Redox thermodynamics of cytochromes c subjected to urea induced unfolding

  • Stefano Monari
  • Antonio Ranieri
  • Giulia Di Rocco
  • Gert van der Zwan
  • Silvia Peressini
  • Claudio Tavagnacco
  • Diego Millo
  • Marco Borsari
Original Paper
First Online:
Received:
Accepted:

Abstract

The thermodynamics of the electron transfer (ET) process for beef heart and yeast cytochromes c and the Lys72Ala/Lys73Ala/Lys79Ala mutant of the latter species subjected to progressive urea-induced unfolding was determined electrochemically. The results indicate the presence of at least three protein forms which were assigned to a low-temperature and a high-temperature His-Met intermediate species and a bis-histidinate form (although the presence of a His-Lys form cannot be excluded). The much lower E°′ value of the bis-histidinate conformer as compared to His-Met ligated species is largely determined by the enthalpic contribution induced by axial ligand substitution. The biphasic E°′ versus T profile for the His-Met species is due to a difference in reduction entropy between the conformers at low and high temperatures. Enthalpy–entropy compensation phenomena for the reduction reaction at varying urea concentration for all the forms of the investigated cytochromes c were addressed and discussed.

Keywords

Cytochrome c Electrochemistry Electron transfer Unfolding Thermodynamics Urea 
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Notes

Acknowledgements

This work was performed with the financial support of MIUR (COFIN 2007, protocollo 20079Y9578_002, Bioelettrochimica: trasferimento di carica in sistemi di rilevanza biologica) and of the University of Modena and Reggio Emilia.

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Copyright information

© Springer Science+Business Media B.V. 2009

Authors and Affiliations

  • Stefano Monari
    • 1
  • Antonio Ranieri
    • 1
  • Giulia Di Rocco
    • 1
  • Gert van der Zwan
    • 2
  • Silvia Peressini
    • 3
  • Claudio Tavagnacco
    • 3
  • Diego Millo
    • 2
  • Marco Borsari
    • 1
  1. 1.Department of ChemistryUniversity of Modena and Reggio EmiliaModenaItaly
  2. 2.Laser Centre-Analytical Chemistry and Applied SpectroscopyVrije Universiteit AmsterdamAmsterdamThe Netherlands
  3. 3.Department of ChemistryUniversity of TriesteTriesteItaly

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