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На сайте журнала Ceramics International (IF 5,532) опубликована статья с участием сотрудников Института  д.б.н. М.В. Хвостова (внс, ЛФИ), д.м.н. Н.А. Жуковой (внс, ЛФИ) и и.б.н., проф.  Т.Г. Толстиковой (завлаб, ЛФИ)

A study on biological properties of titanium implants coated with multisubstituted hydroxyapatite

Mikhail V.Khvostov, Natalia V.Bulina, Natalia A.Zhukova, Elena G.Morenkova, Denis K.Rybin, Svetlana V.Makarova, Sergey V.Leonov, Vladimir S.Gorodov, Vladimir Yu. Ulianitsky, Tatjana G.Tolstikova

Ceramics International, Available online 5 September 2022

https://doi.org/10.1016/j.ceramint.2022.08.067

 

Abstract

In this work, it was found that the composition of hydroxyapatite coatings deposited on a titanium substrate depends on the temperature of detonation products and on the composition of the initial explosive mixture. Depending on the detonation mode, it was possible to obtain a coating of oxyhydroxyapatite containing or not containing an admixture of other calcium orthophosphates. It was shown for the first time that the structure of multisubstituted Zn–Si-hydroxyapatite and Ag–Zn–Si-hydroxyapatite with substitution degree x(Zn) = x(Si) = 0.2 and x(Ag) = 0.1 has lower thermal stability as compared to unsubstituted hydroxyapatite. The formation of a small amount of the α-Ca3(PO4)2 phase upon detonation deposition of the multisubstituted hydroxyapatites was obviously due to structural transformations that occurred when the material was heated by the detonation products. In vivo biological testing of titanium implants coated or not coated with hydroxyapatite revealed that the coating significantly accelerates osteogenesis in the gap between native bone and the implant; this acceleration improved implant fixation. In animals with the uncoated plates, fibrogenesis processes significantly outstripped the osteogenesis. The presence of Zn and Si ions in the apatite coating had a potentiating influence on the osteoinduction caused by hydroxyapatite. Osteogenesis in this case was more complete and characterized by pronounced processes of mineralization of the bone plates. The addition of Ag ions to the Zn–Si-hydroxyapatite at a concentration of 1 at.% did not impair its osteogenic activity and did not have a toxic effect on bone tissue, while imparting antibacterial properties to the material.

 

Альметрики:

A study on biological properties of titanium implants coated with multisubstituted hydroxyapatite   

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В журнале Topics in Current Chemistry (IF 8,905) опубликован обзор сотрудников Института  к.х.н. В.В. Чернышова (нс, ЛФАВ), к.х.н. И.И. Попадюк (нс, ЛФАВ), д.х.н. О.И. Яровой (внс, ЛФАВ) и и чл.-корр. РАН, д.х.н., проф. Н.Ф. Салахутдинова (зав. отделом медицинской химии)


Nitrogen-Containing Heterocyclic Compounds Obtained from Monoterpenes or Their Derivatives: Synthesis and Properties

Vladimir V. Chernyshov, Irina I. Popadyuk, Olga I. Yarovaya & Nariman F. Salakhutdinov

Top Curr Chem (Z) 380, 42 (2022),
Published 11 August 2022

https://doi.org/10.1007/s41061-022-00399-1

 

Abstract

Directed transformation of available natural compounds with native biological activity is a promising area of research in organic and medicinal chemistry aimed at finding effective drug substances. The number of scientific publications devoted to the transformation of natural compounds and investigations of their pharmacological properties, in particular, monoterpenes and their nearest derivatives, increases every year. At the same time, the chemistry of nitrogen-containing heterocyclic compounds has been actively developed since the 1950s after the news that the benzimidazole core is an integral part of the structure of vitamin B12. At the time of writing this review, the data on chemical modifications of monoterpenes and their nearest derivatives leading to formation of compounds with a nitrogen-containing heterocycle core have not been summarized and systematized in terms of chemical transformations. In this review, we tried to summarize the literature data on the preparation and properties of nitrogen-containing heterocyclic compounds synthesized from monoterpenes/monoterpenoids and their nearest derivatives for the period from 2000 to 2021.

