Lomonosov Moscow State University
Chemistry Department
Chemical Kinetics Chair

LABORATORY ON LOW TEMPERATURE CHEMISTRY

Address:
119899 Moscow, Leninskie Gori 1/3
MSU, Chemistry Department
Room 133, 134 (right)
Tel: 7(095)939-5442
E-mail:gbs@kinet.chem.msu.ru

Laboratory on Low Temperature Chemistry was founded in 1974 by initiative of Nobel Prize Winner Academician  N.N.Semenov

The Head of the Laboratory  - Professor, Lomonosov Prize Winner (1976), Honored Scientist of Russian Federation (1997) Gleb Borisovich Sergeev

Laboratory Staff:

Dr.Shabatina Tatyana Igorevna – Senior Scientist, Laboratory Acting Manager

Dr. Sergeev Boris Michailovich - Senior Scientist

Dr. Zagorskii Vyacheslav Victorovich - Senior Scientist

Dr. Komarov Valerii Sergeevich – Research Chemist

Dr. Morosov Yurii Nikolaevich  - Research Chemist

Dr.Soloviev Victor Nikolaevich - Research Chemist

Dr. Kiryuhin Maxim Vladimirovich - Research Chemist

M.Sci.Vlasov Alexei Victorovich - Research Chemist

M.Sci. Bazulin Alexander Feliksovich - Research Chemist

M.Sci. Bochenkov  Vladimir Evgenievich - Research Chemist

M.Sci. Timoshenko Vadim Alexandrovich – Jr. Research Chemist

M.Sci. Mikhalev Sergei Pavlovich – Jr. Research Chemist

Students:

Gorskaya Elena, Belyaev Anatolii, Lasarev Vladimir, Dibov Alexander, Sineva Dina

Main Research Directions:

· Generation, stabilization and reations of metal atoms, clusters and nanoparticles in inert and active matrices in temperature range 10-300 K

· Reactions in cryostructured and molecular organized systems at low temperatures, including liquid crystals and partially ordered solid states

· Cryoformation of metall-mesogenic and metallpolymer nanostructures and study of their  physical and chemical properties

· Size and temperature effects on activity and selectivity of metal nanoparticle’s chemical interactions. Sensor and catalytic properties

· Cryo-condensation of reagent vapors, low temperature UV-, IR-, ESR-spectroscopy, gas chromatography, calorymetry, electrical conductivity measurements

· Molecular  modeling in co-operation with the Laboratory on Chemical Cybernetics (Prof.A.V.Nemukhin)

· Electron  microscopy in  co-operation with the Electron Microscopy Division of Moscow State University

Teaching:

Special courses on Low Temperature Chemistry was founded on the base of the Laboratory on Low Temperature Chemistry, The Head – Professor Gleb B.Sergeev

Prof.Gleb B.Sergeev  holds lectures “ The Bases of Cryochemistry” for graduate students, Ph D students and audience of Special courses on Low Temperature Chemistry. The lectures include following parts: basic methods and technique; molecular, radical and chain radical reactions at low temperatures; cryoreactions of atoms, clusters and nanoparticles of metals; spontaneous reactions through complex formation; reactions in frozen solutions and organized media; cryobiochemical reactions; low temperature applications in science and industry.

Three doctors of science, 29 doctors and more than 50 graduates have been prepared in the laboratory.

Grants:

INTAS 2000-00911, 2 RFFI grants, grant of Russian Federal Programme “Universities of Russia”, grant of Ministry of Science

International Collaboration:

Potsdam University (Germany), University of Southampton (UK), Institute on Low Temperature Physics National Academy of Ukraine ( Kharkov, Ukraine), Armenian Institute for Technical Chemistry (Erevan, Armenia)

Main publications:

Monographies:

1.      G.B.Sergeev, V.A.Batyuk “Cryochemistry”, Mir Publ., Moscow, 1986, P.321

2.      G.B.Sergeev, V.V.Smirnov “ Molecular halogenation of olefines” , MSU Publ., Moscow, 1985, P.240.

3.      V.A.Batyuk, T.I.Shabatina, T.N.Boronina ,G.B.Sergeev. Reactions in Liquid Crystals, Ser. Kinetics and Catalysis, VINITI Publ., Moscow 1990, P.95.

Recent Papers:

1.      G.B Sergeev, V.V Zagorsky,. and M.A Petrukhina,.Nanosize Metal Particles in poly-(para)xylylene films obtained by low temperature co-deposition, J.Mater. Chem., 1995,5,31-34.

