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。     

纳米塑料复合食品包装中的纳米成分及其迁移研究进展

在塑料食品包装中加入纳米材料可以实现很好的机械性、气体阻隔性或抗菌性等优良性能。然而在与食品 接触的过程中这些纳米材料也有可能迁移到食品中,从而对消费者的健康产生威胁,甚至对市场及消费者信心造成 负面影响。对纳米材料进行迁移研究是对其进行风险评估的重要一环,已经得到国内外学者的广泛关注。本文综述 了纳米塑料复合包装的种类、在食品包装中应用较多的纳米材料及其作用,并详细分析了食品包装中纳米材料向食 品或食品模拟物迁移的研究。结果表明：食品包装中纳米材料向食品或食品模拟释放的量较小,但到目前为止,关 于它们是否会以纳米形态释放出来仍然没有达成统一意见。另外,微波处理、塑料助剂的添加可以影响纳米材料的 释放。     

Influence of aqueous food simulants on potential nanoparticle detection in migration studies involving nanoenabled food-contact substances

Research focused on assessing potential consumer exposure to nanoparticles released from nano-enabled food-contact materials (FCMs) has often reached conflicting conclusions regarding the detection of migrating nanoparticles. These conflicting conclusions, coupled with the potential for nanoparticles to be unstable in certain food simulants, has necessitated a closer look at the role played by food simulants recommended for use in nanoparticle migration evaluation. The influence of aqueous food simulants on nanoparticles under migration evaluation conditions is reported herein. The stability of silver nanoparticles (AgNP) spiked into three food simulants (water, 10% ethanol and 3% acetic acid) was investigated using asymmetric flow field-flow fractionation (AF4), ultrafiltration, electron microscopy (EM), and single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS). While 3% acetic acid induced significant oxidative dissolution of AgNP to silver ions, there were very minor to no changes in the physicochemical properties of AgNP in water and 10% ethanol.     

Release of carbon nanoparticles of different size and shape from nanocomposite poly(lactic) acid film into food simulants

ABSTRACT

Poly(lactic) acid (PLA) film with 2 wt% mixed carbon nanofillers of graphene nanoplates (GNPs) and multiwall carbon nanotubes (MWCNTs) in a weight ratio of 1:1 with impurities of fullerene and carbon black (CB) was produced by layer-to-layer deposition and hot pressing. The release of carbon nanoparticles from the film was studied at varying time–temperature conditions and simulants. Migrants in simulant solvents were examined with laser diffraction analysis and transmission electron microscopy (TEM). Film integrity and the presence of migrants on the film surfaces were visualised by scanning electron microscopy (SEM). The partial dissolution of PLA polymer in the solvents was confirmed by swelling tests and differential scanning calorimetry (DSC). Nanoparticle migrants were not detected in the simulants (at the LOD 0.020 μm of the laser diffraction analysis) after migration testing at 40°C for 10 days. However, high-temperature migration testing at 90°C for 4 h provoked a release of GNPs from the film into ethanol, acetic acid and oil-based food simulants. Short carbon nanotubes were observed rarely to release in the most aggressive acetic acid solvent. Obviously, the enhanced molecular mobility at temperatures above the glass transition and partial dissolution of PLA polymer by the food simulant facilitate the diffusion processes. Moreover, shape, size and concentration of nanoparticles play a significant role. Flexible naked GNPs (lateral size 100–1000 nm) easily migrate when the polymer molecules exhibit enhanced mobility, while fibrous MWCNTs (> 1 μm length) formed entangled networks on the film surfaces as the PLA polymer is partly dissolved, preventing their release into food simulants. The impurities of fullerenes and CB (5–30 nm) were of minor concentration in the polymer, therefore their migration is low or undetectable. The total amount of released migrants is below overall migration limits.     

