Shelf Life of Minced Pork in Vacuum-Adsorbed Carvacrol@Natural Zeolite Nanohybrids and Poly-Lactic Acid/Triethyl Citrate/Carvacrol@Natural Zeolite Self-Healable Active Packaging Films.

Enhancing food preservation and safety using environmentally friendly techniques is urgently needed. The aim of this study was to develop food packaging films using biodegradable poly-L-lactic acid (PLA) as biopolymer and carvacrol (CV) essential oil as an antioxidant/antibacterial agent for the replacement of chemical additives. CV was adsorbed onto natural zeolite (NZ) via a new vacuum adsorption method. The novel nanohybrid CV@NZ with a high CV content contained 61.7%wt. CV. Pure NZ and the CV@NZ nanohybrid were successfully dispersed in a PLA/triethyl citrate (TEC) matrix via a melt extrusion process to obtain PLA/TEC/xCV@NZ and PLA/TEC/xNZ nanocomposite films with 5, 10, and 15%wt CV@NZ or pure NZ content. The optimum resulting film PLA/TEC/10CV@NZ contained 10%wt. CV@NZ and exhibited self-healable properties, 22% higher tensile strength, 40% higher elongation at break, 45% higher water barrier, and 40% higher oxygen barrier than the pure PLA/TEC matrix. This film also had a high CV release content, high CV control release rate as well as 2.15 mg/L half maximal effective concentration (EC50) and 0.27 mm and 0.16 mm inhibition zones against Staphylococcus aureus and Salmonella enterica ssp. enterica serovar Typhimurium, respectively. This film not only succeeded in extending the shelf life of fresh minced pork, as shown by the total viable count measurements in four days but also prevented the lipid oxidation of fresh minced pork and provided higher nutritional values of the minced meat, as revealed by the heme iron content determination. It also had much better and acceptable sensory characteristics than the commercial packaging paper.

Νovel Polylactic Acid/Tetraethyl Citrate Self-Healable Active Packaging Films Applied to Pork Fillets' Shelf-Life Extension.

Nowadays, increased food safety and decreased food waste are two of the major global interests. Self-healable active packaging materials are an attractive option to achieve such targets. This property is critical for the hygiene and the consumption appropriateness of the food. Polylactic acid is a very promising polymeric matrix that potentially could replace the widely used low-density polyethylene due to its biobased origin and its easy biodegradable nature. The main drawback of this polymeric matrix is its brittle, fragile nature. On the other hand, tetraethyl citrate is a biobased approved food additive which became an attractive option as a plasticizer for industries seeking alternative materials to replace the traditional petrochemically derived compounds. A novel biobased film exhibiting self-healing behavior suitable for food-active packaging was developed during this study. Polylactic acid's brittleness was reduced drastically by incorporating tetraethyl citrate, and a random cut on the original self-repairing film was fully healed after 120 s. The optimum concentration of tetraethyl citrate in the polylactic acid was around 15% v/w with a water/oxygen barrier close to the relevant of polylactic acid and low migration. According to the EC50 parameter, the antioxidant activity was 300% higher than the relevant of pure polylactic acid, while according to the thiobarbituric acid and heme iron parameters, the film resisted lipid oxidation and deterioration. Finally, the total viable count parameter indicates the strong antimicrobial activity of this sample.

Low-Density Polyethylene-Based Novel Active Packaging Film for Food Shelf-Life Extension via Thyme-Oil Control Release from SBA-15 Nanocarrier.

