Published November 6, 2019 | Version Published
Journal article Open

Bioelectrochemistry of Cytochrome c in a closed bipolar electrochemical cell

  • 1. The Bernal Institute and Department of Chemical Sciences, School of Natural Sciences, University of Limerick (UL), Limerick V94 T9PX, Ireland
  • 2. Laboratoire de Chimie Physique et Microbiologie pour les Matériaux et l'Environnement (LCPME), UMR 7564, CNRS, Université de Lorraine, 405 rue de Vandoeuvre, Villers-lès-Nancy, F-54600, France


The reversible oxidation and reduction of Cytochrome c (Cyt c) is demonstrated with a closed bipolar electrochemical cell (CBPEC). Herein, a 4-electrode configuration was studied with the opposite poles of the bipolar electrode resting in separate aqueous and organic electrolyte solutions, respectively. Using biocompatible indium tin oxide (ITO) slides as the bipolar electrode poles, we investigated the influence of the redox potential of the reductant (decamethyferrocene or dimethylferrocene) in a trifluorotoluene organic phase on the observed voltammetry. Reversible electron transfer was only observed between Cyt c and decamethylferrocene. Use of the weaker dimethylferrocene as the reductant required a larger external bias of the driving electrodes to initiate the electron transfer reaction between the two poles of the bipolar electrode. Consequently, the surface of the ITO slide at the aqueous pole experienced a significant negative cathodic potential and underwent irreversible reduction. The biphasic setup using the 4-electrode CBPEC provides insights into electron transfer processes at an interface between two immiscible electrolyte solutions (ITIES), highlighting the strong probability of observing interfacial electron transfer between decamethylferrocene (but not dimethylferrocene) and Cyt c within the short ~ 1 V polarisable potential window available at an ITIES.


A. G.-Q. acknowledges funding received from an Irish Research Council Government of Ireland Postdoctoral Fellowship Award (grant number GOIPD/2018/252). G. H. is grateful to the French Programme Investissement d'Avenir (PIA) "Lorraine Université d'Excellence" (Reference No. ANR-15-IDEX-04-LUE). for the partial financial support of this work. The authors are grateful to the support of the Irish Research Council and Campus France for travel support between the French and Irish groups through their joint ULYSSES programme.



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Designing Reactive Functionalised Soft Interfaces _ Self-healing soft materials for solar energy conversion, energy storage, and sustainable low cost hydrogen production 13/SIRG/2137
Science Foundation Ireland
SOFT-PHOTOCONVERSION – Solar Energy Conversion without Solid State Architectures: Pushing the Boundaries of Photoconversion Efficiencies at Self-healing Photosensitiser Functionalised Soft Interfaces 716792
European Commission