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標題: | 罐裝飲料中丙二酚A、丙二酚A二環氧甘油醚及其衍生物之溶出情形 Dissolution of Bisphenol A, Bisphenol A Diglycidyl Ether and Its Derivatives in Canned Drinks |
作者: | Mei-Hua Chang 張美華 |
指導教授: | 吳瑞碧,張鴻民 |
關鍵字: | 丙二酚A,丙二酚A二環氧甘油醚,環氧樹脂,溶出,高效液相層析, bisphenol A,bisphenol A diglycidyl ether,epoxy resin,migration,high performance liquid chromatography, |
出版年 : | 2008 |
學位: | 碩士 |
摘要: | 金屬罐為主要食品包裝材料之一,一般罐頭內壁會塗佈樹脂,以避免金屬鐵皮腐蝕,但樹脂與食品接觸時,可能會有樹脂原料丙二酚A (bisphenol A, BPA),或丙二酚A二環氧甘油醚(bisphenol A diglycidyl ether, BADGE)單體溶出。BPA被視為荷爾蒙干擾物質,而BADGE有致癌性疑慮且其化性不穩定,於食品中可能形成衍生物,包括2種水合物[丙二酚A二環氧甘油醚單水合物(bisphenol A (2,3-dihydroxypropyl) glycidyl ether, BADGE•H2O)、丙二酚A二環氧甘油醚二水合物(bisphenol A bis(2,3-dihydroxypropyl) ether, BADGE•2H2O)]及3種含氯化合物[丙二酚A二環氧甘油醚氫氯化物(bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether, BADGE•HCl)、丙二酚A二環氧甘油醚二氫氯化物(bisphenol A bis(3-chloro-2-hydroxypropyl) ether, BADGE•2HCl)和丙二酚A二環氧甘油醚水合物氫氯化物(bisphenol A (3-chloro-2-hydroxypropyl) (2,3-dihydroxypropyl) ether, BADGE• H2O•HCl)],亦具有不同程度的毒性。為瞭解金屬罐容器及罐裝飲料中此類化合物可能溶出情形,必須建立一套簡單、快速、穩定之同步檢測法。本研究以高效液相層析法,配合螢光檢出器檢測,使用之層析管柱為Phenomenex Luna C18(2) (25 cm × 4.6 mm i.d., 5 μm thickness),以乙腈/水/甲醇梯度移動相溶液,於激發波長230 nm、放射波長304 nm可同時檢測上述7種化合物。16件金屬罐檢體採用水、4%醋酸溶液、20%乙醇溶液及正庚烷為食品模擬溶液,進行溶出試驗,結果僅3件檢體檢出BPA,其溶出量為0.002∼0.003 mg/dm2;BADGE及其水合物之總溶出量為未檢出∼0.065 mg/dm2;含氯化合物之總溶出量為未檢出∼0.02 mg/dm2。
罐裝飲料之檢驗方法依基質類型,分別以甲基第三丁基醚或乙腈萃取,經乙腈飽和之正己烷去油脂,再以Sep-Pak C18及Sep-Pak Florisil過濾層析匣淨化,或直接濾膜過濾後,以高效液相層析儀分析定量。添加0.2、0.4及0.8 μg/g混合標準溶液於咖啡檢體中,其平均回收率為80.9∼108.8%,變異係數皆小於5.5%;添加0.05、0.1及0.2 μg/g混合標準溶液於番茄汁檢體中,其平均回收率為81.1∼109.8%,變異係數皆小於5.7%。本檢驗方法之檢出限量BADGE•2H2O、BADGE•H2O•HCl及BADGE•2HCl均為0.003 ppm,BPA、BADGE、BADGE•H2O及BADGE•HCl均為0.005 ppm。將此方法應用於38件市售罐裝飲料之分析檢驗,結果發現,BPA含量為未檢出∼0.173 ppm;BADGE及其水合物之總含量為未檢出∼2.695 ppm;含氯化合物之總含量為未檢出∼0.663 ppm。以上調查結果均符合歐盟規範。 Metal can is a major food packaging material. There is usually a resin coating in the interior wall to protect metal from corrosion. However, the resin in contact with food might result in migration of its components such as bisphenol A (BPA) and the monomer of bisphenol A diglycidyl ether (BADGE). BPA belongs to a group of hor-mone disruptors. BADGE is classified as a mutagen and may readily form hydrolyzed products and chlorohydrin products in food, including bisphenol A (2.3-dihydroxypropyl) glycidyl ether (BADGE•H2O), bisphenol A bis(2,3-dihydroxy propyl) ether (BADGE•2H2O), bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether (BADGE•HCl), bisphenol A bis(3-chloro-2-hydroxypropyl) ether (BADGE•2HCl), and bisphenol A (3-chloro-2-hydroxypropyl) (2,3-dihydroxypropyl) ether (BADGE• H2O•HCl). These derivatives also have different degrees of toxicity. For monitoring the status of migration of these compounds in metal cans, we need to establish a simple, fast, and stable procedure to analyze these 7 compounds simtanenously. A quantitative method using high performance liquid chromatography (HPLC) coupled with a fluo-rescence detector was therefore developed to assay these compounds. The chroma-tographic separation was accomplished by gradient elution of acetonitrile, water and methanol on a Phenomenex Luna C18(2) column (25 cm × 4.6 mm i.d., 5 μm thickness) with a fluorescence detector at 230 nm excitation and 304 nm emission. Migration tests were performed using water, 4% acetic acid solution, 20% ethanol solution and n-heptane as food simulants in a total of 16 metal cans. The results showed that the mi-gration of BPA occurred in only 3 samples in the range of 0.002∼0.003 mg/dm2, and those of BADGE hydrolyzed products and chlorohydrin products were in the range of N.D.∼0.065 mg/dm2 and N.D.∼0.02 mg/dm2, respectively. Depending on the composition of canned drinks, these 7 compounds were ex-tracted with tert-butyl methyl ether or acetonitrile, defatted with n-hexane, cleaned up with Sep-Pak C18 and Florisil, and then analyzed by HPLC. Recovery studies were performed by spiking standard compounds into tomato juice at 0.05, 0.1 and 0.2 μg/g levels and into coffee at 0.2, 0.4 and 0.8 μg/g levels, respectively. Average recoveries in both studies were higher than 80%, and the coefficients of variation were less than 5.7%. The detection limits were 0.003 ppm for BADGE•2H2O, BADGE•H2O•HCl and BADGE•2HCl, and 0.005 ppm for BPA, BADGE, BADGE•H2O and BADGE•HCl. This method was tested in a survey of 38 canned drink samples which were purchased from markets. The results showed that the amounts of bisphenol A, BADGE and its hydro-lyzed and chlorohydrin products were in the range of N.D. ~ 0.173 ppm, N.D. ~ 2.695 ppm, and N.D. ~ 0.663 ppm, respectively, which were in conformity with the regulation of European Union. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/37474 |
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