Molecular dynamics simulations of cellulose allomorphs

CELL 178

James F. Matthews, jfm17@cornell.edu, Department of Food Science, Cornell Univesity, Stocking Hall, Ithaca, NY 14853, Michael E. Himmel, mike_himmel@nrel.gov, National Renewable Energy Laboratory, 1617 Cole Blvd, Golden, CO 80401, and John W. Brady, jwb7@cornell.edu, Department of Food Science, Cornell University, Stocking Hall, Ithaca, NY 14853.
Molecular dynamics simulations of cellulose allomorphs have been performed, both as small hydrated crystallites and as "infinite" crystals. The hydrated crystallites were not subject to artificial constraints imposed by a strict unit cell, as is assumed during diffraction based analysis. This freedom allowed the crystallites to relax and display complex behavior that corresponds to experimental observations such as an overall twisted shape, but there were also significant differences in internal structure. To determine the extent to which these results depend on force field parameters, several carbohydrate parameter sets were used to simulate cellulose Iα and Iβ. The influence of microfibril length and diameter on twist magnitude was as expected with wider microfibrils closer to the proposed hydrogen bonded sheet structures. However, one small diameter microfibril (4x4 chains) showed a significant twist of 5 degrees/nm, as opposed to the more usual 0.5 degrees/nm for microfibrils more plant-like in diameter (6x6 chains).