High-Oxygen-Barrier Multilayer Films Based on Polyhydroxyalkanoates and Cellulose Nanocrystals

This study reports on the development and characterization of organic recyclable high-oxygen-barrier multilayer films based on different commercial polyhydroxyalkanoate (PHA) materials, including a blend with commercial poly(butylene adipate-co-terephthalate) (PBAT), which contained an inner layer of cellulose nanocrystals (CNCs) and an electrospun hot-tack adhesive layer of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) derived from cheese whey (CW). As a result, the full multilayer structures were made from bio-based and/or compostable materials. A characterization of the produced films was carried out in terms of morphological, optical, mechanical, and barrier properties with respect to water vapor, limonene, and oxygen. Results indicate that the multilayer films exhibited a good interlayer adhesion and contact transparency. The stiffness of the multilayers was generally improved upon incorporation of the CNC interlayer, whereas the enhanced elasticity of the blend was reduced to some extent in the multilayer with CNCs, but this was still much higher than for the neat PHAs. In terms of barrier properties, it was found that 1 µm of the CNC interlayer was able to reduce the oxygen permeance between 71% and 86%, while retaining the moisture and aroma barrier of the control materials.

Development of Active Barrier Multilayer Films Based on Electrospun Antimicrobial Hot-Tack Food Waste Derived Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and Cellulose Nanocrystal Interlayers

Active multilayer films based on polyhydroxyalkanoates (PHAs) with and without high barrier coatings of cellulose nanocrystals (CNCs) were herein successfully developed. To this end, an electrospun antimicrobial hot-tack layer made of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) derived from cheese whey, a by-product from the dairy industry, was deposited on a previously manufactured blown film of commercial food contact PHA-based resin. A hybrid combination of oregano essential oil (OEO) and zinc oxide nanoparticles (ZnONPs) were incorporated during the electrospinning process into the PHBV nanofibers at 2.5 and 2.25 wt%, respectively, in order to provide antimicrobial properties. A barrier CNC coating was also applied by casting from an aqueous solution of nanocellulose at 2 wt% using a rod at 1m/min. The whole multilayer structure was thereafter assembled in a pilot roll-to-roll laminating system, where the blown PHA-based film was located as the outer layers while the electrospun antimicrobial hot-tack PHBV layer and the barrier CNC coating were placed as interlayers. The resultant multilayer films, having a final thickness in the 130–150 µm range, were characterized to ascertain their potential in biodegradable food packaging. The multilayers showed contact transparency, interlayer adhesion, improved barrier to water and limonene vapors, and intermediate mechanical performance. Moreover, the films presented high antimicrobial and antioxidant activities in both open and closed systems for up to 15 days. Finally, the food safety of the multilayers was assessed by migration and cytotoxicity tests, demonstrating that the films are safe to use in both alcoholic and acid food simulants and they are also not cytotoxic for Caco-2 cells.

The Impact of Transparency in the Fight Against Corruption

Transparency and corruption are topics with high interest not only for researchers but especially for politicians, citizens and decision takers. Transparency is seen as an important instrument in the fight against corruption. Transparency and corruption phenomena are considered to be the most difficult to assess due to the subjectivity that characterizes them. For this reason, in this study we will show some results based on citizens perception. The method used to collect information regarding citizens perception is questionnaire and than the data are analyzed through a logistic model. Interesting results came out this research such as people who have been in contact with public institutions during the last months have 5,477 times more opportunities to give bribes compared to those who have not been in contact. Transparency is considered a good tool to fight corruption because based on the model result people who know the meaning of the right to information have 86.3% less chance to give bribes than people who do not know the meaning of the right of information. Whereas people who know the Albanian law on the right to information have 48% less chance of bribing than people who do not know this law. Based on these results it is necessary to raise citizen awareness on the use of the right to information as instrument to fight corruption.

