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

doi:10.6023/cjoc202204054

摘要/Abstract

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

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.

Key words: aggregation-induced emission (AIE)+excited-state intramolecular proton yransfer (ESIPT), ClO^–, cell imaging, benzothiazole, fluorescent probe

引用此文

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.

Meng Liu, Yanru Huang, Xiaofei Sun, Lijun Tang. An “Aggregation-Induced Emission+Excited-State Intramolecular Proton Transfer” Mechanisms-Based Benzothiazole Derived Fluorescent Probe and Its ClO^–Recognition[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 345-351.

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图/表 11

图式1. 探针分子HBTY-N的合成路线

Scheme 1. Synthetic route of probe HBTY-N

图1. 在不同Tris含量的EtOH溶液中HBTY的荧光光谱(插图: HBTY固体的荧光照片, λex=366 nm)

Figure 1. Fluorescence spectra of HBTY in EtOH solutions with different Tris contents (Inset: fluorescent photograph of HBTY solids, λex=366 nm)

图2. 在不同Tris含量的EtOH溶液中HBTY在601 nm处荧光强度变化及发射波长(内插图: HBTY在不同溶剂中的丁达尔现象照片, λex=366 nm)

Figure 2. Fluorescence intensity changes at 601 nm and emission wavelength of HBTY in EtOH solutions with different Tris contents (Inset: photograph of the Tyndall phenomenon of HBTY in different solvents, λex=366 nm)

图3. 探针HBTY-N在Tris溶液中分别加入1.5×10–4 mol/L的不同分析物的荧光光谱(λex=366 nm)

Figure 3. Fluorescence spectra of probe HBTY-N in Tris solution upon addition of 1.5×10–4 mol/L different analytes (λex=366 nm)

图4. 探针HBTY-N加入ClO–后荧光强度随时间的变化 (λex=366 nm, λem=601 nm)

Figure 4. Time-dependent fluorescence intensity changes of probe HBTY-N after adding ClO– (λex=366 nm, λem=601 nm)

图5. 干扰离子和ClO–共存时探针HBTY-N在Tris溶液中的荧光发射光谱(λex=366 nm, λem=601 nm)

Figure 5. Fluorescence emission spectra of probe HBTY-N in Tris solution when interfering ions and ClO– coexist (λex=366 nm, λem=601 nm)

图6. 不同pH值时HBTY-N和HBTY-N+ClO–在601 nm处荧光强度变化(λex=366 nm, λem=601 nm)

Figure 6. Uorescence intensity (601 nm) changes of HBTY-N and HBTY-N+ClO– at varied pH values (λex=366 nm, λem=601 nm)

图7. 逐渐增加ClO– (0~1.5×10–4 mol/L)时, 探针HBTY-N在Tris溶液中的荧光光谱(λex=366 nm)

Figure 7. Fluorescence spectra of probe HBTY-N in Tris solution upon incremental addition of ClO– (0~1.5×10–4 mol/L) (λex=366 nm)

图8. 荧光强度(601 nm)与ClO–浓度之间的线性关系(λex=366 nm, λem=601 nm)

Figure 8. Linear relationship between fluorescence intensity (601 nm) and ClO– concentration (λex=366 nm, λem=601 nm)

图9. 载有探针HBTY-N的MCF-7细胞被不同浓度的ClO–溶液处理后的共聚焦荧光图像

Figure 9. Confocal fluorescence images of MCF-7 cells containing probe HBTY-N treated with different concentrations of ClO– solution

图10. 在紫外灯下(a)或日光下(b)载有探针HBTY-N的试纸条暴露于含有不同浓度ClO–的溶液的荧光颜色变化图

Figure 10. Color changes of the probe HBTY-N test stripes after exposure to different concentrations of ClO– under UV light (a) or natural light (b)

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