Effect of microfibril twisting on theoretical powder diffraction patterns of cellulose Iβ

• Published in: Cellulose (London) 2014-04, Vol.21 (2), p.879-884
• Main Authors: Hadden, Jodi A, French, Alfred D, Woods, Robert J
• Format: Article
• Language: English
• Subjects: Bioorganic Chemistry; Cellulose; Ceramics; Chemistry; Chemistry and Materials Science; Composites; Computer simulation; Crystal structure; Crystallites; Crystallography; Diffraction patterns; Dimensional changes; Empirical analysis; Glass; hydrogen bonding; Hydrogen bonds; Impact analysis; Molecular dynamics; Natural Materials; Organic Chemistry; Original Paper; Physical Chemistry; Polymer Sciences; Sustainable Development; Twisting; Unit cell
• ISSN: 0969-0239; 1572-882X
• DOI: 10.1007/s10570-013-0051-z

Previous studies of calculated diffraction patterns for cellulose crystallites suggest that distortions that arise once models have been subjected to molecular dynamics (MD) simulation are the result of both microfibril twisting and changes in unit cell dimensions induced by the empirical force field; to date, it has not been possible to separate the individual contributions of these effects. To provide a better understanding of how twisting manifests in diffraction data, the present study demonstrates a method for generating twisted and linear cellulose structures that can be compared without the bias of dimensional changes, allowing assessment of the impact of twisting alone. Analysis of unit cell dimensions, microfibril volume, hydrogen bond patterns, glycosidic torsion angles, and hydroxymethyl group orientations confirmed that the twisted and linear structures collected with this method were internally consistent, and theoretical powder diffraction patterns for the two were shown to be effectively indistinguishable. These results indicate that differences between calculated patterns for the crystal coordinates and twisted structures from MD simulation can result entirely from changes in unit cell dimensions, and not from microfibril twisting. Although powder diffraction patterns for models in the 81-chain size regime were shown to be unaffected by twisting, suggesting that a modest degree of twist is not inconsistent with available crystallographic data, it may be that other diffraction techniques are capable of detecting this structural difference. Until such time as definitive experimental evidence comes to light, the results of this study suggest that both twisted and linear microfibrils may represent an appropriate model for cellulose Iβ.