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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

葛月琴1,王迪1,汤立军1,侯淑华1,李育龙2   

  1. 1. 渤海大学化学学院 2. 中国农业科学院农产品加工研究所
  • 收稿日期:2026-05-07 修回日期:2026-06-10 出版日期:2026-06-15 发布日期:2026-06-15
  • 通讯作者: 侯淑华 E-mail:housh@buaa.edu.cn
  • 基金资助:
    国家自然科学基金(批准号:22005038)资助

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

GE Yueqin1, WANG Di1, TANG Lijun1, HOU Shuhua1*, LI Yulong2*   

  1. 1. College of Chemistry,Bohai University 2. Institute of Food Science and Technology, Chinese Academy of Agricultural Sciences
  • Received:2026-05-07 Revised:2026-06-10 Online:2026-06-15 Published:2026-06-15
  • Supported by:
    Supported by the National Natural Science Foundation of China(No.22005038)

摘要: 本文设计合成功能化共价有机框架探针COF-TPA,实现对HS-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)上面得到新型的探针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,该探针可以在纯水中对HS-呈现出明显的荧光增强响应,避免传统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它阴离子的干扰,具有较宽的pH(5~13)检测范围,检出限为2.62×10-7 mol/L. 结果表明,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-的测定均展现了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.

关键词: 共价有机框架, 荧光探针, 硫化氢

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.

Key words: Covalent organic framework, Fluorescent probe, H2S

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