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Title: 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:
 [1];  [1];  [1];  [2];  [3];  [2];  [2];  [3];  [4]; ORCiD logo [1]
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  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)
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.
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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
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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.
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@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}
}
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https://doi.org/10.1002/cplu.201600218
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Works referenced in this record:

The Future of Energy Supply: Challenges and Opportunities
journal, January 2007

  • Armaroli, Nicola; Balzani, Vincenzo
  • Angewandte Chemie International Edition, Vol. 46, Issue 1-2
  • DOI: 10.1002/anie.200602373

A Systematic Comparative Study of Hydrogen-Evolving Molecular Catalysts in Aqueous Solutions
journal, September 2015

Unimolecular and bimolecular homolytic reactions of organochromium and organocobalt complexes. Kinetics and equilibria
journal, September 1984

  • Bakac, Andreja; Espenson, James H.
  • Journal of the American Chemical Society, Vol. 106, Issue 18
  • DOI: 10.1021/ja00330a027

Very fast empirical prediction and rationalization of protein pKa values
journal, October 2005

  • Li, Hui; Robertson, Andrew D.; Jensen, Jan H.
  • Proteins: Structure, Function, and Bioinformatics, Vol. 61, Issue 4
  • DOI: 10.1002/prot.20660

Supramolecular Cobaloxime Assemblies for H 2 Photocatalysis: An Initial Solution State Structure−Function Analysis †
journal, November 2010

  • Mulfort, Karen L.; Tiede, David M.
  • The Journal of Physical Chemistry B, Vol. 114, Issue 45
  • DOI: 10.1021/jp1023636

Nature-Driven Photochemistry for Catalytic Solar Hydrogen Production: A Photosystem I–Transition Metal Catalyst Hybrid
journal, October 2011

  • Utschig, Lisa M.; Silver, Sunshine C.; Mulfort, Karen L.
  • Journal of the American Chemical Society, Vol. 133, Issue 41
  • DOI: 10.1021/ja206012r

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988

Crystal structure of rat heme oxygenase-1 in complex with heme
journal, April 2000

Katalytische Wasserstoffoxidation: Beginn einer neuen Eisenzeit
journal, May 2013

Design of metal cofactors activated by a protein-protein electron transfer system
journal, June 2006

  • Ueno, T.; Yokoi, N.; Unno, M.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 25
  • DOI: 10.1073/pnas.0510968103

Splitting Water with Cobalt
journal, July 2011

  • Artero, Vincent; Chavarot-Kerlidou, Murielle; Fontecave, Marc
  • Angewandte Chemie International Edition, Vol. 50, Issue 32
  • DOI: 10.1002/anie.201007987

The pDynamo Program for Molecular Simulations using Hybrid Quantum Chemical and Molecular Mechanical Potentials
journal, June 2008

  • Field, Martin J.
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 7
  • DOI: 10.1021/ct800092p

De novo design of functional proteins: Toward artificial hydrogenases: De Novo Design of Functional Proteins
journal, November 2013

  • Faiella, Marina; Roy, Anindya; Sommer, Dayn
  • Biopolymers, Vol. 100, Issue 6
  • DOI: 10.1002/bip.22420

COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient
journal, January 1993

Histidine-132 Does Not Stabilize a Distal Water Ligand and Is Not an Important Residue for the Enzyme Activity in Heme Oxygenase-1 †
journal, April 1997

  • Matera, Kathryn Mansfield; Zhou, Hong; Migita, Catharina Taiko
  • Biochemistry, Vol. 36, Issue 16
  • DOI: 10.1021/bi962321m

5-Deaza- and 5-Thiariboflavins: A Simple Pathway to Antimetabolites of Vitamin B2
journal, July 1976

  • Janda, Michael; Hemmerich, Peter
  • Angewandte Chemie International Edition in English, Vol. 15, Issue 7
  • DOI: 10.1002/anie.197604431

Hydrogen Evolution Catalyzed by Cobaloximes
journal, December 2009

  • Dempsey, Jillian L.; Brunschwig, Bruce S.; Winkler, Jay R.
  • Accounts of Chemical Research, Vol. 42, Issue 12
  • DOI: 10.1021/ar900253e

Photoreduction of flavoproteins and other biological compounds catalyzed by deazaflavins. Appendix: photochemical formation of deazaflavin dimers
journal, January 1978

