Please use this identifier to cite or link to this item: http://hdl.handle.net/20.500.12779/5225
Title: A Tryptophan Neutral Radical in the Oxidized State of Versatile Peroxidases from Pleurotus Eryngii: A combined Multifrequency EPR and DFT study
Authors: Pogni, Rebecca 
Baratto, Maria Camilla 
C., Teutloff
S., Giansanti
F. J., RUIZ DUENAS
T., Choinowski
K., Piontek
A. T., Martinez
F., Lendzian
Basosi, Riccardo 
Issue Date: 2006
Project: None 
Journal: THE JOURNAL OF BIOLOGICAL CHEMISTRY
Abstract: 
Versatile peroxidases are heme enzymes that combine catalytic properties of lignin peroxidases and manganese peroxidases, being able to oxidizeMn2 as well as phenolic and non-phenolic aromatic compounds in the absence of mediators. The catalytic process (initiated by hydrogen peroxide) is the same as in classical peroxidases, with the involvement of 2 oxidizing equivalents and the formation of the so-called Compound I. This latter state contains an oxoferryl center and an organic cation radical that can be located on either the porphyrin ring or a protein residue. In this study, a radical intermediate in the reaction of versatile peroxidase from the ligninolytic fungus Pleurotus eryngii with H2O2 has been characterized by multifrequency (9.4 and 94 GHz) EPR and assigned to a tryptophan residue. Comparison of experimental data and density functional theory theoretical results strongly suggests the assignment to a tryptophan neutral radical, excluding the assignment to a tryptophan cation radical or a histidine radical. Based on the experimentally determined side chain orientation and comparison with a high resolution crystal structure, the tryptophan neutral radical can be assigned to Trp164 as the site involved in long-range electron transfer for aromatic substrate oxidation.
Description: 
37763
URI: http://hdl.handle.net/20.500.12779/5225
ISSN: 0021-9258
DOI: 10.1074/jbc.M510424200
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