摘要
化学振荡反应是一种典型的非线性非平衡态化学现象,从被科研工作者发现到现在已有一个多世纪的时间。化学振荡反应作为多学科的交叉点,与物理学,生命科学,等学科都有着紧密的联系,所以化学振荡在促进各个学科渗透交流方面,在理论研究方面以及拓展其实际应用方面都有着广阔的前景。现阶段,关于化学振荡反应的研究主要集中在,反应振荡器的设计,反应机理的探究,对化学振荡反应应用的拓展,以及加强化学振荡与计算机模拟的联系等方面。多年来,在化学振荡的领域中已经积累的很多的研究成果,比如发现了很多对振荡反应有催化作用的物质,除了过渡金属离子催化剂以外,四氮杂大环配合物可以作为振荡反应催化剂的发现,更是具有重大的意义。振荡反应的周期循环现象与自然界和人类社会中常见的周期现象是很相似的,而在振荡体系中具有生物酶卟啉环结构的四氮杂大环配合物的出现,使其与生物振荡有了相似的联系。对于生物振荡的体外模拟有着重大的意义。
本论文主要分为四个部分：
1化学振荡反应综述
介绍了关于非线性反应的基础知识,总结了化学振荡反应的发展简史,反应条件,反应类型等。尤其针对Belousov-Zhbaotinskii化学振荡反应进行了较为详细的介绍,对著名的FKN振荡机理和在此机理上建立的关于以四氮杂大环铜为催化剂,苹果酸为底物的振荡反应机理进行分析。同时介绍了现阶段化学振荡反应的相关应用及研究现状。
2酚类药物愈创木酚对四氮杂大环铜催化的B-Z振荡体系的干扰研究
首先根据文献的方法合成实验所需的的催化剂,并对目标产物进行红外光谱和元素分析等方法进行表征。以溴酸钠,D-L苹果酸,四氮杂大环二烯铜和硫酸四个组分建立稳定的B-Z振荡体系。探讨酚类化合物愈创木酚对该B-Z振荡体系的干扰,以及变化振荡体系的各组分浓度对干扰的影响。建立愈创木酚浓度对数与振荡幅度改变量AA之间的线性关系,以及愈创木酚浓度与振荡周期改变量AT之间的线性关系。并对愈创木酚在振荡体系中的干扰机理进行研究。
3酚类药物单宁酸对四氮杂大环铜催化的B-Z振荡体系的干扰研究
单宁酸对大环铜催化的苹果酸为底物的B-Z振荡体系有干扰。随着加入体系的单宁酸的量增加,对振荡体系的抑制时间以及振荡幅度的影响越明显。在一定浓度范围内,我们建立了单宁酸浓度对数与真多抑制时间At的线性关系,和单宁酸浓度对数与振荡幅度改变量△A之间的线性关系。探讨了体系各组分浓度的改变对干扰的影响,并提出可能的干扰机理。
4阴离子表面活性剂十二烷基苯磺酸钠SDBS胶束对大环铜催化的B-Z振体系的影响
研究了阴离子表面活性剂十二烷基苯磺酸钠(SDBS)对四氮杂大环铜催化的新型B-Z化学振荡反应的影响。当加入的SDBS在2.4×10-5mol-L-1-2.4x10-3mol·L-1浓度范围内时,SDBS的浓度与振幅改变量△A呈线性关系；而且SDBS的浓度在2.4x10-5mol·L-102.4mol·L-1范围时与振荡周期改变量△T也存在线性关系。并对SDBS胶束的形成机制及其对B-Z振荡反应的影响做了深入探讨。
Chemical oscillating reaction as a typical phenomenon of nonlinear and non-equilibrium has more than one hundred years of history. Chemical oscillation belongs to a field of crossed subjects, so it has some high relevnce with physics, bioscience, etc. subjects. There is a bright prospect in the research of chemical oscillation reaction in many aspects, such as, promoting the communication of each discipline, establishing stability theoretical and practical foundation. At this stage, the study of chemical oscillation focused on as follows:designing the oscillator, discussing the reaction mechanism, furthering application of chemical oscillation, and enhancing the cooperation between oscillator and computer simulation, etc. Now, many significant research results have been accumulated. More and more catalysts besides transition metal ions could be found and one of these flashpoints is the finding of tetraazamacrocyclic complex [CuL](ClO4)2as chemical oscillator catalyst.(The unsaturated ligand L in the complex [CuL](clO4)2is5,7,7,12,14,14-hexemethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene.) The cyclical phenomena of oscillation reactions and the common cyclical phenomena in nature and our human societies are very similar. We have established a stable B-Z oscillating system not only concerning tetraazamacrocyclic complexes (enzyme-like catalyst) as catalyst but involving intermediates of Krebs cycle as substrate. So it is great significance for mimic studies of biochemical oscillations in vitro. In addition, this Belousov-Zhbaotinskii oscillator could be applied to the aspect of determination. This analytical method equipped with a simple instrument and provides a high selectivity for accurate determination of metal ions, vitamins, polyphenols and surfactants. In this thesis, there are three substances which are applied to research their disturbance on the B-Z oscillating system. These three substances are phenolic compounds, such as guaiacol, tannic and anionic surfactant sodium dodecyl benzene sulphonate (SDBS). We could observe some characteristic responses in the B-Z oscillation system which was perturbed by the chemicals, such as the change of oscillation amplitude (AA), the time of oscillating inhibition (At) or the change of oscillation period (AT). Some relationships which between the characteristic responses and the concentration of chemicals injected into oscillating system could be established, and the interference mechanisms were also discussed.