Альметрики:

Nitrogen-Containing Heterocyclic Compounds Obtained from Monoterpenes or Their Derivatives: Synthesis and Properties   

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В журнале Insects (IF 3,139) опубликована статья с участием сотрудников Института  М.Д. Ганиной (мнс, ГЭИ и ХА) и  к.х.н. С.В. Морозова (внс,

ГЭИ и ХА)

Comparative Analysis of Epicuticular Lipids in Locusta migratoria and Calliptamus italicus: A Possible Role in Susceptibility to Entomopathogenic Fungi

Mariya D. Ganina, Maksim V. Tyurin, Ulzhalgas T. Zhumatayeva, Georgy R. Lednev, Sergey V. Morozov and Vadim Yu. Kryukov

Insects 2022, 13(8)),
Published 16 August 2022

https://doi.org/10.3390/insects13080736

 (This article belongs to the Topic Frontiers in Chemical Ecology)

Simple Summary

The surface lipids of insects protect them from desiccation and may modulate susceptibility to fungal infections. We conducted a comparative analysis of cuticular lipids of the migratory locust and Italian locust. The former inhabits relatively wet landscapes and the latter more arid ones. We analyzed cuticular lipids of these species by gas chromatography with mass spectrometry and found that the Italian locust has a hydrocarbon profile shifted toward long chains as well as a higher content of di- and trimethyl branched hydrocarbons, which is most likely an adaptation to the arid climate and strong temperature fluctuations in its habitats. Meanwhile, the surface of the Italian locust proved to be more hospitable for fungi. The number of Metarhizium conidia attached to the Italian locust cuticle was three-fold greater as compared to the migratory locust. Mortality due to the fungal infection was faster in the Italian locust under laboratory conditions. We propose that species inhabiting arid landscapes rarely encounter fungal pathogens and primarily deal with the problem of desiccation. Therefore, they can afford a cuticle that is hospitable to fungal pathogens.

Abstract

Cuticular lipids protect insects from desiccation and may determine resistance to fungal pathogens. Nonetheless, the trade-off between these lipid functions is still poorly understood. The migratory locust Locusta migratoria and the Italian locust Calliptamus italicus have dissimilar hygrothermal preferences: L. migratoria inhabits areas near water bodies with a reed bed, and C. italicus exploits a wide range of habitats and prefers steppes and semideserts with the predominance of sagebrushes. This paper presents significant differences between these species’ nymphs in epicuticular lipid composition (according to gas chromatography with mass spectrometry) and in susceptibility to Metarhizium robertsii and Beauveria bassiana. The main differences in lipid composition are shifts to longer chain and branched hydrocarbons (di- and trimethylalkanes) in C. italicus compared to L. migratoria. C. italicus also has a slightly higher n-alkane content. Fatty acids showed low concentrations in the extracts, and L. migratoria has a wider range of fatty acids than C. italicus does. Susceptibility to M. robertsii and the number of conidia adhering to the cuticle proved to be significantly higher in C. italicus, although conidia germination percentages on epicuticular extracts did not differ between the species. We propose that the hydrocarbon composition of C. italicus may be an adaptation to a wide range of habitats including arid ones but may make the C. italicus cuticle more hospitable for fungi. View Full-Text


Keywords: alkanes; insect cuticle; climatic adaptations; mycoses; Metarhizium

Альметрики:

Comparative Analysis of Epicuticular Lipids in Locusta migratoria and Calliptamus italicus: A Possible Role in Susceptibility to Entomopathogenic Fungi   

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На сайте журнала Frontiers in Plant Science (IF 6,627) опубликована статья с участием сотрудников Института  к.х.н. С.В. Морозова (внс, ГЭИ и ХА) и к.х.н. Е.И. Черняк (снс, ГЭИ и ХА)

Features of Activity of the Phenylpropanoid Biosynthesis Pathway in Melanin-Accumulating Barley Grains

Anastasiia Y. Glagoleva, Alexander V. Vikhorev, Nikolay A. Shmakov, Sergey V. Morozov, Elena I. Chernyak, Gennady V. Vasiliev, Natalia V. Shatskaya, Elena K. Khlestkina and Olesya Y. Shoeva

Front. Plant Sci., 11 July 2022
Sec. Plant Metabolism and Chemodiversity

https://doi.org/10.3389/fpls.2022.923717


 (This article is part of the Research Topic Insights in Plant Metabolism and Chemodiversity: 2021, View all 11 Articles )

 

