Abstract
In his more recent work, Henri Chanzy explored the nature of cellulose microfibrils that were biosynthesized in vitro, in the absence of physical confinement, i.e. external constraints due to the presence of a solid cell wall against which the nanofibrils would be deposited. Henri Chanzy and his colleagues found out by electron diffraction that cellulose IVI could be generated in the native cell wall. At the macroscopic scale, cellulose IVI could hardly be distinguished from cellulose Iβ in powder patterns because of the superimposition of the various signals. In the present work, the use of strongly textured flax or wood specimens was explored in order to generate strong longitudinal (or meridional) 0 0 l patterns in a very wide range of the reciprocal space and with a high resolution. In order to do so, a diffractometer was used with a parafocusing geometry and long scans permitted to document the 0 0 2 to 0 0 10 diffraction bands with accuracy, including the odd reflections that are normally present when dealing with cellulose IVI or imperfect forms of cellulose I. An omega scan also demonstrated the extreme selectivity of this setup and the very narrow orientation distribution of the sample. Surprisingly, this study showed that both flax fibres and fir wood contained three characteristic reflections that could be readily distinguished from one another and corresponded to characteristic interplanar spacings. A lineshape analysis using the Williamson–Hall approach and the Hosemann theory was performed on the flax sample. The results provide a better insight as to the longitudinal arrangement of cellulose in terms of domain sizes, microstrains or paracrystallinity. The three forms of order, characterized by various interplanar spacings, were present in different amounts in flax and fir, but the exact match of their interplanar spacing reveals some kind of possible universality in the cellulose arrangement.
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Change history
17 October 2023
A Correction to this paper has been published: https://doi.org/10.1007/s10570-023-05498-w
Notes
The z position of the O64 atom was indexed by Gardiner and Sarko as 0.6303 instead of 0.3860, a mistake that was propagated by Zugenmaier in his 2001 review (Gardiner and Sarko 1985; Zugenmaier 2001). The corrected.cif file for cellulose IVI was implemented early on in Duchemin 2017, and the correction is stipulated in the provided.cif file (Duchemin 2017).
These points were confirmed my Yoshiharu Nishiyama in a private communication.
References
Abe K, Nakatsubo F, Yano H (2009) High-strength nanocomposite based on fibrillated chemi-thermomechanical pulp. Compos Sci Technol 69:2434–2437. https://doi.org/10.1016/j.compscitech.2009.06.015
Agarwal UP, Ralph SA, Reiner RS, Baez C (2016) Probing crystallinity of never-dried wood cellulose with Raman spectroscopy. Cellulose 23:125–144. https://doi.org/10.1007/s10570-015-0788-7
Balzar D (1999) Voigt-function model in diffraction line-broadening analysis. Int Union Crystallogr Monogr Crystallogr 10:94–126
Battista OA, Coppick S, Howsmon JA et al (1956) Level-off degree of polymerization. Ind Eng Chem 48:333–335. https://doi.org/10.1021/ie50554a046
Bellesia G, Asztalos A, Shen T et al (2010) In silico studies of crystalline cellulose and its degradation by enzymes. Acta Cryst D 66:1184–1188. https://doi.org/10.1107/S0907444910029483
Billinge SJL (2019) The rise of the X-ray atomic pair distribution function method: a series of fortunate events. Philosoph Transact R Soc Math Phys Eng Sci 377:20180413. https://doi.org/10.1098/rsta.2018.0413
