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2268 VIII , , SOME LANTHANIDE POLYIODIDE COMPLEXES WITH CARBAMIDE: SYNTHESIS AND STRUCTURE Alikberova L.Yu.a, Rukk N.S.a, Lyssenko K.A.b a M.V. Lomonosov Moscow state academy of fine chemical technology (MITHT), Vernadskij av., 86, 119571, Moscow, Russian Federation b A.N. Nesmeyanov institute of organoelement compounds Russian Academy of Sciences (INEOS RAS), Vavilov str., 28, 119991, Moscow, Russian Federation The present work is devoted to investigation of polyiodides of lanthanide complexes with car bamide and related compounds. The mentioned compounds are the perspective ones due to their possible application as non-metallic conducting and superconducting materials1 and they may be of the theoretical interest as the examples of the clathrate-coordination supramolecular compounds.

The complexes LnI3 (4-6)CO(NH2)2 (3-6)I2 xH2O (Ln La, Ce, Nd, Sm, Eu, Tb, Er, Tm, Yb, Lu) have been prepared by the reaction of the respective oxide or carbonate with the slight excess of hydroiodic acid and with subsequent addition of powdered crystalline iodine and carbamide (the molar ratio Ln : I2 : CO(NH2)2 = 1 : 4 : 5). The black columnar crystals of polyiodide complexes were grown at room temperature in a vacuum desiccator during 2-3 d. The results of the chemical analysis are in good agreement with the proposed composition. It has been found that the non monotonous dependence of the LnI3 : I2 molar ratio on the Ln atomic number points toward mani festation of the secondary periodicity.

The single crystal X-ray diffraction studies for a number of complexes demonstrated the coordi nation of carbamide molecules to the metal center through the oxygen atom of the ligand. Except that it has been found that polyiodide chains involves alternating triiodide anions as well as un charged molecules of iodine. These species are included in the one-dimensional polyiodide chains formation in the bulk of the complexes2,3. IR- and Raman spectra studies confirmed the ligand co ordination via oxygen atom as well as the polyiodide ions existence in the structure of the com plexes.

References 1. N. D. Kush, V. N. Laukhin, A. I. Schegolev, E. B.Yagubski, L. Yu. Alikberova, N. S. Rukk, J. Phys.I. France, 1991, No.1, 1365.

2. P. H. Svensson, L. Kloo, Chem. Rev., 2003, 103, 1649.

3. N. S. Rukk., L. Yu. Alikberova. 1-st European Chemistry Congress, 2006, Budapest, Hungary, Abstract Book. 2006, 100.

VIII , , 2007 NOVEL NETWORK POLYMERS BASED ON FUNCTIONALIZED CALIX[4]RESORCINARENES Altshuler H.N., Sapozhnikova L.A., Ostapova E.V., Malyshenko N.V., Shkurenko G.Yu., Altshuler O.H.

Institute of Solid State Chemistry and Mechanochemistry (Kemerovo division), Siberian Branch of Russian Academy of Sciences The experimental and theoretical investigations of formation process of supramolecular assemblies with participation of functionalized cis-calix[4]resorcinarenes at phase of network polymers were carried out.

Novel network polymers repeating units of which contain calix[4]resorcinarenes functionalized by sulphonates, phosphonates or (2-furyl)-hydroxymethyl groups are received:

CH HO OH R= CH3, Ph, Ph-SO3H, Ph-PO3H2 ;


R'= H, SO3H, C R R O HO OH HO HO OH CH p Thermodynamics, the mechanism and kinetics of formation of supramolecular compounds of functionalized calix[4]resorcinarenes with H+, Li+, Na+, Ag+, NH4+, Alk4N+, Ba2+, Cu2+, In3+ cations in network polymers were investigated.

The nanoreactor effect consisting in significant increasing (on 2-3 orders) of interdiffusion streams of cations in network polymers based on calix[4]resorcinarenes containing SO3H groups is found out.

The polymeric composites containing nanoparticles of silver, copper, palladium of the operated size from 2 to 100 nanometers are obtained.

The authors would like to thank the Russian Foundation for Basic Research for financial supporting of this work (project 07-03-9603).


Kazan State Technological University, 420015, K.Marks str. 68, Kazan Joint Institute Nuclear Research (Dubna) When one study a micellar catalysis usually research an influence a micelles on the velocity and path of chemical processes. We believe that it is very important know the influence of substrates and reactionary products on the micellar media. We have studied alteration of the micellar spatial features during the hydrolysis of O-p-nitrophenyl-O,O-dimethyltiophosphate (A) in the cetyl trimethylammonium bromide (CTAB) NaOD D2O system proceeding. We have used the SANS method (small angle neutrons scattering) and we fixed the changing of a scattering vector intensity I(Q), cm-1 from scattering vector (Q) A-1 during the determined time. Primary data processing was produced by means of program SAS, but modeling given was conducted by the program Fitter. At the absence the substrate a slopping crooked I(Q)=f(Q) during the time was not changed. For the system CTAB A (0,0241 g/10 ml) D2O we installed small alterations of characteristic parame ters (Porods invariant, radius of Gyration, volume of associates, aggregations numbers). It may be connected with the gradual solubilisation of O-p-nitrophenyl-O,O-methyltiophosphate anion (stand ing out as a result of the dealkylation reaction proceeding) in CTAB micelles. We have installed that all micelles in the systems under study have a form of the ellipse, which radiuses are enlarged on the measure of passing the hydrolysis.

In alkaline systems CTAB (0,005M)-NaOD (0,05M) A (0,1041 g/10 ml)-D2O and CTAB (0.005M) NaOD (0.05M) A (0.0191 g/10 ml)-D2O we have observed the gradual changing of the length of micelles and the aggregations number, which were more essential, than more source concentration a substrata. The curves of neutron scattering have not maximum. The reason of this phenomenon is absence of interactions between micelles. Only for one system CTAB (0.005M) NaOD (0.05M) A (0.0191 g/10 ml)-D2O at the end of the reaction we have seen weakly denomi nated diffraction maximum. It may be as the result of micelles sequencing, which inhere on the dis tance 186 A.

We believe, that p-nitrophenolate anion, standing out during the reaction proceeding, provokes the growth of CTAB micelles due to the intercalation of p-nitrophenolate anion between micelles, or due to the exchange interaction between the p-nitrophenolate anion with Br- anion, reducing a micelles charge and shaping long associates.

It may be so, that the toxic action of O-p-nitrophenyl-O,O-dimethyltiophosphate is connected with changing a size and form of biostracture also.

VIII , , 2007 SELF-ASSEMBLIES BASED ON WEDGE SHAPED DERIVATIVES OF BENZENE SULFONIC ACID Bakirov A.V.a, Shcherbina M.A.a, Yakunin A.N.a, Xiaomin Zhub, Beginn U.b, Mller M.b, Chvalun S.N.a a Karpov Institute of Physical Chemistry,Vorontsovo Pole 10, 103064 Moscow, b Institute of Technical and Macromolecular Chemistry, RWTH Aachen, Germany To study general principles of self-assembling of smart materials sensitive to various stimula like temperature, pressure, electric or magnetic fields, pH of the solvent etc. the different salts of ben zene sulfonic acid were studied. The examples of caesium 2,3,4- and 3,4,5- tris(dodecyloxy)ben zenesulfonate salts are shown below (Fig. 1).

H3C(CH2)11O H3C(CH2)11O H3C(CH2)11O H3C(CH2)11O SO3Cs H3C(CH2)11O SO3Cs H3C(CH2)11O Fig. 1. Chemical structure of studied derivatives caesium salts of benzene sulfonic acid Compounds with different ions and symmetry of molecular wedges were investigated using WAXS, SAXS, DSC and TOPM methods. To stabilize obtained functional materials due to chemi cal cross-linking the compounds with methacryloyl groups at the end of tails were synthesized.

Comparative X-ray studies of sodium and caesium tris(dodecyloxy)benzenesulfonate with dif ferent symmetry reveal the ordered columnar phase 0h with mesogenes arranged in cylinder struc tures. Heating of the samples led to the transition to disordered columnar phase hd. The analysis of X-ray scattering in small and wide angles by oriented fiber led to conclusion that order-disorder transition is a cooperative process consisting of melting of alkyl tails and mesogene groups and is accompanied by a sharp contraction in the column diameter. The value of this decrease is remark able about 10-25% depending on the type of the ion and attachment of alkyl tails, probably due to the shutting of channel in central part of columns. It is important to underline the order-disorder transition is reversible and rather fast process (it takes a several minutes usually). Thus the synthe sized material can be used as a smart ion selective membrane or a nanoactuator.

Depending on type of ions and its connection in focal point a wide variety of phases could be ob served, including 2D columnar hexagonal ordered and disordered, cubic and monoclinic mesophases, layers structures and 3D crystals.

The financial support by the BMBF (funding 05-03-32904) References 1. Zhu X., Scherbina M.A., Bakirov A.V., Gorzolnik B., Chvalun S.N., Beginn U., Mller M. Methacrylated Self Organizing 2,3,4-Tris(alkoxy)benzenesulfonate a New Concept towards Ion Selective Membrane // Chem. Mater.

