水产品活性包装和智能包装技术的研究进展

水产品贮藏品质对加工保藏技术的要求以及国内消费者对水产品加工食品质量安全的存疑促进了水产品活性包装和智能包装技术的发展。活性包装技术通过包装材料吸收不利保藏的成分,或释放有利保藏的成分,或发挥涂膜抗菌、抗氧化作用,对水产品起到防腐保鲜的作用。智能包装技术通过标签指示剂、信息溯源提高产业链管理效率以及减少消费者对水产品品质和安全的担心。虽然国内外在水果、蔬菜、奶制品等食品上已有新包装技术的应用,但是我国水产品活性包装和智能包装的工业化尚在起步阶段。本文总结了主要的活性包装和智能包装技术,并总结了新包装技术在国外水产品上的应用,以期为我国未来水产品新包装的发展提供借鉴参考。     

包装材料结合活性包装对荞麦半干面常温货架期及品质的影响

为了延长荞麦半干面的常温货架期,以聚偏二氯乙烯(PVDC)和聚乙烯(PE)为包装材料,采用不同活性包装方式(脱氧包装和脱氧结合酒精缓释包装)对其进行包装处理。考察脱氧剂、酒精缓释剂和不同包装材料对荞麦半干面货架期和储藏期间品质的影响。测定荞麦半干面在储藏期间菌落总数、酸度值、p H值、质构特性、感官品质和包装袋内顶空氧气含量、顶空酒精浓度的变化。结果表明:储藏期间菌落总数整体呈现上升趋势,脱氧结合酒精缓释包装协同抑制微生物生长。储藏9 d后,脱氧结合酒精缓释包装的面条菌落总数均未超过106cfu/g,同时显著抑制了理化品质的劣变(P0.05);脱氧剂的吸氧量越大,24 h内除氧速率越快,抑菌效果越显著;相同活性包装方式下,与PE包装材料相比,PVDC包装材料能增强其延长荞麦半干面常温货架期的作用效果。与其他包装方式相比,脱氧(200 m L)结合酒精缓释PVDC包装将荞麦半干面货架期延长至16 d,并且维持了面条储藏期间的品质。     

Development and validation of analytical methods for monomeric and oligomeric migrants from nylon 12 packaging materials

Analytical methods for the determination of laurolactam--the monomer of nylon 12--as well as the cyclic dimer and trimer were established. High performance liquid chromatography using ultraviolet (HPLC-UV) and mass spectrometric detection (HPLC-MS) were both found suitable to identify and quantify monomer, cyclic dimer and trimer well below the specific migration limit (SML) of laurolactam, being 5 mg/kg of food (simulant). Gas chromatography with flame ionisation detection (GC-FID) showed to be an appropriate method for the detection of only laurolactam in aqueous and fatty food simulants. Food simulants could be analysed directly by all three methods, or after a change of solvents. For olive oil, a method for sample clean-up by size-exclusion chromatography (SEC) was established.     

Determination of bisphenol A in, and its migration from, PVC stretch film used for food packaging

Bisphenol A (BPA) is used as an additive in polyvinyl chloride (PVC) products, including stretch films used for food packaging. The BPA contents were investigated of several brands of stretch film bought locally but marketed internationally or throughout Spain and which were presumably produced at different manufacturing plants. Their major components were identified by FTIR (Fourier Transform Infrared Spectrometry) and horizontal attenuated total reflectance, and the migration of BPA from these materials into the standard European Union food simulants was determined by high-performance liquid chromatography (HPLC) using both fluorescence (FL) and ultraviolet (UV) detection, the identity of the analyte being confirmed by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). The two HPLC detection methods had different detection limits (30 μg l^-1 for UV, 3 μg l^-1 for FL), but afforded virtually identical BPA determinations for the samples tested. BPA contents ranging from 40 to 100 mg kg^-1 were found in three of the five PVC-based films analysed, and a content of 500 mg kg^-1 was found in a fourth; for these determinations, extraction into acetonitrile was used. In standard tests of migration into water, 3% acetic acid and olive oil over 10 days at 40°C, migration from a given film was in all cases greatest into olive oil. Migration from the films with non-zero BPA contents ranged from 3 to 31 μg dm^-2, values higher than those reported for many other food-contact materials, but lower than the European Union specific migration limit for BPA. PVC stretch film nevertheless may make a significant contribution to contamination of foodstuffs by BPA, and should be taken into account in estimating BPA intake or exposure to this substance.     

