Effect of Solvent Quality on Structure and Dynamics of Lignin in Solution.

Due to its significant aromatic content, lignin is an attractive source of valuable organic chemicals. As most of the proposed lignin depolymerization processes are expected to be liquid-phase, it is necessary to understand the effect of solvent quality on the structure and dynamics of lignin. Here we use all-atom molecular dynamics simulations to understand the evolution of lignin structure as a function of methanol concentration in methanol/water solution at different temperatures. We utilize two different lignin models: softwood consisting of guaiacyl (G) monomer and hardwood consisting of heteropolymer containing guaiacyl/syringyl (S) with a 1.35:1 ratio. The presence of additional methoxy groups in the hardwood lignin leads to a more extended configuration than softwood lignin with increasing methanol concentration. Structural features (radius of gyration and solvent accessible surface area) of lignin correlate with the strength of intermolecular forces quantified using cohesive energy density. We find that methanol preferentially solvates the nonpolar segments of the lignin polymer while water molecules solvate the polar functional groups. Thus, as the methanol concentration increases, methanol can better solvate lignin polymer, leading to a more extended configuration suitable for catalytic transformation to value-added chemicals.