Comparison of the Recycling Behavior of a Polypropylene Sample Aged in Air and in Marine Water.

During the processing and during their lifetime, polymers are subjected to several environmental stresses-thermomechanical, photo-oxidative, etc.-that can strongly modify their chemical and molecular structure and, consequently, their morphology. Reduction of the molecular weight and formation of double bonds and oxygenated groups are the main changes observed as a consequence of the degradation. As a result of these changes, the macroscopic properties are dramatically modified. These changes can have a relevant effect if the post-consumer plastic manufacts are recycled. In this work, a sample of polypropylene subjected to two different degradation histories-photo-oxidation in air and in marine water-is reprocessed two times in a mini twin-screw extruder in the same processing conditions. The effect of the thermomechanical degradation during the reprocessing is different. Indeed, the less severe degraded sample shows a higher degradation level during reprocessing because the shear stress is larger. This means that the thermomechanical degradation kinetics is larger in the less degraded samples. Nevertheless, the final properties of the recycled polymers are different because the properties of the photo-oxidized samples before reprocessing were very different.

Sustained-Release Powders Based on Polymer Particles for Pulmonary Delivery of Beclomethasone Dipropionate in the Treatment of Lung Inflammation.

Inhaled corticosteroids are the mainstay in the management of lung inflammation associated to chronic lung diseases, such as asthma and chronic obstructive pulmonary disease (COPD). Nonetheless, available inhalation products are mostly short-acting formulations that require frequent administrations and do not always produce the desired anti-inflammatory effects. In this work, the production of inhalable beclomethasone dipropionate (BDP) dry powders based on polymeric particles was attempted. As starting material, the PHEA-g-RhB-g-PLA-g-PEG copolymer was chosen, obtained by grafting 0.6, 2.4 and 3.0 mol%, respectively, of rhodamine (RhB), polylactic acid (PLA) and polyethylene glycol 5000 (PEG) on alpha,beta-poly(N-2-hydroxyethyl)DL-aspartamide (PHEA). The drug was loaded into the polymeric particles (MP) as an inclusion complex (CI) with hydroxypropyl-cyclodextrin (HP-ß-Cyd) (at a stoichiometric ratio of 1:1) or as free form. The spray-drying (SD) process to produce MPs was optimized by keeping the polymer concentration (0.6 wt/vol%) constant in the liquid feed and by varying other parameters such as the drug concentration. The theoretical aerodynamic diameter (daer) values among the MPs are comparable and potentially suitable for inhalation, as confirmed also through evaluation of the experimental mass median aerodynamic diameter (MMADexp). BDP shows a controlled release profile from MPs that is significantly higher (more than tripled) than from Clenil®. In vitro tests on bronchial epithelial cells (16HBE) and adenocarcinomic human alveolar basal epithelial cells (A549) showed that all the MP samples (empty or drug-loaded) were highly biocompatible. None of the systems used induced apoptosis or necrosis. Moreover, the BDP loaded into the particles (BDP-Micro and CI-Micro) was more efficient than free BDP to counteract the effects of cigarette smoke and LPS on release of IL-6 and IL-8.

Influence of Different Environments and Temperatures on the Photo-Oxidation Behaviour of the Polypropylene.

The photo-oxidation of polypropylene at two different temperatures and in three different environments-air, distilled water and sea water-has been followed as a function of the irradiation time. The photo-oxidation kinetic is dramatically dependent on the amount of oxygen available for the oxidation reactions and on the temperature. While the photo-oxidation is very fast in air, the degradation is much slower in the two aqueous media. The degradation in sea water is slightly slower than in distilled water. In all cases, the degradation kinetic increases remarkably with the temperature. This behavior has been attributed to the lower oxygen availability for the oxidation reactions of the polymers. The light difference of the degradation kinetic between the two aqueous media depends on the small difference of the oxygen concentration at the test temperatures of 40 and 70 °C. At the latter temperature, the difference between the degradation kinetic in distilled water and sea water is still less important because increasing the temperature decreases the solubility of the oxygen, and it tends to became very similar in both samples of water.

Flexible mats as promising antimicrobial systems via integration of Thymus capitatus (L.) essential oil into PLA.

Aim: To develop electrospun mats loaded with Thymus capitatus (L.) essential oil (ThymEO) and to study their morpho-mechanical and antimicrobial properties. Materials & methods: Poly(lactic acid) (PLA) mats containing ThymEO were prepared by electrospinning. The effect of ThymEO on the morpho-mechanical properties of fibers was assayed by scanning electron microscopy and dynamometer measurements. The antimicrobial activity of ThymEO delivered either in liquid or vapor phase was assessed through killing curves and invert Petri dishes method. The cytotoxicity was also investigated. Results: The mechanical properties were enhanced by integrating ThymEO into PLA. Both liquid and vapors of ThymEO released from mats caused reductions of microbial viable cells. Negligible cytotoxicity was demonstrated. Conclusion: PLA/ThymEO delivery systems could be suitable for treating microbial infections.

Innovative, ecofriendly biosorbent-biodegrading biofilms for bioremediation of oil- contaminated water.

