Resonance Raman evidence for two conformations involved in the L intermediate of photoactive yellow protein

J Biol Chem. 2004 Jun 4;279(23):23855-8. doi: 10.1074/jbc.C400137200. Epub 2004 Apr 19.

Abstract

The blue light receptor photoactive yellow protein (PYP) displays a photocycle that involves several intermediate states. Here we report resonance Raman spectroscopic investigations of the short-lived red-shifted intermediate denoted PYP(L). We have found that the Raman bands of the carbonyl C=O stretching mode nu(11) as well as the C=C stretching mode nu(13) for the chromophore can be resolved into two peaks, and the ratio of the two components varies as a function of pH with pK(a) approximately 6. The isotope effects on the resonance Raman spectra have confirmed a deprotonated cis-chromophore for the two components. The results indicate the presence of two conformations in the active site of PYP(L). The normal coordinate calculations based on the density functional theory provide a structural model for the two conformations, where the low pH form is possibly an active structure for the protonation reaction generating a following intermediate in the photocycle.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bacterial Proteins / chemistry*
  • Binding Sites
  • Chromatiaceae
  • Halorhodospira halophila / metabolism
  • Hydrogen Bonding
  • Hydrogen-Ion Concentration
  • Kinetics
  • Light
  • Models, Chemical
  • Molecular Conformation
  • Mutation
  • Phenol / chemistry
  • Photoreceptors, Microbial / chemistry*
  • Protein Conformation
  • Proteins
  • Protons
  • Spectrum Analysis, Raman / methods*
  • Vibration

Substances

  • Bacterial Proteins
  • Photoreceptors, Microbial
  • Proteins
  • Protons
  • photoactive yellow protein, Bacteria
  • Phenol