聚乙烯醇薄膜中茶多酚向水中释放的不同动力学模型比较分析

研究聚乙烯醇薄膜中茶多酚向水中释放的不同动力学模型表征。通过释放实验研究了薄膜中茶多酚向水中的释放规律,基于4?种动力学模型对实验数据进行拟合表征,比较分析了不同模型的拟合效果。结果表明：茶多酚释放率随薄膜中茶多酚质量浓度的增加而降低。对比不同模型的拟合效果,Fickian模型和Fickian＋一级动力学模型可以很好地模拟茶多酚的释放（R2≥97.27）,后者更优;Weibull模型的拟合效果较前两个模型差（R2≥85.21）,但是该模型可以很好地模拟从释放开始到平衡初期茶多酚的释放（R2≥92.20）;短期释放模型的拟合效果较好（R2≥91.32）,但其扩散系数与由Fickian模型和Fickian＋一级动力学模型得到的扩散系数相差较大。总的来看,Fickian＋一级动力学模型模拟效果最好,Fickian模型次之,Weibull模型模拟从释放开始到平衡初期过程的效果较好,短期释放模型不适合用于模拟评估聚乙烯醇薄膜中茶多酚整个释放过程中的释放性能。     

纳米二氧化钛对聚乙烯醇吸湿特性及抗菌性能的影响

将纳米二氧化钛掺入聚乙烯醇中,通过溶液流延法制备含有不同质量分数纳米二氧化钛(0.0%,0.5%,1.0%,3.0%,5.0%,7.0%)的聚乙烯醇活性薄膜。研究了经纳米二氧化钛改性后聚乙烯醇薄膜的吸湿特性和抗菌性能。通过等温吸湿特性试验研究薄膜的吸湿特性,并基于GAB等温吸湿模型对试验数据进行拟合表征;分别通过对金黄色葡萄球菌和大肠杆菌的生长抑制试验分析薄膜的抗菌性能。研究结果表明:纳米二氧化钛能赋予聚乙烯醇薄膜优秀的疏水性能,随着薄膜中纳米二氧化钛含量的增加,薄膜的吸湿特性逐渐降低,且当环境相对湿度为11%,33%,57%,75%,84%时,含有7%纳米二氧化钛的聚乙烯醇薄膜相对于纯聚乙烯醇薄膜的平衡含水率分别显著降低了1.53%,3.97%,4.10%,7.20%,10.70%(P0.05);含有不同质量分数纳米二氧化钛的聚乙烯醇活性薄膜的吸湿特性能够用GAB等温吸湿模型进行拟合,且模型的拟合度R~2均达到0.99以上。通过GAB等温吸湿模型拟合的6种聚乙烯醇活性薄膜吸湿曲线整体变化趋势相似,属于Ⅱ型等温吸湿曲线;经纳米二氧化钛改性后的聚乙烯醇薄膜具备了抗菌性能,金黄色葡萄球菌和大肠杆菌菌落的OD_(595)增长趋势随着薄膜中纳米二氧化钛质量分数的增大而减小。经纳米二氧化钛改性的聚乙烯醇薄膜具有良好的疏水性和抗菌性能,预示着其在食品包装贮藏过程中会起到有益的效果。     

多糖基膜内抑菌剂向食品模拟体系中释放的规律

本文研究多糖基抑菌膜(低甲氧基果胶-羧甲基纤维素-山梨酸钾(LMP-CMC-Psb,LCP))内抑菌剂Psb在4℃下的释放动力学。分别探讨了基膜比例LMP:CMC(8:2、6:4、4:6)、Ca Cl2(1%、2%、4%、8%)、蒙脱土(MMT,1%、4%、8%、12%)及Psb(2%、5%、8%、15%)含量变化对Psb向食品模拟液(50%乙醇)中释放的影响;并使用Fickian第二定律方程和简化模型与Psb释放试验数据进行非线性最小二乘法拟合,计算得出扩散系数,进而评估Psb的扩散能力。结果表明:通过调整膜基质LMP和CMC的比例、改变Ca Cl2、MMT在基膜内的浓度可有效地控制Psb的释放速率;提高LMP比例、Ca Cl2和MMT含量均可降低Psb的扩散系数。通过Fickian第二定律拟合结果证实了Fickian模型与Psb的释放有很好的拟合度(R20.98%),说明该拟合具有一定可靠性,可以用来模拟Psb的释放。本文亦发现可通过使用简化模型对Psb的短期释放进行拟合而得的扩散系数评估Psb在抑菌膜内的释放规律,以缩短试验时间。该抑菌材料有望作为可控释放包装体系用于包装食品。     

