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61.
A chiral HWE reagent reacted with an alternative carbonyl group of meso-α-diketones of bicyclo[2.2.1] system to give non-racemic (Z)- and (E)-olefins, respectively. 相似文献
62.
Yoshihiko Nishimori Katsuhiko Kanaizuka Dr. Masaki Murata Dr. Hiroshi Nishihara Prof. 《化学:亚洲杂志》2007,2(3):367-376
Films of linear and branched oligomer wires of Fe(tpy)2 (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C6H4N?NC6H4? S)2 ( 1 ), two bridging ligands, 1,4‐(tpy)2C6H4 ( 3 ) and 1,3,5‐(C?C? tpy)3C6H3 ( 4 ), and metal ions were used. The quantitative complexation of the ligands and FeII ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k1 (s?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k2 (cm2 mol?1 s?1). The strong effect of the electrolyte concentration on both k1 and k2 indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k1 and k2 on the potential gave intrinsic kinetic parameters without overpotential effects: k10=110 s?1, k20=2.6×1012 cm2 mol?1 s?1 for [n Fe 3 ], and k10=100 s?1, k20=4.1×1011 cm2 mol?1 s?1 for [n Fe 4 ] (n=number of complexation cycles). 相似文献
63.
Akira Watanabe 《Tetrahedron letters》2004,45(33):6229-6233
Oxovanadium(V)(salen) complex 4 was found to catalyze Meerwein-Ponndorf-Verley cyanation of aliphatic aldehydes with good to high enantioselectivity. This cyanation showed a positive nonlinear effect. 相似文献
64.
Hiroshi Harada Kanichi Kamiya Hiroyuki Nasu Jun Matsuoka 《Journal of Sol-Gel Science and Technology》1997,10(3):291-300
The sodium dititanate, Na2O·2TiO2 glass was prepared by the sol-gel method. The structure of the glass, especially local environment of Ti4+ ions was examined using X-ray diffraction and X-ray absorption fine structure (XAFS) analyses, and was compared with that of the melt-derived glass with the same composition. It was found that Ti4+ ions are rather in five-fold coordination state, forming TiO5 pyramids with one doubly bonded Ti=O in the gel-glass, while they were in lower coordination state or four-fold coordination in the melt-derived glass. 相似文献
65.
66.
Summary Pyridinium ylide complexes of methylcobaloxime were synthesized by the treatment of an ylide with Co(Hdmg)2 Me(SMe2). The crystal structure of one of the complexes, [Co(Hdmg)2Me C5H5NCHCOPh]C6H6 has been determined by x-ray diffraction techniques. The crystals are monoclinic, space group P21/c, witha = 10.456(5),b = 11.079(4),c = 24.58(1) Å, = 99.58(6), V = 2808 Å3, Z = 4. The Co-C (ylide) bond distance is 2.18 Å and Co-C(methyl) 2.04 Å. C(ylide)-Co-C(methyl) bond angle is 174.9°. The crystal, i.r. and1H n.m.r. data suggest that thetrans-influence of the ylide ligands is larger than that of py, Melm, OH2 or PPh3. 相似文献
67.
Hiroshi Saito Hitoshi Kurabe Eiichi Suzuki Fumio Watari 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》1995,51(14)
The IR spectra (4000-250 cm−1) of CH3SCl and CD3SCl in solid argon have been obtained. Fundamental vibrations, except the torsional vibrations, have been assigned. Normal coordinate analysis has been carried out omitting the torsional modes. 相似文献
68.
Yoshiharu Yamane Yozo Nakamura Hiroyuki Okamoto Hiroshi Ooshima Jyoji Kato 《Applied biochemistry and biotechnology》1995,50(3):317-322
Effects of pH and dissolved oxygen concentration on batchwise riboflavin production by a 5-fluorouracil (5-FU)-resistant mutant
ofArthrobacter sp. were investigated. The reaction was carried out in a jar fermentor. The optimal pH of culture medium was around 7.3.
Dissolved oxygen concentration was almost constant during fermentation at 600 rpm of agitation rate. Production of riboflavin
reached a maximum of 160 mg/L after 70 h fermentation under the agitation rate of 600 rpm, aeration rate of 1.0 L/min, and
pH 7.0. 相似文献
69.
Exciton charge separation in photosynthetic reaction centers from purple bacteria (PbRC) and photosystem II (PSII) occurs exclusively along one of the two pseudo-symmetric branches (active branch) of pigment–protein complexes. The microscopic origin of unidirectional charge separation in photosynthesis remains controversial. Here we elucidate the essential factors leading to unidirectional charge separation in PbRC and PSII, using nonadiabatic quantum dynamics calculations in conjunction with time-dependent density functional theory (TDDFT) with the quantum mechanics/molecular mechanics/polarizable continuum model (QM/MM/PCM) method. This approach accounts for energetics, electronic coupling, and vibronic coupling of the pigment excited states under electrostatic interactions and polarization of whole protein environments. The calculated time constants of charge separation along the active branches of PbRC and PSII are similar to those observed in time-resolved spectroscopic experiments. In PbRC, Tyr-M210 near the accessary bacteriochlorophyll reduces the energy of the intermediate state and drastically accelerates charge separation overcoming the electron–hole interaction. Remarkably, even though both the active and inactive branches in PSII can accept excitons from light-harvesting complexes, charge separation in the inactive branch is prevented by a weak electronic coupling due to symmetry-breaking of the chlorophyll configurations. The exciton in the inactive branch in PSII can be transferred to the active branch via direct and indirect pathways. Subsequently, the ultrafast electron transfer to pheophytin in the active branch prevents exciton back transfer to the inactive branch, thereby achieving unidirectional charge separation.Essential factors leading to unidirectional charge separation in photosynthetic reaction centers are clarified via nonadiabatic quantum dynamics calculations. 相似文献
70.
[reaction: see text] Catalytic, enantioselective Mannich-type reactions of alpha-imino esters bearing readily removable substituents on nitrogen are described. Several N-carbamate-protected alpha-imino esters, which are readily prepared from 2-bromoglycine esters using a polymer-supported amine, reacted with silicon enolates to afford the desired adducts in high yields with high enantioselectivity using a copper(II)-diamine complex. Easy deprotection of the product amine and transformation to free alpha-amino acid derivatives have also been demonstrated. 相似文献