Hydrophobization of surfaces on cellulose nanofibers by enzymatic grafting of partially 2-deoxygenated amylose.

Recently, attention has been paid to cellulose nanofibers, such as 2,2,6,6-tetramethylpiperidine-1-oxyl-oxidized cellulose nanofibers (TOCN), as new bio-based materials. In addition, hydrophobized surface on TOCNs can be expected to provide new applications. Based on our previous finding that partially 2-deoxygenated (P2D)-amylose, which was synthesized by GP-catalyzed enzymatic copolymerization of D-glucal with α-d-glucose 1-phosphate (Glc-1-P) as comonomers, was hydrophobic, in this study, hydrophobization of surfaces on TOCNs was investigated by the GP-catalyzed enzymatic grafting of P2D-amylose chains on TOCNs. After maltooligosaccharide primers were modified on TOCNs, the GP-catalyzed enzymatic copolymerization of D-glucal with Glc-1-P was performed for grafting of P2D-amylose chains. H NMR spectroscopic analysis confirmed the production of P2D-amylose-grafted TOCNs with different 2-deoxyglucose/Glc unit ratios. The powder X-ray diffraction profiles of the products indicated that the entire crystalline structures were strongly affected by the unit ratios and chain lengths of the grafted polysaccharides. The SEM images observed differences in nanofiber diameter in the reaction solutions and surface morphology after film formation, due to grafting of P2D-amylose chains from TOCNs. The water contact angle measurement of a cast film prepared from the product indicated its hydrophobicity.