An “Aggregation-Induced Emission+Excited-State Intramolecular Proton Transfer” Mechanisms-Based Benzothiazole Derived Fluorescent Probe and Its ClO– Recognition

doi:10.6023/cjoc202204054

Abstract

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

Cite this article

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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Fig. & Tab. 11

Scheme 1. Synthetic route of probe HBTY-N

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

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)

Figure 4. Time-dependent fluorescence intensity changes of probe HBTY-N after adding ClO– (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)

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

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

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

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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