3D printed macroporous scaffolds of PCL and inulin-g-P(D,L)LA for bone tissue engineering applications.

Bone repair and tissue-engineering (BTE) approaches require novel biomaterials to produce scaffolds with required structural and biological characteristics and enhanced performances with respect to those currently available. In this study, PCL/INU-PLA hybrid biomaterial was prepared by blending of the aliphatic polyester poly(ε-caprolactone) (PCL) with the amphiphilic graft copolymer Inulin-g-poly(D,L)lactide (INU-PLA) synthetized from biodegradable inulin (INU) and poly(lactic acid) (PLA). The hybrid material was suitable to be processed using fused filament fabrication 3D printing (FFF-3DP) technique rendering macroporous scaffolds. PCL and INU-PLA were firstly blended as thin films through solvent-casting method, and then extruded by hot melt extrusion (HME) in form of filaments processable by FFF-3DP. The physicochemical characterization of the hybrid new material showed high homogeneity, improved surface wettability/hydrophilicity as compared to PCL alone, and right thermal properties for FFF process. The 3D printed scaffolds exhibited dimensional and structural parameters very close to those of the digital model, and mechanical performances compatible with the human trabecular bone. In addition, in comparison to PCL, hybrid scaffolds showed an enhancement of surface properties, swelling ability, and in vitro biodegradation rate. In vitro biocompatibility screening through hemolysis assay, LDH cytotoxicity test on human fibroblasts, CCK-8 cell viability, and osteogenic activity (ALP evaluation) assays on human mesenchymal stem cells showed favorable results.

Assessment of Melt Compounding with Zeolites as an Effective Deodorization Strategy for Mixed Plastic Wastes and Comparison with Degassing.

The emission of off-odors from mechanically recycled plastics severely limits their re-introduction into the market for the production of new objects, for the same use or even for less demanding applications, thus hindering the implementation of an effective circular economy for plastics. The addition of adsorbing agents during the extrusion of polymers represents one of the most promising strategy to reduce the odorous emissions of plastics, due to its characteristics of cost-effectiveness, flexibility and low energy consumption. The novelty of this work lies in the assessment of zeolites as VOC adsorbents during the extrusion of recycled plastics. They appear more suitable than other types of adsorbents, due to their ability to capture and "hold" the adsorbed substances at the high temperatures of the extrusion process. Moreover, the effectiveness of this deodorization strategy was compared with the traditional degassing technique. Two types of mixed polyolefin wastes, coming from completely different collection and recycling processes, were tested: Fil-S (Film-Small), deriving from post-consumer flexible films of small size, and PW (pulper waste), which is the residual plastic waste obtained from the paper recycling process. The melt compounding of the recycled materials with two micrometric zeolites (zeolite 13X and Z310) resulted as more effective in the off-odors removal with respect to degassing. In particular, the highest reduction (-45%) of the Average Odor Intensity (AOI) was measured for both PW/Z310 and Fil-S/13X systems at 4 wt% of the zeolites' amount, compared with the corresponding untreated recyclates. Finally, by combining degassing and melt compounding with zeolites, the best result was obtained for the composite Fil-S/13X, whose Average Odor Intensity resulted as quite close (+22%) to the one of the virgin LDPE.

Effect of PVOH/PLA + Wax Coatings on Physical and Functional Properties of Biodegradable Food Packaging Films.

