超高效液相色谱-串联质谱法测定奶粉中己烯雌酚及玉米赤霉烯酮
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摘要
目的建立超高效液相色谱-串联质谱法测定奶粉中己烯雌酚(diethylstilbestrol,DES)及玉米赤霉烯酮(zearalenone,ZEN)的分析方法。方法采用QuEChERS提取方法,奶粉加水浸润后用乙腈提取,加入氯化钠促使乙腈和水分层,取乙腈层经中性氧化铝小柱净化。以乙腈和水作为流动相,经ACQUITY UPLC?BEH C_(18)色谱柱分离后,利用超高效液相色谱-串联质谱法在电喷雾负离子模式下进行测定,内标法定量。结果DES和ZEN在5.0～100.0μg/L范围内线性关系良好(r~2>0.995),在5、10和50μg/kg 3个加标浓度水平下, DES和ZEN的回收率在91.5%～97.5%和92.5%～95.7%之间,相对标准偏差小于5%。结论该方法灵敏度高,定量准确,可同时测定奶粉中的己烯雌酚及玉米赤霉烯酮。
Objective To establish a method for the determination of diethylstilbestrol(DES) and zearalenone(ZEN) in milk power by ultral performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).Methods The milk powder was infiltrated with water, extracted with acetonitrile by QuEChERS, and purified with neutral alumina column. The separation was achieved using a Waters UPLC?BEH C_(18) column and a binary gradient mobile phase of acetonitrile-water solution. The measurement was carried out by electrospray ionization(ESI) in negative mode under multiple reaction monitoring mode and quantified by internal standard method. Results The linear relation were good in the range of 5.0-100.0 μg/L(r~2>0.995) for DES and ZEN. The recoveries of DES and ZEN were respectively in the range 91.5%-97.5% and 92.5%-95.7%, at 3 spiked concentrations of 5, 10 and 50μg/kg. The relative standard deviations were less than 5%. Conclusion This method is sensitive and accurate,which is suitable for simultaneous determination of diethylstilbestrol and zearalenone in milk power.
Objective To establish a method for the determination of diethylstilbestrol(DES) and zearalenone(ZEN) in milk power by ultral performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).Methods The milk powder was infiltrated with water, extracted with acetonitrile by QuEChERS, and purified with neutral alumina column. The separation was achieved using a Waters UPLC?BEH C_(18) column and a binary gradient mobile phase of acetonitrile-water solution. The measurement was carried out by electrospray ionization(ESI) in negative mode under multiple reaction monitoring mode and quantified by internal standard method. Results The linear relation were good in the range of 5.0-100.0 μg/L(r~2>0.995) for DES and ZEN. The recoveries of DES and ZEN were respectively in the range 91.5%-97.5% and 92.5%-95.7%, at 3 spiked concentrations of 5, 10 and 50μg/kg. The relative standard deviations were less than 5%. Conclusion This method is sensitive and accurate,which is suitable for simultaneous determination of diethylstilbestrol and zearalenone in milk power.
引文
[1]黄芬,叶绍辉,龚振明.己烯雌酚的研究进展[J].中国畜牧兽医,2007,34(2):51-54.Huang F,Ye SH,Gong ZM.The development of diethylstilbestrol[J].China Anim Husb Veter Med,2007,34(2):51-54.
[2]Kioumourtzoglou MA,Coull BA,O'Reilly EJ,et al.Association of exposure to diethylstilbestrol during pregnancy with multigenerational neurodevelopmental deficits[J].JAMA Pediatr,2018,172(7):670-677.
[3]Tournaire M,Devouche E,Epelboin S,et al.Birth defects in children of men exposed in utero to diethylstilbestrol(DES)[J].Therapie,2018,73(5):399-407.
[4]Council Directive 96/22/EC of 29 April 1996 Concerning the Prohibition on the Use in Stockfarming of Certain Substances Having a Hormonal or Thyreostatic Action and of Beta-agonists(1996).Off.J.Eur.Commun.L125:3-9.
