有机/无机复合双光子荧光材料的电化学发光分析研究

The two-photon excited fluorescence (TPF) materials with unique physiochemical properties, have shown large potential applications in biology, medicine and micro-electronics. The electrochemiluminescence (ECL) ananlysis has a series of excellent features, such as simple equipment, high sensitivity and good selectivity, as well as analysis in situ and usefulness in studing reaction mechnism. Innovatively, this project will combine TPF materials with ECL analysis, and research the ECL property and applications of TPF materials, systematically. Using as-synthesized organic ligands (OL) possessing TPF property as reactants, the complexes will be prepared by reacting OL with metal ions, and the compsites prepared by combining OL with sulfides or selenides nanoparticles possessing ECL activity; Based on the test results of making TPF materials shining by using the electrochemical reaction or double electric layer function in stead of laser light source, and of exploring the shining mechnism by using low-temperature time-resolved spectroelectrochemistry and cyclic voltabsorptometry, the novel method will be set up for studying the preperty of the TPF materials; By using TPF materials as probe molecules and constructing biology sensors, a series of ECL analyses based on TPF materials will be built, whose sensitivity, selectivity and steady will be improved by modulating the component of the materials and optimizing test conditions. Significantly, the achievements of the project will innovate the work extent of the ECL analysis, and open up new application areas of the TPF materials.

双光子荧光（TPF）材料具有独特的物化性质，已在生物、医学、微电子等领域显示出巨大的应用潜力。电化学发光（ECL）分析方法具有装置简单、灵敏度高、选择性好，可以进行原位检测、研究反应机理等优点。本项目拟将二者结合起来，系统地研究TPF材料的ECL性质及应用：利用自行设计合成的TPF有机配体与金属离子反应合成配合物、与具有ECL性质的硫化物或硒化物纳米粒子结合制备复合物；利用电化学反应或双电层电场诱导作用代替激光光源使TPF材料受激发光，利用低温时间分辨光谱电化学法及循环伏吸法探讨TPF材料的发光机制，建立研究TPF材料性质的新方法；利用TPF材料作为探针分子，构建生物传感器，通过调整材料组成、优化实验条件，提高分析检测的灵敏度、选择性和稳定性，建立一类以有机/无机复合TPF材料为基础的ECL分析方法。此项目的实施将创新ECL分析的研究内容，开辟TPF材料新的应用领域。

本项目内容涉及有机/无机复合新材料制备及特性探讨，是生物、环境、能源及电子信息等领域的研究热点。非线性光学材料具有独特的结构及性质，电化学发光分析装置简单、灵敏度高，可以进行原位分析检测、研究反应机理。本项目将非线性光学材料、光电转换材料等与电化学发光分析结合起来，研究材料的制备方法及非线性光学性质、光电特性。设计合成了具有非线性光学性质的有机配体及其配合物，将所得配体或配合物与硫化物、硒化物等纳米材料复合，得到了多种有机/无机复合新材料。制备了一系列石墨烯/硫属复合材料，建立了以自催化反应为基础的导电聚合物/硫属复合材料的新颖制备方法，研究了所得材料的非线性光学性质、电化学发光性质，探讨了材料组成结构与性质的相关性。利用所得复合材料作为探针分子，进行生物显影，构建电化学发光传感器，进行生物分析，测定了多巴胺、谷胱甘肽、抗坏血酸、尿酸、DNA等生物分子。为了研究机理，利用晶体三极管的雪崩特性，设计、制作了一台脉宽可调、幅值可调的纳秒级脉冲信号发生器，探讨了所得有机/无机复合物的外场激发发光特性以及外场对电化学发光性质的影响。在项目实施过程中，应用领域由生物分析向能量存储与光电转换方向拓展，研究了所得材料的光电转换特性及超级电容性质，发现了所得复合材料的新颖性质和新的潜在应用领域。