Skip to main content
SpringerLink
Log in

Diffraction from nonperiodic models of cellulose crystals

  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

Powder and fiber diffraction patterns were calculated for model cellulose crystallites with chains 20 glucose units long. Model sizes ranged from four chains to 169 chains, based on cellulose Iβ coordinates. They were subjected to various combinations of energy minimization and molecular dynamics (MD) in water. Disorder induced by MD and one or two layers of water had small effects on the relative intensities, except that together they reduced the low-angle scattering that was otherwise severe enough to shift the 1 \( \bar {1} \) 0 peak. Other shifts in the calculated peaks occurred because the empirical force field used for MD and minimization caused the models to have small discrepancies with the experimental intermolecular distances. Twisting and other disorder induced by minimization or MD increased the breadth of peaks by about 0.2–0.3° 2-θ. Patterns were compared with experimental results. In particular, the calculated fiber patterns revealed a potential for a larger number of experimental diffraction spots to be found for cellulose from some higher plants when crystallites are well-oriented. Either that, or further understanding of those structures is needed. One major use for patterns calculated from models is testing of various proposals for microfibril organization.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Scheme 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

Notes

  1. In a crystal composed of a 10 × 10 array of polymeric molecules, 36 would be on the surface (36%). In a conventional, sub-millimeter size single-crystal for diffraction, the fraction of molecules on the surface is much less than one percent.

  2. The range of the calculated diffraction was selected after consideration of the number of atoms in the model and the number of pixels for which the intensity must be calculated. These factors determine the computer time required for the calculation. Some of the software used for projects other than reported in this paper was limited in the sizes of data arrays that could be handled. Considering that some models were as large as 94,700 atoms and 18 different size crystals were modeled, each with 14 variations of water content, energy minimization and molecular dynamics, the selected step sizes of 0.003 S out to 0.597 S were considered adequate for the present purposes. Larger calculated patterns are definitely possible.

References

  • Alexander LE (1969) X-ray diffraction methods in polymer science. Wiley-Interscience, New York, p. 44 and Appendix 1, T-14

  • Azároff LV, Buerger MJ (1958) The powder method in X-ray crystallography. McGraw-Hill, New York, p 254

    Google Scholar 

  • Baker AA, Helbert W, Sugiyama J, Miles MJ (2000) New insight into cellulose structure by atomic force microscopy shows the Iα crystal phase at near-atomic resolution. Biophys J 79:1139–1145

    Article  CAS  Google Scholar 

  • Basma M, Sundara S, Calgan D, Vernali T, Woods RJ (2001) Solvated ensemble averaging in the calculation of partial atomic charges. J Comput Chem 22:1125–1137

    Article  CAS  Google Scholar 

  • Bellesia G, Asztalos A, Shen T, Langan P, Redondo A, Gnanakaran S (2010) In silico studies of crystalline cellulose and its degradation by enzymes. Acta Crystallogr D Biol Crystallogr 66:1184–1188

    Article  CAS  Google Scholar 

  • Bergenstråhle M, Berglund LA, Mazeau K (2007) Thermal response in crystalline Iβ cellulose: a molecular dynamics study. J Phys Chem B 111:9138–9145

    Article  Google Scholar 

  • Ding S-Y, Himmel ME (2006) The maize primary cell wall microfibril: a new model derived from direct visualization. J Agric Food Chem 54:597–606

    Article  CAS  Google Scholar 

  • Driemeier C, Calligaris GA (2011) Theoretical and experimental developments for accurate determination of crystallinity of cellulose I materials. J Appl Cryst 44:184–192

    Article  CAS  Google Scholar 

  • Elazzouzi-Hafraoui S, Nishiyama Y, Putaux JL, Heux L, Dubreuil F, Rochas C (2008) The shape and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native cellulose. Biomacromolecules 9:57–65

