分散液液微萃取结合气相色谱-四极杆/飞行时间质谱法同时测定饮料中21种邻苯二甲酸酯
|
摘要
目的建立分散液液微萃取(dispersiveliquid-liquidmicroextraction,DLLME)结合气相色谱-四极杆/飞行时间质谱法(gas chromatography high resolution quadrupole time of flight mass spectrometry, GC-Q-TOF/MS)同时测定饮料中21种邻苯二甲酸酯(phthalic acid esters, PAEs)的分析方法。方法样品经正丙醇分散,四氯化碳提取,氮气吹干,正己烷复溶。在该优化的色谱及质谱条件下,采用电子轰击离子源,全扫描方式采集数据,根据碎片离子的精确质量数定性定量。结果 21种邻苯二甲酸酯在5.0～1000.0μg/L范围内呈良好线性关系,相关系数r均大于0.9985,平均回收率为70.1%～109.9%,检出限为1.0～5.0μg/L,定量限为3.0～16.0μg/L,相对标准偏差为3.02%～6.68%。结论该方法具有操作简便、高效快速、回收率高、灵敏度高等优点,可用于分析测定饮料中的21种邻苯二甲酸酯。
Objective To establish a method for determination of 21 kinds of phthalic acid esters(PAEs) in beverage by dispersive liquid-liquid microextraction(DLLME) coupled with gas chromatography-high resolution quadrupole time-of-flight mass spectrometry(GC-Q-TOF/MS). Methods Samples were extracted with N-propanol and carbon tetrachloride, then dried by nitrogen and dissolved with hexane. Under the optimized chromatographic and mass spectral conditions, the result data was obtained with electron impact ion source(EI) and total scan mode. Accurate qualitatuve and quantitative analysis based on the exact mass number of fragment ions were achieved. Results The calibration curves of 21 kinds of PAEs showed good linearities within the concentrations of 5.0-1000.0 μg/L(r>0.9985). The corresponding average recoveries were in the range of 70.1%-109.9%. Futher, the limits of detection(LODs) and the limits of quantitation(LOQs) of the method were 1.0-5.0 μg/L and 3.0-16.0 μg/L, respectively. The relative standard deviations(RSDs) were 3.02%-6.68%. Conclusion This method shows the advantages of simple operation, high efficiency and time-saving, with a high recovery rate as well as a high sensitivity. The method is suitable for the determination of 21 phthalates in beverages.
Objective To establish a method for determination of 21 kinds of phthalic acid esters(PAEs) in beverage by dispersive liquid-liquid microextraction(DLLME) coupled with gas chromatography-high resolution quadrupole time-of-flight mass spectrometry(GC-Q-TOF/MS). Methods Samples were extracted with N-propanol and carbon tetrachloride, then dried by nitrogen and dissolved with hexane. Under the optimized chromatographic and mass spectral conditions, the result data was obtained with electron impact ion source(EI) and total scan mode. Accurate qualitatuve and quantitative analysis based on the exact mass number of fragment ions were achieved. Results The calibration curves of 21 kinds of PAEs showed good linearities within the concentrations of 5.0-1000.0 μg/L(r>0.9985). The corresponding average recoveries were in the range of 70.1%-109.9%. Futher, the limits of detection(LODs) and the limits of quantitation(LOQs) of the method were 1.0-5.0 μg/L and 3.0-16.0 μg/L, respectively. The relative standard deviations(RSDs) were 3.02%-6.68%. Conclusion This method shows the advantages of simple operation, high efficiency and time-saving, with a high recovery rate as well as a high sensitivity. The method is suitable for the determination of 21 phthalates in beverages.
引文
[1]Kim IY,Han SY,Moon AJ.Phthalates inhibit tamoxifen-induced apoptosis in mcf-7 human breast cancer cells[J].Toxicol Env Heal A,2004,67(23-24):2025.
