Thermal treatment of magnesium particles in polylactic acid polymer films elicits the expression of osteogenic differentiation markers and lipidome profile remodeling in human adipose stem cells.

The efficacy of polylactic acid (PLA)/Magnesium (Mg)-based materials for driving stem cells toward bone tissue engineering applications requires specific Mg surface properties to modulate the interface of stem cells with the film. Here, we have developed novel PLA/Mg-based composites and explored their osteogenic differentiation potential on human adipose stem cells (hASCs). Mg-particles/polymer interface was improved by two treatments: heating in oxidative atmosphere (TT) and surface modification with a compatibilizer (PEI). Different contents of Mg particles were dispersed in PLA and composite surface and bulk properties, protein adsorption, stem cell-PLA/Mg interactions, osteogenic markers expressions, and lipids composition profile were evaluated. Mg particles were uniformly distributed on the surface and in the bulk PLA polymer. Improved and modulated particle-polymer adhesion was observed in Mg particle-treated composites. After 21 days in canonical growth culture conditions, hASCs on PLA/MgTT displayed the highest expression of the general osteogenic markers, RUNX2, SSP1, and BGLAP genes, Alkaline Phosphatase, type I Collagen, Osteopontin, and Calcium deposits. Moreover, by LC/MS QTOF mass-spectrophotometry lipidomic analysis, we found in PLA/MgTT-cells, for the first time, a remodeling of the lipid classes composition associated with the osteogenic differentiation. We ascribed these results to MgTT characteristics, which improve Mg availability and composite osteoinductive performance.

Hydroxytyrosol and Oleuropein-Enriched Extracts Obtained from Olive Oil Wastes and By-Products as Active Antioxidant Ingredients for Poly (Vinyl Alcohol)-Based Films.

Oxidative stability of food is one of the most important parameters affecting integrity and consequently nutritional properties of dietary constituents. Antioxidants are widely used to avoid deterioration during transformation, packaging, and storage of food. In this paper, novel poly (vinyl alcohol) (PVA)-based films were prepared by solvent casting method adding an hydroxytyrosol-enriched extract (HTyrE) or an oleuropein-enriched extract (OleE) in different percentages (5, 10 and 20% w/w) and a combination of both at 5% w/w. Both extracts were obtained from olive oil wastes and by-products using a sustainable process based on membrane technologies. Qualitative and quantitative analysis of each sample carried out by high performance liquid chromatography (HPLC) and nuclear resonance magnetic spectroscopy (NMR) proved that the main components were hydroxytyrosol (HTyr) and oleuropein (Ole), respectively, two well-known antioxidant bioactive compounds found in Olea europaea L. All novel formulations were characterized investigating their morphological, optical and antioxidant properties. The promising performances suggest a potential use in active food packaging to preserve oxidative-sensitive food products. Moreover, this research represents a valuable example of reuse and valorization of agro-industrial wastes and by-products according to the circular economy model.

Dielectric Spectroscopy of PP/MWCNT Nanocomposites: Relationship with Crystalline Structure and Injection Molding Condition.

In this paper, we study the correlation between the dielectric behavior of polypropylene/multi-walled carbon nanotube (PP/MWCNT) nanocomposites and the morphology with regard to the crystalline structure, nanofiller dispersion and injection molding conditions. As a result, in the range of the percolation threshold the dielectric behavior shifts to a more frequency-independent behavior, as the mold temperature increases. Moreover, the position further from the gate appears as the most conductive. This effect has been associated to a modification of the morphology of the MWCNT clusters induced by both the flow of the molten polymer during the processing phase and the variation of the crystalline structure, which is increasingly constituted by γ-phase as the mold temperature increases. The obtained results allow one to understand the effect of tuning the processing condition in the frequency-dependent electrical behavior of PP/MWCNT injection-molded nanocomposites, which can be successfully exploited for an advanced process/product design.

Unpatterned Bioactive Poly(Butylene 1,4-Cyclohexanedicarboxylate)-Based Film Fast Induced Neuronal-Like Differentiation of Human Bone Marrow-Mesenchymal Stem Cells.

