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991.
手性配体的空间结构与产物对映选择性的关系 总被引:2,自引:0,他引:2
首次采用4-烷氧羰基噻唑烷、E唑烷作为手性配体,诱导烷基锌对醛类的亲核加成反应,获得产物是烷基化的醛,最高达90%ee,产率98%的(S)-二级醇。系统地考察了该类手性配体三维空间结构变化与产物对映选择性的关系,当配体4-位烷氧羰基上的R、2-位R′基和环体上原子X发生变化时都会引起产物(S)-二 级醇的对映选择性发生规律性变化。对五种不同结构的底物醛在同一手性配体催化下,诱导烷基锌对醛类的亲核加成反应,底物结构变化也会引起(S)-二级醇对映选择性变化。 相似文献
992.
Besides the running buffer, pH of buffer, separation voltage and sampling time, the diluting agent was studied in this paper as one of the important factors influencing the sensitivity in capillary electrophoresis (CE) with amperometric detection (AD) when electrokinectic sampling was used. Clonidine hydrochloride, hydrochlorothiazide and rutin, which are positively charged, neutral and negatively charged, respectively, in aqueous solutions, could be perfectly separated by CE with 25 mmol x L(-1) Na(2)B(4)O(7) - 50 mmol x L(-1) NaH(2)PO(4) as running buffer and detected by measuring their current responses with AD. Before CE running, some kinds of diluents including water, methanol, formamide, running buffer, hydrochloric acid and sodium hydroxide were, respectively, applied to dilute the stock solutions of above three analytes and their effects on the sensitivity of CE-AD were investigated. The results showed that for electrokinetic injection, the current responses of these three analytes were greatly affected in different ways when different diluting agents were used. This method was applied to simultaneously determine the active ingredients in one Chinese compound hypotensor named Zhen Ju Jiang Ya Pian, in which the contents of clonidine hydrochloride, hydrochlorothiazide and rutin is very different as 0.03 mg : 5 mg : 20 mg per tablet, and satisfactory results were obtained by adjusting their sensitivity by selecting the suitable diluting agent. 相似文献
993.
The elastic vibrations of spherical nanoparticles have been widely studied by Raman scattering. However, there exist more than one set of selection rules for Raman scattering from these vibrations. For instance, Kanehisa has stated that only torsional modes with angular momentum l = 2 are Raman-active, while Tanaka et al. proposed that spheroidal modes of even l and torsional modes of odd l are Raman-active. These contradict selection rules of Duval which states that only spheroidal modes of l = 0 or 2 are Raman-active. Our present calculations based on a macroscopic model show that all torsional modes have vanishing intensity in the Raman spectrum. 相似文献
994.
The interaction between anionic surfactants and polyvinylpyrrolidone (PVP) are investigated using 13C NMR, ESR spectroscopy and surface tension measurements at the air/water interface. The behavior of single-chained surfactant,
sodium dodecyl sulphonate (AS), is compared with that of the double-chained surfactant, sodium bis(2-ethylhexyl) phosphate
(NaDEHP). The results showed that a surfactant–polymer complex of “necklace and head structure” is formed in AS aqueous solutions
in the presence of PVP due to the hydrophobic interaction between PVP and AS. The AS micelles nucleate on the polymer hydrophobic
sites, and the mobility of the AS head groups is not affected. But, for NaDEHP surfactant, it was found that PVP is little
effective in influencing the monomer–micelle equilibrium and no surfactant– polymer complex formed in the NaDEHP aqueous solution.
Received: 8 May 1996 Accepted: 14 August 1997 相似文献
995.
