Synthesis and Application of a Fluorescence Turn-on Probe for Hydrogen Sulfide Detection

doi:10.6023/cjoc202603030

Abstract

Hydrogen sulfide (H₂S) is not only a toxic environmental pollutant (commonly found in food spoilage and industrial waste gas) but also an important signaling molecule in organisms. Therefore, it is necessary to develop an effective method to detect hydrogen sulfide. In this paper, TPAB-OH with high fluorescence quantum yield (Φ=35.6%) was designed and synthesized by combining 4-(diphenylamino)-3-hydroxy-[1,1-biphenyl]-4-formaldehyde (TPA-CHO) with 2-aminobenzene-thiol. TPAB-OH reacted with 2,4-dinitrofluorobenzene to produce a new probe TPAB-HS, which has the advantages of a wide pH range (5~12), fast response (10 min), high signal-to-noise ratio and low detection limit (8.56×10^-7 mol/L). In addition, the probe TPAB-HS is also suitable for the detection of HS^- in human breast cancer cells (MCF-7), actual water samples and food samples.

Key words: triphenylamine derivatives, fluorescence probe, hydrogen sulfide, food samples, fluorescence imaging

Cite this article

Long Wang, Yanan Meng, Ruiqi Ren, Mingyu Tian, Lijun Tang. Synthesis and Application of a Fluorescence Turn-on Probe for Hydrogen Sulfide Detection[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 3963-3969.

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Fig. & Tab. 12

Scheme 1. Synthesis route of probe TPAB-HS

Figure 1. Fluorescence spectra changes of TPAB-HS (10 μmol/ L) in THF/H2O (V/V=4/6) solution in the presence of HS- at different concentrations (0~350 μmol/L)

Figure 2. Linear relationship between the fluorescence intensity of TPAB-HS (at 506 nm) and HS- concentration (0~350 μmol/ L)

Figure 3. Fluorescence spectral changes of TPAB-HS (10 μmol/L) in THF/H2O (V/V=4/6) upon addition of various analytes (350 μmol/L)

Figure 4. Fluorescence intensity changes of TPAB-HS (10 μmol/L) in THF/H2O (V/V=4/6) solution containing various anions and biothiols (350 μmol/L) before and after the addition of HS-

Figure 5. Changes in the fluorescence intensity of the probe TPAB-HS and TPAB-HS＋HS- under different pH conditions

Figure 6. Fluorescence intensity changes of the probe TPAB-HS (10 μmol/L) over time in the presence of 350 μmol/L H2S

Scheme 2. Response mechanism of the probe TPAB-HS to HS-

Figure 7. (a) 1H NMR spectrum of the isolated product from the reaction of the probe TPAB-HS with HS-; (b) 1H NMR spectrum of compound TPAB-OH; (c) 1H NMR spectrum of the probe TPAB-HS

Sample	Added/ (μmol•L^-1)	Detect/ (μmol•L^-1)	Recovery/%	RSD/%
River water	40	38.32	95.81	1.11
	60	60.90	101.50	0.85
	80	85.86	107.32	2.97
Lake water	80	81.16	101.45	2.53
	100	97.35	97.35	0.78
	120	126.31	105.26	0.19
Tap water	40	41.26	103.16	1.42
	60	57.70	96.17	0.41
	80	78.54	98.17	0.83

Table 1. Detection of HS- by TPAB-HS in real water samples

Sample	Added/ (μmol•L^-1)	Detect/ (μmol•L^-1)	Recovery/%	RSD/%
Red Wine2	20	19.86	99.31	1.24
	40	41.13	102.86	0.88
	60	59.11	98.52	1.85
Red Wine1	20	22.14	110.69	1.26
	40	39.41	98.53	0.46
	60	57.95	96.59	1.62
Beer2	20	18.35	91.75	1.70
	30	30.64	102.13	1.46
	40	41.95	104.87	1.08
Beer1	80	77.59	96.99	3.16
	100	104.02	104.02	0.47
	120	117.83	98.19	0.31

Table 2. Detection of HS- by TPAB-HS in food samples

Figure 8. Fluorescence images of MCF-7 cells incubated with probe TPAB-HS (10 μmol/L) for 30 min and then incubated with HS- (0, 50, 100, 200, 500 μmol/L) for 30 min (scale bar: 20 μm)

