Ресурсный центр «Магнитно-резонансные методы исследования»

О.М. Нестерова, О.С. Зарубина, В.В. Толстяков, Г.Г. Данагулян, Р.Е. Трифонов, С.Н. Смирнов, П.А. Слепухин, Н.К. Игнатенко, В.А. Островский

“Синтез и строение N-(4,6-диметилпиримидин-2-ил)-2-(5-фенил-2Н-тетразол-2-ил)ацетогидразида и 1-(4,6-диметилпиримидин-2-ил)-3-[(5-фенил-2Н-тетразол-2-ил)метил]-1Н-пиразол-5-ола”

Журнал органической химии, 2017, 53(11), 1726-1728

Синтезированы новые тетразолильные производные 4,6-диметилгидразина, содержащие различные линкерные группы. Определена структура данных соединений методами ЯМР спектроскопии
и рентгеноструктурного анализа

E. G. Vlakh, E. V. Grachova, D. D. Zhukovsky, A. V. Hubina, A. S. Mikhailova, J. R. Shakirova, V. V. Sharoyko, S. P. Tunik, T. B. Tennikova

“Self-assemble nanoparticles based on polypeptides containing C-terminal luminescent Pt-cysteine complex”

Scientific Reports, 2017, 7, Article number 41991
DOI: 10.1038/srep41991

The growing attention to the luminescent nanocarriers is strongly stimulated by their potential application as drug delivery systems and by the necessity to monitor their distribution in cells and tissues. In this communication we report on the synthesis of amphiphilic polypeptides bearing C-terminal phosphorescent label together with preparation of nanoparticles using the polypeptides obtained. The approach suggested is based on a unique and highly technological process where the new phosphorescent Pt-cysteine complex serves as initiator of the ring-opening polymerization of α-amino acid N-carboxyanhydrides to obtain the polypeptides bearing intact the platinum chromophore covalently bound to the polymer chain. It was established that the luminescent label retains unchanged its emission characteristics not only in the polypeptides but also in more complicated nanoaggregates such as the polymer derived amphiphilic block-copolymers and self-assembled nanoparticles. The phosphorescent nanoparticles display no cytotoxicity and hemolytic activity in the tested range of concentrations and easily internalize into living cells that makes possible in vivo cell visualization, including prospective application in time resolved imaging and drug delivery monitoring.

В Октябре выполнено 2347 заявок на сервисные измерения.

Измерено:

• 2218 спектр ¹H
• 366 спектра ¹³C
• 95 спектров DEPT
• 63 спектров COSY
• 19 спектра NOESY
• 52 спектра ³¹Р
• 169 спектров ¹⁹F

Выполнено 242 заявок на исследовательскую работу.

G. Werner, K.S. Rodygin, A.A. Kostin, E.G. Gordeev, A.S. Kashin, V.P. Ananikov

“A solid acetylene reagent with enhanced reactivity: fluoride-mediated functionalization of alcohols and phenols”

Green Chemistry, 2017, 19, 3032–3041
DOI: 10.1039/C7GC00724H

The direct vinylation of an OH group in alcohols and phenols was carried out utilizing a novel CaC₂/KF solid acetylene reagent in a simple K₂CO₃/KOH/DMSO system. The functionalization of a series of hydroxyl-group-containing substrates and the post-modification of biologically active molecules were successfully performed using standard laboratory equipment, providing straightforward access to the corresponding vinyl ethers. The overall process developed involves an atom-economical addition reaction employing only inorganic reagents, which significantly simplifies the reaction set-up and the isolation of products. A mechanistic study revealed a dual role of the F⁻ additive, which both mediates the surface etching/renewal of the calcium carbide particles and activates the C[triple bond, length as m-dash]C bond towards the addition reaction. The development of the fluoride-mediated nucleophilic addition of alcohols eliminates the need for strong bases and may substantially extend the areas of application of this attractive synthetic methodology due to increasing functional group tolerance. As a replacement for dangerous and difficult to handle high-pressure acetylene, we propose the solid reagent CaC₂/KF, which is easy to handle, does not require dedicated laboratory equipment and demonstrates enhanced reactivity of the acetylenic triple bond. Theoretical calculations have shown that fluoride-mediated activation of the hydroxyl group towards nucleophilic addition significantly reduces the activation barrier and facilitates the reaction.

A. M. Afanasenko, D. V. Boyarskaya, I. A. Boyarskaya, T. G. Chulkova, Y. M. Grigoriev, I. E. Kolesnikov, M. S. Avdontceva, T. L. Panikorovskii, A. I. Panin, A. N. Vereshchagin, M. N. Elinson

“Structures and photophysical properties of 3,4-diaryl-1H-pyrrol-2,5-diimines and 2,3-diarylmaleimides”

Journal of Molecular Structure, 2017, 1146, 554–561
DOI: 10.1016/j.molstruc.2017.06.048

Structural features of 3,4-diaryl-1H-pyrrol-2,5-diimines and their derivatives have been studied by molecular spectroscopy techniques, single-crystal X-ray diffraction, and DFT calculations. According to the theoretical calculations, the diimino tautomeric form of 3,4-diaryl-1H-pyrrol-2,5-diimines is more stable in solution than the imino-enamino form. We also found that the structurally related 2,3-diarylmaleimides exist in the solid state in the dimeric diketo form. 3,4-Diaryl-1H-pyrrol-2,5-diimines and 2,3-diarylmaleimides exhibit fluorescence in the blue region of the visible spectrum. The fluorescence spectra have large Stokes shifts. Aryl substituents at the 3,4-positions of 1H-pyrrol-2,5-diimine do not significantly affect fluorescence properties. The insertion of donor substituents into 2,3-diarylmaleimides leads to bathochromic shift of emission bands with hyperchromic effect.

Санкт-Петербургский университет посетила тайская делегация во главе с принцессой Таиланда Махой Чакри Сириндон. Делегация посетила ряд ресурсных центров Научного парка СПбГу. Директор ресурсного центра МРМИ Петр Толстой рассказал об основных направлениях исследований и их реализации в рц МРМИ, об опыте международного сотрудничества с партнерами рц МРМИ.
Подробнее о визите делегации из Таиланда в Научный парк СПбГУ
Репортаж тайского телевидения о посещении Научного парка принцессой Маха Чакри Сириндон

В сентябре выполнено 1921 заявок на сервисные измерения.

Измерено:

• 1821 спектр ¹H
• 296 спектра ¹³C
• 72 спектров DEPT
• 22 спектров COSY
• 22 спектра NOESY
• 27 спектра ³¹Р
• 142 спектров ¹⁹F

Выполнено 219 заявок на исследовательскую работу.