PMID- 24811894 OWN - NLM STAT- MEDLINE DCOM- 20140813 LR - 20140616 IS - 1096-0384 (Electronic) IS - 0003-9861 (Linking) VI - 554 DP - 2014 Jul 15 TI - Redox equilibration after one-electron reduction of cytochrome c oxidase: radical formation and a possible hydrogen relay mechanism. PG - 36-43 LID - S0003-9861(14)00146-5 [pii] LID - 10.1016/j.abb.2014.04.015 [doi] AB - Kinetic studies using UV/visible and EPR spectroscopy were carried out to follow the distribution of electrons within beef heart cytochrome c oxidase (CcO), both active and cyanide-inhibited, following addition of reduced cytochrome c as electron donor. In the initial one-electron reduced state the electron is shared between three redox centers, heme a, CuA and a third site, probably CuB. Using a rapid freeze system and the spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO) a protein radical was also detected. The EPR spectrum of the DMPO adduct of this radical was consistent with tyrosyl radical capture. This may be a feature of a charge relay mechanism involved in some part of the CcO electron transfer system from bound cytochrome c via CuA and heme a to the a3CuB binuclear center. CI - Copyright (c) 2014 Elsevier Inc. All rights reserved. FAU - Ashe, Damian AU - Ashe D AD - Biochemistry Unit, Department of Pre-Clinical Sciences, Faculty of Medical Sciences, University of the West Indies, St. Augustine, Trinidad and Tobago. FAU - Alleyne, Trevor AU - Alleyne T AD - Biochemistry Unit, Department of Pre-Clinical Sciences, Faculty of Medical Sciences, University of the West Indies, St. Augustine, Trinidad and Tobago. FAU - Wilson, Michael AU - Wilson M AD - Molecular Biophysics Research Group, School of Biological Sciences, University of Essex, Colchester, Essex CO4 3SQ, UK. FAU - Svistunenko, Dimitri AU - Svistunenko D AD - Molecular Biophysics Research Group, School of Biological Sciences, University of Essex, Colchester, Essex CO4 3SQ, UK. FAU - Nicholls, Peter AU - Nicholls P AD - Molecular Biophysics Research Group, School of Biological Sciences, University of Essex, Colchester, Essex CO4 3SQ, UK. Electronic address: pnicholl@essex.ac.uk. LA - eng PT - Journal Article DEP - 20140505 PL - United States TA - Arch Biochem Biophys JT - Archives of biochemistry and biophysics JID - 0372430 RN - 0 (Cyclic N-Oxides) RN - 0 (Free Radicals) RN - 0 (Spin Labels) RN - 7170JZ1QF3 (5,5-dimethyl-1-pyrroline-1-oxide) RN - 7YNJ3PO35Z (Hydrogen) RN - 9007-43-6 (Cytochromes c) RN - EC 1.9.3.1 (Electron Transport Complex IV) SB - IM MH - Animals MH - Cattle MH - Cyclic N-Oxides MH - Cytochromes c/chemistry/metabolism MH - Electron Spin Resonance Spectroscopy MH - Electron Transport MH - Electron Transport Complex IV/*chemistry/*metabolism MH - Free Radicals/chemistry/metabolism MH - Horses MH - Hydrogen/metabolism MH - Kinetics MH - Models, Biological MH - Myocardium/enzymology MH - Oxidation-Reduction MH - Spectrophotometry MH - Spin Labels OTO - NOTNLM OT - Amino acid radical OT - Cyanide OT - Cytochrome c oxidase OT - DMPO OT - Electron transfer OT - Spin trap OT - Tryptophan OT - Tyrosine EDAT- 2014/05/09 06:00 MHDA- 2014/08/15 06:00 CRDT- 2014/05/10 06:00 PHST- 2014/02/20 00:00 [received] PHST- 2014/04/09 00:00 [revised] PHST- 2014/04/25 00:00 [accepted] PHST- 2014/05/10 06:00 [entrez] PHST- 2014/05/09 06:00 [pubmed] PHST- 2014/08/15 06:00 [medline] AID - S0003-9861(14)00146-5 [pii] AID - 10.1016/j.abb.2014.04.015 [doi] PST - ppublish SO - Arch Biochem Biophys. 2014 Jul 15;554:36-43. doi: 10.1016/j.abb.2014.04.015. Epub 2014 May 5.