The successive extraction and re-adsorption of a linear β-(1 → 4) xylan extracted from microfibrillated birch pulp was investigated using solid-state CP/MAS 13C NMR spectroscopy, specific surface area measurements, and atomistic molecular dynamics (MD) simulations. The NMR spectra confirmed that when in contact with cellulose after re-adsorption, the xylan molecules altered their conformation from the classical left-handed threefold structure found in the bulk to a different one, presumably a cellulose-like twofold system for quantities up to the equivalent amount of extracted xylan. Combining these observations with specific surface area measurements and the surface occupied by a xylosyl residue, it was possible to show that the re-adsorbed xylan in the modified conformation occurred only within the first adsorbed layer in direct interaction with the cellulose surface. It is only when an excess xylan was added and after full cellulose surface coverage, that the subsequent deposited layers took the classical threefold organization. Following the variation of xylan conformation in terms of sequential xylan addition allowed quantifying the surface of cellulose accessible for a tight adsorption of xylan, not only for microfibrillated birch cellulose, but for other samples as well. The MD simulations confirmed that xylan in threefold conformation had a weaker affinity for the cellulose surface than its twofold counterpart, thus supporting the hypothesis of the twofold conformation for xylan at the cellulose surface. The MD simulations also showed that in contact with cellulose, the adsorbed xylan was mainly organized as an extended molecular chain aligned parallel to the cellulose chain direction.
Cellulose – Springer Journals
Published: Jul 14, 2017
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