Innovative Systems for the Delivery of Naturally Occurring Antimicrobial Volatiles in Active Food-Packaging Technologies for Fresh and Minimally Processed Produce: Stimuli-Responsive Materials.

Certain naturally occurring volatile organic compounds are able to mitigate food spoilage caused by microbial growth. Their considerable vapor pressure enables them to create an antimicrobial atmosphere within a package, and this property can be used for the development of active food-packaging technologies. The volatility of these molecules, however, makes their stabilization difficult and limits their effectiveness. Whilst much research is being undertaken on the use of natural antimicrobial volatiles for inhibiting microbial growth in food, less attention has been paid to the design of controlled-release mechanisms that permit the efficient application of these compounds. Most studies to date either spray the volatile directly onto the fresh product, immerse it in a solution containing the volatile, or embed the volatile in a paper disc to create a vapor in the headspace of a package. More sophisticated alternatives would be delivery systems for the sustained release of volatiles into the package headspace. Such systems are based on the encapsulation of a volatile in organic or inorganic matrices (cyclodextrins, electrospun non-wovens, polymer films, micelles, molecular frameworks, etc.). However, most of these devices lack an efficient triggering mechanism for the release of the volatile; most are activated by humidity. All of these techniques are revised in the present work, and the most recent and innovative methods for entrapping and releasing volatiles based on reversible covalent bonds are also discussed.

ZIF-8 encapsulation improves the antifungal activity of benzaldehyde and methyl anthranilate in films.

In this work, two ZIF-8-based biocomposites were obtained by entrapping the biomolecules benzaldehyde and methyl anthranilate via direct impregnation with fast encapsulation kinetics and high molecule payloads were achieved. The obtained biocomposites exhibit an enhanced antifungal activity against Penicilium expansum after integration in biopolymeric zein films in comparison with the action of free molecules, making these biomaterials promising candidates for food preservation and packaging applications.

pH modulates antibacterial activity of hydroxybenzaldehyde derivatives immobilized in chitosan films via reversible Schiff bases and its application to preserve freshly-squeezed juice.

Antimicrobial food grade hydroxybenzaldehyde derivatives were immobilized on the surface of chitosan films by means of reversible Schiff bases. Spectroscopy and elemental analysis evidenced the different ability of the aldehydes to form Schiff bases with chitosan. Chitosan films modified with Schiff bases of aldehydes exerted antimicrobial properties against E. coli under mild acidic environments. The efficacy of the films lied on the reversibility of synthetized imine bonds and release of the aldehydes which was promoted in mildly acid aqueous solutions. Besides acidity, imine bond reversibility depended on the chemical structure of the aldehyde covalently bonded. Films carrying salicylaldehyde presented the highest in vitro antimicrobial performance and thus, they were chosen to evaluate their effectivity in inhibiting E. coli proliferation in freshly-squeezed carrot-orange juice. Films were successfully activated by the acid environment of the juice and reduced the population of the inoculated pathogen. Salicylaldehyde migrated to the juice did not exert toxic effects on Caco-2 cells.

Pilot-Scale Processing and Functional Properties of Antifungal EVOH-Based Films Containing Methyl Anthranilate Intended for Food Packaging Applications.

Antimicrobial packaging has emerged as an efficient technology to improve the stability of food products. In this study, new formulations based on ethylene vinyl alcohol (EVOH) copolymer were developed by incorporating the volatile methyl anthranilate (MA) at different concentrations as antifungal compound to obtain active films for food packaging. To this end, a twin-screw extruder with a specifically designed screw configuration was employed to produce films at pilot scale. The quantification analyses of MA in the films showed a high retention capacity. Then, the morphological, optical, thermal, mechanical and water vapour barrier performance, as well as the antifungal activity in vitro of the active films, were evaluated. The presence of MA did not affect the transparency or the thermal stability of EVOH-based films, but decreased the glass transition temperature of the copolymer, indicating a plasticizing effect, which was confirmed by an increase in the elongation at break values of the films. Because of the additive-induced plasticization over EVOH, the water vapour permeability slightly increased at 33% and 75% relative humidity values. Finally, the evaluation of the antifungal activity in vitro of the active films containing methyl anthranilate showed a great effectiveness against P. expansum and B. cinerea, demonstrating the potential applicability of the developed films for active food packaging.

Exploiting the Redox Activity of MIL-100(Fe) Carrier Enables Prolonged Carvacrol Antimicrobial Activity.

The design of efficient food contact materials that maintain optimal levels of food safety is of paramount relevance to reduce the increasing number of foodborne illnesses. In this work, we develop a smart composite metal-organic framework (MOF)-based material that fosters a unique prolonged antibacterial activity. The composite is obtained by entrapping a natural food preserving molecule, carvacrol, into a mesoporous MIL-100(Fe) material following a direct and biocompatible impregnation method, and obtaining particularly high payloads. By exploiting the intrinsic redox nature of the MIL-100(Fe) material, it is possible to achieve a prolonged activity against Escherichia coli and Listeria innocua due to a triggered two-step carvacrol release from films containing the carvacrol@MOF composite. Essentially, it was discovered that based on the underlying chemical interaction between MIL-100(Fe) and carvacrol, it is possible to undergo a reversible charge-transfer process between the metallic MOF counterpart and carvacrol upon certain chemical stimuli. During this process, the preferred carvacrol binding site was monitored by infrared, Mössbauer, and electron paramagnetic resonance spectroscopies, and the results are supported by theoretical calculations.

