Pure cellulose exists in several crystalline polymorphs (Hayashi et al. 1975; Sarko 1986) with different packing arrangements. The unit cells or the diffraction patterns of these crystalline structures represent a quantity which mirrors these differences. The unit cells are listed in Table 5.1. The conformation and packing of the cellulose chains are necessary quantities for a complete description of the polymorphs to evaluate their differences in behavior and properties. However, the determination of the cellulose structures is difficult to achieve, with only a few X-ray reflections often observed at low diffraction angles. Nevertheless, these few observed data normally suffice for the determination of the unit cell. Small differences in the size of the unit cells of the same polymorph are found in studies of various cellulose species and by various authors for the same species and may be caused by differences in supermolecular, i.e., morphological structures.
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References
Andress KR (1929) Das Röntgendiagramm der mercerisierten Cellulose. Z Phys Chem B 4:190–206
Atalla RH (1987) The structures of cellulose. In: Atalla RH (ed) The structures of cellulose–characterization of the solid states. ACS symposium series no 340. American Chemical Society, Washington, pp 1–14
Atalla RH, Nagel SC (1974) Cellulose–its regeneration in native lattice. Science 185:522–523
Atalla RH, VanderHart DL (1984) Native cellulose: a composite of two distinct crystalline forms. Science 223:283–284
Atalla RH, VanderHart DL (1989) Studies on the structure of cellulose using Raman spectroscopy and solid state 13C NMR. In: Schuerch C (ed) Cellulose and wood–chemistry and technology. Wiley, New York, pp 169–188
Atalla RH, VanderHart DL (1999) The role of solid state 13C NMR spectroscopy in studies of the nature of native celluloses. Solid State Nucl Magn Reson 15:1–20
Barry AJ, Peterson FC, King AJ (1936) X-ray studies of reactions of cellulose in non-aqueous systems. I. Interaction of cellulose and liquid ammonia. J Am Chem Soc 58:333–337
Blackwell J (2000) Modeling ordered arrays of cellulose chains. Abstracts of papers of the American Chemical Society 219, Cell, part 1, San Francisco, 26 March 2000, p 127
Buléon A, Chanzy H (1980) Single crystals of cellulose IV2: preparation and properties. J Polym Sci A-2 18:1209–1217
Burgeni A, Kratky O (1929) Röntgenspektrographische Beobachtungen an Cellulose. V. Über das Gitter der Hydratcellulose. Z Phys Chem B 4:401–430
Cartier L, Spassky N, Lotz B (1996) Structures frustrées de polymèrs chireaux. C R Acad Sci Paris Sér II b 322:429–435
Chanzy H, Imada K, Vuong R (1978) Electron diffraction from the primary wall of cotton fibers. Protoplasma 94:299–306
Chanzy H, Imada K, Mollard A, Vuong R, Barnoud F (1979) Crystallographic aspects of sub-elementary cellulose fibrils occurring in the wall of rose cells cultured in vitro. Protoplasma 100:303–316
Clark GL, Parker EA (1937) An X-ray diffraction study of the action of liquid ammonia on cellulose and its derivatives. J Phys Chem 41:777–786
Davis DE, Barry AJ, Peterson FC, King AJ (1943) X-ray studies of reactions of cellulose in non-aqueous systems. II. Interaction of cellulose and primary amines. J Am Chem Soc 65:1294–1299
Ellis KC, Warwicker JO (1962) A study of the crystal structure of cellulose I. J Polym Sci 56:339–357
Fink H-P, Walenta E, Kunze J (1999) Zur Struktur cellulosischer Naturfasern. Papier 9:534–542
Finkenstadt VL, Millane RP (1998) Crystal structure of Valonia cellulose Iβ. Macromolecules 31:3776–7783
