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Selective and low potential electrocatalytic oxidation of NADH using a 2,2-diphenyl-1-picrylhydrazyl immobilized graphene oxide-modified glassy carbon electrode

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Abstract

DPPH (2,2-diphenyl-1-picrylhydrazil), a free radical-containing organic compound, is used widely to evaluate the antioxidant properties of plant constituents. Here, we report an efficient electroactive DPPH molecular system with excellent electrocatalytic sensor properties, which is clearly distinct from the traditional free radical-based quenching mechanism. This unusual molecular status was achieved by the electrochemical immobilization of graphene oxide (GO)-stabilized DPPH on a glassy carbon electrode (GCE). Potential cycling of the DPPH adsorbed-GCE/GO between − 1 and 1 V (Ag/AgCl) in a pH 7 solution revealed a stable and well-defined pair of redox peaks with a standard electrode potential, E0′ = 0 ± 0.01 V (Ag/AgCl). Several electrochemical characterization studies as well as surface analysis of the GCE/GO@DPPH-modified electrode by transmission electron microscopy, Raman, and infrared spectroscopy collectively identified the imine/amine groups as the redox centers of the electroactive DPPH on GO. The use of different carbon-supports showed that only oxygen-functionalized GO and MWCNTs could provide major electroactivity for DPPH. This highlights the importance of a strong hydrogen-bonded network structure assisted by the concomitant π-π interactions between the organic moiety and oxygen function groups of carbon for the high electroactivity and stability of the GCE/GO@DPPH-NH/NH2-modified electrode. The developed electrode exhibited remarkable performance towards the electrocatalytic oxidation of NADH at 0 V (Ag/AgCl). The amperometric i-t sensing of NADH showed high sensitivity (488 nA μM−1 cm−2) and an extended linear range (50 to 450 μM) with complete freedom from several common biochemical/chemical interferents, such as ascorbic acid, hydrazine, glucose, cysteine, citric acid, nitrate, and uric acid.

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Acknowledgements

K.C.P. thanks the Korea Federation of Science and Technology Societies (KOFST, Republic of Korea) for offering him the position of Invited Scientist through the “Brain Pool Program.”

Funding

This study was supported by the National Research Foundation of Korea (NRF) funded by the Korea government (MEST) (Grant No. 2017R1A2A1A05001484) and the Department of Science and Technology (DST), Science and Engineering Research Board, Government of India.

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  1. Annamalai Senthil Kumar

    Present address: Institute of Biochemical and Biomedical Engineering, National Taipei University of Technology, Taipei, 10608, Taiwan, Republic of China

Authors and Affiliations

  1. Department of Chemical Engineering, Sunchon National University, Suncheon, 540-742, South Korea

    K. Chandrasekara Pillai & Il-Shik Moon

  2. Nano and Bioelectrochemistry Research Laboratory, Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology University, Vellore, 632 014, India

    K. S. Shalini Devi & Annamalai Senthil Kumar

  3. Carbon dioxide Research and Green Technology Centre, Vellore Institute of Technology University, Vellore, 632 014, India

    Annamalai Senthil Kumar

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  1. K. Chandrasekara Pillai
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Correspondence to K. Chandrasekara Pillai or Il-Shik Moon.

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Pillai, K.C., Shalini Devi, K.S., Senthil Kumar, A. et al. Selective and low potential electrocatalytic oxidation of NADH using a 2,2-diphenyl-1-picrylhydrazyl immobilized graphene oxide-modified glassy carbon electrode. J Solid State Electrochem 22, 3393–3408 (2018). https://doi.org/10.1007/s10008-018-4029-5

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