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

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 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

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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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Fig. & Tab. 19

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

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

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

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

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

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

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

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

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

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

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

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

Figure 13. Mass spectrum of SBODFN after adding H2S

Figure 14. Mass spectrum of DBODFN after adding H2S

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

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

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

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

Figure 17. Synthesis of SBODFN and DBODFN

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单双取代荧光探针的合成及其对硫化氢的检测^★

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

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单双取代荧光探针的合成及其对硫化氢的检测★