Copper release from nano‑copper/polypropylene composite films to food and the forms of copper in food simulants

The influences of temperature, exposure time, different types of polypropylene (PP), (3-Aminopropyl) triethoxysilane (KH550) used as coupling agent, sterilizing conditions on copper migration from nano‑copper/PP composite films into food/ food simulants were explored. Results showed that copper migrated more easily from polypropylene (PPH) films with a maximum rate of 34.51%, compared to those from copolymer polypropylene (PPR) and block copolymer polypropylene (PPB) to 3% acetic acid (w/v). Gamma (γ) irradiation could significantly increase the copper migration (P < 0.05). Different forms of copper were found in different simulants. Copper crystals were found in 10% ethyl alcohol and identified by scanning electron microscopy and energy dispersed analysis of X-rays (SEM-EDX). The hydroxylation (%) of nano‑copper/PP films was less than 100%. These films had certain antioxidant and antimicrobial properties which could extend the shelf life of packaged food. The migration amount of copper into rice vinegar was the largest, with a maximum of 0.65 mg/ kg.Industrial relevanceAlthough nanomaterials are potentially beneficial for food packaging, migration of nanoparticles to the packaged food can be harmful to the human body. Therefore, it is very important to determine the presence and characterize the morphology of nanoparticles in food. In this paper, we have developed a new and effective packaging material containing nanoparticles and have explored the migration form and morphology in food simulants. In conjunction with the results of current study, nano‑copper/PP packaging material can be suggested for maintaining the product quality and has commercial potential.     

Overall migration from commercial coextruded food packaging multilayer films and plastics containers into official EU food simulants

The overall migration from a wide range of commercial five-layer coextruded packaging films into aqueous food simulants (distilled water, 3% aqueous acetic acid) and alternative fatty food simulant (iso-octane) was studied. The overall migration from commercial plastics cups (PS, HIPS, and PP) used for ice-cream or yogurt packaging into distilled water and 3% aqueous acetic acid was also studied. Test conditions for packaging material/food simulant contact and method of overall migration analysis were according to the EU directives and CEN-standards. The results showed that for all tested five-layer films and plastics (PS, HIPS, and PP) cups values of overall migration into aqueous simulants (0.11-0.79 mg/dm², 2.3-15.9 mg/l) and (<0.10-0.41 mg/dm², <0.80-3.1 mg/l) were significantly lower than the upper limit (10 mg/dm²) for overall migration from plastic packaging materials and articles into food and food simulants set by the EU Directive 90/128/EEC and their revisions. The overall migration values from five-layer materials into iso-octane were significantly higher (0.94-8.23 mg/dm², 18.8-164.7 mg/l) than the above values but are still lower than the upper limit for overall migration. Global migration values of five-layer films into aqueous food simulants seems to be independent of material thickness. In contrast, overall migration into iso-octane increases with film thickness.     

聚乳酸抗菌包装中麝香草酚在食品模拟物中迁移规律

研究麝香草酚/聚乳酸包装材料中的抗菌剂麝香草酚在食品模拟物中的迁移行为。在4、10、20、30 ℃条件 下分别将麝香草酚/聚乳酸包装材料浸入蒸馏水溶液、体积分数4%乙酸溶液、正己烷溶液、体积分数10%乙醇溶液 中,通过紫外分光光度法测定食品模拟液中麝香草酚迁移量,分析温度和食品模拟物对麝香草酚迁移量的影响,在 实验数据基础上,采用Piringer方程建立麝香草酚迁移模型,分析验证迁移模型的合理性。结果表明：麝香草酚迁 移量随着迁移温度升高和迁移时间延长而逐渐上升直至平衡,且在4 种食品模拟物中麝香草酚的迁移量大小顺序为： 正己烷＞10%乙醇＞4%乙酸＞蒸馏水;根据幂律方程发现麝香草酚的迁移机制符合Fick扩散定律,且迁移方程扩散系 数随迁移温度升高而增大,分配系数与之相反;Piringer方程能够较好地描述麝香草酚迁移行为。在迁移实验的基础 上构建数学模型,进一步完善基于聚乳酸食品包装材料的迁移理论,以期更好地预测食品包装中麝香草酚的迁移。     

Experimental and theoretical study of LDPE: Evaluation of different food simulants and temperatures

The mass transfer process of additives from plastic packaging to food is of great importance and interest because of the possible harmful effects on the human health. In this work the effect of different food simulants (EtOH 10–50%) and temperatures (28–60 °C) on the specific migration of Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (I-1076) from LDPE films is experimentally and theoretically studied, considering also the antioxidant stability in the food simulants studied at different temperatures.On the other hand, a phenomenological model based on a resistances-in-series which was resolved through the Regula Falsi algorithm according to a routine that considers the income of the structural parameters of the system and experimental conditions in which migration testing was performed. Diffusion coefficients of I-1076 in LDPE were ranged between 8.0E10–14 and 1.2E10–12 (m² s^{− 1}) for temperatures of 28 to 60 °C, respectively. The coupled effect of mass transfer and thermodynamical aspects was analyzed through the parameter Bi/K_P/FS proposed in this work, estimated in order to identify the combined contribution of the transport rate and the availability of the migrant compound in the food phase.     

