Synthesis and Characterization of Triphenylamine-based HClO/ClO-Fluorescent Probes with D-π-A Structure
10.19756/j.issn.0253-3820.241211
- VernacularTitle:具有D-π-A结构的三苯胺类HClO/ClO-荧光探针的合成及其性能研究
- Author:
Yong-Qi TIAN
1
;
Fu-Zhuo LI
;
Xin-Yue YANG
;
Jing ZENG
Author Information
1. 新疆师范大学化学化工学院,乌鲁木齐 830054
- Keywords:
Triphenylamine;
Carbon-carbon double bond;
Hypochlorous acid/hypochlorite;
Fluorescent probe
- From:
Chinese Journal of Analytical Chemistry
2025;53(2):235-245,中插13-中插17
- CountryChina
- Language:Chinese
-
Abstract:
Hypochlorous acid/hypochlorite(HClO/ClO-)plays a key role in biological processes and is commonly used as a disinfectant in drinking water.However,excessive intake of HClO/ClO-can oxidize biomolecules like DNA,RNA,and proteins,causing organ damage.Diseases such as rheumatoid arthritis and Alzheimer's disease can also lead to overproduction of HClO/ClO-.Therefore,accurately detecting HClO/ClO-levels is crucial.In this study,an HClO/ClO-fluorescent probe,NC-TPA-PPh3,was designed and synthesized,with a triphenylamine core as the fluorescent unit,carbon-carbon double bonds as recognition sites,and a quaternary ammonium salt for mitochondria targeting,forming a D-π-A structure.This probe had a fluorescence lifetime of 3.71 ns and a fluorescence quantum yield of 0.51.Upon exposure to HClO/ClO-,the maximum fluorescence emission wavelength of the probe in DMSO/H2O(9∶1,V/V,pH=7.4)solution(20 μmol/L)shifted from 550 nm to 430 nm,with a fluorescence intensity increase of 35.7 times compared to blank probe solution,allowing for selective recognition of HClO/ClO-.The probe also exhibited a large Stokes shift(130 nm)and a low limit of detection(LOD)of 9.16×10-8 mol/L.Based on characterization by proton nuclear magnetic resonance(1H NMR),electrospray ionization-mass spectrometry(ESI-MS),scanning electron microscopy(SEM)and theoretical calculations,it was speculated that NC-TPA-PPh3 recognized HClO/ClO-through oxidative cleavage of the C=C bond in the probe,generating TPA-CHO with lower water solubility and a smaller conjugated structure.This disrupted the D-π-A structure,blocking intramolecular charge transfer(ICT),causing the fluorescence emission peak to blue-shift from 550 nm to 430 nm.Additionally,this process induced an aggregation-induced fluorescence effect,significantly enhancing the fluorescence intensity at 430 nm.
