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Studying the ion transfer across liquid interface of thin organic-film-modified electrodes in the presence of glucose oxidase

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Abstract

A coupled electron-ion transfer reaction at thin organic-film-modified electrodes (TFE) is studied in the presence of glucose oxidase (GOx) under voltammetric conditions. TFE consists of a graphite electrode modified with a nitrobenzene solution of decamethylferrocene (DMFC) as a redox mediator and tetrabuthylammonium perchlorate as an organic-supporting electrolyte, in contact with aqueous buffer solutions containing percholarte ions and GOx. The redox turnover of DMFC coupled with perchlorate transfer across water|nitrobenzene interface composes the coupled electron-ion transfer reaction. Glucose oxidase strongly adsorbs at the liquid|liquid interface affecting the coupled electron-ion transfer reaction by reducing the surface area of the liquid interface, prompting coadsorption of the transferring ion and lowering down slightly the rate of the ion transfer reaction. Although the enzyme exists as a polyvalent anion over the pH interval from 5.6 to 7, it does not participate directly in the ionic current across the liquid interface and percholrate remains the main transferring ion. Raman spectroscopic data, together with the voltammetric data collected by three-phase droplet electrodes, indicate that the adsorption of the enzyme does not depend either on the redox mediator (DMFC) or the organic-supporting electrolyte, while being driven by intrinsic interactions of the enzyme with the organic solvent. The overall electrochemical mechanism is mathematically modeled by considering linear adsorption isotherm of the transferring ion, semi-infinite mass transfer regime, and phenomenological second-order kinetic model.

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Acknowledgments

VM and RG acknowledge Alexander von Humboldt foundation for the financial support from the Research Group Linkage Programme 3.4-Fokoop-DEU/1128670, as well as the support of DAAD foundation through multilateral project “International Masters and Postgraduate Programme in Materials Science and Catalysis” (MatCatNet). VM also acknowledges with gratitude the support through the COST Action CM1302.

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Authors and Affiliations

  1. Institute of Chemistry, Faculty of Natural Sciences and Mathematics, “Ss Cyril and Methodius” University, P.O. Box 162, 1000, Skopje, Republic of Macedonia

    Valentin Mirceski, Biljana Mitrova, Vladimir Ivanovski, Nikolina Mitreska, Angela Aleksovska & Rubin Gulaboski

  2. Faculty of Medical Sciences, “Goce Delcev” University, P.O. Box 201, 2000, Stip, Republic of Macedonia

    Valentin Mirceski & Rubin Gulaboski

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  1. Valentin Mirceski
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  2. Biljana Mitrova
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  4. Nikolina Mitreska
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  6. Rubin Gulaboski
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Correspondence to Valentin Mirceski.

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Mirceski, V., Mitrova, B., Ivanovski, V. et al. Studying the ion transfer across liquid interface of thin organic-film-modified electrodes in the presence of glucose oxidase. J Solid State Electrochem 19, 2331–2342 (2015). https://doi.org/10.1007/s10008-015-2863-2

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  • DOI: https://doi.org/10.1007/s10008-015-2863-2

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