A redox hydrogel protects the O2 -sensitive [FeFe]-hydrogenase from Chlamydomonas reinhardtii from oxidative damage

Angew Chem Int Ed Engl. 2015 Oct 12;54(42):12329-33. doi: 10.1002/anie.201502776. Epub 2015 Jun 12.


The integration of sensitive catalysts in redox matrices opens up the possibility for their protection from deactivating molecules such as O2 . [FeFe]-hydrogenases are enzymes catalyzing H2 oxidation/production which are irreversibly deactivated by O2 . Therefore, their use under aerobic conditions has never been achieved. Integration of such hydrogenases in viologen-modified hydrogel films allows the enzyme to maintain catalytic current for H2 oxidation in the presence of O2 , demonstrating a protection mechanism independent of reactivation processes. Within the hydrogel, electrons from the hydrogenase-catalyzed H2 oxidation are shuttled to the hydrogel-solution interface for O2 reduction. Hence, the harmful O2 molecules do not reach the hydrogenase. We illustrate the potential applications of this protection concept with a biofuel cell under H2 /O2 mixed feed.

Keywords: O2 protection; biocatalysis; biofuel cells; hydrogenases; viologen hydrogel.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chlamydomonas reinhardtii / enzymology*
  • Hydrogel, Polyethylene Glycol Dimethacrylate / chemistry
  • Hydrogel, Polyethylene Glycol Dimethacrylate / metabolism*
  • Hydrogenase / chemistry
  • Hydrogenase / metabolism*
  • Iron-Sulfur Proteins / chemistry
  • Iron-Sulfur Proteins / metabolism*
  • Models, Molecular
  • Molecular Structure
  • Oxidation-Reduction
  • Oxygen / chemistry
  • Oxygen / metabolism*


  • Iron-Sulfur Proteins
  • Hydrogel, Polyethylene Glycol Dimethacrylate
  • iron hydrogenase
  • Hydrogenase
  • Oxygen