用动力学方法研究8,9-苯并-2-亚甲基-1,4,6-三氧螺[4,4]壬烷的聚合反应机理

根据在自由基引发剂存在下,8,9-苯并-2-亚甲基-1,4,6-三氧螺(4,4)壬烷(Ⅰ)可能存在的竞争反应,推导了动力学方程式。用红外光谱法测定了单体的消失速率和苯酞的生成速率。实验结果与推导动力学方程式相符。进一步证明了单体(Ⅰ)的增长反应由加成聚合和开环—异构化—加成这两个反应组成。这两个反应对总速率的相对贡献与单体浓度有关。得到了共聚物的结构。     

A metallo-capped polyrotaxane containing calix[4]arenes and cyclodextrins and its highly selective binding for Ca2+

A water-soluble nanometer-scale metallocapped polyrotaxane has been prepared by the inclusion complexation of azo-calixarenes with metallo-bridged bis(beta-CD)s, displaying highly selective binding for Ca(2+).     

Spectrofluorimetric determination of cysteine by 5-maleimidyl-2-(m-methylphenyl)benzoxazole

A new thiol weak-fluorescence probe, 5-maleimidyl-2-(m-methylphenyl)benzoxazole (MMPB), gives a highly fluorescence product in the presence of Cys. In this paper, MMPB has been developed for the fluorimetric determination of cysteine (Cys). At lambda(ex)/lambda(em) = 305.6/425.6 nm, the linear range is from 0 to 3.3 x 10(-7) mol l(-1) and the detection limit (sigma = 3) of 6.2 x 10(-10) mol l(-1). The main advantage of this method lies in the relative high selectivity compared with the methods using other N-substituted maleimide type of thiol reagents, in which 0.15-fold (molar ratio) of GSH is allowed and most of other amino acids at 100-fold (molar ratio) level had no obvious effect on the results. The proposed method has been applied to the determination of Cys in real samples.     

PA.FPNS: its synthesis and use in spectrophotometric determination of magnesium

A new polymeric chromogenic reagent PA.FPNS has been synthesized by condensing polyallylamine (PA) with 3-(4-formylphenylazo)-4,5-dihydroxynaphthalene-2,7-disulfonic acid (FPNS) and its properties studied. In alkaline media, PA.FPNS reacts with magnesium to form a water-soluble blue complex, whose absorption maximum is at 604 nm. The molar absorptivity (varepsilon) of the complex is 5.2 x 10(4)l mol(-1) cm(-1), which is four times that of the FPNS-Mg complex, and Beer's law is obeyed over the range 0-0.35 mug ml(-1) magnesium. Compared to the corresponding low-molecular-weight FPNS and other chromogenic reagents, PA.FPNS offers considerably improved sensitivity and selectivity for magnesium, which may be attributed to incorporating FPNS into a water-soluble polymer and the effect of the polymeric chain on the reaction microenvironment. Also, a simple and sensitive spectrophotometric method for the determination of magnesium has been developed and applied to water and human fluid samples with satisfactory results.