Describing and modeling the release of an antimicrobial agent from an active PP/EVOH/PP package for salmon

Natural antimicrobial active packaging is an emerging technology for fresh fish preservation in which a chemical compound of natural origin is purposely incorporated into a packaging material to be released into the food surface in order to protect it from spoilage by foodborne microorganisms. The maximum efficiency of an antimicrobial package can only be obtained when an adequate activity is achieved immediately after the packaging operation and is maintained constant throughout the product’s shelf life. This work develops an active package designed for the preservation of fresh farmed salmon in cubes or slices, made up of a rigid polypropylene (PP)/ethylene–vinyl alcohol copolymer (EVOH)/PP tray heat-sealed with an active PP/EVOH/PP film lid in which 6.5% carvacrol is incorporated in the EVOH kernel as an antimicrobial active agent. The work also includes the measurement of the carvacrol kinetics and equilibrium parameters in the preserved salmon fillets, and proposes a mathematical model based on the finite element method to describe and simulate the common performance of the developed package/food system, and to predict its behavior under different working conditions or system configurations with the objective of finding the optimum combination of variables that ensure the best packaging performance. The results obtained from the determination of parameters showed a rapid migration of the active compound through the fish muscle, and a low affinity of the agent molecules for the food matrix. The active package was successfully developed, and the proposed model was satisfactorily used to detect the key factors that govern the package performance, and also to improve the package design by modifying the thickness distribution of the multilayer active film.     

Evaluation of a chitosan-based edible film as carrier of natamycin to improve the storability of Saloio cheese

The purpose of this study was to evaluate the effects of the application of chitosan coating containing natamycin on the physicochemical and microbial properties of semi-hard cheese. Three cheese groups were prepared: samples without coating, samples coated with chitosan and with chitosan containing 0.50 mg mL⁻¹ of natamycin, whose minimum inhibitory concentration was previously determinated on cheese surface. Microbiological analyses showed that natamycin coated samples presented a decrease on moulds/yeasts of 1.1 log (CFU g⁻¹) compared to control after 27 days of storage. Addition of natamycin also affected O₂ and CO₂ permeability, increasing from 7.12 to 7.68 × 10⁻¹⁵ g·(Pa s m)⁻¹, and from 10.69 to 64.58 × 10⁻¹⁴ g·(Pa s m)⁻¹, respectively. The diffusion coefficient values of natamycin from the film to phosphate buffered saline solution and to the cheese were 3.60 × 10⁻¹⁰ and 1.29 × 10⁻¹² cm² s⁻¹, respectively. This study demonstrated that chitosan-based coating/films can be used as release system containing natamycin to create an additional hurdle for moulds/yeasts in cheese thus contributing to extend its shelf-life.     

Experimental and theoretical study of LDPE versus different concentrations of Irganox 1076 and different thickness

This work presents a theoretical and experimental study on the specific migration process, describing the mass transfer of a model migrant Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (I-1076), an antioxidant commonly used in the polyolefins processing. Film samples (LDPE), with initial concentration of Irganox between 1000 and 6000 (mg/kg), and thickness of 50-190 ??m, were placed in contact with fatty (EtOH 95%) and aqueous (EtOH 10%) food simulants at 40 °C for 20 days, in order to obtain the concentration evolution in the food simulant which was measured by HPLC. On the other hand, a phenomenological model based on a resistances-in-series approach was developed considering the diffusion through the polymer film, natural convection in the food simulant and the thermodynamic equilibrium between the polymer and the liquid simulant phase. For the thickest films, the diffusion coefficient of I-1076 through the polymer phase was estimated varying between 1.95·10^− 13 (m² s^− 1) and 2.0·10^− 13 (m² s^− 1) at 40 ºC. On the contrary, the thinnest one shows a significant decrease of the diffusion coefficient value, which was evaluated in 1.0·10^− 14 (m² s^− 1). This modification can be explained by means of a crystal distribution and size in the thinnest polymer film prepared by CAST extrusion. The mathematical model developed is a tool for prediction and analysis which can be used to facilitate the characterization of polymers, and it could predict the response as packaging for food in a specific application.     

Investigation on the presence of sulphites in fresh meat preparations: estimation of an allowable maximum limit

Sulphiting agents are commonly used food additives. They are not allowed in fresh meat preparations. In this work, 2250 fresh meat samples were analysed to establish the maximum concentration of sulphites that can be considered as “natural” and therefore be admitted in fresh meat preparations. The analyses were carried out by an optimised Monier-Williams Method and the positive samples confirmed by ion chromatography. Sulphite concentrations higher than the screening method LOQ (10.0 mg · kg^− 1) were found in 100 samples. Concentrations higher than 76.6 mg · kg^− 1, attributable to sulphiting agent addition, were registered in 40 samples. Concentrations lower than 41.3 mg · kg^− 1 were registered in 60 samples. Taking into account the distribution of sulphite concentrations obtained, it is plausible to estimate a maximum allowable limit of 40.0 mg · kg^− 1 (expressed as SO₂). Below this value the samples can be considered as “compliant”.     