The use of natural raw substances for food preservation could provide a great contribution to food waste reduction, circular economy enhancement, and green process application widening. Recent studies indicated that the use of porous materials as adsorbents for natural essential oils provided nanohybrids with excellent antioxidant and antimicrobial properties. Following this trend in this work, a thymol oil (TEO) rich SBA-15 nanohybrid was prepared and characterized physiochemically with various techniques. This TEO@SBA-15 nanohybrid, along with the pure SBA-15, was extruded with low-density polyethylene (LDPE) to develop novel active packaging films. Results indicated that TEO loading was higher than other porous materials reported recently, and the addition of both pure SBA-15 and TEO@SBA-15 to the LDPE increased the water/oxygen barrier. The film with the higher thyme-oil@SBA-15 nanohybrid content exhibited a slower release kinetic. The antioxidant activity of the final films ignited after 48 h, was in the range of 60-70%, and was almost constant for 7 days. Finally, all tests indicated a sufficient improvement by the addition of thyme-oil@SBA-15 nanohybrids in the pure LDPE matrix and the concentration of wt. 10% of such nanocarriers provided the optimum final LDPE/10TEO@SBE-15 active packaging film. This material could be a potential future product for active packaging applications.

Carvacrol Microemulsion vs. Nanoemulsion as Novel Pork Minced Meat Active Coatings.

Carvacrol is well documented for its antibacterial and antioxidant effects. However, its high volatility has directed researchers toward nanoencapsulation technology according to bioeconomy and sustainability trends. This study examined and compared free carvacrol (FC), carvacrol microemulsion (MC), carvacrol microemulsion busted with chitosan (MMC), and carvacrol nanoemulsions (NC) as active coatings on extending minced pork meat shelf life at 4 ± 1 °C for 9 days, focusing on microbiological, physiochemical, and sensory characteristics. The research involved pre-characterizing droplet sizes, evaluating antioxidants, and determining antibacterial efficacy. The results demonstrated that NC with a 21 nm droplet size exhibited the highest antioxidant and antibacterial activity. All coatings succeeded in extending the preservation of fresh minced pork meat in comparison to the free carvacrol sample (FC). The NC coating showed the highest extension of minced pork meat preservation and maintained meat freshness for 9 days, with a lower TBARs of 0.736 mg MDA/Kg, and effectively reduced mesophilic, lactic acid, and psychotrophic bacterial counts more significantly by 1.2, 2, and 1.3 log, respectively, as compared to FC. Sensory assessments confirmed the acceptability of NC and MCC coatings. Overall, the carvacrol-based nanoemulsion can be considered a novel antioxidant and antimicrobial active coating due to its demonstrated higher efficacy in all the examined tests performed.

The Development of a Novel Sodium Alginate-Based Edible Active Hydrogel Coating and Its Application on Traditional Greek Spreadable Cheese.

The necessity of reducing the greenhouse effect by decreasing the carbon dioxide fingerprint directed the food packaging technology to use biobased raw materials. Alginates, which are derived from brown algae species, are one of the most promising biobased biopolymers for the development of edible active coatings capable of protecting food from oxidation/bacterial spoilage. In this study, sodium alginate, which was plasticized with glycerol and mixed with a biobased thymol/natural halloysite nanohybrid, was used to develop novel edible active coatings. Nanocomposite coatings were also developed in this project by mixing pure halloysite with sodium alginate/glycerol matrix and were used as reference material for comparison reasons. Instrumental analysis indicated a higher compatibility of a thymol/halloysite nanohybrid with a sodium alginate/glycerol matrix compared to pure halloysite with a sodium alginate/glycerol matrix. Increased compatibility resulted in improved tensile properties, water/oxygen barrier properties, and total antioxidant activity. These edible active coatings were applied to traditional Greek spread cheese and showed a reduction in the mesophilic microbial population over one log10 unit (cfu/g) compared to uncoated cheese. Moreover, the reduction in the mesophilic microbial population increased with the increase in halloysite and thymol content, indicating such sodium alginate/glycerol/thymol/halloysite hydrogels as promising edible active coatings for dairy products.

Thymol@Natural Zeolite Nanohybrids for Chitosan/Polyvinyl-Alcohol-Based Hydrogels Applied as Active Pads.

