In this study, thin, polymeric films consisting of poly(vinyl alcohol) (PVA) and chitosan (Ch) with the addition of poly(hexamethylene guanidine) (PHMG) were successfully prepared. The obtained materials were analyzed to determine their physicochemical and biocidal properties. In order to confirm the structure of PHMG, nuclear magnetic resonance spectroscopy (1H NMR) was applied, while in the case of the obtained films, attenuated total reflectance infrared spectroscopy with Fourier transform (FTIR-ATR) was used. The surface morphology of the polymer films was evaluated based on atomic force microscopy. Furthermore, the mechanical properties, color changes, and thermal stability of the obtained materials were determined. Microbiological tests were performed to evaluate the biocidal properties of the new materials with and without the addition of PHMG. These analyses confirmed the biocidal potential of films modified by PHMG and allowed for comparisons of their physicochemical properties with the properties of native films. In summary, films consisting of PVA and PHMG displayed higher antimicrobial potentials against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria in comparison to PVA:Ch-based films with the addition of PHMG.
An experimental protocol of preparation of homogeneous and nanocomposite chitosan (Ch) based membranes supported on polyamide-6 (PA6) films was developed and described in detail. Montmorillonite (MMT) and Cloisite 30B (C30B) nanoclays were used as nanofillers to improve mechanical properties of chitosan films. The surface, mechanical, and transport properties of PA6 supported Ch, Ch/MMT and Ch/C30B membranes were studied and compared with a pristine, non-supported chitosan membrane. Implementation of advanced analytical techniques e.g., SEM reveal the clays nanoparticles are well dispersed in the chitosan matrix. According to AFM images, composite chitosan/nanoclay membranes possess higher roughness compared with unfilled ones. On the other hand, an incorporation of clay particles insignificantly changed the mechanical and thermal properties of the membranes. It was also found that all membranes are hydrophilic and water is preferentially removed from EtOH/H2O and iPrOH/H2O mixtures by pervaporation. Supporting of chitosan and chitosan/nanoclay thin films onto PA6 porous substrate enhanced permeate flux and pervaporation separation index, in comparison to the pristine Ch membrane. Concerning separation factor (β), the highest value equal to 4500 has been found for a chitosan composite membrane containing Cloisite 30B contacting 85/15 wt % iPrOH/H2O mixture. The mentioned membrane was characterized by the normalized flux of 0.5 μm·kg·m−2·h−1. Based on the established data, it was possible to conclude that chitosan membranes are meaningful material in dehydration of azeotropic mixtures. Nevertheless, to boost up the membrane efficiency, the further modification process is required.
Hydrogels based on chitosan are very versatile materials which can be used for tissue engineering as well as in controlled drug delivery systems. One of the methods for obtaining a chitosan-based hydrogel is crosslinking by applying different components. The objective of the present study was to obtain a series of new crosslinked chitosan-based films by means of solvent casting method. Squaric acid—3,4-dihydroxy-3-cyclobutene-1,2-dione—was used as a safe crosslinking agent. The effect of the squaric acid on the structural, mechanical, thermal, and swelling properties of the formed films was determined. It was established that the addition of the squaric acid significantly improved Young’s modulus, tensile strength, and thermal stability of the obtained materials. Moreover, it should be stressed that the samples consisting of chitosan and squaric acid were characterized by a higher swelling than pure chitosan. The detailed characterization proved that squaric acid could be used as a new effective crosslinking agent.