席夫碱共价有机框架荧光探针选择性识别硫化氢及其应用

A Schiff-base Covalent Organic Framework Fluorescent Probe for Selective Recognition of HS⁻ and Its Application

摘要

设计合成了功能化共价有机框架探针COF-TPA， 并实现了对HS⁻的特异性识别. 将小分子三苯胺衍生物荧光探针通过EDC/NHS 活化的方法接枝到带羧基的共价有机框架(Tp-COOH COF)上， 制备了新型的探针COF-TPA. 借助COF骨架预组织的刚性聚集结构和HS^-的离子半径优势， 该探针可在纯水中对HS⁻呈现出明显的荧光增强响应， 避免了传统AIE探针对有机溶剂与浓度调控的依赖. 该探针能够排除食品中生物硫醇及其其它阴离子的干扰， 具有较宽的pH检测范围(5~13)， 检出限为2.62×10⁻⁷ mol/L. 实验结果表明， 该探针具有良好的线性范围、 低检出限和高灵敏度， 在环境水样与酒类基质中对HS⁻的测定均展现出良好的准确度与可靠性， 表明其在食品安全检测方面具有应用潜力.

Abstract

A functionalized covalent organic framework probe, COF-TPA, was designed and synthesized for the specific recognition of HS⁻. The small-molecule triphenylamine derivative fluorescent probe was grafted onto a carboxyl-containing covalent organic framework (Tp-COOH COF) via EDC/NHS activation, yielding the novel probe COF-TPA. By virtue of the preorganized rigid aggregate structure of the COF framework and the extremely small ionic radius of HS⁻, the probe exhibited a marked fluorescence enhancement response toward HS⁻ in pure water, thereby obviating the need for organic solvents and concentration adjustment that conventional AIE probes typically require. The probe was able to effectively eliminate interference from biothiols and other anions present in food matrices, featured a wide applicable pH range (5—13), and achieved a detection limit as low as 2.62×10⁻⁷ mol/L. The results demonstrate that the probe possesses a wide linear range, a low detection limit, and high sensitivity. Satisfactory accuracy and reliability were obtained for the determination of HS⁻ in environmental water samples and alcoholic beverage matrices, indicating its promising potential for application in food safety detection.

关键词

共价有机框架 / 荧光探针 / 硫化氢

Key words

Covalent organic framework (COF) / Fluorescent probe / H₂S

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基金资助

国家自然科学基金(22005038)