Ramón Catalá

Overview of Active Polymer-Based Packaging Technologies for Food Applications

Abstract There has been a growing interest and effort over the last few years in the development of novel food packaging concepts, which can play a proactive role regarding product preservation, shelf-life extension, and even improvement. Several strategies have been devised to exert a positive action over the packaged foodstuff, including retention of desirable molecules (i.e., aldehydes, oxygen) and release of substances (i.e., carbon dioxide, aromas). These new developments have been generally termed active packaging technologies. However, many of these emerging active packaging technologies are finding in the versatility and special properties of plastic materials an efficient vehicle to exploit and enhance their commercial interest. This overview examines the most recent developments and technologies designed to include the active principle within the plastic packaging materials and generally termed active plastics technologies. Due to the novelty of most of these active packaging developments, the s...

Development of New Antioxidant Active Packaging Films Based on Ethylene Vinyl Alcohol Copolymer (EVOH) and Green Tea Extract

Ethylene vinyl alcohol copolymer (EVOH) films containing green tea extract were successfully produced by extrusion. The films were brown and translucent, and the addition of the extract increased the water and oxygen barrier at low relative humidity but increased the water sensitivity, the glass transition temperature, and the crystallinity of the films and improved their thermal resistance. An analysis by HPLC revealed that the antioxidant components of the extract suffered partial degradation during extrusion, reducing the content of catechin gallates and increasing the concentration of free gallic acid. Exposure of the films to various food simulants showed that the liquid simulants increased their capacity to reduce DPPH(•) and ABTS(•+) radicals. The release of green tea extract components into the simulant monitored by HPLC showed that all compounds present in the green tea extract were partially released, although the extent and kinetics of release were dependent on the type of food. In aqueous food simulants, gallic acid was the main antioxidant component released with partition coefficient values ca. 200. In 95% ethanol (fatty food simulant) the K value for gallic acid decreased to 8 and there was a substantial contribution of catechins (K in the 1000 range) to a greatly increased antioxidant efficiency. Kinetically, gallic acid was released more quickly than catechins, owing to its faster diffusivity in the polymer matrix as a consequence of its smaller molecular size, although the most relevant effect is the plasticization of the matrix by alcohol, increasing the diffusion coefficient >10-fold. Therefore, the materials here developed with the combination of antioxidant substances that constitute the green tea extract could be used in the design of antioxidant active packaging for all type of foods, from aqueous to fatty products, the compounds responsible for the protection being those with the higher compatibility with the packaged product.

Characterizing the migration of antioxidants from polypropylene into fatty food simulants

The migration (diffusion and equilibrium) processes of antioxidants (AOs) from polypropylene (PP) films of different thicknesses into n-heptane and 95% ethanol as fatty food simulants were analysed at 20, 37 and 60°C. Heptane fully extracted the AOs from the polymer while a partition equilibrium described the migration to ethanol. The kinetics of migration were also studied via the diffusion coefficients. As expected, diffusion was found to be faster when the polymer was in contact with heptane, due to polymer swelling by the solvent. The kinetics of the process in ethanol was described by different theoretical expressions which are discussed. Equations disregarding partition equilibrium failed to describe the process and the diffusion coefficient values obtained through them were much smaller than the actual ones and dependent on film thickness. The results also showed the significance of food simulant selection in the analysis of food-packaging interactions and migration variability with thickness.

Improving the Antioxidant Protection of Packaged Food by Incorporating Natural Flavonoids into Ethylene-Vinyl Alcohol Copolymer (EVOH) Films

Ethylene-vinyl alcohol copolymer (EVOH) films containing catechin or quercetin as antioxidant agents were successfully produced by extrusion. The addition of these bioactive compounds did not modify greatly their water and oxygen permeabilities, Tg, or crystallinity but improved their thermal resistance. Exposure of the films to different food simulants showed that both compounds were released, although the extent and kinetics of release were dependent on the type of food. In aqueous and alcoholic food simulants their release was greater in the case of the catechin-containing samples. Exposure of the films to isooctane and ethanol 95% (fatty food simulants) provided controversial results; no release was observed in isooctane, whereas both bioactive compounds were extracted by ethanol due to their high solubility in alcohol and the plasticizing effect of ethanol on the polymer. Packaging applications of these films can improve food stability and provide a method for adding such bioactive compounds.

Antifungal properties of gliadin films incorporating cinnamaldehyde and application in active food packaging of bread and cheese spread foodstuffs.

Gliadin films incorporating 1.5, 3 and 5% cinnamaldehyde (g/100g protein) were tested against food-spoilage fungi Penicillium expansum and Aspergillus niger in vitro, and were employed in an active food packaging system for sliced bread and cheese spread. Gliadin films incorporating cinnamaldehyde were highly effective against fungal growth. P. expansum and A. niger were completely inhibited after storage in vitro for 10 days in the presence of films incorporating 3% cinnamaldehyde. Indeed 1.5% cinnamaldehyde was sufficient in the case of P. expansum. The amount of cinnamaldehyde retained in films after storage for 45 days at 20 °C and 0% RH was also sufficient in most cases to prevent fungal growth in vitro. Active food packaging with gliadin films incorporating 5% cinnamaldehyde increased the shelf-life of both sliced bread and cheese spread. Mold growth was observed on sliced bread after 27 days of storage at 23 °C with active packaging, whereas in the control bread packaged without the active film fungal growth appeared around the fourth day. In the cheese spread, no fungi were observed after 26 days of storage at 4 °C when the product was packaged with the active film. However, growth of fungi was observed in control packaged cheese after 16 days of storage. This work demonstrates a noteworthy potential of these novel bioplastics incorporating natural antimicrobial compounds as innovative solutions to be used in active food packaging to extend shelf-life of food products.

