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 and Cramer, Stephen P. (2015) Hydride bridge in [NiFe]-hydrogenase observed by nuclear resonance vibrational spectroscopy. Nature Communications, 6 (1). ISSN 2041-1723
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Abstract
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 57Fe-labelled fully reduced Ni-R form of Desulfovibrio
vulgaris Miyazaki F [NiFe]-hydrogenase. A unique ‘wagging’ mode involving H- motion
perpendicular to the Ni(m-H)57Fe plane was studied using 57Fe-specific nuclear resonance
vibrational spectroscopy and density functional theory (DFT) calculations. On
Ni(m-D)57Fe deuteride substitution, this wagging causes a characteristic perturbation of
Fe–CO/CN bands. Spectra have been interpreted by comparison with Ni(m-H/D)57Fe enzyme
mimics [(dppe)Ni(m-pdt)(m-H/D)57Fe(CO)3] þ and DFT calculations, which collectively
indicate a low-spin Ni(II)(m-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.
Item Type: | Article |
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Keywords: | Hydride bridge; NiFe-hydrogenase; observed; nuclear resonance; vibrational; spectroscopy; |
Academic Unit: | Faculty of Science and Engineering > Chemistry Faculty of Science and Engineering > Research Institutes > Hamilton Institute |
Item ID: | 15494 |
Identification Number: | 10.1038/ncomms8890 |
Depositing User: | Tobias Kraemer |
Date Deposited: | 15 Feb 2022 12:13 |
Journal or Publication Title: | Nature Communications |
Publisher: | Nature Research |
Refereed: | Yes |
Related URLs: | |
URI: | https://mu.eprints-hosting.org/id/eprint/15494 |
Use Licence: | This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here |
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