分散固相萃取结合UPLC-MS/MS测定柑桔中青霉素G及其代谢物残留
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摘要
建立了分散固相萃取结合超高效液相色谱-串联质谱(DSPE/UPLC-MS/MS)快速检测柑桔中青霉素G及其代谢物青霉二酸和去羧青霉噻唑酸的分析方法。样品经80%乙腈提取,十八烷基键合硅胶吸附剂(C_(18))净化。目标残留物经Acquity UPLC~?HSS T3色谱柱分离,以乙腈-0.1%甲酸溶液为流动相进行梯度洗脱,采用正离子多反应监测模式(MRM)检测,基质匹配标准曲线法定量。结果表明,3种目标分析物可在5 min内实现有效快速分离;在5～2 000μg/L质量浓度范围内线性关系良好(r~2≥0.998 1),方法检出限(LOD)为0.5～1μg/kg,定量下限(LOQ)为5～10μg/kg。在3个不同加标水平下,柑桔果肉、果皮和全果中的平均回收率为76.7%～107%,相对标准偏差(RSD)为1.3%～9.6%。该方法快速、简便、灵敏、准确,适用于柑桔中青霉素G及其两种代谢物残留的测定。
A rapid method was developed for the determination of penicillin G and its two metabolites(penillic acid and penilloic acid) residues in citrus by dispersive solid-phase extraction/ultra-high performance liquid chromatography-tandem mass spectrometry(DSPE/UPLC-MS/MS).The citrus samples were extracted with 80% acetonitrile,then purified with C_(18).The analytes were separated on an Acquity UPLC~?HSS T3 column with acetonitrile and 0.1% formic acid solution as mobile phases by gradient elution,and finally detected by tandem mass spectrometry in positive ESI mode(ESI~+).Identification and quantitation were performed by UPLC-MS/MS under multi-reaction monitoring(MRM) mode and matrix-matched standard curve method,respectively.Results showed that three analytes could realize an effective and rapid separation within 5 min.There were good linear relationships for the analytes in the concentration range of 5-2 000 μg/L with their correlation coefficients(r~2) not less than 0.998 1.The limits of detection(LOD) and limits of quantitation(LOQ) of the method were in the ranges of 0.5-1 μg/kg and 5-10 μg/kg,respectively.The spiked recoveries for penicillin G and its metabolites in blank citrus samples were in the range of 76.7%-107%,with relative standard deviations(RSD) of 1.3%-9.6%.The method is rapid,simple,sensitive and accurate,and is suitable for the determination of penicillin G and its two metabolite residues in citrus.
A rapid method was developed for the determination of penicillin G and its two metabolites(penillic acid and penilloic acid) residues in citrus by dispersive solid-phase extraction/ultra-high performance liquid chromatography-tandem mass spectrometry(DSPE/UPLC-MS/MS).The citrus samples were extracted with 80% acetonitrile,then purified with C_(18).The analytes were separated on an Acquity UPLC~?HSS T3 column with acetonitrile and 0.1% formic acid solution as mobile phases by gradient elution,and finally detected by tandem mass spectrometry in positive ESI mode(ESI~+).Identification and quantitation were performed by UPLC-MS/MS under multi-reaction monitoring(MRM) mode and matrix-matched standard curve method,respectively.Results showed that three analytes could realize an effective and rapid separation within 5 min.There were good linear relationships for the analytes in the concentration range of 5-2 000 μg/L with their correlation coefficients(r~2) not less than 0.998 1.The limits of detection(LOD) and limits of quantitation(LOQ) of the method were in the ranges of 0.5-1 μg/kg and 5-10 μg/kg,respectively.The spiked recoveries for penicillin G and its metabolites in blank citrus samples were in the range of 76.7%-107%,with relative standard deviations(RSD) of 1.3%-9.6%.The method is rapid,simple,sensitive and accurate,and is suitable for the determination of penicillin G and its two metabolite residues in citrus.
引文
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[4] Li H R.Chin.Med.Health(李海蓉.中国卫生产业),2011,8(2):107-108.
[5] Ministry of Agriculture.No.235 Bulletin of the Ministry of Agriculture of the People?s Republic of China(农业部.中华人民共和国农业部公告第235号).[2008-06-29].http://jiuban.moa.gov.cn/zwllm/tzgg/gg/200302/t20030226_59300.htm.
[6] Commission Regulation(EU)No.37/2010 of 22 December 2009 on Pharmacologically Active Substances and their Classification Regarding Maximum Residue Limits in Foodstuffs of Animal Origin.Official Journal of the European Union,2009,L15:13.
[7] Samanidou V,Michaelidou K,Kabir A,Furton K G.Food Chem.,2017,224:131-138.
[8] Guo M M,Li Z X,Wang Z,Pan M X,Wu H Y,Xing L H,Sun X J.J.Instrum.Anal.(郭萌萌,李兆新,王智,潘明轩,吴海燕,邢丽红,孙晓杰.分析测试学报),2017,36(3):337-342.
[9] Luiz L D,Bell M J V,da Rocha R A,Leal N L,dos Anjos V D.J.Spectrosc.,2018,2018:1-6.
[10] Chen Y L,Li X L,Yang M,Yang L B,Han X X,Jiang X,Zhao B.Talanta,2017,167(2017):236-241.
[11] Ju S Y.Sci.Technol.Food Ind.(鞠守勇.食品工业科技),2018,39(8):126-129,140.
[12] Canzani D,Hsieh K,Standland M,Hammack W,Aldeek F.J.Chromatogr.B,2017,s(1044/1045):87-94.
[13] Aldeek F,Canzani D,Standland M,Hammack W,Cook J M,Crosswhite M R,Gerard G.J.AOAC Int.,2017,100(1):189-197.
[14] Guo M M,Li Z X,Tan Z J,Wu H Y,Han X Q,Leng K L,Zhai Y X.J.Instrum.Anal.(郭萌萌,李兆新,谭志军,吴海燕,韩现芹,冷凯良,翟毓秀.分析测试学报),2011,30(9):969-975.
[15] Liu C J,Wang H,Du Z X,Jiang Y B,Shan J H,Cai Y H.Chin.J.Anal.Chem.(刘创基,王海,杜振霞,姜艳彬,单吉浩,蔡英华.分析化学),2011,39(5):617-622.
[16] Duan Z H.Effect of Penicillin Mycelial Dreg Fertilizer on Soil Environment and Growth of Tomato.Harbin:Harbin Institute of Technology(段子恒.青霉素菌渣肥对土壤环境和西红柿生长的影响研究.哈尔滨:哈尔滨工业大学),2016.
[17] Liang J J,Shen D,Xu X Y,Ding Y Q,Luo J W.Food Ferment.Ind.(梁晶晶,沈丹,徐潇颖,丁宇琦,罗金文.食品与发酵工业),2018,44(5):265-269.
[18] Luana M,Jorge H M,Amaya Z,Liliana B,Francisco A M,Manuel C.Food Anal.Methods,2012,5:1047-1053.
[19] Aldeek F,Canzani D,Standland M,Crosswhite M R,Hammack W,Gerard G,Cook J M.J.Agric.Food Chem.,2016,64(31):6100-6107.