Nanoscale Characterization of Graphene Oxide-Based Epoxy Nanocomposite Using Inverted Scanning Microwave Microscopy.

Scanning microwave microscopy (SMM) is a novel metrological tool that advances the quantitative, nanometric, high-frequency, electrical characterization of a broad range of materials of technological importance. In this work, we report an inverted near-field scanning microwave microscopy (iSMM) investigation of a graphene oxide-based epoxy nanocomposite material at a nanoscopic level. The high-resolution spatial mapping of local conductance provides a quantitative analysis of the sample's electrical properties. In particular, the electrical conductivity in the order of ∼10-1 S/m as well as the mapping of the dielectric constant with a value of ∼4.7 ± 0.2 are reported and validated by the full-wave electromagnetic modeling of the tip-sample interaction.

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.

PBS-Based Green Copolymer as an Efficient Compatibilizer in Thermoplastic Inedible Wheat Flour/Poly(butylene succinate) Blends.

Considering the current context of research aiming at proposing new bioplastics with low costs and properties similar to fossil-based commodities currently on the market, in the present work, a hybrid blend containing a prevalent amount of cheap inedible cereal flour (70 wt %) and poly(butylene succinate) (PBS) (30 wt %) has been prepared by a simple, eco-friendly, and low-cost processing methodology. In order to improve the interfacial tension and enhance the adhesion between the different phases at the solid state, with consequent improvement in microstructure uniformity and in material mechanical and adhesive performance, the PBS fraction in the blend was replaced with variable amounts (0-25 wt %) of PBS-based green copolymer, which exerted the function of a compatibilizer. The copolymer is characterized by an ad hoc chemical structure, containing six-carbon aliphatic rings, also present in the flour starch structure. The two synthetic polyesters obtained through two-stage melt polycondensation have been deeply characterized from the molecular, thermal, and mechanical points of view. Copolymerization deeply impacts the polymer final properties, the crystallizing ability, and stiffness of the PBS homopolymer being reduced. Also, the prepared ternary blends were deeply investigated in terms of microstructure, thermal, and mechanical properties. Lastly, both pure blend components and ternary blends were subjected to disintegration experiments under composting conditions. The results obtained proved how effective was the compatibilizer action of the copolymer, as evidenced by the investigation conducted on morphology and mechanical properties. Specifically, the mixtures with 15 and 20 wt % Co appeared to be characterized by the best mechanical performance, showing a progressive increase of deformation while preserving good values of elastic modulus and stress. The disintegration rate in compost was found to be higher for the lower amount of copolymer in the ternary blend. However, after 90 days of incubation, the blend richest in copolymer content lost 62% of weight.

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.

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.

Bio-Polyethylene-Based Composites Reinforced with Alkali and Palmitoyl Chloride-Treated Coffee Silverskin.

This work investigates the feasibility of using coffee silverskin (CSS) as a reinforcing agent in biobased polyethylene (BioPE) composites, by adding it in bulk and thin film samples. The effect of two different treatments, alkali bleaching (CSS_A) and esterification with palmitoyl chloride (CSS_P), on mechanical, thermal, morphological and water absorption behavior of produced materials at different CSS loading (10, 20 and 30 wt %) was investigated. A reactive graft copolymerization of BioPE with maleic anhydride was considered in the case of alkali treated CSS. It was found that, when introduced in bulk samples, improvement in the elastic modulus and a reduction in strain at maximum stress were observed with the increase in CSS fraction for the untreated and treated CSS composites, while the low aspect ratio of the CSS particles and their poor adhesion with the polymeric matrix were responsible for reduced ductility in films, decreasing crystallinity values and reduction of elastic moduli. When CSS_A and CSS_P are introduced in the matrix, a substantial reduction in the water uptake is also obtained in films, mainly due to presence of maleated PE, that builds up some interactions to eliminate the amounts of OH groups and hydrophobized CSS, due to the weakened absorption capacity of the functionalized CSS.