Gardiner ES, Sarko A (1985) Packing analysis of carbohydrates and polysaccharides. 16. The crystal structures of cellulose IV1 and IV2. Can J Chem 63:173–180
Gardner KH, Blackwell J (1974) The structure of native cellulose. Biopolymers 13:1975–2001
Gessler K, Krauß N, Steiner T, Betzel C, Sarko A, Sänger W (1995) β-D-Cellotetraose hemihydrate as a structural model for cellulose II. An X-ray diffraction study. J Am Chem Soc 117:11397–11406
Ham JT, Williams DG (1970) The crystal and molecular structure of β-cellobioside-methanol. Acta Crystallogr Sect B 26:1373–1383
Hayashi J, Sufoka A, Ohkita J, Watanabe S (1975) The confirmation of existence of cellulose III1, III2, IV1 and IV2 by the X-ray method. Polym Lett 13:23–27
Hermans PH (1949) Physics and chemistry of cellulose fibres. Elsevier, New York
Hermans PH, Weidinger A (1946) The hydrates of cellulose. J Colloid Sci 1:185–193
Herzog RO, Jancke W (1920a) Röntgenspektrographische Beobachtungen an Zellulose. Z Phys 3:196–198
Herzog RO, Jancke W (1920b) Über den physikalischen Aufbau einiger hochmolekularer organischer Verbindungen. Ber Dtsch Chem Ges 53:2162–2164
Hess K, Gundermann J (1937) Über die Einwirkung von flüssigem Ammoniak auf Cellulosefasern. Ber Dtsch Chem Ges 68:1986–1988
Hess K, Trogus C (1935) Über Ammoniak-Cellulose. Ber Dtsch Chem Ges 70:1788–1799
Hess K, Kiessig H, Gundermann J (1941) Röntgenographische und elektronenmikroskopische Untersuchungen der Vorgänge beim Vermahlen von Cellulose. Z Phys Chem B 49:64–82
Honjo G, Watanabe M (1958) Examination of cellulose fibre by the low-temperature specimen method of electron diffraction and electron microscopy. Nature 181:326–328
Hori R, Wada M (2006) The thermal expansion of cellulose II and III2 crystals. Cellulose 13:281–290
Horii F, Hirai A, Kitamaru R (1987a) Cross-polarization-magic angle spinning carbon-13 NMR approach to the structural analysis of cellulose. In: Atalla RH (ed) The structures of cellulose–characterization of the solid states. ACS symposium series no 340. American Chemical Society, Washington, pp 119–134
Horii F, Yamamoto H, Kitamaru R, Tanahashi M, Higuchi T (1987b) Transformation of native cellulose crystals induced by saturated steam at high temperatures. Macromolecules 20:2949–2951
Imai T, Sugiyama J (1998) Nanodomains of Iα and Iβ cellulose in algal microfibrils. Macromolecules 31:6275–6279
Imai T, Sugiyama J, Itoh T, Horii F (1999) Almost pure Iα cellulose in the cell wall of Glaucocystis. J Struct Biol 127:248–257
Isogai A (1994) Allomorphs of cellulose and other polysaccharides. In: Gilbert RD (ed) Cellulosic polymers. Hanser, Munich, pp 1–24
Isogai A, Usuda M, Kato T, Uryu T, Atalla RH (1989) Solid-state CP/MAS 13C NMR study of cellulose polymorphs. Macromolecules 22:3168–3172
Kolpak FJ, Blackwell J (1976) Determination of the structure of cellulose II. Macromolecules 9:273–278
Kono H, Numata Y (2004) Two-dimensional spin-exchange solid-state NMR study of the crystal structure of cellulose II. Polymer 45:4541–4547
Kono H, Numata Y (2006) Structural investigation of cellulose Iα and Iβ by 2D RFDR NMR spectroscopy: determination of sequence of magnetically inequivalent D-glucose units along cellulose chain. Cellulose 13:317–326
Kono H, Erata T, Takai M (2003) Complete assignment of the CP/MAS 13C NMR spectrum of cellulose III1. Macromolecules 36:3589–3592
Koyama M, Helbert W, Imai T, Sugiyama J, Henrissat B (1997) Parallel-up structure evidences the molecular directionality during biosynthesis of bacterial cellulose. Proc Natl Acad Sci USA 94:9091–9095
