凝胶渗透色谱-气相色谱-串联质谱法测定牛奶中的两种光引发剂
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摘要
建立了采用凝胶渗透色谱(GPC)为净化方式的牛奶中外源性光引发剂二苯甲酮(BP)和4-甲基二苯甲酮(MBP)的气相色谱–串联质谱(GC–MS/MS)测定方法。样品采用乙腈超声辅助提取,经环己烷–乙酸乙酯(体积比为1∶1)溶剂转化后用GPC净化,再通过HP–5MS气相色谱柱分离,最后经串联四极杆质谱仪检测器进行定性、定量同时分析。该方法的线性范围为5～100μg/L,BP和MBP的线性相关系数(r2)分别为0.997 2和0.998 4,方法定量限均为0.025 mg/kg。在空白牛奶样品中加入0.05,0.25,0.50 mg/kg 3个浓度水平的BP和MBP,BP和MBP的平均回收率为74.0%～92.0%,测定结果的相对标准偏差为5.5%～10.9%(n=6)。该方法具有灵敏度高、准确度和精密度好的优点,适合牛奶中BP和MBP两种光引发剂的检测。
A novel analytical method based on gel permeation chromatography(GPC)–gas chromatography tandem mass spectrometry(GC–MS/MS) technique was developed to determinate the contents of two photoinitiators benzophenone(BP) and 4-methylbenzophenone(MBP) in milk. The target compounds were firstly extracted by ultrasound–assisted extraction method using acetonitrile as the extraction solvents,and then purified and enriched by GPC technique. Qualitative and quantitative analyses were carried out for the analytes under tandem mass spectrometry after the chromatographic separation on a HP–5 MS capillary chromatographic column. The results showed that the method had a good linear range from 5 to 100 μg/L,and the correlation coefficients(r2) were 0.997 2 and 0.998 4 for BP and MBP,respectively. The limits of quantification were both 0.025 mg/kg. By adding three different concentrations of 0.05,0.25, 0.50 mg/kg of BP and MBP into the blank milk samples,the recoveries were obtained in the range of 74.0%–92.0% with the relative standard deviations of 5.5%–10.9%(n=6). The method is sensitive,accurate and suitable for the determination of BP and MBP in milk.
A novel analytical method based on gel permeation chromatography(GPC)–gas chromatography tandem mass spectrometry(GC–MS/MS) technique was developed to determinate the contents of two photoinitiators benzophenone(BP) and 4-methylbenzophenone(MBP) in milk. The target compounds were firstly extracted by ultrasound–assisted extraction method using acetonitrile as the extraction solvents,and then purified and enriched by GPC technique. Qualitative and quantitative analyses were carried out for the analytes under tandem mass spectrometry after the chromatographic separation on a HP–5 MS capillary chromatographic column. The results showed that the method had a good linear range from 5 to 100 μg/L,and the correlation coefficients(r2) were 0.997 2 and 0.998 4 for BP and MBP,respectively. The limits of quantification were both 0.025 mg/kg. By adding three different concentrations of 0.05,0.25, 0.50 mg/kg of BP and MBP into the blank milk samples,the recoveries were obtained in the range of 74.0%–92.0% with the relative standard deviations of 5.5%–10.9%(n=6). The method is sensitive,accurate and suitable for the determination of BP and MBP in milk.
引文
[1]张居舟,李静,何俊,等.基于凝胶渗透色谱-气相色谱串联质谱法的食品包装印刷油墨中光引发剂的测定[J].中国印刷与包装研究,2014,6(6):118-123.
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[10]李灿明,柏建国,陈江龙,等.LC-DAD-FLD法测定金属包装彩印面3种光引发剂的迁移量[J].包装工程,2017,9(2):68-73.
[11]韩伟,于艳军,李宁涛,等.气相色谱-质谱法测定食品接触材料表面印刷油墨中的光引发剂[J],色谱,2011,29(5):417-421.
[12]徐文泱,刘漾伦,刘宇,等.气相色谱-质谱法检测湘式挤压糕点中4种光引发剂[J].食品安全质量检测学报,2017(10):3 980-3 986.
[13]SAGRATINI G,CAPRIOLI G,CRISTALLI G,et al.Determination of ink photoinitiators in packaged beverages by gas chromatography-mass spectrometry and liquid chromatographymass spectrometry[J].Chromatogr A,2008,1194:213-220.
