On the Unique Morphology and Elastic Properties of Multi-Jet Electrospun Cashew Gum-Based Fiber Mats.

This study investigates the unique morphology and mechanical properties of multi-jet electrospun cashew gum (CG) when combined with high-molecular-weight polyethylene oxide (PEO) and glycerol. Cashew gum (CG) is a low-cost, non-toxic heteropolysaccharide derived from Anacardium occidentale trees. Initially, the electrospinnability of aqueous solutions of cashew gum alone or in combination with PEO was evaluated. It was found that cashew gum alone was not suitable for electrospinning; thus, adding a small quantity of PEO was needed to create the necessary molecular entanglements for fiber formation. By using a single emitter with a CG:PEO ratio of 85:15, straight and smooth fibers with some defects were obtained. However, additional purification of the cashew gum solution was needed to produce more stable and defect-free straight and smooth fibers. Additionally, the inclusion of glycerol as a plasticizer was required to overcome material fragility. Interestingly, when the optimized formulation was electrospun using multiple simultaneous emitters, thicker aligned fiber bundles were achieved. Furthermore, the resulting oriented fiber mats exhibited unexpectedly high elongation at break under ambient conditions. These findings underscore the potential of this bio-polysaccharide-based formulation for non-direct water contact applications that demand elastic properties.

NMR Analyses and Statistical Modeling of Biobased Polymer Microstructures-A Selected Review.

NMR analysis combined with statistical modeling offers a useful approach to investigate the microstructures of polymers. This article provides a selective review of the developments in both the NMR analysis of biobased polymers and the statistical models that can be used to characterize these materials. The information obtained from NMR and statistical models can provide insights into the microstructure and stereochemistry of appropriate biobased polymers and establish a systematic approach to their analysis. In suitable cases, the analysis can help optimize the synthetic procedures and facilitate the development of new or modified polymeric materials for various applications. Examples are given of the studies of poly(hydroxyalkanoates), poly(lactic acid), and selected polysaccharides, e.g., alginate, pectin, and chitosan. This article may serve as both a reference and a guide for future workers interested in the NMR sequence analysis of biobased materials.

Development of Ciprofloxacin-Loaded Electrospun Yarns of Application Interest as Antimicrobial Surgical Suture Materials.

Surgical site infections (SSI) occur very frequently during post-operative procedures and are often treated with oral antibiotics, which may cause some side effects. This type of infection could be avoided by encapsulating antimicrobial/anti-inflammatory drugs within the surgical suture materials so that they can more efficiently act on the site of action during wound closure, avoiding post-operative bacterial infection and spreading. This work was aimed at developing novel electrospun bio-based anti-infective fibre-based yarns as novel suture materials for preventing surgical site infections. For this, yarns based on flying intertwined microfibres (1.95 ± 0.22 µm) were fabricated in situ during the electrospinning process using a specially designed yarn collector. The electrospun yarn sutures (diameter 300-500 µm) were made of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with different contents of 3HV units and contained ciprofloxacin hydrochloride (CPX) as the antimicrobial active pharmaceutical ingredient (API). The yarns were then analysed by scanning electron microscopy, Fourier transform infrared spectroscopy, wide-angle X-ray scattering, differential scanning calorimetry, and in vitro drug release. The yarns were also analysed in terms of antimicrobial and mechanical properties. The material characterization indicated that the varying polymer molecular architecture affected the attained polymer crystallinity, which was correlated with the different drug-eluting profiles. Moreover, the materials exhibited the inherent stiff behaviour of PHBV, which was further enhanced by the API. Lastly, all the yarn sutures presented antimicrobial properties for a time release of 5 days against both Gram-positive and Gram-negative pathogenic bacteria. The results highlight the potential of the developed antimicrobial electrospun yarns in this study as potential innovative suture materials to prevent surgical infections.

Nanoencapsulation and Nanocoating of Bioactives of Application Interest in Food, Nutraceuticals and Pharma.

