Catalytic mechanism in successive two-step protein-film voltammetry—Theoretical study in square-wave voltammetry

Gulaboski, Rubin and Mihajlov, Ljupco (2011) Catalytic mechanism in successive two-step protein-film voltammetry—Theoretical study in square-wave voltammetry. Biophysical Chemistry, 155 (1). pp. 1-9. ISSN 03014622

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Protein-film voltammetry is established as an effective tool that provides insight to the redox features of
various lipophilic proteins by using a simple methodology. Although the protein-film experimental set up is
relatively simple, the redox mechanisms of many proteins are quite complicated, and very often they cannot
be resolved without having support from adequate mathematical models. In this work we continue our
contribution to modeling relevant redox mechanisms in protein-film voltammetry. We present results from
the theoretical simulations of catalytic mechanism at the two-step successive surface redox reaction under
conditions of square-wave voltammetry. This mechanism is assigned as a surface EEC′, and it can be presented
by the following simplified scheme: A(ads)+ne−⇄B(ads)+ne−⇄C(ads)+Substrate→kcat B(ads). Our
attention is focused on several phenomena of this complex protein-film mechanism, while we give set of
qualitative criteria to distinguish this mechanism from similar ones studied under voltammetric conditions.
Moreover, we also provide hints to use methodologies for the determination of thermodynamic and kinetic
parameters relevant to the protein-film EEC′ mechanism. The considered protein-film EEC′ mechanism is
applicable to all lipophilic redox proteins that undergo electrochemical transformations in more than one
successive electron steps. Such examples exist by proteins containing quinone moiety and some polyvalent
ions of transition metals as redox active sites.

Item Type: Article
Subjects: Natural sciences > Biological sciences
Natural sciences > Chemical sciences
Natural sciences > Matematics
Natural sciences > Physical sciences
Divisions: Faculty of Agriculture
Depositing User: Rubin Gulaboski
Date Deposited: 31 Oct 2012 23:11
Last Modified: 31 Oct 2012 23:11

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