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A molecular dynamics study of the thermal response of crystalline cellulose Iβ

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Abstract

Molecular dynamics simulations were performed to better understand the atomic details of thermal induced transitions in cellulose Iβ. The latest version of the GLYCAM force field series (GLYCAM06) was used for the simulations. The unit cell parameters, density, torsion angles and hydrogen-bonding network of the crystalline polymer were carefully analyzed. The simulated data were validated against the experimental results obtained by X-ray diffraction for the crystal structure of cellulose Iβ at room and high temperatures, as well as against the temperature-dependent IR measurements describing the variation of hydrogen bonding patterns. Distinct low and high temperature structures were identified, with a phase transition temperature of 475–500 K. In the high-temperature structure, all the origin chains rotated around the helix axis by about 30° and the conformation of all hydroxymethyl groups changed from tg to either gt on origin chains or gg on center chains. The hydrogen-bonding network was reorganized along with the phase transition. Compared to the previously employed GROMOS 45a4 force field, GLYCAM06 yields data in much better agreement with experimental observations, which reflects that a cautious parameterization of the nonbonded interaction terms in a force field is critical for the correct prediction of the thermal response in cellulose crystals.

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Acknowledgments

This work was supported by a grant from the Swedish National Infrastructure for Computing (SNIC) for the project “Multiphysics Modeling of Molecular Materials”, SNIC 022/09-25 and by the Swedish Centre for Biomimetic Fibre Engineering (Biomime).

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Authors and Affiliations

  1. Department of Theoretical Chemistry, Royal Institute of Technology, AlbaNova University Centre, 10691, Stockholm, Sweden

    Qiong Zhang & Hans Ågren

  2. Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology, 200237, Shanghai, People’s Republic of China

    Qiong Zhang

  3. Division of Glycoscience, School of Biotechnology, Royal Institute of Technology, Stockholm, Sweden

    Vincent Bulone

  4. School of Science and Technology, Örebro University, 701 82, Örebro, Sweden

    Yaoquan Tu

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  1. Qiong Zhang
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  2. Vincent Bulone
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  4. Yaoquan Tu
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Correspondence to Yaoquan Tu.

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Zhang, Q., Bulone, V., Ågren, H. et al. A molecular dynamics study of the thermal response of crystalline cellulose Iβ. Cellulose 18, 207–221 (2011). https://doi.org/10.1007/s10570-010-9491-x

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