Application of multivariate curve resolution with alternating least squares (ALS) methods to second-order data from capillary electrophoresis diode array detector (CE-DAD) is shown. Second-order data are easily obtained by setting individual data matrix of CE run one in top of the other. Initial qualitative solutions obtained by evolving factor analysis can be further optimized by simultaneous analysis of multiple electrophoresis run data with ALS regression. Quantification is achieved by the comparison of the analyte peak areas with that of pure standards. During the ALS regression procedure, the following constraints were applied: (i) both concentrations and unit pure spectra of the resolved components must be positive; (ii) elution profiles have an unimodal shape; (iii) correspondence exists between common species in the different data matrices; (iv) the pure spectrum of each species is the same in all runs where it is present. The above methods were applied for the determination of dinitrotoluene (DNT) isomeric compounds in overlapping peaks from CE. 相似文献
996.
Cheng Chu Zeng Li Ming Hu Jia Zeng Ru Gang Zhong College of Life Science & Bioengineering Beijing University of Technology Beijing China 《中国化学快报》2007,18(2):130-132
The anodic oxidation of caffeic acid in the presence of acetylacetone or methyl acetoacetate in aqueous solution has been studied by cyclic voltammetry and controlled-potential electrolysis techniques. The result showed that caffeic acid was oxidized to the corresponding o-benzoquinone, which underwent further Michael-addition with acetylacetone or methyl acetoacetate to produce caffeic acid derivative 3,4-dihydroxy-6-(1-acetylacetone)-yl cinnamic acid 4a or 3,4-dihydroxy-6-(1-acetyl-methylacetate)-yl cinnamic acid 4b. 相似文献
997.
Mass spectrometric identification and characterization of steroids using electrospray ionization and tandem mass spectrometry has advantages in drug testing and doping control analysis attributable to limitations of gas chromatography followed by electron ionization mass spectrometry. Steroids with an androstadiene-17beta-ol-3-one nucleus and double bonds located either at C-1 and C-4, C-4 and C-9, or C-4 and C-6 were used to determine characteristic fragmentation pathways. Diagnostic dissociation routes are proposed using deuterium labeling, MS3 experiments, and analyses of structurally closely related compounds. Steroids such as boldenone (androst-1,4-diene-17beta-ol-3-one) produced characteristic product ions at m/z 121, 135, and 147. Compounds with double bonds at C-4 and C-9 generated abundant product ions at m/z 145 and 147. Conjugated double bonds at C-4 and C-6 gave rise to an intense and characteristic signal at m/z 133. Stereochemical differentiation between 5alpha- and 5beta-isomers of androstan-17beta-ol-3-ones was possible because of significant differences in relative abundance of product ions generated by elimination of acetone from alpha,beta-saturated 3-keto steroids. 相似文献
998.
用化学还原法制备了NiB、NiB/Al2O3和NiBSm/Al2O3三种催化剂,它们都呈非晶结构.用等离子耦合发射光谱仪(ICP)对催化剂组分进行了分析,采用差示扫描量热法(DSC)对三种催化剂进行了热稳定性分析.结果表明,载体的引入使非晶态NiB合金的体相组成中B的含量降低.将非晶态NiB合金负载到γ-Al2O3上,可以明显改善非晶态合金的热稳定性,少量Sm可以进一步提高晶化温度.晶化激活能数据亦表明了载体和Sm对非晶结构具有良好的稳定作用.载体和Sm可能通过不同的作用提高了非晶态合金的热稳定性. 相似文献
999.
A novel chemiluminescence (CL) flow system for the determination of quinine is described. It is based on the direct chemiluminescence reaction of quinine and cobalt(III) in sulfuric acid medium. The unstable Co(III) was on-line electrogenerated by constant-current electrolysis. The chemiluminescence intensity was linear with a quinine concentration in the range of 0.1-100 mug ml(-1). The determination limit was 3.3x10(-8) g ml(-1). The whole process could be completed in 1 min. The proposed method is suitable for automatic and continuous analysis, and has been applied successfully to the analysis of quinine in pharmaceutical preparation. 相似文献
1000.
[reaction: see text] Silver iodide catalyzed the three-component coupling of aldehyde, alkyne, and amines to generate propargylic amines with high efficiency in water. The silver-catalyzed reaction is especially effective for reactions involving aliphatic aldehyde. No additional cocatalyst or activator is required. 相似文献