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.     

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 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).     

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.     

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.     

Exposure to copper nanoparticles causes gill injury and acute lethality in zebrafish (Danio rerio)

Increasing use of metallic nanomaterials is likely to result in release of these particles into aqueous environments; however, it is unclear if these materials present a hazard to aquatic organisms. Because some dissolution of metal particles will occur, it is important to distinguish effects of nanoparticulates from dissolved metals. To address this issue, acute toxicity of soluble copper and 80 nm copper nanoparticle suspensions were examined in zebrafish. The results demonstrate that nanocopper is acutely toxic to zebrafish, with a 48 h LC50 concentration of 1.5 mg/L. Rapid aggregation of copper nanoparticles occurred after suspension in water, resulting in 50-60% of added mass leaving the water column. While dissolution of particulate copper occurred, it was insufficient to explain the mortality in nanocopper exposures. Histological and biochemical analysis revealed that the gill was the primary target organ for nanocopper. To further investigate the effects of nanocopper on the gill, zebrafish were exposed to 100 microg/L of nanocopper or to the concentration of soluble copper matching that present due to dissolution of the particles. Under these conditions, nanocopper produced different morphological effects and global gene expression patterns in the gill than soluble copper, clearly demonstrating that the effects of nanocopper on gill are not mediated solely by dissolution.     

纳豆菌对液态糙米醋品质的影响

以糙米为主要原料,以阿魏酸和总酸含量为评价指标,采用单因素试验和正交试验优化液态发酵糙米醋醋酸发酵条件。结果表明,最佳工艺条件为纳豆菌接种量2.0%、初始乙酸含量1.0%、初始酒精度7.0%vol、发酵温度32 ℃。采用优化的液态发酵工艺酿造的糙米醋呈暗黄色、澄清、酸味柔和,总酸含量达7.26 g/100 mL、阿魏酸含量为6.57 mg/L。纳豆菌与醋酸菌混合发酵,提高了糙米醋整体品质,新增了功效成分阿魏酸,提升了糙米醋的功能性。     

葡萄糯米香醋发酵工艺的优化

该研究以葡萄和糯米为原料制备葡萄糯米香醋,以酒精度和感官评分为评价指标,采用正交试验设计优化其酒精发酵工艺条件;以总酸含量和感官评分为评价指标,优化其醋酸发酵工艺条件,并对该产品的挥发性成分、理化指标及感官品质进行分析。结果表明,最佳酒精发酵工艺条件为：葡萄与糯米质量比2∶1、初始糖度23%、葡萄酒高活性干酵母添加量0.22%、发酵温度28℃;最佳醋酸发酵工艺条件为：初始酒精度7%vol、醋酸菌（Acetobacter aceti）接种量5%、发酵温度30℃。在此优化条件下,葡萄糯米香醋共检出31种挥发性成分,其中醇类7种、醛类3种、酸类7种、酯类13种、苯类1种,总酸、总酯含量分别为4.70 g/100 m L、3.18 g/100 m L,葡萄糯米香醋呈红褐色、澄清透亮,口感醇厚、酸甜柔和,具有浓郁的果香和醋香。     

葡萄桑葚复合果醋工艺优化和不同发酵时期的风味成分检测

采用葡萄和桑葚为原料,探讨葡萄桑葚经酒精发酵和醋酸发酵酿制复合果醋的最优发酵工艺。以乙醇浓度,发酵温度,pH及醋酸菌接种量进行单因素实验,以产酸量为响应值,通过响应面试验优化葡萄桑葚复合果醋发酵工艺。结果表明:葡萄桑葚复合果醋发酵最优工艺条件为初始乙醇浓度7.4%,pH5.0,接种量9.8%,温度32 ℃,在此条件下,果醋产酸量最大为5.38 g/100 mL。同时运用电子鼻技术对葡萄桑葚复合果醋不同发酵时期即果醋未进行酒精发酵前的果汁时期、醋酸发酵时期和发酵完成时期进行检测,结合主成分分析（PDA）,负荷加载分析（Loading）及线性判别分析（LDA）,确定葡萄桑葚复合果醋的主要风味成分为氮氧化物、硫化物等,且不同发酵时期的气味差异显著（P<0.05）,不同发酵时期的气味浓度大小顺序为:成品果醋>发酵中期>果汁,说明电子鼻能准确区分不同发酵时期葡萄桑葚复合果醋产品。     

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.     

