Influence of trace metals, acids and ethanol in food-simulating liquids on the retention of alpha-tocopherol in low-density polyethylene film.

The retention of alpha-tocopherol (vitamin E) in low-density polyethylene (LDPE) film was investigated when in contact with different food-simulating liquids. Variations of the aqueous food simulants approved by the EU for testing of interactions between packaging materials and food, and an alternative fatty food simulant (95% aqueous ethanol) were used to study the influence of trace metals and acids, as well as variation in pH and ethanol concentration, on the stability of alpha-tocopherol in the LDPE film. The presence of trace metals in aqueous media accelerated loss of alpha-tocopherol from the film, while the addition of citric or ascorbic acid counteracted this loss. In contact with aqueous ethanol at a concentration of 50% or higher, the loss of alpha-tocopherol from the film was total. However, with solutions containing less than 50% ethanol, the antioxidant was almost completely retained in the film, unless the temperature was increased from 6 to 40 degrees C. For contact with solutions containing ethanol or trace metals, an increase in temperature resulted in a greater loss of alpha-tocopherol from the LDPE film.     

Influence of polymer matrix and adsorption onto silica materials on the migration of alpha-tocopherol into 95% ethanol from active packaging.

In this study, the effect of polymer materials with different polarity, namely low density polyethylene (LDPE) and ethylene vinyl acetate (EVA), on the migration behaviour of alpha-tocopherol from active packaging was investigated. The antioxidant was also adsorbed onto silica materials, namely SBA-15 (Santa Barbara-15) and Syloblock, in order to protect the antioxidant during extrusion and to ensure a controlled and sufficient release during the shelf-life of the food product. Migration experiments were performed at 7.0 +/- 0.5 degrees C and 95% ethanol was used as fatty food simulant. All films contained a high concentration of alpha-tocopherol, approximately 2000 mg kg(-1), to obtain an active packaging. Polymer matrix had a small influence on the migration profile. The migration of 80% of total migrated amount of antioxidant was retarded for 2.4 days by using LDPE instead of EVA. When alpha-tocopherol was adsorbed onto both silica materials, the migration of 80% of total migrated amount of antioxidant was retarded for 3.4 days in comparison to pure alpha-tocopherol. No difference was seen between the migration profiles of alpha-tocopherol adsorbed onto both silica materials. In the case of pure alpha-tocopherol, 82% of the initial amount of alpha-tocopherol in the film migrated into the food simulant at a rather fast migration rate. In the case of adsorption on silica materials, a total migration was observed. These antioxidative films can have positive food applications.     

纳米二氧化钛改性LDPE薄膜中纳米钛粒子在食品模拟物中的迁移研究

为探究纳米改性LDPE薄膜中纳米钛粒子在食品模拟物中的迁移规律,根据欧盟法规(EU)NO.10/2011,分别采用蒸馏水、3%乙酸溶液(m/V)、10%乙醇溶液(V/V)、95%乙醇溶液(V/V)作为中性、酸性、脂肪性和酒精性食品模拟物,研究在不同温度条件下(40℃和70℃)纳米钛粒子的迁移情况,并研究了微波和紫外处理对迁移结果的影响。研究发现,纳米钛粒子在四种食品模拟物中的迁移量从高到低依次为:酸性食品模拟物、中性食品模拟物、酒精性食品模拟物和脂肪性食品模拟物,并且温度的升高能够促进纳米钛粒子的迁移。纳米钛粒子的迁移量范围为0.0046 mg/kg~0.61 mg/kg。此外,微波处理也能够促进纳米钛粒子的迁移,紫外处理则没有这样的促进作用。根据欧盟规定所允许的最大迁移量5 mg/kg,迁移实验表明纳米二氧化钛改性LDPE薄膜能够作为一种安全的食品包装膜。     

Migration of silver from nanosilver–polyethylene composite packaging into food simulants