[14]赵凯,周勇,丁枫芸,等.婴幼儿塑料奶瓶中二苯甲酮和4-甲基二苯甲酮等光引发剂的UHPLC-MS/MS测定[J].塑料科技,2018(3):125-128.
[15]李建勋,孙梦园,胡雪艳,等.顶空固相微萃取结合气相色谱-三重四极杆质谱法快速测定茶叶中11种酰胺类除草剂残留[J].分析测试学报,2017,36(11):1 339-1 345.
[16]颜鸿飞,王美玲,陈练,等.固相萃取-气相色谱-串联质谱法测定茶叶中9种农药残留量[J].化学分析计量,2016,25(6):62-66.
[17]Commission Decision of 14 August 2002 Implementing Council Directive 96/23/EC Concerning the Performance of Analytical Methods and the Interpretation of Results(2002/657/EC)[S].
[2]张居舟,陶固帅,尚光志,等.超高效液相色谱-串联质谱法测定食品塑料包装材料中5种光引发剂及其迁移规律[J].理化检验(化学分册),2017,53(11):1 246-1 251.
[3]RHODES M C,BUCHER J R,PECKHAM J C,et al.Carcinogenesis studies of benzophenone in rats and mice[J].Food chem toxicol,2007,45(5):843-851.
[4]MICHAEL H H,ERIN C G,BENCHUN L,et al.In utero exposure to benzophenone-2 causes hypospadias throughan estrogen receptor dependent mechanism[J].J Urol,2007,178(4):1 637-1 642.
[5]韩伟,于艳军,李宁涛,等.食品接触材料表面印刷油墨中光引发剂的高效液相色谱-串联质谱法检测和迁移研究[J].分析化学,2011,39(9):1 387-1 393.
[6]CAI H M,JI S L,ZHANG J Z,et al.Migration kinetics of four photo-initiators from paper food packaging to solid food stimulants[J].Food additives&contaminants:part A,2017,34(9):1 632-1 642.
[7]黄秀玲,王志伟,胡长鹰,等.毛细管气相色谱法分析UV墨中光引发剂Irgacure-184和Irgacure-651[J].包装工程,2008,29(10):96-98.
[8]ANDERSON W A C,CASTLE L.Benzophenone in cartonboard packaging materials and the factors that influence its migration into food[J].Food addit contam,2003,20:607-618.
[9]Conclusions of the Meeting of 06 March 2009 Standing committee on the food chain and animal health,section toxicological safety[R].European commission health and consumers directorate-general,Brussels,06 March 2009.
[10]李灿明,柏建国,陈江龙,等.LC-DAD-FLD法测定金属包装彩印面3种光引发剂的迁移量[J].包装工程,2017,9(2):68-73.
[11]韩伟,于艳军,李宁涛,等.气相色谱-质谱法测定食品接触材料表面印刷油墨中的光引发剂[J],色谱,2011,29(5):417-421.
[12]徐文泱,刘漾伦,刘宇,等.气相色谱-质谱法检测湘式挤压糕点中4种光引发剂[J].食品安全质量检测学报,2017(10):3 980-3 986.
[13]SAGRATINI G,CAPRIOLI G,CRISTALLI G,et al.Determination of ink photoinitiators in packaged beverages by gas chromatography-mass spectrometry and liquid chromatographymass spectrometry[J].Chromatogr A,2008,1194:213-220.
[14]赵凯,周勇,丁枫芸,等.婴幼儿塑料奶瓶中二苯甲酮和4-甲基二苯甲酮等光引发剂的UHPLC-MS/MS测定[J].塑料科技,2018(3):125-128.
[15]李建勋,孙梦园,胡雪艳,等.顶空固相微萃取结合气相色谱-三重四极杆质谱法快速测定茶叶中11种酰胺类除草剂残留[J].分析测试学报,2017,36(11):1 339-1 345.
[16]颜鸿飞,王美玲,陈练,等.固相萃取-气相色谱-串联质谱法测定茶叶中9种农药残留量[J].化学分析计量,2016,25(6):62-66.
[17]Commission Decision of 14 August 2002 Implementing Council Directive 96/23/EC Concerning the Performance of Analytical Methods and the Interpretation of Results(2002/657/EC)[S].