Non-covalent Interactions Laboratory

Research

Non-covalent Interactions

Non-covalent interaction is the common name for interactions the formation of which does not result in the commonization of the electron density. The energy of non-covalent interactions is much lower than the energy of covalent ones. However, due to their prevalence, non-covalent interactions have a significant influence on the physical, chemical, and structural properties of molecules. These mobile and variable interactions while often not determining the constancy of the composition of a chemical compound in different phase states, govern many of its physical, chemical, and structural properties. These interactions can be found in biopolymers, liquid crystals, supramolecular aggregates, solutions, liquids, and molecular crystals. Non-covalent interactions are ubiquitous, numerous, and functional: every chemical reaction starts with them and every condensed state of matter is maintained by them.

All known to date non-covalent interactions can be classified into four groups: electrostatic, Van-der-Waals, hydrophobic, and π-interaction.

Electrostatic interactions include hydrogen bonding, σ-hole interactions (halogen, pnictogen, halcogen, aerogen, tetrel etc.), agnostic interactions and ionic interactions.

• Halogen bonding occurs due to an attractive interaction between the electrophilic region of the halogen atom (the so-called σ-hole) and the nucleophilic region (such as an unshared electron pair) in another molecule. This interaction is widely used in such fields as supramolecular chemistry, crystallography, and liquid crystal fabrication.
• Hydrogen bonding occurs when a hydrogen atom bonded to a strongly negative atom (fluorine, oxygen, nitrogen, etc.) comes to proximity with another electronegative atom. These bonds are usually stronger than normal dipole-dipole and dispersion forces, but weaker than true covalent and ionic bonds. Hydrogen bonding largely determines the properties of such biologically important substances as proteins and nucleic acids. In particular, secondary structure (e.g., α-helices, β-folds) and tertiary structure in proteins, RNA, and DNA molecules are stabilized by hydrogen bonds.
• Ionic interaction is realized by electrostatic attraction between anions and cations. The most important features of ionic bonding from other types of chemical bonding are its non-directional and non-saturated nature. That is why crystals formed by ionic bonding tend to have various dense packings of the corresponding ions.
• Agostic interaction is the interaction of a coordinationally unsaturated transition metal with the C-H bond, when the two electrons involved in the C-H bond move to the empty d-orbital of the transition metal, resulting in the formation of a three-center two-electron bond. Many catalytic transformations, such as oxidative addition and reductive elimination, presumably involve agostic interactions.

Van-der-Waals interactions include dipole-dipole, dipole-induced dipole, and dispersive interactions.

• Dispersive interaction is caused by the interaction of atoms and molecules with each other due to their own or mutually induced dipole moments. The instantaneous charge distribution of one atom or molecule, characterized by an instantaneous dipole moment, induces an instantaneous dipole moment in another atom or molecule
• The interaction between a dipole and an induced dipole occurs when a polar molecule induces a dipole in an atom or in a non-polar molecule, disturbing the arrangement of electrons in the non-polar member.
• Dipole-dipole interactions occur when two polar molecules interact with each other through space. In this case, the partially negative part of one of the polar molecules is attracted to the partially positive part of the second polar molecule.

Hydrophobic interactions are the attraction between non-polar particles in water (or other polar solvents), which is caused by the thermodynamic disadvantage of water contact with non-polar substances. Hydrophobic interaction takes part in the formation of the tertiary structure of proteins and provides molecular recognition in some supramolecular guest-host complexes. It manifests itself in the formation of micelles and other structures in surfactant solutions.

π-interactions are a type of non-covalent interactions in which an electron-rich π-system can interact with a cation, anion or other π-system. Non-covalent interactions with π-systems are crucial for biological processes such as protein-ligand recognition.

Projects

Organometallic Chemistry

Since the discovery of the basic principles of organometallic compounds by Edward Frankland in the second half of the 19th century, the application of these reagents in organic synthesis began to develop rapidly. Today, the organometallic strategy of functionalization makes it possible to carry out complex transformations with high regio- and stereoselectivity and opens the possibility of introducing substituents in positions that are inaccessible by methods of classical chemistry. In order to further expand the synthetic potential of organoelement compounds, the following projects are being implemented in our laboratory:

• Direct lithiation of aromatic amines and related compounds for the synthesis of their hard-to-reach meta- and peri-derivatives.

