Role of Inorganic Fillers on the Physical Aging and Toughness Loss of PLLA/BaSO4 Composites.

The addition of inorganic fillers has been reported to increase the toughness of poly(l-lactide) (PLLA), but the effect of physical aging in such composites has been neglected. The present work discusses the effect of the still ongoing segmental relaxation in PLLA-based composites filled with BaSO4 inorganic particles in regard of the filler quantity. By means of differential scanning calorimetry, X-ray diffraction, and tensile testing of progressively aged PLLA filled with particles ranging from 0.5-10 wt %, we observed an increase in the mechanical energy required to activate the plastic flow of the primary structure in the PLLA matrix, which resulted in the embrittlement of the majority of composites upon enough aging. Results further clarify the role of debonding in the activation process of PLLA, and the behavior of the composite is described at the segmental level. Only an addition of 10% of particles has effectively preserved a ductile behavior of the samples beyond 150 aging days; therefore, we strongly remark the significance of studying the effect of physical aging in such composites.

Lactide and Ethylene Brassylate-Based Thermoplastic Elastomers and Their Nanocomposites with Carbon Nanotubes: Synthesis, Mechanical Properties and Interaction with Astrocytes.

Polylactide (PLA) is among the most commonly used polymers for biomedical applications thanks to its biodegradability and cytocompatibility. However, its inherent stiffness and brittleness are clearly inappropriate for the regeneration of soft tissues (e.g., neural tissue), which demands biomaterials with soft and elastomeric behavior capable of resembling the mechanical properties of the native tissue. In this work, both L- and D,L-lactide were copolymerized with ethylene brassylate, a macrolactone that represents a promising alternative to previously studied comonomers (e.g., caprolactone) due to its natural origin. The resulting copolymers showed an elastomeric behavior characterized by relatively low Young's modulus, high elongation at break and high strain recovery capacity. The thermoplastic nature of the resulting copolymers allows the incorporation of nanofillers (i.e., carbon nanotubes) that further enable the modulation of their mechanical properties. Additionally, nanostructured scaffolds were easily fabricated through a thermo-pressing process with the aid of a commercially available silicon stamp, providing geometrical cues for the adhesion and elongation of cells representative of the nervous system (i.e., astrocytes). Accordingly, the lactide and ethylene brassylate-based copolymers synthesized herein represent an interesting formulation for the development of polymeric scaffolds intended to be used in the regeneration of soft tissues, thanks to their adjustable mechanical properties, thermoplastic nature and observed cytocompatibility.

Benefits of Polydopamine as Particle/Matrix Interface in Polylactide/PD-BaSO4 Scaffolds.

This work reports the versatility of polydopamine (PD) when applied as a particle coating in a composite of polylactide (PLA). Polydopamine was observed to increase the particle-matrix interface strength and facilitate the adsorption of drugs to the material surface. Here, barium sulfate radiopaque particles were functionalized with polydopamine and integrated into a polylactide matrix, leading to the formulation of a biodegradable and X-ray opaque material with enhanced mechanical properties. Polydopamine functionalized barium sulfate particles also facilitated the adsorption and release of the antibiotic levofloxacin. Analysis of the antibacterial capacity of these composites and the metabolic activity and proliferation of human dermal fibroblasts in vitro demonstrated that these materials are non-cytotoxic and can be 3D printed to formulate complex biocompatible materials for bone fixation devices.

Release mechanisms of urinary tract antibiotics when mixed with bioabsorbable polyesters.

In depth knowledge of the thermal properties of drugs is particularly important when they are designed for incorporation into a thermoplastic polymer matrix. In this paper a representative set of Urinary Tract Infection (UTI) antibiotics were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), and then blended via solvent-casting method with poly(D,L-lactide-co-ε-caprolactone). Of these, amoxicillin, cefdinir, levofloxacin and norfloxacin showed a co-continuous morphology with the polyester, whereas blends with ciprofloxacin, nitrofurantoin and tobramycin resulted in two immiscible phases. E. coli susceptibility results showed that the activity of these antibiotics was not affected by the interactions with the polymer matrix. The presence of the drug did not change the hydrolytic degradation kinetics of this fully amorphous polyester (KMw of ~0.050 days-1). However, the release profiles from the long-term studies (105 days) with a 10 or 30% of antibiotic-loaded films were quite different. While water was able to penetrate the polymer matrix and elute the entire levofloxacin content in the first 8 h, the burst release of cefdinir reached a value under 75%. A more interesting profile was obtained with nitrofurantoin, suggesting that a lengthy treatment is achievable. <30% of the drug was burst released, ~55% eluted by diffusion up to day 42 and the rest driven by the weight loss of the bioabsorbable polyester.

Catechol End-Functionalized Polylactide by Organocatalyzed Ring-Opening Polymerization.

There is a great interest in incorporating catechol moieties into polymers in a controlled manner due to their interesting properties, such as the promotion of adhesion, redox activity or bioactivity. One possibility is to incorporate the catechol as end-group in a polymer chain using a functional initiator by means of controlled polymerization strategies. Nevertheless, the instability of catechol moieties under oxygen and basic pH requires tedious protection and deprotection steps to perform the polymerization in a controlled fashion. In the present work, we explore the organocatalyzed synthesis of catechol end-functional, semi-telechelic polylactide (PLLA) using non-protected dopamine, catechol molecule containing a primary amine, as initiator. NMR and SEC-IR results showed that in the presence of a weak organic base such as triethylamine, the ring-opening polymerization (ROP) of lactide takes place in a controlled manner without need of protecting the cathechol units. To further confirm the end-group fidelity the catechol containing PLLA was characterized by Cyclic Voltammetry and MALDI-TOF confirming the absence of side reaction during the polymerization. In order to exploit the potential of catechol moieties, catechol end-group of PLLA was oxidized to quinone and further reacted with aliphatic amines. In addition, we also confirmed the ability of catechol functionalized PLLA to reduce metal ions to metal nanoparticles to obtain well distributed silver nanoparticles. It is expected that this new route of preparing catechol-PLLA polymers without protection will increase the accessibility of catechol containing biodegradable polymers by ROP.