Direct and efficient enzymatic synthesis of long-chain cellulose from cellobiose in its original form was successfully achieved via the combination of a surfactant-enveloped enzyme (SEE) and a protic acid in an aprotic organic solvent, lithium chloride/N,N-dimethylacetamide system. The SEE biocatalyst was prepared by protecting the surface of cellulase with the nonionic surfactant dioleyl-N-d-glucona-l-glutamate for keeping its enzymatic activity in nonaqueous media. Fourier transform infrared and nuclear magnetic resonance analyses elucidated the successful synthesis of cellulose, β-1,4-linked d-glucopyranose polymer, through the reverse hydrolysis of cellobiose. By using protic acid cocatalysts, a degree of polymerization of as-synthesized cellulose reached more than 120, in a ca. 26% conversion, which was 5 times higher than that obtained in an acid-free SEE system. A novel-concept biocatalysis, i.e., a protic acid-assisted SEE-mediated reaction, enables a facile, one-step chain elongation of carbohydrates without any activation via multistep organic chemistry, and can provide potential applications in the functional design of glycomaterials.
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