Herein, we present poly(butylene 1,4-cyclohexanedicarboxylate) (PBCE) films characterized by an unpatterned microstructure and a specific hydrophobicity, capable of boosting a drastic cytoskeleton architecture remodeling, culminating with the neuronal-like differentiation of human bone marrow-mesenchymal stem cells (hBM-MSCs). We have used two different filming procedures to prepare the films, solvent casting (PBCE) and compression-moulding (PBCE*). PBCE film had a rough and porous surface with spherulite-like aggregations (Ø = 10-20 µm) and was characterized by a water contact angle = 100°. PBCE* showed a smooth and continuous surface without voids and visible spherulite-like aggregations and was more hydrophobic (WCA = 110°). Both surface characteristics were modulated through the copolymerization of different amounts of ether-oxygen-containing co-units into PBCE chemical structure. We showed that only the surface characteristics of PBCE-solvent-casted films steered hBM-MSCs toward a neuronal-like differentiation. hBM-MSCs lost their canonical mesenchymal morphology, acquired a neuronal polarized shape with a long cell protrusion (≥150 µm), expressed neuron-specific class III ß-tubulin and microtubule-associated protein 2 neuronal markers, while nestin, a marker of uncommitted stem cells, was drastically silenced. These events were observed as early as 2-days after cell seeding. Of note, the phenomenon was totally absent on PBCE* film, as hBM-MSCs maintained the mesenchymal shape and behavior and did not express neuronal/glial markers.

Antioxidant Packaging Films Based on Ethylene Vinyl Alcohol Copolymer (EVOH) and Caffeic Acid.

The main objective of this research activity was to design and realize active films with tunable food functional properties. In detail, caffeic acid (CA), a polyphenol with high antioxidant effect, was used as active ingredient in poly (vinyl alcohol-co-ethylene) (EVOH) films at 5 wt.% and 15 wt.% and successfully realized by means of the solvent casting process. Optical, morphological, thermal and mechanical studies were considered to define the effect of the presence of the CA component on the structural properties of the matrix. In addition, moisture content and antioxidant activity were evaluated, to have clear information on the CA effect in terms of functional characteristics of realized food packaging systems. Results from tensile tests showed increased values for strength and deformation at break in EVOH_CA based films. Results from colorimetric and transparency analysis underlined that the presence of caffeic acid in EVOH copolymer induces some alterations, whereas the addition of the active ingredient determined a positive radical scavenging activity of the formulations, confirming the possibility of practically using these polymeric systems in the food packaging sector.

Effect of Injection Molding Conditions on Crystalline Structure and Electrical Resistivity of PP/MWCNT Nanocomposites.

Polypropylene (PP) / multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by melt-mixing and used to manufacture samples by injection molding. The effect of processing conditions on the crystallinity and electrical resistivity was studied. Accordingly, samples were produced varying the mold temperature and injection rate, and the DC electrical resistivity was measured. The morphology of MWCNT clusters was studied by optical and electron microscopy, while X-ray diffraction was used to study the role of the crystalline structure of PP. As a result, an anisotropic electrical behavior induced by the process was observed, which is further influenced by the injection molding processing condition. It was demonstrated that a reduction of electrical resistivity can be obtained by increasing mold temperature and injection rate, which was associated to the formation of the γ-phase and the related inter-cluster morphology of the MWCNT conductive network.

Effect of Lemon Waste Natural Dye and Essential Oil Loaded into Laminar Nanoclays on Thermomechanical and Color Properties of Polyester Based Bionanocomposites.

In this work, polyester-based nanocomposites added with laminar nanoclays (calcined hydrotalcite, HT, and montmorillonite, MMT) loaded with lemon waste natural dye (LD) and essential oil (LEO) were prepared and characterized. The optimal conditions to synthetize the hybrid materials were obtained by using statistically designed experiments. The maximum LD adsorption with HT was found using 5 wt% of surfactant (sodium dodecyl sulfate), 5 wt% of mordant (aluminum potassium sulfate dodecahydrate) and 50% (v/v) ethanol. For MMT, 10 wt% of surfactant (cetylpyridinium bromide), 5 wt% of mordant, 1 wt% of (3-aminopropyl) triethoxysilane and 100% distilled water were used. LEO adsorption at 300 wt% was maximized with MMT, 10 wt% of surfactant and 50 °C following an evaporation/adsorption process. The obtained hybrid nanofillers were incorporated in a polyester-based matrix (INZEA) at different loadings (3, 5, and 7 wt%) and the obtained samples were characterized in terms of thermal stability, tensile behavior, and color properties. HT_LEM-based samples showed a bright yellow color compared to MMT_LEM ones. The presence of lemon hybrid pigments in INZEA-based systems produced a remarkable variation in CIELAB color space values, which was more visible with increasing the nanofillers ratio. A limited mechanical enhancement and reduced thermal stability was observed with the nanopigments addition, suggesting a limited extent of intercalation/exfoliation of MMT and HT in the polymer matrix. MMT_LEM pigments showed higher thermal stability than HT_LEM ones. A significant increase in Young's modulus of nanocomposites loaded with hybrid LEO was observed compared to the biopolymer matrix. The LEO inclusion into the nanoclays efficiently improved its thermal stability, especially for MMT.

