corral Bautista f. s1280 

Correia-da-Silva M. s718 

Cortina J. L. s642 

Coskun A. s1211 

Cossio f. s1362 

Cossio f. P. s819 

Cossu S. s1055, s1055 

Cossy J. s766 

Costa t. s653 

Costas M. s1222, s701, s949, s951, s955, s975 

Cote G. s928 

Cotterell M. s808 

Coufal P. s1136, s1136 

Courtney t. L. s829 

Cox G. s955 

Cozzi P. G. s1345 

Cozzula d. s756 

Creaven B. s1244 

Credi A. s1211, s1211, s734 

Crivillers n. s835 

Cronin L. s1217, s1253, s1254, s666, s697, s733, s999 

Crucianelli M. s728 

Cserep G. B. s1011 

Csincsi A. i. s1314 

Cuadro A. M. s1096 

Cuba v. s928 

Cuerva J. M. s740, s771 

Cui y. s594 

Cujova S. s886 

Cunha-ribeiro L. M. s718 

Curinova P. s1301 

Cussó o. s951 

Custer L. s1124 

Cvacka J. s1130 

Czakler M. s964 

Czanikova K. s1247 

Czirok J. B. s1281 

D 

da ros S. s1281 

dag A. s1067 

d’Agosto f. s792 

dahal P. s1039 

dahaoui S. s1075 

dahlmann h. A. s1011 

dalcanale e. s1058, s1242, s797 

dallas L. s638 

dalmadi i. s677 

dambruoso P. s916 

damian G. s674, s884, s888 

daneshgar P. s867 

daniel v. s857 

daniela M. s1342 



s1374 

chem. Listy 106, s587–s1425 (2012) 


dankesreiter S. s1031 

daphne h. s914 

dard M. s705 

daresta B. e. s916 

daru J. s1357 

darwish M. s758 

dasadia A. s850 

date A. s966 

davidova G. s991 

davis B. s796 

davis B. G. s807 

davison w. s650 

de Angelis f. s728 

de Bank P. s726 

de Cicco M. s1067 

de Cola L. s839 

de Gennaro G. s916 

de Kimpe n. s764 

de La escosura Muniz A. s1256 

de La Mata f. J. s787 

de Lafontaine y. s648 

de Leon f. s931 

de Meijere A. s684 

de Miguel M. s1212 

de nanteuil f. s1100 

de Pablo J. s642 

de Pace A. s620 

de Simone f. s1100 

deac f. s884, s888 

debouttiere P. J. s1198 

déchamps i. s607 

dei L. s632 

deiana L. s1012 

dejlová B. s896 

dejmkova h. s1117, s1139, s1158 

dejon L. s1353 

del rosal i. s788 

delachat A. s813 

delaite C. s786, s793 

delalu h. s1176, s1331, s654 

delay M. s909 

delcombel r. s898 

deleanu C. s1336, s1359 

delevoye L. s788 

delgado J. L. s739, s741 

delgado r. s941 

delgado-Martin J. s925 

delile S. s1143 

delley r. s1280 

delogu G. s1013 

delpoux S. s924 

demarinis Loiotile A. s916 

demin S. s608 

demir n. s907, s914 

demirci Cekic S. s1161 

demircivi P. s647 

demir-ordu o. s1012 

denat f. s1016 

denecke M. A. s639 

deng J. s1319 

denizli G. s1131 

dernedde J. s1246 

desbois n. s1016 

desharnais B. s1067 

deshmukh r. s1217 

desilles n. s1099 


dettori M. A. s1013 

detweiler z. M. s693 

devadoss A. J. s1118 

devaux e. s746 

deylova d. s1156 

dezileau L. s644 

dezortsev S. s864 

dhar B. s1003 

d’hooghe M. s764 

di Bitonto L. s692 

di Gilio A. s916 

dian J. s742 

dias L. d. s1337 

dias r. d. S. s1333 

diaz diaz d. s1003, s1046 

diaz-Cuadros J. C. s1282 

dibenedetto A. s691, s692, s693 

dibla A. s1282 

dickschat A. s1013 

diculescu v. C. s598 

didu A. s1118, s1119 

didu M. s1119 

diederich f. s1360 

diers e. s1014 

dietz C. s948, s950 

dietzek B. s699, s704, s781, s826, s830, 

s862, s864, s893, s988 

dikbas n. s908, s908 

dillenberger S. s1340 

dinisová P. s1119 

dionisio M. s1058 

d’ischia M. s728 

divac v. s1276, s1283, s1312 

djanashvili K. s1295 

djordjevic d. s907 

djurdevic v. s907 

do vale M. L. C. s791 

dodel r. s896 

doerfler J. s1283 

dogan o. s1264, s1267, s1277, s1277, s1284, s1284 

doistau B. s1259 

dold B. s640, s644 

dolezal M. s1305, s1346 

doll K. s1200, s851 

dolomatov M. s864 

domingo C. s666 

dommer S. s1193 

domokos e. s1188, s917 

donahue L. s1014 

donath M. s946 

dondi f. s631 

dong A. s1215 

dong z. s814 

donnadieu B. s700 

donnio B. s1282 

doong r. s1183 

doong r. A. s1175, s959 

dorazco A. s932 

dorkó e. s1329 

dorman G. s664 

dörr G. s699 

dorraji P. s890 

dossena A. s1168, s726 

dott w. s1120 

doubnerova v. s1136 

doye S. s1283, s1306 



s1375 

chem. Listy 106, s587–s1425 (2012) 


drasar P. s1066 

drabowicz J. s1046 

dracinsky M. s1077 

dragisic v. s645 

dragoi B. s1196, s1197, s1197, s1207 

dragone v. s1253 

drahos L. s1281 

dralle K. s983 

drasar P. s1035, s1066, s1086, s1089, 

s1101, s1108, s1278, s1307, 

s1350, s1354, s1362, s1367 

draye M. s662 

dreiack n. s1358 

dreyer C. s1052 

driess M. s702 

drillaud n. s780 

driver S. s808 

drmanic S. s1065, s1334 

drouza C. s1169, s1169, s673, s673, s686 

drweesh S. s982 

dusek M. s865 

duarte A. s1120, s1221, s1287, s609, s909 

duarte A. C. s651 

duarte B. s718 

duarte K. s1120 

duarte K. r. s909 

dubreuil d. s1001, s1056 

ducho C. s1318, s1364 

duczak n. s1257 

dudenko d. s1330 

dudic M. s1218, s1352 

duchstein P. s826 

dukhopelnikov e. s882 

dukic S. s1214 

dulaiova h. s635 

dumitrescu d. G. s844 

dumitriu e. s1197, s1197, s1207 

dunphy e. s954 

dupont L. s651 

duprez d. s1196, s1197, s1197, s1207 

dupuis f. s1330 

duric S. s1285 

durko G. s1249 

durmaz h. s1067, s998 

durmus M. s969, s986, s988 

duroux J. L. s1021 

dusek M. s1021 

dutartre M. s1015 

dutremez S. s1287 

dvorakova d. s1147 

dvoretskov r. s1134, s1157 

dyballa K. s756 

dzhakipbekova d. s1180 

dzhakipbekova n. s1180 

dzidzigury e. s1232 

dzik w. s1285 

dzik w. i. s1273, s765 

dzubak P. s722 

E 

eaton t. s1218 

eavani S. s1250 

ebbesen t. w. s746 

eberhagen f. s1032 

echterhoff A. K. C. s773 

ecker G. s1339 


eckert h. s1013 

efferth t. s1079 

efimenko i. s981 

efimov M. s1219 

eggenspiller A. s1016 

ehrenberg h. s995 

ehterami n. s1016 

eichenauer n. C. s1286 

eichenseer C. M. s1017 

eigner v. s1299, s1301, s1367, s865 

einax J. s911 

eisenhofer A. s1286 

eisner A. s1131 

ekberg C. s928 

ekrem K. s918 

el Azzouzi M. s909 

el hajj A. s1331 

el hassan n. s1075 

el- Senousy w. s1294 

elahe A. s859 

elbayaa r. s1018, s1018 

elbaz-Poulichet f. s644, s924 

el-Beltagy d. s1017 

elbert t. s722, s894 

el-Borai M. s1017 

elias M. s1121 

elisabetta B. s1342 

eliseeva M. n. s1281 

elizarov n. s1018 

elke d. s905 

el-rais M. s1121 

elsakhawy M. s1063 

el-Seidy A. s982 

elstner M. s1118, s1122, s861 

el-zahany e. s982 

emery d. s800 

emmerling f. s709 

enascuta C. s1177 

enders d. s763 

endoh t. s899 

ene C. d. s1336 

enthaler S. s1302 

eom M. o. s1167 

er e. s1244 

erdogan A. s1094 

ergun e. s1131 

ergun u. s1131 

eriksson K. s806 

erker t. s718 

ermilova M. s1171, s1219, s1248 

ermolatev d. s784 

ermolovich y. s1107 

ernst S. s699 

ertl G. s588 

erythropel h.C. s656 

esmaeeli M. s918 

esser B. s612 

essid e. s902 

esteves C. v. s941 

estrin y. s1105, s1366 

etorki A. s1121, s1122 

eul M. s932 

eusebio e. s1198 

eusébio M. e. S. s1204 

eva d. s817 

evren d. s969, s971 



s1376 

chem. Listy 106, s587–s1425 (2012) 


exnerova M. s1338 

eychmüller A. s730 

f 

fabbri d. s1013, s659 

fabbri e. s709 

faber K. s705, s802 

fabian i. s688 

fabio P. s1342 

facca C. s913 

faderl C. s1180 

faggi C. s940 

fagnere C. s1021 

fähnemann S. s709 

fahrnbauer f. s851 

fahs A. s1215 

fahsi K. s1287 

faigl f. s1004, s1190, s1274 

faísca Phillips A. M. s1287 

fakhoury J. s730 

fakhre n. s1123 

falcon-Suarez i. s925 

falini G. s659 

falk f. C. s1070 

färber C. s694 

fargasova A. s1219 

farinha J. P. s748 

farinha J. S. s1239 

farinola G. M. s1286 

farkas e. s886 

farsijani S. s1061 

fattah z. s744 

fazzini P. f. s1240 

fazzini S. s1220 

fedaoui d. s980 

fedotov P. s1149, s603 

feixas f. s871 

fejfar A. s927 

felbermair e. s982 

feldmann K. o. s947 

félix d. s879 

félix v. s863 

femoni C. s680 

feng h. s1103 

feng x. s1271, s1333 

feng z. s1103 

fenger r. s752 

fenselau C. s728 

fenske d. s1081 

ferenc f. s1313 

ferenczi-Palko r. s1029 

feringa B. s736 

fernandes A. s647 

fernandes C. i. s978 

fernandes i. P. s793 

fernandes r. x. s815 

fernández de Luis r. s953 

fernandez i. s819 

fernández-Calderón M. C. s1251 

ferrara G. s1166 

ferreira J. s1288 

ferreira M. J. s793 

ferrer A. s617 

feulner P. s830 

fey S. s704 

feyzi M. s1213 


fialkowski M. s1260, s746 

fidalgo-Maijuan A. s1207 

figo v. s1217 

filimonov v. s1317 

filip J. s1231 

filipovic M. s944 

filo J. s1019 

fin A. s999 

fingerhut A. s1024 

fink K. s608 

fink M. J. s707 

fisar z. s1154 

fischer C. s1019 

fischer C. h. s1222 

fischer f. s752 

fischer J. s1119, s597 

fischer r. A. s939 

fisher-fodor e. s888 

flament S. s1330 

flefel e. M. s1265 

fleischer i. s756 

flesch r. s830 

flidrova K. s1288, s1352 

flitsch S. L. s740 

florea Spiroiu M. s1269 

florencio M. h. s1151 

florjanczyk z. s1311 

fluxa v. s669 

focant J. f. s906 

foerstendorf h. s640 

fojta M. s1003 

fomin M. s1123 

font M. s975 

forczek S. s1101 

forczek S. t. s1321 

forgione P. s1067 

fornelli L. s602 

forster J. s984 

fort y. s1031 

foulquier S. s1330 

fraaije M. s708 

frahm r. s1249 

fraix A. s751 

francesco G. G. s1342 

franco-Pujante C. s1272 

francuz J. s1020 

franchi P. s1241 

frank h. s619 

franke A. s1124 

franke r. s756 

frankova J. s895 

fransen P. s787 

franz A. s754 

fränzle S. s628 

fraser S. s734 

fredy J. w. s735 

freitas A. C. s1120, s1221, s909 

frere P. s1061 

frery n. s906 

frey w. s1032 

freydier r. s644, s924 

friess K. s1090 

frimmel f. h. s909 

frisenda r. s736 

frison e. s1172 

fritzsche M. s1330 



s1377 

chem. Listy 106, s587–s1425 (2012) 


fritzsche r. s1221 

froeba M. s841 

fröhlich J. s1300, s1322, s781 

frontasyeva M. s629, s910 

frumar M. s1206 

frumarova B. s1206 

fruth v. s905 

fry e. A. s812 

frys o. s1124 

fu y. s1222 

fucik v. s724 

fueldner S. s1031 

fuentes de Arriba A. s1289 

fuentes n. s740 

fuerstner A. s762 

fuchs M. s802 

fuhr o. s1081 

fujie M. s1027 

fujimoto z. s893 

fujita M. s732, s837 

fujita n. s840 

funa A. e. s600 

fuse S. s1327 

G 

G. d. r. s900 

Gabb d. s697 

Gabor L. s817 

Gabrielli S. s655 

Gaefke G. s1078 

Gafa v. s1214 

Gagne f. s648 

Gagnon C. s648 

Gahlon h. L. s1011 

Gaidzik n. s775 

Gal A. s832 

Gal n. s1181 

Galandakova A. s1307, s895 

Galaverna G. s1168, s726 

Galina K. s1037 

Galletti P. s1178, s1181, s1289, s659, s722, s777 

Gallo v. s1166, s679 

Galuszka J. s1117 

Gambari r. s709 

Gamblin d. P. s807 

Gan v. s608 

Gandelman M. s760 

Gandon v. s757 

Ganesan A. s1050 

Gaponik n. s730 

Garcia f. s794 

Garcia h. s1212 

Garcia M. s820 

Garcia Martinez J. s654, s682 

Garcia r. s741 

Garcia turiel M. s1289 

Garcia-Borras M. s823, s865, s870 

Garcia-Bosch i. s1222, s951 

Garcia-Martinez J. s1223 

Garcia-ruiz J. M. s740, s810 

Garcia-Simon C. s1222 

Garrone A. s704 

Garwood M. s1228 

Gasilova e. s721 

Gaskell S. s727 

Gasteiger K. s887 


Gates P. J. s772 

Gatti M. s1168 

Gauglitz G. s1129, s1146, s605 

Gauvin r. s788 

Gavrila i. s1266 

Gazit e. s832 

Gebauer M. s1305 

Geidel C. s789 

Geisel K. s1185 

Geissler e. s1186 

Geist M. s1223 

Gelman d. s1062 

Gemeinhardt i. s1246 

Gemel C. s939 

Genet C. s746 

Genovese d. s749 

Gentilucci L. s720 

Georgiades S. s713 

Gerasimova e. s1125 

Gerhards M. s699 

Gerisch A. s1125 

Gessner v. s968 

Gessner v. h. s695 

Geyer A. s711, s896 

Geyer J. s902 

Gezici o. s750 

Ghale G. s887 

Ghermani n. e. s1075 

Ghiasi h. s995 

Ghiasi r. s859, s986, s995 

Ghidini A. s795 

Giacomini d. s1289, s722, s777 

Giammarino G. s880 

Gibert o. s642 

Gigmes d. s770 

Gillet J. M. s1075 

Gilmour r. s1091 

Gilomen B. s1276 

Gindre d. s782 

Giniyatullin r. s1334 

Ginterova P. s1144 

Gioia C. s1091 

Giorgetti M. s1220 

Giralt e. s717 

Girshevitz o. s1224 

Gjelsvik r. s636 

Gjengedal e. s925 

Gjorgjeska B. s1126 

Gladow d. s1051 

Glaesel h. J. s1052 

Glaied o. s786 

Glante S. s1202 

Gläser S. s946 

Gliemann B. s766 

Glodjovic v. s950 

Glueck S. M. s705 

Gniewek A. s696 

Gobé v. s803 

Gock M. s948 

Göckel M. s1290 

Goeb S. s798 

Gohier f. s1061 

Gökagac G. s1181 

Gokmese e. s1126 

Gökmese f. s1127 

Göl C. s986 



s1378 

chem. Listy 106, s587–s1425 (2012) 


Golling f. e. s789 

Gomes h. s1161 

Gomes L. s783 

Gómez L. s1222 

Gómez r. s787 

Gómez-iglesias P. s985 

Gomez-ruiz S. s667, s667 

Goncalves A. s1159 

Goncalves L. s674, s861 

Gonda z. s1290 

Gondek C. s964 

Gonzalez f. s1242 

Gonzalez Jimenez M. s812 

Gonzalez L. s699, s830 

González-Jiménez M. s811 

González-Martín M. L. s1251, s1252 

Goossen L. s1285 

Gooßen L. J. s1268, s765 

Gorb S. n. s740 

Gordana r. s950 

Gordillo G. s751 

Gori d. s1363 

Gossen L. J. s1273 

Gotesman S. s904 

Gotlib-vainshtein K. s1224 

Gottfried o. s1337 

Göttlich r. s1087, s902 

Gottschaldt M. s1102 

Goulley J. s723 

Gourdon A. s1058, s737 

Goux-henry C. s662 

Grabowski M. s1291 

Gradert C. s938 

Graf C. s1246, s729 

Grampp G. s1128, s880 

Grancicova o. s827 

Grasserbauer M. s653 

Grassi A. s787 

Gratzer K. s1020 

Greb L. s1071 

Greenberg M. s713 

Greenvald i. s818 

Greenway G. s645 

Gref r. s751 

Grilliez-vuissoz i. s1330 

Grimm B. s739 

Grishchuk A. s1105, s1366 

Grishina A. s1021 

Grmela A. s643 

Gröger d. s1246 

Gronnow M. s1182, s675 

Gros C. s1016 

Gross J. s705 

Gross z. s678 

Großmann A. s1291 

Grötli M. s1049 

Grubbs r. h. s592 

Gruber B. s1224 

Gruber K. s705 

Grün C. h. s869 

Gruner n. s766 

Grupe S. s760 

Gu h. w. s1127 

Gualandi A. s767 

Guclu K. s915 

Gueckel K. s640 


Guégan J. P. s854 

Guenet A. s735 

Gueye r. s1021 

Guillemin J.C. s854 

Guillon d. s1282 

Guisado-Barrios G. s700 

Gül A. s956, s957 

Gülak S. s1022 

Gulder t. s1292 

Gulder t. A. M. s1292 

Guldi d. s1308, s803 

Guldi d. M. s739 

Guldner L. s906 

Guler B. s1022 

Gulyakevich o. s1107 

Gunay u. S. s1067 

Gunden Goger n. s1128 

Gunduz h. s1023 

Gungor A. s1106, s1107 

Günther A. s639 

Gust d. s738 

Guthmuller J. s699, s830 

Gutiérrez-zorrilla J. M. s1203, s961 

Gutmann t. s1198, s1340 

Guyon f. s936 

Gyollai v. s664 

Gyömöre A. s1329 

Gyurcsanyi e. r. s1281 

H 

ha thi hai y. s1128 

haag r. s1246 

haas t. s802 

hackner B. s1082 

hadad G. M. s904 

hadade n. d. s1336 

haddawi S. s1264 

hadjichristidis n. s786 

hafezi n. s1293 

hagemeier C. s1082 

hager M. d. s1102, s1102, s1293, s791 

haider A. s985 

haider M. s1339 

hajduch J. s764, s1424 

hajduch M. s722 

hájek t. s599 

hajkova z. s927 

hakimi M. A. s714 

hakimyoun A. h. s986 

halaszova S. s827 

hall e. s608 

hamaoka t. s606 

hamblin G. s730 

hamburger M. s1360 

hamdy n. s1294 

hameau A. s1336 

hametner C. s1300, s1322 

hamilton-taylor J. s650 

hammad f. s994 

hammerich M. s1294 

hampel S. s1233 

hamuryudan e. s979 

han K. s1165 

han S. s1335 

hanafi z. s994 

hanefeld u. s1295, s706 



s1379 

chem. Listy 106, s587–s1425 (2012) 


hanekamp J. C. s676 

hanfland M. s1199 

hanganu A. s1160, s1166 

hanni K. d. s735 

hanquet G. s898 

hansen M. r. s1330 

hanslík e. s920 

hanson B. s928 

hanson P. r. s1036 

hansson o. s1174 

hanusek J. s1092 

hanzlova e. s1295 

happ B. s1102 

harada A. s833 

hari d. P. s1084 

harlander C. s1031 

harmatha J. s1035, s1108 

harrar K. s1074 

harris K. s835, s836 

harris n. A. s980 

harris S. J. s808 

hartinger C. G. s684 

hartmann M. s740 

hartmanova L. s1129 

hartwig A. s1246 

harutyunyan S. r. s763 

harzmann G. s736 

hasell t. s820 

hasenknopf B. s1259, s1319, s735 

hashem A. s995 

hashmi A. S. K. s1007, s1098 

hatami S. s612 

hathazi G. d. s888 

hauke S. s1023 

hauptmann J. s1237 

hausen d. s1296 

havel J. s1110 

havel v. s1296 

havlas z. s1424 

havlicek L. s777 

havlova v. s923 

havran L. s1003 

hawkett J. s733 

hayes C. J. s703 

haynes C. s1228 

heilmann J. s1025 

heinemann f. s943, s945, s951 

heinemann f. w. s695 

heinrich A. s1297 

heinrich A. C. J. s1054, s772 

heinrich B. s1282 

held f. s1024 

hell z. s1065 

helm M. s1043 

helten h. s688 

hemgesberg M. s699 

hendel t. s730 

hendriksen P. v. s1203 

henke P. s1225 

henne f. d. s965 

henneicke L. s1056 

hennig A. s612 

henrion d. s1330 

henry M. L. M. s628 

henß A. s684 

heo J. s1206 


herchel r. s934, s935 

herchl r. s1024 

hercigonja r. s1199 

hercko i. s627 

herdtweck e. s1030, s1040, s1099 

herges r. s1081, s878 

hering S. s1339, s718 

herisi n. s1137 

herman P. s891 

hermann G. s704 

hermann P. s1155, s944 

hermann w. s1350 

hernandez Melo d. s1225 

hernandez rubio o. s1289 

herner A. s1297 

herranz M. A. s741 

herrero-davila L. s675 

herrmann A. s1079, s796 

herrmann A. K. s730 

herrmann J. s1025 

herten d. P. s882 

hesemann P. s841 

hespel L. s1025 

hess P. s1226 

hesse J. s717 

hessel v. s801 

hesseler B. s1026 

hessler f. s855 

heutz n. A. s1226 

heyerdahl P. h. s925 

hey-hawkins e. s952 

heymann d. s1000 

hietschold M. s1221 

hilbig u. s1129 

hill J. P. s1230 

himl M. s1026, s1365 

himmel d. s1145 

hinrichs w. s687 

hiraoki t. s1027 

hiratsuka M. s818 

hirsch A. s741 

hirsch A. K. h. s1332 

hirsch J. s1027 

hirsenberger h. s1194 

hirtenlehner C. s968 

hirtopeanu A. s1359 

hissler M. s747 

hizal G. s1067, s998 

hizal J. s1161 

hobbs S. s668 

hocek M. s1003, s1039, s1045, s1093, s724 

hochreuther S. s949 

hodek P. s727 

hodgson d. s1280 

hoeppener S. s849 

hoffman M. s1227 

hoffmann A. s612 

hoffmann K. s612, s903 

hoffmann M. s663 

hofmann C. s1298 

hofmann M. s962 

höger S. s1032, s1078, s1083, s1085, s1324, 

s1328, s1330, s1335, s1348 

hohenleutner A. s1003, s1028, s1083 

höhn C. s695 

hohne M. s703 



s1380 

chem. Listy 106, s587–s1425 (2012) 


hojdova M. s646 

holan M. s1298, s1305 

holcapek M. s1117, s1132 

holden d. s820, s848 

holy P. s1155 

hollaus r. s1299, s998 

hollosi M. s1357 

holthausen M. s694 

holthausen M. h. s960 

holub J. s1299 

holy A. s1077, s604 

holz M. s1028, s1226 

holzer B. s1300, s1322, s781 

holzhauser P. s1133, s1133 

hong h. s1292 

hong J. e. s1227 

hong w. s1078 

hoof S. s1285 

hopf h. s1056 

hoppe A. s989 

hoppe h. s1293 

horka P. s1130 

horkel e. s1300, s1322, s781 

horn A. h. C. s710, s889 

horn C. s1123 

hornicek J. s1307 

hornoiu C. s1188 

horvath d. v. s1029 

horvath e. s643 

horvolgyi z. s1237 

hosseini M. w. s837 

hostalek z. s1300 

hottin A. s1029 

houbenov n. s786 

housecroft C. e. s996 

houskova L. s1158 

hovorka r. s1030 

howes K. s1360 

hrabalek A. s1037, s1064 

hranicek J. s1147, s605 

hrdina r. s853 

hrubosova d. s1162 

hruby t. s1130 

hubbell J. s710 

huber S. s1030, s1099 

huber S. M. s1040 

huc i. s1001, s795 

huc v. s770 

hudecek J. s727 

hudecek o. s1301 

hulot C. s1316 

hülya A. s1292 

hunoldt S. s889 

hunt A. s1182 

hurley K. s1228 

hurski A. s1107 

hutchison J. A. s746 

huuskonen J. s1234 

hwang i. s972 

hwang w. S. s1182 

hylse o. s1323 

hynek v. s1090 

hyslop r. M. s628 

hytteballe S. s1030 


i 

iammarino M. s1167 

iapalucci M. C. s680 

ibrahim M. s933, s985, s992, s993 

ibrahimova v. s750 

idelson A. s1032 

ignjatovic L. s1152, s866 

iino K. s662 

ikaheimonen t. K. s635 

ikonen S. s1307 

ilharco L. M. s1220 

ilia G. s1326, s1362 

iliopoulos K. s782 

illi S. s977 

illner P. s958 

ilovitsh t. s1258 

inal e. K. s1131, s1142 

inokuma y. s837 

inoue C. s1302 

inoue S. s702 

inoue t. s1179 

invernizzi C. s1033 

inzenhofer K. s1303 

ioannou C. s1057 

ionita P. s1268 

iovescu A. s1268, s1269, s1355 

iraqi A. s790 

iremonger S. s843 

irena S. s929 

irsai i. s1303 

isci M. s1277 

ishi-i t. s1033 

isik M. s774 

iskakova S. s927 

iskra J. s1304, s1304 

islam M. M. s816 

isobe h. s1074 

ito y. s1228 

iturrospe A. s1203, s961 

ivanova A. s1125 

ivanovic-Burmazovic i. s687, s944 

iwaura r. s1229 

izarova n. s697, s989 

izarova n. v. s942 

izzet G. s1239, s681 

J 

Jäckel e. s639 

Jackstell r. s756 

Jacobi von wangelin A. s1022, s760 

Jadhav d. s1041 

Jaeger C. s612 

Jagerszki G. s1281 

Jagtap P. s1305 

Jagusiak A. s897 

Jahn u. s1298, s1305 

Jähnigen S. s967 

Jain t. s1229, s1246 

Jakab e. s1249 

Jakabovic J. s1019 

Jakupec M. A. s684 

Jalali f. s890 

Jalink K. s785 

Jalsovszky i. s1249 



s1381 

chem. Listy 106, s587–s1425 (2012) 


