В журнале  Physical Chemistry Chemical Physics,   (IF 3,945) опубликована статья с участием сотрудников Института:  к.х.н. Л.В. Политанской (завлаб, ЛИНИРР), к.х.н. Ю.Ф. Полиенко (снс. ЛАС), к.х.н. В.М. Тормышева (снс, рук. ГИТР) и д.ф.-м.н., проф. Е.Г. Багрянской (Директор НИОХ)

Fullerene-based triplet spin labels: methodology aspects for pulsed dipolar EPR spectroscopy

Ivan O. Timofeev, Larisa V. Politanskaya, Evgeny V. Tretyakov, Yuliya F. Polienko, Victor M. Tormyshev, Elena G. Bagryanskaya, Olesya A. Krumkacheva and Matvey V. Fedin

doi: 10.1039/D1CP05545C

Abstract

Triplet states of photoexcited organic molecules are promising spin labels with advanced spectroscopic properties for pulsed dipolar electron paramagnetic resonance (PD EPR) spectroscopy. Recently proposed triplet fullerene labels have shown great potential for double electron–electron resonance (DEER) distance measurements as “observer spins” due to a high quantum yield of the triplet state, hyperpolarization and relatively narrow EPR spectra. Here, we demonstrate the applicability of fullerene labels to other PD EPR techniques, such as relaxation induced dipolar modulation enhancement (RIDME) and laser induced magnetic dipolar spectroscopy (LaserIMD). In particular, a specific contaminating signal in LaserIMD experiments was observed, explained and mitigated. Comparative analyses of the signal-to-noise (SNR) ratios were performed for all employed methods. DEER on the fullerene–triarylmethyl pair shows the best performance, which allows state-of-the-art DEER acquisition at 100 nM with a SNR of ∼35 within reasonable 42 hours.

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В журнале Dalton Transactions (IF 4,39) опубликована статья с участием сотрудников Института   Е.Б. Николаенковой (нс ЛГетс) и В.П. Кривопалова (снс ЛГетс):

Near-infrared emitting copper(I) complexes with a pyrazolylpyrimidine ligand: exploring relaxation pathways

В журнале  Physical Chemistry Chemical Physics,   (IF 3,945) опубликована статья с участием сотрудников Института:  к.х.н. Т.А. Вагановой (снс, ЛГетС) и  д.х.н. Е.В. Малыхина (гнс. ЛГетС)

How do electron donating substituents affect the electronic structure, molecular topology, vibrational properties and intra- and intermolecular interactions of polyhalogenated pyridines?

doi: 10.1039/D1CP05956D

Abstract

Seven polyhalogenated pyridine derivatives bearing an amino or a hydroxyl group, either at the ortho or para position, were studied using a combined experimental and computational approach. The presence of an electron donating substituent strongly impacted on the geometry, electronic structure, electrostatic properties, molecular topology and vibrational characteristics of these compounds compared to the corresponding polyhalogenated pyridines. In particular the attention was focused on changes in wavenumbers, force constants and intensity of the seven in-plane Ring Normal Modes (RNMs). Due to the nature and position of the substituents, intra- and intermolecular interactions also underwent dramatic modifications, as revealed using Natural Bond Orbital (NBO) analysis, Non-Covalent Interaction (NCI) analysis and Atom-In-Molecule (AIM) theory. Raman and FT-IR spectra of these seven compounds were also collected in solid phase and rationalised by the simulated spectra for hydrogen bonding and/or π–π stacking based homodimers. The present study provides a strategy not only for the vibrational characterisation for the individual compounds, but also for shedding light on the ways of molecular packing in the molecular crystals or cocrystals involving these compounds.

