Briggs-Rauscher化学振荡论文：四氮杂大环镍配合物催化Briggs-Rauscher化学振荡反应的研究.docVIP

Briggs-Rauscher化学振荡论文：四氮杂大环镍配合物催化的Briggs-Rauscher化学振荡反应研究 【中文摘要】化学振荡是一种开放的、远离平衡的非线性反应系统,一定条件下可以自发地组织成时空有序结构,呈现出类似于生命特征的自组织现象。近年来,所发现的四氮杂大环金属配合物参与的化学振荡反应,引起了化学和生物工作者的重视。本文研究了两种四氮杂大环镍配合物(ClO4)2和(ClO4)2参与的Briggs-Rauscher化学振荡反应的振荡行为,L为5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四-4,11-二烯和TIM为2,3,9,10-四甲基-1,4,8,11-四氮杂大环十四-1,3,8,10-四烯。本文第一章介绍了作为非线性非平衡态的代表化学振荡反应简史,产生的基本条件以及常见的化学振荡体系,Briggs-Rauscher化学振荡反应研究现状和研究前景。第二章首先按文献合成四氮杂大环二烯镍(ClO4)2,运用红外光谱和元素分析等现代分析手段进行表征。然后以0.025mol/L的稀硫酸为介质,在冰浴条件下,建立K1O3-乙酰丙酮-H2O2-硫酸-(ClO4)2振荡体系；以0.02mol/L的稀硫酸为介质,同样在冰浴条件下,建立KIO3-乙酰乙酸乙酯-H2O2-硫酸-(ClO4)2振荡体系。详细研究了初始物浓度对振荡行为的影响,以及外添加物如：I-、Ag+等,和温度对振荡行为的影响。结果表明,这两个系统振荡过程中,I-浓度是化学振荡的控制因素,过程中存在自由基步骤,振荡周期(tp)与大环二烯镍和双氧水的浓度(一定浓度范围)有关。第三章按文献方法合成四氮杂大环四烯镍(ClO4)2,采用红外技术和元素分析对目标产物进行表征。以0.15mol/L的硫酸作介质,15±0.5℃温度下,建立KIO3-乙酰乙酸乙酯-H2O2-硫酸-(ClO4)2振荡体系。对该系统进行详细研究,结果表明：该系统极易受初始物浓度,外添加物以及温度影响。振荡过程中I-浓度仍然是化学振荡的控制因素,过程中存在自由基步骤,振荡周期(tp)与大环四烯镍、双氧水和碘酸钾的浓度(一定浓度范围)有关。第四章基于NF(Noyes-Furrow)机理、实验过程中所得结论,结合NiL3+/ NiL2+, 3+/2+的氧化 【英文摘要】Chemical oscillator is an open system which is a typical example of nonlinear and nonequilibrium reaction. It can spontaneously organize to an ordered structure in time and space and shows some characteristics those are similar to self-organize of life. In recently years, a novel chemical oscillating reaction catalyzed by tetraazamacrocyclic complexes have attracted the attention of chemical and biology researchers. In this paper we have studied three chemical oscillators catalyzed by two kinds of macrocyclic nickel(Ⅱ) complex [NiL](ClO4)2 and [Ni(TIM)](ClO4)2, where L=5,7,7,12,14,14-hexemethy-1,4,8,11-tetraazacyclotetradeca -4,11-diene and TIM=2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene.The first chapter introduces the history of the oscillating reaction, the basic conditions of it takes place and several kinds of oscillating systems. We have also described the current situation and the research respect of the Briggs-Rauscher Oscillator.In the second chapter, the catalyst [NiL](C104)2,