    Article  CAS  Google Scholar 

  • Fernandes AN, Thomas LH, Altaner CM, Callow P, Fosyth VT, Apperley DC, Kennedy CJ, Jarvis MC (2011) Nanostructure of cellulose microfibrils in spruce wood. Proc Natl Acad Sci USA 108:E1195–E1203

    Article  Google Scholar 

  • Ford ZM, Stevens ED, Johnson GP, French AD (2005) Determining the crystal structure of cellulose IIII by modeling. Carbohydr Res 340:827–833

    Article  CAS  Google Scholar 

  • Galassi M, Davies J, Theiler J, Gough B, Jungman G, Alken P, Booth M, Rossi F (2009) GNU scientific library. Network Theory Ltd., United Kingdom or see http://www.gnu.org/s/gsl/

  • Hardy BJ, Sarko A (1996) Molecular dynamics simulations and diffraction-based analysis of the native cellulose fibre: structural modelling of the I-α and I-β phases and their interconversion. Polymer 37:1833–1839

    Article  CAS  Google Scholar 

  • Heiner AP, Sugiyama J, Teleman O (1995) Crystalline cellulose Iα and Iβ studied by molecular dynamics simulation. Carbohyr Res 273:207–223

    Article  CAS  Google Scholar 

  • Hosemann R (1962) Crystallinity in high polymers, especially fibres. Polymer 3:349–392

    Article  CAS  Google Scholar 

  • Jorgensen WL, Chandrasekhar J, Madura JD, Impey RW, Klein ML (1983) Comparison of simple potential functions for simulating liquid water. J Chem Phys 79:926–935

    Article  CAS  Google Scholar 

  • Kirschner KN, Woods RJ (2001a) Solvent interactions determine carbohydrate conformations. Proc Natl Acad Sci USA 98:10541–10545

    Article  CAS  Google Scholar 

  • Kirschner KN, Woods RJ (2001b) Quantum mechanical study of the nonbonded forces in water-methanol complexes. J Phys Chem A 105:4150–4155

    Article  CAS  Google Scholar 

  • Kirschner KN, Yongye AB, Tschampel SM, González-Outeiriño J, Daniels CR, Foley BL, Woods RJ (2008) GLYCAM06: a generalizable biomolecular force field, carbohydrates. J Comput Chem 29:622–655

    Article  CAS  Google Scholar 

  • Kroon-Batenburg LMJ, Kroon J (1997) The crystal and molecular structures of cellulose I and II. Glycoconj J 14:677–690

    Article  CAS  Google Scholar 

  • Langan P, Nishiyama Y, Chanzy H (2001) X-ray structure of mercerized cellulose II at 1 Ångstrom resolution. Biomacromolecules 2:410–416

    Article  CAS  Google Scholar 

  • Macrae CF, Gruno IJ, Chisholm JA, Edgington PR, McCabe P, Pidcock E, Rodriguez-Monge L, Taylor R, van de Streek J, Wood PA (2008) Mercury CSD 2.0—new features for the visualization and investigation of crystal structures. J Appl Crystallogr 41:466–470

    Article  CAS  Google Scholar 

  • Matthews JF, Skopec CE, Mason PE, Zuccato P, Torget RW, Sugiyama J, Himmel ME, Brady JW (2006) Computer simulation studies of microcrystalline cellulose Iβ. Carbohydr Res 341:138–152

    Article  CAS  Google Scholar 

  • Mazeau K, Heux L (2003) Molecular dynamics simulations of bulk native crystalline and amorphous structures of cellulose. J Phys Chem B 107:2394–2403

    Article  CAS  Google Scholar 

  • Newman RH (1998) Evidence for assignment of 13C NMR signals to cellulose crystallite surfaces in wood, pulp and isolated celluloses. Holzforschung 52:157–159

    Article  CAS  Google Scholar 

  • Newman RH (2008) Simulation of X-ray diffractograms relevant to the purported polymorphs cellulose IVI and IVII. Cellulose 15:769–778