Jamali S. s941 

Jamróz M. s868 

Janata J. s593, s638 

Jancarik A. s1121 

Jandera P. s1151, s1153, s599 

Jandourek o. s1305 

Jane e. s827 

Jang S. J. s1168 

Jang y. M. s1167 

Jani A. s850 

Jänis J. s869 

Jankovic n. s1276 

Jansa P. s1077, s604 

Jansen M. s1200, s851 

Janssens P. s1273 

Jarmuz M. s1425 

Jaskowska J. s1306 

Jaspers d. s1306 

Jean L. s1068 

Jecmen t. s727 

Jedlickova v. s1132 

Jelfs K. s1206, s848 

Jelinek i. s742 

Jelinek r. s1181 

Jenkins S. s808 

Jennerjahn r. s756 

Jenny t. A. s1326 

Jensen A. A. s646 

Jeon S. i. s1177 

Jeong S. s1176 

Jeong S. K. s1173 

Jerabek P. s866 

Jerca f. A. s1034, s1034 

Jerca v. v. s1034, s1034 

Jessen h. J. s1069 

Jester S. s1083 

Jester S. S. s1032, s1085, s1324, s1328, 

s1335, s1348, s745 

Jho J. y. s1052 

Ji q. s1230 

Jiang S. s1096, s844 

Jiarpinitnun C. s890 

Jilek r. s1170 

Jiménez t. s771 

Jimenez-diaz r. s1213 

Jin M. s1164 

Jin S. s937, s972 

Jindrich J. s742, s768 

Jinkarn t. s1072 

Jiracek J. s894 

Jirak r. s1154 

Jirasko r. s1132 

Jochen t. s905 

Jofuku K. s1202 

Johansson e. M. v. s1307 

Johansson M. J. s1308 

John J. s928 

Johnsen L. s616 

Johnson d. B. s641 

Johnson M. s654 

Johnson t. s758 

Johnston e. s1012, s1097, s1173, s1174, s806 

Jolanda P. s916 

Jolley K. s758 

Jonas d. M. s829 

Jones A. s645 


Jones M. s975 

Jones P. G. s1056 

Jones r. s664 

Jonke A. s593 

Jorda r. s777 

Jordanovic J. s848 

Jorge t. f. s1151 

Jorgensen K. A. s801 

Josephson L. s720 

Joshaghani M. s1213, s1230, s1250, s1250, s941 

Josowicz M. s593 

Joubert L. s1068 

Journot G. s767 

Jovanovic B. s1065, s1334 

Jozsa e. s649 

Judy L. s608 

Juge S. s1015, s1060 

Juhasz i. s1281 

Julien C. s995 

Jumean f. s1132 

Juncosa-rivera r. s925 

Jung e. M. s893 

Jung G. s882 

Jung J. S. s1231 

Jung o. S. s961 

Jung y. s1176 

Jurado A. S. s791 

Juraj G. s1359 

Juranová e. s920 

Jurasek M. s1035, s1086, s1108 

Jurcek o. s1035, s1307 

Jurcik v. s779 

Jurecka P. s868, s876 

Jürgenliemk G. s1025 

Juris r. s749 

Jurkschat K. s948, s950 

Justino C. s1120, s1221, s609, s909 

Justyniak i. s690 

Jux n. s1308, s1322 

K 

Kachkovskyi G. s1180 

Kacirova M. s891 

Kafafy A. h. s721 

Kafka f. s1305 

Kafka S. s1340 

Kahler A. s710 

Kahnt A. s725 

Kainz q. M. s1017, s1036 

Kaiser A. s775, s891 

Kaiser M. s968 

Kalagaev i. s818 

Kalenius e. s869 

Kaleta J. s1327, s1424 

Kaletova e. s1424 

Kalfon-Cohen e. s1224 

Kalina J. s1139 

Kaliner M. s1036 

Kalkan Burat A. s969, s971 

Kalkan e. s908, s908, s914 

Kalmykov S. n. s928 

Kaltbeitzel A. s800 

Kamenik J. s635 

Kaminska A. s1260 

Kaminsky J. s1354 

Kamnev A. A. s652 



s1382 

chem. Listy 106, s587–s1425 (2012) 


Kamradek M. s1133, s1133 

Kandioller w. s684 

Kandoth n. s751 

Kang S. K. s1037 

Kang y. s1103, s1164 

Kani i. s987 

Kann n. s1308 

Kantekin h. s986, s987, s987, s988 

Kaplánek r. s896 

Kaplanova M. s1338 

Kapras v. s1301 

Karabanovich G. s1064 

Karabulut M. s1244 

Karachevtsev f. s1134, s1157 

Karakose A. s1140 

Karban o. s1244 

Kardos G. s1097 

Kardos n. s662 

Karel L. s1129 

Kargin y. s984 

Karim S. s1173 

Kärkäs M. s1173, s1174, s806 

Karlikova M. s1231 

Karlsson e. s1174 

Karnahl M. s988 

Karpacheva G. s1038, s1219, s1232 

Karpov S. v. s1309 

Karsili t. n. v. s808 

Kasak P. s1247 

Kasarci A. s1126 

Kashiwada A. s1232 

Kasicka v. s1121, s604 

Kassab r. s1104 

Kasyutich o. s731 

Kataev e. s1111 

Katerina C. s929 

Kathayat r. S. s1349 

Katz t. s689 

Kaufmann A. s1233 

Kaufmann L. s1233, s1234 

Kaurinovic B. s901 

Kautek w. s828 

Kavelenova S. s901 

Kawasaki S. s1365 

Kaynar G. s1244 

Kebert M. s911 

Kebir n. s1049 

Keceli G. s920, s921, s921 

Keglevich G. s1008 

Kehr S. s839 

Keinan e. s797 

Kele P. s1011, s1297 

Keller i. s695 

Keller M. s1053, s1336 

Kelsen v. s1240 

Kempe r. s1303 

Kempf n. s977 

Keppler B. K. s684 

Keramidas A. s673, s686 

Kern M. s1038 

Kern S. s690 

Kervennic y. s1229 

Kesarkar S. s764 

Kessler S. n. s755 

Kettling u. s657 

Kevresan S. s875 


Khaleel n. d. h. s904 

Khan B. s1285 

Khan f. s678 

Khipach v. s1107 

Khodayari M. s1250 

Khom S. s718 

Khriachtchev L. s845 

Khripach v. s1367, s856 

Khusniyarov M. s698, s951 

Khusniyarov M. M. s974 

Kicková A. s798 

Kielkowski P. s1039 

Kijenski J. s868 

Kilic M. s1193 

Kilianova M. s1234 

Kim d. s972 

Kim d. h. s655 

Kim e. s1164 

Kim h. J. s1177 

Kim J. s1163, s1164, s1184 

Kim J. G. s1177 

Kim K. s752 

Kim M. s1184 

Kim S. s1052, s1184, s1184 

Kim S. h. s1165, s1168, s1310, s655 

Kim S. K. s1134 

Kim y. s937, s972 

Kim y. C. s1039 

Kim y. J. s1177, s1185 

Kimoto h. s1048 

Kimura y. s1205 

Kinart z. s825, s867 

King d. s808 

King r. B. s990 

Kingsley J. s790 

Kirchner K. s971 

Kirsch M. s606 

Kirtman B. s870 

Kiseleva S. s1038 

Kishimoto M. s659 

Kiskinova M. s825 

Kisko G. s677 

Kiss A. s1065 

Kiss n. z. s1008 

Kiss v. s649 

Kitschke P. s963 

Kitson P. J. s1253 

Kivala M. s766 

Klaas r. s1235 

Klán P. s1265 

Klapper M. s789, s800 

Klasek A. s1342 

Klasnja B. s911 

Klebe G. s1332 

Klementová M. s1305, s1346 

Klika K. s1358 

Klimes J. s814 

Klimesova v. s1037, s1064 

Kling M. s729 

Klivar J. s1121 

Kljun J. s684 

Klose f. s805 

Klüfers P. s977, s978, s983 

Knappke C. e. i. s1040 

Knauber t. s1285 

Knibbe r. s1203 



s1383 

chem. Listy 106, s587–s1425 (2012) 


Kniep f. s1030, s1040, s1099 

Knob r. s1144 

Knochel P. s754 

Knorn M. s1309 

Knorr M. s936 

Knowles M. s885 

Ko y. S. s1227, s1310, s609 

Kober t. s928 

Kober v. s940 

Koberova M. s727 

Koca J. s822, s872 

Kocman M. s868, s876 

Koch S. s887 

Kochel A. s994 

Kocik M. s1425 

Kocsis G. s725 

Kocsis L. s664 

Koehler t. s1222 

Koenig B. s1031, s1047, s1243, s884 

Koenig M. s1102 

Koenigs r. s1310 

Koetteritzsch J. s791 

Kogiso M. s1238 

Kohl B. s1311 

Köhl i. s1041 

Kohler f. s810, s878 

Kohler L. s684 

Kohls P. s1041 

Kohutova A. s1424 

Koivula t. s928 

Kojic v. s1020 

Kojio K. s1365 

Koktan J. s1135, s1159 

Kolaczkowski M. s1306 

Kolar M. s1234 

Kolar-Anic L. s1144 

Kolehmainen e. s1035, s1066, s1307, s833 

Kollár L. s1333 

Kolmar h. s613 

Kolorosova A. s1147 

Kolusheva S. s1181 

Komon t. s1311, s868 

Komratova v. s1105, s1366 

Kondinski A. s989 

Kondratuk d. v. s1040 

Konecny M. s742 

Konieczny L. s897 

König B. s1003, s1003, s1025, s1028, 

s1049, s1083, s1084, s1123, 

s1157, s1224, s1286, s1318 

König n. f. s1234 

Kontominas M. s673 

Koos M. s1027 

Korkuna o. s1114 

Kornhaaß C. s1042 

Korobova o. s1171 

Korotvicka A. s1312 

Korshin e. s1042 

Kortz u. s697, s942, s985, s989, s992, 

s992, s993 

Kortz u. s933 

Korzekwa J. s939 

Köse d. A. s1127 

Kosinová P. s876 

Kosma P. s1299, s854 

Kosmrlj J. s1340 


Köster h. s1332 

Kosterina n. s902 

Kostiainen M. s731 

Kostic M. s1276, s1283, s1312 

Kosugi n. s830 

Kotaskova M. s1043 

Kotek J. s933, s944 

Kothe e. s893 

Kotkova z. s944 

Kotora M. s1076, s1088, s1312, s855 

Kötschau A. s911 

Kouklovsky C. s1363 

Kounaves S. s593 

Kousalova J. s1043 

Kovacic S. s846 

Kovacikova L. s898 

Kovacova S. s1313 

Kovacs e. s1004, s1190, s1313 

Kovács h. s912 

Kovacs J. s1188 

Kovacs S. s1314 

Kovacs z. s1188, s643, s917 

Kovaricek P. s1044 

Kovats e. s1235, s1249 

Kowalski P. s1306 

Kowalsky w. s699 

Koyanagi S. s1174 

Kozaris i. s624, s624 

Kozhinov A. s602 

Kozien M. s1244 

Kozisek J. s857 

Kozmon S. s822, s872 

Kral v. s1135, s1159 

Král v. s896 

Kralik A. s1314 

Králová J. s896 

Kralova K. s1305, s1346 

Kramer C. s1315 

Kratochvíl B. s1204, s1367 

Kratochvil J. s1315 

Kraus t. s1021 

Kraus w. s709 

Krause K. s893 

Krause n. s1052, s1098, s1270 

Kraushaar K. s689 

Krausova B. s778 

Krausse n. s1316 

Kravets i. s1125 

Krchnak v. s772 

Krebs M. s1044 

Krecmerova M. s604 

Krejcík L. s1204 

Krejcova z. s1135 

Krenk o. s1315 

Kretschmer f. s1293 

Kreutzer J. s1236 

Kreuzer A. s1045 

Krivosudsky L. s956 

Krizek t. s1136, s1136 

Krizova i. s1021 

Kroke e. s689, s964, s965, s967, s970, s973 

Krol M. s897 

Kronstein M. s1200 

Krossing i. s1145 

Kroutil w. s802 

Krueger A. s740 



s1384 

chem. Listy 106, s587–s1425 (2012) 


Krueger M. s1222 

Krüger M. s892 

Krupa i. s1247 

Krupkova A. s755 

Krystof v. s777 

Kubala M. s1158 

Kuballa t. s617 

Kubat P. s1225 

Kubat v. s1236 

Kubatkin S. s1229 

Kubeil M. s715 

Kubelka t. s1045 

Kubicki M. M. s936 

Kubickova A. s1136 

Kubisa P. s1005 

Kuchar J. s934 

Kudová e. s778, s1301 

Kudryasheva n. s1270 

Kudzin M. s1046 

Kudzin z. s1046 

Kuehbeck d. s1046 

Kuemmel S. s1031, s1047 

Kugimiya A. s606 

Kuhajda K. s875 

Kühl o. s687 

Kuhn A. s595, s744 

Kuhn C. s1316 

Kühn L. s730 

Kuhnert n. s869 

Kuil J. s720, s785 

Kuk J. h. s1163 

Kukacka z. s892 

Kukoc-Modun L. s1145 

Kukueva v. s809 

Kulchat S. s1047 

Kuleshova L. s882 

Kulhanek J. s1043 

Kulkarni A. s851 

Kumar K. s804 

Kumar S. s1309 

Kumbaraci v. s1022, s1023 

Kümmerer K. s650, s904 

Kumsapaya C. s595 

Kun d. s1237 

Kunduraci M. s610 

Kunes J. s1315 

Kunhao L. s654 

Kunhardt d. s1233 

Kunz h. s775 

Kunz o. s1048 

Kuo M. y. s1201 

Kupfer S. s699, s830 

Kuramitsu r. s1164 

Kuramochi h. s636 

Kurdi r. s643 

Kurka P. s1139 

Kurotsu t. s1048 

Kursun G. s1127 

Kurth d. G. s1223 

Kurtz Jr d. M. s888 

Kurz P. s1185 

Kutonova K. s1317 

Kuzmanovic n. s1049 

Kvitek L. s1219, s1231, s1234, s1257 

Kwak M. s796 

Kwon A. h. s1172 


Kwon K. s1164 

Kwon y. u. s1172, s1227, s609 

l 

La Mantia f. s594 

La venia A. s772 

Lachaize S. s1240 

Lachenmeier d. s617 

Lachmann B. s1077 

Lacôte e. s1319 

Lafarge J. s1049 

Lagana A. s623, s623 

Lahtinen M. s1307, s1324 

Lai J. s1124 

Laine t. s1173 

Lainer G. s1059 

Lair v. s1143 

Lajeunesse A. s648 

Lako J. s643 

Lalinde e. s1223, s682 

Lam C. M. s1317 

Lambert C. s898 

Lan y. s933 

Lanari d. s663 

Landgraf S. s1128 

Landman M. s945 

Lang h. s1221 

Lang K. s1351 

Lang t. s1318 

Lange A. s955 

Lange n. s723 

Langer J. J. s1425 

Langer K. s1425 

Lanigan r. s1050 

Lara-Avila S. s1229 

Larnaud f. s1050 

Larranaga A. s948 

Lartaud i. s1330 

Laschat S. s1044, s1071 

Laskay u. s602 

Laskova J. s942 

Laszlo K. s1186 

Latos Grazynski L. s1072 

Latronico M. s1166, s679 

Laub h. s1051 

Laura d. L. C. s1337 

Laurin M. s810 

Laursen B. s1237 

Lazar A. i. s869 

Lazar d. s1194 

Le Blanc A. s1129 

Le Bras J. s1051, s1361 

Leask r. L. s656 

Lebreton J. s1000, s1056 

Lecamp L. s1025 

Lechner r. s1047 

Lee B. L. s1173, s1174 

Lee C. S. s1052 

Lee C. y. s1163 

Lee f. w. s1162 

Lee G. J. s1134 

Lee h. s1164, s1164, s1182, s1183 

Lee J. s1127 

Lee J. S. s1310 

Lee K. s1163 

Lee K. i. s1183 



s1385 

chem. Listy 106, s587–s1425 (2012) 


Lee L. s1184 

Lee M. s1165, s593 

Lee S. d. s1183 

Lee t. C. s869 

Lee w. r. s926 

Lefebvre q. s733 

Léger d. s1021 

Legrand y. M. s844 

Lehn J. M. s1044, s1047, s1081, s1096, 

s1293, s588 

Lehto J. s928 

Lehtonen A. s962 

Leibold M. s694 

Leigh d. A. s735, s953 

Leiner J. s821 

Leitner S. s968 

Leliege A. s773 

Lemercier G. s1214, s607 

Lemke A. s1318 

Lemouchi C. s782 

Lempke L. s1052 

Lemr K. s1143, s1151 

Len C. s780 

Lengyel L. s664 

Lente G. s688 

Lentsch C. s1009 

Leo y. S. s608 

Leonard e. s780 

Léonel e. s1001 

Leonhardt C. s955 

Leonhardt S. s962 

Lepoittevin B. s770 

Lequeux t. s1050 

Lere-Porte J. P. s802 

Leridon h. s906 

Lesage de La haye J. s1319 

Lesma G. s1343 

Lesnichaya v. s1105, s1366 

Lesnikowski z. J. s1006 

Lesnyak v. s730 

Lestari w. w. s952 

Letona r. s931 

Levin y. s1042 

Lewandowski B. s735 

Lewinski J. s690 

Lewis M. s848 

Lhotak P. s1288, s1301, s1352, s1354 

Lhoták P. s1299, s1351 

Li A. s1319 

Li M. s1320 

Li t. s1237, s1246 

Li vigni M. s617 

Li x. s1124 

Li y. s783 

Li z. s610, s839 

Lian r. s925 

Liao h. r. s1175 

Libuda J. s810 

Licbinska M. s643 

Lichtenecker r. s1009 

Lidzey d. G. s790 

Lieberzeit P. s929 

Liles d. s1208, s974 

Liles d. C. s972 

Lim h. S. s1165, s1168 

Lim J. A. s1173 


Lima A. s1175 

Lima L. M. P. s941 

Limtrakul J. s595 

Lin f. s660 

Lin y. S. s1228 

Linares n. s682 

Linck n. s660 

Linclau B. s1050 

Lindhorst t. K. s740 

Lindner B. d. s784 

Lindner L. s978 

Lindner w. s602 

Ling K. s1053 

Ling y. s1103 

Linhardt r. s1053 

Linhart i. s1026, s1314, s1365 

Linshoeft J. s1054, s772 

Lintnerova L. s898 

Lippach A. s1320, s1321 

Lippold M. s964 

Lipshutz B. s856 

Lisa M. s1117 

Lischka h. s781 

Lischke u. s887 

Liskamp r. s776 

Listorti A. s1360 

Liszewska M. s1260 

Litus e. s902 

Litvinovskaya r. s1367 

Liu C. s1206 

Liu S. s1083 

Liu t. s808 

Liu y. s910 

Lloret-fillol J. s949 

Lo Magro S. s1167 

Lobanova i. s942 

Lodi A. s653 

Lodygina v. P. s1309 

Loeb S. J. s729 

Loget G. s595, s744 

Loh t. P. s1302 

Löhr A. s628 

Lommel t. s891 

Long d. s697, s999 

Long d. L. s666 

Longoni G. s680 

Lönnecke P. s952 

Lopes A. s647, s916 

Lopes C. B. s651 

Lopes i. C. s598 

Lopes L. M. f. s1220 

Lopes M. e. s1137 

Lopez Barreiro d. s1178 

Lopéz P. s914 

López-Aranguren oliver P. s666 

Lopez-Carrillo v. s1345 

Lopez-Sanchez B. s1074 

Loredo J. s926 

Lorente r. s787 

Loshchinina e. A. s652 

Losse S. s944 

Lotfi S. s1054, s1137 

Lotz S. s682, s972, s980 

Louis S. s648 

Loukotova S. s1321 

Loullis A. s1165 



s1386 

chem. Listy 106, s587–s1425 (2012) 


Löw n. L. s1234 

Lu M. s1179 

Lu z. s1319 

Lubal P. s1155, s944 

Luben G. s1178 

Lucarini M. s1241 

Ludwig G. s989 

Luetzen A. s1329 

Luis Carlos S. s1178 

Luis J. M. s820, s823, s865, s870 

Lumpi d. s1300, s1322, s781 

Lundberg K. s1308 

Lundell J. s845 

Lungerich d. s1322 

Lüning ulrich P. of. dr. s1041 

Lüning u. s1026, s1068, s1078 

Lupan A. s990 

Lupan i. s888 

Lupenko d. s1323 

Luponosov y. s1214, s1323 

Lupton J. s1083 

Lützen A. s1030 

Lützenkirchen-hecht d. s1249 

Luxenhofer r. s1291 

Lux-Steiner M. Ch. s1222 

Luz P. s647 

Lycka A. s1342 

Lydon C. s666 

M 

Maah M. hd. Jamil s954 

Maalem M. s1138, s1253 

Maccato C. s1220 

Macícková-Cahová h. s1039 

Maciejowska i. s633, s634 

Macquarrie d. s1182, s675 

Madich y. s1002 

Madybekova G. s1062, s929 

Maenhaut w. s725 

Maes B. s716 

Maggini L. s731 

Maggini M. s1172 

Mahboobi S. s1089 

Mahmood A. s1210 

Mahmoodi f. s1250 

Mahmoud w. M. M. s650, s904 

Mahramanlioglu M. s915, s915 

Mai t. t. s1363 

Maia e. s626, s931 

Maier L. s1323 

Maier n. M. s602 

Maier S. s1324, s851 

Maier v. s1144 

Maik S. s990 

Maillou t. s1143 

Maimon e. s958 

Maitani y. s1238 

Maitra u. s1003 

Maiuri M. s699 

Majdik C. s1303 

Majer z. s1357 

Majidi M. s1137 

Majlesi K. s870 

Majoral J. P. s1053, s1336 

Mäkelä t. s1324 

Maksimovic J. s1144 


Maksimovic z. s600 

Mal S. S. s992 

Malferrari d. s1181 

Malgorzata S. s1116 

Malicka J. s1242 

Malig J. s1308 

Malinova L. s1325 

Malisova K. s1138 

Malkov A. s1248 

Malkov G. v. s1309 

Malter M. s1325 

Maltzev e. s1323 

Malygin A. s1248 

Malz r. s1246 

Mamane v. s1031, s1055, s1055 

Mammen L. s789 

Man i. s1359 

Man P. s855, s892 

Mandery h. s660 

Mani f. s665 

Manicardi A. s709, s795 

Manke A. M. s1185 

Manners i. s688, s954 

Manos M. s1057 

Manoylova o. s805 

Manso J. A. s831 

Mantsala P. s1358 

Manzoor Ahmad Malik M. s1332 

Maougal e. s1056 

Maqsood Ahmad Malik M. s1332 

Mara L. s905 

Maranescu B. s1326, s1362 

Maranescu v. s1326 

Marchal ingrain A. s626 

Marchelli r. s1168, s709, s795 

Marchese L. s843 

Marchetti f. s681 

Marchi e. s738 

Maresová d. s920 

Mareda J. s800 

Marek i. s1059 

Maria t. M. r. s1198 

Maric M. s656 

Marini f. s614 

Marin-rodriguez C. s1272 

Markopoulos G. s1056 

Markoulides M. s1057, s799 

Markovic J. s600 

Maron L. s788 

Marques e. f. s879 

Marques f. s718 

Marrocchi A. s663 

Marsura A. s1075 

Martharu A. s1182 

Marti rujas J. s836 

Martin Caba S. s1326 

Martín n. s739, s741 

Martinek v. s866 

Martinelli C. s1286 

Martinez-espin J. S. s1272 

Martini C. s1238, s770 

Martin-Lasanta A. s740 

Martins f. s874 

Martins G. s1255 

Martins J. S. s1240 

Martins M. A. P. s1272 



s1387 

chem. Listy 106, s587–s1425 (2012) 


