«XVIII МЕНДЕЛЕЕВСКИЙ СЪЕЗД ПО ОБЩЕЙ И ПРИКЛАДНОЙ ХИМИИ Москва, 23–28 сентября 2007 г. ТЕЗИСЫ ДОКЛАДОВ Москва – 2007 УДК ...»
(i) a database manager, (ii) a QSPR module for quantitative structure-property modelling and (iii) a generator of virtual combinatorial libraries.
NEW COMPOUNDS DATABASE Virtual Screening ISIDA QSPR module Combinatorial Module Knowledge Base Several popular machine learning methods – Multiple Linear Regression Analysis, k Nearest Neighbours, Support Vector Machines, Associative Neural Netwotks – implemented in the ISIDA package have been used to assess stability of the complexes of metal cations (M) with some organic ligands (L) in water using substructural molecular fragments as descriptors. Several original vari able selection methods were implemented.
The models linking stability constants (logK) and molecular structure have been obtained for data sets of 130, 122, 235 and 1893 molecules forming M:L = 1:1 complexes with Sr, Ca, Ba and Cu(II) cations, respectively. The experimental logK values were critically selected from the IUPAC database and scaled to “standard” conditions (T = 25°C, I = 0.1 M). These structurally diverse data sets include derivatives of monocarboxylic, phosphoric and aminophosphonic acids, mono- and dipodands, crown-ethers and aza-crown ethers, cryptands and some others.
Predictive ability of the models was analyzed using external 5-fold cross validation procedure, in which every compound in the initial data set takes part of one of five test sets.
Developed here structure – logK models can be used for “in silico” design of new selective ligands for metal cations.
2298 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, SUPRAMOLECULAR SYSTEMS BASED ON AMPHIPHILIC SULFONATOCALIX[n]ARENES:
AGGREGATION, CATALYTIC ACTIVITY, PHYSIOLOGICAL EFFECT ON PLANT CELLS Kiseleva Yu.V.a, Ryzhkina I.S.a, Solovieva S.E.a, Pilishkina L.M.a, Konovalov A.I.a, Valitova Yu.N.b a A.E.Arbuzov Institute of Organic and Physical Chemistry KazRC RAS, 8 ul. Akad. Arbuzova 420088 Kazan, Russia b Kazan Institute of Biochemistry and Biophysics KazRC RAS, 2/31 ul. Lobachevskogo 420111 Kazan, Russia Working of biocompatible and biomimetic nanosystems is a urgent problem of the fundamental and applied science. The studies carrying out during the past ten years was shown that p-sulfonatocalix[n]arenes (SCA) are perspective compounds for a creation of these systems1.
The kinetics study of the hydrolysis of phosphorus acid esters (PAE) in supramolecular systems based on SCA was shown that the system based SCADod catalyzes hydrolysis of substrate and system based on SCADod can retard or catalyze the reaction depending on the concentration of calixarene. It was revealed the possibility of regulation reactivity of SCA aggregates by introducing crown-esters and lanthanum (III) in systems. It was shown that micelle solutions of SCADod and SCADod are nanosystems exhibiting different receptor, catalytic, and biological activity depend ing on the macrocycle size.
This work was financially supported by the Russian Foundation for Basic Research (project no. 06-03-32402).
References 1. F. Petter, A.N.Lazar, A.W. Coleman, Chem. Commun., 2006, 2425.
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 STUDY OF MICELLIZATION IN AQUEOS SOLUTIONS OF DISODIUM MONOALKYLSULFOSUCCINATES Kolesnikova E.N., Glukhareva N.A., Duvalov A.L.
Belgorod State University, Department of Biology and Chemistry Pobedy Str. 85,308015, Belgorod, Russia The most important properties of surfactants are their adsorption on interfaces and spontaneous ag gregation in solutions that is micellization. Adsorbing on interfaces and forming micelles surfac tants play a sufficient role in wetting, spreading, dispersing, emulgation, foaming, and others. To understand and to predict surfactants effects in various phenomena and processes in practice, one must know the dependence of properties of surfactants on their structure, peculiarities of surfactants interactions and their interactions with other substances as well as their behaviour in complex sys tems.
The aim of the work is the investigation of aqueous solutions of disodium monoalkylsulfosucci nates that are salts of monoesters of long-chain alcohols and sulfosuccinic acids of the formula ROOCCH2CH(COONa)SO3Na, where R is the alkyl radical C10–C14. Monoalkylsulfosuccinates are used in particular in formulations of cosmetic washing products.
Values of critical micelle concentration (CMC) of the surfactants are determined by methods of conductometry and viscosimetry. Shape factor of micelles is calculated from viscosity isotherms.
When surfactant concentration raises above CMC the shape of the micelles changes rapidly from spherical to ellipsoidal, the transition being more characteristic for higher homologues. Degrees of counterion binding are calculated by different ways that are the CMC dependence on indifferent electrolyte concentration, Fram’ and Evans’ methods basing on specific conductivity isotherms. It is found that the CMC dependence on electrolyte concentration and the Fram’s method give too low degrees of counterion binding. On the base of obtained data the Gibbs free energy of micellization of the surfactants in aqueous solutions is calculated.
2300 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, FORMATION OF CATION-«CAPPED» COMPLEXES BY CROWN-CONTAINING STYRYL DYES Kondratuk D.V.a, Vedernikov A.I.a, Kuz’mina L.G.b, Lobova N.A.a, Valova T.M.a, Barachevskiy V.A.a, Avakyan V.G.a, Howard J.A.K.c, Alfimov M.V.a, Gromov S.P.a a Photochemistry Center of the RAS, Novatorov str. 7a, 119421 Moscow, Russia;
e-mail: email@example.com b Institute of General and Inorganic Chemistry of the RAS, Leninskiy av. 31, 119991 Moscow, Russia c Chemistry Department, Durham University, South Road, Durham DH1 3LE, UK A series of novel crown-containing styryl dyes 1 with N-ammoniumalkyl or N-ammonium xylyl spacers was synthesized using 2-methylbenzothiazolium salts 2 condensation with 4’-formylbenzo-18-crown-6-ether or using quaternization of 2-styrylbenzothiazole 3 by bromal kylammonium salts. Dyes structure and their spectroscopic properties are affirmed to by X-ray analysis, electronic and NMR 1H-spectroscopies, and quantum-chemical calculations.
O O O O S O O O OHC S O S O O 1) RX Me _ O O N+ N+ _ O ClO4 N O 2) HClO ClO4 R R O O O O 2 1: R = (CH2) nNH3ClO4, n = 3 (a), 5 (b), 6 (c);
Et (e) (up to 66%) S S O h 1 S Kd O N + (E)-1c H+ N N O NH + _ h2, + MeCN O H 2 ClO O O O (CH2)6 (CH2) O O O O O H H _ H +N HN cation-'capped' complex + 4 ClO O H O O O H (Z)-1c O O anti-[(E)-1c] O _ _ O O O S O 2 ClO4 2 ClO4 S h O O N+ O O R N R O O O + O O R N+ O (in crystal) R + O N O O O S S O O O O O syn-[(E)-1c]2 rctt- Dyes (E)-1 form stable dimeric complexes in MeCN with anti-“head-to-tail” arrangement of dye molecules due to terminal NH3+ group coordination with crown-ether moiety. Irradiation of 1 re sults in nothing but reversible E-Z isomerization. In the case of 1c,d, a formation of stable cation “capped” complexes in the Z-form is confirmed. In crystal, (E)-1c,e molecules form stacks, in which molecules are arranged in anti- and syn-“head-to-tail” modes. Under irradiation dimeric pair molecules in syn-“head-to-tail” arrangement undergo [2+2]-photocycloaddition reaction yielding exclusively rctt-4 cyclobutane derivative with no crystal distruction.
Financial support from the Russian Foundation for Basic Research, the Russian Academy of Sciences, and the Royal Chemical Society is gratefully acknowledged ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 ASYMMETRICAL ARENE MACROHETEROCYCLES WITH ENDOCYCLIC ATOMS OF PHOSPHORUS ON THE BASIS OF ELEMENTARY BISPHENOLS Kornilov K.N., Blockhin Yu.I., Vasyanina L.K.
The Moscow State University of Technologies and Management, Moscow, Nicoloyamskaya st, 30- Earlier on the basis of elementary bisphenols resorcinol and hydrohinone were synthesized symmet ric phosphorous-containing macrocycles1–3. But with pirocatehol similar researches are not known.
Moreover, till now asymmetrical macrocyclic substances containing simultaneously arene frag ments different specified elementary bisphenols, were not investigated at all.
Between that, cyclophanes with endocyclic atoms of phosphorus, as well as with ecsocyclic4, can be interesting, since depending on the size of their internal cavity, they can be coordinated, in par ticular, with different metals, therefore the reception new metal-complex catalysts is possible5.
Therefore manipulation to similar substanses is perspective from the point of view of creation original supramolecular systems.
With the purpose of study of a basic opportunity of synthesis similar macrocycles the method of molecular assembly, us carries out interaction of bisphosphorous resorcinol 3 with pyrocatehol and hydrohinone 5. Synthesis carried out with the account3,6. However instead of the solvent ace tonitrile, used in these works, we chose more accessible and effective ethylacetate, that allows to reduce time of bisphosphorilic resorcinol from 24 till 2 hours:
O CH3COOEt, 200C O Et2N P P NEt O O -2HNEt + OP(NEt2) OH HO OH CH3COOEt, 200C + 2P(NEt2) -2HNEt OP(NEt2) OH CH3COOEt, 200C O + 3 O 1 HO OH Et2N P P NEt -2HNEt2 O O Is found out, that thus it is not necessary to allocate 3 of a solution, and it is more expedient to carry out synthesis on a method "one pot", taking into account, that derivative of three-valence phosphorus destroyed on air.
