Beyond Solanaceae: Incorporation of Feruloyltyramine and Feruloyloctopamine into Cannabaceae Lignins

The ferulic acid amides feruloyltyramine and feruloyloctopamine have been widely reported as integral constituents in the lignins in several species of Solanaceae in which they function as authentic lignin monomers. In the present study, we demonstrate that these ferulic acid amides are likewise incorporated into the lignins of species within Cannabaceae, including hemp (Cannabis sativa), hops (Humulus lupulus), and European nettle tree (Celtis australis). Structural analyses using Derivatization Followed by Reductive Cleavage (DFRC) and two-dimensional Nuclear Magnetic Resonance (2D-NMR) spectroscopy revealed that these ferulic acid amides are incorporated via 4-O- and 8-O-ether linkages, as well as through 8-5' linkages forming phenylcoumaran structures. Examination of a broad phylogenetic range of plant families demonstrated the absence of these ferulic acid amides from the lignins of all families studied except Solanaceae and Cannabaceae. Given the distant phylogenetic relationship between Solanaceae and Cannabaceae, the recruitment of these ferulic acid amides as lignin monomers in both lineages likely constitutes a case for convergent evolution at the level of lignin biosynthetic pathways. The significance of these ferulic acid amides lies in their unique role as the sole nitrogen-containing phenolic compounds known to participate in lignin formation.