Factoring of the Hyperfine Shifts in the Cyanide Adduct of Lignin Peroxidase from P. chrysosporium

Lucia Banci, Ivano Bertini, Roberta Pierattelli, Ming Tien, Alejandro J. Vila

Research output: Contribution to journalArticle

39 Citations (Scopus)

Abstract

We have used NMR spectroscopy to study the cyanide derivative of lignin peroxidase with the goal of characterizing the electronic structure of this derivative of peroxidases. By using various homonuclear and heteronuclear 2D NMR techniques and by making use of the available X-ray structure of the cyanide-free protein, it has been possible to extend the assignment of the heme substituents and of the protons of some active-site residues. An estimate of the anisotropy and direction of the magnetic susceptibility anisotropy tensor has been obtained from the pseudocontact shifts of protons of residues not directly bound to the heme iron ion. Finally, a factoring of the hyperfine shifts of the heme and proximal histidine protons, as well as of the 13C heme methyls and 15N of the cyanide moiety, is obtained. The contact shift pattern of the heme protons is related to the orientation of the histidine plane. Very large upfield contact shifts are experienced by the aromatic protons of the proximal histidine. The axial magnetic anisotropy is smaller than in metmyoglobin–CN and slightly larger than in horseradish peroxidase–CN. This may reflect the order of the donor strength of the proximal histidine. The z axis of the magnetic susceptibility tensor is found essentially perpendicular to the heme plane.

Original languageEnglish (US)
Pages (from-to)8659-8667
Number of pages9
JournalJournal of the American Chemical Society
Volume117
Issue number33
DOIs
StatePublished - Jan 1 1995

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Chrysosporium
Cyanides
Lignin
Heme
Protons
Histidine
Anisotropy
Magnetic susceptibility
Tensors
Acetonitriles
Derivatives
Armoracia
Biomolecular Nuclear Magnetic Resonance
Magnetic anisotropy
Peroxidases
Nuclear magnetic resonance spectroscopy
Electronic structure
Nuclear magnetic resonance
lignin peroxidase
Catalytic Domain

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Banci, Lucia ; Bertini, Ivano ; Pierattelli, Roberta ; Tien, Ming ; Vila, Alejandro J. / Factoring of the Hyperfine Shifts in the Cyanide Adduct of Lignin Peroxidase from P. chrysosporium. In: Journal of the American Chemical Society. 1995 ; Vol. 117, No. 33. pp. 8659-8667.
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Factoring of the Hyperfine Shifts in the Cyanide Adduct of Lignin Peroxidase from P. chrysosporium. / Banci, Lucia; Bertini, Ivano; Pierattelli, Roberta; Tien, Ming; Vila, Alejandro J.

In: Journal of the American Chemical Society, Vol. 117, No. 33, 01.01.1995, p. 8659-8667.

Research output: Contribution to journalArticle

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