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A label-free ratiometric fluorescent aptasensor based on a peroxidase-mimetic multifunctional ZrFe-MOF for the determination of tetrodotoxin

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Abstract

A Fe/Zr bimetal-organic framework (ZrFe-MOF) is utilized to establish a ratiometric fluorescent aptasensor for the determination of tetrodotoxin (TTX). The multifunctional ZrFe-MOF possesses inherent fluorescence at 445 nm wavelength, peroxidase-mimetic activity, and specific recognition and adsorption capabilities for aptamers, owing to its organic ligand, and Fe and Zr nodes. The peroxidation of o-phenylenediamine (OPD) substrate generates fluorescent 2,3-diaminophenazine (OPDox) at 555 nm wavelength, thus quenching the inherent fluorescence of ZrFe-MOF because of the fluorescence resonance energy transfer (FRET) effect. TTX aptamers, which are absorbed on the material surface without immobilization or fluorescent labeling, inhibit the peroxidase-mimetic activity of ZrFe-MOF. It causes the decreased OPDox fluorescence at 555 nm wavelength and the inverse restoration of ZrFe-MOF fluorescence at 445 nm wavelength. With TTX, the aptamers specifically bind to TTX, triggering rigid complex release from ZrFe-MOF surface and reactivating its peroxidase-mimetic activity. Consequently, the two fluorescence signals exhibit opposite changes. Employing this ratiometric strategy, the determination of TTX is achieved with a detection limit of 0.027 ng/mL and a linear range of 0.05–500 ng/mL. This aptasensor also successfully determines TTX concentrations in puffer fish and clam samples, demonstrating its promising application for monitoring trace TTX in food safety.

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Funding

This work was supported by the National Key Research and Development Program of China (No. 2021YFA0910200).

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Authors and Affiliations

  1. Binzhou Medical University, Yantai, 264003, China

    Sha Liu, Zhiyong Hu, Gaofang Cao & Zhixian Gao

  2. Tianjin Key Laboratory of Risk Assessment and Control Technology for Environment and Food Safety, Tianjin Institute of Environmental and Operational Medicine, Tianjin, 300050, China

    Sha Liu & Zhixian Gao

  3. Yantai Center for Disease Control and Prevention, Yantai, 264003, China

    Yapeng Huo

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  1. Sha Liu
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Contributions

Sha Liu: methodology, investigation, validation, data curation, formal analysis, writing—original draft; Yapeng Huo: data curation, formal analysis, conceptualization, writing—original draft; Zhiyong Hu: investigation, validation, writing—original draft; Gaofang Cao: methodology, project administration, writing—original/reviewing and editing, supervision; Zhixian Gao: conceptualization, project administration, writing—original/reviewing and editing, funding acquisition, supervision. All authors read and approved the final manuscript.

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Correspondence to Gaofang Cao or Zhixian Gao.

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Liu, S., Huo, Y., Hu, Z. et al. A label-free ratiometric fluorescent aptasensor based on a peroxidase-mimetic multifunctional ZrFe-MOF for the determination of tetrodotoxin. Microchim Acta 191, 57 (2024). https://doi.org/10.1007/s00604-023-06118-x

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