This thesis mainly is divided into five parts:
1. The summary of chemical oscillating reaction This chapter review provides a brief introduction to the nonlinear reaction, the history of chemical oscillating reaction, reaction conditions, and types of oscillating reaction. The B-Z oscillating system is set forth in detail, and there are analyses about the famous FKN mechanism and the mechanism of novel oscillator which contains the macrocyclic complexes as catalyst and malic acid as substrate. Meanwhile, we also give some introductions about related applications and the current state of chemical oscillation.
2. Research about disturbance of guaiacol on teraazamacrochclic copper (Ⅱ) complex catalyzed B-Z oscillating system. According to literature, tetraazamacrocyclic copper (Ⅱ) complex [CuL](C104)2was synthesized. We used I.R spectrum and elemental analyses to identify the target product. The novel oscillating system could be established by sodium bromate, D-L malic acid,[CuL](ClO4)2and the sulfuric acid. We explored the interference of guaiacol on the stable oscillator and the influence of experimental variables on the system. There is a linear relationship between the change of the amplitude (AA) and the logarithm of concentration of guaiacol. When the different amount of guaiacol was injected to the oscillating system, the change of the oscillation period (△T) is linearly proportional. The probable mechanism involving the perturbation of guaiacol on the oscillating chemical system was also discussed.
3. Research about disturbance of tannin on teraazamacrochclic copper (Ⅱ) complex catalyzed B-Z oscillating system.
With macrocyclic complex [CuL](C104)2as catalyst and malic acid as the substrate, this B-Z system could be perturbed by tannin. The change of the amplitude (AA) and the time of oscillating inhibition (At) were more obvious with the increase of tannin injected to the oscillating system. There is a linear relationship between the change of the amplitude (△A) and the logarithm of concentration of tannin. There is other linear relationship between, the time of oscillating inhibition (△t) and the logarithm of concentration of tannin. We discussed the influence of experimental variables and the probable interference mechanism.
4. Research about disturbance of anionic surfactant SDBS micelle on teraazamacrochclic copper (Ⅱ) complex catalyzed B-Z oscillating system. This chapter discusses the influence of anionic surfactant SDBS on B-Z oscillating reaction which was catalyzed by a tetraazamacrocyclic copper (Ⅱ) complex. The oscillating system involves sodium bromate-malic acid [CuL](C104)2-sulfuric acid. Experiments show that formation of the SDBS micelles markedly affects the behaviour of the oscillating reaction. It is found that there is a linear relationship between the change in the oscillation amplitude (AA) and the concentration of SDBS, whereas the change in the oscillation period (△T) is linearly proportional to the SDBS concentration. The most likely mechanism that involves the formation of the SDBS micelles and the effects of the micelles on the oscillating chemical system can be understood through the hypothesis that the SDBS micelles are so negatively charged that they attract more [CuL]3+than [CuL]2+. The hypothesis was confirmed by UV-vis spectrophotometric measurements of a constant concentration of [CuL](ClO4)2in different concentrations of SDBS; as the SDBS concentration increased, the absorbance of [CuL](ClCO4)2increased while the maximum absorption wavelength for [CuL](ClCO4)2remained at502nm.
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