Immobilization of microorganisms capable of degrading specific contaminants significantly promotes bioremediation processes. In this study, innovative and ecofriendly biosorbent-biodegrading biofilms have been developed in order to remediate oil-contaminated water. This was achieved by immobilizing hydrocarbon-degrading gammaproteobacteria and actinobacteria on biodegradable oil-adsorbing carriers, based on polylactic acid and polycaprolactone electrospun membranes. High capacities for adhesion and proliferation of bacterial cells were observed by scanning electron microscopy. The bioremediation efficiency of the systems, tested on crude oil and quantified by gas chromatography, showed that immobilization increased hydrocarbon biodegradation by up to 23 % compared with free living bacteria. The resulting biosorbent biodegrading biofilms simultaneously adsorbed 100 % of spilled oil and biodegraded more than 66 % over 10 days, with limited environmental dispersion of cells. Biofilm-mediated bioremediation, using eco-friendly supports, is a low-cost, low-impact, versatile tool for bioremediation of aquatic systems.

Incorporation of an antibiotic in poly(lactic acid) and polypropylene by melt processing.

PURPOSE: In this work an antibiotic, ciprofloxacin (CFX), was incorporated into 2 different polymeric matrices, poly(lactic acid) (PLA) and polypropylene (PP), to provide them with antimicrobial properties. The influence of CFX content on release kinetics and on antimicrobial and mechanical properties was evaluated. METHODS: CFX was incorporated into both the polymers by melt mixing. RESULTS: The effect of CFX incorporation was found to strongly depend on which polymer matrix was used. In particular, the antimicrobial tests revealed that PLA samples containing CFX produced no inhibition zone and only a slight antibacterial activity was observed when the highest concentration of CFX was added to PLA. On the contrary, PP-based materials incorporating CFX, even those containing the smallest concentration of antibiotic, showed antimicrobial activity. These results were found to be in good agreement with the evaluation of the CFX release. CONCLUSIONS: The negative findings of PLA-based systems are attributed to degradation phenomena that occur during the melt processing, involving some interaction between PLA and CFX. A proposed reaction mechanism between CFX and PLA occurring in the melt is presented.

3D polylactide-based scaffolds for studying human hepatocarcinoma processes in vitro.

We evaluated the combination of leaching techniques and melt blending of polymers and particles for the preparation of highly interconnected three-dimensional polymeric porous scaffolds for in vitro studies of human hepatocarcinoma processes. More specifically, sodium chloride and poly(ethylene glycol) (PEG) were used as water-soluble porogens to form porous and solvent-free poly(L,D-lactide) (PLA)-based scaffolds. Several characterization techniques, including porosimetry, image analysis and thermogravimetry, were combined to improve the reliability of measurements and mapping of the size, distribution and microarchitecture of pores. We also investigated the effect of processing, in PLA-based blends, on the simultaneous bulk/surface modifications and pore architectures in the scaffolds, and assessed the effects on human hepatocarcinoma viability and cell adhesion. The influence of PEG molecular weight on the scaffold morphology and cell viability and adhesion were also investigated. Morphological studies indicated that it was possible to obtain scaffolds with well-interconnected pores of assorted sizes. The analysis confirmed that SK-Hep1 cells adhered well to the polymeric support and emitted surface protrusions necessary to grow and differentiate three-dimensional systems. PEGs with higher molecular weight showed the best results in terms of cell adhesion and viability.

Incorporation of nisin in poly (ethylene-co-vinyl acetate) films by melt processing: a study on the antimicrobial properties.

Both industry and academia have shown a growing interest in materials with antimicrobial properties suitable for food packaging applications. In this study, we prepared and characterized thin films of ethylene-co-vinyl acetate (EVA) copolymer with antimicrobial properties. The films were prepared with a film blowing process by incorporating a nisin preparation as an antimicrobial agent in the melt. Two grades of EVA containing 14 and 28% (wt/wt) vinyl acetate (EVA 14 and EVA 28, respectively) and two commercial formulations of nisin with different nominal activities were used. The effect of the nisin concentration also was evaluated. The films with the highest antimicrobial activity were those formulated with nisin at the highest activity and EVA with the highest content of vinyl acetate. The use of the commercial formulation of nisin with high activity in the EVA films allowed reduction in the amount of nisin needed to provide antimicrobial properties. Consequently, the mechanical properties of these films were only slightly inferior to those of the pure polymers. In contrast, films prepared by incorporating more of the nisin with lower activity had poor mechanical properties. The effect of different processing temperatures used in the preparation of the films on the antimicrobial properties of the films also was evaluated. The materials displayed antimicrobial properties even when they were prepared at temperatures as high as 160 °C, probably because of the very short processing time (60 to 90 s) required for preparation.

Control of biofilm formation by poly-ethylene-co-vinyl acetate films incorporating nisin.

The aim of this study was to evaluate the effect of poly-ethylene-co-vinyl acetate (EVA) films incorporating different concentrations (0.1%, 0.5% and 1%) of nisin on the biofilm-forming ability of Listeria monocytogenes ATCC 7644, Staphylococcus aureus 815 and Staphylococcus epidermidis ATCC 35984. Nisin was incorporated into two grades of EVA (EVA14 and EVA28) in the melt during a common film-blowing operation. The efficacy of EVA/nisin films was evaluated by biofilm biomass measurements and Live/Dead staining in combination with fluorescence microscopy. In order to evaluate whether the nisin incorporation could modify the film surface properties, contact angle measurements and scanning electron microscopy were performed. The results revealed the efficacy of EVA14/nisin films in reducing biofilm formation on their surfaces with more evident effect for S. epidermidis than L. monocytogenes and S. aureus strains. In contrast, EVA28/nisin films showed unsatisfactory activity. Fluorescence microscopy confirmed poor biofilm formation on EVA14/nisin films, also characterised by the presence of dead cells. The data presented in this study offer new potential applications for developing strategies aimed to improve the effect of antimicrobial agents.