Archive for a.grevtsev
A.N. Shestakov, A.S. Pankova, P. Golubev, A.F. Khlebnikov, M.A. Kuznetsov
“Brønsted acid mediated cyclizations of ortho-aryl(ethynyl)pyrimidines”
Tetrahedron, 2017, 73 (27-28), 3939–3948
A high-yielding procedure for the synthesis of 5-aryl-4-(arylethynyl)pyrimidines from easily available 2-aryl-3-hydroxyacrylates is reported. These pyrimidines readily undergo cyclization in strong Brønsted acids and, depending on the substitution in alkynylpyrimidines and the water content of the reaction mixture, yield either benzo[f]quinazolines or derivatives of spiro[cyclohexa-2,5-diene-1,5′-cyclopenta[d]pyrimidin]-4-one. In most cases the cyclization proceeds nearly quantitatively. DFT calculations support the proposed mechanisms induced by the protonation of the triple bond in 5-aryl-4-(arylethynyl)pyrimidines. Fluorescent properties of the obtained heterocycles are also described.
Обзорная экскурсия-лекция для студентов физического факультета СПбГУ. В ходе экскурсии студенты посетили лаборатории ЯКР, ЯМР, ЭПР и познакомились с некоторыми особенностями и возможностями оборудования, представленного в рц МРМИ.
В ходе стажировки 18-26 ноября Мазур А.С. успешно освоил методы проведения низкотемпературных измерений спектров ЯМР в широком частотном диапазоне (250 – 500 МГц) на оборудовании представленном в Отделении низкотемпературной физики факультета математики и физики Карлова университета в Праге.
A.I. Solomatina, I.O. Aleksandrova, A.J. Karttunen, S.P. Tunik, I.O. Koshevoy
“Dibenzothiophene-platinated complexes: probing the effect of ancillary ligands on the photophysical performance”
Dalton Transactions, 2017, 46, 3895-3905
Cyclometalation of dibenzothienyl-pyridine (HPyDBT) afforded a series of platinum(II) complexes Pt(PyDBT)(L)Cl (L = DMSO, 1; P(p-C6H4-X)3 (X = H, 2; CF3, 3; OMe, 4; NPh2, 5); 1,3,5-triaza-7-phosphaadamantane, 6; 2,6-dimethylphenyl isocyanide, 7). Chelating bidentate LL ligands formed cationic compounds [Pt(PyDBT)(LL)]+ (LL = 1,2-bis(diphenylphosphino)benzene, 8; 2,2′-bipyridine, 9; 1,10-phenanthroline, 10). Oxidation of a thienyl sulfur atom allowed for the isolation of the sulfone derivative Pt(PyDBT)(PPh3)Cl (11). The title complexes were characterized crystallographically (except 7). Investigation of their photophysical behavior revealed solid state phosphorescence with quantum yields up to 0.45 for neat powders. The ancillary ligands L show a minor influence on the emission energies of the neutral compounds, but affect dramatically the intensity of luminescence. In contrast, the cationic species with diimine ligands demonstrate a significant contribution of the LL fragments into the emissive T1 states that leads to a certain mixing of 3IL and 3LL′CT transitions and causes a substantial bathochromic shift of emission.
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
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.
N.G. Voron’ko, S.R. Derkach, M.A. Vovk, P.M. Tolstoy
“Complexation of κ-carrageenan with gelatin in the aqueous phase analysed by 1H NMR kinetics and relaxation”
Carbohydrate Polymers, 2017, 169, 117–126
The 1H NMR spectroscopy is used to study the kinetics of gelation in the aqueous mixtures of κ-carrageenan with gelatin. The time dependence of NMR signals intensities shows that the kinetics of gel formation consists of classical ‘fast’ (rate constant k ≈ 6 h−1) and ‘slow’ (k ≈ 1 h−1) periods, corresponding to a coil → helix transition and subsequent aggregation of helices. Upon increase of the κ-carrageenan/gelatin (w/w) ratio Z the rate of the fast process slows down by a factor of 1.6–2.4. Further analysis was done by studying the dependence of spin-spin relaxation times of protons of gelatin on Z in the aqueous phase. A qualitative scheme describing hydrogel formation in the complex solution is given. It is hypothesized that at higher concentration of PECs the hydrogel structure network is stabilized by three types of nodes: triple helices of gelatin and intra-/inter-molecular double helices of κ-carrageenan.
В Октябре выполнено 2347 заявок на сервисные измерения.
- 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
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.