Abstract
We have performed molecular dynamics calculations using a revised version of the Gromos56Acarbo force field to understand the consequences of the different potential hydrogen bonding patterns on the structural stability and thermal behavior of the Iα and Iβ forms of native cellulose. For each allomorph, we considered three patterns of hydrogen bonds: two patterns obtained from neutron diffraction data refinement and a regular mixture of the two. Upon annealing, the hydrogen bonding schemes of cellulose Iβ, irrespective of the starting structure, re-arranged into the main hydrogen bond pattern experimentally observed (pattern A). On the other hand, the Iα structures, irrespective of the starting hydrogen bonding pattern, converged to a non-experimental structure where the adjacent chains are shifted along the chain direction by 0.12 nm in the hydrogen-bonded plane, and the hydroxymethyl group conformation alternates between gt and tg along the chain. The exotic structure in Iα might be a consequence of a deficiency in force field parameters and/or potential molecular arrangement in less crystalline cellulose.
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References
Agarwal V, Huber GW, Conner WC Jr, Auerbach SM (2011) Simulating infrared spectra and hydrogen bonding in cellulose Iβ at elevated temperatures. J Chem Phys 135:134506.1–134506.13
Atalla RH, VanderHart DL (1984) Native cellulose: a composite of two distinct crystalline forms. Science 223:283–285
Berendsen HJC, Postma JPM, Van Gunsteren WF, DiNola A, Haak JR (1984) Molecular dynamics with coupling to an external bath. J Chem Phys 81:3684–3690
Bergenstråhle M, Berglund LA, Mazeau K (2007) Thermal response in crystalline Iβ cellulose: a molecular dynamics study. J Phys Chem B 111:9138–9145
Bussi G, Donadio D, Parrinello M (2007) Canonical sampling through velocity rescaling. J Chem Phys 126:014101–014107
Chen P, Nishiyama Y, Mazeau K (2012) Torsional entropy at the origin of the reversible temperature-induced phase transition of cellulose. Macromolecules 45:362–368
Chen P, Nishiyama Y, Mazeau K (in preparation) Atomic partial charges and one Lennard-Jones parameter crucial to model cellulose allomorphs
Essmann U, Perera L, Berkowitz ML, Darden T, Lee H, Pedersen LG (1995) A smooth particle mesh Ewald method. J Chem Phys 103:8577–8593
Fernandes AN, Thomas LH, Altaner CM, Callow P, Forsyth VT, Apperley DC, Kennedy CJ, Jarvis MC (2011) Nanostructure of cellulose microfibrils in spruce wood. Proc Natl Acad Sci USA 108:E1195–E1203
Hansen HS, Hünenberger PH (2011) A reoptimized GROMOS force field for hexopyranose-based carbohydrates accounting for the relative free energies of ring conformers, anomers, epimers, hydroxymethyl rotamers, and glycosidic linkage conformers. J Comput Chem 32:998–1032
Hess B, Bekker H, Berendsen HJC, Fraaije JGEM (1997) LINCS: a linear constraint solver for molecular simulations. J Comput Chem 18:1463–1472
Hess B, Kutzner C, van der Spoel D, Lindahl E (2008) GROMACS 4: algorithms for highly efficient, load-balanced, and scalable molecular simulation. J Chem Theory Comput 4:435–447
Hidaka H, Kim U-J, Wada M (2010) Synchrotron X-ray fiber diffraction study on the thermal expansion behavior of cellulose crystals in tension wood of Japanese poplar in the low-temperature region. Holzforschung 64:167–171
Hori R, Wada M (2005) The thermal expansion of wood cellulose crystals. Cellulose 12:479–484
Horii F, Hirai A, Kitamaru R (1983) Solid-state carbon-13 NMR study of conformations of oligosaccharides and cellulose. Conformation of CH2OH group about the exo-cyclic carbon–carbon bond. Polym Bull 10:357–361
Lee CM, Mohamed NMA, Watts HD, Kubicki JD, Kim SH (2013) Sum-frequency-generation vibration spectroscopy and density functional theory calculations with dispersion corrections (DFT-D2) for cellulose Iα and Iβ. J Phys Chem B 117:6681–6692
Matthews JF, Beckham GT, Bergenstråhle-Wohlert M, Brady JW, Himmel ME, Crowley MF (2012) Comparison of cellulose Iβ simulations with three carbohydrate force fields. J Chem Theory Comput 8:735–748
Mazeau K (2005) Structural micro-heterogeneities of crystalline Iβ-cellulose. Cellulose 12:339–349
Mazeau K, Heux L (2003) Molecular dynamics simulations of bulk native crystalline and amorphous structures of cellulose. J Phys Chem B 107:2394–2403
Nishiyama Y (2009) Structure and properties of the cellulose microfibril. J Wood Sci 55:241–249
Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose Iβ from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 124:9074–9082
Nishiyama Y, Sugiyama J, Chanzy H, Langan P (2003) Crystal structure and hydrogen bonding system in cellulose Iα from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 125:14300–14306
Nishiyama Y, Johnson GP, French AD, Forsyth VT, Langan P (2008) Neutron crystallography, molecular dynamics, and quantum mechanics studies of the nature of hydrogen bonding in cellulose Iβ. Biomacromolecules 9:3133–3140
Wada M (2002) Lateral thermal expansion of cellulose Iβ and IIII polymorphs. J Polym Sci Part B Polym Phys 40:1095–1102
Wada M, Kondo T, Okano T (2003) Thermally induced crystal transformation from cellulose Iα to Iβ. Polym J (Tokyo, Jpn) 35:155–159
Wada M, Hori R, Kim U-J, Sasaki S (2010) X-ray diffraction study on the thermal expansion behavior of cellulose Iβ and its high-temperature phase. Polym Degrad Stab 95:1330–1334
Watanabe A, Morita S, Ozaki Y (2006) Study on temperature-dependent changes in hydrogen bonds in cellulose Iβ by infrared spectroscopy with perturbation-correlation moving-window two-dimensional correlation spectroscopy. Biomacromolecules 7:3164–3170
Watanabe A, Morita S, Ozaki Y (2007) Temperature-dependent changes in hydrogen bonds in cellulose Iα studied by infrared spectroscopy in combination with perturbation-correlation moving-window two-dimensional correlation spectroscopy: comparison with cellulose Iβ. Biomacromolecules 8:2969–2975
Zhang Q, Bulone V, Ågren H, Tu Y (2011) A molecular dynamics study of the thermal response of crystalline cellulose Iβ. Cellulose 18:207–221
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The Centre de Recherches sur les Macromolécules Végétales (CERMAV-CNRS) is affiliated with Université Joseph Fourier and a member of the Institut de Chimie Moléculaire de Grenoble and Institut Carnot PolyNat.
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Chen, P., Nishiyama, Y., Putaux, JL. et al. Diversity of potential hydrogen bonds in cellulose I revealed by molecular dynamics simulation. Cellulose 21, 897–908 (2014). https://doi.org/10.1007/s10570-013-0053-x
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DOI: https://doi.org/10.1007/s10570-013-0053-x