Antonov, Yakubenko Synthesis 2020	Antonov et al. J. Organomet. Chem. 2020

• Study of the structure of organometallic compounds.

Antonov et al. Organometallics. 2020

• Steric activation of the dimethylamino group in the synthesis of polynuclear nitrogen heterocycles.

Antonov et al. Molecules 2020

Modern approach to the study of non-covalent interactions requires the development of methods for the synthesis of new donors and acceptors, which will allow to understand the periodicity of changes in the interaction force from the nature of the elements that make up the binding participants, as well as allow the use of new more sensitive methods of investigation. Within the framework of this direction our laboratory implements the following projects:

• Development of methods for the synthesis of organic acids, oxides, and selenides of group 15 elements.

Yakubenko et al. Phys. Chem. Chem. Phys. 2022

• Synthesis of chiral selenophosphoric acids and study of their catalytic activity ( in collaboration with the University of Regensburg).

Quantum Chemistry

Quantum chemistry methods are based on the principles of quantum mechanics applied to molecular systems. The solution of the quantum chemical problem is reduced to the numerical solution of the Schrödinger equation using various approximations. Modern methods require significant computational resources, therefore calculations are carried out using powerful computational clusters.

Spectroscopy (IR, NMR) and quantum chemistry methods are complement each other. Calculations are used to explain experimentally observed phenomena, to predict experimental results, or to model impossible experiments.

In our laboratory, we solve the problem of finding correlations between the spectral parameters of complexes with hydrogen bonds and their geometry and energy.

Tupikina et al. Phys. Chem. Chem. Phys, 2021	Karpov et al. J. Comput. Chem. 2021	Tupikina et al. Spectrochim. Acta A 2022

We have proposed a new method for quantum-chemical diagnostics of the features of the outer electronic shell of atoms, molecules and complexes with hydrogen bonds. The keystone of this approach is usage of the ³He atom as a probe particle. Our method allows visualization of both proton-acceptor and proton-donor properties of molecular systems and has advantages over conventional methods (MESP, ELF).

Tupikina et al. J. Phys. Chem. A 2017	Tupikina et al. J. Comput. Chem. 2018	Tupikina et al. J. Comput. Chem. 2020

One of the directions of quantum-chemical research in our laboratory is the study of the features of the electronic shells of fragments of biological molecules (amino acids, proteins, enzymes). In particular, prediction of possible directions of nucleophilic attack, study of the influence of additional hydrogen bonds with solvent molecules or side chains of a biological molecule on its reactivity.

NMR Spectroscopy

The nuclear magnetic resonance technique (NMR) is based on the registration of resonant absorption of radio frequency energy by a sample placed in a uniform magnetic field. Radiation is absorbed by nuclei with a nonzero magnetic moment (¹H, ¹³C, ¹⁹F, ³¹P, etc.). NMR spectroscopy is the most important method for determining the structure of organic molecules.

In our laboratory, experimental NMR spectroscopy is used to study the properties of various systems with hydrogen and halogen bonds. In particular, we are working on the development of a methodology for interpreting the experimental values of ³¹P chemical shifts as descriptors of the energy and geometry of the hydrogen bond. Establishing quantitative relationships between the ³¹P chemical shift is complicated (and therefore becomes more curious :)) due to the fact that the phosphorus nucleus is extremely sensitive to many additional factors.

Mulloyarova et al. J. Molec. Struct. 2021	Giba et al. Symmetry, 2021	Yakubenko et al. Phys. Chem. Chem. Phys. 2022

To obtain high-resolution NMR spectra at low temperatures (up to 100 K), we use and refine a unique technique – we use mixtures of liquefied freon gases as solvents. Under such conditions, the processes of proton and molecular exchange are slowed down and signals of complexes of various stoichiometric and isotopic compositions are resolved on the NMR spectra.

