乙炔在铜/石墨阴极上的电催化还原加氢和电引发聚合

采用恒电位电解方法,分别在酸性和碱性两种饱和乙炔的水介质中,探讨了乙炔在铜/石墨阴极上(石墨上电沉积铜和石墨一铜层状嵌入物)的电催化还原和电引发聚合行为。电极对乙炔还原成乙烯表现较高活性和很高选择性(～99%,对气相产物)。对电极上活性组份Cu⁰(或Cu¹)与乙炔分子可能发生的σ—π活化作用和加氢方式进行了讨论。本文还运用现场与非现场Raman光谱技术,考察了在乙快还原的同时,电极表面上形成聚乙炔复盖物的情况,提出了一种电引发聚合机理,能较好地解释实验事实。     

Separation and determination of aconitine alkaloids in traditional Chinese herbs by nonaqueous capillary electrophoresis

An easy, rapid, and simple nonaqueous capillary electrophoresis (NACE) method was developed for the identification and determination of three aconitine alkaloids, hypaconitine (HN), aconitine (AN), and mesaconitine (MN) within 6 min. The most suitable running buffer was composed of 60 mM ammonium acetate, 0.5% acetic acid, and 15% acetonitrile (ACN) in methanol with a fused-silica capillary column (50 cm x 75 microm ID). In the concentration range 12.5-1000 mg/L the calibration curves reveal linear relationships between the peak area for each analyte and its concentration (correlation coefficients: 0.9997 for HN, 0.9999 for AN, and 0.9995 for MN). The relative standard deviations of the migration time and peak area of the three alkaloids were 0.13, 0.57, 0.33 and 2.87, 1.06, 3.49%, respectively. The method was successfully applied to determine the three alkaloids in two commonly used traditional Chinese herbal medicines, the recoveries of the three constituents ranging between 94.7-101.9% for HN, 98.3-102.3% for AN, and 98.1-104.6% for MN.     

C5烃中双环戊二烯过氧化物的分光光度测定

本报道了Ｃ５烃中双环戊二烯过氧化物（ＰＤＣＰＤ）快速准确的分析方法。在ＨＯＣ２Ｈ４ＯＣＨ３－Ｈ２Ｏ介质中，ＰＤＣＰＤ与ＫＩ反应生成Ｉ３＾－而Ｉ３＾－与ＰＤＣＰＤ的量成正比，在λｍａｘ＝３５２ｎｍ处可进行ＰＤＣＰＤ的光度测定，测定下限为３．２×１０＾－５ｍｏｌ／Ｌ，ＳＤ＝０．３４，ＲＳＤ＝１．４０％。     

Nonaqueous capillary electrophoresis for rapid and sensitive determination of fangchinoline and tetrandrine in radix Stephaniae tetrandrae and its medicinal preparations

A simple, rapid, and sensitive non-aqueous capillary electrophoresis procedure with head-column field-amplified sample stacking concentration for the analysis of fangchinoline and tetrandrine is established. Optimum separation and stacking conditions were obtained when the sample was injected at 8 kV for 50 s after preliminary pressure injection of ethanol (16.9 kPa) for 0.6 s and separated with the buffer containing 50 mM ammonium acetate, 0.5% (v/v) acetic acid, and 50% (v/v) acetonitrile in methanol medium at 24 kV applied voltage. The analytes were detected by UV at 214 nm. The two bisbenzylisoquinoline alkaloids can be separated within 6 min and quantified with high sensitivity. The detection limits were 0.30 ng mL(-1) for fangchinoline and 0.34 ng mL(-1) for tetrandrine, which indicated that the sensitivities were at least 1000-fold enhanced over those reported in the literature as obtained by UV detection. The method was applied to the analysis of fangchinoline and tetrandrine in Radix Stephaniae tetrandrae and its medicinal preparations with good results.     