Bioactives are functional molecules that pose several challenges, including poor solubility, low permeability, and low chemical, biochemical, or process stability, resulting in reduced functionality and bioavailability [...].

Electrospun films incorporating humic substances of application interest in sustainable active food packaging.

Sustainable active food packaging is essential to reduce the use of plastics, preserve food quality and minimize the environmental impact. Humic substances (HS) are rich in redox-active compounds, such as quinones, phenols, carboxyl, and hydroxyl moieties, making them functional additives for biopolymeric matrices, such as poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). Herein, composites made by incorporating different amounts of HS into PHBV were developed using the electrospinning technology and converted into homogeneous and continuous films by a thermal post-treatment to obtain a bioactive and biodegradable layer which could be part of a multilayer food packaging solution. The morphology, thermal, optical, mechanical, antioxidant and barrier properties of the resulting PHBV-based films have been evaluated, as well as the antifungal activity against Aspergillus flavus and Candida albicans and the antimicrobial properties against both Gram (+) and Gram (-) bacterial strains. HS show great potential as natural additives for biopolymer matrices, since they confer antioxidant, antimicrobial, and antifungal properties to the resulting materials. In addition, barrier, optical and mechanical properties highlighted that the obtained films are suitable for sustainable active packaging. Therefore, the electrospinning methodology is a promising and sustainable approach to give biowaste a new life through the development of multifunctional materials suitable in the active bio-packaging.

Effect of the Presence of Lignin from Woodflour on the Compostability of PHA-Based Biocomposites: Disintegration, Biodegradation and Microbial Dynamics.

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) has gained attention as a possible substitute for conventional polymers that could be integrated into the organic recycling system. Biocomposites with 15% of pure cellulose (TC) and woodflour (WF) were prepared to analyze the role of lignin on their compostability (58 °C) by tracking the mass loss, CO2 evolution, and the microbial population. Realistic dimensions for typical plastic products (400 µm films), as well as their service performance (thermal stability, rheology), were taken into account in this hybrid study. WF showed lower adhesion with the polymer than TC and favored PHBV thermal degradation during processing, also affecting its rheological behavior. Although all materials disintegrated in 45 days and mineralized in less than 60 days, lignin from woodflour was found to slow down the bioassimilation of PHBV/WF by limiting the access of enzymes and water to easier degradable cellulose and polymer matrix. According to the highest and the lowest weight loss rates, TC incorporation allowed for higher mesophilic bacterial and fungal counts, while WF seemed to hinder fungal growth. At the initial steps, fungi and yeasts seem to be key factors in facilitating the later metabolization of the materials by bacteria.

Dragon's Blood Sap Microencapsulation within Whey Protein Concentrate and Zein Using Electrospraying Assisted by Pressurized Gas Technology.

Dragon's blood sap (DBS) obtained from the bark of Croton lechleri (Müll, Arg.) is a complex herbal remedy of pharmacological interest due to its high content in polyphenols, specifically proanthocyanidins. In this paper, electrospraying assisted by pressurized gas (EAPG) was first compared with freeze-drying to dry natural DBS. Secondly, EAPG was used for the first time to entrap natural DBS at room temperature into two different encapsulation matrices, i.e., whey protein concentrate (WPC) and zein (ZN), using different ratios of encapsulant material: bioactive compound, for instance 2:1 w/w and 1:1 w/w. The obtained particles were characterized in terms of morphology, total soluble polyphenolic content (TSP), antioxidant activity, and photo-oxidation stability during the 40 days of the experiment. Regarding the drying process, EAPG produced spherical particles with sizes of 11.38 ± 4.34 µm, whereas freeze-drying produced irregular particles with a broad particle size distribution. However, no significant differences were detected between DBS dried by EAPG or freeze-drying in TSP, antioxidant activity, and photo-oxidation stability, confirming that EAPG is a mild drying process suitable to dry sensitive bioactive compounds. Regarding the encapsulation process, the DBS encapsulated within the WPC produced smooth spherical microparticles, with average sizes of 11.28 ± 4.28 µm and 12.77 ± 4.54 µm for ratios 1:1 w/w and 2:1 w/w, respectively. The DBS was also encapsulated into ZN producing rough spherical microparticles, with average sizes of 6.37 ± 1.67 µm and 7.58 ± 2.54 µm for ratios 1:1 w/w and 2:1 w/w, respectively. The TSP was not affected during the encapsulation process. However, a slight reduction in antioxidant activity measured by DPPH was observed during encapsulation. An accelerated photo-oxidation test under ultraviolet light confirmed that the encapsulated DBS showed an increased oxidative stability in comparison with the non-encapsulated DBS, with the stability being enhanced for the ratio of 2:1 w/w. Among the encapsulating materials and according to the ATR-FTIR results, ZN showed increased protection against UV light. The obtained results demonstrate the potential of EAPG technology in the drying or encapsulation of sensitive natural bioactive compounds in a continuous process available at an industrial scale, which could be an alternative to freeze-drying.