Cellulose Nanocrystals and Lignin Nanoparticles Extraction from Lemna minor L.: Acid Hydrolysis of Bleached and Ionic Liquid-Treated Biomass.

Using biomass to develop and obtain environmentally friendly and industrially applicable biomaterials is increasingly attracting global interest. Herein, cellulose nanocrystals (CNCs) and lignin nanoparticles (LNPs) were extracted from Lemna minor L., a freshwater free-floating aquatic species commonly called duckweed. To obtain CNCs and LNPs, two different procedures and biomass treatment processes based on bleaching or on the use of an ionic liquid composed of triethylammonium and sulfuric acid ([TEA][HSO4]), followed by acid hydrolysis, were carried out. Then, the effects of these treatments in terms of the thermal, morphological, and chemical properties of the CNCs and LNPs were assessed. The resulting nanostructured materials were characterized by using Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) spectroscopy, thermo-gravimetric analysis (TGA), and scanning electron microscopy (SEM). The results showed that the two methodologies applied resulted in both CNCs and LNPs. However, the bleaching-based treatment produced CNCs with a rod-like shape, length of 100-300 nm and width in the range of 10-30 nm, and higher purity than those obtained with ILs that were spherical in shape. In contrast, regarding lignin, IL made it possible to obtain spherical nanoparticles, as in the case of the other treatment, but they were characterized by higher purity and thermal stability. In conclusion, this research highlights the possibility of obtaining nanostructured biopolymers from an invasive aquatic species that is largely available in nature and how it is possible, by modifying experimental procedures, to obtain nanomaterials with different morphological, purity, and thermal resistance characteristics.

The Bran and Grain Grinding Level Affect the Tensile Characteristics of Bioplastics Derived from Wholegrain Wheat Flours.

The mechanical performance of thermoplastic bulk samples obtained by plasticizing wheat flours differing in grain hardness, alveographic parameters, absence or presence of bran, and grinding level was assessed. Grains of four bread wheat (Triticum aestivum L.) cultivars (Altamira, Aubusson, Blasco, and Bologna) were milled with the aim of producing single-cultivar refined flour (R), or wholegrain flour with fine (F) or coarse (C) grinding. The flours were plasticized, injection molded and tested for tensile properties. The results confirmed that the presence of bran increased the strength (σ) and reduced the elongation at break (ε) of thermoplastics obtained from the flours of each cultivar. The grinding level had an effect, since σ was higher and ε was lower in F than in C samples. SEM analysis of samples revealed that the bran and its texture affected the exposure of starch granules to plasticizer. Composting experiments also revealed that the formulations are able to disintegrate within 21 days with a mass loss rate higher in plastics from F than C flours, while germination tests carried out with cress seeds indicated that it takes two months before the compost loses its phytotoxic effects. Overall, the refining and bran particle size of wheat flours, besides their gluten composition and baking properties, represent novel choice factors to be considered when tailoring the manufacturing of plastic materials for selected requirements and uses.

Novel Nanostructured Scaffolds of Poly(butylene trans-1,4-cyclohexanedicarboxylate)-Based Copolymers with Tailored Hydrophilicity and Stiffness: Implication for Tissue Engineering Modeling.

Here, we present novel biocompatible poly(butylene trans-1,4-cyclohexanedicarboxylate) (PBCE)-based random copolymer nanostructured scaffolds with tailored stiffness and hydrophilicity. The introduction of a butylene diglycolate (BDG) co-unit, containing ether oxygen atoms, along the PBCE chain remarkably improved the hydrophilicity and chain flexibility. The copolymer containing 50 mol% BDG co-units (BDG50) and the parent homopolymer (PBCE) were synthesized and processed as electrospun scaffolds and compression-molded films, added for the sake of comparison. We performed thermal, wettability, and stress-strain measures on the PBCE-derived scaffolds and films. We also conducted biocompatibility studies by evaluating the adhesion and proliferation of multipotent mesenchymal/stromal cells (hBM-MSCs) on each polymeric film and scaffold. We demonstrated that solid-state properties can be tailored by altering sample morphology besides chemical structure. Thus, scaffolds were characterized by a higher hydrophobicity and a lower elastic modulus than the corresponding films. The three-dimensional nanostructure conferred a higher adsorption protein capability to the scaffolds compared to their film counterparts. Finally, the PBCE and BDG50 scaffolds were suitable for the long-term culture of hBM-MSCs. Collectively, the PBCE homopolymer and copolymer are good candidates for tissue engineering applications.

