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Enthalpy/entropy compensation phenomena in the reduction thermodynamics of electron transport metalloproteins

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Abstract

Compensation phenomena between the enthalpy and entropy changes of the reduction reaction for all classes of electron transport metalloproteins, namely cytochromes, iron-sulfur, and blue copper proteins, are brought to light. This is the first comprehensive report on such effects for biological redox reactions. Following Grunwald’s approach for the interpretation of H/S compensation for solution reactions, it is concluded that reduction-induced solvent reorganization effects involving the hydration shell of the molecule dominate the reduction thermodynamics in these species, although they have no net effect on the E° values, owing to exact compensation. Thus the reduction potentials of these species are primarily determined by the selective enthalpic stabilization of one of the two oxidation states due to ligand binding interactions and electrostatics at the metal site and by the entropic effects of reduction-induced changes in protein flexibility.

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Acknowledgements

This work was performed with the financial support of the University of Modena and Reggio Emilia and Fondazione Cassa di Risparmio di Modena 16/4/2002. Prof. G.W. Canters of the Leiden University (The Netherlands) is gratefully acknowledged for helpful discussion.

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Authors and Affiliations

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

    Gianantonio Battistuzzi, Marco Borsari, Giulia Di Rocco, Antonio Ranieri & Marco Sola

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  1. Gianantonio Battistuzzi
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  2. Marco Borsari
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  3. Giulia Di Rocco
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  4. Antonio Ranieri
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  5. Marco Sola
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Correspondence to Marco Sola.

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Battistuzzi, G., Borsari, M., Di Rocco, G. et al. Enthalpy/entropy compensation phenomena in the reduction thermodynamics of electron transport metalloproteins. J Biol Inorg Chem 9, 23–26 (2004). https://doi.org/10.1007/s00775-003-0490-3

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  • DOI: https://doi.org/10.1007/s00775-003-0490-3

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