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Volumn 121, Issue 30, 1999, Pages 7138-7149

Spectroscopic studies and electronic structure description of the high potential type 1 copper site in fungal laccase: Insight into the effect of the axial ligand

Author keywords

[No Author keywords available]

Indexed keywords

FUNGAL PROTEIN; LACCASE;

EID: 0033523261     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991087v     Document Type: Article
Times cited : (117)

References (79)
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    • Messerschmidt, A. Multi-copper Oxidases; Messerschmidt, A., Ed.; World Scientific: River Edge, NJ, 1997.
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    • Messerschmidt, A.1
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    • Anfinsen, C. B., Richards, F. M., Edsall, J. T., Eisenberg, D. S., Ed.; Academic Press: San Diego
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    • (1991) Advances in Protein Chemistry , pp. 145-197
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  • 24
    • 13044262599 scopus 로고    scopus 로고
    • note
    • By perturbed we mean an increase in absorption at 450 nm and a rhombic EPR spectrum.
  • 25
    • 13044313625 scopus 로고    scopus 로고
    • note
    • This enzyme has a high degree of homology with Polyporus versicolor laccase. It should be noted that Polyporus pinsitis is also referred to as Trametes villosa, and Polyporus versicolor is often referred to as Trametes versicolor.
  • 34
    • 13044293424 scopus 로고    scopus 로고
    • note
    • The imidazole ring orientation used in the calculations was similar to that in the plastocyanin crystal structure; small deviations in ring orientation from the crystal structure of plastocyanin are due to placing the Cu in the trigonal plane.
  • 38
    • 0011155515 scopus 로고
    • Segal, G. A., Ed.; Plenum: New York, Chapter 7
    • Connolly, J. W. D. In Modern Theoretical Chemistry; Segal, G. A., Ed.; Plenum: New York, 1979; Chapter 7, pp 105-132.
    • (1979) Modern Theoretical Chemistry , pp. 105-132
    • Connolly, J.W.D.1
  • 49
    • 13044275684 scopus 로고    scopus 로고
    • note
    • Although the splittings are clearly observed in the spectrum, superhyperfine coupling constants were obtained from EPR simulations.
  • 50
    • 13044280280 scopus 로고    scopus 로고
    • note
    • -1 is obscured by contributions from a small heme impurity.
  • 53
    • 13044285467 scopus 로고    scopus 로고
    • note
    • 2+ at low temperature arises from C-terms. C-term intensity requires polarization in two perpendicular directions. However, the low symmetry of the blue copper site removes all orbital degeneracy; therefore, transitions are polarized in only one direction. For low-symmetry sites, the only mechanism for C-term intensity involves spin - orbit coupling between states that mix their orthogonal polarizations.
  • 59
    • 13044270437 scopus 로고    scopus 로고
    • note
    • 17).
  • 61
    • 13044270436 scopus 로고    scopus 로고
    • note
    • -1 the transition energy of the intermediate excited state minus the transition energy of the excited state, (2) the cross product of the polarization of the ground state → intermediate excited-state transition with the polarization of the ground state → excited-state transition, and (3) the spin-orbit coupling of the intermediate excited state and the excited state.
  • 62
    • 13044292074 scopus 로고    scopus 로고
    • note
    • -1) x the angular momentum matrix element.
  • 64
    • 13044292076 scopus 로고    scopus 로고
    • note
    • 35 and calculations indicate that it is negative.
  • 67
    • 13044316737 scopus 로고    scopus 로고
    • note
    • This is in contrast to the 42% Cu character in plastocyanin determined experimentally from Cu L-edge spectroscopy. The difference between the calculated and experimental Cu character most likely relates to the effects of charge partitioning in the intersphere region and sphere overlap in the calculations.
  • 69
    • 13044273635 scopus 로고    scopus 로고
    • note
    • 1 representation of the plastocyanin active site. These more recent plastocyanin Xα-SW calculations give a value of 35% for the S character in the HOMO of plastocyanin. The quantitative difference (3%) in S character between these two plastocyanin calculations is due to differences in charge partitioning in the intersphere regions and differences in sphere overlap.
  • 71
    • 13044292075 scopus 로고    scopus 로고
    • note
    • Relative to intermediate structure B, the small shift in the energy of the xy orbital for the final fungal laccase model likely results from the small increase in the N-Cu-N angle, which places the Cu-N bonds slightly closer to the xy orbital, thereby increasing the antibonding interaction.
  • 77
    • 13044252903 scopus 로고    scopus 로고
    • Personal communication
    • Neese, F. Personal communication.
    • Neese, F.1
  • 78
    • 13044277017 scopus 로고    scopus 로고
    • note
    • As discussed above, this feature is distorted in the fungal laccases because of spectral overlap of the tightly grouped ligand field bands.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.