食品金属罐中14种双酚类物质迁移量的同时测定及杀菌过程对其迁移的影响

为了调查国内食品金属罐中双酚类物质的迁移水平,本文建立了同时测定食品金属罐中14种双酚类物质迁移量的高效液相色谱法,并研究了杀菌过程对双酚类物质迁移的影响及食品金属罐中双酚类物质的迁移规律.结果表明,14种双酚类物质在4种食品模拟物(4％体积乙酸、10％体积乙醇、50％体积乙醇和异辛烷)中线性关系良好,加标回收率为83...     

Chlorohydrins of bisphenol A diglycidyl ether (BADGE) and of bisphenol F diglycidyl ether (BFDGE) in canned foods and ready-to-drink coffees from the Japanese market

BADGE.2HCl and BFDGE.2HCl were determined in 28 samples of ready-to-drink canned coffee and 18 samples of canned vegetables (10 corn, 5 tomatoes and 3 others), all from the Japanese market. HPLC was used as the principal analytical method and GCMS for confirmation of relevant LC fractions. BADGE.2HCl was found to be present in one canned coffee and five samples of corn, BFDGE.2HCl in four samples of canned tomatoes and in one canned corn. No sample was found which exceeded the 1mg/kg limit of the EU for the BADGE chlorohydrins. However the highest concentration was found for the sum of BFDGE.2HCl and BFDGE.HCl.H₂O at a level of 1.5mg/kg. A Beilstein test confirmed that all cans containing foods contaminated with BADGE.2HCl or BFDGE.2HCl had at lest one part coated with a PVC organosol.     

Survey of bisphenol a diglycidyl ether (BADGE) in canned foods.

2,2-Bis(4-hydroxyphenyl)propane bis(2,3-epoxypropyl) ether (BADGE) is used in the manufacture of lacquers for coating the inside of food and beverage cans. In June 1996 the EC Scientific Committee for Food temporarily increased the specific migration limit applying to BADGE to 1 mg/kg pending consideration of additional toxicological data. In order to find out if there is migration of BADGE from can coatings into foods, a 'worst case' sampling exercise has been conducted to survey those canned foods where the propensity for migration of BADGE was judged to be highest. The foods surveyed include canned fish in oil, meat and milk and, altogether, BADGE was determined in 181 retail samples. Analysis for BADGE was conducted, in duplicate, by HPLC with fluorescence detection with confirmation of BADGE identity by GC/MS analysis using selected ion monitoring. BADGE was found at levels exceeding 1 mg/kg in seven of the 15 canned anchovy samples and five of the 22 sardine samples purchased during the period September 1995-July 1996. Infrared analysis of the can coatings provided strong evidence that the higher BADGE levels found were associated with use of PVC organosol lacquers, although in some cases cans coated with organosols gave low BADGE results. For canned sardine samples found to contain greater than 0.5 mg/kg BADGE in the total contents, a replicate can was opened and separate analyses performed on the drained fish and the oil. The results clearly showed that BADGE concentrations in the oil were about 20 times higher than in the drained fish. Further samples of canned sardines and anchovies were purchased in June/July 1997 and, in all cases, BADGE levels were found to be below 1 mg/kg. In the other retail canned foods, BADGE was not detectable (DL = 0.02 mg/kg) or detected at concentrations well below the temporary SML of 1 mg/kg.     

Simultaneous determination of bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether and their hydrolysis and chlorohydroxy derivatives in canned foods

