超高效合相色谱-串联质谱法测定口含烟中对羟基苯甲酸酯
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摘要
建立了QuEChERS-超高效合相色谱-串联质谱法(UPC2-MS/MS)测定口含烟中对羟基苯甲酸酯类防腐剂。采用乙腈提取,基质分散固相萃取净化,UPC2 TM HSS C18SB色谱柱(3.0mm×100mm×1.8μm)分离,内标法定量。优化后的对羟基苯甲酸酯的合相色谱分离条件为:主要流动相为CO2,改性剂为甲醇-异丙醇混合溶液(V/V,1∶1),系统流速1.5mL/min,离子化辅助溶剂(补偿溶剂)为0.1%甲酸-甲醇溶液,动态备压1.03×10~7 Pa,柱温55℃,可在3min内完成单个样品分析。4种成分的线性范围均为0.5~5.0mg/kg;在低、中、高加标水平下,方法的平均回收率为94.6%~105.6%,相对标准偏差小于5%。实际样品测定结果表明,单个成分的含量和多种成分的总含量均小于10 mg/kg,低于GB 2760—2014对于此类防腐剂在食品中添加限量的要求。该方法环境友好、高效、准确,适用于口含烟中对羟基苯甲酸酯类物质的测定。
An effective analytical method using QuEChERS coupled with ultra-performance convergence chromatography-tandem mass spectrometry(UPC2-MS/MS)for determination of p-hydroxybenzoic esters(parabens)in snus was developed.In the present work,acetonitrile was selected as extraction solvent,extraction kit(25 mg PSA,7.5 mg Carbon,150 mg MgSO_4)was evaluted to purify samples.The target analytes were separated on UPC2 TM HSS C18 SB(3.0 mm×100 mm×1.8μm)column,and quantified by internal standard method.The optimal separation conditions on UPC2 were as follows:the main mobile phase was CO_2,and modifier was methanol-isopropanol(V/V,1∶1),the flow rate was 1.5 mL/min,the assistant ionization solvent(compensate solvent)was methanol with 0.1%formic acid,the pressure of automated backpressure regulator(ABPR)was 1.03×107 Pa,and the temperature of column was55℃,the single analysis would complete within 3 min.The calibration curves are linear in the range of 0.5-5.0 mg/kg.The average recoveries of three addition levels are in the range of 94.6%-105.6% with RSD less than 5%.The detection results showed that parabens contents in snus are lower than the limits regulated by national standard GB 2760—2014(<10 mg/kg).The proposed method is environmental friendly,high efficiency,accurate,which is suitable for analysis of parabens in snus.
An effective analytical method using QuEChERS coupled with ultra-performance convergence chromatography-tandem mass spectrometry(UPC2-MS/MS)for determination of p-hydroxybenzoic esters(parabens)in snus was developed.In the present work,acetonitrile was selected as extraction solvent,extraction kit(25 mg PSA,7.5 mg Carbon,150 mg MgSO_4)was evaluted to purify samples.The target analytes were separated on UPC2 TM HSS C18 SB(3.0 mm×100 mm×1.8μm)column,and quantified by internal standard method.The optimal separation conditions on UPC2 were as follows:the main mobile phase was CO_2,and modifier was methanol-isopropanol(V/V,1∶1),the flow rate was 1.5 mL/min,the assistant ionization solvent(compensate solvent)was methanol with 0.1%formic acid,the pressure of automated backpressure regulator(ABPR)was 1.03×107 Pa,and the temperature of column was55℃,the single analysis would complete within 3 min.The calibration curves are linear in the range of 0.5-5.0 mg/kg.The average recoveries of three addition levels are in the range of 94.6%-105.6% with RSD less than 5%.The detection results showed that parabens contents in snus are lower than the limits regulated by national standard GB 2760—2014(<10 mg/kg).The proposed method is environmental friendly,high efficiency,accurate,which is suitable for analysis of parabens in snus.
引文
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[2]THYSSEN J P,ENGKILDE K,LUNDOV MD,et al.Temporal trends of preservative allergy in Denmark(1985-2008)[J].Contact Dermatitis,2010,62(2):102-108.
[3]EFSA.Opinion of the scientific panel on food additives,flavourings,processing aids and materials in contact with food on a request from the Commission related to p-hydroxybenzoates(E214-219)[J].The EFSA Journal,2004,83:1-26.
[4]GB 2760-2011食品添加剂使用卫生标准[S].北京:中国标准出版社,2007.