Biodegradable polymers suffer from inherent performance limitations that severely limit their practical application. Their functionalization by coating technology is a promising strategy to significantly improve their physical properties for food packaging. In this study, we investigated the double coating technique to produce multifunctional, high barrier and heat-sealable biodegradable films. The systems consisted of a web layer, made of poly(lactide) (PLA) and poly(butylene-adipate-co-terephthalate) (PBAT), which was first coated with a poly(vinyl) alcohol based layer, providing high barrier, and then with a second layer of PLA + ethylene-bis-stereamide (EBS) wax (from 0 to 20%), to provide sealability and improve moisture resistance. The films were fully characterized in terms of chemical, thermal, morphological, surface and functional properties. The deposition of the PVOH coating alone, with a thickness of 5 µm, led to a decrease in the oxygen transmission rate from 2200 cm3/m2 d bar, for the neat substrate (thickness of 22 µm), to 8.14 cm3/m2 d bar (thickness of 27 µm). The deposition of the second PLA layer did not affect the barrier properties but provided heat sealability, with a maximum bonding strength equal to 6.53 N/25 mm. The EBS wax incorporation into the PLA slightly increased the surface hydrophobicity, since the water contact angle passed from 65.4°, for the neat polylactide layer, to 71° for the 20% wax concentration. With respect to the substrate, the double-coated films exhibited increased stiffness, with an elastic modulus ca. three times higher, and a reduced elongation at break, which, however still remained above 75%. Overall, the developed double-coated films exhibited performances comparable to those of the most common synthetic polymer films used in the packaging industry, underlining their suitability for the packaging of sensitive foods with high O2-barrier requirements.

Floating Ricobendazole Delivery Systems: A 3D Printing Method by Co-Extrusion of Sodium Alginate and Calcium Chloride.

At present, the use of benzimidazole drugs in veterinary medicine is strongly limited by both pharmacokinetics and formulative issues. In this research, the possibility of applying an innovative semi-solid extrusion 3D printing process in a co-axial configuration was speculated, with the aim of producing a new gastro-retentive dosage form loaded with ricobendazole. To obtain the drug delivery system (DDS), the ionotropic gelation of alginate in combination with a divalent cation during the extrusion was exploited. Two feeds were optimized in accordance with the printing requirements and the drug chemical properties: the crosslinking ink, i.e., a water ethanol mixture containing CaCl2 at two different ratios 0.05 M and 0.1 M, hydroxyethyl cellulose 2% w/v, Tween 85 0.1% v/v and Ricobendazole 5% w/v; and alginate ink, i.e., a sodium alginate solution at 6% w/v. The characterization of the dried DDS obtained from the extrusion of gels containing different amounts of calcium chloride showed a limited effect on the ink extrudability of the crosslinking agent, which on the contrary strongly influenced the final properties of the DDS, with a difference in the polymeric matrix toughness and resulting effects on floating time and drug release.

Nanosilicates in Compatibilized Mixed Recycled Polyolefins: Rheological Behavior and Film Production in a Circular Approach.

Currently, plastic packaging represents a global challenge and has become a key point of attention for governments, media and consumers due to the visibility of the waste it generates. Despite their high resource efficiency, the perceived non-recyclability of polymeric films risks precluding them from being a relevant packaging solution in a circular economy approach. In this regard, the aim of this study was to implement a strategy to try closing the loop, via the mechanical recycling of post-consumer flexible packaging of small size (denoted as Fil-s) to obtain new films. In particular, two lots of Fil-s were used, which are PE/PP blends differing for the PP content and the presence of polar contaminants. The suitability for film blowing extrusion of these recycled materials, as such and after the addition of a compatibilizer and/or a lamellar nanosilicate, was evaluated. It was first evidenced that the difficulty of producing blown films with the pristine recycled materials, due to the frequent bubble breakages, occurring even at low draw ratios. Moreover, the shear and extensional rheological behavior of all Fil-s based systems was usefully correlated with their processability features, evidencing the key roles of the nanofiller to stabilize the bubble and of the compatibilizer to ensure a uniform film deformation, avoiding its premature breakage. Even if the adopted upgrading strategies allowed the production of blown films with both types of Fil-s, the different components of the recycled matrices were proven to significantly affect their processability and final film performances.

Study on Improving the Processability and Properties of Mixed Polyolefin Post-Consumer Plastics for Piping Applications.