Nanoclay migration from food packaging materials

A recent trend is to use nanocomposites materials for food-packaging applications. Different kinds of nanoparticles are incorporated into the polymers to improve their characteristics, and, among them, nanoclay is used to improve their barrier properties to gases. In this work, the results of migration studies with different food simulants (ethanol 10% and acetic acid 3%), temperatures and times (40ºC for 10 days and 70ºC for 2 h) from two commercialised LDPE nanocomposite bags are presented. The migration solutions thus obtained were analysed by ICP-MS to evaluate the amount of aluminium which migrated into the solutions both in dissolved form and as a part of nanoparticles. Aluminium migration was observed for both samples with a maximum migration value of 51.65 ng cm^–2 for the Aisaika bags and 24.14 ng cm^–2 for the Debbie Meyer bags. The presence of spikes working in single-particle mode using ICP-MS indicated that part of this aluminium was present as nanoparticles. The size and morphology of the nanoclay, in both the original material and the migration solutions, was studied by scanning electron microscopy coupled to energy-dispersive X-ray diffraction (SEM-EDX). In this manner, nanoparticles of different morphologies and sizes were found to migrate into the food simulants.     

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.     

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.     

Migration of Chemical Compounds from Packaging Polymers during Microwave,Conventional Heat Treatment,and Storage

Polymeric packaging protects food during storage and transportation, and withstands mechanical and thermal stresses from high‐temperature conventional retort or microwave‐assisted food processing treatments. Chemical compounds that are incorporated within polymeric packaging materials to improve functionality, may interact with food components during processing or storage and migrate into the food. Once these compounds reach a specified limit, food quality and safety may be jeopardized. Possible chemical migrants include plasticizers, antioxidants, thermal stabilizers, slip compounds, and monomers. Chemical migration from food packaging is affected by a number of parameters including the nature and complexity of food, the contact time and temperature of the system, the type of packaging contact layer, and the properties of the migrants. Researchers study the migration of food‐packaging compounds by exposing food or food‐simulating liquids to conventional and microwave heating and storage conditions, primarily through chromatographic or spectroscopic methods; from these data, they develop kinetic and risk assessment models. This review provides a comprehensive overview of the migration of chemical compounds into food or food simulants exposed to various heat treatments and storage conditions, as well as a discussion of regulatory issues.     

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)。     

塑料包装材料化学物迁移试验中食品模拟物的选用

人们对健康的广泛重视引发了国际社会对食品安全的普遍关注。塑料包装材料化学物向食品的迁移与食品安全息息相关,美国FDA、欧盟EC等就此进行了广泛而深入的理论与试验研究。本文综述了包装材料化学物迁移试验中应用的食品模拟物并对其选用作了分析。     

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).     

Properties of polyethylene films with incorporated benzoic anhydride and/or ethyl and propyl esters of 4-hydroxybenzoic acid and their suitability for food packaging

Benzoic anhydride and ethyl and propyl esters of 4-hydroxybenzoic acid (ETP and PRP, respectively, also termed parabens) incorporated into low density polyethylene (LDPE) film were studied with regard to migration into food and food simulants at 6°C and 25°C, and changes in selected properties of the film were investigated. Antimicrobials were incorporated into polymer film in concentrations of 5g/kg and 10g/kg. The addition of parabens into the polymer was more difficult than benzoic anhydride due to their volatility. For benzoic anhydride, 30-40% and 10-20% of the added amount was found to leach from the film into aqueous and olive oil food simulants, respectively. The migration into both water and olive oil followed a very similar course in the case of parabens. Migration levels over 90% and in the range of 70% to 80%, relative to the amount of agent in the film, were determined for ETP and PRP respectively. The incorporation of antimicrobials into the film significantly changed the functional characteristics of the packaging material, i.e. permeability of oxygen, carbon dioxide and water vapour, tensile strength, coefficient of friction, sealing strength and transparency. Shelf life tests with packaged cheese and toasted bread demonstrated the efficiency of the film containing 10g/kg of BA against mould growth on the food surface during storage at 6°C.     

