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991.
Baeyer-Villiger单加氧酶在有机合成中的应用 总被引:3,自引:0,他引:3
综述了Baeyer-Villiger单加氧酶在有机合成中的应用.较之传统的化学反应, 氧化酶催化剂反应有较好的选择性、可控性和经济性. 环己酮加氧酶是一种还原型辅酶I (NADPH)依赖型氧化酶, 是最早被报道能够催化Baeyer-Villiger氧化的酶. 这些重要反应产生了合成化学家很感兴趣的扩环产物. 环己酮加氧酶也是有用的生物催化剂, 由于辅酶再生的问题已被工程菌克服了, 所以能像全细胞催化剂那样使用. 对酮包括杂环酮进行Baeyer-Villiger氧化和动态动力学拆分, 放大这种反应作为合成路线是很有前途的. 相似文献
992.
硝酸甲酯分子间相互作用的DFT和ab initio比较 总被引:5,自引:0,他引:5
用密度泛函理论(DFT)和从头算(ab initio)方法,分别在B3LYP/6 31G和HF/6 31G水平上求得硝酸甲酯三种二聚体的全优化几何构型和电子结构,并用6 311G和6 311++G基组进行总能量计算.对HF/6 31G计算结果进行MP4SDTQ电子相关校正.在各基组下均进行基组叠加误差(BSSE)和零点能(ZPE)校正求得结合能.对6 31G优化构型作振动分析并基于统计热力学求得200~600 K温度下单体和二聚体的热力学性质.详细比较两种方法的相应计算结果,发现DFT求得的分子间距离较短,分子内键长较长,所得结合能均小于相应ab initio计算值. 相似文献
993.
Yamamoto Y Terui N Tachiiri N Minakawa K Matsuo H Kameda T Hasegawa J Sambongi Y Uchiyama S Kobayashi Y Igarashi Y 《Journal of the American Chemical Society》2002,124(39):11574-11575
Paramagnetic NMR and optical studies of the oxidized forms of mesophile Pseudomonas aeruginosa cytochrome c(551) and its quintuple mutant (F7A/V13M/F34Y/E43Y/V78I), and thermophile Hydrogenobacter thermophilus cytochrome c(552) demonstrated that the amino acid side chain packings in the protein interior influence the coordination bond between the heme iron and the axial methionine in the proteins. The strength of heme axial coordinations was found to correlate with the overall protein thermostability. 相似文献
994.
Yi‐Jun Huang Guo‐Rong Qi Yu‐Hua Wang 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1142-1150
A double metal‐cyanide catalyst based on Zn3[Co(CN)6]2 was prepared. This catalyst is very effective for the ring‐opening polymerization of propylene oxide. Polyether polyols of moderate molecular weight having low unsaturation (<0.015 meq/g) can be prepared under mild conditions. The molecular weight of polymer is entirely controlled by a reacted monomer‐to‐initiator ratio. The polymers prepared with stepwise addition of monomer exhibit a narrower molecular weight distribution as compared with those prepared with one‐step addition of monomer. Various compounds containing active hydrogen, except basic compounds and low‐carbon carboxylic acid, may be used as initiators. The reaction rate increases with increasing catalyst amount and decreases with rising initiator concentration. Polymerization involves a rapid exchange reaction between the active species and the dormant species. It was also proven that, to a certain extent, the chain termination of this catalytic system is reversible or temporary. 13C NMR analysis showed that the polymer has a random distribution of the configurational sequences and head‐to‐tail regiosequence. It is assumed that the polymerization proceeds via a cationic coordination mechanism. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1142–1150, 2002 相似文献
995.
An electronic protein transfer technique is described for achieving the rapid and efficient recovery of sodium dodecyl sulfate (SDS)-protein complexes from polyacrylamide gels. This process involves the use of small-dimension capillaries in physical contact with a resolved protein band within the polyacrylamide gel, providing a large potential drop and high electric field strength at the capillary/gel interface. Several factors controlling the electronic protein transfer, including the applied electric field strength, the electrophoresis buffer concentration, and the capillary dimension, are studied to further enhance the use of field-amplification for sample stacking of extracted SDS-protein complexes. As a result of sample stacking, the extracted proteins from a 50 ng gel loading are present in a narrow ( approximately 80 nL) and highly concentrated (0.46 mg/mL or 3.3 x 10(-5) M for cytochrome c) solution plug. Three model proteins with molecular mass ranging from 14 kDa (cytochrome c) to 116 kDa (beta-galactosidase) are stained by Coomassie blue and electrophoretically extracted from gels with protein loadings as low as 50 ng. The capillary format of the electronic protein transfer technique allows direct deposition of extracted proteins onto a matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) target. Various matrices and solvent compositions are evaluated for the analysis of extracted and concentrated SDS-protein complexes using MALDI-MS. The electronic protein transfer technique, when operated under optimized conditions, is demonstrated for the effective (>70% recovery), speedy (less than 5 min), and sensitive MS identification of gel resolved proteins (as low as 50 ng). 相似文献
996.
