В журнале Chemistry - A European Journal   (IF=5,16) опубликована статья  с участием сотрудника Института к.х.н. А.М. Агафонцева (с.н.с, ЛТС)

Ratiometric detection of ATP by fluorescent cyclophanes with bellows‐type sensing mechanism

Aleksandr M. Agafontsev, Tatiana A. Shumilova, Aleksandr S. Oshchepkov, Frank Hampel, Evgeny A Kataev

Chemistry - A European Journal, 

Volume 26 , Issue 44 Special Issue: Young Chemists 2020

August 6, 2020, Pages 9991-9997

This article also appears in:

• Young Chemists 2020

Abstract

Pyrene‐based cyclophanes have been synthesized with the aim to realize a bellows‐type sensing mechanism for the ratiometric detection of nucleotide concentrations in a buffered aqueous solution. The sensing mechanism involves the encapsulation of a nucleobase between two pyrene rings, which affects the monomer‐excimer equilibrium of the receptor in the excited state. The nature of the spacer and its connection pattern to pyrene rings have been varied to achieve high selectivity for ATP. The 1,8‐substituted pyrene‐based cyclophane with the 2,2′‐diaminodiethylamine spacer demonstrates the best selectivity for ATP showing a 50‐fold increase in the monomer‐excimer emission ratio upon saturation with the nucleotide. The receptor can detect ATP within the biological concentrations range over a wide pH range. NMR and spectroscopic studies have revealed the importance of hydrogen bonding and stacking interactions for achieving a required receptor selectivity. The probe has been successfully applied for the real‐time monitoring of creatine kinase activity.

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В журнале Biomedical Optics Express (IF 3,91) опубликована статья с участием сотрудника
Института: к.х.н. А.Ю. Воробьева (зав.лаб, с.н.с ЛФ)

Optical uncaging of ADP reveals the early calcium dynamics in single, freely moving platelets

Abstract

Platelet activation is considered to be a cornerstone in pathogenesis of cardiovascular disease. The assessment of platelet activation at the single-cell level is a promising approach for the research of platelet function in physiological and pathological conditions. Previous studies used the immobilization of platelets on the surface, which significantly alters the activation signaling. Here we show that the use of photolabile “caged” analog of ADP allows one to track the very early stage of platelet activation in single, freely moving cells. In this approach, the diffusion step and ADP receptor ligation are separated in time, and a millisecond-timescale optical pulse may trigger the activation. The technique allows us to measure the delay (lag time) between the stimulus and calcium response in platelets. We also propose a simple model function for calcium peaks, which is in good agreement with the measured data. The proposed technique and model function can be used for in-depth studies of platelet physiology.

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В журнале Dalton Transactions (IF 4,052) опубликована статья с участием сотрудников Института   д.х.н., проф.  А.В. Ткачева (завлаб, ЛТС) и к.х.н. А.М. Агафонцева (снс, ЛТС):

Luminescent Zn(II) and Cd(II) complexes with chiral 2,2′-bipyridine ligands bearing natural monoterpene groups: synthesis, speciation in solution and photophysics

Abstract

Mononuclear zinc(II) and cadmium(II) complexes, ZnLCl₂ (1), CdLCl₂ (2), ZnL¹Cl₂·2H₂O (3), and CdL¹Cl₂·2H₂O (4), with chiral ligands containing a 2,2′-bipyridine moiety and natural terpene (+)-limonene (L) or (+)-3-carene (L¹) moieties were synthesized. In these complexes the L and L¹ ligands are shown to coordinate Zn²⁺ and Cd²⁺ ions through the 2,2′-bipyridine moiety. The acetamide group of the ligands interacts with M²⁺ ions by forming N⋯M>²⁺> and CO⋯M²⁺contacts and N–H⋯Cl hydrogen bonds with coordinated Cl⁻ ions. In solutions the complexes have several conformers differing by the degree of the turn of the acetamide moiety relative to the ligand core and the type of its interaction with the coordination core. The ligands and complexes exhibit luminescence with the quantum yield increasing in the order: ligand < cadmium(II) complex < zinc(II) complex. The complexes 3 and 4 demostrate excitation wavelength independent single-channel fluorescence. As opposed to 3 and 4, the complexes 1 and 2 demonstrate excitation wavelength dependent emission with nanosecond and microsecond lifetimes of the excited states. According to our TD-DFT calculations, an interplay of ligand centered and halide to ligand transitions facilitates two deactivation channels in 1 and 2: S₁–S₀ and T₁–S₀.

