Singlet oxygen-mediated photobleaching of the prosthetic group in hemoglobins and c-phycocyanin

Photochem Photobiol. 1999 Oct;70(4):499-504.

Abstract

Proteins bearing colored prosthetic groups, such as the heme group in hemoglobin or the bilin group in c-phycocyanin, quench singlet oxygen by interactions at the apoprotein and the prosthetic group levels. In both proteins, chemical modification of the chromophore constitutes only a minor reaction pathway. While total deactivation of singlet oxygen takes place with rate constants of 4.0 x 10(9) and 4.2 x 10(8) M-1 s-1 for hemoglobin and phycocyanin, respectively, the bleaching of the chromophore takes place with rate constants of 3.2 x 10(6) and approximately 1 x 10(7) M-1 s-1. Irradiation of phycocyanin with red light bleaches the chromophore with low yields (approximately 0.8 x 10(-4)). Part of this bleaching is mediated by singlet oxygen produced by the irradiation of the bilin group. The low relevance of the singlet oxygen pathway is compatible with a low quantum yield (approximately 10(-3)) of free singlet oxygen production after irradiation of the protein.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Cyanobacteria / chemistry
  • Cyanobacteria / radiation effects
  • Hemoglobins / chemistry
  • Hemoglobins / radiation effects*
  • Humans
  • In Vitro Techniques
  • Methemoglobin / chemistry
  • Methemoglobin / radiation effects
  • Oxygen / chemistry
  • Oxygen / radiation effects
  • Photochemistry
  • Phycocyanin / chemistry
  • Phycocyanin / radiation effects*
  • Singlet Oxygen

Substances

  • Hemoglobins
  • Phycocyanin
  • Singlet Oxygen
  • Methemoglobin
  • Oxygen