Preparation and Material Application of Amylose-Polymer Inclusion Complexes by Enzymatic Polymerization Approach

Abstract

This review presents our researches on the preparation and material application of inclusion complexes that comprises an amylose host and polymeric guests through phosphorylase-catalyzed enzymatic polymerization. Amylose is a well-known polysaccharide and forms inclusion complexes with various hydrophobic small molecules. Pure amylose is produced by enzymatic polymerization by using α-D-glucose 1-phosphate as a monomer and maltooligosaccharide as a primer catalyzed by phosphorylase. We determined that a propagating chain of amylose during enzymatic polymerization wraps around hydrophobic polymers present in the reaction system to form inclusion complexes. We termed this polymerization "vine-twining polymerization" because it is similar to the way vines of a plant grow around a rod. Hierarchical structured amylosic materials, such as hydrogels and films, were fabricated by inclusion complexation through vine-twining polymerization by using copolymers covalently grafted with hydrophobic guest polymers. The enzymatically produced amyloses induced complexation with the guest polymers in the intermolecular graft copolymers, which acted as cross-linking points to form supramolecular hydrogels. By including a film-formable main-chain in the graft copolymer, a supramolecular film was obtained through hydrogelation. Supramolecular polymeric materials were successfully fabricated through vine-twining polymerization by using primer-guest conjugates. The products of vine-twining polymerization form polymeric continuums of inclusion complexes, where the enzymatically produced amylose chains elongate from the conjugates included in the guest segments of the other conjugates.

Synthesis and Characterization of Poly(1,4,7-Trioxacycloundecane-8,11-dione) Macrocyclic Functionalized Hydrogel for High Selectivity Adsorption and Complexation of Bismuth Ion

“…A corresponding stretch for the C-O group appeared at 1090 cm −1 , whereas the bending vibration of C-C group was characteristic Polymers 2018, 10, 662 6 of 13 in the fingerprint region of 550 cm −1 . Identification of these groups necessitated a further study using the JOEL JNM-ECX 400 13 C NMR spectroscopy (Tokyo, Japan) in order to establish how these groups were arranged and connected into a full and coherent chemical structure.…”

“…13 C NMR 13 C NMR analysis was undertaken to establish the types of equivalent carbons in the BCE hydrogel using the cross-polymerization magic angle spinning (CPMAS) technique. This is a high-resolution solid state technique for improving the S/N ratio and minimizing large anisotropic NMR interactions in order to ensure better spectra.…”

“…Identification of these groups necessitated a further study using the JOEL JNM-ECX 400 13 C NMR spectroscopy (Tokyo, Japan) in order to establish how these groups were arranged and connected into a full and coherent chemical structure.…”

“…Host-guest adsorption exploits characteristic morphological properties of substrates to separate and adsorb only the substrates which can fit into the macrocyclic cavities. This phenomenon was adopted from biological macrocyclic chelators [13,14] and supramolecular chemistry [15][16][17]. Attempts to translate this mechanism onto adsorbents have not been very successful, with few exceptions (e.g., the SuperLig ® adsorbent) [18][19][20].…”

Host–Guest Polymer Complexes

“…In this review, we report various possibilities for improving the topographical, mechanical and cell-adhesive properties of aliphatic polyester nanofibers via an electrospinning process [13]. The next two articles discuss the synthesis and characterization of novel inclusion complexes between amylose and polymers, and polysaccharides and metal ions [14,15]. Unlike most of the articles reported in this Special Issue, which are based on CDs, complexation with polysaccharides is unique and hard to accomplish; this review provides a useful starting resource for further research.…”