Mulloyarova et al. Phys. Chem. Chem. Phys. 2018

Our grants

• RSF grant23-13-00095 «Non-covalent interactions with high charge cooperativity» (Prof. Dr. P. Tolstoy).
• RSF grant 24-73-10155«Influence of nuclear dynamics on non-covalent interactions: from fundamental description in model associations to prediction of properties of supramolecular systems»(Dr.E.Tupikina)
• RSF grant 24-73-00030 «C-H activation of azine heterocycles under conditions of cooperative catalysis» (Dr. D.Tonkoglazova).

Publications

2024 г.

1. D.A. Shitov, M.V. Kaplanskiy, E.Yu. Tupikina, « Influence of the Fe(II) Spin State on Iron-Ligand Bonds in Heme Model Iron-Porphyrin Complexes with 4, 5 and 6 Ligands», ChemPlusChem (2024). DOI: 10.1002/cplu.202400550.
2. A.VRozhkov, E.Yu. Tupikina, K.I. Tugashov, V.Yu. Kukushkin, « Pure Heterometallic Spodium Bonding», CrystEngComm2024. DOI: 10.1039/D4CE00825A.
3. A. Paderina, S. Slavova, E. Tupikina, D. Snetkov, E. Grachova, «Aggregation game: changing solid-state emission using different counterions in mono-alkynylphosphoniumPt(II) complexes », Inorganic Chemistry2024. DOI: 10.1021/acs.inorgchem.4c02130.
4. A.S. Zakharov, D.V. Krutin, P.O. Mosalyov, E.Yu. Tupikina, A.S. Antonov, P.M. Tolstoy, V.V. Mulloyarova, “Phosphine Selenides: Versatile NMR Probes for Analyzing Hydrogen OH···Se and Halogen I···Se Bonds”, Physical Chemistry Chemical Physics2024. DOI: 10.1039/D4CP01895H
5. M.V. Kaplanskiy, M.L. Kruglov, A.A. Vanin, E.Yu. Tupikina, “Dynamic of non-covalent interactions during the P–O bond cleavage by ribonuclease A”, Physical Chemistry Chemical Physics2024. DOI: 10.1039/D4CP01888E
6. D.V. Krutin, A.S. Zakharov, E.Yu. Tupikina, V.V. Mulloyarova, “Unveiling the Electronic Structure Peculiarities of Phosphine Selenides as NMR Probes for Non-covalent Interactions: An Experimental and Theoretical Study”, Physical Chemistry Chemical Physics2024. DOI: 10.1039/D4CP01191K
7. J. Eder, A.S. Antonov, E.Yu. Tupikina, R.M. Gschwind, “Chiral Diselenophosphoric Acids for Ion Pair Catalysis: A Novel Approach to Enhance Both Proton Donating and Proton Accepting Properties”, Chem. Eur. J. 2024, e202401793. DOI: 10.1002/chem.202401793
8. E.Yu. Tupikina, M.V. Sigalov, O. Alkhuder, P.M. Tolstoy, “Charge Relay Without Proton Transfer: Coupling of Two Short Hydrogen Bonds via Imidazole in Models of Catalytic Triad of Serine Protease Active Site”, ChemPhysChem2024. DOI: 10.1002/cphc.202300970.
9. D. A. Shitov, D. V. Krutin, E. Y. Tupikina, “Mutual influence of non-covalent interactions formed by imidazole: A systematic quantum-chemical study”, J. Comput. Chem.2024, 45(13), 1046-1060. DOI: 10.1002/jcc.27309.
10. A.Yu. Samsonova, A.Yu. Mikheleva, K.M. Bulanin, N.I. Selivanov, A.S. Mazur, P.M. Tolstoy, C.C. Stoumpos, Y.V. Kapitonov, “Internal Vibrations of Pyridinium Cation in One-Dimensional Halide Perovskites and the Corresponding Halide Salts”, Molecules2024, 29, 78. DOI: 10.3390/molecules29010078.
11. M.A. Kostin, O. Alkhuder, L. Xu, D.V. Krutin, R.E. Asfin, P.M. Tolstoy, “Complexes of phosphine oxides with substituted phenols: hydrogen bond characterization based on shifts of P=O stretching bands”, Phys. Chem. Chem. Phys.2024, 26, 10234-10242. DOI: 10.1039/D3CP05817D.
12. S. Baykova, S. Baykov, K. Geyl, P. Tolstoy, V. Boyarskiy, “N-Pyridylureas as Masked Isocyanates for the Late-Stage Diversification of Pyridine-N-Oxides”, ChemistrySelect2024, 9, e202400720. DOI: 10.1002/slct.202400720.
13. В.А. Розенцвет, Н.А. Саблина, Д.М. Ульянова, П.М. Толстой, «Структурная характеристика низкомолекулярного полибутадиена, синтезированного под действием катионной инициирующей системы», Изв. АН, серияхимическая2024, 73(4), 1035-1045.
14. V.A. Rozentsvet, N.A. Sablina, D.M. Ulyanova, P.M. Tolstoy, “Structural characterization of low molecular weight polybutadiene synthesized using cationic initiation system”, Russ. Chem. Bull.2024, 73(4), 1035-1045. DOI: 10.1007/s11172-024-4218-6.
15. K. Sotiriadis, A.S. Mazur, Peter M. Tolstoy, P. Mácová, A. Viani, “External magnesium sulfate attack on hydrated Portland-limestone cements: Effect of the concurrent presence of sodium chloride in the corrosive environment and metakaolin admixture in the binder”, Cem.Concr. Compos.2024, 151, 105614. DOI: 10.1016/j.cemconcomp.2024.105614.

