Aldehyde-conjugated chitosan-graphene oxide glucodynamers: Ternary cooperative assembly and controlled chemical release.

Simultaneous condensation of aromatic aldehydes (ArxCHO; x = 1-4) on chitosan biopolymer (CS) affords, after water-evaporation, structurally-conjugated aryl-functionalized CS-Arx-f films. Similarly, cooperative assembly of two-dimensional nanometric graphene oxide (GO), aromatic aldehyde and chitosan provides transparent, flexible and crack-free aldehyde-functionalized, ternary-reinforced CS-Arx-GO-f nanocomposite films. Homogenous films were obtained using ortho-hydroxybenzaldehyde Ar1 while the para-hydroxybenzaldehyde Ar4 was prone to packing inside. Textural and mechanical properties were investigated and expectedly, significant improvement was found for CS-Ar1-GO-f because of the great dispersion of the aromatic and the presence of the filler. The sensitivity of unsaturated CN imine bond to hydrolysis was explored for triggering controlled release of aromatics from the as-prepared films. All of them were found to induce a time-dependent aromatic release. It has been moreover observed that the release was significantly delayed in CS-Arx-GO-f compared to CS-Arx-f, a fact attributed to the interplay of the ring with the basal and edges of graphene oxide, through π-π stacking and additional hydrogen bonding interactions. This finding shows that beyond the conventional wisdom using fillers for improving thermal and mechanical properties, the tiny carbon sheets can act as a regulator for aldehyde release, thereby providing a way for more controlled chemical delivery from confined nanocomposites.

Aldehyde-functionalized chitosan-montmorillonite films as dynamically-assembled, switchable-chemical release bioplastics.

Temporal release of synergistic and/or complementary chemicals (e.g.: drugs) is recognized as extremely challenging because of their frequently intertwined kinetic delivery and presently, straightforward concepts enabling to circumvent this bottleneck are missing in the open literature. In this framework, we report herein on aldehyde-functionalized, transparent and flexible chitosan-montmorillonite hybrid films that act as a new generation of eco-friendly, controlled-chemical release bioplastics. These dynamically-assembled nanomaterials are designed by a ternary assembly from biowaste derived chitin biopolymer, aromatic aldehydes and layered clay nanoparticles. On the basis of their geometrical and conformational properties, the oxygenated groups on the grafted aromatics interact preferentially with either the base Schiff belonging to the carbohydrate (via intramolecular CNHO-Ar known as "imine clip") or with the hydroxyl groups belonging to the clay surface (via intermolecular Si-OHO-Ar). The exfoliated clay nanoparticles within the carbohydrate polymer enables either accelerating or slowing down of the imine (CN) hydrolysis depending on the interaction of the conjugated aromatics. This provides the driving force for fine tuning host-guest interactions at the molecular level and constitutes an entry toward subtle discrimination of different chemicals (e.g. complementary fertilizers, synergistic drugs) during their sequential release.

Chitosan-graphene oxide films and CO2-dried porous aerogel microspheres: Interfacial interplay and stability.

The intimate interplay of chitosan (CS) and graphene oxide (GO) in aqueous acidic solution has been explored to design upon casting, nanostructured "brick-and-mortar" films (CS-GO-f) and by acidic-to-basic pH inversion, porous CO2-dried aerogel microspheres (CS-GO-m). Owing to the presence of oxygenated functional groups in GO, good-quality crack-free hybrid films were obtained. Mechanical properties were improved independently of the GO content and it was found that a 20wt% loading affords hybrid film characterized with a Young modulus three times superior to that reached with the same loading of layered clay. The presence of graphene oxide was found to be detrimental for the thermal stability of the polysaccharide at T <350°C, a fact attributed to the well-established decomposition of the oxygenated functional groups of the graphene sheets. Irrespective to the graphene oxide loading, chitosan-graphene oxide mixture preserves the gelation memory of the polysaccharide. Supercritical drying of the resulting soft hydrogels provides macroporous network with surface areas ranging from 226m2g-1 to 554m2g-1. XPS and RAMAN analyses evidenced the selective reduction of GO sheets inside of these microspheres, affording the hitherto unknown macroporous chitosan-entangled-reduced graphene oxide (CS-rGO-m) aerogels. Improvement in both hydrothermal stability (under water reflux) and chemical stability (under acidic conditions) have been noticed for chitosan-graphene oxide microspheres with respect to non-modified chitosan and chitosan-clay bio-hybrids, a result rooted in the substantial hydrophobic character imparted by the addition of graphenic material to the polysaccharide skeleton. In essence, this contribution demonstrates that graphene oxide loading do not disturb neither the filmogenicity of chitosan nor its gelation ability and constitutes a promising route for novel chitosan-based functional hybrid materials.

Insightful understanding of the role of clay topology on the stability of biomimetic hybrid chitosan-clay thin films and CO2-dried porous aerogel microspheres.

Three natural clay-based microstructures, namely layered montmorillonite (MMT), nanotubular halloysite (HNT) and micro-fibrillar sepiolite (SP) were used for the synthesis of hybrid chitosan-clay thin films and porous aerogel microspheres. At a first glance, a decrease in the viscosity of the three gel-forming solutions was noticed as a result of breaking the mutual polymeric chains interaction by the clay microstructure. Upon casting, chitosan-clay films displayed enhanced hydrophilicity in the order CS