Cellulose-based BioNanoMaterials:Structure and Properties

Biological materials such as wood show outstanding properties due to the self assembly of components from molecular to macroscopic size. An emerging nanotechnology-based strategy consists of the isolation of biological components with size in the range from nanometers to micrometers and of the design of human-driven assembly processes to obtain multifunctional materials. The aim of this thesis was to isolate cellulose nanocrystals, with dimensions of around 4-5 nm in width and some hundred nanometers in length, and investigate their assembly processes through weak interactions among them and with small molecules, like water or ions. Knowing their interaction properties and self-assembly is indeed fundamental in order to fully exploit the potential of nanocellulose in its recently emerging applications. In particular, I focused on cellulose nanocrystals supramolecular self-organization both in absence and presence of water, studying cellulose nanocrystals-based films and hydrogels. In dry conditions, the self-assembly of cellulose nanocrystals on a polylactic support was demonstrated to form few micrometers thick films, characterized by a densely packed arrangement of the crystals leaving elongated cavities of about 0.31 nm cross section between them. These cavities provide the pathway for gaseous 2H2 diffusion. Conversely, these films are impermeable barriers for the transport of gaseous molecules such as O2 and CO2. In aqueous solution, instead, cellulose nanocrystals undergo sonication- or cation-assisted entanglement, forming soft hydrogels. Na+, Ca2+ and Al3+ crosslink the nanocrystals and produce stable hydrogels with structurally ordered domains in which water is confined. Since the gelation process is diffusion controlled, small hydrogel objects with different size and shape have been designed by the coordination-driven assembly of supramolecular rod-like cellulose crystallites, using ionotropic gelation as a methodological approach and Ca2+ as a gelling agent. In parallel to material characterization, particular attention was devoted to the possible exploitation of cellulose nanocrystals-based materials in the biomedical field. In this regard, toxicity studies were performed both on the individual nanocrystals and on the films and hydrogels resulting from their assembly. Moreover, a hybrid cellulose-nanocrystals/chitosan material was developed and characterized, which shows some potential to be used as therapeutic delivery system in the gastrointestinal tract. Indeed, though a mould assisted gelation process, composite hydrogels can be produced, which are degraded by human digestive enzymes and release a model protein according to a biphasic kinetic profile.