Currently, food saving, a circular economy, and zero environmental fingerprints are of major interest. Scientific efforts for enhanced food preservation using "green" methods have been intensified. Even though chemicals could achieve such targets effectively, the global trend against the "greenhouse effect" suggests the use of environmentally friendly biobased materials for this purpose. In this study, the promising biopolymer chitosan is incorporated with the promising biodegradable polymer polyvinyl alcohol to produce an improved biopolymeric matrix. This biodegradable biopolymer was further mixed homogeneously with 15% thymol/nano-zeolite nanohybrid material. The properties of the final developed film were improved compared to the relevant values of chitosan/polyvinyl alcohol film. The mechanical properties were enhanced significantly, i.e., there was a 34% increase in Young's modulus and a 4.5% increase in the ultimate tensile strength, while the antioxidant activity increased by 53.4%. The antibacterial activity increased by 134% for Escherichia coli, 87.5% for Staphylococcus aureus, 32% for Listeria monocytogenes, and 9% for Salmonella enterica. The water vapor diffusion coefficient and the oxygen permeability coefficient decreased to -51% and -74%, respectively, and thus, the water vapor and oxygen barrier increased significantly. The active pads were used in strawberries, and the antimicrobial activity evaluation against the mold of fungi was carried out. The visual evaluation shows that the active pads could extend the shelf life duration of strawberries.

Thymol@activated Carbon Nanohybrid for Low-Density Polyethylene-Based Active Packaging Films for Pork Fillets' Shelf-Life Extension.

Τhe replacement of food packaging additives and preservatives with bio-based antioxidant/antibacterial compounds has been a common practice in recent years following the trend of bioeconomy and nanotechnology. Such bio-additives are often enclosed in nanocarriers for a controlled release process. Following this trend in this work, a thymol (TO)-rich activated carbon (AC) nanohybrid was prepared and characterized physicochemically with various techniques. This TO@AC nanohybrid, along with the pure activated carbon, was extruded with low-density polyethylene (LDPE) to develop novel active packaging films. The codenames used in this paper were LDPE/xTO@AC and LDPE/xAC for the nanohybrid and the pure activated carbon, respectively. X-ray diffractometry, Fourier-transform infrared spectroscopy, and scanning electron microscopy measurements showed high dispersity of both the TO@AC nanohybrid and the pure AC in the LDPE matrix, resulting in enhanced mechanical properties. The active film with 15 wt.% of the TO@AC nanohybrid (LDPE/15TO@AC) exhibited a 230% higher water/vapor barrier and 1928% lower oxygen permeability than the pure LDPE film. For this active film, the highest antioxidant activity referred to the DPPH assay (44.4%), the lowest thymol release rate (k2 ≈ 1.5 s-1), and the highest antibacterial activity were recorded, resulting in a 2-day extension of fresh pork fillets' shelf-life.

Development and Evaluation of a Novel-Thymol@Natural-Zeolite/Low-Density-Polyethylene Active Packaging Film: Applications for Pork Fillets Preservation.

Sustainability, the circular economy, and the "greenhouse" effect have led the food packaging industry to use naturally available bio-compounds. The integration of such compounds in packaging films increases food safety and extends food shelf-life. The development of an active/antioxidant packaging film based on the widely commercially used low-density polyethylene, natural zeolite, and Thymol, a natural extract from thyme oil, is presented in this work. The obtained active films were characterized using X-Ray Diffraction, Fourier-Transform Infrared Spectroscopy, Scanning Electron Microscopy, and Differential Scanning Calorimetry techniques. The tensile strength, water-oxygen barrier properties, and total antioxidant activity were measured. Low-density polyethylene incorporated with Thymol@Natural Zeolite at a proportion of 15 wt% was the most promising material and was used as film to wrap-up pork fillets. The thiobarbituric acid (TBA) method and heme iron measurements indicated a delayed lipids oxidation using this film. A linear correlation between the TBA method and heme iron values seems to be established, which could result in a fast method to determine the degree of lipid oxidation in pork fillets. Finally, a two-stage diffusion process during Thymol release was observed, and the values of the diffusion coefficient was 2.09 × 10-7 and 1.21 × 10-8 cm2/s for each stage. The applied pseudo-second sorption model provided a rate constant k2 = 0.01647 (s-1). These results indicate the strong potential of such films to be used as food packaging materials free of E-number preservatives.

