Active Packaging Based on Coupled Nylon/PE Pouches Filled with Active Nano-Hybrid: Effect on the Shelf Life of Fresh Milk.

The study reports on the preparation and characterization of an active packaging based on pouches composed of a coupled system nylon/polyethylene (PE). The PE layer was filled with and active nano-hybrid of layered double hydroxide (LDH) on which it was anchored salicylate, as antimicrobial molecule. The release of the salicylate anchored to the LDH was compared to the release of the molecule free dispersed into the PE and resulted much slower. It was evaluated the efficiency of the active packaging to inhibit Pseudomonas aeruginosa, Escherichia coli, Listeria monocytogenes, Salmonella typhimurium, and Campylobacter. Global migration tests on the PE active layer, using ethanol (50% v/v) as food simulant, demonstrated the possibility of such active nanocomposite to be used for food contact being the migration limits in compliance with those imposed from the EU regulation. Fresh milk was packed into the active pouches and pouches with unfilled PE layer, as control. The pH reduction as function of the time, due to the production of lactic acid, resulted much slower in the active packaging. Total bacterial count (TBC) was evaluated on the milk, either packed into the active packaging or the control, up to 50 days of storage at 4 °C. Shelf life of the milk was evaluated using the Gompertz model. It was demonstrated an increasing of the shelf life of milk packaged in active pouches from 6 days up to 10 days.

Combined Effect of Active Packaging of Polyethylene Filled with a Nano-Carrier of Salicylate and Modified Atmosphere to Improve the Shelf Life of Fresh Blueberries.

Blueberries are popular among consumers for their high nutritional value but are highly perishable due to the microbial decay. The use of active packaging that is able to interact with the food through releasing or absorbing substances can be a valid approach to preserve the quality and increase the fruit's shelf-life. In this paper, an active packaging based on polyethylene (PE) filled with a nano-carrier of salicylate was prepared and characterized. Fresh blueberries were packaged in passive modified atmosphere packaging (pMA) for 13 days at 8 °C. The combination of the active filler in bulk and pMA showed a significant inhibition of mold development and a reduction of the respiration rate of fruits. Moreover, the release of salicylate on blueberries did not alter the fruits' sensory traits and preserved the firmness and the nutritional quality. Finally, the combination of active packaging and pMA resulted a valid solution to extend blueberries' shelf-life up to 13 days.

Formulation of a Bio-Packaging Based on Pure Cellulose Coupled with Cellulose Acetate Treated with Active Coating: Evaluation of Shelf Life of Pasta Ready to Eat.

An active packaging based on pure cellulose coupled with cellulose acetate coated with layered double hydroxide (LDH), hosting 4-hydroxybenzoate (listed in EC-Directive 10/2011) as an antimicrobial agent, was formulated and realized. The release of 4-hydroxybenzoate ionically bonded to the LDH layers was much slower than the molecule freely dispersed into the coating. The capability of the active packaging to inhibit Pseudomonas, Escherichia coli, Salmonella and Lactic Bacteria was evaluated, as well as the global migration with three different food simulant (i.e., acetic acid at 3% (v/v), ethanol at 50% (v/v) and vegetable oil) that demonstrated, in compliance with the migration limits of the EU regulation, the suitability of the prepared packaging to be employed as food contact material. Ready to east cooked tomato pasta was packaged into the active trays and in uncoated, as control, up to 30 days at 4 °C. Organoleptic characteristics, mold evolution, total mesophilic aerobic counts (TBC), Enterobacteriaceae, Lactic Bacteria and Pseudomonas, and in colony forming unit per gram (CFU/g), showed a significant activity of 4-hydroxybenzoate in increasing the shelf life of the pasta ready to eat.

Ionic Liquid as Dispersing Agent of LDH-Carbon Nanotubes into a Biodegradable Vinyl Alcohol Polymer.

A Zn/Al layered double hydroxides (LDHs) hosting carbon nanotubes (80% of CNTs) was synthesized and dispersed into a commercial biodegradable highly amorphous vinyl alcohol polymer at different loading (i.e., 1; 3; 5; 10 wt%). In order to improve the degree of dispersion of the filler into the polymer matrix, an ionic liquid (IL) based on 1-hexadecyl-3-methylimidazolium dimethyl-5-sodiosulfoisophthalate was added to the composites' mixtures. Structural characterization of filler and polymeric composites was carried out. The analysis of thermal, mechanical and electrical properties of the composites, resulted improved compared to the unfilled material, allowed to hypothesize a good dispersion of the LDH-CNTs lamellar filler into the polymer matrix-assisted by the ionic liquid. This was demonstrated comparing electrical conductivity of composite at 5% of LDH-CNTs in the presence and in the absence of IL. The experimental results showed that the electrical conductivity of the sample with IL is four orders of magnitude higher than the one without IL. Furthermore, the percolation threshold of the whole system resulted very low-0.26% of LDH-CNTs loading, which is 0.21% of CNTs.

