Singlet-Oxygen Generation by Peroxidases and Peroxygenases for Chemoenzymatic Synthesis

Chembiochem. 2021 Jan 15;22(2):398-407. doi: 10.1002/cbic.202000326. Epub 2020 Oct 5.

Abstract

Singlet oxygen is a reactive oxygen species undesired in living cells but a rare and valuable reagent in chemical synthesis. We present a fluorescence spectroscopic analysis of the singlet-oxygen formation activity of commercial peroxidases and novel peroxygenases. Singlet-oxygen sensor green (SOSG) is used as fluorogenic singlet oxygen trap. Establishing a kinetic model for the reaction cascade to the fluorescent SOSG endoperoxide permits a kinetic analysis of enzymatic singlet-oxygen formation. All peroxidases and peroxygenases show singlet-oxygen formation. No singlet oxygen activity could be found for any catalase under investigation. Substrate inhibition is observed for all reactive enzymes. The commercial dye-decolorizing peroxidase industrially used for dairy bleaching shows the highest singlet-oxygen activity and the lowest inhibition. This enzyme was immobilized on a textile carrier and successfully applied for a chemical synthesis. Here, ascaridole was synthesized via enzymatically produced singlet oxygen.

Keywords: chemo-enzymatic synthesis; fluorescence; peroxidase; peroxygenase; singlet oxygen; singlet oxygen sensor green.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Fluorescent Dyes / chemistry
  • Mixed Function Oxygenases / chemistry
  • Mixed Function Oxygenases / metabolism*
  • Molecular Structure
  • Peroxidases / chemistry
  • Peroxidases / metabolism*
  • Singlet Oxygen / chemistry
  • Singlet Oxygen / metabolism*

Substances

  • Fluorescent Dyes
  • Singlet Oxygen
  • Mixed Function Oxygenases
  • Peroxidases
  • peroxygenase