一种基于“聚集诱导发光+激发态分子内质子转移”机制的苯并噻唑衍生物荧光探针及其对次氯酸根的识别
收稿日期: 2022-04-22
修回日期: 2022-07-17
网络出版日期: 2022-08-25
基金资助
国家自然科学基金(21878023); 国家自然科学基金(U1608222); 辽宁特聘教授支持计划资助项目
An “Aggregation-Induced Emission+Excited-State Intramolecular Proton Transfer” Mechanisms-Based Benzothiazole Derived Fluorescent Probe and Its ClO– Recognition
Received date: 2022-04-22
Revised date: 2022-07-17
Online published: 2022-08-25
Supported by
National Natural Science Foundation of China(21878023); National Natural Science Foundation of China(U1608222); Program for Distinguished Professor of Liaoning Province
合成了一种基于苯并噻唑衍生物的荧光探针(Z)-O-(2-(苯并[d]噻唑-2-基)-4-(2-氰基-2-(4-氰基苯基)乙烯基)-6-甲基苯基)二甲基硫代氨基甲酸酯(HBTY-N), 探针在Tris溶液(pH=7)中能够通过荧光“Off-On”变化, 高选择性识别ClO–. 向该探针中加入ClO–后溶液由无荧光变为橙红色荧光, 斯托克位移为235 nm, 且识别响应快速. 探针HBTY-N对ClO–的检测限为2.127×10–7 mol/L, pH适用范围为1~10, 并且有较强的抗干扰能力. 机理研究表明, 在ClO–的作用下, 探针通过“氧化去保护”机制释放出具有“聚集诱导发光+激发态分子内质子转移(AIE+ESIPT)”性质的荧光团(Z)-4-(2-(3- (苯并[d]噻唑-2-基)-4-羟基-5-甲基苯基)-1-氰基乙烯基)苄腈(HBTY), 量子产率由0变为42.88%. 此外, 探针HBTY-N可对活细胞中ClO–进行荧光成像, 且对细胞毒性低, 还可用于实际水样中的ClO–检测, 具有潜在的应用价值.
关键词： 聚集诱导发光+激发态分子内质子转移(AIE+ESIPT); ClO–; 细胞成像; 苯并噻唑; 荧光探针
刘梦 , 黄延茹 , 孙小飞 , 汤立军 . 一种基于“聚集诱导发光+激发态分子内质子转移”机制的苯并噻唑衍生物荧光探针及其对次氯酸根的识别[J]. 有机化学, 2023 , 43(1) : 345 -351 . DOI: 10.6023/cjoc202204054
A fluorescent probe (Z)-O-(2-(benzo[d]thiazol-2-yl)-4-(2-cyano-2-(4-cyanophenyl)vinyl)-6-methylphenyl) dimeth- yl cabarmothioate (HBTY-N) based on benzothiazole derivatives was synthesized. The probe can recognize ClO– with high selectivity through fluorescence Off-On change in Tris solution (pH=7). After adding ClO– to the probe, the probe solution changed from no fluorescence to orange-red fluorescence, the Stokes shift is 235 nm, and the recognition response is fast. The detection limit of the probe HBTY-N for ClO– is 2.127×10–7 mol/L, the applicable pH range is 1~10, and it has strong anti- interference ability. Mechanistic studies show that under the action of ClO–, the probe releases the fluorophore (Z)-4-(2- (3-(benzo[d]thiazol-2-yl)-4-hydroxy-5-methylphenyl)-1-cyanovinyl)benzonitrile (HBTY) with “aggregation-induced emission (AIE)+excited-state intramolecular proton yransfer (ESIPT)” properties through the “oxidative deprotection” mechanism, and the quantum yield changes from 0 to 42.88%. In addition, the probe HBTY-N can perform fluorescence imaging of ClO– in living cells with low cytotoxicity, and can also be used for the detection of ClO– in actual water samples, which has potential application value.
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