Isolation, Characterization, and Depolymerization of l-Cysteine Substituted Eucalyptus Lignin

Abstract

Lignin condensation reactions are hard to avoid or control during separation, which is a deterrent to lignin isolation and post-conversation, especially for the full utilization of lignocelluloses. Selective protection of β-aryl ether linkages in the isolation process is crucial to lignin valorization. Herein, a two-step acid/alkali separation method assisted with l-cysteine for eucalyptus lignin separation is developed, and the isolated l-cysteine lignins (LCLs) are comprehensively characterized by 2D NMR, 31P NMR, thioacidolysis, etc. Compared to the two-step control treatment, a much higher β-O-4 content is preserved without reducing the separation efficiency assisted by l-cysteine, which is also significantly higher than alkali lignin and kraft lignin. The results of hydrogenolysis show that LCLs generate a much higher monomer yield than that of control sample. Structural analysis of LCLs suggests that lignin condensation reaction, to some extent, is suppressed by adding l-cysteine during the two-step acid/alkali separation. Further, mechanistic studies using dimeric model compound reveals that l-cysteine may be the α-carbon protective agent in the two-step separation. The role of l-cysteine in the two-step lignin isolation method provides novel insights to the selective fractionation of lignin from biomass, especially for the full valorization of lignocellulosic biomass.