Characterization and antimicrobial activity studies of polypropylene films with carvacrol and thymol for active packaging

Antimicrobial active films based on polypropylene (PP) were prepared by incorporating thymol and carvacrol at three different concentrations: 4, 6 and 8 wt.% of both additives as well as an equimolar mixture of them. A complete thermal, structural, mechanical and functional characterization of all formulations was carried out. SEM micrographs showed certain porosity for films with high additives concentrations. A decrease in elastic modulus was obtained for the active formulations compared with neat PP. The presence of additives did not affect the thermal stability of PP samples, but decreased PP crystallinity and oxygen barrier properties. The presence of thymol and carvacrol also increased stabilization against thermo-oxidative degradation, with higher oxidation induction parameters. Finally, thymol showed higher inhibition against bacterial strain present in food compared with carvacrol, leading to higher antimicrobial activity. The obtained results proved the permanence of certain amounts of the studied additives in the polymer matrix after processing making them able to be used as active additives in PP formulations.     

食品和药品接触材料聚丙烯中添加剂及 物质迁移的液相色谱分析

聚丙烯(PP)塑料被广泛用在食品及药品的包装上,PP中有害物质的迁移现已成为食品及药品安全隐患的重要组成部分,当食品与包装材料直接接触时,残留在PP包装材料里的抗氧剂及分解产物可以迁移到食品中污染食品。由于食品的多样性,因此常用几种食品模拟液来代替食品在实验室各种控制条件下进行迁移试验,因为迁移到模拟液里的添加剂浓度非常小,其浓度的测定常使用灵敏度较高的高效液相色谱法。迁移受到很多因素的影响,比如:接触的时间温度、接触的方式、包装材料的类型、迁移物的性质等。本文综述了聚丙烯包装材料有害物质迁移的研究现状,为我国食品包装行业标准化体系的建立提供一定的理论依据。     

Migration study of carvacrol as a natural antioxidant in high-density polyethylene for active packaging

The migration behaviour of low molecular weight compounds from food packaging materials is one of the key issues in assessing the possibility of use in such applications. The aim of this work was to study the migration of carvacrol (1% and 2% w/w) when added to high-density polyethylene. All materials were exposed to the food simulants olive oil and distilled water separately at 40°C and 25°C. Three significant variables influencing the migration process were considered: incubation temperatures, the initial concentration of antioxidant, and the type of simulant (oil and aqueous). The amount of carvacrol migrating to olive oil was significantly higher than in water because of the higher solubility of this antioxidant in oil. Experimental results agreed reasonably well with those obtained by the application of a simple model derived from Fick's Second Law. Carvacrol could therefore be used in active packaging formulations as its release from the polymer matrix can be controlled.     

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.     

Trends in the use of natural antioxidants in active food packaging: a review

The demand for natural antioxidant active packaging is increasing due to its unquestionable advantages compared with the addition of antioxidants directly to the food. Therefore, the search for antioxidants perceived as natural, namely those that naturally occur in herbs and spices, is a field attracting great interest. In line with this, in the last few years, natural antioxidants such as α-tocopherol, caffeic acid, catechin, quercetin, carvacrol and plant extracts (e.g. rosemary extract) have been incorporated into food packaging. On the other hand, consumers and the food industry are also interested in active biodegradable/compostable packaging and edible films to reduce environmental impact, minimise food loss and minimise contaminants from industrial production and reutilisation by-products. The present review focuses on the natural antioxidants already applied in active food packaging, and it reviews the methods used to determine the oxidation protection effect of antioxidant active films and the methods used to quantify natural antioxidants in food matrices or food simulants. Lastly consumers’ demands and industry trends are also addressed.     

