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Published by eka.rusak, 2022-12-05 03:42:46

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Research Institute of CHEMISTRY

49


Inorganic Chemistry

Department

The Department of Inorganic Chemistry of The graduated the department along with two post-
Peoples' Friendship University of Russia (RUDN) grads having received PhD in Chemistry. Six out
welcomed its first students on November 9, 1961. of those were international students. Members of
Inorganic chemistry department performs both the department are actively using and developing
academic and research functions, many prominent modern physical and chemical methods for studying
chemists have been trained since its establishment. inorganic and organoelement substances, including
In last five years 35 bachelors and masters those based on synchrotron radiation.

+7 495 955-09-76
50 [email protected]


Scientific research conducted at the department is the A wide range of objects, research methods and solved
basis for the edu­c­ational process syllabus and is used scientific and applied probl­ems allow students and graduate
when lecturing and conducting laboratory experiments students to choose a scientific work at the department in
general and special courses, when performing coursework, accordance with their interests and future employment and
graduation (bachelor and master) works, graduate theses. research needs.

51


Professor Boris N. Ivanov-Emin Boris Nikolayevich Ivanov-Emin (1913- Dr. Nikolai U. Venskovsky
Professor Alexey K. Molodkin 1994), an outstanding chemist, headed
the department and led it for more than
10 years (1961-1973). He determined
the field of research of the department
being, namely, the chemistry of simple and
coordination compounds of the elements of
the third group of the periodic system and
lanthanides. Professor Ivanov-Emin is a
pioneer in the study of the chemistry of the
«Mendeleev elements» –scandium, gallium,
germanium, as well as elements for which
D.I. Mendeleev predicted some specific
properties (indium, rhenium).

In 1973, the department was headed (1973-1989) by Doctor of Chemistry,
Professor Alexey Konstantinovich Molodkin (1921-2014), who came to RUDN
from the Institute of Inorganic and General Chemistry of the Academy of Sciences
of the USSR, where he studied the chemistry of thorium and actinides. He
broadened the area of research of the Department, having included synthesis and
study of coordination compounds of transition metals (Cu, Zn, Ni, Co, Mn) with
biologically active ligands. In the late seventies of the last century, the staff of
the Department picked up the study of oxide and halide compounds of rare earth
elements, the interest being caused by their luminescent and optical properties.

During 26 years (from 1989 to 2015) the Department of Inorganic Chemistry
was headed by Dr. Nikolai Ulyanovich Venskovsky, who was also Vice-Rector for
Science in 1995-2006. In 2000 Dr. Venskovsky earned the title Honored Worker
of Higher Professional Education of the Russian Federation, and in 2006 he was
awarded by the Order of Friendship.

From 2015 till nowdays, the department is headed by the Director of the
Research Institute of Chemistry – Prof. Dr. Victor N. Khrustalev.

SCIENTIFIC RESEARCH

At present, the following areas of scientific research of the Department of Inorganic Chemistry of RUDN University
can be pointed out:

The study of the formation of multi-ligand complexes

The study of the formation of multi-ligand complexes, in which the metal ion is a bridge between the amino acid anion
and nucleotide phosphate, as well as the multi-ligand complexes, in which the metal ion coordinates the nucleotide and
side chains of amino acids. Such compounds are models of protein products formed at different stages of biochemical
processes involved in the accumulation and transport of metal ions and bio-active substances in living organisms.

The main subjects of our research in this field are the following:

• modeling and design of future drugs, the possible • complex compounds of copper(II) with L-aspartic
antioxidant, cardiotonic and antitumor activity of acid, L-threonine, as well as a mixed-ligand
which is combined with the lower toxicity of these complex of copper(II) with these ligands inhibit
compounds as compared to those of Cisplatin, peroxidation and the formation of oxygen radicals
as well as potentially having antiviral properties; in lipid systems;
high fungicidal activity of homogeneous ligand
complex compounds of copper(II) and nickel(II) with • copper(II) complex compounds with L-aspartic acid
aspartic acid, threonine, ε-caprolactam, as well as and L-threonine are capable of activating luminol-
mixed ligand complex compounds against late blight dependent chemiluminescence, which allows their
of tomatoes, mildew of cucumbers, gray rot of beans; use as free radical interceptors in biological systems.

52


The Department of INORGANIC CHEMISTRY
The chemistry of interaction of rare platinum metals with
sulfur-containing ligands

The chemistry of interaction of rare you to expand the possibilities of compounds obtained, the patterns
platinum metals (Os, Ru) with sulfur- using osmium dimethyl sulfoxide of their complexation in aqueous
containing ligands (thiocarbamide, complexes as precursors for the solutions and solutions of hydrohalic
dimethyl sulfoxide), systematization synthesis of compounds of a given acids, information on the forms of
of data on the structure and composition and properties. From osmium existence in the studied
properties of the resulting complexes, the practical point of view, they are solutions are of scientific interest
isomerization processes, conditions catalysts for various processes and for the chemistry in general, analysis
of selective formation, stability exhibit biological activity. and technology of osmium and
and interconversions of isomers The data on the behavior can be used to develop various
makes a significant contribution to of osmium(IV) and osmium(VI) analytical techniques, processes of
theoretical chemistry and allows concentration, separation, etc.

Complex oxide ceramics with high ionic conductivity

Complex oxide ceramics with high ionic conductivity are One of the ways to solve the problem is to create
promising objects of research devoted to the creation geometric distortions in the layered crystal structure of
on their basis of materials for modern engineering and the Aurivillius phases by means of directional modification
electronics. of the cationic composition of the bismuth-containing
Coexistence of ferromagnetism and ferroelectricity ferroelectric SrBi2Nb2O9, SrBi2Ta2O9, Bi4Ti3O12 and
in a single crystal structure is rather difficult to Bi5FeTi3O15 ions of d- and f-elements, such as Nd(III),
achieve due to the fact that most ferromagnets are Sm(III), Tb(III),Yb(III), Fe(III), Mn(III), Cr(III), Nb(V), Ta(V).
centrosymmetric and cannot have electric polarization, A comprehensive study of the physical and chemical
and most ferroelectrics contain transition metal ions properties of the obtained phases, starting with phase
that do not have a magnetic moment, i.e. have no formation and ending with electrophysical characteristics
active d-electrons. with the use of DTA/DSC, XRF, IR and dielectric spectroscopy,
Therefore, coexistence of these two phenomena is allows us to establish the regularities of the influence of
suppressed by the local symmetry of the structure, which the cationic composition on various types of ordering in
contributes only to one effect. the crystal structure and choose the optimal conditions for
their production using different types of heat treatment
during synthesis (muffle and microwave annealing).