Shuhua?HanEmail author Wanguo?Hou Jun?Xu Zhengmin?Li 《Colloid and polymer science》2004,282(11):1286-1291
Hollow spherical mesoporous silica was synthesized by using sodium silicate as a precursor and a low concentration of cetyltrimethylammonium bromide (CTAB) (0.154 mol dm–3). The resulting hollow spherical particles were characterized with scanning electron microcopy (SEM), small-angle X-ray diffraction (SXRD), transmission electron microscopy (TEM), and N2 gas adsorption and desorption techniques. The results showed that regular spherical mesoporous silica could be obtained only if the molar ratio of propanol to CTAB was in the range of approximately 8:1–9:1. The spherical particles were hollow (inside), and the shell consisted of smaller particles with a pore structure of hexagonal symmetry. With an increase of the molar ratio of propanol to CTAB, the distance (a value) between centers of two adjacent pores increased, and the pore structure of mesoporous silica became less ordered. N2 adsorption–desorption curves revealed type IV isotherms and H1 hysteresis loops; with an increase of the molar ratio of propanol to CTAB, the pore size with Barrett–Joyner–Halenda (BJH) diameter of the most probable distribution decreased, but the half peak width of the pore size distribution peak increased 相似文献
997.
Yan Xiao Jian Wang Wang Xia Guang Feng Huai You Wang 《Journal of Analytical Chemistry》2007,62(5):438-443
The maximum emission wavelength of dopamine is 317 nm with excitation at 290 nm. The relative fluorescence intensity of dopamine
decreased in the presence of enoxacin, which showed that fluorescence quenching occurred. The Stern-Volmer (S-V) plot showed
a nonlinear relationship between the relative fluorescence intensity of dopamine and the concentration of enoxain. The quenching
mechanism was studied and the results suggested that both dynamic and static quenching processes were responsible for the
observed positive deviation in the S-V plot. When the S-V plot was modified by logarithm, the linear relationship was obtained
between logF
0/F and C in the range of 0.10 to 13.0 μg/mL (where F
0 is the relative fluorescence intensity of dopamine, F is the relative fluorescence intensity of dopamine in the presence of enoxacin, and C is the concentration of enoxacin). The fluorescence quenching method for the determination of enoxacin was developed. The
linear regression equation of the calibration graph of enoxacin was C = 13.70 (logF
0/F) − 0.5836, with the correlation coefficient 0.9984. The detection limit was 2.0 ng/mL and the relative standard deviation
was 2.52%. The effects of pH, the stability of dopamine in the presence of enoxacin, and foreign ions on the determination
of enoxacin have been examined. The recovery of enoxacin was from 94.9 to 103.0% in a human serum sample and from 94.9 to
108.0% in a urine sample. The method is simple, rapid, and can be used for the determination of enoxacin in human serum and
urine samples with satisfactory results.
The text was submitted by the authors in English. 相似文献
998.
Zhaoyang Cheng Shipei Xing Jun Guo Biao Cheng Lan‐Fang Hu Xing‐Hong Zhang Zhan Lu 《中国化学》2019,37(5):457-461
A regioselective double 1,1‐hydrosilylation of terminal aliphatic alkynes with primary silanes catalyzed by one cobalt catalyst has been developed. gem‐Bis(dihydrosilyl)alkanes containing four silicon‐hydrogen bonds are efficiently constructed in an atom‐economical manner. Tolerated substrates include simplest alkyne‐ethyne, a complicated drug derivative and various functionalized terminal aliphatic alkynes. Asymmetric approach using two catalysts is achieved with excellent enantioselectivities to access corresponding chiral products. The transformations of Si—H bonds into Si—C, Si—O, and Si—F bonds and the synthesis of enantioriched α‐hydroxysilane show synthetic utility. 相似文献
999.
Yong Wu Hui-Biao Liu Yong-Jiang Liu Chun-Ying Duan Jun Hu Zheng Hu 《Journal of inclusion phenomena and macrocyclic chemistry》2000,36(4):473-478
A new facile method of synthesis of calix[4]arene amide via the aminolysis of the calix[4]arene esters was reported. One ethyl ester of the compound (2) was aminolysized byn-butylamine. The crystal structure of compound (1)shows that one ethyl ester of compound (1) enters into thecavity of another compound (1) forming a long chainhost-guest supramolecule. From the 2D NMR data, the compound(1) does not assemble in THF or CHCl3 solution. The CH- interaction and crystallization energy might be theimportant driving forces for forming the self-assembledcalix[4]arene. 相似文献
1000.