Preparation of multiformable supramolecular gels through helical complexation by amylose in vine-twining polymerization

Kadokawa, Jun‐ichi; Tanaka, Katsu; Hatanaka, Daisuke; Yamamoto, Katsuhiro

doi:10.1039/c5py00753d

Cited by 15 publications

(11 citation statements)

References 53 publications

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“…The supramolecular hydrogel showed the macroscopic healing behavior when poly(γ-glutamic acid- graft -ε-caprolactone) (PGA- g -PCL) was used for the vine-twining polymerization (Figure ). The supramolecular hydrogel from PGA- g -PCL was cut into two pieces, and a sodium acetate buffer solution containing α-glucan phosphorylase and Glc-1-P was put on the surfaces of the two hydrogel pieces. After the surfaces were contacted, the gels were left standing at 40 °C for 6 h for the progress of the enzymatic polymerization.…”

Section: Transferasesmentioning

confidence: 99%

Enzymes as Green Catalysts for Precision Macromolecular Synthesis

et al. 2016

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The present article comprehensively reviews the macromolecular synthesis using enzymes as catalysts. Among the six main classes of enzymes, the three classes, oxidoreductases, transferases, and hydrolases, have been employed as catalysts for the in vitro macromolecular synthesis and modification reactions. Appropriate design of reaction including monomer and enzyme catalyst produces macromolecules with precisely controlled structure, similarly as in vivo enzymatic reactions. The reaction controls the product structure with respect to substrate selectivity, chemo-selectivity, regio-selectivity, stereoselectivity, and choro-selectivity. Oxidoreductases catalyze various oxidation polymerizations of aromatic compounds as well as vinyl polymerizations. Transferases are effective catalysts for producing polysaccharide having a variety of structure and polyesters. Hydrolases catalyzing the bond-cleaving of macromolecules in vivo, catalyze the reverse reaction for bond forming in vitro to give various polysaccharides and functionalized polyesters. The enzymatic polymerizations allowed the first in vitro synthesis of natural polysaccharides having complicated structures like cellulose, amylose, xylan, chitin, hyaluronan, and chondroitin. These polymerizations are "green" with several respects; nontoxicity of enzyme, high catalyst efficiency, selective reactions under mild conditions using green solvents and renewable starting materials, and producing minimal byproducts. Thus, the enzymatic polymerization is desirable for the environment and contributes to "green polymer chemistry" for maintaining sustainable society.

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Section: Transferasesmentioning

confidence: 99%

Enzymes as Green Catalysts for Precision Macromolecular Synthesis

et al. 2016

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“…The mechanical properties of the hydrogels obtained by vine-twining polymerization using PAA-Na- g -PVL and NaCMC- g -PCL were insufficient for further applications. To improve the mechanical properties of the hydrogels, poly(γ-glutamic acid) (PGA) was used as the main-chain of a graft copolymer ( Figure 6 ) [ 41 ], because its shows better water retention and moisturizing properties. Indeed, vine-twining polymerization using poly(γ-glutamic acid)- graft -poly(ε-caprolactone) (PGA- g -PCL) resulted in a hydrogel with self-standing properties, indicating much better mechanical properties compared to the aforementioned hydrogels.…”

Section: Hierarchical Structured Materials From Amylose-polymer Inmentioning

confidence: 99%

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

2017

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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.

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“…Amylose supramolecular network hydrogels were fabricated through the formation of vine-twined inclusion complexes of amylose during the phosphorylase-catalyzed polymerization. In these studies, the designed graft copolymers, such as poly(acrylic acid sodium salt- graft -δ-valerolactone) (PAA-Na- g -PVL), CMC- graft -PCL (CMC- g -PCL), and poly(γ-glutamic acid- graft -ε-caprolactone) (PGA- g -PCL) were employed as guest polymers ( Figure 14 a) [ 107 , 108 , 109 ], while the hydrophilic main-chains, PAA, CMC, and PGA, acted as the main components of the hydrogels. When the vine-twining polymerization was carried out in the presence of these guest graft copolymers in aqueous acetate buffer solution, the reaction mixtures yielded the supramolecular network hydrogels through inclusion of the graft chains with amylose to form supramolecular copolymers ( Figure 14 b).…”

Section: Preparation Of Amylose Supramolecular Materials By Phosphmentioning

confidence: 99%

“…The macroscopic interfacial healing of a supramolecular hydrogel consisting of PGA- g -PCL was observed through phosphorylase-catalyzed enzymatic polymerization [ 109 ]. The hydrogel formed initially from vine-twining polymerization was cut into two pieces, and a sodium acetate buffer solution containing Glc-1-P and phosphorylase was dropped on the surfaces of the hydrogel pieces.…”

Section: Preparation Of Amylose Supramolecular Materials By Phosphmentioning

confidence: 99%

Precision Synthesis of Functional Polysaccharide Materials by Phosphorylase-Catalyzed Enzymatic Reactions

Kadokawa

2016

Polymers

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Abstract:In this review article, the precise synthesis of functional polysaccharide materials using phosphorylase-catalyzed enzymatic reactions is presented. This particular enzymatic approach has been identified as a powerful tool in preparing well-defined polysaccharide materials. Phosphorylase is an enzyme that has been employed in the synthesis of pure amylose with a precisely controlled structure. Similarly, using a phosphorylase-catalyzed enzymatic polymerization, the chemoenzymatic synthesis of amylose-grafted heteropolysaccharides containing different main-chain polysaccharide structures (e.g., chitin/chitosan, cellulose, alginate, xanthan gum, and carboxymethyl cellulose) was achieved. Amylose-based block, star, and branched polymeric materials have also been prepared using this enzymatic polymerization. Since phosphorylase shows a loose specificity for the recognition of substrates, different sugar residues have been introduced to the non-reducing ends of maltooligosaccharides by phosphorylase-catalyzed glycosylations using analog substrates such as α-D-glucuronic acid and α-D-glucosamine 1-phosphates. By means of such reactions, an amphoteric glycogen and its corresponding hydrogel were successfully prepared. Thermostable phosphorylase was able to tolerate a greater variance in the substrate structures with respect to recognition than potato phosphorylase, and as a result, the enzymatic polymerization of α-D-glucosamine 1-phosphate to produce a chitosan stereoisomer was carried out using this enzyme catalyst, which was then subsequently converted to the chitin stereoisomer by N-acetylation. Amylose supramolecular inclusion complexes with polymeric guests were obtained when the phosphorylase-catalyzed enzymatic polymerization was conducted in the presence of the guest polymers. Since the structure of this polymeric system is similar to the way that a plant vine twines around a rod, this polymerization system has been named "vine-twining polymerization". Through this approach, amylose supramolecular network materials were fabricated using designed graft copolymers. Furthermore, supramolecular inclusion polymers were formed by vine-twining polymerization using primer-guest conjugates.

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Preparation of multiformable supramolecular gels through helical complexation by amylose in vine-twining polymerization

Cited by 15 publications

References 53 publications

Enzymes as Green Catalysts for Precision Macromolecular Synthesis

Enzymes as Green Catalysts for Precision Macromolecular Synthesis

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

Precision Synthesis of Functional Polysaccharide Materials by Phosphorylase-Catalyzed Enzymatic Reactions

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