The structure of the complex of cellulose I with ethylenediamine by X-ray crystallography and cross-polarization/magic angle spinning 13C nuclear magnetic resonance

Wada, Masahisa; Heux, Laurent; Nishiyama, Yoshiharu; Langan, Paul

doi:10.1007/s10570-009-9338-5

Cited by 42 publications

(39 citation statements)

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“…The pair of strong 002 and weak 004 reflections indicates the cellulose chains do not have staggering, a structure analogous to cellulose III I , cellulose I-ammonia complex, and cellulose I-ethylenediamine complex (Wada et al 2004(Wada et al , 2009a. By assuming the same densities for hydrazine and cellulose as those of bulk materials, 1.01 g/cm 3 , and comparing to the volume of unit cell of cellulose I b (0.658 nm 3 , Nishiyama et al 2002), this unit cell volume of the complex leads to the number of hydrazine molecules in unit cell as 3.28, i.e.…”

Section: Resultsmentioning

confidence: 99%

Stoichiometry and stability of cellulose-hydrazine complexes

Kimura

Wada

et al. 2011

Cellulose

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Highly crystalline cellulose samples from green algae (cellulose I) and mercerized ramie (cellulose II) were treated with anhydrous hydrazine and the resulting complexes were analyzed by synchrotron X-ray diffraction and thermogravimetry. Cellulose I-hydrazine complex could be fully described by a two-chain monoclinic unit cell, a = 0.879 nm, b = 1.076 nm, c = 1.038 nm, and c = 122.0°, with space group P2 1 . Cellulose II-hydrazine complex prepared from mercerized ramie gave a different two-chain monoclinic unit cell, a = 1.042 nm, b = 1.046 nm, c = 1.038 nm, c = 129.7°, also with space group P2 1 . Though having different crystal structures, the number of hydrazine molecules per glucopyranoside residue was 0.82 for cellulose I-complex and 0.93 for cellulose II-complex, probable stoichiometric value of 1.0. Hydrazine could be extracted from the complexes by organic solvents retaining the crystalline orders, resulting in the allomorphic conversion to cellulose III I and cellulose III II , both having non-staggered chain arrangements. These features are similar to those of celluloseethylenediamine complexes.

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Section: Resultsmentioning

confidence: 99%

Stoichiometry and stability of cellulose-hydrazine complexes

Kimura

Wada

et al. 2011

Cellulose

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“…The conversion of cellulose I to cellulose III I proceeds via metastable intermediates containing guest molecules such as ammonia or ethylenediamine (Wada et al 2004a;Wada et al 2006;Wada et al 2009;Wada et al 2010). The intermediate states have the GT conformation and layer packing similar to cellulose III I , so kinetic effects can favor formation of cellulose III I rather than Fig.…”

Section: Discussionmentioning

confidence: 99%

Conversion of cellulose Iα to Iβ via a high temperature intermediate (I-HT) and other cellulose phase transformations

2011

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The observation that the hydrothermal conversion of cellulose Ia to cellulose Ib is irreversible has been assumed to be due to the relative free energy of these polymorph phases. We propose an alternative explanation: when cooling the high temperature phase, the barrier to forming Ib is much smaller than the barrier to forming Ia, so kinetics favor the formation of Ib. This explanation is consistent with all available experimental data, and is consistent with the general observation of polymer solid-solid phase transformations via metastable intermediate states. While cellulose Ib may be lower in free energy than Ia, this has not been shown experimentally. Phase transformations of other cellulose polymorphs may be subject to similar kinetic effects when converted via metastable intermediate states.

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“…We have been studying molecular aspects of the conversion of cellulose between the various crystal forms associated with ammonia treatment, using a variety of techniques including crystallography, 13 C CP/MAS NMR, FT-IR, differential scanning calorimetry, and theoretical modeling (Langan et al 1996(Langan et al , 1999Langan 2005;Nishiyama et al 2002Nishiyama et al , 2003Nishiyama et al , 2008Nishiyama et al , 2010aWada 2001;Wada et al 2001Wada et al , 2004Wada et al , 2006Wada et al , 2009a. Large cellulose fibers from seaweeds have been adopted as a model system, because they are highly crystalline and therefore provide high-resolution crystallographic and spectroscopic data.…”

Section: Introductionmentioning

confidence: 99%

Neutron crystallographic and molecular dynamics studies of the structure of ammonia-cellulose I: rearrangement of hydrogen bonding during the treatment of cellulose with ammonia

et al. 2011

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The hydrogen bond arrangement in a complex of cellulose with ammonia has been studied using neutron crystallography in combination with molecular dynamics simulations. The O6 atom of the hydroxymethyl group is donor in a highly occupied hydrogen bond to an ammonia molecule. This rotating ammonia molecule is donor in partially occupied and transient hydrogen bonds to the O2, O3 and O6 atoms of the hydroxyl groups of other chains. The hydrogen atom bound to the O3 atom is disordered but it is almost always involved in some type of hydrogen bonding. It is donated in a hydrogen bond most of the time to the O5 atom on the same chain. However, it also rotates away from this O5 atom to be donated to an ammonia molecule part of the time. On the other hand the hydrogen atom bound to the O2 atom is free from hydrogen bonding most of the time. It is donated in a hydrogen bond to the O6 atom on a neighboring chain only with a relatively small probability. These results provide new insights into how hydrogen bonds are Electronic supplementary material The online version of this article (

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The structure of the complex of cellulose I with ethylenediamine by X-ray crystallography and cross-polarization/magic angle spinning 13C nuclear magnetic resonance

Cited by 42 publications

References 44 publications

Stoichiometry and stability of cellulose-hydrazine complexes

Stoichiometry and stability of cellulose-hydrazine complexes

Conversion of cellulose Iα to Iβ via a high temperature intermediate (I-HT) and other cellulose phase transformations

Neutron crystallographic and molecular dynamics studies of the structure of ammonia-cellulose I: rearrangement of hydrogen bonding during the treatment of cellulose with ammonia

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