高分辨质谱快速筛查牛乳中10种禁用兽药残留
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摘要
采用超高效液相色谱—四级杆飞行时间高分辨质谱(UHPLC-QTOF MS)技术建立了生鲜牛乳中10种雌激素类和氯霉素类药物的快速筛查方法,并建立了此10种化合物的精确分子质量数和二级质谱碎片离子数据库。牛乳样品经乙腈提取,采用QuECh?ERS(Quick,Easy,Cheap,Effective,Rugged and Safe)方法净化。目标药物经Agilent ZORBAX SB C18色谱柱分离,以乙腈和水为流动相进行梯度洗脱,使用Dual AJS ESI源,在负离子模式下进行数据采集,基质匹配标准曲线法定量。结果表明,10种雌激素类和氯霉素类药物的定量下限为10～50μg/kg,在3个加标水平的平均回收率为61.2%～116.3%,相对标准偏差为2.3%～10.8%。结合精确分子质量数、保留时间、同位素丰度和二级特征碎片离子对目标化合物进行快速筛查与确证。该方法快速简便、准确、灵敏度较高,适用于牛乳中雌激素类和氯霉素类药物残留的高通量筛查与定性鉴定。
A comprehensive analytical method was established for the simultaneous determination of 10 estrogens and chloramphenicols in raw milk by ultra performance liquid chromatography-quadrupole time-of-flight mass spectrometry(UHPLC-QTOF MS). The accurate mass and two-stage mass spectrometry databases of 10 compounds were established. The analytes in milk samples were extracted with acetoni-trile. The extracts were cleaned up through QuEChERS(Quick, Easy, Cheap, Effective, Rugged and Safe) method. In the chromatographic analysis of 10 target compounds were separated on an Agilent ZORBAX SB C18 column with the gradient elution using the mobile phases of acetonitrile and water and detected by MS under Dual AJS ESI-mode. Detection was quantified with matrix standard curve. As a result,the limits of quantification(LOQ, S/N = 10) of 10 target compounds were 10～50 μg/kg in milk. The average recoveries of the 10 analyt-es spiked at three concentration levels were ranged from 61.2 % to 116.3 % with the relative standard deviations of 2.3% to 10.8%. The preci-sion mass, retention time, isotopic abundance and two-stage ion mass spectra were employed for the screening and confirmation. This meth-od can be applied to the analysis of the 10 estrogens and chloramphenicols for the high-throughput screening and qualitative identification in raw milk due to its fastness, simplicity and relatively high sensitivity.
A comprehensive analytical method was established for the simultaneous determination of 10 estrogens and chloramphenicols in raw milk by ultra performance liquid chromatography-quadrupole time-of-flight mass spectrometry(UHPLC-QTOF MS). The accurate mass and two-stage mass spectrometry databases of 10 compounds were established. The analytes in milk samples were extracted with acetoni-trile. The extracts were cleaned up through QuEChERS(Quick, Easy, Cheap, Effective, Rugged and Safe) method. In the chromatographic analysis of 10 target compounds were separated on an Agilent ZORBAX SB C18 column with the gradient elution using the mobile phases of acetonitrile and water and detected by MS under Dual AJS ESI-mode. Detection was quantified with matrix standard curve. As a result,the limits of quantification(LOQ, S/N = 10) of 10 target compounds were 10～50 μg/kg in milk. The average recoveries of the 10 analyt-es spiked at three concentration levels were ranged from 61.2 % to 116.3 % with the relative standard deviations of 2.3% to 10.8%. The preci-sion mass, retention time, isotopic abundance and two-stage ion mass spectra were employed for the screening and confirmation. This meth-od can be applied to the analysis of the 10 estrogens and chloramphenicols for the high-throughput screening and qualitative identification in raw milk due to its fastness, simplicity and relatively high sensitivity.
引文
[1] European Union. Commision Regulation(EU)No 37/2010 of 22 December 2009[S].(2015-3-13)[2018-8-16]. http://law.foodmate.net/show-185314.html.
[2]农业部.中华人民共和国农业部公告第235号[S].(2002-12-24)[2018-8-16].http://law.foodmate.net/show-163968.html.
[3]王和兴,周颖,姜庆五.超高效液相色谱-四极杆飞行时间串联质谱法同时分析奶粉中9种雌激素[J].分析化学, 2011, 39(9):1323-1328.
[4]吴永宁,邵兵,沈建忠.兽药残留检测与监控技术[M].北京:化学工业出版社, 2007:27.
[5]蒋春燕,张晓菊,应月青.乳及乳制品中性激素残留的安全现状及检测方法[J].中国乳业, 2011,113:59-61.
[6]罗辉泰,黄晓兰,吴惠勤,等. QuEChERS/液相色谱-串联质谱法同时测定鱼肉中30种激素类及氯霉素类药物残留[J].分析测试学报,2011, 30(12):1329-1337.