聚乙烯醇活性薄膜对大黄鱼保鲜效果及品质动态监控

为研究智能聚乙烯醇活性薄膜对大黄鱼贮藏品质的影响和由于大黄鱼鱼肉p H改变而引起的薄膜动态色差变化,先以溶液流延法制备含有1%纳米二氧化钛和3%花青素的聚乙烯醇活性薄膜,使用其包装大黄鱼贮藏于4℃,再以感官品质、脂质过氧化值、菌落总数、挥发性盐基氮和pH并结合贮藏过程中薄膜色差变化,作为评定大黄鱼在包装贮藏过程中的鲜度指标。结果表明:在4℃贮藏期间,聚乙烯醇/纳米二氧化钛/花青素薄膜包装处理组的感官品质、脂质过氧化值、菌落总数、挥发性盐基氮和pH均优于空白和使用纯聚乙烯醇薄膜包装处理组,且在贮藏第16 d的菌落总数达到7.11lg cfu/g,其他实验组在贮藏第12 d达到7.14lg和7.03lg cfu/g,其货架期延长了4 d。在20 d贮藏期间过程中,聚乙烯醇/纳米二氧化钛/花青素薄膜表现出灰棕色(0 d)、红棕色(4 d)、淡红棕色(8 d)、肉色(12 d)、灰色(16 d)和深灰色(20 d),通过可见的颜色变化依次响应贮藏过程中大黄鱼鱼肉pH的改变。因此,本研究所制备的智能聚乙烯醇活性薄膜不仅有益于食品的贮藏保鲜,还能够作为颜色指示器在食品贮藏过程中起到动态监控的作用。     

不同品种紫薯抗氧化物质及体外抗氧化活性比较

为比较福建产区主栽紫薯抗氧化物质成分含量及其体外抗氧化活性,对7个不同品种紫薯中总酚、总黄酮、总花色苷及花青素组分进行了分析,并测定其清除自由基活性。结果表明:福宁紫3号紫薯中所含抗氧化活性成分如总酚、总黄酮、总花色苷和花青素的含量均为最高。通过高效液相色谱法分析测定紫薯中含有的花青素单体主要为飞燕草色素、芍药色素和矢车菊色素,不同品种紫薯中花青素组成及含量表现出的一定的差异性。福宁紫3号紫薯表现出较强的自由基清除活性,0.5 mg·L-1紫薯鲜样提取液DPPH自由基、OH自由基及ABTS清除率分别达到88.4%、49.1%、90.1%。 相对于其他品种,福宁紫3号紫薯在抗氧化活性成分含量及体外抗氧化活性方面表现最佳。     

紫薯花色苷分离纯化及主要成分的研究

以紫薯花色苷为研究对象,研究了5种大孔树脂和洗脱条件对紫薯花色苷的纯化的影响,并且利用液相色谱与质谱联用技术分离鉴定了紫薯花色苷的主要成分。结果表明,采用AB-8型大孔树脂纯化,原料液p H值为3,洗脱剂乙醇体积分数为60%时,能较好实现花色苷纯化;根据质谱分子离子峰和碎片峰等以及光谱信息鉴定为矢车菊素葡萄糖苷、原花青素、芍药素3-槐糖苷-5-葡萄苷、矢车菊素-3-(6'-咖啡酰槐糖苷)-5-葡糖苷、鞣花单宁、芍药素3-(阿魏酰-羟基苯甲酰槐糖苷)-5-葡萄苷等物质。     

