纳米铜/聚丙烯复合膜中铜向食品模拟物的迁移及其对膜性能的影响

当纳米包装材料与食品接触时,纳米成分可能会迁移到食品中,由于对纳米成分的毒性研究还不充分,可能引发食品安全问题。通过电感耦合等离子体发射光谱仪(inductively coupled plasma optical emission spectrometer, ICP-OES)探究了时间、温度、纳米铜含量、偶联剂、伽马射线辐照、循环使用及乙酸食品模拟物浓度对纳米铜/聚丙烯复合膜中铜向模拟物中迁移的影响,并对比复合膜迁移前后性能的变化。结果表明:复合膜中铜向模拟物中迁移的迁移率随时间和温度的增加而增大,直至平衡;循环使用的复合膜中铜在每次循环时的迁移能力与纳米铜含量有关;伽马射线辐照、乙酸食品模拟物的浓度增大使铜的迁移量显著增大;迁移后复合膜的机械性能较稳定,微观形貌和粗糙度随迁移行为有所变化。     

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。     

食品接触用不锈钢材料中铬元素迁移规律

为探究不同食品加工条件对食品接触用304、316不锈钢中铬(Cr)元素迁移规律的影响,通过全浸泡迁移实验结合电感耦合等离子体质谱检测法(inductively coupled plasma-mass spectrometry, ICP-MS)测得在不同温度、高温煮沸、高压蒸汽灭菌等生产条件下,不锈钢中Cr向体积分数为4%的乙酸食品模拟液中的迁移量随时间的变化情况,分析Cr迁移与生产条件关系。结果表明,不同生产条件下,不锈钢主要组成元素Cr迁移量随接触时间延长及加工温度的升高而增大。20、70℃温度条件下长时间迁移Cr元素平均迁移速率为40℃时的1/3与4倍;煮沸、高压蒸汽灭菌短时迁移时Cr平均迁移速率较40℃分别提高约为4和9倍。温度越高,不锈钢中Cr迁移量越大,尤其是煮沸、高压蒸汽灭菌等特殊工况对重金属向食品模拟物中的迁移具有明显的促进作用。对迁移数据进行拟合发现,Cr迁移行为符合Fick定律,其扩散系数与温度相依性可采用阿伦尼乌斯定律来表示。     

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。     

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。     

食品包装污染物双酚类物质在食品模拟体系中的迁移规律研究

采用4 种食品模拟物包括超纯水、30 g/L乙酸水溶液、10%乙醇水溶液和异辛烷对食品金属罐中4 种双酚物（包括双酚A、双酚F、双酚A二缩水甘油醚和双酚F二缩水甘油醚）迁移情况进行研究,并建立半经验的双酚物迁移规律数学模型。结果表明：4 种双酚物同时在10%乙醇溶液中出现最大迁移,且贮存温度和时间对迁移量变化有显著影响。根据模拟实验得到的迁移数据和Fick第二定律建立数学模型,初步确定扩散系数DP,再根据DP估计得到包材的特征参数AP的范围为35.38～48.48。     

不同结构纳米铜/PP复合膜中铜向食品模拟物的迁移

探究了温度、时间、食品模拟物、氧气,以及聚丙烯(polypropylene,PP)的3种结构(PP-B、PP-R和PPH)对纳米铜/PP复合膜中铜向食品模拟物迁移的影响。将含有纳米铜和经3-氨丙基三乙氧基硅烷((3-Aminopropyl)triethoxysilane,KH550)处理的纳米铜分别添加到PP-B、PP-R和PP-H母粒中制备成相应的纳米铜/PP复合膜。在20、40和70℃下,将复合膜浸泡在食品模拟物中进行迁移实验。铜向食品模拟物的迁移率随着时间和温度的增加而增大直至平衡。酸性食品模拟物中迁移平衡时,在20℃,纳米铜/PP-B复合膜中铜的迁移率最大,PP-R和PP-H中铜的迁移率无显著性差异;40℃时,纳米铜/PP-H中铜的迁移率最大,PP-B和PP-R中铜的迁移率无显著性差异;而在70℃时,仍然是PP-H中铜的迁移率最大,PP-R次之,PP-B中铜的迁移率最小。     

家用料理机Cr和Mn迁移规律及风险估计研究

目的研究市售家用料理机中重金属Cr和Mn迁移规律并对其进行风险评估。方法以市售家用料理机为研究对象,对不同材质料理机在不同的食品模拟物体系中(去离子水,4%乙酸溶液,10%乙醇溶液,50%乙醇溶液)重金属Cr和Mn向食品体系的迁移过程进行动力学分析与扩散模型分析,将Cr和Mn迁出浓度与我国现有标准中重金属限量值进行比较。结果在Cr和Mn迁出风险较高的4%乙酸溶液中,其迁移行为符合一级动力学过程,短期接触时部分迁移符合Fick扩散过程,长期接触时均符合Fick扩散过程。当迁移达到平衡时,4种模拟液中Cr和Mn元素的迁出浓度均低于生活饮用水中限量值。结论 Fick第二定律能较好地应用于料理机中Cr和Mn的迁移研究,在日常使用条件下料理机中Cr和Mn的迁移危害风险较低。     