The antimicrobial activity of microencapsulated thymol and carvacrol

The aim of the present study was to determine the antimicrobial (AM) properties of plastic flexible films with a coating of microcapsules containing carvacrol and thymol as natural AM agents. Microencapsulation of these agents enables their controlled release and leads to the destruction (or growth inhibition) of a broad spectrum of microorganisms such as, Escherichia coli O157:H7, Staphylococcus aureus, Listeria innocua, Saccharomyces cerevisiae and Aspergillus niger. It was found that the studied AM agents are strong inhibitors to the growth of mycelium, but they were not effective against spore germination of mold. Thymol (T) and carvacrol (C) showed a significant AM activity against the studied microorganisms, with minimal inhibitory concentrations (MIC) of 125-250 ppm and 75-375 ppm for thymol and carvacrol respectively. The synergistic effect of combinations of thymol and carvacrol was also studied and it was found that the highest synergism was achieved at a concentration of 50% T and 50% C. The release of the AM agents was carried out at 4 °C during 28 days. The concentration of the microencapsulated AM agents showed a range of zones of inhibition of 4.3-11.3 mm for the microorganisms at 10% of thymol and 10% of carvacrol. At these concentrations the release of the AM agents (within 48 h) was greater than required for the most resistant microorganism (E .coli O157:H7), as reflected by the relatively large zone of inhibition. The results of the present study confirm the suitability of using microencapsulated thymol and carvacrol incorporated in polymer films for AM food packaging.     

Engineering packaging design accounting for transpiration rate: Model development and validation with strawberries

Integrative mathematical modelling for Modified Atmosphere Packaging (MAP) has been used to determine the gas composition inside a package, but can also be used to determine the packaging needs of fresh produce in terms of permeability to gases and water vapour. Transpiration rate (TR) is an important physiological process that influences relative humidity (RH) and condensation inside the package, and ultimately quality and shelf life. Strawberries are an extremely valuable crop, but they are susceptible to grey mould rot, fungal decay, moisture loss and condensation. Quantification of strawberry transpiration rate TR would be required to estimate the packaging material water vapour transmission rate (WVTR) and therefore optimise engineering packaging design. This study investigated (i) the impact of temperature and RH on strawberry TR, (ii) developed a predictive model for quantifying TR, (iii) integrated transpiration rate model into the engineering packaging design and quantified the target WVTR for packaging of strawberry and (iv) validated packaging design by comparison to commercial packaging. Experiments were conducted following an experimental design, considering two factors at three levels (3²), i.e. temperature (5, 10 and 15 °C) and RH (76%, 86% and 96%); TR was recorded during 5 days of storage. The results showed that both RH and temperature had a significant effect on TR. In a given temperature and RH range of study, it varied from 0.24 to 1.16 g/kg h. Mathematical model developed considering the effect of temperature and RH, was further validated at 12 °C and 76% RH, showing very good predictability (R² > 0.997). The TR model was found to be useful for describing the strawberry packaging requisites and for optimal engineering packaging design for strawberry. The target WVTR for achieving optimal RH of 90% at 5 °C was found to be 162 g/m² day. Packaging design validation showed that the package designed considering both gas and water vapour requisites of strawberry yielded favourable results for maintaining quality and shelf life of product.     

Natamycin release from alginate/pectin films for food packaging applications

Single and composite films based on alginate and pectin containing natamycin as active agent were prepared and the release behavior in water and the diffusion coefficients were evaluated. The influence of natamycin on physical attributes of the films was also investigated. Addition of natamycin promoted an increase in soluble matter in water, in the water vapor permeability and in the opacity and a decreased in tensile strength when compared to films without the added anti-microbial agent. The natamycin mass released by immersion of the film in water fitted well to Fick’s second law diffusional model, with effective diffusivity values ranging from 3.2 × 10⁻⁹ (single pectin films) to 9.2 × 10⁻¹² cm²/s (single alginate films). The values of the diffusional exponents ranged between 0.5 and 1.0, suggesting that the transport process had non-Fickian (anomalous) characteristics. The single alginate films exhibit more suitable attributes for application in packaging than the single pectin and the composite films.     