[5]POTOURIDIS T,BERGER E,PTTMANNW.Analysis of alkyl esters of p-hydroxybenzoic acid(parabens)in baby teethers via gas chromatographyquadrupole mass spectrometry(GC-qMS)using a stable isotope dilution assay(SIDA)[J].Analytical Methods,2016,8(17):3 466-3 474.
[6]邱松山,姜翠翠,周如金,等.对羟基苯甲酸酯类化合物抗菌活性的定量构效关系探讨[J].现代食品科技,2014,30(6):98-102.QIU Songshan,JIANG Cuicui,ZHOU Rujin,et al.A QSAR study on antibacterial activity of p-hydroxybenzoate esters[J].Modern Food Science and Technology,2014,30(6):98-102(in Chinese).
[7]PHILLIPS J C,TOPP C S,GANGOLLI S D.The metabolism of ethyl and n-propyl-p-hydroxybenzoate(parabens)in male cats[J].Toxicology Letters,1978,2(4):237-242.
[8]ROUTLEDGE E J,PARKER J,ODUM J,et al.Some alkyl hydroxy benzoate preservatives(parabens)are estrogenic[J].Toxicology and Applied Pharmacology,1998,153(1):12-19.
[9]PUGAZHENDHI D,POPE G S,DARBRE PD.Oestrogenic activity of p-hydroxybenzoic acid(common metabolite of paraben esters)and methylparaben in human breast cancer cell lines[J].Journal of Applied Toxicology,2005,25(4):301-309.
[10]HARVEY P W,EVERETT D J.Significance of the detection of esters of p-hydroxybenzoic acid(parabens)in human breast tumours[J].Journal of Applied Toxicology,2004,24(1):1-4.
[11]EU.Commission Regulation No 358/2014of 9April 2014amending Annexes II and V to Regulation(EC)No 1223/2009of the European Parliament and of the Council on cosmetic products(Text with EEA relevance).
[12]李鹏,王申,张东豫,等.行业标准方法测试口含烟化学指标的适用性[J].烟草科技,2016,49(9):57-62.LI Peng,WANG Shen,ZHANG Dongyu,et al.Suitability of industrial standard methods in testing chemical constituents of oral tobacco products[J].Tobacco Science&Technology,2016,49(9):57-62(in Chinese).
[13]BLANCO E,CASAIS M C,MEJUTO M C,et al.Combination of off-line solid-phase extraction and on-column sample stacking for sensitive determination of parabens and p-hydroxybenzoic acid in waters by non-aqueous capillary electrophoresis[J].Analytica Chimica Acta,2009,647(1):104-111.
[14]高海军,李勇,严飞龙,等.气相色谱法测定食品中6种对羟基苯甲酸酯及其钠盐[J].粮油食品科技,2011,19(3):45-48.GAO Haijun,LI Yong,YAN Feilong,et al.Study on determination of 6parabens and their sodium salts in food by gas chromatography[J].Science and Technology of Cereals,Oils and Foods,2011,19(3):45-48(in Chinese).
[15]JAIN R,MUDIAM M K,CHAUHAN A,et al.Simultaneous derivatisation and preconcentration of parabens in food and other matrices by isobutyl chloroformate and dispersive liquid-liquid microextraction followed by gas chromatographic analysis[J].Food Chemistry,2013,141(1):436-443.
[16]沈昊宇,应丽艳,曹云峰,等.固相萃取-气相色谱/质谱法同时测定化妆品中的邻苯二甲酸酯和对羟基苯甲酸酯[J].色谱,2007,25(2):272-275.SHEN Haoyu,YING Liyan,CAO Yunfeng,et al.Simultaneous determination of phthalates and parabens in cosmetic products by gas chromatography/mass spectrometry coupled with solid phase extraction[J].Chromatography,2007,25(2):272-275(in Chinese).
[17]SHEN H Y,JIANG H L,MAO H L,et al.Simultaneous determination of seven phthalates and four parabens in cosmetic products using HPLC-DAD and GC-MS methods[J].Journal of Separation Science,2007,30(1):48-54.
[18]JARDIM V C,DE P M L,SOARES D D,et al.Determination of parabens in urine samples by microextraction using packed sorbent and ultraperformance liquid chromatography coupled to tandem mass spectrometry[J].Journal of Chromatography B,2015,(974):35-41.
