单双取代荧光探针的合成及其对硫化氢的检测★

doi:10.6023/A26060194

摘要/Abstract

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. 此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(BODIPY), 单双取代, 硫化氢, 固体探针

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 a 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 higher costs and time. Boron-dipyrromethene (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, boron-dipyrromethene (BODIPY), mono-/di-substitution, H₂S, solid-state probes

引用此文

刘聪, 王艺霈, 张天宇, 覃文武. 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, 2026, 84(8): 1283-1293.

Cong Liu, Yipei Wang, Tianyu Zhang, Wenwu Qin. Synthesis of Mono/Di-Substituted Fluorescent Probes for Detection of H₂S^★[J]. Acta Chimica Sinica, 2026, 84(8): 1283-1293.

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图/表 19

图1. SBODFN和DBODFN识别H2S机理图

Figure 1. Mechanism diagram for identifying H2S using SBODFN and DBODFN

图2. (a) SBODFN和(b) DBODFN在HEPES缓冲液中加入和没有加入H2S的荧光发射光谱

Figure 2. Fluorescence emission spectra of (a) SBODFN and (b) DBODFN before and after the addition of H2S in HEPES buffer

图3. 探针(a) SBODFN (593 nm), (b) DBODFN (663 nm)在HEPES缓冲液中加入不同浓度的H2S的时间依赖曲线

Figure 3. Time-dependent curves of (a) SBODFN (593 nm) and (b) DBODFN (663 nm) upon the addition of H2S at varying concentrations in HEPES buffer

图4. (a)探针SBODFN在HEPES缓冲液中与不同分析物反应36 min后在593 nm处的荧光强度; (b)探针DBODFN在HEPES缓冲液中与不同分析物反应42 min后在663 nm处的荧光强度

Figure 4. (a) Fluorescence intensity of SBODFN at 593 nm with the addition of different substances for 36 min in HEPES buffer; (b) Fluorescence intensity of DBODFN at 663 nm with the addition of different substances for 42 min in HEPES buffer

图5. 探针(a) SBODFN, (b) DBODFN在氙灯下持续照射1.5 h的光稳定性

Figure 5. Photostability of (a) SBODFN and (b) DBODFN under continuous irradiation of xenon lamp within 1.5 h

图6. (a)探针SBODFN在HEPES缓冲液中与不同浓度的H2S孵育36 min后的荧光发射光谱; (b)探针SBODFN在HEPES缓冲液中与不同浓度的H2S孵育36 min后在593 nm处荧光强度线性拟合图

Figure 6. (a) Fluorescence emission spectra of SBODFN upon the addition of H2S at varying concentrations for 36 min in HEPES buffer; (b) Linear fitting plot of fluorescence intensity at 593 nm for SBODFN incubated with H2S at varying concentrations for 36 min in HEPES buffer

图7. (a)探针DBODFN在HEPES缓冲液中与不同浓度的H2S孵育42 min后的荧光发射光谱; (b)探针DBODFN在HEPES缓冲液中与不同浓度的H2S孵育42 min后在663 nm处荧光强度线性拟合图

Figure 7. (a) Fluorescence emission spectra of DBODFN upon the addition of H2S at varying concentrations for 42 min in HEPES buffer; (b) linear fitting plot of fluorescence intensity at 663 nm for DBODFN incubated with H2S at varying concentrations for 42 min in HEPES buffer

图8. SBODFN在HEPES缓冲液中(a)在不同温度条件下与(b)在不同pH下H2S孵育36 min后593 nm处的荧光强度

Figure 8. Fluorescence intensity of SBODFN (593 nm) incubated with H2S for 36 min under (a) different temperature and (b) different pH in HEPES buffer

图9. DBODFN在HEPES缓冲液中(a)在不同温度条件下与(b)在不同pH下H2S孵育42 min后663 nm处的荧光强度

Figure 9. Fluorescence intensity of DBODFN (663 nm) incubated with H2S for 42 min under (a) different temperature and (b) different pH in HEPES buffer

图10. (a) SBODFN在HEPES缓冲液中与不同浓度的H2S孵育36 min后的紫外-可见吸收光谱; (b) DBODFN在HEPES缓冲液中与不同浓度的H2S孵育42 min后的紫外-可见吸收光谱

Figure 10. (a) UV-vis absorption spectra of SBODFN incubated with varying concentrations of H2S for 36 min in HEPES buffer; (b) UV-vis absorption spectra of DBODFN incubated with varying concentrations of H2S for 42 min in HEPES buffer

图11. (a) SBODFN加入H2S后和SBODOH的紫外-可见吸收光谱; (b) SBODFN加入H2S后和SBODOH的荧光发射光谱

Figure 11. (a) UV-vis absorption spectra of SBODFN added with H2S and SBODOH; (b) fluorescence emission spectra of SBODFN added with H2S and SBODOH

图12. (a) DBODFN加入H2S后和DBODOH的紫外-可见吸收光谱; (b) DBODFN加入H2S后和DBODOH的荧光发射光谱

Figure 12. (a) UV-vis absorption spectra of DBODFN added with H2S and DBODOH; (b) Fluorescence emission spectra of DBODFN added with H2S and DBODOH

图13. SBODFN加入H2S后的质谱

Figure 13. Mass spectrum of SBODFN after adding H2S

图14. DBODFN加入H2S后的质谱

Figure 14. Mass spectrum of DBODFN after adding H2S

图15. SBODOH和DBODOH的HOMO-LUMO能级

Figure 15. HOMO and LUMO orbital energy levels of SBODOH and DBODOH

图16. (a)在365 nm紫外灯下滴加不同分析物后SBODFN的滤纸条; (b)在365 nm紫外灯下滴加不同分析物后DBODFN的滤纸条

Figure 16. (a) Test strips of SBODFN with different analytes under 365 nm UV irradiation; (b) test strips of DBODFN with different analytes under 365 nm UV irradiation

Sample	Added/(μmol•L^-1)	Fluorescence Intensity	Measured Value /(μmol•L^-1)	Recovery/%	RSD/%
Tap water	380	1858	406	106.82	4.89
		1720	370	97.26
		1828	398	104.74
lake water	380	1817	395	103.98	6.33
		1683	360	94.70
		1862	407	107.09
Yellow River water	380	1689	361	95.11	2.94
		1764	381	100.31
		1697	364	95.67

表1. SBODFN对不同水样中H2S的检测

Table 1. Detection of H2S in different water samples by SBODFN

Sample	Added/(μmol•L^-1)	Fluorescence Intensity	Measured Value /(μmol•L^-1)	Recovery/%	RSD/%
Tap water	440	1781	448	101.73	2.50
		1734	440	99.90
		1654	426	96.80
lake water	440	1761	444	100.95	0.85
		1804	452	102.62
		1773	446	101.42
Yellow River water	440	1823	455	103.36	3.83
		1636	423	96.10
		1787	449	101.96

表2. DBODFN对不同水样中H2S的检测

Table 2. Detection of H2S in different water samples by DBODFN

图17. SBODFN和DBODFN的合成

Figure 17. Synthesis of SBODFN and DBODFN

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