聚乳酸改性树脂活性包装薄膜中活性成分的释放及在三文鱼冷藏保鲜中的应用

目的研究聚乳酸(polylactic acid,PLA)改性树脂活性包装薄膜的抗菌特性,膜中活性成分在模拟液中的释放,及其在三文鱼的冷藏保鲜中的应用。方法以PLA、丁二酸丁二醇酯-己二酸丁二醇酯共聚物(butanediol succinate-butylene adipate,PBSA)为基材,4%香芹酚+4%百里香酚为活性成分,通过双螺杆挤出机共混造粒、流延机制备薄膜,考察薄膜中活性成分的模拟释放过程及在4±1℃冷藏条件下对三文鱼包装保鲜的效果。结果香芹酚和百里香酚的添加提升了改性PLA薄膜的抗菌性能;薄膜中香芹酚和百里香酚在95%乙醇模拟液中的释放量最大,并且两者在不同模拟液中的扩散系数基本和模拟液中的实际释放情况相吻合;其应用于新鲜三文鱼冷藏保鲜时,改性PLA活性包装薄膜包装三文鱼的菌落总数(total viable counts,TVC)、挥发性盐基总氮值(total volatile basic nitrogen,TVBN)均显著低于空白组(P0.05)。结论在(4±1)℃冷藏条件下,PLA/PBSA活性包装薄膜可有效延缓三文鱼的腐败变质,保鲜效果更明显,可延长三文鱼货架期3~4 d。     

乳清蛋白抗菌薄膜中山梨酸钾的扩散性研究

将山梨酸钾添加至乳清分离蛋白成膜液中制成抗菌包装薄膜,通过扩散实验并结合菲克扩散理论,研究了在不同浓度、温度、p H条件下抗菌蛋白薄膜中山梨酸钾的扩散行为。根据幂律模型的扩散指数,发现p H3.8时山梨酸钾的初期释放动力学属于非菲克扩散,而在其他条件下基本符合菲克第一扩散定律。扩散系数研究表明:抗菌膜中山梨酸钾浓度增加,温度升高,p H降低,扩散系数呈非线性增大;模拟液p H3.8时,由于薄膜溶胀性较大,山梨酸钾的扩散系数在35℃条件下高达5.722×10-12m2/s;通过阿伦尼乌斯公式中活化能比较,发现山梨酸钾的扩散系数在p H为3.8的模拟液中最易受温度影响。     

桑椹花青素在小鼠消化道中的动力学变化研究

研究了经口摄入桑椹花青素后,桑椹花青素在消化道中的动力学变化.给小鼠灌胃不同剂量的桑椹花青素混合物,采用比色法检测不同时间消化道中残留的花青素总量.并用HPLC法比较灌胃前样品和小鼠粪便中回收的花青素样品中花青素含量的变化.当灌胃剂量低于12.5mg/鼠时,小鼠粪便中残留的花青素保持较低的水平;当灌胃剂量高于12.5mg/鼠时,小鼠粪便中花青素残留量与荆量呈直线相关.前4h,消化道中花青素残留量呈递减趋势,4 h后花青素残留量变化很小.桑椹花青素经过小鼠消化道后,矢车菊素-3-葡萄糖苷和矢车菊素-3-芸香糖苷的比例发生了倒置,说明矢车菊素-3-葡萄糖苷的吸收率远高于矢车菊素-3-芸香糖苷的.     

紫薯花青素超声波辅助酶法提取工艺优化及其抗氧化性研究

采用单因素试验和响应面试验研究超声波辅助酶法提取紫薯花青素,确定最佳工艺条件为:以95%乙醇—0.1%HCl(体积比4:6)为提取剂,液料比36:1(mL/g),60℃下超声提取35min,纤维素酶添加量2.50 mg/g·紫薯粉。在该条件下紫薯花青素得率达到2.003 mg/g。紫薯花青素还原力和对·OH清除率随浓度增大而增强。在30.00 mg/L时,紫薯花青素对·OH清除率达到80.2%。研究初步揭示了紫薯花青素具有很高的体外抗氧化活性,可以作为天然抗氧化剂进行开发。     

Temperature and pH affect copper release kinetics from copper metal foil and commercial copperware to food simulants