纳米金属/金属氧化物-聚烯烃食品包装膜中纳米成分迁移的扩散系数估算

为探讨Fick第二定律是否符合聚烯烃食品包装膜中纳米成分向食品模拟物的迁移规律,根据已有实验数据,基于Crank模型进行拟合,估算纳米金属/金属氧化物-聚烯烃食品包装膜中纳米成分的扩散系数,并分析温度、聚烯烃、纳米成分和食品模拟物对扩散系数的影响。结果表明：纳米成分向食品模拟物的迁移符合Fick第二定律。温度升高促进纳米成分的迁移,且温度与纳米成分扩散系数的关系符合Arrhenius公式。不同聚烯烃结构对扩散系数的影响不同;聚丙烯3 种结构中,纳米铜和纳米氧化锌在均聚共聚聚丙烯中的扩散系数最大。不同纳米成分质量分数对其扩散系数的影响不同。纳米成分与食品模拟物、聚烯烃之间的溶解度差异也会影响其向食品模拟物迁移。     

Nano-TiO2 particles and high hydrostatic pressure treatment for improving functionality of polyvinyl alcohol and chitosan composite films and nano-TiO2 migration from film matrix in food simulants

This study investigated the impact of nano-TiO₂ and high hydrostatic pressure (HHP) treatment on microstructure, water vapor and gas barrier, antibacterial and mechanical properties of polyvinyl alcohol (PVA)–chitosan (CHI) biodegradable films and determined the migration behavior of TiO₂ nanoparticles from the films to food simulants. Apart from the effect of filler, TiO₂ nanoparticles also could improve the antibacterial activity of the films and play a role as a plasticizer in the films. HHP treatment promoted the interaction between PVA and chitosan molecules, resulting in the formation of more compacted network structures in PVA–CHI films. The migration of TiO₂ from the films was investigated in food simulants including distilled water, acetic acid, ethanol and olive oil, in which the trace amount of TiO₂ (< 4.20 × 10^− 3‰) was only detected in olive oil. HHP treatment at 200–400 MPa significantly reduced migration of TiO₂ nanoparticles from the films.Industrial relevanceResults from this study provide a new application direction of high hydrostatic pressure (HHP) in the field of food packaging materials for improving the functionality of materials. Due to the non-thermal characteristic, HHP in combination with nano-TiO₂ not only improved the mechanical and barrier properties of the biodegradable PVA–CHI composite films (polyvinyl alcohol and chitosan based materials), but also enhanced the antibacterial activity of the films. The HHP treated PVA–CHI–TiO₂ films are very stable in food simulants, such as olive oils. Therefore, the utilization of HHP and nano-TiO₂ is promising in the preparation of food packaging materials with desirable functionalities.     

Mobility of alpha-tocopherol and BHT in LDPE in contact with fatty food simulants.

The migration/sorption behaviour of butylated hydroxytoluene (BHT) and alpha-tocopherol was studied in packaging material in contact with fatty food simulants. Two low-density polyethylene (LDPE) films, containing either BHT or alpha-tocopherol as antioxidants, were stored in contact with sunflower oil or 95% (v/v) ethanol. The antioxidant content was monitored in the films throughout a period of 7 weeks. The migration of alpha-tocopherol into the food simulants was slower than that of BHT. Since alpha-tocopherol was transferred from the film to the simulant to a lesser extent, it is considered to be a more stable antioxidant than BHT when used in an LDPE film in contact with 95% ethanol or sunflower oil.     

Liposomal incorporation of carvacrol and thymol isolated from the essential oil of Origanum dictamnus L. and in vitro antimicrobial activity

The chemical composition of the essential oils from Origanum dictamnus L. (wild and organic cultivated plant) was analysed by GC–MS. Carvacrol, thymol, p-cymene, and γ-terpinene were identified as major constituents and isolated from both samples. The above components were successfully encapsulated in phosphatidyl choline-based liposomes and the possible improvement of their antioxidant and antimicrobial activities was tested against selected microbia. The antimicrobial properties of the oils were tested by a diffusion technique against four Gram positive and four Gram negative bacteria and three human pathogenic fungi, as well as the food-borne pathogen, Listeria monocytogenes. The percentage of the encapsulated carvacrol, the major component of the oil, was determined by GC–FID. In order to investigate any possible synergistic or antagonistic effect between carvacrol/thymol and carvacrol/γ-terpinene, the antimicrobial activities of the mixtures, were also determined before and after encapsulation in liposomes. All tested compounds presented enhanced antimicrobial activities after the encapsulation. Finally, in all cases, their antioxidant activity using differential scanning calorimetry was studied, in order to gain knowledge about their oxidation stability.     

Development of Antioxidant Packaging Material by Applying Corn‐Zein to LLDPE Film in Combination with Phenolic Compounds

