Proton translocation by cytochrome c oxidase can take place without the conserved glutamic acid in subunit I

Biochemistry. 2000 Jul 11;39(27):7863-7. doi: 10.1021/bi000806b.

Abstract

A glutamic acid residue in subunit I of the heme-copper oxidases is highly conserved and has been directly implicated in the O(2) reduction and proton-pumping mechanisms of these respiratory enzymes. Its mutation to residues other than aspartic acid dramatically inhibits activity, and proton translocation is lost. However, this glutamic acid is replaced by a nonacidic residue in some structurally distant members of the heme-copper oxidases, which have a tyrosine residue in the vicinity. Here, using cytochrome c oxidase from Paracoccus denitrificans, we show that replacement of the glutamic acid and a conserved glycine nearby lowers the catalytic activity to <0.1% of the wild-type value. But if, in addition, a phenylalanine that lies close in the structure is changed to tyrosine, the activity rises more than 100-fold and proton translocation is restored. Molecular dynamics simulations suggest that the tyrosine can support a transient array of water molecules that may be essential for proton transfer in the heme-copper oxidases. Surprisingly, the glutamic acid is thus not indispensable, which puts important constraints on the catalytic mechanism of these enzymes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amino Acid Sequence
  • Conserved Sequence*
  • Electron Transport Complex IV / chemistry
  • Electron Transport Complex IV / genetics
  • Electron Transport Complex IV / metabolism*
  • Glutamic Acid / chemistry*
  • Hydrogen Bonding
  • Ion Transport
  • Models, Molecular
  • Mutagenesis, Site-Directed
  • Paracoccus denitrificans / enzymology
  • Protons

Substances

  • Protons
  • Glutamic Acid
  • Electron Transport Complex IV