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1.
Tatyana Shvidenko Kostiantyn NazarenkoKonstantin Shvidenko Aleksandr Kostyuk 《Tetrahedron letters》2014
A facile procedure for the synthesis of benzannelated diazacycloalkanes 3 is elaborated on the basis of reductive cleavage of 1,2-polymethylenebenzimidazoles 2 with DIBAL-H. The reduction of the corresponding salts prepared by treatment of 1,2-polymethylenebenzimidazoles 2 with methyl iodide proceeded differently affording exclusively o-phenylenediamines 10. The limitations and scope of the method were established, and a tentative mechanism proposed. 相似文献
2.
Shunrui Luo Kostiantyn Turcheniuk Ah‐Young Song Aashray Narla Doyoub Kim Alexandre Magasinsky Gleb Yushin 《Angewandte Chemie (International ed. in English)》2020,59(1):403-408
Technologically important composites with enhanced thermal and mechanical properties rely on the reinforcement by the high specific strength ceramic nanofibers or nanowires (NWs) with high aspect ratios. However, conventional synthesis routes to produce such ceramic NWs have prohibitively high cost. Now, direct transformation of bulk Mg‐Li alloys into Mg alkoxide NWs is demonstrated without the use of catalysts, templates, expensive or toxic chemicals, or any external stimuli. This mechanism proceeds through the minimization of strain energy at the boundary of phase transformation front leading to the formation of ultra‐long NWs with tunable dimensions. Such alkoxide NWs can be easily converted in air into ceramic MgO NWs with similar dimensions. The impact of the alloy grain size and Li content, synthesis temperature, inductive and steric effects of alkoxide groups on the diameter, length, composition, ductility, and oxidation of the produced NWs is discussed. 相似文献
3.
Olha S. Panteleieva Vira V. Ponomarova Alexander V. Shtemenko Kostiantyn V. Domasevitch 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(8):753-762
Anion…π interactions are newly recognized weak supramolecular forces which are relevant to many types of electron‐deficient aromatic substrates. Being less competitive with respect to conventional hydrogen bonding, anion…π interactions are only rarely considered as a crystal‐structure‐defining factor. Their significance dramatically increases for polyoxometalate (POM) species, which offer extended oxide surfaces for maintaining dense aromatic/inorganic stacks. The structures of tetrakis(caffeinium) μ12‐silicato‐tetracosa‐μ2‐oxido‐dodecaoxidododecatungsten trihydrate, (C8H11N4O2)4[SiW12O40]·3H2O, (1), and tris(theobrominium) μ12‐phosphato‐tetracosa‐μ2‐oxido‐dodecaoxidododecatungsten ethanol sesquisolvate, (C7H9N4O2)3[PW12O40]·1.5C2H5OH, (2), support the utility of anion…π interactions as a special kind of supramolecular synthon controlling the structures of ionic lattices. Both caffeinium [(HCaf)+ in (1)] and theobrominium cations [(HTbr)+ in (2)] reveal double stacking patterns at both axial sides of the aromatic frameworks, leading to the generation of anion…π…anion bridges. The latter provide the rare face‐to‐face linkage of the anions. In (1), every square face of the metal–oxide cuboctahedra accepts the interaction and the above bridges yield flat square nets, i.e. {(HCaf+)2[SiW12O40]4?}n. Two additional cations afford single stacks only and they terminate the connectivity. Salt (2) retains a two‐dimensional (2D) motif of square nets, with anion…π…anion bridges involving two of the three (HTbr)+ cations. The remaining cations complete a fivefold anion…π environment of [PW12O40]3?, acting as terminal groups. This single anion…π interaction is influenced by the specific pairing of (HTbr)+ cations by double amide‐to‐amide hydrogen bonding. Nevertheless, invariable 2D patterns in (1) and (2) suggest the dominant role of anion…π interactions as the structure‐governing factor, which is applicable to the construction of noncovalent linkages involving Keggin‐type oxometalates. 相似文献
4.
Selective reagent ionisation‐time of flight‐mass spectrometry: a rapid technology for the novel analysis of blends of new psychoactive substances 下载免费PDF全文
Matteo Lanza W. Joe Acton Philipp Sulzer Kostiantyn Breiev Simone Jürschik Alfons Jordan Eugen Hartungen Gernot Hanel Lukas Märk Tilmann D. Märk Chris A. Mayhew 《Journal of mass spectrometry : JMS》2015,50(2):427-431
In this study we demonstrate the potential of selective reagent ionisation‐time of flight‐mass spectrometry for the rapid and selective identification of a popular new psychoactive substance blend called ‘synthacaine’, a mixture that is supposed to imitate the sensory and intoxicating effects of cocaine. Reactions with H3O+ result in protonated parent molecules which can be tentatively assigned to benzocaine and methiopropamine. However, by comparing the product ion branching ratios obtained at two reduced electric field values (90 and 170 Td) for two reagent ions (H3O+ and NO+) to those of the pure chemicals, we show that identification is possible with a much higher level of confidence then when relying solely on the m/z of protonated parent molecules. A rapid and highly selective analytical identification of the constituents of a recreational drug is particularly crucial to medical personnel for the prompt medical treatment of overdoses, toxic effects or allergic reactions. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
5.
