Structural Characterization of the Lignin in the Cortex and Pith of Elephant Grass (Pennisetum purpureum) Stems

The structure of the lignin in the cortex and pith of elephant grass (Pennisetum purpureum) stems was studied both in situ and in isolated milled wood lignins by several analytical methods. The presence of p-coumarate and ferulate in the cortex and pith, as well as in their isolated lignins, was revealed by pyrolysis in the presence of tetramethylammonium hydroxide, and by 2D NMR, and indicated that ferulate acylates the carbohydrates while p-coumarate acylates the lignin polymer. 2D NMR showed a predominance of alkyl aryl ether (beta-O-4') linkages (82% of total interunit linkages), with low amounts of condensed substructures, such as resinols (beta-beta'), phenylcoumarans (beta-5'), and spirodienones (beta-1'). Moreover, the NMR also indicated that these lignins are extensively acylated at the gamma-carbon of the side chain. DFRC analyses confirmed that p-coumarate groups acylate the gamma-OHs of these lignins, and predominantly on syringyl units.