[2]Hsieh TH,Tsai CF,Hsu CY,et al.N-Butyl benzyl phthalate promotes breast cancer progression by inducing expression of lymphoid enhancer factor 1[J].Plos One,2012,7(8):e42750.
[3]Swan SH,Main KM,Liu F,et al.Decrease in anogenital distance among male infant with prenatal phthalate exposure[J].Environ Health Persp,2005,113(8):1056-1061.
[4]Foster PM,Mylchreest E,Gaido KW,et al.Effects of phthalate esters on the developing reproductive tract of male rats[J].Apmis,2015,109(S103):272-277.
[5]Loff PDS,Subotic U,Oulmi-Kagermann,et al.Diethylhexylphthalate extracted by typical newborn lipid emulsions from polyvinylchloride infusion systems causes significant changes in histology of rabbit liver[J].JPEN-Parenter Enter,2007,31(3):188.
[6]Miura Y,Naito M,Ablake M,et al.Short-term effects of di-(2-ethylhexyl)phthalate on testes,liver,kidneys and pancreas in mice[J].Asian J Androl,2007,9(2):199-205.
[7]Akingbemi BT,Ge R,Klinefelter GR,et al.Phthalate-induced leydig cell hyperplasia is associated with multiple endocrine disturbances[J].P Nalt Acad Sci USA.2004,101(3):775-780.
[8]Araki A,Mitsui T,Miyashita C,et al.Association between maternal exposure to di(2-ethylhexyl)phthalate and reproductive hormone levels in fetal blood the Hokkaido study on environment and children's health[J].Plos One,2014,9(10):e109039.
[9]Spade DJ,Hall SJ,Saffarini CM,et al.Differential response to abiraterone acetate and di-n-butyl phthalate in an androgen-sensitive human fetal testis xenograft bioassay[J].Toxicol Sci,2014,138(1):148.
[10]Orsi DD,Gagliardi L,PorràR,et al.A environmentally friendly reversed-phase liquid chromatography method for phthalates determination in nail cosmetics[J].Anal Chim Acta,2006,555(2):238-241.
[11]USA Consumer Product Safety Improvement Act(CPSIA)of 2008[S].
[12]Directives.Commission Directive 2007/19/EC of 30 march 2007amending Directive 2002/72/EC relating to plastic materials and articles intended to come into contact with food and Council Directive85/572/EEC laying down the list of simulants to be used for testing migration of constituents of plastic materials and articles intended to come into contact with foodstuffs[S].
[13]GB 9685-2016食品安全国家标准食品接触材料及制品用添加剂使用标准[S].GB 9685-2016 National food safety standard-Hygienic standards for uses of additives in food containers and packaging materials[S].
[14]食品中可能违法添加的非食用物质和易滥用的食品添加剂名单(第六批)(卫生部公告2011年第16号)[EB/OL].http://www.gov.cn/gzdt/2011-06/01/content_1875150.htm.List of non-edible substances and misusable food additives that may be illegally added in food(sixth batch)(Ministry of Health Announcement No.16 of 2011)[EB/OL].http://www.gov.cn/gzdt/2011-06/01/content_1875150.htm.
[15]董蔚,郭凯,李贺贺,等.Qu ECh ERS-GC-MS联用法检测大麦中14种邻苯二甲酸酯类塑化剂及基质效应的影响[J].食品科学,2016,37(24):156-163.Dong W,Guo K,Li HH,et al.Validation of a QuEChERS-based gas chromatography-mass spectrometry method for analysis of 14 phthalate esters in barley with focus on matrix effects[J].Food Sci,2016,37(24):156-163.
[16]陈秋丽,张朝升,刘宏英,等.生物活性炭降解低浓度邻苯二甲酸酯的挂膜研究[J].中国给水排水,2017,33(1):12-16.Chen QL,Zhang CS,Liu HY,et al.Determination of phthalate acid esters in water by solid-phase extraction and GC-MS[J].Chin Water Wastewater,2017,33(1):12-16.
