固相萃取-超高效液相色谱-串联质谱法快速测定鸡蛋和鸡肉中的7种性激素药物残留量
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摘要
目的建立同时测定鸡蛋和鸡肉中7种性激素类药物残留的快速检测方法。方法鸡蛋和鸡肉中的性激素类药物经乙腈-水溶液(80:20,V:V)提取后,Oasis PRiME HLB固相萃取净化,UPLC-MS/MS法检测,基质匹配外标法定量。结果该方法具有良好的准确度和精密度,在鸡蛋和鸡肉中添加回收率范围分别为78.7%～101.7%和77.9%～104.3%,相对标准偏差(relative standard deviation, RSD)低于8.7%,检出限(limit of detection, LOD,S/N=3)和定量限(limit of quantitation,LOQ,S/N=10)分别为0.02～0.5μg/kg和0.08～2.0μg/kg。结论本方法简便快速,灵敏可靠,适用于鸡蛋和鸡肉中性激素类药物残留高通量快速检测分析。
Objective To establish a method for the simultaneous determination of 7 kinds of hormones residues in eggs and chicken. Methods The hormones residues in eggs and chicken were extracted by cetonitrile/water(80:20, V:V). The extracts were purified by the Oasis PRiME HLB solid phase extraction, then analyzed by ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS), and the matrix-matching external standard method was used to quantify. Results The method had good accuracy and precision, and the recoveries of egg and chicken were 78.7%-101.7% and 77.9%-104.3%, respectively, with the relative standard deviations(RSDs)of lower than 8.7%. The limits of detection(LODs, S/N≥3) and quantification(LOQs, S/N≥10) were 0.02-0.5 μg/kg and 0.8-2.0 μg/kg, respectively. Conclusion The method is simple, fast, sensitive and reliable, which is suitable for the rapid determination of hormones residues in eggs and chicken.
Objective To establish a method for the simultaneous determination of 7 kinds of hormones residues in eggs and chicken. Methods The hormones residues in eggs and chicken were extracted by cetonitrile/water(80:20, V:V). The extracts were purified by the Oasis PRiME HLB solid phase extraction, then analyzed by ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS), and the matrix-matching external standard method was used to quantify. Results The method had good accuracy and precision, and the recoveries of egg and chicken were 78.7%-101.7% and 77.9%-104.3%, respectively, with the relative standard deviations(RSDs)of lower than 8.7%. The limits of detection(LODs, S/N≥3) and quantification(LOQs, S/N≥10) were 0.02-0.5 μg/kg and 0.8-2.0 μg/kg, respectively. Conclusion The method is simple, fast, sensitive and reliable, which is suitable for the rapid determination of hormones residues in eggs and chicken.
引文
[1]刘永华,杨松.浅析动物性食品中性激素残留与检测[J].中国畜牧兽医,2011,38((7):239-241.Liu YH, Yang S. Residues and determination of sex hormone in the animal derived foods[J]. China Anim Husb Vet Med, 2011, 38((7):239-241.
[2]秦伟,刘桂华.动物源性食品中性激素残留检测方法研究进展[J].中国预防医学杂志,2010,11(7):746-749.Qin W, Liu GH. Advances in detection methods of sex hormone residues in animal Derived Food[J]. Chin Prev Med, 2010,11(7):746-749.
[3]动物性食品中兽药最高残留限量-农业部235号公告中华人民共和国农业部公告[EB/OL].[2008-03-04].http://jiuban.moa.gov.cn/zwllm/nybz/200803/t20080304_1028649.htm Maximum residue limits for veterinary drugs in animal Derived Food.Announcement no.235 of the ministry of agriculture of the People's Republic of China[S].[EB/OL].[2008-03-04].http://jiuban.moa.gov.cn/zwllm/nybz/200803/t20080304_1028649.htm
[4]高旭东,黄鑫,郝宝成.等.动物源性食品中性激素残留的危害及检测方法[J].黑龙江畜牧兽医,2015,(11):274-277.Gao XD, Huang X, Hao BC, et al. The harm and detection method of sex hormone residues in animal food[J]. Heilongjiang Anim Sci Vet Med,2015, 11:274-277.
[5]汪竟芝,胡琳,曹莹莹,等.高效液相色谱法检测鸡蛋中四种激素残留贵[J].食品研究与开发,2015, 36(10):94-95.Wang JZ, Hu L, Cao YY, et al. Determination of four anabolic steroids in eggs by high performance liquid chromatographic[J]. Food Res Dev, 2015,36(10):94-95.