A new method for the simultaneous determination of bisphenol A-diglycidyl ether (BADGE), bisphenol F-diglycidyl ether (BFDGE) and their hydrolysis and chlorohydroxy derivatives in canned foods is presented. Oily and aqueous food samples were extracted with tert-butyl methyl ether and acetonitrile, respectively. The compounds in both extracts were determined by using reverse-phase gradient high-performance liquid chromatography with fluorescence detection. Optimization of extraction and chromatographic determination is outlined in detail. After validation the method was used to analyze various canned food samples, such as tuna and sardine in oil, vegetables, fruit cocktails, etc. In none of the samples were significant amounts ( >100 μg/kg) of BADGE or BFDGE found, whereas in most samples BADGE/BFDGE chlorohydroxy compounds were detected. These originate most probably from the use of organosol varnishes instead of epoxy resins. Risk assessment and regulations of these compounds by the European Union are urgently needed. Additionally, the syntheses and characterization of the not available standard compounds bisphenol A-p-glycidyl-p′-(3-chloro-2-hydroxypropyl) ether (BADGE.HCl) and bisphenol A-p-(2,3-dihydroxypropyl)-p′-(3-chloro-2-hydroxypropyl) ether (BADGE.HCl.H₂O) are presented. Received: 28 July 1999 / Revised version: 29 October 1999     

Estimates of per capita exposure to substances migrating from canned foods and beverages.

A study was undertaken by European industry to estimate the consumption of canned beverages and foodstuffs. European can production data were used with adjustments for imports into and out of the EU. It was further assumed that can production, with adjustments, equalled consumption. Owing to the lack of actual consumption country-by-country or household-by-household data throughout Europe, only per capita estimates of consumption were possible. Data were compiled country-by-country for seven major can-producing EU Member States and for eight different types of canned food and two types of canned beverage (beer and soft drinks). The per capita consumption of canned foods was 1.1 cans/person/week, and consumption of canned fish was estimated as 2.2 kg/person/year. The estimate of per capita consumption of canned food was 62 g/person/day or 22.6 kg/person/year. Canned beverages account for about 60% of the consumption of canned foodstuffs. The usefulness of per capita consumption of beverages is questionable because consumption habits may vary more widely than those for canned foods. However, as the migration into beverages is insignificant, these data were added for completeness. Per capita consumption of canned beverages is 67 cans/person/year or 61 g/person/day. From the average can sizes, the surface area of the cans consumed was estimated. The per capita surface area exposure was 0.55 dm(2)/person/day for canned foods and 0.55 dm(2)/person/day for canned beverages, giving 1.1 dm(2)/person/day. Migration of a substance at 0.02 mg dm(2) gives an exposure of 0.01 mg/person/day assuming a per capita consumption, using a surface area model. Migration at 0.12 mg kg(-1) in food gives an exposure of 0.007 mg/person/day using a weight model. Both models assumed migration into all food types at the same level, which is highly unrealistic. Exposure to BADGE from canned foods has been used as a case study. The best estimate for a worst case per capita exposure to BADGE and relevant derivatives was between 6 and 10 micro g/person/day, depending upon the approach and assumptions used.     

Monitoring of bisphenol-A-diglycidyl-ether (BADGE) in canned fish in oil

A survey at the European level was initiated on the quantification of bisphenol-A-diglycidyl-ether (BADGE) in canned fish in oil in order to assess the exposure of BADGE. A total of 382 canned fish samples were collected from all 15 Member States and Switzerland and analysed for BADGE in fish. The fish was extracted first with hexane and reextracted with acetonitrile, followed by a membrane filtration and reverse phase HPLC analysis with fluorescence detection. The analysis of the fish showed that about 3% of the samples contained BADGE at a level above 1mg/kg. The samples exceeding the limit by a larger margin were mostly from anchovy cans and cans manufactured in 1991-1995.     

Determination of Bisphenol A diglycidyl ether (BADGE) and its hydrolysis products in canned oily foods from the Austrian market