PET and Active Coating Based on a LDH Nanofiller Hosting p-Hydroxybenzoate and Food-Grade Zeolites: Evaluation of Antimicrobial Activity of Packaging and Shelf Life of Red Meat.

Layered double hydroxide (LDH) nanofillers were considered as hosts of p-hydroxybenzoate as an antimicrobial molecule for active coating. A food grade resin with LDH-p-hydroxybenzoate and two different types of food grade zeolites was used to prepare active coatings for Polyethylene terephthalate (PET) trays. The release kinetics of the active molecule were followed using UV spectrophotometry and the experimental results were analyzed with the Gallagher-Corrigan model. The thermal properties of the coating mixtures and the PET coating were analyzed and found to be dependent on the coating's composition. On the basis of CO2 transmission rate and off-odors tests, the best coating composition was selected. Global migration in ethanol (10% v/v), acetic acid (3% w/v), and vegetable oil, and specific migration of p-hydroxybenzoic acid revealed the suitability of the material for food contact. Antimicrobial tests on the packaging demonstrated a good inhibition against Salmonella spp. and Campylobacter jejuni. Red meat was packed into the selected active materials and results were compared to uncoated PET packaging. Color tests (browning of the meat) and analysis of Enterobacteriaceae spp. and total viable count evolution up to 10 days of storage demonstrated the capability of the considered active packaging in prolonging the shelf life of red meat.

Ball Milling to Produce Composites Based of Natural Clinoptilolite as a Carrier of Salicylate in Bio-Based PA11.

Antimicrobial packaging systems are recognized as effective approaches to prolong food shelf life. In this context, Bio-based PA11 loaded with a food-grade zeolite were prepared using ball milling technology in the dry state. Zeolite was filled with sodium salicylate, as an antimicrobial agent, and incorporated into the polymer matrix (~50 wt % of salicylate) at different loadings (up to 10 wt %). Structural characterization and an analysis of the physical properties (thermal, barrier, mechanical) were conducted on the composites' films and compared with the unfilled PA11. The successful entrapment of the antimicrobial molecule into the zeolite's cavities was demonstrated by the thermal degradation analysis, showing a delay in the molecule's degradation. Morphological organization, evaluated using SEM analysis, indicated the homogeneous distribution of the filler within the polymer matrix. The filler improves the thermal stability of PA11 and mechanical properties, also enhancing its barrier properties against CO2 and O2. The elongated form of the zeolite particles, evaluated through SEM analysis, was used to model the permeability data. The controlled release of salicylate, evaluated as a function of time and found to depend on the filler loading, was analyzed using the Gallagher‒Corrigan model.

Green pesticides based on cinnamate anion incorporated in layered double hydroxides and dispersed in pectin matrix.

This paper reports the preparation of green pesticides based on nano-hybrids composed of a Layered Double Hydroxide (LDH) with cinnamate anion. The dispersion into a pectin matrix was obtained using high energy ball milling in wet conditions. Structure and physical properties of the fillers and the composites films were evaluated. Controlled release of cinnamate was followed using UV spectrophotometry and the release kinetics were found to be dependent on the filler loading. The experimental results were analyzed by the Gallagher-Corrigan model. Antimicrobial activity was evaluated on different bacterial strains, as well as plant pathogens belonging to the genus Phytophthora using modified agar diffusion, broth microdilution and dual culture methods, respectively. Experimental results suggested the possibility to use the analyzed composites as green protective coatings for crops' protection.

Antimicrobial Membranes of Bio-Based PA 11 and HNTs Filled with Lysozyme Obtained by an Electrospinning Process.

Bio-based membranes were obtained using Polyamide 11 (PA11) from renewable sources and a nano-hybrid composed of halloysite nanotubes (HNTs) filled with lysozyme (50 wt % of lysozyme), as a natural antimicrobial molecule. Composites were prepared using an electrospinning process, varying the nano-hybrid loading (i.e., 1.0, 2.5, 5.0 wt %). The morphology of the membranes was investigated through SEM analysis and there was found to be a narrow average fiber diameter (0.3-0.5 µm). The mechanical properties were analyzed and correlated to the nano-hybrid content. Controlled release of lysozyme was followed using UV spectrophotometry and the release kinetics were found to be dependent on HNTs-lysozyme loading. The experimental results were analyzed by a modified Gallagher-Corrigan model. The application of the produced membranes, as bio-based pads, for extending the shelf life of chicken slices has been tested and evaluated.

Ionic Liquid as Surfactant Agent of Hydrotalcite: Influence on the Final Properties of Polycaprolactone Matrix.