References 32

[1]	Yang Y. X.; Chen L.; Hu X. L.; Zhong K. L.; Li S. D.; Yan X. M.; Zhang J. L.; Tang L. J. Chin. J. Org. Chem. 2023, 43, 308 (in Chinese).
	(杨雅馨, 陈琳, 胡晓玲, 钟克利, 李世迪, 燕小梅, 张璟琳, 汤立军, 有机化学, 2023, 43, 308.) doi: 10.6023/cjoc202207011
[2]	Shen W.; Wang P.; Xie Z.; Zhou H.; Hu Y.; Fu M.; Zhu Q. Talanta 2021, 234, 122621. doi: 10.1016/j.talanta.2021.122621
[3]	Módis K.; Ju Y.; Ahmad A.; Untereiner A. A.; Altaany Z.; Wu L.; Szabo C.; Wang R. Pharmacol. Res. 2016, 113, 116. doi: 10.1016/j.phrs.2016.08.023
[4]	Wu T.; Zheng Z.; Ren J.; Yang Z.; Zhang N.; Guo K.; Chen D.; Gao M.; Chen Y.; Liang X.; Wang Y.; Chen W.; Su Y.; He J.; Wang F. Stem Cell Res. Ther. 2025, 16, 603. doi: 10.1186/s13287-025-04704-9
[5]	Fiorucci S.; Antonelli E.; Mencarelli A.; Orlandi S.; Renga B.; Rizzo G.; Distrutti E.; Shah V.; Morelli A. Hepatology 2005, 42, 539. pmid: 16108046
[6]	Kamoun P.; Belardinelli M.; Chabli A.; Lallouchi K.; Chadefaux-Vekemans B. Am. J. Med. Genet. A 2003, 116A, 310. doi: 10.1002/ajmg.a.v116a:3
[7]	Kamoun P. Med. Hypotheses 2001, 57, 389. pmid: 11516234
[8]	Yang B.; Su M.-M.; Xue Y.-S.; He Z.-X.; Xu C.; Zhu H.-L. Sens. Actuators, B Chem. 2018, 276, 456. doi: 10.1016/j.snb.2018.08.138
[9]	Kang J.; Huo F.; Yao Y.; Yin C. Dyes Pigm. 2019, 171, 107755. doi: 10.1016/j.dyepig.2019.107755
[10]	Lu Y.; Dong B.; Song W.; Kong X.; Mehmood A. H.; Lin W. Anal. Methods 2019, 11, 3301. doi: 10.1039/C9AY00927B
[11]	Zhao Q.; Huo F.; Zhang Y.; Wen Y.; Yin C. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2019, 215, 297. doi: 10.1016/j.saa.2019.02.096 pmid: 30844677
[12]	Liu Y.; Ding Y.; Huang J.; Zhang X.; Fang T.; Zhang Y.; Zheng X.; Yang X. Dyes Pigm. 2017, 138, 112. doi: 10.1016/j.dyepig.2016.11.038
[13]	Lin X.; Lu X.; Zhou J.; Ren H.; Dong X.; Zhao W.; Chen Z. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2019, 213, 416. doi: 10.1016/j.saa.2019.01.085
[14]	Luo Y.; Zhu C.; Du D.; Lin Y. Anal. Chim. Acta 2019, 1061, 1. doi: 10.1016/j.aca.2019.02.045
[15]	Renault K.; Sabot C.; Renard P. Eur. J. Org. Chem. 2015, 2015, 7992. doi: 10.1002/ejoc.v2015.36
[16]	Ma J.; Li F.; Li Q.; Li Y.; Yan C.; Lu X.; Guo Y. New J. Chem. 2018, 42, 19272. doi: 10.1039/C8NJ04208J
[17]	Ren M.; Deng B.; Kong X.; Zhou K.; Liu K.; Xu G.; Lin W. Chem. Commun. 2016, 52, 6415. doi: 10.1039/C6CC00966B
[18]	Sun L.; Wu Y.; Chen J.; Zhong J.; Zeng F.; Wu S. Theranostics 2019, 9, 77. doi: 10.7150/thno.30080
[19]	Takano Y.; Echizen H.; Hanaoka K. Antioxid. Redox Signal. 2017, 27, 669. doi: 10.1089/ars.2017.7070
[20]	Qi F.; Zhang Y.; Wang B.; Chen W.; Yang L.; Yang Z.; Song X. Sens. Actuators B Chem. 2019, 296, 126533. doi: 10.1016/j.snb.2019.05.010
[21]	Pan Y.; Li Y.; Sun X.; Tang L.; Yan X. Dyes Pigm. 2023, 210, 110985. doi: 10.1016/j.dyepig.2022.110985
[22]	Zhong K.; Li Y.; Hu X.; Li Y.; Tang L.; Sun X.; Li X.; Zhang J.; Meng Y.; Ma R.; Wang S.; Li J. Food Chem. 2024, 438, 137987. doi: 10.1016/j.foodchem.2023.137987
[23]	Zhong K.; He Y.; Deng L.; Yan X.; Li X.; Tang Y.; Hou S.; Tang L. Anal. Chim. Acta 2020, 1127, 49. doi: S0003-2670(20)30699-1 pmid: 32800137
[24]	Zhong K.; Hu X.; Zhou S.; Liu X.; Gao X.; Tang L.; Yan X. J. Agric. Food Chem. 2021, 69, 4628. doi: 10.1021/acs.jafc.1c00862
[25]	Zhang K.; Zhang J.; Xi Z.; Li L.-Y.; Gu X.; Zhang Q.-Z.; Yi L. Chem. Sci. 2017, 8, 2776. doi: 10.1039/c6sc05646f pmid: 28553513
[26]	Men J.; Yang X.; Zhang H.; Zhou J. Dyes Pigm. 2018, 153, 206. doi: 10.1016/j.dyepig.2017.12.036
[27]	Zhao Q.; Yin C.; Kang J.; Wen Y.; Huo F. Dyes Pigm. 2018, 159, 166. doi: 10.1016/j.dyepig.2018.06.029
[28]	Zhong K.; Chen L.; Pan Y.; Yan X.; Hou S.; Tang Y.; Gao X.; Li J.; Tang L. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2019, 221, 117135. doi: 10.1016/j.saa.2019.117135
[29]	Zhong K.; Zhou S.; Yan X.; Li X.; Hou S.; Cheng L.; Gao X.; Li Y.; Tang L. Dyes Pigm. 2020, 174, 108049. doi: 10.1016/j.dyepig.2019.108049
[30]	Meng Y.; Yao X.; Zhong K.; Li Y.; Tang L. Eur. J. Org. Chem. 2023, 26, e202300022.
[31]	Jin L.; Tan X.; Dai L.; Bai H.; Wang Q. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2019, 221, 117187. doi: 10.1016/j.saa.2019.117187
[32]	Kang J.; Huo F.; Yin C. Dyes Pigm. 2017, 146, 287. doi: 10.1016/j.dyepig.2017.07.016

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