Journal of Solid State Electrochemistry

, Volume 22, Issue 11, pp 3393–3408 | Cite as

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

  • K. Chandrasekara PillaiEmail author
  • K. S. Shalini Devi
  • Annamalai Senthil Kumar
  • Il-Shik MoonEmail author
Original Paper


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.


DPPH Graphene oxide Free radical/functional group redox activity Electrocatalytic oxidation NADH Amperometric i-t detection 



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 information

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.

Supplementary material

10008_2018_4029_MOESM1_ESM.docx (122 kb)
ESM 1 (DOCX 122 kb)


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Chemical EngineeringSunchon National UniversitySuncheonSouth Korea
  2. 2.Nano and Bioelectrochemistry Research Laboratory, Department of Chemistry, School of Advanced SciencesVellore Institute of Technology UniversityVelloreIndia
  3. 3.Carbon dioxide Research and Green Technology CentreVellore Institute of Technology UniversityVelloreIndia
  4. 4.Institute of Biochemical and Biomedical EngineeringNational Taipei University of TechnologyTaipeiTaiwan, Republic of China

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