[7]冯民,魏云计,朱臻怡,等.高效液相色谱-串联质谱法同时测定饲料中氯霉素、甲砜霉素与氟甲砜霉素残留量[J].分析测试学报,2013, 32(1):117-121.
[8]林小莉,李宁,霍峰,等.气相色谱-质谱法同时测定饲料中6种雌激素类药物[J].分析测试学报, 2016, 35(3):322-326.
[9]刘艳明,王骏,周莉莉,等.超高效液相色谱-串联质谱法测定化妆品中的氯霉素[J].分析实验室, 2010, 29:86-88.
[10]王美玲,颜鸿飞,傅善良,等.高效液相色谱-离子阱飞行时间质谱对保健食品中激素类成分的快速筛查和确证[J].色谱, 2012, 30(10):980-985.
[11]张婷岚,史美云,邸欣,等. 5种雌激素类化合物的电喷雾四级杆飞行时间质谱裂解规律研究[J].药学学报, 2014, 49(4):507-512.
[12]高馥蝶,赵妍,邵兵,等.超高效液相色谱-四极杆-飞行时间质谱法快速筛查牛奶中的农药和兽药残留[J].色谱, 2012, 30(6):560-567.
[13]朱万艳,张欣,杨娟,等.超高效液相色谱-四极杆-飞行时间质谱法同时测定猪肉中多类兽药残留[J].色谱, 2015, 33(9):1002-1008.
[14]李娜,张玉婷,刘磊,等. QuEChERS-超高效液相色谱-串联质谱法测定动物源食品中4类29种禁限用兽药残留[J].色谱, 2014, 32(12):1313-1319.
[15]贡松松,顾欣,曹慧,等.超高效液相色谱-四极杆飞行时间质谱法快速筛查生鲜牛乳中的14种磺胺类药物[J].分析测试学报, 2014,33(12):1342-1348.
[16]曹亚飞,康健,常巧英,等. QuEChERS结合液相色谱-串联质谱法快速测定奶酪中多类兽药残留[J].色谱, 2015, 33(2):132-139.
[2]农业部.中华人民共和国农业部公告第235号[S].(2002-12-24)[2018-8-16].http://law.foodmate.net/show-163968.html.
[3]王和兴,周颖,姜庆五.超高效液相色谱-四极杆飞行时间串联质谱法同时分析奶粉中9种雌激素[J].分析化学, 2011, 39(9):1323-1328.
[4]吴永宁,邵兵,沈建忠.兽药残留检测与监控技术[M].北京:化学工业出版社, 2007:27.
[5]蒋春燕,张晓菊,应月青.乳及乳制品中性激素残留的安全现状及检测方法[J].中国乳业, 2011,113:59-61.
[6]罗辉泰,黄晓兰,吴惠勤,等. QuEChERS/液相色谱-串联质谱法同时测定鱼肉中30种激素类及氯霉素类药物残留[J].分析测试学报,2011, 30(12):1329-1337.
[7]冯民,魏云计,朱臻怡,等.高效液相色谱-串联质谱法同时测定饲料中氯霉素、甲砜霉素与氟甲砜霉素残留量[J].分析测试学报,2013, 32(1):117-121.
[8]林小莉,李宁,霍峰,等.气相色谱-质谱法同时测定饲料中6种雌激素类药物[J].分析测试学报, 2016, 35(3):322-326.
[9]刘艳明,王骏,周莉莉,等.超高效液相色谱-串联质谱法测定化妆品中的氯霉素[J].分析实验室, 2010, 29:86-88.
[10]王美玲,颜鸿飞,傅善良,等.高效液相色谱-离子阱飞行时间质谱对保健食品中激素类成分的快速筛查和确证[J].色谱, 2012, 30(10):980-985.
[11]张婷岚,史美云,邸欣,等. 5种雌激素类化合物的电喷雾四级杆飞行时间质谱裂解规律研究[J].药学学报, 2014, 49(4):507-512.
[12]高馥蝶,赵妍,邵兵,等.超高效液相色谱-四极杆-飞行时间质谱法快速筛查牛奶中的农药和兽药残留[J].色谱, 2012, 30(6):560-567.
[13]朱万艳,张欣,杨娟,等.超高效液相色谱-四极杆-飞行时间质谱法同时测定猪肉中多类兽药残留[J].色谱, 2015, 33(9):1002-1008.
[14]李娜,张玉婷,刘磊,等. QuEChERS-超高效液相色谱-串联质谱法测定动物源食品中4类29种禁限用兽药残留[J].色谱, 2014, 32(12):1313-1319.
[15]贡松松,顾欣,曹慧,等.超高效液相色谱-四极杆飞行时间质谱法快速筛查生鲜牛乳中的14种磺胺类药物[J].分析测试学报, 2014,33(12):1342-1348.
[16]曹亚飞,康健,常巧英,等. QuEChERS结合液相色谱-串联质谱法快速测定奶酪中多类兽药残留[J].色谱, 2015, 33(2):132-139.