The conversion of plant cell-wall lignocellulosic biomass to chemicals for renewable bioenergy and other high-value uses requires overcoming the evolved recalcitrance of biomass to deconstruction. To increase yields biomass is commonly pretreated using physical and/or chemical methods. Recent experimental and computational work has led to significant progress in understanding the molecular-level driving forces governing the structure of native biomass and its deconstruction during pretreatment. The thermodynamics and kinetics determining the three- dimensional configurations and associations of the principal biopolymers involved - cellulose, lignin and hemicellulose - has been characterized. The energetic requirements for the effective fractionation of biomass into lignin and cellulose components for co-valorization have been determined. Of fundamental interest is the detailed understanding of the origin of the kinetic barriers leading to irreversibility of pretreatment processes. A pervading theme is solvation thermodynamics, which plays a critical role in determining biomass structure and susceptibility to breakdown, and provides a path to obtaining a predictive understanding of requirements for effective biomass pretreatment.

Molecular-level driving forces in lignocellulosic biomass deconstruction

256th National Meeting (2018)

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