[5]农业部2002年235号公告-动物性食品中兽药最高限量[S].Ministry of agriculture notice No.235 of 2002-The maximum residue limit of veterinary drugs in animal food[S].
[6]Wozny M,Obremski K,Hliwa P,et al.Feed contamination with zearalenone promotes growth but affects the immune system of rainbow trout[J].Fish Shellfish Immunol,2018,84:680-694.
[7]Cao H,Zhi Y,Xu H,et al.Zearalenone causes embryotoxicity and induces oxidative stress and apoptosis in differentiated human embryonic stem cells[J].Toxicol In Vitro,2018,54:243-250.
[8]Yang Z,Xue KS,Sun X,et al.Toxicogenomic responses to zearalenone in Caenorhabditis elegans reveal possible molecular mechanisms of reproductive toxicity[J].Food Chem Toxicol,2018,122:49-58.
[9]闫昭明,陈清华,陈凤鸣.玉米赤霉烯酮毒性研究[J].动物营养学报,2018,30(9):3453-3458.Yan ZM,Chen QH,Chen FM.Study on toxicity of zearalenone[J].Chin JAnim Nutr,2018,30(9):3453-3458.
[10]Commission Recommendation of 17 August 2006 on the presence of deoxynivalenol,zearalenone,ochratoxin A,T-2 and HT-2 and fumonisins in products intended for animal feeding(Text with EEA relevance).Official Journal L 229:0007-0009.
[11]GB 2761-2017食品安全国家标准食品中真菌毒素限量标准[S].GB 2761-2017 National food safety standard-Limits for mycotoxins in food[S].
[12]Rykaczewska A,Gajecka M,Dabrowski M,et al.Growth performance,selected blood biochemical parameters and body weights of pre-pubertal gilts fed diets supplemented with different doses of zearalenone(ZEN)[J].Toxicon,2018,152:84-94.
[13]Thielecke F,Nugent AP.Contaminants in grain-A major risk for whole grain safety?[J].Nutrients,2018,10(9):1213-1236.
[14]Foubert A,Beloglazova NV,Hedstrom M,et al.Antibody immobilization strategy for the development of a capacitive immunosensor detecting zearalenone[J].Talanta,2019,191:202-208.
[15]Beloglazova N,Lenain P,Tessier M,et al.Bioimprinting for multiplex luminescent detection of deoxynivalenol and zearalenone[J].Talanta,2019,192:169-174.
[16]Socas-Rodriguez B,Asensio-Ramos M,Hernandez-Borges J,et al.Analysis of oestrogenic compounds in dairy products by hollow-fibre liquid-phase microextraction coupled to liquid chromatography[J].Food Chem,2014,149:319-325.
[17]马丽莎,戴晓欣,谢文平,等.QuEChERS/GC-MS法同时测定鱼、虾中的雌二醇与己烯雌酚残留[J].分析测试学报,2015,34(1):62-66.Ma LS,Dai XX,Xie WP,et al.Simultaneous determination of diethvlstilbestrol and estradiol in fish and shrimp by GC-MS with QuEChERS sample preparation[J].J Instrum Anal,2015,34(1):62-66.
[18]GB/T 22992-2008牛奶和奶粉中玉米赤霉醇、玉米赤霉酮、己烯雌酚、己烷雌酚、双烯雌酚残留量的测定液相色谱-串联质谱法[S].GB/T 22992-2008 Determination of zearalanol,zearalanone,diethylstilbestrol,hexetrol and dienoestrol multi-residues in milk and milk powder-LC-MS-MS method[S].
[19]GB 5009.209-2016食品安全国家标准食品中玉米赤霉烯酮的测定[S].GB 5009.209-2016 National food safety standard-Determination of zearlanone in food[S].
[2]Kioumourtzoglou MA,Coull BA,O'Reilly EJ,et al.Association of exposure to diethylstilbestrol during pregnancy with multigenerational neurodevelopmental deficits[J].JAMA Pediatr,2018,172(7):670-677.
[3]Tournaire M,Devouche E,Epelboin S,et al.Birth defects in children of men exposed in utero to diethylstilbestrol(DES)[J].Therapie,2018,73(5):399-407.
