一种响应速率匹配的双反应探针用于荧光识别硫化氢

doi:10.6023/cjoc201905038

有机化学 ›› 2019, Vol. 39 ›› Issue (11): 3277-3282.DOI: 10.6023/cjoc201905038 上一篇下一篇

所属专题：荧光探针-生物传感合辑；有机超分子化学合辑

研究简报

一种响应速率匹配的双反应探针用于荧光识别硫化氢

解畅, 马趁, 贾旭, 张学琪, 魏超*(), 张平竹, 李小六*()

河北大学化学与环境科学学院河北省化学生物学重点实验室药物化学与分子诊断教育部重点实验室河北保定 071002

收稿日期:2019-05-16 发布日期:2019-07-17
通讯作者: 魏超,李小六 E-mail:weichao@hbu.edu.cn;lixl@hbu.cn
基金资助:
国家自然科学基金(21778013);河北省自然科学基金(B2018201234);河北省高等学校科学技术研究(QN2017015);保定市科学研究与发展计划(16zg031);河北大学实验室开放(sy201833);河北大学实验室开放(KYZJX18144)

A Response Rate Matching Dual-Reactable Probe for Fluorescent Recognition of Hydrogen Sulfide

Xie Chang, Ma Chen, Jia Xu, Zhang Xueqi, Wei Chao*(), Zhang Pingzhu, Li Xiaoliu*()

Key Laboratory of Chemical Biology of Hebei Province, Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of Ministry of Education, College of Chemistry and Environmental Science, Hebei University, Baoding, Hebei 071002

Received:2019-05-16 Published:2019-07-17
Contact: Wei Chao,Li Xiaoliu E-mail:weichao@hbu.edu.cn;lixl@hbu.cn
Supported by:
the National Natural Science Foundation of China(21778013);the Natural Science Foundation of Hebei Province(B2018201234);the Colleges and Universities Science Technology Research Project of Hebei Province(QN2017015);the Science Technology Research and Development Guidance Programme Project of Baoding City(16zg031);the Open Fund of Laboratory in Hebei University(sy201833);the Open Fund of Laboratory in Hebei University(KYZJX18144)

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摘要/Abstract

以6-氟-7-氨基香豆素为荧光基团，氟代叠氮和7-硝基苯并氟咱（NBD）-哌嗪为H₂S反应基团和荧光淬灭基团，合成一种双反应H₂S荧光探针.探针对H₂S的识别性质研究表明，探针的两个反应基团与H₂S响应速率匹配，探针对H₂S具有高选择性和灵敏性，其荧光增强约3600倍，检测极限为4.0×10^-8 mol/L.酶活性测试表明，探针可用于胱硫醚β合成酶（CBS）酶活性检测和抑制剂筛选.细胞成像实验表明，探针可用于细胞内H₂S的成像研究.

关键词: 硫化氢, 响应速率, 双反应, 荧光探针

A dual-reactable H₂S fluorescent probe was designed and synthesized by employing ortho-fluoro-substituted coumarin azide and 7-nitrobenzofurazan-piperazine as the H₂S reactive groups and the fluorescence quenching groups. The recognition behaviors of the probe to H₂S were investigated and the results showed that the probe exhibited high selectivity and sensitivity. The fluorescence off-on enhancement was ca. 3600-fold, and the detection limit was 4.0×10^-8 mol/L. The results of enzyme activity test indicated that the probe could be used for cystathionine β-synthase (CBS) activity detection and inhibitor screening. Furthermore, the probe was successfully applied for the imaging of H₂S in living cells.

Key words: hydrogen sulfide, response rate, dual-reactable, fluorescent probe

引用此文

解畅, 马趁, 贾旭, 张学琪, 魏超, 张平竹, 李小六. 一种响应速率匹配的双反应探针用于荧光识别硫化氢[J]. 有机化学, 2019, 39(11): 3277-3282.

Xie Chang, Ma Chen, Jia Xu, Zhang Xueqi, Wei Chao, Zhang Pingzhu, Li Xiaoliu. A Response Rate Matching Dual-Reactable Probe for Fluorescent Recognition of Hydrogen Sulfide[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3277-3282.

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图/表 8

图 1. 已报道的H2S荧光探针1~4和本工作设计的荧光探针5

Figure 1. Reported H2S fluorescent probe 1~4 and probe 5 in this work

图 2. 探针1~5 (1.0×10－6 mol/L)与H2S (2.5×10－4 mol/L)的荧光反应动力学

Figure 2. Fluorescence kinetics of probe 1~5 (1.0×10－6 mol/L) in reaction with H2S (2.5×10－4 mol/L) (a) Time-dependent emission intensity at 440 nm of probe 5 after adding H2S. (b) The relationship between fluorescence intensity at 440 nm and reaction time of probe 1~5 on treatment with H2S

Probe	k_obs/s^－1	K₂/(L·mol^－1·s^－1)	T_1/2/min
1	3.88×10^－3	15.5	2.97
2	1.74×10^－3	6.95	6.65
3	3.31×10^－3	13.2	3.49
4	1.30×10^－3	5.20	8.88
5	1.94×10^－3	7.79	5.93

表 1. 探针1~5与H2S的反应动力学参数

Table 1. Kinetic parameters of probe 1~5 in reaction with H2S

图 3. 探针5的选择性和线性关系

Figure 3. Selectivity and linear relationship of probe 5 (a) Fluorescence responses of probe 5 incubated with various analytes. 1, probe 5; 2, SO32－; 3, SO42－; 4, S2O32－; 5, H2O2; 6, HClO; 7, NO2－; 8, Zn2+; 9, Fe3+; 10, Vc; 11, Cys; 12, Hcy; 13, GSH; 14, H2S. (b) Fluorescence response of probe 5 with different concentrations of H2S (Insert: The emission intensity at 440 nm of probe 5 with different concentrations of H2S). Probe 1.0×10－6 mol/L, Cys and Hcy 1.0×10－3 mol/L, GSH 5×10－3 mol/L, other interferents 1.0×10－4 mol/L; H2S 0~1.50×10－4 mol/L

图 4. 探针的光稳定(a)和热稳定性(b)

Figure 4. Optical stability (a) and thermal stability (b) of the probes UV lamp power 18 W for the optical stability test, 37 and 50 ℃ for the thermal stability test

图 5. 探针5 (1.0×10－6 mol/L)与H2S (1.0×10－4 mol/L)反应的紫外吸收光谱

Figure 5. UV-Vis spectrum of probe 5 (1.0×10－6 mol/L) in reaction with H2S (1.0×10－4 mol/L)

图 6. 探针5用于CBS酶活性检测

Figure 6. Detection of CBS activity using probe 5 (a) The time-dependent emission intensity at 440 nm of probe 5, 10 mmol/L L-Cys and 0~10 μg CBS enzyme. (b) The fluorescence intensity at 440 nm of probe 5 before and after treatment with inhibitors. Probe 1.0×10－5 mol/L, CBS 0.01 μg/μL, inhibitors 1.0×10－3 mol/L

图 7. 探针5用于HeLa细胞H2S荧光成像

Figure 7. Confocal imaging of H2S in HeLa cells using probe 5 (a, b) Cells incubated with probe 5 only; (c, d) Cells co-incubated with probe 5 and D-cysteine; (e, f) Cells incubated with probe 5 firstly, and then incubated with H2S

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一种响应速率匹配的双反应探针用于荧光识别硫化氢

A Response Rate Matching Dual-Reactable Probe for Fluorescent Recognition of Hydrogen Sulfide

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