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В журнале  Успехи химии/Russian Chemical Reviews  (IF 4.612) опубликован обзор сотрудников Института

Ю.А. Тена, к.х.н. Н.М. Трошковой и д.х.н. Е.В. Третьякова

От спин-меченых конденсированных полиароматических соединений к магнитно-активным графеновым наноструктурам

From spin-labelled fused polyaromatic compounds to magnetically active graphene nanostructuresFrom spin-labelled fused polyaromatic compounds to magnetically active graphene nanostructures

Анотация

Молекулярный дизайн магнитно-активных графеновых наноструктур - формирующаяся область науки. Основная цель таких исследований - получение графеновых нанолент и графеновых квантовых точек с заданными электронными, оптическими и магнитными свойствами. В обзоре рассмотрены методы синтеза спин-меченых полициклических ароматических углеводородов - гомологических предшественников графеновых наноструктур. Обсуждены достижения и перспективы развития дизайна магнитно-активных графеновых материалов. Библиография - 134 ссылки.

Abstract

Molecular design of magnetically active graphene nanoscale structures is an emerging field of research. The key goal of this research is to produce graphene nanoribbons and graphene quantum dots with specified electronic, optical and magnetic properties. The review considers methods for the synthesis of spin-labelled polycyclic aromatic hydrocarbons, the homologous precursors of graphene nanostructures and discusses the achievements and prospects of the design of magnetically active graphene materials. Bibliography — 134 references

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This article also appears in: Hot Topic: Carbon, Graphite, and Graphene

Just add water! A range of heterogeneous ‐SO₃H functionalized catalysts were investigated for the first time using the Prins‐Ritter (−)‐isopulegol reaction with benzaldehyde and acetonitrile as a model producing 4‐amido derivatives of octahydro‐2H‐chromenes (as S‐ and R‐diastereomers). A strong effect of water addition prior the reaction on the overall selectivity and the ratio of isomers was found.

На сайте  журнала ChemCatChem (IF 4,495) опубликована статья с участием сотрудников Института:  Н.С. Ли-Жуланова (мнс, ЛНТПС),  д.х.н., проф. РАН К.П. Волчо (гнс, ЛФАФ) и д.х.н., член.-корр. РАН, поф. Н.Ф. Салахутдинова (зав .отделом медицинской химии)

Stereoselectivity Inversion by Water Addition in the −SO₃H‐catalyzed Tandem Prins‐Ritter Reaction for Synthesis of 4‐amidotetrahydropyran Derivatives

Dr. Alexander Yu. Sidorenko,  Nikolai S. Li‐Zhulanov, Päivi Mäki‐Arvela, Thomas Sandberg, Anna V. Kravtsova, Andreia F. Peixoto, Cristina Freire, Konstantin P. Volcho, Nariman F. Salakhutdinov, Vladimir E. Agabekov, Prof. Dmitry Yu. Murzin

