白光发射超分子体系的限域构筑及高维比率发光识别

Recently high performance photoluminescent (PL) probes have received much attention owning to their potential applications in quality inspection and environment monitoring. Conventional PL probes, which rely on single or dual emissions responsive to analyte molecules, demonstrate limited sensitivity and selectivity because the single emissions can be easily affected by many non-analyte factors while the dual emissions can only offer single-ratiometric PL sensing. The purpose of this project is to develop trichromatic and white-light-emitting supramolecular composites as probes by encapsulating judiciously selected and optimal amounts of red/green/blue emitting modules into versatile porous carriers such as MOFs and mesoporous silica. The functional groups from the carriers and luminescent modules and the available spaces between them can be tuned to significantly improve the selectivity for the probes. Then the detection behaviors of the composites toward analytes will be comprehensive studied with the weak interaction sites of the composites as recognition sites, and the three chromophores as signaling subunits. As the emission peak height ratios of the three chromophores are very sensitive to the included analytes, a unique multidimensional ratiometric PL sensing method based on dual ratiometric photoluminescence can be established, which can effectively maximize the available information. Besides, turning the ratios can easily induce PL color change with white color as starting point, which can be utilized as a new strategy for the development of selective naked-eye colorimetric sensors. The sensing mechanisms will be proposed and the relationship of “individual structure design–composite assembly-detection properties” will be revealed. The objective of this proposal is the development of a new type of easily extended, economical, highly selective and sensitive, naked-eye observable PL sensors.

高效发光探针在分析质检、环境监测等领域应用前景广阔。目前该类研究多为单发射型探针，其检测易受干扰；少数为双发射型单比率探针，只可进行一维识别。本课题拟以MOFs /介孔二氧化硅等孔材料为载体，限域负载红、绿、蓝发光模块, 通过精准调控，组装制备三基色型白光发射超分子复合材料探针。通过载体孔道-发光模块间尺寸、功能团的协同提高对于待测物的选择性。以复合物与待测物种的弱作用位点为识别位点，以三个发光团为信号基团，利用三个发射峰强度比值易受待测物影响的特点，首先开发基于双比率发光的高维识别检测方法，放大检测信号实现对小分子/离子/生物分子等的高灵敏检测。其次检测时探针发光颜色多变，且变化以白光为起点，颜色对比度大，可开发易裸眼观测的色差型探针。最后研究相关机理，探索“单体设计-复合组装-检测性能”规律。目标是开发一类适宜推广的经济、高选择、高灵敏、可裸眼观测的发光探针。

高效发光探针在分析质检、环境监测等领域应用前景广阔。目前该类研究多为单发射型探针，其检测易受干扰；少数为双发射型单比率探针，只可进行一维识别。本课题以MOFs为载体负载发光模块制备三基色型白光发射复合材料，以其为探针/传感器实现对小分子/离子/生物分子等的高维比率识别检测。.采用多种方法将红/绿发光模块限域负载到蓝光载体孔道中，通过精准调控，形成二元/三元白光复合材料。设计合成了23个新的化合物、组装了227个二元复合物、42个三元白光复合物。明确了多元复合物的组装规律，解决了多种模块的同时负载、模块间的能量转移、基质-模块的尺寸协同、负载后复合物的稳定性等问题。.具体研究了其中18个化合物、147个二元复合物、13个三元白光复合物的检测传感性质和机理。以复合物与待测物的弱作用位点为识别位点，以三个发光团为信号基团，建立了高维（尤其是三维）比率发光识别检测的方法和体系。开发了10套针对各种挥发性有机物、硝基爆炸物、重金属离子、生物分子等的2维及3维识别检测密码，筛选了9个高选择性、高灵敏复合物探针。该类探针有易制备、自校正、放大检测信号、检测灵敏度高、可用一种探针对多种待测物进行区分检测的特点。检测时探针发光颜色多变，且变化以白光为起点，颜色差异大便于裸眼观测。初步解决了多元客体模块/载体的组装与识别传感能力协调问题，总结了“单体选择设计—复合物组装—识别检测性能调控”的规律，为白光复合材料探针的深入研究及应用提供了坚实的实验及理论依据。.在项目计划的化学物质识别传感的研究以外，进一步研究了机械研磨、温度、激发波长改变等刺激对复合物的发光影响；以及某些多元复合物体系的余辉性质，拓展了MOF-客体型复合物的性能和应用。.发表论文26篇，培养毕业硕士生6名，博士生2名。基本实现并在部分方面超过了申报时所设定的目标，达到了较好的研究水平。