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)。     

聚碳酸酯奶瓶中双酚A单体向食品模拟物迁移规律的研究

研究用食品模拟物浸泡聚碳酸酯奶瓶中双酚A的迁移规律,高效液相色谱法检测模拟物中双酚A,外标法定量。从添加回收率、精密度及线性关系等方面进行相应的方法学研究,模拟物添加量0.1～10μg/mL时,回收率为77.0%～98.7%、变异系数为5%～9.8%,在双酚A的质量浓度为0.1～10μg/mL时相关系数r=0.99996。根据该方法和欧盟有关模拟物规定的指令,检测了聚碳酸酯奶瓶中双酚A在不同模拟物和不同时间内的迁移率。     

高效液相色谱荧光法测定食品包装材料中双酚A及双酚S的迁移量

采用高效液相色谱-荧光法检测食品包装材料中双酚A及双酚S的迁移量,研究不同的模拟液对食品包装材料中双酚A和双酚S迁移的影响以及不同浓度的乙醇溶液对双酚A和双酚S迁移特性的影响。结果表明:该方法在0.001~0.100μg/L范围内线性关系良好,在乙醇模拟液中,双酚A和双酚S的迁移效果好,乙醇浓度越高迁移率越高,相同浓度的乙醇溶液中,接触温度越高,接触时间越长迁移率越高。     

双酚A在食品模拟物中的迁移规律研究

采用高效液相色谱法,对食品接触材料中双酚A在蒸馏水、质量浓度3%乙酸、体积分数为10%乙醇和异辛烷等4种食品模拟物中的迁移规律进行了研究,研究双酚A迁移量与试验的温度、时间、pH和模拟物属性等参数的关系。结果表明:模拟物的属性对双酚A的溶出迁移行为有显著影响,双酚A的溶出迁移量随温度的升高和时间的增加而变大。     

超高压液相色谱-串联质谱法对马口铁罐内涂层中双酚A及其模拟迁移的测定

目的 建立了超高压液相色谱-串联质谱法测定马口铁罐内涂层中双酚A迁移含量的方法。方法 样品经模拟溶液提取后以C18色谱柱分离, UPLC-MS/MS多反应监测模式下进行定性定量分析, 对金属制品内涂层双酚A在不同食品模拟物环境下的迁移行为进行了研究。结果 线性范围为5.0~100.0 μg/L, 最低检测浓度为1.0 μg/L, 回收率为78.6%~85.9%, 相对标准偏差为7.30%~12.60%。结论 双酚A迁移水平受模拟物性质影响, 相对于水性模拟物, 在醇溶性模拟物中更易发生迁移。双酚A迁移水平随迁移试验温度和接触时间的增加而升高。     

超高效液相色谱-串联质谱法测定水性食品模拟物中双酚S的迁移量

本文旨在建立一种高效液相色谱串联三重四级杆质谱测定水性食品模拟物中双酚S的检测方法。方法:按照GB31604.1-2015《食品安全国家标准食品接触材料及制品迁移试验通则》中的有关规定,对样品进行模拟浸泡。浸泡液中的双酚S经超高效液相色谱进行分离,甲醇-水为流动相梯度洗脱,采用质谱电喷雾离子源(ESI)、多反映监测(MRM)负离子模式对双酚S的定量离子和定性离子进行监测。结果:在最佳试验条件下,目标物的峰面积和浓度在5~200μg/L范围内呈良好的线性关系(线形相关系数0.999 0),最低检出限为0.5μg/L,定量限1.5μg/L。结论:该方法分析速度快,灵敏度高,可用于水性食品模拟物中双酚S迁移量的测定。     