A study of cagelike metallacomplexes

The focus of our investigations in the field of framework of cage metallacomplexes, including non-trivial ionic
compounds is a study of cagelike metallacomplexes and multicomponent products.
their supramolecular derivatives. Objects of this type are Cage metallasesquioxanes, including metal ions with
extremely attractive due to enormous variety of molecular high magnetic anisotropy, Co(II) [1], Ni(II) or Fe(III)
architectures. The latter leads to an opportunity to control exhibit a slow dynamic behavior in its magnetization
practically important properties: catalytic, magnetic, (spin glass behavior), which is important for the search
photophysical, medical and many others. Approach, of potential information storage materials and devices.
being elaborated in our group, implies the self-assembly In turn, Cu(II)- [5] and Fe(III)-containing complexes were
cage oxaclusters using different organoelement ligands, proved to be high efficient precatalysts for the important
primarily - silicon- [1] or germanium-based [2] ones. reactions of organic synthesis. For example, amide
This method allows to synthesize Cu-, Co-, Ni-, Fe-, Zn-, production, via the oxidative amidation of benzylic
Cr-containing silicon- or germaniumsesquioxanes of alcohol, could be performed in conditions of very low
different nuclearity and cage’ shape. Intriguing, even in catalyst loading (down to 100 ppm of Cu). In turn, C-H
the case of using of one type of metal ion, Cu(II), it was activation reactions could also be catalyzed excellently,
found possible to isolate complexes drastically different for example, the cyclohexane oxidation at 20 °C, with
in copper centers’ content – from Cu2 [3] to Cu42 [4]. Fe6-cage as precatalyst, gave oxygenates in very high
Main instrument of control on composition/structure of yield of alkanes (48%!).
these products is a proper choice of (i) reactants’ ratio, Recent results point out at significant potential of
(ii) template agents and (iii) reaction media. In turn, it supramolecular organization of polymetallic (transition
was found that an involvement of additional, e.g. N- or
P-based organic ligands, could provide brand new types

53


metal/alkaline metal) cage sesquioxanes. Ways of «hidden» in the central part of cage. The type of arising
individual cage’ reorganization into extended 1D, 2D, supramolecular architectures is governed by the size of
3D architectures were developed. It was found that, alkaline metal ion (the larger ion – the shorter distance
for supramolecular ordering, a nature of alkaline metal between interacting cages), and the nature of solvating
ions is highly influential. Located in external positions to ligands. This observation opens new opportunities for
cage, Na-, K-, Cs- or Rb ions are much more accessible these product applications: in heterogeneous catalysis,
to contacts, providing neighboring cage connectivity, study of porous materials and functional (magnetic/
in comparison to transition metal ions, which are luminescent) properties.

Reactivity of ligands

Many compounds are very inert in a number of chemical Iron, cobalt, Nickel, rare-earth elements in various degrees
reactions. However, their coordination to the metal of oxidation are traditionally used as metal centers, and
center can significantly increase their reactivity. The various organic (acetylene, isothiocyanates, heterocycles
compounds coordinated to the metal center are often of a number of benzimidazole, amines, alcohols,
able to enter into new reactions that are impossible in aldehydes) and inorganic (azides, water, ammonia)
the so-called «metal-free» version. compounds are used as reagents and substrates.

Click-reactions in polymer-analogous transformations of natural and
synthetic polymers

Before the introduction of click reactions in polymeranalogic with new, conveniently and elegantly synthetic methods.
transformation those were largely confined to the classic The vast majority of work in the chemistry of polymers
options, which consist of the formation of esters and is focused on the click reaction of a copper (I) catalyzed
ethers, Schiff bases, and amides etc. The concept of azide-alkyne cycloaddition. In our research group, we are
click chemistry, developed by Sharpless and associates introducing new click-reactions (feol-in, amine-in, etc.) into
about 20 years ago, provided the chemistry of polymers the chemistry of natural and synthetic polymers.

Sonochemistry

Sonochemistry (ultrasound in chemical transformations) Golden acid, etc. These reactions occur in or near the
is a young section of chemistry that studies the effect of cavitation bubbles, where the temperature can reach
ultrasound on chemical processes. Under the influence of 5,000° C and the pressure – 1000 atm. Moreover, the
ultrasound, absolutely amazing chemical transformations peak increase of high temperatures and pressures, as
become possible, such as the disproportion of nitrogen well as their decline to normal occurs extremely quickly,
to ammonia and nitric acid (!), smooth production of over a period of up to 10-6 s. We study the influence of
organomagnetic compounds in non-dried solvents, fast ultrasound on click-reactions, on the stability of polymers,
isomerization of maleic acid into fumaric acid, fast and also on many reactions underlying the synthesis of
production of monodisperse gold nanoparticles from inorganic and organic complexes.

54


The Department of INORGANIC CHEMISTRY

Medicinal chemistry: targeted delivery of drugs

The great Ehrlich dreamed of a magic bullet that acts only (TIPS RAS), Federal Research Center Boreskov Institute of
on the focus of the disease, while not harming healthy cells Catalysis (BIC), research organizations, National Research
of the body. Ehrlich's dream is gradually coming true – more Centre «Kurchatov Institute», The Kazan Scientific Center of
and more publications are devoted to the development the Russian Academy of Sciences, Karpov Institute of Physical
of systems of targeted drug delivery directly to the Chemistry, Russian universities Lomonosov Moscow State
pharmacological target. Our department also contributes University, D.I.Mendeleev University of Chemical Technology
to the development of this area - we are engaged in of Russia, MIREA — Russian Technological University, Saint
systems of targeted delivery of antibiotics based on Petersburg State University, Novosibirsk State University,
nanoplatforms made of modified natural polymers. Kazan Federal University (KFU), Ural Federal University
The Department of inorganic chemistry cooperates (Ekaterinburg).
with the institutes of the Russian Academy of Sciences: As part of our international cooperation program, the
A.N. Nesmeyanov Institute of Organoelement compounds department members are engaged in joint research
Russian Academy of Sciences, Kurnakov Institute of projects with scientists of Georgia Institute of Technology
General and Inorganic Chemistry of the Russian Academy (USA), University of Wisconsin-Madison (USA), New
of Sciences (IGIC RAS), N.D. Zelinsky Institute of Organic Mexico Highlands University (USA), University of
Chemistry, Prokhorov General Physics Institute, The Institute Montpellier (France), CNRS (France), Chemnitz University
of Physical Chemistry and Electrochemistry RAS (IPCE RAS), of Technology (Germany), University of Girona (Spain),
A.V. Topchiev Institute of Petrochemical Synthesis, RAS Hebrew University of Jerusalem (Israel).