In a spectrum HMR31P of connection 6 there is a signal p 144,82 m.s., and in a spectrum 7 p 144,24 m.s. For confirmation of a structure 6 and 7 were connected with sulfur. In result are formed thionphosphates 8 and 9:
OAO 2S PNEt Et2NP 6, (8), OBO,B= A= (9) 8, In spectra HMR31P of these substances the characteristic signals p 75,90 m.s (8), and p 66,53 m.s. (9) are observed. The structure of the received compounds proves to be true by methods IR-spectroscopy and mass-spectrometry.
Thus, by us for the first time are received asymmetrical arene macrocycles with endocyclic at oms of phosphorus containing simultaneously arene fragments of resorcinol and pirocatehol (6, 8) or resorcinol and hydrohinone (7, 9), which further can be used in quality of ligands with various metals.
References 1. Niphantyev E.E., Rasadkina E.N., Yancovich I.V., Vasyanina L.K. Jorn.Obsh.Him., 1999, 1, 36.
2. Niphantyev E.E., Suvorkin S.V, Rasadkina E.N., Selutina O.V., Shishin A.V. Jorn Obsh.Him., 2002, 8, 1263.
3. Nipfantyev E.E., Rasadkina E.N., Evdokimenkova Yu..B. Jorn.Obsh.Him, 2001, 3, 401.
4. P.Phinnokyaro, S.Faila, G.Konsiglio. Izv. Acad. Nayk, Ser.him., 2005, 6, 1313.
5. Blokhin Yu.I., Gusev D.V., Kornilov K.N. Abstracts “Advanced science in organic chemistry”, Sudak, Crimea, June 26-30, 2006, c. 141.
6. Niphantyev E.E., Rasadkina E.N., Yancovich I.V. Journ.Obsh.Him., 1997, 11, 1812.
2302 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, pH-CONTROLLED GUEST-TRANSLOCATION BETWEEN TWO RESORCINARENE HOSTS Korshin D.E., Ziganshina A.Y., Kharlamov S.V., Kazakova E.Kh., Latypov S.K., Konovalov A.I.
A. E. Arbuzov Institute of Organic & Physical Chemistry KSC RAS;
Arbuzov str. 8, 420088 Kazan, RUSSIA, e-mail: e-mail:firstname.lastname@example.org Here we report a new three-component supramolecular system which is able to work as pH controlled molecular machine. The system consists of two stationary parts (derivatives of resorci narene) and one mobile part capable to move from one stationary part to another under external stimuli – the changes of pH media. Two derivatives of resorcinarene with electron-donating and electron-deficient groups were chosen as stationary parts. pH-indicator – methyl yellow was used as the mobile part of the supramolecular system. Preliminary result shows that the changing of pH media causes to the moving of mobile part of the system.
The research was supported by the Russian Foundation for Basic Research (Grants ## 05-03-32558-a, 06-03-32199 a) ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 STUDY OF BENZODITHIACROWN ETHERS AND THEIR COMPLEXES WITH PALLADIUM SALTS BY HOMO- AND HETERONUCLEAR 2D NMR Kurchavov N.A., Dmitrieva S.N., Sidorenko N.I., Vedernikov A.I., Freidzon A.Ya., Gromov S.P.
Photochemistry Center, Russian Academy of Sciences, ul. Novatorov 7a, Moscow, 119421 Russia.
E-mail: email@example.com A series of nitrobenzothia- and dithiacrown ethers is synthesized and the complexes of these crown ethers with divalent palladium salts are obtained. The structure of the benzothiacrown ethers and their complexes with palladium salts is studied by various NMR methods (COSY, NOESY, HMBC, HSQC, and 13C). The electronic and geometrical structures of the free benzodithiacrown ethers and their complexes with palladium chloride are calculated using density functional theory (DFT) with an all-electron relativistic basis set. The calculated structures are used for interpretation of NMR data.
According to the calculations, the PdS2Cl2 fragment in these complexes is a planar square with cis arrangement of the ligands.
S S O O O PdCl PdCl O S O O X X S S O O PdCl2 O O X O S X = -NO2, -CHO The 1:1 benzodithiacrown ether complexes with palladium salts are rather rigid structures, which results in that all the protons of the methylene groups of the crown ether moiety become magneti cally inequivalent and give different NMR signals. This makes their 1H NMR spectra rather com plex. To completely identify the signals, the chemical shifts of all the protons were calculated by DFT.
2304 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, STUDY OF STABILITY AND STRUCTURE OF PHENYL- AND BENZOAZA-15(18)-CROWN-5(6) ETHER COMPLEXES WITH METAL AND AMMONIUM CATIONS BY VARIOUS NMR METHODS Kurchavov N.A., Vedernikov A.I., Dmitrieva S.N., Churakova M.V., Tikhonova O.V., Freidzon A.Ya., Avakyan V.G., Gromov S.P.
Photochemistry Center, Russian Academy of Sciences, ul. Novatorov 7a, Moscow, 119421 Russia.
E-mail: firstname.lastname@example.org Complexation of promising azacrown ether derivatives, phenylazacrown (I) and benzoazacrown (II) ethers, is studied by NMR.
R O O N O O X N n O O X O O n I II X = NO2, CHO;
R = H, Alk;
n = 1, Complexation of functionalized benzo- and phenylaza-15(18)-crown-5(6) ethers with alkali and alkaline-earth cations, ammonium, and ethylammonium was studied by 1H NMR titration in MeCN-d3, and the stability constants of the corresponding complexes were determined. The stabil ity constants were calculated using HypNMR program;
they correspond to 1(L):1(Mm+) and 2(L):1(Mm+) complexes.
R O O N O Mn+ O X N Mn+ n O X O O n O I II M = Na, K, Ca, Ba, NH4, and EtNH The regularities of complexation as a function of the macrocycle size, the substituent in the ben zene ring, and the nature of the cation are considered. The stabilities of the complexes of different benzo- and phenylazacrown ethers and their analogs without nitrogen were compared. It is found that the complexing capacity of benzoazacrown ethers II is comparable to that of benzocrown ethers and is much higher than that of phenylazacrown ethers I.
C, NOESY, and COSY NMR spectra of benzo- and phenylazacrown ethers and their com plexes were obtained. The structures and stabilities of M:L = 1:1 and 1:2 complexes of these crown ethers were calculated by the density functional (DFT) method using a PBE functional and a triple zeta basis set. The results agree with the experimental data.
This work was financially supported by the Presidium and Division of Russian Academy of Sciences and Russian Foundation for Basic Research.
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 MORPHOLOGY OF TEFLON F AND OF SUPERDISPERSED POLYTTETRAFLUOROETHYLENE Kuryavyi V.G.a, Bouznik V.M.b, a Institute of Chemistry, Far East Branch of Russian Academy of Sciences, pr. 100-letiya Vladivostoka, 159, Vladivostok 690022, Russia, E-mail: email@example.com b Institute of Ceramic Materials Physical Chemical Problems, Russian Academy of Science, Moskow Electronic scanning microscope (ESM), electronic transmission microscope (TEM) and atomic force microscope (AFM) there were applying for study of morphological construction industrial teflon (F4) and superdispersed polytetrafluoroethylene (UPTFE). Possibility of different methods is evaluated. The most information is received with use the AFM method.– fig. 1. For reception addi tional data about construction of UPTFE it was studied the construction of particles by ruined fric tion and way of nanolithography. Main results proposed to discussion are:
The F4 is characterized presence of supramolecular structures in the manner of chains long sev eral micron. The chains are built from firmly clamped blocks with their transverse sizes ~ 100 nm.
From chains are formed microplates, as is well known, inveigled in piles. The blocks are coupled in monolithic material firmly. The layered construction is discovered by us and for UPTFE particles.
The blocks by sizes ~ 100 nm are formed in microparticle by diameter ~ 1 micron. The traction an nanoblocks in UPTFE, unlike F4, sleazy, since they easy divide under the action of friction force.
Blocks themselves are formed from else more smaller particles and nanofilms. On lower dimen sioned level in UPTFE are present the overmolecular nanostructures in the manner of fiber by di ameter less 3 nm. Difference in morphological construction F4 and UPTFE, probably, is caused dif ferent long polymeric molecules in considered material and greatly different number of molecules forming volume of the individual overmolecular structures of first least dimensioned level. In UPTFE these parameters answer nanostructured in areas by sizes less 100 nm material.
a b Fig. 1. AFM image of block construction of UPTFE particle (a), AFM image of nanofibers in UPTFE particle. a – maximum transverse size particles 1.1 micron, b – square 1919 nm.
Financial support from Far East Branch of RAS (projects N 06-III-A-04-089) is gratefully acknowledged.
