An integrated instrumental and theoretical approach to quantitative electrode kinetic studies based on large amplitude Fourier transformed a.c. voltammetry: A mini review

Bond, Alan M.; Elton, Darrell; Guo, SiXuan; Kennedy, Gareth; Mashkina, Elena; Simonov, Alexandr N.

doi:10.1016/j.elecom.2015.04.017

Cited by 69 publications

(100 citation statements)

References 26 publications

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“…Direct-current voltammograms were measured with an Ivium CompactStat potentiostat, and FTacV measurements were performed using custom-made instrumentation described elsewhere (11,14). All electrochemical experiments were performed under a N 2 atmosphere in a glove box (manufactured by University of York Chemistry Mechanical and Electronic Workshops).…”

Section: Methodsmentioning

confidence: 99%

“…Fourier-transformed alternating-current voltammetry (FTacV) is a technique that offers the ability to measure catalytic chemical redox reactions and reversible electron transfer processes in a single experiment (11,12). In the FTacV measurement, a large-amplitude sine wave of frequency f is superimposed on a linear voltage-time sweep (11,(13)(14)(15)) and the resulting current-time response is measured and then Fourier transformed (FT) into the frequency domain to give a power spectrum of harmonic contributions at frequencies f, 2f, 3f, etc. Band selection of the individual harmonics followed by inverse FT resolves the data back into the time domain.…”

Section: Significancementioning

confidence: 99%

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Electrochemical evidence that pyranopterin redox chemistry controls the catalysis of YedY, a mononuclear Mo enzyme

Adamson

Simonov

Kierzek

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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A long-standing contradiction in the field of mononuclear Mo enzyme research is that small-molecule chemistry on active-site mimic compounds predicts ligand participation in the electron transfer reactions, but biochemical measurements only suggest metal-centered catalytic electron transfer. With the simultaneous measurement of substrate turnover and reversible electron transfer that is provided by Fourier-transformed alternating-current voltammetry, we show that Escherichia coli YedY is a mononuclear Mo enzyme that reconciles this conflict. In YedY, addition of three protons and three electrons to the well-characterized "as-isolated" Mo(V) oxidation state is needed to initiate the catalytic reduction of either dimethyl sulfoxide or trimethylamine N-oxide. Based on comparison with earlier studies and our UV-vis redox titration data, we assign the reversible oneproton and one-electron reduction process centered around +174 mV vs. standard hydrogen electrode at pH 7 to a Mo(V)-to-Mo(IV) conversion but ascribe the two-proton and two-electron transition occurring at negative potential to the organic pyranopterin ligand system. We predict that a dihydro-to-tetrahydro transition is needed to generate the catalytically active state of the enzyme. This is a previously unidentified mechanism, suggested by the structural simplicity of YedY, a protein in which Mo is the only metal site.Fourier-transformed alternating-current voltammetry | mononuclear molybdenum enzyme | protein film electrochemistry | pyranopterin | YedY

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Section: Methodsmentioning

confidence: 99%

Section: Significancementioning

confidence: 99%

Electrochemical evidence that pyranopterin redox chemistry controls the catalysis of YedY, a mononuclear Mo enzyme

Adamson

Simonov

Kierzek

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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“…In order to obtain further insights into the enzymatic mechanism of MnxG, electrochemical and kinetic studies have been undertaken, as reported in our recent publication . Direct current (dc) and Fourier transformed (FT) alternating current (ac) voltammetric analysis of MnxEF immobilised on the self‐assembled monolayer of 6‐mercaptohexanoic acid (MHA) on a Au electrode have provided values of the apparent (effective) reversible potentials ( E app ) for the T2Cu sites in these subunits as 0.33–0.35 V vs . normal hydrogen electrode (NHE; hereinafter all potentials are provided vs .…”

Section: Introductionmentioning

confidence: 99%

Probing Electron Transfer in the Manganese‐Oxide‐Forming MnxEFG Protein Complex using Fourier Transformed AC Voltammetry: Understanding the Oxidative Priming Effect

et al. 2017

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MnxG, a multicopper oxidase, is an enzyme from the marine Bacillus species, which produces manganese oxide minerals through the aerobic oxidation of dissolved Mn2+ − a key process in global manganese geochemical cycling. When isolated in an active form as a part of the MnxEFG protein complex, the enzymatic activity of MnxG is substantially enhanced by mild oxidative priming. Herein, the mechanism for this effect is probed by using direct current (dc) and Fourier transformed alternating current (ac) voltammetric analysis of the MnxEFG complex and the catalytically inactive MnxEF subunit immobilised on a carbon electrode. Analysis of these ac voltammetric data reveals a significant enhancement in the rate of electron transfer in the Type 2 Cu sites upon oxidative priming of the enzyme, which is attributed to the improved catalytic activity of MnxG in the MnxEFG protein complex.

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“…The core idea is based on inspecting electrochemical data collected by conducting a SW voltammetric experiment combined with a multisampling current procedure [20]. Indeed, a similar idea for advanced analysis of electrochemical data collected by a voltammetric experiment was already introduced by Bond et al based on the advanced large amplitude Fourier transformed a.c. voltammetry [21].…”

Section: Introductionmentioning

confidence: 99%

“…k s, sur = 30 and 25 s À1 , the splitting is observed at sampling time of t s = 42 and 48 ms, respectively. Thus, an analogous methodology to the previously reported one [2,3,21,35,36] can be developed for kinetic and mechanistic characterization of the electrode reaction by recording a single experiment only. …”

mentioning

confidence: 99%

Characterizing electrode reactions by multisampling the current in square-wave voltammetry

Mirčeski

Guziejewski

Bozem

et al. 2016

Electrochimica Acta

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A B S T R A C TA novel and simple methodology for characterization of electrode processes by square-wave voltammetry (SWV), considered as a complex repetitive double-step chronoamperometric experiment, is proposed. Specifically, the sampling of the current at the very end of each potential pulse, as common in conventional SWV, is replaced with a multisampling protocol during each potential pulse, resulting in generation of a series of corresponding multisampled SW voltammograms constructed out of a single measurement. The evolution of such voltammograms reflects the chronoamperometric properties of the current in the course of each potential pulse, thus being specific to electrode mechanism and electrode kinetics. The proposed methodology could serve as a basis for modification of common SWV mode in commercially available instrumentation for the purpose of an advanced characterization of electrode processes. The methodology is theoretically illustrated by the analysis of three kinetically controlled common electrode mechanisms, such as the electrode reaction of a solution resident and surface confined redox couples, as well as the regenerative catalytic electrode mechanism (EC'), while the experimental verification is done with the electrode reaction of Eu 3+ /Eu 2+ and azobenzene/ hydrazobenzene redox couples.

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An integrated instrumental and theoretical approach to quantitative electrode kinetic studies based on large amplitude Fourier transformed a.c. voltammetry: A mini review

Cited by 69 publications

References 26 publications

Electrochemical evidence that pyranopterin redox chemistry controls the catalysis of YedY, a mononuclear Mo enzyme

Electrochemical evidence that pyranopterin redox chemistry controls the catalysis of YedY, a mononuclear Mo enzyme

Probing Electron Transfer in the Manganese‐Oxide‐Forming MnxEFG Protein Complex using Fourier Transformed AC Voltammetry: Understanding the Oxidative Priming Effect

Characterizing electrode reactions by multisampling the current in square-wave voltammetry

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