ABSTRACT

Copper (Cu) metal and alloys are used in cookware and other food contact surfaces due to their desirable properties for various applications. However, Cu metal can ionise and subsequently transfer to food and beverages under certain conditions. Here, we tested how pH and temperature affected Cu release kinetics using model systems utilising Cu metal foil and commercially available copperware. Cu foil and copperware were exposed to food simulants composed of 3% (w:w) aqueous solutions of citric acid, malic acid, acetic acid, or deionised (DI) water at temperatures ranging from 4°C to 60°C. An additional pilot experiment tested how simulated long-term cleaning affected subsequent Cu release from lined and unlined copperware to 3% citric acid. Food simulants were then analysed by ICP-MS for total Cu. After 180 min, incubation of Cu metal foil with acid-containing food simulants at 4°C resulted in Cu release ranging from 8.7 - 14.0 µg cm^?2, while 21.5–38.1 µg cm^?2 was released at 60°C. In contrast, Cu transfer from metal foil to DI water was relatively low, with <0.6 µg cm^?2 released after 180 min at 60°C. With citric acid food simulant, lined copperware released between 0.6 and 3.0 µg Cu cm^?2 over 180 min at the set temperatures, while unlined copperware released approximately 25–45 fold higher amounts of Cu (26.9–74.6 µg cm^?2) over this same time period. In contrast, use of DI water food simulant resulted in Cu release of <0.1 µg cm^?2 for the lined copperware and <2 µg cm^?2 for the unlined type. No significant effect of simulated long-term cleaning on Cu release from copperware was observed. These data indicate that Cu release is affected by temperature and pH, and that specific steps can be taken to limit Cu metal release from food contact surfaces to foods and beverages.     

Migration of silver from commercial plastic food containers and implications for consumer exposure assessment

Food storage containers with embedded silver as an antibacterial agent promise longer durability of food. For risk assessment the release of this silver into the stored food and resulting human exposure need to be known. For the purpose of exposure assessment, silver migration from commercial plastic containers with declared content of ‘nano-’ or ‘micro-silver’ into different food simulants (water, 10% ethanol, 3% acetic acid, olive oil) was quantitatively determined by ICP-MS and the form of the released silver was investigated. The highest migration of silver was observed for the acidic food simulant with 30 ng silver cm^?2 contact surface within 10 days at 20°C. In a second and third use cycle, migration dropped by a factor of up to 10, so that the maximum cumulated release over three use cycles was 34 ng cm^?2. The silver release over time was described using a power function and a numerical model that simulates Fickian diffusion through the plastic material. The released silver was found to be in ionic form, but also in the form of silver nanoparticles (around 12%). Consumer exposure to the total amount of silver released from the food containers is low in comparison with the background silver exposure of the general population, but since natural background concentrations are only known for ionic silver, the exposure to silver nanoparticles is not directly comparable with a safe background level.     

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.     

Nano-TiO2 particles and high hydrostatic pressure treatment for improving functionality of polyvinyl alcohol and chitosan composite films and nano-TiO2 migration from film matrix in food simulants

This study investigated the impact of nano-TiO₂ and high hydrostatic pressure (HHP) treatment on microstructure, water vapor and gas barrier, antibacterial and mechanical properties of polyvinyl alcohol (PVA)–chitosan (CHI) biodegradable films and determined the migration behavior of TiO₂ nanoparticles from the films to food simulants. Apart from the effect of filler, TiO₂ nanoparticles also could improve the antibacterial activity of the films and play a role as a plasticizer in the films. HHP treatment promoted the interaction between PVA and chitosan molecules, resulting in the formation of more compacted network structures in PVA–CHI films. The migration of TiO₂ from the films was investigated in food simulants including distilled water, acetic acid, ethanol and olive oil, in which the trace amount of TiO₂ (< 4.20 × 10^− 3‰) was only detected in olive oil. HHP treatment at 200–400 MPa significantly reduced migration of TiO₂ nanoparticles from the films.Industrial relevanceResults from this study provide a new application direction of high hydrostatic pressure (HHP) in the field of food packaging materials for improving the functionality of materials. Due to the non-thermal characteristic, HHP in combination with nano-TiO₂ not only improved the mechanical and barrier properties of the biodegradable PVA–CHI composite films (polyvinyl alcohol and chitosan based materials), but also enhanced the antibacterial activity of the films. The HHP treated PVA–CHI–TiO₂ films are very stable in food simulants, such as olive oils. Therefore, the utilization of HHP and nano-TiO₂ is promising in the preparation of food packaging materials with desirable functionalities.     

