Characterisation of bacterial cellulose partly acetylated by dimethylacetamide/lithium chloride

Cellulose is a water-insoluble polysaccharide used at an industrial scale for the manufacture of paper and films or in the dust form, natural, hydrolysed or derivatised. The cellulose produced by G. hansenii (former A. xylinum) has a structure identical to that of plants, but is free of lignin and hemicellulose, with several unique physical–chemical properties. The main barrier to the use of cellulose is its insolubility in water and most organic solvents, but soluble derivatives can be obtained with the use of ionic solvents. Bacterial cellulose, produced in a static, 4% glucose medium, was dissolved in hot DMAc/LiCl (120, 150 or 170 °C). The solution was analysed by 13C NMR, and the effect of the dissolution on the crystalline state was shown by X-ray crystallography. The crystalline structure was lost upon dissolution, becoming amorphous; this was also observed for Avicel® plant cellulose. The soluble cellulose was partly acetylated in acetic anhydride with acetic anhydride-cellulose ratios of 1:50, 1:6 and 1:12 (w/v). The resulting cellulose acetates were examined by infrared spectroscopy, and the best result was 43% (w/v). The degree of acetylation was determined via 1H NMR spectroscopy by comparing the area of the glucose ring at 2.60–5.20 ppm and that of the methyl proton of the acetate group at 1.80–2.20 ppm. The 13C NMR spectra showed acetylation at C6 ≫ C2 > C3 at 60–80 ppm, with C1 signals at ~ 100–104 ppm. The derivatisation of bacterial cellulose in DMAc/LiCl/acetic anhydride (1:4:50, v/v/v) gave rise to 87% substitution. The process of dissolution of the bacterial cellulose is essential for the analysis of the insoluble polymer in water, facilitating analysis and characterisation of these composites by 13C NMR spectroscopy, size exclusion chromatography and light scattering techniques.