RECENT SELECTED PAPERS [8] D.B. Eremin, D.A. Boiko, E.V. Borkovskaya, V.N. Khrustalev,
V.M. Chernyshev, V.P. Ananikov, «Ten-fold boost of catalytic
[1] M.V. Solovev, O.V. Chashchikhin, P.V. Dorovatovskii, performance in thiol-yne click reaction enabled by a palladium
V.N. Khrustalev, A.S. Zyubin, T.S. Zyubina, O.V. Kravchenko, diketonate complex with a hexafluoroacetylacetonate ligand»,
A.A. Zaytsev, Yu.A. Dobrovolsky, «Hydrolysis of Mg(BH4)2 and its Catalysis Science & Technology, 2018, 8, pp. 3073-3080.
coordination compounds as a way to obtain hydrogen», Journal of
Power Sources, 2018, 377, pp. 93-102. [9] O.V. Khazipov, M.A. Shevchenko, A.Yu. Chernenko, A.V. Astakhov,
D.V. Pasyukov, D.B. Eremin, Ya.V. Zubavichus, V.N. Khrustalev,
[2] A.N. Bilyachenko, V.N. Khrustalev, Ya.V. Zubavichus, V.M. Chernyshev, V.P. Ananikov, «Fast and slow release of catalytically
L.S. Shul’pina, A.N.Kulakova, X. Bantreil, F. Lamaty, M.M. Levitsky, active species in metal/NHC systems induced by aliphatic amines»,
E.I. Gutsul, E.S. Shubina, G.B. Shul’pin, «Heptanuclear Fe5Cu2- Organometallics, 2018, 37, pp. 1483-1492.
phenylgermsesquioxane containing 2,2’-bipyridine: synthesis,
structure, and catalytic activity in oxidation of C-H compounds», [10] J.E. Yarnell, I. Davydenko, P.V. Dorovatovskii, V.N. Khrustalev,
Inorganic Chemistry, 2018, 57, pp. 528-534. T.V. Timofeeva, F.N. Castellano, S.R. Marder, C. Risko, S. Barlow,
«Positional effects from σ-bonded platinum(II) on intersystem
[3] A.N. Bilyachenko, M.M. Levitsky, V.N. Khrustalev, Ya.V. Zubavichus, crossing rates in perylenediimide complexes: synthesis, structures,
L.S. Shul’pina, E.S. Shubina, G.B. Shul’pin, «Mild and regioselective and photophysical properties», Journal of Physical Chemistry C,
hydroxylation of methyl group in neocuproine: approach to an N,O- 2018, 122, pp. 13848-13862.
ligated Cu6 cage phenylsilsesquioxane», Organometallics, 2018, 37,
pp. 168-171. [11] V.A. Tuskaev, S.V. Zubkevich, D. Saracheno, S.Ch. Gagievaa,
P.V. Dorovatovskii, E.G. Kononova, V.N. Khrustalev, D.N. Zarubin,
[4] G.A. Chesnokov, M.A. Topchiy, A.F. Asachenko, N.V. Muravyev, B.M. Bulychev, Yu.V. Kissin, «Nickel(II) complexes with tripodal NNN
L.I. Grishin, A.S. Nikiforova, V.V. Utochnikova, V.B. Rybakov, ligands as homogenous and supported catalysts for ethylene
V.N. Khrustalev, M.S. Nechaev, «Rare earth metal complexes oligomerization», Molecular Catalysis, 2019, 464, pp. 29-38.
with 5,5’-bitetrazolate ligand: synthesis, structure, luminescent
properties, and combustion catalysis», European Journal of Inorganic [12] V.M.Chernyshev, A.V. Astakhov, I.E.Chikunov, R.V.Tyurin,
Chemistry, 2018, pp. 805-815. D.B. Eremin, G.S. Ranny, V.N. Khrustalev, V.P. Ananikov, «Pd and Pt
catalyst poisoning in the study of reaction mechanisms: what does
[5] A.N. Bilyachenko, V.N. Khrustalev, Ya.V. Zubavichus, the mercury test mean for catalysis?», ACS Catalysis, 2019, 9,
A.V. Vologzhanina, G.S. Astakhov, E.I. Gutsul, E.S. Shubina, pp. 2984-2995.
M.M. Levitsky, «High-nuclearity (Cu8-based) cage silsesquioxanes:
Synthesis and structural study», Crystal Growth & Design, 2018, 18, [13] A.Yu. Mitrofanov, Y. Rousselin, V.N. Khrustalev, A.V. Cheprakov,
2452-2457. A. Bessmertnykh-Lemeune, I.P. Beletskaya, «Facile synthesis and
self-assembly of zinc (2-diethoxy-phosphorylethynyl)porphyrins»,
[6] A. Ravi, A.S. Oshchepkov, K.E. German, G.A. Kirakosyan, European Journal of Inorganic Chemistry, 2019, pp. 1313-1328.
A.V. Safonov, V.N. Khrustalev, E.A. Kataev, «Finding receptor design
for selective recognition of perrhenate and pertechnetate: hydrogen [14] E.Yu. Zakharova, E.O. Dobroljubov, S.M. Kazakov, V.N. Khrustalev,
vs. halogen bonding», Chemical Communications, 2018, 54, pp. A.N. Kuznetsov, «Ternary palladium – Group 12 metal compounds of
4826-4829. the Pd5TlAs-type: A case study», Journal of Solid State Chemistry,
2019, 276, pp. 217-225.
[7] A.N. Bilyachenko, M.M. Levitsky, A.A. Korlyukov, V.N. Khrustalev,
Ya.V. Zubavichus, L.S. Shul’pina, E.S. Shubina, A.V. Vologzhanina,
G.B. Shul’pin, «Heptanuclear cage Cu(II)-silsesquioxanes: synthesis,
structure and catalytic activity», European Journal of Inorganic
Chemistry, 2018, pp. 2505-2511.

55


Organic Chemistry

Department

The Organic Chemitry Departmenty was Prof. Prostakov was further accumulated by
founded together with the Science Faculty Professor A.V. Varlamov, the second Head of the
in 1960. The department was firstly headed Department, who led the team during the period
by Professor N.S. Prostakov, who started his of perestroika in 1990’s and 2000’s. Professor
work at Peoples’ Friendship University after Leonid G. Voskressensky became Head of the
working under the guidance of Academician department in 2016, and since that time has been
I.O. Nazarov. A strong scientific basis laid by keeping the traditions of the scientific school.

+7 495 955-07-79
[email protected]


The research interests of Organic Chemistry department Loughborough University (UK), Hanoi National University
are focused on the areas of heterocyclic chemistry, (Vietnam), Tehran University (Iran), Leuven University
development of novel domino and multicomponent (Belgium), and others. The work is financially supported
reactions, with recently added interests in alkene by Russian Foundation for Basic Research (RFBR),
metathesis and photocatalysis fields. The department Russian Science Foundation (RSF) and RUDN University
has strong collaborations with foreign institutions, e.g. excellence program 5-100.
Bari University (Italy), Duesseldorf University (Germany),

57


Professor Nikolay S. Prostakov Professor Alexey V. Varlamov Professor Leonid G. Voskressensky

While still a graduate student, Professor N.S. Prostakov headed the Since 2016 the department has
N.S. Prostakov together with department for 29 years. In 1989, been headed by Professor Leonid
Aсademicians N.I. Nazarov and M.F. his student and follower - Professor G. Voskressensky, Prof. Varlamov’s
Mashkovsky developed the synthesis Alexey V. Varlamov, Honored Worker student.
of the Promedol (Trimeperidine) of the Higher School of the Russian Prof. Voskressensky is a graduate
analgesic and introduced the tech­ Federation, became Head of the of the Department of Organic
no­logy for its production into Department. Chemistry, RUDN University,
industry. The Associate Professors A.V. Varlamov is one of the founders Member of the International
N.M. Mikhailova and N.N. Mikheeva of the school of heterocyclic Society of Heterocyclic Compounds,
took an active participation in the chemists at RUDN University. Prof. Professor of the Russian Academy
Promedol development process. This Varlamov led the department for of Sciences, Deputy Editor-in-
drug is still widely used in medicine. 27 years. Under his supervision, the Chief of the journal «Chemistry of
Currently, promedol is produced department continued its further Heterocyclic Compounds», guest
in India by the Rusanpharma successful development. During that lecturer at the Universities of
pharmaceutical company, which is time, more than 100 PhD theses in Ghent, Bari and Cardiff.
headed by Dr. Navin Saxena, a former organic chemistry were defended.
student of Professors Prostakov N.S.
and Varlamov A.V.

The Department of Organic Chemistry trains chemists specializing in the chemistry of heterocyclic compounds.
Over the entire period of its existence, more than 120 people have graduated from the department with a PhD
degree; 46 of them are graduate students from India, Africa, Asia and Latin America.

Current research of Organic Chemistry Department, RUDN University is in the following fields:
• Chemistry of Heterocyclic Compounds; • Photocatalysis;
• Multicomponent and Domino reactions; • Synthesis of biologically active compounds;
• Catalysis by organic molecules and transition metals; • Fluorophore synthesis.