Abstract

Barley (Hordeum vulgare L.) grain pigmentation is caused by two types of phenolic compounds: anthocyanins (which are flavonoids) give a blue or purple color, and melanins (which are products of enzymatic oxidation and polymerization of phenolic compounds) give a black or brown color. Genes Ant1 and Ant2 determine the synthesis of purple anthocyanins in the grain pericarp, whereas melanins are formed under the control of the Blp1 gene in hulls and pericarp tissues. Unlike anthocyanin synthesis, melanin synthesis is poorly understood. The objective of the current work was to reveal features of the phenylpropanoid biosynthesis pathway functioning in melanin-accumulating barley grains. For this purpose, comparative transcriptomic and metabolomic analyses of three barley near-isogenic lines accumulating anthocyanins, melanins, or both in the grain, were performed. A comparative analysis of mRNA libraries constructed for three stages of spike development (booting, late milk, and early dough) showed transcriptional activation of genes encoding enzymes of the general phenylpropanoid pathway in all the lines regardless of pigmentation; however, as the spike matured, unique transcriptomic patterns associated with melanin and anthocyanin synthesis stood out. Secondary activation of transcription of the genes encoding enzymes of the general phenylpropanoid pathway together with genes of monolignol synthesis was revealed in the line accumulating only melanin. This pattern differs from the one observed in the anthocyanin-accumulating lines, where — together with the genes of general phenylpropanoid and monolignol synthesis pathways — flavonoid biosynthesis genes were found to be upregulated, with earlier activation of these genes in the line accumulating both types of pigments. These transcriptomic shifts may underlie the observed differences in concentrations of phenylpropanoid metabolites analyzed in the grain at a late developmental stage by high-performance liquid chromatography. Both melanin-accumulating lines showed an increased total level of benzoic acids. By contrast, anthocyanin-accumulating lines showed higher concentrations of flavonoids and p-coumaric and ferulic acids. A possible negative effect of melanogenesis on the total flavonoid content and a positive influence on the anthocyanin content were noted in the line accumulating both types of pigments. As a conclusion, redirection of metabolic fluxes in the phenylpropanoid biosynthesis pathway occurs when melanin is synthesized.

 

Альметрики:

Features of Activity of the Phenylpropanoid Biosynthesis Pathway in Melanin-Accumulating Barley Grains   

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В журнале International Journal of Molecular Sciences   (IF=6,208) опубликована статья  с участием сотрудников Института: д.х.н. Е.С. Стоянова (внс, ЛМР) и И.В. Стояновой (инженер ЛМР):

The Chloronium Cation [(C2H3)2Cl+] and Unsaturated C4-Carbocations with C=C and C≡C Bonds in Their Solid Salts and in Solutions: An H1/C13 NMR and Infrared Spectroscopic Study



Evgenii S. Stoyanov  and Irina V. Stoyanova

Int. J. Mol. Sci. 2022, 23(16), 9111;
Publication Date: Mayr 1, 2022


 https://doi.org/10.3390/ijms23169111

(This article belongs to the Special Issue Structure, Energy and Dynamics of Molecular Interactions)


Abstract

Solid salts of the divinyl chloronium (C2H3)2Cl+ cation (I) and unsaturated C4H6Cl+ and C4H7+ carbocations with the highly stable CHB11Hal11− anion (Hal=F, Cl) were obtained for the first time. At 120 °C, the salt of the chloronium cation decomposes, yielding a salt of the C4H5+ cation. This thermally stable (up to 200 °C) carbocation is methyl propargyl, CH≡C-C+-H-CH3 (VI), which, according to quantum chemical calculations, should be energetically much less favorable than other isomers of the C4H7+ cations. Cation VI readily attaches HCl to the formal triple C≡C bond to form the CHCl=CH-C+H-CH3 cation (VII). In infrared spectra of cations I, VI, and VII, frequencies of C=C and C≡C stretches are significantly lower than those predicted by calculations (by 400–500 cm−1). Infrared and 1H/13C magic-angle spinning NMR spectra of solid salts of cations I and VI and high-resolution 1H/13C NMR spectra of VII in solution in SO2ClF were interpreted. On the basis of the spectroscopic data, the charge and electron density distribution in the cations are discussed. View Full-Text

Keywords: chloronium cation; vinyl and propargyl carbocations; magic-angle spinning NMR measurements


Альметрики: 

The Chloronium Cation [(C2H3)2Cl+] and Unsaturated C4-Carbocations with C=C and C≡C Bonds in Their Solid Salts and in Solutions: An H1/C13 NMR and Infrared Spectroscopic Study   

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В журнале Organic & Biomolecular Chemistry (IF 3,89) опубликована статья с участием сотрудников Института  снс(к.х.н.) А.М. Генаева и снс Г.Е.  Сальникова


DFT insights into superelectrophilic activation of α,β-unsaturated nitriles and ketones in superacids

Alexander M. Genaev, George E. Salnikov and Konstantin Yu. Koltunov

Org. Biomol. Chem., 2022,20, 6799-6808,
first published on 06 Aug 2022

 

 
https://doi.org/10.1039/D2OB01141G



 C9DT043251

Abstract

Superelectrophilic activation of α,β-unsaturated carbonyl compounds and their isoelectronic analogs, proceeding normally under superacidic conditions, have led to a great variety of beneficial synthetic transformations. However, the essence of such activation is not yet fully recognized, while a number of alternative views on the subject have been discussed at length in the literature. Here, taking the example of virtual reactions of cinnamonitrile and benzalacetone with benzene, their feasible mechanistic variants, including multiple protonation (coordination to AlCl3) of the reactants, were analyzed based on density functional theory (DFT). It is revealed that the most plausible reaction pathways involve the initial N- or O-protonation (coordination to AlCl3) of the activated compounds followed by subsequent protonation on the α-C-atom. Dicationic superelectrophiles thus formed ensure practically barrier-free reactions with benzene in addition to a more favorable energetic profile of their generating, which is in marked contrast to other potential reaction pathways.