Development, Characterization, and Evaluation as Food Active Packaging of Low-Density-Polyethylene-Based Films Incorporated with Rich in Thymol Halloysite Nanohybrid for Fresh "Scaloppini" Type Pork Meat Fillets Preservation.

A new era is rising in food packaging and preservation, with a consequent focus on transition to "greener" and environmentally friendly techniques. The environmental problems that are emerging nowadays impose use of natural materials for food packaging applications, replacement of chemical preservatives with natural organic extractions, such as essential oils, and targeting of new achievements, such as further extension of food shelf-life. According to this new philosophy, most of the used materials for food packaging should be recyclable, natural or bio-based, and/or edible. The aim of this work was to investigate use and efficiency of a novel food packaging developed based on commercial LDPE polymer incorporated with natural material halloysite impregnated with natural extract of thyme oil. Moreover, a direct correlation between the stiff TBARS method and the easiest heme iron measurements method was scanned to test food lesions easier and faster. The result of this study was development of the LDPE/10TO@HNT film, which contains the optimum amount of a hybrid nanostructure and is capable to be used as an efficient active food packaging film. Furthermore, a linear correlation seems to connect the TBARS and heme iron measurements.

Kiwi Fruits Preservation Using Novel Edible Active Coatings Based on Rich Thymol Halloysite Nanostructures and Chitosan/Polyvinyl Alcohol Gels.

The concept of this study is the replacement of previous fossil-based techniques for food packaging and food shelf-life extension, with novel more green processes and materials following the spirit of circular economy and the global trend for environmentally positive fingerprints. A novel adsorption process to produce thymol-halloysite nanohybrids is presented in this work. The high dispersion of this thymol-halloysite nanostructure in chitosan biopolymer is one of the goals of this study. The incorporation of this biodegradable matrix with poly-vinyl-alcohol produced a very promising food-packaging film. Mechanical, water-oxygen barrier, antimicrobial, and antioxidant properties were measured. Transparency levels were also tested using a UV-vis instrument. Moreover, the developed films were tested in-vivo for the preservation and the extension of the shelf-life of kiwi fruits. In all cases, results indicated that the increased fraction of thymol from thyme oil significantly enhances the antimicrobial and antioxidant activity of the prepared chitosan-poly-vinyl- alcohol gel. The use of the halloysite increases the mechanical and water-oxygen barrier properties and leads to a control release process of thymol which extends the preservation and the shelf-life of kiwi fruits. Finally, the results indicated that the halloysite improves the properties of the chitosan/poly-vinyl-alcohol films, and the thymol makes them further advantageous.

Nanocomposite Film Development Based on Chitosan/Polyvinyl Alcohol Using ZnO@Montmorillonite and ZnO@Halloysite Hybrid Nanostructures for Active Food Packaging Applications.

The global turn from the linear to the circular economy imposes changes in common activities such as food packaging. The use of biodegradable materials such as polyvinyl alcohol, natural raw materials such as clays, and food byproducts such as chitosan to develop novel food packaging films attracts the interest of industrial and institutional research centers. In this study, novel hybrid nanostructures were synthesized via the growth of zinc oxide nanorods on the surface of two nanoclays. The obtained nanostructures were incorporated with chitosan/polyvinyl alcohol composite either as nanoreinforcement or as an active agent to develop packaging films. The developed films were characterized via XRD, FTIR, mechanical, water-vapor diffusion, water sorption, and oxygen permeability measurements. Antimicrobial activity measurements were carried out against four different pathogen microorganisms. XRD indicated the formation of an intercalated nanocomposite structure for both types of nanoclays. Furthermore, improved tensile, water/oxygen barrier, and antimicrobial properties were recorded for all films compared to the pure chitosan/polyvinyl alcohol film. Overall, the results indicated that the use of the bio-based developed films led to an extension of food shelf life and could be used as novel active food packaging materials. Among them, the most promising film was the 6% wt. ZnO@halloysite.

