RESUMEN
Cinnamaldehyde is a natural product with antibacterial, antifungal, and anti-inflammatory properties, poorly stable in environmental conditions. Systems for the controlled release of cinnamaldehyde are of great interest to the food and pharmaceutical industries. Here, a new oxide-based construct for the release of cinnamaldehyde catalyzed by acidic pH was obtained by a facile grafting method based on amino-silane linkers and imine chemistry. The grafting procedure led to a loading of ca. 5 molecules/nm2, determined on oxide powders with CHN and TGA measurements. The covalent grafting of cinnamaldehyde, demonstrated by FTIR analyses, preserved the molecule stability, simplifying storage. Release tests were performed at different pH values (between 5.0 and 7.4). Thanks to imine chemistry, a fast cinnamaldehyde (CIN) release was observed in a pH 5.0 environment. Using 1 mg/mL suspensions, CIN concentrations within the range adopted in the food industry were obtained (12.4 ppm). The grafting procedure was also performed on a porous film based on a photocatalytic oxide, demonstrating the versatility of this method, adaptable to both powders and macroscopic materials. By taking advantage of the photoactivity of the oxide, regeneration of the fouled film was achieved upon UV irradiation for 1 h, opening the door to reusable devices for the controlled release of cinnamaldehyde.
RESUMEN
Polyamide 6 (PA6) suffers from fast degradation in humid conditions due to hydrolysis of amide bonds, which limits its durability. The addition of nanotubular fillers represents a viable strategy for overcoming this issue, although the additive/polymer interface at high filler content can become privileged site for moisture accumulation. As a cost-effective and versatile material, halloysite nanotubes (HNT) were investigated to prepare PA6 nanocomposites with very low loadings (1-45% w/w). The roles of the physicochemical properties of two differently sourced HNT, of filler functionalization with (3-aminopropyl)triethoxysilane and of dispersion techniques (in situ polymerization vs. melt blending) were investigated. The aspect ratio (5 vs. 15) and surface charge (-31 vs. -59 mV) of the two HNT proved crucial in determining their distribution within the polymer matrix. In situ polymerization of functionalized HNT leads to enclosed and well-penetrated filler within the polymer matrix. PA6 nanocomposites crystal growth and nucleation type were studied according to Avrami theory, as well as the formation of different crystalline structures (α and γ forms). After 1680 h of ageing, functionalized HNT reduced the diffusion of water into polymer, lowering water uptake after 600 h up to 90%, increasing the materials durability also regarding molecular weights and rheological behavior.
