The enzymatic synthesis of cellulose-like substance via a non-biosynthetic pathway has been achieved by transglycosylation in an aqueous system of the corresponding substrate, cellotriose for cellulolytic enzyme endo-acting endoglucanase I (EG I) from Hypocrea jecorina. A significant amount of water-insoluble product precipitated out from the reaction system. MALDI-TOF mass analysis showed that the resulting precipitate had a degree of polymerization (DP) of up to 16 from cellotriose. Solid-state (13)C NMR spectrum of the resulting water-insoluble product revealed that all carbon resonance lines were assigned to two kinds of anhydroglucose residues in the corresponding structure of cellulose II. X-ray diffraction (XRD) measurement as well as (13)C NMR analysis showed that the crystal structure corresponds to cellulose II with a high degree of crystallinity. We propose the multiple oligomers form highly crystalline cellulose II as a result of self-assembly via oligomer-oligomer interaction when they precipitate.
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