@article{137075ec7d66411289a8125b11f385a3,
title = "Artificial Hydrogenases Based on Cobaloximes and Heme Oxygenase",
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.",
keywords = "biohybrids, cobalt, enzyme models, heme proteins, hydrogen evolution",
author = "Marine Bacchi and Elias Veinberg and Field, {Martin J.} and Jens Niklas and Toshitaka Matsui and Tiede, {D. M.} and Poluektov, {Oleg G.} and Masao Ikeda-Saito and Marc Fontecave and Vincent Artero",
note = "Funding Information: We acknowledge support from the French National Research Agency (LABEX program ARCANE; grant ANR-11-LABX-0003-01), the COST Action CM1202 PERSPECT-H2O, and the Life Science Division of the CEA (Irtelis and 2011 DSV-Energy programs). This material is based upon studies supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, through grant DE-AC02-6CH11357 at Argonne National Laboratory. Studies at Tohoku University were supported by Grants-in-Aid for Scientific Research (M.I.-S., 2412006, 24350081; T.M., 23550186, 25109504, 15K05555, 15H00912) from JSPS and MEXT, Japan. Publisher Copyright: {\textcopyright} 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Copyright: Copyright 2016 Elsevier B.V., All rights reserved.",
year = "2016",
month = oct,
day = "1",
doi = "10.1002/cplu.201600218",
language = "English",
volume = "81",
pages = "1083--1089",
journal = "ChemPlusChem",
issn = "2192-6506",
publisher = "Wiley-VCH Verlag",
number = "10",
}