Analysis of food packaging UV inks for chemicals with potential to migrate into food simulants

Ultraviolet (UV) inks are an alternative formulation system to the more usual paste or liquid inks (oils or solvents based) that dry mainly by evaporation or penetration into the printed substrate. Based on acrylic acid chemistry, UV inks dry (the exact term is 'curing') by the chemical process of photopolymerization. Their composition (acrylate monomers and oligomers together with photo-initiators) exposed to UV emission lamps on the printing press units enable the transformation of the freshly printed ink layer into a tack-free film. For UV inks intended for primary food packaging, special care has to be paid to potential migrating species like small photo-initiator molecules and acrylate monomers not cross-linked in the formed network. The paper presents chromatographic methods to ascertain the level of ink ingredients potentially available to migrate into food simulants (migration tests). GC/MS was employed to quantify the levels of photo-initiators or acrylic esters (acrylates).     

Migration of model contaminants from PET bottles: influence of temperature, food simulant and functional barrier

To simulate post-consumer recycled plastics, selected model contaminants were incorporated into PET bottles using a time saving method. Migration into 3% acetic acid, a cola-type beverage and 95% ethanol was followed during 1 year of storage at 20 and 40°C. Aroma compounds previously found in post-consumer PET material were used as model contaminants. Benzaldehyde was found to migrate to the highest extent. Storage at 40°C affected the bottle material and this might be one reason for the high migration values of these bottles. Migration into ethanol was up to 20 times higher than into 3% acetic acid or a cola-type beverage. Bottles with a functional barrier resisted migration into food simulants even when filled with 95% ethanol and stored for 1 year at 40°C. Differential scanning calorimetry measurements showed that ethanol was interacting with the plastic material. This resulted in a lower glass transition temperature of bottles stored with ethanol compared with bottles stored empty or with other food simulants.     

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.     

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.     

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.     

采用ICP-MS研究聚酯类食品包装材料中锑向食品模拟物的迁移规律

目的 建立聚酯(PET)和4种食品模拟物中锑的电感耦合等离子体质谱(ICP-MS)测定方法.用该方法研究PET中的锑向水、10％(V/V)乙醇溶液、3％(W/V)乙酸水溶液和精炼橄榄油4种食品模拟物迁移的行为与浸泡时间、温度、食品模拟物属性、锑初始含量等参数的关系.方法 在不同的温度下,将不同的PET浸泡于食品模拟物中,于一定的时间点吸取少量浸泡液,用ICP-MS测定其含量.结果 ICP-MS方法回收率在94.3％ ～96.1％之间,相对标准偏差在1.38％ ～3.31％之间.结论 锑迁出量随温度升高而增加;随着时间的延长,锑迁出量逐渐增加,一定时间后达到迁移平衡;大部分PET材料本底含量越高迁出量越高;PET中锑易于在酸性食品模拟物中迁出,应少食用PET包装的酸性食品.     

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。     

Assessment of the migration potential of nanosilver from nanoparticle-coated low-density polyethylene food packaging into food simulants

An experimental nanosilver-coated low-density polyethylene (LDPE) food packaging was incubated with food simulants using a conventional oven and tested for migration according to European Commission Regulation No. 10/2011. The commercial LDPE films were coated using a layer-by-layer (LbL) technique and three levels of silver (Ag) precursor concentration (0.5%, 2% and 5% silver nitrate (AgNO₃), respectively) were used to attach antimicrobial Ag. The experimental migration study conditions (time, temperature and food simulant) under conventional oven heating (10 days at 60°C, 2 h at 70°C, 2 h at 60°C or 10 days at 70°C) were chosen to simulate the worst-case storage period of over 6 months. In addition, migration was quantified under microwave heating. The total Ag migrant levels in the food simulants were quantified by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Mean migration levels obtained by ICP-AES for oven heating were in the range 0.01–1.75 mg l^?1. Migration observed for microwave heating was found to be significantly higher when compared with oven heating for similar temperatures (100°C) and identical exposure times (2 min). In each of the packaging materials and food simulants tested, the presence of nanoparticles (NPs) was confirmed by scanning electron microscopy (SEM). On inspection of the migration observed under conventional oven heating, an important finding was the significant reduction in migration resulting from the increased Ag precursor concentration used to attach Ag on the LDPE LbL-coated films. This observation merits further investigation into the LbL coating process used, as it suggests potential for process modifications to reduce migration. In turn, any reduction in NP migration below regulatory limits could greatly support the antimicrobial silver nanoparticle (AgNP)-LDPE LbL-coated films being used as a food packaging material.