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Identification of medium- and mechanism-related pitfalls towards improved performance and applicability of electrochemical mercury(II) aptasensors

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Abstract

The importance of understanding the mercury (II) ion interactions with thymine-rich DNA sequences is the reason for multiple comparative investigations carried out with the use of optical detection techniques directly in the depth of solution. However, the results of such investigations have limited applicability in the interpretation of the Hg2+ binding phenomenon by DNA sequences in thin, interfacial (electrode/solution), self-organized monolayers immobilized on polarizable surfaces, often used for sensing purposes in electrochemical biosensors. Overlooking the careful optimization of the measurement conditions is the source of discrepancies in the interpretation of the registered electrochemical signal. In this study, the chosen effects accompanying the efficiency of surface related recognition of Hg2+ by polyThymine DNA sequences labelled with methylene blue were investigated by voltammetry, QCM and spectro-electrochemical techniques. As was shown, the composition of the biosensing layer and buffers or the analytical procedures have a significant impact on the registered electrochemical readout which translates into signal stability, the biosensor’s working parameters or even the mechanism of detection. After elucidation of the above factors, the complete and ready-to-use biosensor-based analytical solution was proposed offering subpicomolar mercury ion determination with high selectivity (also in aqueous real samples), reusability, and high signal stability even after long-term storage. The developed procedures were successfully used during the miniaturization process with self-prepared (PVD) elastic transducers. The obtained sensor, together with the simplicity of its use, low manufacturing cost, and attractive analytical parameters (i.e., LOD < < Hg2+ WHO limit) can present an interesting alternative for on-site mercury ion detection in environmental samples.

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Acknowledgements

This work was financially supported by the Warsaw University of Technology (under the NChem4 program) and The National Centre for Research and Development under the III program TECHMATSTRATEG—Strategic research and development program ‘Modern material technologies—TECHMATSTRATEG’ no. TECHMATSTRATEG-III/0042/2019-00 and acronym ASTACUS, ‘Biopolymer materials with chemically and genetically programmed heavy metals selectivity for new generation of ultra-sensitive biosensors’.

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Authors and Affiliations

  1. Faculty of Chemistry, Warsaw University of Technology, Stanisława Noakowskiego 3, 00-664, Warsaw, Poland

    Anna Szymczyk, Martyna Popiołek, Robert Ziółkowski & Elżbieta Malinowska

  2. Doctoral School, Warsaw University of Technology, Plac Politechniki 1, 00-661, Warsaw, Poland

    Anna Szymczyk

  3. Centre for Advanced Materials and Technologies CEZAMAT, Warsaw University of Technology, Poleczki 19, 02-822, Warsaw, Poland

    Jakub Krzemiński & Elżbieta Malinowska

  4. Faculty of Chemistry, Warsaw University of Technology, Koszykowa 75, 00-664, Warsaw, Poland

    Marcin Olszewski

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  1. Anna Szymczyk
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Correspondence to Robert Ziółkowski.

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Szymczyk, A., Popiołek, M., Krzemiński, J. et al. Identification of medium- and mechanism-related pitfalls towards improved performance and applicability of electrochemical mercury(II) aptasensors. Microchim Acta 191, 189 (2024). https://doi.org/10.1007/s00604-024-06272-w

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