Artificial Hydrogenases Based on Cobaloximes and Heme Oxygenase

Marine Bacchi, Elias Veinberg, Martin J. Field, Jens Niklas, Toshitaka Matsui, D. M. Tiede, Oleg G. Poluektov, Masao Ikeda-Saito, Marc Fontecave, Vincent Artero

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The insertion of cobaloxime catalysts in the heme-binding pocket of heme oxygenase (HO) yields artificial hydrogenases active for H2 evolution in neutral aqueous solutions. These novel biohybrids have been purified and characterized by using UV/visible and EPR spectroscopy. These analyses revealed the presence of two distinct binding conformations, thereby providing the cobaloxime with hydrophobic and hydrophilic environments, respectively. Quantum chemical/molecular mechanical docking calculations found open and closed conformations of the binding pocket owing to mobile amino acid residues. HO-based biohybrids incorporating a {Co(dmgH)2} (dmgH2=dimethylglyoxime) catalytic center displayed up to threefold increased turnover numbers with respect to the cobaloxime alone or to analogous sperm whale myoglobin adducts. This study thus provides a strong basis for further improvement of such biohybrids, using well-designed modifications of the second and outer coordination spheres, through site-directed mutagenesis of the host protein.

Original languageEnglish
Pages (from-to)1083-1089
Number of pages7
JournalChemPlusChem
Volume81
Issue number10
DOIs
Publication statusPublished - 2016 Oct 1

Keywords

  • biohybrids
  • cobalt
  • enzyme models
  • heme proteins
  • hydrogen evolution

ASJC Scopus subject areas

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Artificial Hydrogenases Based on Cobaloximes and Heme Oxygenase'. Together they form a unique fingerprint.

  • Cite this

    Bacchi, M., Veinberg, E., Field, M. J., Niklas, J., Matsui, T., Tiede, D. M., Poluektov, O. G., Ikeda-Saito, M., Fontecave, M., & Artero, V. (2016). Artificial Hydrogenases Based on Cobaloximes and Heme Oxygenase. ChemPlusChem, 81(10), 1083-1089. https://doi.org/10.1002/cplu.201600218