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

Rencoret, Jorge; Rosado, Mario J.; Kim, Hoon; Timokhin, Vitaliy I.; Gutiérrez, Ana; Bausch, Florian; Rosenau, Thomas; Potthast, Antje; Ralph, John; del Río, José C.

doi:10.1093/plphys/kiab469

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

Journal Article · Mon Oct 18 00:00:00 EDT 2021 · Plant Physiology (Bethesda)

DOI:https://doi.org/10.1093/plphys/kiab469· OSTI ID:1846255

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Instituto de Recursos Naturales y Agrobiología de Sevilla (IRNAS), Seville (Spain); Department of Plant Biotechnology, Instituto de Recursos Naturales y Agrobiologı´a de Sevilla
Instituto de Recursos Naturales y Agrobiología de Sevilla (IRNAS), Seville (Spain)
Great Lakes Bioenergy Research Center (GLBRC), Madison, WI (United States); Univ. of Wisconsin, Madison, WI (United States)
Univ. of Natural Resources and Life Sciences Vienna (BOKU), Tulln (Austria)

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.

View Accepted Manuscript (DOE)

Research Organization:: Great Lakes Bioenergy Research Center (GLBRC), Madison, WI (United States)

Sponsoring Organization:: Consejeria de Transformacion Economica, Industria, Conocimiento y Universidades; European Regional Development Fund; Spanish Ministry of Science, Innovation and Universities; Spanish State Research Agency; USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: SC0018409

OSTI ID:: 1846255

Journal Information:: Plant Physiology (Bethesda), Journal Name: Plant Physiology (Bethesda) Journal Issue: 1 Vol. 188; ISSN 0032-0889

Publisher:: American Society of Plant BiologistsCopyright Statement

Country of Publication:: United States

Language:: English

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