The Optimization of Pressure-Assisted Microsyringe (PAM) 3D Printing Parameters for the Development of Sustainable Starch-Based Patches.

The aim of this work was to develop sustainable patches for wound application, using the biopolymer starch, created using a low-cost 3D printing PAM device. The composition of a starch gel was optimized for PAM extrusion: corn starch 10% w/w, ß-glucan water suspension (filler, 1% w/w), glycerol (plasticizer, 29% w/w), and water 60% w/w. The most suitable 3D printing parameters were optimized as well (nozzle size 0.8 mm, layer height 0.2 mm, infill 100%, volumetric flow rate 3.02 mm3/s, and print speed 15 mm/s). The suitable conditions for post-printing drying were set at 37 °C for 24 h. The obtained patch was homogenous but with low mechanical resistance. To solve this problem, the starch gel was extruded over an alginate support, which, after drying, becomes an integral part of the product, constituting the backing layer of the final formulation. This approach significantly improved the physicochemical and post-printing properties of the final bilayer patch, showing suitable mechanical properties such as elastic modulus (3.80 ± 0.82 MPa), strength (0.92 ± 0.08 MPa), and deformation at break (50 ± 1%). The obtained results suggest the possibility of low-cost production of patches for wound treatment by additive manufacturing technology.

Polymeric Patches Based on Chitosan/Green Clay Composites and Hazelnut Shell Extract as Bio-Sustainable Medication for Wounds.

Hazelnut shells, the main waste deriving from hazelnut processing, represent an interesting source of active molecules useful in pharmaceutics, although they have not yet been examined in depth. A hydrosoluble extract (hazelnut shell extract, HSE) was prepared by the maceration method using a hydroalcoholic solution and used as the active ingredient of patches (prepared by casting method) consisting of composites of highly deacetylated chitosan and green clay. In vitro studies showed that the formulation containing HSE is able to stimulate keratinocyte growth, which is useful for healing purposes, and to inhibit the growth of S. aureus (Log CFU/mL 0.95 vs. 8.85 of the control after 48 h); this bacterium is often responsible for wound infections and is difficult to treat by conventional antibiotics due to its antibiotic resistance. The produced patches showed suitable tensile properties that are necessary to withstand mechanical stress during both the removal from the packaging and application. The obtained results suggest that the developed patch could be a suitable product to treat wounds.

Formulation and characterization of sustainable bioadhesive films for wound treatment based on barley ß-glucan extract obtained using the high power ultrasonic technique.

ß-glucan is a well-known functional and bioactive food ingredient. Recently, some studies highlighted several interesting pharmacological activities, such as hypocholesterolemic, hypoglycemic, immunomodulatory, antitumor, antioxidant and anti-inflammatory. The aim of this study is to evaluate a novel application of ß-glucan, obtained from barley, for the development of formulations for skin use. Several water suspensions were obtained from barley flour of different particle sizes treated by high power ultrasonic (HPU) technique. Barley flour fraction in the range of 400-500 µm allowed to obtain a stable suspension, represented both by a water soluble and water insoluble fraction of ß-glucans, that showed excellent film forming ability. The plasticizer sorbitol as well as the bioadhesive biopolymer acacia gum were added to this suspension in order to obtain a gel suitable to prepare films by casting. The obtained films demonstrated suitable mechanical properties and ability to stimulate in vitro keratinocytes growth suggesting its possible application in dermatological field as for wound treatment. This study demonstrated the dual use of barley suspension: as excipient and as active ingredient.