Альметрики:

DFT insights into superelectrophilic activation of α,β-unsaturated nitriles and ketones in superacids   

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В журнале Pharmaceuticals (IF 5,215) опубликована статья с участием сотрудников Института: к.х.н. И.В. Ильиной (снс, ЛФАВ), д.х.н., проф РАН К.П. Волчо (гнс ЛФАВ) д.х.н. Ю.В. Гатилова (в.н.с. ГРСА, ЦСИ),  к.х.н. Д.К. Корчагиной  и чл.-корр. РАН, д.х.н., проф. Н.Ф. Салахутдинова (зав. отделом медицинской химии)

Biotransformation of (–)-Isopulegol by Rhodococcus rhodochrous

Irina B. Ivshina, Natalia A. Luchnikova, Polina Yu. Maltseva, Irina V. Ilyina, Konstantin P. Volcho, Yurii V. Gatilov, Dina V. Korchagina, Nadezhda A. Kostrikina, Vladimir V. Sorokin, Andrey L. Mulyukin and Nariman F. Salakhutdinov

Pharmaceuticals 2022, 15(8), 964 Published: 03 August 2022

(This article belongs to the Special Issue Natural Products as Drug Candidates for Redox-Related Human Disease)

https://doi.org/10.3390/ph15080964

 pharmaceuticals 15 00964 ag 550

Abstract

The ability of actinobacteria of the genus Rhodococcus to biotransform the monoterpenoid (–)-isopulegol has been established for the first time. R. rhodochrous strain IEGM 1362 was selected as a bacterium capable of metabolizing (–)-isopulegol to form new, previously unknown, 10-hydroxy (2) and 10-carboxy (3) derivatives, which may presumably have antitumor activity and act as respiratory stimulants and cancer prevention agents. In the experiments, optimal conditions were selected to provide the maximum target catalytic activity of rhodococci. Using up-to-date (TEM, AFM-CLSM, and EDX) and traditional (cell size, roughness, and zeta potential measurements) biophysical and microbiological methods, it was shown that (–)-isopulegol and halloysite nanotubes did not negatively affect the bacterial cells. The data obtained expand our knowledge of the biocatalytic potential of rhodococci and their possible involvement in the synthesis of pharmacologically active compounds from plant derivatives. View Full-Text

Keywords: biotransformation; halloysite nanotubes; (–)-isopulegol; monoterpenoid; Rhodococcus rhodochrous

Альметрики: 

Biotransformation of (–)-Isopulegol by Rhodococcus rhodochrous   

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В журнале  Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy,   (IF 4.831) опубликована статья в соавторстве с сотрудниками Института:  к.х.н. Т.В. Вагановой (снс, ЛГетС), д.х.н. Е.В. Малыхина (гнс. ЛЭАСМ) и д.х.н. Ю.В. Гатилова (внс, ГРСА ЦСИ)

Synthetic approach for the control of self-doping in luminescent organic semiconductors

Enrico Benassi, Tamara Vaganova, Evgenij Malykhin, Yurij Gatilov, Lazzat Nurtay, Haiyan Fanc

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
Volume 281, 15 November 2022, 121632
Available online 16 July 2022
doi: 10.1016/j.saa.2022.121632

 

Highlights

  • Mg doped CuCrO2 is a promising inorganic hole transport material for perovskite solar cells.
  • The analyzed device showed that 50 nm of both ETL and HTL thickness is quite sufficient to produce the highest efficiency.
  • Pb free, environmentally benign PSC performs outstanding efficiency 27.53% obtained through simulation.
  • The temperature gradient is almost constant (.0125) at higher temperature from 320K offer greater device stability.

Graphical abstract

Six polyhalogenated di- or triamino pyridines were synthesised and structurally characterised by means of single crystal X-Ray diffraction. Their supramolecular synthons were studied by means of vibrational (FT-IR and Raman) spectroscopies and Quantum calculations. Features identified in spectra of the solid samples were distinctive of the formation of supramolecular (in particular, hydrogen bond) interactions. Quantitative correlations were established among the dimerisation energies, the ring structure and quantitative characteristics of spectra.