Abstract: Functional active packaging materials were successfully developed by incorporating antioxidant agents into corn‐zein‐laminated linear low‐density polyethylene (LLDPE) film. The minimum effective concentrations of the active compounds (for example, thymol, carvacrol, eugenol) were determined and these compounds were then laminated into LLDPE films to develop corn‐zein‐laminated films with antioxidant agents. The release rate of antioxidant agents in gas and liquid media were determined along with the mechanical and water barrier properties of the films containing these compounds. Tensile strength and percentage elongation at break were reduced in the corn‐zein‐laminated LLDPE films when compared to typical LLDPE film. Furthermore, the ability of the corn‐zein‐laminated films to repel moisture decreased by approximately 12.2%, but was improved by incorporating hydrophobic antioxidant compounds in the corn‐zein layer. Examination of release kinetics in the gas and liquid phases verified that antioxidants were effectively released from the films and inhibited oxidation during testing. Finally, the films were used for fresh ground beef packaging, and effectively inhibited lipid oxidation and had a positive effect on the color stability of beef patties during storage. These results indicate that the developed antioxidant films are a novel active packaging material that can be effectively implemented by the food industry to improve the quality and safety of foods. Practical Application: Zein protein, a by‐product of corn processing industry, was laminated into plastic films in combination with natural phenolic compounds to develop antioxidant packaging films. The films demonstrated their efficient release patterns of antioxidant compounds, which are suitable for packaging applications and food protection.     

Controlled Release System by Active Gelatin Film Incorporated with β-Cyclodextrin-Thymol Inclusion Complexes

Essential oils such as thymol are added to food packaging film to obtain active films with antimicrobial and antioxidant properties. However, thymol is insoluble in water, and release rate of thymol is usually too fast. Therefore, a need exists to increase thymol solubility and to deliver thymol in a controlled manner from film matrix to food surface. In this study, spray dried inclusion complexes of β-cyclodextrin/thymol (1:1 molar ratio) was incorporated into gelatin solution to obtain active gelatin films. Both inclusion complexes and active films showed sustained release of thymol. Physical properties and thymol release kinetics were evaluated for active films. For gelatin films with 8.25% (mass ratio) inclusion complexes, complete thymol release took 235 h, compared with 38 h for thymol release from inclusion complexes. The diffusion coefficient reached 2.04?×?10^?15 m² s^?1.     

食品包装材料中双酚A迁移量的测定

建立采用高效液相色谱法对塑料食品包装材料中双酚A向食品模拟物迁移量的检测方法。使用4种食品模拟物：水、质量分数为4%乙酸溶液、体积分数30%的乙醇溶液和脂肪类模拟物(正己烷、异辛烷和橄榄油)。结果表明,双酚A在与食品塑料包装接触过程中,无论在何种情况下都会向食品模拟物中迁移,尤其向醇类模拟物中迁移最严重;在温度超过60℃时,双酚A向食品模拟物中的迁移率骤增;在微波加热条件,高火700W功率时双酚A向食品模拟物中的迁移速率最快。该方法检测限为0.3ng/mL,线性范围为0.5～100ng/mL,线性相关系数为0.9997,回收率在92.0%～102.4%之间,相对标准偏差≤2.84%(n=5)。     

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.     

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.     

Effectiveness of polypropylene film as a barrier to migration from recycled paperboard packaging to fatty and high-moisture food.

The capability of a polypropylene (PP) film barrier to prevent migration of residual contaminants from recycled paperboard into food simulants was studied. Anthracene, benzophenone, methyl stearate and pentachlorophenol were chosen as chemical surrogates to represent classes of contaminants likely to be found in recycled paper/paperboard. Each surrogate was spiked into a test specimen made of seven thin virgin paper layers at concentrations of 1-50 mg kg(-1). Test specimen were dried, stacked and sandwiched with PP films, laminated with PP film and then subjected to migration experiments using a compression cell maintained at 100 degrees C for 2 h. The concentration of the surrogates in the test specimen and in 95% ethanol, isopropanol and 10% ethanol food-simulating solvents was determined by gas chromatography with flame ionization and electron capture detection. The results show that although the concentrations of the surrogates in the food simulants decreased with an increase in PP film thickness, they were still high and generally resulted in dietary concentrations >0.5 microg kg(-1), the level that US Food and Drug Administration would equate with negligible risk for a contaminant migrating from food packaging. Only at the lowest spiking level (1 mg kg(-1) benzophenone) did migration from the paperboard through a 0.127-mm PP film result in a dietary concentration of 相似文献   

Alternative fatty food simulants and diffusion kinetics of nylon 12 food packaging.

The migration of laurolactam and cyclic di- and trimer of nylon 12 was assessed using three different films and five food simulants (olive oil, isooctane, 95% ethanol, 50% ethanol, water). Substitute test conditions for migration into olive oil according to European Union Directive EC/97/48 were applied using 95% ethanol and isooctane. Results showed that 95% ethanol overestimated while isooctane underestimated the respective migration into olive oil. Water was the best olive oil substitute, as migration of laurolactam into water and olive oil using the same temperature gave similar results. Additionally, diffusion kinetics of laurolactam were investigated by migration kinetic studies using isooctane and olive oil. Diffusion coefficients determined with isooctane were significantly higher than those found using olive oil. It was proved that isooctane had an interaction and olive oil was inert to the polymer. The diffusion conductance parameter, A(p), for nylon 12 determined using olive oil ranged from 0.3 to 0.6.