Atomistic origins of biomass recalcitrance in organosolv pretreatment

TitleAtomistic origins of biomass recalcitrance in organosolv pretreatment
Publication TypeJournal Article
Year of Publication2023
AuthorsSarkar, D, Santiago, IJ, Vermaas, JV
Date Published2023/05/15
ISBN Number0009-2509
KeywordsBiomass recalcitrance, Free energy, Lignocellulosic interaction, molecular dynamics, Organosolv pretreatment

Separation of lignocellulosic biomass components for use in sustainable energy and biomaterials applications remains challenging, since biopolymers such as cellulose and hemicellulose carbohydrates and polyaromatic lignin are found in close proximity within the plant secondary cell wall. Organic solvents have been used to pretreat recalcitrant biomass and separate the interacting polymers, solubilizing the lignin fraction for lignin-first valorization approaches. However, no single organosolv pretreatment approach has proven superior for heterogeneous biomass samples. Here we present a complementary atomic view of interactions between biomass components using molecular simulations, specific to lignin and cellulose, resolving mechanistic hypotheses for how lignin-cellulose composition influences separation processes. Using lignin-cellulose binding free energy calculated using molecular simulations, we find polar protic solvents such as methanol and ethanol separate lignin from cellulose, irrespective of the charge on the lignin monomer. Aprotic organic solvents (DMSO, THF, 1,4-dioxane) separate uncharged lignin (phenols and monolignols) from cellulose, while charged lignin (cinnamates) prefer binding to cellulose.

Short TitleChemical Engineering Science