食品接触用塑料包装中纳米材料迁移的研究进展

纳米材料的特殊效应使其在食品包装领域得到了快速的发展。然而纳米材料是否会迁移到食品中,对人类健康产生影响,这一问题尚未解决,因此纳米材料的安全性仍需要进一步证实,对纳米材料进行迁移研究是对其进行风险评估的重要环节。综述了近年来纳米复合材料在食品接触用塑料包装中的应用,以及纳米复合材料中纳米成分的检测和表征,详细分析了国内外学者对于纳米材料向食品或食品模拟物迁移的研究进展。但是由于缺乏有效的食品包装材料中纳米粒子的鉴定和分离方法、迁移试验方法不完善,加上纳米材料稳定性的原因和分析表征技术的限制,目前为止,人们对于纳米材料能否迁移到食品或食品模拟物中仍未达成统一意见。     

纳米氧化锌/低密度聚乙烯膜中锌向食品的迁移研究

目的研究纳米氧化锌/低密度聚乙烯膜(low density polyethylene film,LDPE)中锌(Zn)向食品的迁移行为,探究其迁移规律。方法选取2种食品模拟物(3%乙酸及超纯水)及真实食品(食用白醋及瓶装水),在3种不同实验温度下(70、40及20℃),研究锌向食品模拟物的迁移规律。采用扫描电子显微镜(scanning electron microscope,SEM)和原子力显微镜(atomic force microscope,AFM)表征纳米ZnO/LDPE膜的表面形貌。结果锌向酸性模拟物中的迁移率远远大于水性模拟物中的迁移率,其中锌向酸性模拟物中的最大迁移率分别为22.7%,20.3%及18.6%(ZL-1,ZL-2及ZL-2#),向水性模拟物中的最大迁移率分别为9.9%,5.7%及4.9%(ZL-1,ZL-2及ZL-2#);锌向酸性食品的迁移量(1.59~5.03 mg/g)同样高于向水性食品的迁移量(2.98~24.60μg/g);随着纳米ZnO的初始含量变大迁移率变小;而偶联剂的加入对锌的迁移有一定的抑制作用。随着纳米ZnO浓度的增加,在薄膜中观察到纳米ZnO的不规则形貌。结论纳米ZnO/LDPE膜不适合在高温下包装食物,且其在酸性食品中的安全隐患高于水性食品。     

Determination of the mass transport properties of chemical additives in polypropylene material/simulated food system

The mass transport process (migration) of five additives from three different types of polypropylene (PP) films into selected food simulants was studied. The migration tests were carried out at different time-temperature conditions, and the concentration of additives in polymer matrix and food simulants were analysed by high-performance liquid chromatography (HPLC). With all data, the mass transport properties for migration kinetics (partition and diffusion coefficients) were determined. Results showed that the partition coefficient was affected significantly by the temperature and simulants’ properties, whereas little affected by the types of PP film and molecular weight of substance. The polarity, structure and shape of substances can also have an influence in their partition between the polymer matrix and food simulants. Additionally, comparison results between the experimental diffusion coefficients and the calculated values by Piringer model suggested that the current migration model with the default modelling parameters for PP does not describe realistically the diffusion coefficients of additives. The calculated diffusion coefficients were greater than the experimental values, as a consequence, the migration of chemical additives will be overestimated. For more realistic migration calculations, more accurate modelling parameters in Piringer model should be established and the effect of food on migration should be high interest in future work.     

食品包装纸中紫外吸收剂向固态模拟物的迁移行为

研究4种紫外吸收剂,即2-(2’-羟基-3’,5’-二叔丁基苯基)-5-氯代苯并三唑(UV-327)、2-(2-羟基-5-甲基苯基)苯并三氮唑(UV-P)、2-羟基-4-甲氧基二苯甲酮(UV-9)和2-羟基-4-正辛氧基二苯甲酮(UV-531)在50、75℃和100℃3个温度条件下从食品包装牛皮纸迁移到固态食品模拟物Tenax~?中的迁移规律和影响因素。结果表明:随着温度的升高,紫外吸收剂的迁移速度加快,迁移量增加。此外,不同紫外吸收剂本身的物理化学性质(相对分子质量、油水分配系数等)也对其迁移规律和平衡迁移率产生了重要影响。在上述实验的基础上建立数学模型,以达到预测迁移量的目的。数据证明,所构建的模型可很好地预测在达到迁移平衡前,紫外吸收剂从牛皮纸迁移到Tenax~?中的迁移量。     

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.     

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.     

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.     

Prediction of worst case migration: presentation of a rigorous methodology

An improvement of the Piringer model, allowing the prediction of a worst case migration from packaging to food is presented here. The authors are proposing other constants for the calculation of the upperbound value of the diffusion coefficient, using experimental data determined by a film to film method. Considering the plasticizing effects of food simulants, a model involving the variation of the diffusion coefficient versus space and time must be used. Future fields of investigation are discussed: the relationship between diffusion coefficients and the volume of the migrant (instead of molar mass), and the variation of diffusion coefficient activation energy with temperature.     

Migration of photoinitiators from paper to fatty food simulants: experimental studies and model application

The migration of five different photoinitiators from kraft paper to two fatty food simulants, Tenax^® and 95% ethanol, was investigated under different conditions. The effects of temperature and storage time, as well as the physicochemical properties of the photoinitiators on migration, were discussed. Mathematical models based on Fick’s second law generated from two cases, single- and two-side contacts, were applied to predict the migration behaviour from the paper to the food simulants. The partition coefficients estimated from the model decreased with temperature. The diffusion coefficients of the selected photoinitiators from the paper ranged from 1.55 × 10^–10 to 7.54 × 10^–9 cm² s^?1 for Tenax and from 2.79 × 10^–9 to 8.03 × 10^–8 cm² s^?1 for 95% ethanol. The results indicate that the applied model can predict the migration of photoinitiators in the initial short period before equilibrium, and the migration from paper to Tenax through a single-side contact demonstrated an especially high concordance.     

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.