Photocatalytic Hydrogen Production and Carbon Dioxide Reduction Catalyzed by an Artificial Cobalt Hemoprotein
Oliveira Udry, Guillermo A. (University Paris-Saclay. Institut de Chimie Moleculaire des Matériaux d'Orsay)
Tiessler-Sala, Laura (Universitat Autònoma de Barcelona. Departament de Química)
Pugliese, Eva (University Paris-Saclay. Institut de Chimie Moleculaire des Matériaux d'Orsay)
Urvoas, Agathe (University Paris-Saclay. Institute for Integrative Biology of the Cell)
Halime, Zakaria (University Paris-Saclay. Institut de Chimie Moleculaire des Matériaux d'Orsay)
Maréchal, Jean-Didier (Universitat Autònoma de Barcelona. Departament de Química)
Mahy, Jean-Pierre (University Paris-Saclay. Institut de Chimie Moleculaire des Matériaux d'Orsay)
Ricoux, Remy (University Paris-Saclay. Institut de Chimie Moleculaire des Matériaux d'Orsay)

Data:	2022
Resum:	The covalent insertion of a cobalt heme into the cavity of an artificial protein named alpha Rep (αRep) leads to an artificial cobalt hemoprotein that is active as a catalyst not only for the photo-induced production of H, but also for the reduction of CO in a neutral aqueous solution. This new artificial metalloenzyme has been purified and characterized by Matrix Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS), circular dichroism, and UltraViolet-Visible spectroscopy. Using theoretical experiments, the structure of this biohybrid and the positioning of the residues near the metal complex were examined, which made it possible to complete the coordination of the cobalt ion by an axial glutamine Gln283 ligand. While the Co(III)-porphyrin catalyst alone showed weak catalytic activity for both reactions, 10 times more H and four times more CO were produced when the Co(III)-porphyrin complex was buried in the hydrophobic cavity of the protein. This study thus provides a solid basis for further improvement of these biohybrids using well-designed modifications of the second and outer coordination sphere by site-directed mutagenesis of the host protein.
Drets:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Llengua:	Anglès
Document:	Article ; recerca ; Versió publicada
Publicat a:	International journal of molecular sciences, Vol. 23, Issue 23 (December 2022) , art. 14640, ISSN 1422-0067

DOI: 10.3390/ijms232314640
PMID: 36498969

15 p, 3.4 MB

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