Electrospun Multilayered Films Based on Poly(3-hydroxybutyrate-co-3-hydroxyvalerate), Copolyamide 1010/1014, and Electrosprayed Nanostructured Silica.

In this research, bio-based electrospun multilayered films for food packaging applications with good barrier properties and close to superhydrophobic behavior were developed. For this purpose, two different biopolymers, a low-melting point and fully bio-based synthetic aliphatic copolyamide 1010/1014 (PA1010/1014) and the microbially synthesized poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and food-contact-complying organomodified silica (SiO2) nanostructured microparticles, were processed by electrospinning. The production of the multilayer structure was finally obtained by means of a thermal post-treatment, with the aim to laminate all of the components by virtue of the so-called interfiber coalescence process. The so developed fully electrospun films were characterized according to their morphology, their permeance to water vapor and oxygen, the mechanical properties, and their water contact angle properties. Interestingly, the annealed electrospun copolyamide did not show the expected improved barrier behavior as a monolayer. However, when it was built into a multilayer form, the whole assembly exhibited a good barrier, an improved mechanical performance compared to pure PHBV, an apparent water contact angle of ca. 146°, and a sliding angle of 8°. Consequently, these new biopolymer-based multilayer films could be a bio-based alternative to be potentially considered in more environmentally friendly food packaging strategies.

Development and Characterization of Electrospun Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Biopapers Containing Cerium Oxide Nanoparticles for Active Food Packaging Applications.

Food quality is mainly affected by oxygen through oxidative reactions and the proliferation of microorganisms, generating changes in its taste, odor, and color. The work presented here describes the generation and further characterization of films with active oxygen scavenging properties made of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) loaded with cerium oxide nanoparticles (CeO2NPs) obtained by electrospinning coupled to a subsequent annealing process, which could be used as coating or interlayer in a multilayer concept for food packaging applications. The aim of this work is to explore the capacities of these novel biopolymeric composites in terms of O2 scavenging capacity, as well as antioxidant, antimicrobial, barrier, thermal, and mechanical properties. To obtain such biopapers, different ratios of CeO2NPs were incorporated into a PHBV solution with hexadecyltrimethylammonium bromide (CTAB) as a surfactant. The produced films were analyzed in terms of antioxidant, thermal, antioxidant, antimicrobial, optical, morphological and barrier properties, and oxygen scavenging activity. According to the results, the nanofiller showed some reduction of the thermal stability of the biopolyester but exhibited antimicrobial and antioxidant properties. In terms of passive barrier properties, the CeO2NPs decreased the permeability to water vapor but increased the limonene and oxygen permeability of the biopolymer matrix slightly. Nevertheless, the oxygen scavenging activity of the nanocomposites showed significant results and improved further by incorporating the surfactant CTAB. The PHBV nanocomposite biopapers developed in this study appear as very interesting constituents for the potential design of new active organic recyclable packaging materials.

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Electrospun Nanofibers Containing Natural Deep Eutectic Solvents Exhibiting a 3D Rugose Morphology and Charge Retention Properties.

