A priori crystal structure prediction of native celluloses

The packing of β‐1,4‐glucopyranose chains has been modeled to further elaborate the molecular structures of native cellulose microfibrils. A chain pairing procedure was implemented that evaluates the optimal interchain distance and energy for all possible settings of the two chains. Starting with a rigid model of an isolated chain, its interaction with a second chain was studied at various helix‐axis translations and mutual rotational orientations while keeping the chains at van der Waals separation. For each setting, the sum of the van der Waals and hydrogen‐bonding energy was calculated. No energy minimization was performed during the initial screening, but the energy and interchain distances were mapped to a three‐dimensional grid, with evaluation of parallel settings of the cellulose chains. The emergence of several energy minima suggests that parallel chains of cellulose can be paired in a variety of stable orientations. A further analysis considered all possible parallel arrangements occurring between a cellulose chain pair and a further cellulose chain. Among all the low‐energy three‐chain models, only a few of them yield closely packed three‐dimensional arrangements. From these, unit‐cell dimensions as well as lattice symmetry were derived; interestingly two of them correspond closely to the observed allomorphs of crystalline native cellulose. The most favorable structural models were then optimized using a minicrystal procedure in conjunction with the MM3 force field. The two best crystal lattice predictions were for a triclinic (P1) and a monoclinic (P21) arrangement with unit cell dimensions a = 0.63, b = 0.69, c = 1.036 nm, α = 113.0, β = 121.1, γ = 76.0°, and a = 0.87, b = 0.75, c = 1.036 nm, γ = 94.1°, respectively. They correspond closely to the respective lattice symmetry and unit‐cell dimensions that have been reported for cellulose Iα and cellulose Iβ allomorphs. The suitability of the modeling protocol is endorsed by the agreement between the predicted and experimental unit‐cell dimensions. The results provide pertinent information toward the construction of macromolecular models of microfibrils. © 2000 John Wiley & Sons, Inc. Biopoly 54: 342–354, 2000