Effect of ionizing radiation on the physicochemical and mechanical properties of commercial monolayer flexible plastics packaging materials

The effect of γ-radiation doses (5, 10, 30 kGy) on the mechanical properties, gas and water vapour permeability, infrared (IR) spectra, and overall migration into aqueous and alternative fatty food simulants of commercial monolayer flexible packaging films ethylene vinyl acetate (EVA), high-density polyethylene (HDPE), polystyrene (PS), bi-axially oriented polypropylene (BOPP), low-density polyethylene (LDPE) and Ionomer was studied. For comparison purposes, respective non-irradiated (control) films were also studied. The results showed that radiation doses of 5, 10 and 30 kGy did not induce any statistically significant changes in the permeability of all studied films to gases (oxygen and carbon dioxide) and water vapour. Likewise, IR spectra of all studied films showed no significant differences after all absorbed doses. The mechanical properties (tensile strength, percentage elongation at break and Young's modulus) of all studied films remained unaffected after absorbed doses of 5 and 10 kGy. In contrast, the tensile strength of HDPE, BOPP and Ionomer films irradiated at a dose of 30kGy decreased. In addition, the percentage elongation at break of LDPE and Ionomer films irradiated at a dose of 30 kGy decreased while Young's modulus of all samples remained unaffected. All mechanical properties of PS and EVA films remained unaffected after radiation at 30 kGy. Radiation (all absorbed doses) resulted in no statistically significant differences in overall migration values into distilled water for all studied films. For 3% aqueous acetic acid, absorbed doses of 5 and 10 kGy did not affect overall migration values of all investigated samples with the exception of the Ionomer film, for which the overall migration value decreased at 10 kGy. An absorbed dose of 30 kGy caused an increase in BOPP overall migration values and a decrease in Ionomer overall migration values. In contrast, a dose of 30 kGy induced no changes in overall migration values of EVA, HDPE, LDPE and PS films into the same simulant. There were no statistically significant differences in overall migration values of EVA, PS and LDPE films into iso-octane for all absorbed doses. In contrast, a dose of 30 kGy resulted in an increase in overall migration values of BOPP and a respective decrease in HDPE and Ionomer films.     

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.     

Past, current and potential utilisation of active and intelligent packaging systems for meat and muscle-based products: A review

Interest in the use of active and intelligent packaging systems for meat and meat products has increased in recent years. Active packaging refers to the incorporation of additives into packaging systems with the aim of maintaining or extending meat product quality and shelf-life. Active packaging systems discussed include oxygen scavengers, carbon dioxide scavengers and emitters, moisture control agents and anti-microbial packaging technologies. Intelligent packaging systems are those that monitor the condition of packaged foods to give information regarding the quality of the packaged food during transport and storage. The potential of sensor technologies, indicators (including integrity, freshness and time-temperature (TTI) indicators) and radio frequency identification (RFID) are evaluated for potential use in meat and meat products. Recognition of the benefits of active and intelligent packaging technologies by the food industry, development of economically viable packaging systems and increased consumer acceptance is necessary for commercial realisation of these packaging technologies.     

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.     

Tailoring fatty food simulants made from solvent mixtures (2): determining the equivalent migration behaviour of olive oil and of solvents in the case of polyolefins

It is suggested that solvent mixtures consisting of an ester and of an inert solvent can be used as fatty food simulants capable of having the same migration behaviour as olive oil with plastics. Migration tests carried out with low-density polyethylene for 20 and 48h in an 8 and 5% mixture of tert-butyl acetate in ethanol respectively gave results equivalent to those obtained with olive oil after 10 days at 40°C. The use of solvent mixtures facilitated the analysis and improved detection limits, giving good repeatability. Furthermore, the more rapid migration in solvent mixtures can be particularly useful for industrial controls as alternative test methods.     

