В журнале International Journal of Pharmaceutics  (IF 5,875) опубликована статья  с участием научных сотрудников Института   к.б.н. С.В. Анькова (нс ЛФИ) и д.б.н. проф. Т.Г. Толстиковой (завлаб ЛФИ) :

Aerosol Inhalation Delivery of Cefazolin in Mice: Pharmacokinetic Measurements and Antibacterial Effect

Abstract

Aerosol inhalation delivery of cefazolin, a broad-spectrum first-generation cephalosporin antibiotic, was investigated. Inhalation system based on ultrasonic nebulizer was developed for the generation of dry cefazolin aerosol within mean particle diameter range 0.5–3.0 μm and mass concentration 0.01–3 μg/cm³. Pharmacokinetic measurements were carried out for the aerosolized form of cefazolin delivered in mice using nose-only chamber. Cefazolin concentrations in blood serum and in the lungs of mice were measured as a function of time by means of high performance liquid chromatography. Body-delivered dose depending on particle size, concentration and inhalation time as well as other pharmacokinetic parameters were determined. The antibacterial effect of aerosolized cefazolin was assessed through the aerosol inhalation treatment of mice infected with Klebsiella pneumoniae. Survival rate for infected mice after the treatment with cefazolin aerosol demonstrated high antibacterial efficiency of the inhalation delivery of cefazolin in comparison with intraperitoneal delivery.

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В  журнале Physical Chemistry Chemical Physics,   (IF 3,676) опубликована статья с участием сотрудников Института:  к.х.н. Т.А. Вагановой (снс, ЛГеТС) и д.х.н. Е.В. Малыхина (гнс, ЛГеТС)

Impact of fluorination and chlorination on the electronic structure, topology and in-plane ring normal modes of pyridines

Abstract

Seven partially and fully fluorinated/chlorinated pyridines were investigated by means of FT-IR and Raman spectroscopy combined with quantum chemical calculations, mainly aiming to detect how the nature and position of F and Cl substituents affect the in-plane ring normal modes (RNMs) of pyridines in terms of vibrational wavenumbers, force constants, IR intensities and Raman activities. Taking pyridine as the reference, the RNMs and some derived RNMs through coupling with related C–X (X = F, Cl) stretching vibrations were identified on the basis of their composition in terms of internal coordinates. The impact of fluorination and chlorination on these RNMs was also discussed from the perspective of frontier molecular orbitals (MOs), maps of the molecular electrostatic potential (MEP) and the molecular topology. Natural bond orbital (NBO) analysis revealed the consequences of substitutions on the intramolecular charge delocalisation and consequently the ring bond strength. Moreover, the effects of anharmonicity of the potential on vibrational frequencies were presented and discussed.

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В журнале Gels  (IF 5,875) опубликована статья  с участием сотрудника Института   к.х.н. И.А. Кирилюка (завлаб ЛАС) :

Acidic and Electrosurface Properties of Binary TiO₂–SiO₂ Xerogels Using EPR of pH-Sensitive Nitroxides

Abstract

The binary xerogels TiO₂-SiO₂ are widely used as catalysts and their carriers in organic synthesis. Characterization and adjustment of the electrostatic properties of the surface and the local acidity inside the pores, are necessary for the further development of TiO₂-SiO₂ xerogels applications. This research investigates acid–base equilibria in the pores, and the surface electrostatic potential (SEP) of binary TiO₂-SiO₂ xerogels, by the EPR of stable pH-sensitive nitroxide radicals. These radicals are small enough to penetrate directly into the pores, and to be adsorbed onto the surface of the material under study. This makes it possible to obtain valuable information on the acidic and electrosurface properties of the studied system. The highest negative surface electrical charge associated with surface electrical potential (SEP) was equal to −196 ± 6 mV. It was induced by the surface of the sample with a 7% TiO₂ content. The local acidity inside the pores of this sample was found to be higher, by approximately 1.49 pH units, as compared to that in the external bulk solution. View Full-Text

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На сайте журнала 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) 

Boosting activity, thermostability, and lifetime of iron ethylene polymerization catalysts through gem-dimethyl substitution and incorporation of ortho-cycloalkyl substituents