In the present study, electrospun nanofibers of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), a biodegradable polyester, containing natural deep eutectic solvents (NADES) were obtained and reported for the first time, exhibiting an unreported 3D morphology and enhanced charge retention properties. Choline chloride (ChCl)/urea/water in a molar ratio of 1:2:1 was used as the NADES model system. Electrospun nanofibers were produced from a 10 wt % solution of PHBV containing 26 wt % NADES with respect to the polymer and were deposited on different substrates, that is, aluminum foil and non-woven spunbond polypropylene (PP). The morphology and charge retention ability were characterized under different conditions and on different substrates. The attained fiber morphology for the NADES-containing mats showed an average fiber diameter of around 300 nm, whereas the pure PHBV polymer under the same conditions produced electrospun fibers of around 880 nm. However, the deposition of PHBV/ChCl/urea/water fibers resulted in a surprising macroscopic rugose 3D surface morphology made of aligned nanofibers when processed at 50% relative humidity (RH). The nanofiber grammages above which this 3D morphology, associated with NADES-induced charge retention, formed was found to be dependent on the substrate used and RH. This morphology was not seen at 20% RH nor when pure PHBV was produced. Charge stability studies revealed that PHBV/ChCl/urea/water nanofibers exhibited lasting charge retention, especially when sandwiched between spunbond polypropylene textiles. Finally, such multilayer structures containing a very thin double layer of PHBV/ChCl/urea/water fibers after corona treatment exhibited improved paraffin aerosol penetration, which was ascribed to the combination of thinner fibers and their charge retention capacity. The here-developed electrospun PHBV fibers containing NADES demonstrated for the first time a new potential application as electret filter media.

Postharvest Quality Improvement of Tomato (Solanum lycopersicum L.) Fruit Using a Nanomultilayer Coating Containing Aloe vera.

The effectiveness of an alginate/chitosan nanomultilayer coating without (NM) and with Aloe vera liquid fraction (NM+Av) was evaluated on the postharvest quality of tomato fruit at 20 °C and 85% relative humidity (RH) to simulate direct consumption. Both nanomultilayer coatings had comparable effects on firmness and pH values. However, the NM+Av coating significantly reduced weight loss (4.5 ± 0.2%) and molds and yeasts (3.5-4.0 log CFU g-1) compared to uncoated fruit (16.2 ± 1.2% and 8.0 ± 0.0 log CFU g-1, respectively). It notably lowered O2 consumption by 70% and a 52% decrease in CO2 production, inhibiting ethylene synthesis. Visual evaluation confirmed NM+Av's efficacy in preserving the postharvest quality of tomato. The preservation of color, indicated by the Minolta color (a*/b*) values, demonstrated NM+Av's ability to keep the light red stage compared to uncoated fruit. The favorable effects of NM+Av coating on enhancing postharvest quality indicates it as a potential alternative for large-scale tomato fruit preservation.

Development of Multilayer Ciprofloxacin Hydrochloride Electrospun Patches for Buccal Drug Delivery.

Bacterial infections in the oral cavity can become a serious problem causing pain, sores and swelling for several weeks. This type of infection could be alleviated using mucoadhesive delivery systems, allowing local administration of the antibiotic to inhibit bacterial spreading. This work reports the development of a multilayer antibiotic patch containing ciprofloxacin hydrochloride (CPX)-loaded electrospun fibers for the treatment of such infections. For this, the release kinetics of the CPX-loaded fibers was modulated using different ratios of polyester blends. The selected reservoir layer was analyzed by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), wide angle x-ray scattering (WAXS) and differential scanning calorimetry (DSC). These analyses confirmed the presence and good distribution of the drug in the fibers and that the drug is in an amorphous state within the reservoir layer. To enhance mucoadhesion whilst ensuring drug directionality, the reservoir layer was assembled to a backing and an adhesive layer. This multilayer patch was assessed in terms of in vitro drug release, adhesion and antimicrobial properties. The multilayer strategy showed excellent antimicrobial properties over time and also a strong adhesion patch time in the volunteers for an average of 7 h. These results highlight the capabilities of multilayer electrospun patches as platforms to treat oral infections.

