量子点电化学发光研究进展及展望

doi:10.7503/cjcu20200390

摘要/Abstract

摘要：

电化学发光因具有低背景、高灵敏度的优势已成为当前最先进的体外诊断技术之一. 以三联吡啶钌为代表的分子型电化学发光体系虽然实现了商业化应用, 但其光学性质已无法满足电化学发光分析的发展需求. 量子点作为新一代的理想发光材料在电化学发光领域表现出巨大的应用前景. 然而, 由于对量子点电化学发光的过程和机理研究尚不充分, 目前量子点电化学发光的各项性能均有待提升. 本文聚焦于量子点电化学发光领域的关键科学问题, 在总结该领域重要研究进展的基础上, 指出光谱学、合成化学及电分析化学等多领域学科交叉是未来量子点电化学发光研究的重要发展方向.

关键词: 量子点, 电化学发光, 机理, 表面缺陷, 免疫分析

Abstract:

Electrochemiluminescence(ECL) has become one of the most advanced immunodiagnostic method due to its near-zero background and high sensitivity. Ruthenium(Ⅱ) tris(bipyridine)[Ru(bpy)₃²⁺] and its derivatives have been applied in commercial diagnostics, but their optical properties can not meet the requirement of state-of-art ECL analysis. Quantum dots(QDs) possess outstanding luminescence properties and seem to be ideal for developing a new generation of ECL emitters. However, the mechanism of ECL generation from QDs deserves further in-depth investigations and the ECL performance of QDs also needs to be improved. In this review, we focus on the important advancements and key scientific issues of QDs ECL. After an overview of the developments of the field, future perspectives about the developments of QDs ECL are also exhibited. We believe that spectroscopy, synthesis chemistry and electrochemistry should be combined together to advance the research.

Key words: Quantum dots, Electrochemiluminescence, Mechanism, Surface trap, Immunoassay

中图分类号:

O646

TrendMD:

曹芷源, 孙慧, 苏彬. 量子点电化学发光研究进展及展望. 高等学校化学学报, 2020, 41(9): 1945.

CAO Zhiyuan, SUN Hui, SU Bin. Electrochemiluminescence of Quantum Dots: Research Progress and Future Perspectives. Chem. J. Chinese Universities, 2020, 41(9): 1945.

图/表 10

Fig.1 Effect of surface traps on ECL properties of QDs

Fig.2 Band?edge and trap emission of QDs ECL

Fig.5 Effects of surface states on CdTe/CdS(A, B)[33] and CdTe/ZnSe(C)[34] core/shell QDs(A) Schematic illustration of adjusting surface states of QDs by surface decoration with counterions; (B) ECL intensity-potential curves of CdTe/CdS@GCE(a), CdTe/CdS/S2-@GCE(b), and CdTe/CdS/Cd2+@GCE(c) in 50 mmol/L tris-HCl buffer containing 0.1 mol/L (NH4)2S2O8, the inset shows the corresponding ECL spectra; (C) ECL intensity-potential curves of CdTe/ZnSe/S2-@GCE (black), CdTe/ZnSe/Cd2+@GCE(blue), and CdTe/ZnSe/Zn2+@GCE(red).(A, B) Copyright 2018, Wiley-VCH Veriag GmbH & Co. KGaA, Weinheim; (C) Copyright 2018, American Chemical Society.

Fig.6 Schematic illustration of spectrum?resolved triplex color ECL immunoassay using dual?stabilizer?capped QDs as tags[51](D) a. GCE; b. GCE|ABA; c. GCE|ABA-Ab1-Ag-Ab2; d. GCE|ABA-Ab1-Ag-Ab2-NCs.Copyright 2018, American Chemical Society.

Fig.7 ECL spectra of PEG?COOH capped CdSe/ZnS core/shell QDs(A)[56], absorption(dashed line) and emission(solid line) spectra of CdSe/ZnS core/shell QDs before(in toluene, black) and after(in water, red) ligand exchange with DAET(B)[55]The solid blue line in (B) shows the ECL spectrum of Nafion/CdSe/ZnS QDs film.(A) Copyright 2010, Royal Society of Chemistry; (B) Copyright 2011, Royal Society of Chemistry.

Fig.8 Synthetic procedures of CdSeTe/CdS/ZnS core/shell/shell QDs(A), PL spectra of CdSeTe/CdS core/shell(i and iii) and corresponding CdSeTe/CdS/ZnS core/shell/shell QDs(ii and iv)(B), schematic illustration of construction of ECL energy transfer immunosensor(C) and calibration curves for determination of CEA based on ECL energy transfer(curve 1) and traditional antigen-antibody recognition(curve 2) strategies(D)[58]Copyright 2013, Springer Nature.

Fig.9 PL(top) and potential-dependent ECL spectra(bottom) of CdSe(A), CdSe/CdS core/shell(B), and CdSe/CdS/ZnS core/shell/shell QDs(C)The insets compare the PL and ECL spectra of CdSe/CdS core/shell and CdSe/CdS/ZnS core/shell/shell QDs[59].Copyright 2020, American Chemical Society.

Fig.10 PL(top) and ECL spectra(bottom) of green?, yellow?, and red?emitting CdSe/CdS/ZnS core/shell/shell QDs(A), potential?dependent ECL spectra of the ternary mixture of green?, yellow?, and red?emitting QDs(B), ECL spectra of the ternary mixture under three different potentials(C—E)[59]The insets show the corresponding ECL photographs.Copyright 2020, American Chemical Society.

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