58


The Department of ORGANIC CHEMISTRY

DOMINO REACTIONS

Domino approaches to various heterocyclic systems This domino sequence is triggered by a thermal
are of significant importance as they are time and [3,3]-sigmatropic rearrangement, followed by an
resource efficient. In the past decades, Prof. Leonid intramolecular nucleophilic addition of a nitrogen
G. Voskressensky’s group developed a series of atom to the allene fragment. The consequent oxidation
Michael addition triggered domino reactions based of an electron-enriched double bond by atmospheric
on N-containing heterocycles and electron-deficient oxygen furnishes pyrroles with aminoethyl moiety.
alkynes. In particular, this work included a novel pseudo After tautomerisation in anaerobic conditions
three-component reaction of 2-imidazolines and 1,2,3,4-tetrahydro­pyra­zinoindoles are formed.
terminal alkynes with electron- withdrawing groups to
form polysubstituted imidazolidines and their further
transformations to pharmaceutically relevant pyrroles
1-3  (Scheme 1).

Scheme 1

59


In the field of isocyanide-based MCRs Prof. Leonid G. and various nucleophiles, such as alcohols, anilines and
Voskressensky’s group has established a three- component amines leading to a series of indole derivatives 4-7 with
reaction of 3-arylidene- 3H-indolium salts, isocyanides the yields up to 90% (Scheme 2).

Scheme 2
These reactions present a new practical synthetic approach to a series of compounds possessing a privileged indole
scaffold and also extend isocyanide-based MCRs by using vinylogous iminium ions

SELECTED PAPERS

[1]  Festa, A.A., Storozhenko, O.A., Golantsov, N.E., Subramani, K., No- S., Voskressensky, L.G., Altomare, C.D. A New Class of 1-Aryl-5,6-di-
vikov, R.A., Zaitseva, S.O., Baranov, M.S., Varlamov, A.V., Voskressensky, hydropyrrolo[2,1-a]isoquinoline Derivatives as Reversers of P-Gly-
L.G. // Homophtalonitrile for Multicomponent Reactions: Syntheses coprotein-Mediated Multidrug Resistance in Tumor Cells (2018)
and Optical Properties of o-Cyanophenyl- or Indol-3-yl-Substituted ChemMedChem, 13 (15), pp. 1588-1596.
Chromeno[2,3-c]isoquinolin-5-Amines (2019) ChemistryOpen, 8 (1),
pp. 23-30. [4]  Bariwal, J., Voskressensky, L.G., Van Der Eycken, E.V. // Recent
advances in spirocyclization of indole derivatives (2018) Chemical
[2]  Festa, A.A., Zalte, R.R., Golantsov, N.E., Varlamov, A.V., Van Der Ey- Society Reviews, 47 (11), pp. 3831-3848.
cken, E.V., Voskressensky, L.G. // DBU-Catalyzed Alkyne-Imidate Cycli-
zation toward 1-Alkoxypyrazino[1,2- a]indole Synthesis (2018) Journal [5]  Storozhenko, O.A., Festa, A.A., Ndoutoume, D.R.B., Aksenov, A.V., Var-
of Organic Chemistry, 83 (16), pp. 9305-9311. lamov, A.V., Voskressensky, L.G. // Mn-mediated sequential three-com-
ponent domino Knoevenagel/cyclization/Michael addition/oxidative
[3]  Nevskaya, A.A., Matveeva, M.D., Borisova, T.N., Niso, M., Co- cyclization reaction towards annulated imidazo[1,2-a]pyridines (2018)
labufo, N.A., Boccarelli, A., Purgatorio, R., de Candia, M., Cellamare, Beilstein Journal of Organic Chemistry, 14, pp. 3078-3087.

60


The Department of ORGANIC CHEMISTRY
Electrochemical synthesis of 1,2,3,4-tetrahydroisoquinoline-1-carbonitrile

The electrosynthesis of 1,2,3,4-tetrahydroisoquinoline- dihydroisoquinolin-2-ium iodide and the electrogenerated
1-carbonitrile by acetonitrile reduction is a green and acetonitrile formed under low temperature conditions,
safe strategy to replace the traditional cyanation. Herein when a solution of dry acetonitrile is electrolyzed at a
we have prepared the 1,2,3,4-tetrahydroisoquinoline-1- graphite sheet as a cathode and a magnesium rod as an
carbonitrile with good yields by a simple reaction between anode in an undivided cell.

Scheme 3:
Electrochemical synthesis of 1,2,3,4-tetrahydroisoquinoline-1-carbonitrile

As a result, the reaction proceeds through the ‘in situ’ formation of cyanide, which is accompanied with the extrusion
of methane gas, due to by the decomposition of the first radical-anion acetonitrile (as shown in Scheme 4).

The electrogenerated acetonitrile ii) is used to produce the nucleophilic cyanide; there is
i) has a good advantage to produce the in situ formation no need to introduce any toxic reagent
of cyanide which reacts with the substituted iminium
salts very fast,

Scheme 4:
A plausible mechanism for the decomposition of the radical anion acetonitrile and the tetrahydroisoquinoline-1-carbonitrile

61


Underlying the binding interaction mechanism of bio-active
compounds into protein/DNA molecule using various spectroscopy and
computational techniques

SUBRAMANI KARTHIKEYAN research work is related design and develop new effective drugs in biomedicine
to the study of the interaction mechanism of various in near future. At present he is working on underlying the
medicinally important compounds binding interaction binding information of a biologically important compound
mechanism at DNA and protein level, SUBRAMANI of pyrazino[1,2-a]indole derivative in ctDNA, 1-imino-
KARTHIKEYAN works in collaboration with the 1,2-dihydropyrazino[1,2-a]indol-3(4H)-one binding
Department of Organic Chemistry, RUDN University, interaction mechanism with bovine serum albumin and
carrying out various optical spectroscopic experiments 5-hydroxytryptamine receptor 1B and 3-(6-bromo-1H-
for newly synthesized organic compounds. The scientist indol-3-yl)-5-(1H-indol-3-yl)-5,6-dihydropyrazin-2(1H)-
studies the technical know- how of various spectroscopic one binding information on ctDNA and bovine serum
experiments UV-Vis, FTIR, Photoluminescence, the albumin complex using various optical spectroscopy,
time correlated single photon counting system and the molecular docking , molecular dynamics, DFT and
Circular Dichroism spectrometer. The scientist also quantum chemical calculation techniques. SUBRAMANI
expertizes different software (Schrodinger, DESMOND, KARTHIKEYAN favors an interdisciplinary approach
Jaguar, Material studio and Gaussian) to model and to solving biological questions and has incorporated
purpose binding site of various biologically active organic synthetic chemistry as well as cell biological, biophysical
compounds at DNA and protein level. This will help to and biochemical approaches to his research.

(a)

(b)
NH

N NH

O

BSA
5-hydroxytryptamine receptor 1B

ctDNA
Figure shows:
(a) chemical structure of pyrazino[1,2-a]indole derivative and best binding pose in ctDNA system
(b) schematic representation of 1-imino-1,2-dihydropyrazino[1,2-a] indol-3(4H)-one binding interaction mechanism with bovine
serum albumin and 5-hydroxytryptamine receptor 1B

62


The Department of ORGANIC CHEMISTRY
1,3-Dipolar cycloaddition of α-metalated isocyanides to aromatic enaminones
as a direct and convenient approach to 1H-2-aryl-4-aroylpyrroles

O O
Ar1
N + C N Ar2 t-BuOK, DMF, 0°C Ar1 Ar2
NH
instantly
easy operation

The [3+2] cycloadditions reactions represent convenient enamines, which can be used as synthetic equivalents of,
and experimentally easy approach towards five- as a dipolarophile in such processes, makes it possible to
membered heterocycles. The copper(I)-catalyzed azide – exclude the catalysis from this reaction, while maintaining
alkyne [3+2] cycloaddition (CuAAC) reaction is one of the regioselectivity. Due to the polarization of the double bond,
most popular and frequently used methods. The simplicity one of the two possible regioisomers is formed. Another
of the execution and regioselectivity are the main important point of using enamines is their availability and
advantages of these reactions. On the other hand, using the synthesis simplicity.