Martins S. s1239 

Martinu t. s1295 

Marques e. f. s791 

Marvaud v. s735 

Maryutina t. s1149 

Marzocca A. s916 

Masat M. s1327 

Mascarenas J. L. s711 

Masek v. s1219 

Masiol M. s912, s913, s913 

Masseroni d. s1058 

Mastalerz M. s1311, s799, s847 

Mas-torrent M. s835 

Mastrorilli P. s1166, s679 

Masui h. s1327 

Mata r. s860, s871, s874, s879 

Matache M. s1336 

Mateos Gil J. s741 

Matern A. s1125 

Mateus P. s941 

Mathé-Allainmat M. s1000, s1056 

Matile S. s1004, s1347, s800, s804, s999 

Matito e. s820, s871, s876 

Matousova e. s1315 

Matsko n. s846 

Matsuda K. s1232 

Matsumoto S. s1179 

Matsuno t. s1074 

Matt B. s1239, s681 

Matthäus C. s893 

Matthias S. s958 

Mattioli C. s1058 

Mattoussi h. s748 

Matuska r. s872 

Matveeva G. s721 

Maubon d. s714 

Maulide n. s759 

Maurer C. s993 

Maxim M. s1269, s1355 

May r. s1328 

Mayer i. s876 

Mayes w. s645 

Mayor M. s1218, s1226, s1259, s736 

Mayr h. s1051, s1280 

Mazal C. s1328 

Mazzoni r. s681 

McBurney r. t. s953 

Mcelhoney K. s593 

McGinley J. s1243 

Mcinnes e. s733 

McLaughlin C. s730 

McLeod M. s1337 

Mcneill K. s649, s652 

Mechau n. s1360 

Mecinovic J. s898 

Meda P. s723 

Meffre A. s1240 

Meguellati K. s1047 

Mehdaoui B. s1240 

Mehdi h. s1329 

Mehlich J. s630 

Mehring M. s1221, s955, s962, s963, s990 

Meier B. s1059 

Meier w. s792 

Meireles A. M. C. s1204 

Mejuch t. s1059 


Melavuori M. s845 

Melcher B. s810 

Melero J. S. s985 

Melo Jorge M. e. s1240, s1255 

Memarian n. s657 

Mena i. s694 

Menand M. s1239 

Mende f. s1367 

Mendes da Silva J. f. s761 

Menezes r. C. s864, s893 

Menna e. s1255 

Mennucci B. s815 

Ménová P. s724 

Mereiter K. s971 

Merkoci A. s1256 

Merna J. s1300 

Meroni d. s849 

Merten d. s911 

Mertens f. s1202 

Mertlikova-Kaiserova h. s1077 

Merz K. s1226 

Messadi A. s651 

Mestek o. s1138 

Mestrinho e. s1137 

Meszaros A. s1349, s1357 

Metrangolo P. s836 

Metsa-Ketela M. s1358 

Metson J. s975 

Meunier Prest r. s1060 

Meyer A. s1330 

Meyer K. s810 

Meyer M. s1330 

Meyer r. s639 

Meyer S. s1201 

Meyer-eppler G. s1329 

Meyer-ilse J. s864 

Meyers S. s633 

Meyerstein d. s1241, s952, s958 

Mezei P. d. s1281 

Meziere C. s782 

Mezzina e. s1241 

Micali n. s1216 

Michaelides A. s814 

Michalak A. s1425 

Michel C. s823 

Michl J. s764, s1218, s1327, s1424 

s1424 

Micksch M. s960 

Micolova P. s722 

Mietton f. s714 

Mihailescu C. s1268 

Mihalache M. L. s1160, s1166 

Mihovilovic M. d. s1339, s707, s718, s719 

Mika J. s1139 

Mika L. t. s1097 

Mikes M. s1117 

Mikhailovsky S. s1248 

Mikhaylov A. s1334 

Mikkelsen L. s1203 

Mikyskova h. s604 

Milan P. s1359 

Milata v. s1092, s627, s770 

Mildner f. s1331 

Milek M. s698, s974 

Milek t. s826 

Milenkovic M. s866 



s1388 

chem. Listy 106, s587–s1425 (2012) 


Milenkovic n. s1188 

Milfelner M. s1263 

Milione S. s687 

Miller B. s633 

Millini r. s848 

Milstein d. s591 

Minca i. s905 

Mineo P. s1060 

Minko e. s1090 

Minois P. s1060 

Miras h. s666, s733 

Mirmohseni A. s1054 

Miro Sabate C. s1176, s1331, s654 

Mironova e. s1219, s991 

Misicák r. s798 

Miskovicova M. s1154 

Misztal K. s1242 

Mitarai M. s659 

Mitchell S. s697 

Mitchell t. s625 

Mitric r. s817 

Miyasaka K. s840 

Miyata M. s838 

Miyazawa M. s893 

Miyoshi d. s899 

Mizera J. s1125 

Mladkova J. s894 

Mlynsky v. s872 

Mochizuki C. s1205 

Modau e. s1208 

Moeller M. s1120 

Moffitt M. s748 

Mogilireddy v. s607 

Mohamadou A. s651 

Mohamed S. s1063 

Mohammad L. s1054 

Mohmmad younus wani M. s1332 

Mohsen M. s721 

Mohtat B. s1061 

Moita M. L. s874 

Mojmir n. s929 

Moldoveanu i. s598 

Molina Sanchez P. s1217, s666 

Molinari M. s1214 

Molon M. s939 

Moloney M. s1000 

Moloney M. G. s1090 

Momma M. s893 

Monajjemi M. s867 

Monard G. s1330 

Monari A. s821 

Mondal M. s1332 

Mondal S. s771 

Mondes v. s729 

Monincova L. s724, s886 

Monkowius u. s968 

Monsu Scolaro L. s1216, s1252, s940 

Montalti M. s749 

Monteiro o. C. s1255 

Montellano P. s1242 

Montmeat P. s802 

Mooney v. L. s812 

Moore A. L. s738 

Moore t. A. s738 

Morain B. s810 

Morales r. s931 


Moran J. s1243, s1244 

Morandi G. s1025 

Moreau J. s1214 

Morel e. s735 

Moreno M. S. M. s1333 

Morgan M. s889 

Moriga t. s1202, s1208 

Morrison C. s1124 

Morscheidt w. s928 

Moser f. s631 

Mosinger J. s1225, s751 

Mot A. C. s674, s885, s888 

Mota A. J. s740 

Motakef Ghomi M. r. s1209 

Moth-Poulsen K. s1229 

Motokuchou S. s1365 

Motz G. s1303 

Mousavi Moghadam A. s1080, s1344 

Moussa d. s1104 

Moussa J. s681 

Moussallem C. s1061 

Mracec M. s1326, s1362 

Mucha M. s1139 

Mueller A. s1243 

Mueller h. s1199 

Mueller t. s1295 

Muhler M. s1226 

Müllen K. s1228, s1271, s1333, s1360, s790, s800 

Müller C. e. s715, s853 

Muller J. s894 

Müller K. s639 

Müller M. s1082 

Müller P. s1265 

Müller t. J. J. s699 

Münch A. s1202 

Munoz-fernández M. A. s787 

Murai K. s1202, s1208 

Murakami S. s1179 

Murashima t. s899 

Muratov d. s1232 

Muresan L. e. s1196 

Muromachi S. s691 

Murray B. s1243, s1244 

Musa S. s1062 

Muscarella M. s1167 

Mushtakova S. s617 

Musolino M. s1343 

Mustafa M. hd. rais s954 

Musumeci r. s722 

Mutaliyeva B. s1062, s929 

Mutti f. G. s802 

Muzafarov A. s1323 

Muzart J. s1361 

N 

nachon f. s1068 

nadaroglu h. s907, s908, s908, s914, s918 

naderi h. s1080 

nadri S. s1213, s941 

naffrechoux e. s662 

nagendiran A. s1097 

naglah A. s1106 

nagy B. s1186 

nagy t. s1357 

nagy t. z. s1314 

nakagawa t. s1208 



s1389 

chem. Listy 106, s587–s1425 (2012) 


nakamura h. s1006 

nakano S. s899 

nakayama K. s1063 

nakazawa C. s1048 

nalbantoglu f. s1244 

nam h. s1127 

nam S. C. s1173, s1176 

nam w. s685 

nanni d. s1220 

narita A. s1333 

nariya B. s850 

nassar M. s1063 

nastova i. s1245, s873 

nasun- Saygili G. s647 

natour S. s1064 

nau w. M. s869, s887 

naumkin f. s1245, s873 

navratil r. s1295 

navratil t. s646 

nechab M. s771 

negro C. s914 

neier r. s1033, s767 

nemec i. s934 

nemec M. s921, s922, s923, s928 

nemecek J. s1064 

nemeckova A. s1139 

nemes G. s1344, s997 

nemeth B. s854 

nemeth J. s1065 

neo S. S. s814 

neouze M. s845 

neouze M. A. s1200 

neri d. s796 

neuburger M. s996 

neufeld K. s1203, s707 

neufuss S. s921, s929 

neumann M. s1031, s608, s970 

neumann t. s704 

neves A. C. B. s1337 

neves r. s651 

ng C. h. s954 

ng S. w. s954 

nguyen B. t. t. s608 

nickovic S. s907 

nicolescu A. s1282, s1336 

nielsen C. J. s863 

nielsen J. L. s693 

niemi J. s1358 

niewiadomski P. s868 

nikitenko S. s662 

nikitina v. e. s652 

nikolaev A. s1334 

nikolic J. s1065, s1334 

nikolic n. s1076 

nischan n. s967 

nishiura y. s775 

nitschke J. r. s733 

nocito f. s692 

noe C. r. s1077 

noel t. s1273, s762, s801 

nogueira i. s651 

noh t. h. s961 

nolte r. s731 

norcliffe J. s1280 

nordmeyer d. s1246 

norgaard K. s1237, s1246 


north M. s661 

noseck u. s922 

nöske r. s970 

novák M. s622 

novak P. s727, s855, s892 

novák z. s1290, s1314, s1349, s1357 

novakova v. s1279 

novakova z. s1066, s1247 

novosad J. s1236 

novotná r. s935 

novotny v. s1140 

nsouli n. s989 

nunes C. d. s963, s978 

nunes t. G. s963 

nunes y. s1240, s1255 

nunez A. s1096 

nurullah S. s1148 

nuryyeva S. s1425 

nyholm L. s596 

o 

obsil t. s891 

obsilova v. s891 

oca M. L. s1141 

occhiuto i. s1216 

odell B. s807 

o’donoghue A. s782 

o’donoghue A. C. s1317 

o’donovan L. s726 

ochoa-Puentes C. s884 

oeckler o. s851, s852 

oh J. M. s1168 

oh t. s1335 

ohlendorf G. s1335 

ohlmann d. M. s1268 

ohmura r. s1174, s659, s662, s691, s818 

ohnishi-Kameyama M. s1229 

ohta t. s1063 

ohtaki K. s1179 

oja t. s1358 

okamoto S. s1066 

okamoto y. s1056 

oklestkova J. s777 

olejnickova J. s1170 

olejniczak A. B. s1006 

oleko A. s906 

oliveira A. s1161 

oliveira J. s874 

oliveira-Brett A. M. s598 

oliver r. s1094 

olson A. s704 

Ölzer e. s1126 

omastova M. s1247 

omtvedt J. P. s928 

omurtag P. S. s1067 

ondel eymin M. J. s1060 

ondruschka B. s656, s821 

o’neil G. s593 

onganer y. s1111, s1112, s1112, s1113, s1113, s1115 

onjia A. s1152 

oprea o. s1195 

oprescu e. e. s1177 

orbay A. s1142 

ordonez A. s926 

orekhova n. s1171, s1219, s1248 

orenes r. A. s1272 



s1390 

chem. Listy 106, s587–s1425 (2012) 


oreshkin i. s1171 

orinak A. s1256 

orinakova r. s1247, s1256 

orlanducci S. s1216 

orlov A. s1038 

orlovic S. s911 

oro L. A. s694 

ortega L. s948 

ortgies d. s1067 

ortiz M. C. s1141, s616 

orvig C. s983 

osako M. s636 

oscarsson S. s806 

ostrand-rosenberg S. s728 

ostrovskii o. s901 

osuna S. s823, s865 

osz K. s649 

otte P. s1068 

otto S. s780 

otyepka M. s872, s876 

ouali A. s1336 

ouchaou K. s1187 

oueis e. s1068 

Öz S. s1142, s1149 

ozbas f. s915, s915 

ozbek M. s1244 

ozden t. s1244 

ozerov A. s901 

ozgen o. s915, s915 

Özkaramete e. s1142, s610 

Özkinali S. s1069 

P 

Pabisch S. s993 

Pabst A. s1069 

Pace A. s1255 

Pacchioni G. s822 

Pacha-olivenza M. A. s1251 

Pache A. s1203, s961 

Pacheco M. J. s647, s906, s916 

Paczkowska M. s895 

Paesani f. s1242 

Palcut M. s1203 

Palermo C. s1167 

Palm G. J. s687 

Palmas P. s1143 

Palmgren P. s806 

Palmieri A. s655 

Palszegi t. s827 

Panacek A. s1219, s1231, s1234, s1257 

Pandey G. s1041 

Pandiyarajan C. K. s792 

Pansu r. s802 

Panteleitchouk t. s1120 

Panyala n. r. s1110 

Panzer r. s1070 

Paolella S. s726 

Papastefanou C. s673 

Papic P. s645 

Papouskova B. s1143 

Pappalardo L. s1132 

Paradas M. s771 

Paradies J. s1070, s1071 

Paraschivescu C. s1336 

Parastar h. s618 

Parchmann i. s632 


Parella t. s975 

Paria S. s1074 

Park A. s1332 

Park h. K. s1134 

Park h. y. s1167 

Park J. s937, s972 

Park J. h. s1177 

Park J. w. s1163 

Park K. s1176 

Park n. s1071 

Park S. s1163, s1184 

Park S. J. s1168 

Park S. K. s1165 

Park y. s926 

Parker J. s672 

Parker S. C. s996 

Paruch K. s1313, s1323 

Parviainen A. s641 

Parvu M. s885 

Parvulescu v. s1092 

Parvulescu v. i. s1191 

Pasdar h. s986 

Pasfield L. s1337 

Pasquinet e. s1143, s802 

Pasta M. s594 

Pastori n. s767 

Pastva J. s976 

Pasztor-huszar K. s677 

Patarin J. s849 

Patrick t. s1016 

Pauk v. s1143 

Paulikat M. s871 

Paulus f. s1246 

Pavel o. d. s1092, s1186 

Pavlath A. s629 

Pavlista M. s1206 

Pavlov G. M. s1102 

Pavlychev A. A. s830 

Pavoni B. s912, s913, s913 

Pawlicki M. s1072 

Pechyen C. s1072, s1248 

Peckova K. s1130, s597 

Pedroso de Lima M. C. s791 

Peh A. e. K. s608 

Pehlken C. s947 

Pejic n. s1144, s1160 

Pejov L. s873 

Pejova B. s1245 

Pekker S. s1235, s1249 

Pellecchia C. s687 

Pelloux h. s714 

Peluso P. s1055, s1055 

Pena-Mendez e. M. s1110 

Pennell M. s1073 

Pereira e. s651 

Pereira M. M. s1198, s1333, s1337 

Pereira r. s909 

Peretz S. s1269 

Perevyazko i. s1102 

Perhaita i. s1196, s1344 

Perin J. L. s792 

Perinka n. s1338 

Perlikova P. s1073 

Perman J. s1218 

Perrier A. s1336 

Perutz r. n. s996 



s1391 

chem. Listy 106, s587–s1425 (2012) 


Peruzzini M. s665, s679 

Peschel L. s715 

Peter K. s1263 

Petermann L. s976 

Peters w. K. s829 

Petersen J. s817 

Petho B. s1290 

Petkovic S. s866 

Petr J. s1144, s930 

Petrar P. s997 

Petruzelka L. s1154 

Petukhov A. s818 

Petukhova n. s818 

Petunin P. s1317 

Petzinger e. s902 

Peuchmaur M. s714 

Pezron i. s780 

Pezzella A. s728 

Pezzolesi L. s1178 

Pfaffeneder t. s1082 

Pfeffer J. s802 

Pfirrmann S. s688 

Pfitzner A. s1031 

Pfleiderer S. s1249 

Pflieger r. s662 

Pfund e. s1050 

Phetsang w. s890 

Philippot K. s1198 

Phulwale B. v. s1328 

Piarulli u. s700 

Pidchenko i. s922 

Piehler t. s1030 

Piekarska B. s897 

Piemontesi C. s813 

Pietruszka J. s1274, s1286, s707, s778 

Pievo r. s1241 

Pigeaux M. s1338 

Pignataro B. s1217, s1255, s712, s744 

Pilard J. f. s1007 

Pilnacek K. s1090 

Pilsl L. s1074 

Pilz d. s976 

Pinakoulaki e. s1165 

Pingoud A. s902 

Pinheiro L. s874 

Pintado M. s1161 

Pinter B. s917 

Pinto A. P. s1137 

Pinto d. C. G. A. s1001 

Pinto i. S. S. s1187 

Pinto J. s1339 

Pinto M. s718 

Pinto v. s793 

Piot C. s924 

Pipelier M. s1001 

Pirtsch M. s1074 

Pivesso P. s1175 

Pivetta t. s1110 

Pivodova v. s895 

Piwowar M. s877 

Pizzo f. s663 

Plain J. s1262 

Plasser f. s781 

Plenge J. s729, s877 

Plutino M. r. s940 

Podobedov r. s981 


Poeta P. s1159 

Pohl r. s1298 

Poisson G. s1075, s621 

Poisson J. f. s1010 

Pokorny K. s939 

Polinskaya M. s1214 

Polivkova M. s930 

Pombeiro A. s683 

Pompach P. s892 

Ponomarenko S. s1214, s1323 

Popov S. s1152 

Popovic B. s911 

Popovic M. s901 

Popovici e. J. s1196, s1344 

Popp A. s1089 

Popp J. s699, s781, s826, s830, s862, s893, s988 

Popsavin M. s1020 

Popsavin v. s1020 

Pori M. s1289, s722, s777 

Porsch t. s694 

Posa M. s875, s875 

Pospisil L. s1424 

Pospisil P. s643 

Postils v. s820 

Postnikov P. s1317 

Potopnyk M. s1075 

Pototschnig G. s1339 

Pöttgen r. s932 

Pouget C. s1021 

Pour M. s1315 

Powell A. K. s933 

Pozdeev o. s1042 

Pozzo P. d. s726 

Prado varela A. f. s761 

Prandi B. s726 

Prato M. s739 

Prats Montalban J. M. s617 

Prchalova e. s1076 

Prekodravac B. s1076 

Presser A. s1059 

Pretorius r. s945 

Prikaznov A. s942 

Prikryl J. s1206 

Primo A. s658 

Privalov t. s1173 

Procházková e. s1077 

Prodi L. s749 

Proisl K. s1340 

Prokop A. s1102 

Prosperini S. s767 

Proust A. s1239, s681 

Prucek r. s1219, s1234, s1257 

Prusty d. K. s796 

Pryanichnikova A. s929 

Puchberger M. s993 

Puchta r. s686, s883, s939, s949, s958 

Puetz K. s1145 

Pujol A. s737 

Pulido d. s787 

Punta C. s767 

Putala M. s1019, s798 

Putun A. e. s1193 

Putun e. s1193 

Pykal M. s868, s876 

Pyykko P. s813 

queva S. s1077 



s1392 

chem. Listy 106, s587–s1425 (2012) 


quignard f. s1091, s1187, s658 

quintanilha A. s668 

R 

raboch J. s1154 

rac v. s1199 

radeka M. s1188, s1194 

rademann K. s1256, s752 

radenkovic n. s1312 

radic n. s1145 

radojevic i. s950 

radtke v. s1145 

radu A. s1177 

raduly i. s1188, s643 

raduly L. s1188, s643 

raessler M. s601 

rafiee e. s1213, s1230, s1250, s1250, s941 

raindl J. s922 

rajacopal B. s884 

rajakovic L. s1152 

rak J. s896 

rakic v. s1199 

ramadan A. s997 

rambousek L. s1301 

ramos-Cordoba e. s876 

rampazzo e. s749 

rampazzo G. s912, s913 

ranc v. s1219 

ranca A. s1166 

ranogajec J. s1188, s1194 

rapantova n. s643 

rarova L. s1101, s777 

räsänen M. s845 

raschpichler C. s877 

rasmussen K. s880 

rastelli G. s1068 

rasulova n. s1323 

ratajczyk t. s1340 

rau S. s1146, s1352, s699, s830, s862, 

s943, s944, s947, s976, s988 

rauch G. s1078 

rauch-Kröhnert u. s1246 

raymo f. s750 

razic S. s600 

reale S. s728 

reany o. s797 

reau r. s747 

reck L. s1078 

reddy K. r. s1046 

redey A. s1188, s643, s917 

redini f. s1000 

reeh P. s1331 

reetz M. t. s589, s589 

reich t. s638 

reinoso S. s1203, s961 

reis M. s874 

reiser o. s1017, s1036, s1041, s1045, 

s1053, s1074, s1074, s1180, 

s1309 

reissig h. s1271, s1364 

reissig h. u. s1051 

reiter C. s1079 

remko M. s898 

renard P. y. s1068 

renaudineau S. s1239 

repovsky d. s827 


resch-Genger u. s612, s903 

resnati G. s836 

resongles e. s644, s924 

respaud M. s1240 

retegan t. s928 

reutenauer P. s1360 

rezabkova L. s891 

rezaei M. s1210 

rezanka M. s768 

rezanka P. s1135 

rezinkova y. s981 

reznik v. s1334 

rgaard K. n. s1229 

riala M. s1079, s799 

ribagorda M. s740 

ribas x. s1222, s701, s951, s955, s975 

ribeiro A. e. s1159 

ribeiro t. s748 

ricci A. s1091 

ricci L. s1058 

richards r. s1251, s660 

richards r. M. s1191 

richardt G. s1330 

richarz r. s1292 

richel A. s1191 

richert C. s891 

richmond C. s1254 

richter C. s1246 

rico M. s1223 

rieger J. s1319, s792 

riemer M. s1080 

riezman h. s999 

riisiö A. s962 

rinfray C. s1239 

rioux S. s1067 

rissanen K. s1008, s1035, s1093, s1234, s1324, s953 

riva S. s706 

rizk h. s1017 

roberts d. s1151 

robitzer M. s1091, s1187, s658 

rocha d. h. A. s1001 

rocha G. s658 

rocha-Santos t. s1120, s1221, s609, s909 

rochat S. s1341 

rochefort d. s1116, s594 

rockstroh n. s1352 

rodriguez J. s768 

rodriguez Moran J. s1289 

rodriguez Perez L. s741 

rodríguez-Cano A. s1251, s1252 

rodríguez-Márquez i. s771 

roeder A. s896 

roehr M. s817 

rogerson M. s645 

roh J. s1037, s1064 

rohovec J. s646 

rohwer L. s695 

roithova J. s1351 

rollet M. s770 

romano-rodriguez A. s1213 

romeo A. s1216, s1252 

romero A. s1242 

romieu A. s1068 

rominger f. s1007 

roncali J. s773 

ronchin L. s1191 



s1393 

chem. Listy 106, s587–s1425 (2012) 


ronco C. s1068 

roost C. s1341 

rosa P. s980 

rosado M. t. S. s1204 

rosatella A. s783 

rosca P. s1177 

rosca S. s1160, s1166 

rose n. s898 

roseiro t. s1204 

rosenthal t. s851, s852 

rosnes M. h. s1253 

rossi B. s767 

roterman-Konieczna i. s877, s897 

roth K. s670 

röttger y. s896 

roubeau o. s680 

rouchal M. s1275 

rouden J. s1338 

rouessac v. s802 

roullin G. s1214 

rousseau t. s773 

rousselin y. s936 

roux A. s999 

roux S. s607 

röver i. s964 

rovira C. s835 

rovisco A. s1240 

royer S. s1196, s1197, s1197, s1207 

royo M. s787 

rozati S. M. s657 

rozbesky d. s855 

rudic o. s1188, s1194 

rudic S. s807 

rudolf o. s1342 

rudolf P. s809 

rudroff f. s707 

ruecker h. s897 

ruehl e. s830 

rueping M. s1310 

rüffer t. s962, s989 

ruggeri G. s1058 

rühl e. s1246, s729, s877 

ruhlmann L. s1319 

ruiz de La oliva A. s1254 

ruiz Sierra G. s1116 

rukk n. s991 

rulisek L. s1021 

rumlova t. s1146 

rupar P. s954 

rutjes f. s719 

rutledge d. s615 

rutter J. s846 

ryabov A. s683 

ryakshina A. s902 

rybarska J. s897 

rybina A. s882 

rybinova M. s1147 

rydchuk M. s1171 

rychlovsky P. s1147, s605 

ryslava h. s1136 

s 

Sabata S. s1351 

Sabot C. s1068 

Sabry n. M. s1265 

Sacchetti A. s1342, s1343 


Sachdev h. s1228 

Sacinti C. s1128 

Saez Araoz r. s1222 

Safi B. s1138, s1253 

Safi J. s1262 

Safi Shalamzari M. s725 

Sagar r. s807 

Saglam B. s1343 

Sahin o.i. s1161 

Sahoo d. s723 

Saidi M. s1138, s1147, s1253 

Saidulu G. s1046 

Saka e. t. s986, s987, s987 

Sakac M. s1076 

Sakai n. s1347, s800, s999, s999 

Sakamoto h. s662 

Sakamoto J. s1320, s1346, s747 

Sakamoto y. s840 

Salbu B. s928 

Salice P. s1255 

Salisova M. s898 

Salle M. s798 

Salmi M. s681 

Salon J. s770 

Salvador P. s876 

Salzer r. s606, s625 

Sama J. s1213 

Samal M. s1121 

Samide A. s1118, s1119 

Samori C. s1178, s659 

Samori G. s1178 

Samori P. s743 

San felices L. s1203, s961 

Sanchez d. M. A. s1286 

Sanchez L. s794 

Sánchez M. i. s711 

Sánchez M. S. s616 

Sanchez S. s679 

Sanchez-Martin r. M. s1307 

Sanchez-nieves J. s787 

Sandberg M. n. s812 

Sanli n. s1109, s1140, s1141 

Sanli S. s1109, s1140, s1141, s1148 

Sans Sangorrin v. s1254 

Santos L. M. n. B. f. s1339 

Santos P. v. f. s598 

Santos S. s874 

Saoudi A. s906 

Saponar A. s1344 

Saptalena L. G. s1148 

Sarabia L. s1141 

Sarabia L. A. s616 

Saraiva M. S. s963 

Sarap n. s1144 

Sarbu C. s674 

Sarbu L. s905 

Sarek J. s722 

Sarjadi M. S. Sarjadi s790 

Sarreshteh dari z. s1080, s1344 

Sarris J. s943 

Sartorio C. s1255 

Sashuk v. s746 

Sasson y. s664 

Sattasathuchana t. s878 

Sattler d. s990 

Sattler J. s802 



s1394 

chem. Listy 106, s587–s1425 (2012) 