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В журнале   Biomedicine & Pharmacotherapy   (IF 6,529) опубликована статья, соавторами которой являются сотрудники Института к.х.н. Хоменко (снс, ЛФАВ), д.х.н., проф. РАН К.П. Волчо (гнс, ЛФАВ)  и чл.-корр. РАН, д.х.н., проф. Н.Ф. Салахутдинов (зав. отделом медицинской химии)

Vitalii S. Moskaliuk, Rimma V. Kozhemyakina, Darya V. Bazovkina, Elena Terenina, Tatyana M. Khomenko, Konstantin P. Volcho, Nariman F.Salakhutdinov, Alexander V. Kulikov, Vladimir S. Naumenko,Elizabeth Kulikova

Biomedicine & Pharmacotherapy, Volume 147, March 2022, 112667


doi:10.1016/j.biopha.2022.112667

Abstract

Striatal-enriched protein tyrosine phosphatase (STEP) is a signal transduction protein involved in the pathogenesis of neuropathologies. A STEP inhibitor (TC-2153) has antipsychotic and antidepressant effects. Here, we evaluated the role of STEP in fear-induced aggression using Norway rats selectively bred for 90 generations for either high aggression toward humans (aggressive rats) or its absence (tame rats). We studied the effects of acute administration of TC-2153 on behavior and STEP expression in the brain of these animals and the influence of chronic treatment with TC-2153 on the behavior and STEP expression in aggressive rats in comparison with classic antidepressant fluoxetine, which is known to exert antiaggressive action. Acute TC-2153 administration decreased the aggressive reaction to humans in aggressive rats, while having no impact on the friendly behavior of tame rats. Moreover, in the elevated plus-maze test, the drug had an anxiolytic effect on both aggressive and tame rats. Aggressive rats demonstrated elevated levels of a STEP isoform (STEP46) as compared to tame animals, whereas acute TC-2153 administration significantly reduced STEP46 protein concentration in the brain of aggressive rats. Chronic treatment of aggressive rats with either TC-2153 or fluoxetine attenuated fear-induced aggression. Chronic administration of fluoxetine enhanced the exploratory activity in the elevated plus-maze test and decreased the STEP46 protein level in aggressive rats’ hippocampus, whereas chronic TC-2153 administration did not affect these parameters. Thus, STEP46 can play an important role in the mechanisms of aggression and may mediate antiaggressive effects of TC-2153 and fluoxetine.

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В журнале  Успехи химии/Russian Chemical Reviews  (IF 6.926) опубликован обзор в соавторстве с сотрудником Института

к.х.н. Д.И. Мажукина (снс, ЛАС)

Сопряженные нитроксильные радикалы [Conjugated nitroxide radicals]

Анотация

В последнее время в области органических парамагнетиков — стабильных радикалов и высокоспиновых систем — преобладали работы прикладного характера. Сформировалось несколько магистральных направлений применения и, соответственно, функционально-ориентированного синтеза органических радикалов и полирадикалов. В настоящем обзоре рассмотрено одно из этих направлений, в котором главную роль играют так называемые сопряженные нитроксильные радикалы. Их специфика заключается в наличии любого непредельного фрагмента (кратной связи C=C, C=N или C=O, ароматического либо гетероароматического цикла, конденсированных полиароматических систем) по соседству с нитроксильной группой. Продемонстрированы достижения химии сопряженных нитроксилов, обсуждены особенности их физико-химических свойств, магнитно-структурные корреляции и сферы практического применения. Библиография — 641 ссылка.

Ключевые слова: органические парамагнетики, нитроксильные радикалы, гибридные феноксил-нитроксилы, делокализация неспаренного электрона, электрохимия, высокоспиновые системы, молекулярный магнетизм, квантово-химические расчеты, параметры спин гамильтониана, теоретическое предсказание магнитных мотивов, корреляции структура-свойство

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В журнале Gels  (IF 4,702) опубликована статья  с участием сотрудников Института   Д.Г. Трофимова (вед. инженер ЛАС), Т.В. Рыбаловой (нс, ГРСА) и к.х.н. И.А. Кирилюка (завлаб ЛАС) :

