Synthesis of Amylosic Supramolecular Materials by Glucan Phosphorylase-Catalyzed Enzymatic Polymerization According to the Vine-Twining Approach

Abstract

This article overviews the synthesis of amylosic supramolecular materials through inclusion complexation in glucan phosphorylase (GP)-catalyzed enzymatic polymerization. Amylose is a polysaccharide that is known to form inclusion complexes with a number of hydrophobic small guest molecules. A pure amylose can be synthesized by the enzymatic polymerization of α-d-glucose 1-phosphate monomer with a maltooligosaccharide primer catalyzed by GP. The author has reported that the propagating amylosic chain in the enzymatic polymerization twines around hydrophobic polymers present in aqueous reaction media to form supramolecular inclusion complexes. As it is similar to the way that vines of a plant grow around a rod, this polymerization is termed ‘vine-twining polymerization’. Amylosic supramolecular network materials have been obtained through the vine-twining polymerization by using copolymers, where hydrophobic guest polymers are covalently grafted on hydrophilic main-chain polymers. The enzymatically produced amylosic chains form complexes with the guest polymers among graft copolymers, which act as cross-linking points to form supramolecular networks, resulting in the formation of soft materials, such as gels and films. Vine-twining polymerization using appropriately designed guest polymers has also been performed, which leads to supramolecular products that exhibit new functionality.1 Introduction2 Vine-Twining Polymerization to Form Supramolecular Inclusion Complexes3 Selective Complexation of Amylose toward Guest Polymers in Vine-Twining Polymerization4 Hierarchical Architecture of Amylosic Supramolecular Network Materials by Vine-Twining Polymerization Approach5 Hierarchical Fabrication of Amylosic Supramolecular Materials by Vine-Twining Polymerization Using Designed Guest Polymers6 Conclusions