[19]陈晓红,赵永刚,姚珊珊,等.超快速液相色谱串联质谱法测定黄酒和葡萄酒中的9种防腐剂和甜味剂[J].色谱,2011,29(12):1 147-1 154.CHEN Xiaohong,ZHAO Yonggang,YAOShanshan,et al.Simultaneous determination of nine preservatives and sweeteners in yellow wine and wine by ultrafast liquid chromatographytandem mass spectrometry[J].Chromatography,2011,29(12):1 147-1 154(in Chinese).
[20]吴刚,赵珊红,吴俭俭,等.基于超高效液相色谱-串联质谱法的纺织品中7种尼泊金酯类防腐剂测定[J].纺织学报,2012,33(1):96-101.WU Gang,ZHAO Shanhong,WU Jianjian,et al.Determination of 7nipagin esters in textiles by ultrahigh performance liquid chromatography in combination with mass spectrometry[J].Journal of Textile Research,2012,33(1):96-101(in Chinese).
[21]WANG P G,ZHOU W.Rapid determination of parabens in personal care products by stable isotope GC-MS/MS with dynamic selected reaction monitoring[J].Journal of Separation Science,2013,36(11):1 781-1 787.
[22]曹淑瑞,刘治勇,张雷,等.高效液相色谱法同时测定食品中6种对羟基苯甲酸酯[J].分析化学,2012,40(4):529-533.CAO Shurui,LIU Zhiyong,ZHANG Lei,et al.Simultaneous determination of six kinds of4-hydrobenzoic acid ester in food using high performance liquid chromatography-diode array detection[J].Chinese Journal of Analytical Chemistry,2012,40(4):529-533(in Chinese).
[23]张勋,刘韬,吴连鹏,等.高效液相色谱-串联质谱法测定多种食品中7种酚类抗氧化剂和对羟基苯甲酸酯类防腐剂[J].食品与发酵工业,2016,42(11):206-211.ZHANG Xun,LIU Tao,WU Lianpeng,et al.Determination of seven phenolic antioxidants and of p-hydroxybenzoate antiseptics in various foods by LC-MS/MS method[J].Food and Fermentation Industrials,2016,42(11):206-211(in Chinese).
[2]THYSSEN J P,ENGKILDE K,LUNDOV MD,et al.Temporal trends of preservative allergy in Denmark(1985-2008)[J].Contact Dermatitis,2010,62(2):102-108.
[3]EFSA.Opinion of the scientific panel on food additives,flavourings,processing aids and materials in contact with food on a request from the Commission related to p-hydroxybenzoates(E214-219)[J].The EFSA Journal,2004,83:1-26.
[4]GB 2760-2011食品添加剂使用卫生标准[S].北京:中国标准出版社,2007.
[5]POTOURIDIS T,BERGER E,PTTMANNW.Analysis of alkyl esters of p-hydroxybenzoic acid(parabens)in baby teethers via gas chromatographyquadrupole mass spectrometry(GC-qMS)using a stable isotope dilution assay(SIDA)[J].Analytical Methods,2016,8(17):3 466-3 474.
[6]邱松山,姜翠翠,周如金,等.对羟基苯甲酸酯类化合物抗菌活性的定量构效关系探讨[J].现代食品科技,2014,30(6):98-102.QIU Songshan,JIANG Cuicui,ZHOU Rujin,et al.A QSAR study on antibacterial activity of p-hydroxybenzoate esters[J].Modern Food Science and Technology,2014,30(6):98-102(in Chinese).
[7]PHILLIPS J C,TOPP C S,GANGOLLI S D.The metabolism of ethyl and n-propyl-p-hydroxybenzoate(parabens)in male cats[J].Toxicology Letters,1978,2(4):237-242.
[8]ROUTLEDGE E J,PARKER J,ODUM J,et al.Some alkyl hydroxy benzoate preservatives(parabens)are estrogenic[J].Toxicology and Applied Pharmacology,1998,153(1):12-19.
[9]PUGAZHENDHI D,POPE G S,DARBRE PD.Oestrogenic activity of p-hydroxybenzoic acid(common metabolite of paraben esters)and methylparaben in human breast cancer cell lines[J].Journal of Applied Toxicology,2005,25(4):301-309.
[10]HARVEY P W,EVERETT D J.Significance of the detection of esters of p-hydroxybenzoic acid(parabens)in human breast tumours[J].Journal of Applied Toxicology,2004,24(1):1-4.
[11]EU.Commission Regulation No 358/2014of 9April 2014amending Annexes II and V to Regulation(EC)No 1223/2009of the European Parliament and of the Council on cosmetic products(Text with EEA relevance).