2022

1. A. Yakubenko, A. Puzyk, V. Korostelev, V. Mulloyarova, E. Tupikina, P. Tolstoy, A. Antonov, “Oxidation of triphenylpnictogens and complexation of resulted di-phenylpnictoginic acids in solution and solid state”, Phys. Chem. Chem. Phys. 2022, accepted. DOI: 10.1039/D2CP00286H.
2. E. Tupikina, A.A. Titova, M.V. Kaplanskiy, E.R. Chakalov, M.A. Kostin, P.M. Tolstoy, “Estimations of OH···N hydrogen bond length from positions and intensities of IR bands”, Spectrochimica Acta A 2022, accepted. DOI: 10.1016/j.saa.2022.121172
3. M.A. Kostin, S.A. Pylaeva, P.M. Tolstoy, “Phosphine oxides as NMR and IR spectroscopic probes for the estimation of the geometry and energy of hydrogen bonds: PO…H-A hydrogen bonds”, Phys. Chem. Chem. Phys. 2022, 24, 7121-7133. DOI: 10.1039/D1CP05939D.
4. Aliyarova, I.S., Tupikina, E.Yu., Ivanov, D.M., Kukushkin, V. Yu., “Metal-Involving Halogen Bonding Including Gold(I) as a Nucleophilic Partner. The Case of Isomorphic Dichloroaurate(I)Halomethane Cocrystals”, Inorganic Chemistry 2022, 61, 5, 2558–2567. DOI: 10.1021/acs.inorgchem.1c03482.
5. K. Sotiriadis, K. Aspiotis, A. Mazur, P. Tolstoy, E. Badogiannis, S. Tsivilis, “Characterization of Old Concrete from a Heritage Structure of Inousses Cluster of Islands”, Lect. Notes Civ. Eng. 2022, 209, 80-89. DOI: 10.1007/978-3-030-90788-4_7.
6. M. Nikishina, L. Perelomov, Y. Atroshchenko, E. Ivanova, L. Mukhtorov, P. Tolstoy, “Sorption of fulvic acids and their compounds with heavy metal ions on clay minerals”, Soil Syst. 2022, 6, 2. DOI: 10.3390/soilsystems6010002.
7. V. Rozentsvet, N. Sablina, D. Ulyanova, S. Kostjuk, P. Tolstoy, “Structure of terminal units of polybutadiene synthesized via anionic mechanism”, Polym. Bull. 2022, 79, 1239-1256. DOI: 10.1007/s00289-021-03549-5.
8. F. Shakirova, U. Markova, P. Tolstoy, A. Bulatov, A. Shishov, “A new hydrophobic deep eutectic solvent based on thymol and 4-(dimethylamino)benzaldehyde: derivatization and microextraction of urea”, J. Mol. Liquids 2022, 353, 118820. DOI: 10.1016/j.molliq.2022.118820.
9. A. Mazur, P. Tolstoy, K. Sotiriadis, “13С, 27Al and 29Si NMR investigation of the hydration kinetics of Portland-limestone cement pastes containing CH3-COO–R+ (R=H or Na)”, Materials 2022, 15, 2004. DOI: 10.3390/ma15062004.
10. В.А. Розенцвет, Д.М. Ульянова, Н.А. Саблина, М.Г. Кузнецова, П.М. Толстой, «Полимеризация 1,3-пентадиена под действием катионных каталитических систем на основе алюминийорганических соединений», Известия АН 2022, 4, 787-795.
11. V.A. Rozentsvet, D.M. Ulyanova, N.A. Sablina, S.V. Kostjuk, P.M. Tolstoy, I.A. Novakov, “Cationic polymerization of butadiene using alkyl aluminum compounds as co-initiators: an efficient approach toward solid polybutadienes”, Polym. Chem. 2022, 3, 1596-1607. DOI: 10.1039/d1py01684a.