2006. V.18. (19). PP.4667-4673.

2. Beginn U., Yan L., Chvalun S.N., Scherbina M.A., Bakirov A., Mller M. Thermotropic Columnar Mesophases of Wedge-shaped Benzene Sulfonic Acid Mesogens // Liquid Crystals. In press.


A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str., 8, 420088, Kazan, Russia The construction of new polymer materials for the application in photonics and optoelectronics at tracts significant attention of the researchers during two last decades1. In this connection the key problem is the translation of microscopic non-linear optical (NLO) response, exhibited by the or ganic chromophores incorporated with the polymer, into the macroscopic NLO activity of the mate rial. The present day research in this field is associated with the search for the specific supramolecu lar arrangement of the chromophores favoring the predefined physical properties2, namely, the sec ond harmonic generation (SHG) or electro-optic (EO) modulation. In case of the 2nd order NLO ma terials the design of non-centrosymmetric material with optimized orientation of the chromophores is needed to avoid cancellation of the non-linear susceptibility. The formation of supramolecular structures, in particular through hydrogen bonding, appears to be a promising way of maximizing the second-order NLO responses.

We have used a number of approaches based on quantum chemical calculations of molecular hy perpolarizabilities to study the molecular arrangement of chromophores through the formation of hydrogen bonds. The effect of dielectric medium was modeled by the interaction with the solvent, clusters of different structure being analyzed. The effect of environment on the formation of mo lecular associates is studied by the example of a prototype NLO chromophore p-nitroaniline (PNA).

The quantum-chemical calculations of chromophore electric properties (dipole moments, polariza bilities and first hyperpolarizabilities) are performed at the nonempirical TDHF/aug-cc-pVDZ level3, the continuum approach in the framework of Polarizable Continuum Model (PCM) was ex ploited to study the solvent effect on (hyper)polarizability. The account of the specific solute solvent interactions via the hydrogen bonds formation was examined in the framework of the su permolecule approach3. To study the total effect of the medium the semicontinuum approach, ac counting explicitly the interaction between PNA and solvent molecules and treating the bulk solvent as a continuum, was used.

To study the effect of the conformation of the bearing chain on the NLO properties of the chro mophore we have performed Monte-Carlo Conformational Search and Molecular Dynamics simula tions of the molecular systems based on bisphenol-A diglycidyl ether with PNA chromophore in the bearing chain4. The mutual arrangement of chromophores and its influence on the electric proper ties of the molecular system are analyzed.

References 1. Nonlinear Optical Effects and Materials, (Ed.: P. Gnter), Springer, 2002, p.

2. J.M. Lehn, Angew. Chem. Int. Ed. 1990, 29, 1304.

3. M.Yu. Balakina, O.D. Fominykh Int J Quant Chem 2007, 107 (in press).

4. M.Yu. Balakina, O.D. Fominykh, F. Rua, V. Branchadell Int J Quant Chem 2007, 107 (in press).


THE MELTING POINTS OF ION LIQUIDS AND STABILITY CONSTANTS OF SUPRAMOLECULAR COMPLEXES Baskin I.I.a, Zhokhova N.I.a, Varnek A.b, Kireeva N.b, Tetko I.V.c, Solovyov V.P.d a Department of Chemistry, Moscow State University, Leninskie Gory 1/3, 119992 Moscow, Russia b Laboratoire dInfochimie, UMR 7551 CNRS, Universit Louis Pasteur, 4, rue B. Pascal, Strasbourg 67000, France c Institute of Bioorganic Chemistry and Petrochemistry, Kiev, Ukraine d Institute of Physical Chemistry, Russian Academy of Sciences, Leninskiy prospect 31a, 119991 Moscow, Russia The need of creating new materials based on supramolecular complexes and nanomolecular struc tures necessitates the development of computational approaches capable of predicting various prop erties depending on the stability of intermolecular interactions and molecular recognition. Along with the molecular modeling approaches, the methods of chemoinformatics based on statistical processing of databases containing relevant experimental data start to play an important role in this field nowadays.

In this study, a big battery of modern machine learning approaches, ranging from traditional multiple linear regression up to advanced types of artificial neural networks and kernel-based sup port vector machines, in conjunction with the use of various types of molecular descriptors, ranging from easy-to-compute graph-topology based fragmental descriptors and topological indices up to 3D descriptors, was applied to study the ability of these methods to predict properties depending on intermolecular interactions. The case studies included predicting the melting points of ion liquids and the stability constants of crown ether complexes with several metals as well as the stability con stants of host-guest inclusion complexes of organic ligands with beta-cyclodextrines. For the case of the melting points of ion liquids, which play an important role in modern green chemistry technologies and for which this property is an important technical parameter, several tested ap proaches have demonstrated comparable performance limited by the reproducibility and the com plexity of the solid-liquid phase transition phenomenon. Machine learning methods have also shown good performance in predicting stability constants of crown-ether and beta-cyclodextrine complexes.

This works was carried out in the framework of ARCUS Alsace Russia/Ukraine project.

References 1. A. Varnek, N. Kireeva, I. V. Tetko, I. I. Baskin, V. P. Solov'ev, J. Chem. Inf. Mod. 2007, 47, ASAP article.

2274 VIII , , SYNTHESIS, STUDYING OF THE PROPERTIES OF NEW POLYMERIC SORBENTS ON THE BASIS OF THE PHOSPHORYL-CONTAINING COMPOUNDS Baulin V.E.a, Turanov A.N.b, Karandashev V.K.c, Ermakov A.I.d a Institute Physiologically Active Compounds of the RAS, Chernogolovka, Moscow Region b Institute of Solid State Physics of the RAS, Chernogolovka, Moscow Region c Institute of Microelectronics Technology and Highly Purity Materials of the RA S, Chernogolovka, Moscow Region d The State unitary enterprise Moscow scientifically production association Radon baulin@phyche.ac.ru One of perspective directions of practical use of results of scientific development is reception of polymeric sorbents which can be used at realization of ecological monitoring of an environment.

For the definition of the majority of the most radiotoxic elements (90Sr, 210Pb, 210Po, isotopes ra dium and plutonium) use methods and -spectrometry. Thus a determining stage for a technique of the analysis as a whole is concentration of isotopes of defined elements with simultaneous dump in natural and stirring elements. The analysis of tendencies of development of modern analytical methods of ecological monitoring shows, that the most effective technology for concentration of determined elements is use of effect of the quest-host linkage by means of a selective complex agents of various structure. It is known, that phosphoryl-containing compounds are capable to bind effectively and selectively ions of various metals, and by experts in the field of chemical design are developed the convenient methods of the synthesis as of the elementary compoumds (tributyl phos phate), and compounds with enough complex structure (phosphoryl-containing crown-ethers).

Within the limits of the present work with use of various technologies a number of sorbents by ad sorption on a neutral polymeric matrix (PAN) phosphoryl-containing compounds I-III are received.

O O O O O PO O P P O O O P O II III I The choice of phosphoryl-containing compounds for use in sorbents was made on the basis of preliminary experiments on liquid extraction. Dependence of physical and chemical properties of received sorbents on conditions of their reception (ultrasonic and the microwave influence, intro duction of ionic liquids, speeds of addition of reagents) is investigated.

VIII , , 2007 DNA-SURFACTANT COMPLEX IN MIXTURES OF ALCOHOLS AND WATER Bilalov A.a, Leal C.b, Lindman B.b a Physical and Colloid Chemistry, Kazan State Technological University, K.Marxa str., 68, Kazan 420015, Russia b Physical Chemistry 1, Center of Chemistry and Chemical Engineering, University of Lund, POB 124, Lund 22100, Sweden Polyelectrolyte-surfactant complexes represent a class of materials formed noncovalently by self assembly, and possessing nanoscopic order. These materials often exhibit a rich phase behavior, and, by changing temperature, charge density, hydrophobic content, etc., polyelectrolyte-surfactant complexes can be tailored to better realize certain macroscopic properties. In addition to the funda mental interest in the principles governing phase behavior, aggregation, and precipitation of polye lectrolyte-surfactant mixtures, understanding the behavior of these complex systems is crucial for technological applications concerning detergents, paints, shampoos, cosmetics, and others. When biopolymers such as DNA or proteins are associated with surfactants, then novel biotechnological applications such as DNA protection and purification, drug, and nonviral gene delivery become possible.

