Investigating the role of the strong field ligands in [FeFe] hydrogenase: spectroscopic and functional characterization of a semi-synthetic mono-cyanide active site.


Journal

Chemical science
ISSN: 2041-6520
Titre abrégé: Chem Sci
Pays: England
ID NLM: 101545951

Informations de publication

Date de publication:
28 Sep 2022
Historique:
received: 22 04 2022
accepted: 05 08 2022
entrez: 2 11 2022
pubmed: 3 11 2022
medline: 3 11 2022
Statut: epublish

Résumé

Artificial maturation of hydrogenases provides a path towards generating new semi-synthetic enzymes with novel catalytic properties. Here enzymes featuring a synthetic asymmetric mono-cyanide cofactor have been prepared using two different hydrogenase scaffolds. Their structure and reactivity was investigated in order to elucidate the design rationale behind the native di-cyanide cofactor, and by extension the second coordination sphere of the active-site pocket. Surprisingly, the choice of host enzyme was found to have a dramatic impact on reactivity. Moreover, the study shows that synthetic manipulations of the active-site can significantly increase inhibitor tolerance, as compared to native [FeFe] hydrogenase, while retaining the enzyme's native capacity for reversible catalysis.

Identifiants

pubmed: 36320473
doi: 10.1039/d2sc02271k
pii: d2sc02271k
pmc: PMC9516953
doi:

Types de publication

Journal Article

Langues

eng

Pagination

11058-11064

Informations de copyright

This journal is © The Royal Society of Chemistry.

Déclaration de conflit d'intérêts

There are no conflicts to declare.

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Auteurs

Marco Lorenzi (M)

Department of Chemistry - Ångström, Molecular Biomimetics, Uppsala University Lägerhyddsvägen 1 75120 Uppsala Sweden Gustav.berggren@kemi.uu.se.

Joe Gellett (J)

Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford South Parks Road OX1 3QR UK patricia.rodriguezmacia@chem.ox.ac.uk.

Afridi Zamader (A)

Department of Chemistry - Ångström, Molecular Biomimetics, Uppsala University Lägerhyddsvägen 1 75120 Uppsala Sweden Gustav.berggren@kemi.uu.se.
Laboratoire de Chimie et Biologie des Metaux, iRTSV-LCBM/Biocat, Commissariat à l'Energie Atomique (CEA) Grenoble 17, Rue des Martyrs, UMR 5249 38054 Grenoble Cedex 09 France.

Moritz Senger (M)

Department of Chemistry - Ångström, Physical Chemistry, Uppsala University Lägerhyddsvägen 1 75120 Uppsala Sweden.

Zehui Duan (Z)

Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford South Parks Road OX1 3QR UK patricia.rodriguezmacia@chem.ox.ac.uk.

Patricia Rodríguez-Maciá (P)

Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford South Parks Road OX1 3QR UK patricia.rodriguezmacia@chem.ox.ac.uk.

Gustav Berggren (G)

Department of Chemistry - Ångström, Molecular Biomimetics, Uppsala University Lägerhyddsvägen 1 75120 Uppsala Sweden Gustav.berggren@kemi.uu.se.

Classifications MeSH