Effect of Whey Protein Purity on the Characteristics of Algae Oil-Loaded Encapsulates Obtained by Electrospraying Assisted by Pressurized Gas.

In this paper, the effect of protein purity in three different whey protein grades on the characteristics of algae oil encapsulates obtained via room-temperature electrospraying assisted by pressurized gas (EAPG) encapsulation process was studied. Three different commercial grades of whey protein purity were evaluated, namely 35, 80, and 90 wt.%. Oil nanodroplets with an average size of 600 nm were homogeneously entrapped into whey protein microparticles 3 µm in size. However, the sphericity and the surface smoothness of the microparticles increased by increasing the protein purity in the grades of whey protein studied. The porosity of the microparticles was also dependent on protein purity as determined by nitrogen adsorption-desorption isotherms, being smaller for larger contents of protein. Interestingly, the lowest extractable oil was obtained with WP35, probably due to the high content of lactose. The peroxide values confirmed the superior protective effect of the protein, obtaining the smallest peroxide value for WP90, a result that is consistent with its reduced porosity and with its lower permeability to oxygen, as confirmed by the fluorescence decay-oxygen consumption method. The accelerated stability assay against oxidation confirmed the higher protection of the WP80 and WP90. In addition, the increased content in protein implied a higher thermal stability according to the thermogravimetric analysis. These results further confirm the importance of the adequate selection of the composition of wall materials together with the encapsulation method.

Development and Characterization of Fully Renewable and Biodegradable Polyhydroxyalkanoate Blends with Improved Thermoformability.

Poly(3-hydroxybutyrate-co-3-valerate) (PHBV), being one of the most studied and commercially available polyhydroxyalkanoates (PHAs), presents an intrinsic brittleness and narrow processing window that currently hinders its use in several plastic applications. The aim of this study was to develop a biodegradable PHA-based blend by combining PHBV with poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), another copolyester of the PHA family that shows a more ductile behavior. Blends of PHBV with 20% wt., 30% wt., and 40% wt. of PHBH were obtained by melt mixing, processed by cast extrusion in the form of films, and characterized in terms of their morphology, crystallization behavior, thermal stability, mechanical properties, and thermoformability. Full miscibility of both biopolymers was observed in the amorphous phase due to the presence of a single delta peak, ranging from 4.5 °C to 13.7 °C. Moreover, the incorporation of PHBH hindered the crystallization process of PHBV by decreasing the spherulite growth rate from 1.0 µm/min to 0.3 µm/min. However, for the entire composition range studied, the high brittleness of the resulting materials remained since the presence of PHBH did not prevent the PHBV crystalline phase from governing the mechanical behavior of the blend. Interestingly, the addition of PHBH greatly improved the thermoformability by widening the processing window of PHBV by 7 s, as a result of the increase in the melt strength of the blends even for the lowest PHBH content.

Antimutagenic and Antiproliferative Activity of the Coccoloba uvifera L. Extract Loaded in Nanofibers of Gelatin/Agave Fructans Elaborated by Electrospinning.

BACKGROUND: The Coccoloba uvifera L. species is currently considered an important source of compounds of high biological value such as lupeol. This is related to different and important biological activities to human health. OBJECTIVE: The objective of this study was to encapsulate the C. uvifera extract in nanofibers made with the biopolymers gelatin (G)/high-grade polymerization agave fructans (HDPAF) in the proportions 1:0, 1:1, 1:2, 1:3 and 0:1, through the electrospinning process, in addition to evaluating the antimutagenic and antiproliferative properties of the encapsulated extract. METHODS: The physicochemical characteristics of the nanofibers were evaluated, as well as the antiproliferative and antimutagenic activities of the encapsulated and unencapsulated extract. SEM evaluation shows nanofibers of smooth, continuous morphology and nanometric size (50-250 nm). The TGA, FTIR-ATR, HPLC-MS analyses reveal the presence of the extract in the nanofibers. RESULTS: The extract did not show a mutagenic effect during the development of the Ames test, on the other hand, the MTT test showed the antiproliferative effect at the concentrations of 50 and 100 µg/mL of extract. CONCLUSION: The extract of C. uvifera loaded in nanofibers elaborated by electrospinning with the G/HDPAF biopolymers conserves its antimutagenic and antiproliferative properties.