The primary objective of this work was to investigate and understand the self-assembly behavior of a DNA-cationic surfactant complex in mixtures of n-alcohols and water. The phase diagrams were established and the different regions of the phase diagram characterized with respect to micro structure by 2H NMR, small-angle X-ray scattering (SAXS), and other techniques. The DNA-DTA (dodecyltrimethylammonium) surfactant is soluble in all of the studied alcohols, showing increased solubility from decanol down to ethanol. Different liquid crystalline phases are observed when wa ter is added to DNA-DTA/n-alcohol solutions. The liquid crystalline region (LC) is located in the center of the phase diagrams, and the LC area becomes more extended for alcohols with shorter chain length. The samples in this area have a solidlike morphology and show strong optical bire fringence. For higher n-alcohol contents, the liquid crystalline phase appears to be of the reversed hexagonal type for all of the studied systems. For the part with lower alcohol content, lamellar phases are encountered. There is a coexistence of the two LC phases on the transition from the la mellar phase to the hexagonal phase. In this region, the 2H NMR spectra display two splittings of different width, one for each LC phase. For samples on the same tie-line, the magnitudes of the splittings remain nearly unchanged, while the intensities of the peaks for the lamellar and the hex agonal splitting change;

this is a good indication of the correctness of the phase diagram. We inves tigated the role of the alcohol as cosolvent or cosurfactant by measuring the variation of the inter layer distance as the alcohol content was added. Ethanol acts as a cosolvent, while higher alcohols function as cosurfactants. The effect of salt in the LC region was studied for the DNA DTA/decanol/water system. Increasing the ionic strength in the water component of the mixture causes an increase in the unit cell dimensions of both the hexagonal and the lamellar phases. Add ing salt loosens the DNA aggregate due to electrostatic screening. Furthermore, we observe the oc currence of mixed lamellar and hexagonal phases at high salt content. When we go from the ternary mixtures with decanol, octanol, and hexanol to the DNA-DTA/butanol/water mixtures, major dif ferences in the phase behavior start to arise. The phase diagram is more complicated, and there is an occurrence of a new phase denoted by S. This phase region is very small and has many characteris tics of the disordered sponge (L3) phase often found in simple surfactant systems.

2276 VIII , , NEW TYPE OF STRUCTURAL ORGANIZATION OF COMPLEXES OF CALIXSALENES AND THEIR REDUCED ANALOGUES WITH TRANSITION METALS Borisova N.E.a, Reshetova M.D.a, Khrustalev V.N.b, Aleksandrov G.G.c, Ustunuyk Yu.A.a, Eremenko I.L.c a M.V. Lomonosov Moscow State University, Chemistry Department,Moscow, E-mail Boris ova.Nataliya@gmail.com b A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow c N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, e-mail: ilerem@igic.ras.ru The ability of macrocyclic azomethines to form polynuclear complexes in which ions of metals enter into an inner cavity of macrocyclic ligand is well-known. We have shown that macrocyclic Schiff bases are capable of forming complexes of other type also. The reaction of 1 with salts of a palladium or nickel leads to formation of complexes in which metal ions OH HN N do not enter into a cavity of calixsalene. Bonding of metal ions with ni trogen atoms of NH-groups of two molecules (fig. 1) led to dimer forma- NH OH N tion in which macrocycles have bowl-like conformation. In turn, dimers are joined into a network of crossed supramolecular tubes due to stacking interactions between phenyl rings of o-phenylenediamine units. The walls of the mentioned tubes are formed by hydrophobic organic ligands. Metal atoms and molecules of water located in the internal hydrophilic cavity of the molecule (fig.1). The array of hydrogen bonds between NH-groups hydroxy-groups and water molecules is observed inside the hydrophilic cavity. Two chlorine atoms are hydrogen bonded to phenolic hydroxy-groups also. The reduced analogues of calixsalenes also are capable of forming polynuclear complexes of similar type. Taken in concert, these results illustrate the potential versa tility of the new type of the structural organization of the calixsalene complexes.

Cl 3 Pd N Cl O O2 3 O Cl N10 Pd N Cl Fig. 1. Perspective views of a tubular palladium complex (L2 (PdCl2) 2) according to X-Ray data The RFBR are gratefully acknowledged for financial support (project 05-03-32684).

VIII , , 2007 SUPRAMOLECULAR D-A COMPLEXES ON THE BASIS BISCROWNAZOBENZEN AND DI(AMMONIOALKYL) VIOLOGEN ANALOGUES Botsmanova A.A.a, Vedernikov A.I.a, Kuzmina L.G.b, Howard J.A.K.c, Basok S.S.d, Alfimov M.V.a, Gromov S.P.a a Photochemistry Center the Russian Academy of Sciences, Moscow, Russia b Institute of General and Inorganic Chemistry the Russian Academy of Sciences, Moscow, Russia c Chemistry Department of Durham University, Durham, UK d Physicochemical Institute of the NAS, Odessa, Ukraine Supramolecular D-A complexes 3 between acceptors 1 (viologen and di(ammonioalkyl) derivatives of viologen analogues) and. bis(18-crown-6)azobenzene 2 were studied using absorption, lumines cence and 1H NMR spectroscopies, and X-ray diffraction.

A K 1+ N N A A N N + N N+ + + O A H 3N (CH2 ) (CH2) NH n n_ + + O O N N O 4 ClO 1, n = 2, 3 N O O O N O O O O + + N N O The complex formation between 1 and 2 is found to be driven by three principal factors: (1) the main contribution to the thermodynamic stability is made by host-guest bonding between the crown ether units of 2 and the ammonium groups of 1;

(2) through-space interactions between acceptors and donors 2 provide an additional contribution to the stability;

(3) geometrical correspondence components. The spatial structure of the highly stable bimolecular complex 3 was established, this confirmed its double-decker structure in which the ammonium groups of the acceptor molecule are involved in host-guest complexes with the crown-ether fragments of the azobenzene molecule and their conjugated fragments are arranged one above another.

This work was supported Russian Foundation for Basic Research, the Royal Society, Russian Academy of Sciences.

2278 VIII , , CHEMICAL MODIFICATIONS OF SIRNA Chernolovskaya E.L., Kabilova T.O., Kruglova N.A., Vlassov V.V.

Novosibirsk 630090, Lavrentiev ave., 8, Inatitute of Chemical Biology and Fundamental Medicine SB RAS Small interfering RNAs (siRNA) are considered as potent agents for specific gene silencing. Based on small interfering RNAs and their chemically modified analogous the inhibitors of MDR1 and myc genes were developed. It was demonstrated, that silencing of c-myc and N-myc expression by siRNAs and dsRNAs resulted in inhibition or even arrest of proliferation of human carcinoma and neuroblastomas. Anti-MDR1-siRNAs were found to inhibit expression of target gene and to reverse multiple drug resistance phenotype of cancer cells. The developed siRNA induce death of cancer cells in the presence of 30-times lower concentrations of cytostatics than well tolerated before.

Mapping of nuclease-sensitive sites in siRNAs in the presence of serum revealed that the degrada tion of siRNA occurs predominantly via cleavage of UpG, CpA and UpA sites by endonucleases. It was found that modification of these sites by 2-O-methyl-analogous of rybonucleotides considera bly enhances nuclease resistance of siRNA. Random substitution of the same or even greater num ber of rybonucleotides with the modified analogous increases the melting temperature of the du plex, but do not enhance the siRNA nuclease resistance. Modification of the sensitive sites only slightly reduces the silencing activity of siRNA and greatly increase the duration of silencing effect.

The obtained data allow us to formulate the algorithm for addressed modification of siRNA which provide highly efficient siRNA causing long-lasted silencing effect.

We applied the algorithm of modification to the fork-like siRNA (with 4 and 1 substitution in sense strand) and siRNA with weakened center, which contain 3 GU pair instead of GC (the sub stitution was made in antisense strand of siRNA). The data demonstrate that the modification effi ciently protects imperfect duplexes from nuclease degradation. siRNA with 4 unpaired bases at 5` end of antisense strand and siRNA with weakened center exhibited the highest silencing activity especially at lower concentrations compared to both 2-O-methyl modified siRNA with classical structure and to unmodified siRNA.

New technology for regulation of gene expression based on siRNA gives opportunity to develop the therapeutics for differentiation therapy of cancer and pharmacological control of disease-related genes.

This work was supported by Russian Academy of Sciences (programs Molecular and cellular bilogy, Sciences to Medicicne) SB RAS (integration grant No. 5.10) and INTAS (grant INTAS/SBRAS No. 06-1000013-9117).

References 1. E.B. Logashenko, et all., DAN, chemical serias, V.386, No. 2, P. 274-276.

2. E.B. Logashenko, et all., Nucleosides, Nucleotides & Nucleic Acids, 2004, V. 23, N. 6-7, P. 861- 3. T.O. Kabilova, et all. Nucleosides, Nucleotides & Nucleic Acids, 2004, V. 23, N. 6-7, P. 867-872.

4. Kabilova T.O., et all., Oligonucleotides, 2006, 16, 15-25.

5. E.B. Logashenko, et all., Rus Chem Bull, 2006, No. 7, P. 1227-1235.

6. Kabilova T.O., et all., Annals of NY Acad. of Sci., 2006, V. 1091, P. 425-236.


Photochemistry Center, Russian Academy of Sciences, 7A Novatorov str., Moscow 119421, Russia E-mail: dmitrieva@photonics.ru Of particular interest from the standpoint of using crown fragments in photosensitive ligands are those crown compounds in which the nitrogen atom occurs in conjugation with the chromophore.

These azacrown compounds absorb at markedly longer wavelengths than crown ether derivatives.

Currently, phenylazacrown ether derivatives are most widely used for these purposes;

however, they suffer from a substantial drawback, in particular, their complexation constants with metal ions are relatively low. In this respect, benzoannelated derivatives of azacrown ethers can have substan tial advantages.

The new strategy we develop for the synthesis of functional derivatives of azacrown ethers in which nitrogen is conjugated with the benzene ring by stepwise transformation of readily available benzocrown ethers is a promising alternative to the existing methods of synthesis of 1-aza-2,3 benzocrown ethers.