[6]周艳飞.高效液相色谱法测定黄体酮、丙酸睾酮及苯甲酸雌二醇含量[J].中国兽药杂志,2003,37(12):19-21.Zhou YF, Determination of progesterone, testosterone propionate and estradiol benzoate by high performance liquid chromatographic[J]. Chin J Vet Drug, 2003,37(12):19-21.
[7]丁雅韵,徐晓云,谢孟峡,等.动物组织中己烯雌酚残留的基体固相扩散-气相色谱-质谱分析方法研究[J].分析化学,2003, 31(11):1356-1359.Ding YY, Xu XY, Xie MX, et al. Matrix solid-phase dispersion coupled with gas chromatography-mass spectrometry for the analysis of trace residue of diethylstilboestrol in animal tissue[J]. Chin J Anal Chem, 2003,31(11):1356-1359.
[8]陈捷,秦燕,张美金.气相色谱-质谱法检测动物肌肉组织中残留的甾类同化激素[J].色谱,2006, 24(1):19-22.Chen J, Qin Y, Zhang MJ. Determination of anabolic steroid hormones in animal muscle t issues by gas chromatography/mass spectrometry[J].Chin J Chromatogr, 2006, 24(1):19-22.
[9] Fun M, Huang S, Lin T, Determination of residual anabolic steroid in meatby gas chromatography-ion trap-mass spectrometer[J]. Talanta, 2004,64(2):408-414.
[10] Seo J,Kim HY, Chung BC,et al. Simultaneous determination of anabolic steroids and synthetic hormones in meat by freezing-lipid filtration,solid-phase extraction and gas chromatography-mass spectrometry[J]. J Chromatogr A, 2005,1067(1-2):303-309.
[11]严凤,李丹妮,张文刚,等.鸡肉中的激素类药物多残留检测超高效液相-串联质谱法研究[J].中国兽药杂志,2008,42(3):16-19.Yan F, Li DN,Zhang WG, et al. Research of hormones multi-residues in chicken by ultra performance liquid chromatography-tandem mass spectrometry[J]. Chin J Vet Drug, 2008,42(3):16-19.
[12]动物源性食品中11种激素残留检测液相色谱-串联质谱法:农业部1031号公告-1-2008[S].Determination of sex hormones in animal products LC-MS/MS method.Notice no. 1031 of the ministry of agriculture 1-2008[S].
[13] SN/T 2677-2010进出口动物源性食品中雄性激素类药物残留量检测方法液相色谱-质谱/质谱法[S].SN/T 2677-2010Determination of androgen residues in foodstuffs of animal origin for import and export-LC-MS/MS method[S].
[14]王飞,宓捷波,葛含光.超高压液相色谱-串联质谱法快速测定牛肉、牛肾中3种甾类同化激素药物残留量[J].质谱学报,2019, 40(1):83-89.Wang F, Mi JB, Ge HG Quick Determination of three hormones residues in beef and kidney by HPLC-MS/MS[J]. J Chin Mass Spectrom Soc,2019, 40(1):83-89.
[15]李宁,张玉龙,林涛,等.UPLC-MS法同时测定牛奶中磺胺类、喹诺酮类、甾体激素类及四环素类兽药残留[J].分析测试学报,2016, 35(6):714-718.Li N, Zhang YL, Lin T, et al. Analysis of sulfonamide, quinolones, steroid hormones and tetracyclines residues in milk by ultra performance liquid chromatography-mass spectrometry[J]. J Instrum Anal, 2016, 35(6):714-718.
[16]蔡勤仁,冯家望,张毅,等.液相色谱-串联质谱结合谱库检索法同时测定猪组织中12种类固醇激素[J].色谱,2011,29(8):712-717.Cai QR, Feng JW, Zhang Y, et al. Determination of 12 steroid hormone residues in pig tissues by liquid chromatography-tandem mass spectrometry combining with library search[J]. Chin J Chromatogr, 2011,29(8):712-717.
[17]冯月超,贾丽,王建凤,等.超高效液相色谱-质谱联用法检测鱼肉中23种性激素残留量[J].食品安全质量检测学报,2018, 9(16):4417-4426.Feng YC, Jia L, Wang JF, et al. Determination of 23 kinds of sex hormones in fish using ultra performance liquid chromatography-tandem mass spectrometry[J]. J Food Saf Qual, 2018, 9(16):4417-4426.