2306 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, SINGLE-WALL CARBON NANOTUBES SOLUBILIZED IN AQUEOUS MICELLAR SOLUTIONS OF CALIXARENES – NEW SUPRAMOLECULAR SYSTEMS Lobach A.S.a, Spitsina N.G.a, Ryzhkina I.S.b, Kiseleva Yu.V.b, Pilishkina L.M.b, Solov’eva S.E.b, Knyazeva I.R.b, Konovalov A.I.b a Institute of Problems of Chemical Physics, RAS, 142432 Chernogolovka, Moscow Region, Russia b A.E. Arbuzov Institute of Organic and Physical Chemistry RAS, 420088 Kazan, Russia Single-wall carbon nanotubes (SWNT) as new nanosized materials, which demonstrate unique physicochemical and physicomechanical properties, have high enough potential to be used in vari ous fields of science and technology1. SWNT can find wide technological application only if there are well developed methods of nondestructive solubilization of nanotubes in different solvents.
Such methods are based on a noncovalent interaction of amphiphilic molecules with the nanotube surface. Now there are publications on solubilization of SWNT in aqueous micellar solutions of dif ferent surfactants2–3.
The present work reports the study of solubilization of SWNT in aqueous micellar solutions of amphiphilic calixarenes, which are new type of surfactats, and the investigation of resulting suspen sions by optical methods. SWNT used in the work were prepared by electric arc sputtering of graphite in the presence of a Ni/Y2O3 (1:1) catalyst and had a 1.46 ± 0.15 nm distribution in diame ter. Calixresorcinarenes containing aminomethyl groups on the upper rim 14 and phosphorus bearing alkyl fragments on the lower rim 25 of calixarene as well as p–sulfonato-calix[n]arenes (n = 4,6) modified by butyl 3 and dodecyl 4 substituents were used as micelle forming surfactans6.
For the first time we found that aqueous solutions of calixarenes form stable suspensions of nanotubes at concentrations lower than those of conventional surfactants. It was shown by optical methods that among calixarenes tested highest dispersion ability (mg nanotubes/mg calixarenes) is exhibited by calixresorcinarene 2, which has the best surface-active properties. Additionally to high dispersive power, p–sulfonato-calix[n]arenes (3, 4) show ability to pull apart nanotube bundles to separate nanotubes due to the presence of both benzene rings and long hydrophobic tails and hy drophilic sulfonate groups. Calixarenes studied by us are also able to extract selectively nanotubes from suspensions of starting nanotube material that can be used in purification of nanotubes.
This work was financially supported by the Russian Foundation for Basic Research (project nos. 05-03-33132, 06 03-32402) References 1. A.V. Eletskii, UPN 2007, 177, 233.
2. W. Wenseleers et al., Adv. Funct. Mater. 2004, 14, 1105.
3. D.A. Britzab and A.N. Khlobystov, Chem. Soc. Rev. 2006, 35, 637.
4. A.R. Burilov at al. Russ. J. Gen. Chem. 2007, 77, 105.
5. I.S. Ryzhkina at al. Russ. Chem. Bull., Int. Ed. 53, 1520 (2004).
6. S. Shinkai, in: Calixarene, a Versalite Class of Macrocyclic Compounds, J. Vicens and V. Bohmer (eds.), (Kluwer, Dordrecht, 1990), p.173.
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 PHOTOCHEMISTRY OF THE CROWN-CONTAINING STYRYLQUINOLINE AND THEIR COMPLEXES WITH ALKALINE EARTH METAL Lobazova I.Ya.a, Mashura M.M.a, Fedorova O.A.a, Fedorov Yu.V.a, Gulakova E.N.a, Alfimov M.V.a, Saltiel J.b a Photochemistry Center of Russian Academy of Sciences, Novatorov str., 7a, Moscow, 117421, Russia.
b Department of Chemistry and Biochemistry, The Florida State university, Tallahassee, Florida 32306-4390, firstname.lastname@example.org;
Photochromic compounds have received great interest in the last years due to their application such as ophthalmic lens, transparencies, plastic films, promising materials for the information imaging and storage, etc. Incorporation of a crown ether moiety which is able to bind metal ions into the spi rocompound skeleton can be explored to tune the photochromic properties by using complexing process.
It was shown that photochemical transformation of crown-containing 4-styrylpyridine strictly dependent on the presence of metal cations coordinated with crown ether moiety. Thus, irradiation of acetonitrile solution of crown-containing 4-styrilquinoline results in the reversible electrocyclic reaction formation of the corresponding dihydrobenzophenanthridine. An irradiation of the same solution with presence of Mg2+ cations leads to E-Z isomerisation reaction with formation of the complexed Z-isomer. Photoirradiation of Ba2+ complex gives [2+2]-photocycloaddition reaction with formation of one isomer of cyclobutane derivatives.
[2+2]-Photocycloaddition E,Z-Photoisomerization N N Ba2+ Mg2+ O O O O N N OO O 365 nm O O 365 nm O O O O O O O O O 70% 365 nm 84% Electrocyclic reaction OO H O O N H O O O 93% Acknowledgment. The study was supported by CRDF (Grant RC2-2344-MO-02), INTAS (Grant 03-51-4696), RFBR (Projects No. 06-03-32899 and 05-03-32268).
2308 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, SYNTHESIS, DIMERIZATION AND [2+2]-AUTOPHOTOCYCLOADDITION OF CROWN-CONTAINING STYRYL DYES WITH AMMONIOALKYL SUBSTITUENTS Lobova N.A.a, Vedernikov A.I.a, Kuz’mina L.G.b, Dmitrieva S.N.a, Strelenko Yu.A.c, Howard J.A.K.d, Alfimov M.V.a, Gromov S.P.a a Photochemistry Centre of the RAS, 7a Novatorov st., Moscow 119421, Russia, e-mail: email@example.com b Institute of General and Inorganic Chemistry of the RAS, Moscow c Institute of Organic Chemistry of the RAS, Moscow d Chemistry Department of Durham University, Durham, UK Synthesis of novel styryl dyes 1 containing terminal NH3+ group in N-substituent was elaborated.
Dyes 1 spontaneously form stable dimeric complexes 2 in both solid state and MeCN and CH2Cl2 solution due to complexation of crown-ether moiety with NH3+ group. The dimers have a head-to-tail stacking structure. Stability constants of dimers 2 were estimated by 1H NMR titration in MeCN-d3 (lgKd up to 8.0).
1. RX Ar-CH=O + R Hetar CH _ Py, EtOH 2. HClO4 ClO or Ppy, MeOH Ar + Hetar CH3 R Hetar _ ClO Ar-CH=O 1. RX Ar _ Hetar AlkO M+ 2. HClO DMS or DMF O O O CH CH3 Y O N O, S Hetar CH3 = O O Ar =,, CH3 ;
O O O N N N m Y = O, NCH3;
m = 0, R = Et, (CH2)nNH3 Br, n = 2, 3;
X = Br, OTs MeCN or h CH2Cl (spontaneously) 1 2 + = crown-ether fragment = heterocyclic moiety = (CH2)nNH Irradiation of dimers 2 by visible light in solution, thin polycrystalline film or monocrystal leads to efficient stereospecific reaction of [2+2]-photocycloaddition giving single rctt-isomer of cyclobutane derivative 3. The possibility and the efficiency of cycloaddition depend on nature of heterocyclic moiety, length of ammonioalkyl substituent, size and type of crown-ether fragment.
Structures of 1-3 were studied using X-ray diffraction and NMR spectroscopy. Dyes 1 can be util ized in systems of registration and storage of information.
This work was financially supported by the Russian Foundation for Basic Research, the Russian Academy of Sci ences and the Royal Society of Chemistry.
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 SYNTHESIS OF NEW CHROMOIONOFORES ON THE BASIS OF POLYETHER COMPOUNDS Logacheva N.M., Al Ansary Y.F., Shnipov AV., Salomatina G.S., Baulin V.E., Tsivadze A.Yu.
Institute of physical chemistry and electrochemistry by A.N.Frumkin, Moscow, Russia firstname.lastname@example.org Recently photosensitive materials based on the highly organized supramolecular systems are a sub ject of steadfast attention.
The main principles of creation of such systems are the programmed assembly based on molecu lar coordination and methods of purposeful molecular design of initial organic compounds. Molecu lar coordination is inherent both for of some acyclic fragments (terpyridines and o-phosphoryl contain phenols) and for poly-ethers macrocycles (crown-ethers) and for tetrtrapyrroles macrocyclic compounds (porphines). Association in one molecule of acyclic coordinating fragments and macro cyclic poly-ethers fragments leads to additional opportunities for self-organizing. Presence of pho tosensitive fragments (for example-N=N-), possibly, will allow to operate of the process of su pramolecular assembly by means of light influence. However there is no fundamental theory of de sign of such compounds and the mechanism of molecular recognition is studied insufficiently. De scribed in the literature compounds are not always synthetically accessible and do not possess a set of the properties, allowing to solve practical problems (thermal stability, stability to ageing, effec tive transport of energy).
O O O HO O O OH O O O O O O P O O N O N N N O N HN O N N CH O NH N N N N N N N N N N II III IV I In the present work we develop methods of synthesis of the compounds (I-IV). The structures of the received compounds (I-IV) are confirmed by a nuclear magnetic resonance (1H, 31P) and IR spectra. A number of the solid complexes with d- and f-metals are received and characterized.
