While lignin is traditionally defined as a polymer of the cinnamyl alcohols, it has also been found to exhibit extensive plasticity through the incorporation of other units into the macromolecule.  Such cross-linking may be the result of natural mutations, induced genetic manipulation or inherent to the lignin itself.  The current work addresses the latter point through an examination of lignin-tricin and lignin-ferulate cross-linking.  The flavonoid tricin has been found to generally occur in the lignin of monocots, where it is proposed to function as a nucleation site for lignin.  Ferulate esters with polysaccharides can further react through homocoupling or cross-coupling with monolignols, and may also act as nucleation sites for the subsequent polymerization steps.  By the application of quantum mechanically based density functional theory calculations, the current work is concerned with determining the thermodynamics of the coupling reactions between tricin, the methyl-ferulate ester and cinnamyl alcohols.  Furthermore, bond dissociation energies of the products, with implications for overcoming recalcitrance in biorefinery settings, are presented.

Density functional theory study of cross-coupling of lignin with tricin and ferulates

255th National Meeting (2018)

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