Stable chitosan/PVA-based hydrogels were obtained by combining covalent and physical cross-linking methods. As covalent cross-linkers, epoxy agents with different chain lengths were used, while freeze–thaw cycles were applied for additional physical cross-linking. The chemical structure of the hydrogel was examined by FTIR spectroscopy whereas the morphology was analyzed by SEM, showing well-defined pores with dimensions of around 50 μm in diameter. It was proved that gel fraction and the network morphology were deeply influenced by the synthesis conditions. Chitosan/PVA hydrogel showed a relative high swelling rate, reaching equilibrium in the first hour. The values obtained for the elastic modulus were relatively low (3–30 kPa); as a result, these hydrogels are soft and very flexible, and are ideal candidates for medical applications as wound or oral dressings. In addition, the natural antimicrobial activity of chitosan was enhanced by in situ generation of silver nanoparticles (AgNPs) under UV irradiation. The total amount of Ag from hydrogel was determined by elemental analyses and its crystalline state was confirmed by XRD. The CS/PVA hydrogels entrapped with AgNPs exhibited high inhibitory activity against S. aureus and K. pneumonia. The vitality tests confirmed the lack of cytotoxicity of CS/PVA hydrogels without and with AgNPs.

The therapeutic efficiency of plant extracts has been limited by their poor pharmaceutical availability. Hydrogels have promising potential to be applied as wound dressings due to their high capacity to absorb exudates and their enhanced performance in loading and releasing plant extracts. In this work, pullulan/poly (vinyl alcohol) (P/PVA) hydrogels were first prepared using an eco-friendly method based on both a covalent and physical cross-linking approach. Then, the hydrogels were loaded with the hydroalcoholic extract of Calendula officinalis by a simple post-loading immersion method. Different loading capacities were investigated in terms of the physico-chemical properties, chemical composition, mechanical properties, and water absorption. The hydrogels exhibited high loading efficiency due to the hydrogen bonding interactions between polymer and extract. The water retention capacity as well as the mechanical properties decreased with the increase in the extract amount in hydrogel. However, higher amounts of extract in the hydrogel improved the bioadhesiveness. The release of extract from hydrogels was controlled by the Fickian diffusion mechanism. Extract-loaded hydrogels expressed high antioxidant activity, reaching 70% DPPH radical scavenging after 15 min immersion in buffer solution at pH 5.5. Additionally, loaded hydrogels showed a high antibacterial activity against Gram-positive and Gram-negative bacteria and were non-cytotoxic against HDFa cells.