In this work, bio-based products composed of blends of a star-shaped poly(d,l-lactide) (star-PDLLA) and a conventional linear poly(l-lactide) (linear-PLLA) are produced by typical large-scale manufacturing techniques for thermoplastic blends. In the first case, the two polymers are blended through melt extrusion, producing pellets that are subsequently compression-molded into the final bio-based polymer films. Alternatively, the star/linear poly(lactide) (PLA) materials are developed by direct blending through injection molding, a process that generally applies after a preblending extrusion step to ensure proper mixing. Thermomechanical degradation induced by the different processes is evaluated, and the performances of the final star/linear PLA products are thoroughly compared. The effect of the short-branched, amorphous, star polymeric component on thermal, mechanical, and rheological properties of the conventional PLLA is comprehensively investigated, revealing that the star-PDLLA incorporation promotes the formation of a more flexible and tougher material with reduced capability of crystallization. Most importantly, star-PDLLA decreases the melt viscosity of the final material, while increasing the shear-thinning behavior, hence facilitating melt flow during manufacturing. Such properties lead to enhanced material ductility and processability, with respect to typically brittle and viscous conventional PLLA-based materials. Moreover, the tuning of final material performances can be achieved by simply varying the star-PDLLA content.

We describe how the organocatalytic, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)-based lactide ring-opening polymerization can be effectively performed in a very polar solvent, N-methylpyrrolidone (NMP). Due to a low ceiling temperature, this "living" mechanism has been unreported to date, but we here demonstrate that through a combination of low temperature and repeated monomer additions (starve-fed process), this mechanism enables the generation of a plethora of multifunctional homo- and (stereo)block-poly(lactide)s (PLAs) with exquisite control of the molecular weight dispersity (typically Đ < 1.1) and topology (from linear through 4-, 6-, or 8-armed stars and up to ∼140 armed combs). They are scarcely obtainable or inaccessible through more classical synthetic methods due to the poor solubility of multifunctional initiators (polyols) in most organic solvents and monomer melts. In these precisely designed structures, branching significantly altered the nature of the materials' hydrolytic degradation, allowing them to acquire a pronounced surface character (as opposed to the bulk degradation of linear polymers). Finally, we have assessed the amenability of this method to in situ block copolymerization by using the tacticity of PLLA blocks in PLLA-b-PDLLA versus PDLLA-b-PLLA (L-LA polymerized before or after DL-LA) as a sensitive method to detect (stereochemical) defects.

Polyvinylpyrrolidone (commonly known as povidone or PVP) rapidly dissolves in water. This significantly hinders its use in sustained release formulations developed for the biomedical field. Electrospun fibers of PVP dissolve even faster due to larger surface to volume ratio. In this work, we propose a way to circumvent this problem by developing and using functional fibrous materials in hydrogel form. In particular, we demonstrate that ethanolic solutions of PVP containing two hydroxycinnamic acid derivatives, namely p-coumaric and ferulic acids could be electrospun into functional hydrogel fiber mats. After electrospinning, the formed composite mats were first thermally treated at 130 degrees C for 20 h and subsequently were immersed in aqueous media, where they turned into hydrogels. Thermal annealing did not degrade hydroxycinnamic acid derivatives, preserving their functionality. We propose these hydrogel fiber mats as potential wound dressings and to that end, in vitro tests showed up to 8 days of antioxidants' release, and consequent protection of A549 epithelial cells against oxidative stresses. Biocompatibility tests using human red blood cells, A549 and HaCaT cell lines indicated no adverse effects. Model studies of mice skin burns induced by UV-B radiation showed that the hydrogel fiber dressings significantly reduced the levels of matrix metallopeptidase, (MMP-9), and glutathione peroxidase 1 (GPX-1), which are usually upregulated by reactive oxidative species on burnt skin. Finally, ex-vivo human skin investigations demonstrated skin regeneration and control of the inflammatory phase as indicated by low levels of pro-inflammatory cytokines (IL-6 and IL-8). Therefore, our outcomes indicate that the developed PVP-based fiber hydrogels, produced using a simple protocol, are promising candidates for active wound dressings.

All-PLA blends have been fabricated by an easily scalable and green melt-blending of linear-PLLA and 3-armed star-shaped PDLLA at different proportions (100:0, 95:5, 90:10, 80:20, and 50:50, w:w). The fabrication process, carried out in a hot-press, consisted of three steps: an initial heating of the thoroughly blended polymer mixtures at 170 degrees C for 5 min, a second heating at 170 degrees C for 5 min with a pressure of 200 Pa, and a final cooling at room temperature during 20 min keeping the same pressure. This methodology resulted in very homogenous amorphous samples, as revealed by XRD and DSC. The incorporation of star-PDLLA toughened the polylactide matrix by a clear ductilization, opening opportunities for the expanded use of the developed blends in different applications, due to their increased processability. DSC analysis revealed indeed that by increasing star-PDLLA content it is possible to gradually reduce the T-g, as well as the capability of crystallization of the linear-PLLA component. Such properties determine a plasticizing effect on the final blends. The increased content of the star component turned the films from transparent to translucent and decreases the thermal decomposition temperatures, which remain in any case very well above room temperature. The water vapor transmission rates varied with the star-PDLLA content between values characteristic for isolating to breathable films, thus allowing the use of these blends in different applications such as food packaging and biomedical devices. Finally, no important changes of water contact angle and water uptake were observed between the different blends. Despite the negligible effect of seawater on the biodegradation of commercial PLA, star-PDLLA-containing blends showed high biodegradation rates at short-times in marine environments, reinforcing the environmentally friendly character of polylactide.