Artificial hydrogenases based on cobaloximes and heme oxygenase
Abstract
Abstract The insertion of cobaloxime catalysts in the heme‐binding pocket of heme oxygenase (HO) yields artificial hydrogenases active for H 2 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 } (dmgH 2 =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.
- Authors:
-
- Univ. Grenoble Alpes, Grenoble Cedex (France)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Tohoku Univ., Sendai (Japan)
- Univ. Grenoble Alpes, Grenoble Cedex (France); Univ. Pierre et Marie Curie, Paris (France)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1351308
- Alternate Identifier(s):
- OSTI ID: 1401439
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemPlusChem
- Additional Journal Information:
- Journal Volume: 81; Journal Issue: 10; Journal ID: ISSN 2192-6506
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biohybrid species; hydrogen evolution; artificial enzymes; bioinspired chemistry; cobalt; heme proteins; enzyme models; biohybrids
Citation Formats
Bacchi, Marine, Veinberg, Elias, Field, Martin J., Niklas, Jens, Matsui, Toshitaka, Tiede, David M., Poluektov, Oleg G., Ikeda-Saito, Masao, Fontecave, Marc, and Artero, Vincent. Artificial hydrogenases based on cobaloximes and heme oxygenase. United States: N. p., 2016.
Web. doi:10.1002/cplu.201600218.
Bacchi, Marine, Veinberg, Elias, Field, Martin J., Niklas, Jens, Matsui, Toshitaka, Tiede, David M., Poluektov, Oleg G., Ikeda-Saito, Masao, Fontecave, Marc, & Artero, Vincent. Artificial hydrogenases based on cobaloximes and heme oxygenase. United States. https://doi.org/10.1002/cplu.201600218
Bacchi, Marine, Veinberg, Elias, Field, Martin J., Niklas, Jens, Matsui, Toshitaka, Tiede, David M., Poluektov, Oleg G., Ikeda-Saito, Masao, Fontecave, Marc, and Artero, Vincent. Mon .
"Artificial hydrogenases based on cobaloximes and heme oxygenase". United States. https://doi.org/10.1002/cplu.201600218. https://www.osti.gov/servlets/purl/1351308.
@article{osti_1351308,
title = {Artificial hydrogenases based on cobaloximes and heme oxygenase},
author = {Bacchi, Marine and Veinberg, Elias and Field, Martin J. and Niklas, Jens and Matsui, Toshitaka and Tiede, David M. and Poluektov, Oleg G. and Ikeda-Saito, Masao and Fontecave, Marc and Artero, Vincent},
abstractNote = {Abstract The insertion of cobaloxime catalysts in the heme‐binding pocket of heme oxygenase (HO) yields artificial hydrogenases active for H 2 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 } (dmgH 2 =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.},
doi = {10.1002/cplu.201600218},
journal = {ChemPlusChem},
number = 10,
volume = 81,
place = {United States},
year = {Mon Jun 06 00:00:00 EDT 2016},
month = {Mon Jun 06 00:00:00 EDT 2016}
}
Web of Science
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