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  

Synthesis and Characterization of Triphenylamine-based HClO/ClO^(-)Fluorescent Probes with D-π-A Structure

作　　者：田勇琪 李富卓 杨欣月 曾竟[1] TIAN Yong-Qi;LI Fu-Zhuo;YANG Xin-Yue;ZENG Jing(School of Chemistry and Chemical Engineering,Xinjiang Normal University,Urumqi 830054,China)

机构地区：[1]新疆师范大学化学化工学院,乌鲁木齐830054

出　　处：《分析化学》2025年第2期235-245,共11页Chinese Journal of Analytical Chemistry

基　　金：新疆维吾尔自治区自然科学基金项目(No.2022D01A95)资助。

摘　　要：次氯酸/次氯酸盐(HClO/ClO^(-))在各种生物过程中具有重要作用,常用于饮用水消毒,但过量摄入HClO/ClO^(-)会导致DNA、RNA和蛋白质等生物分子氧化,进而损伤人体器官;此外,类风湿性关节炎、阿尔茨海默病等疾病也会诱导HClO/ClO^(-)的过量产生。因此,准确、高效识别HClO/ClO^(-)与检测其浓度水平具有重要意义。本研究设计合成了以三苯胺基为荧光母体、碳碳双键为识别位点、季鏻盐为线粒体靶向基团且具有D-π-A结构的HClO/ClO^(-)荧光探针NC-TPA-PPh3。探针的荧光寿命为3.71 ns,荧光量子产率为0.51。在DMSO/H_(2)O(9∶1,V/V,pH=7.4)溶液中,当HClO/ClO^(-)存在时,20μmol/L探针的最大荧光发射波长从550 nm蓝移至430 nm,荧光强度比探针空白溶液增强了35.7倍,据此可以实现对HClO/ClO^(-)的选择性识别。此探针具有Stokes位移大(130 nm)和检出限低(9.16×10^(-8)mol/L)的优势。基于核磁共振氢谱(^(1)H NMR)、电喷雾质谱(ESI-MS)、扫描电子显微镜(SEM)和理论计算结果,推测探针NC-TPA-PPh3识别HClO/ClO^(-)时,ClO^(-)氧化断裂探针NC-TPA-PPh3结构中的C=C键,生成了具有更低水溶性和更小共轭结构的TPA-CHO。该过程不仅破坏了探针的D-π-A结构,阻断了分子内电荷转移(ICT)过程,引起荧光发射峰从550 nm蓝移至430 nm,还诱发了聚集诱导荧光效应,使430 nm处的荧光强度显著增强。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/H_(2)O(9∶1,V/V,pH=7.4)solution(20μmol/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(^(1)H 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.

关 键 词：三苯胺 碳碳双键 次氯酸/次氯酸根 荧光探针 

分 类 号：O65[理学—分析化学]