 Bisphenol A diglycidyl ether (BADGE) is determined in canned oily foods from Austria using a new simplified HPLC method. Samples are extracted with pentane, back extracted with methanol, and finally dissolved in the mobile phase (cyclohexane/tert–butyl methyl ether). Separation is performed on a normal-phase HPLC column using fluorescence detection. Verification of the BADGE-containing peak is carried out by using off-line GC-MS. Additionally, the synthesis and determination of BADGE hydrolysis products, Bisphenol A bis(2,3-dihydroxypropyl) ether (BADGE.2H₂O) and Bisphenol A glycidyl (2,3-dihydroxypropyl) ether (BADGE.H₂O) are presented. From 67 analyzed cans, containing various fatty meat or fish products, 16% were above the maximum quantity of 1 mg/kg tolerated by the European Community, 45% were in the range between 0.1–1 mg/kg, 24% between 0.02 and 0.1 mg/kg, and in 15% the BADGE concentrations were below the detection limit of 0.02 mg/kg. The hydrolysis product BADGE.H₂O was not detected in any sample, whereas BADGE.2H₂O was found in some samples up to a concentration of 0.5 mg/kg. Received: 11 May 1998 / Revised version: 1 July 1998     

Review of the toxicology, human exposure and safety assessment for bisphenol A diglycidylether (BADGE).

BADGE (whose chemical names are bisphenol A diglycidylether and 2,2-bis(4-(2,3-epoxypropyl)phenyl)propane) is the lowest molecular weight oligomer in commercial epoxy resins and the major component in commercial liquid epoxy resins. The major application areas for epoxy resins are protective coatings and civil engineering. Additional applications include printed circuit boards, composites, adhesives and tooling, while a relatively small amount of epoxy resins (< 10%) finds use in protective coatings inside food and drink cans. The use of BADGE in food-contact applications was first regulated through EC Directive 2002/16/EC and amended in EC Directive 2004/13/EC with migration levels in food-contact applications being generally well below the regulatory thresholds. The paper discusses the commercial use of BADGE focusing on the current knowledge of human exposure from canned food applications. To assess the safety of this application, the exposure data are compared with no adverse effect levels (NOAEL) from various toxicological investigations with BADGE including reproductive and developmental assays, endocrine toxicity investigations, and sub-chronic and chronic assays. Consumer exposure to BADGE is almost exclusively from migration of BADGE from can coatings into food. Using a worst-case scenario that assumes BADGE migrates at the same level into all types of food, the estimated per capita daily intake for a 60-kg individual is approximately 0.16 microg kg(-1) body weight day(-1). A review of one- and two-generation reproduction studies and developmental investigations found no evidence of reproductive or endocrine toxicity, the upper ranges of dosing being determined by maternal toxicity. The lack of endocrine toxicity in the reproductive and developmental toxicological tests is supported by negative results from both in vivo and in vitro assays designed specifically to detect oestrogenic and androgenic properties of BADGE. An examination of data from sub-chronic and chronic toxicological studies support a NOAEL of 50 mg kg(-1) body weight day(-1) from the 90-day study, and a NOAEL of 15 mg kg(-1) body weight day(-1) (male rats) from the 2-year carcinogenicity study. Both NOAELS are considered appropriate for risk assessment. Comparing the estimated daily human intake of 0.16 microg kg(-1) body weight day(-1) with the NOAELS of 50 and 15 mg kg(-1) body weight day(-1) shows human exposure to BADGE from can coatings is between 250,000 and 100,000-fold lower than the NOAELs from the most sensitive toxicology tests. These large margins of safety together with lack of reproductive, developmental, endocrine and carcinogenic effects supports the continued use of BADGE for use in articles intended to come into contact with foodstuffs.     

Bisphenol A diglycidyl ether (BADGE) migrating from packaging material ‘disappears’ in food: reaction with food components

Bisphenol A diglycidyl ether (BADGE) is widely used as a monomer for coatings and adhesives for food-contact applications. Previous publications indicate that, after migration from packaging into foodstuffs, BADGE undergoes various reactions with unidentified food components. In order to elucidate the fate of BADGE, losses were determined after incubation with different foodstuffs and food components. Food proteins were identified as the main reaction partner with BADGE. Adduct formation was found with nucleophilic side-chains of amino acids. In vitro, cysteine exhibited significant activity. The previously reported occurrence of methylthio-derivatives of BADGE in foodstuffs was shown to originate from the reaction of BADGE with methionine. BADGE-methylthio derivatives can, therefore, be used as marker substances in foodstuffs for protein reactions with BADGE. The reported results offer a new viewpoint on the evaluation of BADGE migration. The hydrolysis and hydrochlorination derivatives subject to European legislation make up only a fraction of the totally migrated BADGE, and a further concern is that the toxic or allergenic potential of the protein adducts are unknown.     