  • Massey, Vincent; Hemmerich, Peter; Knappe, W. R.
  • Biochemistry, Vol. 17, Issue 1
  • DOI: 10.1021/bi00594a002

Wasserspaltung mit Cobalt
journal, July 2011

  • Artero, Vincent; Chavarot-Kerlidou, Murielle; Fontecave, Marc
  • Angewandte Chemie, Vol. 123, Issue 32
  • DOI: 10.1002/ange.201007987

Direkter Leistungsvergleich eines bioinspirierten synthetischen Ni-Katalysators und einer [NiFe]-Hydrogenase, beide kovalent an eine Elektrode gebunden
journal, July 2015

  • Rodriguez-Maciá, Patricia; Dutta, Arnab; Lubitz, Wolfgang
  • Angewandte Chemie, Vol. 127, Issue 42
  • DOI: 10.1002/ange.201502364

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

The inactivation of yeast enolase by 2,3-butanedione
journal, September 1978

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Light-driven hydrogen production from Photosystem I-catalyst hybrids
journal, April 2015

  • Utschig, Lisa M.; Soltau, Sarah R.; Tiede, David M.
  • Current Opinion in Chemical Biology, Vol. 25
  • DOI: 10.1016/j.cbpa.2014.11.019

Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids
journal, January 1996

  • Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian
  • Journal of the American Chemical Society, Vol. 118, Issue 45
  • DOI: 10.1021/ja9621760

Calculation of Solvent Shifts on Electronic g -Tensors with the Conductor-Like Screening Model (COSMO) and Its Self-Consistent Generalization to Real Solvents (Direct COSMO-RS)
journal, February 2006

  • Sinnecker, Sebastian; Rajendran, Arivazhagan; Klamt, Andreas
  • The Journal of Physical Chemistry A, Vol. 110, Issue 6
  • DOI: 10.1021/jp056016z

The Crystal Structures of the Ferric and Ferrous Forms of the Heme Complex of HmuO, a Heme Oxygenase of Corynebacterium diphtheriae
journal, November 2003

  • Hirotsu, Shoko; Chu, Grace C.; Unno, Masaki
  • Journal of Biological Chemistry, Vol. 279, Issue 12
  • DOI: 10.1074/jbc.M311631200

The Hydrogen Catalyst Cobaloxime: A Multifrequency EPR and DFT Study of Cobaloxime’s Electronic Structure
journal, February 2012

  • Niklas, Jens; Mardis, Kristy L.; Rakhimov, Rakhim R.
  • The Journal of Physical Chemistry B, Vol. 116, Issue 9
  • DOI: 10.1021/jp209395n

Proton Electroreduction Catalyzed by Cobaloximes:  Functional Models for Hydrogenases
journal, June 2005

  • Razavet, Mathieu; Artero, Vincent; Fontecave, Marc
  • Inorganic Chemistry, Vol. 44, Issue 13
  • DOI: 10.1021/ic050167z

Hydrogen Evolution from Neutral Water under Aerobic Conditions Catalyzed by Cobalt Microperoxidase-11
journal, December 2013

  • Kleingardner, Jesse G.; Kandemir, Banu; Bren, Kara L.
  • Journal of the American Chemical Society, Vol. 136, Issue 1
  • DOI: 10.1021/ja406818h

Direct Comparison of the Performance of a Bio-inspired Synthetic Nickel Catalyst and a [NiFe]-Hydrogenase, Both Covalently Attached to Electrodes
journal, July 2015

  • Rodriguez-Maciá, Patricia; Dutta, Arnab; Lubitz, Wolfgang
  • Angewandte Chemie International Edition, Vol. 54, Issue 42
  • DOI: 10.1002/anie.201502364

Artificial hydrogenases: biohybrid and supramolecular systems for catalytic hydrogen production or uptake
journal, April 2015

Mimicking hydrogenases: From biomimetics to artificial enzymes
journal, July 2014

  • Simmons, Trevor R.; Berggren, Gustav; Bacchi, Marine
  • Coordination Chemistry Reviews, Vol. 270-271
  • DOI: 10.1016/j.ccr.2013.12.018

Organocobalt chemistry of vitamin B12 model compounds (cobaloximes)
journal, April 1968