Postharvest Quality of Fresh-Cut Carrots Packaged in Plastic Films Containing Silver Nanoparticles

Active food packaging containing antimicrobial additive goes beyond traditional functions of packaging, once it can extend food shelf life maintaining its quality, safety and reducing postharvest losses by controlling food spoilage. Among several antimicrobial additives employed in polymeric films for packaging, metallic nanoparticles outstand due to its facility for synthesis, low-cost of production, and intense antimicrobial properties. In this work, extruded plain films of low-density polyethylene (LDPE) containing silver nanoparticles (AgNPs) embedded in SiO₂ and TiO₂ carriers (namely MS and MT, respectively) were produced and used as active packaging for maintaining the physicochemical and microbiological quality of carrots (Daucus Carota L. cv. Brasília). The neat (LDPE) and composite films containing MS and MT were characterized by scanning electron microscopy and permeability to oxygen and used for packaging fresh-cut sliced carrots stored at 10 °C for 10 days. After the storage time, the physicochemical properties of carrots were characterized, while the antimicrobial properties of films and AgNP migration were investigated. Our results revealed that both MT and MS packages showed antimicrobial activity even for films containing low concentration of AgNP. In addition, AgNP antimicrobial activity demonstrated to be carrier-dependent, once MT-LDPE showed improved performance compared to MS-LDPE. Regarding the physicochemical properties of packaged carrot, lower soluble solids and weight loss and higher levels of ascorbic acid were observed for carrots packaged with MT-LDPE films (compared to MS-LDPE), leading to a better postharvest quality conservation. Such differences observed in physicochemical properties of carrots are related to the distinct antimicrobial and film permeability properties for each composite film. In addition, under the conditions employed in this study, AgNP migration from the packages to fresh-cut carrot was not observed, which is highly desirable for food packaging safety, indicating the potential of such active packages for food preservation application.     

Effect of antioxidants and light stabilisers on silver migration from nanosilver-polyethylene composite packaging films into food simulants

The effect of exposure time, temperature and food simulants, especially additives, on the release of silver from nanosilver-polyethylene composite films to food simulants was studied. Two different type of nanosilver-polyethylene composite films (with or without additives) were chosen to conduct the experiment with the aim of exploring the behaviour of silver migration. It was shown that the migration of silver into 50% ethanol at 40 and 70°C was much less than that into 3% acetic acid. With the increase of exposure time and temperature, the release of silver increased. The migration even continued after a long exposure time (14 days at 20°C, 10 days at 40°C, and 6 days at 70°C respectively). Only about 0.15‰ of silver migrated from composite films with the additives into 3% acetic acid after 6 days of exposure at 70°C, while about 1.3% of silver migrated from composite films that did not contain additives under the same conditions. This could be because the addition of the antioxidants and light stabilisers prevents silver from being oxidised, which is an important way for the release of silver.     

A Note — Production of Vinegar from Whey

Cheese whey supplemented with lactose was employed to produce vinegar. Whey was first transformed into an alcoholic beverage via fermentation with the yeast Kluyveromyces fragilis, and then the alcoholic product was employed as a substrate for an acetic acid fermentation. The bacteria used for the acetic acid production process were isolated from a starter culture provided by a vinegar factory. The bacteria employed were classified as Acetobacter pasteurianus. The vinegar obtained had a concentration of acetic acid between 5 and 6% (v/v). Ethyl acetate and fusel alcohols (isobutanol, 2‐methyl‐1‐butanol and 3‐methyl‐1‐butanol) were detected in the final product. The process and the substrates employed satisfied FAO requirements that the product was acceptable for human consumption. The efficiency of bio‐transformation of ethanol into acetic acid was 84%.     

Directional isolation of ethanol-tolerant acetic acid bacteria from industrial fermented vinegar

The aim of this study was to isolate indigenous ethanol-tolerant acetic acid bacteria (AAB) from industrial fermented vinegar. As routine phenotypic methods for AAB isolation and identification appear to be very time-consuming and not so accurate, we adopted a two-step isolation strategy in the present study. In the preliminary screening step, GYEC agar plates with 3–10 % (v/v) ethanol as selective stress were utilized to recover potential AAB strains with ethanol tolerance from vinegar samples. In the rescreening process, acetic acid bacterial genus’ specific adhA gene was amplified as an effective DNA target for directional detection of real AAB so that non-AAB isolates could be eliminated rapidly. In this way, an AAB pure isolate named ET-7-3 with 7 % (v/v) ethanol tolerance was successfully isolated and further identified to Acetobacter pasteurianus according to 16S rDNA sequencing and phylogenetic analysis. Summarizing, by the use of ethanol as selective stress combined with molecular identification method, ethanol-tolerant AAB could be isolated from industrial fermented vinegar with both efficiency and accuracy.     

