氧化铜纳米颗粒(CuO nanoparticles,CuO-NPs)被认为是一种功能性助剂,添加到包装材料中,可以提高包装的阻隔性能、机械性能,并为包装材料提供广谱抑菌性。然而纳米氧化铜的过量迁移会对人体健康造成潜在危害。该研究采用电感耦合等离子体发射光谱仪研究了纳米氧化铜添加量、迁移时间、紫外照射对低密度聚乙烯/线性低密度聚乙烯-纳米氧化铜复合膜中铜向5 g/L柠檬酸溶液迁移的影响,并使用傅里叶变换红外光谱仪、差示扫描量热仪、紫外-可见光光谱仪、高分辨扫描电镜对纳米氧化铜的迁移机理进行研究。结果表明,在70 ℃,2~24 h的迁移实验中,迁移量均随迁移时间的延长而增大,4种复合膜中铜向5 g/L柠檬酸溶液的迁移量是5.92~33.83 μg/dm2;紫外照射引起了复合膜的光降解,使复合膜中的迁移量显著增加;柠檬酸可以通过薄膜表面的缺陷和孔洞渗入材料当中,溶解并促进 CuO-NPs的迁移。
CuO nanoparticles (CuO-NPs) is believed to be an efficient functional agent, which can be used in food packaging to enhance the barrier, mechanical and antibacterial property. However, an excessive dose of CuO-NPs could be harmful to human health. This paper focused on the effects of contents of CuO-NPs, temperature, immersion time, UV irradiation and circular usage have on its migration to 5 g/L citric acid by inductively coupled plasma-optical emission spectrometry (ICP-OES). The migration mechanism of CuO-NPs was studied via fourier transform infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), scanning electron microscopy (SEM). The results showed that the migration of copper in the four nanocomposite films were 5.92-33.83 μg/dm2 at 70 ℃ for 2-24 hours. The migration amount increased with the increase of migration time. Ultraviolet irradiation caused the photodegradation of the CuO nanocomposite films, which significantly increased the amount of migration in the CuO nanocomposite films. Citric acid could penetrate the material through defects and holes on the surface of the film, dissolving and facilitating the migration of CuO-NPs.
[1] ABRAHAM D, GEORGE K E, FRANCIS D J. Studies on LDPE/LLDPE blends[J]. Angew Makromol Chem, 1992,200(1):15-25.
[2] SOUZA V G L, RIBEIRO-SANTOS R, RODRIGUES P F, et al. Nanomaterial Migration from Composites into Food Matrices[M]. Hoboken: John Wiley & Sons, Inc.,2018:401-436.
[3] 王琦, 卢珊,胡长鹰. 纳米铜食品抗菌包装材料的研究进展[J]. 包装工程, 2019, 40(5): 64-71.
[4] GURIANOV Y, NAKONECHNY F, ALBO Y, et al. Antibacterial Composites of cuprous oxide nanoparticles and polyethylene[J]. International Journal of Molecular Sciences, 2019,20(2):439.
[5] SELVI J, MAHALAKSHMI S, PARTHASARATHY V, et al. Optical, thermal, mechanical properties, and non‐isothermal degradation kinetic studies on PVA/CuO nanocomposites[J]. Polymer Composites, 2019,40(9):3 737-3 748.
[6] HASHEMINYA S,MOKARRAM R R,GHANBARZADEH B, et al. Physicochemical, mechanical, optical, microstructural and antimicrobial properties of novel kefiran-carboxymethyl cellulose biocomposite films as influenced by copper oxide nanoparticles (CuO-NPs) [J]. Food Packaging and Shelf Life, 2018, 17: 196-204.
[7] DELGADO K, QUIJADA R, PALMA R, et al. Polypropylene with embedded copper metal or copper oxide nanoparticles as a novel plastic antimicrobial agent[J]. Lett Appl Microbiol, 2011,53(1):50-54.
[8] MOЁZZI F, HEDAYATI S A, GHADERMAZI A. Ecotoxicological impacts of exposure to copper oxide nanoparticles on the gill of the Swan mussel, Anodonta cygnea (Linnaeus, 1758)[J]. Molluscan Research, 2018,38(3):187-197.
