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Thermodynamic and kinetic aspects of the electron transfer reaction of bovine cytochrome c immobilized on 4-mercaptopyridine and 11-mercapto-1-undecanoic acid films

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Abstract

Bovine cytochrome c (cyt c) was adsorbed on a polycrystalline gold electrode coated with 4-mercaptopyridine and 11-mercapto-1-undecanoic acid self-assembled monolayers (SAMs) and the thermodynamics and kinetics of the heterogeneous protein-electrode electron transfer (ET) reaction were determined by cyclic voltammetry. The E°′ values for the immobilized protein were found to be lower than those for the corresponding diffusing species. The thermodynamic parameters for protein reduction ( \( \Updelta {H}_{{\rm rc}} ^{{\circ \prime }} \) and \(\Updelta{S}_{{\rm rc}}^{{\circ \prime }} \)) indicate that the stabilization of the ferric state due to protein–SAM interaction is enthalpic in origin. The kinetic data suggest that a tunneling mechanism is involved in the ET reaction: the distance between the redox center of the protein and the electrode surface can be efficiently evaluated using the Marcus equation.

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Acknowledgment

This work was supported by the Ministero dell’Università e della Ricerca Scientifica e Tecnologica (MURST).

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Authors and Affiliations

  1. Department of Chemistry, University of Modena and Reggio Emilia, Via Campi 183, 41100, Modena, Italy

    Stefano Monari, Gianantonio Battistuzzi, Marco Borsari, Antonio Ranieri & Marco Sola

  2. Laser Centre – Analytical Chemistry and Applied Spectroscopy, Vrije Universiteit Amsterdam, De Boelelaan 1081, 1081 HV, Amsterdam, The Netherlands

    Diego Millo, Cees Gooijer & Gert van der Zwan

Authors
  1. Stefano Monari
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  2. Gianantonio Battistuzzi
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  3. Marco Borsari
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  4. Diego Millo
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  5. Cees Gooijer
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  6. Gert van der Zwan
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  7. Antonio Ranieri
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  8. Marco Sola
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Correspondence to Marco Borsari.

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Monari, S., Battistuzzi, G., Borsari, M. et al. Thermodynamic and kinetic aspects of the electron transfer reaction of bovine cytochrome c immobilized on 4-mercaptopyridine and 11-mercapto-1-undecanoic acid films. J Appl Electrochem 38, 885–891 (2008). https://doi.org/10.1007/s10800-008-9493-7

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  • DOI: https://doi.org/10.1007/s10800-008-9493-7

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