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Artificial hydrogenases based on cobaloximes and heme oxygenase

Journal Article · · ChemPlusChem
 [1];  [1];  [1];  [2];  [3];  [2];  [2];  [3];  [4];  [1]
  1. Univ. Grenoble Alpes, Grenoble Cedex (France)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Tohoku Univ., Sendai (Japan)
  4. Univ. Grenoble Alpes, Grenoble Cedex (France); Univ. Pierre et Marie Curie, Paris (France)
+ Show Author Affiliations
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. Here, 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.
Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1351308
Alternate ID(s):
OSTI ID: 1401439
Journal Information:
ChemPlusChem, Journal Name: ChemPlusChem Journal Issue: 10 Vol. 81; ISSN 2192-6506
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (5)

Supramolecular assembly of cobaloxime on nanoring-coated carbon nanotubes: addressing the stability of the pyridine–cobalt linkage under hydrogen evolution turnover conditions journal January 2016
From protein engineering to artificial enzymes – biological and biomimetic approaches towards sustainable hydrogen production journal January 2018
A protocol for quantifying hydrogen evolution by dye-sensitized molecular photocathodes and its implementation for evaluating a new covalent architecture based on an optimized dye-catalyst dyad journal January 2018
Host–guest chemistry between cyclodextrin and a hydrogen evolution catalyst cobaloxime journal January 2019
Chicken fat for catalysis: a scaffold is as important for molecular complexes for energy transformations as it is for enzymes in catalytic function journal January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
artificial enzymes
biohybrid species
biohybrids
bioinspired chemistry
cobalt
enzyme models
heme proteins
hydrogen evolution