Thermomechanical and Morphological Properties of Poly(ethylene terephthalate)/Anhydrous Calcium Terephthalate Nanocomposites.

Calcium terephthalate anhydrous salts (CATAS), synthetized by reaction of terephthalic acid with metal (Ca) oxide were incorporated at different weight contents (0-30 wt. %) in recycled Poly(ethylene terephthalate) (rPET) by melt processing. Their structure, morphology, thermal and mechanical properties (tensile and flexural behavior) were investigated. Results of tensile strength of the different formulations showed that when the CATAS content increased from 0.1 to 0.4 wt. %, tangible changes were observed (variation of tensile strength from 65.5 to 69.4 MPa, increasing value for E from 2887 up to 3131 MPa, respectively for neat rPET and rPET_0.4CATAS). A threshold weight amount (0.4 wt. %) of CATAS was also found, by formation at low loading, of a rigid amorphous fraction at the rPET/CATAS interface, due to the aromatic interactions (π-π conjugation) between the matrix and the filler. Above the threshold, a restriction of rPET/CATAS molecular chains mobility was detected, due to the formation of hybrid mechanical percolation networks. Additionally, enhanced thermal stability of CATAS filled rPET was registered at high content (Tmax shift from 426 to 441 °C, respectively, for rPET and rPET_30CATAS), essentially due to chemical compatibility between terephthalate salts and polymer molecules, rich in stable aromatic rings. The singularity of a cold crystallization event, identified at the same loading level, confirmed the presence of an equilibrium state between nucleation and blocking effect of amorphous phase, basically related to the characteristic common terephthalate structure of synthetized Ca-Metal Organic Framework and the rPET matrix.

UV Protective, Antioxidant, Antibacterial and Compostable Polylactic Acid Composites Containing Pristine and Chemically Modified Lignin Nanoparticles.

Polylactic acid (PLA) films containing 1 wt % and 3 wt % of lignin nanoparticles (pristine (LNP), chemically modified with citric acid (caLNP) and acetylated (aLNP)) were prepared by extrusion and characterized in terms of their overall performance as food packaging materials. Morphological, mechanical, thermal, UV-Vis barrier, antioxidant and antibacterial properties were assayed; appropriate migration values in food simulants and disintegration in simulated composting conditions were also verified. The results obtained indicated that all lignin nanoparticles succeeded in conferring UV-blocking, antioxidant and antibacterial properties to the PLA films, especially at the higher filler loadings assayed. Chemical modification of the fillers partially reduced the UV protection and the antioxidant properties of the resulting composites, but it induced better nanoparticles dispersion, reduced aggregates size, enhanced ductility and improved aesthetic quality of the films through reduction of the characteristic dark color of lignin. Migration tests and disintegration assays of the nanocomposites in simulated composting conditions indicated that, irrespectively of their formulation, the multifunctional nanocomposite films prepared behaved similarly to neat PLA.

Synergic Effect of Nanolignin and Metal Oxide Nanoparticles into Poly(l-lactide) Bionanocomposites: Material Properties, Antioxidant Activity, and Antibacterial Performance.

Binary and ternary poly(l-lactide) (PLLA)-based nanocomposites, containing nanolignin (1 wt %) and different metal oxide nanoparticles (0.5 wt %, Ag2O, TiO2, WO3, Fe2O3, and ZnFe2O4), were realized by solvent casting, and their morphological, thermal, surface, optical, antioxidant, and antimicrobial characterizations were performed. The presence of metal oxide nanoparticles at the selected weight concentration affects the surface microstructure of the PLLA polymer, and this outcome is particle-type dependent, according to the shape, morphology, and chemical properties of the selected nanoparticles (NPs). Analogously, wettability of PLLA-based nanocomposites was slightly modified by the presence of hydrophobic lignin nanoparticles and different shaped metal oxides. Results of differential scanning calorimetry (DSC) and X-ray powder diffraction (XRD) tests confirmed that nanoparticle addition confined the mobility of the amorphous phase, increasing at the same time the formation of more numerous but less perfect PLLA crystals. Interestingly, antioxidant activity was also obtained in ternary-based nanocomposites, where a synergic effect of lignin and metal oxide nanoparticles was obtained. Antibacterial tests showed manifest activity of TiO2 and Ag2O nanoparticles containing PLLA films, and the time dependence was more evident for Staphylococcus aureus than for Escherichia coli. Lignin nanoparticles are able to provide protection against UV light while still allowing visible light to pass and even surpass the UV-protection capacity provided by many inorganic nanoparticles. This makes them an attractive renewable additive for the realization of PLLA/metal oxide nanocomposites in the fields of food, drug packaging, and biomedical industry, where antibacterial and antioxidant properties are required.