Kroon-Batenburg LMJ, Bouma B, Kroon J (1996) Stability of cellulose structures by MD simulations. Could mercerized cellulose II be parallel? Macromolecules 29:5695–5699
Langan P, Nishiyama Y, Chanzy H (1999) A revised structure and hydrogen-bonding system in cellulose II from a neutron fiber diffraction analysis. J Am Chem Soc 121:9940–9946
Langan P, Nishiyama Y, Chanzy H (2001) X-ray structure of mercerized cellulose II at 1 Å resolution. Biomacromolecules 2:410–416
Langan P, Sukumar N, Nishiyama Y, Chanzy H (2005) Synchrotron X-ray structures of cellulose Iβ and regenerated cellulose II at ambient temperature and 100 K. Cellulose 12:551–562
Lee DM, Blackwell J (1981a) Cellulose-hydrazine complexes. J Polym Sci B 19:459–465
Lee DM, Blackwell J (1981b) Structure of cellulose II hydrate. Biopolymers 20:2165–2179
Lee DM, Blackwell J, Litt MH (1983) Structure of a cellulose II-hydrazine complex. Biopolymers 22:1383–1399
Lee DM, Burnfield KE, Blackwell J (1984) Structure of a cellulose I-ethylenediamine complex. Biopolymers 23:111–126
Legrand C (1951) Recherches sur la cellulose III régénérée de l’ammoniac-cellulose. J Polym Sci 7:333–339
Leung F, Marchessault RH (1973) Crystal structure of β-D, 1→4 xylobiose hexaacetate. Chem 51:1215–1222
Mo F, Jensen LH (1978) The crystal structure of a β-(1→4) linked disaccharide, α-N, N′-diacetylchitobiose monohydrate. Acta Crystallogr Sect B 34:1562–1569
Macchi E, Marx-Figini M, Fischer EW (1968) Elektronenbeugungsuntersuchungen an nativer und umgefällter Cellulose. Makromol Chem 120:235–237
Maréchal Y, Chanzy H (2000) The hydrogen bond network in IM cellulose as observed by infrared spectrometry. J Mol Struct 523:183–196
Marrinan HJ, Mann J (1956) Infrared spectra of crystalline modifications of cellulose. J Polym Sci 21:301–311
Nishimura H, Sarko A (1987a) Mercerization of cellulose. III. Changes in crystallite sizes. J Appl Polym Sci 33:855–866
Nishimura H, Sarko A (1987b) Mercerization of cellulose. IV. Mechanism of mercerization and crystallite sizes. J Appl Polym Sci 33:867–874
Nishimura H, Sarko A (1991) Mercerization of cellulose. 6. Crystal and molecular structure of Na-cellulose IV. Macromolecules 24:771–778
Nishimura H, Okano T, Sarko A (1991) Mercerization of cellulose. 5. Crystal and molecular structure of Na-cellulose I. Macromolecules 24:759–770
Nishiyama Y, Sugiyama J, Chanzy H, Langan P (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
Nishiyama Y, Chanzy H, Langan P (2003) Crystal structure and hydrogen-bonding system in cellulose Iα from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 125:14300–14306
Numata Y, Kono H, Kawano S, Erata T, Takai M (2003) Cross-polarization/magic-angle spinning 13C nuclear magnetic resonance study of cellulose I-ethylenediamine complex. J Biosci Bioeng 96:461–466
Okano T, Sarko A (1984) Mercerization of cellulose. I. X-ray diffraction evidence for intermediate structures. J Appl Polym Sci 29:4175–4182
Okano T, Sarko A (1985) Mercerization of cellulose. II. Alkali-cellulose intermediates and a possible mercerization mechanism. J Appl Polym Sci 30:325–332
Peralta-Inga Z, Johnson GP, Dowd MK, Rendleman JA, Stevens ED, French AD (2002) The crystal structure of the P-cellobiose·2·NaI·2·H2O complex in the context of related structures and conformational analysis. Carbohydr Res 337:851–861
Pertsin AJ, Nugmanov OK, Marchenko GN, Kitaigorodsky AI (1984) Crystal structure of cellulose polymorphs by potential energy calculations: 1. Most probable models for mercerized cellulose. Polymer 25:107–114