HPLC法测定食品接触材料中BPA迁移量的不确定度评定

参考GB/T 23296.16-2009《食品接触材料高分子材料食品模拟物中2,2-二(4-羟基苯基)丙烷(双酚A)的测定高效液相色谱法》测定食品接触材料(金属空罐)的双酚A迁移量。通过分析测定过程中的各种不确定度来源,计算各不确定度分量,得出金属空罐的双酚A迁移量为0.005 53 mg/dm~2,扩展不确定度为0.000 38 mg/dm~2。比较各不确定度分量大小可知,高效液相色谱法测定食品接触金属空罐双酚A迁移量的不确定度主要来自双酚A标品的纯度和标准曲线的拟合。     

高效液相色谱-串联质谱法同时测定食品接触材料中11种双酚A类和3种烷基酚类化合物迁移量

目的建立高效液相色谱-串联质谱(high performance liquid chromatography-tandem mass spectrometry,LC-MS/MS)法同时测定食品接触材料中11种双酚类及3种烷基酚类化合物。方法 14种目标化合物在塑料制品中通过与食品模拟物在一定温度、时间接触的状态下迁移到食品模拟物中,以T_3色谱柱进行分离,甲醇:乙腈(1:1,V:V)-5 mmol/L乙酸铵水为流动相洗脱,采用电喷雾离子源(electrospray ionization,ESI),多反应监测(multiple reaction monitoring,MRM)负离子模式进行扫描测定。结果 14种酚类化合物的色谱分离良好,1～200μg/L质量浓度范围内与其峰面积均呈线性关系(双酚S为0.240.0μg/L),且线性关系良好(r~2≥0.995)。方法检出限为0.01-0.78μg/L;加标回收率范围为84.5%～99.2%,相对标准偏差(relative standard deviation,RSD)为0.7%～12.4%。结论该方法快速可靠、准确简便,适用于食品接触材料中双酚A类化合物和烷基酚类化合物的检测。     

塑料食品包装材料中双酚A的迁移量检测

目的检测液体食品模拟物中源于塑料包装材料的双酚A(bisphenol A,BPA)的迁移量。方法建立高效液相色谱检测双酚A的方法学,通过液体食品模拟物探讨了时间、温度、酸度、乙醇浓度、微波加热时间、油脂6种因素对BPA迁移率的影响。结果 BPA在0.0464~1.044μg/m L内线性关系良好(r2=0.9993),精密度、稳定性、重复性的RSD分别为0.81%、1.42%、2.59%,加样回收率范围为95.0%~96.9%,RSD为0.80%。通过对液体食品模拟物中BPA含量的检测,发现随着储存时间延长、温度升高、酸度和乙醇浓度增加、微波加热时间延长、油脂增加,BPA从塑料食品包装材料转移到饮用品中的迁移率增加。结论正确使用塑料食品包装,对于减少BPA在体内蓄积至关重要。     

高效液相荧光法对5种罐装食品模拟物中双酚类化合物的迁移分析

双酚A及双酚类环氧衍生物是一种内分泌干扰物,易从金属罐头涂层迁移到食品内容物中。本文建立了一个高效液相色谱-荧光检测法同时检测罐头模拟物中14种双酚类化合物的分析方法。在10～1000ng/mL质量浓度范围,双酚A和各双酚类环氧衍生物的响应峰面积与其相应浓度呈良好相关性,最低检出限在1.41～3.66ng/mL之间;在10～250ng/mL添加水平范围内,平均回收率在72.55%～102.79%之间,日内和日间相对标准偏差均小于10%。之后将此方法应用于测定食品罐头中该双酚类化合物在不同食品模拟物中的迁移情况。     

Migration of bisphenol A from polycarbonate baby bottles under real use conditions

Migration of the potential endocrine disrupter, bisphenol A (BPA), from 31 polycarbonate (PC) baby bottles into aqueous food simulants was studied under real repetitive use, using a sensitive and fully validated liquid chromatographic method with fluorescence detection. Confirmation of the presence of BPA was performed by liquid chromatography-mass spectrometry (LC-MS). The effects of cleaning in a dishwasher or with a brush, sterilization with boiling water and the temperature of migration were examined. It was shown that temperature was the crucial factor for the migration of BPA from the plastic bottles to water. All samples released BPA in the concentration range 2.4-14.3 µg kg^-1 when filled with boiled water and left at ambient temperature for 45 min. The decrease of BPA release in the sterilization water and in the food simulant over 12 cycles of use indicated that the hypothesis of polymer degradation in water is dubious. Estimated infantile dietary exposure, regarding the use of PC baby bottles, ranged between 0.2 and 2.2 µg kg^-1 bw day^-1, which is below the Tolerable Daily Intake of 50 µg kg^-1 bw recently established by EFSA.     