[17]李拥军,熊文明,陈坚文,等.固相萃取/高效液相色谱-串联质谱法测定罗非鱼中9种邻苯二甲酸酯[J].分析测试学报,2012,31(3):278-283.Li YJ,Xiong WM,Chen JW,et al.Determination of nine phthalic acid esters in tilapia by solid phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry[J].J Instrum Anal,2012,31(3):278-283.
[18]张海婧,胡小键,林少彬.固相萃取-超高效液相色谱串联质谱法测定饮用水中15种邻苯二甲酸酯[J].分析化学,2014,42(9):1281-1287.Zhang HJ,Hu XJ,Lin SB.Determination of 15 phthalate esters in drinking water by solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry[J].Chin J Anal Chem,2014,42(9):1281-1287.
[19]张泽明,张洪海,李建龙,等.固相微萃取-气相色谱-质谱联用测定海水与沉积物中邻苯二甲酸酯类污染物[J].分析化学,2017,45(3):348-356.Zhang ZM,Zhang HH,Li JL,et al.Determination of phthalic acid esters in seawater and sediment by solid-phase microextraction and gas chromatography-mass spectrometry[J].Chin J Anal Chem,2017,45(3):348-356.
[20]李正义,张金龙,殷乐,等.气相色谱-质谱法测定橡皮擦中五种邻苯二甲酸酯增塑剂含量[J].分析科学学报,2017,33(1):52-56.Li ZY,Zhang JL,Yin Y,et al.Determination of five phthalate acid esters plasticizers in eraser by gas chromatography-mass spectrometry[J].J Anal Sci,2017,33(1):52-56.
[21]王春,翟俊峰,黄雪梅,等.基于超分子溶剂分散液液微萃取技术测定食品接触材料中8种邻苯二甲酸酯的迁移量[J].质谱学报,2019,40(1):21-31.Wang C,Zhai JF,Huang XM,et al.Migration of 8 phthalic acid esters from food contact materials by supramolecular solvents-based dispersive liquid-liquid microextraction[J].Chin Mass Spectr Soc,2019,40(1):21-31.
[22]贾宁,许恒智,胡亚丽,等.固相萃取-气相色谱法测定北京市水样中的邻苯二甲酸酯[J].分析试验室,2005,(11):23-26.Jia N,Xu HZ,Hu YL,et al.Determination of the phthalates in water samples in Beijing city by solid-phase extraction and gas chromatography[J].Chin J Anal Lab,2005,(11):23-26.
[23]李婷,汤智,洪武兴.分散固相萃取-气相色谱-质谱法测定含油脂食品中17种邻苯二甲酸酯[J].分析化学,2012,40(3):391-396.Li T,Tang Z,Hong WX.Determination of 17 phthalic acid esters in fatty food by dispersive solid phase extraction-gas chromatography-mass spectrometry[J].Chin J Anal Chem,2012,40(3):391-396.
[24]郑向华,林立毅,方恩华,等.固相萃取-气相色谱-质谱法测定食品中23种邻苯二甲酸酯[J].色谱,2012,30(1):27-32.Zheng XH,Lin LY,Fang EH,et al.Determination of 23 phthalate esters in food by solid-phase extraction coupled with gas chromatography-mass spectrometry[J].Chin J Chromatogr,2012,30(1):27-32.
[25]王莉,王斌,董浩,等.GC-MS/MS法对焙烤食品及其塑料包装材料中25种磷酸三酯类与邻苯二甲酸酯类化合物的同时测定[J].分析测试学报,2017,36(11):1287-1295.Wang L,Wang B,Dong H,et al.Simultaneous determination of 25organophosphate esters and phthalate esters compounds in baked foods and plastic packing materials by GC-MS/MS[J].J Instrum Anal,2017,36(11):1287-1295.
