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

溶液中反应动态过程的研究及其在分析化学中的应用

• 批准号: 06303005
• 负责人: KAWASHIMA Takuji
• 金额: $ 6.72万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Co-operative Research (A)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06303005/
• 关键词: Reaction in Solution; Dynamic Process; Chemiluminescence; Caaalytic Effect; Solvent Extraction; Flow-injection Analysis; Ion Association Reaction; Structure of Metal Complexes in Solution

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

采用过氧化物酶（POD）催化鲁米诺化学发光法（CL）测定Cu（II）催化氧化谷胱甘肽（GSH）过程中产生的H_2O_2。通过使用arthromicesromosusPOD（阿普）获得最大光发射，并且发现其依赖于GSH的浓度：因此可以容易地测定微量的GSH。研究了反胶束中金属催化氧化鲁米诺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。对超氧阴离子自由基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。金属卟啉形成的速率比开链配体形成络合物的速率慢几个数量级。反应速率的巨大差异是由于较不灵活的卟啉环和 ...更多信息 对于引入的金属离子，卟啉上的孤对电子更不易接近。用X射线衍射法研究了金属离子形成卟啉的动力学机理，并直接观察了所谓的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-甲基-N-苯并噻唑啉酮腙（MBTH）氧化偶联反应的催化作用，建立了流动注射法测定痕量Cr（Ⅲ）的新方法。（2-羟基-3-磺丙基）-3-甲基苯胺（ADOS）。在Cr（III）和H_2O_2存在下，MBTH与ADOS反应生成深色染料，EDTA和phen对Cr（III）的催化作用表现出很大的活化作用。利用该反应建立了一种灵敏的催化测定Cr（III）的方法，并成功地应用于机动车尾气颗粒物和参考河水中Cr的测定。在碱性介质中，H_2O_2催化氧化原儿茶酸的反应用于痕量锰的柱后检测。利用金属Nitros-PAPS络合物与EDTA的配体取代反应，建立了停流流动注射分析体系，同时测定了Ni和Fe，并研究了多羧酸配体与金属显色剂络合物的配体取代反应动力学及外加配体的催化作用。本文研究了新合成的8-羟基喹啉衍生物对Ga（III）的萃取，得到了疏水性8-羟基喹啉中烷基取代基的空间效应的详细信息。三苯甲烷阳离子染料可用于溶剂萃取、沉淀、液-液界面吸附、膜过滤等离子体的分离和测定。对阳离子染料进行了平衡和动力学研究。根据实验结果设计合成了三种阳离子染料

项目成果

T.Saito, M.Okuyama, M.Minagawa, T.Kamidate, H.Watanabe, K.Haraguchi: "Solvent extraction of lanthanoids (III) and yttrium (III) with N-alkylcarbonyl-N-(4-chlorophenyl) hydroxylamines" Bill.Chem.Soc.Jan.67. 2107-2110 (1994)

T.Saito、M.Okuyama、M.Minakawa、T.Kamidate、H.Watanabe、K.Haraguchi：“用 N-烷基羰基-N-(4-氯苯基) 羟胺溶剂萃取镧系元素 (III) 和钇 (III)

T. Segawa: "Determination of peroxidase with a chemiluminescence reaction of homogentisic acid γ-lactone in nonaqueous media" Analytical Sciences. 11. 581-586 (1995)

T. Sekawa：“通过非水介质中尿黑酸 γ-内酯的化学发光反应测定过氧化物酶”，《分析科学》11. 581-586 (1995)。

S. Motomizu: "Ultra trace determination of phosphate ion based on liltration-dissolution and flow-through spectrophotometric measurement" Analytical Sciences. 11. 155-160 (1995)

S. Motomizu：“基于过滤溶解和流通分光光度测量的磷酸根离子的超痕量测定”分析科学。

T.Segawa: "Determination of peroxidase with a chemiluminescence reaction of homogentisic acid gamma-lactone in nonaqueous media" Analytical Sciences. 11. 581-586 (1995)

T.Sekawa：“通过非水介质中尿黑酸γ-内酯的化学发光反应测定过氧化物酶”分析科学。

T.Kamidate, A.Katayama, H.Ichihashi,H.Watanabe: "Characterization of peroxidases in luminol chemiluminescence coupled with copper-catalysed oxidation of cysteamine" J.Biolumin.Chemilumin.9. 279-286 (1994)

T.Kamidate、A.Katayama、H.Ich​​ihashi、H.Watanabe：“鲁米诺化学发光中过氧化物酶的表征与铜催化的半胱胺氧化”J.Biolumin.Chemilumin.9。