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DOI: https://doi.org/10.6023/A26060194

研究论文

单双取代荧光探针的合成及其对硫化氢的检测★

  • Liu Cong ,
  • Wang Yipei ,
  • Zhang Tianyu ,
  • Qin ,
  • Wenwu
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  • 兰州大学 化学化工学院 兰州 730000
★“纪念兰州大学化学学科创建80周年”专辑

收稿日期: 2026-06-10

  网络出版日期: 2026-08-25

基金资助

该项目得到了国家自然科学基金（21771092）的支持

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Synthesis of Mono/Di-Substituted Fluorescent Probes for Detection of H2S

  • 刘聪 ,
  • 王艺霈 ,
  • 张天宇 ,
  • 覃文武
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  • College of Chemistry and Chemical Engineering, Lanzhou University, lanzhou 730000

Received date: 2026-06-10

  Online published: 2026-08-25

Supported by

The project was supported by the National Natural ScienceFoundation of China (21771092).

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摘要

硫化氢（H2S）是一种高毒性气体污染物,其精准检测在环境监测、工业安全及生物医学领域具有重要意义。本研究设计合成了基于氟硼二吡咯(BODIPY)的单取代荧光探针SBODFN和双取代荧光探针DBODFN,用于H2S的检测。探针分子中2,4-二硝基苯基（DNP）通过强吸电子效应抑制分子内电荷转移（ICT）,导致初始荧光淬灭。H2S诱导醚键断裂释放羟基后,ICT效应恢复使荧光显著增强. DBODFN因扩展共轭结构表现出更强的ICT效应,其荧光发射（663 nm,红色）较SBODFN（593 nm,橘黄色）明显红移。定量分析表明,SBODFN在300~475 μmol/L范围内检测限为0.38 μmol/L,而DBODFN在更宽的150~650 μmol/L范围内检测限达0.20 μmol/L。两种探针均可作为固态荧光探针实现H2S可视化检测。最后,两种探针均在三种不同水样中完成了对H2S的定量检测,为环境水样中 H2S的可视化定量检测提供了简便有效的分子传感策略。

关键词： 荧光探针; 氟硼二吡咯; 单双取代; 硫化氢; 固体探针

本文引用格式

Liu Cong , Wang Yipei , Zhang Tianyu , Qin , Wenwu . 单双取代荧光探针的合成及其对硫化氢的检测★[J]. 化学学报, 0 : 26060194 -26060194 . DOI: 10.6023/A26060194

Abstract

Hydrogen sulfide (H2S) is a highly toxic gaseous pollutant. It is of significant importance to achieve precise detection of H2S in multiple fields including environmental monitoring, industrial safety, and biomedicine. The use of single probe for detecting H2S may lead to error due to the complex and changeable nature of the actual environment, while the synthesis of traditional dual probes requires more cost and time. BODIPY fluorophores exhibit excellent optical properties and multiple modification sites. Therefore, this study designed and synthesized mono-substituted fluorescent probe SBODFN and di-substituted fluorescent probe DBODFN based on BODIPY for the detection of H2S. In these probes, the 2,4-dinitrophenyl (DNP) group strongly suppressed intramolecular charge transfer (ICT) through its electron-withdrawing effect, resulting in initial fluorescence quenching. Upon H2S-induced cleavage of the ether bond to release the hydroxyl group, the restored ICT effect led to significant fluorescence enhancement. DBODFN exhibited a stronger ICT effect due to its extended conjugated structure, displaying a markedly red-shifted fluorescence emission (663 nm, red) compared to SBODFN (593 nm, orange-yellow). Both SBODFN and DBODFN exhibited rapid response times and excellent selectivity. SBODFN and DBODFN completely reacted with H2S within 36 min and 42 min, respectively. The detection of H2S by both SBODFN and DBODFN was not affected by other analytes including cations, anions, and small molecules. Quantitative analysis revealed that SBODFN had a detection limit of 0.38 μmol/L within the concentration range of 300-475 μmol/L, while DBODFN achieved a lower detection limit of 0.20 μmol/L across a broader concentration range of 150-650 μmol/L. The formation of SBODOH and DBODOH was confirmed by the comparison of UV-Vis absorption and fluorescence spectra, as well as by mass spectrometry. The energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of SBODOH (2.524 eV) was larger than that of DBODOH (2.233 eV), which was consistent with the experimentally measured emission wavelengths. SBODFN and DBODFN could serve as solid-state fluorescent probes for visual detection of H2S. Finally, SBODFN and DBODFN successfully achieved quantitative detection of H2S in three different types of water samples.

Key words： fluorescent probe; BODIPY; mono-/di-substitution; H2S; solid-state probes

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