[2]Hsieh TH,Tsai CF,Hsu CY,et al.N-Butyl benzyl phthalate promotes breast cancer progression by inducing expression of lymphoid enhancer factor 1[J].Plos One,2012,7(8):e42750.
[3]Swan SH,Main KM,Liu F,et al.Decrease in anogenital distance among male infant with prenatal phthalate exposure[J].Environ Health Persp,2005,113(8):1056-1061.
[4]Foster PM,Mylchreest E,Gaido KW,et al.Effects of phthalate esters on the developing reproductive tract of male rats[J].Apmis,2015,109(S103):272-277.
[5]Loff PDS,Subotic U,Oulmi-Kagermann,et al.Diethylhexylphthalate extracted by typical newborn lipid emulsions from polyvinylchloride infusion systems causes significant changes in histology of rabbit liver[J].JPEN-Parenter Enter,2007,31(3):188.
[6]Miura Y,Naito M,Ablake M,et al.Short-term effects of di-(2-ethylhexyl)phthalate on testes,liver,kidneys and pancreas in mice[J].Asian J Androl,2007,9(2):199-205.
[7]Akingbemi BT,Ge R,Klinefelter GR,et al.Phthalate-induced leydig cell hyperplasia is associated with multiple endocrine disturbances[J].P Nalt Acad Sci USA.2004,101(3):775-780.
[8]Araki A,Mitsui T,Miyashita C,et al.Association between maternal exposure to di(2-ethylhexyl)phthalate and reproductive hormone levels in fetal blood the Hokkaido study on environment and children's health[J].Plos One,2014,9(10):e109039.
[9]Spade DJ,Hall SJ,Saffarini CM,et al.Differential response to abiraterone acetate and di-n-butyl phthalate in an androgen-sensitive human fetal testis xenograft bioassay[J].Toxicol Sci,2014,138(1):148.
[10]Orsi DD,Gagliardi L,PorràR,et al.A environmentally friendly reversed-phase liquid chromatography method for phthalates determination in nail cosmetics[J].Anal Chim Acta,2006,555(2):238-241.
[11]USA Consumer Product Safety Improvement Act(CPSIA)of 2008[S].
[12]Directives.Commission Directive 2007/19/EC of 30 march 2007amending Directive 2002/72/EC relating to plastic materials and articles intended to come into contact with food and Council Directive85/572/EEC laying down the list of simulants to be used for testing migration of constituents of plastic materials and articles intended to come into contact with foodstuffs[S].
[13]GB 9685-2016食品安全国家标准食品接触材料及制品用添加剂使用标准[S].GB 9685-2016 National food safety standard-Hygienic standards for uses of additives in food containers and packaging materials[S].
[14]食品中可能违法添加的非食用物质和易滥用的食品添加剂名单(第六批)(卫生部公告2011年第16号)[EB/OL].http://www.gov.cn/gzdt/2011-06/01/content_1875150.htm.List of non-edible substances and misusable food additives that may be illegally added in food(sixth batch)(Ministry of Health Announcement No.16 of 2011)[EB/OL].http://www.gov.cn/gzdt/2011-06/01/content_1875150.htm.
[15]董蔚,郭凯,李贺贺,等.Qu ECh ERS-GC-MS联用法检测大麦中14种邻苯二甲酸酯类塑化剂及基质效应的影响[J].食品科学,2016,37(24):156-163.Dong W,Guo K,Li HH,et al.Validation of a QuEChERS-based gas chromatography-mass spectrometry method for analysis of 14 phthalate esters in barley with focus on matrix effects[J].Food Sci,2016,37(24):156-163.
[16]陈秋丽,张朝升,刘宏英,等.生物活性炭降解低浓度邻苯二甲酸酯的挂膜研究[J].中国给水排水,2017,33(1):12-16.Chen QL,Zhang CS,Liu HY,et al.Determination of phthalate acid esters in water by solid-phase extraction and GC-MS[J].Chin Water Wastewater,2017,33(1):12-16.