Billinge SJL, Kanatzidis MG (2004) Beyond crystallography: the study of disorder, nanocrystallinity and crystallographically challenged materials with pair distribution functions. Chem Commun 0749–760. https://doi.org/10.1039/B309577K
Buleon A, Chanzy H (1980) Single crystals of cellulose IVII: preparation and properties. J Polym Sci Polym Phys Ed 18:1209–1217. https://doi.org/10.1002/pol.1980.180180604
Buleon A, Chanzy H, Roche E (1976) Epitaxial crystallization of cellulose II on valonia cellulose. J Polym Sci Polym Phys Ed 14:1913–1916. https://doi.org/10.1002/pol.1976.180141016
Buleon A, Chanzy H, Roche E (1977) Shish kebab-like structures of cellulose. J Polym Sci Polym Lett Ed 15:265–270. https://doi.org/10.1002/pol.1977.130150502
Chan J, Coen E (2020) Interaction between autonomous and microtubule guidance systems controls cellulose synthase trajectories. Curr Biol. https://doi.org/10.1016/j.cub.2019.12.066
Chanzy H, Imada K, Vuong R (1978) Electron diffraction from the primary wall of cotton fibers. Protoplasma 94:299–306. https://doi.org/10.1007/BF01276778
Chanzy H, Imada K, Mollard A et al (1979) Crystallographic aspects of sub-elementary cellulose fibrils occurring in the wall of rose cells culturedin vitro. Protoplasma 100:303–316. https://doi.org/10.1007/BF01279318
Chen P, Terenzi C, Furó I et al (2019) Quantifying localized macromolecular dynamics within hydrated cellulose fibril aggregates. Macromolecules 52:7278–7288. https://doi.org/10.1021/acs.macromol.9b00472
Delhez R, Keijser TH, Mittemeijer EJ (1982) Determination of crystallite size and lattice distortions through X-ray diffraction line profile analysis. Fresenius’ J Anal Chem 312:1–16
Deligey F, Frank MA, Cho SH et al (2022) Structure of in vitro-synthesized cellulose fibrils viewed by cryo-electron tomography and 13C natural-abundance dynamic nuclear polarization solid-state NMR. Biomacromol. https://doi.org/10.1021/acs.biomac.1c01674
Duchemin B (2017) Size, shape, orientation and crystallinity of cellulose Iβ by X-ray powder diffraction using a free spreadsheet program. Cellulose 24:2727–2741. https://doi.org/10.1007/s10570-017-1318-6
Duchemin B, Newman R, Staiger M (2007) Phase transformations in microcrystalline cellulose due to partial dissolution. Cellulose 14:311–320
Ellefsen Ø, Wang Lund E, Andvord Tønnessen B, Øien K (1957) Studies on cellulose charaterization by means of X-ray methods. Norsk Skogindustri 8:284–293
Fink H-P, Philipp B, Paul D et al (1987) The structure of amorphous cellulose as revealed by wide-angle X-ray scattering. Polymer 28:1265–1270
French AD, Kim HJ (2018) Cotton fiber structure. Cotton fiber: physics, chemistry and biology 13–39
French AD, Johnson GP (2009) Cellulose and the twofold screw axis: modeling and experimental arguments. Cellulose 16:959–973. https://doi.org/10.1007/s10570-009-9347-4
Fujita M, Himmelspach R, Hocart CH et al (2011) Cortical microtubules optimize cell-wall crystallinity to drive unidirectional growth in Arabidopsis. Plant J 66:915–928
Fujita M, Lechner B, Barton DA et al (2012) The missing link: do cortical microtubules define plasma membrane nanodomains that modulate cellulose biosynthesis? Protoplasma 249:59–67
Funahashi R, Okita Y, Hondo H et al (2017) Different conformations of surface cellulose molecules in native cellulose microfibrils revealed by layer-by-layer peeling. Biomacromol 18:3687–3694. https://doi.org/10.1021/acs.biomac.7b01173
Gardiner ES, Sarko A (1985) Packing analysis of carbohydrates and polysaccharides. 16. The crystal structures of celluloses IVI and IVII. Can J Chem 63:173–180. https://doi.org/10.1139/v85-027
Guinier A (1963) X-ray diffraction in crystals, imperfect crystals, and amorphous bodies. W. H. Freeman and Company, San Francisco and London