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.     

Target and non-target analysis of migrants from PVC-coated cans using UHPLC-Q-Orbitrap MS: evaluation of long-term migration testing

A simple, rapid and sensitive method for analyzing multi-target and non-target additives in polyvinyl chloride (PVC) food can coatings using ultra-high-performance liquid chromatography coupled to quadrupole-orbital ion-trap mass spectrometry was developed. This procedure was used to study the behaviour of a cross-linking agent, benzoguanamine (BGA), two slip agents, oleamide and erucamide, and 18 other commonly used plasticisers including phthalates, adipates, sebacates, acetyl tributyl citrate and epoxidised soybean or linseed oils. This optimised method was used to detect these analytes in food simulants (water and 3% acetic acid) in a long-term migration test of PVC-coated food cans for a period ranging from 1 day to 1.5 years at 40°C. Although very low detection limits (5 ng ml^–1) were obtained for the majority of compounds, none of the monitored plasticisers and slip agents was detected in simulants extracted from cans over the period of the test. However, the presence of BGA in both aqueous food simulants was confirmed based on high-resolution mass spectrometry, product ion spectra and analysis of a reference standard. The BGA concentration in both simulants continued to increase with storage time: after 1.5 years storage in aqueous food simulants at 40°C, BGA was detected at concentrations up to 84 µg dm^–2. We believe this is the first study describing the long-term migration capacity of BGA from any vinyl coating material intended for use in PVC-coated food cans. Our results may have implications for migration test protocols for food cans that will be stored for extended time periods.     

Modelling natamycin release from alginate/chitosan active films

In antimicrobial active films, the active agent is incorporated in the polymeric matrix and is released from the film to the product surface where most deterioration processes take place. In this study, films structured solely by alginate and by blends of alginate:chitosan (82.5:17.5 and 65:35) were obtained by casting. The film formulations received natamycin (4 and 8 g/100 g biopolymer) as antimicrobial agent. Films were characterised according to their thickness and morphology. Diffusion experiments in water indicated very slow release kinetics of the antimicrobial, being markedly hindered in the alginate and chitosan composite films, probably due to electrostatic interactions between chitosan and natamycin. Fickian diffusion prevailed and the diffusion coefficients found for the films varied from 2.6 × 10^?11 to 2.5 × 10^?12 cm² s^?1.     

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.     

Study of silver ion migration from melt-blended and layered-deposited silver polyethylene nanocomposite into food simulants and apple juice

Colloidal silver nanoparticles were prepared via chemical reduction using polyethylene glycol (PEG) as a reducing agent, stabiliser and solvent. Silver polyethylene nanocomposites were produced via two methods, namely: melt blending and layer-by-layer (LBL) deposition of silver nanoparticles onto a polyethylene film. The silver ion release from either melt-blended or LBL-deposited nanocomposites into a food simulant and apple juice during 30 days at 4°C and 40°C was determined by atomic absorption spectroscopy. The effects of incorporating or coating of silver nanoparticles, silver concentration, contact media, temperature and time on silver ion migration were evaluated using factorial design. The diffusion coefficients of silver ions into the food simulants and apple juice were calculated using the Miltz model. The results indicated that the production method of nanocomposite, silver concentration, temperature, time and contact media showed a significant effect (p < 0.05) on silver ion migration. The quantity of silver ion migration from the nanocomposites into the food simulants and apple juice was less than the cytotoxicity-level concentration (10 mg kg^?1) in all cases over 30 days. The coating of silver nanoparticles, higher silver concentration in the nanocomposite, higher temperature and acidic property of contact liquid all promoted the silver ion release from the nanocomposite films. The migration of silver ions from nanocomposites obeyed first-order diffusion kinetics.