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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.

In this paper, we report the formation of hierarchically self-assembled nanofiber films from amylose-grafted sodium carboxymethyl celluloses (NaCMCs) that were synthesized by a chemoenzymatic approach. First, maltooligosaccharide primer-grafted NaCMCs were prepared by a chemical reaction using two kinds of NaCMCs with different degrees of polymerization (DPs) from Avicel and cotton sources. Then, phosphorylase-catalyzed enzymatic polymerization of α-D-glucose 1-phosphate from the nonreducing ends of the primer chains on the products was conducted to produce the prescribed amylose-grafted NaCMCs. The films were obtained by drying aqueous alkaline solutions of the amylose-grafted NaCMCs. The scanning electron microscopy (SEM) image of the film fabricated from the material with the higher DP from the cotton source showed a clear, self-assembled, highly condensed tangle of nanofibers. The SEM image of the material with the lower DP from the Avicel source, on the other hand, showed an unclear nanofiber morphology. These results indicate that the DPs of the main chains in the materials strongly affected the hierarchically self-assembled nanofiber formation. The SEM images of the films after washing out the alkali, furthermore, showed that the fibers partially merged with each other at the interfacial area owing to the double helix formation between the amylose-grafted chains. The mechanical properties of the films under tensile mode also depended on the self-assembled morphologies of the amylose-grafted NaCMCs from the different sources.