2021

12. A.A. Yakubenko, V.V. Karpov, E.Yu. Tupikina, A.S. Antonov, “Lithiation of 2,4,5,7-Tetrabromo-1,8-bis(dimethylamino)naphthalene: Peculiarities of Directing Groups' Effects and the Possibility of Polymetalation”, Organometallics 2021, 40(21), 3627–36368. DOI: 10.1021/acs.organomet.1c00489.
13. V. Lyutoev, T. Shumilova, A. Mazur, P. Tolstoy, “NMR spectral characteristics of ultrahigh-pressure high-temperature impact glasses of the giant Kara astrobleme (Pay-Khoy, Russia)”, Minerals 2021, 11, 1418. DOI: 10.3390/min11121418.
14. В.А. Розенцвет, Н.А. Саблина, Д.М. Ульянова, П.М. Толстой, И.А. Новаков, «Полимеризация изопрена под действием катионных каталитических систем на основе триэтилалюминия», Доклады РАН 2021, 499, 66-70. DOI: 10.31857/S2686953521040063. V.A. Rozentsvet, N.A. Sablina, D.M. Ulyanova, P.M. Tolstoy, I.A. Novakov, “Polymerization of Isoprene Using Cationic Catalytic Systems Based on Triethylaluminum”, Doklady Phys Chem. 2021, 499, 73-76. DOI: 10.1134/S0012501621080017.
15. E.Yu. Tupikina, P.M. Tolstoy, A.A. Titova, M.A. Kostin, G.S. Denisov, “Estimations of FH···X hydrogen bond energies from IR intensities: Iogansen's rule revisited”, J. Comput. Chem. 2021, 41. DOI: 10.1002/jcc.26482
16. E.Y. Tupikina, S.G. Yastrebov, , “Molecular Complexes of Glycine with Cations H⁺, Ca²⁺, and Phosphine Oxide H₃PO”, Technical Physics Letters 2021, 47(2), 147–149. DOI: 10.1134/S1063785021020140.
17. I.S. Giba, P.M. Tolstoy, “Self-assembly of tetrahedral hydrogen-bonded cage tetramers of phosphonic acid”, Symmetry 2021, 13, 258. DOI: 10.3390/sym13020258.
18. I.S. Giba, V.V. Mulloyarova, G.S. Denisov, P.M. Tolstoy, “Sensitivity of ³¹P NMR chemical shifts to hydrogen bond geometry and molecular conformation for complexes of phosphinic acids with pyridines”, Magn. Reson. Chem. 2021, 59(4), 465–477. DOI: 10.1002/mrc.5123.
19. V.V. Mulloyarova, A.M. Puzyk, A.A. Efimova, A.S. Antonov, R.A. Evarestov, I.S. Aliyarova, R.E. Asfin, P.M. Tolstoy, “Solid-State and Solution-State Self-Association of Dimethylarsinic Acid: IR, NMR and Theoretical Study”, J. Mol. Struct. 2021, 1234, 130176. DOI: 10.1016/j.molstruc.2021.130176.
