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631.
[reaction: see text] Unusual stereoselectivity changes, i.e., enhancement and inversion of enantioselectivity with increasing temperature, were observed in the asymmetric reduction of methyl benzoylformate with chiral 1,4-dihydropyridines possessing amino acid residues as ligating chiral auxiliaries. The differential activation parameters, DeltaDeltaH(S-R) and DeltaDeltaS(S-R), obtained from the Eyring plots demonstrate that the entropy term controls the enantiodifferentiating step, accounting for the observed unique temperature dependencies. 相似文献
632.
High-mannose-type oligosaccharides, which are cotranslationally introduced to nascent polypeptides, play important roles in glycoprotein quality control. This process is highly complex, involving a number of lectins, chaperones, and glycan-processing enzymes. For example, calnexin and calreticulin (CRT) are molecular chaperones that recognize monoglucosylated forms of high-mannose-type glycans. UDP-glucose : glycoprotein glucosyltransferase (UGGT) only glucosylates high-mannose-type glycans attached to partially folded proteins. Fbs1 is a component of ubiquitin ligase that recognizes sugar chains. Although recent studies have clarified the properties of these proteins, most of them used oligosaccharides derived from natural sources, which contain structural heterogeneity. In order to gain a more precise understanding, we started our program to comprehensively synthesize high-mannose-type glycans associated with a protein quality control system. Additionally, investigation of artificial glycoproteins led us to the discovery of the first nonpeptidic substrate of UGGT. These synthetic oligosaccharide probes have allowed us to conduct quantitative evaluations of the activity and specificity of CRT, Fbs1, and UGGT. 相似文献
633.
The electronic structures of heme a of cytochrome c oxidase in the redox states were studied, using hybrid density functional theory with a polarizable continuum model and a point charge model. We found that the most stable electronic configurations of the d electrons of the Fe ion are determined by the orbital interactions of the d orbitals of the Fe ion with the π orbitals of the porphyrin ring and the His residues. The redox reaction of the Fe ion influences the charge density on the formyl group through the π conjugation of the porphyrin ring. In addition, we found the charge transfer from the Fe ion to the propionate group of heme a in the redox change despite the lack of the π‐conjugation. We elucidated that the charge propagation originates from the heme a structure itself and that the origin of the charge delocalization to the heme propionate is the orbital interactions between the d orbital of the Fe ion and the p orbitals of the carboxylate part of the heme propionate via the π conjugation of the porphyrin ring and the σ* orbital of the C? C bond of the propionate group. The electrostatic effect by surrounding proteins enhances the charge transfer from the Fe ion to the propionate group. These results indicate that heme propionate groups serve electron mediators in electron transfer as well as electrostatic anchors, and that proteins surrounding the active site reinforce the congenital abilities of the cofactors. © 2009 Wiley Periodicals, Inc. J Comput Chem 2010 相似文献
634.
Y. Takano K.N. Liou P. Yang 《Journal of Quantitative Spectroscopy & Radiative Transfer》2012,113(14):1836-1843
Analytical solutions are presented for Fraunhofer diffraction by the following nonspherical particles: rectangular parallelepiped, hexagonal cylinder, spheroid, and three-axis ellipsoid. Using these solutions, numerical results for the diffracted intensity of these particles in specific orientations and 3-D random orientation for an ensemble of particles of the same size are presented and discussed in terms of their minima and maxima that occur in intensity patterns, which differ substantially from their spherical counterparts. 相似文献
635.
Yasuna Kawasaki Keita Deguchi Satoshi Demura Tohru Watanabe Hiroyuki Okazaki Toshinori Ozaki Takahide Yamaguchi Hiroyuki Takeya Yoshihiko Takano 《Solid State Communications》2012,152(13):1135-1138
Phase diagrams of as-grown and O2-annealed FeTe1?xSex determined from magnetic susceptibility measurement were obtained. For as-grown samples, the antiferromagnetic order was fully suppressed in the range region x≥0.15, and weak superconductivity appeared when x≥0.1. Beginning at x=0.5, weak superconductivity was found to evolve into bulk superconductivity. Interestingly, for O2-annealed samples, complete suppression of magnetic order and the occurrence of bulk superconductivity were observed when x≥0.1. We found that O2-annealing induces bulk superconductivity for FeTe1?xSex. Oxygen probably plays a key role in the suppression of the magnetic order and the appearance of bulk superconductivity. 相似文献
636.
Dr. Hiroki Hayashi Dr. Hideaki Takano Hitomi Katsuyama Dr. Yu Harabuchi Prof. Satoshi Maeda Prof. Tsuyoshi Mita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(39):10040-10047
A three-component reaction (3CR) for the synthesis of difluoroglycine derivatives has been achieved by using amines, difluorocarbene (generated in situ), and the abundant, inexpensive, and nontoxic C1 source CO2. Various tert-amines and pyridine, (iso)quinoline, imidazole, thiazole, and pyrazole derivatives were incorporated, and the corresponding products were isolated in solid form without purification by column chromatography on silica gel. Detailed reaction profiles of the 3CR were obtained from computational analysis using DFT calculations, and the results critically suggest that simple ammonia is not applicable to this reaction. In addition, as strongly supported by computational predictions, a new reagent that can generate difluorocarbene at 0 °C without any additives was discovered. Finally, radical substitution reactions of the obtained difluoroglycine derivatives under photoredox conditions, as well as a synthetic application as an N-heterocyclic carbene ligand are shown. 相似文献