The relationship between two aminopolysaccharide stereoisomers, namely α-(1→4)- and β-(1→4)-linked (N-acetyl)-D-glucosamine polymers, is of significant interest within the field of polysaccharide science, as they correspond to amino analogs of the representative abundant natural polysaccharides, viz. amylose and cellulose. While the latter glucosamine polymer is the basis of well-known natural polysaccharides, chitin and chitosan (linear polysaccharides composed of β-(1→4)-linked N-acetyl-D-glucosamine and D-glucosamine), to the best of our knowledge, the former (α-(1→4)-linked) has not been observed in nature. For the purpose of these studies, the synthesis of such non-natural aminopolysaccharides was performed by the thermostable α-glucan phosphorylase (from Aquifex aeolicus VF5)-catalyzed enzymatic polymerization of α-D-glucosamine 1-phosphate (GlcN-1-P), via successive α-glucosaminylations, in ammonia buffer containing Mg(2+) ions, resulting in the production of the α-(1→4)-linked D-glucosamine polymers, corresponding to the structure of the chitosan stereoisomer. Subsequent N-acetylation of the products gave the aminopolysaccharides, corresponding to the chitin stereoisomer.
This article reports the enzymatic synthesis of dendritic amphoteric α-glucans having both glucuronic acid and glucosamine residues at the non-reducing ends by thermostable phosphorylase-catalyzed successive glucuronylation and glucosaminylation of a glucan dendrimer having α-(1 → 4)-glucan non-reducing ends using α-D-glucuronic acid 1-phosphate and α-D-glucosamine 1-phosphate as glycosyl donors, respectively. The structure of the products is confirmed by the (1)H NMR analysis. The products exhibit inherent isoelectric points (pIs) determined by the ζ-potential measurement. These materials self-assemble in water at pH = pI to form large aggregates, but disassemble at pH shifted from pI.
In this study, we found that thermostable α-glucan phosphorylase from Aquifex aeolicus VF5 catalyzed enzymatic successive α-mannosylations of maltotriose using α-d-mannose 1-phosphate as a glycosyl donor to produce nonnatural heterooligosaccharides composed of α-(1 → 4)-linked oligo-mannose residues at a nonreducing end of maltotriose.
n +Glc-1-P. Under the conditions in the large donor/acceptor ratios, successive glucosylations at the elongating nonreducing end from maltooligosaccharide as a primer take place by α-glucan
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