At the same time, the interest in the chemistry of pyrroles is caused by their versatile use both in medical and technical
areas. For example, 1-alkyl-2-aryl-4- (naphthoyl) pyrroles show high affinity for the CB1 and CB2 cannabinoid receptors
(JWH series). Also, 1H-2-aryl- 4-aroylpyrroles are used in the synthesis of potential antiprotozoal agents that show
high activity (Fig. 1).

Antiprotozoal N JWH series OR
agents N

Cl N
Alk
Cl N
R Alk = Propyl, Buntyl, Penyl, Hexyl, Heptyl
R = CH3, C2H5, OCH3, F, CI, CF3, NO2
R = H, CH3

Fig. 1. Chemical structure of some biological active 2-aryl-4-aroylpyrroles

There are many approaches for the construction of a which can be considered to be the synthetic equivalents
pyrrole cycle. One of them is the interaction of substituted of acetylenes, with α-metalated isocyanides has been
methyl isocyanides with activated double bonds. The developed Efimov’s group. In contrast to other methods,
activation of these bonds can be carried out by various this strategy offers an operationally simple single-step
substituents, such as SO2, NO2 , CN, SMe or C=O groups. procedure, catalyst-free conditions, and demonstrates a
The methods toward pyrroles were carefully elaborated broad substrate scope. The importance of this reaction
on the basis of the catalytic reaction of α-metalated for various biological active compounds has also been
isocyanides to acetylenes. established.
Now, a new approach toward the 2,4-disubstituted pyrroles
on the basis of the interaction of aromatic enaminones, Ilya Efimov, Maria Matveeva, Rafael Luque, Leonid Voskressensky//1,3-
Dipolar cycloaddition of α-metalated isocyanides to enamines
and enaminones: Direct and convenient approach to 1H-2,4-
disubstituted pyrroles (2019) European Journal of Organic Chemistry,
doi.org/10.1002/ejoc.201901776

Fig. 2. Chemical structure of new 1H-2-aryl-4-aroylpyrroles

63


Physical & Colloidal
Chemistry Department

One of the main research areas of the Physical and materials and substances allows to overcome a
Colloidal Chemistry Department is fundamental number of various problems, among which are the
investigations in catalytic science. catalyst activity and selectivity, the improvement
Currently, one of the most pressing scientific of the existing and the creation of new materials
problems is the creation of nano-materials and for various reactions. An urgent problem is the
catalytic technologies based on nano-materials. development of the theoretical and experimental
The insight into the nanoscale functioning bases for the synthesis and characterization of
substances with predefined properties.

+7 495 955-08-49
[email protected]


For many years, the main research areas in the Physical and Colloidal Chemistry Department have been the following:

• prediction of the catalytic activity; • analysis of electronic interactions in surface
• kinetic and mechanistic studies of catalytic reactions; processes;
• development of а scientific basis for catalyst
• analysis of various forms of adsorption.
preparation;

65


The founder of the Department of Physical and Colloid Chemistry and
its leader for 39 years was Vladimir Mikhailovich Gryaznov (17.07.1922 –
19.05.2001) – Laureate of the Russian Federation in the field of science
and technology, Honored worker of the Science and Technology of Russia,
Member of the Russian Academy of Sciences, Honored member of the
International Academy of the Sciences Graduate School. Academician
V.M. Gryaznov discovered the properties of metal catalysts in a dimeric
gas state (in collaboration with V.I. Shimulis and V.D. Yagodovsky, priority
09/16/1960, diploma № 312 from 12/26/1985) and the phenomenon
of conjugation reactions to membrane catalysts (in collaboration with
V.S. Smirnov, L.K.  Ivanova and A. Mishchenko, priority of 06.12.1964,
diploma № 97 from 04/20/1971). The author of numerous scientific
publications, including the monograph: «Catalysis with noble metals.
Dynamic characteristics» published in the Moscow Publishing House
«Nauka» in 1989. Academician Gryaznov is the author of the invention
of «Method of chemical processes with elimination and addition of
hydrogen» (copyright certificate № 2740092, 27.08.1964).

SCIENTIFIC RESEARCH

Research of a new generation of catalysts based on metal nano-particles in
inert matrices

The design of effective and selective catalysts, stable at The scientists carry out the researches with the use of
high temperatures and resistant to coke formation, and catalysts related to a new generation: metal nano-particles
membrane-catalytic systems for hydro-dehydrogenation in inert matrices, carbon nano-tubes as well as catalysts
processes, for hydrocarbons conversion and for olefins based on aluminum oxide with an active phase applied on
production from the mixtures of carbon oxides (Under the the inner surface. These catalysts are considered ones of
supervision of Head the Department Professor Yuri M. Serov, the promising systems for highly efficient processes for
Associate Professor Tatiana F. Sheshko, Senior Lecturer producing light olefins, dry (carbon dioxide) reforming of
Ekaterina B. Markova) methane, hydrogenation-dehydrogenation reactions and
low-temperature cracking of hydrocarbons.

66


PHYSICAL & COLLOIDAL CHEMISTRY Department

Among the studies are the membrane catalysis and first time it has been found that the difference in the
membrane separation techniques, purification and catalytic activity of various bimetal samples is caused by
concentration of substances, gas chromatographic the diffusion rate of weakly bounded hydrogen (HI) on
analysis of air content, water and soil, including toxic the surface of the catalyst through the contact boundary
organic substances in the environment, and the between the metal particles (spillover- effect), and due to
development and improvement of chromatographic a jumpover-effect when the CHx radicals from one center
methods. It has been establshed that the ratio of the to another, where (they) undergoe further hydrogenation.
saturated and unsaturated hydrocarbons in the product Currently, the catalytic properties of nano-structured
mixture are mainly determined by the number of hydrogen perovskite- type oxides obtained by ceramic and sol-gel
atoms that can migrate from one active site to another, technology and having variable cation composition were
as well as by the composition of these centers. The studied in the hydrogenation of carbon monoxide. The
transformation of the solid sample into nano-particles results revealed that layered oxides show high stability
and increasing dispersity during catalyst distribution and selectivity (up to 70% for ethylene and propylene),
on the support, let to achieve the higher metal atoms and that their catalytic propeties can be varied either
coordinative unsaturation and, as a consequence, lead by the method of synthesis or by introduction into the
to a change in metal-carbon, metal-hydrogen binding composition of various substitute ions (compensators),
energy and also to a redistribution in a favor to the as well as by plasma chemical treatment, heat treatment
weakly bounded hydrogen in the ratio HI: HII. For the and their combinations.

Design and activation of nano- and microporouscatalysts

The design and activation of
nano- and microporous catalysts
based on zirconium phosphates
and complex oxides of different
composition for dehydration and
dehydrogenation reactions (Prof.
Victor D. Yagodovskiy, Prof. Irina I.
Mikhalenko, Associate Prof. Anna
I. Pylinina, Senior Lecture Elena I.
Knyazeva).

The main research area is
the catalytic chemistry of the
solid electrolyte and the metal
nanoparticles of 1B groups with
the original way of their activation
by the use of plasma-, photo-and
cryochemistry methods.