Abstract

A range of heterogeneous ‐SO₃H functionalized catalysts including carbon and halloysite nanotubes, commercial K10 clay, Amberlyst‐15 etc. was investigated for the first time using as a model the Prins‐Ritter reaction of (−)‐isopulegol with benzaldehyde and acetonitrile producing 4‐amido derivatives of octahydro‐2H‐chromenes (as (S)‐ and (R)‐diastereomers). A strong effect of water addition prior the reaction on the overall selectivity and the ratio of isomers in the case of heterogeneous and homogeneous (p‐toluenesulfonic acid) catalysis was found for the first time. The yield of the (R)‐diastereomer sharply increased with increasing amount of added water, while the S‐isomer prevailed with a minimum amount of added water. Experimental results and DFT calculations clearly indicate a kinetic control for R‐amide formation. Typically synthesis of 4‐amidooctahydro‐2H‐chromenes requires subzero temperatures and toxic catalysts, which were avoided in the current work. Nevertheless, the yield of the desired products (up to 83 %) at 30 °C after water addition exceeded the values reported previously. Thus, adding water is a simple and a very effective method for controlling both the yield and stereoselectivity of the Prins‐Ritter reaction products under mild conditions.

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В журналу Materials Science and Engineering: C  (IF 4,959) опубликована статья с участием сотрудников Института:  д.м.н. Н.А. Жуковой (внс, ЛФИ), д.б.н. М.В. Хвостова (снс, ЛФИ), к.б.н.А.В. Павловой (нс, ЛФИ) и д.б.н., проф. Т.Г. Толстиковой (завлаб, ЛФИ)

Biodegradable poly(l-lactide)/calcium phosphate composites with improved properties for orthopedics: Effect of filler and polymer crystallinity

Varvara A.Demina, Sergei V. Krasheninnikov, Alexander I. Buzin, Roman A. Kamyshinsky, Natalya V. Sadovskaya, Evgeny N. Goncharov, Natalya A. Zhukova, Mikhail V. Khvostov, Alla V. Pavlova, Tatjana G. Tolstikova, Nikita G. Sedush, Sergei N. Chvalun

Materials Science and Engineering: C Volume 112, July 2020, 110813 ,
Publication Date:March 06, 2020


https://doi.org/10.1016/j.msec.2020.110813

Abstract

Biodegradable poly(l-lactide)/calcium phosphate composites are promising materials for fabrication of bone fixation implants with improved properties. Multistage compounding was proposed as an efficient method for the preparation of biodegradable poly(l-lactide)/calcium phosphate composites with submicron filler dispersion and mechanical characteristics similar to native bone. The improvement of the characteristics is caused both by the filler itself and by the increase of polymer crystallinity due to the nucleation effect. The technique allows to fabricate biodegradable composites with controlled properties by varying concentration and type of the filler as well as degree of PLLA matrix crystallinity. Animal studies revealed that all the composites were biocompatible and non-toxic.

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В журналу Journal of Membrane Science (IF 7,015) опубликована статья с участием сотрудника Института   к.х.н. И.А.Кирилюка (завлаб, ЛАС):

Electrostatic properties of inner nanopore surfaces of anodic aluminum oxide membranes upon high temperature annealing revealed by EPR of pH-sensitive spin probes and labels

Abstract

Anodic aluminum oxide (AAO) membranes are versatile nanomaterials that combine the chemically stable and mechanically robust properties of ceramics with homogeneous nanoscale organization that can be tuned to desirable pore diameters and lengths. The AAO substrates feature high surface area that is readily accessible to large and small molecules, making these nanostructures uniquely suited for many possible applications. Examples include templated self-assembly of macroscopically aligned biological membranes and substrates for heterogeneous catalysis. For further development of such applications, one would like to characterize and tune the electrostatic properties of the inner pore surface as well as the local acidity within the nanochannels. Here, we employed electron paramagnetic resonance (EPR) spectroscopy of a small molecule – ionizable nitroxide – as a reporter of the average local acidity in the nanochannels and the local electrostatic potential in the immediate vicinity of the pore surface. The former was achieved by measuring EPR spectra of this molecular probe diffusing in an aqueous phase confined in the AAO nanochannels while for the latter the nitroxide was covalently attached to the hydroxyl group of the alumina surface. We show that the local acidity within the nanochannels is increased by as much as ≈1.48 pH units vs. the pH of bulk solution by decreasing the pore diameter down to ca. 31 nm. Furthermore, the positive surface charge of the as-prepared AAO could be decreased and even switched to a negative surface charge upon annealing the membranes first to 700 °C and then to 1200 °C. For as-prepared AAO, the local electrostatic potential reaches ψ= (163 ± 5) mV for the nitroxide label covalently attached to AAO and located about 0.5 nm away from the surface. Overall, we demonstrate that the acid-based properties of the aqueous volume confined by the AAO nanopores pores can be tuned by either changing the pore diameter from ca. 71 to 31 nm or by thermal annealing to switch the sign of the surface charge. These observations provide a simple and robust means to tailor these versatile high-surface-area nanomaterials for specific applications that depend on acid-base equilibria.

