褪黑素及其重要衍生物的化学发光和电致化学发光行为的研究

【作者】 黄福新；

【导师】 陈国南； 吴晓苹；

【作者基本信息】 福州大学 ， 分析化学， 2002， 硕士

【摘要】 本论文共分三章，包括文献综述、褪黑素及其重要衍生物的化学发光行为的研究、以及褪黑素及其重要衍生物的电致化学发光行为的研究。 第一章是文献综述部分，首先介绍褪黑素及其重要衍生物的概况，包括褪黑素的发现、褪黑素的生物合成和人工合成、褪黑素在机体内的生理代谢过程、褪黑素及其重要衍生物的生物学机能及其开发研究意义、以及褪黑素及其重要衍生物的测定方法的评述。然后分别阐述化学发光和电致化学发光的原理以及它们在某些吲哚类衍生物中的研究和应用。 第二章是以酸性高锰酸钾-甲醛的化学发光体系为基础，采用流动注射系统，详细研究了褪黑素及其重要衍生物（N-乙酰-5-羟色胺、5-甲氧基色胺、5-甲氧基吲哚-3-乙酸和6-羟基褪黑素）的化学发光行为。实验结果表明，褪黑素及其重要衍生物的化学发光行为与酸介质、pH值、流速、高锰酸钾浓度和甲醛浓度等因素有关，其中，甲醛是对褪黑素及其重要衍生物和酸性高锰酸钾的化学发光起明显的增强作用，由此分别建立了褪黑素及其重要衍生物的化学发光强度与浓度之间的线性关系。鉴于褪黑素在自然界、生物界中广泛存在和它在临床上的重要作用，本章建立了一种简便、快速测定实际样品中低含量褪黑素的新方法，该方法的特点是灵敏度较高、线性范围较宽、检测限较低。鉴于褪黑素及其重要衍生物的结构相似性，本章重点研究了褪黑素的化学发光光谱、荧光光谱和紫外吸收光谱来分别讨论褪黑素及其重要衍生物在酸性高锰酸钾和甲醛体系中的可能的化学发光反应机理。 第三章首次利用Ru（bpy）₃²⁺化合物对褪黑素及其重要衍生物的ECL行为进行研究。实验结果表明，在碱性的BR缓冲液中，褪黑素及其重要衍生物都有明显地增强Ru（bpy）₃²⁺的ECL，其增强的发光强度与施加的电位扫描方式和速度、缓冲液的类型、体系的pH值、Ru（bpy）₃²⁺的浓度等因素有关。经过条件的优化选择，褪黑素及其重要衍生物分别在不同的浓度范围内，发光强度与浓度成良好的线性关系或对数线性关系。鉴于褪黑素的独特的生物学机能和它在临床上的广泛应用，我们建立了一种测定实际商品药品中的低浓度褪黑素含量的方法，该方法的特点是容易实现、操作简便、仪器简单、体系稳定、结果可靠。鉴于褪黑素及其重要衍生物的分子结构的相似性，本文重点研究了在碱性BR缓冲体系中的R3比py)3＊一褪黑素的循环伏安特性、荧光光谱和电致化学发光光谱，首次提出褪黑素及其重要衍生物增强Ru比py)5h化合物ECL可能的电致化学发光反应机理。更多还原

【Abstract】 This paper consists of three chapters,which includes the review, the study on the chemiluminescence behavior of melatonin and its important derivatives, and the study on the electrogenerated chemiluminescence behavior of melatonin and its important derivatives.In chapter l,the review includes the finding of melatonin,the biosynthesis and artifical synthesis of melatonin,the physiological metabolism of melatonin,the biological function of melatonin and its important derivatives,the importance of further study of melatonin and its important derivatives, and the determination of melatonin and its important derivatives.Then the mechanism of chemiluminescence and electrogenerated chemiluminescence and their study and application in the indole derivatives are reviewed respectively.In chapter 2,the flow injection chemiluminescence behaviar of melatonin and its important derivatives(N-acetyl-5-hydroxytriptamine , 5-Methoxytriptamine , 5-Methoxyindolyl acetic acid , N- acetyl-5-Methoxy-6-Hydroxy-triptamine ) in acidic solution containing potassium permanganate and formaldehyde was studied in detail.It was founded that the chemiluminescence behaviar of melatonin and its important derivatives was largely depended on the acidic medium,the value of pH,the rate of carrier solution,the concentraction of potassium permanganate and formaldehyde,and that the chemiluminescence intensity of melatonin and its important derivatives was greatly enhanced in the present of formaldehyde.The linear relationship between the intensity of chemiluminescence and the concentraction for the melatonin and its important derivatives was established respectively under the optimum condition.As the wide existence of melatonin in the circles of nature or biology and its important application in clinic,a new simple rapid method has been developed for the determination of low concentraction melatonin in samples,this method has the advantages of high sensitivity,wide range of linear and low detection limit. The chemiluminescence spectrum,the fluorometric spectrum and ultraviolet absorbed spectrum of melatonin in acidic solution containing potassium permanganate andformaldehyde were studied in detail,and the mechanisms of cheminescence reaction of melatonin and its important derivatives in this system were also discussed.In chapter 3, the electrogenerated chemiluminescence behaviar of melatonin and its important derivatives in the presence of Ru(bpy)a +was studied firstly.lt was founded thatthe electrogenerated chemiluminescence intensity of tri(2,2’-bipyridine)ruthenium(II)Ru(bpy)32+ in alkaline solution was enhanced in the presence of melatonin and its important derivatives,and that the increasing intensity of electrogenerated chemiluminescence was depended on the scanning modes of the applied potential ,the rate of the scanning potential,the types of buffer solution,the value of pH,the concentraction of tri(2,2’-bipyridine)ruthenium(II)Ru(bpy)32+.Under the optimum conditions, the linear relationship or the logarithm linear relationship between the intensity of electrogenerated chemiluminescence and the concentraction for the melatonin and its important derivatives was attained respectively.As the widely biological function of melatonin and its important application in clinic ,a new method has been developed for the determination of low concentraction melatonin in samples,this method are more realizable,more operable,stable and reliable.The cyclic voltammetry.the electrogenerated chemiluminescence spectrum,and the fluorometric spectrum of melatonin and tri(2,2’-bipyridine)ruthenium(II)Ru(bpy)32+ in alkaline solution were studied in detail,and the mechanisms of electrogenerated cheminescence reaction of tri(2,2’-bipyridine)ruthenium(II)Ru(bpy)32+ in alkaline solution with melatonin and its important derivatives were proposed firstly.更多还原