双酚A单克隆抗体的制备及酶联免疫分析方法的建立

采用活泼酯法将双酚A的结构类似物双酚酸与载体蛋白偶联制备人工抗原,用制备的人工抗原免疫BALB/c小鼠,采用聚乙二醇法进行细胞融合制备双酚A单克隆抗体,成功获得一株分泌抗双酚A单克隆抗体的细胞株3H1,经鉴定抗体属于IgG1亚型,轻链为κ,并建立了间接竞争酶联免疫分析法。线性范围为1～50 ng/mL,最低检测限为0.43 ng/mL,半数抑制浓度为6.56 ng/mL。回收率为82.83%～101.94%,变异系数为2.94%～12.95%。该方法具有较高的灵敏度和特异性,具有良好的应用前景。     

免疫亲和柱净化-高效液相色谱法检测两种饮料中双酚A含量

建立了免疫亲和柱净化-高效液相色谱荧光检测法(IAC-HPLC-FL)检测豆奶及橙汁饮料中的双酚A含量。采用甲醇提取、离心、磷酸缓冲溶液稀释后,经免疫亲和柱纯化,用1 mL甲醇-水(80:20,体积/体积)洗脱,应用高效液相色谱法检测。以C₁₈柱为分离色谱柱,甲醇-水(60:40,v/v)溶液为流动相洗脱,流速0.4 mL/min,柱温30℃,进样量10 μL,荧光检测器检测,激发波长228 nm,发射波长310 nm。结果表明:在1.0~300.0 ng/mL的浓度范围内,双酚A的浓度与峰面积呈良好的线性关系(相关系数R2=0.9998),检出限定为1 ng/mL。平均回收率为82.5%~104.6%,相对标准差为2.3%~6.4%。分别选取玻璃瓶装和塑料瓶装的豆奶和橙汁饮料进行双酚A含量检测,玻璃瓶装的豆奶和橙汁饮料中双酚A含量均小于检出限1 ng/mL,而某款塑料瓶装的豆奶和橙汁饮料检测出极其微量的双酚A,其双酚A含量分别为1.44、1.57 ng/mL,处于可接受水平。该方法简单快速、灵敏度高、重复性好,能够有效地分离和检测饮料中的双酚A,适用于豆奶和橙汁等饮料中的双酚A的测定。     

Migration of bisphenol A from polycarbonate baby bottles under real use conditions

Migration of the potential endocrine disrupter, bisphenol A (BPA), from 31 polycarbonate (PC) baby bottles into aqueous food simulants was studied under real repetitive use, using a sensitive and fully validated liquid chromatographic method with fluorescence detection. Confirmation of the presence of BPA was performed by liquid chromatography–mass spectrometry (LC–MS). The effects of cleaning in a dishwasher or with a brush, sterilization with boiling water and the temperature of migration were examined. It was shown that temperature was the crucial factor for the migration of BPA from the plastic bottles to water. All samples released BPA in the concentration range 2.4–14.3 µg kg^?1 when filled with boiled water and left at ambient temperature for 45 min. The decrease of BPA release in the sterilization water and in the food simulant over 12 cycles of use indicated that the hypothesis of polymer degradation in water is dubious. Estimated infantile dietary exposure, regarding the use of PC baby bottles, ranged between 0.2 and 2.2 µg kg^?1 bw day^?1, which is below the Tolerable Daily Intake of 50 µg kg^?1 bw recently established by EFSA.     