Preparation and Applications of Green Thermoplastic and Thermosetting Nanocomposites Based on Nanolignin.

The development of bio-based materials is of great importance in the present environmental circumstances; hence, research has greatly advanced in the valorization of lignin from lignocellulosic wastes. Lignin is a natural polymer with a crosslinked structure, valuable antiradical activity, unique thermal- and UV-absorption properties, and biodegradability, which justify its use in several prospective and useful application sectors. The active functionalities of lignin promote its use as a valuable material to be adopted in the composite and nanocomposites arenas, being useful and suitable for consideration both for the synthesis of matrices and as a nanofiller. The aim of this review is to summarize, after a brief introduction on the need for alternative green solutions to petroleum-based plastics, the synthesis methods for bio-based and/or biodegradable thermoplastic and thermosetting nanocomposites, along with the application of lignin nanoparticles in all green polymeric matrices, thus generating responsiveness towards the sustainable use of this valuable product in the environment.

Synthesis of a Lignin/Zinc Oxide Hybrid Nanoparticles System and Its Application by Nano-Priming in Maize.

Nanotechnologies are attracting attention in various scientific fields for their technological and application potential, including their use as bio-activators and nanocarriers in agriculture. This work aimed to synthesize a hybrid material (ZnO@LNP) consisting of lignin nanoparticles containing zinc oxide (4 wt %). The synthesized ZnO hybrid material showed catalytic effect toward thermal degradation, as evidenced by the TGA investigation, while both spectroscopic and contact angle measurements confirmed a modification of surface hydrophilicity for the lignin nanoparticles due to the presence of hydrophobic zinc oxide. In addition, the antioxidant activity of the ZnO@LNP and the zinc release of this material were evaluated. At the application level, this study proposes for the first time the use of such a hybrid system to prime maize seeds by exploiting the release characteristics of this material. Concerning the dosage applied, ZnO@LNP promoted inductive effects on the early stages of seed development and plant growth and biomass development of young seedlings. In particular, the ZnO@LNP stimulated, in the primed seeds, a higher content of chlorophyll, carotenoids, anthocyanins, total phenols, and a better antioxidant activity, as supported by the lower levels of lipid peroxidation found when compared to the control samples.

Wound Dressing: Combination of Acacia Gum/PVP/Cyclic Dextrin in Bioadhesive Patches Loaded with Grape Seed Extract.

The success of wound treatment is conditioned by the combination of both suitable active ingredients and formulation. Grape seed extract (GSE), a waste by-product obtained by grape processing, is a natural source rich in many phenolic compounds responsible for antioxidant, anti-inflammatory, and antimicrobial activities and for this reason useful to be used in a wound care product. Bioadhesive polymeric patches have been realized by combining acacia gum (AG) and polyvinylpyrrolidone (PVP). Prototypes were prepared by considering different AG/PVP ratios and the most suitable in terms of mechanical and bioadhesion properties resulted in the 9.5/1.0 ratio. This patch was loaded with GSE combined with cyclic dextrin (CD) to obtain the molecular dispersion of the active ingredient in the dried formulation. The loaded patch resulted mechanically resistant and able to release GSE by a sustained mechanism reaching concentrations able to stimulate keratinocytes' growth, to exert both antibacterial and antioxidant activities.

Natural Active Ingredients for Poly (Lactic Acid)-Based Materials: State of the Art and Perspectives.

This review describes the state of the art in the field of poly (lactic acid) (PLA)-based materials activated by natural compounds and extracts (active ingredients, AIs) from plant sources for food and biomedical applications. With a multidisciplinary approach, after a description of the synthesis and properties of PLA, special attention was paid to the chemical properties and unconventional extraction technologies of AIs used for PLA activation. Innovative techniques for the incorporation of AIs into PLA; characterization and the antioxidant and antimicrobial properties of the novel materials were discussed. In view of future perspectives, this study has evidenced that some aspects need to be further investigated from joint research between academia and industry, according to the green chemistry principles and circular economy strategy.

