Formation and structure of the complexes of sub-elementary fibrils of bacterial cellulose with fluorescent brightener molecules

The formation and structure of the complexes of sub-elementary fibrils (SEFs) of bacterial cellulose with fluorescent brightener (FB) molecules have been investigated using WAXD, SEM, and computer calculations of WAXD profiles. It is confirmed for the first time that the SEF-FB complexes are formed in 10 min by washing the cultivation product, which is prepared by the culture of Acetobacter xylinum in the presence of FB, with the pH 7 citrate–phosphate buffer solution and their thin sheet-like structure is grown almost two-dimensionally in 24 h in the medium. The same SEF-FB complexes are also produced by washing the product with NaCl aqueous solutions having concentrations higher than 0.1 wt%, while the original SEF structure is unchanged at lower concentrations. This indicates that the concentration of salt ions in washing media is a main factor to dominate the formation of the SEF-FB complexes from the cultivation product. The calculations of WAXD profiles reveal that the chain-slid, parallel-set, and sheet-slid/contracted models well reproduce the WAXD profile observed for the SEF-FB complexes. In these models, the following modifications are conducted in the a,b-modified unit cell of cellulose Iβ; the slide of the center chain along the b″ axis, the rotation of each chain around its own molecular axis, and the slide and contraction of the individual sheets composed of the center or origin chains. A single FB molecule is successfully packed into an energetically-allowable space in between the (010) planes in the 2a″ × b″ × 4c″ cell for the chain-slid model or in between the corresponding planes for the parallel-set and sheet-slid/contracted models. However, the detailed structure of FB in the complex is not yet determined due to the low crystallinity of the complexes.