Performance of Thyme Oil@Na-Montmorillonite and Thyme Oil@Organo-Modified Montmorillonite Nanostructures on the Development of Melt-Extruded Poly-L-lactic Acid Antioxidant Active Packaging Films.

Today, the use of natural biodegradable materials in the production processes is more and more adopted by industry to achieve cyclic economy targets and to improve environmental and human health indexes. Active packaging is the latest trend for food preservation. In this work, nanostructures were prepared by incorporation of thyme oil with natural natrium-montmorillonite and organo-montmorillonite with two different techniques, direct impregnation and the green evaporation-adsorption process. Such nanostructures were mixed with poly-L-lactic-acid for the first time via an extrusion molding process to develop a new packaging film. Comparisons of morphological, mechanical, and other basic properties for food packaging were carried out via XRD, FTIR, TG, SEM/EDS, oxygen and water vapor permeation, and antimicrobial and antioxidant activity for the first time. Results showed that poly-L-lactic-acid could be modified with clays and essential oils to produce improved active packaging films. The final product exhibits food odor prevention characteristics and shelf-life extension capabilities, and it could be used for active packaging. The films based on OrgMt clay seems to be more promising, while the thyme oil addition improves their behavior as active packaging. The PLLA/3%TO@OrgMt and PLLA/5%TO@OrgMt films were qualified between the tested samples as the most promising materials for this purpose.

Synthesis of a Novel Chitosan/Basil Oil Blend and Development of Novel Low Density Poly Ethylene/Chitosan/Basil Oil Active Packaging Films Following a Melt-Extrusion Process for Enhancing Chicken Breast Fillets Shelf-Life.

An innovative process for the adsorption of the hydrophobic Basil-Oil (BO) into the hydrophilic food byproduct chitosan (CS) and the development of an advanced low-density polyethylene/chitosan/basil-oil (LDPE/CS_BO) active packaging film was investigated in this work. The idea of this study was the use of the BO as both a bioactive agent and a compatibilizer. The CS was modified to a CS_BO hydrophobic blend via a green evaporation/adsorption process. This blend was incorporated directly in the LDPE to produce films with advanced properties. All the obtained composite films exhibited improved packaging properties. The film with 10% CS_BO content exhibited the best packaging properties, i.e., 33.0% higher tensile stress, 31.0% higher water barrier, 54.3% higher oxygen barrier, and 12.3% higher antioxidant activity values compared to the corresponding values of the LDPE films. The lipid oxidation values of chicken breast fillets which were packaged under vacuum using this film were measured after seven and after fourteen days of storage. These values were found to be lower by around 41% and 45%, respectively, compared with the corresponding lipid oxidation values of pure LDPE film.

Development of ZnO/Na-Montmorillonite Hybrid Nanostructures Used for PVOH/ZnO/Na-Montmorillonite Active Packaging Films Preparation via a Melt-Extrusion Process.

Nowadays, the shelf-life extension of foods is a topic of major interest because of its environmental and economic benefits. For this purpose, various methods like deep-freezing, ultra-high-temperature pasteurization, drying methods, use of chemicals, controlled-atmosphere preservation, ionizing irradiation, and were investigated. During the last years, the smart packaging for foods using natural biodegradable components is of great interest because it provides positive environmental fingerprint and high shelf-life extension. In the present work, a new nanostructured composite material, the ZnO/Na-Montmorillonite hybrid, was developed. The high antimicrobial properties of the 3-D ZnO material in combination with the high barrier and strength properties of the 2-D Na-Montmorillonite material provided a high promising component for food smart packaging applications. As an extra innovation of this process, the ZnO nanorods coated the external surface of the Na-Montmorillonite and it was not intercalated into the clay as a pillaring material. This new material was incorporated with a 3% w/w composition with a biodegradable poly(vinyl)alcohol (PVOH) polymeric matrix which also exhibits antimicrobial activity. The final product was tested via XRD, FTIR, SEM, tensile test, water sorption, water vapor permeability, oxygen permeability UV-vis, and anti-microbial activity tests and it exhibited advanced mechanical and antimicrobial properties, especially for a ZnO/Na-Montmorillonite fraction of 4:1.