R O O O N O O O O X X O O n n n = 0-2;

X = CHO, NO2;

R = H, Alkyl The stability constants of complexes formed by N-methylbenzoazacrown ethers and their struc tural analogues with alkali metal, alkaline-earth metal, and ammonium cations were determined by H NMR titration in CD3CN. High stability of complexes of N-methyl derivatives of ben zoazacrown ethers is demonstrated, comparable with or even exceeding the stability of ben zocrown-ether complexes and markedly exceeding the stability of complexes of phenylazacrown ethers with the same macrocycle size. The structures of azacrown ethers and their complexes with Ba(ClO4)2 were studied by X-ray diffraction. A high degree of pre-organization of N methylbenzoazacrown ethers toward the formation of complexes with metal and ammonium cations was noted, which is due to the clear-cut pyramidal geometry of the nitrogen atom and the orienta tion of the lone electron pairs of most heteroatoms towards the center of the macroheterocycle.

Promising characteristics of the N-methylbenzoazacrown ethers as ligands for Group I, II metal cations and ammonium ions and the arrangement of the nitrogen atom in the para-position of the formyl or nitro group in the benzene ring allow one to predict their use in effective optical molecu lar sensors.

This work was financialy supported by the Russian Foundation for Basic Research, the Russian Academy of Sci ences, and the Royal Society of Chemistry.


Photochemistry Center of Russian Academy of Sciences, Novatorov str., 7a, Moscow, 117421, Russia;

dobmarina@mail.ru Azacrown-ethers are of great interest as sensors on metal cations, therefore they may be used in chemical analysis, monitoring of environment, medicine1. Azacrowns have intermediate complexat ing properties between oxygen crown-ethers formed strong complexes with alkaline and alkaline earth metal cations, and cyclames formed complexes with heavy metal cations. Modification of ionophore by means of addition of N-substitutes enables to increase stabilities of complexes of such substances with metal cations and their selectivity in comparison with similar crown ethers2. Inves tigation of complexing properties of benzodiaza-15-crown-5 ether derivatives 1-3 in presence of different metal cations is the purpose of this work.

R' 1: R= HCO, R'= Me N O 2: R= H, R'= (CH2)5COOH O O R N 3: R= HCO, R'= CH2COOH R' The stability and composition of complexes of benzodiazacrown-ether derivatives 1 and 2 with metal cations of different nature was studied by potentiometric titration in water. The measurements showed that compound 1 forms different complexes of medium strengths with Ag+, Pb2+, Cu2+, Cd2+, Ni2+ and Mg2+. Substitution of Me-group of ligand 1 on (CH2)nCOOH leads to increasing sta bilities of complexes with metal cations due to additional binding of cation by carboxyl side arms (compound 2). The results reveal that ligands form no complexes with calcium and barium ions in water.

The stability constants of complexes of compound 3 with europium (III) cation in water were de termined. The results obtained was used for study of catalytic activity of Eu3+ complexes in bis(p nitrophenyl)phosphate hydrolysis.

This work was supported by RFBR (Projects 05-03-32268 and 06-03-32899) and Federal Agency on Science and Innovations.

References 1. E. Blasius, P.G. Maurer. Makromol. Chem., 1977, 178(3), 649-657.

2. K.E. Krakowiak, J.S. Bradshaw, D.J. Zamecka-Krakowiak. Chem. Rev., 1989, 89, 929-972.

VIII , , 2007 NEW N-(4-BENZO-15-CROWN-5)-2-(AMINO-N-TOSYL)-PHENYLALDIMINE COMPLEXES: STRUCTURES AND ION SELECTIVE PROPERTIES Dorokhov A.V.a, Chernyshov D.Yu.b, Burlov A.S.c, Garnovskii A.D.c, Minacheva L.H.d, Sergienko V.S.d, Ivanova I.S.d, Aslanov L.A.e, Chernyshev V.V.ae, Tsivadze A.Yu.a a A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Moscow, Russia b ESRF, BP 220, F-38043, Grenoble CEDEX, France c Department of Organic Chemistry, Rostov State University, Rostov-on-Don, Russia d N.S. Kurnakov Institute of General and Inorganic Chemistry, Moscow, Russia e Department of Chemistry, Moscow State University, Moscow, Russia New complexes of N-(4-benzo-15-crown-5)-2-(amino-N-tosyl)phenylaldimine (HL) with transition metals (Zn, Cu) and LiNCS have been synthesized. The crystal structure of CuL2 and LiNCSHL has been determined from the synchrotron powder diffraction data and the crystal structure of ZnL from XRD data. A comparison of CuL2 and ZnL2 shows different conformations of the crowns in each molecule in the crystalline state. Even the two crowns in two ligands of CuL2 have different conformations.

Potentiometric selectivity measurements for HL, ZnL2 and CuL2 in the plasticized polyvinyl chloride membranes have been carried out. HL, ZnL2 and CuL2 was found to demonstrate signifi cant differences in their selectivity:

HL: Pb2+Ag+K+Rb+Cu2+NaCs+Sr2+NH4+ ZnL2: Ag+Pb2+K+Cu2+Rb+Cs+Ba2+Na+NH4+ CuL2: Cu2+K+NH4+Na+RbCs+Pb2+Ba2+Ag+.

To understand why the conformations of CuL2 and ZnL2 in the solid state are different and to es timate their probable geometries in a solution we have carried out a computational investigation of these complexes by DFT (density functional theory) using the X-ray structures as input geometries (fig. 1).

The most important distinction of ZnL2 from the CuL2 complex is the almost perpendicular ori entation of the two mean planes of the ligands L, with a dihedral angle of 89 (68 for CuL2). The value of this dihedral angle defines the dimensions of the access area, where an ion has an oppor tunity to bind to the macrocycle without steric obstacles the closer to 90 the larger the access area. If this assumption is valid, the potentiometric selectivity constants kpotPb2+/ion for ZnL2 are to correspond with those for HL, which has a maximal possible access area, and experimental meas urements of transport properties in PVC membranes show this tendency.

Fig. 1. The comparative plots of ZnL2 (a), CuL2 (b) and LiNCSHL (c) geometries after DFT op timization (grey) and as taken from the crystal structure (black).

2282 VIII , , ARYLFERROCENES AND COMPLEXES OF GOLD AS BUILDING BLOCKS IN DESIGN OF NEW LIQUID CRYSTAL MATERIALS Dyadchenko V.P.a, Makarov M.V.a, Belov N.M.a, Lemenovskii D.A.a, Bruce A.E.b, Bruce M.R.M.b, Lysenko K.A.c, Antipin M.Yu.c a M.V.Lomonosov Moscow State University, Department of Chemistry, Russian Federation, 119992, Moscow, Leninskie Gory, 1-3.

b University of Maine, Department of Chemistry, Orono, Maine, ME 04469-5706, USA c A.N.Nesmeyanov INEOS RAN, Russian Federation, 119991, Moscow, Vavilova, 28.

This report deals with investigations aimed at development of new family of mesogens based on polyphenylene derivatives of ferrocene.

As building blocks for these mesogens we used frameworks of ferrocenylbiphenyl and terphenyl.The design of new mesogens containing ferrocene, is based on three strategically variable sites of the molecule, i.e.: 1) number of phenylene fragments (n);

2) a substituent (R) in second cyclopentadienyl ring of ferrocene moiety;

3) bridging group (Z) which connects additional struc tural fragments to polyphenylene core.

Z OCnH2n+ n Fe R Coordinated gold(I) atom was used as such a bridge (Z) in the research besides traditional or ganic groups. The introduction of gold in the molecule gives an additional factor for organization of structure: so-called aurophilic interactions which lead to short contacts between gold atoms of neighbor molecules.

An investigation of thermal behavior of the synthesized compounds by POM and DSC metods revealed that an ability of these compounds to exist as LC is determined significantly by the number of phenylene moieties incorporated in calamitic fragments of the molecules. The best (on the ba sis of POM and DSC) characteristics are revealed by ferrocenyl derivatives of terphenyl. When al kyl group in second cyclopentadienyl ring of ferrocene is present, the transition temperature drops in comparison with non-substituted compound. More long being the alkyl chain more significant is the drop of transition temperature.

Stacking interactions and chain structures which include gold atoms and ferrocenyl groups were detected in crystals of the synthesized compounds. These structural factors together with reversible red-ox transformations, inherent in gold and ferrocene, make compounds of this type perspective for a creation of new anisotropic conducting materials.

This research was carried out with the financial support from NSF grant No. CHE-9810077.

References 1. M.V.Makarov, D.A.Lemenovskii, A.E.Bruce, M.R.M.Bruce, V.P.Dyadchenko, Liquid Cryst., 2006, 33, 485.