An analytical method for the determination of silver in food simulants (3% (w/v) aqueous acetic acid or 95% (v/v) aqueous ethanol) was developed based on inductively coupled plasma mass spectrometry (ICP-MS). Recoveries ranged from 87% to 109% and RSDs ranged from 0.7% to 7.8%. The procedure was applied to determine the migration of silver from nanosilver–polyethylene food packaging film into food simulants at different temperatures and migration times. Results indicated that the maximum migration ratios were 1.70%, 3.00% and 5.60% for 3% (w/v) aqueous acetic acid at 20, 40 and 70°C, respectively, while for 95% (v/v) aqueous ethanol the maximum migration ratios were 0.24%, 0.23% and 0.22% at 20, 40 and 70°C.     

Migration of silver from nanosilver-polyethylene composite packaging into food simulants

An analytical method for the determination of silver in food simulants (3% (w/v) aqueous acetic acid or 95% (v/v) aqueous ethanol) was developed based on inductively coupled plasma mass spectrometry (ICP-MS). Recoveries ranged from 87% to 109% and RSDs ranged from 0.7% to 7.8%. The procedure was applied to determine the migration of silver from nanosilver-polyethylene food packaging film into food simulants at different temperatures and migration times. Results indicated that the maximum migration ratios were 1.70%, 3.00% and 5.60% for 3% (w/v) aqueous acetic acid at 20, 40 and 70 °C, respectively, while for 95% (v/v) aqueous ethanol the maximum migration ratios were 0.24%, 0.23% and 0.22% at 20, 40 and 70 °C.     

Study of the partition coefficients Kp/f of seven model migrants from LDPE polymer in contact with food simulants

This study evaluated the influence of parameters such as temperature and type of low-density polyethylene (LDPE) film on the log K_p/f values of seven model migrants in food simulants. Two different types of LDPE films contaminated by extrusion and immersion were placed in contact with three food simulants including 20% ethanol, 50% ethanol and olive oil under several time–temperature conditions. Results suggest that most log K_p/f values are little affected by these parameters in this study. In addition, the relation between log K_p/f and log P_o/w was established for each food simulant and regression lines, as well as correlation coefficients, were calculated. Correlations were compared with data from real foodstuffs. Data presented in this study could be valuable in assigning certain foods to particular food simulants as well as predicting the mass transfer of potential migrants into different types of food or food simulants, avoiding tedious and expensive laboratory analysis. The results could be especially useful for regulatory agencies as well as for the food industry.     

High-temperature migration of antioxidants from polyolefins

Migration rates of radiolabelled antioxidants, Irganox-1010 (I-1010) and Irganox-1076 (I-1076), were measured from low- and high-density polyethylenes (LDPE, HDPE) and polypropylene (PP) at temperatures up to 135 degrees C. Water, 8 and 95 per cent aqueous ethanol and corn oil were employed as food simulating liquids (FSL). The experiments were conducted in a high-pressure cell in a manner that allowed contact between the polyolefin plaque and the FSL only during the test period and not while being heated. The migrations of the antioxidants varied with the square root of time, and the Fickian diffusion coefficients could be correlated with temperature in an Arrhenius fashion. Under comparable test conditions, antioxidant migrations were largest from PP for aqueous simulants, but for non-aqueous simulants the highest losses were from LDPE. In both instances lowest losses were from HDPE. In most instances there was little difference between the migration behaviour of I-1010 and I-1076. A few tests were conducted to measure the antioxidant migrations to foods. The losses were usually larger than those to water but below those to corn oil.     