20. В.А. Розенцвет, Н.А. Саблина, Д.М. Ульянова, С.Н. Смирнов, П.М. Толстой, «Строение полимерной цепи поли-1,3-пентадиена, синтезированного на стереоспецифической каталитической системе», Известия АН 2021, 4, 773-779. V.A. Rozentsvet, N.A. Sablina, D.M. Ulyanova, S.N. Smirnov, P.M. Tolstoy, “Structure of the polymer chain of poly(1,3-pentadiene) synthesized using a stereospecific catalytic system”, Russ. Chem. Bull. 2021, 70(4), 773-779. DOI: 10.1007/s11172-021-3150-2.
21. B. Koeppe, J. Guo, P.M. Tolstoy, H.-H. Limbach, “NMR and UV-vis spectroscopic studies of models for the hydrogen bond system in the active site of photoactive yellow protein: hydrogen bond cooperativity and medium effects”, J. Phys. Chem. B 2021, 125, 22, 5874-5884. DOI: 10.1021/acs.jpcb.0c09923.
22. Ł. Hetmańczyk, P. Szklarz, A. Kwocz, M. Wierzejewska, M. Pagacz-Kostrzewa, M.Ya. Melnikov, P.M. Tolstoy, A. Filarowski, “Polymorphism and Conformational Equilibrium for Nitro-Acetophenone in the Solid State and Under the Matrix Condition”, Molecules 2021, 26, 3109. DOI: 10.3390/molecules26113109.
23. E.Yu. Tupikina, V.V. Karpov, P.M. Tolstoy, “On the influence of water molecules on the outer electronic shells of R–SeH, R–Se(–) and R–SeOH fragments in selenocysteine amino acid residue”, Phys. Chem. Chem. Phys. 2021, 23, 13965-13970. DOI: 10.1039/D1CP01345A.
24. J. Savosina, M. Agafonova-Moroz, M. Khaydukova, A. Legin, V. Babain, P. Tolstoy, D. Kirsanov, “On the radiolytic stability of potentiometric sensors with plasticized polymeric membranes”, Chemosensors 2021, 9, 214. DOI: 10.3390/chemosensors9080214.
25. E. Bulatov, T. Eskelinen, A. Ivanov, P. Tolstoy, E. Kalenius, P. Hirva, M. Haukka, “Noncovalent axial I∙∙∙Pt∙∙∙I interactions in platinum(II) complexes strengthen in the excited state”, ChemPhysChem 2021, 22, 1-7. DOI: 10.1002/cphc.202100468.
26. Ł. Hetmańczyk, E.A. Goremychkin, J. Waliszewski, M.V. Vener, P. Lipkowski, P.M. Tolstoy, A. Filarowski, “Spectroscopic identification of hydrogen bond vibrations and quasi-isostructural polymorphism in N-salicylideneaniline”, Molecules 2021, 26, 5043. DOI: 10.3390/molecules26165043.
27. V. Karpov, A. Puzyk, P. Tolstoy, E. Tupikina, “Hydration of selenolate moiety: ab initio investigation of properties of O–H···Se(–) hydrogen bonds in CH₃Se(–)∙∙∙(H₂O)_n clusters”, J. Comput. Chem. 2021, 42, 2014-2023. DOI: 10.1002/jcc.26733.
28. V. Rozentsvet, N. Sablina, D. Ulyanova, S. Kostjuk, P. Tolstoy, “Structure of terminal units of polybutadiene synthesized via anionic mechanism”, Polym. Bull. 2021, accepted. DOI: 10.1007/s00289-021-03549-5.

