Flavonoids naringenin chalcone, naringenin, dihydrotricin, and tricin are lignin monomers in papyrus. 2022

Jorge Rencoret, and Mario J Rosado, and Hoon Kim, and Vitaliy I Timokhin, and Ana Gutiérrez, and Florian Bausch, and Thomas Rosenau, and Antje Potthast, and John Ralph, and José C Del Río
Instituto de Recursos Naturales y Agrobiología de Sevilla (IRNAS), CSIC, Avda. Reina Mercedes, 10, 41012-Seville, Spain.

Recent studies demonstrate that several polyphenolic compounds produced from beyond the canonical monolignol biosynthetic pathways can behave as lignin monomers, participating in radical coupling reactions and being incorporated into lignin polymers. Here, we show various classes of flavonoids, the chalconoid naringenin chalcone, the flavanones naringenin and dihydrotricin, and the flavone tricin, incorporated into the lignin polymer of papyrus (Cyperus papyrus L.) rind. These flavonoids were released from the rind lignin by Derivatization Followed by Reductive Cleavage (DFRC), a chemical degradative method that cleaves the β-ether linkages, indicating that at least a fraction of each was integrated into the lignin as β-ether-linked structures. Due to the particular structure of tricin and dihydrotricin, whose C-3' and C-5' positions at their B-rings are occupied by methoxy groups, these compounds can only be incorporated into the lignin through 4'-O-β bonds. However, naringenin chalcone and naringenin have no substituents at these positions and can therefore form additional carbon-carbon linkages, including 3'- or 5'-β linkages that form phenylcoumaran structures not susceptible to cleavage by DFRC. Furthermore, Nuclear Magnetic Resonance analysis indicated that naringenin chalcone can also form additional linkages through its conjugated double bond. The discovery expands the range of flavonoids incorporated into natural lignins, further broadens the traditional definition of lignin, and enhances the premise that any phenolic compound present at the cell wall during lignification could be oxidized and potentially integrated into the lignin structure, depending only on its chemical compatibility. This study indicates that papyrus lignin has a unique structure, as it is the only lignin known to date that integrates such a diversity of phenolic compounds from different classes of flavonoids. This discovery will open up new ways to engineer and design lignins with specific properties and for enhanced value.

UI MeSH Term Description Entries
D008031 Lignin The most abundant natural aromatic organic polymer found in all vascular plants. Lignin together with cellulose and hemicellulose are the major cell wall components of the fibers of all wood and grass species. Lignin is composed of coniferyl, p-coumaryl, and sinapyl alcohols in varying ratios in different plant species. (From Merck Index, 11th ed) Lignins
D004534 Egypt A country in northern Africa, bordering the Mediterranean Sea, between Libya and the Gaza Strip, and the Red Sea north of Sudan, and includes the Asian Sinai Peninsula Its capital is Cairo. Arab Republic of Egypt,United Arab Republic
D005419 Flavonoids A group of phenyl benzopyrans named for having structures like FLAVONES. 2-Phenyl-Benzopyran,2-Phenyl-Chromene,Bioflavonoid,Bioflavonoids,Flavonoid,2-Phenyl-Benzopyrans,2-Phenyl-Chromenes,2 Phenyl Benzopyran,2 Phenyl Benzopyrans,2 Phenyl Chromene,2 Phenyl Chromenes
D001665 Binding Sites The parts of a macromolecule that directly participate in its specific combination with another molecule. Combining Site,Binding Site,Combining Sites,Site, Binding,Site, Combining,Sites, Binding,Sites, Combining
D015394 Molecular Structure The location of the atoms, groups or ions relative to one another in a molecule, as well as the number, type and location of covalent bonds. Structure, Molecular,Molecular Structures,Structures, Molecular
D053898 Biosynthetic Pathways Sets of enzymatic reactions occurring in organisms and that form biochemicals by making new covalent bonds. Biosynthetic Pathway,Pathway, Biosynthetic,Pathways, Biosynthetic
D029786 Cyperus A plant genus of the family CYPERACEAE. SESQUITERPENES are found in some of the species. Flat Sedge,Flatsedge,Nut Sedge,Sedge, Flat,Sedge, Nut,Yellow Nutgrass,Chufa,Cyperus esculentus,Chufas,Flat Sedges,Flatsedges,Nut Sedges,Nutgrass, Yellow,Nutgrasses, Yellow,Sedges, Flat,Sedges, Nut,Yellow Nutgrasses

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