[12]李鹏,王申,张东豫,等.行业标准方法测试口含烟化学指标的适用性[J].烟草科技,2016,49(9):57-62.LI Peng,WANG Shen,ZHANG Dongyu,et al.Suitability of industrial standard methods in testing chemical constituents of oral tobacco products[J].Tobacco Science&Technology,2016,49(9):57-62(in Chinese).
[13]BLANCO E,CASAIS M C,MEJUTO M C,et al.Combination of off-line solid-phase extraction and on-column sample stacking for sensitive determination of parabens and p-hydroxybenzoic acid in waters by non-aqueous capillary electrophoresis[J].Analytica Chimica Acta,2009,647(1):104-111.
[14]高海军,李勇,严飞龙,等.气相色谱法测定食品中6种对羟基苯甲酸酯及其钠盐[J].粮油食品科技,2011,19(3):45-48.GAO Haijun,LI Yong,YAN Feilong,et al.Study on determination of 6parabens and their sodium salts in food by gas chromatography[J].Science and Technology of Cereals,Oils and Foods,2011,19(3):45-48(in Chinese).
[15]JAIN R,MUDIAM M K,CHAUHAN A,et al.Simultaneous derivatisation and preconcentration of parabens in food and other matrices by isobutyl chloroformate and dispersive liquid-liquid microextraction followed by gas chromatographic analysis[J].Food Chemistry,2013,141(1):436-443.
[16]沈昊宇,应丽艳,曹云峰,等.固相萃取-气相色谱/质谱法同时测定化妆品中的邻苯二甲酸酯和对羟基苯甲酸酯[J].色谱,2007,25(2):272-275.SHEN Haoyu,YING Liyan,CAO Yunfeng,et al.Simultaneous determination of phthalates and parabens in cosmetic products by gas chromatography/mass spectrometry coupled with solid phase extraction[J].Chromatography,2007,25(2):272-275(in Chinese).
[17]SHEN H Y,JIANG H L,MAO H L,et al.Simultaneous determination of seven phthalates and four parabens in cosmetic products using HPLC-DAD and GC-MS methods[J].Journal of Separation Science,2007,30(1):48-54.
[18]JARDIM V C,DE P M L,SOARES D D,et al.Determination of parabens in urine samples by microextraction using packed sorbent and ultraperformance liquid chromatography coupled to tandem mass spectrometry[J].Journal of Chromatography B,2015,(974):35-41.
[19]陈晓红,赵永刚,姚珊珊,等.超快速液相色谱串联质谱法测定黄酒和葡萄酒中的9种防腐剂和甜味剂[J].色谱,2011,29(12):1 147-1 154.CHEN Xiaohong,ZHAO Yonggang,YAOShanshan,et al.Simultaneous determination of nine preservatives and sweeteners in yellow wine and wine by ultrafast liquid chromatographytandem mass spectrometry[J].Chromatography,2011,29(12):1 147-1 154(in Chinese).
[20]吴刚,赵珊红,吴俭俭,等.基于超高效液相色谱-串联质谱法的纺织品中7种尼泊金酯类防腐剂测定[J].纺织学报,2012,33(1):96-101.WU Gang,ZHAO Shanhong,WU Jianjian,et al.Determination of 7nipagin esters in textiles by ultrahigh performance liquid chromatography in combination with mass spectrometry[J].Journal of Textile Research,2012,33(1):96-101(in Chinese).
[21]WANG P G,ZHOU W.Rapid determination of parabens in personal care products by stable isotope GC-MS/MS with dynamic selected reaction monitoring[J].Journal of Separation Science,2013,36(11):1 781-1 787.
[22]曹淑瑞,刘治勇,张雷,等.高效液相色谱法同时测定食品中6种对羟基苯甲酸酯[J].分析化学,2012,40(4):529-533.CAO Shurui,LIU Zhiyong,ZHANG Lei,et al.Simultaneous determination of six kinds of4-hydrobenzoic acid ester in food using high performance liquid chromatography-diode array detection[J].Chinese Journal of Analytical Chemistry,2012,40(4):529-533(in Chinese).
[23]张勋,刘韬,吴连鹏,等.高效液相色谱-串联质谱法测定多种食品中7种酚类抗氧化剂和对羟基苯甲酸酯类防腐剂[J].食品与发酵工业,2016,42(11):206-211.ZHANG Xun,LIU Tao,WU Lianpeng,et al.Determination of seven phenolic antioxidants and of p-hydroxybenzoate antiseptics in various foods by LC-MS/MS method[J].Food and Fermentation Industrials,2016,42(11):206-211(in Chinese).