响应面法优化玫瑰醋糟酶解工艺

针对玫瑰醋糟组织致密,高酸性的特点,从水解度的角度出发,通过采用响应面方法对玫瑰醋糟中的大米蛋白提取过程中的温度、酶用量、pH等工艺条件进行了优化.采用Plackett-Burman(PB)设计法,对不同的酶用量、固液比、温度、时间、pH值5个因素对大米蛋白水解度的影响进行评价.结果表明:温度、酶用量、pH值为米糟蛋白提取过程中的主要影响因素,用中心组合设计及响应面分析法确定主要因素的最优条件,为温度56.8℃、酶用量1.1％、pH7.9,得到大米蛋白提取液的水解度为10.04％.     

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.     

Migration study of caprolactam from polyamide 6 sheets into food simulants

Caprolactam, used in manufacturing polyamide (PA) 6, may threaten human health. Here, PA 6 sheets were produced by using a twin-screw extruder to evaluate its safety. Caprolactam migration concentrations from the PA 6 sheets into food simulants were evaluated according to the standard migration test conditions under the Korean Food Standards Codex (KFSC). Concentrations were investigated under various food simulants (distilled water, 4% acetic acid, 20 and 50% ethanol, and heptane) and storage conditions (at 25, 60, and 95 °C). Caprolactam migration concentrations into food simulants were determined as follows: 4% acetic acid (0.982 mg/L), distilled water (0.851 mg/L), 50% ethanol (0.624 mg/L), 20% ethanol (0.328 mg/L), and n-heptane (not detected). Migrations were determined to be under the regulatory concentration (15 mg/L) according to the KFSC test conditions. Taken together, these results verified that the standard migration test conditions by KFSC were reliable to evaluate the safety of PA 6.     

雪莲果西番莲复合果醋发酵工艺的研究

以雪莲果和西番莲为原料,选用葡萄酒用活性干酵母、醋酸杆菌作为发酵菌种进行液体发酵酿造雪莲果西番莲复合果醋,对酒精发酵、醋酸发酵及果醋澄清等工艺进行研究,确定最佳加工工艺参数。结果表明:酒精发酵的最佳条件为:初始糖度14%,酵母菌接种量0.012%,发酵温度28℃;醋酸发酵的最佳条件为:发酵温度34℃、酒精度8%vol、发酵时间4d、接种量4%;硅藻土用量为0.06%,澄清效果较佳,透光率可达90.5%。酿制出来的雪莲果西番莲复合果醋澄清透亮,醋味浓郁,同时具有雪莲果和西番莲的特殊清香味。     

Survival of planktonic and sessile Acetobacter cerevisiae

This study was designed to investigate the individual or combined effects of ethanol (4–12%), glucose (10–30%) and acetic acid (0–6%) on survival of planktonic and sessile cells of one strain belonging to the new species Acetobacter cerevisiae isolated from traditional balsamic vinegar. The results confirm that the planktonic cells’ survival was negatively affected by ethanol and by acetic acid; moreover, there was a positive correlation between survival and glucose concentration. On the contrary, biofilm formation was observed only in the absence of acetic acid, which was the most affecting variable on the natural ability of cells to attach and grow on surfaces. The obtained results supply new information about the physiology of a novel Acetobacter species and about its natural capability to develop biofilms so that improved control over balsamic vinegar fermentation could be implemented in the future.     

Copper-based nanoparticles for biopolymer-based functional films in food packaging applications

This review summarizes the latest developments in the design, fabrication, and application of various Cu-based nanofillers to prepare biopolymer-based functional packaging films, focusing on the effects of inorganic nanoparticles on the optical, mechanical, gas barrier properties, moisture sensitivity, and functional properties of the films. In addition, the potential application of Cu-based nanoparticle-added biopolymer films for fresh food preservation and the effect of nanoparticle migration on food safety were discussed. The incorporation of Cu-based nanoparticles improved the film properties with enhanced functional performance. Cu-based nanoparticles such as copper oxide, copper sulfide, copper ions, and copper alloys affect biopolymer-based films differently. The properties of composite films containing Cu-based nanoparticles depend on the concentration of the filler, the state of dispersion, and the interaction of the nanoparticles with the biopolymer matrix in the film. The composite film filled with Cu-based nanoparticles effectively extended the shelf life by maintaining the quality of various fresh foods and securing safety. However, studies on the migration characteristics and safety of copper-based nanoparticle food packaging films are currently being conducted on plastic-based films such as polyethylene, and research on bio-based films is limited.