Nanobiomaterials and Bioeffectors for the Theranostics of Socially Significant Diseases Laboratory

The synthesis of new types of polyhedral and cellular coordination compounds; modeling and experimental study of their antiviral, antitumor and antifibrilogenic activity; creation of «topological drugs» for transcriptional inhibition of enzymes, biochemical and medical samples, antifibrilogenic, antiviral and antitumor compounds, as well as nature-like catalytic systems for the most significant chemical processes and hybrid organo-inorganic and magnetic materials based on these compounds.

Data on the occurrence of clathrochelate chirality caused by their binding to chiral organic molecules and macromolecules of proteins have been obtained. The induced chirality and, accordingly, the appearance of circular dichroism spectra of cellular metal complexes, due to their supramolecular binding to optically active organic molecules and to protein macromolecules, has first been found. Such complexes are promising molecular chiral samples both to establish the macromolecule structure of these proteins and study their conformational transitions.

The first stable «classical» iron(I) complex, which exhibited high chemical stability in strongly acidic environments, has been obtained and structurally characterized.

The methods for obtaining pseudo-macrobicyclic complexes of cobalt with close-borate counterions have been developed. The first high-spin cobalt (II) pseudoclatrochelate with a volumetric closo-borate counterdianion formed by crosslinking with a solvent molecule as an H-acceptor has been obtained. The complex is characterized by a high anisotropy of the magnetic susceptibility tensor and has the properties of a monoionic monomolecular magnet. Its H-bound solvent molecule is subject to substitution under the action of stronger hydrogen bond acceptors. This compound is a promising reactive precursor to create new molecular magnetic materials.

The methods for the synthesis of new hybrid carboranoclatrochelates have been developed. Propargylamine iron(II) clathrochelates have been obtained by means of nucleophilic substitution of chloroclatrochelate precursors under the action of an excess of propargylamine. Their further functionalization using the 1,3-dipolar cycloaddition reaction has resulted in the first hybrid carboranoclatrochelates with a labile spacer fragment between their polyhedral centers.

1. Genrikh E. Zelinsky Researcher, Ph.D. (Chemistry)
2. Anna A. Bovkunova Junior Researcher
3. Ekaterina V. Krivogina Junior Researcher
4. Nikita A. Selivanov Junior Researcher
5. Anastasia A. Egorova Junior Researcher
6. Il’ya P. Limarev Junior Researcher
7. Daniil A. Kozlov Junior Researcher
8. Mikhail I. Razumov Junior Researcher
9. Tatyana M. Bushkova Junior Researcher
10. Aleksey V. Nelyubin Junior Researcher
11. Aleksey V. Golubev Junior Researcher
12. Aleksandr S. Belov Leading Researcher, Dr. of Sciences (Chemistry)
13. Semyon V. Dudkin Senior Researcher, Ph.D. (Chemistry)
14. Svetlana A. Belova Junior Researcher
15. Alexander S. Chuprin Senior Research Assistant

