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Nanocomposites based on carbon nanotubes and redox-active polymers synthesized in a deep eutectic solvent as a new electrochemical sensing platform

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Abstract

The redox polymer poly(methylene blue) was synthesized by electropolymerization in ethaline deep eutectic solvent (PMBDES), and employed in a new nanostructured composite together with carbon nanotubes (CNT). The polymer was formed either before or after CNT deposition on glassy carbon electrodes (GCE) to obtain GCE/PMBDES/CNT and GCE/CNT/PMBDES modified electrodes, respectively. The morphology of the hybrid films was investigated by scanning electron microscopy, and their electrochemical performance by cyclic voltammetry and electrochemical impedance spectroscopy. The composite with the highest faradaic response and electronic conductivity was identified and applied as a platform for the determination of ascorbic acid by fixed potential amperometry at +0.2 V vs. Ag/AgCl, and acetaminophen by square wave voltammetry and differential pulse voltammetry at +0.67 V vs. Ag/AgCl. The limits of detection of the best sensor configurations are 1.7 μM for AA, and 1.6 μM for APAP, and respective electrochemical sensitivities are 2.2 μA cm-2 μM−1 and 68.7 μA cm-2μ​M-1. The applicability of the electrochemical sensors was demonstrated by the successful quantification of both these key analytes in complex pharmaceutical formulations.

Poly(methylene blue) electrosynthesized in ethaline deep eutectic solvent (PMBDES) and employed in a nanostructured composite with CNT (PMBDES-CNT). PMBDES-CNT sensors characterized by SEM and electrochemical methods and applied to ascorbate (AA) and acetaminophen (APAP) electrochemical detection in pharmaceutical formulations.

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Acknowledgements

The authors are grateful for financial support from the Romanian National Authority for Scientific Research, CNCS - UEFISCDI, project number PNII-RU-TE-2014-4-0460 and from the Fundação para a Ciência e a Tecnologia (FCT), Portugal projects PTDC/QEQ-QAN/2201/2014, in the framework of Project 3599-PPCDT, and UID/EMS/00285/2013 (both co-financed by the European Community Fund FEDER), for financial support. O.H. thanks UMF for the internal grant number 7690/56/15.04.2016. M.M.B. thanks FCT for a postdoctoral fellowship SFRH/BPD/72656/2010.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Sciences and Technology, University of Coimbra, 3004-535, Coimbra, Portugal

    Oana Hosu, Madalina M. Barsan & Christopher M. A. Brett

  2. Department of Analytical Chemistry, Faculty of Pharmacy, “Iuliu Haţieganu” University of Medicine and Pharmacy, 400349, Cluj-Napoca, Romania

    Oana Hosu, Cecilia Cristea & Robert Săndulescu

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  1. Oana Hosu
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  2. Madalina M. Barsan
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  5. Christopher M. A. Brett
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Correspondence to Christopher M. A. Brett.

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Hosu, O., Barsan, M.M., Cristea, C. et al. Nanocomposites based on carbon nanotubes and redox-active polymers synthesized in a deep eutectic solvent as a new electrochemical sensing platform. Microchim Acta 184, 3919–3927 (2017). https://doi.org/10.1007/s00604-017-2420-z

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