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Flow injection enzymatic biosensor for aldehydes based on a Meldola Blue-Ni complex electrochemical mediator

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Abstract

Carbon nanofibers (CNF) are efficient electrode modifiers in electrochemical biosensors that enhance the electrochemical active area, induce electrocatalytic effect toward the oxidation of the enzymatic cofactor nicotinamide adenine dinucleotide (reduced form, NADH), and enable the quantitative immobilization of enzymes. Combining CNF with efficient and stable mediators radically augments the speed of electron transfer between NADH and solid electrodes and leads to electrochemical sensors characterized by high sensitivity and stability. The main aim of this work was to investigate the performance of a novel mediator for NADH with advantageously low solubility in an electrochemical detector based on a screen-printed CNF electrode as well as its potential in biosensing. Using a mediator, prepared from Meldola Blue and Ni hexamine chloride, a stable and sensitive electrochemical NADH sensor is provided with a detection limit of 0.5 μmol L−1. Further on, covalent immobilization of a recently described aldehyde dehydrogenase from the Antarctic Flavobacterium PL002 strain on the surface of the mediator-modified electrode produced a stable biosensor for the detection of aldehydes. When integrated in a flow injection analysis (FIA) setup with amperometric detection at 0.1 V vs. Ag/AgCl, the measurement of benzaldehyde with a detection limit of 10 μmol L−1 over a linear range of 30–300 μmol L−1 is possible. Determination of trace benzaldehyde impurities in a pharmaceutical excipient was also demonstrated and results compared with a chromatographic method.

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Acknowledgments

The authors wish to thank Medana Zamfir, Institute of Biology of the Romanian Academy, for the support with HPLC measurements.

Funding

This study was financially supported by the Romanian Executive Agency for Higher Education, Research, Development and Innovation (UEFISCDI), through PN-III-P2-2.1-PED-2016-0116 grant and ERANET-M-ENZ4IFACES contract 166/01.05.2020 for Ana Maria Titoiu, Georgiana Necula-Petrareanu, Cristina Purcarea and Alina Vasilescu.

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Author notes

  1. Ana Maria Titoiu and Georgiana Necula-Petrareanu contributed equally to this work.

Authors and Affiliations

  1. International Centre of Biodynamics, 1B Intrarea Portocalelor, 060101, Bucharest, Romania

    Ana Maria Titoiu & Alina Vasilescu

  2. Institute of Biology, 296 Splaiul Independentei, 060031, Bucharest, Romania

    Georgiana Necula-Petrareanu & Cristina Purcarea

  3. Coordination and Supramolecular Chemistry Laboratory, “Ilie Murgulescu” Institute of Physical Chemistry, Romanian Academy, Splaiul Independentei 202, 060021, Bucharest, Romania

    Diana Visinescu

  4. National Institute for Laser, Plasma and Radiation Physics (INFLPR), 409 Atomistilor, 077125, Magurele, Romania

    Valentina Dinca, Anca Bonciu & Cristian N. Mihailescu

  5. Faculty of Physics, University of Bucharest, 077125, Magurele, Romania

    Anca Bonciu

  6. Univ. Lille, CNRS, Centrale Lille, Univ. Polytechnique Hauts-de-France, UMR 8520 - IEMN, F-59000, Lille, France

    Rabah Boukherroub & Sabine Szunerits

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  1. Ana Maria Titoiu
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Correspondence to Alina Vasilescu.

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Titoiu, A.M., Necula-Petrareanu, G., Visinescu, D. et al. Flow injection enzymatic biosensor for aldehydes based on a Meldola Blue-Ni complex electrochemical mediator. Microchim Acta 187, 550 (2020). https://doi.org/10.1007/s00604-020-04477-3

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