金属有机框架材料在电化学/电化学发光免疫分析中的应用

doi:10.13208/j.electrochem.2218003

摘要/Abstract

摘要：

设计和研制具有超灵敏、高精度、选择性好的免疫传感器对于疾病的早期诊断和筛查以及疾病治疗过程的监测具有十分重要的意义。其中，电化学免疫分析法和电化学发光（ECL）免疫分析法，由于具有稳定性好、灵敏度高、线性范围宽、可控性好等优点而备受关注，已成为当前的研究热点之一。金属有机框架（MOFs）作为一类新型的多孔晶体材料，由于其具有比表面积大、化学稳定性好、孔径和纳米级骨架结构可调节等优点，在电化学和ECL免疫传感器的制备中得到了广泛的应用。MOFs不仅可以作为固定生物识别分子的敏感平台，还可以用于富集痕量分析物和信号分子来放大分析信号，提高电化学或ECL免疫分析的灵敏度。目前，科研人员已合成各种各样具有不同性能和形貌的MOFs纳米材料，并用于开发高性能的电化学免疫传感器和ECL免疫传感器。本文综述了不同类型的基于MOFs纳米材料的电化学/ECL免疫传感器的制备及其在免疫分析中的检测应用。研究表明，MOFs不仅可以作为电极表面修饰的基底、信号探针（包括电活性标记分子和电化学发光发光标记探针）、催化活性标记物，还可以作为负载各种生物分子、纳米材料的载体，最终可用于灵敏的电化学和ECL检测。此外，本综述还讨论了未来发展功能化MOFs纳米材料的挑战和机遇，并为未来设计和制造基于MOFs的高性能免疫传感器提出了一些指导性意见。

关键词: 金属有机框架, 电化学免疫传感器, 电化学发光法免疫传感器, 免疫分析

Abstract:

Development of ultrasensitive, highly accurate and selective immunosensors is significant for the early diagnosis, screening, and monitoring of diseases. Electrochemical and electrochemiluminescent (ECL) immunoassays have both attracted great attention and become a current research hotspot due to their advantages such as good stability, high sensitivity and selectivity, wide linear range, and good controllability. Metal-organic frameworks (MOFs), as a new class of porous crystalline materials, have been widely applied in electrochemical and ECL immunosensors owing to their large specific surface area, good chemical stability, as well as adjustable pore size and nanoscale framework structures. Various MOF nanomaterials with different properties for the development of high-performance electrochemical and ECL immunosensors can be achieved, because they can be applied as sensitive platforms for immobilizing biological recognition molecules, enriching the trace analytes and signal molecules, amplifying the signal and enhancing the sensitivity of the electrochemical or ECL immunoassays. This review summarizes various types of MOFs-based immunosensors and their assays application, in which MOFs act as electrode matrices, signal probes (either as electroactive labels or as emitter labels), carriers or catalytic labels for sensitive electrochemical and ECL detections. Moreover, challenges and future opportunities for the development of the functionalized MOFs are discussed to provide a guidance on the design and fabrication of high-performance MOFs-based immunosensors in the future.

Key words: Metal organic frameworks, electrochemical immunosensors, electrochemiluminescent immunosensors, immunoassays

覃晓丽, 詹子颖, Sara Jahanghiri, Kenneth Chu, 张丛洋, 丁志峰. 金属有机框架材料在电化学/电化学发光免疫分析中的应用[J]. 电化学（中英文）, 2023, 29(6): 2218003.

Xiao-Li Qin, Zi-Ying Zhan, Sara Jahanghiri, Kenneth Chu, Cong-Yang Zhang, Zhi-Feng Ding. Metal-Organic Frameworks for Electrochemical and Electrochemiluminescent Immunoassay[J]. Journal of Electrochemistry, 2023, 29(6): 2218003.

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Sensor material	Target	Linear range (ng mL^-1)	LOD (ng mL^-1)	Ref.
HKUST-1 Cu-MOFs	NT-proBNP	0.5×10^-6-500	0.33×10^-6	[43]
Ag-MOFs	CEA	0.05-120	8×10^-6	[44]
AuNPs/Cu-MOFs	C-reactive protein	1-400	0.2	[45]
AuNPs/Cu-MOFs	CEA	0.1-80	0.03	[46]

Labeled composition	Surface				Ref.
Fe(III)-MIL-88B-NH₂@ZnSeQDs	electropolymerized dopamine MIP	SCCA	0.1×10^-3- 100 ng·mL^-1	31 fg·mL^-1	[67]
SnS₂QDs@MIL-101(Cr)	CuS/2D high porous carbon	Carbohydrate antigen 24-2	0.1×10^-3- 100 U·mL^-1	15 μU·mL^-1	[68]
Ag⁺@UiO-66-NH₂@CdWS	Au/rGO	PSA	0.1×10^-3- 10 ng·mL^-1	38 fg·mL^-1	[69]
Ti(IV)-MIL-125	AgNCs-Sem@AuNPs	NT-proBNP	2.5×10^-4- 100 ng·mL^-1	0.11 pg·mL^-1	[70]
Fe₃O₄@PDA-Cu_xO	MIL-101(AI):Ru-PEI-Au	Procalcitonin	5×10^-4- 100 ng·mL^-1	0.18 pg·mL^-1	[71]
Ru-MOFs	Pd@Au-L-Cys	Apo-A1	1×10^-6- 1.00 ng mL^-1	1 fg·mL^-1	[72]
MMOF@CdSnS	Ag@rGO	AFP	1×10^-6- 100 ng·mL^-1	0.2 fg·mL^-1	[73]
Co-MOFs/ABEI	Fe₃O₄@PPy-Au	Aβ42	1×10^-5- 100 ng·mL^-1	3 fg·mL^-1	[74]
/	Ce-MOF@g-C₃N₄/Au	NT-proBNP	5×10^-3- 20 ng·mL^-1	3.59 pg·mL^-1	[75]
/	MOF-545-Zn@MoS₂QDs	CEA	0.18 - 1000 ng·mL^-1	0.45 pg·mL^-1	[76]
/	Ru(bpy)₃²⁺@UiO-66-NH₂	CA15-3	5×10^-4- 500 U·mL^-1	0.17705 μU·mL^-1	[77]
/	Ru-MOFs	FABP	1.5×10^-4 - 150 ng·mL^-1	2.6 fg·mL^-1	[78]