 

2022_07_18_VagMalGat_n

 

Abstract

Supramolecular synthon is identified as a unit and provides important structural and energetic information in the study of organic crystals. However, the direct estimation of the supramolecular interaction remains challenging. In the present work six polyhalogenated di– or triamino pyridines were synthesised, their crystalline structure was characterised, and corresponding supramolecular synthons were studied using a combination of quantum mechanical calculations and FT–IR and Raman spectroscopy. Some distinctive features were identified especially for three vibrational normal modes (RNMs) related to the pyridine ring (viz. RNM1, RNM3 and RNM7) in the vibrational spectra (FT–IR and Raman) of the solid samples, which are due to the supramolecular interactions, hydrogen bond (hb) in particular, according to the quantum mechanical calculations. The comparison between the IR and Raman spectra of experimental and simulated results indicates that the adjacent intermolecular hydrogen bonds between two same molecules extensively exist in the solid samples. Moreover, some quantitative correlation was established among the dimerisation energies for hb dimers (hb1 dimers for compounds 1 and 2), the ring structure defined by the distribution of the substituents and quantitative characteristics of the vibrational spectra, for instance, the splitting magnitudes for RNM3(2) in IR spectra and the peak gap between RNM1 and RNM2 in Raman spectra.

Альметрики: 

SIntermolecular Interactions in the Crystalline Structure of Some Polyhalogenated Di– and Triamino Pyridines: Spectroscopical Perspectives   

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В журнале  Materials Chemistry Frontiers,   (IF 8.683) опубликована статья сотрудников Института:  д.х.н. А.Д. Куимова (мнс, ЛОЭ), к.х.н. К.С. Мельниковой-Беккер (снс. ЛОЭ), Н.А. Шумилова (мнс, ЛОЭ), И.Р. Коскина (мнс, ЛОЭ), к.х.н. А.А. Сониной (нс, ЛОЭ), к.х.н. И.К. Шундриной (снс, ЛЭАСМ, ГТ ЦСИ) и к.х.н. М.С. Казанцева (завлаб ЛОЭ)

Synthetic approach for the control of self-doping in luminescent organic semiconductors

Anatoly D. Kuimov, Christina S. Becker, Nikita A. Shumilov, Igor P. Koskin, Alina A. Sonina, Vladislav Yu. Komarov, Inna K. Shundrina and Maxim S. Kazantsev

Mater. Chem. Front., 2022,6(16), 2244-2255
first published on 05 Jul 2022

doi: 10.1039/D2QM00345G

2022_07_15_MChF

 

Abstract

Molecular doping of organic luminescent materials is an efficient tool to tune their optoelectronic properties. In particular, self-doping by luminescent longer-conjugation chain chemical by-products is a convenient way to obtain highly emissive organic semiconductors. Although the self-doping approach allows us to avoid the necessity of dopant synthesis, to realize the self-doping and optimize dopant concentration there is a need for a stepwise gradual purification of a material which may be problematic. Here we report a synthetic approach allowing us to control self-doping in luminescent organic semiconductors based on arylene-vinylene co-oligomers. We designed 1,2-bis(5-(4-octylphenyl)thiophen-2-yl)ethene (C8-BPTE) and synthesized it via two pathways yielding batches with different self-dopant concentrations. Our approach does not require a complex purification and excludes a possible degradation of the materials under sublimation or chromatography conditions. The optical properties of C8-BPTE crystals have been demonstrated to be finely tuned by simple mixing of synthesized batches of the material in a desired proportion, the increase of self-doped material content showed an increase in PL QY by up to 1.7 times and caused a red shift of photoluminescence spectra. Moreover, C8-BPTE demonstrated good film-formation ability and the substrate-inclined crystallization showed an efficient way to control crystal lateral size and its orientation on the substrate. C8-BPTE thin-film also demonstrated good p-type charge transport in solution-processed organic field-effect transistors with mobility of up to 0.1 cm2 V−1 s−1.

Альметрики: 

Synthetic approach for the control of self-doping in luminescent organic semiconductors   

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На сайте журнала  Physical Chemistry Chemical Physics,   (IF 3,945) опубликована статья сотрудников Института:  д.х.н. Л.Н. Щеголевой (внс, ЛЭАСМ),  и к.х.н. И.В. Береговой (снс. ЛЭАСМ)

Potential energy surfaces of a stacked dimer of benzene and its radical cation: what remains and what appears

Irina V. Beregovayaand Lyudmila N. Shchegoleva

Phys. Chem. Chem. Phys., 2022,
First published on 29 June 2022

doi: 10.1039/D2CP01691E

2022_01_PHHP_Bagr.jpg

 

