新型喹啉基近红外HSO3-双模式探针的构建及生物成像

doi:10.6023/A26040114

摘要/Abstract

SO₂作为生物体内重要的气体分子, 其浓度异常与呼吸系统及中枢神经系统疾病等多种生理病理过程密切相关. SO₂在水溶液中主要以HSO₃⁻的形式存在, 因此, 开发高对比度、高特异性的检测HSO₃⁻的方法对于探究SO₂的生理功能及相关疾病的预防和早期诊断具有重要意义. 本研究设计合成了一种基于A-π-A结构的喹啉基新型荧光探针QS-EC. 该探针在初始状态下处于“暗态”, 而与HSO₃⁻发生特异性识别后, 通过1,4-亲核加成反应, 其结构转变为D-π-A构型, 恢复分子内电荷转移(Intramolecular Charge Transfer, ICT)效应, 从而实现溶液颜色加深与荧光开启的双模式响应. 此外, 探针QS-EC对HSO₃⁻表现出优异的光学性能, 具有超快速响应、灵敏度高、检测限低、抗干扰能力强、适用pH范围广等优点. 细胞成像实验证实了QS-EC能够用于监测活细胞中外源及内源性HSO₃⁻的动态变化. 更重要的是, 在活体斑马鱼成像中, QS-EC表现出高对比度的红色荧光开启信号, 成功实现了对体内HSO₃⁻的可视化追踪, 进一步验证了其优异的体内适用性. 本研究为QS-EC在SO₂相关疾病早期诊断方面的应用提供了坚实的理论依据.

关键词: 二氧化硫, 荧光探针, 双模式响应, 分子内电荷转移, 细胞成像

SO₂is an important gaseous signaling molecule in living organisms, and its abnormal concentration is closely associated with various physiological and pathological processes, including respiratory and central nervous system diseases. SO₂ exists mainly as HSO₃⁻ in aqueous solution, making the development of highly specific and high-contrast detection methods for HSO₃⁻ crucial for studying the physiological functions of SO₂and the early diagnosis of related diseases. In this study, a quinoline-based near-infrared fluorescent probe, QS-EC, with an A-π-A structure was designed and synthesized. The probe initially exists in a fluorescent "dark state." Upon specific 1,4-nucleophilic addition with HSO₃⁻, its structure transforms into a D-π-A configuration, restoring the intramolecular charge transfer (ICT) effect and resulting in a dual-mode response of solution color deepening and fluorescence turn-on. The optical performance of QS-EC was systematically evaluated using UV-Vis and fluorescence spectroscopy. Spectroscopic results showed that the QS-EC responded to HSO₃⁻ within 3 s, with a detection limit of 14.69 nmol/L, and remains stable within a pH range of 6~13. Competitive experiments demonstrated that QS-EC exhibits high selectivity for HSO₃⁻ without interference from other anions or biothiols. It is worth emphasizing that QS-EC enables efficient detection of HSO₃⁻, which not only simplifies the detection process but also significantly enhances the probe's practicality and biocompatibility. Furthermore, MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetra- zolium bromide) assays were used to evaluate its biocompatibility, revealing that cell viability remained above 80% after incubation with 0~20 μmol/L of QS-EC for 24 h, confirming its low cytotoxicity. For cellular imaging, QS-EC successfully enabled dynamic monitoring of both exogenous and endogenous HSO₃⁻ in live cells. Further in vivo imaging experiments in zebrafish model showed a high signal-to-noise ratio red fluorescence turn-on signal, with fluorescence intensity increasing as the HSO₃⁻ concentration rose. This indicates that QS-EC is capable of visually tracking HSO₃⁻ distribution in complex living environments. Through systematic evaluation from molecular design and spectral performance to cellular and in vivo applications, this study fully demonstrates the potential of QS-EC for early diagnosis research in SO₂-related diseases.

Key words: sulfur dioxide, fluorescent probe, dual-mode, intramolecular charge transfer, cellular imaging

引用此文

田明玉, 孟令莹, 钟克利, 汤立军, 宋锋玲. 新型喹啉基近红外HSO₃^-双模式探针的构建及生物成像[J]. 化学学报, 2026, 84(9): 1435-1441.

Mingyu Tian, Lingying Meng, Keli Zhong, Lijun Tang, Fengling Song. Construction of a Novel Near-Infrared Dual-Mode Probe Based on Quinoline for HSO₃^- and Its Imaging Applications[J]. Acta Chimica Sinica, 2026, 84(9): 1435-1441.

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图/表 7

图1. QS-EC的合成路线

Figure 1. Synthetic route of QS-EC

图2. (a)向QS-EC的溶液中加入不同浓度HSO3⁻ (0~40 μmol/L)时的紫外可见吸收光谱; (b)向QS-EC的溶液中加入不同浓度HSO3⁻ (0~40 μmol/L)时的荧光光谱; (c) 660 nm处荧光强度与HSO3⁻浓度的线性关系

Figure 2. (a) UV-Vis absorption spectra of different concentrations of HSO3⁻ (0~40 μmol/L) added to the aqueous solution of QS-EC; (b) fluorescence spectra of different concentrations of HSO3⁻ (0~40 μmol/L) added to the aqueous solution of QS-EC; and (c) linearity of fluorescence intensity at 660 nm versus HSO₃⁻ concentration

图3. (a) QS-EC与不同分析物响应的紫外吸收光谱; (b) QS-EC与不同分析物反应的荧光选择性实验和QS-EC在不同分析物存在下加入HSO3⁻的竞争性实验

Figure 3. (a) UV-Vis absorption spectra of QS-EC reacting with different analytes; (b) fluorescence selectivity experiments of QS-EC reacting with different analytes and competition experiments of QS-EC adding HSO3⁻ in the presence of different analytes

图4. (a) pH对QS-EC与HSO3⁻反应体系荧光强度的影响; (b) QS-EC加入HSO3⁻后溶液颜色变化的视频截图; (c)光稳定性曲线

Figure 4. (a) Effect of pH on fluorescence intensity of the QS-EC reaction system with HSO3⁻; (b) Video screenshots of the solution color change of QS-EC upon addition of HSO3⁻; (c) Photostability curve

图5. 探针QS-EC对HSO3⁻的传感机制

Figure 5. The sensing mechanism of QS-EC to HSO3⁻

图6. (a)不同浓度的探针QS-EC (1、5、10、15、20 μmol/L)与MCF-7细胞共孵育后的细胞存活率; (b) MCF-7细胞中外源性HSO3⁻ (5、10、30 μmol/L)的荧光成像图; (c) MCF-7细胞中内源性HSO3⁻的荧光成像

Figure 6. (a) Cell viability of MCF-7 cells after co-incubation with different concentrations of QS-EC (1, 5, 10, 15, 20 μmol/L). (b) Fluorescence images of exogenous HSO3⁻ (5, 10, 30 μmol/L) in MCF-7 cells. (c) Fluorescence imaging of endogenous HSO3⁻ in MCF-7 cells

图7. (a) QS-EC (10 μmol/L)预处理的斑马鱼和不同浓度的HSO3⁻ (0、10、30、50 μmol/L)共孵育的荧光成像图; (b)荧光强度图

Figure 7. Fluorescence imaging (a) and fluorescence intensity (b) of zebrafish pretreated with QS-EC (10 μmol/L) and co-incubated with different concentrations of HSO3⁻ (0, 10, 30, 50 μmol/L)

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新型喹啉基近红外HSO₃^-双模式探针的构建及生物成像

Construction of a Novel Near-Infrared Dual-Mode Probe Based on Quinoline for HSO₃^- and Its Imaging Applications

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