高稳定性荧光环糊精框架材料的合成及其对消毒副产物的快速灵敏检测

Although the concentration of disinfection by-product (DBPs) in drinking water is low, it is seriously harmful to human health. However, the detection of DBPs in drinking water is still dominated by chromatography, mass spectrometry and other expensive instruments. Therefore, development of new sensing materials or technologies is urgent to realize rapid, sensitive and real-time detection. The green cyclodextrin-based metal-organic framework materials (CD-MOFs) demonstrate excellent reversible, selective adsorption and ion transport properties by means of molecular-size cavities and abundant microporous structures. However, the morphology and size of reported CD-MOFs are difficult to control and its hydrolytically stability is poor. Apart from utilization as adsorption materials, the wide applications have been hampered due to its poor multifunctionality. In this project, with amino acid-modified cyclodextrin used as fluorescent organic ligand, transition metal, lanthanide metal and metal nanocluster as metal centers, fluorescent CD-MOFs are synthesized by means of microwave, ultrasound and other auxiliary technology. According to the molecular structure of certain kind of DBPs, CD-MOFs with adjustable morphology and size, good hydrolytically stability and fluorescence properties will be designed. The research of this project will provide a new strategy for the controllable synthesis of high stability and multi-functional CD-MOFs tuned structures and customized functionalities, and contribute for establishment of a new sensitive and rapid detection method for different types of DBPs.

饮用水中消毒副产物（DBPs）浓度虽低却对人类健康具有严重危害，然而目前针对DBPs的检测仍以色谱、质谱等大型仪器检测为主。为实现快速、灵敏、实时检测，迫切需要开发新的传感材料或技术。基于环糊精的绿色金属-有机框架材料（CD-MOFs）借助分子尺寸的空腔及丰富的微孔结构，具有优异的可逆、选择性吸附及离子传输性能。然而，已报道的CD-MOFs形貌尺寸难以调控、水稳定性差，除作为吸附材料外，功能性不足，在实际环境中难以广泛应用。本项目拟采用改性环糊精作为荧光有机配体，借助微波、超声等辅助手段，与过渡金属、镧系金属、金属纳米簇等不同金属中心进行组装，根据各类DBPs的分子结构特征，设计合成系列形貌尺寸可调、具有良好水稳定性和荧光性能的CD-MOFs。通过本项目的研究，不仅为高稳定性且多功能CD-MOFs的可控合成提供新的思路，而且为建立针对不同类型DBPs的灵敏快速检测的新方法提供研究基础。

为了实现对饮用水中浓度低但危害大的消毒副产物的快速、灵敏、便携式检测，亟需开发基于新型传感材料的高效荧光分析方法。本项目首先开发了基于氨基酸修饰的环糊精及其衍生的非常规天然发光材料，提出了基于分子水平受限空间的增强簇集发光的新策略，提高了非常规发光材料的荧光量子产率并拓展了发光范围，实现了对卤代苯醌（检测范围0.1-10 ppm，检测限低至0.018 ppm）、卤代乙酸（检测范围0-50 ppm，检测限低至0.0075 ppm）等消毒副产物的可视化荧光分析，也为合成具有良好荧光性能的环糊精衍生材料（CD-MOF）提供了基础。此外，本项目以小分子交联策略解决了CD-MOF材料的水稳定性差的问题，为合成具有良好水稳定性的CD-MOF提供了解决方案。在此基础上通过负载染料探针的策略实现了对消毒过程中次生亚氯酸盐的高灵敏检测（检测范围0-15 ppm）。最后，本项目研发了手机支持的便携荧光检测设备，通过荧光图像分析，实现了对三氯乙酸类消毒副产物的可视化、便携检测。本项目研究推进了基于环糊精的各类衍生荧光材料对多种消毒副产物的荧光分析方的发展，对突破原位、高灵敏度、高特异性、可视化、便携检测痕量环境污染物检测方法的技术瓶颈具有重要的科学意义。针对研发新型荧光传感技术和便携式检测设备的持续创新是环境监测行业的需求和核心推动力，项目研究结果对荧光传感器的未来发展方向和应用前景具有一定的指导作用。