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The structure of celluloses

Published online by Cambridge University Press:  29 February 2012

Masahisa Wada ,
Yoshiharu Nishiyama ,
Henri Chanzy ,
Trevor Forsyth  and
Paul Langan
Masahisa Wada
Affiliation:
Department of Biomaterials Science, Graduate School of Agriculture and Life Sciences, The University of Tokyo, Tokyo 113-8657, Japan
Yoshiharu Nishiyama
Affiliation:
Centre de Recherches sur les Macromolécules Végétales-CNRS, affiliated with the Joseph Fourier University of Grenoble, BP 53, 38041 Grenoble Cedex 9, France
Henri Chanzy
Affiliation:
Centre de Recherches sur les Macromolécules Végétales-CNRS, affiliated with the Joseph Fourier University of Grenoble, BP 53, 38041 Grenoble Cedex 9, France
Trevor Forsyth
Affiliation:
Institute Laue-Langevin, Avenue des Martyrs, 38042, Grenoble Cedex 9, Franceand School of Chemistry and Physics, Lennard Jones Lab, Keele University, Keele, Staffordshire ST5 5BG, United Kingdom
Paul Langan*
Affiliation:
Bioscience Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 and Department of Chemistry, University of Toledo, Toledo, Ohio 53606
*
Author to whom correspondence should be addressed. Electronic mail: langan.paul@lanl.gov
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Abstract

X-ray and neutron fiber diffraction has been used to study cellulose as it is converted from its naturally occurring crystal phase, cellulose I, to an activated crystal phase, cellulose IIII, by ammonia treatment. The detailed crystal structures determined for cellulose Iβ, an intermediate ammonia-cellulose I complex, and cellulose IIII, reveal a structural transition pathway: hydrogen bonded sheets of chains in cellulose Iβ slip with respect to each other to accommodate the penetrating ammonia guest molecules in the intermediate complex. On evaporation of ammonia from the intermediate complex, there is a relative small change in chain packing as an inter-sheet ammonia bridge is replaced by an inter-sheet hydrogen bond in cellulose IIII. When cellulose IIII is heated it converts back to cellulose Iβ. Both ammonia-cellulose I and cellulose IIII have extended chains of cooperative hydrogen bonds in relatively open crystal structures that may add to their susceptibility to rapid change.

Keywords

cellulosehydrogen bondneutron crystallographyX-ray crystallographyfiber
Type
X-Ray Diffraction
Information
Powder Diffraction , Volume 23 , Issue 2 , June 2008 , pp. 92 - 95
Copyright
Copyright © Cambridge University Press 2008

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References

Horii, F., Yamamoto, H., Kitamaru, R., Tanahashi, M., and Higuchi, T. (1987). “Transformation of native cellulose crystals induced by saturated steam at high temperatures,” Macromolecules MAMOBX 20, 2946–2949.CrossRefGoogle Scholar
Igarashi, K., Wada, M., and Samejima, M. (2007). “Activation of crystalline cellulose to cellulose IIII results in efficient hydrolysis by cellobiohydrolase,” FEBS J. ZZZZZZ 274, 1785–1792.Google Scholar
Langan, P. (2005). “Neutron diffraction from fibers,” Crystallogr. Rev. CRRVEN 11, 125–147.Google Scholar
Langan, P., Nishiyama, Y., and Chanzy, H. (1999). “A revised structure and hydrogen-bonding system in cellulose II from a neutron fiber diffraction analysis,” J. Am. Chem. Soc. JACSAT 121, 9940–9946.Google Scholar
Langan, P., Nishiyama, Y., and Chanzy, H. (2001). “X-ray structure of mercerized cellulose II at 1 Å resolution,” Biomacromolecules BOMAF6 2, 410–416.Google Scholar
Langan, P., Sukumar, N., Nishiyama, Y., and Chanzy, H. (2005). “Synchrotron x-ray structures of cellulose Iβ and regenerated cellulose II at ambient temperature and 100 K,” Cellulose 12, 551–562.Google Scholar
Nishiyama, Y., Wada, M., Kuga, S., and Okano, T. (1997). “Cellulose microcrystal film of high uniaxial orientation,” Macromolecules MAMOBX 30, 6395–6397.Google Scholar
Nishiyama, N., and Langan, P. (2000). “Modeling diffraction patterns from textured polycrystalline samples,” Fibre Diffr. Rev. 9, 18–23.Google Scholar
Nishiyama, Y., Langan, P., and Chanzy, H. (2002). “Crystal structure and hydrogen-bonding system in cellulose Iβ from synchrotron x-ray and neutron fiber diffraction,” J. Am. Chem. Soc. JACSAT 10.1021/ja0257319 124, 9074–9082.CrossRefGoogle ScholarPubMed
Nishiyama, Y., Sugiyama, J., Chanzy, H., and Langan, P. (2003). “Crystal structure and hydrogen bonding system in cellulose Iα from synchrotron x-ray and neutron fiber diffraction,” J. Am. Chem. Soc. JACSAT 10.1021/ja037055w 125, 14300–14306.Google Scholar
Sheldrick, G. M. (1997). SHELX-97, Program for the Refinement of Single-Crystal Diffraction Data (Computer Software), Georg–August University of Göttingen, Göttingen, Germany.Google Scholar
Wada, M. (2002). “Lateral thermal expansion of cellulose Iβ and IIII polymorphs,” J. Polym. Sci., Part B: Polym. Phys. JPBPEM 40, 1095–1102.Google Scholar
Wada, M., Heux, L., Isogai, A., Nishiyama, Y., Chanzy, H., and Sugiyama, J. (2001). “Improved structural data of cellulose IIII prepared in supercritical ammonia,” Macromolecules MAMOBX 34, 1237–1243.Google Scholar
Wada, M., Chanzy, H., Nishiyama, Y., and Langan, P. (2004). “Cellulose IIII crystal structure and hydrogen bonding by synchrotron x-ray and neutron fiber diffraction,” Macromolecules MAMOBX 37, 8548–8555.CrossRefGoogle Scholar
Wada, M., Nishiyama, Y., and Langan, P. (2006). “X-ray structure of ammonia-cellulose I: New insights into the conversion of cellulose I to cellulose IIII,” Macromolecules MAMOBX 39, 2947–2952.Google Scholar