β环糊精修饰金电极的制备及其在电化学分析中的应用.docVIP

南京航空航天大学硕士学位论文 摘 要 超分子化学在电化学方面的研究在近几年已开始兴起，并成为电化 学分析研究的前沿课题之一。环糊精作为第二代超分子的构筑体，其内 腔疏水而外部亲水，可以与许多有机、无机和生物分子形成包合物，从 而成为超分子化学工作者感兴趣的研究对象。目前，在研究环糊精在电 极表面的自组装行为、利用环糊精构造超分子器件等方面都取得了较好 的进展。本论文围绕环糊精超分子体系在电化学分析方面的研究，作了 以下研究工作: （1）用紫外-可见光谱分析了环糊精能与偶氮苯形成包合物。制备了 磺酰化-β-环糊精修饰金电极，利用环糊精的超分子特性研究了该修饰 电极在痕量测量中的应用。结果表明该电极灵敏性较高，且对环境无污 染。 （2）用光谱法研究了环糊精与对苯醌和蒽醌的相互作用，结果表明 在自由状态下两种醌都能和环糊精形成包结物，但对苯醌与环糊精的包 结比为 1：1，蒽醌与其包结比为 1：2，为进一步试验做好了准备。 （3）研究了一种制备环糊精修饰金电极的新途径。该方法操作较简 单，原料价格较便宜，周期较短。修饰电极上的环糊精能与偶氮苯发生 包合反应，表明该修饰电极可进一步用做环糊精自组装膜传感器的研究 与应用。 （4）运用第四章所制备的环糊精修饰金电极，讨论了环糊精修饰金 电极作为分子尺寸选择性传感器的可能性，说明只有尺寸小于环糊精空 腔尺寸的分子，才能够检测出来，所以该修饰电极可用于构筑分子尺寸 选择性传感器。 关键词：β-环糊精，金电极，偶氮苯，对苯醌，蒽醌，电化学分析 i β-环糊精修饰金电极的制备及其在电化学分析中的应用 ABSTRACT The chemists in electroanalysis had attached the importance to supramolecular chemistry recently. Cyclodextrins with interior hydrophobic and exterior hydrophilic environment can accommodate organic, inorganic and biological molecules, therefore they have been paid much attention by the researchers of supramolecular chemistry. At present, there are developments in the study on the CD self-assembly behavior on the electrode surface and the construction of supramolecular devices with CDs. In this thesis, following researches are carried out in electroanalysis of CD supramolecular chemistry: (1) The interaction between β-cyclodextrin and azobenzene was researched by Uv-vis spectroscopy, then fabricated the 6-OTs- β- cyclodextrin modified Au electrode and employed it to detect low concentration azobenzene. The results suggested that the detection sensitivity was high enough, and it was nonpoisonous. (2) From Uv-vis spectroscopy it can be seen that both benzoquinone and anthraquinone could be included by free β-cyclodextrin, but two β-cyclodextrin molecules only can included one anthraquinone molecules. (3) A new method for fabrication of β-cyclodextrin modified Au electrode was found. This method was easy, inexpensive and time saving. The cyclodextrin mondified on Au electrode