The applications of solid electrolytes in catalytic reactions high-temperature electrochemical devices, including fuel
of alcohols are being studied. The influence of the role of cells. For SE-catalysts characterization the methods XRD,
the composition, structural state and surface modifica- XPS, IR, UVS, SEM, TEM, acidity/basicity surface titration
tion of NASICON and PEROVSKIT-like materials on the is being used. The basic structure double sodium –
adsorption and catalytic properties is being investigated. zirconium phosphate is a framework with a large number
These groups of catalysts represent the solid electrolytes of the voids of various sizes and geometries (conducting
(SE) with cationic and anionic conductivity respectively. channels) that can be filled with various polyvalent
Thus, for several years, the group of scientists of the cations. As the number of oxygen vacancies in BIMEVOX
Department have been working on the theoretical and oxides grows the coordination number of vanadium
practical issues in the design and activation of nano- and cation falls. This can be used to control the strength
microporous catalysts based on zirconium phosphates and of the surface acid centers, and thus, the selectivity of
complex oxides of different composition for dehydration various processes. This is why NASICON and BIMEVOX
and dehydrogenation reactions. A new type of catalysts structures are considered the promising catalysts of
from the NASICON-family and PEROVSKIT-family acid-base and oxidation– reduction reactions, including
considered to be perspective in the selective alcohol the dehydration and dehydrogenation of alcohols. The
transformation to desired products. A special interest to relationship between physico-chemistry properties
the complex Na-Zr-phosphates (NASICON) with cationic (such as conductive, redox potential of doped ion) and
conductivity and to complex perovskite oxides (BiMEVOX) catalytic properties of SE is shown. The results have
with the anionic conductivity is caused by their possible been published in more than 60 works and reported at
use as oxygen-permeable membranes and electrodes for the Russian and International conferences.

67


Computer design of the photomagnetic materials

The computer design of the Under radiation, spiropirans their components of the magnetic sub
photo­magnetic materials (Prof. state, which affects the magnetic lattice with the most constant
Konstantin V. Bozhenko together sublattice, thereby changing its exchange interaction (J). The more
with the Vice-President of the RAS  magnetic properties. The control constant J is, the greater the changes
Academician Sergei Aldoshin). of the magnetic properties of in the magnetic properties under
materials by using light, opens new the action of radiation are. Based on
These materials have both photo­ possibilities for the storage and the findings, the recommendations
chromic and magnetic properties, transformation of information and related to the selection of the
and consist of the layers of a energy, etc. Using the precision most effective components of the
sub lattice and in between layers quantum-chemical calculations we magnetic sublattice have been given
of photo chromic spiropirans. have carried out the search of the to chemists.

The research of a new catalysts’ generation

The theoretical study of the surprising properties of Among the questions, which arouse interest, are as follows:
molecular systems of light elements (Professor Konstantin • the transformation of the circular structures to
V. Bozhenkо together with Professor Alexander I. Boldyrev,
Utah State University, USA) molecular wheels;
In this field different surprising systems and their • graphene aromatic properties;
properties are studied, not connected with the same • the possibility of the existence of double-helix
subject, but cause the continued (-ing) interest in a
large number of chemists. The confirmation of that structures in Inorganic Chemistry.
are the publications in leading international chemical The professors of the Physical Chemistry and Colloidal
journals. Chemistry Departmenst have more than 500 scientific
papers, including 300 articles published in major journals
(The Journal of Physical Chemistry, Kinetics and Catalysis,
Colloid Journal, Journal of Applied Chemistry, Mendeleev
Communication, Butlerov Communication etc.).

68


PHYSICAL & COLLOIDAL CHEMISTRY Department

Alexander G. Cherednichenko
Dr Sc. (Chemistry), Head of the Department
of Physical and Colloid Chemistry
Under his administration and with
the   participation of A.G.  Cherednichenko
12  industrial plants and technological site
have been created and put into operation.

Viktor D. Yagodovsky Yuri M. Serov Irina I. Mikhalenko Konstantin V. Bozhenko
Dr.Sc.(Chemistry),Professor, D r.   S c .   (C h e m is t r y ), Dr. Sc. (Chemistry), Professor, D r.   S c .   (C h e m is t r y ),
Professor-consultant of the Professor-consultant of the Professor of the Department Professor, Professor of the
Department of Physical and Department of Physical and of Physical and Colloid Department of Physical
Colloid Chemistry. Colloid Chemistry. Chemistry. and Colloid Chemistry.
The influence of the surface According to the results of Irina I. Mikhalenko delivers Currently Konstantin  V.
treatment of metal catalysts the research, he received lectures on «Physical and Bozhenko together with
and adsorbents by glow 14 copyright certificates for Colloidal Chemistry». In Academicians S.M.  Aldo­
discharge plasma in various the inventions, published 2006 a new course «Nan- shin and V.I. Minkinis is
gases on their activity is more than 90 articles. ochemistry and Nanot­ech­ working on creating
currently being studied. no­logy» was made by her. bifunctional materials.

RECENT SELECTED PAPERS [5]  Yafarova, L.V., Chislova, I.V., Zvereva, I.A., Kost, V.V., Sheshko, T.F.
Sol–gel synthesis and investigation of catalysts on the basis of
[1]  Kulichenko, M., Fedik, N., Bozhenko, K.V., Boldyrev, A.I. Hydrated
Sulfate Clusters SO42-(H2O)n (n = 1-40): Charge Distribution perovskite-type oxides GdMO3 (M = Fe, Co) 2019 Journal of Sol-Gel
Through Solvation Shells and Stabilization 2019 Journal of Physical Science and Technology
Chemistry B
[6]  Shulga, A., Butusov, L.A., Boruleva, E.A. Kurilkin, V.V., Kochneva,
[2]  Kulichenko, M., Fedik, N., Bozhenko, K.V., Boldyrev, A.I. Inorganic M.V. Fluorescent properties of gd-doped zno nanonporous networks
Molecular Electride Mg4O3: Structure, Bonding, and Nonlinear Optical & its application in optical biosensing 2018 Journal of Physics:
Properties 2019 Chemistry - A European Journal Conference Series

[3]  Baranov, N.I., Bozhenko, K.V., Breslavskaya, N.N., Mikhailova, T.Y., [7]  Butusov, L.A., Chudinova, G.K., Kochneva, M.V., Hayrullina, I.A.,
Dolin, S.P. Comparative Quantum-Chemical Analysis of the Structure Kudryavtsev, O.S. Fluorescence properties of Tb-doped ZnO porous
and Relative Stability of Oxyanions of Main-Group Elements of the network thin film grown on monocrystalline silicon substrate 2018
Second and Third Periods 2019 Russian Journal of Inorganic Chemistry Materials Science Forum

[4]  Mikhalenko, I.I., Gorbunov, S.V., Roshan, N.R., Chistov, E.M., [8]  Markova, E.B., Cherednichenko, A.G., Simonov, V.N. Odintsova,
Burkhanov, G.S. Characteristics of hydrogen sorption/desorption for M.V., Lyadov, A.S. Propane Conversion in the Presence of Alumina-
palladium foil doped by yttrium 2018 Journal of Physics: Conference Based Aerogel 2019 Petroleum Chemistry
Series

69


General Chemistry

Department

+7 495 955-08-60
[email protected]


The Department of General Chemistry of the Science veteran of the Great Patriotic War, Honored Worker
Faculty was allocated as an independent structural of Science and Technology, Professor Emeritus of the
unit from the Department of Inorganic Chemistry Peoples' Friendship University, Corresponding Member
of the Peoples' Friendship University in 1981. The of the International Academy of Sciences of Teacher
founder of the department was Boris Efimovich Education at the Department of Chemistry. He headed
Zaitsev, Professor, Doctor of Science in Chemistry, the department from 1981 to 1997.

