Информация о публикации, соавторами которой являются   сотрудники Института к.б.н. Д.С. Баев (снс,ЛФИ), д.б.н., проф. Т.Г. Толстикова (завлаб ЛФИ), д.х.н.О.И. Яровая (внс, ЛФАВ) и чл.-корр. РАН, д.х.н., проф. Н.Ф. Салахутдинов (зав. отделом медицинской химии), размещена на обложке журнала   ACS Medicinal Chemistry Letters,   (IF 4,345) 

January 13, 2022
Volume 13, Issue 1
Pages 1-149

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Results of the experiments performed with bispidine compounds showed that 14 compounds exhibited anti-3CLpro activity in the concentration range of 1–10 µM, and 3 samples exhibited submicromolar activity.

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Design and Evaluation of Bispidine-Based SARS-CoV-2 Main Protease Inhibitors

Dmitriy Shcherbakov, Dmitriy Baev, Mikhail Kalinin, Alexander Dalinger, Varvara Chirkova, Svetlana Belenkaya, Aleksei Khvostov, Dmitry Krut’ko, Aleksei Medved’ko, Ekaterina Volosnikova, Elena Sharlaeva, Daniil Shanshin, Tatyana Tolstikova, Olga Yarovaya*, Rinat Maksyutov, Nariman Salakhutdinov, and Sergey Vatsadze

ACS Med. Chem. Lett. 2022, 13, 1, 140–147
Publication Date (Web):September 29, 2021

doi:10.1021/acsmedchemlett.1c00299

Abstract

For the first time, derivatives of 3,7-diazabicyclo[3.3.1]nonane (bispidine) were proposed as potential inhibitors of the SARS-CoV-2 main viral protease (3-chymotrypsin-like, 3CLpro). Based on the created pharmacophore model of the active site of the protease, a group of compounds were modeled and tested for activity against 3CLpro. The 3CLpro activity was measured using the fluorogenic substrate Dabcyl-VNSTLQSGLRK(FAM)MA; the efficiency of the proposed approach was confirmed by comparison with literature data for ebselen and disulfiram. The results of the experiments performed with bispidine compounds showed that 14 compounds exhibited activity in the concentration range 1–10 μM, and 3 samples exhibited submicromolar activity. The structure–activity relationship studies showed that the molecules containing a carbonyl group in the ninth position of the bicycle exhibited the maximum activity. Based on the experimental and theoretical results obtained, further directions for the development of this topic were proposed.

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В  журнале Applied Catalysis A: General   (IF=5.706) опубликована статья  с участием сотрудников Института: к.х.н. И.В. Ильиной (снс, ЛФАВ), к.х.н. Н.С. Ли-Жуланова (нс, ЛФАВ), к.х.н. Д.В. Корчагиной (снс, ГЯМР) , д.х.н, проф. РАН К.П. Волчо (гнс, ЛФАВ) и  чл.-корр. РАН, д.х.н., проф.  Н. Ф. Салахутдинова (рук. отдела ОМХ, завлаб ЛФАВ)

Clays catalyzed cascade Prins and Prins-Friedel-Crafts reactions for synthesis of terpenoid-derived polycyclic compounds

A.Yu. Sidorenko, Yu.M. Kurban, A.V. Kravtsova, I.V. I'ina, N.S. Li-Zhulanov, D.V. Korchagina, J.E. Sánchez-Velandia, A. Aho, K.P. Volcho, N.F. Salakhutdinov, D.Yu. Murzin, V.E. Agabekov

