Mechanistic aspects of the electrochemical oxidation of dihydronicotinamide adenine dinucleotide (NADH)

Moiroux, Jacques; Elving, Philip J.

doi:10.1021/ja00541a024

Cited by 220 publications

(119 citation statements)

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“…As such, the development of robust methods of analysis for NADH is of considerable importance, with electrochemical methods proving particularly effective. The mechanism of NADH oxidation has been studied extensively by Moiroux and Elving [2][3][4][5] and it is well established that at neutral pH, NADH undergoes a two-electron one-proton oxidation process of the ECE (electron transfer-chemical step-electron transfer) type: (1) (2) (3) A wide range of carbon electrode materials have received considerable attention for NADH electro-oxidation, including glassy carbon, 4,6 carbon paste, 7 carbon nanotubes, 8,9 graphene 10 and graphene composites, [11][12][13] pyrolytic graphite 14 and boron-doped diamond. 15 The study of NADH oxidation on bare carbon electrode surfaces is non-trivial.…”

Section: Introductionmentioning

confidence: 99%

“…The electrochemistry of NADH at conducting diamond has received attention, but the focus has mainly been on hydrogen-terminated diamond, 15,21 with oxygen terminated diamond 14 receiving only scant attention. Despite its importance as a well-defined model surface for sp 2 carbon, there are no reports of NADH oxidation at highly oriented pyrolytic graphite (HOPG) electrodes. It is important to note that the oxidation of NADH has been investigated at edge plane pyrolytic graphite (EPPG) and basal plane pyrolytic graphite (BPPG), 14 but these materials should not be confused with HOPG.…”

Section: Introductionmentioning

confidence: 99%

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Electrochemical oxidation of dihydronicotinamide adenine dinucleotide (NADH): comparison of highly oriented pyrolytic graphite (HOPG) and polycrystalline boron-doped diamond (pBDD) electrodes

Maddar

Lazenby

Patel

et al. 2016

Phys. Chem. Chem. Phys.

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(2016) Electrochemical oxidation of dihydronicotinamide adenine dinucleotide (NADH) : Comparison of highly oriented pyrolytic graphite (HOPG) and polycrystalline boron-doped diamond (pBDD) electrodes. Physical Chemistry Chemical Physics. Permanent WRAP URL:http://wrap.warwick.ac.uk/81637 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work of researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for-profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. The electro-oxidation of nicotinamide adenine dinucleotide (NADH) is studied at bare surfaces of highly oriented pyrolytic graphite (HOPG) and semi-metallic polycrystalline boron-doped diamond (pBDD). A comparison of these two carbon electrode materials is interesting because they possess broadly similar densities of electronic states that are much lower than most metal electrodes, but graphite has carbon sp 2 -hybridization, while in diamond the carbon is sp 3 -hybridised, with resulting major differences in bulk structure and surface termination. Using cyclic voltammetry (CV), it is shown that NADH oxidation is facile at HOPG surfaces but the reaction products tend to strongly adsorb, which causes rapid deactivation of the electrode activity. This is an important factor that needs to be taken into account when assessing HOPG and its intrinsic activity. It is also shown that NADH itself adsorbs at HOPG, a fact that has not been recognized previously, but has implications for understanding the mechanism of the electro-oxidation process. Although pBDD was found to be less susceptible to surface fouling, pBDD is not immune to deterioration of the electrode response, and the reaction showed more sluggish kinetics on this electrode. Scanning electrochemical cell microscopy (SECCM) highlights a significant voltammetric variation in electroactivity between different crystal surface facets that are presented to solution with a pBDD electrode. The electroactivity of different grains correlates with the local dopant level, as visualized by field emission-scanning electron microscopy. SECCM measurements further prove that the basal plane of HOPG has high activity towards NADH electro-oxidation. These new insights on NADH voltammetry are useful for the design of optimal carbon-based electrodes for NADH electroanalysis.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electrochemical oxidation of dihydronicotinamide adenine dinucleotide (NADH): comparison of highly oriented pyrolytic graphite (HOPG) and polycrystalline boron-doped diamond (pBDD) electrodes

Maddar

Lazenby

Patel

et al. 2016

Phys. Chem. Chem. Phys.

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“…1,2,7 The oxidation of NADH is known to follow an ECE mechanism with a rate-limiting step in the first electron transfer. 2,6 Various redox mediators with quinone groups making two-electron and hydride transfer possible were reported as good candidates. 2,7,[8][9][10] Recently, carbon nanotubes were employed as a promising electrode material giving enhanced performances with less overpotentials and enhanced sensitivities.…”

Section: 6mentioning

confidence: 99%

Enhanced Electrocatalytic Activity for the NADH Oxidation with Oxidatively Treated Carbon Nanotubes Incorporated on a Redox Polymer Modified Electrode