[9] LIM J P, BAEG G H, SRINIVASAN D K, et al. Potential adverse effects of engineered nanomaterials commonly used in food on the miRNome[J]. Food and Chemical Toxicology, 2017,109:771-779.
[10] AMENTA V, ASCHBERGER K, ARENA M, et al. Regulatory aspects of nanotechnology in the agri/feed/food sector in EU and non-EU countries[J]. Regulatory Toxicology and Pharmacology, 2015,73(1):463-476.
[11] DUNCAN T V, PILLAI K. Release of engineered nanomaterials from polymer nanocomposites: diffusion, dissolution, and desorption[J]. ACS Appl Mater Interfaces, 2015,7(1):2-19.
[12] DUNCAN T V. Release of engineered nanomaterials from polymer nanocomposites: the effect of matrix degradation[J]. ACS Appl Mater Interfaces, 2015,7(1):20-39.
[13] KOCZKUR K M, MOURDIKOUDIS S, POLAVARAPU L, et al. Polyvinylpyrrolidone (PVP) in nanoparticle synthesis[J]. Dalton Trans, 2015,44(41):17 883-17 905.
[14] 石玉杰,胡长鹰,姜紫薇,等. 不同结构纳米铜/PP复合膜中铜向食品模拟物的迁移[J]. 食品与发酵工业, 2018. 44(01), 92-97.
[15] 卢珊,胡长鹰,张勤军,等. 纳米铜/LDPE复合膜中铜向奶制品的迁移研究[J/OL].食品科学:1-9[2020-04-07].http://kns.cnki.net/kcms/detail/11.2206.TS.20190709.1135.002.html.
[16] LIU F, HU C Y, ZHAO Q, et al. Migration of copper from nanocopper/LDPE composite films[J]. Food Addit Contam Part A Chem Anal Control Expo Risk Assess, 2016,33(11):1 741-1 749.
[17] NEVES C J M E. Characterization of fractionated LLDPE by DSC, FTIR, and SEC[J]. Journal of Applied Polymer Science, 1993,50:817-824.
[18] BLAINE R L. Thermal Applications Note.TN048 Polymer Heats of Fusion[S]. New Castle DE, TA Instruments, 2002.
[19] 姜紫薇,胡长鹰,石玉杰,等. 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[J]. 食品与发酵工业, 2019, 45(5): 68-74.
[20] GULMINE J V, JANISSEK P R, HEISE H M, et al. Polyethylene characterization by FTIR[J]. Polymer Testing, 2002,21(5):557-563.
[21] ROY S, RHIM J. Melanin-mediated synthesis of copper oxide nanoparticles and preparation of functional Agar/CuO NP Nanocomposite Films[J]. Journal of Nanomaterials, 2019,2019:1-10.
[22] ADDO N S, GOODWIN D G, SUNG L, et al. Long-term wear effects on nanosilver release from commercially available food contact materials[J]. Food Addit Contam Part A Chem Anal Control Expo Risk Assess, 2019,36(11):1 757-1 768.
[23] ZAN L, FA W J, WANG S L. Novel photodegradable low-density polyethylene-TiO2 nanocomposite film.[J]. Environmental science & technology,2006,40(5), 1 681-1 685.
[24] HAN C, ZHAO A, VARUGHESE E, et al. Evaluating weathering of food packaging polyethylene-nano-clay composites: Release of nanoparticles and their impacts[J]. NanoImpact, 2018,9:61-71.
[25] DE GEYTER N, MORENT R, LEYS C. Surface characterization of plasma-modified polyethylene by contact angle experiments and ATR-FTIR spectroscopy[J]. Surface and Interface Analysis, 2008,40(3-4):608-611.
[26] VELICHKOVA H, PETROVA I, KOTSILKOV S, et al. Influence of polymer swelling and dissolution into food simulants on the release of graphene nanoplates and carbon nanotubes from poly(lactic) acid and polypropylene composite films[J]. Journal of Applied Polymer Science, 2017,134(44):45 469.