Antioxidants Release from Solvent-Cast PLA Film: Investigation of PLA Antioxidant-Active Packaging

The release study of natural antioxidants, i.e., ascorbyl palmitate and α-tocopherol, and synthetic phenolic antioxidants including butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, and tert-butylhydroquinone (TBHQ) from polylactic acid (PLA) film into food simulants were accomplished. PLA antioxidant films were placed in contact with 95, 50, and 10 % ethanol at 40 and 20 °C. Released antioxidants were regularly measured by high-performance liquid chromatography system for 60 days. Ascorbyl palmitate was completely degraded during film preparation and is not a suitable antioxidant for PLA antioxidant-active packaging. The diffusion coefficient (D) and partition coefficient (K) of antioxidants were calculated based on obtained data. Diffusion of the antioxidants from PLA to the simulants showed a Fick’s behavior with the diffusion coefficient (D) value between 10^?9 and 10^?11 cm² s^?1 with 0–100 % of release. Faster and higher release of antioxidants occurred at 40 °C according to Arrhenius law. At 40 °C, TBHQ in 95 % ethanol decomposed to 2-tert-butyl-1,4-benzoquinone and other quinone derivatives, and α-tocopherol in 50 % ethanol decomposed to some unknown neoformed compounds. Antioxidants molecular weight, Log P, simulant polarity, and temperature were the most influencing factors on antioxidants release rate from PLA films in contact with food simulants. The D and K coefficients of studied antioxidants from PLA in three food simulants and two temperatures can be used to create PLA antioxidant-active packaging to continually control the oxidation reactions in diverse foodstuffs to ensure higher food qualities. The PLA antioxidant-active packaging approach also permits to reduce the amounts of directly added antioxidants in foods to provide safer foods.     

Retention of α-tocopherol in low-density polyethylene (LDPE) and polypropylene (PP) in contact with foodstuffs and food-simulating liquids

Alpha-tocopherol occurs as a natural antioxidant in many foods and has also found use as a stabiliser in polymeric packaging materials. During storage of a food in contact with a plastic material, α-tocopherol may be released from the packaging material and transferred into the food. An active packaging application with the transfer of a substance, such as an antioxidant, from a packaging material to a food may help to prolong the shelf-life of the food. In this study, the retention of α-tocopherol in low-density polyethylene (LDPE) and polypropylene (PP) was investigated for contact with liquid foods with different fat contents and food simulants with different ethanol contents. The PP film exhibited excellent retention of α-tocopherol when in contact with all media, whereas some losses were observed from the LDPE film. A number of factors including fat, alcohol and organic acid contents of the various foodstuffs seemed to influence the loss of α-tocopherol from the LDPE film. © 1999 Society of Chemical Industry     

Study of the release of limonene present in chitosan films enriched with bergamot oil in food simulants

Chitosan films containing different concentrations of bergamot oil (BO) were obtained and the migration of limonene, the major oil component, to five liquid food simulants (aqueous solutions with 0%, 10%, 50% and 95% of ethanol and isooctane) was studied at 20 °C. The losses of BO and limonene during the film drying were also quantified. The release kinetics of limonene from chitosan matrix was described using an empirical model which relates the reduced concentration loss of limonene and the square root of time. The results show that kinetic constants for all films increased exponentially when the ethanol concentration increased in the aqueous system and were slightly greater when the film thickness was lower. Composite films remain intact in isooctane CH-BO and no release of limonene was observed. Hydration of the film to promote molecular mobility was essential to ensure the compound release.     

纳米银-聚乙烯复合包装中银对2 种抗氧化剂向食品模拟物迁移的影响

探究纳米银-聚乙烯复合包装中纳米银成分的存在对2 种抗氧化剂（Irganox1076和Irgafos168）向食品模拟物迁移规律的影响。将含有抗氧化剂的聚乙烯包装膜和同时含有抗氧化剂与纳米银的复合包装膜裁成正方形若干,分别浸泡于正己烷和体积分数95%乙醇溶液2 种食品模拟物中,密封后在20、40 ℃以及70 ℃条件下进行迁移实验。食品模拟物中2 种抗氧化剂的加标回收率在79.3%～108.0%之间,相对标准偏差在0.7%～5.3%之间。2 种抗氧化剂的迁移会随着迁移温度的升高以及迁移时间的延长而增加直至达到迁移平衡,且其在正己烷模拟物中的迁移量大于在体积分数95%乙醇模拟物中的迁移量;含纳米银聚乙烯塑料比不含纳米银聚乙烯塑料中的抗氧化剂向食品模拟物中的迁移量小,表明纳米银成分的存在可以抑制包装中的抗氧化剂向食品模拟物中的迁移。     

