Unraveling variations of crystalline cellulose induced by ionic liquid and their effects on enzymatic hydrolysis

Ionic liquid (IL) is one of the pretreatment processes gaining considerable interests to remove the native recalcitrance of lignocellulose. But the cellulose crystalline transformation during the pretreatment and their correlations with enzymatic digestibility have not been fully elucidated. Microcrystalline cellulose (Avicel) and holocellulose, which have differential sources and original crystallinity, were respectively pretreated with 1-butyl-3-methylimidazolium chloride ([C4min]Cl). Cellulose crystalline variations as well as chemical and morphological changes were determined. Crystallinity of different materials was proved to influence the effects of pretreatment and following enzymatic digestibility. Recrystallized cellulose Iβ was revealed from slight initial cellulose Iα of Avicel, which was accomplished via formation of intermediate paracrystalline phases. The conversion yield of IL pretreated Avicel displayed no obvious changes, mainly resulted from initial high crystalline order and the recrystallization behavior. Recalcitrance of holocellulose was destroyed during cellulose allomorph transformation and hemicelluloses extraction, contributing to significant increase of glucose yield up to 92.20%. Explicit comprehension on cellulose supramolecular structure may help provide more efficient process for bioconversion after IL pretreatment.