1. Y.Z. Voloshin, I.G. Belaya, R. Krämer, Cage metal complexes: clathrochelates revisited, Springer, Heidelberg, 2017.
2. V.B. Kovalska, S.V. Vakarov, M.V. Kuperman, M.Yu. Losytskyy, E. Gumienna–Kontecka, Y.Z. Voloshin, O.A. Varzatskii, Induced chirality of the cage metal complexes switched by their supramolecular and covalent bindings, Dalton Trans., 2018, 47, 1036–10525.
3. Y.Z. Voloshin, V.V. Novikov, Y.V. Nelyubina, A.S. Belov, D.M. Roitershtein, A. Savitsky, A. Mokhir, J. Sutter, M.E. Miehlich, K. Meyer, Synthesis and characterization of an Fe(I) cage complex with high stability towards strong H-acids, Chem. Commun., 2018, 54, 3436–3439.
4. Y.Z. Voloshin, N.V. Chornenka, A.S. Belov, S.A. Grigoriev, A.S. Pushkarev, P. Millet, V.N. Kalinichenko, D.A. Oranskiy, A.G. Dedov, Preparation and Electrochemistry of Iron, Ruthenium, and Cobalt(II) Hexaphenanthrene Clathrochelates Designed for Efficient Electrocatalytic Hydrogen Production and Their Physisorption on Carbon Materials,
   J. Electrochem.Soc., 2019, 166, H598–H607.
5. V.Kovalska, M.Kuperman, M.Losytskyy, S.Vakarov, S.Potocki, S.Yarmoluk, Y.Voloshin, O.Varzatskii, E.Gumienna-Kontecka, Induced CD of iron(II) clathrochelates: sensing of the structural and conformational alterations of serum albumins, Metallomics, 2019, 11, 338 – 348.
6. V.Kovalska, S.Vakarov, M.Losytskyy, M.Kuperman, N.Chornenka, Y.Toporivska, E.Gumienna-Kontecka, Y.Voloshin, O.Varzatskii, A.Mokhir, Dicarboxyl-terminated iron(II) clathrochelates as ICD-reporters for globular proteins, RSC Adv., 2019, 9, 24218–2423.
7. Y.Z. Voloshin, V.M.Buznik, A.G. Dedov, New types of the hybrid functional materials based on cage metal complexes for (electro)catalytic hydrogen production, Pure & Applied Chemistry, 2020, 92, 7, 1159–1174.
8. A.S. Belov, Y.Z. Voloshin, A.A. Pavlov, Y.V. Nelyubina, S.A. Belova, Y.V. Zubavichus, V.V. Avdeeva, N. Efimov, E.A. Malinina, K.Y. Zhizhin, N.T. Kuznetsov, Solvent-induced encapsulation of cobalt(II) ion by a boron-capped tris-pyrazoloximate, Inorg.Chem., 2020, 59, 9, 5845–5853 (a cover article).
9. A.L. Popov, B. Han, A.M. Ermakov, I.V. Savintseva, O.N. Ermakova, N.R. Popova, A.B. Shcherbakov, T.O. Shekunova, O.S. Ivanova, D.A. Kozlov, A.E. Baranchikov, V.K. Ivanov, PVP-stabilized tungsten oxide nanoparticles: pH sensitive anti-cancer platform with high cytotoxicity, Materials Science and Engineering C, 2020, 108, 110494.

M.R. Sokolov, Y.Y. Enakieva, A.D. Yapryntsev, A.A. Shiryaev, A.I. Zvyagina, M.A. Kalinina, Intercalation of porphyrin–based SURMOF in layered Eu(III) hydroxide: an approach toward symbimetic hybrid materials, Adv. Funct. Mater., 2020, 2000681

Grants of the Russian Science Foundation

• 19-73-00300 «Synthesis and chemical transformations of new types of macrobicyclic iron(II) tris-dioximates with reactive terminal apical and rib groups-precursors of clathrochelate bioeffectors with vector groups or a group for their targeted delivery to biological systems».

Grants of the Russian Foundation for Basic Research

• 19-33-60047 «Structural design and synthesis of paramagnetic cobalt(II) clathrochelates with terminal donor groups as macrobicyclic ligand synthons, i.e. precursors of magnetically active coordination capsules and their diamagnetic iron (II)-containing analogues, that are promising elements of quantum logic cells and molecular computers».
• 18-03-00675 «The application of new metal-promoted (catalyzed) reactions of reactive macrobicyclic precursors for the synthesis of clathrochelate complexes and ligands that are promising elements of molecular electronics and precursors of magnetic and (electro)catalytic materials».

• N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences(INEOS RAS) (Moscow, Russia)
• Lomonosov Moscow State University (Moscow, Russia)
• National Research Center “Kurchatov Institute » (Moscow, Russia)
• Gubkin Russian State University of Oil and Gas (National Research University) (Russia, Moscow)
• V. Topchiev Institute of Petrochemical Synthesis of the Russian Academy of Sciences (Moscow, Russia)
• I. Vernadsky Institute of General and Inorganic Chemistry (Kiev, Ukraine)
• Institute of Molecular Biology and Genetics of NASU (Ukraine, Kiev)
• University of Heidelberg (Germany, Heidelberg)
• University of Erlangen-Nuremberg (Germany, Erlangen)
• University of Wroclaw (Poland, Wroclaw)
• Orsay Institute of Molecular Chemistry and Materials, University of Paris-Sud (France, Orsay)
• Institute of Inorganic Chemistry, University of Vienna (Austria, Vienna)
• University of Manchester (UK, Manchester)