Journal
JOURNAL OF SYNCHROTRON RADIATION
Volume 22, Issue -, Pages 1334-1344Publisher
INT UNION CRYSTALLOGRAPHY
DOI: 10.1107/S1600577515017816
Keywords
nuclear resonance vibrational spectroscopy; NRVS; ultra-weak signal; [NiFe] hydrogenase; Ni-R; Ni-H-Fe wag mode; iron hydride
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Funding
- NIH [GM-65440]
- DOE Office of Biological and Environmental Research
- BMBF [03SF0355C]
- EU/Energy Network project SOLAR-H2 (FP7) [212508]
- DFG - Cluster of Excellence RESOLV [EXC1069]
- Max Planck Society
- JASRI [2012A0032-2013B0032, 2014B1032]
- RIKEN [20120107, 20130022]
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Direct spectroscopic evidence for a hydride bridge in the Ni-R form of [NiFe] hydrogenase has been obtained using iron-specific nuclear resonance vibrational spectroscopy (NRVS). The Ni-H-Fe wag mode at 675 cm(-1) is the first spectroscopic evidence for a bridging hydride in Ni-R as well as the first iron-hydride-related NRVS feature observed for a biological system. Although density function theory (DFT) calculation assisted the determination of the Ni-R structure, it did not predict the Ni-H-Fe wag mode at similar to 675 cm(-1) before NRVS. Instead, the observed Ni-H-Fe mode provided a critical reference for the DFT calculations. While the overall science about Ni-R is presented and discussed elsewhere, this article focuses on the long and strenuous experimental journey to search for and experimentally identify the Ni-H-Fe wag mode in a Ni-R sample. As a methodology, the results presented here will go beyond Ni-R and hydrogenase research and will also be of interest to other scientists who use synchrotron radiation for measuring dilute samples or weak spectroscopic features.
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