Abstract

A stepwise qualitative consideration of the reduction in symmetry for the highly symmetrical “right sandwich” and “twisted sandwich” structures of the stacked benzene dimer caused by the pseudo-Jahn–Teller effect made it possible to construct a scheme of the potential energy surface (PES) of this dimer. Thirty-six equivalent structures of minimum energy are ordered on this extremely flat surface, transforming into each other in an almost barrier-free manner. There are two kinds of these transformations, both of which are pseudorotation. The transformation pathways inherent in this neutral dimer are also characteristic of its radical cation (RC). Structural transformations of the RC are inextricably linked with changes in its electronic state since its stationary structures relate to different electronic states. (C6H6)2+˙ exists in the form of two orbital isomers, each of which “pseudorotates” on its own area of the PES. During the pseudorotation, the SOMO distribution on the fragments of (C6H6)2+˙ changes, which is identical to what occurs during the pseudorotation of the Jahn–Teller benzene RC. These areas are connected by pairwise interconversions of their minimum energy structures. The interconversion of the orbital isomers is a bypassing of conical intersections between corresponding electronic states, which occurs through a synchronized pseudorotation of the fragments. The conclusions of the qualitative consideration and the results of quantum chemical calculations of various levels performed for (C6H6)2+˙ are in full agreement with each other. The revealed features of the structure of the PES of the two reference systems in studying the intermolecular and ion–molecule interactions are the basis for considering their more complex analogs, primarily their less symmetrical ones.

Альметрики: 

Potential energy surfaces of a stacked dimer of benzene and its radical cation: what remains and what appears   

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В журнале Dalton Transactions (IF 4,39) опубликована статья с участием сотрудников Института    Е.Б. Николаенковой (нс ЛГетс) и д.х.н.А.Я. Тихонова (гнс ЛГетс):

N-Hydroxy–N-oxide photoinduced tautomerization and excitation wavelength dependent luminescence of ESIPT-capable zinc(ii) complexes with a rationally designed 1-hydroxy-2,4-di(pyridin-2-yl)-1H-imidazole ESIPT-ligand

Nikita A. Shekhovtsov, Katerina A. Vinogradova, Sofia N. Vorobyova, Alexey S. Berezin, Victor F. Plyusnin, Dmitry Yu. Naumov, Natalia V. Pervukhina, Elena B. Nikolaenkova, Alexsei Ya. Tikhonov and Mark B. Bushuev  


Dalton Trans., 2022, V. 51, N 25, Pp. 9818-9835,
First published on 01 Jun 2022


https://doi.org/10.1039/D2DT01232D

 2022_DaltonTrans_Nikolaenkova_Tikhonov

Abstract

The ability of 1-hydroxy-1H-imidazoles to undergo proton transfer processes and to exist in N-hydroxy and N-oxide tautomeric forms can be used in coordination chemistry for the design of ESIPT-capable complexes. A series of ESIPT-capable zinc(II) complexes [Zn(HL)Hal2] (Hal = Cl, Br, I) with a rationally designed ESIPT-ligand 1-hydroxy-5-methyl-2,4-di(pyridin-2-yl)-1H-imidazole (HL) featuring spatially separated metal binding and ESIPT sites have been synthesized and characterized. Crystals of these compounds consist of a mixture of two isomers of [Zn(HL)Hal2]. Only a major isomer has a short intramolecular hydrogen bond O–H⋯N as a pre-requisite for ESIPT. In the solid state, the complexes [Zn(HL)Hal2] demonstrate temperature- and excitation wavelength dependent fluorescence in the cyan region due to the interplay of two intraligand fluorescence channels with excited state lifetimes spanning from 0.2 to 4.3 ns. The coordination of HL by Zn2+ ions results in an increase in the photoluminescence efficiency, and the photoluminescence quantum yields (PLQYs) of the complexes reach 12% at λex = 300 nm and 27% at λex = 400 nm in comparison with the PLQY of free HL of ca. 2%. Quantum chemical calculations indicate that N-hydroxy–N-oxide phototautomerization is both thermodynamically and kinetically favourable in the S1 state for [Zn(HL)Hal2]. The proton transfer induces considerable geometrical reorganizations and therefore results in large Stokes shifts of ca. 230 nm. In contrast, auxiliary ESIPT-incapable complexes [ZnL2][Zn(OAc)2]2·2H2O and [ZnL2][ZnCl2]2·4H2O with the deprotonated ligand exhibit excitation wavelength independent emission in the violet region with the Stokes shift reduced to ca. 130 nm.

Альметрики: 

N-Hydroxy–N-oxide photoinduced tautomerization and excitation wavelength dependent luminescence of ESIPT-capable zinc(ii) complexes with a rationally designed 1-hydroxy-2,4-di(pyridin-2-yl)-1H-imidazole ESIPT-ligand   

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На сайте  журнала Viruses   (IF=5,048) опубликована статья  с участием сотрудников Института: д.х.н. О.И. Яровой (внс, ЛФАВ), к.х.н. А.С. Соколовой (снс ЛФАВ), Е.Д. Мордвиновой (лаборант ЛФАВ), к.х.н. А.Д. Рогачева (снс ЛФАВ)  и чл.-корр. РАН, д.х.н., проф. Н.Ф. Салахутдинова (зав. отделом медицинской химии)