Structural and chromatic characterization of a new Malvidin 3-glucoside–vanillyl–catechin pigment

A new pigment, resulting from the reaction between malvidin 3-glucoside and catechin in the presence of vanillin, was detected in a model solution. This newly formed anthocyanin-aryl-flavanol adduct was structurally characterized by 1D and 2D NMR and mass spectrometry, and its chromatic characteristics were studied by UV–Vis techniques. The new pigment was shown to have a wavelength of maximum absorption in the visible region (λ_max) of 549 nm, conferring on it a purple colour, and a molar extinction coefficient value (ε) of 12,247 l · mol⁻¹ · cm⁻¹.     

The effect of diets supplemented with thyme essential oils and rosemary extract on the deterioration of farmed gilthead seabream (Sparus aurata) during storage on ice

The effect on quality were assessed for gilthead seabream fed five different diets: control (basal diet); BHT (basal diet with 200 mg kg⁻¹ of butylated hydroxytoluene); rosemary (basal diet with 600 mg kg⁻¹ of rosemary extract - Rosmarinus officinalis); carvacrol (basal diet with 500 mg kg⁻¹ of essential oil of Thymbra capitata, carvacrol chemotype); and thymol (basal diet with 500 mg g⁻¹ of essential oil of Thymus zygis, subspecies gracilis, thymol chemotype). After 18 weeks of experimentation, the animals were stored on ice at 4 °C for 0, 7, 14, and 21 days. Physical-chemical, microbiological and sensory analyses were carried out at each sampling point to determine the degree of deterioration in the gilthead seabream. Lower indices of oxidation were observed in animals who were administered feeds supplemented with BHT, carvacrol and (to a lesser degree) rosemary. Lower bacteria counts were observed for the BHT and thymol groups, in addition to a slower deterioration in terms of sensory perception. Accordingly, the addition of natural antioxidants to the diet may have an added effect on fish quality, delaying post mortem deterioration.     

Effect of dehydration on the quality and storage stability of immature dates (Pheonix dactylifera)

Dates (Pheonix dactylifera) harvested from Kutch district of Gujarat, India were processed for the development of dehydrated dates. Dates grown in the Kutch region of Gujarat are harvested before maturation, i.e. Khalal stage to prevent spoilage caused due to rains. The processing and dehydration conditions for the preparation of dehydrated dates from immature date fruits were evaluated. Processing of dates by blanching in water at 96±1 °C and subsequent dehydration at 60±2 °C for 18-20 h resulted in good quality dehydrated dates as compared to the dates dried without heat treatment. The dehydrated dates were found to be acceptable with respect to colour, flavour, taste and overall quality. The dehydrated dates contained a total sugars of 520 g kg⁻¹, reducing sugars of 415.1 g kg⁻¹, tannins 13.5 g kg⁻¹ and ascorbic acid 33.7 mg kg⁻¹. Equilibrium relative humidity (ERH) of the dehydrated dates was found to be 75.9% with an initial moisture content of 159 g kg⁻¹. The dehydrated dates packed in 75 μ low-density polyethylene packaging material were shelf stable for 6 months at room temperature. The dehydrated dates remained acceptable during the storage period.     

Spray-dried rosemary extracts: Physicochemical and antioxidant properties

In this work, spray-dried rosemary extracts were obtained. A 3³ Box-Behnken design was followed to evaluate the influence of drying conditions on the contents of chemical markers and “in vitro” antioxidant activity of the powder. Although the dry products lost some of their polyphenols, they still had antioxidant activities (IC₅₀) ranging from 17.6 to 24.8 μg · mL⁻¹. Analysis of variance proved that studied factors and some of their interactions significantly affected most of the quality indicators. The best combination of conditions to use for obtaining dry rosemary extracts with adequate physicochemical and functional properties involves an extract feed rate of 6 mL · min⁻¹, a drying air inlet temperature of 140 °C and a spray nozzle air flow rate of 50 L · min⁻¹.     

Composition of oregano essential oil (Origanum vulgare) as affected by drying method

The influence of the drying method on volatile compounds of Origanum vulgare was evaluated. The drying methods tested were convective (CD) at 60 °C and vacuum-microwave (VMD), as well as a combination of convective pre-drying and VM finish-drying (CPD–VMFD). The volatile compounds of fresh and dried oregano were extracted by steam-hydrodistillation and analyzed by GC–MS. Oregano drying kinetics was described by a simple exponential model for CD and CPD–VMFD, while VMD kinetics consisted of two periods: linear until a critical point and exponential beyond that point. Thirty-four compounds were tentatively identified, with carvacrol, thymol, and γ-terpinene, being the major components. The total volatiles concentration of fresh oregano (33.0 g kg⁻¹) decreased significantly during drying, independently of the method used (CD: 10.2 g kg⁻¹, CPD–VMFD: 13.1 g kg⁻¹, and VMD: 27.9 g kg⁻¹). The final conclusion was that VM dehydrated Polish oregano was of better aromatic quality than that dried using hot air.     