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

Applied Organometallic Chemistry,  
Online Version of Record before inclusion in an issue, e6376

Abstract

Six types of ferrous chloride complex, [2-(ArN=CMe)-8-(ArN)-7,7-Me₂C₉H₆N]FeCl₂ (Ar=2-(C₅H₉)-6-MeC₆H₃ Fe1, 2-(C₆H₁₁)-6-MeC₆H₃ Fe2, 2-(C₈H₁₅)-6-MeC₆H₃ Fe3, 2-(C₅H₉)-4,6-Me₂C₆H₂ Fe4, 2-(C₆H₁₁)-4,6-Me₂C₆H₂ Fe5, 2-(C₈H₁₅)-4,6-Me₂C₆H₂ Fe6), each bearing a gem-dimethyl-substituted N,N,N-chelating ligand that differs in the ortho-cycloalkyl ring size and para-substituent of the N-aryl groups, are disclosed. All complexes have been prepared by a straightforward one-flask route and characterized by FT-IR spectroscopy and elemental analysis. In the case of Fe1, oxidation to form the oxo-bridged diferric species [2-(2-(C₅H₉)-6-MeC₆H₃N=CMe)-8-(2-(C₅H₉)-6-MeC₆H₃N)-7,7-Me₂C₉H₆N]FeCl(μ-O)FeCl₃ (Fe1') has been demonstrated and its structural identity confirmed by single crystal X-ray diffraction. Following treatment with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), Fe1–Fe6 exhibited optimal catalytic activities at 60°C for ethylene polymerization [up to 2.35 × 10⁷ g of PE (mol of Fe)⁻¹ h⁻¹ for Fe1/MMAO] producing linear polyethylene; even over prolonged run times, high activities were maintained. Moreover, this family of iron catalysts exhibited remarkable thermostability by displaying appreciable activity at temperatures as high as 100°C [activity up to 7.8 × 10⁶ g of PE (mol of Fe)⁻¹ h⁻¹]. By varying the ring size of the ortho-cycloalkyl and para-R² group (R² = H, Me), excellent control over molecular weight of the polyethylenes could be achieved with values in the range 1.4–67.8 kg mol⁻¹ obtainable. In addition, end-group analysis of the polymers generated with Fe/MAO or Fe/MMAO revealed that both β-H elimination and chain transfer to aluminum are competitive processes during chain termination.

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В журнале CrystEngComm, 2021, V. 23, N 7, Pp 4767-4781   (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) М. Сухова (лаборант ЛГетС) и д.х.н. Е.В. Малыхина (гнс ЛГетС)

Co-crystals of polyhalogenated diaminobenzonitriles with 18-crown-6: effect of fluorine on the stoichiometry and supramolecular structure

Abstract

A series of polyhalogenated diaminobenzonitriles and 18-crown-6 ether were used to reveal the dependence of the stoichiometry and supramolecular structure of co-crystals on various factors. 2,6-Diamino-3,5-difluoro-, 2,6-diamino-4-chloro-3,5-difluoro-, and 2,6-diamino-4-chloro-3-fluorobenzonitriles, as well as 2,4-diamino-3,5-difluorobenzonitrile give 1 : 1 co-crystals regardless of the diamine : crown ratio in the crystallization solution (from 2.5 : 1 to 1 : 2.5) and the nature of the solvent. According to X-ray diffraction data, the supramolecular structures of these co-crystals can be considered as 1D assemblies with the only structure-forming N–H⋯O_cr hydrogen bond. 2,4-Diamino-3,5,6-triflurobenzonitrile forms no 1 : 1 co-crystal, but yields co-crystals of 4 : 3 (under most of the studied conditions) and 2 : 1 (in CCl₄ solution) stoichiometry. The N–H⋯NC hydrogen bond and p⋯π electron interactions, along with the N–H⋯O_cr H-bond, participate in the formation of the 3D supramolecular structures of these co-crystals. The effect of the number of F atoms on the co-crystallization behaviour of difluoro- and trifluoro-2,4-diaminobenzonitriles was rationalized using quantum-chemical computations of the interaction energies of N–H⋯NC bonded pairs of these diamines in the experimental crystals and DFT simulated models. The DSC curves of each co-crystal contain a single peak corresponding to a crystal-to-liquid phase transition (melting), which does not change in melting–crystallization cycles, indicating that the stoichiometry and crystal structure are reproducible.

