Protein-film voltammetry (PFV) is a versatile tool designed to provide insight into the enzymes physiological
functions by studying the redox properties of various oxido-reductases with suitable voltammetric
technique. The determination of the thermodynamic and kinetic parameters relevant to protein’s physiological
properties is achieved via methodologies established from theoretical considerations of various
mechanisms in PFV. So far, the majority of the mathematical models in PFV have been developed for redox
proteins undergoing a single-step electron transfer reactions. However, there are many oxido-reductases
containing quinone moieties or polyvalent ions of transition metals like Mo, Mn, W, Fe or Co as redox
centers, whose redox chemistry can be described only via mathematical models considering successive
two-step electron transformation. In this work we consider theoretically the protein-film redox mechanisms
of the EE (Electrochemical–Electrochemical), ECE (Electrochemical–Chemical–Electrochemical),
and EECat (Electrochemical–Electrochemical–Catalytic) systems under conditions of cyclic staircase
voltammetry. We also propose methodologies to determine the kinetics of electron transfer steps by all
considered mechanisms. The experimentalists working with PFV can get large benefits from the simulated
voltammograms given in this work
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