新型荧光/EPR双功能次氯酸探针的构建及性能

doi:10.7503/cjcu20170193

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (9): 1542.doi: 10.7503/cjcu20170193

新型荧光/EPR双功能次氯酸探针的构建及性能

刘辉强¹, 彭超¹(), 陈宁², 刘阳平¹()

1. 天津市临床药物关键技术重点实验室, 天津医科大学药学院, 天津 300070
2. 天津医科大学口腔医院, 天津 300070

收稿日期:2017-03-31 出版日期:2017-09-10 发布日期:2017-07-04
作者简介:联系人简介: 刘阳平, 男, 博士, 教授, 博士生导师, 主要从事氧化还原检测与评价方面的研究. E-mail: liuyangping@tmu.edu.cn;彭超, 女, 实验师, 主要从事小分子荧光探针的合成、表征与应用研究. E-mail: pengchao@tmu.edu.cn
基金资助:
国家自然科学基金(批准号: 31500684, 21572161)和天津市应用基础与前沿技术研究计划项目(批准号: 15JCYBJC23700, 15JCZDJC32300)资助

Novel Fluorescent/EPR Difunctional Probe for Detecting Hypochlorite^†

LIU Huiqiang¹, PENG Chao^1,^*(), CHEN Ning², LIU Yangping^1,^*()

1. School of Pharmacy, Tianjin Medical University, Tianjin 300070, China
2. Tianjin Medical University Stomatological Hospital, Tianjin 300070, China

Received:2017-03-31 Online:2017-09-10 Published:2017-07-04
Contact: PENG Chao,LIU Yangping E-mail:pengchao@tmu.edu.cn;liuyangping@tmu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.31500684, 21572161) and the Tianjin Research Program of Application Foundation and Advanced Technology, China(Nos.15JCYBJC23700, 15JCZDJC32300)

摘要/Abstract

摘要：

构建了一种新型香豆素-萘酰亚胺荧光/电子顺磁共振双功能探针CNNOH, 并结合荧光光谱、电子顺磁共振(EPR)波谱和紫外-可见吸收光谱对其性能进行了研究. 结果表明, 该探针可结合荧光光谱的灵敏性和EPR波谱的特异性进行次氯酸的检测; 由于香豆素与萘酰亚胺之间存在荧光共振能量转移(FRET)效应, 探针分子具有较大的Stokes位移(135 nm), 可有效避免由激发光导致的杂散光对检测的干扰. 该双功能探针具有检出限低(0.214 μmol/L)、反应速度快(~10 s)、检测范围宽(0~5 mmol/L)、选择性好及在生理条件下稳定的特点, 预期在活体细胞检测方面有良好的应用前景.

关键词: 次氯酸, 荧光探针, 电子顺磁共振波谱, 荧光共振能量转移, 自由基

Abstract:

To detect hypochlorite effectively and multimodally in biological system, a novel fluorescence/EPR dual probe CNNOH was designed and synthesized based on coumarin and naphthalimide derivatives. The phy-sicochemical properties of CNNOH and its reaction with hypochlorite were studied in detail by fluorescence, electron paramagnetic resonance(EPR) and ultraviolet-visible spectroscopies. The results showed that hypochlorite can be detected using CNNOH by fluorescence and EPR spectroscopies with integrated advantages of both techniques. Owing to fluorescence resonance energy transfer(FRET) effect between the two fluorophores, the probe exhibits a large Stokes shift(135 nm) and thus effectively eliminates interference from of stray light. This dual probe has multiple advantages, such as low detection limit(0.214 μmol/L), short response time to hypochlorite(ca. 10 s), measurement of hypochlorite over a wide range of concentrations(0—5 mmol/L) as well as good selectivity and stability of CNNOH under physiological conditions. Therefore, the new probe shows great potentials in detecting or imaging hypochlorite in living cells and this molecular design provides new insights into the development of new probes for hypochlorite.

Key words: Hypochlorite, Fluorescent probe, Electron paramagnetic resonance(EPR), Fluorescence resonance energy transfer(FRET), Free radical

中图分类号:

O657

TrendMD:

刘辉强, 彭超, 陈宁, 刘阳平. 新型荧光/EPR双功能次氯酸探针的构建及性能. 高等学校化学学报, 2017, 38(9): 1542.

LIU Huiqiang, PENG Chao, CHEN Ning, LIU Yangping. Novel Fluorescent/EPR Difunctional Probe for Detecting Hypochlorite^†. Chem. J. Chinese Universities, 2017, 38(9): 1542.

图/表 6

Scheme 1 Synthetic route of CNNOH

Fig.1 Absorption spectra of 10 μmol/L of CNNOH(a), compound 4(b) or compound 5(c) in PBS buffer(A), fluorescence spectra of 1 μmol/L of CNNOH(a), compound 4(b) or compound 5(c)(B) and overlap of fluorescence spectra(a) of compound 5(donor, 10 μmol/L) and absorption spectra(b) of compound 4(acceptor, 1 μmol/L)(C)

Fig.2 Fluorescence intensity changes of CNNOH(1 μmol/L) in the presence of 10 μmol/L(a) or 50 μmol/L(b) ClO-

Fig.3 Spectra changes of CNNOH upon addition of ClO-(A) Absorption spectra of CNNOH(10 μmol/L) with the reaction of ClO-(0—1 mmol/L); (B) fluorescence spectra of CNNOH(1 μmol/L) with the reaction of ClO-(0—100 μmol/L); (C) EPR spectra of CNNOH(50 μmol/L) with the reaction of ClO-(0, 0.5, 2.5, 5 mmol/L); (D) fitting curve of EPR intensity with different concentrations of ClO-(0, 0.5, 1, 2, 3, 4, 5 mmol/L).

Fig.4 Fluorescence intensity of CNNOH after reaction with various ROS

Fig.5 Effects of pH value on stabilities of CNNOH(a) and its product with ClO-(b)

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新型荧光/EPR双功能次氯酸探针的构建及性能

Novel Fluorescent/EPR Difunctional Probe for Detecting Hypochlorite^†

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新型荧光/EPR双功能次氯酸探针的构建及性能

Novel Fluorescent/EPR Difunctional Probe for Detecting Hypochlorite†

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