[4]Council Directive 96/22/EC of 29 April 1996 Concerning the Prohibition on the Use in Stockfarming of Certain Substances Having a Hormonal or Thyreostatic Action and of Beta-agonists(1996).Off.J.Eur.Commun.L125:3-9.
[5]农业部2002年235号公告-动物性食品中兽药最高限量[S].Ministry of agriculture notice No.235 of 2002-The maximum residue limit of veterinary drugs in animal food[S].
[6]Wozny M,Obremski K,Hliwa P,et al.Feed contamination with zearalenone promotes growth but affects the immune system of rainbow trout[J].Fish Shellfish Immunol,2018,84:680-694.
[7]Cao H,Zhi Y,Xu H,et al.Zearalenone causes embryotoxicity and induces oxidative stress and apoptosis in differentiated human embryonic stem cells[J].Toxicol In Vitro,2018,54:243-250.
[8]Yang Z,Xue KS,Sun X,et al.Toxicogenomic responses to zearalenone in Caenorhabditis elegans reveal possible molecular mechanisms of reproductive toxicity[J].Food Chem Toxicol,2018,122:49-58.
[9]闫昭明,陈清华,陈凤鸣.玉米赤霉烯酮毒性研究[J].动物营养学报,2018,30(9):3453-3458.Yan ZM,Chen QH,Chen FM.Study on toxicity of zearalenone[J].Chin JAnim Nutr,2018,30(9):3453-3458.
[10]Commission Recommendation of 17 August 2006 on the presence of deoxynivalenol,zearalenone,ochratoxin A,T-2 and HT-2 and fumonisins in products intended for animal feeding(Text with EEA relevance).Official Journal L 229:0007-0009.
[11]GB 2761-2017食品安全国家标准食品中真菌毒素限量标准[S].GB 2761-2017 National food safety standard-Limits for mycotoxins in food[S].
[12]Rykaczewska A,Gajecka M,Dabrowski M,et al.Growth performance,selected blood biochemical parameters and body weights of pre-pubertal gilts fed diets supplemented with different doses of zearalenone(ZEN)[J].Toxicon,2018,152:84-94.
[13]Thielecke F,Nugent AP.Contaminants in grain-A major risk for whole grain safety?[J].Nutrients,2018,10(9):1213-1236.
[14]Foubert A,Beloglazova NV,Hedstrom M,et al.Antibody immobilization strategy for the development of a capacitive immunosensor detecting zearalenone[J].Talanta,2019,191:202-208.
[15]Beloglazova N,Lenain P,Tessier M,et al.Bioimprinting for multiplex luminescent detection of deoxynivalenol and zearalenone[J].Talanta,2019,192:169-174.
[16]Socas-Rodriguez B,Asensio-Ramos M,Hernandez-Borges J,et al.Analysis of oestrogenic compounds in dairy products by hollow-fibre liquid-phase microextraction coupled to liquid chromatography[J].Food Chem,2014,149:319-325.
[17]马丽莎,戴晓欣,谢文平,等.QuEChERS/GC-MS法同时测定鱼、虾中的雌二醇与己烯雌酚残留[J].分析测试学报,2015,34(1):62-66.Ma LS,Dai XX,Xie WP,et al.Simultaneous determination of diethvlstilbestrol and estradiol in fish and shrimp by GC-MS with QuEChERS sample preparation[J].J Instrum Anal,2015,34(1):62-66.
[18]GB/T 22992-2008牛奶和奶粉中玉米赤霉醇、玉米赤霉酮、己烯雌酚、己烷雌酚、双烯雌酚残留量的测定液相色谱-串联质谱法[S].GB/T 22992-2008 Determination of zearalanol,zearalanone,diethylstilbestrol,hexetrol and dienoestrol multi-residues in milk and milk powder-LC-MS-MS method[S].
[19]GB 5009.209-2016食品安全国家标准食品中玉米赤霉烯酮的测定[S].GB 5009.209-2016 National food safety standard-Determination of zearlanone in food[S].