Tag Archive for Толстой

J Therm Anal Calorim, 2017

M. Brusnikina, O. Silyukov, M. Chislov, T. Volkova, A. Proshin, A. Mazur, P. Tolstoy, I. Terekhova

“Effect of cyclodextrin complexation on solubility of novel anti-Alzheimer 1,2,4-thiadiazole derivative”

J Therm Anal Calorim, 2017
DOI: 10.1007/s10973-017-6252-1

источник: https://link.springer.com/journal/10973

New 1,2,4-thiadiazole derivative displaying neuroprotective potential and high activity in the treatment of Alzheimer’s disease has been synthesized. The objective of this study was to improve the aqueous solubility of this drug-like compound by means of complex formation with native and hydroxypropylated β-cyclodextrins. To this end, aqueous solubility of 1,2,4-thiadiazole derivative was investigated in the presence of β-cyclodextrins. It was shown that the phase solubility diagrams are of Bs type demonstrating the initial increase in thiadiazole solubility in solutions of cyclodextrins (concentration up to 0.01 mol kg−1) followed by a solubility decrease due to the precipitation of the complexes formed. In comparison with β-cyclodextrin, hydroxypropyl-β-cyclodextrin displays more pronounced solubilizing action since it forms more stable complexes with thiadiazole. Solid complexes of 1,2,4-thiadiazole derivative with β-cyclodextrins were prepared by grinding and freeze-drying methods. DSC, TG, hot-stage microscopy, solid-state 13C MAS CP/TOSS NMR, powder X-ray diffractometry and FTIR spectroscopy were used to prove the existence of complexes in the solid state. Solubility of the obtained formulations was also examined. It was found that complexes of thiadiazole with hydroxypropyl-β-cyclodextrin exhibited higher solubility in phosphate buffer (pH 7.4) compared with pure thiadiazole and its complexes with β-cyclodextrin.


Обзорная экскурсия, посвященная деятельности РЦ МРМИ, проведена для делегации из посольства Тайланда.

Участиники конференции Менделеев-2017

Поток гостей и участников конференции Менделеев-2017 в РЦ МРМИ продолжается. Нас радуют возникающие у гостей вопросы о механизмах сотрудничества и «первых шагах», необходимых для начала практической деятельности на базе Научного Парка СПбГУ в РЦ МРМИ. Надеемся, что краткие вводные экскурсии, в ходе которых мы рассказываем об оборудовании и возможностях РЦ, добавят в наши ряды новых пользователей с их новыми проектами и задачами.



На базе Санкт-Петербургского государственного университета 4–7 апреля 2017 г проходит конференция Менделеев-2017.  Для участников конференции организованы экскурсии в РЦ МРМИ, Наши сотрудники демонстрируют возможности РЦ и расказывают о различных текущих проектах и решаемых экспериментальных задачах.

Рабочая встреча

В рамках запланированной рабочей встречи РЦ МРМИ посетили представителей ГК «Росатом», ПИЯФ, СПбГУ. В ходе демонстрационной экскурсии проходило обсуждение образовательных программ магистратуры и аспирантуры, возможностей рц для создания направленных курсов для обучающихся и стажирующихся студентов.


Сегодня в РЦ МРМИ прошла обзорная экскурсия для гостей из Агенства Стратегических Инициатив. В рамках экскурсии проведена демонстрация оборудования, приведены примеры некоторых решаемых задач пользователей РЦ. Обсуждались особености постановки исследовательских задач и пути их решения.

Molecules, 2016, 21, 1657-1/19

L. Sobczyk, D. Chudoba, P.M. Tolstoy, A. Filarowski

“Some Brief Notes on Theoretical and Experimental Investigations of Intramolecular Hydrogen Bonding”

Molecules, 2016, 21, 1657-1/19

A review of selected literature data related to intramolecular hydrogen bonding in ortho-hydroxyaryl Schiff bases, ortho-hydroxyaryl ketones, ortho-hydroxyaryl amides, proton sponges and ortho-hydroxyaryl Mannich bases is presented. The paper reports on the application of experimental spectroscopic measurements (IR and NMR) and quantum-mechanical calculations for investigations of the proton transfer processes, the potential energy curves, tautomeric equilibrium, aromaticity etc. Finally, the equilibrium between the intra- and inter-molecular hydrogen bonds in amides is discussed.


Phys. Chem. Chem. Phys., 2016, accepted

B. Koeppe, S.A. Pylaeva, C. Allolio, D. Sebastiani, E.T.J. Nibbering, G.S. Denisov, H.-H. Limbach, P.M. Tolstoy

“Polar solvent fluctuations drive proton transfer in hydrogen bonded complexes of carboxylic acid with pyridines: NMR, IR and ab initio MD study”

Phys. Chem. Chem. Phys., 2016, accepted


We study a series of intermolecular hydrogen-bonded 1 : 1 complexes formed by chloroacetic acid with 19 substituted pyridines and one aliphatic amine dissolved in CD2Cl2 at low temperature by 1H and 13C NMR and FTIR spectroscopy. The hydrogen bond geometries in these complexes vary from molecular (O–H…N) to zwitterionic (O…H–N+) ones, while NMR spectra show the formation of short strong hydrogen bonds in intermediate cases. Analysis of CQO stretching and asymmetric CO2 stretching bands in FTIR spectra
reveal the presence of proton tautomerism. On the basis of these data, we construct the overall proton transfer pathway. In addition to that, we also study by use of ab initio molecular dynamics the complex formed by chloroacetic acid with 2-methylpyridine, surrounded by 71 CD2Cl2 molecules, revealing a dualmaximum distribution of hydrogen bond geometries in solution. The analysis of the calculated trajectory shows that the proton jumps between molecular and zwitterionic forms are indeed driven by dipole–dipole solvent–solute interactions, but the primary cause of the jumps is the formation/breaking of weak CH…O bonds from solvent molecules to oxygen atoms of the carboxylate group.


New J. Chem., 2016, 40, 10028-10040

A.V. Artem’ev, E.P. Doronina, M.I. Rakhmanova, A.O. Sutyrina, I.Yu. Bagryanskaya, P.M. Tolstoy, A.L. Gushchin, A.S. Mazur, N.K. Gusarova, B.A. Trofimov

“Luminescent CuI thiocyanate complexes based on tris(2-pyridyl)phosphine and its oxide: from mono-, di- and trinuclear species to coordination polymer”

New J. Chem., 2016, 40, 10028-10040


Tris(2-pyridyl)phosphine oxide reacts with CuSCN to form a variety of luminescent complexes, depending on the specified metal-to-ligand ratio and the solvent used, viz. mononuclear [Cu(N,N′,N′′-Py3P=O)(NCS)], dinuclear (N,N′-Py3P=O)Cu(SCN NCS)Cu[(N,N′-Py3P=O)], their co-crystal (2 : 1, correspondingly) and trinuclear {Cu(NCS)[SCNCu(N,N′,N′′-Py3P=O)]2}. In the solid state, these complexes feature red-orange emission upon UV photoexcitation. The reaction of tris(2-pyridyl)phosphine with CuSCN quantitatively produces an almost insoluble coordination polymer, [Cu(Py3P)NCS]n, which exhibits bright green emission. The synthesized compounds are the first members of the hitherto unknown family of Cu(I) thiocyanate complexes supported by tripodal ligands.



Обзорная экскурсия для студентов-бакалавров 4 курса химического факультета. П.М. Толстой провел вводную лекцию для наших посетителей, М.А. Вовк, А.С. Мазур, С.М. Сухаржевский провели демонстрацию ЯМР, ЯКР и ЭПР спектрометров.