Work is executed at financial support of the Program of basic researches of presidium of the RAS «The develop ment of methods of reception of chemical substances and creation of new materials» the subroutine «The organic and hybrid nanostructured materials for Photonics»
2310 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, IONOPHORIC RETINAL ANALOGS: SYNTHESIS AND PROPERTIES Lukin A.Yu.a, Laptev A.V.a, Belikov N.E.a, Barachevsky V.A.b, Gromov S.P.b, Vedernikov A.I.b, Demina O.V.c, Varfolomeev S.D.c, Shvets V.I.a, Khodonov A.A.a a M.V. Lomonosov State Academy of Fine Chemical Technology, 119571, Moscow, Vernadskogo 86, Russia;
b Photochemistry Center RAS, 119421, Moscow, Novatorov 7a, Russia;
c N.M. Emanuel Institute of Biochemical Physics RAS, 119334, Moscow, Kosygina 4, Russia.
Nowadays the design of a new synthetic methods for the introduction of ionophoric fragments in the various type biologically active compound molecules is under extensive investigation. The pur pose is to discover molecules whose spectroscopic behaviour changes drastically upon cation bind ing.
Modified retinoids, containing various reporter groups have been widely used over the last years for determining structure of retinal-containing proteins (visual rhodopsin, bacteriorhodopsin et all).
In this connection design methods for the preparation of new crown-containing polyenic com pounds and its conjugates with bacteriorhodopsin are of immense interest. We designed and de scribed an effective synthetic route for the preparation of unsaturated crowned compounds with variable length of the conjugation chain, different crown-ether nature and ring size and terminal po lar group type. This synthetic route involved the Horner-Emmons olefination of the corresponding 4’-formylbenzocrown ethers using the C5-phosphonate reagent, containing the cyano terminal group. For conversion of the cyano group into the aldehyde function we used a one-step procedure of DIBAL reduction.
An investigation of spectral properties and ion-binding capability was conducted for the crowned and reference compounds and its complexes with bacterioopsin from Halobacterium salinarum.
O R (1 a - e ) R= Где (a) (c) (b) O O S O O O O O O O O O O O S O (d) (e) S O O O O O O S This work was supported by President of RF grant for young PhD (project MK-5333.2007.4).
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 SUPRAMOLECULAR COMPLEXES OF CROWN-CONTAINING OLIGOTHIOPHENES WITH ALKALINE EARTH METAL CATIONS Lukovskaya E.V.a, Bobylyova A.A.a, Fedorova O.A.a, Fedorov Yu.V.b, Marmois E.c, Jonusauskas G.c, Kardashev S.V.a, Maksimov A.L.a, Mizerev A.A.a, Anisimov A.V.a a Department of Chemistry, M.V.Lomonosov Moscow State University, Leninskie Gory, 119992 Moscow, Russia b Photochemistry Center of RAS, Novatorov str., 7a,119421 Moscow, Russia c Centre de Physique Moleculare Optique et Hertzienne U.M.R.
5798 Universite Bordeaux 1, Bordeaux, France Unique electronic and optoelectronic properties of oligothiophenes make them suitable materials for organic and organometallic conductors, light-emitting diodes, optoelectronic and chemosensor de vices and for photovoltaics. Molecular recognizing groups, e.g. ionofors, covalently attached to polythiophene chain can modulate, switch and amplify the electron transport properties of the con jugated systems.
In the present research we synthesized polythiophene derivatives with crown-containing styryl and vinylpyridyne groups in 2 and 3 position of thiophene ring. Complex formation of prepared compounds was studied with Mg2+ and Ba2+ cations by means of NMR- and optical spectroscopy as well as ESI MASS spectrometry and electrochemical studies. It was found that addition of Ba2+ cations causes the formation of only intermolecular sandwich complexes only in case of 2 substituted derivatives. On the contrary, in the presence of Ba2+ cations 3-substituted derivatives form only itramolecular sandwich complexes of high stability. Formation of complexes causes changes in optical spectra, electrochemical response depends on the type of complexes formed by interaction of poythiophene derivatives with metal cations.
O O O O O O S S O O S O O n O O O O O O S S O O S O O n 2Ba2+ O O S S O R S CH2 n O O Ba2+ Ba 2+ S O O O O O O O S O O S O N S O n O O S O O O S O N O O O S n = 0, The research was done by financial support of INTAS 03-51-4696 and program of Russian Academy of Sciences 07-03-00724.
2312 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, FEATURES OF MOLECULAR INTERACTIONS WITHIN SMALL RIBOSOMAL SUBUNITS OF MAMMALIAN RIBOSOMES Malygin A.A., Yan’shina D.D., Parakhnevich N.M., Karpova G.G.
Institute of Chemical Biology and Fundamental Medicine SB RAS, prospekt Lavrentieva, 8, Novosibirsk, 630090, Russia In all living organisms proteins are synthesized on ribosomes, the macromolecular cellular machin eries. Structural organization of prokaryotic ribosomes is well studied to date by means of various approaches such as cryo-electron microscopy, X-ray crystallographic analysis, site-directed mutagenesis with the subsequent reconstitution of mutant ribosomal subunits, etc. However, appli cation of these approaches to more complex eukaryotic ribosomes is limited due to various difficul ties. This significantly retards progress in studying higher ribosomes and forces investigators to look for other approaches. Here, we investigated dissociation of proteins from human 40S ribo somal subunit in gradient of LiCl concentration (0.3 – 1.5 M) in the presence of 4 mM MgCl2 and 0.5 M KCl. It was found that dissociation of proteins from 40S subunit occurs gradually in wide range (0.8 – 1.5 M) of monovalent ions concentrations in contrast to 30S subunits that are dissoci ated stepwise and at higher salt concentration. Moreover, the most strongly bound to the 18S rRNA human ribosomal proteins S7, S10, S16 and S19 dissociate completely at 1M LiCl, while core 30S proteins dissociate only in the presence of urea and higher salt concentration. To reveal features of interaction of 18S rRNA with human ribosomal proteins (rps) S5 and S16 (homologous to prokary otic rpS7p and rpS9p, respectively), we used the recombinant proteins and RNA transcript model ing fragment of 3’-major domain1,2. This fragment corresponds to 16S rRNA region that is known to bind rpS7p and rpS9p;
it is also known that rpS9p is unable to bind to 16S rRNA without rpS7p.
We showed that both human rpS5 and rpS16 can bind to the RNA transcript in a specific manner independently of each other and form a stable binary complex with apparent association constants equal to (2.5 ± 0.5)•108 M-1 and (7.7 ± 0.6)•107 M-1, respectively. Using enzymatic and chemical footprinting, we found nucleotides of the RNA transcript whose accessibilities to RNases and modi fying agents changed upon binding of rpS16 alone or together with rpS5. Based on these results, one can conclude that, despite of different ways of binding of human rpS5 and rpS16 and their pro karyotic counterparts rpS7p and rpS9p with 3’-major rRNA domain during in vitro assembly of the small ribosomal subunit, binding sites of the homologous proteins on the rRNA have in general similar structure.
The work was supported by Russian Foundation for Basic Research (grant # 05-04-48393-a) References 1. D.D. Yanshina, A.A. Malygin, G.G. Karpova, Mol. biol. 2006, 40, 460.
2. D.D. Yanshina, A.A. Malygin, G.G. Karpova, Mol. biol. 2007, 41, in press.
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 HETEROLEPTIC SANDWICH YTTRIUM AND TERBIUM CROWNPHTHALOCYANINATES:
SYNTHESIS AND SUPRAMOLECULAR CHEMISTRY Martynov A.G.ab, Zubareva O.V.a, Sakharov S.G.b, Gorbunova Yu.G.ab, Tsivadze A.Yu.ab a Institute of Physical Chemistry and Electrochemistry RAS (119991, Moscow, Leninsky pr., 31), b Institute of General and Inorganic Chemistry RAS (119991, Moscow, Leninsky pr., 31) email@example.com Synthesis and studies of novel molecular building blocks for the development of new functional supramolecular materials are important tasks of modern chemistry. Herein we report the synthesis and investigation of supramolecular chemistry of new receptors – heteroleptic triple-decker crownphthalocyaninates (Pc)M[(15C5)4Pc]M(Pc), [(15C5)4Pc]M[(15C5)4Pc]M(Pc) and [(15C5)4Pc]M(Pc)M(Pc), where M = Tb and Y;
15C5 – 15-crown-5, Pc – phthalocyaninate dianion.
It was demonstrated, that lanthanum diphthalocyaninate, La(Pc)2 can act as an efficient donor of phthalocyaninate-dianion in the synthesis of heteroleptic triple-decker complexes. The reaction be tween La(Pc)2, H2[(15C5)4Pc] and M(acac)3·nH2O, M=Tb and Y let firstly obtain heteroleptic tri ple-decker complexes – (Pc)M[(15C5)4Pc]M(Pc), [(15C5)4Pc]M[(15C5)4Pc]M(Pc) in high yields.
Application of more stable unsubstituted diphthalocyaninates – M(Pc)2 in this reaction let firstly obtain [(15C5)4Pc]M(Pc)M(Pc), M=Tb, Y. All the synthesized complexes were characterized by means of MALDI TOF mass-spectra and UV-Vis and 1H-NMR spectra. Paramagnetic nature of Tb3+ leads to strong up-field shift of all proton resonance signals of its complexes to = –150 ppm in comparison with diamagnetic yttrium complexes.