Borneol Ester Derivatives as Entry Inhibitors of a Wide Spectrum of SARS-CoV-2 Viruses

Olga I. Yarovaya, Dmitriy N. Shcherbakov, Sophia S. Borisevich, Anastasiya S. Sokolova, Maxim A. Gureev, Edward M. Khamitov, Nadezda B. Rudometova, Anastasiya V. Zybkina, Ekaterina D. Mordvinova, Anna V. Zaykovskaya, Artem D. Rogachev, Oleg V. Pyankov, Rinat A. Maksyutov and Nariman F. Salakhutdinov

Viruses 2022, 14(6), 1295
Publication Date: Jun 14, 2022


 https://doi.org/10.3390/v14061295

(This article belongs to the Special Issue SARS-CoV-2 and Other Coronaviruses)


Abstract

In the present work we studied the antiviral activity of the home library of monoterpenoid derivatives using the pseudoviral systems of our development, which have glycoproteins of the SARS-CoV-2 virus strains Wuhan and Delta on their surface. We found that borneol derivatives with a tertiary nitrogen atom can exhibit activity at the early stages of viral replication. In order to search for potential binding sites of ligands with glycoprotein, we carried out additional biological tests to study the inhibition of the re-receptor-binding domain of protein S. For the compounds that showed activity on the pseudoviral system, a study using three strains of the infectious SARS-CoV-2 virus was carried out. As a result, two leader compounds were found that showed activity on the Wuhan, Delta, and Omicron strains. Based on the biological results, we searched for the potential binding site of the leader compounds using molecular dynamics and molecular docking methods. We suggested that the compounds can bind in conserved regions of the central helices and/or heptad repeats of glycoprotein S of SARS-CoV-2 viruses. View Full-TextIt is known that epoxide-bearing compounds display pronounced pharmacological activities, and the epoxidation of natural metabolites can be a promising strategy to improve their bioactivity. Here, we report the design, synthesis and evaluation of biological properties of αO-SM and βO-SM, novel epoxides of soloxolone methyl (SM), a cyanoenone-bearing derivative of 18βH-glycyrrhetinic acid. We demonstrated that the replacement of a double-bound within the cyanoenone pharmacophore group of SM with α- and β-epoxide moieties did not abrogate the high antitumor and anti-inflammatory potentials of the triterpenoid. It was found that novel SM epoxides induced the death of tumor cells at low micromolar concentrations (IC50(24h) = 0.7–4.1 µM) via the induction of mitochondrial-mediated apoptosis, reinforced intracellular accumulation of doxorubicin in B16 melanoma cells, probably by direct interaction with key drug efflux pumps (P-glycoprotein, MRP1, MXR1), and the suppressed pro-metastatic phenotype of B16 cells, effectively inhibiting their metastasis in a murine model. Moreover, αO-SM and βO-SM hampered macrophage functionality in vitro (motility, NO production) and significantly suppressed carrageenan-induced peritonitis in vivo. Furthermore, the effect of the stereoisomerism of SM epoxides on the mentioned bioactivities and toxic profiles of these compounds in vivo were evaluated. Considering the comparable antitumor and anti-inflammatory effects of SM epoxides with SM and reference drugs (dacarbazine, dexamethasone), αO-SM and βO-SM can be considered novel promising antitumor and anti-inflammatory drug candidates.

Keywords: SARS-CoV-2; coronavirus surface protein S-spike; pseudoviral system; terpene; borneol; molecular dynamics; molecular docking


Альметрики: 

Borneol Ester Derivatives as Entry Inhibitors of a Wide Spectrum of SARS-CoV-2 Viruses   

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В журале Hydrometallurgy (IF 4,156) опубликована статья с участием сотрудников Института: д.х.н. А.Я. Тихонова (гнс, ЛГетС),  к.х.н. В.И. Маматюка (внс, ЛМР) и  к.х.н. Е.В.Карповой (снс, рук. группы ГОС)

Recovery of indium from sulfate solutions with D2EHPA in the presence of organic proton-donor additives

N.A.Grigorieva, Yu.Fleitlikh, A.Ya.Tikhonov,  V.I.Mamatyuk, E.V.Karpova, O.A.Logutenko

Hydrometallurgy, V. 213, August 2022, 105925,
Available online 11 June 2022


https://doi.org/10.1016/j.hydromet.2022.105925

Highlights

  • The state of D2EHPA in CCl4 in the presence of proton-donor additives HA was studied.

  • interaction between D2EHPA (HR) and HA was shown to occur.

  • Antagonistic extraction of indium by mixtures of D2EHPA and additives is observed.

  • D2EHPA and 2-ethylhexanol system is most efficient for In extraction and stripping.