Haigler CH, Roberts AW (2019) Structure/function relationships in the rosette cellulose synthesis complex illuminated by an evolutionary perspective. Cellulose 26:227–247. https://doi.org/10.1007/s10570-018-2157-9
Hall WH (1949) X-ray line broadening in metals. Proc Phys Soc London, Sect A 62:741
Hearle JWS (1963) The development of ideas of fine structure. Butterworth, The Textile Institute, London-Manchester
Helbert W, Sugiyama J, Ishihara M, Yamanaka S (1997) Characterization of native crystalline cellulose in the cell walls of Oomycota. J Biotechnol 57:29–37. https://doi.org/10.1016/S0168-1656(97)00084-9
Hill SJ, Kirby NM, Mudie ST et al (2010) Effect of drying and rewetting of wood on cellulose molecular packing. 64:421–427. https://doi.org/10.1515/hf.2010.065
Hindeleh AM, Hosemann R (1988) Paracrystals representing the physical state of matter. J Phys C Solid State Phys 21:4155–4170
Hofmann D, Walenta E (1987) An improved single-line method for the wide-angle X-ray scattering profile analysis of polymers. Polymer 28:1271–1276. https://doi.org/10.1016/0032-3861(87)90436-8
Hosemann R (1950) Der ideale Parakristall und die von ihm gestreute kohärente Röntgenstrahlung. Z Physik 128:465–492. https://doi.org/10.1007/BF01330029
Hosemann R, Bagchi SN (1954) Diffraction effects of crystals with deformation faults. Phys Rev 94:71–74. https://doi.org/10.1103/PhysRev.94.71
Hosemann R, Hentschel MP, Baltacalleja FJ et al (1985) The alpha-star-constant, equilibrium state and bearing net planes in polymers, bio-polymers and catalysts. J Phys C Solid State Phys 18:961–971
Hush JM, Hawes CR, Overall RL (1990) Interphase microtubule re-orientation predicts a new cell polarity in wounded pea roots. J Cell Sci 96:47–61. https://doi.org/10.1242/jcs.96.1.47
Jones FW (1938) The measurement of particle size by the X-ray method. Proc R Soc Lond A 166:16–43
Kennedy CJ, Cameron GJ, Šturcová A et al (2007) Microfibril diameter in celery collenchyma cellulose: X-ray scattering and NMR evidence. Cellulose 14:235. https://doi.org/10.1007/s10570-007-9116-1
Khelifi Z, Allal MA, Abou-bekr N et al (2018) The mechanical and crystallographic evolution of stipa tenacissima leaves during in-soil biodegradation. J Renew Mat 6:336–346
Kiessig H (1939) Untersuchungen über die Gitterstruktur der natürlichen Cellulose. Z Phys Chem 43B:79–102. https://doi.org/10.1515/zpch-1939-4308
Kuga S, Brown Jr RM (1991) Physical structure of cellulose microfibrils: implications for biogenesis. In: Biosynthesis and biodegradation of cellulose. Marcel Dekker New York, pp 125–142
Kulshreshtha AK, Dweltz NE (1971) The Fourier coefficients of paracrystalline X-ray diffraction. Acta Cryst A 27:670–675. https://doi.org/10.1107/S0567739471001426
Kulshreshtha AK, Patil NB, Dweltz NE, Radhakrishnan T (1969) Axial order in Ramie. Text Res J 39:1158–1161. https://doi.org/10.1177/004051756903901211
Kulshreshtha AK, Patel AR, Baddi NT, Srivastava HC (1977) Studies on never-dried cotton. J Polym Sci Polym Chem Ed 15:165–183. https://doi.org/10.1002/pol.1977.170150116
Lai-Kee-Him J, Chanzy H, Müller M et al (2002) In vitro versus in vivo cellulose microfibrils from plant primary wall synthases: structural differences*. J Biol Chem 277:36931–36939. https://doi.org/10.1074/jbc.M203530200
Leboucher J, Bazin P, Goux D et al (2020) High-yield cellulose hydrolysis by HCl vapor: co-crystallization, deuterium accessibility and high-temperature thermal stability. Cellulose 27:3085–3105. https://doi.org/10.1007/s10570-020-03002-2