Lignin Nanoparticles: A Promising Tool to Improve Maize Physiological, Biochemical, and Chemical Traits.

Lignin, and its derivatives, are the subject of current research for the exciting properties shown by this biomass. Particularly attractive are lignin nanoparticles for their eco- and biocompatibility compared to other nanomaterials. In this context, the effect of nanostructured lignin microparticles (LNP), obtained from alkaline lignin by acid treatment, on maize plants was investigated. To this end, maize seeds were primed with LNP at five concentrations: 80 mg L-1 (T80), 312 mg L-1 (T312), 1250 mg L-1 (T1250), 5000 mg L-1 (T5000) and 20,000 mg L-1 (T20000). Concerning the dose applied, LNP prompted positive effects on the first stages of maize development (germination and radicle length). Furthermore, the study of plant growth, biochemical and chemical parameters on the developed plants indicated that concerning the dose applied. LNP stimulated beneficial effects on the seedlings (fresh weight and length of shoots and roots). Besides, specific treatments increased the content of chlorophyll (a and b), carotenoid, and anthocyanin. Finally, the soluble protein content showed a positive trend in response to specific dosages. These effects are significant, given the essential biological function performed by these biomolecules. In conclusion, this research indicates as the nanostructured lignin microparticles can be used, at appropriate dosages, to induce positive biological responses in maize. This beneficial action deserves attention as it candidates LNP for biostimulating a crop through seed priming.

Evaluation of the Factors Affecting the Disintegration under a Composting Process of Poly(lactic acid)/Poly(3-hydroxybutyrate) (PLA/PHB) Blends.

The overall migration behavior and the disintegration under composting conditions of films based on plasticized poly(lactic acid)/poly(3-hydroxybutyrate) (PLA-PHB) blends were studied, with the main aim of determining the feasibility of their application as biodegradable food packaging materials. The role of composition in the disintegration process was evaluated by monitoring the changes in physical and thermal properties that originated during the degradation process. PLA and PHB were blended in two weight ratios with 15 wt% of tributyrin, using a Haake mixer and then compression molded into ~150 µm films. We found that the migration level of all of the studied blends was below check intended meaning retained in non-polar simulants, while only plasticized blends could withstand the contact with polar solvents. The disintegration of all of the materials in compost at 58 °C was completed within 42 days; the plasticized PHB underwent the fastest degradation, taking only 14 days. The presence of the TB plasticizer speeded up the degradation process. Different degradation mechanisms were identified for PLA and PHB. To evaluate the annealing effect separately from bacteria degradation, the influence of temperature on materials in the absence of a compost environment was also studied. With the increasing time of degradation in compost, both melting temperature and maximum degradation temperature progressively decreased, while the crystallinity degree increased, indicating that the samples were definitely degrading and that the amorphous regions were preferentially eroded by bacteria.

Migration and Degradation in Composting Environment of Active Polylactic Acid Bilayer Nanocomposites Films: Combined Role of Umbelliferone, Lignin and Cellulose Nanostructures.

This study was dedicated to the functional characterization of innovative poly(lactic acid) (PLA)-based bilayer films containing lignocellulosic nanostructures (cellulose nanocrystals (CNCs) or lignin nanoparticles (LNPs)) and umbelliferone (UMB) as active ingredients (AIs), prepared to be used as active food packaging. Materials proved to have active properties associated with the antioxidant action of UMB and LNPs, as the combination of both ingredients in the bilayer formulations produced a positive synergic effect inducing the highest antioxidant capacity. The results of overall migration for the PLA bilayer systems combining CNCs or LNPs and UMB revealed that none of these samples exceeded the overall migration limit required by the current normative for food packaging materials in both non-polar and polar simulants. Finally, all the hydrophobic monolayer and bilayer films were completely disintegrated in composting conditions in less than 18 days of incubation, providing a good insight on the potential use of these materials for application as active and compostable food packaging.