Vanillin release from poly(vinyl alcohol)-bacterial cellulose mono and multilayer films

Mono and multilayer materials from PVA and BC incorporating vanillin as natural antimicrobial ingredient were prepared. The composite films were characterized by means of scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The release mechanism of vanillin from composites films was investigated using a pseudo first order model. The diffusion coefficients, calculated with Fick’s law of diffusion, are ranging from 1.69 × 10⁻¹² to 3.84 × 10⁻¹² m² s⁻¹. The vanillin release is influenced by films composition; the multilayer films being promising in order to achieve controlled release of vanillin.     

Effect of high carbon dioxide atmosphere packaging and soluble gas stabilization pre-treatment on the shelf-life and quality of chicken drumsticks

The effects of an aerobic modified atmosphere packaging (MAP) (70% CO₂, 15% O₂ and 15% N₂) with and without a CO₂ 3-h soluble gas stabilization (SGS) pre-treatment of chicken drumsticks were determined for various package and product quality characteristics. The CO₂ dissolved into drumsticks was determined. The equilibrium between CO₂ dissolved in drumsticks and CO₂ in head space was reached within 48 h after packaging, showing highest values of CO₂ in SGS pre-treated samples. This greater availability of CO₂ resulted in lower counts of TAB and Pseudomonas in SGS than in MAP drumsticks. Package collapse was significantly reduced in SGS samples. The average of CO₂ dissolved in the MAP treatment was 567 mg CO₂ kg^− 1 of chicken and, 361 mg CO₂ kg^− 1 of chicken during the MAP treatment, in SGS pre-treated samples. This difference could be the quantity of CO₂ dissolved during SGS pre-treatment.     

Thin layer drying characteristics of rapeseed (Brassica napus L.)

This study was performed to determine the most appropriate thin layer drying model and the effective moisture diffusivity of rapeseed. The thin layer drying tests were conducted at three different combinations of drying air temperature levels of 40, 50, and 60 °C and relative humidity levels of 30, 45, and 60%. The thin layer drying characteristics of rapeseed were determined. The Page (1949) model was the most adequate model for describing the thin layer drying of rapeseed. Drying occurred in the falling rate period and the rate of moisture removal from rapeseed was governed by the rate of water diffusion to the surface of the seed. Effective moisture diffusivities were calculated based on the diffusion equation for a spherical shape using Fick’s second law. Effective moisture diffusivity during drying varied from 1.72 × 10⁻¹¹ to 3.31 × 10⁻¹¹ m² s⁻¹ over the temperature range. The dependence of moisture diffusivity on temperature was described by an Arrhenius-type equation. The activation energy for moisture diffusion during drying was 28.47 kJ mol⁻¹.     

Release and antioxidant activity of carvacrol and thymol from polypropylene active packaging films

The migration of antioxidant (AO) agents, carvacrol and thymol, from polypropylene (PP) packaging films containing the studied compounds at 80 g/kg separately and an equimolar mixture of them into food simulants was investigated. Fast and reliable analytical procedures were developed and validated for the analysis of the studied AOs in food simulants. For aqueous food simulants, solid phase extraction followed by GC–MS analysis was performed. Fatty food simulants were directly analysed by GC–MS and HPLC-UV for isooctane and ethanol 950 mL/L, respectively. The release of AOs from the films was dependent on the type of food stimulant and AO incorporated. In particular, high levels of migration were obtained for both AOs into isooctane, showing thymol higher migration. The release kinetics of AOs from PP films showed a Fichian behaviour with diffusion coefficients ranging from 1 to 2 × 10⁻¹⁴ m²/s; except for the diffusion into isooctane where 4-6 higher values were obtained. The antioxidant activity of migration extracts was confirmed by the DPPH method, showing thymol a higher antioxidant capacity especially into isooctane with a 42.2% of inhibition. The obtained results suggest that carvacrol and thymol show a potential use as AOs for active packaging for extending the shelf-life of food products.     