Shin¹,

Shin²,

Kang³

2012

Bulletin of the Korean Chemical Society

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The electrochemical oxidation of dihydronicotinamide adenine dinucleotide (NADH) has drawn many attentions for use of its oxidized form (NAD + ) as an enzymatic cofactor in many dehydrogenase based biosensors and biofuel cells. 1,2At neutral pH, NADH/NAD + couple has a formal potential of −0.320 V (vs NHE), 3 but large oxidation overpotentials are generally required.2,4 In addition to this problem, direct oxidation of NADH shows unwanted side reactions or adsorption of the product. 5,6To avoid these problems, many studies using various electrocatalysts were reported. In this point of view, mediatormodified electrodes and electrochemical sensing designs were reviewed.1,2,7 The oxidation of NADH is known to follow an ECE mechanism with a rate-limiting step in the first electron transfer.2,6 Various redox mediators with quinone groups making two-electron and hydride transfer possible were reported as good candidates. 2,7,[8][9][10] Recently, carbon nanotubes were employed as a promising electrode material giving enhanced performances with less overpotentials and enhanced sensitivities.11-14 The carbon nanotubes (CNTs) in the nanocomposite films show good charge transport properties resulting in less overpotentials and good stabilities. 12,15In the present study, a redox polymer, the copolymer of polyacrylamide and poly(N-vinylimidazole) complexed with [Os(4,4'-dimethyl-2,2'-bipyridine), was employed for the electron transfer mediator for NADH oxidation. The redox polymers have been utilized for mediating electrons between the redox centers of enzymes and electrode surfaces.16,17 Some oxidase enzymes were "wired" to carbon electrodes and efficient electrocatalytic reactions such as glucose oxidation and O 2 reductions were reported. [16][17][18][19] At an electrode with a hydrogel film of the redox polymer, which is not a quinone-like mediator, catalytic electro-oxidation of NADH, but only a partial fraction, was measured. A composite film of the redox polymer and oxidatively treated single-walled carbon nanotubes (SWNTs) was applied on an edge plane graphite electrode surface. At this newly prepared electrode, an enhanced activity showing most NADH catalytically oxidized with less overpotential was achieved. As far as we know, the present redox polymer-CNT composite system, which is not a quinone type mediator, is first for the electrocatalytic NADH oxidation.Cyclic voltammograms obtained in a 2.0 mM NADH solution at bare EPG and RP/EPG electrodes for Figures 1(a) and 1(b), respectively, were shown. (For abbreviations of electrode types, consult the experimental section.) Voltammograms obtained in a pure supporting electrolyte were also shown as dashed curves. In Figure 1(a), only one oxidation wave for NADH oxidation was observed with a peak potential of 0.34 V. In Figure 1(b), in the absence of .

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“…Although the reversible potential of NADH oxidation is −0.32 V vs. a normal hydrogen electrode (NHE) (Chenault and Whitesides 1987), both the anodic oxidation of NAD(P)H and the cathodic reduction of NAD(P) + are chemically irreversible and need high overpotentials (Moiroux and Elving 1980). These overpotentials lead to the oxidation of other electroactive species in the solution, which generates a current that interferes with the analysis (Prieto-Simón and Fàbregas 2004).…”

Section: Introductionmentioning

confidence: 99%

Immobilized redox mediators for electrochemical NAD(P)+ regeneration

Kochius

Magnusson

Hollmann

et al. 2012

Appl Microbiol Biotechnol

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The applicability of dissolved redox mediators for NAD(P) + regeneration has been demonstrated several times. Nevertheless, the use of mediators in solutions for sensor applications is not a very convenient strategy since the analysis is not reagentless and long stabilization times occur. The most important drawbacks of dissolved mediators in biocatalytic applications are interferences during product purification, limited reusability of the mediators, and their cost-intensive elimination from wastewater. Therefore, the use of immobilized mediators has both economic and ecological advantages. This work critically reviews the current stateof-art of immobilized redox mediators for electrochemical NAD(P) + regeneration. Various surface modification techniques, such as adsorption polymerization and covalent linkage, as well as the corresponding NAD(P) + regeneration rates and the operational stability of the immobilized mediator films, will be discussed. By comparison with other existing regeneration systems, the technical potential and future perspectives of biocatalytic redox reactions based on electrochemically fed immobilized mediators will be assessed.

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Mechanistic aspects of the electrochemical oxidation of dihydronicotinamide adenine dinucleotide (NADH)

Cited by 220 publications

References 0 publications

Electrochemical oxidation of dihydronicotinamide adenine dinucleotide (NADH): comparison of highly oriented pyrolytic graphite (HOPG) and polycrystalline boron-doped diamond (pBDD) electrodes

Electrochemical oxidation of dihydronicotinamide adenine dinucleotide (NADH): comparison of highly oriented pyrolytic graphite (HOPG) and polycrystalline boron-doped diamond (pBDD) electrodes

Enhanced Electrocatalytic Activity for the NADH Oxidation with Oxidatively Treated Carbon Nanotubes Incorporated on a Redox Polymer Modified Electrode

Immobilized redox mediators for electrochemical NAD(P)+ regeneration

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