Search

The oral delivery of macromolecular therapeutics to the intestinal tract requires novel, robust, and controlled formulations. Here, we report on fabrication by molding of composite hydrogel cylinders made of cellulose nanocrystals (CNCs) and chitosan (Cht) and their performance as delivery vehicles. CNCs provide excellent mechanical and chemical stress resistance, whereas Cht allows scaffold degradation by enzyme digestion. The release of a representative medium size protein (bovine serum albumin) dispersed in the hydrogel is slow and shows a sigmoidal profile; meanwhile, the hydrogel scaffold degrades according to a preferred route, that is the cylinder is eroded along the vertical axis. The cup-like, scarcely interconnected porous network, with a gradient of hardness along the cylinder axis, and the compact skin-like layer covering the lateral wall which stayed in contact with the mold during gelification, explain the preferred erosion direction and the long-term protein release. The possible effect of the molding process on hydrogel structure suggests that molding could be a simple and cheap way to favor surface compaction and directional scaffold degradation.

The influence of the physical, rheological, and process parameters on the cellulose nanocrystal (CNC) drops before and after external gelation in a CaCl2 solution was investigated. The dominant role of the CNC’s colloidal suspension properties, such as the viscous force, inertial, and surface tension forces in the fluid dynamics was quantitatively evaluated in the formation of drops and jellified beads. The similarity and difference between the behavior of carbohydrate polymers and rod-like crystallites such as CNC were enlightened. Pump-driven and centrifugally-driven external gelation approaches were followed to obtain CNC hydrogel beads with tunable size and regular shape. A superior morphological control—that is, a more regular shape and smaller dimension of the beads—were obtained by centrifugal force-driven gelation. These results suggest that even by using a simple set-up and a low-speed centrifuge device, the extrusion of a colloidal solution through a small nozzle under a centrifugal field is an efficient approach for the production of CNC hydrogel beads with good reproducibility, control over the bead morphology and size monodispersion.

We have studied the kinetics of gas transport through films made of self-assembled cellulose nanofibrils (CNF) by a time-resolved mass spectroscopy technique. Few micrometers thick films deposited on polylactic acid (PLA) substrates act as impermeable barriers for CO2, O2, and N2 and reduce the 2H2 (deuterium) and He permeation flux by a factor of ∼103 with respect to the uncoated substrate. Penetrant transport is controlled by the solution-diffusion mechanism and the coating acts as a diffusive barrier. 2H2 and He diffusivity values are in the 10–10 and 10–9 cm2 s–1 range, respectively, and their migration occurs by thermally activated process with 39 ± 1 and 33 ± 2 kJ mol–1 activation energy. Positron annihilation lifetime spectroscopy analysis indicates that the diffusive path between the packed nanofibrils consists of elongated cavities with cross-sectional size ∼ 0.31 nm. Results evidence that the selective transport of the small size penetrants is due to sieving effects and that small penetrant tran...

Sol-gel transition of carboxylated cellulose nanocrystals has been investigated using rheology, SAXS, NMR and optical spectroscopies to unveil the distinctive roles of ultrasound treatments and addition of various cations. Besides cellulose fiber fragmentation, sonication treatment induces fast gelling of the solution. The gelation is independent of the addition of cations, while the final rheological properties are highly influenced by the type, concentration and sequence of the operations since the cations must be added prior to sonication to produce stiff gels. The gel elastic modulus was found to increase proportionally to the ionic charge rather than the cationic size. In cases where ions were added after sonication, SAXS analysis of the Na+ hydrogel and Ca2+ hydrogel indicated the presence of structurally ordered domains in which water is confined, and 1H-NMR investigation showed the dynamics of water exchange within the hydrogels. Conversely, separated phases containing essentially free water were characteristic of the hydrogels obtained by sonication after Ca2+ addition, confirming that this ion induces irreversible fiber aggregation. The rheological properties of the hydrogels depend on the duration of the ultrasound treatments, enabling the design of programmed materials with tailored energy dissipation response.

The design of materials capable of mechanical responses to physical and chemical stimuli represents one of the most exciting and challenging areas of scientific research because of the huge number of their potential applications. This article is focused on the molecular events occurring in thin films of carboxylated nanocellulose fibers, which are capable of converting water gradients into mechanical movements at the macroscopic scale. The analysis of the mechano-actuation, and of the conditions to obtain it, shows that the film movement is fast and reproducible, the gradient intensity is transduced into rate of displacement, and the response is observed at vapor pressures as low as 1.2 mm Hg. The actuation mechanism is associated to an efficient and reversible water sorption process by the hydrophilic nanocellulose fibers at the film interface. Conversely, water desorption is slow and follows a kinetic behavior supporting the presence of two binding sites for water molecules. The adsorbed water induces swelling of the surface nanocellulose layers and local structural rearrangement, however transitions between ordered and random coil conformations are not observed. The understanding of the actuation mechanisms of nanocellulose offers exciting opportunities to design macroscopic structures responding to chemical gradients by the assembly of simple molecular components.