VIII , , 2007 POLYPYRIDYL RUTHENIUM(II) COMPLEXES AS ANTENNA FRAGMENTS FOR SUPRAMOLECULAR SYSTEMS Ershov A.Yu.a, Litke S.V.b a Institute of Chemistry of St. Petersburg State University, 198904 St. Petersburg, Petergof, Universitetskii pr. b Institute of Physics of St. Petersburg State University, 198904 St. Petersburg, Petergof, Ulianovskaya ul. To build up a polynuclear photocatalitic systems is important to get a photostable separate antenna fragments possessing intensive absorption bands for a visible part of the spectrum and a long-lived excited states. Polypyridyl ruthenium(II) complexes are of great interest in the study of excited state redox and sensitization processes due to the low-lying metal-to-ligand charge transfer (MLCT) ex cited states. Some of these complexes have relatively high luminescence lifetimes and quantum yields so that they present interesting opportunities as building blocks in the design of photochemi cal molecular devices. The lifetime of the lowest 3MLCT excited state of these complexes is dra matically limited by ligand field states (3dd). Thermal population of the 3dd states from 3MLCT state leads to fast nonradiative decay or photochemical decomposition of the complexes and, as the result, the efficiency of electron or energy transfer from the antenna-fragment is decreased1.

Photochemical stability is one of the most important properties of mono- and polynuclear com plexes to be used in photocatalytic supramolecular systems for solar energy conversion. With a goal to elaborate attractive photocatalitic systems based on polypyridyl ruthenium(II) compounds the influence of different ligands on the spectral-kinetic characteristics and photochemical behavior of the following mixed-ligand complexes have been analyzed and discussed: cis-[Ru(bpy)2(L)Cl]+, bpy= 2,2-bipyridyl;

L= NH3, 4-substituted pyridines (py-Y, Y= H, Me, Ph, NH2,CN, COOH), pyrazine (pyz),2,4 PR3 (R= Et, Ph, OPh);

and cis-[Ru(bpy)2(L)(X)]n+, L= 4,4-bipyridyl (4,4-bpy) and PPh3;

X= Cl-, Br-, NCS-, NO2-, CN-, NH3, MeCN. The linear correlation between the lumines cence energy of the complexes and the pKa value of the ligands is found. The results are discussed in terms of the electronic structures and the excited state energy scheme of the complexes. Different possibilities for population of the 3dd state are also examined.

The published5 and the last obtained results on intramolecular energy transfer in unsymmetrical binuclear ruthenium(II) complexes [Cl(bpy)2Ru(BL)Ru(bpy)2(NO2)]2+ with the bridging ligands BL= pyz, 4,4-bpy, trans-1,2-bis(4-pyridyl)ethylene, trans-1,2-bis(4-pyridyl)ethane, trans-1,2 bis(diphenylphosphino)ethylene and 1,2-bis(diphenylphosphino)- ethane are discussed also. On the basis of low temperature (77K) luminescence lifetime and quantum yield measurements in EtOH MeOH (4:1) glasses the radiative and nonradiative rate constants for deactivation of the lowest ex cited state are determined. It was founded out that the introduction of phosphines in the coordina tion sphere of the complexes increase the energy of the lowest singlet and triplet charge-transfer states d(Ru) *(bpy) and decrease the rate of nonradiative decay of the lowest excited state of the complexes. Polypyridyl ligands with donor substituents, CN- and diphosphine ligands suit better for ruthenium(II) building blocks as efficient antenna fragment for supramolecular systems.

References 1. J.H. Alstrum-Acevedo, M.K. Brennaman, T.J. Meyer, Inorg. Chem. 2005, 44, 6802.

2. A.Yu. Ershov, A.D. Shashko, O.V. Sizova, N.I. Ivanova, Russ. J. of General Chemistry 2002, 72, 1327.

3. A.Yu. Ershov, A.D. Shashko, O.V. Sizova, et all. Russ. J. of General Chemistry, 73, 135.

4. S.V. Litke, T.V. Mezentseva, G.N. Lyalin, A.Yu. Ershov, Optics and Spectroscopy 2003, 95, 917.

5. S.V. Litke, T.V. Udalova, G.N. Lyalin, A.Yu. Ershov, Optics and Spectroscopy 2005, 99, 905.

2284 VIII , , ELECTROCHEMICAL SOLID-CONTACT SENSORS BASED ON THIACALIX[4]ARENE DERIVATIVES Evtugyn G.A.a, Stoikova E.E.a, Belyakova S.V.a, Shamagsumova R.V.a, Budnikov H.C.a, Stoikov I.I.b, Antipin I.S.b a Analytical Chemistry Department of Kazan State University, 420008, Kazan, Russian Federation b Organic Chemistry Department of Kazan State University, 420008, Kazan, Russian Federation Thin-film electrochemical sensors for potentiomeric and amperometric determination of transient metal ions and organic acids have been developed. Prior to deposition of synthetic receptors based on thiacalix[4]arene platform, the electrodes were coated with poly-ionic materials obtained by electropolymerization (polyaniline, polymeric phenothiazine dyes) or by deposition from organic solvent (Nafion). It was shown, that these materials provided high reproducibility and stability of main electrochemical characteristics of the sensors as well as reversibility of the response toward the analyte. On the example of thiacalix[4]arene conformers with morpholide, hydrazide, pyridine and pyrrolidine fragments (see Figure), the influence of the substituents and receptor conformation on the selectivity of transient metal ions complexation was investigated. The comparative investiga tion of extraction of silver ions and interfering metals and of the sensor characteristic made it possi ble to estimate the contribution of steric factors to the selectivity of the sensor signals.

S S S S S S S S S S S S O OO O O OO O O OO O O O O O O O O O O N NH NH N HN HN O O O N HN HN N NH NH NH NH N NH N NH N N Novel methods for potentiometric determination of silver ions in the presence of 1000-100 000 fold excess of Cu(II), Cd, Pb, alkali- and alkali-earth metal ions, 10-1000 fold excess of Fe(III) and Hg(II) ions were suggested. Potentiometric sensor array consisted of two or three receptors with different individual selectivity toward the analytes was successfully used for simultaneous determi nation of two or three metal ions. As was shown, the sensor response can be predicted using mathematical discrimination methods including artificial neural nets and principal component analysis. EDTA, citric, malic and oxalic acids were determined in accordance with their effect on the interaction of Fe(III) and Ag ions with thiacalixarene investigated.

Financial support of Russian Foundation for basic research (grant 04-03-97511-r ofi) and REC-007 is gratefully ac knowledged.

VIII , , 2007 THE FORMATION OF TERNARY COMPLEXES POLYPYRIDINE-ION LANTHANIDES-P-SULFONATOTHIACALIX[4]ARENE IN AQUEOUS SOLUTIONS Fedorenko S.V., Mustafina A.R., Zairov R.R., Ucharova A.U., Konovalova O.D., Gubaidullin A.T., Solovieva S.E., Antipin I.S., Konovalov A.I.

Russia, Kazan, 420088, Arbuzov str., 8, A.E. Arbuzov Institute of Organic and Physical Chemistry Lanthanide complexes are a top of current interest due to their unique magnetic and optical properties, which can be used in chemistry, medicine and biol- N ogy as luminescent markers, sensors and MRI agents. The design of high luminescent system in terms of lanthanide complexes requires following N acid solution factors: 1) lanthanide ions should be shielded from SO - SO3 solvent molecules;

2) triplet level of ligands should -O3S SO3 be in agreement with emission level of metal;

3) the ligand should form kinetically and thermodynami- Ln3+ cally stable complexes. Calixarenes and their deriva- S S S tives are known as ligand, satisfying these require S OH OH ments. Many lanthanide complexes with thia- and O OH sulfonyl analogues of calix[4]arene derivatives ex hibit high luminescent properties. Moreover p sulfonatothiacalix[4]arenes and their thia- and sul- neutral fonyl analogues are of particular importance due to (alkaline) solution their watersolubility and manifold binding ability towards metal ions, organic substrates and metal complexes. Such versatile complex ability enables the inclusion of the additional ligand, which can modify luminescence properties of lanthanide complex with calixarene.

The interaction p-sulfonatothiacalix[4]arene and Ln(L)n(NO3)3 (where Ln = La, Tb, Gd(III) and L = 2,2-dipyridine (dipy), 1,10-phenanthroline (phen), 2,2:6,2-terpyridine (terpy), n = 2 for dipy and phen, n=1 for terpy) was investigated by X-ray and NMR relaxation, H1 NMR UV-VIS, lumi nescence spectroscopy in aqueous solutions. Structure of ternary complexes TCAS-lanthanide ion-L was found to be dependent on pH and stability of Ln(L)n3+. The change of pH from acidic to neutral and alkaline solutions results in the migration of lanthanide ion from sulfo- to phenolate groups of TCAS. Though all the types of TCAS-Tb(III)-L complexes exhibit pH-dependent luminescence, the inclusion of polypyridine in the cavity of TCAS exert some effect on Tb-centered luminescence.

We thank RFBR (grant N 07-03-00282) for financial support.


A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences Vavilov str. 28, 119991 Moscow, Russia. E-mail: H-Bond@ineos.ac.ru A new type of hydrogen bonding characteristic for transition metal and main group hydrides (so called dihydrogen bonding) was recently found and investigated13. Main group hydrides exem plify the potential for the application of unconventional dihydrogen bonds in supramolecular chem istry and in material design via crystal engineering. Polyhedral boron hydrides have several proton accepting centers, and can form the different types of dihydrogen bonded complexes.

