Regeneration behavior of chitosan from ionic liquid using water and alcohols as anti-solvents

While ionic liquids (ILs) have been considered as effective and "green" solvents for biopolymer processing, regeneration of IL-dissolved biopolymers could largely impact biopolymer structure and properties. This study indicates that the reconstitution of chitosan structure during regeneration from 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) depends on anti-solvent (water, methanol or ethanol) largely. Irrespective of anti-solvent, the chitosan chemical structure was not varied by dissolution or regeneration. With water, the regenerated chitosan had the highest crystallinity index of 54.18%, followed by those with methanol (35.07%) and ethanol (25.65%). Water as an anti-solvent could promote chitosan chain rearrangement, leading to the formation of an ordered aggregated structure and crystallites. Density functional theory (DFT) simulation indicates that the number of hydrogen bonds formed between anti-solvents and [Emim][OAc] was in the order of water > methanol > ethanol. With water used for regeneration, the aggregation and rearrangement of chitosan chains occurred more easily.