Preparation and Characterization of Electrospun Polysaccharide FucoPol-Based Nanofiber Systems.

The electrospinnability of FucoPol, a bacterial exopolysaccharide, is presented for the first time, evaluated alone and in combination with other polymers, such as polyethylene oxide (PEO) and pullulan. The obtained fibers were characterized in terms of their morphological, structural and thermal properties. Pure FucoPol fibers could not be obtained due to FucoPol's low water solubility and a lack of molecular entanglements. Nanofibers were obtained via blending with PEO and pullulan. FucoPol:PEO (1:3 w/w) showed fibers with well-defined cylindrical structure, since the higher molecular weight of PEO helps the continuity of the erupted jet towards the collector, forming stable fibers. WAXS, DSC and TGA showed that FucoPol is an amorphous biopolymer, stable until 220 °C, whereas FucoPol-PEO fibers were stable until 140 °C, and FucoPol:pullulan fibers were stable until 130 °C. Interestingly, blended components influenced one another in intermolecular order, since new peaks associated to intermolecular hierarchical assemblies were seen by WAXS. These results make FucoPol-based systems viable candidates for production of nanofibers for packaging, agriculture, biomedicine, pharmacy and cosmetic applications.

Role of Plasticizers on PHB/bio-TPE Blends Compatibilized by Reactive Extrusion.

Poly(hydroxybutyrate) (PHB) is a biopolymer biologically synthesized by controlled bacterial fermentation from a wide variety of microorganisms. PHB is proposed as a potential green alternative to commonly used plastics in packaging, due to its biodegradability and biocompatibility. However, if PHB is to replace commodities, it has some limitations regarding its thermo-mechanical performance to overcome. Among them are its critically the low toughness values at room temperature and poor thermoforming ability. With the aim of overcoming these weaknesses, in this work, blends of PHB with the addition of a biodegradable thermoplastic elastomer (bio-TPE) were prepared and evaluated. Films of such compounds were made by cast extrusion. In order to enhance the compatibility of both polymers during the extrusion process, three different reactive agents (poly-hexametylene diisocianate, triglycidyl isocyanurate, and Joncryl® ADR-4368) were assessed. The morphology and mechanical- and thermal properties of the films obtained were analyzed. In addition, the thermoforming ability of the produced films was evaluated. The results show that the plasticizers present in the bio-TPE interacted with the reactive agents, making them chemical competitors and altering the outcome of the blends.

Super-Repellent Paper Coated with Electrospun Biopolymers and Electrosprayed Silica of Interest in Food Packaging Applications.

In the current work, a super-repellent biopaper suitable for food contact applications was developed. To do this, three different kinds of biopolymers, namely polylactide (PLA), poly(ε-caprolactone) (PCL), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), and hydrophobic silica microparticles (SiO2), were sequentially processed by electrohydrodynamic processing (EDHP). As a first step, the ultrathin biopolymer fibers were deposited onto a commercial food contact cellulose paper by electrospinning and, thereafter, the nanostructured silica was sequentially electrosprayed. The multilayer coated papers were annealed at different temperatures to promote adhesion between the layers and enhance the super-repellent properties. The developed coatings were characterized in terms of morphology, permeance to water vapor, adhesion, mechanical resistance, and contact and sliding angle. The resultant multilayer biopapers presented a hierarchical micro/nanostructured surface with an apparent water contact angle (WCA) higher than 155° and sliding angle (SA) lower than 10° for all the tested biopolymers used. Among the different multilayer approaches, it was observed that the paper/PHBV/SiO2 showed the best performance, in terms of water vapor permeance; resistance after the tape peeling-off test; and food super-repelling properties to water, yogurt, and custard. Overall, this study presents the successful generation of super-repellent biopapers coated with PLA, PCL, or PHBV along with hydrophobic silica microparticles and its effectiveness for easy emptying food packaging applications to reduce food waste.