Leppänen K, Bjurhager I, Peura M et al (2011) X-ray scattering and microtomography study on the structural changes of never-dried silver birch, European aspen and hybrid aspen during drying. Holzforschung 65:865–873. https://doi.org/10.1515/HF.2011.108
Li S, Lei L, Yingling YG, Gu Y (2015) Microtubules and cellulose biosynthesis: the emergence of new players. Curr Opin Plant Biol 28:76–82. https://doi.org/10.1016/j.pbi.2015.09.002
Lutterotti L, Scardi P (1990) Simultaneous structure and size–strain refinement by the Rietveld method. J Appl Crystallogr 23:246–252
Marrinan HJ, Mann J (1956) Infrared spectra of the crystalline modifications of cellulose. J Polym Sci 21:301–311. https://doi.org/10.1002/pol.1956.120219812
Mittemeijer EJ, Welzel U (2008) The “state of the art” of the diffraction analysis of crystallite size and lattice strain. Z Kristallogr 223:552–560
Motta Neves R, Ornaghi HL, Duchemin B et al (2022) Grafting amount and structural characteristics of microcrystalline cellulose functionalized with different aminosilane contents. Cellulose 1–16
Müller M, Murphy B, Burghammer M et al (2004) Identification of ancient textile fibres from Khirbet Qumran caves using synchrotron radiation microbeam diffraction. Spectrochim Acta Part B 59:1669–1674. https://doi.org/10.1016/j.sab.2004.07.018
Nandi RK, Kuo HK, Schlosberg W et al (1984) Single-peak methods for Fourier analysis of peak shapes. J Appl Crystallogr 17:22–26. https://doi.org/10.1107/S0021889884010943
Newman RH (2008) Simulation of X-ray diffractograms relevant to the purported polymorphs cellulose IVI and IVII. Cellulose 15:769–778. https://doi.org/10.1007/s10570-008-9225-5
Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose Ibeta from synchrotron X-ray and neutron fibre diffraction. J Am Chem Soc 124:9074–9082
Nishiyama Y, Johnson GP, French AD (2012) Diffraction from nonperiodic models of cellulose crystals. Cellulose 19:319–336. https://doi.org/10.1007/s10570-012-9652-1
Nishiyama Y, Langan P, O’Neill H et al (2014) Structural coarsening of aspen wood by hydrothermal pretreatment monitored by small- and wide-angle scattering of X-rays and neutrons on oriented specimens. Cellulose 21:1015–1024. https://doi.org/10.1007/s10570-013-0069-2
Nixon BT, Mansouri K, Singh A et al (2016) Comparative structural and computational analysis supports eighteen cellulose synthases in the plant cellulose synthesis complex. Sci Rep 6:28696. https://doi.org/10.1038/srep28696
O’Connor RT, DuPré EF, Mitcham D (1958) Applications of infrared absorption spectroscopy to investigations of cotton and modified cottons. Text Res J 28:382–392. https://doi.org/10.1177/004051755802800503
Oehme DP, Yang H, Kubicki JD (2018) An evaluation of the structures of cellulose generated by the CHARMM force field: comparisons to in planta cellulose. Cellulose 25:3755–3777. https://doi.org/10.1007/s10570-018-1793-4
Ogawa Y, Nishiyama Y, Mazeau K (2020) Drying-induced bending deformation of cellulose nanocrystals studied by molecular dynamics simulations. Cellulose 27:9779–9786. https://doi.org/10.1007/s10570-020-03451-9
Pereira PHF, Ornaghi Júnior HL, Coutinho LV et al (2020) Obtaining cellulose nanocrystals from pineapple crown fibers by free-chlorite hydrolysis with sulfuric acid: physical, chemical and structural characterization. Cellulose 27:5745–5756. https://doi.org/10.1007/s10570-020-03179-6
Phyo P, Wang T, Yang Y et al (2018) Direct determination of hydroxymethyl conformations of plant cell wall cellulose using 1H polarization transfer solid-state NMR. Biomacromolcules 19:1485–1497. https://doi.org/10.1021/acs.biomac.8b00039
Preston RD (1962) The sub-microscopic morphology of cellulose. Polymer 3:511–528. https://doi.org/10.1016/0032-3861(62)90099-X
