Functional and anionic cellulose-interacting polymers by selective chemo-enzymatic carboxylation of galactose-containing polysaccharides.

Carboxylated, anionic polysaccharides were selectively prepared using a combination of enzymatic and chemical reactions. The galactose-containing polysaccharides studied were spruce galactoglucomannan, guar galactomannan, and tamarind galactoxyloglucan. The galactosyl units of the polysaccharides were first oxidized with galactose oxidase (EC 1.1.3.9) and then selectively carboxylated, resulting in the galacturonic acid derivatives with good conversion and yield. The degrees of oxidation (DO) of the products were determined by gas chromatography-mass spectrometry (GC-MS). A novel feasible electrospray ionization-mass spectrometry (ESI-MS) method was also developed for the determination of DO. The solution properties and charge densities of the products were investigated. The interaction of the products with cellulose was studied by two methods, bulk sorption onto bleached birch kraft pulp and adsorption onto nanocellulose ultrathin films by quartz crystal microbalance with dissipation (QCM-D). To study the effect of the location of the carboxylic acid groups on the physicochemical properties, polysaccharides were also oxidized by 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated reaction producing polyuronic acids. The chemo-enzymatically oxidized galacturonic polysaccharides with an unmodified backbone had a better ability to interact with cellulose than the TEMPO-oxidized products. The selectively carboxylated polysaccharides can be further exploited, as such, or in the targeted functionalization of cellulose surfaces.

Mediation of the nanotribological properties of cellulose by chitosan adsorption.

Cellulosic model surfaces functionalized with chitosan, a naturally occurring cationic biomacromolecule, by in situ adsorption have been studied with an atomic force microscope (AFM) in colloidal probe configuration. The interaction forces on approach and separation, as well as the nanotribological properties, were shown to be highly pH-dependent, and a significant difference in the behavior was seen before and after chitosan adsorption. In general, all forces on approach showed a highly repulsive interaction at shorter distances due to deformation of the probe. At high pH, before chitosan adsorption, a long-range electrostatic repulsion was observed, consistent with DLVO theory. However, at low pH no electrostatic contribution was found before adsorption, probably due to charge neutralization of carboxyl groups. After chitosan adsorption, repulsive forces acting over a much longer distance than predicted by DLVO theory were present at low pH. This effect was ascribed to chain extension of the chitosan species of which the magnitude and the range of the force increased dramatically with higher charge at low pH. In all cases, a typical saw-tooth patterned adhesion was present, with pull-off events occurring at different separations. The frequency of these events after chitosan adsorption was greatly increased at longer distances. Additionally, the adsorbed chitosan markedly reduced the friction, where the largest effect was a 7-fold decrease of the friction coefficient observed at low pH.

Comparison of multilayer formation between different cellulose nanofibrils and cationic polymers.

The multilayer formation between polyelectrolytes of opposite charge offers possibility for creating new tailored materials. Exchanging one or both components for charged nanofibrillated cellulose (NFC) further increases the variety of achievable properties. We explored this by introducing unmodified, low charged NFC and high charged TEMPO-oxidized NFC. Systematic evaluation of the effect of both NFC charge and properties of cationic polyelectrolytes on the structure of the multilayers was performed. As the cationic component cationic NFC was compared with two different cationic polyelectrolytes, poly(dimethyldiallylammoniumchloride) and cationic starch. Quartz crystal microbalance with dissipation (QCM-D) was used to monitor the multilayer formation and AFM colloidal probe microscopy (CPM) was further applied to probe surface interactions in order to gain information about fundamental interactions and layer properties. Generally, the results verified the characteristic multilayer formation between NFC of different charge and how the properties of formed multilayers can be tuned. However, the strong nonelectrostatic affinity between cellulosic fibrils was observed. CPM measurements revealed monotonically repulsive forces, which were in good correspondence with the QCM-D observations. Significant increase in adhesive forces was detected between the swollen high charged NFC.

Functionalization of nanofibrillated cellulose with silver nanoclusters: fluorescence and antibacterial activity.

Native cellulose nanofibers are functionalized using luminescent metal nanoclusters to form a novel type of functional nanocellulose/nanocluster composite. Previously, various types of cellulose fibers have been functionalized with large, non-luminescent metal nanoparticles. Here, mechanically strong native cellulose nanofibers, also called nanofibrillatedcellulose (NFC), microfibrillatedcellulose (MFC) ornanocellulose, disintegrated from macroscopic cellulose pulp fibers are used as support for small and fluorescent silver nanoclusters. The functionalization occurs in a supramolecular manner, mediated by poly(methacrylic acid) that protects nanoclusters while it allows hydrogen bonding with cellulose, leading to composites with fluorescence and antibacterial activity.