71


Zaitsev B.E. was a famous expert in the field of
spectroscopy and quantum chemistry, author of
numerous papers on spectral methods of study of
organic and complex compounds. His research interests
identified the direction of the research activities of the
department. Under the guidance of prof. Zaitsev B.E.,
7 doctoral and more than 50 Ph.D. theses have been
completed and defended by both Russian and foreign
researchers.

The first members of the department were Dr. Professor Viktor V. Davydov
Gridassova R.K., Ivlieva V.I., Zaytseva V.A., Ryabov
Professor Boris E. Zaitsev M.A., Susanina T.N., Odinets Z.K., and others.
Currently, the department staff, in addition to
teaching activities (in English and Russian), are
actively and fruitfully investigating the directional
synthesis, structure and prediction of the properties
of metal compounds with biologically active
organic ligands using both experimental methods
and quantum chemical modeling.

From 1997 until nowadays, the department is headed by Professor V.V. Davydov,
Doctor of Science in Chemistry, participant in the aftermath of the accident at the
Chernobyl NPP (1986), Honored Worker of Higher Professional Education of the
Russian Federation, Honored Worker of Science and Technology of the Russian
Federation.

SCIENTIFIC RESEARCH

Redox-reactions in coordination chemistry

Together with the teaching staffs and postgraduates dihydroisoquinoline derivatives and other polyfunctional
of the department, as well as with the co-wokers heterocyclic ligands possessing biological activity were
from N.S. Kurnakov Institute of General and Inorganic performed at the department.
Chemistry of the Russian Academy of Sciences and the A large number of novel both mono- and polynuclear
Institute of Technical Chemistry of the Ural Branch of complex compounds were isolated, the synthesis of some
the Russian Academy of Sciences, under the supervision of them were simultaneously accompanied by redox
of V.V. Davydov a series of research works on the processes and reactions of intra-ligand transformations.
synthesis and study of coordination compounds with

Synthesis and studies of porphyrin-like compounds

Over the past 5 years, the department teacher staff chain, mononuclear complex compounds that are similar
and graduate students under the supervision of to phthalocyanine derivatives are promising for use as
associate professor Dr. Kolyadina N.M. novel methods drugs in photodynamic therapy of cancer have been
for the synthesis of attracting and promising porphyrins developed. The polynuclear coordination compounds of
containing jointed crown ether substituents with the above ligands can be used to isolate nanoparticles
different numbers of oxygen atoms in the polyester with desired structural properties.

72


The Department of GENERAL CHEMISTRY

Novel metal containing dyes and pigments

Under the supervision of professor, Doctor of Science The crystal structure determination indicated both
in Chemistry Kovalchukova O.V., the department staff traditional and unexpected coordination modes in the
conduct intense research in the field of synthesis, above compounds.
structure and spectral investigations of metal complexes The equilibria of the reactions of complex formation
with polyfunctional azo-containing aromatic and in the solutions were studied with spectroscopic and
heteroaromatic ligands. potentiometric methods, and the formation constants
A large variety of both organic and metal containing were calculated.
complex compounds were isolated and identified
by FT IR, 1H NMR, ESR, and UV–Vis spectroscopy.

The performed tests showed a good activity of the novel azo-compounds and their metal complexes as potential dyes
and pigments for wool and polyamide materials. The dyed fabrics exhibited an excellent fastness for washing, dry and
wet rubbing, as well as light fastness which varied from moderate to very good.

CH3 CH3 CH3

HO OH HO OH HO OH

CI-N2+Ar CI-N2+Ar1

N NN

OH N OH N OH N
Ar Ar Ar1

pH < 1 pH > 7

73


Application of products of chemical transformation of 2,4,6-trinitrotoluene
in coordination chemistry

Among various technogenic environmental problems, the characteristics with the intensive colors from yellow to
recycling of explosives removed from ammunition of arms blue depending upon substituent in the aryl radical.
is of a great significance nowadays. The transformation As it was shown by the X-Ray Single Crystal analysis,
of explosive trinitrotoluene into non-explosive products is the reaction of nitrosation of MPG leads to formation
based upon reduction of highly energetic nitro-groups into of the anionic form of a triketo-dihydroxyimino
ecologically safe amino-groups and/or their substitution tautomer:Addition of the dihydroxyimino-MPG aqueous
by hydroxy-groups. As the eco-friendly methods of solutions to the solutions containing cations of heavy
transformation of the technogenic wastes into products metals (Cr3+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Ba2+,
of civil needs are required, the new aspects of the Pb2+) which are reported as urban and industrial pollutants
further chemical transformation of MPG were studied. In of natural waters and soils provoked rapid and practically
collaboration with the department of Organic Chemistry full precipitation of complex compounds.
of the A.N. Kosygin Russian State University, more than The introduction of hydroxyimino groups to the composition
100 new azo-compounds and their metal complexes of azo dyes derived from MPG increases their anti-fungal
were isolated. All the obtained substances were tested activity and formation constants of their metal complexes.
as acid and disperse dyes for wool, polycapramide and
polyester fibers. Majority of them showed good coloristic

Metal complexes as precursors of nano-sized metal oxide catalysts

The hydrothermal method of isolation of nano- The modification of the surface of TiO2 nanoparticles
particles of metal oxides is of benefit among other by the cations of divalent transition metals decreases
methods because of rather low temperatures of the energy band gap of the nanoparticles and increases
decomposition of metal complexes with organic ligands. their activity as p0hotocatalysts in the reactions of
The metal complexes of N-nitroso-N-hydroxylamines photodegradation of harmful organic wastes under
of different composition as well as polyphenols and UV and visible light.
alpha-hydroxyaromatic carboxylic acids were used as
precursors of metal oxides nano-sized particles.

Quantum chemical modeling of the organic ligands and their metal complexes

The researches in the field of N NN
theoretical modeling of spatial and N N
electronic structures of complex
compounds are conducted at the O N
department under the guidance Cu
of associate professor, Dr. Ryabov O
M.A. The methods of quantum- C1
chemical calculations at various
approximations let determine the N N N
spectral characteristics and criteria N N
for the structure and coordination
modes of structurally labile ligands O N
in their metal complexes. These
research methods under are O
being actively mastered by young Zn
scientists and graduate students,
who present the results of their C1
calculations in the scientific and
dissertation presentations.

74


The Department of GENERAL CHEMISTRY

RECENT SELECTED PAPERS

[1] Absalan, Y., Ryabov, M.A., Kovalchukova, O.V. Thermal [5] Kotsuba V.E., Freidzon A.Ya., Polyanskaya N.A., Kolyadina N.M.
decomposition of bimetallic titanium complexes: A new method Template effect of pyridinium salts in the synthesis of crown-
for synthesizing doped titanium nano-sized catalysts and meso-tetraphenylporphyrin. Macroheterocycles, 2018, V. 11. No 2,
photocatalytic application. Мaterials Science and Engineering C, pp. 162-165.
2019, V. 97, pp. 813-826.
[6] Kovalchukova O. V., Ryabov M. A., Dorovatovskii P. V., Zubavichus
[2] Absalan Ya., Fortalnova E., Lobanov N., Dobrokhotova E., Y. V., Utenyshev A. N., Kuznetsov D. N., Volyansky O. V., Voronkova
Kovalchukova O. Ti(IV) complexes with some diphenols as precursors V. K., Khrustalev V. N. Synthesis and characterization of a series of
for TiO2 nano-sized catalysts. Journal of Organometallic Chemistry, novel metal complexes of N-heterocyclic azo-colorants derived from
2018, V. 859, pp. 80-91. 4-azo-pyrazol-5-one. Polyhedron, 2017, V. 121, pp. 41-52.