Influence of solvent absorption on the migration of Irganox 1076 from LDPE

The effect of solvent absorption on additive migration was studied by relating the diffusion coefficient ( D ) of Irganox 1076 to the maximum solvent absorption of different solvents in low-density polyethylene (LDPE) film. Solvents tested were ethanol, isopropanol, isooctane, ethylacetate, cyclohexane, tributyrin, tricaprylin and olive oil. Diffusion and partition coefficients were determined by fitting the migration curves, i.e. the concentration of Irganox 1076 in solvent as a function of time, with Fick's diffusion equation. The results for the low molecular weight solvents show that with increasing maximum solvent absorption, D of Irganox 1076 is increasing as well. This trend is not observed for the two triglycerides and olive oil. In spite of absorption, no increase in D was observed. The obtained result is the basis of an extended predictive migration model that, besides migrant and polymer properties, is also based on the maximum solvent absorption in the polymer.     

Tailoring fatty food simulants made from solvent mixtures (1): comparison of methanol, ethanol and isopropanol behaviour with polystyrene

To investigate the use of solvent mixtures as test media replacing olive oil in migration tests, the interaction of polystyrene with mixtures composed of various amounts of tert.butyl acetate (mimicking the ester functions of oil) and of a low molecular weight alcohol (methanol, ethanol and isopropanol as inert co-solvent) was studied, using FTIR. Isopropanol, which has a lesser tendency to form hydrogen bonds in the plastic, can be used as main component of alternative fatty test media, its aggressiveness to polystyrene being tailored by adjusting the concentration of tert.butyl acetate. Concentrations below 20% seem useful on the basis of the mechanism of displacement of the alcohols.     

Development of cellulose-based bactericidal nanocomposites containing silver nanoparticles and their use as active food packaging

The use of nanomaterials, including metallic as active fillers in polymeric nanocomposites for food packaging has been extensively investigated. Silver nanoparticles (AgNPs), in particular, have been exploited for technological applications as bactericidal agents. In this paper, AgNPs were incorporated into a hydroxypropyl methylcellulose (HPMC) matrix for applications as food packaging materials. The average sizes of the silver nanoparticles were 41 nm and 100 nm, respectively. Mechanical analyses and water vapor barrier properties of the HPMC/AgNPs nanocomposites were analysed. The best results were observed for films containing smaller (41 nm) AgNPs. The antibacterial properties of HPMC/AgNPs thin films were evaluated based on the diameter of inhibition zone in a disk diffusion test against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The disk diffusion studies revealed a greater bactericidal effectiveness for nanocomposites films containing 41 nm Ag nanoparticles.     

Use of endospore-forming bacteria as an active oxygen scavenger in plastic packaging materials

The incorporation of active oxygen scavengers in polymer packaging materials is essential to allow packaging of oxidation sensitive products. Opposed to the currently available chemical oxygen scavengers, systems based upon natural and biological components could have advantages towards consumer perception and sustainability. A modelsystem for a new oxygen scavenging poly(ethylene terephthalate) (PET) bottle is proposed using an endospore-forming bacteria genus Bacillus amyloliquefaciens as the active ingredient. Spores were incorporated in poly(ethylene terephthalate, 1,4-cyclohexane dimethanol) (PETG), an amorphous PET copolymer having a considerable lower processing temperature and higher moisture absorption compared to PET. To asses spore viability after incorporation, a method was optimized to extract spores from PETG using a chloroform/water mixture. Samples were also analyzed using a Live/Dead BacLight Bacterial Viability kit. It was shown that endospores were able to survive incorporation in PETG at 210 °C. Incorporated spores could actively consume oxygen for minimum 15 days, after an activation period of 1–2 days at 30 °C under high humidity conditions.

Industrial relevance

The study describes a modelsystem for the use of incorporated spores genus Bacillus amyloliquefaciens as an active oxygen scavenger in PET multilayer bottles using PETG as the middle layer material. Industrially, oxygen scavengers using incorporated viable spores as the active compound could have advantages towards consumer perception, recyclability, safety, material compatibility, production costs, … compared to currently available chemical oxygen scavengers.     