Applied Catalysis A: General

Volume 629,  05 January 2022, 118395

Abstract

The Prins/Friedel-Crafts cascade reactions of the terpenoid trans-4-hydroxymethyl-2-carene (synthesized from 3-carene) with aromatic aldehydes were systematically studied for the first time on acidic mesoporous clays (halloysite, illite, montmorillonites). Both the reaction rate and selectivity to the desired polycyclic product with tetrahydrofuran moiety increased with an increase in the catalyst acidity and their drying temperature, indicating that relatively strong Brønsted and Lewis acid sites favored their formation. The best activity and selectivity (up to 97%) was demonstrated over commercial montmorillonite K-10 with acidity of ca. 100 μmol/g. In contrast, on strongest acids (resin Amberlyst-15), dehydration/aromatization of the substrate was observed. It was shown, that mesoporosity of the catalyst is one of the key factors governing catalytic behavior. The presence of at least one an electron-donor substituent at the meta-position of benzaldehyde is critical for the Prins-Friedel-Crafts reaction. Overall, available montmorillonites are an effective replacement for homogeneous catalysts for the Prins/Friedel-Crafts cascade reactions.

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В журнале Pharmaceutics (IF 6,321) опубликована статья с участием сотрудников Института   д.б.н.,  М. В. Хвостова (внс, ЛФИ),  Е.Д. Гладковой (мнс ЛНТПС), к.б.н.С.А. Борисова (нс ЛФИ), д.м.н. Н. А. Жуковой (внс ЛФИ), к.б.н. Н.К. Марениной (мнс ЛФИ), Ю.В. Мешковой (инжененр ЛФИ), д.х.н. О.А. Лузиной (внс ЛФАВ) и д.б.н., проф. Т.Г. Толстиковой (завлаб ЛФИ) и д.х.н., чл.-корр. РАН, проф. Н.Ф. Салахутдинова К.П. Волчо (зав. отделом, завлаб ЛФАВ ):

Discovery of the First in Class 9-N-Berberine Derivative as Hypoglycemic Agent with Extra-Strong Action

В журнале  Nanoscale,   (IF 7,790) опубликована статья с участием сотрудницы Института  к.х.н. Е.А. Чулановой (нс, ЛГетС)

Photoactive ultrathin molecular nanosheets with reversible lanthanide binding terpyridine centers

Zian Tang, Elena Chulanova, Maria Küllmer, Andreas Winter, Julian Picker, Christof Neumann, Kristin Schreyer, Felix Herrmann-Westendorf, Andreas Arnlind, Benjamin Dietzek, Ulrich S. Schubert and Andrey Turchanin

The Journal of Physical Chemistry Letters, 2021,13(7), 20583-20591
Publication Date (Web):November 22, 2021

doi: 10.1039/D1NR05430A

Abstract

In recent years, functional molecular nanosheets have attracted much attention in the fields of sensors and energy storage. Here, we present an approach for the synthesis of photoactive metal–organic nanosheets with ultimate molecular thickness. To this end, we apply low-energy electron irradiation induced cross-linking of 4′-(2,2′:6′,2′′-terpyridine-4′-yl)-1,1′-biphenyl-4-thiol self-assembled monolayers on gold to convert them into functional ∼1 nm thick carbon nanomembranes possessing the ability to reversibly complex lanthanide ions (Ln-CNMs). The obtained Ln-CNMs can be prepared on a large-scale (>10 cm²) and inherit the photoactivity of the pristine terpyridine lanthanide complex (Ln(III)-tpy). Moreover, they possess mechanical stability as free-standing sheets over micrometer sized openings. The presented methodology paves a simple and robust way for the preparation of ultrathin nanosheets with tailored photoactive properties for application in photocatalytic and energy conversion devices.

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В журнале Applied Organometallic Chemistry   (IF=4,015) опубликована статья  с участием сотрудников Института д.х.н. И.И. Олейника (в.н.с, ЛЭАСМ) и  к.х.н. И.В. Олейник (с.н.с, ЛЭАСМ) 

Ring size enlargement in an ortho-cycloalkyl-substituted bis(imino)pyridine-cobalt ethylene polymerization catalyst and its impact on performance and polymer properties

Mingyang Han,Ivan I. Oleynik,Ming Liu,Yanping Ma,Irina V. Oleynik,Gregory A. Solan,Tongling Liang,Wen-Hua Sun

Applied Organometallic Chemistry,  V.36, N 2, February 2022, e6529
First published: 02 December 2021

