title: Lignin peroxidase-catalyzed oxidation of sulfonated azo dyes generates novel sulfophenyl hydroperoxides.
abstract: Lignin peroxidase (LiP) is an extracellular enzyme produced by the lignin-degrading fungus Phanerochaete chrysosporium and is involved in azo dye degradation by this organism. In this study, LiP oxidation of the sulfonated azo dyes 4-(4'-sulfophenylazo)-2,6- dimethylphenol (I), Orange II [1-(4'-sulfophenylazo)-2-naphthol] (II), a dimethyl analog of Orange II [1-(2',6'-dimethyl-4'-sulfophenylazo)-2-naphthol] (III), and 4-(4'-sulfonamidophenylazo)-2,6-dimehtylphenol (IV) was examined. Azo dye I was oxidized to 2,6-dimethyl-1,4-benzoquinone and 4-sulfophenyl hydroperoxide. Orange II (II) was oxidized to 1,2-naphthoquinone and 4-sulfophenyl hydroperoxide. The dimethyl analog of Orange II (III) was oxidized to 1,2-naphthoquinone and 2,6-dimethyl-4-sulfophenyl hydroperoxide. Azo dye IV was oxidized predominantly to 2,6-dimethyl-1,4-benzoquinone and another product, tentatively characterized as 4-sulfonamidophenyl hydroperoxide. In the 18O-labeling studies with 18O2, oxygen incorporation into the phenyl hydroperoxides from the oxidation of I and III was observed. A mechanism for azo dye degradation consistent with product identification and the 18O-labeling studies is proposed. Two successive one-electron oxidations of the phenolic ring of an azo dye by the H2O2-oxidized forms of LiP produces a carbonium ion. Then water attacks the phenolic carbon bearing the azo linkage, producing an unstable hydroxy intermediate which breaks down to yield a quinone and a sulfo- or sulfonamidophenyldiazene. The phenyldiazene is oxidized by O2 to generate the corresponding phenyldiazene radical, which eliminates N2 to yield a sulfo- or sulfonamidophenyl radical. O2 scavenges the latter to yield the corresponding hydroperoxide.(ABSTRACT TRUNCATED AT 250 WORDS)
authors.affiliation: Department of Chemistry, Biochemistry, and Molecular Biology, Oregon Graduate Institute of Science & Technology, Portland 97291-1000, USA.
authors.forename: M
authors.initials: M
authors.lastname: Chivukula
authors.forename: J T
authors.initials: JT
authors.lastname: Spadaro
authors.forename: V
authors.initials: V
authors.lastname: Renganathan
mesh_terms: D001391:Azo Compounds / Q000378:metabolism*; D001487:Basidiomycota / Q000201:enzymology*; D001557:Benzenesulfonates / Q000378:metabolism*; D004396:Coloring Agents; D013058:Mass Spectrometry; D009282:Naphthalenesulfonates / Q000378:metabolism*; D010084:Oxidation-Reduction; D010544:Peroxidases / Q000378:metabolism*; D010545:Peroxides / Q000378:metabolism
chemical_list: D001391:Azo Compounds; D001557:Benzenesulfonates; D004396:Coloring Agents; D009282:Naphthalenesulfonates; D010545:Peroxides; D010544:Peroxidases; C042858:lignin peroxidase