多巴胺醌功能化的量子点荧光探针构建及其pH响应研究

doi:10.15541/jim20250169

无机材料学报 ›› 2026, Vol. 41 ›› Issue (2): 225-233.DOI: 10.15541/jim20250169 CSTR: 32189.14.10.15541/jim20250169

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.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 出版日期:2025-06-05 网络出版日期:2025-06-05
通讯作者: 侯小琪, 副研究员. E-mail: houxiaoqi@ucas.ac.cn;
刘宣勇, 研究员. E-mail: xyliu@mail.sic.ac.cn
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)

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

WANG Zheng¹^,²^,³(), HOU Xiaoqi¹^,³(), LIU Xuanyong¹^,²^,³()

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, 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 Published:2025-06-05 Online:2025-06-05
Contact: HOU Xiaoqi, associate professor. E-mail: houxiaoqi@ucas.ac.cn;
LIU Xuanyong, professor. E-mail: xyliu@mail.sic.ac.cn
About author:WANG Zheng (2000-), male, Master candidate. E-mail: wangzheng22@mails.ucas.ac.cn
Supported by:
Key Research and Development Program of Zhejiang Province(2024C03080);Research Funds of Hangzhou Institute for Advanced Study, UCAS(2023HIAS-Y020)

摘要/Abstract

摘要：

量子点(Quantum Dots, QDs)凭借其优异的光致发光特性, 在生物检测领域展现出重要的应用价值。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QDs, 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QDs荧光探针。实验结果表明: 氨基化的CdSe/CdS/ZnS QDs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QDs的荧光猝灭作用。对于1 nmol QDs, DA-ITC投入量为4~40 μg/nmol时, 在pH 5.0~10.0范围内, 探针的荧光强度呈现随pH增加而线性降低的趋势(线性拟合常数R²>0.90)。当DA-ITC投入量为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 (QDs) 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 design and construct a CdSe/CdS/ZnS core-shell structured QD to improve the fluorescence quantum yield and stability. Additionally, the modification with mercaptoethylamine (MEA) and dopamine-isothiocyanate (DA-ITC) results in improved QD fluorescent probe exhibiting a highly sensitive pH response. Experimental results indicate that the amino-protected CdSe/CdS/ZnS QDs possess excellent optical properties. Following modification with DA-ITC, the probe exhibits highly sensitive pH response. The underlying response mechanism is attributed to fluorescence quenching effect of the dopamine quinone (DQ), which is formed by oxidation in surface ligands on the QDs under alkaline conditions. For 1 nmol QDs, when the input amount of DA-ITC is in the range of 4-40 μg/nmol, the fluorescence intensity of the probe reveals a linear decreasing trend with increasing pH from 5.0 to 10.0 (R²>0.90). 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 cytocompatibility, allowing for effective application in fluorescence imaging for monitoring of cell pH.

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

中图分类号:

O649

王政, 侯小琪, 刘宣勇. 多巴胺醌功能化的量子点荧光探针构建及其pH响应研究[J]. 无机材料学报, 2026, 41(2): 225-233.

WANG Zheng, HOU Xiaoqi, LIU Xuanyong. Functionalized Quantum Dot Fluorescent Probes with Dopamine Quinone: Construction and pH Response[J]. Journal of Inorganic Materials, 2026, 41(2): 225-233.

图/表 13

图1 QDs的制备过程、微观形貌及尺寸分布

Fig. 1 Schematic of preparation, micromorphologies and size distributions of QDs (a) Preparation process of QDs; (b-d) TEM images of CdSe QDs (b), CdSe/CdS QDs (c) and CdSe/CdS/ZnS QDs (d),with insets showing size distribution histograms

图2 QDs的结构表征、元素分布及光学性质

Fig. 2 Structural characterization, element distribution and optical properties of QDs (a) XPS spectra, (b) XRD patterns, (d) PL and UV-Vis spectra, and (e) transient PL spectra of QDs;(c) EDS mappings of CdSe/CdS/ZnS QDs with inset showing HRTEM image

图3 QDs基pH响应探针的制备过程、表征和光学性质

Fig. 3 Schematic of preparation, characterization and optical properties of QDs-based pH probes (a) Preparation of pH probe; (b) FT-IR spectra of pH probe at different phases; (c) PL spectra and (d) transient PL spectra of QDs before and after MEA ligand exchange; (e) UV-Vis spectra, (f) PL spectra and (g) transient PL spectra of QDs before and after linking DA-ITC (40 μg/nmol)

图4 DA-ITC投入量对QDs基pH响应探针光学性质的影响

Fig. 4 Effect of DA-ITC input on optical properties of QDs-based pH probes (a) PL spectra; (b) Variation of PL peak intensity; (c) Transient PL spectra

图5 不同DA-ITC投入量的探针对pH变化的响应效果

Fig. 5 Response effects of probes with different DA-ITC input amounts on pH changes

图6 探针的细胞毒性及其在细胞体系中的pH响应效果

Fig. 6 Cytotoxicity of probe and its pH response effect in the cellular system (a, b) Cytotoxicity of probe to L929 cells (a) and 4T1 cells (b); (c) Fluorescence imaging of probe responses to intracellular pH change

图7 GSH对荧光探针光学性质的影响及荧光探针pH响应机制

Fig. 7 Effect of GSH on the optical properties of fluorescent probes and pH response mechanism of probes (a, b) Same concentration of GSH and MEA incubated with probe for 30 min: (a) PL spectra and (b) transient PL spectra of probe; (c-e) Different concentration of GSH incubated with probe for 30 min: (c) PL spectra, (d) variation of PL peak intensity and (e) transient PL spectra of probe; (f) Schematic of the mechanism of fluorescence probe response to pH change. Colorful figures are available on website

表S1 油溶性量子点的光学性质

Table S1 Optical properties of oil-soluble QDs

QDs	The first exciton absorption peak/nm	PL peak/nm	FHWM/nm	PL decay lifetime/ns	χ_R₂
CdSe	558.0	571.5	26.0	/	/
CdSe/CdS	609.5	622.0	25.3	19.35	0.95
CdSe/CdS/ZnS	609.0	625.0	28.4	21.20	1.24

表S2 不同DA-ITC投入量的探针荧光响应pH的拟合

Table S2 Fitting of probe fluorescence response pH under different DA-ITC input amounts

Amount of input/(μg·nmol^-1)	y = b×x + a	R²
0.4	y = -28309x + 587440	0.4777
4	y = -56370x + 670873	0.9097
20	y = -44246x + 522045	0.9869
40	y = -11429x + 141699	0.9667
80	y = -53.148x + 4116.5	0.0249

图S1 CdSe/CdS/ZnS量子点的元素分布(a)及EDS线扫图(b)

Fig. S1 Element distribution (a) and EDS line scan image (b) of CdSe/CdS/ZnS quantum dots

图S2 CdSe核QDs上生长CdS和ZnS层过程中的光学性质变化

Fig. S2 Variation of optical properties during growth of CdS and ZnS layers on CdSe core QDs (a) PL spectra; (b) UV-Vis spectra; (c, d) Transient PL spectra

图S3 不同DA-ITC投入量的探针在不同pH环境中的光学性质变化

Fig. S3 Variation of optical properties of probes with different DA-ITC inputs in different pH environments (a, b) 4 μg/nmol; (c, d) 20 μg/nmol; (e, f) 40 μg/nmol; (g, h) 80 μg/nmol

图S4 探针在细胞内pH荧光成像的荧光强度

Fig. S4 Fluorescence intensity of probe in intracellular pH fluorescence imaging

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多巴胺醌功能化的量子点荧光探针构建及其pH响应研究

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

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