The structure of the complex of cellulose I with ethylenediamine by X-ray crystallography and cross-polarization/magic angle spinning 13C nuclear magnetic resonance
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X-ray crystallographic and cross-polarization/magic angle spinning 13C nuclear magnetic resonance techniques have been used to study an ethylenediamine (EDA)-cellulose I complex, a transient structure in the cellulose I to cellulose IIII conversion. The crystal structure (space group P21; a = 4.546 Å, b = 11.330 Å, c = 10.368 Å and γ = 94.017°) corresponds to a one-chain unit cell with one glucosyl residue in the asymmetric unit, a gt conformation for the hydroxymethyl group, and one EDA molecule per glucosyl residue. Unusually, there are no O–H···O hydrogen bonds between the cellulose chains; the chains are arranged in hydrophobic stacks, stabilized by hydrogen bonds to the amine groups of bridging EDA molecules. This new structure is an example of a complex in which the cellulose chains are isolated from each other, and provides a number of insights into the structural pathway followed during the conversion of cellulose I to cellulose IIII through EDA treatment.
KeywordsX-ray crystallography NMR Cellulose Ethylenediamine
We thank beam line BL38B1 at the SPring-8, Japan, for use of facilities. MW was supported by a Grant-in-Aid for Scientific Research (18780131). This study was partly funded by the French Agence Nationale de la Recherche. PL was supported in part by the Office of Biological and Environmental Research of the Department of Energy, a grant from the National Institute of Medical Sciences of the National Institutes of Health (1R01GM071939-01), and a Laboratory Directed Research and Development grant from Los Alamos National Laboratory (20080001DR).
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