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Ratiometric electrochemical determination of hydroxyl radical based on graphite paper modified with metal–organic frameworks and impregnated with salicylic acid

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Abstract

Hydroxyl radical (•OH) detection is pivotal in medicine, biochemistry and environmental chemistry. Yet, electrochemical method–specific detection is challenging because of hydroxyl radicals’ high reactivity and short half-life. In this study, we aimed to modify the electrode surface with a specific recognition probe for •OH. To achieve this, we conducted a one-step hydrothermal process to fabricate a CoZnMOF bimetallic organic framework directly onto conductive graphite paper (Gp). Subsequently, we introduced salicylic acid (SA) and methylene blue (MB), which easily penetrated the pores of CoZnMOF. By selectively capturing •OH by SA and leveraging the electrochemical signal generated by the reaction product, we successfully developed an electrochemical sensor Gp/CoZnMOF/SA + MB. The prepared sensor exhibited a good linear relationship with •OH concentrations ranging from 1.25 to 1200 nM, with a detection limit of 0.2 nM. Additionally, the sensor demonstrated excellent reproducibility and accuracy due to the incorporation of an internal reference. It exhibited remarkable selectivity for •OH detection, unaffected by other electrochemically active substances. The establishment of this sensor provides a way to construct MOF-modified sensors for the selective detection of other reactive oxygen species (ROS), offering a valuable experimental basis for ROS-related disease research and environmental safety investigations.

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Funding

This study was financially supported by the Excellent Youth Fund of Henan Province (Grant No. 232300421084), National Natural Science Foundation of China (Grant No. 22104078, 22005185, 22074089), Natural Science Foundation of Henan Province (Grant No. 232300421234), Program for Science & Technology Innovation Talents in Universities of Henan Province (No. 24HASTIT003), Program for Innovative Research Team (in Science and Technology) in University of Henan Province (No. 24IRTSTHN003) and Henan Joint International Research Laboratory of Chemo/Biosensing and Early Diagnosis of Major Diseases.

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  1. Hui Dong and Zhenlong Jiang contributed equally.

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  1. Henan Key Laboratory of Biomolecular Recognition and Sensing, College of Chemistry and Chemical Engineering, Henan Joint International Research Laboratory of Chemo/Biosensing and Early Diagnosis of Major Diseases, Shangqiu Normal University, Shangqiu, 476000, People’s Republic of China

    Hui Dong, Zhenlong Jiang, Yanan Chen, Huabo Han, Yanli Zhou, Maotian Xu & Lantao Liu

  2. School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, 453007, People’s Republic of China

    Zhenlong Jiang, Yanli Zhou, Xiaobing Wang & Lantao Liu

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  1. Hui Dong
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Hui Dong and Zhenlong Jiang contributed equally to this work. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

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Dong, H., Jiang, Z., Chen, Y. et al. Ratiometric electrochemical determination of hydroxyl radical based on graphite paper modified with metal–organic frameworks and impregnated with salicylic acid. Microchim Acta 191, 121 (2024). https://doi.org/10.1007/s00604-024-06202-w

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