A Novel Class of Cost Effective and High Performance Composites Based on Terephthalate Salts Reinforced Polyether Ether Ketone.

Poly(ether ether ketone) (PEEK)-based nanocomposites have been realized with incorporation (0-30 wt %) of anhydrous calcium terephthalate salts (CATAS), synthetized by reaction of terephtalic acid with the metal (Ca) oxide, by means of a melt processing. Their structure, morphology, thermal, and mechanical properties have been investigated. Scanning electron microscopy observations confirmed homogeneous dispersion of nanometer-sized fillers and a toughened fracture morphology even at the higher content, while thermal characterization confirmed an unvaried thermal stability and unmodified crystalline structure of the reference PEEK matrix. A negligible nucleating effect was evidenced, while a blocking effect of the amorphous phase fraction provide composites with increased stiffness, confirmed by enhanced values of G' and shifts of glass transition peak to higher temperatures, for restriction in chain mobility imposed by CATAS. The proposed solutions aimed to enlarge the application range of high performance costly PEEK-based composites, by using thermally stable nanofillers with limited costs and easily controllable synthesis phase.

Active Role of ZnO Nanorods in Thermomechanical and Barrier Performance of Poly(vinyl alcohol-co-ethylene) Formulations for Flexible Packaging.

Poly(vinyl alcohol-co-ethylene) (EVOH) films containing zinc oxide nanorods (ZnO Nrods) at 0.1, 0.5, and 1 wt%, were realized by solvent casting. The effect of ZnO Nrods content on morphological, thermal, optical, mechanical, and oxygen permeability properties were analyzed. In addition, moisture content and accelerated-aging test studies were performed, with the intention to determine the influence of zinc oxide nanofillers on the functional characteristics of realized packaging systems. Tensile properties showed increased values for strength and deformation-at-break in EVOH-based formulations reinforced with 0.1 and 0.5 wt% of zinc oxide nanorods. Results from the colorimetric and transparency investigations underlined that the presence of ZnO Nrods in EVOH copolymer did not induce evident alterations. In addition, after the accelerated-aging test, the colorimetric test confirmed the possibility for these materials to be used in the packaging sector. This behavior was induced by the presence of zinc oxide nanofillers that act as a UV block that made them useful as an efficient absorber of UV radiation.

Maleinized Linseed Oil as Epoxy Resin Hardener for Composites with High Bio Content Obtained from Linen Byproducts.

Green composites, with more than 78 wt.% of products obtained from linen linum usitatissimum, were developed in this research work. Epoxidized linseed oil (ELO) was used as bio-based resin, a mix of nadic methyl anhydride (MNA) and maleinized linseed oil (MLO) were used as cross-linkers and finally, flax fabrics were used to obtain composite laminates by resin transfer molding (RTM). The flax fibers were modified using amino-silane, glycidyl-silane and maleic anhydride treatment in order to increase the compatibility between lignocellulosic fibers and the polymeric matrix. Mechanical and thermal properties were studied by flexural, tensile and impact test, as well as dynamic mechanical analyses (DMA) to study the viscoelastic behavior. Contrary to what could be expected, when fibers are previously treated in presence of MLO, a reduction of anchorage points is obtained causing a substantial increase in the ductile properties compared with composites without previous fiber treatment or without MLO.

Antimicrobial Properties and Cytocompatibility of PLGA/Ag Nanocomposites.

The purpose of this study was to investigate the antimicrobial properties of multifunctional nanocomposites based on poly(dl-Lactide-co-Glycolide) (PLGA) and increasing concentration of silver (Ag) nanoparticles and their effects on cell viability for biomedical applications. PLGA nanocomposite films, produced by solvent casting with 1 wt%, 3 wt% and 7 wt% of Ag nanoparticles were investigated and surface properties were characterized by atomic force microscopy and contact angle measurements. Antibacterial tests were performed using an Escherichia coli RB and Staphylococcus aureus 8325-4 strains. The cell viability and morphology were performed with a murine fibroblast cell line (L929) and a human osteosarcoma cell line (SAOS-2) by cell viability assay and electron microscopy observations. Matrix protein secretion and deposition were also quantified by enzyme-linked immunosorbent assay (ELISA). The results suggest that the PLGA film morphology can be modified introducing a small percentage of silver nanoparticles, which induce the onset of porous round-like microstructures and also affect the wettability. The PLGA/Ag films having silver nanoparticles of more than 3 wt% showed antibacterial effects against E. coli and S. aureus. Furthermore, silver-containing PLGA films displayed also a good cytocompatibility when assayed with L929 and SAOS-2 cells; indicating the PLGA/3Ag nanocomposite film as a promising candidate for tissue engineering applications.