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DEPARTMENT OF PHYSICOCHEMICAL INVESTIGATIONS

Head of department: Assoc. Prof. Dr. M.I. Povolotskii

Head of department: Assoc. Prof. Dr. M.I. Povolotskii

Department of physicochemical researches (the previous name is Department of molecular structure and spectroscopy) was found in 1968. The founder and first head of the Department was Prof. Yu.P. Egorov. Since 1995 the department is headed by Dr. M.I. Povolotskii. The analytic laboratory headed by N.I. Kuznetsova is a constituent part of the Department.

The main scientific direction of the Department is a study of the molecular and electronic structure of organic and organoelement compounds, synthesized in the Institute of Organic Chemistry of NAS of Ukraine. For this purpose, X-ray single-crystal diffraction method (XRD), nuclear magnetic resonance (NMR) spectroscopy, optical (UV/Vis and IR) spectroscopy, gas and liquid chromatography, element analysis of organic and organoelement compounds and quantum chemical calculations) are used in the Department.

The available NMR spectrometers Varian VXR-300 and Gemini-200BB make it possible to study molecular structures and conformations of the synthesized organic and organoelement compounds, check their purity and collect their spectral characteristics.

For X-ray diffraction studies of chemical compounds a monocrystal diffractometer Bruker SMART APEX II and two four-circle diffractometers Enraf-Nonius CAD-4 are used. This modern equipment allows us to determine molecular structure not only for crystal samples, but also for those ones, which are liquid or gas under normal conditions. The available diffractometers are suitable for observing phase transformations, studying conformational properties of compounds and also for investigating subtle effects of their molecular and electronic structure. A variety of classes of chemical species, including organic, inorganic and organoelement compounds, was studied by XRD method. In particular, this approach is widely used for investigation of structure of dyes, biologically active species and new chemical compounds, which are prospective as sensors for information storage and for the transportation and storage of retained gases under relatively low pressure.

Department members carry out theoretical studies of structure, electron distribution and reactivity of organic and organoelement compounds using modern quantum chemistry methods. The technical capacity and available program packets (TURBOMOLE, ORCA, GROMACS etc.) allow us to perform a broad spectrum of theoretical investigations. It includes molecular mechanics/molecular dynamics and docking for biochemical species, hybrid approaches QM/MM (DFT/ molecular mechanics) and precise calculations for organic molecules in vacuum, in solution and in crystal using the periodic boundary conditions (CRYSTAL-09 program set).

Using IR and UV-spectroscopy reactivity of organic and organoelement compounds and their ability to form complexes are studied. Using gas and liquid chromatography, in the Department pharmacokinetic for drugs is investigated and new methods of the chromatographical analysis are developed. In the analytic laboratory, quantitative element analysis of organic and organoelement compounds are carried out using the automatic analyzers “Саrlo-Еrba” (Italy).

Main scientific achievements of the Department.

The programs have been developed for calculating thermodynamic characteristics of dynamic processes in NMR spectra and for conformational analyses of cyclic structures. Theoretically (using quantum chemical calculations at the DFT level of approximation) and experimentally (using dynamic NMR approaches) some conformational transformations in organic and organoelement compounds have been studied. The potential energy surfaces and mechanisms for a series of chemical reactions have been investigated by quantum chemical methods. The factors influencing thermodynamic stability and reactivity of heteroatom-substituted carbenes have been analyzed. The structure of calixarenes and structurally similar species have been studied by means of theoretical and spectroscopic methods. By X-ray diffraction method some special structural peculiarities of have been elucidated for several thousand of new chemical substances from various categories.

Generalizing the data of the molecular and crystal structures of low-coordinated phosphorus compounds elucidated by X-ray analysis, multinuclear NMR spectroscopy and quantum chemical calculations, the foundation has been laid for the structural chemistry of phosphorus-containing compounds with unconventional phosphorus coordination.

Department stuff:

  • Dr. Mark I. Povolotskii
  • Dr. Vladimir V. Pirozhenko
  • Dr. Alexander B. Rozhenko
  • Dr. Eduard B. Rusanov
  • Dr. Olga I. Kalchenko
  • Igor V. Boldyrev
  • Andrey A. Kirilchuk
  • Yury G. Vlasenko
  • Nataliya I. Kuznetsova
  • Elena A. Smertenko
  • Valentina S. Shafranova
  • Tatiana A. Romanika
  • Leila L. Saava
  • Viktoriya V. Falkivs’ka

Science and Technology cooperation:

  • Prof. Dr. Uwe Manthe, Prof. Dr. Wolfgang W. Schoeller, Chair of Theoretical Chemistry, Department of chemistry, University of Bielefeld, Germany.
  • Prof. Dr. Jochen Mattay, Chair of Organic Chemistry, Department of chemistry, University of Bielefeld, Germany.
  • Prof. Jerzy Leszczynski, Department of Chemistry and Biochemistry, Jackson State University, Jackson, Mississippi, USA.
  • Alexander von Humboldt Foundation, Bonn, Germany.
  • The Science and Technology Center in Ukraine (STCU).

