新型聚集诱导发光型荧光探针的制备及其对钍、铀酰离子识别性能研究

Thorium and Uranium are important nuclear resources. Because of the widespread use of them and their toxic properties, the development of efficient analysis techniques for the determination of Thorium and Uranium are the essential links for their safe utilization and environmental monitoring. Based on the tetraphenylethylene as fluorophore, the present project focuses on the coordination of Thorium and Uranyl ion, combined with superior properties of fluorescent probes of aggregation-induced emission (AIE) to carry out the design of the molecular structure of fluorescent probes. The AIE fluorescent probes of Thorium and Uranyl ion will be synthesized, respectively. A new method for the preparation of the functional molecular devices of actinide metals would be established. In order to obtain the fluorescent probes with high selectivity, sensitivity and strong anti-interference ability, the selectivity, sensitivity, and quantitative analysis capability of these probes will also be researched by fluorescence spectroscopy. More importantly, the colorimetric recognition of Thorium and Uranyl ions will be carried out by AIE fluorescent probes to provide a more rapid, simple and intuitive analysis method for the determination of actinide ions. The relationship between the molecular structure and the recognition capability will be explored for revealing the coordination mechanism of actinide metal ions. By the end of this research, new aspects and ideas will be provided for improving and designing new probes, extraction agents, and adsorption materials for the actinide metals.

钍、铀是重要的核资源，鉴于其重要而广泛的应用性以及高危害性，发展高效的钍、铀分析技术是保障钍、铀资源安全利用和环境监测必不可少的环节。本课题拟针对钍、铀酰离子的配位特点，结合最新型的聚集诱导发光（AIE）型荧光探针的优越性质，基于具有AIE性质的四苯乙烯作为荧光团进行合理的结构设计；通过有机合成分别制备针对钍、铀酰离子识别的AIE型荧光探针，建立新型锕系金属功能分子器件的制备方法；并通过荧光光谱法研究探针对于钍、铀酰离子的选择性、灵敏度、定量分析能力等性能，以获得高选择性，高灵敏度和强抗干扰能力的荧光探针；更重要的是利用AIE型荧光探针的特点研究其对钍、铀酰离子的比色识别性能，在无需大型分析仪器的情况下为锕系金属离子的检测提供一种更快速、简便、直观的分析方法；深入研究分子结构与识别性能的关系，为理解锕系金属离子的配位机制，改进和设计新型锕系离子探针、萃取剂和吸附材料提供必要的实验数据。

本课题基于四苯乙烯结构的特殊聚集诱导发光性质，利用Suzuki偶联反应制备了一系列具有四苯乙烯结构的化合物物作为荧光传感器用于对钍、铀酰等金属离子的识别分析研究。传感器具有极好的选择性和抗干扰能力，可以在复杂条件下实现对目标金属的高效识别分析，同时由于聚集诱导发光性质，在无需光谱仪的情况下就能够通过明显的光信号变化实现对于目标金属的检测分析。其中TPE-2荧光传感器可以在紫外灯下高效实现对铀酰离子的比色识别，可视识别效果达到ppm级；TPE-3荧光传感器是首例报道的钍离子聚集诱导发光型荧光传感器，可以实现对ppb级钍离子的比色识别，论文发表以后被评选为该期Chem. Asian J.的封底文章。综上，本课题的研究极大简化了对于水溶液中钍、铀酰离子的检测分析过程，研究成果有望应用在环境样品中钍、铀酰的快速检测。