First synthesis of a polysaccharide-supported lignin model compound and study of its oxidation promoted by lignin peroxidase.
Veratrylchitosan, a polysaccharide-supported lignin model compound, has been synthesised by covalently attaching 3-(3,4-dimethoxybenzyloxy)propionic acid to the polysaccharide chitosan through an amide linkage. When this polymer was used as a substrate in the oxidation promoted by lignin peroxidase (LiP), significant decomposition of the lignin model resulted in the formation of veratraldehyde. The oxidation mechanism involves an initial transfer of one electron from chitosan to the active species of LiP (LiP I) followed by C(alpha)-H deprotonation of an aromatic cation radical. A benzylic radical is then formed which is further oxidised to a benzyl cation. Reaction with water and hydrolysis of the hemiacetal then lead to veratraldehyde formation. An increase in the yields of the oxidation product is observed in the presence of the mediator 2-chloro-1,4-dimethoxybenzene, thus indicating that a more efficient degradation results from the transfer of an electron from the polymer to the radical cation of the mediator.
D'Acunzo
Francesca
F
Dipartimento di Chimica, Università degli Studi di Roma "La Sapienza" and Istituto CNR di Metodologie Chimiche (IMC-CNR), Sezione Meccanismi di Reazione, P.le A. Moro, 5 I-00185 Rome, Italy.
Lanzalunga
Osvaldo
O
D000840:Anisoles / Q000737:chemistry; D001547:Benzaldehydes / Q000032:analysis; D001592:Benzyl Alcohols / Q000737:chemistry / Q000378:metabolism; D002686:Chitin / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry* / Q000378:metabolism; D048271:Chitosan; D002722:Chlorobenzenes / Q000737:chemistry; D005609:Free Radicals / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D010084:Oxidation-Reduction; D010544:Peroxidases / Q000378:metabolism*
D000840:Anisoles; D001547:Benzaldehydes; D001592:Benzyl Alcohols; D002722:Chlorobenzenes; D005609:Free Radicals; D002686:Chitin; C116014:2-chloro-1,4-dimethoxybenzene; D048271:Chitosan; D010544:Peroxidases; C042858:lignin peroxidase; C042197:veratryl alcohol; C427725:veratraldehyde