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This study focused on the assembly characteristics of debranched xylan onto cellulose surfaces. A rye arabinoxylan polymer with an initial arabinose/xylose ratio of 0.53 was debranched with an oxalic acid treatment as a function of time. The resulting samples contained reduced arabinose/xylose ratios significantly affecting the molecular architecture and solution behavior of the biopolymer. With this treatment, an almost linear xylan with arabinose DS of only 0.04 was obtained. The removal of arabinose units resulted in the self-assembly of the debranched polymer in water into stable nanoparticle aggregates with a size around 300 nm with a gradual increase in crystallinity of the isolated xylan. Using quartz crystal microbalance with dissipation monitoring, the adsorption of xylan onto model cellulose surfaces was quantified. Compared to the nonmodified xylan, the adsorption of debranched xylan increased from 0.6 to 5.5 mg m(-2). Additionally, adsorption kinetics suggest that the nanoparticles rapidly adsorbed to the cellulose surfaces compared to the arabinoxylan. In summary, a control of the molecular structure of xylan influences its ability to form a new class of polysaccharide nanoparticles in aqueous suspensions and its interaction with nanocellulose surfaces.

Arabinoxylans (AX) from rye were partly debranched by chemical hydrolysis methods, and AXs differing in arabinosyl substitution were acetylated using chemical methods. The resulting materials are film forming, and these films underwent molecular structural analysis and were tested for their material properties. The composition and structure of the modified polymers were determined using high performance anion exchange chromatography and two dimensional nuclear magnetic resonance; it was shown that all free hydroxyl groups (of both xylose and arabinose) were acetylated. Further characterizations were done by dynamic mechanical analysis and thermo‐gravimetric analysis to evaluate the thermal behavior of the material. The observed glass transition temperatures (Tg) increased with a decrease in arabinosyl substitutions. The thermal degradation temperatures were all close to 380°C. The mechanical properties were characterized with tensile tests of the films. Tensile tests showed that the strain at break, which reflects the flexibility of the material, was significantly higher at higher arabinosyl substitution levels. The elastic Young's modulus was not significantly affected, although a tendency was seen toward a less stiff material at higher arabinosyl substitution. The ultimate strength of the materials was remarkably high in all cases, around 60 MPa, with little difference between them. Considering these properties, a great potential is foreseen in the application of acetylated arabinoxylans as packaging films and as matrix for composites. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012