Reaction Specificity of Metal Complexes at Reversed Micellar Interface and Its Application to Chemiluminescence Analysis

金属配合物反胶束界面反应特异性及其在化学发光分析中的应用

• 批准号: 10440223
• 负责人: FUJIWARA Terufumi
• 金额: $ 8.32万
• 依托单位: Hiroshima University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10440223/
• 关键词: Reverse Micelle; Coordination Equihbrium; Metal Complex; Chemiluminescence Reaction; Catalysis; Solvatochromism; Visible Absorption Spectrum; Stopped-Flow Spectrophotometer

In recent years, there has been an increasing interest in developing the numerous analytical applications of surfactant micellar systems that have the ability to concentrate and to compartmentalize within their distinct microstructured regions compounds of different nature. For chemiluminescence (CL) measurements, we have used a reversed micellar system as a medium, which provide a unique and versatile reaction field. The center of a reversed micellar core is filled with water surrounded by surfactant polar heads. We have pointed out that a surfactant-water interface of the reverse micelle could play a significant role in the CL reaction processes with metal complexes: At the reversed micellar interface, metal ions are produced transiently from the dissociation of metal complexes and then immediately catalyze the CL reaction in the aqueous phase.In order to enhance and/or improve the analytical performance of this method based on the reversed micellar-mediated CL reaction, there has be … More en a great need to understand the reaction specificity of metal complexes at the reversed micellar interface and further the unique function of reverse micelles as microreactors for analytical use. Thus, this research focused on the following : (1) Solvatochromic shifts of absorption spectra of (5, 10, 15, 20-tetraphenylporphyrinato)zinc(II) and 1, 4, 8, 11-tetramethyl-1, 4, 8, 11-tetraaza-cyclotetradecanenickel(II) dispersed as a probe in reversed micellar solutions and reversed micellar effects on the coordination equilibria of anions and water to the metal complexes. (2) Acid-dissociation of the zinc(II) complex with 5, 10, 15, 20-tetraphenyl-porphyine and formation of tris iron(II) complex with 2, 2'-bipyridine at the reversed micellar interface, investigated by using a stopped-flow spectrophotometer. (3) Reversed micellar mediated luminol CL reactions with the iron(III) complex of 8-quinolinol and the oxovanadium(IV) complex of acetylacetone. (4) Development of new flow-injection methods based on solvent extraction coupled on-line to the reversed micellar-mediated CL detection system for trace-level determinations of iron(II, III), iodide and/or iodine and atropine. Less

近年来，人们对开发表面活性剂胶束系统的众多分析应用越来越感兴趣，这些系统能够在其不同的微结构区域内浓缩和分隔不同性质的化合物。反胶束体系作为介质，提供了独特且多功能的反应场，反胶束核心的中心充满了水，周围有表面活性剂极性头。反胶束在与金属配合物的化学发光反应过程中发挥着重要作用：在反胶束界面，金属配合物解离瞬间产生金属离子，然后立即催化水相中的化学发光反应。 /或提高这种基于反胶束介导的化学发光反应的方法的分析性能，非常需要了解金属配合物在反胶束界面处的反应特异性以及反胶束作为分析用微反应器的独特功能因此，本研究重点关注以下内容：（1）（5,10,15,20-四苯基卟啉）锌（II）和1的吸收光谱的溶剂化变色位移。 4,8,11-四甲基-1,4,8,11-四氮杂-环十四烯镍(II)分散作为反胶束溶液中的探针以及反胶束对阴离子和水与金属配合物的配位平衡的影响 (2) 锌 (II) 配合物与 5, 10, 15, 20-四苯基卟啉的酸解离。使用停流分光光度计研究在反胶束界面处与 2, 2'-联吡啶形成三铁 (II) 络合物。 (3) 与 8-羟基喹啉的铁 (III) 络合物和乙酰丙酮的氧钒 (IV) 络合物进行反向胶束介导的鲁米诺 CL 反应 (4) 开发基于在线耦合的溶剂萃取的新流动注射方法。反胶束介导的化学发光检测系统，用于痕量测定铁（II、III）、碘化物和/或碘和阿托品。