Hydrophobization of Natural Polymers by Enzymatic Grafting of Hydrophobic Polysaccharides, Partially 2-Deoxygenated Amyloses

This review overviews the efficient hydrophobization method of hydrophilic natural polymers, which has been developed by means of glucan phosphorylase (GP)-induced enzymatic grafting of unnatural heteropolysaccharides, that is, partially 2-deoxygenated (P2D)-amyloses. The enzymatic polymerization technique is well known as a useful approach to prepare polysaccharides with well-defined structures. The authors have found that the hydrophobicity of P2D-amylose, synthesized by the thermostable GP (from Aquifex aeolicus VF5)-induced enzymatic copolymerization of α-d-glucose 1-phosphate (Glc-1-P)/d-glucal as comonomers, started from maltooligosaccharide primers. Based on this finding, glycogen, a hydrophilic spherical natural polysaccharide, was hydrophobized by means of the thermostable GP-induced enzymatic functionalization of the P2D-amylose chains because glycogen acted as the polymeric primer for the GP catalysis. After introducing the maltooligosaccharide primers onto hydrophilic natural polymers with carboxylate groups—such as poly(γ-glutamic acid), carboxymethyl cellulose, and alginic acid—via chemical reactions, the thermostable GP-induced enzymatic copolymerization of Glc-1-P/d-glucal was carried out using the resulting polymeric primers, enabling their hydrophobization through the grafting of P2D-amylose chains (the chemoenzymatic approach). Moreover, the chemoenzymatic method has extensively been employed for hydrophobization of the surfaces on natural polysaccharide nanofibers, such as cellulose and chitin nanofibers.