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

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，这些系统具有在其不同的微观结构区域内浓缩和划分不同性质的化合物的能力。对于化学发光（CL）的测量，我们使用了一个反胶束体系作为介质，它提供了一个独特的和通用的反应场。一个反向胶束核心的中心充满了水，周围是表面活性剂的极性头。我们指出，表面活性剂-水的反胶束界面可以在与金属配合物的CL反应过程中发挥重要作用：在反胶束界面上，金属配合物的解离会瞬间产生金属离子，然后立即催化水相中的CL反应。为了增强和/或改进这种基于反胶束催化CL反应的方法的分析性能，更需要了解金属配合物在反胶束界面上的反应特异性，并进一步了解反胶束作为微反应器在分析中的独特功能。因此，本研究的重点是：(1)（5,10,15,20 -四苯基卟啉）锌（II）和(1,4,8,11 -四甲基- 1,4,8,11 -四氮杂环十四烯镍（II）作为探针分散在反胶束溶液中的吸收光谱的溶剂变色，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)用止流分光光度计研究了锌（II）配合物与5,10,15,20 -四苯基卟啉的酸解离和三铁（II）配合物与2,2 '-联吡啶在反胶束界面上的形成。(3)与8-喹啉酚的铁（III）配合物和乙酰丙酮的氧钒（IV）配合物发生逆转胶束介导的鲁米诺CL反应。(4)建立了基于溶剂萃取在线耦合反胶束介导CL检测系统的新型流动注射方法，用于痕量铁（II， III）、碘化物和/或碘和阿托品的检测。少

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