  • Schrauzer, Gerhard N.
  • Accounts of Chemical Research, Vol. 1, Issue 4
  • DOI: 10.1021/ar50004a001

5-Desaza- und 5-Thiariboflavine: Ein einfacher Weg zu Antimetaboliten des Vitamins B2
journal, July 1976

(Photo)chemistry of 5-Deazaflavin. A Clue to the Mechanism of Flavin-Dependent (De)hydrogenation
journal, March 1979

Aqueous light driven hydrogen production by a Ru–ferredoxin–Co biohybrid
journal, January 2015

  • Soltau, S. R.; Niklas, J.; Dahlberg, P. D.
  • Chemical Communications, Vol. 51, Issue 53
  • DOI: 10.1039/C5CC03006D

Toward the rational benchmarking of homogeneous H 2 -evolving catalysts
journal, January 2014

  • Artero, Vincent; Saveant, Jean-Michel
  • Energy Environ. Sci., Vol. 7, Issue 11
  • DOI: 10.1039/C4EE01709A

Conversion of a protein to a homogeneous asymmetric hydrogenation catalyst by site-specific modification with a diphosphinerhodium(I) moiety
journal, January 1978

  • Wilson, Michael E.; Whitesides, George M.
  • Journal of the American Chemical Society, Vol. 100, Issue 1
  • DOI: 10.1021/ja00469a064

Optimization of parameters for semiempirical methods V: Modification of NDDO approximations and application to 70 elements
journal, September 2007

Heme Degradation as Catalyzed by a Recombinant Bacterial Heme Oxygenase (Hmu O) from Corynebacterium diphtheriae
journal, July 1999

  • Chu, Grace C.; Katakura, Koki; Zhang, Xuhong
  • Journal of Biological Chemistry, Vol. 274, Issue 30
  • DOI: 10.1074/jbc.274.30.21319

Alkylcobalamins and alkylcobaloximes. Electronic structure, spectra, and mechanism of photodealkylation
journal, May 1970

  • Schrauzer, Gerhard N.; Lee, Lian-Pin.; Sibert, John W.
  • Journal of the American Chemical Society, Vol. 92, Issue 10
  • DOI: 10.1021/ja00713a012

Protein Design: Toward Functional Metalloenzymes
journal, January 2014

  • Yu, Fangting; Cangelosi, Virginia M.; Zastrow, Melissa L.
  • Chemical Reviews, Vol. 114, Issue 7
  • DOI: 10.1021/cr400458x

Instantaneous, stoichiometric generation of powerfully reducing states of protein active sites using Eu(ii) and polyaminocarboxylate ligands
journal, January 2003

  • Vincent, Kylie A.; Tilley, Gareth J.; Quammie, Nina C.
  • Chemical Communications, Issue 20
  • DOI: 10.1039/b308188e

EasySpin, a comprehensive software package for spectral simulation and analysis in EPR
journal, January 2006

Catalytic Hydrogen Oxidation: Dawn of a New Iron Age
journal, May 2013

  • Simmons, Trevor R.; Artero, Vincent
  • Angewandte Chemie International Edition, Vol. 52, Issue 24
  • DOI: 10.1002/anie.201302908

Dioxygen Activation for the Self-Degradation of Heme: Reaction Mechanism and Regulation of Heme Oxygenase
journal, April 2010

  • Matsui, Toshitaka; Iwasaki, Mari; Sugiyama, Ryota
  • Inorganic Chemistry, Vol. 49, Issue 8
  • DOI: 10.1021/ic901869t

Die Zukunft der Energieversorgung – Herausforderungen und Chancen
journal, January 2007

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

Hydrogenases
journal, March 2014

  • Lubitz, Wolfgang; Ogata, Hideaki; Rüdiger, Olaf
  • Chemical Reviews, Vol. 114, Issue 8
  • DOI: 10.1021/cr4005814

Nickel-Substituted Rubredoxin as a Minimal Enzyme Model for Hydrogenase
journal, August 2015

Cobaloxime-Based Artificial Hydrogenases
journal, July 2014

  • Bacchi, Marine; Berggren, Gustav; Niklas, Jens
  • Inorganic Chemistry, Vol. 53, Issue 15
  • DOI: 10.1021/ic501014c

The ORCA program system: The ORCA program system
journal, June 2011

  • Neese, Frank
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1
  • DOI: 10.1002/wcms.81
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