Saulnier S. s1345 

Sautet P. s823, s824 

Sauve S. s648 

Savoia d. s767 

Savonina e. s1149, s603 

Sayikli C. s1150 

Sazelova P. s604 

Sberveglieri G. s1172, s657 

Scamporrino e. s1060 

Scanlan e. M. s807 

Schaefer t. s705 

Schaefers f. s1292 

Schaeffer G. s1081 

Schäfer J. s704 

Schaller G. s1081 

Schalley C. A. s1093, s1233, s1234, s990 

Scharnweber d. s705 

Schatz J. s1193, s1290, s1331 

Schatz P. of. dr. Juergen s1190 

Schaumberg C. s1256 

Scheblykin i. s781 

Schedler u. s612 

Scherf u. s789 

Scherman o. A. s869 

Schettino v. s839 

Scheurer A. s939 

Schiesser S. s1082 

Schildbach d. s985 

Schiller A. s1118, s1122, s611, s685, s861, s946, s957 

Schindler S. s1087, s684, s977 

Schinkel M. s1082 

Schlesiger d. s1316 

Schlesinger M. s881, s962 

Schleyer P. v. r. s1322 

Schlüter A. d. s1262, s1320, s747 

Schlüter d. s1346 

Schmeide K. s639 

Schmeisser M. s939 

Schmid w. s1009, s1084, s998 

Schmidbauer S. s1028, s1083 

Schmidt B. s1018, s1023, s1048, s1080, s774 

Schmidt d. s1293, s965 

Schmidt r. s656 

Schmidtchen f. s1099 

Schmitt f. s968 

Schmitt M. s988 

Schmitt y. s699 

Schmitz d. s1032, s1083 

Schmitz P. s1348 

Schmölzer C. s1084 

Schnabel M. s1320 

Schnakenburg G. s1335 

Schneider M. s650, s852 

Schneider M. w. s799 

Schneider r. s1235 

Schneider S. s887 

Schnorr J. s1246 

Schnorr J. M. s612 

Schnürch M. s718 

Schoen J. C. s851 

Schöffmann A. s718 

Schofield C. s898 

Scholz f. s1424 

Schönfelder n. s1348 

Schreiner P. r. s1085, s1298, s853 

Schröder d. s1155, s1295 


Schröder h. s1234 

Schroder M. s847 

Schröder t. s851, s852 

Schroll P. s1084, s1286 

Schröter P. s968 

Schubert u. S. s1102, s1102, s1201, s1217, 

s1236, s1293, s781, s849, 

s964, s979, s982, s993 

Schuler S. M. M. s1085 

Schulz S. s947 

Schulz t. s1036, s694 

Schumm B. s1125 

Schuster t. s789 

Schütt C. s878 

Schütz S. s699 

Schwartz t. s746 

Schwarz h. s591 

Schwarz t. s718, s977 

Schwarzer A. s689, s973 

Schwedtmann K. s960 

Schweez C. s1085 

Schwegmann h. s909 

Schwendt P. s956 

Schwenzer B. s1233, s705 

Schwikowski M. s637 

Scopelleti r. s932 

Scott L. t. s1281 

Sebastian r. s1345 

Sebastiani d. s1330 

Sebej P. s1265 

Sebela d. s1170 

Sebenyi A. s875, s875 

Sebesta f. s635, s922, s923 

Sedlak d. s1076 

Seeman n. s834 

Segler S. A. w. s1054, s772 

Seidel f. s1221 

Seifert A. s955 

Seilerová L. s1204 

Seitz o. s1367 

Seitz w. s739 

Sekirnik r. s898 

Sellevag S. r. s863 

Sells d. s733 

Sem d. s704 

Sembera f. s764 

Semenov v. s1334 

Semioshkin A. s942 

Semisch A. s1246 

Sen f. s1181 

Sen S. s1181 

Senf A. A. s1233 

Seng h. L. s954 

Sengupta S. s812 

Senila M. s644 

Seniori S. s679 

Senocak n. s1149 

Seo B. s1134 

Seo y. s1335 

Seong r. s1164 

Sepelak J. s827 

Septelean r. s997 

Sepúlveda A. e. s682, s1223 

Serdaroglu e. s830 

Serein-Spirau f. s802 

Sério S. s1240, s1255 



s1395 

chem. Listy 106, s587–s1425 (2012) 


Sermon P. s1205, s852 

Serpell C. s730 

Serra i. s931 

Serrano e. s1223, s682 

Serrano-Plana J. s955 

Serrya r. s721 

Servalli M. s1346 

Servusova B. s1346 

Sesalan B.S. s969 

Sessler M. s1190 

Setnicka v. s1130, s1154 

Sevcik J. s1144 

Sevcik r. s944 

Severin K. s932, s937 

Sevim A. M. s957 

Sezgintürk M. K. s1150 

Sforazzini G. s1347 

Sforza S. s1168, s709, s726 

Sfriso A. s913 

Sgarbi e. s1168 

Shaban S. s997 

Shaffer C. s1295 

Shaheen K. s1347 

Shaik S. s819 

Shakeri M. s806 

Shames A. s958 

Shamsiev r. s991 

Sharafutdinova d. s1334 

Shaw S. s903 

Shen J. s1056 

Shepherd h. s820 

Sheppard t. s1050, s1073 

Sherina n. s1110 

Shevchenko n. s721 

Shibata M. s1205 

Shilun q. s842 

Shimamura A. s975 

Shimizu G. s843 

Shimizu M. s765 

Shimizu t. s1238 

Shin d. w. s1168 

Shin J. h. s1127, s1134 

Shiotsuki t. s893 

Shishilov o. s981, s984 

Shmatova e. s901 

Shoyele S. s1257 

Shtykov S. s607 

Shubely M. s1258 

Shubina t. s695 

Si z. s1424 

Sidebottom A. s716 

Siegel J. S. s1266, s1276, s1281, s1341, s858 

Siemeling u. s694 

Sierra C. A. s1286 

Sierra ramos A. f. s1286 

Sigmund e. s1348 

Silaghi-dumitrescu r. s674, s884, s885, s888 

Silaghi-dumitrescu L. s997 

Silha t. s934 

Sillanpää r. s962 

Silva A. s1288 

Silva A. M. G. s1339 

Silva A. M. S. s1001, s1057, s1086, s1339 

Silva L. s1120 

Silva L. C. s1255 

Silva M. r. s1204 


Silva Pereira M. i. s1137 

Silva S. s879 

Silva S. G. s791 

Silva v. s1288 

Silva v. L. M. s1057, s1339 

Silvani A. s1343 

Silvestrin S. s1172 

Silvi S. s1211, s1211, s734 

Sima M. s644 

Simak o. s1354 

Simandi B. s1190 

Simao C. s835 

Simeonov S. s783 

Simko d. s1357 

Simon A. s1281 

Simon G. s917 

Simon P. s677 

Simon r. C. s1274 

Simon rubio L. s1289 

Simon Sarkadi L. s620, s677 

Simons J. P. s807 

Simsir h. s1012 

Simunek P. s1009 

Sin d. w. M. s1162 

Sinai A. s1349 

Sindelar v. s1296 

Sindelár v. s1356 

Sinha K. M. s797 

Sinn S. s861 

Sipek M. s1090 

Sisa M. s1350 

Siva Pereira M.i. s1240 

Skach K. s1350 

Sivaev i. s942 

Skalova L. s1132 

Skantarova L. s1256 

Skapin t. s873 

Skarnemark G. s928 

Skeríková v. s599, s1153 

Skipperud L. s928 

Skorpilova L. s1086 

Skriba A. s1351 

Skrivanj S. s1152 

Skryabina A. s991 

Skudas r. s613 

Skuterud L. s636 

Skvorova L. s1135, s1146 

Slanina t. s1265 

Slaninova J. s724, s886 

Slavícek J. s1351 

Slavik P. s1352 

Slavíková B. s778, s1301 

Sleiman h. s730 

Slovak v. s1189, s1192 

Slovakova K. s1151 

Slugovc C. s846 

Smejkal P. s927 

Smith A. s622 

Smith C. i. e. s712 

Smith n. w. s600 

Smith S. s1053 

Smulders M. M. J. s733 

Smyth S. A. s648 

Snauwaert h. s1002 

Soares h. M. v. M. s1187 

Sobota M. s810 



s1396 

chem. Listy 106, s587–s1425 (2012) 


Socher e. s889 

Socoteanu G. M. s1189 

Sodre J. r. s1178, s653 

Soin A. s1149 

Sokolowski K. s690 

Sola M. s701, s820, s823, s865, s870, s871 

Soldati r. s1289, s777 

Solinova v. s604 

Sollogoub M. s1239 

Soltys K. s690 

Somogyi v. s1188, s917 

Söncksen L. s936 

Song J. h. s1185 

Soni r. s758 

Soos t. s1029, s1097, s1361 

Soós t. s1329 

Sormaz M. s1077 

Sormova K. s605 

Sorsche d. s1352 

Sortino S. s751 

Sorus M. s733 

Sostaric i. s600 

Söthje d. s1015 

Sotolar r. s1170 

Soukup J. s1151, s599 

Soulard M. s849 

Sousa e. s718 

Sousa i. s874 

Sousa J. L. C. s1086 

Sousa M. s1212 

Souza P. s653 

Soydaner u. s996 

Sozzani P. s1195, s834 

Spampinato S. s720 

Speicher A. s1325, s1348, s1353 

Spencer A. P. s829 

Spendlikova i. s922, s923 

Speranza v. s787 

Spies S. s891 

Spiess h. w. s1330 

Spiridon M. C. s1034 

Spirina J. s1209 

Spitaleri f. s1060 

Spivakov B. s603 

Spiwok v. s872 

Sponer J. s872 

Spork A. P. s1318 

Squizzato S. s912, s913 

Sredovic i. s1152 

Sreedhar B. s1309 

Srinivasan A. s1257 

Srinivasan S. s611 

Staehle r. s944, s976 

Stajner d. s911 

Stangenberg r. s790 

Stanglmair C. s1087 

Stanisic S. s1152, s866 

Stanislav M. s1359 

Stanislawski B. s613 

Stanková M. s599, s1153 

Stara i. s1121 

Stark w. J. s1036 

Stary i. s1121 

Stastna K. s635 

Staubitz A. s1054, s1297, s1355, s772 

Stavarache C. s1359 


Stefaniuk A. s1353 

Stefano C. s938 

Stefanovic o. s950 

Stefan-van Staden r. i. s598 

Stefelova J. s1189 

Steier P. s923 

Stein A. s840 

Steinbach J. s709, s715, s717, s889 

Steinbach M. s1087 

Steinborn d. s989 

Steinborn M. s983 

Steiner G. s606 

Steinhart h. s672 

Steinke n. s1123 

Steinkellner G. s705 

Steinmann S. s813 

Steinnes e. s636 

Stejskal f. s1354 

Stejskal J. s1338 

Stenclova P. s1088 

Stenclová z. s1119 

Stepan e. s1177 

Stepanek M. s891 

Stepanek o. s1088 

Stepanek P. s1354 

Stephan h. s709, s715, s715, s717, s889 

Steudtner r. s639 

Steunenberg P. s785 

Stibor i. s1094, s764 

Stiborova M. s866 

Sticht h. s710, s889 

Stierand P. s920 

Stiewe C. s852 

Stinga G. s1034, s1034, s1268, s1269, s1355 

Stirling A. s1357 

Stoddart J. f. s1211 

Stogniy M. s942 

Stochel G. s945 

Stojkovic J. s645 

Stolarikova J. s1037, s1064 

Stolle A. s656, s821 

Stolper t. s879 

Stopa B. s897 

Stopa G. s945 

Stoppioni P. s665, s679 

Straka J. s724 

Strassner t. s1036, s959, s960, s967 

Strauch P. s970, s973 

Strbanova S. s621 

Streb C. s701, s974, s981 

Streifinger B. s1089 

Streit h. C. s952 

Strianese M. s687 

Strizik L. s1206 

Strle G. s769 

Strnad M. s777 

Strohmann C. s985 

Stromme M. s925 

Strueben J. s1355 

Studer A. s1013 

Studzinska S. s1115, s857 

Stufano P. s693 

Stumpf P. s1246 

Stündel A. s896 

Sturala J. s1356 

Sturla S.J. s1011 



s1397 

chem. Listy 106, s587–s1425 (2012) 


Stutz C. s749 

Stutz yaunner r. s761 

Stylianou M. s1169, s686 

Styskalik A. s1236 

Suchomel P. s1257 

Sudy B. s880 

Sugimoto n. s899 

Suginaka t. s662 

Sugiyama h. s708 

Suh S. K. s1163 

Sukenik C. s1210, s1258 

Sukenik C. n. s1224 

Sukhov B. s721 

Suksi J. s922 

Sulc M. s727, s891 

Sulovsky P. s1143 

Sun B. s678 

Sun J. s1174 

Sun y. s740 

Sun z. s1103 

Suptil J. s662 

Surin n. s1214, s1323 

Suss-fink G. s678 

Sustekova J. s1089 

Sutyagina e. s818 

Suzen S. s1153, s899 

Suzuki r. s893 

Svec f. s599 

Svec J. s1356 

Svehlakova t. s722 

Svoboda i. s1142, s1149 

Svoboda J. s1088, s881 

Svobodova h. s833 

Swager t. M. s1341, s612 

Swart M. s823, s865 

Swarts J. s974 

Swarts P. s974 

Sykora J. s1352 

Symes M. s666, s999 

Symes M. d. s1253 

Synooka o. s1293 

Synowiecki M. s1179 

Synytsya A. s1154 

Sypaseuth f. d. s1285 

Syrovy t. s1338 

Sysel P. s1090 

Szabo f. s1357 

Szabó f. s1290 

Szabo J. s917 

Szabo nagy A. s917 

Szabo o. s886 

Szantay C. s1361 

Szecsenyi A. s1190 

Szekely e. s1190 

Szemmelveisz K. s912 

Szidat S. s637 

Szilvagyi G. s1357 

Szoecs v. s827 

Szpilman A. s757 

Szterenberg L. s1072 

Szulmanowicz M. s696 

Szumna A. s794 

Szuppa t. s656 

Szyfter K. s1425 


t 

tabouche A. s919 

tachikawa S. s1006 

taddia M. s627 

taft h. s675 

tagliavini e. s1178, s1181, s659 

tahtinen P. s1358 

tai C. w. s1097, s806 

takahashi t. s1327, s775 

takahashi-umebayashi M. s999 

takeya S. s691 

talinli n. s1022, s1023 

tan K. s954 

tan S. w. B. s1090 

tanaka h. s775 

tanaka K. s1258 

tanchoux n. s1091 

tang y. s863 

tanyeli C. s774 

tanzer e. M. s1091 

taraba B. s1192 

tarabek J. s1155 

tarabová d. s1092 

taran f. s1187, s658 

tarko L. s1359 

tarnowska K. s1425 

tase A. s893 

tasgin e. s907, s918 

tasic A. s866 

tatarkovic M. s1154, s1154 

tateishi-Karimata h. s899 

tauber K. s802 

tauler r. s618 

taupitz M. s1246 

tavares d. S. s651 

taylor J. s843 

tecimer M. A. s1284 

tedeschi t. s1168, s709, s726 

teixeira J. A. C. s1339 

telgheder u. s1148 

tellkamp t. s1358 

temprano i. s808 

tenne M. s959 

tenora L. s1359 

teodorescu f. s1092, s1359 

terasaki o. s840 

terraneo G. s836 

terryn C. s1214 

teslyar G. s1114 

tettenborn o. s628 

teusch C. s1360 

thalhammer A. s898 

thanakkasaranee S. s1072 

thiedemann B. s772 

thiel w. s816 

thiel w. r. s699 

thiele t. s612 

thies S. s878 

thomas C. M. s788 

thomas S. s761 

thorring h. s636 

thorwirth r. s656 

thumann S. s1290 

thurner A. s1274 



s1398 

chem. Listy 106, s587–s1425 (2012) 


tian y. s1103, s1103 

tiao h. C. s1201 

tiburcio J. s1225, s1242 

tichy M. s1093 

tiersch B. s970 

timári G. s1314 

tirayut v. s1094 

tisovsky P. s857 

tißler A. s805 

toader M. s1221 

todasca C. s1160, s1166 

tognetti v. s1068 

toh C. S. s608 

tokuda h. s1347 

tölle K. s1226 

tolomelli A. s720 

tomasek J. s1190 

tonetti C. s726 

toolaram A. P. s650 

topic f. s1093 

toprak M. s1112 

torabi f. s918 

torri C. s659 

tóth e. s933 

toth K. s1281 

toughrai S. s792 

trabolsi C. s1425 

trader d. s716 

tran d. n. s1075 

traoré M. s714, s803 

trávnícek z. s934, s935 

trewin A. s1206, s820, s844, s848 

trifunovic J. s875 

trifunovic S. s950 

triggiani M. s1166 

trinca L. s1266 

triska J. s1170 

trmcic M. s1280 

trnka t. s822 

troff r. w. s1093 

tronnier A. s967 

trusova M. s1317 

truss M. s1082 

trzeciak A. s696 

tsaousi K. s1169, s673 

tschammer n. s1049 

tschan M. s788 

tschierlei S. s988 

tsien r. y. s590 

tsikin A. s617 

tskhovrebov A. s937 

tsogoeva S. B. s1024, s1079 

tsuboi M. s1232 

tsuchiya h. s1170 

tsuchiya w. s893 

tsybin y. s602 

tsybizova A. s1155 

tucek J. s1234 

tuczek f. s936, s938 

tucher J. s981 

tudose M. s1189, s1268 

tugarova A. v. s652 

tunca u. s1067, s998 

tuncel d. s750 

tundo P. s661 

turano P. s900 


turczel G. s1313 

turebekova G. s1180 

turecek f. s723 

turel i. s684 

turgut y. s1094 

turner P. s1073 

tutino M. s916 

tvaroska i. s822 

tyurenkov i. s901 

tzanis L. s849 

tzeng B. C. s969 

tzschucke C. C. s1285 

U 

uckardes h. s991 

uckun z. s1153 

ugalde J. M. s871 

ugur M. h. s1106, s1107 

uhlir J. s928 

ulbrich K. s1094 

ulrich S. s1095 

ulrichova J. s1307, s895 

unciti-Broceta A. s1307 

unger y. s959 

ungureanu A. s1196, s1197, s1197, s1207 

unkelbach C. s985 

unold J. s1095 

urankar d. s1340 

urban e. s1077 

urban J. s1153 

urbaniak P. s1046 

urner L. s1360 

uroos M. s703 

urtiaga M. K. s1207 

ussawadilokrit A. s1248 

utasi A. s643 

utczas M. s1190 

uygun o. s1150 

V 

v v S r. P. s900 

vaccaro L. s663 

vacek J. s1158 

vaden t. d. s807 

vafaie Sefti M. s1080, s1344 

vagfoldi z. s725 

vaidhyanathan r. s843 

valasek M. s1259, s764 

do vale M. L. C. s791 

valentin L. s684 

vales K. s1301 

valla C. s1077 

valla J. s654 

van Berkel S. S. s1275 

van Boekel M. s671 

van der eycken e. s785 

van der eycken J. s1002, s1273, s762 

van der Lee A. s802, s844 

van der westhuizen B. s974 

van der westhuizen J. s630 

van der zant h. s736 

van eldik r. s690, s883, s939, s945, s949, s958, s997 

van Gulick L. s1214 

van Jaarsveld n. s972 

van Leeuwen f. s720, s785 

van rooyen P. s1208 



s1399 

chem. Listy 106, s587–s1425 (2012) 


van Staden J. f. s598 

van Staden J. K. f. s596 

van Staden r. i. s596 

vandentorren S. s906 

vandyck K. s762 

vanek J. s1155, s944 

vanek v. s894 

vanthuyne n. s771 

vantomme G. s1096 

vaquero J. J. s1096 

varella e. s624, s624 

varga e. s1097 

varga S. s1361 

vargas Jentzsch A. s800 

vasheghani-farahani e. s1344 

vasile A. s1188 

vasile B. s1195 

vasilescu d. S. s1034 

vasold r. s1028, s1083 

vass e. s1357 

vass i. s917 

vasseur A. s1361 

vavasori A. s1191 

vavrova K. s1037, s1064 

vaz P. d. s978 

vázquez M. e. s711 

vázquez o. s711 

vazquez-Gonzalez A. M. s925 

vecer J. s891 

veciana J. s835 

vega L. f. s666 

veinot J. s742 

veinot J. G. C. s1227 

vejsová M. s1305 

velders A. s785 

veldkamp B. s828 

velic d. s627, s827 

ventura C. s874 

ventura K. s1124, s1131 

venturi M. s1211, s734 

verho o. s1012, s1097, s806 

vermesan h. s1118 

vermeylen r. s725 

verrier C. s1010 

very t. s821 

verziu M. s1191 

vesela P. s1192 

veszprémi t. s854 

vetchinkina e. P. s652 

vetulani J. s631 

veverkova L. s1159 

viau L. s1287 

vicente A. A. s1339 

viceriat A. s1010 

vícha r. s1275 

vickers C. s703 

vida n. s1101 

vidal K. s948 

videnska K. s923 

viehweger K. s717 

viel S. s770 

viers J. s644 

vilar r. s713 

vilcekova z. s934 

vilhelmsen M. h. s1098 

villafane f. s985 


villani v. s880 

villegas C. s739, s741 

vincze-Csom v. s643 

vineis C. s726 

vins P. s1362 

viola A. s720 

vioux A. s1287 

visa A. s1326, s1362 

visin f. s913 

viswambharan B. s1363 

vitvarová t. s881 

vives G. s1259, s735 

vladimir S. s1154 

vlaisavljevic S. s901 

vlasiou M. s673 

vlasov v. A. s652 

vlk M. s722 

vo h. t. s1182 

voburka z. s724 

voda r. s1192 

vohlidal J. s1088 

vohlídal J. s881 

voicu G. s1195 

vokal A. s928 

vokral i. s1132 

volant A. s924 

völkl J. s1193 

vollertsen J. s648 

vollmer d. s789 

vomiero A. s1172, s657 

von tümpling w. s911 

von wrochem f. s1424 

vopicka o. s1090 

vorkamp K. s1114 

vorotyntsev A. s935 

vorotyntsev i. s818 

vorotyntsev v. s1260 

vos J. G. s944 

vostalova J. s1117 

vostracka t. s1154 

vranckx S. s815 

vrchotova n. s1170 

vrkoslav v. s1130 

vrublevska t. s1114 

vukotic v. n. s729 

vuluga d. M. s1034, s1034 

vyklicky L. Jr. s1301, s778 

vyklicky v. s1301, s778 

vyskocil v. s1135, s1146, s1156, s597 

vytrasova J. s1162 

W 

wächtler M. s699, s830, s862 

wacker L. s637 

wadhwa K. s1425 

wagner B. s1098 

wagner n. L. s812 

wagner t. s1206 

wakasugi A. s1238 

walczak B. s614, s614 

wales d. s1245 

wallner G. s923 

walshe A. s924 

waltar A. e. s638 

walter n. G. s872 

walter S. s1030, s1099 



s1400 

chem. Listy 106, s587–s1425 (2012) 


walter S. M. s1040 

walther M. s686, s709, s881, s883 

wandlowski t. s1078 

wang d. s1104 

wang h. s1099 

wang w. s1103 

wang x. s810 

wangler t. s648 

warakulwit C. s595 

warchol J. s1425 

ward M. d. s834 

ward t. s756 

wardle n. s943 

waser J. s1100 

waser M. s1020, s1024, s758 

wasielewski M. s828 

wassermann B. s830, s877 

wasserscheid P. s810 

watters d. s790 

weber e. s1019 

wedzicha B. s671, s676 

wegener J. s800 

wegner h. A. s755 

wei z. s1237 

weigand J. J. s946, s947, s960, s965 

s1070, s773 

weiher f. s711 

weiner S. s832 

weingart h. s887 

weinstein J. A. s996 

weis M. s1019 

welther A. s1100 

wende r. C. s853 

wende w. s902 

wenge A. M. s808 

wennemers h. s776 

wentzell P. s613 

wenz G. s1296, s1320, s1321 

werner i. s1363 

westerlind u. s775 

westermann B. s1275 

wet r. s1178 

whiddon francillard B. s624 

white n. G. s863 

whittell G. s954 

whittingham w. s1101 

wickleder C. s952 

wickleder M. s932 

widyaya v. t. s1182 

wielens B. s613 

wild A. s1102 

willner i. s737 

wills M. s758 

wilsdorf M. s1364 

wimmer L. s718 

wimmer z. s1006, s1086, s1089, s1101, s1307, s1321 

wimmerova M. s1307 

winkler K. s1260 

winn C. s1101 

winter A. s1102, s1102, s781, s973 

winterhalter M. s887 

wintner J. s1265 

wirsing A. s877 

wirtz M. s882 

wirz J. s1265 

witt A. s698, s951 


woell C. s838 

wohlrab S. s663 

wohnig S. s1364 

wojciechowski t. s1260 

wollgarten M. s1256 

wolun-Cholewa M. s1425 

wolska M. s690 

won S. s1164 

wong A. s608 

wong y. C. s1162 

wong y. S. s714, s803 

worrall J. s884 

worsfold P. s603 

worsley M. s1205 

wright A. s846 

wu P. s814 

wu S. s814 

wu y. t. s806 

wuensch C. s705 

wunderlich n. s1193 

würtele C. s977 

würth C. s612, s903 

wuthrich K. s590 

wuttke e. s1156 

X 

xiang y. s933, s942, s993 

xiao C. s840 

xie L. s1103, s1103 

xu G. s1104 

Y 

yagci y. s788 

yakimova M. s1157 

yaku h. s899 

yalcin S. s919 

yamaguchi J. s759 

yamahata A. s1208 

yamamoto h. s853 

yamane i. s1232 

yamazaki t. s893 

yammine P. s1104 

yang S. s1261 

yankova A. s901 

yanovych d. s1171 

yardeni G. s1241, s952 

yarimkaya Bas S. s1128 

yaroslavtsev A. s1171, s1219 

yasar o. s1193 

yasmeen f. s725 

yasser o. s1264 

yasuoka K. s818 

yates P. s634 

yeasmin z. s1244 

yefet M. s797 

yi h. s790 

yi L. s1187 

yildiz G. s1142 

yilmaz n. s1149, s610 

yim C. s1052 

yim J. h. s1105, s1310 

ying J. y. s654 

yogendra S. s773 

yoon S. K. s1052 

yoon w. y. s655 

yoon y. s1173, s1176 



s1401 

chem. Listy 106, s587–s1425 (2012) 


yoshinaga K. s1365 

youssef A. s994 

youssef n. s982 

yu B. y. s655 

yu h. s1261, s1262, s1319 

yuan h. s720 

yuce n. s1153 

yun h. S. s926 

yun K. h. s1039 

yun S. s937, s972 

yusop r. M. s1307 

yuzhakova t. s1188, s643 

Z 

zaarour L. s1262 

zabarska n. s943 

zabel A. s973 

zabrocka L. s1425 

zaccheroni n. s749 

zacchini S. s680, s681 

zacharovova K. s1365 

zadny J. s1121 

zadok A. s1258 

zagami r. s1216 

zagorac d. s851 

zagvozdkina t. s1134, s1157 

zahl A. s939, s958 

zahn d. s826, s881, s990 

zahn d. r. t. s1221 

zahoor M. s915, s915 

zaitsev v. s901, s902 

zakharova L. s1042 

zakharova M. s942 

zalesak B. s895 

zalewska K. s665 

zalewski P. s895 

zamalyutin v. s991 

zampese J. A. s996 

zamyatina A. s1299, s854 

zanni t. s1157 

zanotti v. s681 

zaouris d. K. s808 

zapf A. s637 

zarra S. s733 

zatloukalova M. s1158 

zavadilova A. s922 

zavazalova J. s1158 

zaverkina M. s1105, s1366 

zavoianu r. s1186 

zboril r. s1219 

zednik J. s1088 

zedník J. s881 

zeitler e. L. s693 

zeitler K. s1031 

zelenka t. s1366 

zemanek G. s897 

zemtsov L. s1219, s1232 

zengin e. s1022 

zenneck u. s695 

zevenhoven r. s692 

zewail M. s1106 

zeytuni e. s1106, s1107 

zgazar M. s1090 

zhabinskii v. s1107, s856 

zhang B. s1262 

zhang h. s650 


zhang J. s1228 

zhang w. s792 

zhang x. s610, s792 

zhang y. s830 

zhao S. s1103, s1103 

zhdanova A. s902 

zhivotova e. s882 

zhu B. s1319 

zhu K. s729 

zhurov K. s602 

zhylitskaya h. s1367 

zidki t. s1241 

ziereis K. s1089 

zigah d. s595, s744 

ziganshina e. s597 

zilbermann i. s1241, s952, s958 

zilm K. w. s812 

zima J. s1117, s1139, s1158 

zimcik P. s1279 

zimmermann t. s1108 

zinchenko A. s882 

zindler M. s1026 

zitterbart r. s1367 

zivanovic v. s645 

ziyatdinova G. s597 

znaleziona J. s1117, s1144 

zobrist J. s644 

zoric d. s1188, s1194 

zrineh A. s909 

zucek K. s1130 

zuilhof h. s783 

zuravka i. s902 

zvatora P. s1159 


list of Keywords 

s1402 

chem. Listy 106, s587–s1425 (2012) 