The interactions of [B10H10]2, [B12H12]2, [B12H11SCN]2, [B10H9OH]2 with various OH, mono and bidentate NH (indole, pyrazole, imidazole, p-nitroanilines,) and CH (o-carborane, dichloro-o carborane) acids were analyzed by means of IR and NMR (180-290K) spectroscopy and DFT cal culations. The site of coordination for all of species studied was found to be hydride hydrogen.

Spectral, structural and thermodynamic characteristic of dihydrogen bonded complexes were ob tained. The enthalpy values (-Ho) of complexes formation were found to vary in the range 2 6 kcal/mol depending on the proton donor and hydride strength. The geometry, energy, and electron redistribution of computed structures were also analyzed. The unusual coordination of bidentate proton donors (containing NH2 and CH groups) was found. The competition between classical and non-classical coordination centres was demonstrated on examples of [B12H11SCN]2, [B10H9OH]2.

Dual reactivity of [B10H9OH]2 and carboranes as acids and bases in supramolecular compositions based on dihydrogen bonding will be discussed.

This work was supported by Russian Foundation for Basic Research (07-03-00739) and INTAS YSF (06 1000014-5809).

1. R. Coustecean, J.E. Jackson, Chem. Rev., 2001, 101, 2. L.M. Epstein, E.S. Shubina, Coord. Chem. Rev., 2002, 231, 165.

3. L.M. Epstein, N.V. Belkova, E.S. Shubina, Acc. Chem. Res. 2005, 38, VIII , , 2007 {MII4O4} (M = CO, NI) PIVALATES WITH CUBANE CORE:

THERMAL CONTROLLED SINTHESIS, STRUCTURE, MAGNETIC PROPERTIES AND SOLID-STATE THERMOLYSIS Fomina I.G.a, Dobrokhotova Zh.V.a, Aleksandrov G.G.a, Proshenkina O.Yu.a, Kovba M.L.b, Ikorskii V.N. c, Novotortsev V.M.a, Eremenko I.L.a a N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky prosp., 119991 Moscow, Russian Federation.

b Department of Chemistry, M. V. Lomonosov Moscow State University, 1 Leninskie Gory, 119992 Moscow, Russian Federation.

c International Tomography Center, Siberian Branch of the Russian Academy of Sciences, 3a ul. Institutskaya, 630090 Novosibirsk, Russian Federation Methods for the thermal target synthesis of the {MII4(3-O)4}(M = Co, Ni) pivalate clusters with heterocubane core were developed. It was found that, the interaction of pivalate polymer [Co(OOCBut)2]n or cyclic hexamer [Ni(OOCBut)2]6 with 4,5-dimethyl-1,2-phenylenediamine in EtOH or MeOH in dependence on the thermal synthesis conditions result in heterocubane {MII4(3-O)4}-clusters isostructural [MII4(3-OH)4(1-OOCCMe3)3(-(NH2)2C6H2Me2)3(1 (NH2)2C6H2Me2)3]+(OOCCMe3)-, M = Co (1), Ni (2) and [Ni4(3-OMe)4(1-OOCCMe3)(2 OOCCMe3)(2-OOCCMe3)2(2-(NH2)2C6H2Me2)2(MeOH)] (3) or isostructural mononuclear com plexes M(2-(NH2)2C6H2Me2)(1-(NH2)2C6H2Me2)2(OOCCMe3)2 (M = Co (4), Ni (5)), respectively.

It was shown, that mild thermolysis of monomers 4 and 5 in EtOH results in formation of 1 and 2, respectively. Conditions of the hydroxyl bridges substitution onto metoxide ones upon the interac tion of [MII4(3-OH)2(2-OOCCMe3)4(2-OOCCMe3)2(EtOH)4]2EtOH (M = Co, Ni) complexes with planar tetranuclear metal core and MeOH were found. The formation of known cubanes [MII4(3-OMe)4(2-OOCCMe3)2(2-OOCCMe3)2(MeOH)4] (M = Co (6)1, Ni (7)2) in this case was observed.

The X-ray single crystal diffraction analysis for all compounds synthesized and magnetic inves tigations for complexes 1, 2, 5 were performed.

The investigation of solid state thermal decomposition of complexes 1, 2, 4-7 (by DSC and TGA methods) is of big interest because the possibility to find the factors determining the thermal stabil ity of these compounds. The influence of the nature of metal centers and ligand environment onto thermal stability of complexes and phase composition of thermolysis solid products was studied.

This study was financially supported by the Russian Foundation for Basic Research (Project Nos 07-03-00408, 07 03-00707, 05-03-32767, 05-03-32794, 06-03-08086), the Division of Chemistry and Materials Science of the Russian Academy of Sciences (Target Program of Basic Research "Chemistry and Physical Chemistry of Supramolecular Sys tems and Atomic Clusters"), and the Presidium of the Russian Academy of Sciences (Programs "Molecular Design of Magnetoactive Compounds and Materials (Molecular Magnets)") and "Polyfunctional Materials for Molecular Elec tronics").

References 1. G. Arom, A. S.Batsanov, P. Christian, M. Helliwell, A. Parkin, S. Parsons, A. A. Smith,G. A. Timco, 2. R. E. P. Winpenny, Chem. Eur. J., 2003, 9, 5142.

3. G. Chaboussant, R. Basler, H.-U. Gudel, S. Ochsenbein, A. Parkin, S. Parsons, G. Rajaraman, A. Sieber, 4. A. A. Smith, G. A. Timco, R. E. P. Winpenny, Dalton Trans., 2004, 2758.


Photochemistry Center, Russian Academy of Sciences, ul. Novatorov 7a, Moscow, 119421 Russia.

E-mail: sanya@photonics.ru The absorption spectra of styryl dyes were calculated by time-dependent density functional method.

The dyes of interest were (p-dimethylamino)styrylbenzothiazolium dye and its form with a proto nated amino group as a model, different conformers of the free aza-15(18)-crown-5(6)-containing styryl dyes, and their complexes with alkali (K+ and Na+) and alkaline-earth (Ca2+ and Sr2+) cations.

The electronic and geometrical structure of the excited states producing the long-wave (*) ab sorption bands is studied.

O O O O + X N X M N M n n O O O + m m N O N R R R R X = S, R = Et, R1 = H, n = 1;

M = Na, K, Ca, Sr;

m = 1, It is found that the spectra of the free model dye and free azacrown-containing dyes virtually co incide in the long-wave region, and the conformation of the crown ether moiety has no effect on the position of the long-wave maximum. Interaction with alkali cations only slightly blue-shifts this absorption maximum. Interaction with alkaline-earth cations causes a noticeable hypsochromic shift of the long-wave absorption band in the conformers with the metalnitrogen bond. The complex conformers without metalnitrogen bond show only slight blue shift. The structure of the free model dye and the free azacrown-containing dyes changes from the "quinoid" form in the ground state to the "benzenoid" form in the excited state. The protonation of the model dye as well as the complexation of the azacrown-containing dyes with alkaline-earth cations reverses the dye structure to the "benzenoid" form in the ground state and to the "quinoid" form in the excited state.

Local effects of solvation of the cation in the macrocycle cavity are taken into account through the supermolecule approach. Microsolvation of the cation by water molecules results in the stabili zation of the complex conformers without metalnitrogen bond. These structures exhibit the absorp tion bands in the long-wave region close to the absorption bands of the free uncomplexed dye.

The possibility of the photocontrol of cation binding by such azacrown-containing dyes is stud ied.

This work was supported by the Russian Foundation for Basic Research, project nos. 06-03-32434 and 05-03 32911.

VIII , , 2007 AB INITIO STUDY OF ABSORPTION SPECTRA OF MONOMERS AND DIMERS OF CYANINE DYES Freidzon A.Ya., Vladimirova K.G., Zakharova G.V., Bagatur'yants A.A., Alfimov M.V.

Photochemistry Center, Russian Academy of Sciences, ul. Novatorov 7a, Moscow, 119421 Russia.

E-mail: kgvladi@gmail.com The geometrical and electronic structure of the 8,9-cis- and all-trans-isomers of some symmetric cyanine dyes and a series of their dimers are calculated by the density functional method (DFT).

The absorption spectra of the monomers and dimers are calculated by the time-dependent density functional method (TD DFT).

The process of cis-trans-isomerization of I, II, and IV was studied and the structures of the cor responding transition states were determined. It is found that the energies of the 8,9-cis- and all trans-isomers differ only slightly, which makes the transitions between them easy. The barrier for the cis-trans-isomerization of meso-substituted dyes I and III is lower than that of the unsubstituted dye II, in agreement with the experimental data. The potential energy curves along the intrinsic re action coordinate (IRC) are constructed for the S0, S1, and T1 states using the TD DFT method.

C2H C2H5 C2H C2H + + N N N N S S S S CH I II R R R R + + N N N N H3CO OCH S S S S C2H5 C2H III IV R = C3H6SO3, CH It is also found that only the 8,9-cis-form of the dyes III and IV with R = C3H6SO3 can form the dimers exhibiting the spectra different from the monomer spectrum. The chromophores in these dimers are stacked. It is shown that, depending on the arrangement of the monomeric units in the dimer (large or small shift in the chromophore plane), the long-wave absorption band can undergo either bathochromic or hypsochromic shift relative to the monomer. The calculated absorption spec tra qualitatively agree with the experiment.