Determination of bisphenol A in foods using GC/MS

An analytical method using GC/MS was developed for bisphenol A (BPA) in foods and BPA was determined in canned foods and fresh foods such as vegetables, fruit and meat. BPA was extracted with acetone from the samples and the extract was concentrated at under 40 degrees C in vacuo to afford an aqueous solution, which was washed with hexane after alkalization and extracted with 50% diethyl ether-hexane after acidification. Extracts were cleaned up on a PSA and/or a C18 cartridge column, and BPA was derivatized with heptafluorobutyric anhydride and determined by GC/MS (SIM). This method was applicable to the detection and determination of BPA residues in food samples at the level of 1 ng/g. Among canned foods, BPA was found in 6 corned beef, 1 chicken, 9 sweet corn and 3 bean samples at the levels of 17-602 ng/g, 212 ng/g, 2.3-75 ng/g and 3.5-26 ng/g, respectively. BPA was also detected in 1 retort soup and 1 retort pack product at the levels of 11 ng/g and 86 ng/g, respectively. As for dairy products, BPA was not detected in butter and milk. Among fresh foods, BPA was detected in 2 fish and 3 liver samples at the levels of trace (tr)-6.2 ng/g and tr-2.2 ng/g, respectively. In vegetables, fruits and chocolates, a trace level of BPA was detected in only 1 chocolate. Traces of BPA were also detected in 3 samples of 6 boxed lunches.     

纺织品中双酚 A 检测用表面等离子体共振传感器的表面预处理

针对纺织服装中双酚 A（BPA）分子量小,直接采用表面等离子体共振（SPR）技术难以精准检测的问题,采用传感器表面预处理方法和溶液竞争原理来扩大响应信号,对其进行定性定量检测。为更好地使双酚Ａ?牛血清白蛋白抗原（BPA?BSA）和传感芯片进行氨基偶联,从传感芯片的选择、修饰溶液的pH 值、离子浓度、BPA?BSA 抗原的最佳浓度４ 个因素出发,运用控制变量法,探索双酚Ａ 检测中传感芯片的最佳修饰条件。结果表明：当采用羧甲基葡聚糖组装（CM5） 芯片、修饰液pH 值为4.5、离子浓度为10 mmol/L、BPA?BSA 质量浓度为50 μg/mL 时,BPA?BSA 的氨基偶联修饰效果最佳,且预处理方法简便快捷,BPA 无需精度提纯,特异性识别度高,可应用在纺织品双酚 A 检测中。     

超高效液相色谱串联质谱法测定全蛋粉中的双酚A和双酚S

建立超高效液相色谱-串联质谱测定全蛋粉中双酚A和双酚S的检测方法。全蛋粉经水复溶后经乙腈提取,提取液使用分散系固相萃取-基质增强脂质去除产品进行除脂,使用Oasis PRiME HLB小柱进一步净化,使用超高效液相串联质谱测定,负离子多反应监测(MRM)模式测定,内标法定量。结果显示:双酚A在1~50 μg/kg范围内呈线性,相关系数为0.9991,加标回收率为98.8%~105.0%,日内和日间相对标准偏差分别为3.84%~8.58%和5.65%~8.74%,检出限为0.3 μg/kg,定量限为1.0 μg/kg;双酚S在0.4~20 μg/kg范围内呈线性,相关系数为0.9995,加标回收率为98.5%~102.5%,日内和日间相对标准偏差分别为3.01%~7.86%和3.18%~7.03%,检出限为0.1 μg/kg,定量限为0.3 μg/kg。实际样品测定结果分别为:双酚A 2.4~3.8 μg/kg;双酚S 0.48~0.82 μg/kg。本方法前处理简单、高灵敏度适用于全蛋粉中双酚A和双酚S的日常测定。     

Sensitive determination of bisphenol A and bisphenol F in canned food using a solid-phase microextraction fibre coated with single-walled carbon nanotubes before GC/MS