Polymer additive migration to foods - a direct comparison of experimental data and values calculated from migration models for high density polyethylene (HDPE)

To reduce the amount of compliance testing for food contact polymers the use of migration modelling has been proposed. This study was conducted to provide valid data for the independent evaluation of two such diffusion-based models using a range of different high density polyethylene (HDPE) polymers and plastics additives. Seventy-two experimental migration data have been obtained in triplicate and used to evaluate two Fickian-based migration models in the prediction of specific migration of four HDPE additives into olive oil. All tests were conducted using olive oil, representing the most severe case for fatty foods with test conditions of 2h at 70oC, 6h at 70oC, 10 days at 40oC representing short term exposures at high temperatures and room temperature storage. Predicted migration values were calculated by inserting the measured initial concentration of additive in the polymers (Cp,0) into the equations together with known variables such as additive molecular weight, temperature and exposure time. The results indicate that both models predict migration values into olive oil close to, or in excess of, the experimental results. The Piringer migration model, using the 'exact' calculations of the Migratest Lite program, gave an overestimation for 83% of the migration values generated in this study. The highest overestimation was 3.7 times the measured value. For all measurements, the predicted migration from the Migratest Lite program was greater than 50% of the observed value. The FDA model was found more accurately to predict migration in most situations but underestimated migration more frequently. Differences in the polymer specification had little effect on specific migration of the additives investigated.     

Extension of the shelf-life of foal meat with two antioxidant active packaging systems

The objective of this study was to investigate the effect of antioxidant active system on physico-chemical properties, the microbial counts, lipid and protein stability and the sensory properties' changes of foal steaks during storage time. The experimental packaging systems were: (i) control group was packaged without active film, (ii) ATOX group was packed with active film containing a 2% of an oregano essential oil and (iii) ATGT group was packed with active film containing 1% of a green tea extract. Samples were filled with 80% O₂/20%CO₂ atmosphere and displayed under illumination at 2 °C for 14 days. Microbial populations were reduced up to 3.60 log CFU/g on day 14 of storage with the most pronounced effect being achieved by green tea film. Active films with oregano led to a significant (P < 0.001) inhibition of metmyoglobin formation. The use of oregano active film resulted in a decreased lipid and protein oxidation of foal steaks. Active films with oregano were significantly (P < 0.05) more efficient than those with green tea extended fresh odour and colour from 7 to 14 days compared to the control.     

Polymer additive migration to foods-a direct comparison of experimental data and values calculated from migration models for polypropylene

To reduce the amount of compliance testing for food contact polymers the use of migration modelling is under discussion and being evaluated by an EU Commission funded project (Evaluation of Migration Models No. SMT4-CT98-7513). The work reported in this paper was exclusively funded by industry to provide data for the independent evaluation of a diffusion based model using eight different samples of polypropylene (PP) covering the range of polymers specification and five commonly used plastics additives. One hundred and fifty experimental migration data have been obtained in triplicate and used to evaluate a Fickian-based migration model in the prediction of specific migration of five additives into olive oil. All tests were conducted using olive oil, representing the most severe case for fatty foods, with test conditions of 2h at 121 ° C, 2h at 70 ° C and 10 days at 40 ° C, representing short term exposures at high temperatures and room temperature storage. Predicted migration values were calculated using the Piringer 'Migratest Lite' model by entering the measured initial concentration of additive in the polymers(C_p,0) in to the equations together with known variables such as additive molecular weight, temperature and exposure time. Where necessary the data generated in this study have been used to update the model. The results indicate the Piringer migration model, using the 'exact' calculations of the Migratest Lite program, predicted migration values into olive oil close to, or in excess of, the experimental results for > 97% of the migration values generated in this study. For all measurements, the predicted migration from the Migratest Lite program was greater than 70% of the observed value. This study has identified the possibility that random co-polymers of propylene and ethylene give higher migration than other grades of polypropylenes and could be treated as a separate case. However, further work on more samples of random co-polymers is required to confirm this finding.     

Influence of flavour absorption on oxygen permeation through LDPE, PP, PC and PET plastics food packaging

The effect of flavour absorption on the oxygen permeability of low-density polyethylene (LDPE), polypropylene (PP), polycarbonate (PC) and polyethylene terephthalate (PET) was studied using an isostatic continuous flow system. Polymer samples were exposed to a model solution containing limonene, hexyl acetate, nonanone and decanal at 40°C. After exposure, one part of each sample was analysed for absorbed flavour compounds using a Large Volume Injection GC Ultrasonic 'in vial' extraction method, and from the other part, oxygen permeability was measured in a permeation cell at 25°C. After 8h of exposure, LDPE and PP samples showed a significant linear (R² = 0.82 and 0.99) increase in oxygen permeability of 21 and 130%, respectively. Owing to swelling of the polymer samples resulting from flavour absorption, the structure of the polymeric network changed (i.e. opened) and consequently increased oxygen permeability. The oxygen permeability of exposed PC showed a significant linear (R² = 0.78) decrease of 11% after 21 days. PC obviously did not swell like LDPE or PP. Therefore, it was suggested that absorbed flavour compounds occupied or blocked 'microcavities' through which normally oxygen is transported. Absorption of flavour compounds by PET did not affect the oxygen permeability of PET significantly.     

