Title: Oxidative cleavage of non-phenolic β-O-4 lignin model dimers by an extracellular aromatic peroxygenase
Author: Kinne, Matthias; Poraj-Kobielska, Marzena; Ullrich, Rene; Nousiainen, Paula; Sipilä, Jussi; Scheibner, Katrin; Hammel, Kenneth E.; Hofrichter, Martin;
Source: Holzforschung. Vol. 65, no. 5 (Aug. 2011): p. 673-679.
Publication Series: Scientific Journal (JRNL)
Description: The extracellular aromatic peroxygenase of the agaric fungus Agrocybe aegerita catalyzed the H2O2-dependent cleavage of non-phenolic arylgiycerol-ß-aryl ethers (ß-O-4 ethers). For instance 1-(3,4-dimethoxyphenyl)-2-(2-methoxy-phenoxy)propane-1,3-diol, a recalcitrant dimeric lignin model compound that represents the major non-phenolic substructure in lignin, was selectively O-demethylated at the para-methoxy group to give formaldehyde and 1-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)propane-1,3-diol. The phenol moiety of the latter compound was then enzymatically oxidized into phenoxy radicals and a quinoid cation, which initiated the autocatalytic cleavage of the dimer and the formation of monomers such as 2-methoxy-1,4-benzoquinone and phenoxyl-substituted propionic acid. The introduction of 18O from H218O2 and H218O2 at different positions into the products provided information about the routes of ether cleavage. Studies with a 14C-labeled lignin model dimer showed that more than 70% of the intermediates formed were further coupled to form polymers with molecular masses above 10 kDa. The results indicate that fungal aromatic peroxygenases may be involved in the bioconversion of methoxylated plant ingredients originating from lignin or other sources.
Keywords: Wood-decaying fungi, biodegradation, oxidation, chemical reactions, enzymes, biotechnology, industrial applications, Basidiomycetes, catalysis, fungi, fungal enzymes, lignin, dimers, oxygenases, peroxidase, hydroxylation, hydrogen peroxide, ethers, formaldehyde, phenols, monomers, peroxygenase, Agrocybe aegerita, cleavage, wood decay, decay fungi, bioconversion, biorefining, lignin model compound, O-dealkylation
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Kinne, Matthias; Poraj-Kobielska, Marzena; Ullrich, Rene; Nousiainen, Paula; Sipilä, Jussi; Scheibner, Katrin; Hammel, Kenneth E.; Hofrichter, Martin; 2011. Oxidative cleavage of non-phenolic β-O-4 lignin model dimers by an extracellular aromatic peroxygenase. Holzforschung. Vol. 65, no. 5 (Aug. 2011): p. 673-679.
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