This work was supported by the Russian Foundation for Basic Research, project 05-03-32911.

2290 VIII , , SELECTIVITY AND SUPRAMOLECULAR ORGANIZATION IN EPOXIDATION OF POLYUNSATURATED FATTY ACID BY DIOXIRANE REAGENT Grabovskiy S.A.a, Kabalnova N.N.a, Ferreri C.b, Chatgilialoglu C.b a Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71 prosp. Oktybrya, 450054 Ufa, Russian Federation.

b ISOF, Consiglio Nazionale delle Ricerche, Via. P. Gobetti 101, 40129, Bologna, Italy.

The use of dimethyldioxirane as an alternative to the classical epoxidizing agents is proposed in the case of polyunsaturated fatty acids. With fatty acid methyl esters this is a convenient method for avoiding acidic conditions, using different solvents, and simplifying the isolation procedures, with less contamination due to by-products. Moreover, it could be applied to free fatty acids in water. In this case, the supramolecular organization of fatty acids in water influenced the reaction outcome and the regioselective epoxidation of the double bonds could be achieved. The interaction of the epoxidizing agent preferentially occurred with the double bonds closest to the aqueous-micelle in terface. For the first time the preferential epoxidation of linoleic acid to 9,10-monoepoxide was car ried out with high yield and a 65% regioselectivity.

OOOO OO OO O O O O 1.8 : In the case of arachidonic acid micelles, the regioselective outcome with formation of the four possible mono-epoxide isomers was studied under different conditions. Under appropriate condi tions, it resulted to be a convenient synthesis of (R,S)-5:6-epoxy-eicosatrienoic acid, whereas in re verse micelles epoxidation mostly gave (R,S)-14:15-epoxy-eicosatrienoic acid.

Ratio of mono-epoxides in case epoxidation arachidonic acid micelles 5,6- / 8,9- / 11,12- / 14,15- 5,6- / 8,9- / 11,12- / 14,15 H2O, 0.8 eq. of oxidant CCl4, 0.8 eq. of oxidant These results can contribute to lipidomic studies of PUFA monoepoxide regioisomers and be further extended with their use as intermediates to trans lipids.

The authors thank the CNR and the RAS for the support given for the exchange visits.


Institute of Chemical Biology and Fundamental Medicine SB RAS, prospekt Lavrentieva, 8, Novosibirsk, 630090, Russia Today one of the most informative approaches to study structural and functional topography of mammalian ribosomes, whose crystals suitable for X-ray analysis remain inavailable, is affinity cross-linking. This approach is based on application of photoactivatable derivatives of oligoribonu cleotides as mRNA analogues. To investigate arrangement of mRNA binding channel of the human 80S ribosome, we used mRNA analogues that bore a Val or Phe codon and perfluorophenyl azide group attached via various linkers to the C5 atom of U, N7 atom of G or to the 5-terminal phos phate. We found that 18S rRNA neighbors mRNA predominantly in the region of the codon anticodon interactions (i.e., the A site and the P site codons). mRNA positions 3 of the A site codon are surrounded mainly by proteins;

environment of mRNA nucleotides 5 of the E site codon consists exclusively of ribosomal proteins. Nucleotides of 18S rRNA and ribosomal proteins cross linked to modified mRNA nucleotides in positions from -9 to +12 with respect to the first nucleo tide of the P site codon are identified13. Comparison of the results obtained with known data on the prokaryotic ribosome lead to a conclusion that all rRNA nucleotides neighboring mRNA form a conserved ribosomal core that is structurally similar in all kingdoms. At the same time, we found significant differences between the protein environments of mRNA on the mammalian and the pro karyotic ribosomes. First, in eukaryotes ribosomal proteins contribute much more in the formation of mRNA binding channel than in prokaryotes. Second, on the human ribosome, mRNA 5 of the E site codon neighbors mainly protein S26 that has no prokaryotic counterpart. Second, the P site and the E site codons in the 80S ribosome are surrounded with proteins S3, S6 and S26;

only one of these proteins, S3, has a prokaryotic counterpart. Finally, mRNA codon at the A site (the decoding site) of the human ribosome neighbors protein S15 whose prokaryotic orthologue is known to be located away from the 30S ribosomal decoding site. These differences may be related to the more complex mechanism of regulation of protein synthesis in eukaryotes as compared to prokaryotes.

Probably, eukaryote-specific ribosomal proteins that participate in formation of the mRNA binding channel of the eukaryotic ribosome, are targets for various regulatory factors that affect efficiency and accuracy of translation.

The work was supported by Russian Foundation for Basic Research (grant #05-04-48357-a).

References 1. D. Graifer, M. Molotkov, V. Styazhkina, N. Demeshkina, K. Bulygin, A. Eremina, A. Ivanov, E. Laletina, A.

Venyaminova, G. Karpova, Nucleic Acids Res. 2004, 32, 3282.

2. M.V Molotkov., D.M. Graifer, N.A. Demeshkina, M.N. Repkova, A.G. Venyaminova, G.G.Karpova, Molecular Biology (Moscow) 2005, 39, 999.

3. M.V. Molotkov, D.M Graifer., E.A. Popugaeva, K.N. Bulygin, M.I. Meschaninova, A.G. Venyaminova, G.G. Kar pova, RNA Biology 2006, 3, 122.

2292 VIII , , SUPRAMOLECULAR COMPLEXES OF POLYANILINE WITH POLYAMIDOSULFONIC ACIDS AND THEIR BIOLOGYCAL APPLICATIONS Gribkova O.L.a, Ivanova V.T.b, Kurochkina Y.E.b, Ivanov V.F.a, Nekrasov A.A.a, Manykin A.A.b, Vannikov A.V.a a A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, RAS Moscow, Leninskii prospect 31, Russia. Gribkova@elchem.ac.ru b D.I. Ivanovsky Research Institute of Virology RAMS Moscow, Gamaleya st. Chemical matrix synthesis of polyaniline (PAn) in the presence of polyamidosulfonic acids is car ried out to prepare their interpolymer complexes with wide spectrum of physical chemical proper ties which determine the possibilities of their application.

We have studied the matrix chemical synthesis of interpolymer complex of PAn and poly(2 acrylamido-2-methyl-1-propanosulfonic acid) (PAMPSA) and possibilities of its application in bi ology and medicine. The acceleration of aniline polymerization in the presence of PAMPSA (as compared to HCl) was observed owing to a high degree of association of aniline with the polyacid, which ensures high local concentration of aniline and hydrogen ions in the vicinity of the polyacid molecule. PAn-PAMPSA interpolymer complex is soluble in water and water-organic mixtures.

The PAn-PAMPSA films demonstrated excellent electrochemical stability and good film-forming properties1. The electron microscopic investigations revealed the formation of interpolymer com plexes with the length up to 500 nm and diameter within 30-40 nm. Besides the linear associates of these complexes with the length up to 1500 nm were observed.

It was shown that PAn-PAMPSA films in combination with nematic liquid crystals may be used for the influenza viruses detection. The crystal-like structures formed by influenza antigen-antibody complexes on the surface of PAn-PAMPSA films were first detected2.

In the report we present the study of adsorption properties of influenza A and B viruses which were isolated in 1977-2007 on PAn-PAMPSA interpolymer complex. It was shown that influenza A and B viruses interacted with this sorbent apart from the antigenic properties of surface proteins.

The immobilized viruses were able to interact with homological antibodies from immune sera. The other proteins as bovine sera albumin widely used in immunology adsorb on this sorbent as well.

The authors gratefully acknowledge financial support from the International Science and Technology Center (pro ject 3070).

References 1. V.F. Ivanov, O.L. Gribkova, K.V. Tcheberiako, A.A. Nekrasov, V.A. Tverskoj, A.V. Vannikov, Russ. J. Electro chem., 2004 40 299.

2. V.F. Ivanov, V.T. Ivanova, M.G. Tomilin, R.O. Rakutina, M.Y. Yablokov, Patent Ru 2290444, 2006.

VIII , , 2007 THE ELECTROCARBOXYLATION OF INCLUSION COMPLEXES OF -CYCLODEXTRINE WITH -HALOGENALKYLAROMATIC COMPOUNDS Grinberg V.A.a, Stepanov A.A.b, Grachev M.K.c a A.N.Frumkin Institute of Phisical Chemistry and Electrochemistry Russian Academy of Sciences, 119991, Moscow, Leninsky Prospect 31, Russia b N.A.Nesmejanov Institute of Organo-Element compounds Russian Academy of Sciences, 119991, Moscow, Vavilova str. 28, Russia c Moscow State Pedagogical University,Chemistry Department, 119021 Moscow, Nesvizski per.3, Russia The ability to form the guest host type inclusion complexes with various organic and inorganic compounds is an important feature of cyclodextrines and their derivatives characteristic of cavern ous systems. On account of this ability they have been widely used in many interdisciplinary ap plied fields1,2 and also as model systems for investigation of non-covalent interactions in processes of complex formation3. If the host molecules are optically active upon introduction of the race mate guest only one of enantiomers get principally into inclusion complex composition.

Cyclodextrine being the most known natural optically active compound able to play the host part is used for splitting of isomers.