Marco?Dozzi Yuriy?Kozachenko Yuliya?Mishura Kostiantyn?RalchenkoEmail authorView authors OrcID profile 《Statistical Inference for Stochastic Processes》2018,21(1):21-52
We construct the least-square estimator for the unknown drift parameter in the multifractional Ornstein–Uhlenbeck model and establish its strong consistency in the non-ergodic case. The proofs are based on the asymptotic bounds with probability 1 for the rate of the growth of the trajectories of multifractional Brownian motion (mBm) and of some other functionals of mBm, including increments and fractional derivatives. As the auxiliary results having independent interest, we produce the asymptotic bounds with probability 1 for the rate of the growth of the trajectories of the general Gaussian process and some functionals of it, in terms of the covariance function of its increments. 相似文献
6.
Dmytro I. Sierov Illia V. Dzhulai Kateryna I. Siryk Kostiantyn V. Shvydenko Tetiana I. Shvydenko Prof. Dr. Kostiantyn Nazarenko Prof. Dr. Aleksandr Kostyuk Oleksandr S. Liashuk Prof. Dr. Oleksandr O. Grygorenko 《European journal of organic chemistry》2023,26(34):e202300538
A systematic study on the SnAr reaction of halogenated fluoropyridines and (hetero)aliphatic nitrile anions as an approach to the synthesis of functionalized pyridines bearing a (cyclo)alkyl or saturated heterocyclic substituent by is described. The scope of the method was demonstrated on a wide range of (hetero)aliphatic nitriles (including three- to six-membered cycloalkane derivatives and N-, O-, S-containing saturated heterocycles) and all isomeric halogenated 2-and 4-fluoropyridines. High chemo- and regioselectivity (i. e., exclusive substitution of the fluorine atom), as well as excellent scalability of the proposed reaction sequence were demonstrated (up to 450 g for the arylation step or up to 77 g of cycloalkylpyridine over two steps in a single run). The utility of the synthesized products was illustrated in the additional functional group transformations resulting in synthetically valuable pyridine-containing building blocks. 相似文献
7.
Shunrui Luo Dr. Kostiantyn Turcheniuk Ah-Young Song Aashray Narla Doyoub Kim Dr. Alexandre Magasinsky Prof. Gleb Yushin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(1):411-416
Technologically important composites with enhanced thermal and mechanical properties rely on the reinforcement by the high specific strength ceramic nanofibers or nanowires (NWs) with high aspect ratios. However, conventional synthesis routes to produce such ceramic NWs have prohibitively high cost. Now, direct transformation of bulk Mg-Li alloys into Mg alkoxide NWs is demonstrated without the use of catalysts, templates, expensive or toxic chemicals, or any external stimuli. This mechanism proceeds through the minimization of strain energy at the boundary of phase transformation front leading to the formation of ultra-long NWs with tunable dimensions. Such alkoxide NWs can be easily converted in air into ceramic MgO NWs with similar dimensions. The impact of the alloy grain size and Li content, synthesis temperature, inductive and steric effects of alkoxide groups on the diameter, length, composition, ductility, and oxidation of the produced NWs is discussed. 相似文献
8.
Sergey Holovach Dr. Kostiantyn P. Melnykov Artem Skreminskiy Maksym Herasymchuk Olha Tavlui Danylo Aloshyn Dr. Petro Borysko Prof. Dr. Alexander B. Rozhenko Prof. Dr. Sergey V. Ryabukhin Prof. Dr. Dmitriy M. Volochnyuk Prof. Dr. Oleksandr O. Grygorenko 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(19):e202200331
Physico-chemical properties important to drug discovery (pKa, LogP, and aqueous solubility), as well as metabolic stability, were studied for a series of functionalized gem-difluorinated cycloalkanes and compared to those of non-fluorinated and acyclic counterparts to evaluate the impact of the fluorination. It was found that the influence of the CF2 moiety on the acidity/basicity of the corresponding carboxylic acids and amines was defined by inductive the effect of the fluorine atoms and was nearly the same for acyclic and cyclic aliphatic compounds. Lipophilicity and aqueous solubility followed more complex trends and were affected by the position of the fluorine atoms, ring size, and even the nature of the functional group present; also, significant differences were found for the acyclic and cyclic series. Also, gem-difluorination either did not affect or slightly improved the metabolic stability of the corresponding model derivatives. The presented results can be used as a guide for rational drug design employing fluorine and establish the first chapter in a catalog of the key in vitro properties of fluorinated cycloalkanes. 相似文献
9.
Kostiantyn Kulyk Valentyna Ishchenko Borys Palyanytsya Volodymyr Khylya Mykola Borysenko Tetiana Kulyk 《Journal of mass spectrometry : JMS》2010,45(7):750-761
The interactions between coumarins and the surface of fumed SiO2, CeO2/SiO2, TiO2/SiO2 and Al2O3/SiO2 were assessed by means of temperature‐programed desorption mass spectrometry. The different stages of the thermolysis of coumarin were identified and an analysis of the underlying reactions was performed. The kinetic parameters of the involved reactions were thus obtained. The decomposition of thiazolyl‐substituted coumarins was found to proceed through a ‘thiazole–thiazine’ ring expansion in the adsorbed state. A linear correlation between the sigma constants (Σσ) of the coumarin substituents and the activation energy of CO2 formation was obtained. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
10.
Peng Xu Da Zhao Florian Berger Aboubakr Hamad Jens Rickmeier Roland Petzold Mykhailo Kondratiuk Kostiantyn Bohdan Tobias Ritter 《Angewandte Chemie (International ed. in English)》2020,59(5):1956-1960
Site‐selective functionalization of C?H bonds in small complex molecules is a long‐standing challenge in organic chemistry. Herein, we report a broadly applicable and site‐selective aromatic C?H dibenzothiophenylation reaction. The conceptual advantage of this transformation is further demonstrated through the two‐step C?H [18F]fluorination of a series of marketed small‐molecule drugs. 相似文献