2.      G.B. Sergeev and M.A. Petrukhina Encapsulation of Small Metal Particles in Solid Organic Matrices. Progress in Solid State Chemistry, 1996, v.24, ¹4, 183-211.

3.      G.B.Sergeev, M.Yu.Efremov. Size effects in reactions of solid organic compounds with metal particles. –Mol.Cryst.Liq.Cryst., 1996, 278, 17-25.

4.      T.I.Shabatina, E.V. Vovk, T.V.Khasanova, G.N.Andreev, G.B.Sergeev. Spectroscopic investigation of molecular aggregation in thin condensate films of polar liquid crystals. Supramolecular Science, 1997, 4, 485-489.

5.      G.V Bushueva, V.V Zagorsky, G.M Zinenkova, M.A Petrukhina, O.P.Revokatov,. and G.B.Sergeev, TEM investigation of poly-para-xylylene metal containing films, Bull. of the Russian Acad. .of Science, Ser. Phys., 1997, 61, 1871.

6.      V.Solov'ev, G.Sergeev, A.Nemukhin, T.Burt, I.Topol'. IR-matrix isolation and ab initio identification of products of the reactions of CH3Cl and CH3Br with magnesium.-J.Phys.Chem.,A, 1997, v.101 (46), 8625-8630.

7.      W.E.Klotzbuecher, M.A.Petrukhina, G.B.Sergeev. Holmium atoms and small clusters in inert matrices.-J.Phys.Chem.A, 1997, 101, 4548-4554.

8.      G.B.Sergeev, V.V Zagorsky, M.A Petrukhina, S.A.Zav'yalov, E.I.Grigor'ev, L.I.Trakhtenberg. Preliminary study of the interaction of metal nanoparticle-containing poly-para-xylylene films with ammonia.- Analyt. Commun., 1997, 34, 113

9.      G.B.Sergeev. Reactions in solid low temperature co-condensates. –Mol.Cryst.Liq.Cryst., 1998, 313, 155-166.

10.  N.V.Ozhegova, A.V.Nemukhin, T.I.Shabatina, G.B.Sergeev. Modeling structure and spectra of silver complexes in condensate films of polar liquid crystals. Mendeleev Commun., 1998, N6, 218.

11.  A.Yu.Ermilov, A.V.Nemukhin, G.B.Sergeev.Structure of mixed metal clusters.- Bull. of the Russian Acad. of Science, Ser. Phys., 1998, 62, 1169.

12.  B.M.Sergeev, G.B.Sergeev, A.N.Prusov.- Cryochemical synthesis of bimetallic nanoparticles in silver-lead-methylacrylate system.-Mendeleev Commun., 1998, p.1.

13.  V.V.Zagorskii, V.E.Botchenkov, S.V.Ivashko, G.B.Sergeev.-Cryochemical Synthesis and Physical-chemical properties of nano-dispersed metallopolymers. Nanostructured Materials, 1999, 12, 863.

14.  V.N.Solov'ev, E.V.Polykarpov, A.V. Nemukhin, G.B.Sergeev. Matrix isolation and ab initio study of the reactions of magnesium atoms and clusters with CO2, C2H4, CO2/C2H4 mixtures: formation of cyclic complexes. - J.Phys.Chem.A, 1999, 103 (34), 6721-6725.

15.  G.B.Sergeev, B.M.Sergeev, T.I.Shabatina, A.V.Nemukhin, V.V.Zagorskii, Cryosynthesis and properties of meal-organic nanomaterials.- Nanostructured Materials, 1999,12, 1113.

16.  T.I. Shabatina, E.V. Vovk, N.V.Ozhegova, Yu.N.Morozov, A.V. Nemukhin, G.B. Sergeev. Synthesis and properties of metal-mesogenic nanostructures. Material Science and Engineering, 1999, v.8, N9, 53-56.

17.  B.M.Sergeev, V.A.Kasaikin, E.V.Litmanovich, G.B.Sergeev. Cryochemical Synthesis and Properties of silver nanoparticle dispersions stabilised by poly-(2-dimethylaminoethyl methacrylate).- Mendeleev Commun., 1999, N4, p.130-132.

18.  V.V. Zagorsky, V.E. Bochenkov, S.V. Ivashko, G.B. Sergeev. Electric conductivity of organic films, containing nanosize metal particles. Material Science and Engineering,1999, v.8, N9, 329-334.

