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111.
O. V. Bykhovskaya I. M. Aladzheva I. V. Leontieva P. V. Petrovskii T. A. Mastryukova M. I. Kabachnii 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Direction of alkylation of phosphoranes (I) depends on the nature of the substituent Y and the alkylating agent. Unsubstituted phosphorane reacts with CH3J yielding only the product of C-methylation (II), whereas the reaction with Me2SO4 proceeds at both ends of the OPC-triad, preferably yielding the O-alkylation product (IIIa, 80%). 相似文献
112.
Leonardo M. da Costa Stanislav R. Stoyanov Raimundo N. Damasceno José Walkimar de M. Carneiro 《International journal of quantum chemistry》2013,113(24):2621-2628
Density Functional Theory (UB3LYP/6‐311++G(d,p)) calculations of the affinity of the pentaaqua nickel(II) complex for a set of phosphoryl [O?P(H)(CH3)(PhR)], imino [HN?C(CH3)(PhR)], thiocarbonyl [S?C(CH3)(PhR)] and carbonyl [O?C(CH3)(PhR)] ligands were performed, where R?NH2, OCH3, OH, CH3, H, Cl, CN, and NO2 is a substituent at the para‐position of a phenyl ring.The affinity of the pentaaqua nickel(II) complex for these ligands was analized and quantified in terms of interaction enthalpy (ΔH), Gibbs free energy (ΔG298), geometric and electronic parameters of the resultant octahedral complexes. The ΔH and ΔG298 results show that the ligand coordination strength increases in the following order: carbonyl < thiocarbonyl < imino < phosphoryl. This coordination strength order is also observed in the analysis of the metal‐ligand distances and charges on the ligand atom that interacts with the Ni(II) cation. The electronic character of the substituent R is the main parameter that affects the strength of the metal‐ligand coordination. Ligands containing electron‐donating groups (NH2, OCH3, OH) have more exothermic ΔH and ΔG298 than ligands with electron‐withdrawing groups (Cl, CN, NO2). The metal‐ligand interaction decomposed by means of the energy decomposition analysis (EDA) method shows that the electronic character of the ligand modulates all the components of the metal‐ligand interaction. The absolute softness of the free ligands is correlated with the covalent contribution to the instantaneous interaction energy calculated using the EDA method. © 2013 Wiley Periodicals, Inc. 相似文献
113.
114.
Stanislav Standara Petr Kulhánek Radek Marek Michal Straka 《Journal of computational chemistry》2013,34(22):1890-1898
The isotropic 129Xe nuclear magnetic resonance (NMR) chemical shift (CS) in Xe@C60 dissolved in liquid benzene was calculated by piecewise approximation to faithfully simulate the experimental conditions and to evaluate the role of different physical factors influencing the 129Xe NMR CS. The 129Xe shielding constant was obtained by averaging the 129Xe nuclear magnetic shieldings calculated for snapshots obtained from the molecular dynamics trajectory of the Xe@C60 system embedded in a periodic box of benzene molecules. Relativistic corrections were added at the Breit–Pauli perturbation theory (BPPT) level, included the solvent, and were dynamically averaged. It is demonstrated that the contribution of internal dynamics of the Xe@C60 system represents about 8% of the total nonrelativistic NMR CS, whereas the effects of dynamical solvent add another 8%. The dynamically averaged relativistic effects contribute by 9% to the total calculated 129Xe NMR CS. The final theoretical value of 172.7 ppm corresponds well to the experimental 129Xe CS of 179.2 ppm and lies within the estimated errors of the model. The presented computational protocol serves as a prototype for calculations of 129Xe NMR parameters in different Xe atom guest–host systems. © 2013 Wiley Periodicals, Inc. 相似文献
115.
Dr. Laia Vilà‐Nadal Dr. Scott G. Mitchell Dr. Stanislav Markov Dr. Christoph Busche Dr. Vihar Georgiev Prof. Asen Asenov Prof. Leroy Cronin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16502-16511
We explore the concept that the incorporation of polyoxometalates (POMs) into complementary metal oxide semiconductor (CMOS) technologies could offer a fundamentally better way to design and engineer new types of data storage devices, due to the enhanced electronic complementarity with SiO2, high redox potentials, and multiple redox states accessible to polyoxometalate clusters. To explore this we constructed a custom‐built simulation domain bridge. Connecting DFT, for the quantum mechanical modelling part, and mesoscopic device modelling, confirms the theoretical basis for the proposed advantages of POMs in non‐volatile molecular memories (NVMM) or flash‐RAM. 相似文献
116.