[3] Olga V. Kovalchukova, Al Tahan Rana Abdulilla Abbas, Svetlana [7] Kovalchukova O. V., Dorovatovskii P. V., Zubavichus Y. V., Bozhenko K.
B. Strashnova, Pavel V. Strashnov. Tautomeric transformations and V., Utenyshev A. N., R. Alabada, Volyansky O. V., Khrustalev V. N. An unusual
electronic structures of azopyrazolone dyes and their metal complexes. coordination of a 4-azopyrazol-5-one heterocyclic derivative with metals.
Reviews in Inorganic Chemistry, 2018. V. 38. No 3. pp. 87-101. Synthesis, X-ray studies, spectroscopic characteristics, and theoretical
modeling. Inorganica Chimica Acta, 2017, V. 466, pp. 266 – 273.
[4] Yahya Absalan, Olga Kovalchukova, Irena Bratchikova. Doped
rare and transition metal perovskite-type titanate nanoparticles:
A new method for developing synthesizing and photocatalytic
ability. Journal of Molecular Liquids, 2018. V. 268, pp. 882-894.

75


Shared Research and Educational

Center of Physico-Chemical Studies

+7 495 955-09-42
[email protected]


of New Materials, Substances &
Catalytic Systems

The Research and Educational Center is equipped and catalytic systems in gaseous, liquid and
with modern instruments that allow to carry solid form. Measurements of physico-chemical
out elemental, molecular, phase and structural properties and biological activity screening can
analysis of a wide range of substances, materials be performed as well.

77


Nikolai N. Lobanov born 1960 in USSR. Master's degree with honors in
physical chemistry from Mendeleev Institute of Chemical Technology,
received his PhD in physical chemistry from Kurnakov Institute of
General and Inorganic Chemistry of the Academy of Sciences of the
USSR in 1986. After that N. Lobanov received a permanent position
at Peoples’ Friendship University of Russia. In 1994 - Visiting Research
Scientist at the University of Coimbra, Portugal (Grant of the EC
Commission). Since 1996 - Head of the Laboratory of X-ray Analysis
and Crystal Chemistry and the Associate Professor of the Department
of Inorganic Chemistry. Since 2014 –Director of the Shared Research
and Educational Center of Physic-Chemical Studies of New Materials,
Substances and Catalytic Systems at the RUDN University. Research
interests in X-ray analysis and Crystal Chemistry. More than 80 papers
published in peer-reviewed journals.

Director of the Research Centre
Dr. Nikolai N. Lobanov

ORGANIC MATERIAL STUDIES GROUP

Equipment: • Thermo Focus DSQ II mass • Chromatec Crystal 5000M gas
• Agilent 6470 TQ LCMS-system spectrometer coupled with chromatograph
• Euro EA-3000 CHNOS analyzer a gas chromatograph
Qualitative and quantitative analysis
of mixtures of natural and synthetic
organic compounds, pharmaceuti-
cals, products of oil processing. De-
termination of pesticides and other
toxicants in water, air and soil.
Ultra-sensitive and express-targeted
analysis of organic compounds in
complex mixtures, including synthetic
organic compounds, pharmaceuticals
and metabolites. Fast polarity
switching speed and minimized
MRM transition time realize high-
throughput MRM analysis.
Elemental analysis of synthetic
compounds, soils and other C,H,N,S-
containing materials.

Agilent 6470 TQ LCMS-system

SPECTRAL STUDIES GROUP • Nicolet 6700/iS50 FT-IR spectrometer,
• Hitachi F-7100 spectrofluorimeter
Equipment: • FT-801 FT-IR spectrometer
• Shimadzu AA-7000 atomic absorption
spectrophotometer with a flame atomization
• Clever C-31 X-ray fluorescent spectrophotometer
• TECAN Infinite -1000 microplate reader
78


Shared Research & Educational Center of
PHYSICO-CHEMICAL STUDIES OF NEW MATERIALS, SUBSTANCES AND CATALYTIC SYSTEMS

Determination of elements from subjects can be analyzed, such as
sodium to uranium in a range of food products, alcohol-containing
0.0001 - 100% content allows to products, oil refining products,
work with small samples (starting ceramics, glass, metals and alloys,
with 50 µL). Heavy metals content absorbents, catalysts and reaction
can be determined in foodstuffs, products. The X-ray fluorescent
water, soil, pharmaceuticals, spectrophotometer Clever C-31
biological liquids, materials for allows non-destructive express
medicine. A wide range of test analysis of materials.

Shimadzu AA-7000 atomic
absorption spectrophotometer

with a flame atomization
Performing multi-component anal-
ysis of organic and inorganic sam-
ples (solid, liquid and gaseous) in
the spectral range from 350 to
7800 cm-1, as well as in the far re-
gion up to 50 cm-1.

Clever C-31 X-ray fluorescent spectrophotometer

Screening of biological activity of
chemical compounds on the TECAN
Infinite 1000 microplate reader.
Modified acetylcholinesterase inhib-
itor assays allow to use this piece
of equipment to robustly determine
novel inhibitor compounds in series
of substances provided by our clients.
TECAN Infinite -1000 microplate reader

Hitachi F-7100 spectrofluorimeter Nicolet 6700/iS50 FT-IR spectrometer

79


LABORATORY OF X-RAY ANALYSIS AND CRYSTAL CHEMISTRY

Equipment:

• DRON-7 X-ray powder diffractometer

Qualitative and quantitative phase analysis of crystalline Line profile analysis for the determination of
materials by X-ray diffraction. microstructural data: small crystallite sizes, microstrains
Precise determination of different structural properties and their distribution functions. X-ray analysis of residual
of crystalline materials (metals, alloys, catalytic systems, stress state.
semiconductor etc.) from X-ray diffraction data. Studies of Polymorphism.

Studies of the influence of different technological
treatment on the microstructure and properties of
crystalline materials.

CHEMICAL REACTIVITY RESEARCH GROUP

Equipment:
• Reactors for hydrogenation reactions H-CUBE Pro
• Photochemical reactor Ace Glass
Catalytic hydrogenation and deu-
teration of aromatic (heteroaro-
matic) systems, functional groups
and double (triple) bonds in organic
compounds. The H-Cube Pro allows
carrying out the reactions of cata-
lytic hydrogenation and deuteration,
which are conducted at high pressure
(up to 100 atm) and temperatures of
10-150 °C.
Research in the field of UV-initiated
chemical reactions. Photo- and
microwave irradiation are the
most efficient ways for promoting
chemical reactions, leading to
different organic and inorganic
substances and materials.
.
International student summer
schools are regularly held at the
Shared Research and Educational
Center of Physico-Chemical Studies
of New Materials, Substances and
Catalytic Systems. There are 6
continuing education programs.
After graduation, specialists are
issued certificates confirming their
educational achievements.

Reactors for hydrogenation
reactions H-CUBE Pro

80


International Russian-French student summer school «Modern Physico-Chemical Methods in Chemistry. Fragrances & Fine chemistry»
together with the University of Nice Sofia Antipolis


117198, Moscow, Miklukho-Maklaya str. 6
Tel.: +7 499 936-87-87
www.rudn.ru
[email protected]

115419, Moscow, Ordzhonikidze str. 3
Tel.: +7 495 952-26-44
[email protected]


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