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В журналу ACS Sustainable Chem. Eng. (IF 6,97) опубликована статья с участием сотрудницы Института   д.х.н. М.В. Еделевой (снс, ЛМР):

No Catalyst Added Hydrogen Peroxide Oxidation of Dextran: An Environmentally Friendly Route to Multifunctional Polymers

Ekaterina V. Pronina, Yuri A. Vorotnikov, Tatiana N. Pozmogova, Anastasiya O. Solovieva, Svetlana M. Miroshnichenko, Pavel E. Plyusnin, Denis P. Pishchur, Ilia V. Eltsov, Mariya V. Edeleva, Michael A. Shestopalov, Olga A. Efremova

ACS Sustainable Chem. Eng. 2020, 8, 13, 5371-5379,
Publication Date:March 16, 2020


https://doi.org/10.1021/acssuschemeng.0c01030

Abstract

The paper demonstrates a “greener” oxidation of dextran polymer of various molecular masses, the component of many industrially and pharmaceutically important materials, by aqueous H₂O₂ in a no catalyst added setting that produced a multifunctional oxidized dextran. Specifically, on the top of common functional groups (hydroxo, carbonyl, and carboxylic acids), the freshly peroxide oxidized dextran had also a significant number of peroxo-groups, which endowed the polymer with significant cytotoxic properties, as demonstrated on a larynx carcinoma cell line. We also have shown that the peroxo-groups could be easily removed in an alkaline media to yield nontoxic oxidized dextran polymers.

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В журналу Bioorganic Chemistry (IF 3,926) опубликована статья с участием сотрудников Института   к.х.н. С.О. Куранова (нс, ЛНТПС ), д.х.н. О.А. Лузиной (внс ЛФАВ) и д.х.н., чл.-корр. РАН, проф.  Н.Ф. Салахутдинова (зав.оделом, ОМХ, завлаб , ЛФАВ):

Exploring bulky natural and natural-like periphery in the design of p-(benzyloxy)phenylpropionic acid agonists of free fatty acid receptor 1 (GPR40)

Abstract

Six derivatives of 3-phenylpropionic acid bearing various natural and natural-like, spatially defined peripheral motifs have been synthesized and evaluated in vitro for free fatty acid receptor 1 (FFA1) activation. Two frontrunner compounds (bearing a bornyl and cytosine groups) were evaluated in an oral glucose tolerance test in mice where both demonstrated the ability to sustain blood glucose levels following a glucose challenge. The bornyl compound displayed a somewhat superior, dose-dependent efficacy and, therefore, can be regarded as a lead compounds for further development as a therapeutic agent for type 2 diabetes mellitus. Its high affinity to FFA1 was rationalized by docking experiments.

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Preparation of Multi‐Spin Systems: A Case Study of Tolane‐Bridged Verdazyl‐Based Hetero‐Diradicals

Darya E. Votkina, Pavel V. Petunin, Svetlana I. Zhivetyeva, Irina Yu. Bagryanskaya, Mikhail N. Uvarov, Maxim S. Kazantsev,  Marina E. Trusova,  Evgeny V. Tretyakov,  Pavel S. Postnikov

European Journal of Organic Chemistry, Volume 2020, Issue13, April 7, 2020 Pages 1996-2004

Dear Prof. Bagryanskaya,
I am writing on behalf of the Editorial Board to thank and congratulate you for your recent contribution to PCCP, Photochemistry of Tris(2,3,5,6-tetrathiaaryl)methyl Radicals in Various Solutions, DOI: 10.1039/C9CP06213K.
I am delighted to let you know that this was extremely well received, and has been selected by our Editors as a 2019 HOT PCCP article. Please find the collection, now including your publication, here .
As part of the 2019 HOT articles collection, your article will shortly be made free to access until the end of June 2020, and announced to the PCCP community.
Thank you once again for your excellent contribution, and we look forward to receiving your next submission to PCCP.

