No abstract

We achieved to synthesize a novel inclusion supramolecular polymer composed of continuum of amylose-poly(tetrahydrofuran) (PTHF) inclusion complexes by phosphorylase-catalyzed enzymatic polymerization using a maltoheptaose-PTHF conjugate according vine-twining polymerization manner. The 1 H NMR and X-ray diffraction measurements indicated the presence of the inclusion complex structure in the product. The GPC peak of the amylose segment, which was dissociated by heating the vine-twining polymerization product, shifted to the lower molecular weight region, compared with that of the product, supporting the structure of the inclusion supramolecular polymer. The product by the G-1-P/G7-PTHF feed ratio = 100 was the supramolecular polymer composed of continuum of the amylose-PTHF inclusion complexes, whereas both inclusion complexes and amylose double helixes were present in the product by the G-1-P/G7-PTHF feed ratio over 200.

This paper describes the evaluation of the stability of amylose–polymer inclusion complexes under solution state in dimethyl sulfoxide (DMSO) depending on guest polymers. The three complexes were prepared by the vine-twining polymerization method using polytetrahydrofuran (PTHF), poly(ε-caprolactone) (PCL), and poly(l-lactide) (PLLA) as guest polymers. The stability investigation was conducted at desired temperatures (25, 30, 40, 60 °C) in DMSO solutions of the complexes. Consequently, the amylose–PTHF inclusion complex was dissociated at 25 °C, while the other complexes were stable under the same conditions. When the temperatures were elevated, the amylose–PCL and amylose–PLLA complexes were dissociated at 40 and 60 °C, respectively. We also found that amylose inclusion supramolecular polymers which were prepared by the vine-twining polymerization using primer-guest conjugates formed films by the acetylation of amylose segments. The film from acetylated amylose–PLLA supramolecular polymer had higher storage modulus than that from acetylated amylose–PTHF supramolecular polymer, as a function of temperature.