[18]郝杰,姜洁,余建龙,等.固相萃取-超高效液相色谱-串联质谱法同时测定动物源性食品中多种兽药残留[J].食品科学,2017, 38(12):266-272.Hao J, Jiang J, Yu JL, et al. Simultaneous determination of multi-veterinary drug residues in animal-origin food by solid phase extraction coupled with ultra performance liquid chromatography-tandem mass spectrometry[J]. Food Sci, 2017,38(12):266-272.
[19]张婧,潘娟,严凤,等.基于PRiME HLB前处理技术的鸡蛋中四环素类药物的快速筛选方法研究[J].中国兽药杂志,2018, 52(3):52-57.Zhang J, Pan J, Yan F, et al. PRiME HLB based effective screening method for tetracyclines in eggs[J]. Chin J Vet Drug, 2018,52(3):52-57.
[20]尹伶灵,陈燕,杨修镇,等.超高效液相色谱串联质谱法快速检测鸡蛋和鸡肉中的非泼罗尼及其代谢物的残留量[J].食品安全质量检测学报,2017, 8(12):4776-4781.Yin LL, Chen Y, Yang XZ, et al. Rapid determination of fipronil and its metabolite residues in eggs and chicken by ultra performance liquid chromatography tandem mass spectrometry[J]. J Food Saf Qual, 2017,8(12):4776-4781.
[21] NY/T 1896-2010兽药残留实验室质量控制规范[S].NY/T 1896-2010 Criterion on quality control of laboratories for residue analysis of veterinary drugs[S].
[2]秦伟,刘桂华.动物源性食品中性激素残留检测方法研究进展[J].中国预防医学杂志,2010,11(7):746-749.Qin W, Liu GH. Advances in detection methods of sex hormone residues in animal Derived Food[J]. Chin Prev Med, 2010,11(7):746-749.
[3]动物性食品中兽药最高残留限量-农业部235号公告中华人民共和国农业部公告[EB/OL].[2008-03-04].http://jiuban.moa.gov.cn/zwllm/nybz/200803/t20080304_1028649.htm Maximum residue limits for veterinary drugs in animal Derived Food.Announcement no.235 of the ministry of agriculture of the People's Republic of China[S].[EB/OL].[2008-03-04].http://jiuban.moa.gov.cn/zwllm/nybz/200803/t20080304_1028649.htm
[4]高旭东,黄鑫,郝宝成.等.动物源性食品中性激素残留的危害及检测方法[J].黑龙江畜牧兽医,2015,(11):274-277.Gao XD, Huang X, Hao BC, et al. The harm and detection method of sex hormone residues in animal food[J]. Heilongjiang Anim Sci Vet Med,2015, 11:274-277.
[5]汪竟芝,胡琳,曹莹莹,等.高效液相色谱法检测鸡蛋中四种激素残留贵[J].食品研究与开发,2015, 36(10):94-95.Wang JZ, Hu L, Cao YY, et al. Determination of four anabolic steroids in eggs by high performance liquid chromatographic[J]. Food Res Dev, 2015,36(10):94-95.
[6]周艳飞.高效液相色谱法测定黄体酮、丙酸睾酮及苯甲酸雌二醇含量[J].中国兽药杂志,2003,37(12):19-21.Zhou YF, Determination of progesterone, testosterone propionate and estradiol benzoate by high performance liquid chromatographic[J]. Chin J Vet Drug, 2003,37(12):19-21.
[7]丁雅韵,徐晓云,谢孟峡,等.动物组织中己烯雌酚残留的基体固相扩散-气相色谱-质谱分析方法研究[J].分析化学,2003, 31(11):1356-1359.Ding YY, Xu XY, Xie MX, et al. Matrix solid-phase dispersion coupled with gas chromatography-mass spectrometry for the analysis of trace residue of diethylstilboestrol in animal tissue[J]. Chin J Anal Chem, 2003,31(11):1356-1359.
[8]陈捷,秦燕,张美金.气相色谱-质谱法检测动物肌肉组织中残留的甾类同化激素[J].色谱,2006, 24(1):19-22.Chen J, Qin Y, Zhang MJ. Determination of anabolic steroid hormones in animal muscle t issues by gas chromatography/mass spectrometry[J].Chin J Chromatogr, 2006, 24(1):19-22.
[9] Fun M, Huang S, Lin T, Determination of residual anabolic steroid in meatby gas chromatography-ion trap-mass spectrometer[J]. Talanta, 2004,64(2):408-414.
