Redox state of peroxy and ferryl intermediates in cytochrome c oxidase catalysis

Biochemistry. 1999 May 11;38(19):6270-5. doi: 10.1021/bi982541v.

Abstract

The redox states of the "peroxy" (P) and "ferryl" (F) intermediates formed during reoxidation of reduced bovine cytochrome c oxidase have been probed by reduction with both ferrocytochrome c and acetylpyridine NADH under anaerobic conditions using optical spectroscopy. The reduction of the P and F forms revealed that both are in very similar redox states. One-electron reduction of either the P or F form yields an optical spectrum primarily due to oxidized enzyme implying that the heme iron of cytochrome a3 is in the ferryl state in both forms. The F and P forms were found to be 1 and less than 1.3 oxidizing equiv, respectively, above the oxidized enzyme. The slightly higher oxidation state in the P form is interpreted as being due to an optically undetectable redox center presumably located in the binuclear cavity.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Catalysis
  • Cytochrome c Group / metabolism
  • Electron Transport Complex IV / metabolism*
  • NADP / analogs & derivatives
  • NADP / metabolism
  • Oxidation-Reduction
  • Spectrum Analysis
  • Substrate Specificity

Substances

  • Cytochrome c Group
  • 3-acetylpyridine-adenine dinucleotide phosphate
  • NADP
  • Electron Transport Complex IV