PMID- 21939635 OWN - NLM STAT- MEDLINE DCOM- 20120510 LR - 20211020 IS - 0006-3002 (Print) IS - 0006-3002 (Electronic) IS - 0006-3002 (Linking) VI - 1817 IP - 4 DP - 2012 Apr TI - Design of photoactive ruthenium complexes to study electron transfer and proton pumping in cytochrome oxidase. PG - 567-74 LID - 10.1016/j.bbabio.2011.08.012 [doi] AB - This review describes the development and application of photoactive ruthenium complexes to study electron transfer and proton pumping reactions in cytochrome c oxidase (CcO). CcO uses four electrons from Cc to reduce O(2) to two waters, and pumps four protons across the membrane. The electron transfer reactions in cytochrome oxidase are very rapid, and cannot be resolved by stopped-flow mixing techniques. Methods have been developed to covalently attach a photoactive tris(bipyridine)ruthenium group [Ru(II)] to Cc to form Ru-39-Cc. Photoexcitation of Ru(II) to the excited state Ru(II*), a strong reductant, leads to rapid electron transfer to the ferric heme group in Cc, followed by electron transfer to Cu(A) in CcO with a rate constant of 60,000s(-1). Ruthenium kinetics and mutagenesis studies have been used to define the domain for the interaction between Cc and CcO. New ruthenium dimers have also been developed to rapidly inject electrons into Cu(A) of CcO with yields as high as 60%, allowing measurement of the kinetics of electron transfer and proton release at each step in the oxygen reduction mechanism. CI - Copyright A(c) 2011 Elsevier B.V. All rights reserved. FAU - Durham, Bill AU - Durham B AD - Department of Chemistry and Biochemistry, University of Arkansas, Fayetteville, AR, USA. bdurham@uark.edu FAU - Millett, Francis AU - Millett F LA - eng GR - 1P30RR031154-01/RR/NCRR NIH HHS/United States GR - F32 GM020488/GM/NIGMS NIH HHS/United States GR - R01 GM020488-36/GM/NIGMS NIH HHS/United States GR - GM20488/GM/NIGMS NIH HHS/United States GR - R01 GM020488/GM/NIGMS NIH HHS/United States GR - P30 RR031154-02/RR/NCRR NIH HHS/United States GR - P30 GM103450/GM/NIGMS NIH HHS/United States GR - P30 RR031154/RR/NCRR NIH HHS/United States PT - Journal Article PT - Research Support, N.I.H., Extramural PT - Review DEP - 20110910 PL - Netherlands TA - Biochim Biophys Acta JT - Biochimica et biophysica acta JID - 0217513 RN - 0 (Organometallic Compounds) RN - 0 (Protons) RN - 7UI0TKC3U5 (Ruthenium) RN - 9007-43-6 (Cytochromes c) RN - EC 1.9.3.1 (Electron Transport Complex IV) SB - IM MH - Animals MH - Biological Transport/radiation effects MH - Cattle MH - Cytochromes c/chemistry/metabolism MH - Electron Transport/radiation effects MH - Electron Transport Complex IV/*chemistry/metabolism MH - Models, Molecular MH - Organometallic Compounds/*chemistry/metabolism MH - Oxidation-Reduction/radiation effects MH - *Protons MH - Ruthenium/*chemistry/metabolism PMC - PMC3246025 MID - NIHMS325362 EDAT- 2011/09/24 06:00 MHDA- 2012/05/11 06:00 PMCR- 2013/04/01 CRDT- 2011/09/24 06:00 PHST- 2011/06/16 00:00 [received] PHST- 2011/08/25 00:00 [revised] PHST- 2011/08/26 00:00 [accepted] PHST- 2011/09/24 06:00 [entrez] PHST- 2011/09/24 06:00 [pubmed] PHST- 2012/05/11 06:00 [medline] PHST- 2013/04/01 00:00 [pmc-release] AID - S0005-2728(11)00211-8 [pii] AID - 10.1016/j.bbabio.2011.08.012 [doi] PST - ppublish SO - Biochim Biophys Acta. 2012 Apr;1817(4):567-74. doi: 10.1016/j.bbabio.2011.08.012. Epub 2011 Sep 10.