Kathryn Gempf M. Sci. MRSC
Development Editor,
Journals Royal Society of Chemistry

В журнале Physical Chemistry Chemical Physics, Vol. 22, Iss. 3, 1019-1026, 2020  (IF 3,567) опубликована статья с участием сотрудников Института:   А.А. Кужелева, В.М. Тормышева,  О.Ю. Рогожниковой, М.В. Еделевой и Е.Г. Багрянской

Photochemistry of tris(2,3,5,6-tetrathiaaryl)methyl radicals in various solutions

Abstract

During the last decades, persistent tris(2,3,5,6-tetrathiaaryl)methyl radicals (TAMs) have attracted much attention due to their applications in oximetry, EPR tomography, and as spin labels in pulsed dipolar EPR spectroscopy. Recently, researchers proposed to use TAM radicals as spin labels and/or a partner for photoinduced spin labels. Thus, the questions of their photochemical stability and mechanism of degradation under UV irradiation have become relevant and important. In this study, steady-state photolysis and flash photolysis of TAM radicals were investigated. A detailed mechanism of TAM phototransformations was proposed and confirmed by NMR, gel permeation chromatography, and mass-spectrometric analyses of the products.

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В журнале Dalton Transactions (IF 4,052) опубликована статья с участием сотрудников Института   д.х.н. И.И. Олейника (внс, ЛЭИСМ ) и к.х.н. И.В. Олейник (снс, ЛЭАСМ):

High molecular weight polyethylenes of narrow dispersity promoted using bis(arylimino)cyclohepta[b]pyridine-cobalt catalysts ortho-substituted with benzhydryl & cycloalkyl groups

Abstract

A one-pot template strategy has been utilized to synthesize sterically enhanced bis(imino)cyclohepta[b]pyridine-cobalt(II) chlorides, [2-{(Ar)NCMe}-9-{N(Ar)}C₁₀H₁₀N]CoCl₂ (Ar = 2-(C₅H₉) -4,6-(CHPh₂)₂C₆H₂ Co1, 2-(C₆H₁₁)-4,6-(CHPh₂)₂C₆H₂  Co2, 2-(C₈H₁₅)-4,6-(CHPh₂) ₂C₆H₂ Co3, 2-(C₁₂H₂₃)-4,6-(CHPh₂ )₂C₆H₂ Co4, 2,6-(C₅H₉)₂ -4-(CHPh₂)C₆H₂ Co5). All five complexes have been characterized by a combination of FT-IR spectroscopy, elemental analysis and single crystal X-ray diffraction. The molecular structures of Co1, Co3 and Co5 highlight the substantial steric hindrance imparted by the 2-cycloalkyl-6-benzhydryl or 2,6-dicyclopentyl ortho-substitution pattern; distorted square pyramidal geometries are exhibited in each case. On activation with methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all the complexes (apart from Co4/MAO) were active ethylene polymerization catalysts (up to 3.70 ? 10⁶ g PE per mol (Co) per h for Co5/MMAO), operating effectively at temperatures between 50 °C and 60 °C, producing polyethylenes with high molecular weights (up to 589.5 kg mol^-1 for Co3/MAO). Furthermore, all polymers were highly linear (T_m > 130 °C) with narrow dispersities (M_w/M_n range: 2.0–3.0). The coexistence of two chain termination pathways, β-H elimination and transfer to aluminum, has been demonstrated using ¹³ C/¹H NMR spectroscopy.

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