• This article is part of the themed collections: Supramolecular & Polymorphism and CrystEngComm HOT articles

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В журнале Chemosphere (IF 7,086) опубликована статья с участием сотрудника Института   к.х.н. С. В. Морозова (завлаб ЛЭИиХА) 

Supercritical water oxidation of chlorinated waste from pulp and paper mill

Chemosphere,  2021, V. 238, November 2021, 131239

https://doi.org/10.1016/j.chemosphere.2021.131239

 

Abstract

The article presents the research results of the oxidation of watered toxic waste from the pulp and paper industry (sludge-lignin, the empirical formula of organic matter CH_1.51N_0.05S_0.03Cl_0.01O_0.54) in supercritical water-oxygen (SCW/O₂) fluid. The experiments were carried out using a flow tube reactor at a pressure of 25 MPa, temperature gradient along its vertical axis (from top to bottom: 390–600 °C), sludge-lignin flow rate of 9.5–14.5 g/min, oxygen ratio OR = 0.73–2.52, using NaOH (1.6 wt%) as a catalyst. Employing gas chromatography – mass spectrometry, polychlorophenols were identified in the composition of sludge-lignin, in which 2,4,6-trichlorophenol was the main component. The total yield of extracted phenols and chlorophenols per sludge-lignin organic matter was 20.82 and 2.88 μg/g, respectively. It is revealed that the conversion rate of sludge-lignin in SCW/O₂ fluid is limited by heterogeneous oxidation of the carbonized residue, and is determined by the O₂ content in the reaction mixture. At OR ≥ 1.16, only CO₂, CO, N₂, and N₂O were detected in the volatile oxidation products. An increase in OR from 0.73 to 2.52 leads to a decrease in the total content of phenols (from 45540.1 to 129.3 μg/dm³) and chlorophenols (from 51.4 to 2.2 μg/dm³) in the water collected at the reactor outlet. It is shown that 2,6-dichlorophenol and 2-chlorophenol are the most resistant to oxidation. From the analysis of the initial sludge-lignin and mineral residues, it follows that the bulk of the chlorine contained in its organic matter is converted into NaCl in the course of oxidation.

Keywords: Waste disposal, Phenols, Chlorophenols, Supercritical water oxidation, Alkali catalyst

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Supercritical water oxidation of chlorinated waste from pulp and paper mill   

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В журнале Pharmaceuticals (IF 5,863) опубликована статья с участием сотрудников Института   д.х.н., проф. Э. Э. Шульц (завлаб ЛМХ) и Т.В. Рыбаловой (нс ГРСА) 

Calcium Chelidonate: Semi-Synthesis, Crystallography, and Osteoinductive Activity In Vitro and In Vivo

В престижном журнала The Journal of the American Chemical Society (JACS) (IF 15,419) опубликована статья с участием сотрудников Института   д.х.н. И.Ю. Багрянской (внс, рук. группы ГРСА), к.х.н. И.К. Шундриной (снс, ЛМР, рук. группы ГТ) и к.х.н. М.C. Казанцева (завлаб ЛОЭ):

Platform for High-Spin Molecules: A Verdazyl-Nitronyl Nitroxide Triradical with Quartet Ground State

J. Am. Chem. Soc. 2021, 143, 21, 8164–8176

Publication Date:May 21, 2021

https://doi.org/10.1021/jacs.1c02938

Получен и структурно охарактеризован гетероспиновый квартетный трирадикал, содержащий оксовердазил и два нитронилнитроксильных фрагмента. Трирадикал устойчив на воздухе и обладает высокой термической стабильностью в инертной атмосфере. Данные магнитных измерений указывают на достаточно сильные внутримолекулярные обменные ферромагнитные взаимодействия между парамагнитными центрами. Полученный гетероспиновый трирадикал с квартетным основным состоянием может служить платформой для получения дендримерных высокоспиновых систем.