Spectrophotometric and NMR titration of the synthesized receptors with potassium acetate solu tion was performed. It was demonstrated, that [(15C5)4Pc]M(Pc)M(Pc) form cofacial supramolecu lar dimers in the presence of K+. The isomeric complexes (Pc)M[(15C5)4Pc]M(Pc) do not form su pramolecular aggregates in the presence of K+ because of sterical hindrance. In the case of [(15C5)4Pc]M[(15C5)4Pc]M(Pc) the observed modifications of UV-Vis and 1H-NMR spectra sug gest, that K+ cations intercalate between the crown-substituted ligands, affecting the geometrical and optical properties of the complexes (Fig. 1). Thus, such complexes can be perspective compo nents of molecular switchers, which are affected by alkali metal ions.
This work was supported by the Russian Foundation for Basic Research (grant 05-03-32984) and Russian Academy of Science (Programs of Fundamental Researches). The authors also thank European Research Association “Su prachem” for supporting this research.
2314 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, THE METHOD OF A SURFACE TENSION MEASUREMENTS OF THE HORSE SERUM Milaeva I.V., Zaitsev S.Yu., Maximov V.I., Beschastnova Yu.M.
Moscow state academy of veterinary medicine and biotechnology, Ak. Skriabin str.23, Moscow Biological fluids of the people and animals have a complicated chemical composition, that depends on the physiology- biochemical status of organism.
New "integrated" characteristics of biological liquids can be the parameters of their surface ten sion (ST) which recently have started to be investigated for diagnostics of some human diseases in the medical research centers of Germany and Ukraine1. Works in this direction for animals it is not known.
The aim of our work was to study the surface tension of the horse blood serum and lipid-protein systems. The surface tension has been measured by instrument BPA-1P by the maximum bubble pressure method at the surface lifetime in the range of 1 to 100 s. The most indicative are parameters: 1 (at time of existence of a surface t=1 s), 100 (an equilib rium ST at t) and (a tangent of a slope of an inclination for dynamic tensiogramms). The sur face tension of bovine serum albumin in concentrations 30-80 g/l, sodium chlorides in concentra tions 120-160 mM, lecitin in concentrations 1-4 mM and their mixtures have been studied.
In the individual BSA solutions surface tension reduced to 56-57 mN/m, in the case of addition of lecitin solution surface tension reduced to lower values, but addition of sodium chlorides solution reduced surface tension much less. These effects were in due to the adsorption of surface active and inactive substances at the interface. Mixtures of lecitin with water and sodium chlorides solutions had surface tension values similar to these of water. Addition of sodium chlorides to the lecitin dis persion increased values of surface tension 1 from 71,60±0,24 to 72,42±0,22 mN/m and decrease 100 from 67,28±0,25 to 51,92±0,08 mN/m. In the complicated three-component mixtures (BSA, lecitin, sodium chlorides) the salt concentration had the main influence on 1, bat protein and lipid – on 100.
The horses of elder age have higher values of surface tension: stallions – 73,44±0,35мН/м ( years), 72,87±0,28мН/м (3 years);
mares – 73,53±0,51мН/м (4 years), 71,92±0,31мН/м (3 years).
The value of incline angle of curves of mares lower, that of stallions. Thus, for mares =5,1±1, mH/m-1 s1/2;
for stallions =7,5±1,86 mH/m-1 s1/2. The obtained data proved the change of values of surface tension in dependence of horses sex and age.
Thus, the method of interphasial tensiometry gives valuable information about the animal organ ism and can be used as novel biochemical method for earlier diagnostics and control for human and animal status2.
This work was supported by RFBR and Rector of MSAVMB.
References 1. V.N. Kazakov, O.V. Sinyachenko, V.B. Fainerman, Dynamic surface tensiometry in medicine, 2003,1-126.
2. Milaeva I.V., Zaitsev S.Yu., Maximov V.I., Russian veterinary medicine journal, 2006, 5, 26-27.
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 THE ELECTROSTATIC IMMOBILIZATION OF TETRAMETHYLSULFONATORESORCINARENES AND THEIR ASSOCIATES WITH ORGANIC SUBSTRATES ON THE ION-EXCHANGE RESIN Morozova Ju.E., Shalaeva Ja.V., Makarova N.A., Kazakova E.Kh., Konovalov A.I.
A.E. Arbuzov Institute of Organic & Physical Chemistry, Rusian Academy of Science Arbuzov str., 8 420088 Kazan, RUSSIA Two amphiphilic host molecules – macrocyclic resorcinarenes 1 and 2, bearing four negative charged sulfonate groups on the upper rim1, were used for immobilization due to electrostatic inter actions on the ion-exchange resin Amberlite IRA 900-Cl. The modified anion-exchange resins are able to the selective sorption of the polar organic medicinal substrates – 1,2-dihydro-4,6-dimethyl N(-oxyethyl)-2-oxopyrimidin (Xymedon) and O,O-dimethyl-1,1-dimethyl-3 oxobuthylphosphonate (Dimephosphonum) 4 – from the aqueous solutions.
It was shown that anion-exchange resins modified by host molecules 1 and 2 have different ca pacity from the host capacity in the aqueous solution. The sorption capacity of immobilized macro cycles can be enhanced or decreased. The latter depend both on the host-guest bonding sites and the macrocyclic adsorption aggregate fashion.
The adsorption kinetics, competitive adsorption and the modes of immobilization structure on the anion-exchange resins surface will be discussed.
This work is supported by Russian Foundation of the Basic Researches N 06-03-32189 and Pro grams 7 and 8 of the Division of Chemistry and Material Science RAS.
References 1. E.Kh. Kazakova, N.A. Makarova, A.Yu. Ziganshina, L.A. Muslinkina, A.A. Muslinkin, W.D. Habicher Tetrahedron Letters. 2000, 41, 10111.
2. J.E. Morozova, E.Kh. Kazakova, E.Ph. Gubanov, N.A. Makarova, V.P. Archipov, T.V. Timoshina, Z.Sh. Idijatullin, W.D. Habicher, A.I. Konovalov. J. Inclusion Phenom. Macrocyclic Chem. 2006, 55, 173.
2316 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, THERMAL, DIELECTRICAL AND VOLUME PROPERTIES OF SYSTEMS WITH SPECIFIC INTERMOLECULAR INTERACTIONS Nosikova L.A.a, Kudryashova Z.A.a, Syrbu S.A.b a Moscov State Academy of Fine Chemical Technology, Moscow, Russia b Ivanovo State University, Ivanovo, Russia E-mail: firstname.lastname@example.org For the mesophase formation, the geometry of molecules should be anisotropic. Peculiarity of in termolecular interactions between compounds influence anisotropy of molecules. At present time, the synthesis of LC-compounds with H-bonding between molecules is perspective.
The influence of non-mesogen on intermolecular interactions in p-n-alxoxybenzoic asids is stud ied. In this work, the p-n-hexyloxybenzoic acid (I) – p-n-heptyloxybenzoic acid (II), p-n hexyloxybenzoic acid (I)- biphenyl(III), p-n-heptyloxybenzoic acid (II)- biphenyl(III) system was studied by thermal analyses (DTA, PPM), dielectric study and dilatometry. The phase diagrams of I-II, I-III, II-III systems is obtained.
The analysis of the results of different experimental methods show differences in data. So, in low-temperature range of I-II system, thermal analysis has shown the existence of continuous solid and nematic solutions. Heating up 95.9 C of composition with 65.5 mol.% II gives rise to eutectic reaction between solid and smectic solutions and formation of nematic solution. At this time, XRD, dielectric study discovered the formation of new compound and limited solutions on the base of ini tial I, II mesogens or new compound.
The influence of non-mezogen biphenyl on the stability region of mesophase1 and dielectric properties in LC-acids were studied in systems I-III and II-III. It has shown that introduction of biphenyl to 30 mol.% (I-III) and to 50 mol.% (II-III) leads to increasing of dielectric anisotropy as compared with to pure acids. The thermal analyses has shown that mesophase exists only up to mol.% III (I-III) and to 25 mol.% III (II-III) An increase in the content of III in the systems de stroys the intermolecular bonds in acids destroys, nematic phase disappear.
It is interesting to note that in II-III system introduction of biphenyl broke the sequence of for mation of the mesophase and nematic phase (N) formed before smectic phase (S). The smectic phase is more sensitive to changes of composition in systems than nematic phase. In I-II, II-III sys tems, smectic phase disappears when other component is 6 mol.% other component.
Taking into account results of our investigation of p-n-alkoxybenzoic acid – non-mesogen sys tems that not always the influence of non-mesogen on the stability of mesophase coincides with changes of anisotropic properties.
The work was supported by grant RPN.220.127.116.11. References 1. Nosikova L.A., Kudryashova Z.A. Liquid crystals and applicat. 2003.2.124-127.
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 TASK SPECIFIC IONIC LIQUIDS: NEW AGENTS FOR THE EXTRACTION OF U(VI) Ouadi A., Klimchuk O., Gaillard C., Jobin E., Billard I.
Institut Pluridisciplinaire Hubert Curien, DRS, ULP, CNRS, IN2P3, 23 rue du Lss, 67037 Strasbourg cedex 2, France A very promising approach for metal extraction is the concept of Task-Specific Ionic Liquids (TSILs). These compounds, consisting of extracting entities grafted on the cation of the ionic liquid, combine the properties of ionic liquids (non volatility, non flammability…) together with those of classical extracting compounds. By grafting complexing substructures on the organic cation of RTILs, the obtained TSILs would behave both as the organic phase and as the extracting agent, simply suppressing the problems encountered with extractant/solvent miscibility and extracting species and solvent recovery. At present, this concept has been the subject of very few studies in the field of separation.