Reactive Melt Mixing of Poly(3-Hydroxybutyrate)/Rice Husk Flour Composites with Purified Biosustainably Produced Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate)

Novel green composites based on commercial poly(3-hydroxybutyrate) (PHB) filled with 10 wt % rice husk flour (RHF) were melt-compounded in a mini-mixer unit using triglycidyl isocyanurate (TGIC) as compatibilizer and dicumyl peroxide (DCP) as initiator. Purified poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) produced by mixed bacterial cultures derived from fruit pulp waste was then incorporated into the green composite in contents in the 5–50 wt % range. Films for testing were obtained thereafter by thermo-compression and characterized. Results showed that the incorporation of up to 20 wt % of biowaste derived PHBV yielded green composite films with a high contact transparency, relatively low crystallinity, high thermal stability, improved mechanical ductility, and medium barrier performance to water vapor and aroma. This study puts forth the potential use of purified biosustainably produced PHBV as a cost-effective additive to develop more affordable and waste valorized food packaging articles.

Antimicrobial and Antioxidant Performance of Various Essential Oils and Natural Extracts and Their Incorporation into Biowaste Derived Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Layers Made from Electrospun Ultrathin Fibers

In this research, the antibacterial and antioxidant properties of oregano essential oil (OEO), rosemary extract (RE), and green tea extract (GTE) were evaluated. These active substances were encapsulated into ultrathin fibers of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) derived from fruit waste using solution electrospinning, and the resultant electrospun mats were annealed to produce continuous films. The incorporation of the active substances resulted in PHBV films with a relatively high contact transparency, but it also induced a slightly yellow appearance and increased the films opacity. Whereas OEO significantly reduced the onset of thermal degradation of PHBV, both the RE and GTE-containing PHBV films showed a thermal stability profile that was similar to the neat PHBV film. In any case, all the active PHBV films were stable up to approximately 200 °C. The incorporation of the active substances also resulted in a significant decrease in hydrophobicity. The antimicrobial and antioxidant activity of the films were finally evaluated in both open and closed systems for up to 15 days in order to anticipate the real packaging conditions. The results showed that the electrospun OEO-containing PHBV films presented the highest antimicrobial activity against two strains of food-borne bacteria, as well as the most significant antioxidant performance, ascribed to the films high content in carvacrol and thymol. Therefore, the PHBV films developed in this study presented high antimicrobial and antioxidant properties, and they can be applied as active layers to prolong the shelf life of the foods in biopackaging applications.

Electrospun Poly(ethylene-co-vinyl alcohol)/Graphene Nanoplatelets Composites of Interest in Intelligent Food Packaging Applications

Graphene nanoplatelets (GNPs) were synthetized from graphite powder and, thereafter, embedded in poly(ethylene-co-vinyl alcohol) (EVOH) fibers by electrospinning in the 0.1–2 wt.-% range. The morphological, chemical, and thermal characterization performed on the electrospun nanocomposite fibers mats revealed that the GNPs were efficiently dispersed and rolled along the EVOH fibrilar matrix up to contents of 0.5 wt.-%. Additionally, the dielectric behavior of the nanocomposite fibers was evaluated as a function of the frequency range and GNPs content. The obtained results indicated that their dielectric constant rapidly decreased with the frequency increase and only increased at low GNPs loadings while the nanocomposite fiber mats became electrically conductive, with the maximum at 0.5 wt.-% GNPs content. Finally, the electrospun mats were subjected to a thermal post-treatment and dark films with a high contact transparency were obtained, suggesting that the nanocomposites can be used either in a nonwoven fibers form or in a continuous film form. This study demonstrates the potential of electrospinning as a promising technology to produce GNPs-containing materials with high electrical conductivity that can be of potential interest in intelligent packaging applications as “smart” labels or tags.

Selective interface transparency in graphene nanoribbon based molecular junctions

We investigate the interface effects in graphene based all-carbon molecular electronics and probe opposite effects with respect to the intrinsic feature of an embedded core graphene nanoflake (GNF). For metallic GNFs, good/poor contact transparency occurs when the core device aligns with the center/edge of the electrode. The situation is reversed for a semiconducting GNF as a device.