A study on the migration of organic pollutants from recycled paperboard packaging materials to solid food matrices

Paper and board are widely used as food packaging materials, mainly for disposable products. As public interest in conservation of natural resources has accelerated in the past several years, the use of recycled paper and board has increased. Recycled fiber materials can be used in certain limits as food contact materials. The safety of recycled fiber-based materials for food contact applications is largely dictated by the ability of post-consumer contaminants to be absorbed into recycled materials and later released by the packaging material and trapped on the food. The present work was undertaken with the aim of investigating the physicochemical behavior of selected model contaminants on paper and board, in contact with foodstuffs thus producing a fundamental set of data about their mobility from recycled paper and board into foods. More specifically, the kinetics of migration of selected model contaminants (surrogates) from contaminated recycled paper packaging samples into dry foodstuffs with different fat content was studied using a method based on solvent extraction and GC-FID quantification. Results showed the ability of selected contaminants of various types and various volatilities to potentially transfer to dry foods. The proportion of substances migrated to food was strongly dependent on the nature of the paper samples, fat content of the food, chemical nature and volatility of the migrant. The highest level of migration of organic pollutants was observed for the substrate with the highest fat content. Furthermore, it is shown that contact time and temperature have a significant effect on migration of model contaminants into foods.     

Modelling of simultaneous two-sided migration into water and olive oil from nylon food packaging

Nylon 6 and nylon 12 food packaging materials used as sausage casings are typically exposed to fatty food on one side and boiling water on the other during the cooking process. To simulate the migration behaviour under these conditions, a special migration cell was constructed and filled with olive oil on one side of the polymer and water on the other to find out what amounts of the migrants will transfer to either side and phase at 100 °C. Results show that when a nylon 6 film is exposed to the conditions as described above, total mass transfer of the monomer—caprolactam—into the water phase occurs after 2 h at 100 °C. Nylon 12 sausage casings release similar amounts of their monomer—laurolactam—into both the aqueous and oil phase. An existing computer migration model was adapted to simulate the situation of simultaneous two-sided migration applying previously determined diffusion and partitioning coefficients. The suitability of the model was confirmed by experimental data.     

Effect of oxygen absorber, nitrogen flushing, packaging material oxygen transmission rate and storage conditions on quality retention of raw whole unpeeled almond kernels (Prunus dulcis)

The present study investigated the effect of active packaging, nitrogen flushing, container oxygen barrier and storage conditions on quality retention of raw whole unpeeled almonds. Almond kernels were packaged in: a) polyethylene terephthalate//low-density polyethylene (PET//LDPE), and b) low-density polyethylene/ethylene vinyl alcohol/low-density polyethylene (LDPE/EVOH/LDPE) pouches under N_2, with or without an oxygen absorber, heat-sealed and stored for a period of 12 months. Quality parameters monitored were: peroxide value (PV), hexanal content, color, fatty acid composition and volatile compounds. PV ranged between 0.17 for fresh almonds and 9.22 meq O₂/kg oil for almonds packaged in PET//LDPE pouches under N₂ exposed to light at 20 °C after 12 months of storage. Respective values for hexanal were <28.5 μg/kg and 4.88 mg/kg. Polyunsaturated fatty acids (PUFA) and saturated fatty acids (SFA) increased with a parallel decrease of monounsaturated fatty acids (MFA) after 12 months of storage in all treatments. Likewise, volatile compounds such as aldehydes, ketones, alcohols, alkanes and aromatic hydrocarbons increased indicating enhanced lipid oxidation. Color was the parameter least affected. Use of the oxygen absorber provided a shelf life of at least 12 months for all samples irrespective of container oxygen barrier, lighting conditions and storage temperature.