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A single-crystal ENDOR and density functional theory study of the oxidized states of the [NiFe] hydrogenase from Desulfovibrio vulgaris Miyazaki F
- Source :
- Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry. 11(1)
- Publication Year :
- 2005
-
Abstract
- The catalytic center of the [NiFe] hydrogenase of Desulfovibrio vulgaris Miyazaki F in the oxidized states was investigated by electron paramagnetic resonance and electron-nuclear double resonance spectroscopy applied to single crystals of the enzyme. The experimental results were compared with density functional theory (DFT) calculations. For the Ni-B state, three hyperfine tensors could be determined. Two tensors have large isotropic hyperfine coupling constants and are assigned to the beta-CH2 protons of the Cys-549 that provides one of the bridging sulfur ligands between Ni and Fe in the active center. From a comparison of the orientation of the third hyperfine tensor with the tensor obtained from DFT calculations an OH- bridging ligand has been identified in the Ni-B state. For the Ni-A state broader signals were observed. The signals of the third proton, as observed for the "ready" state Ni-B, were not observed at the same spectral position for Ni-A, confirming a structural difference involving the bridging ligand in the "unready" state of the enzyme.
- Subjects :
- Hydrogenase
Protein Conformation
Ligands
Biochemistry
law.invention
Inorganic Chemistry
Computational chemistry
law
Cysteine
Desulfovibrio vulgaris
Electron paramagnetic resonance
Hyperfine structure
Quantitative Biology::Biomolecules
Electron nuclear double resonance
Binding Sites
biology
Chemistry
Electron Spin Resonance Spectroscopy
Resonance
Bridging ligand
biology.organism_classification
Crystallography
Density functional theory
Protons
Crystallization
Oxidation-Reduction
Sulfur
Subjects
Details
- ISSN :
- 09498257
- Volume :
- 11
- Issue :
- 1
- Database :
- OpenAIRE
- Journal :
- Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry
- Accession number :
- edsair.doi.dedup.....a4afba7a37c07bd6bcbb2130d48d6a56