Physical properties of a composite film containing sunflower seed meal protein and its application in packaging smoked duck meat

Sunflower seed meal protein (SP) films were prepared using various plasticizers, cross-linking agents, Cloisite Na⁺ or red algae, and their physical properties, such as tensile strength (TS), elongation at break (E), and water vapor permeability (WVP) were determined. The TS, E, and WVP of the SP film containing sucrose and fructose (2:1) as a plasticizer and cinnamaldehyde as a cross-linking agent were 3.05 MPa, 34.42%, and 2.25 × 10⁻⁹ g m/m² s Pa, respectively. The incorporation of Cloisite Na⁺ improved the physical properties of the SP film. The TS of the SP/Cloisite Na⁺ composite film containing 3% Cloisite Na⁺ increased by 2.19 MPa, and the WVP of the composite film decreased by 0.52 × 10⁻⁹ g m/m² s Pa compared to the SP film. The incorporation of red algae also improved the TS of the SP film. The TS of the SP composite film containing 1.2% red algae increased by 3.82 MPa compared to the SP film. In addition, an SP/red algae composite film containing grapefruit seed extract (GSE) was prepared and used in food packaging. After 12 days of storage, the population of Listeria monocytogenes inoculated on smoked duck meats packed with the SP/red algae composite film containing 1.2% GSE decreased by 1.31 log CFU/g compared to the control packaging. Therefore, these results suggest that SP composite films can be prepared by the addition of red algae to the SP film–forming solution and that the SP/red algae composite film containing GSE can be used as an antimicrobial food packaging material.     

Development and characterization of a nanomultilayer coating of pectin and chitosan – Evaluation of its gas barrier properties and application on ‘Tommy Atkins’ mangoes

A nanomultilayer coating made of food-grade, bio-based materials (consisting of five nanolayers of pectin and chitosan) was produced. This coating was firstly characterized in terms of the water vapor, oxygen and carbon dioxide permeabilities; these parameters exhibited values of 0.019 ± 0.005 × 10⁻¹¹, 0.069 ± 0.066 × 10⁻¹⁴ and 44.8 ± 32 × 10⁻¹⁴ g m/(Pa s m²), respectively, and are of the same order of magnitude of those found in other nanomultilayer systems. The nanomultilayer system was applied on whole ‘Tommy Atkins’ mangoes and the layers’ adsorption was confirmed by changes in the contact angle of the coated fruits’ skin. After 45 d of storage, uncoated mangoes presented a higher mass loss, higher total soluble solids and lower titratable acidity in comparison with coated mangoes. Uncoated mangoes had also a damaged and wrinkled appearance, showing evidence of microbial spoilage, and the flesh exhibited a slightly brownish color, in comparison with the coated mangoes. These results suggest a positive effect of the coating on gas flow reduction and on the consequent extension of the shelf-life of mangoes.     

Ethyl-carbamate determination by gas chromatography–mass spectrometry at different stages of production of a traditional Brazilian spirit

Ethyl carbamate (EC), which is probably carcinogenic to humans, can be produced during the alcoholic fermentation of sugar-cane juice to give cachaça. The stages to produce cachaça are obtainment of sugar-cane juice, sugar-cane fermentation to wine, and obtainment of distilled fractions and residue. In order to investigate the presence of EC in the wine and in the fractions of the distillation process, as well as in the vinasse (the residue left after distillation), gas chromatography–mass spectrometry was employed. After the fermentation phase, the wine showed an average content of 122 mg L⁻¹ of EC. Average EC content in distilled fractions was 59.7 mg L⁻¹ for head, 52 μg·L⁻¹ for heart and 1.57 mg L⁻¹ for tail. EC content was 53.1 mg L⁻¹ for vinasse. The results showed that it is essential to separate the head and tail fractions to ensure cachaça quality, with respect to EC content.     

Mathematical modeling of swelling in high moisture whey protein gels

Gels prepared from whey proteins can be used for controlled release of nutrients or active ingredients in food systems. The objective of this study was to characterize the water uptake by these hydrophilic gels to aid in the design of release systems. Whey protein isolate (WPI) gels (17% w/w protein) of different aspect ratios were submersed in aqueous solution at pH 7.0. Modeling of mass uptake is presented in terms of Case I (Fickian diffusion) and Case II (kinetic) models. Due to the extent of swelling, the Fickian diffusion with moving boundaries provided the most realistic reflection of the physics. An optimization routine provided the best fit values for the diffusivity. The average diffusivity for the smaller gels (with an initial radius of 6.7 mm) was 1.40 × 10⁻¹⁰ m²/s. The average diffusivity of the larger gels (with an initial radius of 8.5 mm) was 0.79 × 10⁻¹⁰ m²/s. The average diffusivities differed due to the slight variation in the composition of the gels. The model also yielded instantaneous values of the radius and sample length. The functionality of moisture uptake and total surface area was linear. The Fickian diffusion with moving boundary model can be extended to evaluate different geometries for controlled release systems.