A reliable and sensitive method for simultaneous determination of bisphenol A (BPA) and bisphenol F (BPF) in canned food by gas chromatography-mass spectrometry (GC/MS) is described after extraction and pre-concentration by a new solid-phase microextraction (SPME) adsorbent. The potential of single-walled carbon nanotubes (SWCNTs) as SPME adsorbent for the pre-concentration of environmental contaminants has been investigated in recent years. This work was carried out to investigate the feasibility of SWCNTs as a headspace SPME adsorbent for the determination of bisphenol derivatives in canned food. Potential factors affecting the extraction efficiency, including extraction time, extraction temperature, desorption time, desorption temperature, and salinity were optimized. Calibration curves were linear (r ²≥ 0.994) over the concentration range from 0.30 to 60 µg kg^?1. For both target analytes, the limit of detection (LOD) at signal-to-noise (S/N) ratio of 3 was 0.10 µg kg^?1. In addition, a comparative study between the SWCNT and a commercial polydimethylsiloxane (PDMS) SPME fibre for the determination of bisphenol derivatives in canned food was conducted. SWCNT fibre showed higher extraction capacity, better thermal stability (over 350°C) and longer life span (over 150 times) than the commercial PDMS fibre. The method was successfully applied to determine BPA in canned food samples which were purchased from local markets. BPA was found in some of the samples within the concentration range from 0.5 to 5.2 µg kg^?1.     

High Sensitive Method for Determination of the Toxic Bisphenol A in Food/Beverage Packaging and Thermal Paper Using Glassy Carbon Electrode Modified with Carbon Black Nanoparticles

A voltammetric method for fast and high sensitive determination of Bisphenol A (BPA) using glassy carbon electrode (GC) modified with carbon black nanoparticles (CB) was developed. Cyclic voltammetry study in the 0.1 M phosphates of pH = 7.0 gave single anodic peak at 578 mV. Adsorption-controlled oxidation of BPA was found to be irreversible with the participation of two electrons and two protons. The proposed CB/GC electrode significantly improved the oxidation peak current of BPA compared to the bare electrode. Under the optimum conditions, calibration curve was linear in the concentration of BPA from 0.01 to 3 × 10^?6 mol L^?1 with the detection limit of 3.4 × 10^?9 mol L^?1. Moreover, the proposed method was successfully validated by studying the recovery of BPA in commonly available samples: thermal paper (receipt, ticket) and food/beverages packaging. This paper introduces carbon black as a new, perspective material for electrode modification used in voltammetry.     

Determination of bisphenol A in, and its migration from, PVC stretch film used for food packaging

Bisphenol A (BPA) is used as an additive in polyvinyl chloride (PVC) products, including stretch films used for food packaging. The BPA contents were investigated of several brands of stretch film bought locally but marketed internationally or throughout Spain and which were presumably produced at different manufacturing plants. Their major components were identified by FTIR (Fourier Transform Infrared Spectrometry) and horizontal attenuated total reflectance, and the migration of BPA from these materials into the standard European Union food simulants was determined by high-performance liquid chromatography (HPLC) using both fluorescence (FL) and ultraviolet (UV) detection, the identity of the analyte being confirmed by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). The two HPLC detection methods had different detection limits (30 μg l^-1 for UV, 3 μg l^-1 for FL), but afforded virtually identical BPA determinations for the samples tested. BPA contents ranging from 40 to 100 mg kg^-1 were found in three of the five PVC-based films analysed, and a content of 500 mg kg^-1 was found in a fourth; for these determinations, extraction into acetonitrile was used. In standard tests of migration into water, 3% acetic acid and olive oil over 10 days at 40°C, migration from a given film was in all cases greatest into olive oil. Migration from the films with non-zero BPA contents ranged from 3 to 31 μg dm^-2, values higher than those reported for many other food-contact materials, but lower than the European Union specific migration limit for BPA. PVC stretch film nevertheless may make a significant contribution to contamination of foodstuffs by BPA, and should be taken into account in estimating BPA intake or exposure to this substance.