This study focuses on the upgrading strategies to make Fil-s (acronym for film-small), a polyolefin-based material coming from the mechanical recycling of post-consumer flexible packaging, fit for re-use in the piping sector. The effects of washing treatments (at cold and hot conditions) and the addition of an experimental compatibilizer on the chemical-physical properties of Fil-s were first assessed. The measurements of some key properties (density, melt flow index, flexural modulus, yield strength), for both Fil-s as such and the different developed Fil-s based systems, was also conducted in order to evaluate the suitability of this complex and challenging waste stream to replace virgin PE-based pipe and fitting products, in compliance to ASTM D3350 standard. The outcomes of the present work contributed to define a code, for each Fil-s system investigated, useful for identifying the level of their performance in piping applications. All the recyclates were extruded as pipes by using a pilot scale plant, but the process resulted more stable and continuous with the compatibilized Fil-s, as it was deducible from its flow properties. Moreover, the best mechanical performances were exhibited by the hot-washed Fil-s pipes, with an increase in pipe stiffness equal to 65% respect to the unwashed sample.

Nanotechnology-Based Strategy to Upgrade the Performances of Plastic Flexible Film Waste.

The aim of this work was to improve the performances of Fil-s (film-small), a recycled material obtained from plastic flexible film waste that is made of polyethylene and a minor amount of polypropylene, with traces of polar contaminants (polyamides, maleic anhydride, etc.). The idea was to upgrade the material's mechanical properties by applying a nanotechnology-based strategy that takes advantage of the composition of Fil-s. In particular, different amounts of copolyamide (CoPA) and its masterbatch with an organic-modified nanosilicate were melt compounded with Fil-s in a twin-screw extruder. The good affinity between Fil-s and CoPA, proved by means of spectroscopic and rheological analysis, allowed for the obtaining of a well-refined morphology for the neat and hybrid blends. This resulted in very interesting increments of the strain at break, which was particularly impressive (10 times higher) in the case of the blend with the lower amount of copolyamide masterbatch, but without sacrificing the stiffness and strength of Fil-s.

Rheological Properties of Cystic Fibrosis Bronchial Secretion and in Vitro Drug Permeation Study: The Effect of Sodium Bicarbonate.

BACKGROUND: Cystic fibrosis (CF) is characterized by a thick, sticky mucus responsible for both airway obstruction and resistance to drug diffusion, reducing the effectiveness of drug delivery to the lung. Studies of drug-mucus interaction may be a crucial step in therapeutic management of CF. In the present research, the effect of a saline solution of sodium bicarbonate (100 mM) on sputum viscosity and the permeation properties of ketoprofen lysinate (Klys) from a previously developed dry powder inhaler were evaluated. METHODS: Rheological measurements were performed using an ARES rotational rheometer (Rheometrics, Inc.) with a parallel plate geometry. The gel fraction, separated from the liquid phase of various sputum samples from CF patients was loaded onto the plate. The elastic (G') and the viscous (G") moduli, tan δ (ratio of G" to G') and η* (complex viscosity) were evaluated as frequency-dependent parameters. Drug permeation across CF sputum from dry powders was studied by means of Franz-type vertical diffusion cells. The experiments were conducted on untreated sputum and on sputum treated with bicarbonate. RESULTS: Rheological studies showed that the elastic modulus (G') was always greater than the viscous modulus (G") and the viscosity decreased with increasing frequency, as for pseudo-plastic fluids. Bicarbonate caused a downward shift of both the elastic and viscous moduli, with a reduction in complex viscosity. As to drug permeation, the untreated sputum slowed down drug dissolution and permeation compared to buffer permeability (control). Permeation studies across CF sputum treated with bicarbonate showed higher Klys dissolution/permeation than untreated sputum. CONCLUSIONS: The interesting results confirm the previously reported bicarbonate. effectiveness in CF; this weak base seems to act by decreasing high viscosity of the CF bronchial secretion and, potentially, resulting in better mucus clearance and in fighting pulmonary infections.