2020

29. K. Sotiriadis, P. Mácová, A.S. Mazur, A. Viani, P.M. Tolstoy, S. Tsivilis, “Long-term thaumasite sulfate attack on Portland-limestone cement concrete: A multi-technique analytical approach for assessing phase assemblage”, Cement and Concrete Research 2020, 130, 105995. DOI: 10.1016/j.cemconres.2020.105995.
30. N.M. Kuznetsov, S.I. Belousov, A.V. Bakirov, S.N. Chvalun, R.A. Kamyshinsky, A.A. Mikhutkin, A.L. Vasiliev, P.M. Tolstoy, A.S. Mazur, E.D. Eidelman, E.B. Yudina, A.Ya. Vul', “Unique rheological behavior of detonation nanodiamond hydrosols: the nature of sol-gel transition”, Carbon 2020, 161, 486-494. DOI: 10.1016/j.carbon.2020.01.054.
31. A.Yu. Baranov, A.S. Berezin, D.G. Samsonenko, A.S. Mazur, P.M. Tolstoy, V.F. Plyusnin, I.E. Kolesnikov, A.V. Artem'ev, “New Cu(I) halide complexes showing TADF combined with room temperature phosphorescence: the balance tuned by halogens”, Dalton Trans. 2020, 49, 3155-3163. DOI: 10.1039/D0DT00192A.
32. I. Kritskiy, T. Volkova, S. Ivanov, A. Mazur, P. Tolstoy, I. Terekhova, “Methotrexate-Loaded Metal-Organic Frameworks on the Basis of γ-Cyclodextrin: Design, Characterization, in Vitro and in Vivo Investigation”, Materials Science and Engineering C 2020, 111, 10774. DOI: 10.1016/j.msec.2020.110774.
33. V.А. Rozentsvet, N.А. Sablina, D.M. Ulyanova, P.M. Tolstoy, S.N. Smirnov, I.A. Novakov, “Identification of the structure of polybutadiene terminal units by NMR spectroscopy with T2-filter”, Doklady Phys. Chem. 2020, 491, 40-42. DOI: 10.1134/S0012501620040028.
34. V. Rozentsvet, N. Sablina, D. Ulyanova, M. Kuznetsova, S. Kostjuk, P. Tolstoy, “A new approach towards investigation of structure of terminal units of poly(1,3-pentadiene) using T2-filtered NMR spectroscopy”, Macromol. Chem. Phys. 2020, 2000168. DOI: 10.1002/macp.202000168.
35. A.S. Antonov, V.V. Karpov, E.Yu. Tupikina, P.M. Tolstoy, M.A. Vovk, “Aggregation Behavior of Lithionaphthalenes in Solution: Experimental and Theoretical Study”, Organometallics 2020, 39, 3705. DOI: 10.1021/acs.organomet.0c00524.
36. A.S. Antonov, E.Yu. Tupikina, V.V. Karpov, V.V. Mulloyarova, V.G. Bardakov, “Sterically Facilitated Intramolecular Nucleophilic NMe2 Group Substitution in the Synthesis of Fused Isoxazoles: Theoretical Study”, Molecules, 2020, 25, 5977. DOI: 10.3390/molecules25245977.
37. A.S. Antonov, V.G. Bardakov, V.V. Mulloyarova, “Sterically facilitated meta-lithiation of arenes, containing electron-donating groups”, J. Org. Chem. 2020, 906, 121068. DOI: 10.1016/j.jorganchem.2019.121068
38. A.A. Antonov, A.A. Yakubenko, “Noncovalent Li···H Interaction in the Synthesis of peri-Disubstituted Naphthalene Proton Sponges”, Synthesis 2020; 52, 98-104. DOI: 10.1055/s-0039-1690230
39. E. Yu. Tupikina, G. S. Denisov, A. S. Antonov, P. M. Tolstoy, “Unusual behaviour of the spin-spin coupling constant 1JCH upon formation of CH•••X hydrogen bond”, Phys. Chem. Chem. Phys. 2020, 22, 1994-2000. DOI: 10.1039/C9CP05964D
40. E. Yu. Tupikina, K. G. Tokhadze, G. S. Denisov, P. M. Tolstoy, “Lone pairs mapping by Laplacian of ³He NMR chemical shift”, J. Comput. Chem. 2020, 41, 1194-1199. DOI: 10.1002/jcc.26166.