A novel class of hydrophobic ionic liquids based on quaternary ammonium cation and bearing phosphoryl group was synthesized. The preliminary results described here show that high D values can be achieved for the separation of U(VI).
O P O BuO, Tf2N NR N H BuO P 2 R= CH BuO Cl BuO O, Tf2N NR P BuO O BuO 3 R= CH O O P P BuO BuO, Tf2N NR BuO BuO 5 R= C2H Scheme 1. General synthesis of new TSILs 2318 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, SUPRAMOLECULAR COMPLEX FORMATION OF PHOTOCHROMIC CROWN-CONTAINING BENZOPYRANE WITH DIFFERENT METAL CATIONS Paramonov S.V.a, Fedorova O.A.b, Fedorov Y.V.b, Strokach Y.V.b, Valova T.M.b, Perevalov V.P.a, Lokshin V.c, Samat A.c a D.Mendeleev University of Chemistry and Technology of Russia, Moscow, Russia b Photochemistry Center of RAS, Moscow, Russia c Universit de la Mditerrane, Marseille, France Photochromic compounds have received great interest in the last years due to their application such as ophthalmic lens, transparencies, plastic films, promising materials for the information imaging and storage, etc. The electrocyclic reactions have proved to be especially suitable as a basis for photochromic systems. Incorporation of a crown ether moiety, which is able to bind metal ions into the benzopyrane skeleton, can be explored to tune the photochromic properties by using complex ing process. We represent the first example of benzopyrane annulated with crown ether moiety.
O O h O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O Crown ether moiety in closed form is involved in an effective complexing processes. Magnesium cations form inclusive types of complexes while it appeared barium ions to generate sandwich complexes. The presence of metal cations influences on spectral properties both of opened and closed forms as well as on stability of opened form. We suggest the formation of different structure complexes of opened form and in particular anion-“capped” complexes.
The research was supported by grant RFBR 05-03-32268, CNRS-RAS exchange program.
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 SUPRAMOLECULAR ASSEMBLIES FORMED BY LANTHANIDE SCHIFF BASE COMPLEXES DERIVED FROM PIRIDOXAL AND AMINO ACIDS Puntus L.N.a, Lyssenko K.A.b, Zhuravlev K.P.a, Pekareva I.S.a a Laboratory of Molecular Nanoelectronics, Institute of Radio Engineering & Electronics, Russian Academy of Sciences, 11-7 Mokhovaya, Moscow, 125009, Russia, email@example.com b A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, GSP-1, 28 Vavilov Street, Moscow, 119991, Russia A design of the luminescence systems with guided properties is very attractive task. The numerous lanthanide complexes have been intensively studied in order to find the methods to manage these light conversion molecular devices1. However many questions of the influence of supramolecular structure on the photophysical properties of lanthanide systems are still opened. A choice of the presented lanthanide Schiff base (SB) systems is due to their biological importance and some luminescence advantages originated from the structural features of SBs2.
Europium complexes of Schiff bases with 1:1 and 1:2 H CH2OH (M:Lig) stoichiometric rations ([Eu(PL-Asp)(H2O)4](H2O) H (1) and [Eu(PL-His)2(H2O)2]Cl(H2O)4 (2)) have been synthe C N C COOH N sized and structurally characterized by single crystal X-ray diffraction technique. The europium polyhedron in 1 and 2 H R complexes is antiprism with considerable degree of distortion H C OH due to different nature of bonded atoms and length bond Schiff-base variation. In the solid state, complex 2 forms supramolecular networks via relatively strong intra- and intermolecular stacking and H-bonding interactions, while complex 1 are arranged in crystal by dimers via intermolecular stacking interaction of moder ate strength. Combined analysis of the luminescence and phosphorescence spectra has been used to describe the luminescence properties of SB complexes and to estimate the efficiency of energy transfer processes. As a result the effective intramolecular energy transfer from the ligands to euro pium ion has been revealed. In order to value the influence of intermolecular interactions the analy sis of the luminescence spectra, lifetimes of EuIII excited states and vibronic interaction has been performed in aqueous solutions containing these SBs as well.
One found that the intense intramolecular stacking interac 5 D0 FJ, J=0- tion between pyridoxal rings remarkably increases the stabil complex ity constant of EuIII 1:2 species of both amino acids in solu tion. The latter together with effective intramolecular energy transfer makes the lanthanide SBs perspective as a lumines cence materials for biological and medical applications.
complex Hence the influence of supramolecular architectures formed by stacking and hydrogen bonds in the crystals of the n lanthanide SB complexes on the photophysical properties and 600 stability of these systems is discussed.
Fig. 1. Luminescence spectra This work is supported by Russian Science Support Foundation.
References 1. J.-M. Lehn, Angewandte Chemie International Edition, 1988, 1, 89.
2. R. D. Archer, H. Chen, Inorg. Chem., 1998, 37, 2089.
2320 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, SUPRAMOLECULAR COMPLEX FORMATION OF THE OXATHIACROWN-ETHERS WITH VICINAL DESPOSITION OF SULFUR ATOMS Rakhmanov E.V., Bobyleva A.A., Fedorova O.A., Tulyakova E.V., Marikutsa A.V., Anisimov A.V.
Chemistry Department, Moscow State University, 119992, Moscow, Russia The discovery of the phenomenon of the ability of the crown ethers and its heteroatomic analogues to the complex formation is one of the main acheivements in the morden organic chemistry. This resulted in the formation of the novel branch in chemistry – supramolecular chemistry. The com plex formation of macrocyclic compounds depends on size of macrocyclic cavity as well as on composition of heteroatoms (O, S, N, Se, P, Te) and its disposition in macrocycle. In the present investigation the complex formation of the crown ether compounds with vicinal desposition of sul fur atoms was studied. It is known in literature that introducing of sulfur atoms into the macrocyclic cavity leads to the obtaining ligands which are able to bind different heavy and transition metal cations. Whereas, the disposition of sulfur atoms in macrocycle influences substantially on the se lectivity of complex formation process1 We suggested that ligands with vicinal desposition of sulfur atoms should effectively bind with metal cations of group of platinum.
( )n z O z( )n X O O Y S O R R S n = 1, R R R, R1 =, X = OH, Y = SH, Z = Cl R = H, R1 = CN, CH2Ph, X = Y = Br, Z = SH COH R = H, R1 = CH2-, X = Y = TsO, Z = SH MeO In the present research the results of the investigation of selectivity of complex formation of the novel dithiacrown ether ligands with cations of different nature, the values of the stability constants measured for Ag+ and Pb2+ are presented. The composition of the formed complexes was obtained from ESI-mass-specrtra, the structure of complexes were analyzed by applying of NMR spectros copy and X-ray method..
The obtained complexons were studied in experiments on extraction of metal cations from water to organic phase. It was found that compounds possess high extraction ability to Ag+ and Pb2+ cations.
The work is fulfilled by Financial Support of RBFR (№ 05-03-33201) and INTAS 03-51-4696.
References 1. A.B. Xopoшутин, A.B. Aниcимoв. Poc. xим. ж., 2007, XLIX, № 6, 47-58.
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 STEREOSPECIFIC PHOTO INITIATED [2+2] CYCLOADDITION REACTIONS IN THE SERIES OF CHALCONO-PODANDS Rusinov G.L., Ovchinnikova I.G., Fedorova O.V., Slepukhin P.A., Charushin V.N.
I. Ya. Postovsky Institute of Organic Synthesis of RAS, 22 ul. S.Kovalevskoi, 620219 Ekaterinburg, Russian Federation E-mail: firstname.lastname@example.org Due to short distances (0.36 – 0.37 nm) between two double C=C bonds in chalcono-podands 1 the intermolecular solid-state reaction has been found to occur when crystals of 1 are irradiated with UV-light. The reaction proceeds stereospecifically and results in the formation of oligomeric mole cules 2 bearing the cyclobutane fragment. Contrary to that, the intramolecular cyclization takes place when the compound 1 is allowed to react in a solution in the presence of potassium ions K+, thus giving cyclobutanes 3 bearing the fragment of crown-ethers.
C(O)Ph n* C(O)Ph * O O O O O O Ph(O)C Ph(O)C O K+ O O O O 1 Work is executed with financial support of the Russian Foundation for Basic Research (grants № 06-03-33172, 06 03-08144, 07-03-96113) and the Presidium of the Russian Academy of Science (the project «Design of new su pramolecular structures containing heterocyclic fragments»).
2322 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, SUPRAMOLECULAR SYSTEMS BASED ON MELAFEN AND SURFACTANTS Ryzhkina I.S., Murtazina L.I., Timosheva A.P., Kiseleva Yu.V., Fattakhov S.G., Konovalov A.I.
A.E.Arbuzov Institute of Organic and Physical Chemistry KazRC RAS, 8 ul. Akad. Arbuzova 420088 Kazan, Russia Fax: (843) 273 22 53. E-mail: email@example.com Melafen (melamine salt of bis(oxymethyl)phosphinic acid) is the highly effective growth regulator of plants, which presents considerable interest for a use in agriculture and biotechnology. The study of effect of melafen on the growth and the energy exchange of plant cells, on the physicochemical state of biological membranes reveals that melafen has a high physiology activity at low concentra tions. In this connection the further study of the action of melafen on the systems of different level of complication and organization is very useful and actual.
