Journal ArticleDOI
Enzyme electrokinetics: using protein film voltammetry to investigate redox enzymes and their mechanisms.
Christophe Léger,Sean Elliott,Sean Elliott,Kevin R. Hoke,Lars J. C. Jeuken,Lars J. C. Jeuken,and Anne K. Jones,Fraser A. Armstrong +7 more
TLDR
The principles of protein film voltammetry are outlined by discussing some recent results from this laboratory, and the potential dimension is introduced into enzyme kinetics.Abstract:
Protein film voltammetry is a relatively new approach to studying redox enzymes, the concept being that a sample of a redox protein is configured as a film on an electrode and probed by a variety of electrochemical techniques. The enzyme molecules are bound at the electrode surface in such a way that there is fast electron transfer and complete retention of the chemistry of the active site that is observed in more conventional experiments. Modulations of the electrode potential or catalytic turnover result in the movement of electrons to, from, and within the enzyme; this is detected as a current that varies in characteristic ways with time and potential. Henceforth, the potential dimension is introduced into enzyme kinetics. The presence of additional intrinsic redox centers for providing fast intramolecular electron transfer between a buried active site and the protein surface is an important factor. Centers which carry out cooperative two-electron transfer, most obviously flavins, produce a particularl...read more
Citations
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Shewanella secretes flavins that mediate extracellular electron transfer
Enrico Marsili,Daniel B. Baron,Indraneel D. Shikhare,Dan Coursolle,Jeffrey A. Gralnick,Daniel R. Bond +5 more
TL;DR: In situ demonstration of flavin production, and sequestration at surfaces, requires the paradigm of soluble redox shuttles in geochemistry to be adjusted to include binding and modification of surfaces.
Journal ArticleDOI
Enzymes as working or inspirational electrocatalysts for fuel cells and electrolysis.
TL;DR: Fuel cells vary greatly in their power output, ranging from large-scale building-integrated systems, known as “combined heat and power” systems, to those that provide just enough power to operate electronics in special circumstances, such as an implanted device for sensing and controlling glucose levels in the body.
Journal ArticleDOI
Investigating and Exploiting the Electrocatalytic Properties of Hydrogenases
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Direct Electrochemistry of Redox Enzymes as a Tool for Mechanistic Studies
TL;DR: This review regards the use of dynamic electrochemistry to study the mechanism of redox enzymes, with exclusive emphasis on the configuration where the protein is adsorbed onto an electrode and electron tranfer is direct.
Journal ArticleDOI
Reversible interconversion of carbon dioxide and formate by an electroactive enzyme.
TL;DR: FDH1 demonstrates the feasibility of interconverting CO2 and formate electrochemically, and it is a template for the development of robust synthetic catalysts suitable for practical applications.
References
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Journal ArticleDOI
Reaction of complex metalloproteins studied by protein-film voltammetry
TL;DR: In this paper, a review explores applications of voltammetric methods for observing reactions of complex metalloproteins, and particular emphasis is given to the ability to study reactions that are coupled to and may open the primary electron exchange processes.
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Effect of a dispersion of interfacial electron transfer rates on steady state catalytic electron transport in [NiFe]-hydrogenase and other enzymes
TL;DR: In this paper, a residual slope in voltammograms is observed, which is unexpected from all simple considerations of electrochemical kinetics, and it is observed in experiments carried out with the [NiFe]-hydrogenase from NiFe hydroxide.
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Interpreting the Catalytic Voltammetry of Electroactive Enzymes Adsorbed on Electrodes
TL;DR: In this paper, the shape, height, steepness, and potential of voltammetric waveforms displayed by redox enzymes adsorbed on electrodes are analyzed to reveal and quantify important mechanistic characteristics of the active sites involved in catalysis and to elucidate the contributions of different factors in determining the overall electron-transport rates.
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Direct Detection and Measurement of Electron Relays in a Multicentered Enzyme: Voltammetry of Electrode-Surface Films of E. coli Fumarate Reductase, an Iron−Sulfur Flavoprotein
TL;DR: In this article, the membrane-extrinsic catalytic domain of E. coli fumarate reductase (FrdAB) adsorbs to electroactive monolayer coverage at a rotating pyrolytic graphite edge electrode, giving characteristic voltammetric signals that are resolved and assigned to redoxactive sites.
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Electrocatalytic Voltammetry of Succinate Dehydrogenase: Direct Quantification of the Catalytic Properties of a Complex Electron-Transport Enzyme
TL;DR: It is revealed that under reversible conditions, SDH is biased to catalyze fumarate reduction (reversal of the tricarboxylic acid cycle) at pH values below 7.7.