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无机材料学报

• 研究论文 •    

多巴胺醌功能化的量子点荧光探针构建及其pH响应研究

王政1,2,3, 侯小琪1,3, 刘宣勇1,2,3   

  1. 1.国科大杭州高等研究院, 化学与材料科学学院,杭州 310024;
    2.中国科学院 上海硅酸盐研究所,关键陶瓷材料全国重点实验室,上海 200050;
    3.中国科学院大学,北京 100049
  • 收稿日期:2025-04-23 修回日期:2025-05-27
  • 作者简介:王 政(2000-), 男, 硕士研究生. E-mail: wangzheng22@mails.ucas.ac.cn
  • 基金资助:
    浙江省重点研发计划(2024C03080); 国科大杭州高等研究院自主部署科研项目(2023HIAS-Y020)

Construction and pH Response of Functionalized Quantum Dot Fluorescent Probes with Dopamine Quinone

WANG Zheng1,2,3, HOU XiaoQi1,3, LIU XuanYong1,2,3   

  1. 1. School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, China;
    2. State Key Laboratory of High-Performance Ceramics & Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China;
    3. University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2025-04-23 Revised:2025-05-27
  • About author:WANG Zheng (2000-), male, Master candidate. E-mail: wangzheng22@mails.ucas.ac.cn
  • Supported by:
    The Key Research and Development Program of Zhejiang Province (2024C03080); the Research Funds of Hangzhou Institute for Advanced Study, UCAS (2023HIAS-Y020)

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摘要： 量子点凭借其优异的光致发光特性,在生物检测领域展现出重要应用价值。其中,pH作为调控生理功能的关键参数,其高灵敏度响应具有重要意义。然而,传统pH荧光探针常受限于灵敏度不足或稳定性较差的问题。基于此,本研究采用能带工程优化设计,构建CdSe/CdS/ZnS核壳结构量子点,以提高其荧光量子产率和稳定性。进一步通过巯基乙胺(Mercaptoethylamine, MEA)和多巴胺异硫氰酸酯(Dopamine-Isothiocyanate, DA-ITC)修饰,制备得到具有高灵敏度pH响应的量子点荧光探针。实验结果表明：氨基化的CdSe/CdS/ZnS量子点具有优异的光学性质。经DA-ITC修饰后,探针表现出高灵敏度的pH响应性能,其响应机制源于碱性条件下表面配体氧化形成的多巴胺醌(Dopamine quinone, DQ)对量子点的荧光猝灭作用。对于1 nmol量子点,DA-ITC的投入量为4~40 μg/nmol,在pH 5.0~10.0范围内, 探针的荧光强度呈现随pH增加而线性降低的现象(R2>90%)。当DA-ITC加入量为20 μg/nmol时,探针的pH响应效果最佳,其线性拟合常数为0.9869。此外,该探针具有良好的细胞相容性,能够有效应用于细胞pH荧光成像监测研究。

关键词: 量子点, 核壳结构, pH响应, 氧化还原

Abstract: Quantum dots have demonstrated significant potential in the field of biological detection due to their excellent photoluminescence properties. As one of the key parameters in regulating physiological functions, pH response with high sensitivity is of great significance. However, conventional pH fluorescent probes are frequently limited by insufficient sensitivity or poor stability. In this work, band gap engineering was used to optimize the design and construct a CdSe/CdS/ZnS core-shell structured quantum dot to improve the fluorescence quantum yield and stability. Additionally, the modification with mercaptoethylamine (MEA) and dopamine-isothiocyanate (DA-ITC) result in the development of a quantum dot fluorescent probe exhibiting a highly sensitive pH response. Experimental results indicate that the amino-protected CdSe/CdS/ZnS quantum dots possess excellent optical properties. Following modification with DA-ITC, the probe exhibits highly sensitive pH response performance. The underlying response mechanism is attributed to the fluorescence quenching effect of the dopamine quinone (DQ), which is formed by oxidation in the surface ligands under alkaline conditions on the quantum dots. For 1 nmol quantum dots, when the input amount of DA-ITC is within the range of 4 to 40 μg/nmol, the fluorescence intensity of the probe reveals a linear decrease trend with increasing pH ranging from 5.0 to 10.0 (R2>90%). Notably, when the addition of DA-ITC is set at 20 μg/nmol, the probe demonstrates optimal pH responsiveness(R2=0.9869). Moreover, this probe has good cell compatibility, allowing for effectively application in fluorescence imaging for monitoring of cell pH.

Key words: quantum dots, core-shell structure, pH response, redox

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