Study of Dynamic Process of Reactions in Solution and its Application to Analytical Chemistry

过氧化物酶(POD)催化的鲁米诺化学发光(CL)用于检测Cu(II)催化氧化谷胱甘肽(GSH)过程中形成的H_2O_2。通过使用节肢动物 POD (ARP) 获得最大光发射，并且发现最大光发射取决于 GSH 的浓度：因此可以轻松测定微量的 GSH。研究了反胶束中金属催化鲁米诺氧化的化学发光机理及其在分析化学中的应用：指出水池在化学发光过程中起着重要作用。对涉及超氧自由基的诱导电子转移反应进行了动力学和机理研究，并开发了痕量 Cu (II) 和亚硝酸的新方法。金属卟啉的形成速率比开链配体的络合物形成速率慢几个数量级。反应速率的巨大差异是由于卟啉环的柔性较差，以及卟啉上的​​孤对电子对进入的金属离子的影响较小。采用分光光度法研究了金属离子形成变形卟啉的动力学机理，并通过X射线、核磁共振和激光光解等技术直接观察了所谓坐顶配合物的中间体。基于Cr(III)对3-甲基-2-苯并噻唑啉酮腙(MBTH)与N-乙基-N-氧化偶联的催化作用，建立了流动注射法测定痕量Cr(III)。 (2-羟基-3-磺基丙酰)-3-甲基苯胺(ADOS)。 MBTH在Cr(III)和H_2O_2存在下与ADOS反应生成浓色染料。EDTA和phen对Cr(III)的催化作用表现出很大的活化作用。利用该反应开发了一种灵敏的Cr(III)催化方法，并成功应用于汽车尾气颗粒物和参考河水中Cr的测定。利用H_2O_2在碱性介质中催化氧化原儿茶酸的反应，实现痕量Mn的灵敏柱后检测。通过金属Nitros-PAPS复合物与EDTA的配体取代反应，成功开发了停流FIA系统并同时测定Ni和Fe。还研究了金属-显色配体络合物与多羧基配体的配体取代反应的动力学方面以及附加配体的催化效果。研究了用新制备的 8-羟基喹啉衍生物萃取 Ga (III)，以获得有关疏水性 8-羟基喹啉部分中烷基取代基的空间效应的详细信息。阳离子三苯甲烷染料已用于离子的分离和测定，并结合溶剂萃取、沉淀、液-液界面吸附和膜过滤。对阳离子染料进行了平衡和动力学研究。根据实验结果设计并合成了三种阳离子染料 Less

The peroxidase (POD) -catalyzed luminol chemiluminescence (CL) was used for the detection of H_2O_2 formed during the catalytic oxidation of glutation (GSH) by Cu (II). The maximum light emission was obtained by using arthromices romosus POD (ARP) and was found to be dependent on the concentration of GSH : thus a minute amount of GSH can easily be determined. A CL emission mechanism in metal-catalyzed oxidation of luminol in reverse micelles and its application to analytical chemistry was studied : it has bee pointed out the water pool plays an important role in the CL process. Kinetics and mechanistic studies on induced electron-transfer reactions involving superoxide radicals were carried out and new methods for traces of Cu (II) and nitrous acid were developed. The rates of metalloporphyrin formation are several orders of magnitude slower than that of the complex formation of open-chain ligands. The great difference in the reaction rate is due to a less flexible porpyirin ring and a … More less accessible lone-pair electrone on the porphyrin for the incoming metal ions. The dynamic mechanism of metal ion into deformed porphyirins were studied spectrophotometrically and the intermediate of the so-called sitting-atop complex was directly observed by X-ray, NMR and laser photolysis etc. Flow injection method was developed for the determination of traces of Cr (III) based on its catalytic effect on the oxidative coupling of 3-methyl-2-benzothiazolinone hydrazon (MBTH) with N-ethyl-N- (2-hydroxy-3-sulfopropyr)-3-methylaniline (ADOS). MBTH reacts with ADOS to form an intense colored dye in the presence of Cr (III) and H_2O_2 EDTA and phen showed large activating effect on the catalysis of Cr (III). By using this reaction a sensitive catalytic method for Cr (III) was developed and the methods was successfully applied to the determination of Cr in Vehicle Exhaust Particulates and reference river water. Catalytic oxidation reaction of protocatechuic acid by H_2O_2 in an alkaline medium was used for the sensitive post column detection of trace amounts of Mn. Stopped-flow FIA system and the simultaneous determination of Ni and Fe was successfully developed by ligand-substitution reaction of metal Nitros-PAPS somplexes with EDTA.Dynamic aspects of ligand-substitution reaction of a metal-chromgenic ligand complex with a polycarboxilic ligand and the catalytic effect of an additional ligand were also studied. The extraction of Ga (III) with newly prepared 8-qinolinol derivatives has been studies to obtain detailed informations concerning the steric effect of the alkyl substiuents in the hydrophobic 8-quinolinol moiety. Cationic triphenylmethane dyes have been used for the separation and determination of ions coupled with solvent extraction, precipitation, adsorption at liquid-liquid interface, and membrane filtration. Equilibria and kinetic studies on the cationic dyes have been performed. Three cationic dyes were desighnd and synthesized from the experimental res Less