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Density functional theory (DFT) calculations have been carried out for cellobiose and xylan chosen as models for cellulose and hemicellulose, respectively, in gas phase, implicit and explicit solvent (water, methanol, and the ionic liquid, 1,3-dimethylimidazolium acetate) media using plane wave and atom centered basis set approaches in order to find out lowest energy conformers and configurations. Geometry, vibrational properties, and (1)H and (13)C NMR chemical shift values have been discussed under all three conditions. Calculations predict that inter- and intramolecular hydrogen bonding play an important role in the dissolution processes. In the gas phase and in implicit solvent, the anti-anti conformer of cellobiose and the anti-syn conformer of xylan are the most stable due to the formation of a large number of intramolecular hydrogen bonds. However, in the cluster calculations containing ion pairs of the ionic liquid (IL) surrounding the cellulosic units, the anti-syn conformer of cellobiose is more stable as intramolecular hydrogen bonds are substituted by intermolecular ones formed with the ions of the IL. The complexes of cellobiose (or of xylan) with the ions of the ionic liquid are stable with large negative binding energies ranging between -21 and -55 kcal mol(-1). The predicted (1)H NMR values of the lowest energy cellobiose conformers are in good agreement with the experimental value. Xylan binds stronger with the IL than cellobiose does by 20 kcal mol(-1). Furthermore, the two pentose rings in xylan are rotated by 60° to each other in contrast to their coplanarity in cellobiose, which can explain the higher solubility and the amorphous nature of hemicellulose in ionic liquids. The fewer number of hydroxyl groups in xylan (relative to cellobiose) does not affect the number of cations present in its first solvation shell while the number of anions is reduced.

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