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.

The effect of a quenching treatment applied on heated cast sheet extruded films of two poly(lactic acid) (PLA)\ud commercial grades, with different optical purities, was studied. The thermal and mechanical properties of the films, as well\ud as their fracture behavior, were assessed by differential scanning calorimetry (DSC), tensile tests, and the essential work of\ud fracture (EWF) approach. The heating-quenching treatment causes a de-aging effect with an increase in the free volume of\ud polymer chains evidenced by a decrease in the glass transition temperature (Tg) and a decrease in the tensile stiffness and\ud yield stress. As a result, there is an abrupt increase in ductility, finding a dramatic change in the fracture behavior, from brittle\ud to ductile. The use of digital image correlation (DIC) of the strain field analysis during fracture testing has allowed relating\ud the decrease on the yield stress promoted by quenching with the crack propagation kinetics. The use of the EWF method\ud to characterize the fracture toughness of PLA has allowed to measure this enhancement on toughness, finding that the specific\ud essential work of fracture (we) and the plastic term (!wp) parameters increased 120% and 1200%, respectively, after\ud the quenching process.Peer ReviewedPostprint (published version

PLA bio-blends with a predominantly biosourced PA10.10 in the composition range 10-50 wt% were prepared by melt blending in order to overcome the advanced brittleness of PLA. Due to the inherent immiscibility of the blends, 30 wt% of PA was needed to achieve a brittle-to-ductile transition and a co-continuous morphology was predicted at 58 wt% of PA. The initial enhancement of the PLA rheological behaviour through the environmentally friendly reactive extrusion process yielded a finer and more homogeneous microstructure and hence enhanced the mechanical properties of the bioblends at much lower PA contents. The brittle-to-ductile transition could be achieved with only 10 wt% and co-continuity was observed already at 44 wt% of PA. Results indicate the significant potential of modifying PLA flow behaviour as a promising green manufacturing method toward expanding PLA-based bio-blends applications.

The effect of processing conditions on the final morphology of Poly(Lactic Acid) (PLA) with bio-based Polyamide 10.10 (PA) 70/30 blends is analyzed in this paper. Two types of PLA were used: Commercial (neat PLA) and a rheologically modified PLA (PLA REx ), with higher melt elasticity produced by reactive extrusion. To evaluate the ability of in situ micro-fibrillation (µf) of PA phase during blend compounding by twin-screw extrusion, two processing parameters were varied: (i) Screw speed rotation (rpm); and (ii) take-up velocity, to induce a hot stretching with different Draw Ratios (DR). The potential ability of PA-µf in both bio-blends was evaluated by the viscosity (p) and elasticity (k') ratios determined from the rheological tests of pristine polymers. When PLA REx was used, the requirements for PA-µf was fulfilled in the shear rate range observed at the extrusion die. Scanning electron microscopy (SEM) observations revealed that, unlike neat PLA, PLA REx promoted PA-µf without hot stretching and the aspect ratio increased as DR increased. For neat PLA-based blends, PA-µf was promoted during the hot stretching stage. DMTA analysis revealed that the use of PLA REx PLA REx resulted in a better mechanical performance in the rubbery region (T > Tg PLA-phase ) due to the PA-µf morphology obtained.

Poly(lactic acid) (PLA) and biosourced polyamide (PA) bioblends, with a variable PA weight content of 10–50%, were prepared by melt blending in order to overcome the high brittleness of PLA. During processing, the properties of the melt were stabilized and enhanced by the addition of a styrene-acrylic multi-functional-epoxide oligomeric reactive agent (SAmfE). The general analytical equation (GAE) was used to evaluate the kinetic parameters of the thermal degradation of PLA within bioblends. Various empirical and theoretical solid-state mechanisms were tested to find the best kinetic model. In order to study the effect of PA on the PLA matrix, only the first stage of the thermal degradation was taken into consideration in the kinetic analysis (α < 0.4). On the other hand, standardized conversion functions were evaluated. Given that it is not easy to visualize the best accordance between experimental and theoretical values of standardized conversion functions, an index, based on the integral mean error, was evaluated to quantitatively support our findings relative to the best reaction mechanism. It was demonstrated that the most probable mechanism for the thermal degradation of PLA is the random scission of macromolecular chains. Moreover, y(α) master plots, which are independent of activation energy values, were used to confirm that the selected reaction mechanism was the most adequate. Activation energy values were calculated as a function of PA content. Moreover, the onset thermal stability of PLA was also determined.