Global and specific migration of antioxidants from polypropylene films into food simulants.

Global migration and specific migration of antioxidants (AOs--Irgafos 168 [tris(2,4-di-tert-butylphenyl) phosphite], Irganox 1076 [octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl-propionate], and Hostanox SE2 (distery thiodipropionate)--from polypropylene (PP) films into food simulants (water, 3% acetic acid, 95% ethanol, olive oil, and heptane) were studied. Films (50, 100, and 200 microns thick) were exposed to simulants at temperature-time conditions simulating migration under retorting and long-term storage. Global migration into aqueous simulants was independent of film thickness and conditions of exposure, so it seems as if the migration process was limited to the dissolution of migrants on the contacting surface. Global migration to fatty food simulants was dependent on simulant, conditions of exposure, and in some cases film thickness. Specific AO migration was analyzed from dry residues obtained from global migration analysis. Migration of AOs into aqueous simulants was below the detection limit (0.01 mg/dm2). Migration into fatty food simulants was dependent on the simulant. The extractive power of simulants was similar to that observed in global migration studies. Specific migration into heptane was independent of the polymer mass, though dependent on the thickness. Migration into ethanol was dependent on both mass and thickness. A theoretical discussion about the controversial effect of thickness on migration results, based on the kinetics of the process, is presented.

Modelling permeation through porous polymeric films for modified atmosphere packaging

The use of perforated packaging films is increasing with the application of modified atmosphere packaging for fresh produce. These films provide high to very high mass exchange rates. However, irrespective of the chemistry of the material, mass transport through such films cannot be described using conventional permeability equations (Henrys plus Ficks laws). Other expressions such as Knudsens law, gas diffusivities or Poiseuilles hydrodynamic flow can be applicable. The application of these laws is discussed and their corresponding range of validity is provided. These laws were also applied to model experimental permeation rates of oxygen and water and were further used to describe the headspace evolution of two fruit products in modified atmosphere packaging. In the light of these results, the contribution of different factors to the headspace evolution is discussed.

Food aroma partition between packaging materials and fatty food simulants

By means of thermal desorption experiments, the partition equilibrium (partition coefficient, K) was analysed for six food aroma components (d-limonene, n-decane, ethyl caproate, phenylethanol, n-hexanol and hexanal) between three sealable polymer films suitable for direct food contact (ultra-low density polyethylene, ULDPE; ionomer, ION; and polyester, PET) and four fatty food simulants (ethanol 95%, EtOH; sunflower oil, Oil; n-heptane, HEP; and iso-octane, OCT). The results showed that aroma scalping is highly dependent on the fatty food simulant utilized. Polar aroma components were more sorbed into polymers in the presence of a non-polar fatty food simulant, and vice versa. K values in the presence of Oil were always between those in EtOH and in HEP or OCT. In general, PET was the packaging film which showed the lowest partition coefficient for non-polar components while ULDPE showed the lowest partition for polar aromas. The partition equilibrium of mixed d-limonene, ethyl caproate, and n-hexanol was also determined. The differences in K values between isolated aromas and mixed aromas were small. In general, the most sorbed aroma showed increased partition by mixture while the partition of the least sorbed was reduced.

Antimicrobial packaging of chicken fillets based on the release of carvacrol from chitosan/cyclodextrin films

Chitosan/cyclodextrin films (CS:CD) incorporating carvacrol were obtained by casting, and conditioned at 23°C and 75% relative humidity prior to being immersed in liquid carvacrol until they reached sorption equilibrium. In a previous work, the in vitro antimicrobial activity of these films was studied. In this work, active films were used to inhibit microbial growth in packaged chicken breast fillets. Samples of CS:CD films loaded with carvacrol, of different sizes and thus with different quantities of antimicrobial agent, were stuck to the aluminium lid used to seal PP/EVOH/PP cups containing 25g of chicken fillets. These samples were stored for 9days at 4°C. The packages were hermetically sealed and it was confirmed that they provided an infinite barrier to carvacrol. The partition of the antimicrobial agent within the food/packaging system was analysed. The antimicrobial devices rapidly released a large percentage of the agent load, amounts that were gained by the adhesive coating of the lid and especially by the chicken fillets. The latter were the main sorbent phase, with average concentrations ranging between 200 and 5000mg/Kg during the period of storage. The microbiota of the packaged fresh chicken fillets - mesophiles, psychrophiles, Pseudomonas spp., enterobacteria, lactic acid bacteria and yeasts and fungi - were analysed and monitored during storage. A general microbial inhibition was observed, increasing with the size of the active device. Inhibition with a 24cm(2) device ranged from 0.3 log reductions against lactic acid bacteria to 1.8logs against yeasts and fungi. However, the large amount of antimicrobial that was sorbed or that reacted with the fillet caused an unacceptable sensory deterioration. These high sorption values are probably due to a great chemical compatibility between chicken proteins and carvacrol.

Evaluation of Permeability Through Permeation Experiments: Isostatic and Quasi‐isostatic Methods Compared

Isostatic and quasi-isostatic permeation experiments were used to characterize the permeability of 1-hexanol through polypropylene films. The quasi- isostatic method was considered as an isostatic experiment at the limit a of null purging stream flow rate. Permeability values obtained through the isostatic method showed dependency on the purging stream flow rate. The extrapolated value at zero purging stream flow rate is in agreement with the data obtained via the quasi-isostatic procedure. Diffusion coefficient values were also determined. The isostatically obtained diffusion coefficients behave similarly to P. However, the value at zero flow rate differs significantly from the value obtained through the quasi-isostatic method. From these results the validity of permeation experiments for the evaluation of the diffusion coefficient is questioned.