Release of butylated hydroxytoluene from an active film packaging to Asadero cheese and its effect on oxidation and odor stability

Antioxidant active packaging consisting of coextruded films made of low density polyethylene (LDPE) added with 0, 8, and 14 mg/g of butylated hydroxytoluene (BHT) and polyamide 6/66 were fabricated. The release of BHT from the films to Asadero cheese was determined. Most of the BHT was diffused from the LDPE layer to the cheese during the first 20 d of storage at 5°C. Diffusion coefficient for the diffusion of BHT from the films 8 and 14 to the cheese was calculated as 6.24E-12 and 6.26E-12 cm²/s, respectively. The release of BHT from the film added with 8 mg/g of the antioxidant in the LDPE layer complied with the legal limit established for food products. However, the film added with 14 mg/g of the antioxidant exceeded that limit. The film added with 8 mg/g of BHT maintained the same levels of oxidized odor from 20 to 100 d of storage.     

Antioxidant migration resistance of SiOx layer in SiOx/PLA coated film

As novel materials for food contact packaging, inorganic silicon oxide (SiO_x) films are high barrier property materials that have been developed rapidly and have attracted the attention of many manufacturers. For the safe use of SiO_x films for food packaging it is vital to study the interaction between SiO_x layers and food contaminants, as well as the function of a SiO_x barrier layer in antioxidant migration resistance. In this study, we deposited a SiO_x layer on polylactic acid (PLA)-based films to prepare SiO_x/PLA coated films by plasma-enhanced chemical vapour deposition. Additionally, we compared PLA-based films and SiO_x/PLA coated films in terms of the migration of different antioxidants (e.g. t-butylhydroquinone [TBHQ], butylated hydroxyanisole [BHA], and butylated hydroxytoluene [BHT]) via specific migration experiments and then investigated the effects of a SiO_x layer on antioxidant migration under different conditions. The results indicate that antioxidant migration from SiO_x/PLA coated films is similar to that for PLA-based films: with increase of temperature, decrease of food simulant polarity, and increase of single-sided contact time, the antioxidant migration rate and amount in SiO_x/PLA coated films increase. The SiO_x barrier layer significantly reduced the amount of migration of antioxidants with small and similar molecular weights and similar physical and chemical properties, while the degree of migration blocking was not significantly different among the studied antioxidants. However, the migration was affected by temperature and food simulant. Depending on the food simulants considered, the migration amount in SiO_x/PLA coated films was reduced compared with that in PLA-based films by 42–46%, 44–47%, and 44–46% for TBHQ, BHA, and BHT, respectively.     

The migration of Irganox 1010 antioxidant from high-density polyethylene and polypropylene into a series of potential fatty-food simulants

Alternatives to highly-volatile ethanol or analytically complex cooking oil were examined as potential fatty-food simulants which would undergo high-temperature exposures to food-packaging polymers in food-packaging evaluation studies. The alternatives consisted of alcohols containing four to eight carbons. As test cases, the migration of Irganox 1010 antioxidant from high-density polyethylene and polypropylene into the higher alcohols was compared to the migration of Irganox 1010 into aqueous ethanol solutions and cooking oil, the US Food and Drug Administration's currently recommended fatty-food simulants. The data obtained showed slightly greater migration of the antioxidant into 95% ethanol than into cooking oil, and slightly less migration into 50% ethanol than into cooking oil. The migration of the antioxidant into the alcohols consisting of four or more carbons was much greater than the migration observed in cooking oil. In many experiments the polymers became depleted of the antioxidant prior to the end of the short, high-temperature exposure period (i.e. 2 h at 250 degrees F) to the higher alcohols. Also, for all experiments run under the same time/temperature/simulant conditions, migration of the antioxidant was greater from polypropylene than from high-density polyethylene. Diffusion coefficients generated for 95% ethanol and corn oil from these data compare closely with data from the literature.     

