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  Spectroscopic investigations of a semi-synthetic [FeFe] hydrogenase with propane di-selenol as bridging ligand in the binuclear subsite: comparison to the wild type and propane di-thiol variants

Sommer, C., Rumpel, S., Roy, S., Farès, C., Artero, V., Fontecave, M., et al. (2018). Spectroscopic investigations of a semi-synthetic [FeFe] hydrogenase with propane di-selenol as bridging ligand in the binuclear subsite: comparison to the wild type and propane di-thiol variants. Journal of Biological Inorganic Chemistry, 23(3), 481-491. doi:10.1007/s00775-018-1558-4.

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 Creators:
Sommer, C.1, Author
Rumpel, S.1, Author
Roy, S.2, Author
Farès, C.3, Author              
Artero, V.2, Author
Fontecave, M.4, Author
Reijerse, E.1, Author
Lubitz, W.1, Author
Affiliations:
1Max-Planck-Institut für Chemische Energiekonversion, Mülheim an der Ruhr, Germany, ou_persistent22              
2Laboratoire de Chimie et Biologie des Métaux, Université Grenoble Alpes, CEA/BIG, CNRS, Grenoble, France, ou_persistent22              
3Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445623              
4Laboratoire de Chimie des Processus Biologiques, Collège de France, Université Pierre et Marie Curie, CNRS, UMR 8229, PSL Research University, Paris, France, ou_persistent22              

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Free keywords: [FeFe] Hydrogenase; Chalcogenic substitution; Nuclear magnetic resonance; Electron paramagnetic resonance; FTIR spectroelectrochemistry
 Abstract: [FeFe] Hydrogenases catalyze the reversible conversion of H2 into electrons and protons. Their catalytic site, the H-cluster, contains a generic [4Fe–4S]H cluster coupled to a [2Fe]H subsite [Fe2(ADT)(CO)3(CN)2]2−, ADT = µ(SCH2)2NH. Heterologously expressed [FeFe] hydrogenases (apo-hydrogenase) lack the [2Fe]H unit, but this can be incorporated through artificial maturation with a synthetic precursor [Fe2(ADT)(CO)4(CN)2]2−. Maturation with a [2Fe] complex in which the essential ADT amine moiety has been replaced by CH2 (PDT = propane-dithiolate) results in a low activity enzyme with structural and spectroscopic properties similar to those of the native enzyme, but with simplified redox behavior. Here, we study the effect of sulfur-to-selenium (S-to-Se) substitution in the bridging PDT ligand incorporated in the [FeFe] hydrogenase HydA1 from Chlamydomonas reinhardtii using magnetic resonance (EPR, NMR), FTIR and spectroelectrochemistry. The resulting HydA1-PDSe enzyme shows the same redox behavior as the parent HydA1-PDT. In addition, a state is observed in which extraneous CO is bound to the open coordination site of the [2Fe]H unit. This state was previously observed only in the native enzyme HydA1-ADT and not in HydA1-PDT. The spectroscopic features and redox behavior of HydA1-PDSe, resulting from maturation with [Fe2(PDSe)(CO)4(CN)2]2−, are discussed in terms of spin and charge density shifts and provide interesting insight into the electronic structure of the H-cluster. We also studied the effect of S-to-Se substitution in the [4Fe–4S] subcluster. The reduced form of HydA1 containing only the [4Fe–4Se]H cluster shows a characteristic S = 7/2 spin state which converts back into the S = 1/2 spin state upon maturation with a [2Fe]–PDT/ADT complex.

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Language(s): eng - English
 Dates: 2018-02-022018-03-302018-04-072018-05-01
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1007/s00775-018-1558-4
 Degree: -

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Title: Journal of Biological Inorganic Chemistry
Source Genre: Journal
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Publ. Info: Berlin : Springer
Pages: - Volume / Issue: 23 (3) Sequence Number: - Start / End Page: 481 - 491 Identifier: ISSN: 0949-8257
CoNE: https://pure.mpg.de/cone/journals/resource/954925573943