This paper reports the surface treatment of layered double hydroxide (LDH) by using ionic liquid (IL) composed of phosphonium cation combined with 2-ethylhexanoate (EHT) counter anion as surfactant agent. Then, different amounts (1, 3, 5 and 7 wt %) of thermally stable organically modified LDH (up to 350 °C) denoted LDH-EHT were incorporated into polycaprolactone (PCL) matrix by mechanical milling. The influence of LDH-EHT loading has been investigated on the physical properties, such as the thermal and barrier properties, as well as the morphologies of the resulting nanocomposites. Thus, intercalated or microcomposite morphologies were obtained depending on the LDH-EHT loading, leading to significant reduction of the diffusion coefficient respect to water vapor. The modulation of barrier properties, using low functionalized filler amount, is a very important aspect for materials in packaging applications.

Phosphonium ionic liquid as interfacial agent of layered double hydroxide: Application to a pectin matrix.

Phosphonium ionic liquid (IL) combined with 2-ethylhexanoate counter anion has been used as interfacial agent of layered double hydroxide (LDH). First, the intercalation of hexanoate anion between the LDH layers was confirmed by thermogravimetric analysis (TGA) and X-ray diffraction (XRD). Then, this thermally stable organophilic LDH was introduced at different amount (1, 3 and 5wt%) into pectin matrix leading to an increase of the thermal stability of the resulting nanocomposites (+35-40°C). In addition, the good distribution of the modified LDH led to an increase of the mechanical performances through the elastic moduli (+60%) as well as a significant increase of the water barrier properties of two orders of magnitude for the pectin containing 5wt% of LDH-Ionic Liquid.

Nanocomposites Based on PCL and Halloysite Nanotubes Filled with Lysozyme: Effect of Draw Ratio on the Physical Properties and Release Analysis.

Halloysite nanotubes (HNTs) were loaded with lsozyme, as antimicrobial molecule, at a HNTs/lysozyme ratio of 1:1. Such a nano-hybrid was incorporated into a poly (ε-caprolactone) (PCL) matrix at 10 wt % and films were obtained. The nano-composites were submitted to a cold drawn process at three different draw ratios, λ = 3, 4, and 5, where λ is l(final length)/l0(initial length). Morphology, physical, and barrier properties of the starting nanocomposite and drawn samples were studied, and correlated to the release of the lysozyme molecule. It was demonstrated that with a simple mechanical treatment it is possible to obtain controlled release systems for specific active packaging requirements.

Pectin functionalized with natural fatty acids as antimicrobial agent.

Several pectin derivatives were prepared by chemical modifications of the polysaccharide with natural fatty acids. The obtained biodegradable pectin-based materials, pectin-linoleate, pectin-oleate and pectin-palmitate, were investigated for their antimicrobial activity against several bacterial strains, Staphylococcus aureus and Escherichia coli. Good results were obtained for pectin-oleate and pectin-linoleate, which inhibit the growth of the selected microorganisms by 50-70%. They exert the better antimicrobial activity against S. aureus. Subsequently, the pectin-oleate and the pectin-linoleate samples were coated on polyethylene films and were assessed for their capacity to capture the oxygen molecules, reducing its penetration into the polymeric support. These results confirmed a possible application of the new materials in the field of active food packaging.

Deposition of LDH on plasma treated polylactic acid to reduce water permeability.

A simple and scalable deposition process was developed to prepare polylactic acid (PLA) coatings with enhanced water barrier properties for food packaging applications. This method based on electrostatic interactions between the positively charged layers of layered double hydroxides (LDHs) modified with ionic liquids (ILs) and the negatively charged plasma treated polylactic acid leads to homogeneous, stable, and highly durable coatings. Deposition of the LDH coatings increases the surface hydrophobicity of the neat PLA, which results to a decrease in water permeability by about 35%.

Solvent-free synthesis of modified pectin compounds promoted by microwave irradiation.

Microwave-assisted solvent-free modification of pectin was successfully accomplished, consisting in the esterification of several fatty acids by pectin alcoholic functions. The reaction was performed by simply mixing the reagents with a catalytic amount of the inorganic base (potassium carbonate) and irradiating the obtained mixture with microwaves for a short time (3-6 min). The replacement of the traditional heating with a microwave source allowed the development of a new synthetic protocol which provided increased yield of the final products, since it eliminates the small amount of degraded polysaccharide produced during traditional oil bath heating. The desired esters were fully characterized by FT-IR spectroscopy and thermogravimetric analysis.

Synthesis and physical properties of new layered double hydroxides based on ionic liquids: application to a polylactide matrix.

