荧光环三唑鎓受体的合成及其水相介质中阴离子识别

项目名称： 荧光环三唑鎓受体的合成及其水相介质中阴离子识别

项目编号： No.21462027

项目类型： 地区科学基金项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 曹迁永

作者单位： 南昌大学

项目金额： 50万元

中文摘要： 水相识别阴离子化学传感器的设计与合成是超分子化学领域的研究热点与难点。含多作用位点大环阴离子受体由于好的预组织性与刚性有可能用于水相阴离子识别，但基于环三唑鎓受体例子尚不多，且有阴离子识别选择性差、缺乏易于检测信号单元等缺点。本申请项目拟开展具有荧光信号响应、能用于水相识别阴离子环三唑鎓的研究。通过点击反应/烷基化反应合成出系列含蒽荧光团、多个三唑鎓或三唑鎓/酰胺阴离子识别单元、空腔内径可调、柔性与刚性三唑鎓大环受体；通过荧光光谱法研究受体分子在有机溶剂及含水溶液中阴离子识别能力；通过核磁滴定、DFT计算及X-Ray单晶衍射研究其识别机理；理解受体分子大环效应与多重键合作用对提高阴离子水相识别能力的机制；揭示受体分子环构型及尺寸对提高阴离子识别选择性的影响。为设计合成能用于水相中识别阴离子三唑鎓阴离子荧光化学传感器提供实验依据及理论证明。

中文关键词： 三唑鎓；大环受体；阴离子识别；水相；荧光

英文摘要： Man-made receptors for anion sensing and recognition in aqueous solutions is a hot topic in suprachemistry. Some macrocyclic receptors with multiple binding sites have good affinity in aqueous solutions for their high degree of preorganisation and rigidity. However, triazolium-based macrocycles are still rare, with poor selectivity and sensitivity in aqueous solutions, and absent easily detectable signal moiety. In this regard, we decide to investigate a new type of macrocycle anions receptors by combining the triazolium donors with fluorescent subunits, which can sesing and recognition anions by fluorescent signals in aqueous solutions. With multiple triazolium (C-H)+ or amide/triazolium N-H/(C-H)+ as the anion binding sites, anthracene as the fluorescent unit, a series of soft and rigid triazolium cyclophanes with different size cavity will be synthesized. Their recognition ability toward various anions (F-, Cl-, Br-, I-,CN-, CH3COO-, HSO4-, H2PO4- and HP2O73-) in organic or aqueous solution will be investigated by emission spectra. Their binding mode, binding constant and bind mechanism will further be investigated by emission titration, 1H NMR titration, DFT calculation and X-ray crystal analysis. This project will provide new insight to design novel fluorescent chemosenors for anion recognition in aqueous solutions with high selectivity and sensitivity, and the design based on the present project can be further modified to construct more developed systems.

英文关键词： Triazolium;Macrocyclic receptors;Anions recognition;Aqueous solution;Fluorescence