Bisphenol A diglycidyl ether (BADGE) migrating from packaging material 'disappears' in food: reaction with food components.

Bisphenol A diglycidyl ether (BADGE) is widely used as a monomer for coatings and adhesives for food-contact applications. Previous publications indicate that, after migration from packaging into foodstuffs, BADGE undergoes various reactions with unidentified food components. In order to elucidate the fate of BADGE, losses were determined after incubation with different foodstuffs and food components. Food proteins were identified as the main reaction partner with BADGE. Adduct formation was found with nucleophilic side-chains of amino acids. In vitro, cysteine exhibited significant activity. The previously reported occurrence of methylthio-derivatives of BADGE in foodstuffs was shown to originate from the reaction of BADGE with methionine. BADGE-methylthio derivatives can, therefore, be used as marker substances in foodstuffs for protein reactions with BADGE. The reported results offer a new viewpoint on the evaluation of BADGE migration. The hydrolysis and hydrochlorination derivatives subject to European legislation make up only a fraction of the totally migrated BADGE, and a further concern is that the toxic or allergenic potential of the protein adducts are unknown.     

Bisphenol A diglycidyl ether (BADGE) migrating from packaging material 'disappears' in food: reaction with food components

Bisphenol A diglycidyl ether (BADGE) is widely used as a monomer for coatings and adhesives for food-contact applications. Previous publications indicate that, after migration from packaging into foodstuffs, BADGE undergoes various reactions with unidentified food components. In order to elucidate the fate of BADGE, losses were determined after incubation with different foodstuffs and food components. Food proteins were identified as the main reaction partner with BADGE. Adduct formation was found with nucleophilic side-chains of amino acids. In vitro, cysteine exhibited significant activity. The previously reported occurrence of methylthio-derivatives of BADGE in foodstuffs was shown to originate from the reaction of BADGE with methionine. BADGE-methylthio derivatives can, therefore, be used as marker substances in foodstuffs for protein reactions with BADGE. The reported results offer a new viewpoint on the evaluation of BADGE migration. The hydrolysis and hydrochlorination derivatives subject to European legislation make up only a fraction of the totally migrated BADGE, and a further concern is that the toxic or allergenic potential of the protein adducts are unknown.     

钠盐与AT毒素对烟苗根生长的影响

为确定不同钠盐对烟草赤星病菌AT毒素毒性的影响,作者采用摩擦接种处理、浇根处理、种子根处理3种生物测定方法确定了以烟草种子根处理法作为烟草赤星病菌的毒性测定方法。用10种化合物分别以5种不同浓度与AT毒素混合接种烟苗,分别以单独接种毒素稀释液与无菌水作对照。根长测定数据经DPS软件统计分析,结果表明单独施用AT毒素明显抑制烟苗根的生长,差异极显著;氢氧化钠、硝酸钠、苯甲酸钠、酒石酸钠均不能改变毒素对根长的影响,碳酸钠(200mg/mL)、酒石酸钾钠(200mg/mL)、四硼酸钠(0.02~0.2mg/mL)、氟化钠(0.2~2mg/mL)、柠檬酸钠(0.2mg/mL-200mg/mL)、钼酸钠(0.02~2mg/mL)对烟草赤星病菌毒素有明显钝化作用,以钼酸钠0.02mg/mL浓度处理效果最好,其次为柠檬酸钠0.2mg/mL处理;钼酸钠20~200mg/mL处理可增加AT毒素的毒性,浓度越大效果越显著。      