[2,3-a]Pyridine Benzamide s883 

[3+2] Cycloaddiotn reaction s1016 

[60]fullerene s1079 

[60]fullerene, [4+2] monoadducts s1057 

§-thalassemia Patients s1123 

1,2-addition s763 

1,2-phthaldehyde s1336 

1,3,4-oxadiazole s1336 

1,3-benzoxazin-4-one s1340 

1,3-dipolar cycloaddition s1309, s1367 

1,4-addition s962 

1h-nMr s1166 

1h-rMn s1160 

2-Acetylthiophene s1347 

2-amino-4h-chromene s1061 

2-aryltetrahydrofurans s1023 

2-hydroxymethyl-oxazolidinones s692 

2-oxazolines s1034 

3,4-di(methylene)tetrahydrothiophene-1,1-dioxide s1057 

3-aminoquinoline-2,4-diones s1342 

3d-qSAr s900 

3-hydroxyquinoline-2,4-diones s1342 

4-methylimidazole s1165 

4-methylpentan-2-one s1177 

5-amino salicylic acid s1254 

5-aminopyrimidines s1077 

7-hydroxycumarine s1061 

A3-coupling s784 

Ab initio s845 

ab initio 6-31G method s867 

Ab initio calculations s654, s808, s815, s818, 

s819, s860, s862, s863, 

s871, s872, s873, s874, 

s876, s879, s1130, s1226, 

s1242 

ab initio energy landscape s1200 

abcg2 s884 

Abramov-type phosphonylation s1277 

Absorption s640, s689 

absorption correction s865 

acid drainage s925 

Acid mine drainage s640, s642, s926 

acid mine drainage (AMd) s924 

acid-base dissociation constants s1121 

Acidity s642, s645, s782, s1148 

Acridone s900 

acrylates s868 

acryloyl chloride s1069 

actinide s639 

Actinides s638 

activated sludge s693 

Activation s679 

Activation energy s816 

active lone pairs s1200 

actuator s1247 

Acyclic n-nucleosides s1347 

a-cyclodextrin s610 

Acylation s780, s853, s1004, s1036, s1042 

acylhydrazone s1332 

adhesion s655 

adsorption s641, s647, s666, s705, 

s737, s793, s814, s842, 

s873, s1062, s1199, s1231, 

s1335 

Adsorption of As(iii) s915 

Adsorption of humic acid s915 


Adsorption studies s908, s908 

adulteration s673 

aggregation s721, s889, s986, s1033, 

s1216, s1219, s1252, s1278, 

s1319, s1335 

agostic interactions s871 

a-iminocarboxamide-nickel(ii) Catalyst s1327 

air pollution s910 

Alcohols s653, s670, s683, s707, 

s758, s806, s1226, s1276, 

s1283 

Aldehydes s1070, s1103, s1276, s1289, s1293 

Aldol reaction s1084, s1264, s1269, s1363 

algae s1178 

Alkalinity s1138 

Alkaloids s759, s804, s930, s1100, 

s1180, s1291, s1325, s1361 

Alkanes s591, s683, s864 

alkenes s684, s1050, s1071, s1082 

alkyl isocyanides s1061 

alkyl/aryl pyrenyl sulfoxides s1349 

Alkylation s831, s894, s1011, s1020, s1057 

Alkyne s806 

Alkynes s684, s1011, s1066, s1078, 

s1098, s1218, s1328 

Allenes s1052 

Allosteric indicator displacement assay s861 

Allosterism s1243 

alloys s1251, s1252 

allylation s1059, s1074 

allylsilane addition s1284 

alternative solvents s1182 

Aluminium s661, s1163 

Aluminum s1105, s1201 

Alzheimer’s disease s896 

Amalgams s597, s1135, s1146 

Amberlyst-15 s1023 

amides s773, s1006, s1050, s1052, 

s1070, s1089, s1101, s1306 

amination s761, s769, s801, s802, s1042 

amine ligands s997 

amines s689, s1006, s1050, s1289, s1293 

amino acid s606, s899 

Amino acids s651, s665, s720, s765, 

s791, s833, s879, s942, 

s1009, s1020, s1046, s1060, 

s1069, s1084, s1106, s1168, 

s1318, s1333, s1338, s1345, 

s1363 

Amino alcohols s767 

amino silane s1176 

aminoacids s1269 

Aminoalkylphosphonic acids s1046 

aminobisphenol s962 

Aminocarbonylation s1333 

ammonia s818 

Ammonia synthesis s808 

Amorphous materials s832, s965, s1206 

Amperometric detection s1139 

Amperometric gas sensor s1134 

Amperometry s1117 

amphiphiles s787, s789, s790, s1025, 

s1169, s1317 

amphiphilic block copolymer s792 

AMP-PAn s635 

Amyloid beta-peptides s710, s889 



s1403 

chem. Listy 106, s587–s1425 (2012) 


amyloid-§ peptide s896 

analgesic agent s1274 

analysis s899, s922 

analysis of variance s614 

Analytical chemistry s1146, s1152 

analytical method s1083, s1257 

Analytical methods s596, s599, s600, s604, 

s611, s612, s613, s614, 

s616, s637, s662, s673, 

s859, s917, s1036, s1055, 

s1102, s1114, s1124, s1128, 

s1135, s1138, s1141, s1145, 

s1148, s1154, s1154, s1156, 

s1160, s1161 

Analytical techniques s1123 

Anayltical method s1168 

Angiogenesis s898 

anhydrides s1311 

Anion recognition s863, s1324 

anions s800, s835, s932, s953, 

s1035, s1155, s1159, s1222, 

s1290, s1296, s1331 

Annulation s804, s1100 

Annulenes s1322 

Anodic oxidation s647, s906, s916 

anthelmintic drug s1132 

anthranilic acid s1340 

Anthropogenic s918 

Antibiotics s676, s684, s716, s719, 

s722, s895, s983, s1064, 

s1090, s1171, s1318, s1364 

Antibodies s602, s1129 

anti-cancer agents s1079 

antidepressant s648 

antiferromagnetic interaction s934 

antifungal agents s950, s1101 

Anti-impotence drugs s1164 

Antimicrobial s1265 

antimicrobial peptides s886 

Anti-mir s709 

antimony s924, s950 

Antioxidant s674, s897, s899, s1125 

antioxidant activity s1119, s1161 

antioxidants s597, s678, s722, s901, 

s901, s1077, s1086, s1161, 

s1169, s1180, s1307 

Antiproliferation s721, s1170 

antiproliferative activity s982 

antiprotozoal s1059 

Antiprotozoal agents s714 

anti-tubercular activity s874 

antitumor s1254 

Antitumor activity s1347 

Antitumor agents s713, s896, s902, s957, 

s1020, s1101, s1220 

antiviral activity s1294 

antiviral agents s787, s1042, s1141 

AoP s688 

Apocarbonic anhydrase s914 

apparent molar volumes s825 

Appel reaction s1365 

aprotic solvents s1065 

Aptasensor s1127 

Aquatic environment s904 

Aqueous s1280 

aqueous normal phase LC s1151 


Aqueous solution s914 

areal repeat units s747 

Arenes s765, s774, s1014, s1285 

Aromatic Chemistry s858 

Aromatic substitution s1043, s1349 

Aromaticity s819, s871, s1169, s1322 

aromatics s747 

arsenic s641, s912, s1152 

Artesunic acid s1079 

Artificial metalloenzymes s756 

artificial photosynthesis s988 

Aryl azides s1309 

arylaminooxazoles s898 

arylation s1084, s1314, s1337 

arylguanines s1314 

Aryl-Chlorides s1022 

aryne chemistry s1015 

Arynes s1314 

ascorbate s884 

Aspartame s1343 

Association constant s867 

asymmetric allylic alkylation s762 

Asymmetric amplification s817 

asymmetric catalysis s589, s665, s700, s707, 

s754, s758, s758, s759, 

s762, s763, s778, s779, 

s783, s1012, s1020, s1087, 

s1094, s1258, s1273, s1289, 

s1317 

asymmetric cyclopropanation s1074 

asymmetric hydrogenation s762 

Asymmetric reaction s1277 

asymmetric reduction s1094 

Asymmetric synthesis s703, s707, s754, s774, 

s855, s956, s1024, s1044, 

s1071, s1088, s1100, s1264, 

s1273, s1277, s1278, s1282, 

s1286, s1287, s1308, s1363 

Atmospheric chemistry s637, s863 

Atom transfer radical polymerization s1104 

atomic absorption spectrometry s1147 

atomic alloys s593 

atomic force microscopy s849 

Atomic force microscopy (AfM) s1215 

atomic metals s593 

atom-transfer radical addition s1074 

Atr ft-ir s639 

Atropisomerism s1002, s1055, s1055, s1244 

attenuated total reflexion s613 

Aurophilicity s860 

Autocatalysis s737, s780, s817, s1024 

Autoxidation s1007 

auxin s1101 

Avrami equation s1344 

axial chirality s1325, s1348 

aza-bisoxazoline ligands s1074 

azahelicenes s1121 

Azasugars s1023 

azetidines s1313 

Azide s1280 

Azides s1002, s1011, s1043, s1297, 

s1299 

aziridinyl phosphonates s1284 

Azo compounds s654, s780, s798, s1040, 

s1041, s1114, s1211, s1266, 

s1272, s1355, s1358 



s1404 

chem. Listy 106, s587–s1425 (2012) 


azobenzene s734, s738, s1028, s1034, s1034 

azomethine s1061 

azomethine ylides s1267 

Baby foods s1140 

Bacteria-modified red mud s908 

Bacteria-modified silica fume s908 

bactericidal activity s1126 

bacteriorhodopsin s604 

barite s1138 

Barium aluminoborate glass s1253 

Barrier properties s1072 

base s1092 

base materials s1186 

basicity s643 

Bdd electrode s647 

Bentonite s919 

benzene s872 

Benzenesulfonamides s890 

benzobarrelene s962 

Benzofuroxan s1149 

Benzoxanthene s1022 

Beta-Cell s723 

beta-hydroxamides s1094 

betalain s674, s861 

betuline s818 

Biaryls s1022, s1055, s1055, s1080, s1348 

Bibenzimidazole s1352 

bile acid s1066 

bile acids, mixed micelle, tween s875 

bimodal imaging s735 

binaphthyl derivatives s798 

Binary mixtures s867 

Binding constant s890 

binfuctional catalysis s1013 

Binol s1198 

bioaccumulation s648 

Bioaccumulationfactor s911 

bioactive molecules s766 

Biocatalysis s703, s705, s706, s707, 

s707, s708, s778, s802, 

s1292, s1342 

biocide leaching s648 

Bioconjugate chemistry s1297 

Biodegradation s904 

biodiesel s659, s926 

bio-fixation s690 

biofuels s1178 

biogenic amines s677 

biogeochemistry s603 

biogeometallury s640 

biochar s925 

Bioinformatics s613 

Bioinorganic chemistry s684, s685, s686, s756, 

s810, s819, s832, s983, 

s1185 

biological activity s642, s684, s724, s740, 

s788, s793, s897, s901, 

s1000, s1025, s1049, s1071, 

s1108, s1159, s1170, s1180, 

s1251, s1257, s1287 

biomarker c-erbB-3 s1150 

Biomass s653, s675, s970, s1091, s1178, s1180 

biomass burning s916 

Biomaterial s710 

Biomemetics s997 

Biomimetic synthesis s703, s810, s1292 


biomolecules s807 

Bioorganic chemistry s721, s796, s892, s1069, 

s1082, s1164, s1330, s1367 

Biophysics s885, s891 

Biopolymer s1215 

biopolymers s1303 

bio-polymers s728 

Biorefining s675 

Biosensor s606, s608, s1150 

biosensors s595, s608, s609, s687, 

s792, s876, s1120, s1123, 

s1129, s1146, s1221 

biosorption s919 

biosynthesis s703, s1292, s1318 

biotechnology s712 

Biotin-avidin technology s756 

Biotransformations s652, s705, s892 

bipolar electrochemistry s744 

Bismuth s881, s950, s1156 

bismuth nanoparticles s1256 

bismuth oxide s990 

bismuth oxido cluster s990 

Block Copolymers s787, s789, s792, s793, 

s796, s834, s1038, s1291, 

s1303, s1341 

block co-polymers s954 

blocking layer s1172 

blood substitutes s888 

Blue phophorescent s937 

Bodipy s1320 

Bolaamphiphiles s1229 

Bond energy s859 

bond theory s820, s871 

book s620 

borane s1329 

borane reduction s1094 

Boranes s942, s1071 

Borates s1050, s1080, s1112, s1285 

Boron s805, s1036, s1050, s1111, 

s1177, s1286, s1295 

Boron-doped diamond anode s916 

borylation s1281 

Bovine Serum Alb_min (BSA) s1113, s1113 

bowl-shaped molecules s1056 

Br?nsted acid-base s1317 

Brassinolide s1107 

Brassinosteroids s856, s1107, s1367 

brazilian program s1175 

Breast cancer s604, s1150 

breast cancer resistance protein s884 

Bridging ligands s679, s953, s985 

Bromhexine s1139 

bromine s1321 

Bruker s1125 

buffer layer s1222 

Bulk heterojunction solar cells s790 

Cadmium s645, s912, s1109, s1137 

Cadmium removal s908, s908 

Cadmium telluride s1236 

caesium-137 s920 

Cage compounds s695, s799, s820, s823, 

s844, s946, s961, s1245 

calcite s642 

calcium s692 

Calculated water exchange reactions s883 

calix[4]arene s1069, s1299 



s1405 

chem. Listy 106, s587–s1425 (2012) 


calix[4]arenes s1301, s1352 

calixarene s1019, s1288 

Calixarenes s767, s794, s1281, s1354 

Calixarenes, polymers, macrocycles s770 

Calorimetry s786, s1204, s1204 

cancer s590, s713, s720, s892, 

s1029, s1102, s1148, s1154, 

s1233, s1279 

Cancer cell line s883 

Candida albicans s1332 

Capability of detection s1141 

Capillary s1165 

capillary electrophoresis s1144 

capsaicin s1131 

capture s1176 

Caramel s1165 

carbanion s989 

Carbanions s695, s768, s968, s1280 

carbazole s1311 

carbendazim, BAM s648 

Carbene s682, s968, s972 

Carbene homologues s702 

Carbene ligands s694, s695, s696, s938, 

s959, s960, s967, s968, 

s1216, s1270, s1354 

Carbenes s694, s760, s945 

carbenoid s989 

carbenoids s695 

Carbides s680, s970 

Carbocations s1099, s1345 

carbohydrate s872, s1029 

Carbohydrates s601, s740, s783, s854, 

s977, s1063, s1084, s1118, 

s1122, s1299, s1364 

Carbon s637, s740, s1216 

Carbon aerogel s1366 

Carbon Allotropes s803 

Carbon ceramic electrode s1137 

Carbon dioxide s690, s690, s1111, s1112, s1176 

carbon dioxide capture s1177 

Carbon dioxide fixation s661, s662, s665, s689, 

s691, s842, s1174, s1193, 

s1300 

carbon material s1192 

carbon nanotube s741 

carbon nanotubes s739, s744, s1247 

carbonation s692 

carbonyl s981 

carbonyl compounds s1059 

Carbonyl ligands s680, s938 

Carbonylation s694, s756, s1191, s1300 

carboranes s942, s1006 

carborate anion s764 

Carboxamide dimers s1333 

carboxylate s981, s984 

Carboxylate ligands s696 

carboxylation s665, s683, s705 

carboxylic acid s825 

carboxylic acids s705, s765, s979, s1000, s1050 

cardiovascular diseases s1117 

career days s669 

Carotenoids s1161 


CArS (Coherent Anti-Stokes raman Scattering) s606 

cascade s1267 

cascade reaction s802 

catalase s907 

Catalysis s678, s683, s701, s760, 

s761, s856, s950, s962, 

s962, s981, s987, s1095, 

s1098, s1100, s1295, s1336 

Catalyst s654, s796, s1022, s1105, s1219, s1248 

Catalyst reuseability s1185 

catalyst support s655 

catalysts s592 

catalytic reduction s935 

Catechol oxidases s997 

catecholamines s812 

Catenanes s737 

Cation s960 

Cations s591, s787, s946, s965, s1096 

caustic magnesia s642 

Cavitands s794, s797, s1058, s1242 

CBS-4M s1142, s1149 

C-C activation s765, s1273, s1312 

C-C bond formation s1046 

C-C coupling s761, s766, s774, s1001, 

s1002, s1067, s1088, s1218, 

s1285, s1285, s1302, s1317, 

s1326 

Cd spectroscopy s893 

C-debenzylation s1342 

Cell Adhesion s726, s783, s1028 

cell culture media s1116 

cell delivery s1307 

cell migration/invasion inhibitor s1319 

cellular uptake s1238 

Cellulose - based carbon aerogels s1189 

cellulose acetate s818 

Cellulose-based polymer s1215 

Ceramics s970, s1188, s1194, s1203 

Cerium s663 

cesium s635 

C-f activation s1266 

C-Glycosides s1354 

C-h activation s591, s694, s696, s716, 

s759, s759, s769, s819, 

s823, s951, s1014, s1018, 

s1042, s1051, s1082, s1281, 

s1285, s1349, s1357, s1361 

C-h functionalization s1286 

cinchona alkaloids s1338 

cinnamadehyde hydrogenation s1197 

cinnamaldehyde s1197 

Circular dichroism s724, s864, s953, s1055, 

s1130, s1135, s1154, s1154, 

s1216, s1354, s1358 

cis-trans isomerization s1034 

civilization s619 

clathrate s659 

Clathrates s662, s691, s1174 

Clay s1223 

Clays s809 

Clean synthesis s663, s1182 

Cleavage reactions s872 

click s1322 



s1406 

chem. Listy 106, s587–s1425 (2012) 


Click chemistry s658, s737, s784, s788, 

s797, s801, s842, s943, 

s998, s1002, s1011, s1035, 

s1035, s1049, s1056, s1068, 

s1086, s1243, s1275, s1281, 

s1282, s1296, s1297 

cluster compound s939, s979 

Cluster compounds s680, s694, s881, s942, s964, s1245 

clusters s830 

Co s993 

C-o coupling s765 

Co2 s692 

Co2 and So2 s847 

Co2 capture s843 

Co2 Capture, Amino Acids, Amine s1173 

coagulation/flocculation s905 

coal mine s925 

Cobalt s944, s949, s951, s978, 

s987, s987, s990, s1213, 

s1300 

Cobalt(ii)-Glycine complex s1127 

Co-crystal s1198 

cocrystals s1235, s1249 

Codoping s1175 

Cof s1079 

Cofactors s1123 

Collaboration s633 

Collagen s711 

Colloid s1365 

Colloids s721, s1338 

comb-copolymer s1104 

Combinatorial chemistry s700, s1002, s1047, s1096, 

s1293, s1327 

combinatorial synthesis s1028 

combustion s912 

Competency s927 

Competing ions s651 

compchem s623 

Complexation s639, s1365 

complexes s682, s980 

Composition s1166 

Computational Chemistry s591, s610, s811, s815, 

s819, s820, s830, s854, 

s878, s879, s1206, s1208, 

s1245, s1339 

Computational methods s1343 

Computational study s821 

conbustion s916 

condensation s682 

conducting materials s789, s824, s1038, s1078, 

s1184, s1184, s1293, s1338 

conducting polymer/platinum composites s1133, s1133 

Configuration determination s1055 

confinement s810 

Conformation analysis s710, s978, s1091, s1102, 

s1130, s1204, s1343 

conformation condition s1062 

conformational effects s807 

Congo red s897 

conjugate addition s1041 

conjugated oligomers s1083 

Conjugated polymers s790 

Conjugation s766, s1040, s1057, s1085, 

s1101, s1345 

contaminated biomass s912 

Contaminated municipal waste s636 


contamination s646 

continuous flow chemistry s664 

continuum cluster s859 

controlled-radical polymerization s792 

Cooperative effects s1187 

cooperativity s1013 

coordination s747 

coordination compounds s940 

coordination frameworks s969 

coordination chemistry s939 

Coordination modes s948, s967, s977, s978, s983 

Co-phthalocyanine s910 

Copolymerization s1066, s1102, s1335 

co-polymers s888 

copper s612, s701, s709, s715, 

s717, s774, s889, s936, 

s954, s955, s975, s977, 

s996, s1065, s1074, s1087, 

s1111, s1155, s1223, s1232, 

s1243, s1273, s1349 

copper catalysis s763 

copper catalyst s784 

Copper Complexes s941 

Copper removal s914 

copper, cobalt s1197 

copper-picolinate s1203 

Coprecipitation s903 

corannulene s1281 

core-shell nanoparticles s1261 

Cork s651 

Corrosion s1118 

Coumarin s1265 

Coumarin 120 s1115 

Coumarin 35 (C35) s1113, s1113 

coupling agent s1090 

coupling reactions s766 

CPd/dCPd s1182 

cracking s654 

cross - linking s1189 

cross coupling s941, s1086 

Cross dehydrogenative Coupling s1310 

Cross-bridged cyclen s941 

Cross-coupling s696, s701, s719, s736, 

s754, s759, s760, s761, 

s772, s801, s960, s975, 

s1014, s1022, s1042, s1045, 

s1054, s1070, s1097, s1273, 

s1286, s1297, s1322, s1328, 

s1357, s1361 

Cross-Couplings s856, s1230 

crown ethers s734 

Crystal engineering s799, s834, s837, s844, 

s847, s1174, s1346 

Crystal enginnering s659 

Crystal growth s659, s786, s810, s835, 

s837, s850, s850, s1174, 

s1204, s1307 

Crystal structure s997 

crystallization s1039, s1205, s1260 

Crystallization behaviors s1248 

crystallographic computing s865 

C-S, C-Se, C-P bond forming reactions s975 

Ct complex s1265 

Cu s1183 

Cu(ii) complexes s935 

Cupper(ii)-Glycine complex s1126 



s1407 

chem. Listy 106, s587–s1425 (2012) 