41. E.Yu. Tupikina, K.G. Tokhadze, V.V. Karpov, G.S. Denisov, P.M. Tolstoy, “Stretching force constants as descriptors of energy and geometry of F···HF hydrogen bonds”, Spectrochim. Acta A 2020, 241, 118677. DOI: 10.1016/j.saa.2020.118677.
42. A.S. Mazur, M.A. Vovk, P.M. Tolstoy, “Solid-state NMR of carbon nanostructures (graphite, graphene, carbon nanotubes, nanodiamonds, fullerene) in 2000-2019: a mini-review”, Fuller. Nanotub. Car. N. 2020, 28(3), 202-213. DOI: 10.1080/1536383X.2019.1686622.
43. A.S. Ostras’, D.M. Ivanov, A.S. Novikov, P.M. Tolstoy, “Phosphine oxides as spectroscopic halogen bond descriptors: IR and NMR correlations with interatomic distances and complexation energy”, Molecules 2020, 25, 1406. DOI: 10.3390/molecules25061406.
44. V.Y. Mikshiev, A.F. Pozharskii, A. Filarowski, A.S. Novikov, A.S. Antonov, P.M. Tolstoy, M.A. Vovk, O.V. Khoroshilova, “ How strong hydrogen bond with amide nitrogen atom is?”, ChemPhysChem, 2020, 21, 651-658. DOI: 10.1002/cphc.201901104.
45. V.V. Mulloyarova, D.O. Ustimchuk, A. Filarowski, P.M. Tolstoy, «H/D Isotope Effects on ¹H NMR Chemical Shifts in Cyclic Heterodimers and Heterotrimers of Phosphinic and Phosphoric Acids», Molecules 2020, 25, 1907. DOI: 10.3390/molecules25081907.
46. K. Jóźwiak, A. Jezierska, J.J. Panek, E.A. Goremychkin, P.M. Tolstoy, I.G. Shenderovich, A. Filarowski, “Inter- vs. intra-molecular hydrogen bond patterns and proton dynamics in phthalic acid associates”, Molecules 2020, 25, 4720. DOI: 10.3390/molecules25204720.
47. V. Torres-Barthelemy, N. Pérez-Hernández, I.G. Shenderovich, P.M. Tolstoy, G.S. Denisov, H.-H. Limbach, “NMR-detected Host-Guest Proton Exchange as a novel Tool to study Surface/Volume Ratios and Filling of Cavities of mesoporous Solids”, J. Phys. Chem. C 2020, 124(40), 22082-22095. DOI: 10.1021/acs.jpcc.0c04889.
48. P. Piękoś, A. Jezierska, J. Panek, E.A. Goremychkin, A. Pozharskii, A. Antonov, P. Tolstoy, A. Filarowski, “Symmetry/asymmetry of NHN hydrogen bond in protonated 1,8-bis(dimethylamino)naphthalene”, Symmetry 2020, 12, 1924. DOI: 10.3390/sym12111924.
49. S.N. Yunusova, D.S. Bolotin, M.A. Vovk, P.M. Tolstoy, V.Yu. Kukushkin, “Tetrabromomethane as an Organic Catalyst: a Kinetic Study of CBr₄-Catalyzed Schiff Condensation”, Eur. J. Org. Chem. 2020, 6763-6769. DOI: 10.1002/ejoc.202001180.
50. D.L. Melnikova, Z.F. Badrieva, M.A. Kostin, C. Maller, M. Stas, A. Buczek, M.A. Broda, T. Kupka, A.-M. Kelterer, P.M. Tolstoy, V.D. Skirda, “On Complex Formation Between 5-Fluorouracil and beta-Cyclodextrin in Solution and in the Solid State: IR Markers and Detection of Short-Lived Complexes by Diffusion NMR”, Molecules 2020, 25, 5706. DOI: 10.3390/molecules25235706.

Information for students

The Laboratory welcomes 1^st-4^th year students for graduation works and research works in the following areas:

• NMR spectroscopy (Prof. Dr. Peter M. Tolstoy, room 2150, This email address is being protected from spambots. You need JavaScript enabled to view it.)
• Organometallic chemistry (Dr.DariaI. Tonkoglazova,This email address is being protected from spambots. You need JavaScript enabled to view it.; Dr. Semyon V. Tsybulin, This email address is being protected from spambots. You need JavaScript enabled to view it., room 2135)
• Quantum chemistry (Dr. Elena Yu. Tupikina, room 2123)