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Polymerization of monolignols by redox shuttle-mediated enzymatic oxidation: a new model in lignin biosynthesis I.
- Source :
-
The Plant cell [Plant Cell] 2002 Aug; Vol. 14 (8), pp. 1953-62. - Publication Year :
- 2002
-
Abstract
- Lignin is one of the most abundant biopolymers, and it has a complex racemic structure. It may be formed by a radical polymerization initiated by redox enzymes, but much remains unknown about the process, such as how molecules as large as enzymes can generate the compact structure of the lignified plant cell wall. We have synthesized lignin oligomers according to a new concept, in which peroxidase is never in direct contact with the lignin monomers coniferaldehyde and coniferyl alcohol. Instead, manganese oxalate worked as a diffusible redox shuttle, first being oxidized from Mn(II) to Mn(III) by a peroxidase and then being reduced to Mn(II) by a simultaneous oxidation of the lignin monomers to radicals that formed covalent linkages of the lignin type. Furthermore, a high molecular mass polymer was generated by oxidation of coniferyl alcohol by Mn(III) acetate in a dioxane and water mixture. This polymer was very similar to natural spruce wood lignin, according to its NMR spectrum. The possible involvement of a redox shuttle/peroxidase system in lignin biosynthesis is discussed.
- Subjects :
- Acrolein chemistry
Acrolein metabolism
Biopolymers chemistry
Catalysis
Cell Wall metabolism
Chromatography methods
Lignin chemical synthesis
Magnetic Resonance Spectroscopy
Manganese metabolism
Manganese Compounds metabolism
Models, Chemical
Oxidation-Reduction
Oxygen metabolism
Peroxidases metabolism
Phenols chemistry
Phenols metabolism
Wood
Acrolein analogs & derivatives
Biopolymers metabolism
Enzymes metabolism
Lignin biosynthesis
Subjects
Details
- Language :
- English
- ISSN :
- 1040-4651
- Volume :
- 14
- Issue :
- 8
- Database :
- MEDLINE
- Journal :
- The Plant cell
- Publication Type :
- Academic Journal
- Accession number :
- 12172033
- Full Text :
- https://doi.org/10.1105/tpc.001487