期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 136, 期 45, 页码 15942-15954出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja505720m
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资金
- NIH [GM-65440]
- NSF [CHE 1308384]
- DOE Office of Biological and Environmental Research
- Deutsche Forschungsgemeinschaft (DFG) via the Unifying Concepts in Catalysis (UniCat) Excellence Cluster
- Direct For Mathematical & Physical Scien [1308384] Funding Source: National Science Foundation
- Division Of Chemistry [1308384] Funding Source: National Science Foundation
The properties of CO-inhibited Azotobacter vinelandii (Av) Mo-nitrogenase (N(2)ase) have been examined by the combined application of nuclear resonance vibrational spectroscopy (NRVS), extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT). Dramatic changes in the NRVS are seen under high-CO conditions, especially in a 188 cm(1) mode associated with symmetric breathing of the central cage of the FeMo-cofactor. Similar changes are reproduced with the alpha-H195Q N(2)ase variant. In the frequency region above 450 cm(1), additional features are seen that are assigned to Fe-CO bending and stretching modes (confirmed by (CO)-C-13 isotope shifts). The EXAFS for wild-type N(2)ase shows evidence for a significant cluster distortion under high-CO conditions, most dramatically in the splitting of the interaction between Mo and the shell of Fe atoms originally at 5.08 angstrom in the resting enzyme. A DFT model with both a terminal -CO and a partially reduced -CHO ligand bound to adjacent Fe sites is consistent with both earlier FT-IR experiments, and the present EXAFS and NRVS observations for the wild-type enzyme. Another DFT model with two terminal CO ligands on the adjacent Fe atoms yields Fe-CO bands consistent with the alpha-H195Q variant NRVS. The calculations also shed light on the vibrational shake modes of the interstitial atom inside the central cage, and their interaction with the Fe-CO modes. Implications for the CO and N-2 reactivity of N(2)ase are discussed.
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