基于苯并吡喃点亮型硫化氢荧光探针在食品检测中的应用与细胞成像

doi:10.6023/cjoc202311014

有机化学 ›› 2024, Vol. 44 ›› Issue (6): 2027-2032.DOI: 10.6023/cjoc202311014 上一篇下一篇

研究论文

基于苯并吡喃点亮型硫化氢荧光探针在食品检测中的应用与细胞成像

刘琳^a,†, 陈琳^b,†, 胡晓玲^a, 钟克利^a^,^*(), 张璟琳^c^,^*(), 汤立军^a

a 渤海大学化学与材料工程学院辽宁锦州 121013
b 辽宁省检验检测认证中心沈阳 110000
c 北京工商大学中国轻工业酿酒分子工程重点实验室北京 100048

收稿日期:2023-11-14 修回日期:2024-01-14 发布日期:2024-02-19
作者简介:
^†共同第一作者
基金资助:
辽宁省教育厅科研基金(LJKMZ20221480); 北京工商大学中国轻工业酿酒分子工程重点实验室开放课题(BME-202202); 渤海大学海洋研究所开放(BDHYYJY2023008)

Application and Cell Imaging of Turn-On Fluorescent Probe for Hydrogen Sulfide Based on Benzopyran in Food Samples

Lin Liu^a,†, Lin Chen^b,†, Xiaoling Hu^a, Keli Zhong^a,*(), Jinglin Zhang^c,*(), Lijun Tang^a

a College of Chemistry and Material Engineering, Bohai University, Jinzhou, Liaoning 121013
b Liaoning Inspection, Examination & Certification Centre, Shenyang 110000
c Key Laboratory of Brewing Molecular Engineering of China Light Industry, Beijing Technology and Business University, Beijing 100048

Received:2023-11-14 Revised:2024-01-14 Published:2024-02-19
Contact: * E-mail: zhongkeli2000@bhu.edu.cn; zhangjinglin@btbu.edu.cn
About author:
^†These authors contributed equally to this work.
Supported by:
Scientific Research Fund of Liaoning Provincial Education Department(LJKMZ20221480); Open Project Program of the Key Laboratory of Brewing Molecular Engineering of China Light Industry(BME-202202); Open Project of Institute of Ocean of Bohai University(BDHYYJY2023008)

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摘要/Abstract

硫化氢(H₂S)不仅参与人体生理调节, 也对酒的风味和口感有影响. 合成了一种2,4-二硝基苯修饰的苯并吡喃衍生物(DCM-dip), 该化合物在二甲基亚砜(DMSO)/磷酸缓冲溶液(PBS) (V:V=8:2, pH=8)溶液中没有荧光, H₂S与其发生硫解反应释放出具有荧光的中间体, 进而实现荧光点亮识别H₂S. DCM-dip识别H₂S的响应时间为20 min, 检测限为2.82 μmol/L, pH适用范围为8~11, 且具有较大的斯托克斯位移(123 nm), 避免了背景干扰. 应用研究表明, DCM-dip可用于红酒、啤酒样品中检测H₂S, 可对活细胞中H₂S进行荧光成像.

关键词: 苯并吡喃, 点亮型, 硫化氢, 荧光探针, 食品样品

Hydrogen sulfide (H₂S) is not only involved in the physiological regulation of human body, but also has an impact on the flavor and taste of wine. Therefore, a benzopyran derivative modified by 2,4-dinitrobenzene (DCM-dip) was synthesized, which had no fluorescence in dimethyl sulfoxide (DMSO)/phosphate buffered saline (PBS) (V:V=8:2, pH=8) solution. DCM-dip underwent a thiolysis reaction with H₂S to release the intermediate with fluorescence, which showed a fluorescence turn-on response for recognition of H₂S. DCM-dip recognized H₂S with a response time of 20 min, a detection limit of 2.82 μmol/L, pH application range of 8~11 and a large Stokes shift (123 nm), avoiding background interference. The application research indicates that DCM-dip can be used to detect H₂S in red wine and beer samples, and image for H₂S in living cells.

Key words: benzopyran, turn-on, hydrogen sulfide, fluorescent probe, food sample

引用此文

刘琳, 陈琳, 胡晓玲, 钟克利, 张璟琳, 汤立军. 基于苯并吡喃点亮型硫化氢荧光探针在食品检测中的应用与细胞成像[J]. 有机化学, 2024, 44(6): 2027-2032.

Lin Liu, Lin Chen, Xiaoling Hu, Keli Zhong, Jinglin Zhang, Lijun Tang. Application and Cell Imaging of Turn-On Fluorescent Probe for Hydrogen Sulfide Based on Benzopyran in Food Samples[J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 2027-2032.

