Hydride bridge in [NiFe]-hydrogenase observed by nuclear resonance vibrational spectroscopy

نویسندگان

  • Hideaki Ogata
  • Tobias Krämer
  • Hongxin Wang
  • David Schilter
  • Vladimir Pelmenschikov
  • Maurice van Gastel
  • Frank Neese
  • Thomas B Rauchfuss
  • Leland B Gee
  • Aubrey D Scott
  • Yoshitaka Yoda
  • Yoshihito Tanaka
  • Wolfgang Lubitz
  • Stephen P Cramer
چکیده

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 (57)Fe-labelled fully reduced Ni-R form of Desulfovibrio vulgaris Miyazaki F [NiFe]-hydrogenase. A unique 'wagging' mode involving H(-) motion perpendicular to the Ni(μ-H)(57)Fe plane was studied using (57)Fe-specific nuclear resonance vibrational spectroscopy and density functional theory (DFT) calculations. On Ni(μ-D)(57)Fe deuteride substitution, this wagging causes a characteristic perturbation of Fe-CO/CN bands. Spectra have been interpreted by comparison with Ni(μ-H/D)(57)Fe enzyme mimics [(dppe)Ni(μ-pdt)(μ-H/D)(57)Fe(CO)3](+) and DFT calculations, which collectively indicate a low-spin Ni(II)(μ-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.

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عنوان ژورنال:

دوره 6  شماره 

صفحات  -

تاریخ انتشار 2015