Deconstruction of biomass enabled by local demixing of cosolvents at cellulose and lignin surfaces

Significance The use of plant biomass for the production of fuels and chemicals is of critical economic and environmental importance, but has posed a formidable challenge, due to the recalcitrance of biomass to deconstruction. We report direct experimental and computational evidence of a simple physical chemical principle that explains the success of mixing an organic cosolvent, tetrahydrofuran, with water to overcome this recalcitrance. The hydrophilic and hydrophobic biomass surfaces are solvated by single-component nanoclusters of complementary polarity. This principle can serve as a guide for designing even more effective technologies for solubilizing and fractionating biomass. The results further highlight the role of nanoscale fluctuations of molecular solvents in driving changes in the structure of the solutes.