Novel LDPE/Chitosan Rosemary and Melissa Extract Nanostructured Active Packaging Films.

The increased global market trend for food packaging is imposing new improved methods for the extension of shelf-life and quality of food products. Active packaging, which is based on the incorporation of additives into packaging materials, is becoming significant for this purpose. In this work, nanostructured low-density polyethylene (LDPE) was combined with chitosan (CS) to aim for a food packaging development with an increased oxygen permeability barrier and higher antimicrobial activity. Furthermore, essential oil extracts as rosemary (RO) and Melissa (MO) were added to this packaging matrix in order to improve its antioxidant properties and vanish food odor problems. The novel nanostructured active packaging film was tested using laboratory instrumental methods, such as thermogravimetry (TG), Fourier-transform infrared (FTIR) spectrometry, the X-ray diffraction (XRD) method, a dilatometer for tensile properties (DMA), and an oxygen permeation analyzer (OPA). Moreover, laboratorian tests according to ASTM standards were carried out for the estimation of water sorption, water vapor permeability, overall migration, and, finally, the antioxidant properties of such films. The experimental results have indicated that the final material exhibits advanced properties. More specifically, chitosan addition was observed to lead to an enhanced oxygen and water-vapor permeability barrier while the extracted essential oil addition led to enhanced tensile strength and antioxidant properties.

Preparation, characterization, mechanical, barrier and antimicrobial properties of chitosan/PVOH/clay nanocomposites.

In the current study low molecular weight poly(vinylalcohol) (PVOH) was used to prepare chitosan/PVOH blends and chitosan/PVOH/montmorillonite nanocomposites via a reflux - solution - heat pressing method. The effect of PVOH content and montmorillonite type (hydrophylic vs. organically modified) on the morphology, mechanical, thermomechanical, barrier and antimicrobial properties of the obtained polymer blends and nanocomposite films was studied. Higher amounts of PVOH (20 and 30%) resulted in plasticization of the films, with an increase in the elongation at break and decrease of the stiffness and the strength while effective blending between chitosan and PVOH chains was observed based on the XRD and DMA findings. Addition of PVOH was beneficial for water and oxygen barrier properties of the obtained films while it did not influence the antimicrobial activity of films against the growth of Escherichia coli. Intercalated structures were obtained after the addition of hydrophilic and organo-modified clays leading into stiffening of the nano-modified films and enhancement of their barrier and antimicrobial properties.

Preparation, characterization, mechanical and barrier properties investigation of chitosan-clay nanocomposites.

In the current study the effect of dilution of chitosan acetate solution and of the use of a reflux-solution method on the morphology, the mechanical and water barrier properties of chitosan based nanocomposites is being investigated. Two series of nanocomposite films from two chitosan acetate solutions with 2 w/v% and 1 w/v% in chitosan were prepared, with 3, 5 and 10 wt% Na-montmorillonite (NaMMT) and/or 30 wt% glycerol. Intercalation of NaMMT was more effective in films based on 2 w/v% solutions which presented decreased hydrated crystallinity. Upon NaMMT addition an enhancement was found in stiffness and strength (up to 100%) and a remarkable decrease in the elongation at break (up to 75%) and water vapor permeability (WVP) (up to 65%). This enhancement was less pronounced in 1 w/v% systems. Addition of glycerol had a negative effect on the stiffness, strength and WVP, and a positive effect on the elongation at break and the absorbed water. Compared with the conventional solution cast method, the reflux treatment led to a significant improvement of the tested properties of nanocomposite films.