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Volumn 126, Issue 15, 2004, Pages 4991-5000

Oxygen Activation by the Noncoupled Binuclear Copper Site in Peptidylglycine α-Hydroxylating Monooxygenase. Reaction Mechanism and Role of the Noncoupled Nature of the Active Site

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ANALYSIS; CATALYSIS; COPPER; ELECTRONS; GLYCEROL; HYDROXYLATION; ORGANOMETALLICS; THERMODYNAMICS;

EID: 1942504122     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja031564g     Document Type: Article
Times cited : (262)

References (64)
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    • The bond lengths in the geometry optimized structures presented here are slightly longer than those determined experimentally. This is due to the basis set (LanL2Dz) employed in the geometry optimizations. The reaction energies calculated with the triple-ζ TZV basis set are not significantly affected by these small geometry differences. See: Szilagyi, R. K.; Metz, M.; Solomon, E. I. J. Phys. Chem. A 2002, 106, 2994. Schenk, G.; Pau, M. Y. M.; Solomon, E. I. J Am. Chem. Soc. 2004, 126, 505.
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  • 30
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    • The bond lengths in the geometry optimized structures presented here are slightly longer than those determined experimentally. This is due to the basis set (LanL2Dz) employed in the geometry optimizations. The reaction energies calculated with the triple-ζ TZV basis set are not significantly affected by these small geometry differences. See: Szilagyi, R. K.; Metz, M.; Solomon, E. I. J. Phys. Chem. A 2002, 106, 2994. Schenk, G.; Pau, M. Y. M.; Solomon, E. I. J Am. Chem. Soc. 2004, 126, 505.
    • (2004) J Am. Chem. Soc. , vol.126 , pp. 505
    • Schenk, G.1    Pau, M.Y.M.2    Solomon, E.I.3
  • 34
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    • 2 intermediate for H-atom abstraction from the substrate. (Prigge, S. T.; Mains, R. E.; Eipper, B. A.; Amzel, L. M. Cell. Mol. Life Sci. 2000, 57, 1236.) Since the formation of this species is highly unfavorable, it is excluded from further evaluation.
    • (2000) Cell. Mol. Life Sci. , vol.57 , pp. 1236
    • Prigge, S.T.1    Mains, R.E.2    Eipper, B.A.3    Amzel, L.M.4
  • 36
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    • note
    • M-superoxide intermediate. Therefore, this end-on superoxide species is likely comparable to or slightly less reactive than the side-on superoxide species, not considering the steric effects of their different binding geometries.
  • 39
    • 1942439571 scopus 로고    scopus 로고
    • note
    • M-OOH intermediate is sterically inaccessible, it is a unlikely pathway.
  • 40
    • 1942439573 scopus 로고    scopus 로고
    • note
    • The positions of α-carbons of Met/His ligands were kept frozen during the optimizations. The orientation of the FmG substrate was also fixed by freezing the relative angles and dihedrals of all heavy atoms relative to the Met/His α-carbons, except for the two oxygen atoms of the carboxylate group, to reduce the computational cost. The constraints on the substrate FmG in the PES calculations should have a very small effect on the overall energetics because the constrained angles and dihedrals changed little in geometry optimizations of isolated molecules (Figure S1C-E, Supporting Information).
  • 41
    • 1942535651 scopus 로고    scopus 로고
    • note
    • The difference in ΔE between the PES calculations and the energetics calculations with isolated molecules is due to the slight geometry differences and different intermolecular interactions among the reactants and products.
  • 42
    • 1942535650 scopus 로고    scopus 로고
    • note
    • O-C = 3.0 Å.
  • 45
    • 1942439572 scopus 로고    scopus 로고
    • note
    • M-OOH intermediate 3.
  • 46
    • 0004052075 scopus 로고
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    • (1991) Oxygen Chemistry
    • Sawyer, D.T.1
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    • M-superoxo pathway undergoing electrophilic attack. Epoxidation reactivities have been reported for some metal-superoxo species. See: Talsi, E. P.; Babenko, V. P.; Shubin, A. A.; Chinakov, V. D.; Nekipelov, V. M.; Zamaraev, K. I. Inorg. Chem. 1987, 26, 3871. Nakatsuji, H.; Hu, Z.-M.; Nakai, H.; Ikeda, K. Surf. Sci. 1997, 387, 328.
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  • 53
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    • M-superoxo pathway undergoing electrophilic attack. Epoxidation reactivities have been reported for some metal-superoxo species. See: Talsi, E. P.; Babenko, V. P.; Shubin, A. A.; Chinakov, V. D.; Nekipelov, V. M.; Zamaraev, K. I. Inorg. Chem. 1987, 26, 3871. Nakatsuji, H.; Hu, Z.-M.; Nakai, H.; Ikeda, K. Surf. Sci. 1997, 387, 328.
    • (1987) Inorg. Chem. , vol.26 , pp. 3871
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  • 54
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    • M-superoxo pathway undergoing electrophilic attack. Epoxidation reactivities have been reported for some metal-superoxo species. See: Talsi, E. P.; Babenko, V. P.; Shubin, A. A.; Chinakov, V. D.; Nekipelov, V. M.; Zamaraev, K. I. Inorg. Chem. 1987, 26, 3871. Nakatsuji, H.; Hu, Z.-M.; Nakai, H.; Ikeda, K. Surf. Sci. 1997, 387, 328.
    • (1997) Surf. Sci. , vol.387 , pp. 328
    • Nakatsuji, H.1    Hu, Z.-M.2    Nakai, H.3    Ikeda, K.4


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.