Cuprates s973 

Cvt s850 

cyanides s837, s982, s1289 

cyanido complexes s934 

cyanobacterial hepatotoxins s598 

cyanoethylation s1092 

Cyanosilylation s1337 

Cyclability s959 

Cyclen s941 

cyclic esters s1311 

cyclic voltammetry s649, s890, s924, s996, 

s1126, s1128, s1424 

Cyclisation s661, s1180 

Cyclization s1002, s1007, s1012, s1024, 

s1029, s1042, s1052, s1057, 

s1086, s1098, s1100, s1103, 

s1271, s1283, s1298, s1305 

Cycloaddition s695, s714, s755, s791, 

s845, s1066, s1088, s1314, 

s1333, s1337, s1346 

cycloadditions s823, s865 

cyclodehydration s1340 

Cyclodextrin s735, s833, s1320 

Cyclodextrin complexes s1343 

Cyclodextrins s768, s827, s1021, s1204 

Cyclohexene oxidation s987 

cycloisomerization s757, s1263 

Cyclooligomerization s1324 

Cyclopentadienyl ligands s755, s1363 

cyclopropylphosphonates s1287 

cyclovoltammetry s1156 

cytochrome b5, s866 

cytochrome c s884, s1215 

cytochrome p450 s866 

Cytochromes s727 

cytotoxicity s791, s883, s892, s949, 

s954, s991, s1006, s1181, 

s1315 

danube s917 

data fusion s615 

dBP, BBP, dehP s1163 

dearomatization s1059 

decarboxylation s1180, s1269, s1338 

decontamination s929 

deemulgation s1062 

defects s816 

degradation s693 

dehalogenation s760 

dehydrogenation s1326 

dendrimer s1323, s1334 

dendrimers s720, s731, s755, s787, 

s790, s938, s1053, s1214, 

s1262, s1336, s1362, s1425 

dendronized polymers s1262, s1323 

density s825 

density functional calculations s591, s689, s771, s781, 

s788, s814, s820, s822, 

s823, s823, s824, s865, 

s868, s872, s880, s967, 

s971, s1075, s1208, s1351 

density functional theory s813, s824, s990 

densiy s1253 

depolymerization s1320 

deposition s1221 

deracemisation s759 

determination s1123, s1140, s1140 


devices s1061 

dft s861, s1149 

dft calculations s610, s963 

di s1131 

diabetes s723 

diacetylene s1287 

diamino-benzodifuran s1061 

diastereoselective synthesis s1059 

diastereoselectivity s991, s1031, s1274, s1298, s1358 

diazaanthracene s1320 

diazenyl s1069 

diazo compounds s595, s774, s1009, s1018, 

s1317, s1358 

diazoacetates s1074 

diazonium salts s1084 

diels-Alder reaction s1233 

diene s962 

diesel component s1177 

diethanolamines s950 

differential pulse voltammetry s608, s1139 

diffusion coefficient s1144 

dihydrocapsaicin s1131 

diiron complexes s681 

dilactams s1075 

dilatation coefficient s1253 

dilatometric curves s1253 

dimerization s1033 

dimethyl Carbonate s661 

dimethyl phthalate s910 

dioxin s906 

direct synthesis s1179 

disinfectant s1126 

disperse alkaline substrate s642 

dissociation energies s610 

dissolved organic Matter s650 

distillation s1260 

divergence entropy s877 

dMSo oxidation s1077 

dnA s711, s712, s731, s737, 

s796, s811, s862, s879, s890, 

s891, s899, s954, s969 

dnA adducts s1314 

dnA cleavage s724, s902, s1039 

dnA damage s713, s1011 

dnA interaction s598 

dnA methylation s1082 

dnA nanotechnology s834 

dnA recognition s1011 

dnA Structures s730 

docking s900 

domino reaction s803 

domino reactions s765, s804, s1298, s1305, s1316 

donor acceptor systems s805 

donor-acceptor s1033 

donor-Acceptor pairs s1212 

donor-acceptor systems s741, s1218, s1293, s1324, s1360 

dopamines s1243 

doping s1196 

double Logarithmic Plot s1113 

doxorubicin s1238 

drilling mud s1138 

drinking water s1140 

drug s601 

drug delivery s730, s750, s796, s946, 

s1025, s1148, s1204, s1228, 

s1233, s1244 



s1408 

chem. Listy 106, s587–s1425 (2012) 


drug design s719, s778, s898, s1000, 

s1141, s1306, s1307, s1323, 

s1332, s1343 

drug discovery s718, s721, s894, s898, 

s901, s1005, s1056, s1090 

drug load s1238 

drug screening s712 

drug-delivery s796 

dye loading kinetics s1172 

dye sensitized solar cells s1172 

dyes/Pigments s893, s930, s1123, s1143, s1345 

dye-sensitized solar cell s1172 

dye-surfactant interaction s1112 

dynamic covalent chemistry s1044 

dynamic kinetic resolution s1274 

eCd s1357 

education s619, s633, s928 

efficiency of impregnation s1147 

elastomers s1282 

e-learning s624, s928, s929 

elecroanalysis s598 

electrical conductivity s867 

electrical double layer s1138 

electride s870 

electroanalysis s598 

electroanalytical chemistry s1126, s1127 

electrocoagulation s647 

electrochemical glucose detection s609 

electrochemical impedance spectroscopy s1150, s1150 

s1424 

electrochemical oxidation s1110 

electrochemical sensing s1127 

electrochemical simulation s1127 

electrochemistry s593, s594, s595, s595, 

s596, s597, s666, s788, 

s825, s947, s958, s1001, 

s1003, s1109, s1128, s1135, 

s1137, s1143, s1146, s1156, 

s1158, s1173, s1180, s1184, 

s1184, s1217, s1242, s1247, 

s1296 

elechromic s1425 

electron diffraction s848, s850 

electron exchange columns s958 

electron microscopy s1038, s1188 

electron spin resonance s1167 

electron transfer s590, s681, s739, s741, 

s828, s880, s988, s1128, 

s1250, s1255, s1305, s1324, 

s1360 

electron transport s740, s1078, s1184, s1184, s1360 

electron-deficient compounds s1341 

electronic structure s814, s820, s824, s860, s871 

electronic transport s824 

electro-oxidative lithography s849 

electrophilic substitution s769 

electrophoresis s604, s768, s1136, s1136, s1157 

electroplating s1205 

electrorheological fluid s1223 

electrospray ionization s1155 

electrostatic interaction s868 

eLf s820 

elimination s610 

eLiSA method s1162 

emission s1033 

enaminone s1294 


enantiomer separations s602 

enantioselective catalysis s756 

enantioselective synthesis s1313 

enantioselectivity s604, s703, s706, s714, 

s769, s817, s963, s1004, 

s1025, s1045, s1055, s1078, 

s1085, s1091, s1091, s1094, 

s1316, s1358, s1361 

enantioseparation s753 

enediynes s771 

energy s1175 

energy Conversion s653, s701, s1178, s1179, 

s1184, s1184, s1185, s1255 

energy dissipation s604 

energy landscape s851 

energy relationships s1115 

energy transfer s659, s738, s746, s815, 

s938, s1214, s1360 

enolethers s1092 

enteromorpha linza s919 

environment s650, s906 

environmental ethics s631 

environmental chemistry s602, s635, s637, s638, 

s641, s642, s643, s645, 

s646, s649, s652, s656, 

s725, s863, s909, s913, 

s913, s1008, s1137, s1152, 

s1158, s1179, s1189 

environmental sample s921 

environmental stress s907, s918 

enzymatic Co2 reduction s693 

enzymatic polymerization s1303 

enzyme s606, s715 

enzyme catalysis s611, s706, s708, s872, 

s894, s898, s1190, s1321 

enzyme design s756 

enzyme models s685, s704, s892 

enzymes s589, s712, s816, s954, 

s1004, s1068, s1118, s1136, 

s1332 

epibrassinolide s1107 

epitaxy s1209 

epithermal neutron activation analysis s910 

epoxidation s803, s963, s978, s1085 

ePr spectroscopy s1169, s1241 

equilibrium constant s868 

equilibrium study s886 

ergosterol s1332 

escherichia coli s1148 

eSr s880 

esterification s659 

ethanol s1219 

ethics s619, s930 

ethics - transdisciplinary education - s628 

-scientific and enterprise responsibility 

ethics of science s630 

ethylene s612 

euclidean distance s614 

evaluation s634 

evolved gas analysis s1344 

exAfS spectroscopy s1220 

excited state s821 

excited-state dynamics s781 

exchange interactions s970, s1037, s1293 

exons s877 

experimental design s616 



s1409 

chem. Listy 106, s587–s1425 (2012) 


explicit solvent s859 

extraction s929, s1149 

extraction by ultrasonic probe s1124 

eycn s669 

facade coating s648 

factor detection s615 

false compliance s1141 

fatty acid biosynthesis s719 

fatty acids s653, s1268 

fault detetection s617 

feCrAl s655 

feedback s634 

femtochemistry s827 

fermentation s613 

fermented food s677 

ferrocene s1043, s1316 

ferrocene-modified silica nanoparticle s1127 

ferrocenyl diphosphine s763 

ferromagnetic interaction s934 

fibers s601 

fire extinguishing substances s809 

fischer carbene complex s980 

flame radicals s809 

flavin s1087 

flavonoid s674 

flavour formation s672 

flow s1254 

flow cytometry s1332 

flow chemistry s663 

flow injection s603 

flow injection analysis s1139 

flow systems s596 

flue gas purification s664 

fluoprescence s1086 

fluorescence s605, s687, s699, s711, 

s748, s781, s802, s838, 

s1011, s1031, s1049, s1088, 

s1111, s1115, s1120, s1224, 

s1226, s1279, s1297, s1320, 

s1321, s1349, s1362, s1364 

fluorescence anisotropy s1327 

fluorescence quenching s861 

fluorescence resonance energy s1113 

transfer Method (fret) 

fluorescence sensor s1019 

fluorescence spectroscopy s611, s612, s784, 

s785, s891, s1113, s1113, 

s1122, s1226, s1270 

fluorescence, fluorescent dyes s887 

fluorescent nanoparticles s750 

fluorescent probes s590, s595, s611, s720, 

s784, s795, s882, s932, 

s1043, s1118, s1157, s1268, 

s1297, s1301, s1307 

fluoresence s742 

fluoride s1324 

fluorides s701 

fluorinated s764, s979 

fluorinated ligands s755, s880 

fluorination s1073 

fluorine s652, s801, s1016, s1050, 

s1051, s1052, s1091, s1285 

food s676 

food additive s1168 

food analysis s617 

food production s671 


food quality s671 

food safety s671 

food waste s675 

formic acid s845 

franck-Condon factor s878 

freely rotating chains s1032 

freshwater s650 

fret s1011, s1122, s1355 

friedel_Crafts s1266 

fuel cells s1181, s1203 

fuels s1175 

fukushima s635 

fullerene s741, s1060 

fullerenes s739, s799, s823, s865, 

s947, s1235, s1249, s1330, 

s1351 

functional ligands s1093 

functional thin films s744 

functionalisation s773 

functionalization s961, s1281 

functionalized adlayers s1095 

fungicide s1162 

fusarium s1162 

fused-ring systems s772, s1031, s1326, s766 

future s619 

gabapentin s890 

Gadolinium s607 

Ga-Ge-Sb-S s1206 

Gallic Acid s647 

gallium s757, s983 

Gallium oxide s1227 

Gallium sulfide s1227 

gamma-alumina (?-Al2o3) s873 

ganglioside s775 

Gas chromatography s616, s1147, s1159, s1165, 

s1169, s1202, s1321 

gas chromatography/mass spectrometry s725, s1124, 

s1167 

gas phase s807 

gas phase reactions s727 

gas sensors s593 

Gas storage s842, s847 

gasoline adulteration s1175 

gas-phase s869 

Gas-phase chemistry s821 

Gas-phase reactions s836, s1226, s1275 

GC-MS s1160, s1166 

GC-MS(ei-SiM) s1163 

GCxGC-MS s618 

Gef2 s1200 

gel polymer electrolyte s1106, s1107 

Gelation time s1080 

Gels s833, s1003, s1012 

gentamycin s1116 

geochemical archive s646 

geomicrobiology s640 

Germanium s1227 

Glasses s663, s860, s882 

Glassy carbon paste electrode s1139 

global warming s1176 

glycerol s1177 

glycerol carbonate s692 

Glycoconjugates s718, s740, s854, s1102 

glycolipids s723 

Glycopeptides s775 

Glycoproteins s892 



s1410 

chem. Listy 106, s587–s1425 (2012) 


glycosylation s775, s822, s854 

Gold s679, s752, s813, s942, 

s968, s984, s1007, s1052, 

s1073, s1098, s1098, s1216, 

s1220, s1254, s1262, s1263, 

s1270 

gold nanoparticles s753 

gold surface s1095, s1294 

Gould-Jacobs reaction s770 

G-quadruplexes s713 

grafted particles s958 

Grafting s1365 

granite s923 

grant proposals s667 

Grape seed oil s1166 

graphene s593, s739, s741, s741, 

s747, s809, s868, s876, 

s1058, s1184, s1237, s1246, 

s1271, s1333 

Green chemistry s641, s652, s656, s656, 

s658, s660, s661, s662, 

s662, s665, s683, s696, 

s773, s783, s806, s856, 

s895, s1008, s1047, s1061, 

s1067, s1070, s1091, s1097, 

s1182, s1189, s1192, s1200, 

s1251, s1304, s1304 

green marine algae s919 

green materials s1193 

Green rust s903 

greenhouse gas s1176 

Grignard metathesis s1296 

Grignard reaction s769, s1044 

GSt s851 

halogen bonds s804 

halogen dance reaction s1300 

halogenation s1001, s1075, s1288, s1292, 

s1304, s1321 

halogens s1030, s1040, s1099 

harmonic oscillator s878 

h-bonded systems s604 

hCn s873 

health s906 

heat treatment s1205 

heavy metal s919 

heavy metals s911, s912, s913 

heavy-element chemistry s813 

heck reaction s941, s1001, s1018, s1045, s1361 

helical structures s740, s794, s838, s1001, s1010 

helium nanodroplets s1261 

hemerythrin s888 

hemoglobin s888 

heparin s605 

herbicide s1101, s1140 

herbs s1119 

heterocycles s661, s718, s719, s754, s755, 

s764, s766, s766, s767, 

s772, s772, s777, s933, 

s973, s1002, s1004, s1005, 

s1009, s1037, s1042, s1052, 

s1054, s1064, s1066, s1074, 

s1075, s1090, s1098, s1098, 

s1275, s1283, s1285, s1296, 

s1312, s1313, s1353 


heterocyclic s1340 

heterogeneous catalysis s652, s658, s660, s663, 

s730, s752, s806, s824, 

s978, s1012, s1013, s1064, 

s1065, s1080, s1097, s1103, 

s1188, s1220, s1224, s1250, 

s1251, s1255, s1258 

heterogeneous catalysts s692, s1191 

heterogeneous catalytic oxdation s664 

heterogeneous photocatalysis s1031 

heterogenous catalysis s663, s767, s1250 

heterogenous catalysts s976 

heterometallic complexes s1016, s1093 

hetocycles s1096 

hexadecyltrimethylammonium bromide s647 

hexakis-adduct s1079 

hexamethylenetetramine s1080 

hierarchically assembled zno s657 

high hydrostatic pressure s677 

high performance liquid chromatography s857 

high pressure chemistry s839 

higher Amino Sugars s998 

highlybranched polymers s1309 

high-pressure chemistry s1111, s1112 

high-purity substances s1260 

high-troughput screening s897 

histaminergic blockers s1018 

histaminic receptor s1018 

history s619, s620 

history of chemistry s626 

history of Science s621, s626, s627, s632, s931 

homoallenyl azines s1359 

homodimers s1079 

homogeneous catalysis s694, s696, s696, s701, 

s716, s755, s756, s757, 

s760, s765, s823, s944, 

s971, s992, s1014, s1023, 

s1042, s1047, s1051, s1054, 

s1066, s1082, s1098, s1185, 

s1191, s1285, s1291, s1302, 

s1361 

homogeneous cataylsis s1073 

homogenous catalysis s769 

homotaurine s811 

honey s673 

hormones s612 

host cell protein s613 

host-guess systems s1208 

host-guest s869 

host-guest complexes s1234 

host-guest chemistry s1301 

host-guest system s1275 

host-guest systems s733, s797, s837, s842, 

s1021, s1058, s1068, s1068, 

s1244 

hPLC/uv/MS s1131 

huisgen cycloaddition s1300 

human plasma s1116 

hybrid materials s1195, s1236 

hybrid nanostructures s748 

hybrids s961 

hydrates s659, s662, s691, s1174 

hydrazine s1331 

hydrazinobenzimidazole s1347 

hydrazones s896, s1096, s1275 

hydroamination s1306 



s1411 

chem. Listy 106, s587–s1425 (2012) 


hydroaminoalkylation s1306 

hydrocarbon s1276 

hydrocarbon chemistry s1056 

hydrocarbons s1130 

hydroformylation s1337 

hydroformylation/Strecker reaction s1333 

hydrogel s1046 

hydrogels s1344 

hydrogen s949, s1178, s1245, s1354 

hydrogen bond s1033 

hydrogen bonding s1287 

hydrogen bonds s700, s733, s734, s754, 

s767, s769, s794, s805, 

s814, s834, s863, s870, 

s882, s934, s1012, s1068, 

s1289 

hydrogen bones s818 

hydrogen peroxide s1179 

hydrogen production s976 

hydrogen separation s1177 

hydrogen transfer s771, s880 

hydrogenation s678, s700, s758, s761, 

s767, s779, s971, s1071, 

s1097, s1100, s1182, s1196, 

s1197, s1207, s1273, s1308 

hydrogen-bond patterns s844 

hydrochemistry s925 

hydrophobic core s877 

hydrophobic effect s1037 

hydrophobic zeolite s849 

hydrotalcites s1186 

hydrothermal s959 

hydrothermal stability s1223 

hydrothermal synthesis s953, s1209 

hydroxamate based siderophores s886 

hydroxamate complexes s886 

hydroxy phosphonate s1277 

hyperbranched polyimide s1090 

hyperbranched polymers s1309 

hyper-coordinated s960 

hyperpolarizabilities s870 

hyperpolarizability s986 

hypervalent compound s803 

hypervalent compounds s701, s1304 

hypervalent iodine s1059 

chalcogenides s1206 

Chalcogens s1196 

charge transfer s748, s766, s828, s862, 

s1075, s1208, s1289 

Cheese s677, s1141 

Chelate s972 

Chelates s715, s1363 

Chelidonium majus s885 

chemical durability s1253 

chemical education s634 

Chemical characterization s916 

Chemical Speciation s650 

Chemical vapor deposition s850, s1213, s1228 

chemiluminescence s1279 

chemiluminescence detection s606 

Chemisorption s689 

Chemistry s676, s930 

Chemistry education s626 

Chemistry ethics s630 

chemistry lecturer s633 

chemistry proposals s667 


chemoenzymatic s1274 

Chemoinformatics s614, s619 

chemometrics s615, s616, s617, s618, 

s673 

chemoselective one-pot 1,4- s1057 

-elimination/[4+2] cycloaddition/aromatization 

Chemoselectivity s1054 

Chemosensors s742, s1349 

Chiral s1079 

Chiral auxiliaries s1088, s1130 

chiral dirhodium complex s1357 

chiral imidate ligands s762 

chiral ligands s1284 

Chiral resolution s1055, s1056 

chiral sulfoxide s1348 

Chirality s665, s740, s753, s794, 

s794, s817, s838, s956, 

s1024, s1064, s1135, s1308, 

s1363 

Chiroptical spectroscopy s1357 

chiroptical switches s798 

chitosan s1046, s1254 

chloride s984 

chloride poisoning s1133 

chlorine s913, s1321 

cholesterol s1086 

Chromatography s602, s1351 

Chromium s913, s1300 

Chromium triacetate s1080 

chromogenetic substrate s1027 

chromophore s1223, s1265 

Chromophores s766, s812, s1031 

Chronoamperometry s1127 

ibuprofen s906 

iCP-AeS s1134, s1157 

identifying tracers in gasoline by GC/MS s1175 

illegal compounds s1164 

imaging agents s709, s717, s720, s749, 

s889, s933, s1136, s1228 

imidazoquinoline s770 

imine exchange s1044 

imines s1277 

immobilization s685, s705, s716, s1032 

immobilization mechanism s1192 

immunoassays s897, s1256, s1146 

immunoglobulin s897 

immunochemistry s609, s1221 

impact resistance s1248 

impregnation s959 

imprinting s1082 

in vitro antiradical activity s935 

inclusion compounds s691, s818, s835 

indium s971, s1302 

indium mediated Allylation s998 

indole s899, s1353 

industrial Chemistry s611, s627, s1063, s1103, 

s1111, s1112, s1339 

industrial residues s1193 

inelastic neutron scattering s847 

infant formula s1163 

inflammation s897, s1000, s1246, s1267 

infrared s810 

infrastructure s929 

inhibitors s715, s722, s777, s894, 

s898, s1029, s1049, s1068, 

s1246, s1313, s1332 



s1412 

chem. Listy 106, s587–s1425 (2012) 


inkjet printing s712 

inner-phase reactions s869 

innovation s927 

inorganic Chemistry s667, s1253 

insertion s689, s690, s783 

in-situ oxidation s989 

insulin s1106 

intensive schools s624 

intensive workshops s624 

intercalations s658, s1223 

interfaces s746, s797, s825, s1007, s1328 

intergrowth s851 

international exchange s633 

intramolecular cyclization s1359 

intramolecular diels-Alder s1319 

intramolecular Charge transfer (iCt) s1115 

iodine s836, s1288, s1304, s1349 

iodine(iii) s1292 

ion exchange s651, s654, s966, s1176 

ion exchange resins s868 

ion channels s718, s1339 

ion chromatography s912 

ion mobility s727 

ion pair s1190 

ion pairs s651 

ion selective electrode s650 

ion transport s804 

ionic conduction s814 

ionic conductivity s1106, s1107 

ionic liquid s810 

ionic liquids s651, s662, s665, s841, 

s880, s899, s939, s945, 

s958, s973, s1032, s1036, 

s1116, s1128, s1181, s1193, 

s1200, s1216 

ionization potentials s864 

ionophores s1281 

ir s994, s1142 

ir spectroscopy s606, s1165, s1351 

iridium s694, s1083, s1312 

iridium Complexes s1028 

iridium(iii) complex s937, s972 

iron s678, s680, s683, s760, 

s761, s761, s819, s971, s974, 

s1100, s1123, s1213, s1234, 

s1290 

iron sulphide s808 

iron(ii) s980 

iron-Catalysis s1022 

irradiated foods s1167 

ir-spectroscopy s818 

isomerizations780, s1023, s1034, s1049, s1244, s1268, s1358 

isomers s859, s873 

isoniazide s1137 

isonicotinic acid s1065, s1334 

isophthaloyl dichloride s1075 

isothiocyanic acid s1342 

isotopes s638 

isotopic labeling s782, s1009, s1082, s1301, s1318 

isotopic labelling s637 

ito s849 

ivermectin s1132 

Jana2006 s865 

Julia reaction s1050 

Juvenile hormone binding protein s893 

keggin s1203 


ketal s1177 

ketones s1045, s1052, s1103, s1276, 

s1289, s1304, s1357 

key competences s624 

Kinetic modelling s821 

kinetic parameters s868 

Kinetic resolution s611, s1004, s1094, s1190, s1258 

Kinetics s611, s637, s649, s671, 

s683, s690, s733, s782, 

s811, s812, s815, s817, 

s831, s863, s944, s945, 

s949, s951, s1024, s1051, 

s1095, s1097, s1136, s1137, 

s1145, s1202, s1203, s1216, 

s1267, s1280, s1283, s1325, 

s1331 

Kinetics Parameters s1344 

kinetin s935 

Lab-Automation s1327 

Label-free s1127 

Labeling s1107 

laccase s674 

laccase induction s885 

Lactams s722, s777, s1315 

Landfill leachate s647 

Langmuir-Blodgett s1218 

Langmuir-Blodgett films s809, s1255 

languages for specific purposes s624 

lanthanide complexes s1155 

Lanthanides s731, s944, s1242 

lanthanoids s989 

laser ablation s1256 

Laser spectroscopy s808, s826, s862 

lateral substitution s1019 

Late-transition metal s1310 

layered compounds s658, s848, s1189 

layered double hydroxides s1186 

LC/MS s1164 

LC/PdA s1164 

lead s645, s813, s912, s913 

lead sulfide s851 

learning object s623 

Lewis acids s755, s757, s854, s1103 

Lewis adsorption sites s873 

Li ion battery s959 

Li ion diffusion s816 

Li-batteries s995 

library s775 

ligand s962 

Ligand coordination s980 

Ligand design s720, s760, s782, s889, 

s957, s996, s1008, s1270, 

s1306, s1330 

ligand effects s699, s949, s1267 

ligands effects s696 

Light s751 

lignin s1191 

Li-ion Batteries s953 

Linear free energy relationship s1280 

Linear free energy relationships s1051 

linear solvation s1115 

Lini1/3Mn1/3Co1/3o2 s995 

lipid s926, s1025, s1117 

lipid peroxidation s1077 

Lipids s887, s1165, s1170 

lipophilicity s778, s874 



s1413 

chem. Listy 106, s587–s1425 (2012) 


liposome s1232 

liposomes s1006, s1129, s1318 

liposomes, s887 

Liquid Crystals s1033, s1282, s1330 

liquid chromatography s599, s600, s726, s1120, 

s1124, s1128, s1136, s1138, 

s1139, s1140, s1148, s1151, 

s1153, s1158, s1162, s1167, 

s1168, s1169, s1171 

Liquid paraffin s1168 

lithiated sulfoxide s989 

Lithiation s1355 

lithium s695, s754, s957, s968 

lithium battery s948 

lithium nitride s814 

Lithium titanium disulphide s816 

Lithium vanadium fluoride s816 

Lithogenous s918 

lithography s1221 

Living ethics s629 

L-lactide s1310 

LLdPe film s1072 

Logic gate s861 

long-chain branch s1039 

Lubricant s1105 

Luminescence s731, s748, s749, s750, 

s785, s845, s862, s936, 

s943, s973, s996, s1192, 

s1195, s1196, s1200, 

s1206, s1211, s1214, s1323 

luminescence properties s781 

luminescent probe s1155 

luminiscent s1223 

Macrocapillary columns s1147 

macrocycle s1075, s1083 

Macrocycles s780, s799, s863, s887, 

s944, s956, s991, s1072, 

s1078, s1081, s1085, s1218, 

s1296, s1311, s1324, s1328, 

s1330, s1356 

macrocyclic imide s1265 

Macrocyclic ligands s941, s982, s1016, s1136, s1155 

Magnesium s692, s754, s933, s1210, s1325 

magnetic s910 

magnetic materials s994 

Magnetic nanoparticles s1309 

Magnetic properties s680, s698, s731, s749, 

s932, s934, s951, s974, 

s978, s982, s992, s992, 

s1036, s1228, s1234, s1240, 

s1250 

magnetism s980, s1231 

magnets s993 

magnolol s1013 

Maillard reaction s672 

Main group elements s702, s873, s965, s1245 

main group chemistry s688 

Maingroup s960 

MALdi matrices s1130 

man s619 

Manganese s678, s933, s946, s951, 

s984, s992, s1116, s1174, 

s1196 

manganese and cobalt ions s886 

manganese complexes s934 

Mannich s1269 


Mannich bases s765, s1024 

marine environment s603 

mass spectrometer s610 

Mass spectrometry s596, s602, s613, s666, 

s723, s725, s726, s727, 

s727, s728, s728, s733, 

s827, s855, s892, s942, 

s1051, s1082, s1083, s1110, 

s1117, s1138, s1143, s1151, 

s1155, s1159, s1162, s1168, 

s1169, s1171, s1257, s1351 

Mass spectroscopy s1170, s1281 

Mass spectrum s1131 

material science s1164, s1217, s1251, s1252 

Materials Chemistry s858 

Materials scienc s1033 

Materials science s595, s643, s705, s726, 

s791, s809, s824, s832, 

s833, s834, s845, s846, 

s847, s1188, s1194 

Matrix isolation s845 

MCr-ALS s618 

medical chemistry s670, s714 

Medicinal application s856 

Medicinal chemistry s705, s714, s718, s718, 

s719, s889, s1014, s1020, 

s1037, s1049, s1064, s1139, 

s1154, s1154, s1278, s1313 

Medium-ring compounds s785 

mechanical properties s1063, s1072 

mechanism s683, s713 

mechanisms s688 

mechanisms of reaction s952 

mechanochromic luminescence s969 

membrane s608, s1248 

membrane fusion s1232 

Membrane proteins s727, s792, s812, s887 

membrane reactor s1219 

Membranes s885, s1129, s1170, s1181 

Memory of chirality s771 

mephedrone s1026 

Mercury s646, s664, s913, s1138, s1152 

mesoionic carbenes s700 

Mesoporous s1227 

Mesoporous film s609 

Mesoporous materials s654, s682, s699, s730, 

s840, s841, s963, s1032, 

s1195, s1207, s1223, s1228 

mesoporous molecular sieves s976 

mesoporous silica nanoparticles s1013, s1212 

metabolism s670, s1026, s1166 

metabolites s601 

metabolomics data analysis s615 

metal alkoxides s993 

metal alloy membrane s1177 

Metal and metalloid contamination s644 

metal bioavailability s925 

metal catalyzed asymmetric synthesis s1284 

metal catalyzed reactions s656 

metal complex s738, s1027 

metal complexes s1093, s1125, s1318 

metal foam s655 

metal nanoparticles s748 

Metal organic framewords s1287 

metal organic framework materials s847 

metal phosphonate s1362 



s1414 

chem. Listy 106, s587–s1425 (2012) 