The inclusion complexes of -cyclodextrine with halogenalkylaromatic compounds in particular -cyclodextrine/1-(4-isobuthylphenyl)ethyl chloride (I) and -cyclodextrine/2-chlorethyl-6 methoxynaphtalene (II) have been synthesized, separated and characterized.

It was found that electroreduction of the inclusion complexes (I) and (II) on glassy carbon in nonaqueous DMF occurs at potentials (approximately 100 mV and 20 mV respectively) more nega tive than electroreduction of initial 1-(4-isobuthylphenyl)ethyl chloride and 2-chlorethyl-6 methoxynaphtalene. It was shown that preparative electrocarboxylation of the inclusion complexes (I) and (II) at glassy carbon cathode using sacrificial magnesium anode in DMF results in the for mation of S-form 2-(4-isobuthylphenyl)-propionic acid (S-ibuprophen) and S-form 2-(6-methoxy-2 naphtyl)-propionic acid (naproxen) with high enantiomeric excess (~90%). The formation of dimers and hydrides from corresponding intermediately formed radicals is observed along with acids for mation.

At the formation of -cyclodextrine inclusion complexes with halogenalkylaromatic compounds S-enantiomers enter preferentially into -cyclodextrine cavity and thus upon their electrocarboxyla tion the racemization does not take place the latter explaining for high enantiomeric excess of S-ibuprophen and naproxen.

The present work has been supported by Russian Academy of Sciences in the frame of Complex program Directive synthesis of substances with assigned properties and production of functional materials on their basis.

References 1. J. Szejtli, Chem. Rev. 1998, 98, 1743.

2. A.R Hedges, Chem. Rev. 1998, 98, 2035.

3. G. Wenz, Angew. Chem. Int. Ed. Engl. 1994, 33, 803.


Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, 119991, Moscow, Leninski prospect This work deals with man-made molecular rotors from the point of view of their potential utility for molecular machinery. In accordance with real world analogues, we study their counterparts: turn stiles;





A molecular rotor consists of two parts which can rotate relative to each other. As an example we investigate theoretically the sandwichtype phthalocyanine (Pc) and porphyrine (Por) com plexes MPc2, MPor2, MPcPor. Here the rings have equilibrium staggered conformation;

the angles between them may change from 6 to 45.

Sandwich phthalocyanine complexes may be considered as redox-driven molecular rotors. The rotation results in the change of skew angle between the upper and lower Pc rings. The change of the oxidation state can also induce redox-driven elongation and contraction of the complex, as a re sult of very different distances between metal ion and the ligands in different oxidation states. So the assembly can be used as artificial muscles relaxing and contracting.

The idea of molecular gears is based on:

1) different rotation barriers for Pc, Por, and other rings;

2) different sizes of cations (for example, Ce3+ and Gd3+).

The molecular rotor capable of producing useful work is considered as molecular motor. The ro tation barrier depends on the structure of complexes. The random rotor motion has been observed for -oxosilicon phthalocyanine dimers and trimers 1. We propose the similar rotor motion in the oxo dimeric iron (III) phthalocyanine 2. The change in rotational barrier in 2 is achieved by tunabil ity of R substituents.


A PRECISE DILATOMETRIC STUDY Kartsev V.N., Shtykov S.N., Pankin K.E.

Saratov State University, Russia,410012, Saratov, Astrakhanskaya Str., E-mail: ShtykovSN@info.sgu.ru It is well-known that volumetric and compressibility studies can contribute to our understanding the intermolecular forces which govern the properties of aqueous solutions as well as solute-solute, sol ute-solvent interactions and influence of solute molecules on the structure of water network. Tradi tionally, these investigations have been focused on a small organic molecules (alcohols, amines etc.) dissolved in water. Surprisingly, the volumetric properties of aqueous solutions of cyclodex trins (CD) that can clarify to our understanding of their effect on the water structure as well as in termolecular forces, which govern the properties of the solutions, are not investigated in details and practically no publications devoted to their inclusion host-guest complexes too. The driving forces for guest incorporation into the CD cavity are hydrophobic interactions, hydrogen bonding and steric effect. The formation of inclusion complex in aqueous solutions results in a substantial rearrangement and removal of the water molecules originally hydrated to both the CD and guest molecules. Moreover, this process also induces the release of high-energy water molecules from the CD cavity into the bulk water. The cavity water molecules are entropically unfavorable because of an incomplete intermolecular hydrogen-bonding network and hence they have another properties then molecules in the bulk water1.

The aim of this work a precise dilatometric study of the aqueous solutions of 2-hydroxypropyl -cyclodextrin (2-HP--CD). Density (), isothermal compressibility (T), and thermal volumetric expansion coefficient ()2 were measured with high accuracy at the several temperatures for 2-HP -CD aqueous solutions with errors 1x10-2%, 1%, and 2%, respectively. The pressure drop P and temperature drop T amounted to 4 105 Pa and 0.4 K, respectively. The results of experiment by the example of isothermal compressibility are listed in the Table below.

Table. Isothermal compressibility (T 1011, Pa-1) of 2-HP--CD aqueous solution t, C 10 15 20 25 30 35 40 45 W* 0.51 47.0 46.2 45.0 44.8 44.4 44.0 43.5 43.8 43. 1.01 46.5 45.8 45.0 44.4 44.1 43.9 43.7 43.6 43. 5.61 45.2 44.4 43.8 43.3 42.9 42.7 42.6 42.6 42. 9.02 44.1 43.4 42.7 42.3 42.0 41.9 41.8 41.9 41. 15.24 42.4 41.7 41.1 40.6 40.3 40.3 40.2 40.3 40. 20.30 40.8 40.1 39.7 39.4 39.3 39.4 39.5 39.7 39. It was found that the hydrogen bond network does not change in the presence of 2-HP--CD molecules up the concentration of 20.30 mass%. The hydration type of 2-HP--CD was discussed.

Acknowledgements This work was supported by Federal Agency of Science, contract no. 02.513.11. References 1. A. Szafranek, J. Szafranek, J. Incl. Phenom. 1998, 30, 2. V.N. Kartsev, Russ. J. Phys. Chem. 2003, 77, 2296 VIII , , PERSPECTIVE OF THE DEPLETED URANIUM DIOXIDE APPLICATION AS AN ENGINEERED GEOCHEMICAL BARRIER Khodyakov A.A., Zakharova E.V., Proshin I.M., Ermolaev V.M.

IPCE RAS, 31 Leninsky Prospect, 119991 Moscow To justify the possibility of the depleted UO2 application as a material for the engineered geochemi cal barrier in SNF repositories one should necessarily have the data on the UO2 water permeability, on its capacity to retain the radioactive waste, the information on the UO2 structural characteristics, solubility and sorption properties.

Results of the experiments show that as time of the sample contact with water increases, the fil tration coefficient (K) of UO2 falls (see Fig.1). The decrease in K of UO2 on account of the pore space volume reduction is related to the stabilization of the UO2 leaching products (LP) in pores.

The heat impact and the ionizing radiation intensify the process of UO2 LP formation. It was found that at the boundary of the liquid (water) and solid phase (UO2 powder) the double electric layer is formed. In acidic (0.1 H) solutions the UO2 surface carry the positive charge, and in neutral solu tions the negative charge. The double electric layer binding the ions present in water decreases the pore space volume, similarly to the LP.

From the dynamic sorption experiments with 237Np (NpO2+) the working uranium dioxide bed length was determined at Lo=3.07 mm, and the unused bed length was h=1.32 mm. 99Tc (99TcO4-) is not retained by the UO2 surface but, similarly to water, is partially retained by the uranium dioxide bed due to the decrease in pore space caused by the uranium leaching. The ionizing radiation does not lead to the formation of any paramagnetic defects in UO2 samples. However it was found that UO2 sludge irradiated with electrons and gamma quanta adsorb 237Np (NpO2+) by a factor of 2- less as compared to non-irradiated samples (see Fig.2). It is attributed to the radiation-induced de fects in the surface structure.

The results given in this work prove the fact that according to its filtering characteristics, radia tion stability, and the sorption parameters, UO2 might be considered as the effective enough mate rial for an engineered geochemical barrier.

0, 0, , m/day Sorption factor, % 0, 0, 20 70 120 0 2 4 Time, days Time, hr Fig. 1. Variation kinetics of the filtration coef- Fig. 2. Sorption of Np (co= 236 Bqcm-3) by ficient (K) through the UO2 barrier. non-irradiated UO2 samples (1) and by -irradiated UO2 sludge (2).

The work was performed under the financial support of the ISTC No.2694.


COMPUTER AIDED DESIGN OF NEW METAL BINDERS Kireeva N.ab, Marcou G.a, Soloviev V.P.b, Fourches D.a, Varnek A.a a Universite Louis Pasteur, 4, rue B.Pascal, Strasbourg, France b Institute of Physical Chemistry and Electrochemistry, RAS, Leninsky pr-t, 31, Moscow, Russia Chemoinformatics technologies can be efficiently used for establishing quantitative relationships between structure and metal binding affinity of organic molecules. For this purpose we used the ISIDA (In Silico Design and Data Analysis) program package, which includes three main elements:

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