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Protein Electrochemistry: Questions and Answers

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Biophotoelectrochemistry: From Bioelectrochemistry to Biophotovoltaics

Part of the book series: Advances in Biochemical Engineering/Biotechnology ((ABE,volume 158))

Abstract

This chapter presents the fundamentals of electrochemistry in the context of protein electrochemistry. We discuss redox proteins and enzymes that are not photoactive. Of course, the principles described herein also apply to photobioelectrochemistry, as discussed in later chapters of this book. Depending on which experiment is considered, electron transfer between proteins and electrodes can be either direct or mediated, and achieved in a variety of configurations: with the protein and/or the mediator free to diffuse in solution, immobilized in a thick, hydrated film, or adsorbed as a sub-monolayer on the electrode. The experiments can be performed with the goal to study the protein or to use it. Here emphasis is on mechanistic studies, which are easier in the configuration where the protein is adsorbed and electron transfer is direct, but we also explain the interpretation of signals obtained when diffusion processes affect the response.

This chapter is organized as a series of responses to questions. Questions 1–5 are related to the basics of electrochemistry: what does “potential” or “current” mean, what does an electrochemical set-up look like? Questions 6–9 are related to the distinction between adsorbed and diffusive redox species. The answers to questions 10–13 explain the interpretation of slow and fast scan voltammetry with redox proteins. Questions 14–19 deal with catalytic electrochemistry, when the protein studied is actually an enzyme. Questions 20, 21 and 22 are general.

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Notes

  1. 1.

    This claim is based on a model that considers this electron relay center as the only redox center in the enzyme [64], which, of course, can only predict that the catalytic potential is the potential of this center. Models that take into account the redox transformations of the active site and of an electron transfer relay (and electron transfer between the two) predict that the catalytic potential may or may not match the potential of one of these redox centers, depending on how the rates of intramolecular electron transfer compare to those that describe the transformations of the active site [3, 63].

  2. 2.

    To demonstrate this, let us consider the transformation between A and B according to \( A\underset{k_{-1}}{\overset{k_1}{\rightleftharpoons }}B \) The change in concentrations obeys the differential equation \( d\left[A\right]/dt=-{k}_1\left[A\right]+{k}_{-1}\left({C}_0-\left[A\right]\right) \) , where C 0 = [A] + [B]. The solution is \( \left[\mathrm{A}\right]=D\times \exp \left[-\left({k}_1+{k}_{-1}\right)t\right]+{C}_0{k}_{-1}/\left({k}_1+{k}_{-1}\right) \) where D is an integration constant.

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  1. Laboratoire de Bioénergétique et Ingénierie des Protéines, CNRS/Aix-Marseille Université, Marseille, France

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    Lars J.C. Jeuken

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Fourmond, V., Léger, C. (2016). Protein Electrochemistry: Questions and Answers. In: Jeuken, L. (eds) Biophotoelectrochemistry: From Bioelectrochemistry to Biophotovoltaics. Advances in Biochemical Engineering/Biotechnology, vol 158. Springer, Cham. https://doi.org/10.1007/10_2015_5016

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