    Article  CAS  Google Scholar 

  • Nishiyama Y (2009) Structure and properties of the cellulose microfibril. J Wood Sci 55:241–249

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Nishiyama Y, Sugiyama J, Chanzy H, Langan P (2003a) Crystal structure and hydrogen bonding system in cellulose Iα, from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 125:14300–14306

    Article  CAS  Google Scholar 

  • Nishiyama Y, Kim UJ, Kim DY, Katsumata KS, May RP, Langan P (2003b) Periodic disorder along ramie cellulose microfibrils. Biomacromolecules 4:1013–1017

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Nishiyama Y, Noishiki Y, Wada M (2011) X-ray structure of anhydrous β-chitin at 1 Å resolution. Macromolecules 44:950–957

    Article  CAS  Google Scholar 

  • Patterson A (1939) The Scherrer formula for X-ray particle size determination. Phys Rev 56:978–982

    Article  CAS  Google Scholar 

  • Pettersen EF, Goddard TD, Huang CC, Couch GS, Greenblatt DM, Meng EC, Ferrin TE (2004) UCSF Chimera—A visualization system for exploratory research and analysis. J Comput Chem 25:1605–1612

    Article  CAS  Google Scholar 

  • Rasband WS (2011) ImageJ. U. S. National Institutes of Health, Bethesda, Maryland, USA. http://imagej.nih.gov/ij/

  • Rowland SP, Roberts EJ, Bose JL (1971) Availability and state of order of hydroxyl groups on the surfaces of microstructural units of crystalline cotton cellulose. J Polym Sci A-1 9:1431–1440

    Google Scholar 

  • Spek AL (2008) PLATON, a multipurpose crystallographic tool. Utrecht University, Utrecht, The Netherlands. http://www.cryst.chem.uu.nl/platon/pl000000.html

  • Wada M, Okano T, Sugiyama J (1997) Synchrotron-radiated X-ray and neutron diffraction study of native cellulose. Cellulose 4:221–232

    Article  CAS  Google Scholar 

  • Wada M, Chanzy H, Nishiyama Y, Langan P (2004) Cellulose IIII crystal structure and hydrogen bonding by synchrotron X-ray and neutron fiber diffraction. Macromolecules 37:8548–8555

    Article  CAS  Google Scholar 

  • Wada M, Heux L, Nishiyama Y, Langan P (2009) X-ray crystallographic, scanning microprobe X-ray diffraction, and cross-polarized/magic angle spinning 13C NMR studies of the structure of cellulose IIIII. Biomacromolecules 10:302–309

    Article  CAS  Google Scholar 

  • Wojdyr M (2011) http://www.unipress.waw.pl/debyer and http://code.google.com/p/debyer/wiki/debyer

  • Yui T, Okayama N, Hayashi S (2010) Structure conversions of cellulose IIII crystal models in solution state: a molecular dynamics study. Cellulose 17:679–691

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We thank Paul Langan and Henri Chanzy for helpful comments on a draft of this paper. Jodi Hadden contributed thoughts on twisted crystals.

Author information

Authors and Affiliations

  1. Centre de Recherche sur les Macromolécules Végétales (CERMAV), Joseph Fourier University of Grenoble, BP 53, 38041, Grenoble Cedex 9, France

    Yoshiharu Nishiyama

  2. United States Department of Agriculture, Southern Regional Research Center (SRRC), 1100 Robert E. Lee Boulevard, New Orleans, LA, 70124, USA

    Glenn P. Johnson & Alfred D. French

Authors
  1. Yoshiharu Nishiyama
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Glenn P. Johnson
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Alfred D. French
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Yoshiharu Nishiyama or Alfred D. French.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Nishiyama, Y., Johnson, G.P. & French, A.D. Diffraction from nonperiodic models of cellulose crystals. Cellulose 19, 319–336 (2012). https://doi.org/10.1007/s10570-012-9652-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-012-9652-1

Keywords

Search

Navigation