[10] Seo J,Kim HY, Chung BC,et al. Simultaneous determination of anabolic steroids and synthetic hormones in meat by freezing-lipid filtration,solid-phase extraction and gas chromatography-mass spectrometry[J]. J Chromatogr A, 2005,1067(1-2):303-309.
[11]严凤,李丹妮,张文刚,等.鸡肉中的激素类药物多残留检测超高效液相-串联质谱法研究[J].中国兽药杂志,2008,42(3):16-19.Yan F, Li DN,Zhang WG, et al. Research of hormones multi-residues in chicken by ultra performance liquid chromatography-tandem mass spectrometry[J]. Chin J Vet Drug, 2008,42(3):16-19.
[12]动物源性食品中11种激素残留检测液相色谱-串联质谱法:农业部1031号公告-1-2008[S].Determination of sex hormones in animal products LC-MS/MS method.Notice no. 1031 of the ministry of agriculture 1-2008[S].
[13] SN/T 2677-2010进出口动物源性食品中雄性激素类药物残留量检测方法液相色谱-质谱/质谱法[S].SN/T 2677-2010Determination of androgen residues in foodstuffs of animal origin for import and export-LC-MS/MS method[S].
[14]王飞,宓捷波,葛含光.超高压液相色谱-串联质谱法快速测定牛肉、牛肾中3种甾类同化激素药物残留量[J].质谱学报,2019, 40(1):83-89.Wang F, Mi JB, Ge HG Quick Determination of three hormones residues in beef and kidney by HPLC-MS/MS[J]. J Chin Mass Spectrom Soc,2019, 40(1):83-89.
[15]李宁,张玉龙,林涛,等.UPLC-MS法同时测定牛奶中磺胺类、喹诺酮类、甾体激素类及四环素类兽药残留[J].分析测试学报,2016, 35(6):714-718.Li N, Zhang YL, Lin T, et al. Analysis of sulfonamide, quinolones, steroid hormones and tetracyclines residues in milk by ultra performance liquid chromatography-mass spectrometry[J]. J Instrum Anal, 2016, 35(6):714-718.
[16]蔡勤仁,冯家望,张毅,等.液相色谱-串联质谱结合谱库检索法同时测定猪组织中12种类固醇激素[J].色谱,2011,29(8):712-717.Cai QR, Feng JW, Zhang Y, et al. Determination of 12 steroid hormone residues in pig tissues by liquid chromatography-tandem mass spectrometry combining with library search[J]. Chin J Chromatogr, 2011,29(8):712-717.
[17]冯月超,贾丽,王建凤,等.超高效液相色谱-质谱联用法检测鱼肉中23种性激素残留量[J].食品安全质量检测学报,2018, 9(16):4417-4426.Feng YC, Jia L, Wang JF, et al. Determination of 23 kinds of sex hormones in fish using ultra performance liquid chromatography-tandem mass spectrometry[J]. J Food Saf Qual, 2018, 9(16):4417-4426.
[18]郝杰,姜洁,余建龙,等.固相萃取-超高效液相色谱-串联质谱法同时测定动物源性食品中多种兽药残留[J].食品科学,2017, 38(12):266-272.Hao J, Jiang J, Yu JL, et al. Simultaneous determination of multi-veterinary drug residues in animal-origin food by solid phase extraction coupled with ultra performance liquid chromatography-tandem mass spectrometry[J]. Food Sci, 2017,38(12):266-272.
[19]张婧,潘娟,严凤,等.基于PRiME HLB前处理技术的鸡蛋中四环素类药物的快速筛选方法研究[J].中国兽药杂志,2018, 52(3):52-57.Zhang J, Pan J, Yan F, et al. PRiME HLB based effective screening method for tetracyclines in eggs[J]. Chin J Vet Drug, 2018,52(3):52-57.
[20]尹伶灵,陈燕,杨修镇,等.超高效液相色谱串联质谱法快速检测鸡蛋和鸡肉中的非泼罗尼及其代谢物的残留量[J].食品安全质量检测学报,2017, 8(12):4776-4781.Yin LL, Chen Y, Yang XZ, et al. Rapid determination of fipronil and its metabolite residues in eggs and chicken by ultra performance liquid chromatography tandem mass spectrometry[J]. J Food Saf Qual, 2017,8(12):4776-4781.
[21] NY/T 1896-2010兽药残留实验室质量控制规范[S].NY/T 1896-2010 Criterion on quality control of laboratories for residue analysis of veterinary drugs[S].