【作者】 谭晓芳；

【导师】 吴芳英；

【作者基本信息】 南昌大学 ， 分析化学， 2006， 硕士

【摘要】 由于阴离子在生命科学、药物领域、化学催化、环境等方面起着重要的作用和影响，近年来，阴离子的研究引起了相关领域科研工作者的高度重视。阴离子的配位研究包括阴离子识别和阴离子传感两个过程。识别与传感阴离子的关键是设计合理的主体分子，主体分子由识别基团和信号报告基团组成。当阴离子与识别基团结合时，改变了信号报告基团的微环境，表现出吸收光谱或荧光光谱的变化，从而实现阴离子的光化学传感。 本论文合成了一系列8-羟基喹啉偶氮衍生物主体，通过紫外一可见分光光度法及荧光光谱法研究了其与多种阴离子的相互作用，建立了灵敏度高、选择性好并能裸眼检测或荧光传感阴离子的新体系。全文分五章，其主要内容如下： 第一章简要介绍了超分予化学、分子识别的概念，阴离子研究的意义及现状、阴离子的结构特征及识别受体设计的一般原则。对近六年来国内外有关阴离子生色及荧光化学识别与传感文献进行了简要的评述，在此基础上提出本论文的构想。 第二章主要阐述了设计合成的一系列8-羟基喹啉偶氮类衍生物的合成路线，包括5-（8-羟基喹啉）偶氮-4′-苯（BAZQH）、5-（8-羟基喹啉）偶氮-4′-对二甲氨基苯（DMABAZQH）、5-（8-羟基喹啉）偶氮-4′-甲基苯（MBAZQH）、5-（8-羟基喹啉）偶氮-4′-氰基苯（CNBAZQH）、5-（8-羟基喹啉）偶氮-4′-硝基苯（NBAZQH）。借助核磁仪将它们进行了结构表征，并运用紫外-可见光谱法研究主体分子与阴离子的相互作用以获取阴离子识别与传感的信息。 第三章应用吸收光谱法研究了主体分子BAZQH与阴离子间的相互作用，在BAZQH的乙腈溶液中，AcO^-、F^-、H₂PO₄^-均能诱导主体分子的吸收光谱发生显著的变化，观察到溶液由无色变成红色，从而可裸眼检测，然而该主体未能选择性识别阴离子。 为实现阴离子识别的选择性，试图改变8-羟基喹啉-偶氮苯上的取代基团，调节取代基给电子能力的大小，分别合成了-N（CH₃）₂、-CH₃、-CN、-NO₂四种取代化合物，由吸收光谱实验所得信息可知：DMABAZQH、MBAZQH均能独特性识别F^-，而对其它的阴离子却无响应，故可应用于F^-选择性识别研究中。 第四章为了拓展喹啉偶氮主体的应用空间，将金属配合物应用于阴离子的识别研究中。由于8-羟基喹啉是金属的广络试剂，筛选出Ni²⁺、Co²⁺等金属离子的稳定配合物，并研究了其与阴离子的相互作用，建立了HSO₄^-、H₂PO₄^-选择性识别的新体系。 考察了CNBAZQH-Ni²⁺配合物的光谱特性并将其应用于阴离子识别研究中。研究结果表明，Ni²⁺金属配合物可传感不同的阴离子，但对HSO₄^-具有独特的光谱响应，据此建立了选择性识别HSO₄^-新体系，并探讨其作用机理。更多还原

【Abstract】 Anion coordination research has recently been a hot topic of supramolecular chemistry because of the important role in a wide range of chemical and biological processes, and considerable attention has been focused on the design of host molecules that can recognize and sense anion species selectively through optical responses. Colorimetric and fluorescent detection and sensing are widely used either owing to the low cost or lack of expensive equipment or its high sensibility as a versatile tool in analytical chemistry, biochemistry, cell biology.The interaction between a series of hosts with anions were investigated via colorimetric detection and fluorescent spectroscopy. This thesis consists of five chapters as follows:1. The development of anion recognition in the past six years was briefly reviewed which contented: some basic concepts such as supramolecular chemistry, anion recognition, the colorimetric and fluorescent sensors for anions.2. A series of 5-（8-hydroxyquinoline）-azo-4’-substituted phenyl derivatives were synthesized and characterized by ¹H NMR, Their sensing of anions were explored using UV-vis spectroscopy or fluorescence spectroscopy.3. The interactions between artificial hosts and anions such as AcO^-, F^-, H₂PO₄^-, Cl^- and Br in acetonitrile were investigated by UV-vis spectroscopy. Results indicated that hydrogen-bonding complexes were formed between hosts and anions, which induced remarkable color change. It was found that the selectivity of hosts to anions could be efficiently tuned by substitution at the phenyl moiety. 5-（8-hydroxyquinoline）-azo-4’-methyl phenyl （MBAZQH） was capable of selectively binding fluoride anion over other anions. A 1:1 model complex was formed between MBAZQH and fluoride. The solution of MBAZQH turned red from colorless and a new absorption band peaked at 508 nm appeared. The association constant of MBAZQH-F^- complex was 2.5×10⁴ mol^-1 L. However, no obvious color changes were observed upon addition of one equivalence of other anions such as AcO", H₂PO₄^-, Cl^- and Br^-. This selective colorimetric assay for fluoride was developed.4. A 1:1 model complex between CNBAZQH and nickel ion was formed and the association constant of CNBAZQH-Ni²⁺ was 9.2×10⁶ mo^-1 L. The metal-ligand complex of CNBAZQH-Ni²⁺ was demonstrated to selectively sense HSO₄^- over other anions such as AcO^-, F, H₂PO₄^-, Cl and Br^- by using naked-eye colorimetric assay. The complex exhibits the remarkable color change from red to colorless upon introducing HSO₄^- in acetonitrile. The mechanism was proposed that the competitive binding occurred between HSO₄^- and ligand更多还原