Trans-2-Hexenal-Based Antifungal Packaging to Extend the Shelf Life of Strawberries.

Strawberries are valuable because of their nutritional value, but they are also highly perishable fruits. Fungal decay is the overriding factor that alters the overall quality of fresh strawberries. Because no hygienic treatments to reduce the initial microbial load are feasible, molds develop during postharvest when using conventional packaging. In this study, an antifungal packaging system for strawberries was developed to improve safety and quality. Trans-2-hexenal (HXAL), a natural compound in strawberries, was incorporated into the modified atmosphere packaging (MAP) systems. Zero, 100, and 250 µL of HXAL were included in cellulosic pads and were covered with a polyamide coating to control its release. The pads were placed on the bottom of plastic trays; an amount of250 g of strawberries was added, flow packed in micro-perforated PP bags, and stored at 4 °C for 14 days. Fungal infection was monitored during the storage period, and the optical and textural properties of the strawberries were measured at days 0 and 14. Analysis of the package headspace was conducted to check for the HXAL concentration. HXAL was partially retained in the fruits and was converted into hexyl acetate and 2-hexen-1-ol acetate, but this was only measurably present in the headspace of the active systems. Mold growth was fully inhibited in active packaging although the strawberries were softer and darker than those in the control packages. The active package was not as efficient if the fruits were stored under thermal-abuse conditions (15 and 22 °C).

Hot-Melt-Extruded Active Films Prepared from EVOH/Trans-Cinnamaldehyde Blends Intended for Food Packaging Applications.

In this work, novel active films based on ethylene vinyl alcohol copolymer (EVOH) and cinnamaldehyde (CIN) were successfully obtained employing a hybrid technique consisting of a two-step protocol involving the preparation of a polymeric EVOH-CIN masterbatch by solvent-casting for its further utilization in the preparation of bioactive EVOH-based films by melt extrusion processing. The influence of CIN over the EVOH matrix was studied in terms of optical, morphological, thermal, and mechanical properties. Optically transparent films were obtained and the incorporation of cinnamaldehyde resulted in yellow-colored films, producing a blocking effect in the UV region. A decrease in the glass transition temperature was observed in the formulations containing cinnamaldehyde, indicating a plasticizing effect. This phenomenon was confirmed by an increase in the elongation at break values of the extruded films. Results from thermogravimetric analysis determined a slight decrease in the thermal stability of EVOH provoked by the vaporization of the bioactive compound. Bioactive properties of the films were also studied; the presence of residual cinnamaldehyde in EVOH after being subjected to an extrusion process conferred some radical scavenging activity determined by the DPPH assay whereas films were able to exert antifungal activity in vapor phase against Penicillium expansum. Therefore, the present work shows the potential of the hybrid technique employed in this study for the preparation of bioactive films by a ready industrial process technology for food packaging applications.

Development of antifungal biopolymers based on dynamic imines as responsive release systems for the postharvest preservation of blackberry fruit.

This study describes the synthesis and reversibility of Schiff bases from chitosan and bioactive compounds, and their application in the antifungal packaging of fruit. Imine bonds between primary amine groups of chitosan and carbonyl groups of antifungal aldehydes were synthesised and their reversibility was assayed in an aqueous medium under different acidic conditions. The mechanism of action of the dynamers is based on the hydrolysis of imine bond and the release of the active agent. The new films were effective at inhibiting the growth of Penicillium expansum and Botrytis cinerea, and their effectivity depended on the degree of hydrolysis achieved which was greater when the bonds were hydrolysed in a mild acidic medium. A double bottom cylindrical tray was used for the responsive antimicrobial packaging of blackberries. The package extended shelf-life of berries from 3 to 12 days without causing phytotoxic effects on the fruit being safe for human consumption.

Development and optimization of antifungal packaging for sliced pan loaf based on garlic as active agent and bread aroma as aroma corrector.

The aim of the present work was the development of antimicrobial films containing garlic extract to be applied as active packaging for preservative-free sliced pan loaf, with the goal of extending its shelf-life. First, the antimicrobial capacity of garlic extract, a compound used as active agent, was tested against Penicillium expansum by the disc diffusion method. The extract showed high antimicrobial activity, 0.1 µL per Petri dish being the minimum inhibitory amount, and 0.25 µL the minimum fungicidal amount. Bread aroma was also used to mask the pungent odour of garlic and it was confirmed to have no antimicrobial activity. Subsequently, polyethylene (PE) aqueous emulsion and ethylene-vinyl alcohol copolymer (EVOH) and zein hydroalcoholic solutions containing 0.25 and 0.5% (w/w per dry polymer) of garlic extract and bread aroma were used to coat PE films, producing PE/PE, PE/EVOH and PE/zein active films. The antimicrobial capacity of the films was studied in vitro against Penicillium expansum, and in vivo with natural sliced bread. The results showed that all the films presented some antimicrobial activity, PE film coated with zein containing 0.5% of garlic extract and bread aroma being the film presenting the best results, maintaining bread free of mould infection for 30 days. Sensory tests showed that the addition of 1% of bread aroma improved the sensory experience of consumers and also revealed good purchase intention.