 

Abstract

Di(2-ethylhexyl)phosphoric acid (D2EHPA, HR) is widely used for solvent extraction of indium from acidic leaching solutions, but indium stripping from the loaded organic phase is difficult because of the high affinity of indium for the extractant. Adding proton-donor additives (HA) to the D2EHPA solution is a way to achieve high stripping efficiency for indium. In this work, monocarboxylic acids, aliphatic alcohols, and phenol derivatives were used as additives. Nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy of the organic phases confirm the formation of intermolecular associates (H-complexes) between all additives and D2EHPA. In the case of alcohols and substituted phenols, the interaction of oxygen atoms of alcohols or phenols with the proton of the hydroxyl group of D2EHPA is predominant, while in the case of monocarboxylic acids, an interaction between the hydroxyl proton of the acid and the P=O group of D2EHPA mainly occurs. Despite the high In distribution ratio with D2EHPA (100−1000), in all cases investigated the introduction of additives into the organic phase led to an antagonistic extraction effect, however it facilitated efficient In stripping from the loaded organic phase. This effect depends significantly on the type and structure of the additive. Indium extraction in the presence of additives decreases in the series 4-bromophenol >4-t-butylphenol > octanol, 2-ethylhexanol >4-nitrophenol >2-nitrophenol >2,6-di-t-butylphenol, octanoic acid > Versatic 10. Extraction systems containing D2EHPA and 2-ethylhexanol can be used to recover indium from various industrial solutions, in particular, from those derived from lead‑zinc production and from liquid crystal display panel wastes.

 

Альметрики: 

Recovery of indium from sulfate solutions with D2EHPA in the presence of organic proton-donor additives   

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В журнале International Journal of Molecular Sciences   (IF=6,208) опубликована статья  с участием сотрудников Института: к.х.н. О.В. Саломатиной (снс, ЛФАВ), Н.И. Комаровой (вед инженер ЛФАВ) и чл.-корр. РАН, д.х.н., проф. Н.Ф. Салахутдинова (зав. отделом медицинской химии)


Novel Epoxides of Soloxolone Methyl: An Effect of the Formation of Oxirane Ring and Stereoisomerism on Cytotoxic Profile, Anti-Metastatic and Anti-Inflammatory Activities In Vitro and In Vivo

Oksana V. Salomatina, Aleksandra V. Sen’kova, Arseny D. Moralev, Innokenty A. Savin, Nina I. Komarova, Nariman F. Salakhutdinov, Marina A. Zenkova and Andrey V. Markov

Int. J. Mol. Sci. 2022, 23(11), 6214
Publication Date: Mayr 1, 2022


 https://doi.org/10.3390/ijms23116214

(This article belongs to the Special Issue Cytotoxicity on Pharmaceutical Interactions in Chemotherapy)


Abstract

It is known that epoxide-bearing compounds display pronounced pharmacological activities, and the epoxidation of natural metabolites can be a promising strategy to improve their bioactivity. Here, we report the design, synthesis and evaluation of biological properties of αO-SM and βO-SM, novel epoxides of soloxolone methyl (SM), a cyanoenone-bearing derivative of 18βH-glycyrrhetinic acid. We demonstrated that the replacement of a double-bound within the cyanoenone pharmacophore group of SM with α- and β-epoxide moieties did not abrogate the high antitumor and anti-inflammatory potentials of the triterpenoid. It was found that novel SM epoxides induced the death of tumor cells at low micromolar concentrations (IC50(24h) = 0.7–4.1 µM) via the induction of mitochondrial-mediated apoptosis, reinforced intracellular accumulation of doxorubicin in B16 melanoma cells, probably by direct interaction with key drug efflux pumps (P-glycoprotein, MRP1, MXR1), and the suppressed pro-metastatic phenotype of B16 cells, effectively inhibiting their metastasis in a murine model. Moreover, αO-SM and βO-SM hampered macrophage functionality in vitro (motility, NO production) and significantly suppressed carrageenan-induced peritonitis in vivo. Furthermore, the effect of the stereoisomerism of SM epoxides on the mentioned bioactivities and toxic profiles of these compounds in vivo were evaluated. Considering the comparable antitumor and anti-inflammatory effects of SM epoxides with SM and reference drugs (dacarbazine, dexamethasone), αO-SM and βO-SM can be considered novel promising antitumor and anti-inflammatory drug candidates.

Keywords: soloxolone methyl; epoxide; pharmacophore group; apoptosis; anti-metastatic activity; anti-inflammatory activity; toxicity; 18βH-glycyrrhetinic acid; ABC transporters; CDDO-Me


Альметрики: 

Novel Epoxides of Soloxolone Methyl: An Effect of the Formation of Oxirane Ring and Stereoisomerism on Cytotoxic Profile, Anti-Metastatic and Anti-Inflammatory Activities In Vitro and In Vivo   

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