柱芳烃选择性识别及其在电化学研究中的应用研究

Pillar[n] arenes (PnAs) is new class of macrocyclic molecules, which are made up of hydroquinone unitis linked by methylene bridges at para- positions. Compared with calixarenes, PnAs are highly sensitive to guest molecules due to their symmetrical architectures and very rigid cavities. In this proposal, the corresponding pillarenes and their derivatives were designed and synthesized, and then complexation behaviors of pillarenes towards different guest molecules were further extensively studied in order to pillarenes screening tests and optimization of molecular recognition. Subsequently, the pillarenes hosts were modifield onto the surface of graphene oxide, and then to be fixed onto the surface of glass carbon electrode to prepare graphene-based pillarene modified electrodes for electrochemical analysis, electrodegradation of dyes and electroorganic synthesis etc. In addition, nano-metal catalysts were also introduced onto the surface of modified electrodes so as to significantly improve current response characteristics owing to supramolecular enrichment capability towards guests together with a cooperative effect of nano-metal catalysts, and kinetic, themodynamic data for electrocatalysis were also measured. In short, this project not only demonstrates new experimental principles for seeking more durable, accurate and selective sensors for organic guests, but also brings forward useful theoretical guidance for us.

柱芳烃是由对苯二酚或对苯二酚醚通过亚甲基桥在苯环的对位连接而成的一类具有刚性的圆柱型空腔环状低聚物, 因而与杯芳烃相比，其对客体分子具有更好的选择性。本项目拟合成系列柱芳烃超分子主体化合物及其衍生物，研究柱芳烃对模型分子诸如吡啶盐、吡虫啉、多巴胺、甲基蓝、二茂铁等有机药物或染料客体分子超分子识别特性，筛选出对特定客体分子具有选择性识别能力的柱芳烃主体化合物，均匀修饰到氧化石墨烯表面，以玻碳、Pt等电极为基体，制备具有超分子选择性识别功能的柱芳烃修饰电极，用于电化学分析、有机污染物的电化学降解和有机电解合成等研究领域。为提升修饰电极的电流响应特性，将金属纳米催化剂引入到修饰电极表面，测量在超分子识别与催化剂协同作用下，电化学催化反应的动力学与热力学特征数据，为开发性能稳定、灵敏度高、选择性好的针对有机小分子客体的传感器提供必要的理论和实验支撑

本项目成功合成系列柱芳烃超分子主体化合物及其衍生物，研究柱芳烃对有机小分子药物姜黄素、百草枯等超分子识别特性，筛选出对特定客体分子具有选择性识别能力的柱芳烃主体化合物，均匀修饰到氧化石墨烯表面，以玻碳、Pt等电极为基体，制备具有超分子选择性识别功能的柱芳烃修饰电极，用于电化学分析、超级电容器、锂离子电池等研究领域。为提升修饰电极的电流响应特性，将金属纳米催化剂引入到修饰电极表面，测量在超分子识别与催化剂协同作用下，电化学催化反应的动力学与热力学特征数据，为开发性能稳定、灵敏度高、选择性好的针对有机小分子客体的传感器提供必要的理论和实验支撑。此外，我们也进一步拓展了柱芳烃、环糊精等超分子复合材料在能源储存和转换，以及催化领域的应用。