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Volumn 120, Issue 34, 1998, Pages 8724-8738

Spectroscopic studies of oxidized manganese catalase and μ-oxo-bridged dimanganese(III) model complexes: Electronic structure of the active site and its relation to catalysis

Author keywords

[No Author keywords available]

Indexed keywords

AZIDE; CATALASE; LIGAND; MANGANESE OXIDE;

EID: 0032475384     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja981394l     Document Type: Article
Times cited : (60)

References (106)
  • 18
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    • Pecoraro, V. L., Ed.; VCH Publishers: New York
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    • Ph.D. Thesis, The University of Michigan
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    • Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK 2100, Denmark
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    • Ligfield Version 0.85
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  • 47
    • 3543104606 scopus 로고    scopus 로고
    • ∈ and Δ∈ are given per Mn(III)/Mn(III) dimer of OxMnCAT
    • ∈ and Δ∈ are given per Mn(III)/Mn(III) dimer of OxMnCAT.
  • 48
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    • -1
    • -1.
  • 49
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    • Mansucript in preparation
    • -1 band appears to be much sharper than in solution spectra recorded at room temperature. This is due to strong antiferromagnetic exchange interactions in the corresponding excited state and will be discussed elsewhere. Brunold, T. C.; Gamelin, D. R.; Solomon, E. I. Mansucript in preparation.
    • Brunold, T.C.1    Gamelin, D.R.2    Solomon, E.I.3
  • 50
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    • note
    • 2O the molecular x′, y′, and z′ axes coincide with the crystallographic c, a, and b axes, respectively.
  • 56
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    • Previous calculations in ref 47b have focused on calculating ground-state exchange coupling constants and charge and spin densities
    • (a) Previous calculations in ref 47b have focused on calculating ground-state exchange coupling constants and charge and spin densities.
  • 61
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    • note
    • -1) can be eliminated for two reasons: (i) Jahn-Teller distortions in Mn(III) complexes will ensure a sufficiently large separation of the single unoccupied d orbital from the occupied orbitals and (ii) the low-lying excited state would spin-orbit couple to the ground state, giving rise to an imbalance between positive and negative MCD intensity.
  • 68
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    • note
    • -1 (azide bound form). While the absolute D values have little meaning, their positive signs and similar magnitudes underline the high resemblance of the two data sets.
  • 75
    • 3543104605 scopus 로고    scopus 로고
    • The sign change does not require that D passes through O: Along the Berry pseudorotation coordinate, E increases to maximum rhombicity and a reorientation of the coordinate system is required
    • The sign change does not require that D passes through O: Along the Berry pseudorotation coordinate, E increases to maximum rhombicity and a reorientation of the coordinate system is required.
  • 76
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    • Note that this represents the effective electronic symmetry for the Mn ions and does not rule out distortion along a coordinate leading toward square pyramidal geometry
    • Note that this represents the effective electronic symmetry for the Mn ions and does not rule out distortion along a coordinate leading toward square pyramidal geometry.
  • 79
    • 3543054318 scopus 로고    scopus 로고
    • note
    • AH calculations performed on the OxMnCAT and MnSOD models afforded a monodentate carboxylate based HOMO mainly localized on the noncoordinating oxygen atom. In the protein this orbital will be stabilized by hydrogen bonding interactions, and it has therefore been omitted in the analysis of the computational results.
  • 80
    • 3543135059 scopus 로고    scopus 로고
    • note
    • 2-based unoccupied spin-down MO is stabilized relative to the other Mn d-based unoccupied spin down MOs (Figure 9) due to substantial delocalization onto Mn2 and/or mixing with the Mn 4s orbital.
  • 82
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    • note
    • 3,72
  • 89
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    • note
    • The quality of the fit (obtained under the assumption that the bandwidths do not change upon azide binding) suffers from large band distortions arising from spin-orbit coupling between the quintet and triplet LF excited states.
  • 90
    • 0029944136 scopus 로고    scopus 로고
    • Addition of azide to MnSOD at 295 K results in a five-coordinate complex that interconverts to a six-coordinate species at low temperatures. This change in coordination number is accompanied by a decrease in integrated intensity of about 50%. Whittaker, M. M.; Whittaker, J. M. Biochemistry 1996, 35, 6762.
    • (1996) Biochemistry , vol.35 , pp. 6762
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    • note
    • -1. In view of the simplicity of this model the correspondence is satisfactory.
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    • Oxford University Press: New York
    • Sawyer, D. T. Oxygen Chemistry; Oxford University Press: New York, 1991; p 21.
    • (1991) Oxygen Chemistry , pp. 21
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    • It is noteworthy that Mn catalase isolated from T. thermophilus undergoes complete autoxidation to the Mn(III)/Mn(III) level and that pH influences the rate but not the extent of oxidation. Khangulov, S. V.; Barynin, V. V.; Antonyuk-Barynina, S. V. Biochim. Biophys. Acta 1990, 1020, 25.
    • (1990) Biochim. Biophys. Acta , vol.1020 , pp. 25
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  • 102
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    • 2(III/ III) reduction potentials are identical
    • 2(III/ III) reduction potentials are identical.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.