Study of the effect of Cal-Red on the secondary structure of human serum albumin by spectroscopic techniques

The effect of Cal-Red on the structure of human serum albumin (HSA) was studied using Resonance light scattering (RLS), Fourier transformed Infrared (FT-IR) and Circular dichroism (CD) spectroscopic methods. The RLS spectroscopic results show that the RLS intensity of HSA was significantly increased in the presence of Cal-Red. The binding parameters of HSA with Cal-Red were studied at different temperatures of 289, 299, 309 and 319 K at pH 4.1. It is indicated by the Scatchard plots that the binding constant K decreased from 4.03 × 10⁸ to 7.59 × 10⁷ l/mol and the maximum binding number N decreased from 215 to 152 with increasing the temperature, respectively. The binding process was exothermic and spontaneous, as indicated by the thermodynamic analyses, and the major part of the binding energy is hydrophobic interaction. The enthalpy change ΔH⁰, the free energy change ΔG⁰ and the entropy change ΔS⁰ of 289 K were calculated to be −42.75 kJ/mol, −47.56 kJ/mol and 16.66 J/mol K, respectively. The alterations of protein secondary structure in the presence of Cal-Red in aqueous solution were quantitatively calculated from FT-IR and CD spectroscopy with reductions of -helices content about 5%, β-turn from 10% to 2% and with increases of β-sheet from 38% to 51%.     

Application of a modified simplex method to the multivariable optimization of a new FIA system for the determination of osmium

A methodology based on the coupling of experimental design and a modified simplex method is proposed for the optimization of a new flow injection-kinetic system for the spectrophotometric determination of Os (IV) with m-acetylchlorophosphonazo, which has for the first time been used as chromogenic reagent in the quantitative analysis of this element. An orthogonal array design is utilized to design the experimental protocol, in which six variables are varied simultaneously, and obtain the initial simplex using 25 experiments. A modified simplex method is applied to continuously optimize the data of the orthogonal array design; the search for optimum conditions of ¶6 variables using the modified simplex method required only 25 experiments. The efficiency and simplicity of the coupling of the experimental design and the modified simplex method are attractive for the development of new analytical methods. The method has been applied to the determination of Os (IV) in a refined ore as well as in a secondary alloy and provided satisfactory results.     

CE with Field-Enhanced Stacking for Rapid and Sensitive Determination of Umbelliferone,Rutin and Aesculetin in Prunella vulgaris

A new capillary electrophoresis procedure with field-enhanced stacking concentration for the analysis of umbelliferone, rutin and aesculetin in Prunella vulgaris is established for the first time. After optimization of the separation and concentration conditions, the three analytes can be separated within 6 min and quantified with high sensitivity. The method was useful for qualitative and quantitative analysis of umbelliferone, rutin and aesculetin in Prunella vulgaris with recovery of 97.5 to 105.3%.

     

钯的流动注射光度分析钯(Ⅱ)-金橙G-溴化十六烷基吡啶体系

本文建立了以金橙G(1-苯偶氮基-2-萘酚-6,8-二磺酸钠)为显色剂,在表面活性剂溴化十六烷基吡啶CPB增敏作用下测钯的新的流动注射分光光度法。方法简便、快速,具有良好的选择性。在数倍贵金属离子存在下,可不经分离直接在水相测定矿石中的钯的含量,结果令人满意。     

Determination of proteins by flow injection analysis coupled with the Rayleigh light scattering technique

A novel flow injection analysis (FIA) method with Rayleigh light scattering (RLS) detection was developed for the determination of protein concentrations. This method is based on the weak intensity of RLS of p-nitrohenzene-azo-3,6 disulfo-1-amino-8-naphthol-7-azo-benzene disodium salt (Amide Black-10B) which can be enhanced by addition of protein in weakly acidic solution. It has proved that the application of this method to quantify the proteins by using human serum albumin was available in real samples. In addition, this method is very sensitive (the determination limits are 0.11 μg/mL for human serum albumen (HSA) and 0.85 μg/mL for bovine serum albumen, BSA), simple, rapid and tolerance of most interfering substances. The FIA-RLS method was more stabile than the general RLS method and the average R.S.D. value of FIA-RLS less than general RLS. The effects of different interfering substances will be also examined. The amount of proteins in human serum sample was determined and the maximum relative error was no more than 3.00% as well as the recovery was between 94.9 and 105.9%.