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

doi:10.6023/cjoc202012024

摘要/Abstract

摘要为了有针对性地高选择荧光识别硫化氢(H₂S), 以香豆素为核心组块与三唑并噻二唑芳香稠并杂环拼接,设计合成了3个比率型荧光探针4a~4c, 借助红外光谱(IR)、核磁共振(NMR)和高分辨质谱(HRMS)等对其进行了结构表征. 通过荧光光谱法, 研究发现3个探针均具有优良的荧光性能, 说明探针分子整体结构设计合理, 均表现出较高的荧光量子产率(0.6752, 0.6639, 0.6128)和大的斯托克斯位移(138, 131, 128 nm). 3个探针对H₂S均具有高选择和高灵敏性识别, 其检测限(LOD)分别为0.19, 0.21, 0.25 µmol•L ^–1. 其中4a显示了最优的效果, 说明分子中苯环4位斥电基团的存在使共轭体系电子密度升高, 有利于探针性能的优化. 此外探针与H₂S作用后, 颜色从无色变为深黄色, 可以实现H₂S的“裸眼检测”. 探针4a~4c成功应用于实际水样中H₂S的定性定量检测.

关键词: 硫化氢, 香豆素, 比率型荧光探针

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

引用此文

张成路, 张彦朋, 王华玉, 赵洹影, 尚美彤, 张璐, 李香玲, 王一鸣. 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[J]. 有机化学, 2021, 41(6): 2384-2392.

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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图/表 12

图式1. 目标化合物的合成

Scheme 1. Synthesis of target molecules

图1. 荧光探针4a~4c与H2S作用的紫外滴定光谱

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

图2. 荧光探针4a~4c荧光强度随H2S浓度变化的线性关系

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

图3. 荧光探针4a~4c的最大斯托克斯位移

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

图4. 探针4a~4c与H2S的反应时间

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

图5. 4a~4c在不同pH值条件下的点线图

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

图6. 4a~4c (20 μmol•L –1)对不同检测物的荧光响应

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

图7. 探针4a~4c对不同分析物的竞争性反应

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

图8. (a) 4a, (b) 3a和(c)加入Na2S的4a的核磁共振氢谱

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

图9. (a) 4a和(b)加入Na2S的4a高分辨质谱

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

图10. 4a~4c在不同实际水样中荧光光谱图

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

表1. 测定不同水样中的H2S

Table 1. Determination of hydrogen sulfide in different water samples

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