Asymmetric synthesis XXVII: Asymmetric catalytic trimethylsilylcyanation of aldehydes by novel Ti-chiral Schiff base complexes

Enantioselective catalytic trimethylsilylcyanations of aldehydes with 48% to 92% e.e. have been studied using the novel Ti-chiral Schiff base complexes. We have found that the catalyst led to high enantoselectivity when the molar ratio of the Schiff base 1 to Ti(O-i-Pr)₄ was 2:1.     

Preparation of AgBiVMoO/-Al2O3 Catalysts for the Partial Oxidation of Propane

A novel mixed sol method was developed for the preparation of supported catalysts. Analyses by means of XRD and BET show that a 40%AgBiVMoO/γ-Al2O3 catalyst prepared by this method possessed high specific surface area and high dispersion of the active phase. As a result, high acrylic acid selectivity of 8.5% was obtained when the catalyst was used in the reaction of propane partial oxidation to acrylic acid in a fixed-bed reactor.     

Amperometric detection of catecholamines with liquid chromatography at a novelly constructed prussian blue chemically modified electrode

A novel Prussian blue chemically modified electrode (CME) was constructed and characterized for liquid chromatography electrochemical detection (LCEC) of catecholamines. Both anodic and cathodic peaks could be obtained by monitoring at constant applied potential at anodic and slightly cathodic potential ranges (0.3-0.7 and -0.2-0.1 V vs. SCE), respectively. When arranged in a series configuration, using the modified electrodes as generating and collecting detectors, extremely high effective collection efficiencies of 0.91 (for norepinephrine) and 0.58 (for dihydroxyphenylacetic acid) were achieved in dual-electrode LCEC for catecholamines; and a linear response range over 3 orders of magnitude and a detection limit of 10 pg were obtained with a downstream CME as the indicating detector.     

Sequential transition States and the valley-ridge inflection point in the formation of a semibullvalene

[structure: see text] Two sequential transition states are calculated at the B3LYP/6-31G(d,p) level for the deazetization of 3b. The intrinsic reaction coordinate for loss of nitrogen passes through a transition state and then a valley-ridge inflection point and ultimately leads to the transition state for the Cope rearrangement of semibullvalene 4b. The energetic and geometrical consequences are discussed.     

贮氢材料电极循环寿命的定量预测定时放电半衰期法的应用

贮氢材料电极循环寿命的定量预测定时放电半衰期法的应用韩剑文，袁满雪，周作祥，赖城明（南开大学化学系天津３０００７１）关键词：贮氢电极，循环寿命，半衰期。前文￣［１］讨论了应用定终点电位放电半衰期法来预测贮氢材料电极循环寿命的问题。本文讨论如何采用定时...     

高效液相色谱检测Zn（Ⅱ）、Cd（Ⅱ）、Co（Ⅱ）、Pb（Ⅱ）、Ni（Ⅱ）、Cu（Ⅱ）、Hg（Ⅱ）

用双-(2-羟乙基)二硫代甲酸铵(HEDC)在反相液相色谱中作检测某些金属离子的衍生化试剂，HEDC的金属螯合物微溶于水，可直接水样注射于C18柱中进行检测，范围为0．006～10mg／L相对偏差1％～2％，检测波长254nm，金属汞的整合物在HPLC分析前进行浓缩富集检测限可低至0．06～25μg／L，相对偏差小于2％。     

Direct test of the Gaussian-chain model for treating residual charge-charge interactions in the unfolded state of proteins

The Gaussian-chain model for treating residual charge-charge interactions was critically tested by recent experimental pK(a) results for individual Asp, Glu, and His residues in the unfolded drkN SH3 domain. Predicted pK(a)'s were in good agreement with experiment. The clustering of Asp and Glu residues along the sequence was suggested to limit pK(a) shifts and contribute to the folding stability by destabilizing the unfolded state.     

Dynamic behaviour of river colloidal and dissolved organic matter through cross-flow ultrafiltration system

Through cross-flow filtration (CFF) with a 1-kDa regenerated cellulose Pellicon 2 module, the ultrafiltration characteristics of river organic matter from Longford Stream, UK, were investigated. The concentration of organic carbon (OC) in the retentate in the Longford Stream samples increased substantially with the concentration factor (cf), reaching approximately 40 mg/L at cf 15. The results of dissolved organic carbon (DOC) and colloidal organic carbon (COC) analysis, tracking the isolation of colloids from river waters, show that 2 mg/L of COC was present in those samples and good OC mass balance (77-101%) was achieved. Fluorescence measurements were carried out for the investigation of retentate and permeate behaviour of coloured dissolved organic materials (CDOM). The concentrations of CDOM in both the retentate and permeate increased with increasing cf, although CDOM were significantly more concentrated in the retentate. The permeation model expressing the correlation between log[CDOM] in the permeate and logcf was able to describe the permeation behaviour of CDOM in the river water with regression coefficients (r(2)) of 0.94 and 0.98. Dry weight analysis indicated that the levels of organic colloidal particles were from 49 to 71%, and between 29 and 51% of colloidal particles present were inorganic. COC as a percentage of DOC was found to be 10-16% for Longford Stream samples.     

Studies of the thermal degradation of acetaminophen using a conventional HPLC approach and electrospray ionization-mass spectrometry

The thermal degradation of acetaminophen is studied via conventional accelerated aging studies by initially thermally stressing the compound at temperatures between 160 degrees C and 190 degrees C and measuring the rate of decomposition by reversed-phase high-performance liquid chromatography. Rates of decomposition of the compound in the dry state and the activation energy for the process are determined and compared with previously published kinetic and thermodynamic data for the degradation of acetaminophen in solution. In addition, the thermal fragmentation of acetaminophen under electrospray ionization (ESI) conditions using an interface with a heated capillary inlet is studied and the apparent activation energy for this process also is characterized. A comparison of the data shows that acetaminophen is significantly more stable in the dry state than in solution. However, the gas-phase fragmentation of acetaminophen under ESI conditions occurs more readily than either dry- or solution-state degradation. Although the resulting electrospray fragmentation mimics the breakdown product that is formed when the compound undergoes either acid or base catalyzed hydrolysis in aqueous solutions, the mechanism that produces the fragment ion appears to involve a two-step process. Initially, the parent ion forms of the analyte are produced in the spray region of the interface followed by wall-catalyzed decomposition and re-ionization in the heated inlet capillary of the spectrometer.