Synthesis and Application of Triazolothiadiazole-Coumarin Based Ratiometric Fluorescent Probes for Highly Selective Detection of H2S

doi:10.6023/cjoc202012024

Abstract

Three triazolothiadiazole-coumarin based ratiometric fluorescent probes (4a~4c) for detection of H₂S were designed and synthesized. Their structures were confirmed by IR, NMR and HRMS. Through fluorescence spectra, the probes expressed excellent fluorescent properties, which indicates that the design of the molecular structure was rational. The three probes all displayed highly quantum yields (0.6752, 0.6639, 0.6128), large Stokes shift (138, 131, 128 nm).They all exhibited high selectivity and sensitivity against H₂S. The limit of detection were 0.19, 0.21 and 0.25 µmol•L ^–1 respectively. Especially, probe 4a has the optimum efficiency,this result shows that the electron-donating group at 4-position of benzene is in favor of the optimization of fluorescent properties, owing to the accretion of electron density of the conjugated system. Besides, the three probes were all able to sense H₂S by “naked-eye” according to the change in color from colorless to deep yellow. The probes can be applied to recognize H ₂S in actual water samples qualitatively and quantitatively.

Key words: hydrogen sulfide, Coumarin, ratiometric fluorescent probe

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Chenglu Zhang, Yanpeng Zhang, Huayu Wang, Huanying Zhao, Meitong Shang, Lu Zhang, Xiangling Li, Yiming Wang. Synthesis and Application of Triazolothiadiazole-Coumarin Based Ratiometric Fluorescent Probes for Highly Selective Detection of H₂S[J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2384-2392.

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Fig. & Tab. 12

Scheme 1. Synthesis of target molecules

Figure 1. UV-vis absorption spectrum of 4a~4c (10 µmol•L –1) in presence of H2S (0~60 µmol•L –1)

Figure 2. Linear relationship between fluorescence intensity of fluorescent probe 4a~4c and H2S concentration

Figure 3. large stokes shift of 4a~4c

Figure 4. Time-dependent fluorescence intensity ratio of 4a~4c (10 µmol•L –1) in the absence/presence of H2S (100 µmol•L –1)

Figure 5. Dot plot of fluorescent probe 4a~4c at different pH values

Figure 6. Fluorescence intensity ratio of 4a~4c (20 μmol•L –1) to different detection substances (1) Thr, (2) Ser, (3) Ca2+, (4) L-Ile, (5) Val, (6) H-Cys, (7) probe, (8) Gly, (9) Pro, (10) Cys, (11) ClO3–, (12) NO2–, (13) H2PO4–, (14) Co3+, (15) ClO–, (16) Ni2+, (17) Tyr, (18) HClO4, (19) H2S

Figure 7. Competitive binding assay responses of 4a~4c towards various analytes (λex=430, 425, 423 nm) (1) blank, (2) Thr, (3) Ser, (4) Ca2+, (5) L-Ile, (6) Val, (7) H-Cys, (8) Gly, (9) Pro, (10) Cys, (11) ClO3–, (12) NO2–, (13) H2PO4–, (14) Co3+, (15) ClO–, (16) Ni2+, (17) Tyr, (18) HClO4, (19) probe

Figure 8. 1H NMR spectra of (a) 4a, (b) 3a and (c) 4a with Na2S

Figure 9. HMRS of (a) 4a and (b) 4a with Na2S

Figure 10. Fluorescence spectra of 4a~4c in different real water samples

Sample	c(H₂S)/(µmol•L^–1)	Recovery/%
Sample	c(H₂S)/(µmol•L^–1)	4a	4b	4c
Tap water	5	93.4	94.2	91.1
	10	95.9	96.7	94.6
	15	99.3	98.6	95.8
River water	5	94.2	93.9	94.7
	10	96.3	96.2	95.8
	15	98.2	98.1	99.6
Sea water	5	96.7	96.1	95.9
	10	99.1	98.6	99.2
	15	100.6	99.7	100.2
Mineral water	5	94.2	93.6	93.4
	10	98.8	96.5	95.7
	15	99.3	99.1	97.6

Table 1. Determination of hydrogen sulfide in different water samples

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基于三唑并噻二唑-香豆素体系的高选择性识别硫化氢比率型荧光探针的合成及应用

Synthesis and Application of Triazolothiadiazole-Coumarin Based Ratiometric Fluorescent Probes for Highly Selective Detection of H₂S

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