Dr. Andrey Y. Khalimon Prof. Dr. Stanislav K. Ignatov Andrey I. Okhapkin Dipl.‐Ing. Razvan Simionescu Prof. Dr. Lyudmila G. Kuzmina Prof. Dr. Judith A. K. Howard Dr. Georgii I. Nikonov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8573-8590
The reactions of bis(borohydride) complexes [(RN?)Mo(BH4)2(PMe3)2] ( 4 : R=2,6‐Me2C6H3; 5 : R=2,6‐iPr2C6H3) with hydrosilanes afford new silyl hydride derivatives [(RN?)Mo(H)(SiR′3)(PMe3)3] ( 3 : R=Ar, R′3=H2Ph; 8 : R=Ar′, R′3=H2Ph; 9 : R=Ar, R′3=(OEt)3; 10 : R=Ar, R′3=HMePh). These compounds can also be conveniently prepared by reacting [(RN?)Mo(H)(Cl)(PMe3)3] with one equivalent of LiBH4 in the presence of a silane. Complex 3 undergoes intramolecular and intermolecular phosphine exchange, as well as exchange between the silyl ligand and the free silane. Kinetic and DFT studies show that the intermolecular phosphine exchange occurs through the predissociation of a PMe3 group, which, surprisingly, is facilitated by the silane. The intramolecular exchange proceeds through a new non‐Bailar‐twist pathway. The silyl/silane exchange proceeds through an unusual MoVI intermediate, [(ArN?)Mo(H)2(SiH2Ph)2(PMe3)2] ( 19 ). Complex 3 was found to be the catalyst of a variety of hydrosilylation reactions of carbonyl compounds (aldehydes and ketones) and nitriles, as well as of silane alcoholysis. Stoichiometric mechanistic studies of the hydrosilylation of acetone, supported by DFT calculations, suggest the operation of an unexpected mechanism, in that the silyl ligand of compound 3 plays an unusual role as a spectator ligand. The addition of acetone to compound 3 leads to the formation of [trans‐(ArN)Mo(OiPr)(SiH2Ph)(PMe3)2] ( 18 ). This latter species does not undergo the elimination of a Si? O group (which corresponds to the conventional Ojima′s mechanism of hydrosilylation). Rather, complex 18 undergoes unusual reversible β‐CH activation of the isopropoxy ligand. In the hydrosilylation of benzaldehyde, the reaction proceeds through the formation of a new intermediate bis(benzaldehyde) adduct, [(ArN?)Mo(η2‐PhC(O)H)2(PMe3)], which reacts further with hydrosilane through a η1‐silane complex, as studied by DFT calculations. 相似文献
117.
Stanislav N. Naryzhny Andrey V. Lisitsa Victor G. Zgoda Elena A. Ponomarenko Alexander I. Archakov 《Electrophoresis》2014,35(6):895-900
Insufficient sensitivity of methods for detection of proteins at a single molecule level does not yet allow obtaining the whole image of human proteome. But to go further, we need at least to know the proteome size, or how many different protein species compose this proteome. This is the task that could be at least partially realized by the method described in this article. The approach used in our study is based on detection of protein spots in 2DE after staining by protein dyes with various sensitivities. As the different protein spots contain different protein species, counting the spots opens a way for estimation of number of protein species. The function representing the dependence of the number of protein spots on sensitivity or LOD of protein dyes was generated. And extrapolation of this function curve to theoretical point of the maximum sensitivity (detection of a single smallest polypeptide) allowed to counting the number of different molecules (polypeptide species) at the concentration level of a single polypeptide per proteome. Using this approach, it was estimated that the minimal numbers of protein species for model objects, Escherichia coli and Pirococcus furiosus, are 6200 and 3400, respectively. We expect a single human cell (HepG2) to contain minimum 70 000 protein species. 相似文献
118.
