Preparation of inclusion complexes composed of amylose and biodegradable poly(glycolic acid-co-ɛ-caprolactone) by vine-twining polymerization and their lipase-catalyzed hydrolysis behavior

Abstract

In this study, we found that amylose-poly(glycolic acid-co-e-caprolactone) (P(GA-co-CL)) inclusion complexes were formed when phosphorylase-catalyzed enzymatic polymerization was performed in the presence of biodegradable P(GA-co-CL)s according to a vine-twining polymerization process. The X-ray diffraction patterns of the products showed the typical diffraction peaks due to inclusion complexes composed of amylose and guest compounds. In addition, the 1 H NMR spectra of the products showed the signals due to amylose and P(GA-co-CL), in spite of washing with good solvents for P(GA-co-CL), such as acetone and chloroform. These results suggested that the products were inclusion complexes composed of amylose and P(GA-co-CL). The compositional ratio of GA unit to CL unit in P(GA-co-CL)s did not affect the inclusion behavior of amylose. On the other hand, the results in the vine-twining polymerization using amorphous P(GA-co-CL)s and a crystalline poly(glycolic acid-block-ecaprolactone) (P(GA-b-CL)) as guest polymers indicated that the crystallinity of the guest copolymers strongly affected the formation of inclusion complexes with amylose. In addition, we found that lipase-catalyzed hydrolysis of P(GA-co-CL) in the inclusion complex was partly inhibited, probably because amylose, which surrounded P(GA-co-CL), prevented the approach of lipase.

An Amylose‐Poly(l‐lactide) Inclusion Supramolecular Polymer: Enzymatic Synthesis by Means of Vine‐Twining Polymerization Using a Primer–Guest Conjugate

“…By means of the enzymatic method for direct construction of polysaccharides, [13][14][15][16][17][18][19] we have developed the new methodology for the preparation of inclusion complexes composed of amylose and synthetic polymers, [20][21][22][23][24][25][26][27][28][29] which was achieved by phosphorylase-catalyzed enzymatic polymerization forming amylose in the presence of guest polymers. Phosphorylase-catalyzed enzymatic polymerization using α -D -glucose 1-phosphate (G-1-P) as a monomer proceeds with the regio-and stereo-selective construction of an α -glycosidic bond under mild conditions, leading to the direct formation of amylose in aqueous media.…”

“…The representation of the above reaction system for the construction of such amylose‐polymer inclusion complex is similar to the way that vines of plants grow twining around a rod. Accordingly, we have proposed that this polymerization method is named “vine‐twining poly­merization.” As the guest polymers for this polymerization system, hydrophobic polyethers, polyesters, and polycarbonates have been used to form corresponding inclusion complexes with amylose. In addition, the vine‐twining polymerization has been applied to selective inclusion by amylose toward polymers with particular structures, molecular weight distributions, and chiralities .…”

Microsecond kinetics in model single- and double-stranded amylose polymers

“…1 A major dietary component, amylose is also used as a thickener, stabilizer and gelling agent in foods, cosmetics, textiles and paper. 2 It has recently been employed as a prototype biotechnological device, with notable successes in host–guest inclusion 3,4 and for improving the biocompatibility of carbon nanotubes, 5 drugs and flavor ingredients. 6 These diverse current and potential applications stem from the dynamic molecular shape of amylose, which gives rise to characteristic helices and self-association.…”

Polyurethanes with separately tunable biodegradation behavior and mechanical properties for tissue engineering

“…Glycolide to ε‐caprolactone ratios were calculated based on the corresponding proton peak areas of the glycolide and ε‐caprolactone methylene (Figure B). As it can be seen in Table , under controlled polymerization conditions, [GA]/[CL] ratios of the synthesized macrodiols are close to those in the feed, but the glycolide contribution in the macrodiols is slightly less than that in the feed, possibly because of sublimation of the monomer during the reaction …”