Regioselective and Water-Promoted Surface Esterification of Never-Dried Cellulose Fibers Towards Nanofibers with Adjustable Surface Energy

A new regioselective route is introduced for surface modification of biological colloids in the presence of water. Taking the case of cellulose nanofibers (CNFs), we demonstrate a site-specific (93% selective) reaction between the primary surface hydroxyl groups (C6-OH) of cellulose and acyl imidazoles. Cellulose nanofibers bearing C6-acetyl and C6-iso-butyl groups, with a degree of substitution of up to 1 mmol·g–1 are obtained upon surface esterification, affording CNFs of adjustable surface energy. The morphological and structural features of the nanofibers remain largely unaffected, but the regioselective surface reactions enable tailoring the interfacial interactions, as demonstrated in oil/water Pickering emulsions. Our method precludes the need for drying or exchange with organic solvents for surface esterification, otherwise needed in the synthesis of esterified colloids and polysaccharides. Moreover, the method is well suited for application at high-solid content, opening the possibility for implementation in reactive extrusion and compounding. The proposed acylation is introduced as a sustainable approach that benefits from the presence of water and affords a high chemical substitution selectivity.