Stanislav S. Stoyko Andrew J. Craig Joshua W. Kotchey Jennifer A. Aitken 《Acta Crystallographica. Section C, Structural Chemistry》2021,77(1):1-10
The new quaternary thiosilicate, Li2PbSiS4 (dilithium lead silicon tetrasulfide), was prepared in an evacuated fused‐silica tube via high‐temperature, solid‐state synthesis at 800 °C, followed by slow cooling. The crystal structure was solved and refined using single‐crystal X‐ray diffraction data. By strict definition, the title compound crystallizes in the stannite structure type; however, this type of structure can also be described as a compressed chalcopyrite‐like structure. The Li+ cation lies on a crystallographic fourfold rotoinversion axis, while the Pb2+ and Si4+ cations reside at the intersection of the fourfold rotoinversion axis with a twofold axis and a mirror plane. The Li+ and Si4+ cations in this structure are tetrahedrally coordinated, while the larger Pb2+ cation adopts a distorted eight‐coordinate dodecahedral coordination. These units join together via corner‐ and edge‐sharing to create a dense, three‐dimensional structure. Powder X‐ray diffraction indicates that the title compound is the major phase of the reaction product. Electronic structure calculations, performed using the full potential linearized augmented plane wave method within density functional theory (DFT), indicate that Li2PbSiS4 is a semiconductor with an indirect bandgap of 2.22 eV, which compares well with the measured optical bandgap of 2.51 eV. The noncentrosymmetric crystal structure and relatively wide bandgap designate this compound to be of interest for IR nonlinear optics. 相似文献
119.
Stanislav Kozin Vladimir Skrebitsky Rodion Kondratenko Alexander Kravtsov Elena Butina Arkady Moiseev Vadim Malyshko Mikhail Baryshev Anna Elkina Stepan Dzhimak 《Molecules (Basel, Switzerland)》2021,26(7)
The deuterium content modification in an organism has a neuroprotective effect during the hypoxia model, affecting anxiety, memory and stress resistance. The aim of this work was to elucidate the possible mechanisms of the medium D/H composition modification on nerve cells. We studied the effect of an incubation medium with a 50 ppm deuterium content compared to a medium with 150 ppm on: (1) the activity of Wistar rats’ hippocampus CA1 field neurons, (2) the level of cultured cerebellar neuron death during glucose deprivation and temperature stress, (3) mitochondrial membrane potential (MMP) and the generation of reactive oxygen species in cultures of cerebellar neurons. The results of the analysis showed that the incubation of hippocampal sections in a medium with a 50 ppm deuterium reduced the amplitude of the pop-spike. The restoration of neuron activity was observed when sections were returned to the incubation medium with a 150 ppm deuterium content. An environment with a 50 ppm deuterium did not significantly affect the level of reactive oxygen species in neuron cultures, while MMP decreased by 16–20%. In experiments with glucose deprivation and temperature stress, the medium with 50 ppm increased the death of neurons. Thus, a short exposure of nerve cells in the medium with 50 ppm deuterium acts as an additional stressful factor, which is possibly associated with the violation of the cell energy balance. The decrease in the mitochondrial membrane potential, which is known to be associated with ATP synthesis, indicates that this effect may be associated with the cell energy imbalance. The decrease in the activity of the CA1 field hippocampal neurons may reflect reversible adaptive changes in the operation of fast-reacting ion channels. 相似文献
120.
Synthesis and Biochemical Evaluation of Warhead-Decorated Psoralens as (Immuno)Proteasome Inhibitors
Eva Shannon Schiffrer Matic Proj Martina Gobec Luka Rejc Andrej terman Janez Mravljak Stanislav Gobec Izidor Sosi
《Molecules (Basel, Switzerland)》2021,26(2)
The immunoproteasome is a multicatalytic protease that is predominantly expressed in cells of hematopoietic origin. Its elevated expression has been associated with autoimmune diseases, various types of cancer, and inflammatory diseases. Selective inhibition of its catalytic activities is therefore a viable approach for the treatment of these diseases. However, the development of immunoproteasome-selective inhibitors with non-peptidic scaffolds remains a challenging task. We previously reported 7H-furo[3,2-g]chromen-7-one (psoralen)-based compounds with an oxathiazolone warhead as selective inhibitors of the chymotrypsin-like (β5i) subunit of immunoproteasome. Here, we describe the influence of the electrophilic warhead variations at position 3 of the psoralen core on the inhibitory potencies. Despite mapping the chemical space with different warheads, all compounds showed decreased inhibition of the β5i subunit of immunoproteasome in comparison to the parent oxathiazolone-based compound. Although suboptimal, these results provide crucial information about structure–activity relationships that will serve as guidance for the further design of (immuno)proteasome inhibitors. 相似文献