Abstract
A protocol was developed to freeze-trap (at 150 K) cellulose as it is undergoing liquid ammonia pretreatment, and then to collect X-ray diffraction data from the freeze-trapped reactants as the reaction is allowed to proceed and ammonia is allowed to melt and then evaporate, leaving ammonia-cellulose I. Cellulose adopts a new two-chain crystal form, which we call low temperature phase ammonia-cellulose I (two-chains and ~ten ammonia molecules within a unit cell of a = 15.49 Å, b = 11.35 Å, c = 10.42 Å and γ = 143.5°). A schematic model was developed that is characterized by sheets of hydrophobically stacked cellulose-chains with hydrophilic channels between them that are filled with ammonia molecules. Neighboring chains in these sheets have either different conformations or are staggered with respect to each other. As ammonia is allowed to evaporate, the unit cell size is reduced by a factor of two as the two independent chains become identical.
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References
Atalla RH, Vanderhart DL (1984) Native cellulose: a composite of two distinct crystalline forms. Science 223:283–285. doi:10.1126/science.223.4633.283
Barry AJ, Peterson FC, King AJ (1936) X-ray studies of reactions of cellulose in non-aqueous systems. I. Interaction of cellulose and liquid ammonia1. J Am Chem Soc 58:333–337
Bellesia G, Chundawat SPS, Langan P et al (2011) Probing the early events associated with liquid ammonia pretreatment of native crystalline cellulose. J Phys Chem B 115:9782–9788. doi:10.1021/jp2048844
Chanzy H, Henrissat B, Vuong R, Revol JF (1986) Structural changes of cellulose crystals during the reversible transformation cellulose IIII in Valonia. Holzforschung 25–30
Chundawat SPS, Bellesia G, Uppugundla N et al (2011a) Restructuring the crystalline cellulose hydrogen bond network enhances its depolymerization rate. J Am Chem Soc 133:11163–11174. doi:10.1021/ja2011115
Chundawat SPS, Donohoe BS, da C Sousa L et al (2011b) Multi-scale visualization and characterization of lignocellulosic plant cell wall deconstruction during thermochemical pretreatment. Energy Environ Sci 4:973–984. doi:10.1039/C0EE00574F
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. doi:10.1021/j150384a001
Davis WE, Barry AJ, Peterson FC, King AJ (1943) X-ray studies of reactions of cellulose in non-aqueous systems. II. Interaction of cellulose and primary amines1. J Am Chem Soc 65:1294–1299. doi:10.1021/ja01247a012
Igarashi K, Wada M, Samejima M (2007) Activation of crystalline cellulose to cellulose IIII results in efficient hydrolysis by cellobiohydrolase. FEBS J 274:1785–1792. doi:10.1111/j.1742-4658.2007.05727.x
Lewin M, Roldan LG (1971) The effect of liquid anhydrous ammonia in the structure and morphology of cotton cellulose. J Polym Sci Part C Polym Symp 36:213–229. doi:10.1002/polc.5070360115
Lewin M, Rau RO, Sello SB (1974) The role of liquid ammonia in functional textile finishes. Text Res J 44:680–686. doi:10.1177/004051757404400907
Narten AH (1977) Liquid ammonia: molecular correlation functions from x-ray diffraction. J Chem Phys 66:3117
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. doi:10.1021/ja0257319
Nishiyama Y, Sugiyama J, 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. doi:10.1021/ja037055w
Nishiyama Y, Wada M, Hanson BL, Langan P (2010) Time-resolved X-ray diffraction microprobe studies of the conversion of cellulose I to ethylenediamine-cellulose I. Cellulose 17:735–745. doi:10.1007/s10570-010-9415-9
Nishiyama Y, Noishiki Y, Wada M (2011) X-ray structure of anhydrous β-chitin at 1 Å resolution. Macromolecules 44:950–957. doi:10.1021/ma102240r
Pandey SN, Nair P (1975) A study of the effect of anhydrous liquid ammonia treatment on cotton. Text Res J 45:648–653. doi:10.1177/004051757504500902
Ricci MA, Nardone M, Ricci FP et al (1995) Microscopic structure of low temperature liquid ammonia: a neutron diffraction experiment. J Chem Phys 102:7650
Rousselle MA, Nelson ML, Hassenboehler CB, Legendre DC (1976) Liquid-ammonia and caustic mercerization of cotton fibers: changes in fine structure and mechanical properties. Text Res J 46:304–310. doi:10.1177/004051757604600412
Sawada D, Nishiyama Y, Langan P et al (2012) Water in crystalline fibers of dihydrate β-chitin results in unexpected absence of intramolecular hydrogen bonding. PLoS ONE 7:e39376. doi:10.1371/journal.pone.0039376
Sugiyama J, Harada H, Saiki H (1987) Crystalline morphology of Valonia macrophysa cellulose IIII revealed by direct lattice imaging. Int J Biol Macromol 9:122–130. doi:10.1016/0141-8130(87)90039-0
Sugiyama J, Persson J, Chanzy H (1991a) Combined infrared and electron diffraction study of the polymorphism of native celluloses. Macromolecules 24:2461–2466. doi:10.1021/ma00009a050
Sugiyama J, Vuong R, Chanzy H (1991b) Electron diffraction study on the two crystalline phases occurring in native cellulose from an algal cell wall. Macromolecules 24:4168–4175. doi:10.1021/ma00014a033
Teymouri F, Laureano-Perez L, Alizadeh H, Dale BE (2005) Optimization of the ammonia fiber explosion (AFEX) treatment parameters for enzymatic hydrolysis of corn stover. Bioresour Technol 96:2014–2018. doi:10.1016/j.biortech.2005.01.016
Wada M (2001) In situ observation of the crystalline transformation from cellulose IIII to Iβ. Macromolecules 34:3271–3275. doi:10.1021/ma0013354
Wada M, Okano T, Sugiyama J (1997) Synchrotron-radiated X-ray and neutron diffraction study of native cellulose. Cellulose 4:221–232
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. doi:10.1021/ma0485585
Wada M, Nishiyama Y, Langan P (2006) X-ray structure of ammonia − cellulose I: new insights into the conversion of cellulose i to cellulose IIII. Macromolecules 39:2947–2952. doi:10.1021/ma060228s
Wada M, Nishiyama Y, Bellesia G et al (2011) Neutron crystallographic and molecular dynamics studies of the structure of ammonia-cellulose I: rearrangement of hydrogen bonding during the treatment of cellulose with ammonia. Cellulose 18:191–206
Yamamoto H, Horii F (1993) CPMAS carbon-13 NMR analysis of the crystal transformation induced for Valonia cellulose by annealing at high temperatures. Macromolecules 26:1313–1317. doi:10.1021/ma00058a020
Yoshiharu N, Shigenori K, Masahisa W, Takeshi O (1997) Cellulose microcrystal film of high uniaxial orientation. Macromolecules 30:6395–6397. doi:10.1021/ma970503y
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This work was funded by the Genomic Science Program of the Office of Biological and Environmental Research, US Department of Energy, under FWP ERKP752.
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Sawada, D., Hanson, L., Wada, M. et al. The initial structure of cellulose during ammonia pretreatment. Cellulose 21, 1117–1126 (2014). https://doi.org/10.1007/s10570-014-0218-2
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DOI: https://doi.org/10.1007/s10570-014-0218-2