Ionic liquids based on tetraalkylphosphonium salts combined with different anions (decanoate and dodecylsulfonate) have been used as intercalating agents of layered double hydroxides (LDHs) by ion exchange. The synthesized phosphonium-treated LDHs display a dramatically improved thermal degradation and a significant increase in the interlayer distance as confirmed by thermogravimetric analysis (TGA) and X-ray Diffraction (XRD), respectively. To highlight the effect of thermostable ionic liquids, a very low amount of LDHs has been introduced within a polylactide (PLA) matrix and PLA/LDHs nanocomposites have been processed in melt by twin-screw extrusion. Then, transmission electron microscopy (TEM) analysis has been used to investigate the influence of ILs on the different morphologies of these nanocomposites. Even though the thermal stability of PLA matrix decreased, an excellent stiffness-toughness compromise has been obtained.

Pectins filled with LDH-antimicrobial molecules: preparation, characterization and physical properties.

Nanohybrids of layered double hydroxide (LDH) with intercalated active molecules: benzoate, 2,4-dichlorobenzoate, para-hydroxybenzoate and ortho-hydroxybenzoate, were incorporated into pectins from apples through high energy ball milling in the presence of water. Cast films were obtained and analysed. X-ray diffraction analysis showed a complete destructuration of all nanohybrids in the pectin matrix. Thermogravimetric analysis showed a better thermal resistance of pectin in the presence of fillers, especially para-hydroxybenzoate and ortho-hydroxybenzoate. Mechanical properties showed an improvement of elastic modulus in particular for LDH-para-hydroxybenzoate nanohybrid, due probably to a better interaction between pectin matrix and nanohybrid layers. Barrier properties (sorption and diffusion) to water vapour showed improvement in the dependence on the intercalated active molecule, the best improvement was achieved for composites containing para-hydroxybenzoate molecules, suggesting that the interaction between the filler phase and the polymer plays an important role in sorption and diffusion phenomena. Incorporation of these active molecules gave antimicrobial properties to the composite films giving opportunities in the field of active packaging.

Physical and water sorption properties of chemically modified pectin with an environmentally friendly process.

A synthetic process was developed to modify pectin samples under solvent free conditions, obtaining pectin at increasing concentration of palmitic, oleic, and linoleic acids. The weight loss of the modified powders showed a degradation path very similar to the pure pectin, indicating that the pristine structure was preserved after the chemical modification. A decreasing mass of evaporating water on increasing the fatty acid concentration, in particular for the palmitic acid modification, indicated a reduced water sorption by the modified powders. Differential scanning calorimetry confirmed the thermogravimetric results and in addition indicated the crystallization of the lateral chains in the case of palmitic-acid-modified pectins. This result was confirmed by X-ray diffractograms of the palmitic acid samples, indicating the main crystallization of the form C, although possible orientation phenomena can be inferred. The sorption curves of either the pristine pectin or the modified samples showed a dual sorption behavior. The sorption curves were interpreted by the BET and GAB equations, both giving very similar results. Palmitic acid modification was very effective in reducing all sorption parameters, whereas in the case of oleic and linoleic acids, only at high concentrations was the hydrophobic influence detected.

New polymeric composites based on poly(-caprolactone) and layered double hydroxides containing antimicrobial species.

Benzoate (Bz), 2,4-dichlorobenzoate (BzDC), and p- and o-hydroxybenzoate (p- and o-BzOH) anions with antimicrobial activity have been intercalated into [Zn(0.65)Al(0.35)(OH)(2)](NO(3))(0.35).0.6H(2)O, layered double hydroxide (LDH), via anion-exchange reactions. The composition of the obtained intercalation compounds, determined by chemical, thermogravimetric, and ion chromatographic analyses, indicates that benzoate and benzoate derivative anions replace the nitrate counteranions, almost completely. Information on the interactions of the intercalated anions with the inorganic layer have been obtained from Fourier transform IR absorption spectroscopy and powder X-ray diffraction of the samples. It has been found that both the nature and the position of the aromatic ring substituents affect the value of the basal distance and the host-guest hydrogen bond network. Knowledge of the chemical composition, basal distance, and van der Waals dimensions of the guests has finally allowed the proposal of structural models of the intercalation compounds that have been used as fillers of poly(caprolactone), a biodegradable polymer. Films of polymeric composites were obtained by hot-pressing the powders of polymer and filler previously milled by a high-energy ball milling procedure. X-ray diffraction analysis and optical and scanning electron microscopy of the composites indicate that the LDH samples containing BzDC anions are delaminated into the polymeric matrix, whereas those containing p-BzOH anions maintain for the most part the crystal packing and give rise to microcomposites. Intermediate behavior was found for LDH modified with Bz and o-BzOH anions because exfoliated and partly intercalated composites were obtained. Preliminary antimicrobial tests indicate that the composites are able to inhibit the Saccharomyces cerevisiae growth of 40% in comparison with the growth in a pure culture medium. The composites can be studied as the model for "active packaging" systems because of the antimicrobial properties of the anions anchored to the LDH layer.