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图/表 8

图式1. DCM-dip的合成

Scheme 1. Synthesis of DCM-dip

图1. (a) DCM-dip(10 μmol/L)在DMSO/PBS (V:V=8:2, pH=8)中加入各种分析物(610 μmol/L)后荧光光谱变化(λex=400 nm)及(b)向DCM-dip中的添加各种阴离子的荧光变化

Figure 1. (a) Fluorescence spectra changes of DCM-dip (10 μmol/L) after adding various analytes (610 μmol/L) in DMSO/ PBS (V:V=8:2, pH=8) solution (λex=400 nm) and (b) fluorescence changes of various anions added to DCM-dip 1: F–, 2: Cl–, 3: Br–, 4: $\mathrm{HPO}_{4}^{2-}$, 5: $\mathrm{SO}_{4}^{2-}$, 6: $\mathrm{N}_{3}^{-}$, 7: SCN–, 8: I–, 9: $\mathrm{S}_{2} \mathrm{O}_{3}^{-}$, 10: $\mathrm{CO}_{3}^{2-}$, 11: CH3COO–, 12: PPi, 13: $\mathrm{C}_{2} \mathrm{O}_{4}^{2-}$, 14: $\mathrm{HCO}_{3}^{-}$, 15: $\mathrm{NO}_{2}^{-}$, 16: $\mathrm{S}_{2} \mathrm{O}_{3}^{2-}$, 17: HS–

图2. DCM-dip(10 μmol/L)在DMSO/PBS (V:V=8:2, pH=8)中加入不同浓度HS– (0~610 μmol/L)的荧光光谱变化(λex=400 nm)

Figure 2. Fluorescence spectra changes of DCM-dip (10 μmol/L) with addition of different concentrations of HS– (0~610 μmol/L) in DMSO/PBS (V:V=8:2, pH=8) solution (λex=400 nm) Insert: the linear relationship between the concentration of HS– and the fluorescence intensity of DCM-dip (523 nm).

图3. 在加入各种阴离子(610 μmol/L)的DCM-dip (10 μmol/L) DMSO/PBS (V:V=8:2, pH=8)溶液中继续加入HS–前后的荧光强度(523 nm)变化(λex=400 nm)

Figure 3. Fluorescence intensity (523 nm) changes of DCM-dip (10 μmol/L) containing various anions (610 μmol/L) in the DMSO/PBS (V:V=8:2, pH=8) solution before and after addtion of HS– (λex=400 nm)

图4. DCM-dip识别H2S的机制及其应用识别H2S的机制及其应用

Figure 4. Mechanism of DCM-dip recognition of H2S and application of DCM-dip

图5. 在(a)红酒和(b)啤酒样品中DCM-dip (10 μmol/L)的荧光强度随HS–浓度(70~120 μmol/L)的变化

Figure 5. Fluorescence intensity changes of DCM-dip (10 μmol/L) upon adding HS– (70~120 μmol/L) in (a) red wine and (b) beer samples

Sample	Added/(μmol/L)	Found/(μmol/L)	Recovery/%	RSD/% (n=3)
Red wine 1	70 80 90	70.06 79.69 90.69	100.0 99.6 100.7	0.62 0.76 0.66
Red wine 2	70 80 90	72.87 79.72 91.33	104.1 99.6 101.4	0.52 0.46 0.80
Beer 1	80 90 100	80.50 90.59 100.21	100.6 100.6 100.2	0.85 2.13 0.65
Beer 2	80 90 100	79.71 90.21 100.99	99.6 100.2 100.9	0.42 0.45 0.65

表1. DCM-dip检测红酒、啤酒中HS–浓度的结果

Table 1. Data of HS– concentrations detected by DCM-dip in red wines and beer samples

图6. 在37 ℃下MCF-7细胞中加入DCM-dip (10 μmol/L)孵育30 min, 再加入HS– (100, 200, 500, 1000 μmol/L)孵育30 min后的明场(左侧)和暗场(右侧)照片[λex=458 nm, 绿色通道 (510~550 nm)]

Figure 6. Bright-field (left) and dark field (right) image of MCF-7 cells which were incubated for 30 min after addition of DCM-dip (10 μmol/L) and then incubated for another 30 min after addition of HS– (100, 200, 500, 1000 μmol/L) at 37 ℃ [λex=458 nm, green channel (510~550 nm)]

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基于苯并吡喃点亮型硫化氢荧光探针在食品检测中的应用与细胞成像

Application and Cell Imaging of Turn-On Fluorescent Probe for Hydrogen Sulfide Based on Benzopyran in Food Samples

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