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41.
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
42.
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
43.
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
44.
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
45.
[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
46.
The pinacol reaction of beta-halogenated alpha,beta-unsaturated aldehydes was promoted by titanium tetraiodide to give coupling products in good yields with high dl-selectivity. Subsequent reduction with H(2)/Pd-C gave saturated vic-diols in good yields. Heck coupling reaction enabled the displacement of halogens with vinyl groups without the loss of stereochemical integrities. [reaction: see text] 相似文献
47.
Mikio Hori Tadashi Kataoka Hiroshi Shimizu Akihiko Tomoto 《Tetrahedron letters》1981,22(37):3629-3632
1-Benzoyl-2-methy1-3,4-dihydro-2-thianaphthalene () underwent novel intermolecular 1,4-rearrangement in refluxing toluene to give an enol ether , while rearrangement of 2-phenyl derivative proceeded intramolecularly in refluxing xylene to afford a 1,4-rearranged enol ether . On the other hand, ylides were refluxed in alcohols to afford some ring-opened products . 相似文献
48.
Synthesis and photochemical properties of photoactivated antitumor prodrugs releasing 5-fluorouracil
A new family of antitumor prodrugs (1-3) of 5-fluorouracil (5-FU) possessing photolabile 2-nitrobenzyl chromophores have been designed and synthesized to investigate the efficiency and mechanism of photoactivated 5-FU release upon UV-irradiation at lambda(ex)= 365 nm. The photoactivated prodrug 3 derived from conjugation of 2 with a tumor-homing cyclic peptide Cys-Asn-Gly-Arg-Cys (CNGRC) was so designed as to manifest a tumor-targeting function. 相似文献
49.
2-Alkyl-1-alkylthioisoquinolinium salts were readily prepared from 2-alkyl-1(2H)-isoquinolones via 2-alkyl1(2H)-thioisoquinolones in two steps. Under mild conditions, the reaction of 2-alkyl-1-alkylthioisoquinolinium salts with active methylene compounds in the presence of sodium hydride afforded 2-alkyl-1-(substituted methylene)iso-quinolines in good yields. Pyrrolo[2,1-a]isoquinolines were synthesized by the cyclization of 2-benzyl-1-(substituted methylene)isoquinolines using acetic anhydride. 相似文献
50.
Minimal contracted Gaussian basis sets are presented for Ga through Cd. Characteristically these Gaussian-based minimal sets give far better d orbital energies than those by minimal STO basis sets. These new basis sets were tested on Br2 for which a new benchmark calculation was also performed. The test result is satisfactory in that these basis sets produce good general agreement with the near Hartree–Fock calculation with respect to the molecular spectroscopic constants. 相似文献