Prosa TJ, Moulton J, Heeger AJ, Winokur MJ (1999) Diffraction line-shape analysis of poly(3-dodecylthiophene): a study of layer disorder through the liquid crystalline polymer transition. Macromolecules 32:4000–4009. https://doi.org/10.1021/ma981059h
Qian X, Ding S-Y, Nimlos MR et al (2005) Atomic and electronic structures of molecular crystalline cellulose Iβ: a first-principles investigation. Macromolecules 38:10580–10589. https://doi.org/10.1021/ma051683b
Scardi P, Leoni M (1999) Fourier modelling of the anisotropic line broadening of X-ray diffraction profiles due to line and plane lattice defects. J Appl Cryst 32:671–682. https://doi.org/10.1107/S002188989900374X
Scardi P, Leoni M, Delhez R (2004) Line broadening analysis using integral breadth methods: a critical review. J Appl Cryst 37:381–390. https://doi.org/10.1107/S0021889804004583
Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Textile Res J 29:786–794
Stokes AR, Wilson AJC (1944) The diffraction of X rays by distorted crystal aggregates-I. Proceedings of the Physical Society 56:174
Thomas LH, Altaner CM, Jarvis MC (2013) Identifying multiple forms of lateral disorder in cellulose fibres. J Appl Cryst 46:972–979. https://doi.org/10.1107/S002188981301056X
Ungár T, Borbély A (1996) The effect of dislocation contrast on X-ray line broadening: a new approach to line profile analysis. Appl Phys Lett 69:3173–3175
Viëtor RJ, Newman RH, Ha M-A et al (2002) Conformational features of crystal-surface cellulose from higher plants. Plant J 30:721–731
Wada M, Heux L, Sugiyama J (2004) Polymorphism of cellulose I family: reinvestigation of cellulose IVI. Biomacromol 5:1385–1391
Warren BE, Averbach BL (1950) The effect of cold-work distortion on X-ray patterns. J Appl Phys 21:595–599. https://doi.org/10.1063/1.1699713
Warren BE, Averbach BL (1952) The separation of cold-work distortion and particle size broadening in X-ray patterns. J Appl Phys 23:497–497. https://doi.org/10.1063/1.1702234
Williamson GK, Hall WH (1953) X-ray line broadening from filed aluminium and wolfram. Acta Metall 1:22–31
Woodcock C, Sarko A (1980) Packing analysis of carbohydrates and polysaccharides. 11. Molecular and crystal structure of native ramie cellulose. Macromolecules 13:1183–1187
Wunderlich B, Kreitmeier SN (1995) Defects in polymer crystals. MRS Bull 20:17–22. https://doi.org/10.1557/S0883769400034886
Yinghua W (1987) Lorentz—polarization factor for correction of diffraction-line profiles. J Appl Cryst 20:258–259. https://doi.org/10.1107/S0021889887086746
Zhong R, Cui D, Ye Z-H (2019) Secondary cell wall biosynthesis. New Phytol 221:1703–1723. https://doi.org/10.1111/nph.15537
Zugenmaier P (2001) Conformation and packing of various crystalline cellulose fibers. Prog Polym Sci 26:1341–1417
Acknowledgments
The author would like to thank LABEX EMC3 for the funding of the Bragg–Brentano HD optics used for the X-ray measurements. He would also like to thank Henri Chanzy and Yoshiharu Nishiyama for discussions on the ultrastructure of flax fibre crystallites and on longitudinal aspects of the cellulose ultrastructure, as well as Alfred French for critical comments on the manuscript.
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BD did the sample preparation, the measurements, the python programming, the figures and the writing. No other contributor to declare.
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Duchemin, B. Longitudinal orders in the flax cell wall re-examined by lineshape analysis of the X-ray diffraction 00l profile up to l = 10. Cellulose 30, 8169–8184 (2023). https://doi.org/10.1007/s10570-023-05421-3
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DOI: https://doi.org/10.1007/s10570-023-05421-3