Abstract
The crystal structure of the native Iβ-allomorph of cellulose [Nishiyama et al. 2002. J. Am. Chem. Soc. 124: 9074–9082] reveals subtle but significant conformational differences between the two different chains and also a multiplicity of positions of the hydrogen atoms of the HO2 and HO6 hydroxyl groups. Two structures differing in the hydrogen bonding networks were then proposed, however, the static or dynamic origin of the observed disorder remains to be specified. Molecular modelling was used to address this question: 18 minicrystal and 2 macrocrystal models of cellulose were generated differing by the initial orientations of the HO2 and HO6 hydroxyl groups; among which the two proposed structures (called N1 and N16) together with a random structure which respect the experimental percentage of hydroxyl hydrogen orientations. Results showed that only 10 of the studied combinations were stable, the major structure (N1) defined by crystallographers was estimated viable whereas not the minor one (N16). All the calculated data from the retained crystals, which describe the solid dimensions, the individual chain conformations and the supermolecular organisation, 1/ remained stable at their equilibrium value during the dynamics and 2/ were sensitive to the initial positions of the hydrogen atoms. Analysis of the hydrogen bonds revealed that sheet stacking might be stabilised by unexpected hydrogen bonds in addition to hydrophobic interactions. Our results thus favoured local disorders which involve a limited number of chains; they revealed the structural microheterogeneity of the Iβ-phase of cellulose and a complex disorder of its corresponding hydrogen bonding networks.
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References
M.S. Baird A.C. O’Sullivan W.B. Banks (1998) ArticleTitleA native cellulose microfibril model Cellulose 5 89–111 Occurrence Handle10.1023/A:1009220830595
D. Silva Perez ParticleDa R. Ruggiero L.C. Morais A.E.H. Machado K. Mazeau (2004) ArticleTitleTheoretical and experimental studies on the adsorption of aromatic compounds onto cellulose Langmuir 20 3151–3158 Occurrence Handle15875842
T.C. Davidson R.H. Newman M.J. Ryan (2004) ArticleTitleVariations in the fibre repeat between samples of cellulose I from different sources Carbohydrate Res. 339 2889–2893 Occurrence Handle10.1016/j.carres.2004.10.005
French A.D. and Dowd M.K. 1993. Conformational analysis of cellobiose with MM3. Cellulose: Chem. Biochem. Mater. Aspects, HorwoodLondon, UK CODEN: 59RAA9, pp. 51–56.
A.D. French G.P. Johnson (2004) ArticleTitleWhat crystals of small analogs are trying to tell us about cellulose structure Cellulose (Dordrecht Netherlands) 11 5–22 Occurrence Handle10.1023/B:CELL.0000014765.94239.fe
J. Ganster J. Blackwell (1996) ArticleTitleNpH-MD-simulations of the elastic moduli of cellulose II at room temperature J. Mol. Model. [Electronic Publication] 2 278–285
M. Ioelovich E. Larina (1999) ArticleTitleParameters of crystalline structure and their influence on the reactivity of cellulose I Cellulose Chem. Technol. 33 3–12
M. Jarvis (2003) ArticleTitleChemistry: cellulose stacks up Nature (London, United Kingdom) 426 611–612
L.M.K. Kroon-Batenburg B. Bouma J. Kroon (1996) ArticleTitleStability of cellulose structures studied by MD simulations? Could mercerized cellulose II be parallel Macromolecules 29 5695–5699 Occurrence Handle10.1021/ma9518058
J.R. Maple (1994) ArticleTitleDerivation of class II force fields. 3. Characterization of a quantum force field for the alkanes Israel J. Chem. 34 195–231
J. Maple U. Dinur A.T. Hagler (1988) ArticleTitleDerivation of force fields for molecular mechanics and dynamics from ab initio energy surfaces Proc. Natl. Acad. Sci. USA 85 5350–5354
J.R. Maple M.J. Hwang T.P. Stockfisch U. Dinur M. Waldman C.S. Ewing A.T. Hagler (1994) ArticleTitleDerivation of class II force fields. I. Methodology and quantum force field for the alkyl functional group and alkane molecules J. Comp. Chem. 15 162–182 Occurrence Handle10.1002/jcc.540150207
K. Mazeau L. Heux (2003) ArticleTitleMolecular dynamics simulations of bulk native crystalline and amorphous structures of cellulose J. Phys. Chem. B 107 2394–2403 Occurrence Handle10.1021/jp0219395
K. Mazeau C. Vergelati (2002) ArticleTitleAtomistic modeling of the adsorption of benzophenone onto cellulosic surfaces Langmuir 18 1919–1927 Occurrence Handle10.1021/la010792q
S. Neyertz A. Pizzi A. Merlin B. Maigret D. Brown X. Deglise (2000) ArticleTitleA new all-atom force field for crystalline cellulose I J. Appl. Polymer Sci. 78 1939–1946 Occurrence Handle10.1002/1097-4628(20001209)78:11<1939::AID-APP130>3.0.CO;2-9
Y. Nishiyama P. Langan H. Chanzy (2002) ArticleTitleCrystal structure and hydrogen-bonding system in cellulose Ib from synchrotron X-ray and neutron fiber diffraction J. Am. Chem. Soc. 124 9074–9082 Occurrence Handle10.1021/ja0257319 Occurrence Handle12149011
Y. Nishiyama J. Sugiyama H. Chanzy P. Langan (2003) ArticleTitleCrystal structure and hydrogen bonding system in cellulose Ia from synchrotron X-ray and neutron fiber diffraction J. Am. Chem. Soc. 125 14300–14306 Occurrence Handle10.1021/ja037055w Occurrence Handle14624578
S. Nosé (1984) ArticleTitleA molecular dynamics method for simulations in the canonical ensemble Mol. Phys. 52 255–268
M. Parrinello A. Rahman (1981) ArticleTitlePolymorphic transitions in single crystals: a new molecular dynamics method J. Appl. Phys. 52 7182–7190 Occurrence Handle10.1063/1.328693
H. Sun (1995) ArticleTitleAb initio calculations and force field development for computer simulation of polysilanes Macromolecules 28 701–712 Occurrence Handle10.1021/ma00107a006
H. Sun S.J. Mumby J.R. Maple A.T. Hagler (1994) ArticleTitleAn ab initio CFF93 all-atom force field for polycarbonates J. Am. Chem. Soc. 116 2978–2987 Occurrence Handle10.1021/ja00086a030
L. Verlet (1967) ArticleTitleComputer experiments on classical fluids. I. Thermodynamical properties of Lennard–Jones molecules Phys. Rev. 159 98–103 Occurrence Handle10.1103/PhysRev.159.98
M. Wada (2002) ArticleTitleLateral thermal expansion of cellulose Ib and IIII polymorphs J. Polymer Sci. Part B: Polymer Phys. 40 1095–1102 Occurrence Handle10.1002/polb.10166
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Mazeau, K. Structural Micro-heterogeneities of Crystalline Iβ-cellulose. Cellulose 12, 339–349 (2005). https://doi.org/10.1007/s10570-005-2200-5
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DOI: https://doi.org/10.1007/s10570-005-2200-5