metal supported catalysts s1197, s1197 

Metalation s1274, s1350 

metallaboranes s990 

Metallacycles s859, s985 

Metallic glass s1205 

metallocenes s855 

Metalloenzymes s706, s771 

Metallomesogens s680 

metal-organic frameworks s729, s782, s785, s838, 

s841, s936, s1030, s1202, 

s1207, s1258, s1326, s1345 

Metals s651, s1207 

metastable phases s990 

Metathesis s592, s882, s1009, s1010, 

s1023, s1032, s1076, s1095, 

s1096, s1182, s1190, s1268, 

s1291, s1316 

methanol oxidation s1181 

Methicillin-resistant Staphylococcus aureus (MrSA) s890 

Methyl radicals s1241 

Meyer-Schuster rearrangement s1073 

micelles s827, s1035, s1268, s1290, 

s1355 

Micelles,Molecular recognition s875 

Microalgae s926 

microAnalyzer s1148 

microarrays s712 

microbial water quality monitoring s1148 

Microcystin-Lr s598 

microelectrode s598 

Micromotors s744 

Micropore materails s844 

microporous carbon polymers s846 

Microporous materials s600, s697, s699, s820, 

s842, s848, s848, s966, 

s982, s1206, s1260 

Microreactors s664, s801, s1063 

Microspheres s1335 

microsystems s596 

Microwave s1106, s1182, s1305 

microwave digestion s921 

Microwave chemistry s749, s785, s1005, s1008, 

s1187, s1339 

Microwave irradiation s1017, s1185 

microwave-assisted organic synthesis s784 

Michael addition s706, s720, s768, s1024, 

s1029, s1042, s1053, s1097, 

s1233, s1267, s1298, s1302 

mild drying impregnation s1197 

mine tailings s925 

mine water s645, s925 

Mine-affected river s644 

mineral s692 

mineral nutrition s911 

mining s646 

Mitsunobu reaction s1365 

mixed matrix material s1090 

MM/GBSA s900 

Mo(vi) s962 

mobility s1019 

Model program s633 

Modified Backbone s709 

Modified nucleobases s795 

Modified Solid Phase s1106 

Mofs s843 


Molecular devices s698, s734, s735, s738, 

s873, s974, s1195, s1211 

Molecular diversity s714, s768, s804 

molecular dynamics s710, s817, s818, s820, 

s826, s844, s848, s860, 

s868, s874, s876, s881, 

s889, s1044, s1242, s1272, 

s1272 

Molecular electronics s732, s736, s737, s743, 

s744, s1229, s1237, s1239, 

s1246, s1328, s1360 

Molecular evolution s1293 

Molecular function s858 

Molecular imaging s723 

molecular layering s1248 

Molecular logic s861 

Molecular Logic Gates s943 

molecular machines s734, s736 

Molecular modeling s811, s819, s866, s1306 

molecular motor s736 

molecular motors s1044 

molecular muscle s1294 

molecular objects s1262 

Molecular Probes s723 

molecular recognition s711, s717, s732, s735, 

s742, s780, s798, s833, 

s842, s1019, s1055, s1058, 

s1068, s1157, s1242, s1243, 

s1243, s1244, s1281, s1289, 

s1318 

Molecular rotors s1327 

molecular sheets s747 

Molecular switch s1259 

molecular switches s734, s943 

Molecular tweezers s1259 

Molecular wire s1316 

molecular wires s1156 

Molybdenum s733, s936, s938, s963, 

s978, s1095, s1187 

monitoring s613, s917, s1163, s1164 

monoclonal antibody s613 

Monolayer s1218 

monolayers s746, s783, s1247, s1258, s1346 

monolayers on glass s1028 

monometallic supported nanoparticles s1196 

Montmorillonite-sorbitol s1248 

moss biomonitoring s910 

Mucin MuC1 s775 

multianalyte s596 

multiblock multicomponent copolymers s786 

multicompartment micelles s786 

Multi-component reaction s1327 

Multicomponent reactions s767, s768, s1253, s1289 

Multi-component reactions s785 

multidisciplinarity s620 

multifunctional ligands s993 

Multilateral environmental Agreements s631 

Multimetal complex s980 

multiple bonding s997 

multiple sclerosis s615 

Multivalency s1234 

multivariate curve resolution s617 

Multivariate image analysis s617 

Mustard Compounds s661 

Mutagenesis s704 



s1415 

chem. Listy 106, s587–s1425 (2012) 


mutiple bonds s871 

Mycobacterium s1305 

Mycobacterium tuberculosis s704 

Myers-Saito cyclization s771 

Myocardial ischemia/reperfusion injury s1134 

n ligands s680, s694, s881, s950, 

s1008, s1016, s1087 

n, S co-doping s1208 

n,n-donor ligands s984 

n,P ligands s996 

n-acyl-n’-arylidene-hydrazines s1336 

nAdh regeneration s693 

nano-adhesion s1215 

nanocatalyst s1250 

nanocomposit s1054 

nanocomposite s1039, s1209, s1254 

nanodiamond s1219 

nanofibers s1229 

nano-filler s1039 

nano-friction s1215 

nanochannel s608 

nanochemistry s743 

nanomaterials s734 

nanomechanical devices s834 

nanomembrane s867 

nanoparticle s710, s1250 

nanoparticles s590, s595, s612, s652, 

s678, s680, s682, s721, 

s730, s731, s740, s742, 

s746, s749, s749, s750, 

s751, s752, s761, s776, 

s806, s810, s826, s830, 

s845, s860, s955, s978, 

s990, s1017, s1036, s1053, 

s1097, s1159, s1196, s1198, 

s1207, s1214, s1215, s1220, 

s1220, s1226, s1227, s1228, 

s1229, s1230, s1231, s1231, 

s1232, s1234, s1236, s1239, 

s1240, s1241, s1244, s1246, 

s1249, s1250, s1254, s1256, 

s1257, s1257, s1260, s1262, 

s1309, s1335 

nanoporous material s1310 

nanoscale order s744 

nanoscaled hybrid Materials s963 

nanosilica s1072 

nano-sized doped ito s994 

nanostructure s851, s852, s1209 

nanostructures s593, s660, s685, s721, 

s729, s730, s732, s733, 

s737, s746, s752, s752, 

s787, s802, s820, s844, 

s850, s885, s946, s1037, 

s1038, s1040, s1210, s1213, 

s1214, s1216, s1217, s1221, 

s1222, s1226, s1229, s1231, 

s1246, s1247, s1251, s1260, 

s1328 

nanotechnolgy s1217 

nanotechnologie s1262 

nanotechnology s594, s596, s731, s743, 

s750, s838, s1211, s1211, 

s1213, s1233, s1235, s1237, 

s1240, s1242, s1244, s1255 

nanotube s1238 


nanotubes s593, s609, s612, s731, 

s741, s953, s1221, s1233, 

s1255 

naphtalene s872 

napthalenediimide s1226 

natural fillers s1193 

natural pigment s674, s861 

natural product s658 

natural products s703, s706, s716, s718, 

s728, s766, s778, s793, 

s804, s930, s1005, s1007, 

s1025, s1044, s1045, s1071, 

s1091, s1159, s1170, s1187, 

s1271, s1286, s1291, s1292, 

s1292, s1315, s1325, s1337, 

s1348, s1353, s1364 

n-Connected objects s834 

n-donor ligands s939 

neotame s1343 

ners887 

network s669 

neurotransmitters s598 

nhC ligands s976 

n-heterocyclic carbenes s757 

ni s993 

ni alloys s1134, s1157 

ni(ii) complexes s700 

ni,Cd, Pb s919 

nickel s684, s826, s911, s933, 

s966, s982, s1210, s1256, 

s1302, s1354, s1363 

nickel complexes s958 

nickel chloride s935 

nickel(ii) s934 

nicotinic acid s1065, s1334 

nir s1141 

nirosation s811 

nitric oxide s751, s1134 

nitrides s610, s1217 

nitrile oxides s1367 

nitrite s811, s981 

nitroazidobenzene s1142, s1149 

nitrogen s1176, s1271 

nitrogen fixation s936 

nitrogen heterocycles s694, s784, s1001, s1031, 

s1057, s1063, s1270, s1288 

nitrogen oxides s637, s664, s685, s945, s957 

nitrogen-doped graphene s1228 

nitrosation s812 

nitrosyl s981 

n-ligands s1088 

nLo s1034 

n-methylimidazole-4,5-dicarbonitrile s1043 

nMr s590, s673, s697, s717, 

s1027, s1340 

nMr spectroscopy s617, s654, s673, s768, 

s782, s794, s812, s854, 

s881, s970, s977, s978, 

s983, s991, s1001, s1048, 

s1057, s1060, s1086, s1166, 

s1176, s1182, s1198, s1244, 

s1288, s1343, s1358 

nMr titration s939, s1234 

nMr-measurements s958 

noble metals s697 

nodularin s598 



s1416 

chem. Listy 106, s587–s1425 (2012) 


non linear optical properties s870 

non-aqueous capillary electrophoresis s1121 

noncovalent interactions s760, s800, s813, s1011, 

s1030, s1040, s1272, s1272 

non-covalent interactions s610, s1099 

non-linear modeling s614 

nonlinear optics s729, s782, s820 

nonstoichiometric compounds s691 

nuclear Chemistry s928, s929 

nuclear magnetic resonance s704 

nuclear waste s924 

nucleating agents s1054 

nucleic acids s1039 

nucleophilic addition s767, s1315 

nucleophilic aromatic substitution s1045 

nucleophilic substitution s1345 

nucleophilic vinylic substitution s770 

nucleophilicity s958 

nucleosides s604, s831, s1003, s1011, 

s1045, s1073, s1318, s1323 

nucleosomes s713 

nucleotides s604, s857, s1111, s1229, s1364 

nucleus-independent chemical shift (niCS) s986 

nylon s802 

o- effect s1131 

o ligands s983 

o2 plasma s1201 

octadecyltrichlorosilane s849 

ofet s1322 

oil products s1149 

oled s1028, s1321 

oLeds s937 

olefin s592 

olefin metathesis s976 

olefination s1050 

oleic acid s926 

oligoene s806 

oligomeric macrocycles s1334 

oligomerization s1328 

oligonucleotides s712, s724, s1003, s1233 

oligosaccharides s723, s1027 

oligothiophene s1019 

o-o activation s686, s955, s1087, s1304 

oPe s1316 

operando s810 

optical activity s753 

optical spectroscopy s1083 

optimization s1124 

ordered mesoporous carbon spheres s959 

organic catalysis s784 

organic electronics s773, s1300, s1360 

organic field-effect transistor s1019 

organic field-effect transistors s1201 

organic Chemistry s667 

organic Materials s842 

organic matter s651 

organic peroxides s1279, s1356 

organic photovoltaics s790 

organic semiconductors s1019 

organic solar cells s773 

organic-inorganic hybrid composites s699, s955, s1303, 

s1319 


organocatalysis s735, s758, s774, s782, 

s853, s1010, s1012, s1020, 

s1024, s1029, s1046, s1047, 

s1064, s1085, s1097, s1233, 

s1264, s1269, s1287, s1289, 

s1292, s1298, s1310, s1317, 

s1336, s1338, s1356, s1361 

organocatalyst s1277, s1284 

organometallic s939, s1277 

organometallic mixed-valent chemistry s1156 

organometallics s766 

organozinc s939 

origin s673 

oscillatory reaction s1144 

oxidant s987 

oxidation s589, s596, s663, s683, 

s706, s707, s708, s725, 

s783, s803, s806, s902, 

s905, s977, s987, s992, 

s1029, s1041, s1072, s1076, 

s1114, s1165, s1186, s1188, 

s1203, s1226, s1276, s1290, 

s1298, s1304, s1357 

oxidation state s922 

oxidations s658 

oxidative damage s907, s918 

oxidative dehydrogenation s1248 

oxidative stress s918 

oxides s947 

oxidoreductases s704, s706 

oxo Cluster s1236 

oxone s688 

oxygen s1007, s1134 

oxygen evolution s984 

oxygen evolving complex s984 

oxygen heterocycles s610, s1086 

oxygenation s708 

ozone s905 

ozonolysis s725, s1045 

P ligand s945 

P ligands s1014 

PAh s917 

Palladiujm s941 

Palladium s663, s696, s697, s754, 

s774, s806, s932, s950, 

s960, s977, s978, s981, 

s1002, s1012, s1014, s1018, 

s1042, s1051, s1065, s1067, 

s1070, s1080, s1094, s1222, 

s1226, s1230, s1273, s1285, 

s1307, s1312, s1315, s1349, 

s1357, s1361 

Palladium catalyzed epoxide opening s998 

palladium cytalysed cross-coupling s1093 

Para hydrogen s1340 

Para hydrogen induced polarization s1340 

paraoxonase s907 

Partial Least Squares s1141 

passivation s1222 

passive remediation s642 

Patulin s1140 

Pb(ii) adsorption s1192 

Pbo2 s906 

Pd catalyzed reaction s1083 

Pd-catalyzed o?C allylic rearrangement s1319 

Pd-ni-P s1205 



s1417 

chem. Listy 106, s587–s1425 (2012) 


Pdt application s979 

Peach processing s1161 

Pedot s1212 

pentacene s1201, s1322 

Peptide s715, s717, s776, s1106 

Peptide nucleic Acid s709, s795 

Peptides s613, s705, s711, s711, 

s720, s724, s726, s785, 

s853, s874, s879, s887, 

s1004, s1085, s1164, s1168, 

s1298, s1364, s1367 

Peptidomimetics s720, s772, s1050, s1291, s1343 

Pericyclic reaction s791, s819 

periodic acid s1340 

Periodic mesoporous organosilica s841 

periodic network s747 

Perlite s647 

pernitride s851 

perovskite s948 

Perovskite phases s1240 

peroxidase s907 

peroxide s884 

Peroxides s683, s1007, s1304 

peroxyoxalate s1279 

perylenediimides s1212 

ph s748 

ph induced changes s1215 

Pharmaceutical s1117 

pharmaceuticals s648, s650 

Pharmacophore s900 

pharmacophore model s1018 

Phase diagrams s662, s882 

phase transformation s969 

Phase transitions s835, s881, s882 

phase-transfer catalysis s758, s1020, s1024 

phenol s1013 

phenolic acids s1151 

phenolic compaunds s907, s918 

phenolic compounds s1119 

Phenolics s1161 

phenylboronic acid derivative s1232 

Pheromones s930 

Philosophy of chemistry s626 

phonon confinement effects s1245 

Phosphane ligands s679, s695, s938, s948, 

s1198, s1308, s1363 

Phosphanes s947 

phosphasilapropene s997 

Phosphate s1280 

Phosphine s941 

phosphine borane s1060 

Phosphines s1070, s1071 

Phospholipids s894, s1299 

phospholipids vesicles s886 

Phosphonomethionine s1046 

Phosphorescence s1028 

Phosphorous ligands s1022 

phosphorus s747, s773, s946, s960, 

s965, s967, s1000, s1008, s1070 

Phosphorylation s1069, s1278, s1299 

photoactivation s839 

Photoaffinity labeling s727 

Photocages s750 

photocatalysis s660, s910, s975, s976, 

s990, s1041, s1084, s1087, 

s1180, s1286, s1310 


Photocatalytic hydrogen evolution s1175 

photocatalytic property s1209 

Photodynamic s1112 

Photodynamic theraphy s969 

photodynamic therapy s986, s988, s1214 

photo-electrochemistry s693 

photoelectron spectroscopy s825, s854, s877 

photochemical hydrogen evolution s988 

Photochemistry s627, s649, s681, s698, 

s701, s714, s726, s738, 

s783, s788, s808, s871, 

s943, s947, s974, s981, 

s996, s1003, s1041, s1047, 

s1049, s1074, s1173, s1174, 

s1225, s1231, s1346, s1352 

Photochromism s738, s746, s750, s780, s968, s1225 

photoisomerization s738 

photoluminescence s742 

Photolysis s649, s904 

photooxidation s730 

Photophysics s699, s738, s746, s781, 

s815, s828, s830, s938, 

s967, s988, s1225, s1353 

Photoprotein s1270 

photoredox catalysis s1041 

Photoremovable protecting groups s1265 

photoresponsive behavior s1034 

Photosensitizer s988 

Photostimulated luminescence s1167 

photoswitchable monolayers s1028 

Photosynthesis s832 

photosystems s804 

Phthalates s1163 

Phthalocyanine s986, s987, s987, s988 

Phthalocyanines s956, s969, s971, s1225, s1279 

Phwe, s1131 

Physical Chemistry s667 

Phytoextraction s911, s911 

Phytohormones s856 

Phytochemistry s1170 

phytoremediation s911 

P-chiral secondary phosphine oxides s1015 

Pi interactions s1012, s1326, s1328, s1335 

picolinic acid s1065, s1334 

pincer ligands s700 

piroxicam s1144 

pit lake s925 

pKa prediction s859 

plasma chemistry s1179 

platencin s719 

platensimycin s719 

platform s1095 

platform concept s1294 

Platinabenzene s986 

Platinum s679, s697, s713, s932, 

s949, s959, s967, s1102 

platinum deposition s1133 

platinum nanoparticles s1181 

platinum(ii) complexes s940 

plga s1214 

Pnicogens s946 

p-nitrophenyl glycoside s1027 

polarization s821 

pollution s645 

Poly(ethylene) s1104 

Poly(vinyl alcohol) s1335 



s1418 

chem. Listy 106, s587–s1425 (2012) 


Poly(vinyl triazole) s1365 

polyacetylene s764 

Polyacrilonitrile derivatives s1062 

Polyalphaolefin s1105 

polyanion s787 

Polyanions s718 

polyaromatic hydrocarbon s1281 

polyaromatic hydrocarbons s1266 

Polycaprolactone s793 

polycyanurate s1015 

Polycycles s1098, s1276, s1326, s1333 

Polycyclic Aromatic hydrocarbon s806 

polydiacetylene s1287 

Polydimethylsiloxane s793 

polyelectrolyte s1252 

Polyethyleneimine s1080 

polyferrocenosilane s954 

polyglutamic acid s1027 

Polyhalides s836 

Polyketides s1358 

Polymer s1015, s1034 

Polymer Gel s1080 

Polymer Micelles s750 

polymeric nanocomposite s1247 

polymerization s595, s788, s880, s955, 

s965, s998, s1005, s1038, 

s1048, s1066, s1067, s1095, 

s1099, s1102, s1103, s1105, 

s1182, s1262, s1297, s1300, 

s1310, s1319, s1325 

polymerization in dispersed systems s792 

polymerizations s688 

polymers s599, s600, s612, s656, 

s685, s750, s752, s769, 

s786, s788, s789, s791, 

s793, s857, s882, s946, 

s998, s1000, s1004, s1007, 

s1025, s1034, s1036, s1037, 

s1049, s1052, s1058, s1067, 

s1099, s1151, s1153, s1161, 

s1184, s1192, s1239, s1244, 

s1253, s1262, s1266, s1268, 

s1269, s1282, s1291, s1293, 

s1296, s1297, s1319, s1321, 

s1338, s1341, s1353, s1355 

Polymorphism s1204, s1307 

Polynuclear s933 

polyoxometalate s681, s942, s989, s993, 

s1203, s1239, s1250 

polyoxometalates s666, s697, s697, s715, s733, 

s933, s961, s984, s992, 

s992, s1254, s1319 

polyphenol oxidase s907, s918 

polyphosphazenes s688 

polypropylene s1039, s1248 

polyrotaxane s735 

Polyurethane block copolymers s1105, s1366 

Polyvinylpyyrolidone (PvP) s1115 

poplar s911 

Porous networks s842 

porous silicon s742 

Porous solids s843 

Porphyrin s678, s1207, s1252, s1351 

Porphyrinoids s732, s817, s1016, s1040, 

s1060, s1072, s1185, s1225, 

s1278, s1350, s1360 


portfolio s927 

potentiometric s1144 

potentiometric selectivity s593 

Potentiometry s1125 

powder x-ray diffraction s847 

p-quinol s1059 

practical exercise s929 

Precaution s676 

precipitation s907 

prenylated compund s1013 

preparing temperature s1201 

primary alcohols s802 

Principal Component Analysis s617, s1160, s1166 

process intensification s656 

prochiral ketone s1094 

pro-oxidant s674 

propargylamines s784 

Propargylic alcohols s1073 

Propylene Glycol s1110 

Protecting groups s854, s891, s1086 

Protective Groups s1286 

protein s606, s717 

protein aggregation s896 

protein design s1367 

Protein engineering s590, s608 

Protein expression s1267 

Protein modifications s796 

protein regulation s885 

protein structures s855, s889, s891 

Protein surface s717 

Protein-protein interactions s891 

Proteins s590, s599, s885, s902, 

s1069, s1165, s1256 

proteomics s602, s613, s726, s727, s728 

protic solvents s1334 

proton acceptor s690 

Proton transport s1026, s1270 

Protonation s782, s830 

proton-catalyzed s1266 

pseudo-first order s1092 

Pseudorotaxanes s1234 

Pt(0) s1241 

p-tert-butyl calix[6]arene derivatives s1344 

p-type Gallium Arsenide s693 

Public image s629 

Push-pull chromphores s1043 

Pymerization s1425 

Pyrazinamide s1305 

pyrazinoquinoline s770 

pyrazole s1294 

Pyrazolidine s1016, s1331 

pyrazolo[3,4-d]pyridazine s1294 

pyrimidine salts s1356 

pyrimidinophane s1334 

pyrimido[4,5-b]indole ribonucleosides s1093 

pyrimidopteridines s1077 

Pyrolysis s1366 

pyrolytic carbon s659 

Pyronine y s1112 

pyrrolidine iminosugars s1359 

pyrrolo[1,2-b]pyrazoles s1359 

qM/MM s816, s821 

qM/MM simulations s863 

qsar software s1359 

quantitative structure-property relationship s874 

quantity injection s1147 



s1419 

chem. Listy 106, s587–s1425 (2012) 


quantum dots s742, s748, s748, s750, 

s829, s1211, s1245 

quantum Chemistry s686, s813, s815, s822, 

s864, s876, s878, s991, 

s1176 

quaternization s988 

quenching s748 

quercetin s674 

quinoline s971 

quinoline-2,4-diones s1342 

quinones s649, s1123 

quntum-chemical calculation s809 

radical s674 

radical cascades s771 

radical reactions s767, s771, s863, s1075, 

s1298, s1305 

radicals s835, s952, s1084, s1169, 

s1241, s1271 

radioactive cesium s636 

radioactive contamination s636, s920 

radiochemistry s635, s637, s638, s640, 

s720, s924, s928, s931 

radiopacity s1335 

radiopharmaceutical s715 

radiopharmaceuticals s709, s717 

radium-226 s920 

radium-228 s920 

rAft polymerization s748 

raman spectroscopy s606, s826, s828, s862, 

s893, s1154, s1154, s1219, 

s1228, s1333 

rare earth elements s640 

rare earths s788, s991, s1206, s1336 

raschig process s1331 

rat heart model s1134 

rate constants s952 

reaction Mechamisms s819 

reaction mechanism s688, s821 

reaction mechanisms s652, s686, s686, s690, 

s746, s816, s822, s880, 

s882, s949, s1024, s1051, 

s1302, s1317 

reaction order s1344 

reaction pathways s824 

reaction rate Constant s1344 

reactive intermediate s688 

reactive intermediates s685, s764 

reactivity s682, s972 

rearrangement s610, s670, s695, s821, s1313 

rearrangement reactions s1023 

receptors s778, s1222, s1290, s1296, 

s1331, s1356 

reclamation s925 

recycling s1015 

red mud s908 

redox cycles s958 

redox chemistry s596, s686, s688, s902, 

s1074, s1123, s1145, s1188, 

s1272, s1341 

redox processes s639 

reduction s652, s758, s865, s947, 

s960, s1087, s1145, s1191, 

s1257, s1342 

reflectometric interference spectroscopy (rifS) s1129 

reforming s1219 


regioselectivity s765, s799, s823, s865, 

s1045, s1068, s1077, s1273, 

s1274, s1316 

rechargeable battery s1106 

relativistic effects s813 

renewable s1015, s1182 

renewable resources s653, s675, s1025, s1094, s1178 

research funding s633 

retention s923 

reverse Micelle s1115 

reversible addition-fragmentation chain transfer s792 

rhenium s983, s996 

rhenium(iv) s994 

rhodium s652, s694, s1312 

ribozymes s872 

rifampin s1137 

rigid polyurethane foam s1054 

rigid-rod polymer s1320 

ring closing metathesis s1048 

ring expansion s764 

ring opening metathesis polymerization s846 

ring-opening polymerization s788, s1004, s1291 

rio earth Summit s631 

risk s676 

risk management s620 

river bottom sediments s920 

river water s1140 

rnA s876 

rotaxane s1233 

rotaxanes s729, s735, s797, s1026, 

s1085, s1211, s1225, s1241, 

s1272, s1272 

ru(ii) complexes s1214 

rubrerythrin s888 

ruthenium s592, s678, s684, s685, 

s696, s699, s716, s758, 

s826, s830, s862, s882, 

s938, s943, s944, s947, 

s976, s1014, s1023, s1032, 

s1082, s1156, s1173, s1198, 

s1220, s1308, s1316, s1351, 

s1352 

S Ligands s936 

Saccharide probe s861 

Salt Bridge Containing Polar Pocket s898 

salt effect s1164 

salt spray environment s1118 

Samarium s1271 

Sandwich complexes s873 

sausage s677 

scanning Kelvin probe microscopy s849 

Scanning probe microscopy s927, s1058 

scanning tunneling microscopy s745, s1032 

Scatchard Plot s1113 

science s619 

Scientific responsibility s629 

Sclerotinia sclerotiorum s885 

Screening s1028 

seawater s635 

secondary batteries s1107 

sector model s859 

sediment s917, s918 

Sedimentary archive s644 

selective solvents s786 

selediazoloquinoline s770 



s1420 

chem. Listy 106, s587–s1425 (2012) 