Raymond S, Henrissat B, Tran Qui D, Kvick Å, Chanzy H (1995a) The crystal structure of methyl β-cellotrioside monohydrate 0.25 ethanolate and its relationship to cellulose II. Carbohydr Res 277:209–229
Raymond S, Heyraud A, Tran Qui D, Kvick Å, Chanzy H (1995b) Crystal and molecular structure of β-D-cellotetraose hemihydrate as a model of cellulose II. Macromolecules 28:2096–2100
Sakurada J, Hutino K (1936) Über die Quellung der Zellulose durch Wasser. Kolloid-Z 77:346–351
Sarko A (1986) Recent X-ray crystallographic studies of celluloses. In: Young RA, Rowell RM (eds) Cellulose–structure, modification and hydrolysis. Wiley, New York, pp 29–49
Sarko A, Muggli R (1974) Packing analysis of carbohydrates and polysaccharides. III. Valonia cellulose and cellulose II. Macromolecules 7:486–494
Sarko A, Southwick J, Hayashi J (1976) Packing analysis of carbohydrates and polysaccharides. 7. Crystal structure of cellulose III1 and its relationship to other cellulose polymorphs. Macromolecules 9:857–867
Sheldrick GM (1997) SHELX-97. Program for the refinement of crystal structures. University of Göttingen
Sternberg U, Koch F-T, Prieß W, Witter R (2003) Crystal structure refinements of cellulose polymorphs using solid state 13C chemical shifts. Cellulose 10:189–199
Stipanovic AJ, Sarko A (1976) Packing analysis of carbohydrates and polysaccharides. 6. Molecular and crystal structure of regenerated cellulose II. Macromolecules 9:851–857
Sugiyama J, Okano T, Yamamote H, Horii F (1990) Transformation of Valonia cellulose crystals by an alkaline hydrothermal treatment. Macromolecules 23:3196–3198
Sugiyama J, Vuong R, Chanzy H (1991) Electron diffraction study on the two crystalline phases occurring in native cellulose from an algal cell wall. Macromolecules 24:4168–4175
VanderHart DL, Atalla RH (1984) Studies of microstructure in native cellulose using solid-state 13C NMR. Macromolecules 17:1465–1472
Wada M (2002) Lateral thermal expansion of cellulose Iβ and III1 polymorphs. J Polym Sci B 40:1095–1102
Wada M, Heux L, Isogai A, Nishiyama Y, Chanzy H, Sugiyama J (2001) Improved structural data of cellulose III1 prepared in supercritical ammonia. Macromolecules 34:1237–1243
Wada M, Kondo T, Okano T (2003) Thermally induced crystal transformation from cellulose Iα to Iβ. Polymer J 35:155–159
Wada M, Heux L, Sugiyama J (2004a) Polymorphism of cellulose I family: reinvestigation of cellulose IV. Biomacromolecules 5:1385–1391
Wada M, Chanzy H, Nishiyama Y, Langan P (2004b) Cellulose III1 crystal structure and hydrogen bonding by synchrotron X-ray and neutron fiber diffraction. Macromolecules 37:8548–8555
Wada M, Nishiyama Y, Langan P (2006) X-ray structure of ammonia-cellulose I: new insights into the conversion of cellulose I to cellulose III1. Macromolecules 39:2947–2952
Watanabe S, Takai M, Hayashi J (1968) An X-ray study on cellulose triacetate. J Polym Sci C 23:825–835
Whitaker PM, Nieduszynski IA, Atkins EDT (1974) Structural aspects of soda-cellulose II. Polymer 15:125–127
Woodcock C, Sarko A (1980) Packing analysis of carbohydrates and polysaccharides. 11. Molecular and crystal structure of native ramie cellulose. Macromolecules 13:1183–1187
Zugenmaier P (1974) Conformation and packing analysis of polysaccharides. I: mannan. Biopolymers 13:1127–1139
Zugenmaier P (2001) Conformation and packing of various crystalline cellulose fibers. Prog Polym Sci 26:1341–1417
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(2008). Cellulose. In: Crystalline Cellulose and Derivatives. Springer Series in Wood Science. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-540-73934-0_5
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