4-Dialkylamino-2,5-dihydroimidazol-1-oxyls with Functional Groups at the Position 2 and at the Exocyclic Nitrogen: The pH-Sensitive Spin Labels

Abstract

Local acidity and electrostatic interactions are associated both with catalytic properties and the adsorption activity of various materials, and with the vital functions of biomolecules. The observation of acid–base equilibria in stable free radicals using EPR spectroscopy represents a convenient method for monitoring pH changes and the investigation of surface electrostatics, the advantages of which are especially evident in opaque and turbid samples and in porous materials such as xerogels. Imidazoline nitroxides are the most commonly used pH-sensitive spin probes and labels due to the high sensitivity of the parameters of the EPR spectra to pH changes, their small size, and their well-developed chemistry. In this work, several new derivatives of 4-(N,N-dialkylamino)-2,5-dihydrioimidazol-1-oxyl, with functional groups suitable for specific binding, were synthesized. The dependence of the parameters of their EPR spectra on pH was studied. Several showed a pK_a close to 7.4, following the pH changes in a normal physiological range, and some demonstrated a monotonous change of the hyperfine coupling constant by 0.14 mT upon pH variation by four units. View Full-Text

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В журнале CrystEngComm  (IF 3,545) опубликована статья с участием сотрудников Института  к.х.н. Т.А. Вагановой (снс ЛГетС), д.х.н. Ю.В. Гатилова (внс  ГРСА), к.х.н. И.П.  Чуйкова (нс ЛМР, ГОС) и д.х.н. Е.В. Малыхина (гнс ЛГетС)

Polyhalogenated aminobenzonitriles vs their co-crystals with 18-crown-6: amino group position as a tool to control crystal packing and solid-state fluorescence

Abstract

A series of para- and ortho-aminobenzonitriles differing in the nature and number of halogen substituents were used to synthesize 2:1 co-crystals with 18-crown-6 ether. The supramolecular structure of the obtained co-crystals as well as aminobenzonitrile crystals was studied in detail using single-crystal X-ray diffraction. Incorporation of the crown ether into the crystal matrix of arylamine results in the replacement of the H-bonds between amine molecules (N–H⋯NC and N–H⋯F) by the bond with a crown oxygen atom (N–H⋯O_cr). The crystal packing rearrangement modifies the π-electron interactions between aminobenzonitrile molecules both in the type of contact (C–F⋯π, C–Cl⋯π, CN⋯π, π⋯π) and mutual arrangement of the stacked molecules (parallel/anti-parallel, displaced/rotated). These transformations cause a change in the solid-state fluorescence characteristics of aminobenzonitriles: co-crystallization is accompanied by a bathochromic shift of the fluorescence maximum in the case of para-isomers and by a hypsochromic shift in the case of ortho-isomers; the magnitude of this effect depends on the number of halogen substituents. Exploration of the nature of the intra- and intermolecular interactions, along with the excited states of the molecules in the gas phase, in aminobenzonitrile crystals and their co-crystals, using state-of-the-art TD-DFT calculations evidences that, depending on the NH₂ group position, insertion of the crown ether causes either an increase in the change of the dipole moment upon photo excitation/emission with a subsequent increase in the Stokes shifts (para-aminobenzonitriles) or a decrease in these characteristics (ortho-aminobenzonitriles). This is consistent with the strengthening or weakening of π-electron aggregation in pairs of para- or ortho-aminobenzonitrile molecules, respectively, upon co-crystallization. A quantitative model that can clearly distinguish the different behaviours of ortho- and para-substituted molecules and provides an analytical tool of wide-ranging validity was proposed. The central importance of the mutual arrangement of the functions playing the role of the H-bond donor and acceptor was established; this finding may be exploited as a design tool to purposefully modify the molecular packing and tune the solid-state photophysical properties. Using DSC, the co-crystals' structure was found to self-organize in the same way upon crystallization from solution and from the melt and to regenerate in the melting–crystallization cycle.

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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

About the Cover:

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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