The purpose of the present work is the study of the self-association of melafen in aqueous and organic (chloroform) media and the interaction of this compound with surfactants (sodium deoxy cholate (SDC), sodium dodecyl sulfate, cetyltrimethylammonium bromide (CTAB), palmethylsul fobetain, N-cetyl-N,N-dimethyl-N-(2-hydroxiethy)lammonium bromide) and their micellar aggre gates. The association of melafen in the presence end in the absence of surfactants has been studied by permittivity measurements, conductivity, tensometry and dynamic light scattering. It was found, that melafen in water and chloroform exists as associates having the sizes from 130-120 nm to 50 60 nm depending on the concentration of melafen. These results can indicate that in the both media the mechanism of intermolecular interaction of melafen associates with the solvent structures is the same. We think that in these media the formation of nanosystem capable to self-regulation of size depending on melafen concentration occurs.
The surface tension study of melafen aqueous solutions (10-12-10-2 mol L-1) depending on surfac tant concentration (10-9–10-2 mol L-1) provides support for melafen and water at the some concen trations form supramolelular polymer structure interacting with surfactant polar groups with forma tion of surface active complex melafen/surfactant. The distinctive shape of dependence =lgCsurf suggesting the formation of melafen/surfactant complex was revealed only for SDC and CTAB hav ing carboxyl and ammonium groups. These groups widely present in a composition of membrane proteins and lipids. The sizes of complexes and mixed micelles melafen/surfactants at concentration of melafen 10-8 mol L-1 equal 55 and 75 nm, correspondingly.
This work was financially supported by the Russian Foundation for Basic Research (project no. 06-03-32402).
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 SYNTHESIS, COMPLEXATION, AND [2+2]-PHOTOCYCLOADITION OF NEW STYRYL DYES CONTAINING N-AMMONIOALKYL SUBSTITUENT Sazonov S.K., Loginov P.S., Vedernikov A.I., Lobova N.A., Kuz’mina L.G., Howard J.A.K., Alfimov M.V., Gromov S.P.
Photochemistry Center of the RAS, 7A Novatorov str., Moscow 119421, RF;
E-mail: firstname.lastname@example.org A series of 4-styrylpyridines 1 and relative styryl dyes 2 containing N-ammonioalkyl substituent were synthesized to study their complex formation properties towards 18-crown-6-containing 4-styrylpyridines 3 and 4. In acetonitrile, dyes 2 and crown ethers 3 or 4 were found to form stable complexes 5 due to host-guest interaction between NH3+ group and 18-crown-6 fragment (lg K = 2.93.8). 1H NMR data showed that, in the supramolecular complexes 5, two styryl molecules are predominantly placed one under another with “head-to-tail” mutual arrangement.
R 1, 2 : R1, R2 = H, Cl, OMe, R1 + + H3N (CH2) N SMe, NO2, NMe2;
n = 2- n N R _ R2 2 ClO 1 + n- N R O O O O + O N Et N 1 O + R O NH O O O O O O _ O ClO O O O O X 3 5 : X = N, N+Et h MeCN + 2 3 or 4 5 + = benzo-18-crown-6 fragment = (CH2)nNH = pyridine residue = C6H3R1R Irradiation of complexes 5 led to a stereospecific reaction of [2+2]-photocycloaddition with for mation of cyclobutane derivatives 6. Efficiency of the photoreaction was established to be influ enced strongly by structure of 2-4.
Financial support from the RFBR, the RSC, and the RAS is acknowledged.
2324 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, MICELLES AS STABLE SUPRAMOLECULAR STRUCTURES Shchekin A.K., Rusanov A.I., Kuni F.M.
St Petersburg State University, St Petersburg, Russia Dual nature of amphiphilic molecules of surfactants determines a variety of their properties. A pe culiar property is an ability of surfactant molecules to self-organization in both polar and non-polar solvents and formation of stable supramolecular structures. Spherical and cylindrical micelles are the examples of such structures. These structures exist in surfactant solutions at room temperatures.
Because the micellar concentrations are sensitive to variations of physical and chemical parameters, micelles play an important role in equilibria and relaxation processes in surfactant solutions and liquid-crystalline systems.
We developed in the last few years a systematic description of many-scale relaxation processes with participation of spherical and cylindrical micelles. We used1,2 a general kinetic approach based on the methods of nucleation theory and recent development of the thermodynamic models for mo lecular aggregates of surfactants. The fact that micelles are relatively stable structures, determines the hierarchy of fast and slow processes in surfactant solutions. Fast processes lead to establishing separate quasi-equilibria of spherical and cylindrical micelles which are not followed by break of old or appearance of new micelles.1,3 Slow relaxation processes in surfactant solutions provide es tablishing an overall equilibrium through break and formation of micelles at direct and back transi tions over the potential barriers for spherical and cylindrical micelles.1, We also developed the kinetic theory of individual stages of fast and slow relaxation in solutions with spherical and cylindrical micelles. Usually, when one speaks about the relaxation time, he as sumes the characteristic time for an exponentially decaying disturbance. However, the regime of exponential decay is achieved at the final stage of relaxation only, when the deviations of monomer and micellar concentrations from their quasi-equilibrium or equilibrium values become very small.
In addition to the final stage of relaxation with the exponential law of decay of concentration dis turbances in time, the preceding stage with the power law variation of concentrations in time has significance in the whole relaxation. It is just the power law stage when the main nonlinear changes in relaxing parameters of micellar solution occur that can be clearly fixed in experiment. An impor tant peculiarity of the power law stage of relaxation in comparison with the stage of exponential relaxation is the dependence of characteristic times and the total duration of the power law stage on the way how, from above or from below, the relaxing characteristics of micellar solution approach to their equilibrium values.
The work was done under the financial support of RFBR (grant 07-03-00245) and program 7 of RAS “Chemistry and physicochemistry of supramolecular systems and atomic clusters”.
References 1. A.K. Shchekin, F.M. Kuni, A.P. Grinin, A.I. Rusanov. In “Nucleation Theory and Applications”, Ed. J. W. P.
Schmelzer. WILEY-VCH, Berlin – Weinheim, 2004. P. 397.
2. F.M. Kuni, A.K. Shchekin, A.I. Rusanov, A.P. Grinin, Langmuir 2006, 22, 1534.
3. A.K. Shchekin, F.M. Kuni, A.P. Grinin, A.I. Rusanov. Colloid Journal. 2006, 68, 277.
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 STRUCTURE AND STABILITY OF THE LANTHANIDE CRYPTATES IN SOLUTIONS Shestakova A.K.a, Chertkov V.A.b a State Research Institute of Chemistry and Technology of Organoelement Compounds, Moscow, 111123, Russia b Department of Chemistry, Lomonosov Moscow State University, Moscow, 119992, Russia Stable complexes of azacrownethers and cryptands with different metal ions are known for about two decades. Of special interest are the lanthanide derivatives due to their superb hydrolytic cleav age of biocidic phosphate esters, DNA and RNA.
We have studied the complexation of MX3 (M = La, Eu and Pr;
X = Cl, NO3 and SO3CF3) with 1,10-diaza-18-crown-6 with R = H at N (I), R = n-C10H23 (II), cryptand (III) and cryptand (IV). The 1H and 13C NMR spectra revealed for the complexes different types of co ordination sphere for the lanthanide ions. The nature of solvent is important factor for controlling the ligature type. In classical innersphere complexes, metal atom binds to all co-ordination sites of the ligands (first of all N-atoms). Complexation leads to dramatic effect on conformation of the ligand, which studied by detailed analysis of multiplet structure of high resolution 1H NMR spectra and supported for the most important cases by X-Ray studies. 139La NMR provides important in formation on the structure of first co-ordination shell of the lanthanide complexes in solutions.
Complexation with monocyclic ligands I and II leads to deshielding effect of 139La nuclei by ppm, while co-ordination with bicyclic IV (D3h-symmetry complex) enlarges shielding by 100- ppm. The innersphere complexes of host-guest type are rigid on the NMR time scale. Their struc ture analysis was performed using the whole magnitude of NMR spectral information, first of all the spin-spin coupling network for the diamagnetic La(III) complexes. Comparison of the chemical shifts for the diamagnetic La(III) and paramagnetic Eu(III) and Pr(III) complexes provides a contact and pseudocontact shielding terms for both 1H and 13C nuclei, which also allows the geometry in terpretation.
Monocyclic ligands I and II form complexes with C2v –symmetry and cis-conformation in weak solvating solvents (chloroform, acetonitrile, methanol), which supported also by Xray data of com plex between lanthanum nitrate and macrocycle I.1 The complexes with cryptand are highly stable even in water solutions. We show, that complexes with the cryptand of the type EuX3L (X = Cl, NO3 and SO3CF3;
L = IV) exist in the two forms: with D3h and C2v-symmetry. In contrast to monocyclic ligands, lanthanide cryptates are formed slowly on NMR time scale (see e.g.2). We present here results of the kinetics studies of their formation for europium chloride and triflate in methanol solution. Xray diffraction data revealed the structure of innersphere almost C2v– symmetrical complex with cryptand and hydrated lanthanum triflate. A series of ECP quantum chemical calculations (Lanl2dz approach) supports the structure of complexes under study. Experi mental vicinal spin-spin coupling constants between protons of neighboring CH2-groups for com plexes of lanthanum salts with macrocyclic ligands I and III in solutions (CDCl3, CD3OD and CD3CN) are in good agreement with the ab’inito calculated ones (PFT DFT with Ub3lyp and 6G/311(d) basis set). The conformation of the biggest loop of the cryptand is close to that of 1,10-diaza-18-crown-6 in their lanthanum complexes.