selenium s652, s923, s1147, s1312 

Selenophene s1300 

Selenophene ring fragmentation s1300 

Self assembly s1038, s1335 

self evaluation s623 

Self-assembl s1033 

Self-Assembled 3d Crystals s834 

self-assembled monolayer s1201, s1424 

self-assembled monolayers s745, s1032 

Self-assembly s729, s732, s733, s737, 

s743, s744, s746, s752, 

s780, s791, s792, s794, 

s794, s798, s805, s809, 

s810, s833, s835, s836, 

s953, s954, s985, s989, 

s1008, s1012, s1030, s1081, 

s1089, s1093, s1211, s1216, 

s1217, s1224, s1229, s1246, 

s1247, s1251, s1252, s1254, 

s1258, s1272, s1303, s1324 

Self-healing s833 

self-organization s744 

self-study training s929 

semiconductors s742, s781, s789, s996, 

s1061, s1192, s1326, s1362 

semiempieical calculations s1362 

sensing s796 

Sensitizers s649 

sensor s1111 

Sensors s595, s611, s612, s797, 

s802, s1118, s1122, s1143, 

s1213, s1214, s1224, s1243, 

s1256, s1341 

Separation s1351 

separation strategies s603 

sequential injection analysis s605 

Serbia s907 

service oriented s623 

sewage sludge s925 

shape persistence s1262 

shape-persistent macrocycles s745 

shape-persistent molecules s1032 

Schiff base s1131 

Schiff bases s799, s812, s847, s896, s954, s956, s991, s1293 

Schiff-base s1265 

schwertmannite s903 

Si ligands s702 

sialic acids s775 

Signal enhancement s1340 

Silanes s755, s769, s970, s985, 

s1051, s1221, s1354 

silica s1090 

Silica fume s908, s914 

silica hydride material s1151 

Silicates s1200, s1217 

silicon s689, s702, s742, s754, s913, 

s964, s965, s967, s1221, 

s1242, s1260 

silicon analysis s1157 

Silicon based s1277 

Silicon- based s1264 

silicon nanocrystals s742 

silicon tetrachloride s935 

Silver s679, s968, s1073, s1231, 

s1234, s1235, s1247, s1257, 

s1273 


Silver bromide nanocrystal s1209 

Silver nanoparticles s1135, s1219 

Silver vanadium oxide s953 

silyl cations s1266 

singet oxygen s751 

single crystal diffraction s1125 

Single-molecule studies s736, s743, s882, s1078 

Singlet oxygen s649, s969, s986, s1014, 

s1225, s1239, s1279 

single-wall carbon nanotubes s1105, s1366 

six carbon (6-C) synthon, 2,2’-bisallyl diradical s1057 

skills s929 

skutterudite s851 

Small ring systems s777 

SMArt x2S s1125 

smokeless powder s1124 

sodium s1164 

software package GiS-inteGro s910 

soil s1149 

sol gel s904 

solar cells s1212 

Solar energy Conversion s803 

Sold-Phase Peptide-Synthesis s711 

Sol-gel s1137 

Sol-Gel Process s1213 

Sol-Gel processes s682, s699, s730, s966, 

s1200, s1201, s1220, s1237, 

s1249, s1366 

Solid acid catalyst s659 

solid catalysts s1092 

solid electrolyte s948 

solid phase s884 

solid state chemistry s839 

Solid state photopolymerization s1320 

Solid state structures s848, s1206 

solid superacid s1177 

solid/liquid interface s1032 

solid/liquid-interface s745 

Solid-phase synthesis s713, s716, s749, s772, 

s775, s891, s1002, s1111, 

s1112, s1367 

solid-state chemistry s656 

Solid-state reactions s836, s837, s966 

Solid-state structures s814, s835, s837, s838, 

s959, s967, s1202, s1345 

Solubility s971 

solutions s827 

solvated electron s604 

Solvent effect s1141 

solvent effects s815, s870, s1303, s1304 

Solvent free s1295 

solvent properties s958 

solvent-free conditions s663 

solvent-free synthesis s656 

Solvolysis s1030, s1040 

solvothermal synthesis s994 

Sorption s651 

South African education s630 

Soxhlet extraction s1124 

speciation s639, s646, s924 

spectroelectrochemistry s1156 

spectrometric detection s603 

spectroscopic investigation s1252 

spectroscopy s807, s890 

Spent Bleaching earth s915, s915 

Spent catalysts s1187 



s1421 

chem. Listy 106, s587–s1425 (2012) 


Spent nuclear fuel s924 

Spin crossover s680, s698, s736, s951, s974, s980 

Spinel phases s1231 

Spiro compound s803 

Spiro compounds s1098, s1313 

spme s601 

SPMe-LC/MSn s1116 

spray deposition s657 

Spray-iLGAr s1222 

squaramide s1338 

Square wave voltammetry s1137 

squid s995 

stability s884 

stable intermediates s952 

Stacking interactions s795, s845 

staff development s633 

static/dynamic light scattering s786 

stationary phase s857 

stationary phases s1115 

Statistical thermodynamics s666 

stereochemically s1200 

Stereochemistry s858 

Stereoselective epoxidation of enals s998 

Steric hindrance s695 

steroid s1066 

steroids s778, s833, s855, s1006, 

s1006, s1035, s1035, s1076, 

s1076, s1089, s1101, s1278, 

s1301, s1307, s1333, s1350, 

s1350, s1367 

Stockholm Convention on Persistent s631 

organic Pollutants 

stockings s620 

storm water s648 

strained molecules s714 

stress-strain properties and s1105, s1366 

structural parameters 

Strontium s919, s1187 

strontium determination s921 

Structural Biology s590, s704, s855, s898 

structural dynamics s827 

Structural Genomics s590 

Structural properties s994 

Structure s682 

structure elucidation s602, s680, s725, s893 

structure characterization s850 

structure prediction s851 

structure variation s814 

structure-acidity relationship s654 

Structure-activity realtionships s1339 

Structure-activity relationships s727, s778, s860, s902, 

s1170, s1330 

Stt-type zeolite s849 

subcritical drying s1189 

Subsidy driven research s630 

substituent effect s986 

Substituent effects s699, s808, s1051 

Substituents effects s1288 

Substituted Styrenes s1022 

sucrose s1075 

sugars s807 

sulfamethoxazole s1183 

Sulfamide-Ligands s1306 

sulfinylimidate s1010 

Sulfonamides s904, s1114, s1290 

sulfonation s659, s787 


sulfoxidation s1356 

Sulfur s641, s913, s1043, s1067 

Sulfur heterocycles s773, s781, s798, s965, s1155 

Sulfur oxides s664 

sulphonamide s1294 

Sunflower s911 

superbase s1313 

superconductors s1199 

Supercritical fluid s1227 

supercritical fluids s666, s1190 

Supported catalyst s1250, s1250 

Supported catalysts s788, s1207, s1251 

Supramolecular s1218, s1352 

Supramolecular complexes s1110 

supramolecular electronics s743 

Supramolecular chemistry s611, s697, s700, s730, 

s731, s733, s734, s739, 

s743, s768, s780, s794, 

s795, s798, s800, s802, 

s805, s833, s837, s838, 

s858, s881, s887, s938, 

s947, s953, s1001, s1003, 

s1008, s1012, s1019, s1026, 

s1030, s1040, s1047, s1058, 

s1058, s1068, s1078, s1081, 

s1088, s1093, s1096, s1102, 

s1102, s1118, s1190, s1211, 

s1216, s1218, s1222, s1223, 

s1225, s1229, s1239, s1241, 

s1242, s1242, s1243, s1243, 

s1249, s1252, s1258, s1259, 

s1296, s1318, s1331, s1354, 

s1360 

supramolecular ligand s897 

supramolecular species s940 

surface analysis s612, s848, s964, s1000, 

s1240, s1255, s1366 

Surface chemistry s783, s792, s824, s825, 

s838, s860, s964, s1037, 

s1198, s1252, s1258, s1318, 

s1335 

Surface patterning s793 

surface plasmon resonance s1260 

Surface science s808 

surface water s917 

surface-initiated polymerization s804 

Surfactants s597, s780, s791, s826, 

s879, s1062, s1269 

Sustainability s640, s671 

sustainable food production s672 

Sustainable Chemistry s630, s661, s701, s756, 

s773, s853, s914, s947, 

s964, s981, s1014, s1082, 

s1173, s1174, s1191, s1235, 

s1268, s1339 

Suzuki coupling s1348, s1359 

Swimmers s744 

switchable solvents s1178 

Synchrotron s903 

synthesis s791, s856, s899, s987, 

s1027, s1262, s1265, s1334 

Synthesis design s703, s722, s737, s769, 

s777, s785, s855, s857, 

s892, s1016, s1043, s1060, 

s1070, s1103, s1192, s1267, 

s1306 



s1422 

chem. Listy 106, s587–s1425 (2012) 


synthesis route s948 

Synthetic Biology s796 

synthetic carbon allotrope s741 

Synthetic design s1108 

synthetic methods s703, s759, s761, s764, 

s766, s768, s768, s774, 

s796, s854, s942, s1000, 

s1001, s1009, s1010, s1020, 

s1025, s1030, s1096, s1100, 

s1103, s1103, s1202, s1202, 

s1278, s1291, s1299, s1302, 

s1323, s1350 

Synthetic vaccines s775 

t2 toxin s1162 

table olive Processing wastewater s916 

tandem mass spectrometry s1132 

tandem reactions s1337 

target recognition s1232 

teaching s634, s930 

teaching competency s929 

teleme s1160 

tellurides s852 

teM s994 

template syntheses s841 

template Synthesis s799, s840, s1040, s1085 

templated self-sorting s804 

terbium Complexes s943 

terpenoids s930, s1108 

terpyridine coordination compounds s781 

tertiary alcohol s763 

test method s1134, s1157 

tetrahydrofuranyl ethers s1023 

tetrasubstituted stereocenters s771 

tetrazole s1332 

texture s617 

tG s1142 

therapy s751 

thermal analysis s1149, s1344 

thermal conductivity s1054 

thermal conductivty s1188, s1194 

thermal decomposition s1142 

thermal treatment s1195 

thermodynamic and redox stability s886 

thermodynamic equilibrium calculation s636 

thermodynamic stability s607 

thermodynamics s671, s870, s899, s1099, 

s1179, s1199, s1202 

thermoelectric s852 

thermoelectric materials s1256 

thermoelectrics s851 

thermochemistry s1178 

thermoluminescence s1167 

thermoset s1015 

thiadiazolo Benzamide s883 

thiazol derivatives s982 

thick film s1147 

thin film solar cells s1222 

thin films s802, s1156, s1217, s1237, 

s1240, s1255, s1255, s1338 

thiobenzanilides s874 

thiophene s773, s1043 

thiophosphate s1280 

thioredoxin system s704 

third generation photovoltaics s657 

thrombin s1127 

time-resolved spectroscopy s699, s704, s828, s830, 

s864, s877 

tin s955, s1163 

tio 2 


s1183 

tio 2 nanotube arrays s1175 

tio-PAn s922 

titania s910 

titanium s755, s767, s964, s993, s1251, s1252 

titanium oxide s923 

titanium-catalyzed s1306 

titaniumu dioxide photocatalyst s1208 

topochemical polymerisation s1287 

topochemical reaction s747 

topochemistry s1235 

topological Control s834 

total synthesis s719, s759, s759, s766, 

s778, s1005, s1010, s1045, 

s1278, s1302, s1319, s1350, 

s1353, s1367 

toxicity s650 

toxicology s646, s909 

trace analysis s1138, s1143 

trace metal s918 

training s928 

transcription factors s711 

transferases s822 

transferfactor s911 

transformation products s650, s904 

transition metal s810 

transition metal catalysis s762 

transition metal complexes s982 

transition metal nanoparticles s952 

transition metals s642, s651, s695, s702, 

s759, s912, s913, s945, 

s948, s968, s992, s1169, 

s1297, s1336, s1355 

transititon metal complexes s1126, s1127 

transmembrane-peptide s1232 

transmission electron microscopy s786, s1256 

triazine s1101 

triazole s1322 

triazole derivatives s1347 

triazoles s1309 

triclosan s693, s905 

tricyclic analogues of purines s1365 

tridentate ligands s736, s961, s1302 

triethylaluminum s1311 

trilobolide s1035 

tripodal ligand s940 

tripodal ligands s977 

tripodal Phosphane Ligands s936 

tuberculosis s1305 

tumor growth s1150 

tungsten s945 

tungstoarsenate s989 

tunnelling s845 

twin Polymerization s963 

two-photon absorption s1214 

tyramine s812 

ullmann-Goldberg mechanisms s975 

ultra high performance liquid chromatography s1132 

ultrafast s827 

ultrafast spectroscopy s829 

ultramicroelectrode s1126 

ultrasound s1187 

ultrasounds s1191 



s1423 

chem. Listy 106, s587–s1425 (2012) 


ultraviolet absorption maximum s1065, s1334 

umpolung s765 

unsymmetrical Phthalocyanine s979 

up-conversion s1206 

uracil s1334 

uracil derivatives s795 

uranium s643, s922, s922, s923, s924 

urethane formation s1309 

urethane-triazole s1309 

uSA 300 CA-MrSA s890 

uv / vis spectroscopy s605 

uv measurements s1066 

uv photochemical generation s1147 

uv treatment s650 

uv/vis spectroscopy s649, s684, s808, s870, 

s881, s895, s945, s951, 

s1035, s1060, s1088, s1089, 

s1114, s1116, s1124, s1141, 

s1145, s1159, s1161, s1165, 

s1170, s1327, s1333 

uv-vis s639 

uv-vis spectroscopy s1237, s1255, s1317 

vacancy formation s814 

valence isomerization s698, s951 

vanadates s984 

vanadium s666, s686, s956, s981, s1177 

variable Selection s615 

vCd s1357 

vegf s1150 

vegf-r1 s1150 

veGfr2 tyrosine kinase s898 

vermiculite s647 

vesicles s879, s1224, s1243 

vibrational contributions s870 

vibrational spectroscopy s606, s818, s826 

vinylallene s1263 

vinylic nucleophilic substitution reaction s1092 

vinyltriethoxysilane s1072 

viologen s1425 

virtual campus s624 

virtual community s623 

virus s608 

viruses s731 

visible light s1084, s1183, s1310 

visible-light photocatalysis s1031 

vitamin C s907 

vitamins s864 

vitrification s919 

volatile form s1147 

voltammetry s595, s597, s597, s1109, 

s1117, s1135, s1140, s1146, 

s1156 

wacker oxidation s1319 

washcoat s655 

waste incineration s636 

waste prevention s917, s1194 

waste water treatment s693, s905 

wasterwater, red mud s905 

wastewater s648, s908, s908, s914, 

s1110 

water s663, s914 

water chemistry s641, s641, s643, s645, 

s675, s733, s771, s1021, 

s1080, s1190, s1201, s1270, 

s1339, s1345 

water intrusion-extrusion experiments s849 


water reduction s949 

water splitting s701, s739, s944, s949, 

s1173, s1174, s1185 

water-adding quantity s1208 

water-hexane impregnation s1196 

waterproofing s1193 

water-soluble ions s907 

wavelets s617 

wax esters s1130 

wet chemistry s922 

whAM model s650 

white phosphorus s679 

white-brined cheese s1160 

wide Angle Scattering s903 

withasomnine s1359 

wittig reaction s1001 

women s620 

writing s667, s667 

xanes s922 

xAneS/exAfS s639 

xanthene s1265 

xenon s845 

xPA/rad14 s887 

x-ray s827 

x-ray absorption spectroscopy s1220 

x-ray absorption pectroscopy s825 

x-ray absorption spectroscopy s637, s638, s830, s1249 

x-ray crystallography s893 

x-ray diffraction s654, s782, s799, s832, 

s837, s848, s892, s936, 

s973, s977, s979, s983, 

s991, s1137, s1176, s1188, 

s1204, s1208, s1213, s1240, 

s1249, s1272 

x-ray difraction s991, s1232 

x-ray fluorescence s1132 

x-ray photoelectron spectroscopy s1424 

x-ray techniques s639 

yeast extract s885 

ynol ether s1010 

young chemist s669 

zeolite s919 

zeolites s654, s848, s966, s1199 

zeta potentiel s1138 

zinc s645, s686, s754, s939, 

s971, s986, s988, s1232 

zinc alkyls s690 

zinc hydroxide s690 

zinc isotopy s644 

zinc oxide s975 

zinc selenide s1245 

zirconia s609 

zirconium s966 

zn(ii) coordination polymers s781 

zno s1054, s1195 

znS nanodots s1222 

zwitterions s737 


s1424 

chem. Listy 106, s587–s1425 (2012) 

Appendix – late papers 


o - 5 2 7 

SinGLet fiSSion for effiCient dye-SenSitized 

SoLAr CeLLS 

z. hAvLAS 1 1, 2 

, J. MiChL 

1 Institute of Organic Chemistry and Biochemistry, 

Academy of Sciences of the Czech Republic, Flemingovo nam. 2, 

166 10 Prague 6, Czech Republic 

2 Department of Chemistry and Biochemistry, 

University of Colorado, Boulder, Colorado 80309-0215, 

United States 

Singlet Fission is a spin-allowed process in which a molecular 

chromophore excited into its singlet state shares energy with a 

nearby ground state chromophore, producing a pair of triplet 

excited chromophores initially coupled into an overall singlet. In 

a more detailed description, the initial singlet state actually is a 

coherent superposition of eigenstates of the total Hamiltonian 

operator that includes electron spin-spin and Zeeman interactions 

that dictate its further fate, along with possible spatial diffusion, 

internal conversion, intersystem crossing, and other possible 

competing processes. 

Although, the Singlet Fission is known is some special cases 

of crystalline aromatic hydrocarbons for a half of century, using 

of this process for increasing of the solar cell efficiency is a new 

topic. It includes studies of several steps and interplay of 

theoretical, synthetic, and spectroscopic procedures, namely: 

• Selection of the proper chromophore which satisfies 

the following conditions: E(S 1) ≥ 2 E(T 1) but also 

E(T 2) ≥ 2 E(T 1). We have observed that 1,3-diphenyl- 

-isobenzofuran satisfies these conditions and yields 200 % 

of triplet states in a crystalline state. 

• For practical reasons, the S 1 excitation energy should be 

around 2.2 eV. Searching for structures with this property 

is done by extensive set of quantum chemical calculations 

of excited states. We have already preselected a few 

structures which have to be now synthesized and studied 

experimentally. 

• For effective Singlet Fission process proper mutual 

orientation of chomophore pairs is essential. We have 

developed a simple Hamiltonian model and performed 

numerical calculations for different orientations of 

chromophores. The rules for the geometrical requirements 

resulted from these calculations will be discussed. 

• Preparation of a dye with both chromophores in ideal 

positions, either by self-organization or by synthesis of 

supermolecule with both chromophores properly arranged 

in it. 

• The final stage requires separation of charges of individual 

triplet chromophores, transport of the charges to the TiO 2 

semiconductor and injection of the electrons to the 

semiconductor. 

We will report on progress in the first three steps, the last 

two steps still need to be solved. 


P - 0 8 8 8 

direCt ALKyLAtion of GoLd SurfACe 

e. KALetovA 1 , A. KohutovA 1 , z. Si 1 , J. KALetA 1 , 

f. SChoLz 2 , J. hAJduCh 1 , L. PoSPiSiL 3 , 

f. von wroCheM 2 , z. BAStL 4 , J. MiChL 5 


Organic synthesis, Prague, Czech Republic 

2 Sony Deutschland GmbH, Stuttgart Technology Center, 


3 J. Heyrovsky Institute of Physical Chemistry AS CR v.v.i., 

Department of Molecular Electrochemistry, Prague, 


4 J. Heyrovsky Institute of Physical Chemistry AS CR v.v.i., 

Department of Spectroscopy, Prague, Czech Republic 

5 University of Colorado, Department of Chemistry and 

Biochemistry, Boulder, USA 

We report methods for ambient solution coating of a gold 

surface with a self-limiting monolayer containing alkyl chains 

attached by one or more C-Au bonds, and no other elements. The 

alkyl transfer agents are alkyl derivatives of metals such as Sn, 

Hg, Ge, and others. This is a generalization of our previous 

finding that under ambient conditions solutions of alkylated 

stannanes deposit alkyl-containing monolayers on gold surface, [1] 

and is in accord with break-junction conductivity measurements 

on single molecules attached to gold through carbon by transfer 

from trimethylstannyl derivatives. [2] 

Acknowledgment. The research leading to these results has 



(FP7/2007-2013) / ERC grant agreement no. 227756 and the 

European Commission (FP7-FUNMOL 213382) and was 

also supported by the Institute of Organic Chemistry and 

Biochemistry, Academy of Sciences of the Czech Republic RVO: 

61388963 and the Grant Agency of the Czech Republic 

203/09/J058. 

references 

1. Khobragade, D.; Stensrud, E. S.; Mucha, M.; Smith, J. R.; 

Pohl, R.; Stibor, I.; Michl, J. Langmuir 2010, 26, 8483. 

2. Cheng, Z. L.; Skouta, R.; Vázquez, H.; Widawsky, J. R.; 

Schneebeli, S.; Chen, W.; Hybertsen, M. S.; Breslow, R.; 

Venkataraman, L. Nat. Nanotechnol. 2011, 6, 353. 

Keywords: Self-assembled monolayer; X-ray photoelectron 

spectroscopy; Cyclic voltammetry; Electrochemical impedance 

spectroscopy; 


s1425 

chem. Listy 106, s587–s1425 (2012) 

Appendix – late papers 

P - 1 0 2 0 

PurPLe-to-trAnSMiSSive eLeCtroChroMiC 

SwitChinG of vioLoGen-BASed dendriMer 

C. trABoLSi 1 , K. wAdhwA 1 , S. nuryyevA 1 

1 New York University Abu Dhabi (NYUAD), Chemistry, 

Abu Dhabi, United Arab Emirates 

The growing threats brought about by climate changed 

promoted by human activities have gained a large amount of 

serious attention from both the private and government sectors. 

Climate change brought about by manmade emissions of CO by 2 

the combustion of fossil fuels has many consequences associated 

with it, including drought, more violent storms, and de-glaciation 

just to name a few. Curtailing CO emissions is a major objective 

2 

to achieve in order to mediate against these threats. So-called 

smart windows based on electrochromic materials offer a 

promising way of regulating the amount of light permitted 

to enter a building. Towards this end we have designed a 

viologen(BIPY 2+)-based dendrimeric material that has, under its 

reduced form, significant absorption in the UV, visible, and near 

infrared regions of the solar spectrum. The ability of two BIPY•+ 

radical cations to undergo π-dimerization (also known as 

pimerization) is driven by radical-radical interactions mostly 

involving spin pairing of the two spins into a singlet state. As a 

consequence of dimerization the absorption band characteristic of 

viologen radical cation at ~600 nm becomes blue-shifted, 

resulting in a purple color, and a significant absorption band in 

the NIR region of the spectrum emerges. In the case of methyl 

viologen radical cation, this dimerization only occurs at 

relatively large concentrations or low temperatures in MeCN 

solutions. A large amount of research efforts has gone towards 

enhancing the stability of these dimers in solution, including 

host-guest chemistry, mechanostereochemistry, and covalent 

preorganization. Herein, we present a strategy of covalent 

preorganization in a viologen dendrimer containing six viologen 

units. The electrochromic properties of our dendrimer were first 

investigated in solution using electrochemistry, UV-Vis-NIR 

and spectroelectrochemistry. The switching ability of the 

hexa-viologen dendrimer was then tested on ITO electrodes. The 

prepared window exhibited a reversible color change from 

transparent to purple upon reduction. 

Keywords: Electrochromic; Viologen; Dendrimers; 

Pymerization; 


P - 1 0 2 1 

new BioMediCAL And teChniCAL APPLiCAtionS 

of nAnoMAteriALS 

J.J. LAnGer 1 , K. LAnGer 1 , A. MiChALAK 1 , 

K. BArtKowiAK 1 , L. zABroCKA 2 , J. KoCiK 3 , 

J. wArChoL 4 , M. woLun-ChoLewA 4 , K. Szyfter 5 , 

M. JArMuz 5 , K. tArnowSKA 1 

1 Adam Mickiewicz University in Poznan, Faculty of Chemistry, 

Laboratory for Materials Physicochemistry and Nanotechnology, 

Grunwaldzka 10, PL-63100 Srem, Poland 

2 Biological Threats Identification and Countermeasure Centre of 

Military Institute of Hygiene and Epidemiology, Pulawy, Poland 

3 Military Institute of Hygiene and Epidemiology, Warszawa, 

Poland 

4 Medical University of Poznan, Poland 

5 Institute of Human Genetics of the Polish Academy of Sciences, 

Poznan, Poland 

Advances in nanoscience make it possible an unusual 

progress in biomedical applications. 

It concerns also our current studies. Non-specific, 

physicochemical interactions of polymer micro- and nanofibrils 

with biomolecules and whole living cells lead to a number of 

important biomedical applications in diagnostics and tissues 

engineering (nanomedicine), microbiology and biotechnology. 

These will be discussed with regard to interaction and analysis of 

bioactive molecules and biomarkers (nanosensors), as well as 

living cells (nanobiodetectors), including detection of cancer cells, 

bacteria and spores. Modifications of polymer nanofibrils lead to 

highly-specific interactions giving better sensitivity and more 

specific response. Fast and sensitive devices for detection of 

bacteria and spores are of particular interest for health care, 

security and defense. 

A network of polymer micro- and nanofibrils was used as a 

3D scaffold for cell culture in vitro. New material and technique 

can be applied not only in tissues engineering, but also in large 

scale bioreactors. 

These problems will be presented basing on the results of 

our newest experiments.

4th EucheMs chemistry congress

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