[17]李拥军,熊文明,陈坚文,等.固相萃取/高效液相色谱-串联质谱法测定罗非鱼中9种邻苯二甲酸酯[J].分析测试学报,2012,31(3):278-283.Li YJ,Xiong WM,Chen JW,et al.Determination of nine phthalic acid esters in tilapia by solid phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry[J].J Instrum Anal,2012,31(3):278-283.
[18]张海婧,胡小键,林少彬.固相萃取-超高效液相色谱串联质谱法测定饮用水中15种邻苯二甲酸酯[J].分析化学,2014,42(9):1281-1287.Zhang HJ,Hu XJ,Lin SB.Determination of 15 phthalate esters in drinking water by solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry[J].Chin J Anal Chem,2014,42(9):1281-1287.
[19]张泽明,张洪海,李建龙,等.固相微萃取-气相色谱-质谱联用测定海水与沉积物中邻苯二甲酸酯类污染物[J].分析化学,2017,45(3):348-356.Zhang ZM,Zhang HH,Li JL,et al.Determination of phthalic acid esters in seawater and sediment by solid-phase microextraction and gas chromatography-mass spectrometry[J].Chin J Anal Chem,2017,45(3):348-356.
[20]李正义,张金龙,殷乐,等.气相色谱-质谱法测定橡皮擦中五种邻苯二甲酸酯增塑剂含量[J].分析科学学报,2017,33(1):52-56.Li ZY,Zhang JL,Yin Y,et al.Determination of five phthalate acid esters plasticizers in eraser by gas chromatography-mass spectrometry[J].J Anal Sci,2017,33(1):52-56.
[21]王春,翟俊峰,黄雪梅,等.基于超分子溶剂分散液液微萃取技术测定食品接触材料中8种邻苯二甲酸酯的迁移量[J].质谱学报,2019,40(1):21-31.Wang C,Zhai JF,Huang XM,et al.Migration of 8 phthalic acid esters from food contact materials by supramolecular solvents-based dispersive liquid-liquid microextraction[J].Chin Mass Spectr Soc,2019,40(1):21-31.
[22]贾宁,许恒智,胡亚丽,等.固相萃取-气相色谱法测定北京市水样中的邻苯二甲酸酯[J].分析试验室,2005,(11):23-26.Jia N,Xu HZ,Hu YL,et al.Determination of the phthalates in water samples in Beijing city by solid-phase extraction and gas chromatography[J].Chin J Anal Lab,2005,(11):23-26.
[23]李婷,汤智,洪武兴.分散固相萃取-气相色谱-质谱法测定含油脂食品中17种邻苯二甲酸酯[J].分析化学,2012,40(3):391-396.Li T,Tang Z,Hong WX.Determination of 17 phthalic acid esters in fatty food by dispersive solid phase extraction-gas chromatography-mass spectrometry[J].Chin J Anal Chem,2012,40(3):391-396.
[24]郑向华,林立毅,方恩华,等.固相萃取-气相色谱-质谱法测定食品中23种邻苯二甲酸酯[J].色谱,2012,30(1):27-32.Zheng XH,Lin LY,Fang EH,et al.Determination of 23 phthalate esters in food by solid-phase extraction coupled with gas chromatography-mass spectrometry[J].Chin J Chromatogr,2012,30(1):27-32.
[25]王莉,王斌,董浩,等.GC-MS/MS法对焙烤食品及其塑料包装材料中25种磷酸三酯类与邻苯二甲酸酯类化合物的同时测定[J].分析测试学报,2017,36(11):1287-1295.Wang L,Wang B,Dong H,et al.Simultaneous determination of 25organophosphate esters and phthalate esters compounds in baked foods and plastic packing materials by GC-MS/MS[J].J Instrum Anal,2017,36(11):1287-1295.