Acknowledgements: This research was supported by the Russian Foundation for Basic Research (Grant 06-03 32800), and AVH Research Fellowship.
References 1. A.K. Shestakova, V.A. Chertkov, H.-J. Schneider, K.A. Lysenko, Org. Letters, 2001, 3, 325.
2. A.K. Shestakova, V.A. Chertkov, H.-J. Schneider, Tetr. Letters, 2000, 41, 6753.
2326 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, THE EFFECT OF MEDIA ON FORMATION OF SUPRAMOLECULAR POLYELECTROLYTE – SURFACTANT COMLEXES Shilova S.V., Tretyakova A.Y., Bezrukov A.N., Barabanov W.P.
Kazan state technological university, 68, ul. Karla Marksa, Kazan Self – organization in such systems as polyelectrolyte – micelle forming surfactant leads to forma tion of nanosized polymeric structures (polymer – colloid complexes). As a system in a distin guished new heterogeneous state, it can be used as a catalyst, sorbent, precipitator, dispersion sys tem stabilizer, biologically active substance and also in model analysis of cell membranes1. Due to their distinctive ability to change properties following environmental fluctuations (temperature, pH, system composition), polymer – colloid complexes fall into category of so called «smart» poly mers2.
The task of this research is to reveal the function of media in formation of polymer – colloid complexes and its use for guided influence on properties of polyelectrolyte – surfactant complexes.
Research objects: cationic polyelectrolytes (quaternized poly-4-vinylpyridine compounds and poly-N-benzyl-N,N,N-dimethylmethacryloiloxyethylammonium chloride) and anionic surfactant (sodium dodecylsulfate). This research was carried out in water – aliphatic alcohol solutions (methanol, ethanol and isopropanol) with variable ratio of components.
The binding characteristics, hydrodynamic properties and stability of polymer – surfactant com plexes have extreme nature. Small additions of ethanol and isopropanol in complex solvents ( vol.% for ethanol and 10 vol.% for isopropanol respectively) reduce surfactant’s concentration cor responding to intensive electrostatic binding of surfactant by polyelectrolyte. The increase of methanol’s concentration to 30 vol.% doesn’t show any visible difference to surfactant binding in aqueous solution. Further adding of all studied alcohols into complex solution reduces ability of polyelectrolyte to form complexes with surfactant.
This effect of nature and composition of solvent on formation and dissipation of polymer – col loid complexes is an opportunity to control the formation – dissipation process of polyelectrolyte – surfactant complexes by varying solvent’s structure.
The research is carried out under financial assistance of the Academy of Sciences of Tatarstan (№07 7.4.2/2007(ФП) References 1. Goddard E.D. Colloids and Surfaces 1986, 3, 301.
2. Гaлaeв И.Ю. Уcпexи xимии 1995, 5, 505.
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 NEW PHOSPHORYL-CONTAINING COMPOUNDS WITH DIAZA BOND AS SELECTIVE LIGANDS FOR CATION CU2+ Shnipov A.V.a, Ivanova I.S.b, Pjatova E.N.b, Minacheva L.H.b, Baulin V.E.a, Tsivadze A.Yu.a a Institute of Physical Chemistry and Electrochemistry named after A.N. Frumkin. RAS Leninskiy p. 31, Moscow, 119991, Russia b Institute of Inorganic and General Chemistry named after N.S. Kurnakov RAS, Leninskiy p. 31, Moscow, 117907, Russia The coordination ability of phosphoryl group is widely employed in design of different complexa tion agents. Compounds containing the fragments with double diaza bond are interesting as light sensitive switching substances. It was ascertained that cis- and trans- forms of this compounds have different ion-selective properties. Aiming to find readily available selective and effective complexa tion agents, which may be used as active components of light sensitive material the compounds (I IV) have been investigated:
O P HO O O O P NN P N O O N I II O O O HO O O P P O N O O O N III IV A series of metal complexes with L = I-IV of general formula CuL2H2O, M(NO3)32L2H2O (M = Er, Nd) have been synthesized. Some of their properties (solubility, thermal stability, vibration spectra) have been investigated. The structure of CuL2H2O (L=I) has been studied by X-ray crys tallography. The electrochemical behavior of plasticized PVC membranes containing compounds (I-IV) has been investigated. The new Cu2+-selective electrode based on PVC membrane containing I is suggested. The electrode shows high selectivity in presence of mono- and divalent cations and potentiometric determination of Cu2+ is possible in presence alkali, alkaline earth and heavy metals.
The advantages of the suggested electrode in comparison with other types of Cu2+selective elec trodes are discussed.
The work was supported by the program of RAS “Theoretical and experimental studying of the nature of chemical bond and mechanisms of the major chemical reactions and processes” and the program of RAS “Development of methods of reception of chemical substances and creation of new materials”.
2328 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, SYNTHESIS AND COORDINATION OF THE FUNCTIONAL DERIVATIVES OF BENZOTHIACROWN COMPOUNDS WITH PALLADIUM(II) Sidorenko N.I.a, Dmitrieva S.N.b, Vedernikov A.I.b, Kuz’mina L.G.c, Kurchavov N.A.b, Buslaeva T.M.a, Gromov S.P.b a M.V. Lomonosov Moscow State Academy of Fine Chemical Technology, Vernadsky av. 86, 119573, Moscow, Russia, e-mail: email@example.com;
b Photochemistry Center of RAS, Novatorov str. 7A, Moscow 119421, Russia;
c N.S. Kurnakov Institute of General and Inorganic Chemistry of the RAS, Leninsky av. 31., 119991 Moscow, Russia It is known that the sulfur-containing macroheterocycles are effective for coordination with transi tion metals cations. Such compounds may be used as selective extragents, in the ion-selective elec trodes, for the modification of chromatographic sorbents. For the expansion of the practical applica tion of crown compounds the study of coordination properties of there the most important func tional derivatives has the great importance.
In the present study the synthesis and investigation of the complexes of crown compounds (L) with palladium (II) are presented.
X O X, Y = S, O;
Y Z = NO2, CHO;
O Z n=0- X n L It was determined that the reactions of benzodithiacrown compounds with Pd(CH3CN)2Cl2 and Pd(OAc)2 in equimolar ratio lead to the formation of complexes with composition PdCl2L and Pd(OAc)2L. In case of nitrobenzomonothiacrown compound (X = O, Y = S) the formation of com plex PdCl2L2 is possible.
The structures of the obtained complexes have been proved by the NMR and elemental analysis.
The structures of the 4’-formylbenzodithia-12(21)-crown-4(7)-compounds and 4’ nitrobenzodithia-18-crown-6-compound were investigated by the X-ray diffraction. In these com plexes the palladium(II) forms two coordination bonds with sulfur atoms of the macroheterocycle and two bonds with the chlorine atoms. The four form the plane coordination sphere of palla dium(II). The sulfur and chlorine atoms have the cis-arragement in the case of 12- fnd 18 membered macroheterocycles and trans-arragement in case of 21-membered one.
The nitrobenzodithiacrown compounds have been tested as extragents of palladium(II) salts from hydrochloric acid solutions.
This work is supported by the Russian Fondation for Basic Research (project № 06-03-32456) and the Russian Academy of Science.
ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 THE EFFECT OF A SOLVENT MODIFIER IN THE CESIUM EXTRACTION BY A CALIXARENE: A MOLECULAR DYNAMICS STUDY OF THE OIL PHASE AND THE OIL – WATER INTERFACE Sieffert N., Wipff G.
Laboratoire MSM, UMR CNRS 7177, Institut de Chimie, Universit Louis Pasteur 4 rue B. Pascal, 67 000 Strasbourg (France).
firstname.lastname@example.org Abstract. We report a molecular dynamics study of the effect of a fluorinated lipophilic alcohol “cs3” used as phase modifier in the solvent extraction of Cs+ NO3- by a calixarene (L). It is shown that adding cs3 to a dry chloroform phase improves the solvation of all extraction partners, and especially of NO3- via strong H-bonding interactions with the –OH and terminal –CF2H protons of cs3. When contacted with an aqueous phase, the modifiers adsorb at the liquid-liquid interface and stabilize the formation of water nanodroplets. Calixarene complexes also adsorb at the aqueous interface in the presence of modifiers, confirming the importance of interfacial phenomena in the assisted cation extraction process. The microscopic insights obtained by the simulations are consis tent with experimental results and allow us to better understand why the extraction is enhanced after addition of modifiers to the organic phase.
OMe MeO O O Cs+ O O OO LCs+ LCs+NO3– (cs3)2 (a) OCF2CF2H O OH (b) cs + – Snapshot of the LCs NO3 complex (a) and typical water nanodroplet (b) in chloroform+modifiers solution.
2330 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, THE DINUCLEAR CALIXARENE BASED METAL COMPLEXES AS A BASIS OF MOLECULAR DEVICES Skripacheva V.V., Mustafina A.R., Burilov V.A., Yanilkin V.V., Nastapova N.V., Stepanov A.S., Solovieva S.E., Antipin I.S., Konovalov A.I.