Abstract
The paper describes molecular dynamics (MD) simulations on the crystal structures of the Iβ and II phases of cellulose. Structural proposals for each of these were made in the 1970s on the basis of X-ray diffraction data. However, due to the limited resolution of these data some controversies remained and details on hydrogen bonding could not be directly obtained. In contrast to structure factor amplitudes in X-ray diffraction, energies, as obtained from MD simulations, are very sensitive to the positions of the hydroxyl hydrogen atoms. Therefore the latter technique is very suitable for obtaining such structural details. MD simulations of the Iβ phase clearly shows preference for one of the two possible models in which the chains are packed in a parallel orientation. Only the parallel-down mode (in the definition of Gardner and Blackwell (1974) J Biopolym 13: 1975-2001) presents a stable structure. The hydrogen bonding consists of two intramolecular hydrogen bonds parallel to the glycosidic linkage for both chains, and two intralayer hydrogen bonds. The layers are packed hydrophobically. All hydroxymethyl group are positioned in the tg conformation. For the cellulose II form it was found that, in contrast to what seemed to emerge from the X-ray fibre diffraction data, both independent chains had the gt conformation. This idea already existed because of elastic moduli calculations and 13C-solid state NMR data. Recently, the structure of cellotetraose was determined. There appear to be a striking similarity between the structure obtained from the MD simulations and this cellotetraose structure in terms of packing of the two independent molecules, the hydrogen bonding network and the conformations of the hydroxymethyl group, which were also gt for both molecules. The structure forms a 3D hydrogen bonded network, and the contribution from electrostatics to the packing is more pronounced than in case of the Iβ structure. In contrast to what is expected, in view of the irreversible transition of the cellulose I to II form, the energies of the Iβ form is found to be lower than that of II by 1 kcal mol-1 per cellobiose.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Gardner KH, Blackwell J (1974) J Biopolym 13: 1975–2001.
Sarko A, Muggli R (1974) Macromolecules 7: 486–94.
Woodcock C, Sarko A (1980) Macromolecules 13: 1183–87.
French AD (1978) Carbohydr Res 61: 67–80.
Kolpak FJ, Blackwell J (1976) Macromolecules 9: 273–78.
Stipanovic AJ, Sarko A (1976) Macromolecules 9:851–57.
Atalla RH, van der Hart DL (1984) Science 223: 283–85.
Chanzy H, Henrissat B (1985) FEBS Lett 184: 285–88.
Heiner AP, Sugiyama J, Telleman O (1995) Carbohydr Res 273: 207–23.
Hardy BJ, Sarko A (1995) Polymer Preprint, ACS (Anaheim meeting) 36:640.
Kroon-Batenburg LMJ, Bouma B, Kroon J (1996) Macromolecules 29: 5695–99.
van Gunsteren WF, Berendsen HJC, GROMOS (1987) University of Groningen, The Netherlands.
Koehler J, Saenger W, van Gunsteren WF (1987) Eur Biophys J 15: 197–210.
van Eijck BP (1994) Mol Simulation 13: 221–30.
Kouwijzer MLCE, van Eijck BP, Kroes SJ, Kroon J (1993) J Comp Chem 14: 1281–89.
Haigler CH, Brown RM Jr, Benziman M (1980) Science 210: 903–06.
Sugyiama J, Vuong R, Chanzy H (1991) Macromolecules 24: 4168.
Horii F, Hirai F, Kitamaru R (1983) Polym Bull 10: 357–61.
Kroon-Batenburg LMJ, Kroon J, Northolt MG (1986) Polym Comm 27: 290–92.
French AD, Miller DP, Aabloo A (1993) Int J Biol Macromol 15: 30–36.
Gessler K, Krauss N, Steiner T, Betzel C, Sandmann C, Saenger W (1994) Science 266: 1027–29.
Raymond S, Heyraud A, Tran Qui D, Kvick A, Chanzy H, (1995) Macromolecules 28: 2096–100.
Gessler N, Krauss N, Steiner T, Betzel C, Sarko A, Saenger W (1995) J Am Chem Soc 117: 11397–406.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kroon-Batenburg, L., Kroon, J. The crystal and molecular structures of cellulose I and II. Glycoconj J 14, 677–690 (1997). https://doi.org/10.1023/A:1018509231331
Issue Date:
DOI: https://doi.org/10.1023/A:1018509231331