Migration of copper from nanocopper/LDPE composite films

Three nanocopper/low-density polyethylene (LDPE) composite films were tested in food simulants (3% acetic acid and 10% ethanol) and real food matrices (rice vinegar, bottled water and Chinese liquor) to explore the behaviours of copper migration using ICP-OES and GFAAS. The effects of exposure time, temperature, nanocopper concentration and contact media on the release of copper from nanocopper/LDPE composite films were studied. It was shown that the migration of copper into 10% ethanol was much less than that into 3% acetic acid at the same conditions. With the increase of nanocopper concentration, exposure time and temperature, the release of copper increased. Copper migration does not appear to be significant in the case of bottled water and Chinese liquor compared with rice vinegar with a maximum value of 0.54 μg mL^?1 for the CF-0.25# bags at 70°C for 2 h. The presence and morphology of copper nanoparticles in the films and the topographical changes of the films were confirmed by field emission scanning electron microscope (FE-SEM) and atomic force microscope (AFM). In this manner, copper nanoparticles of different morphologies, sizes and distribution were found, and samples with higher nanocopper concentration had a more irregular topography. In the case of Fourier transform infrared spectroscopy (FTIR), no chemical bonds formed between copper nanoparticles and LDPE. Copper nanoparticles were just as physically dispersed in LDPE.     

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.     

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.     

纳米银-聚乙烯复合包装中助剂对银向食品模拟物迁移的影响

为探究纳米银-聚乙烯复合包装中添加剂对纳米银颗粒向食品模拟物迁移的影响,在20、40 ℃和70 ℃条件下分别将空白纳米银聚乙烯复合包装和含有助剂（抗氧化剂1076、抗氧化剂168、光稳定剂622和光稳定剂944）的纳米银聚乙烯复合包装在3 g/100 mL乙酸溶液和体积分数50%乙醇溶液两种食品模拟物中浸泡1～30 h,然后蒸干定容并用电感耦合等离子体质谱测定银的含量。结果表明：食品模拟物中银的加标回收率在84.19%～115.69%之间,相对标准偏差在3.21%～8.75%之间;在8 h内塑料中的添加剂会促进银向两种食品模拟物的迁移;同时银的迁移率会随着迁移温度的升高和迁移时间的增加而增大直至平衡;平衡时,塑料中的添加剂反而阻碍银向这两种食品模拟物的迁移;银在酸性模拟物中的迁移率大于在酒精类模拟物中的迁移率。     

Migration of Ti from nano-TiO2-polyethylene composite packaging into food simulants

An analytical method based on ICP-MS was developed for the determination of Ti in food simulants (3% (w/v) aqueous acetic acid and 50% (v/v) aqueous ethanol). The method was used to determine the migration of Ti from nano-TiO₂-PE films used for food packaging into food simulants under different temperature and migration time conditions. The maximum migration amounts into 3% (w/v) aqueous acetic acid were 1.4 ± 0.02, 6.3 ± 0.5 and 12.1 ± 0.2 μg kg^?1 at 25, 70 and 100°C, respectively, while into 50% (v/v) aqueous ethanol, the maximum migration amounts were 0.5 ± 0.1, 0.6 ± 0.03 and 2.1 ± 0.1 μg kg^?1 at 25, 70 and 100°C, respectively. Increasing the additive content in the film promoted migration of nanoparticles. The results indicated that the migration of nanoparticles might occur via dissolution from the surface and cut edges of the solid phase (film) into the liquid phase (food simulant).