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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents

ID: 713099.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Hydride bridge in [NiFe]-hydrogenase observed by nuclear resonance vibrational spectroscopy
Authors:Ogata, Hideaki; Krämer, Tobias; Wang, Hongxin; Schilter, David; Pelmenschikov, Vladimir; van Gastel, Maurice; Neese, Frank; Rauchfuss, Thomas B.; Gee, Leland B.; Scott, Aubrey D.; Yoda, Yoshitaka; Tanaka, Yoshihito; Lubitz, Wolfgang; Cramer, Stephen P.
Date of Publication (YYYY-MM-DD):2015
Title of Journal:Nature Communications
Journal Abbrev.:Nature Com.
Sequence Number of Article:7890
Review Status:Internal review
Audience:Experts Only
Abstract / Description:The metabolism of many anaerobes relies on [NiFe]-hydrogenases, whose characterization when bound to substrates has proven non-trivial. Presented here is direct evidence for a hydride bridge in the active site of the Fe-57-labelled fully reduced Ni-R form of Desulfovibrio vulgaris Miyazaki F [NiFe]-hydrogenase. A unique 'wagging' mode involving H- motion perpendicular to the Ni(mu-H)Fe-57 plane was studied using Fe-57-specific nuclear resonance vibrational spectroscopy and density functional theory (DFT) calculations. On Ni(mu-D)Fe-57 deuteride substitution, this wagging causes a characteristic perturbation of Fe-CO/CN bands. Spectra have been interpreted by comparison with Ni(mu-H/D)Fe-57 enzyme mimics [(dppe)Ni(mu-pdt)(mu-H/D)Fe-57(CO) 3](+) and DFT calculations, which collectively indicate a low-spin Ni(II)(mu-H)Fe(II) core for Ni-R, with H- binding Ni more tightly than Fe. The present methodology is also relevant to characterizing Fe-H moieties in other important natural and synthetic catalysts.
Comment of the Author/Creator:Date: 2015, AUG 2015
External Publication Status:published
Document Type:Article
Version Comment:Automatic journal name synchronization
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
External Affiliations:[Wang,H.; Gee,L.; Scott,A.D.] Univ.Calif.Davis,Dept.Chem.,Davis,CA 95616 USA.
[Cramer,S.] Univ.Calif.Berkeley, Lawrence Berkeley Natl.Lab., Div.Phys.Biosci., Berkeley, CA 94720 USA.
[Schilter,D.; Rauchfuss,T.; ] Univ.Illinois,Dept.Chem., Urbana, IL 61801 USA.
[Pelmenschikov,V.] Tech.Univ.Berlin,Inst.Chem., D-10623 Berlin, Germany.
[Yoda,Y.;] Div.Res.&Utilizat, Sayo, Hyogo 6795198, Japan.
[Tanaka,Y.] RIKEN, Mat.Dynam.Lab., Sayo, Hyogo 6795148, Japan.
Identifiers:ISI:000360344600002 [ID No:1]
ISSN:2041-1723 [ID No:2]
DOI:10.1038/ncomms8890 [ID No:3]
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