19.  G.B.Sergeev, T.I.Shabatina, V.N.Solov'ev, V.V.Zagorskii.Spectroscopic study of low temperature interactions in metal-organic so-condensates// Spectrochimica Acta, 2000,V56 N13 p. 2527-2537

20.  T.I.Shabatina, V.V.Vlasov, E.V.Vovk, D.J.Stufkens, G.B.Sergeev. Spectroscopic study of low temperature interactions in Sm-mesogenic cyanophenyl co-condensates // Spectrochimica Acta, 2000, V.56, N13, p. 2539-2543

21.  Sergeev G.B. Nanochemistry of metals, Russian Chemical Reviews, 2001.v. 70 (10),p.808.;

22.  Sergeev G.B., Shabatina T.I., Solov'ev V.N., Zagorskii V.V.Reactions of Solid Organic Compounds with Metal Species, Mol.Cryst.Liq.Cryst., 2001, v.356, p.111;

23.  Sergeev B.M., Sergeev G.B., Kasaikin V.A., Litmanovich E.A.,Prusov A.N. Low-Temperature Synthesis and Properties of Silver NanoparticlesStabilised by Acrylic Polymers, Mol.Cryst.Liq.Cryst., 2001, v.356,p.121;

24.  Shabatina T.I., Vovk E.V., Morosov Yu.N., Timoshenko V.A., Sergeev G.B. Spectroscopic Study of Silver-Containing MesogenicCyanobiphenyls in Solid Phase, Mol.Cryst.Liq.Cryst., 2001, v.356, p. 143;

25.  Shabatina T.I., Vovk E.V., Morosov Yu.N., Timoshenko V.A., Sergeev G.B. Thermal behavior of silver-containing mesogenic cyanobiphenyl films. Colloids and Surfaces A: Physicochemical and Engineering aspects, 2002, pp.255-259,

26.  Botchenkov V.E., Stephan N.,.Brehmer L,.Zagorskii V.V, Sergeev G.B. Sensor activity of thin polymer containing lead nanoparticles. Colloids and Surfaces A: Physicochemical and Engineering aspects, 2002, pp.911-915.

32. Sergeev G.B., Shabatina T.I. Low temperature surface chemistry and nanostructures. Surface Science, 2002, 500, 628-655.

Main results:

  •     The development of the kinetic description of the reactions in frozen solutions, liquid crystals, solid state cryochemical reactions. For reactions in frozen solutions the structural-kinetic model was developed , that  considered the temperature dependencies of  media properties.
  •     The kinetic model have been developed for reactions in liquid crystals that considered the self-association and order fluctuations in mesophase and isotropic phase.
  •     The selective chemical processes were carried out and new cryochemical methods of methastable solutions, high porous crystals and inclusion compounds formation were found.
  •     The experimental approach for the investigation of  low temperature co-condensates including metal atoms and clusters has been developed. The mechanisms of low temperature Grignard  reaction and alkohols reduction were established and  cryochemical methods  for synthesis of  high volatile lanthanides compounds have been developed.
  •     The role of molecular complexes in cryochemical reactions was established for molecular halogenation and hydrohalogenation of olefines, the competition of  molecular, radical and ionic reactions was analysed.
  •     The kinetics of nitroxides formation was shown use as a sensitive kinetic probe for local ordering and molecular dynamic changes. The kinetic model for radical reactions in plastic mesogens has been developed.
  •     The concepts of the effect of mechanical stresses, formation prehistory of the samples, the film sample thickness and the size of metal cluster (the number of atoms in cluster) on cryochemical reactions have been developed.
  •     Matrix isolation method has been developed and cryochemical reactions of atoms and clusters of magnesium and samarium with some small molecules were studied. The higher activity of metal clusters in comparison with their atoms was shown. Spectral data were confirmed by the results of quantum chemistry calculations.
  •     The methods of formation and stabilisation of metal nanoparticles of 5-10 nm in size have been developed using monomers polymerized at low temperatures and  acrylic monomers. The inclusion of silver nanoparticles, obtained by cryosynthesis and by chemical reduction in reversed micelles. 
  •     The cryoformation of silver and copper nanoparticles including in liquid crystalline matrix has been performed. It was shown the possibility of unusual chemical transformations of metal nanoparticles at low temperatures and of new catalytic and sensor systems obtaining.
  •     The methods ofcryotensimetry, electrical conductivity measurements, low temparature film differential calorimetry  were developed  for film co-condensate samples study.
  •     The main problem for developing  investigations is the connection between the reactive specie size and their reactivity. The new research directions have been established – cryonanochemistry and metal  nanochemistry.
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