Bisphenol A (BPA) and its source in foods in Japanese markets

The determination of bisphenol A (BPA) and/or bisphenol A diglycidyl ether (BADGE) in foods sold in Japanese markets and in water leached from six epoxy resin cans with similar diameters was carried out using high-performance liquid chromatography (HPLC) with electrochemical detection (LC/ECD), LC-mass spectrometric detection (LC/MS) and LC-tandem mass spectrometric detection (LC/MS/MS). BPA concentrations were 0-842 ng g^-1 for 48 canned foods, 0-14 ng g^-1 for 23 foods in plastic containers, and 0-1 ng g^-1 for 16 foods in paper containers. No BADGE was detected in three canned foods. There was no difference in leaching concentrations of BPA into glycine buffers at pHs 8 and 11, and water. The amounts of BPA leached into water from six epoxy resin cans held at 121°C for 20 min were almost the same as the cans' contents and were much higher than the amounts leached from cans held at or below 80°C for 60 min. The amount leached depended on the type of can, but not on the amount of BADGE leached from the cans. Considerably more BPA than BADGE leached to water from six cans. Two cans whose contents had high concentrations of BPA showed no BADGE leaching even at 121°C, suggesting the different kinds of epoxy resin can linings from others. The results imply that the main source of human exposure to BPA is food from cans with linings that contain high percentages of BPA as an additive or an unforeseen contaminant.     

Estimation of intake of bisphenol-A-diglycidyl-ether (BADGE) from canned fish consumption in Europe and migration survey

The exposure to bisphenol-A-diglycidyl-ether (BADGE) from canned fish in oil was assessed from consumption data collected for each Member State of the European Union and Switzerland, and migration data from a European survey on 382 samples. Trade figures were used when no consumption data were available. The average consumption of canned fish in Europe was 2.3kg per person per year, with values ranging from 0.2kg per person per year in the United Kingdom to 5.1kg per person per year in Denmark. The exposure to BADGE was calculated as μg per person per day. The data indicated that exposure to BADGE was in the range below 4mg per person per year, i.e. 9 μg per person per day, hence a fairly low exposure in part due to the fact that canned fish is a relatively minor dietary item. An approximation assuming the general figure of a 60kg adult, would thus be 0.15 μg/kg body weight per day. This is a fairly limited exposure considering the provisional limit in food had been set a 1mg/kg and assumed 1kg of food ingested. In countries for which increased exposure was found, the reason was mainly caused by one individual sample exhibiting a high concentration rather than a larger number of samples with mildly elevated concentrations.     

Occurrence of bisphenol-F-diglycidyl ether (BFDGE) in fish canned in oil

The levels of bisphenol-F-diglycidyl ether (BFDGE) were quantified as part of a European survey on the migration of residues of epoxy resins into oil from canned fish. The contents of BFDGE in cans, lids and fish collected from all 15 Member States of the European Union and Switzerland were analysed in 382 samples. Cans and lids were separately extracted with acetonitrile. The extraction from fish was carried out with hexane followed by re-extraction with acetonitrile. The analysis was performed by reverse phase HPL C with fluorescence detection. BFDGE could be detected in 12% of the fish, 24% of the cans and 18% of the lids. Only 3% of the fish contained BFDGE in concentrations considerably above 1mg/kg. In addition to the presented data, a comparison was made with the levels of BADGE (bisphenol-A-diglycidyl ether)analysed in the same products in the context of a previous study.     

食品罐内壁涂层中双酚A-二缩水甘油醚双水合物的迁移特性的数值仿真与实验研究

对金属罐内壁涂层中的有害物质(双酚A-二缩水甘油醚双水合物,以下简称BADGE·2H2O)向食品模拟液在给定条件下的迁移特性进行了数值仿真,并与对应条件下的实验结果进行了对比、分析。结果表明:温度、初始浓度、涂层厚度对物质迁移的影响较大;对于给定的温度,温度越高,则迁移达到平衡时所需要的时间越短,迁移量越大;对于给定的初始浓度和涂层厚度,初始浓度越大,涂层厚度越厚,则迁移量越大;同时,在不同温度下,BADGE·2H2O从食品罐内壁涂层向水性模拟液迁移的数值解与实验值最大差值为0.023μg/mL。数值仿真与实验结果有较好的一致性。     

