Abstract
Metal–organic frameworks (MOFs), as porous materials, have great potential for exploring high-performance electrochemiluminescence (ECL) probes. However, the constrained applicability of MOFs in the realm of ECL biosensing is primarily attributed to their inadequate water stability, which consequently impairs the overall ECL efficiency. Herein, we developed a competitive ECL biosensor based on a novel tightest structural ruthenium-based organic framework emitter combining the proximity hybridization-induced catalytic hairpin assembly (CHA) strategy and the quenching effect between the Ru-MOF and ferrocene for detecting paraquat (PQ). Through a simple hydrothermal synthesis strategy, ruthenium and 2,2ʹ-bipyrimidine (bpm) are head-to-head self-assembled to obtain a novel tightest structural Ru-MOF. Due to the metal–ligand charge-transfer (MLCT) effect between ruthenium and the bpm ligand and the connectivity between the internal chromophore units, the Ru-MOF exhibits strong ECL emissions. Meanwhile, the coordination-driven Ru-MOF utilizes strong metal–organic coordination bonds as building blocks, which effectively solves the problem of serious leakage of chromophores caused by water solubility. The sensitive analysis of PQ is realized in the range of 1 pg/mL to 1 ng/mL with a detection limit of 0.352 pg/mL. The tightest structural Ru-MOF driven by the coordination of ruthenium and bridging ligands (2,2ʹ-bipyrimidine, bpm) provides new horizons for exploring high-performance MOF-based ECL probes for quantitative analysis of biomarkers.
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Funding
This work was financially supported by the National Natural Science Foundation (NNSF) of China (81972024 and 52172154) and the Natural Science Foundation of Chongqing (cstc2020jcyj-msxmX0332), China.
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Ling Qin, conceptualization, methodology, investigation, data analysis, and writing, original draft; Wenbin Liang, conceptualization, supervision, and writing, review and editing; Weiguo Yang, investigation; Shenghan Tang, data analysis; Ruo Yuan, resources and project administration; Yan Li, supervision, project administration, and writing, review and editing; Jun Yang, supervision, funding acquisition, and writing, review and editing; Shanshan Hu, writing, review and editing, and funding acquisition.
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This study has been approved by the Human Ethics Committee of the Ninth People’s Hospital of Chongqing, China (2020-LS-009), and has been performed in accordance with the ethical standards.
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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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Qin, L., Liang, W., Yang, W. et al. The tightest self-assembled ruthenium metal–organic framework combined with proximity hybridization for ultrasensitive electrochemiluminescence analysis of paraquat. Anal Bioanal Chem (2024). https://doi.org/10.1007/s00216-024-05237-5
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DOI: https://doi.org/10.1007/s00216-024-05237-5