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Volumn 42, Issue 3, 2003, Pages 696-708

Electronic structure contributions to electron-transfer reactivity in iron-sulfur active sites: 3. Kinetics of electron transfer

Author keywords

[No Author keywords available]

Indexed keywords

RUBREDOXIN;

EID: 0037429246     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic0203320     Document Type: Article
Times cited : (50)

References (74)
  • 23
    • 0013059427 scopus 로고    scopus 로고
    • note
    • Bond distances for tetrathiolate are average values for a series of ferrous (CSD: DOKPUO, LAJFUX, PAFVIB, PTHPFE10, VAPVUD, ZAGYIP) and ferric (CSD: BOSTOS, CANCUP, CANDAW, JURHIN, OXYSFEO10) structures.
  • 40
    • 0013060401 scopus 로고    scopus 로고
    • note
    • The negative charge of these complexes in the gas phase contributes to the overestimate of the Fe-X bond distances. The deviation is larger for the tetrachloride, which is unsurprising because of the poorer charge distribution in this complex relative to the tetrathiolate.
  • 42
    • 0013109182 scopus 로고    scopus 로고
    • note
    • The relationship between the distorting force and the bond changes upon oxidation for the Morse-type potential is compared to that occurring in a harmonic field in the Supporting Information. The linear relationship in a harmonic field is dampened by the anharmonicity in the Morse potential; this deviation increases as the distorting force increases.
  • 50
    • 0013059898 scopus 로고    scopus 로고
    • note
    • x2-y2 orbital is lowest in energy and becomes the RAMO.
  • 53
    • 0013153047 scopus 로고    scopus 로고
    • note
    • The RAMO was considered to point towards the surface of the protein in ref 18. The full calculation of the active-site region provides the correct orientation of the RAMO with respect to the protein structure.
  • 71
    • 0013152166 scopus 로고    scopus 로고
    • note
    • Some additional factors further lower the distorting force in the tetrathiolate. The electrostatic charge model should be redistributed within the ligand, and the model assumes that only a single distorting mode is consequential.
  • 72
    • 0013109183 scopus 로고    scopus 로고
    • note
    • Recent studies have suggested that structural rearrangement of the active site could be sufficient to allow direct access to the iron. The crystallographic data used to support this proposal show a water molecule near the active site but still ∼4 Å away from the iron itself. The water is in close contact with one of the surface cysteinates and would ultimately allow for effective solvent-mediated electron transfer through the cysteinate ligand.
  • 73
    • 0013060403 scopus 로고    scopus 로고
    • note
    • The importance of the H-bond pathways can be seen by recalculating the rate constant using the CEM structure where the active-site H-bonds have been broken. In this case, the rate constant drops by approximately 30%.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.