Abstract

Four unsymmetrical examples of bis(arylimino)pyridines that each possess an ortho-cycloalkyl substituent of unique ring size, 2-{CMeN(2,4,6-Me₃C₆H₂)}-6-{CMeN(2,4-(CHPh₂)₂-6-RC₆H₂)}C₅H₃N (R = cyclopentyl L1, cyclohexyl L2, cyclooctyl L3, cyclododecyl L4), have been prepared and employed as reactants in the formation of the corresponding cobaltous chloride complexes, (N,N,N′)CoCl₂ (Co1–Co4). Structural characterization of Co2 and Co3 spotlights the five-coordinate geometry and the steric disparity imposed on the metal center by the inequivalent N-mesityl and N-2,4-dibenzyhydryl-6-cycloalkylphenyl groups. Co1–Co4 all proved productive precatalysts for ethylene polymerization achieving optimal performance at a temperature of 60°C on activation with either MAO or MMAO. Cyclopentyl-containing Co1 displayed the highest level (up to 10.3 × 10⁶ g PE per mol [Co] per h), whereas its cyclododecyl counterpart Co4 the lowest (down to 0.14 × 10⁶ g PE per mol [Co] per h). Strictly linear polyethylenes were produced with molecular weights spanning the range 22.0–36.0 kg per mol for Co1–Co4/MAO and 22.6–33.6 kg per mol for Co1–Co4/MMAO, with cyclohexyl Co2 producing the highest values with either activator. With the exception of the polymer produced using Co4, all catalysts afforded narrow unimodal distributions (M_w/M_n range: 1.7–2.2) for the polyethylenes in line with single site active species. By contrast, Co4 bearing the largest and conformationally flexible cycloalkyl group formed polyethylenes that were distinctly bimodal, which would imply the presence of two active species. End-group analysis of lower molecular weight polymer samples identified vinyl groups congruent with a termination step involving β-H elimination.

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В журнале  Physical Chemistry Chemical Physics,   (IF 3,676) опубликована статья с участием сотрудников Института:  Д.С. Одинцова (мнс, ЛЭАСМ), к.х.н. И.К. Шундриной (с.н.с. ЛЭАСМ), д.х.н. Л.А. Шундрина (зав. ЛЭАСМ)

Spectroelectrochemical study of the reduction of 2-methyl-9H-thioxanthene-9-one and its S,S-dioxide and electronic absorption spectra of their molecular ions

doi: 10.1039/D1CP04464H

Abstract

2-Methyl-9H-thioxanthene-9-one (1) and its S,S-dioxide (2) are the precursors of pendant groups that determine the reduction potentials of electro-active polyimides, which exhibit electrochromic behavior and are used in organic electronics. Electrochemical reduction of 1 and 2 leads to the formation of the corresponding persistent radical anions and dianion (for S,S-dioxide). Using 3D spectroelectrochemistry, all anions have been shown to exhibit strong absorption in the UV-VIS-NIR wavelength region. Electronic absorption spectra of 1 and 2 and their negative ions were interpreted using time-dependent DFT. According to the calculations, the most intense electronic transitions of the dianions 1²⁻ and 2²⁻ in the visible region exhibit hypsochromic shift compared to the intense transitions of the corresponding radical anions and have much higher oscillator strengths, which was confirmed experimentally for 2. An empirical kinetic model was proposed based on the analysis of the total charge passed through the cell during electrolysis and on the established mechanism of electrochemical reduction. This model perfectly described the UV-VIS-NIR optical density time dependences observed on 3D spectroelectrochemical surfaces for both compounds 1 and 2. This made it possible to explain the differences in the electrochromic behaviour of ambibolar electro-active polyimides with pendant groups based on 1, 2.

