Swelling behavior of the cellulose Iβ crystal models by molecular dynamics

The various crystal models of cellulose Iβ, each differing in crystal size, have been studied by computer simulation using the amber molecular-dynamics package and the GLYCAM parameters. The four types of crystal model were constructed by a combination of two base-plane sizes, consisting of either 24 or 48 chains and two chain lengths having either 10 or 20 residues. The base planes of the crystal models were composed by the edges of the [1, 1, 0], [1, −1, 0], and [1, 0, 0] crystal planes, where the [1, 1, 0] plane was assigned to the longest edge. The crystal models were soaked in water boxes to investigate their swelling behavior. Unexpectedly, the crystal models twisted quickly to form a slightly right-handed shape during the initial ∼50 ps and that, in a steady, swollen state, the twisted forms remained for the rest of the simulation time. In spite of such overall deformation, the inner part of the swollen model fairly reproduced the important structural features of the original crystal structure, such as the rotational positions of the substituent groups and the hydrogen-bonding scheme. On heating the crystal model up to 550 K, the twisted shape was conserved in most of the temperature range, while the initial conformations of the substituent groups deviated above ∼430 K, followed by appreciable disordering in chain sheets at higher temperatures. It is suggested that some internal tensions are involved within a chain sheet of the initial structure. In the course of swelling, some of these tensions were released to introduce a twisted shape in the crystal models.

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