Li Lin, Ding Yilei, Zhang Chun, Xian Haiyu, Chen Shuoran, Dai Guoliang, Wang Xiaomei, Ye Changqing
School of Materials Science and Engineering, Jiangsu Collaborative Innovation Center of Technology and Material of Water Treatment, Suzhou University of Science and Technology, Suzhou, 215009, P. R. China.
School of Chemistry and Life Sciences, Suzhou University of Science and Technology, Suzhou, 215009, P.R. China.
J Phys Chem B. 2022 May 5;126(17):3276-3282. doi: 10.1021/acs.jpcb.2c00928. Epub 2022 Mar 29.
Detection of magnesium ion has been of great significance considering its critical physiological activities. Herein, we report ratiometric fluorescence detection of Mg with high sensitivity and selectivity based on triplet-triplet annihilation (TTA) upconversion for the first time. Crown-ether functionalized anthracene derivatives were synthesized, which bifunctionally acted as not only annihilators to construct TTA upconversion systems but also the recognition probes for Mg based on the photoinduced electron transfer (PET) mechanism. Their photophysical properties with the absence and presence of Mg were comprehensively studied. It was found that solvents strongly influenced the photophysical properties and Mg-responsiveness. TTA upconversion systems with PtOEP as the sensitizer were further established and investigated. It turned out PtOEP/9-AEC in DCM exhibited an excellent linear relationship ( = 0.9979) between the intensity ratio (the integrated upconverted luminescence intensity () over the integrated downshifted phosphorescence intensity (), /) and the concentration of Mg under the excitation of 532 nm with a limit of detection value of 2.52 μM and a high selectivity to Mg. This work opened a new perspective of designs and applications of TTA-upconversion-based ratiometric fluorescence for ion detection.
鉴于镁离子重要的生理活性，其检测具有重大意义。在此，我们首次报道了基于三重态-三重态湮灭（TTA）上转换的高灵敏度和高选择性的镁离子比率荧光检测方法。合成了冠醚功能化的蒽衍生物，其具有双重功能，不仅作为湮灭剂构建TTA上转换体系，还基于光致电子转移（PET）机制作为镁离子的识别探针。全面研究了它们在有无镁离子情况下的光物理性质。发现溶剂对光物理性质和镁离子响应性有强烈影响。进一步建立并研究了以PtOEP作为敏化剂的TTA上转换体系。结果表明，在532 nm激发下，二氯甲烷中的PtOEP/9-AEC在强度比（上转换发光积分强度（）与下移磷光积分强度（）之比，/）和镁离子浓度之间呈现出良好的线性关系（ = 0.9979），检测限为2.52 μM，对镁离子具有高选择性。这项工作为基于TTA上转换的比率荧光离子检测的设计和应用开辟了新的视角。
