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941.
942.
A theoretical study of geminal and vicinal 77Se‐1 H coupling constants in the benchmark dimethyl and diethyl selenides has been performed at the SOPPA level followed by the NJC analysis within the NBO approach to reveal their stereochemical behavior in respect with the three main structural factors, namely, (i) the dihedral angle dependences, (ii) the bond angle dependences and (iii) the lone pair effects. It has been demonstrated that both geminal and vicinal couplings provide a unique stereospecificity in respect with the orientational lone pair effect together with the geometry of a coupling pathway, which is of prime importance for the stereochemical studies of organoselenium compounds. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
943.
David Poger Wilfred F. Van Gunsteren Alan E. Mark 《Journal of computational chemistry》2010,31(6):1117-1125
A new force field for the simulation of dipalmitoylphosphatidylcholine (DPPC) in the liquid‐crystalline, fluid phase at zero surface tension is presented. The structure of the bilayer with the area per lipid (0.629 nm2; experiment 0.629–0.64 nm2), the volume per lipid (1.226 nm3; experiment 1.229–1.232 nm3), and the ordering of the palmitoyl chains (order parameters) are all in very good agreement with experiment. Experimental electron density profiles are well reproduced in particular with regard to the penetration of water into the bilayer. The force field was further validated by simulating the spontaneous assembly of DPPC into a bilayer in water. Notably, the timescale on which membrane sealing was observed using this model appears closer to the timescales for membrane resealing suggested by electroporation experiments than previous simulations using existing models. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 相似文献
944.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(7):1841-1845
Supramolecular crystalline assembly constitutes a rational approach to bioengineer intracellular structures. Here, biocrystals of clofazimine (CFZ) that form in vivo within macrophages were measured to have marked curvature. Isolated crystals, however, showed reduced curvature suggesting that intracellular forces bend these drug crystals. Consistent with the ability of biocrystals to elastically deform, the inherent crystal structure of the principal molecular component of the biocrystals—the hydrochloride salt of CFZ (CFZ‐HCl)—has a corrugated packing along the (001) face and weak dispersive bonding in multiple directions. These characteristics were previously found to be linked to the elasticity of other organic crystals. Internal stress in bent CFZ‐HCl led to photoelastic effects on the azimuthal orientation of polarized light transmittance. We propose that elastic, intracellular crystals can serve as templates to construct functional microdevices with different applications. 相似文献
945.
The spiro-compound 3′H-spiro[indole-3,2′-[1,3]benzothiazole-2(1H)-one (IBTH2) was synthesized and its structure was determined using spectroscopic techniques (FTIR, 1H NMR and mass) and X-ray crystallography. This ligand possesses different centers for coordination. Reactions of [M(CO)6], M = Cr, Mo or W with IBTH2 in THF under reduced pressure were studied. For chromium a complex with molecular formula [Cr(ITP)2] was isolated; where ITP is the opened form of the ligand which occurred through Cspiro–S bond, while [Mo(CO)5(IBTH2)] and [W(CO)5(IBTH2)] were isolated from the reaction of IBTH2 with molybdenum and tungsten carbonyls, respectively. All complexes were characterized by elemental analysis, IR, mass and 1H NMR spectroscopy. The biological activity of the ligand and its complexes were studied and compared with the parent compound isatin. 相似文献
946.
947.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(41):12655-12659
Antibodies are important biopharmaceuticals, but almost all existing antibody‐based drugs are limited to targeting antigens located at the cell exterior because of the inability of antibodies to enter the cell interior. Available methods for intracellular delivery of antibodies have major shortcomings. Herein, we report an approach to encapsulate native antibodies in a biodegradable silica nanoquencher (BS‐qNP), which could undergo efficient cellular uptake and intracellular degradation to release antibodies only under hypoxic conditions. By coating the surface of BS‐qNP with cell‐penetrating poly(disulfide)s (CPD), the delivered antibodies (or other proteins) avoided endolysosomal trapping. Doping of the silica coating with a fluorescent dye and a dark hole quencher further endowed BS‐qNP with hypoxia‐responsive fluorescence turn‐on property. Our antibody delivery system thus provides the first platform capable of stable encapsulation, efficient uptake, on‐demand antibody release, and imaging of release/cell state. 相似文献
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949.
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