Area-Selective Depolymerization of Hydroxycinnamates Visualized by Raman Imaging in Miscanthus sinensis cv. Cell Wall

Lignin-carbohydrate complexes (LCCs) are regarded as a barrier for lignocellulosic biomass refinery. Here, confocal Raman microspectroscopy has been used to visualize the dissolution of hydroxycinnamates (HCMs) incorporated into LCCs by ether and ester bonds for energy crops Miscanthus sinensis cv. during successive NaOH (2.5% w/w) treatment. Raman spectral analysis indicated that mild NaOH treatment resulted in a higher proportion of HCM depolymerization in highly lignified middle lamella areas (>66.0%) than carbohydrate-abundant secondary walls. Furthermore, Raman imaging revealed preferential depolymerization of lignin from the sclerenchyma fiber (Sf) and parenchyma (Par) secondary wall with an increment of treatment time from 0 to 25 min, while middle lamella areas of Sf and Par were less affected where the depolymerization of HCMs was closely related with that of lignin (coefficient factors > 0.96). A better understanding of the depolymerization behavior for HCMs accompanied by lignin depolymerization was important to break LCC bonds in herbaceous biomass efficiently.