 

Abstract

Thermally resistant air-stable organic triradicals with a quartet ground state and a large energy gap between spin states are still unique compounds. In this work, we succeeded to design and prepare the first highly stable triradical, consisting of oxoverdazyl and nitronyl nitroxide radical fragments, with a quartet ground state. The triradical and its diradical precursor were synthesized via a palladium-catalyzed cross-coupling reaction of diiodoverdazyl with nitronyl nitroxide-2-ide gold(I) complex. Both paramagnetic compounds were fully characterized by single-crystal X-ray diffraction analysis, superconducting quantum interference device magnetometry, EPR spectroscopy in various matrices, and cyclic voltammetry. In the diradical, the verdazyl and nitronyl nitroxide centers demonstrated full reversibility of redox process, while for the triradical, the electrochemical reduction and oxidation proceed at practically the same redox potentials, but become quasi-reversible. A series of high-level CASSCF/NEVPT2 calculations was performed to predict inter- and intramolecular exchange interactions in crystals of di- and triradicals and to establish their magnetic motifs. Based on the predicted magnetic motifs, the temperature dependences of the magnetic susceptibility were analyzed, and the singlet–triplet (135 ± 10 cm^–1) and doublet-quartet (17 ± 2 and 152 ± 19 cm^–1) splitting was found to be moderate. Unique high stability of synthesized verdazyl-nitronylnitroxide triradical opens new perspectives for further functionalization and design of high-spin systems with four or more spins.

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Platform for High-Spin Molecules: A Verdazyl-Nitronyl Nitroxide Triradical with Quartet Ground State   

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В журнале Pharmaceuticals (IF 5,863) опубликована статья с участием сотрудников Института   к.х.н. К.С.Ковалевой, д.х.н. О.И.  Яровой, к.х.н. К.Ю. Пономарева, м.н.с. Е.С. Можайцева, к.х.н. Е.В. Суслова  и д.х.н., проф., чл.-корр. РАН Н.Ф. Салахутдинова

Design, Synthesis, and Molecular Docking Study of New Tyrosyl-DNA Phosphodiesterase 1 (TDP1) Inhibitors Combining Resin Acids and Adamantane Moieties

Cтатья  сотрудников Института: к.х.н. А.А. Сониной (нс, ЛОЭ), к.х.н. К.С. Мельниковой-Беккер (снс, ЛОЭ), А.Д. Куимова (мнс, ЛОЭ),  к.х.н. И.К. Шундриной (снс, ЛЭАСМ)  и к.х.н.М.С. Казанцева (завлаб ЛОЭ) размещена на обложке престижного  журнала CrystEngComm  (IF=3.117).

Alkyl-substituted bis(4-((9H-fluoren-9-ylidene)methyl)phenyl)thiophenes: weakening of intermolecular interactions and additive-assisted crystallization

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

CrystEngComm, 2021,V. 23, N 14, Pp 2654-2664l

Abstract

Aggregation-induced emission (AIE) materials find their applications in organic optoelectronics, bio-imaging and sensors. In this work, we introduced alkyl substituents in AIE-active bis(4-((9H-fluoren-9-ylidene)methyl)phenyl)thiophene and elucidated their effect on the molecular and crystal structures, crystallization and optical properties of materials. Ethyl-containing (C2-BFMPT) and octyl-containing (C8-BFMPT) 2,5-bis(4-((2,7-dialkyl-9H-fluoren-9-ylidene)methyl)phenyl)thiophenes were synthesized in 4 steps. The introduction of alkyl groups weakened intermolecular interactions, decreased the crystal quality, melting point, and density, and increased the solubility of materials. Octyl-containing derivative was demonstrated to generate two crystal forms obtained by the native (form I) and additive-assisted (form II) crystallizations. The latter appeared to have a better crystal quality. C–H⋯π interactions and an extensive positional disorder were revealed for both derivatives. In C8-BFMPT crystals (form II) only a half of molecular backbones were well localized due to multiple intermolecular C–H⋯π interactions, whereas another half demonstrated a high positional disorder. The AIE effect with a negligible photoluminescence (PL) quantum yield (QY) in solution and a PL QY of 5% for C2-BFMPT and 2% for C8-BFMPT (form II) crystals was demonstrated. The cooling of the C8-BFMPT form II resulted in 10-fold increase of PL QY. The introduction of alkyl-substituents and additive-assisted crystallization are highlighted as powerful tools for the control of crystal packing, morphology, polymorphism and the optical performance of AIE-materials..