两种黄酮类铜(II)配合物的制备及体外抗氧化活性

为了研究黄酮化合物与金属离子协同作用增加抗氧化活性的构效关系,本文分别以天然黄酮化合物金雀异黄酮和山奈酚为原料,在无水乙醇-水混合溶剂中制备了2个铜(II)配合物。采用元素分析、络合滴定、红外光谱、电子吸收光谱和热重分析对2个目标配合物的组成及结构进行了分析,通过NBT光照还原法和水杨酸法测定了配合物的体外抗氧化活性。结果表明,在配合物的分子结构中,黄酮母核上的羰基氧和羟基氧与中心铜离子双齿配位,摩尔比为2:1,推测分子式为[Cu(Gen)₂(H₂O)₂]·3H₂O(Gen=金雀异黄酮)(1)和[Cu(Kae)₂(H₂O)₂]·1.5H₂O(Kae=山奈酚)(2)。在本实验条件下,配合物清除O₂-·的IC₅₀分别为0.250和0.646 μmol/L,起主要作用的是中心铜离子;清除OH·的IC₅₀分别为158和129 μmol/L,黄酮配体发挥主导作用。配合物具有良好的清除O₂-·和OH·的能力,且中心铜离子和黄酮配体显示出协同抗氧化活性。     

高浓度培养乳酸菌发酵培养基的优化

对一株已经证实具有耐酸、耐胆汁的乳杆菌R8菌株进行培养基的优化研究,以菌体密度为检测指标,采用单因素实验和正交设计实验优化发酵培养基组分,为该益生菌应用于改善胃肠道的健康食品奠定基础。结果显示,该菌最佳发酵配方为:葡萄糖20.0 g,酵母粉30.0 g,MnSO₄·4H₂O 0.075 g,MgSO₄·7H₂O 2.0 g,KH₂PO₄ 2.5 g,柠檬酸铵2.5 g,CH₃COONa·3H₂O 6.25 g,Tween80 1.0 mL,pH6.2。培养基配方经过系统筛选和优化后,菌体浓度(OD_{600 nm})达到2.38。     

青辣椒腌制过程中护色技术的研究

以青色朝天椒为研究对象,通过正交实验设计对青色朝天椒腌制工艺进行了优化,并对青色朝天椒腌制过程中的护色措施进行了研究。研究结果表明:青色朝天椒最佳腌制条件为:腌制时间4d、食盐含量6%、发酵温度30℃、菌种比例（植物乳杆菌∶肠膜明串珠菌）1∶2、接种量2%;青色朝天椒腌制过程中最佳护色措施为:在腌制液中CuSO₄.5H₂O为90mg/L、ZnSO₄.7H₂O为120mg/L、V_C为60mg/L。     

聚偏氟乙烯/FeCl3复合纤维膜柔性传感器的制备及其性能

为制备灵敏度高的柔性传感器,将六水合三氯化铁(FeCl₃·6H₂O)加入聚偏氟乙烯(PVDF)中,采用静电纺丝法制备PVDF/FeCl₃复合纤维膜并组装成传感器。借助扫描电子显微镜、X射线衍射仪、傅里叶变换红外光谱仪、接触角分析仪等对纤维膜的形貌、结构、润湿性、力学性能及压电性能进行表征。结果表明:适量的FeCl₃·6H₂O 添加可增加纤维膜中β晶型的相对含量,进而有效提高传感器的压电输出性能,但过多FeCl₃·6H₂O会抑制β晶型的形成;当FeCl₃·6H₂O质量分数为0.5%时,纤维晶体结构中β晶型的比例达到最大值68.74%,最高输出电压达到约5 V;传感器对激振过程的反应时间可达0.025 s,且在不同激振频率下的响应时间基本一致,动态高频时具有较高的压电输出。