Difference in Macroscopic Morphologies of Amylosic Supramolecular Networks Depending on Guest Polymers in Vine-Twining Polymerization

Amylose, a natural polysaccharide, acts as a host molecule to form supramolecular inclusion complexes in its enzymatically formation process, that is, phosphorylase-catalyzed enzymatic polymerization using the α-d-glucose 1-phosphate monomer and the maltooligosaccharide primer, in the presence of appropriate guest polymers (vine-twining polymerization). Furthermore, in the vine-twining polymerization using maltooligosaccharide primer-grafted polymers, such as maltoheptaose (G(7))-grafted poly(γ-glutamic acid) (PGA), in the presence of poly(ε-caprolactone) (PCL), the enzymatically elongated amylose graft chains have formed inclusion complexes with PCL among the PGA main-chains to construct supramolecular networks. Either hydrogelation or aggregation as a macroscopic morphology from the products was observed in accordance with PCL/primer feed ratios. In this study, we evaluated macroscopic morphologies from such amylosic supramolecular networks with different guest polymers in the vine-twining polymerization using G(7)-grafted PGA in the presence of polytetrahydrofuran (PTHF), PCL, and poly(l-lactide) (PLLA). Consequently, we found that the reaction mixture using PTHF totally turned into a hydrogel form, whereas the products using PCL and PLLA were aggregated in the reaction mixtures. The produced networks were characterized by powder X-ray diffraction and scanning electron microscopic measurements. The difference in the macroscopic morphologies was reasonably explained by stabilities of the complexes depending on the guest polymers.