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В  журнале  The Journal of Physical Chemistry Letters,   (IF 6,475) опубликована статья с участием сотрудницы Института  к.ф.-м.н. И.В. Береговой (снс, ЛЭАСМ)

An Updated View of Primary Ionization Processes in Polar Liquids

doi: 10.1021/acs.jpclett.1c03388

Abstract

According to picosecond radiolysis data, primary radical cations in irradiated carbonates are very rapidly deprotonated. At the same time, analysis of the radiation-induced fluorescence from carbonate solutions indicates the formation of solvent-related radical cationic species with a relatively long lifetime. We use quantum chemical methods to develop a model of carbonate ionization that reconciles these conflicting data. Using ethylene carbonate as an example and assuming that its molecules exist in solution as a collection of dimeric associates, we show that both processes are the result of the loss of an electron from such dimers. This demonstrates that the generally accepted conceptualization of a primary ionization event, based on the idea of the formation of a radical cation of an individual molecule of an irradiated substance, requires revision in the case of polar aprotic liquids that tend to form molecular associates.

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В журнале Pharmaceutics (IF 6,321) опубликована статья с участием сотрудников Института   к.х.н.,  Е. В. Суслов (зам.дир. по науке, завлаб ЛНТПС),  Е.С. Можайцева (мнс ЛНТПС), А.А. Мункуева (аспирант, мнс ЛНТПС), Д. Цыпышева (мнс ЛФАВ, аспирант), к.х.н. А.Д. Рогачева (снс ЛФАВ) и д.х.н. К.П. Волчо (гнс, ЛФАВ):

Novel Multitarget Hydroxamic Acids with a Natural Origin CAP Group against Alzheimer’s Disease: Synthesis, Docking and Biological Evaluation

В журнале International Journal of Molecular Sciences   (IF=5,923) опубликована статья  с участием сотрудника Института: к.х.н.С.С. Хуцишвили (снс ЛМР)

Novel Nanobiocomposites Based on Natural Polysaccharides as Universal Trophic Low-Dose Micronutrients

Spartak S. Khutsishvili,Alla I. Perfileva,Olga A. Nozhkina,Tatjana V. Ganenko and Konstantin V. Krutovsky

Int. J. Mol. Sci. 2021, 22(21), 12006
Publication Date: November 5, 2021

(This article belongs to the Special Issue Biopolymer Composites: Synthesis, properties and Applications)

Abstract

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В журнале International Journal of Molecular Sciences   (IF=5,923) опубликована статья  с участием сотрудников Института: к.х.н.Ю.Ф. Полиенко (снс ЛАС) и  к.х.н. И.А. Кирилюка (завлаб ЛАС)

Peek Inside the Water Mixtures of Ionic Liquids at Molecular Level: Microscopic Properties Probed by EPR Spectroscopy

Mikhail Yu. Ivanov,Yuliya F. Polienko ,Igor A. Kirilyuk ,Sergey A. Prikhod’ko ,Nicolay Yu. Adonin  and Matvey V. Fedin

Int. J. Mol. Sci. 2021, 22(21), 11900
Publication Date: November 2, 2021

(This article belongs to the Special Issue Advanced Research in Green Chemistry)

Abstract

Many ionic liquids (ILs) can be mixed with water, forming either true solutions or emulsions. This favors their applications in many respects, but at the same time might strongly alter their physicochemical properties. A number of methods exist for studying the macroscopic properties of such mixtures, whereas understanding their characteristics at micro/nanoscale is rather challenging. In this work we investigate microscopic properties, such as viscosity and local structuring, in binary water mixtures of IL [Bmim]BF₄ in liquid and glassy states. For this sake, we use continuous wave and pulse electron paramagnetic resonance (EPR) spectroscopy with dedicated spin probes, located preferably in IL-rich domains or distributed in IL- and water-rich domains. We demonstrate that the glassy-state nanostructuring of IL-rich domains is very similar to that in neat ILs. At the same time, in liquid state the residual water makes local viscosity in IL-rich domains noticeably different compared to neat ILs, even though the overwhelming amount of water is contained in water-rich domains. These results have to be taken into account in various applications of IL-water mixtures, especially in those cases demanding the combinations of optimum micro- and macroscopic characteristics. View Full-Text

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