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В журнале Applied Catalysis A: General   (IF=5.006) опубликована статья  с участием сотрудников Института: к.х.н. И.В. Ильиной (снс, ЛФАВ), Н.С. Ли-Жуланова (нс, ЛНТПС), к.х.н. Д.В. Корчагиной (снс, ГЯМР), к.х.н. О.В. Ардашова (снс, ЛФАВ), 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)

Catalytic synthesis of terpenoid-derived hexahydro-2H-chromenes with analgesic activity over halloysite nanotubes

A.Yu.Sidorenko, Yu.M.Kurban, I.V.Il'ina, N.S.Li-Zhulanov, D.V.Korchagina, O.V.Ardashov, J.Wärnå, K.P.Volcho, N.F.Salakhutdinov, D.Yu.Murzin, V.E.Agabekov

Applied Catalysis A: General

Volume 618, 25 May 2021, 118144

Abstract

Condensation of α-pinene derived p-menta-1,8-diene-5,6-diol (diol) with decanal was studied for the first time over modified halloysite nanotubes (HNT). The yield of the desired hexahydro-2H-chromene-4,8-diol with analgesic activity was 76–80 % practically not depending on the catalyst type, while selectivity to 4S-isomer decreased, and to 4R-isomer increased with increasing acidity. The highest selectivity to 4S-diastereomer (48.1 %) on halloysite is a result of weak acidity of this catalyst. DFT optimization of the key intermediate structure shows that the nucleophile attack proceeds at the equatorial position with the 4S-diastereomer formation, which was preferred on halloysite. On strong Brønsted (Amberlyst-15) and Lewis (scandium triflate) acids the target product yield did not exceed 37 % because of dehydration. Halloysite nanocatalysts displayed a stable performance. In the case of diol reaction with a set of carbonyl compounds, the yields of hexahydro-2H-chromene-4,8-diols (up to 88.0%) and the ratio of its 4S/4R isomers (up to 21.0) were significantly higher than on other catalysts.

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На сайте журнала Bioorganic Chemistry (IF 4,567) опубликована статья с участием сотрудников Института   к.т.н. С.А. Попова (снс, ЛМХ ) и д.х.н., проф. Э.Э. Шульц (завлаб ЛМХ):

Design and Linkage Optimization of Ursane-Thalidomide-Based PROTACs and Identification of Their Targeted-Degradation Properties to MDM2 Protein

Abstract

Ursolic acid (UA) is an accessible triterpenoid, widely applied in the design and synthesis of antitumor compounds. However, the mechanism of its anti-tumor effect is still unclear. To verify the molecular mechanism of its biological activity, based on the bifunctional activity of ubiquitination and subsequent proteasomal degradation of the target protein of the proteolysis-targeting chimeras (PROTACs) strategy, here we report the design, synthesis and cellular activity of six UA PROTAC hydrochloride compounds 1A-1F, in which UA acts as the binding ligand of the PROTAC and is linked to thalidomide (E3 ligand) through a series of synthetic linkers. The results revealed that compound 1B, connected with a POE-3 (3-Polyoxyether) possessed remarkable in vitro antitumor activity (with the IC₅₀ value of 0.23∼0.39 μM against A549, Huh7, HepG2). WB results demonstrated that the administration of compound 1B induced significant degradation of MDM2 (only 25% to that of SM1), and promoted the expression of P21 and PUMA proteins, and thus inhibited the proliferation (77.67% of 1B vs 60.37% of CON in G1 phase) and promoted the apoptosis (26.74% of 1B vs 3.35% of CON) of A549 cells. This work demonstrated proof of designing the efficient target protein degradation by UA PROTACs with the POE linkers. In addition, we confirmed that UA possess the characteristic of targeted-binding the protein of murine double minute-2 protein (MDM2). This will lay a foundation for the comprehensive utilization of forest natural compound UA.

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