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51.
The most effective optical isomer (1R-cis) of permethric acid (2, R = H), a potent intermediate in the production of synthetic pyrethroid, was enantioselectively prepared.  相似文献   
52.
We studied biogas fermentation from alcohol waste fluid to evaluate the anaerobic digestion process and the production of vitamin B12 as a byproduct. Anaerobic digestion using acclimated methanogens was performed using the continuously stirred tank reactor (CSTR) and fixed-bed reactor packed with rock wool as carrier material at 55°C. We also studied the effects of metal ions added to the culture broth on methane and vitamin B12 formation. Vitamin B12 production was 2.92 mg/L in the broth of the fixed-bed reactor, twice that of the CSTR. The optimum concentrations of trace metal ions added to the culture liquid for methane and vitamin B12 production were 1.0 and 8 mL/L for the CSTR and fixed-bed reactor, respectively. Furthermore, an effective method for extracting and purifying vitamin B12 from digested fluid was developed.  相似文献   
53.
6-Oxoprostaglandin E1 methyl ester was synthesized in a single pot from (R)-4-t-butyldimethylsiloxy-2-cyclopentenone by organocopper conjugate addition with an ω side-chain unit, trapping of the resulting enolate with 6-methoxycarbonyl-2-nitrohex-1-ene, and treatment with aqueous titanium(III) trichloride. Hydrolysis of the methyl ester was accomplished by porcine liver esterase. 6-Oxoprostaglandin F, was obtained from 6-nitroprostaglandin E1 methyl ester in four steps.  相似文献   
54.
The magnetic susceptibility of UO2ThO2 solid solutions has been measured from room temperature to 2.0 K. The magnetic moment and the Weiss constant have been determined in the temperature range in which the Curie-Weiss law holds. For the solid solutions showing antiferromagnetic transition, the Néel temperature has been also determined. These values decrease monotonically with increasing ThO2 concentration. The results were analyzed using the molecular field theory which includes the interaction between next-nearest neighbor spins. The interactions between nearest neighbor spins, J1, and those between next-nearest neighbor spins, J2, both decrease with increasing ThO2 concentration. The change of J1 with composition is larger than that of J2. The effect of magnetic dilution with ThO2 is considered to be stronger on the interaction between nearest neighbor uranium ions.  相似文献   
55.
The index of hydrophobicity of DNA interior was estimated by measuring fluorescence spectra of psoralen derivatives associated with DNA. The environment around 5-MOP associated with DNA was as hydrophobic (Dk = 34) as methanol, suggesting that the molecules reside at the space between the base-pairs in B-form DNA. This is also true for 8-MOP. Thus, planar and aromatic molecules of 5- and 8-MOP are more stable in the interior of DNA than in aqueous medium due to hydrophobic affinity.  相似文献   
56.
Enantiomer-differentiating ester syntheses from acid salts, chlorides, and an anhydride were studied in the presence of optically active polyamines. Enantiomer selection occurred in reactions of a racemic salt with an achiral alkyl bromide and vice versa, which is good evidence of the importance of activation of the carboxylate group by complexation of the counterion and activation of alkyl bromide by the formation of a quaternary salt with polyamine under solid–liquid, phase-transfer reaction conditions. Only small optical activity was observed in the products of acid anhydride or chloride with alcohol.  相似文献   
57.
We have applied cavity ring-down spectroscopy to a kinetic study of the reaction of NO3 with CH2I2 in 25–100 Torr of N2 diluent at 298 K. The rate constant of reaction of NO3 + CH2I2 is determined to be (4.0 ± 1.2) × 10−13 cm3 molecule−1 s−1 in 100 Torr of N2 diluent at 298 K. The rate constant increases with increasing pressure of buffer gas below 100 Torr. The reaction of CH2I2 with NO3 has the potential importance at nighttime in the atmosphere.  相似文献   
58.
Nomura A  Sugiura Y 《Inorganic chemistry》2002,41(14):3693-3698
Little is known about the contribution of individual zinc-ligating amino acid residues for coupling between zinc binding and protein folding in zinc finger domains. To understand such roles of each zinc ligand, four zinc finger mutant peptides corresponding to the second zinc finger domain of Sp1 were synthesized. In the mutant peptides, glycine was substituted for one of four zinc ligands. Their metal binding and folding properties were spectroscopically characterized and compared to those of the native zinc finger peptide. In particular, the electronic charge-transfer and d-d bands of the Co(II)-substituted peptide complexes were used to examine the metal coordination number and geometry. Fluorescence emission studies revealed that the mutant peptides are capable of binding zinc despite removing one ligand. Circular dichroism results clearly showed the induction of an alpha-helix by zinc binding. In addition, the structures of certain mutant zinc finger peptides were simulated by molecular dynamics calculation. The information indicates that His23 and the hydrophobic core formed between the alpha-helix and the beta-sheet play an essential role in alpha-helix induction. This report demonstrates that each ligand does not contribute equally to alpha-helix formation and coordination geometry in the zinc finger peptide.  相似文献   
59.
From the standpoint of protein dynamics and metalloprotein design, it is interesting to create an artificial protein which induces structural change and regulates its function by metal-ion binding. We engineered a novel protein, "Antennafinger (Ant-F)", whose structure and function can be controlled with Zn(II), by introducing the consensus sequence of a Cys(2)His(2)-type zinc finger protein into a non-metalloprotein scaffold, an Antennapedia homeodomain mutant (Ant-wt), selected using a motif-searching system. The circular dichroism studies demonstrate that Ant-F has secondary structures similar to Ant-wt and also changes its conformation due to Zn(II)-binding. The optical absorption spectra of the Co(II) complexes of Ant-F and its derivative proteins suggest that the geometry of the metal center of holo-Ant-F is tetrahedral and that the mutated Cys(2)His(2) residues are involved in the complex formation. In addition, the gel mobility shift assay reveals that the DNA binding activity of Ant-F can be regulated through Zn(II)-induced structural alteration. These results provide valuable information about the dynamic properties of proteins and a novel concept for metalloprotein design.  相似文献   
60.
(Ss)-3-(p-Tolylsufinyl)-2-furaldimine was synthesized, and condensation of the chiral furaldimine with lithium ester enolates has been examined. The product distribution of the reaction is dependent upon reaction conditions and on the kind of the substituent placed on the esters. Disubstituted ester enolate resulted in the exclusive formation of (4R)-beta-lactam, while unsubstituted, tert-butyl ester enolate preferentially gave (3R)-beta-amino ester. With the monosubstituted ester enolates, the condensation afforded (4R)-beta-lactams and/or (3R)-beta-amino esters as major products. This method has been applied to an efficient route to chiral furyl beta-lactams.  相似文献   
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