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Etching of Ag nanoparticles triggered bidirectional regulation for electrochemiluminescence ratiometric immunoassay

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Abstract

A highly efficient ratiometric electrochemiluminescence (ECL) immunoassay was explored by bidirectionally regulating the ECL intensity of two luminophors. The immunoassay was conducted in a split-type mode consisting of an ECL detection procedure and a sandwich immunoreaction. The ECL detection was executed using a dual-disk glassy carbon electrode modified with two potential-resolved luminophors (g-C3N4-Ag and Ru-MOF-Ag nanocomposites), and the sandwich immunoreaction using glucose oxidase (GOx)-modified SiO2 nanospheres as labels was carried out in a 96-well plate. The Ag nanoparticles (NPs) acted as bifunctional units both for triggering the resonance energy transfer (RET) with g-C3N4 and for accelerating the electron transfer rate of the Ru-MOF-Ag ECL reaction. When the H2O2 catalyzed by GOx in the 96-well plate was transferred to the dual-disk glass carbon electrode, the doped Ag NPs in the two luminophors could be etched, thus destroying the RET between C3N4 and the accelerated reaction to Ru-MOF, resulting in an opposite trend in the ECL signal outputted from the dual disks. Using the ratio of the two signals for quantification, the constructed immunosensor for a model target, i.e. myoglobin, exhibited a low detection limit of 4.7 × 10–14 g/mL. The ingenious combination of ECL ratiometry, bifunctional Ag NPs, and a split-type strategy effectively reduces environmental and human errors, offering a more precise and sensitive analysis for complex samples.

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Funding

The study received funding from the National Natural Science Foundation of China (Grant No. 22304146, 21874115, and 21675136), Program for Innovative Research Team (in Science and Technology) in the University of Henan Province (24IRTSTHN004), the Natural Science Foundation of Henan Province (232300420389), Key Scientific Research Project of Higher Education Institutions in Henan Province (24A150037, 22A150022), Shandong Key Laboratory of Biochemical Analysis (SKLBA2205), and the Nanhu Scholars Program for Young Scholars of Xinyang Normal University (XYNU).

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Xinyang Key Laboratory of Functional Nanomaterials for Bioanalysis, Xinyang Normal University, NO. 237 in Nanhu Road, Xinyang, 464000, Henan, China

    Yu-Ling Wang, Xiang-Mei Liu, Jun-Tao Cao & Yan-Ming Liu

  2. Xinyang Central Hospital, Xinyang, 464000, China

    Shu-Wei Ren

  3. Shandong Key Laboratory of Biochemical Analysis, Qingdao University of Science and Technology, Qingdao, 266042, China

    Yu-Ling Wang

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  1. Yu-Ling Wang
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Contributions

Yu-Ling Wang: Methodology, Investigation, Supervision, Project administration, Writing—modification. Xiang-Mei Liu: Conceptualization, Methodology, Investigation, Writing—original draft. Shu-Wei Ren: Validation. Jun-Tao Cao: Conceptualization, Methodology, Supervision, Project administration, Resource provision, Writing—original draft, Writing—review & editing. Yan-Ming Liu: Conceptualization, Methodology, Supervision, Project administration, Resource provision, Writing—original draft, Writing—review & editing.

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Correspondence to Jun-Tao Cao or Yan-Ming Liu.

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Ethics approval

Samples of human serum were obtained from the Affiliated Hospital of Xinyang Normal University with the approval of its ethics committee (XFEC-2023–029).

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The human serum samples used in this study were collected with the consent of the volunteers. The study was approved by the experimental ethics committee of Xinyang Normal University and its affiliated hospital.

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The authors declare no competing interests.

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Published in the topical collection Emerging Trends in Electrochemical Analysis with guest editors Sabine Szunerits, Wei Wang, and Adam T. Woolley.

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Wang, YL., Liu, XM., Ren, SW. et al. Etching of Ag nanoparticles triggered bidirectional regulation for electrochemiluminescence ratiometric immunoassay. Anal Bioanal Chem (2024). https://doi.org/10.1007/s00216-024-05277-x

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