 

Publications:

1. P. Jutzi, A. Mix, B. Neumann, B. Rummel, W. W. Schoeller, H.-G. Stammler, A.B. Rozhenko. Reversible Transformation of a Stable Monomeric Silicon(II) Compound into a Stable Disilene by Phase Transfer: Experimental and Theoretical Studies of the System {[(Me3Si)2N](Me5C5)Si}n with n = 1,2. J. Amer. Chem. Soc. 2009, 131, p. 12137–12143.

2. T. Westermann, R. Brodbeck, A.B. Rozhenko, W.W. Schoeller, U. Manthe. Photodissociation of methyl iodide embedded in host-guest complex: a full dimensional (189D) quantum dynamics study of CH3I@resorc[4]arene. J. Chem. Phys. 2011, 135, 184102.

3. R.M.Burgess, I.M.Konovets,L.S.Kipnis, A.V.Lyashenko V.A. Grintsov, A. N. Petrov, A.V. Terletskaya, M.V.Milyukin, M.I. Povolotskii, V.Y.Demchenko, T. Bogoslovskaya, Y.V.Topkin, T.V.Vorobyova, L. M. Portis, Kay T. Ho. Distribution, magnitude and characterization of the toxicity of Ukrainian estuarine sediments. Marine Pollution Bulletin, 2011, 62, p. 2442-2462.

4. A.B. Rozhenko, W.W. Schoeller, M.C. Letzel, B. Decker, J. Mattay. Anion-p Interactions in Adducts of Anionic Guests with Octahydroxy-pyridine[4]arene: Theoretical and Experimental Study. New J. Chem. 2013, 37, р. 356–365.

5. O.I. Guzyr, S.V. Zasukha, Yu.G. Vlasenko, A.N. Chernega, A.B. Rozhenko, Yu.G. Shermolovich, Simple Route to Adducts of (Amino)(aryl)carbene with Phosphorus Pentafluoride. Eur. J. Inorg. Chem. 2013, p. 4154–4158.

6. A. V. Ruban, A. B. Rozhenko, V. V. Pirozhenko, S. V. Shishkina, O. V. Shishkin, A. M. Sikorsky, S. O. Cherenok, V. I. Kalchenko, Tetrahedron Lett. 2013, 54, 3496–3499.

7. A.S. Degtyarenko, E.B. Rusanov,  A. Bauza, A. Frontera, H. Krautscheid, A.N. Chernega, A.A. Mokhir, K.V. Domasevitch. Self assembly cavitand precisely recognizing hexafluorosilicate: a concerted action of two coordination and twelve CH—F bonds. Chem. Comm. 2013, 49, p 9018-9020.

8. L.F. Lourie, Y.A. Serguchev, M.V. Ponomarenko, E.B. Rusanov, V.M. Vovk, N.V. Ignat’ev. Electrophilic fluorocyclization of unsaturated alcohols ionic liquids. Tetrahedron, 2013, 69, p. 833-838.

9. G.A. Senchyk, A.B. Lysenko, H. Krautscheid, , E.B. Rusanov, A.N. Chernega, K.W. Kramer, S.-X. Liu,  K.V. Domasevitch. Functionalized adamantane tectons used in the design of mixed-ligand cooper(II) 1,2,4-triazolyl/carboxylate metal-organic frameworks.  Inorg. Chem. 2013, 52, p. 863-972.

10. V.A. Sukach, V.M. Tkachuk, V.M. Shoba, V.V. Pirozhenko, E.B. Rusanov, A.A. Chekotilo, G.-V. Roschenthaler, V.M. Vovk. Control of regio- and enantioselectivity in the asymmetric organocatalytic addition of acetone to 4-(trifluoromethyl)pyrimidin-2(1H)ones. Eur. J. Org. Chem. 2014, p 1452-1460.

11. A.B. Rozhenko, W.W. Schoeller, J. Leszczynski, On the Stability of Perfluoroalkyl-Substituted Singlet Carbenes: A Coupled-Cluster Quantum Chemical Study. J. Phys. Chem. A, 2014, 118, p.1470-1488.

12. A.B. Rozhenko. Density functional theory calculations of enzyme-inhibitor interactions in medicinal chemistry and drug design. In: Application of Computational Techniques in Pharmacy and Medicine #3. Springer, will be published soon.