The healing of chronic wounds requires intensive medical intervention at huge healthcare costs. Dressing materials should consider the multifactorial nature of these wounds comprising deleterious proteolytic and oxidative enzymes and high bacterial load. In this work, multifunctional hydrogels for chronic wound application were produced by enzymatic cross-linking of thiolated chitosan and gallic acid. The hydrogels combine several beneficial to wound healing properties, controlling the matrix metalloproteinases (MMPs) and myeloperoxidase (MPO) activities, oxidative stress, and bacterial contamination. In vitro studies revealed above 90% antioxidant activity, and MPO and collagenase inhibition by up to 98 and 23%, respectively. Ex vivo studies with venous leg ulcer exudates confirmed the inhibitory capacity of the dressings against MPO and MMPs. Additionally, the hydrogels reduced the population of the most frequently encountered in nonhealing wounds bacterial strains. The stable at physiological conditions and resistant to lysozyme degradation hydrogels showed high biocompatibility with human skin fibroblasts.

One-step reactive extrusion-calendering process (REX-Calendering) was used in order to obtain sheets of 1mm from two PD,L-LA extrusion grades modified with a styrene-acrylic multifunctional oligomeric agent. In a preliminary internal mixer study, torque versus time was monitored in order to determine chain extender ratios and reaction time. Once all parameters were optimized, reactive extrusion experiments were performed. Independently of the processing method employed, under the same processing conditions, PD,L-LA with the lower D enantiomer molar content revealed a higher reactivity towards the reactive agent, induced by its higher thermal sensitivity. REXCalendering process seemed to minimize the degradations reactions during processing, although a competition between degradation and chain extension/branching reactions took place in both processes. Finally, the rheological characterization revealed a higher degree of modification in the melt rheological behaviour for REX-Calendered samples

In this study the dynamic viscoelastic properties of three structurally modified poly(lactic acid) (PLA) samples processed through reactive extrusion were analyzed. While classical chromatographic and spectroscopic techniques exhibited limited sensitivity to the presence of topological changes, rheological measurements confirmed the presence of non-uniform branched macromolecules, holding sparsely long chain branches. According to the processing conditions used, the flow activation energy and the thermorheologically simple behavior remained roughly unaffected for PLA-REX containing an amount of modified chains up to 24%. Distinctly separated relaxation processes in a broader transition zone were observed in the complex viscosity function (|¿*(¿)|) of all PLA-REX samples. The “extended Carreau-Yassuda” model and an extension of the Havriliak-Negami model, proposed in this work, were used to capture the main characteristics of |¿*(¿)| experimental data. Both fitted models were inverted to molecular weight distribution (MWD) spectrum using the numerical inversion technique of Shaw and Tuminello and these were compared with size exclusion chromatography (SEC) MWDs. It was shown that the resolution of the predicted bimodal MWDs was enhanced when the model used to fit|¿*(¿)| data was exempted from the Cox-Merz rule and included a complex time dependence. Based on the MWDs deduced from solely melt measurements, a procedure was described to quantitatively estimate the amount of modified chains.Peer ReviewedPostprint (author’s final draft