Development and Characterization of Electrospun Fiber-Based Poly(ethylene-co-vinyl Alcohol) Films of Application Interest as High-Gas-Barrier Interlayers in Food Packaging.

In the present study, poly(ethylene-co-vinyl alcohol) with 44 mol % ethylene content (EVOH44) was managed to be processed, for the first time, by electrospinning assisted by the coaxial technology of solvent jacket. In addition to this, different suspensions of cellulose nanocrystals (CNCs), with contents ranging from 0.1 to 1.0 wt %, were also electrospun to obtain hybrid bio-/non-bio nanocomposites. The resultant fiber mats were thereafter optimally annealed to promote interfiber coalescence at 145 °C, below the EVOH44 melting point, leading to continuous transparent fiber-based films. The morphological analysis revealed the successful distribution of CNCs into EVOH44 up to contents of 0.5 wt %. The incorporation of CNCs into the ethylene-vinyl alcohol copolymer caused a decrease in the crystallization and melting temperatures (TC and Tm) of about 12 and 7 °C, respectively, and also crystallinity. However, the incorporation of CNCs led to enhanced thermal stability of the copolymer matrix for a nanofiller content of 1.0 wt %. Furthermore, the incorporation of 0.1 and 0.5 wt % CNCs produced increases in the tensile modulus (E) of ca. 38% and 28%, respectively, but also yielded a reduction in the elongation at break and toughness. The oxygen barrier of the hybrid nanocomposite fiber-based films decreased with increasing the CNCs content, but they were seen to remain high barrier, especially in the low relative humidity (RH) regime, i.e., at 20% RH, showing permeability values lower than 0.6 × 10-20 m3·m·m-2·Pa-1·s-1. In general terms, an optimal balance in physical properties was found for the hybrid copolymer composite with a CNC loading of 0.1 wt %. On the overall, the present study demonstrates the potential of annealed electrospun fiber-based high-barrier polymers, with or without CNCs, to develop novel barrier interlayers to be used as food packaging constituents.

Nanostructured Valsartan Microparticles with Enhanced Bioavailability Produced by High-Throughput Electrohydrodynamic Room-Temperature Atomization.

The high-throughput drying and encapsulation technique called electrospraying assisted by pressurized gas (EAPG) was used for the first time to produce nanostructured valsartan within microparticles of excipients. Valsartan, a poorly absorbed and lipid-soluble drug, was selected since it is considered a good model for BCS class II drugs. Two different polymeric matrices were selected as excipients, i.e., hydroxypropyl methylcellulose (HPMC) and lactose monohydrate, while Span 20 was used as a surfactant. The produced 80% valsartan loading formulations were characterized in terms of morphology, crystallinity, in vitro release, in vitro Caco-2 cells' permeability, and in vivo pharmacokinetic study. Spherical microparticles of ca. 4 µm were obtained within which valsartan nanoparticles were seen to range from 150 to 650 nm. Wide-angle X-ray scattering and differential scanning calorimetry confirmed that valsartan had a lower and/or more ill-defined crystallinity than the commercial source, and photon correlation spectroscopy and transmission electron microscopy proved that it was dispersed and distributed in the form of nanoparticles of controlled size. In vitro dissolution tests showed that the HPMC formulation with the lowest API particle size, i.e., 150 nm, dissolved 2.5-fold faster than the commercial valsartan in the first 10 min. This formulation also showed a 4-fold faster in vitro permeability than the commercial valsartan and a 3-fold higher systemic exposure than the commercial sample. The results proved the potential of the EAPG processing technique for the production of safe-to-handle microparticles containing high quantities of a highly dispersed and distributed nanonized BCS class II model drug with enhanced bioavailability.