基于QuEChERS-GC-QQQ-MS/MS法同时测定知母中58种农药残留
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摘要
目的建立基于QuEChERS-GC-QQQ-MS/MS的知母中58种农药残留同时定量分析方法。方法采用岛津TQ8050三重四极杆气质联用仪,Shimadzu SH-Rxi-5Sil MS毛细管柱(30 m×0.25 mm,0.25μm)为色谱柱;进样口温度为250℃,进样量为1.0μL,不分流进样,高压进样压力为250 k Pa;载气为高纯氦气,载气控制方式为恒线速度模式;色谱柱体积流量为1.69 mL/min,线速度为47.2 cm/s,吹扫流量为5 mL/min;程序升温:初始温度为50℃,保持1 min,先以25℃/min升温至125℃,再以10℃/min升温至300℃,保持15 min;柱平衡时间为0.5 min。采用QuEChERS法提取、净化供试品溶液;配制基质匹配标准曲线;使用稳定的同位素内标进行校正等3个措施共同消除基质效应。结果成功建立并验证了一种基于QuEChERS-GC-QQQ-MS/MS的知母中58种农药残留同时定量分析方法。通过对不同产地、野生与栽培品种、不同规格的知母药材进行58种农药残留量的定量测定,结果显示30个批次内共有6个批次知母药材检测到了微量的p,p′-滴滴伊(p,p′-DDE),3个批次检测到了氟乐灵,2个批次检测到了毒死蜱,1个批次检测到了微量的仲丁灵。结论建立的基于QuEChERS-GC-QQQ-MS/MS的知母中58种农药残留同时定量分析方法具有较好的适用性,对其他中药材农药多残留检测方法的建立具有参考价值。
Objective To establish a simultaneous quantitative analysis method of 58 pesticide residues in Anemarrhena asphodeloides based on QuEChERS-GC-QQQ-MS/MS technique. Methods This study was performed on a Shimadzu GC-QQQ-MS/MS spectrometer, equipped with a SHIMADZU SH-Rxi-5 Sil MS column(30 m × 0.25 mm, 0.25 μm). The temperature of injection port was 250 ℃, the injection volume was 1.0 μL, the injection mode was splitless, the injection pressure was 250 k Pa; The carrier gas was high purity helium and the carrier gas control mode was constant linear velocity mode; The column flow rate was 1.69 mL/min, the line speed was 47.2 cm/s, the purge flow rate was 5 mL/min. The temperature rise method was the gradient program: The initial temperature was 50 ℃, hold the state for 1 min, first raise the temperature to 125 ℃ with 25 ℃/min, then raise the temperature to 300 ℃ with 10 ℃/min, keep the state for 15 min; The balance time was 0.5 min. The QuEChERS method was used to purify the test sample solutions, and the calibration was carried out using the standard curve of blank matrix matching, using a stable isotope internal standard for quantitative. Results Quantitative determination of 58 pesticide residues in 30 batches of A. asphodeloides samples was carried out. The results showed that there were five batches of samples detecting a small amount of p,p′-DDE, three batches of samples were detected trifluralin, two batches of samples were detected chlorpyrifos, and one batch of samples were detected butralin. Conclusion The development and validation quantitative analysis method of 58 pesticide residues based on QuEChERS-GC-QQQ-MS/MS has good applicability, which is of reference value for the establishment of other pesticide residues in herbs.
Objective To establish a simultaneous quantitative analysis method of 58 pesticide residues in Anemarrhena asphodeloides based on QuEChERS-GC-QQQ-MS/MS technique. Methods This study was performed on a Shimadzu GC-QQQ-MS/MS spectrometer, equipped with a SHIMADZU SH-Rxi-5 Sil MS column(30 m × 0.25 mm, 0.25 μm). The temperature of injection port was 250 ℃, the injection volume was 1.0 μL, the injection mode was splitless, the injection pressure was 250 k Pa; The carrier gas was high purity helium and the carrier gas control mode was constant linear velocity mode; The column flow rate was 1.69 mL/min, the line speed was 47.2 cm/s, the purge flow rate was 5 mL/min. The temperature rise method was the gradient program: The initial temperature was 50 ℃, hold the state for 1 min, first raise the temperature to 125 ℃ with 25 ℃/min, then raise the temperature to 300 ℃ with 10 ℃/min, keep the state for 15 min; The balance time was 0.5 min. The QuEChERS method was used to purify the test sample solutions, and the calibration was carried out using the standard curve of blank matrix matching, using a stable isotope internal standard for quantitative. Results Quantitative determination of 58 pesticide residues in 30 batches of A. asphodeloides samples was carried out. The results showed that there were five batches of samples detecting a small amount of p,p′-DDE, three batches of samples were detected trifluralin, two batches of samples were detected chlorpyrifos, and one batch of samples were detected butralin. Conclusion The development and validation quantitative analysis method of 58 pesticide residues based on QuEChERS-GC-QQQ-MS/MS has good applicability, which is of reference value for the establishment of other pesticide residues in herbs.
引文
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[15]Moreno-González D,Alcántara-Durán J,Gilbert-López B,et al.Matrix-effect free quantitative liquid chromatography mass spectrometry analysis in complex matrices using nanoflow LC with integrated emitter tip and high dilution factors[J].J Chromatogr A,2017,doi:10.1016/j.chroma.2017.09.006.
[16]贺利民,刘祥国,曾振灵.气相色谱分析农药残留的基质效应及其解决方法[J].色谱,2008,26(1):98-104.
[17]盛静,管健,吴永江,等.气相色谱-质谱联用法测定杭白菊中32种残留农药[J].中草药,2008,39(10):1568-1572.
[2]霍卫,姜丽.2013年中药材和中药饮片出口分析[J].中国现代中药,2014,16(3):241-243.
[3]傅巧真,林慧彬,林建强,等.中药材农药残留原因及防治措施的研究进展[J].时珍国医国药,2014,25(4):925-927.
[4]王丽丽,夏会龙.我国中草药中农药残留的特点[J].中草药,2007,38(3):471-474.
[5]孔令军,张娅婷,庞会利,等.中药材农药残留的研究进展[J].中国实验方剂学杂志,2015,21(21):231-234.
[6]李淑芬,全灿,王幼君,等.中药材中农药残留的脱除与检测研究[J].中草药,2004,35(2):232-234.
[7]Li Y,Pang G F,Fan C L,et al.Hierarchical cluster analysis of matrix effects on 110 pesticide residues in 28tea matrixes[J].J AOAC Int,2013,96(6):1453-1465.
[8]Tsuchiyama T,Katsuhara M,Nakajima M,et al.Compensation of matrix effects in gas chromatography-mass spectrometry analysis of pesticides using a combination of matrix matching and multiple isotopically labeled internal standards[J].J ChromatogrA,2017,doi:10.1016/j.chroma.2017.09.072.
[9]黄宝勇.果蔬中农药多残留的气相色谱-质谱方法与基质效应的研究[D].北京:中国农业大学,2005.
[10]中国药典[S].一部.2015.
[11]Anastassiades M,Lehotay S J,Schenck F J,et al.Fast and easy multiresidue method employing acetonitrile extraction/partitioning and“dispersive solid-phase extraction”for the determination of pesticide residues in produce[J].J AOAC Int,2003,86(2):412-431.
[12]Martins M L,Kemmerich M,Prestes O D,et al.Evaluation of an alternative fluorinated sorbent for dispersive solid-phase extraction clean-up of the quick,easy,cheap,effective,rugged,and safe method for pesticide residues analysis[J].J Chromatogr A,2017,doi:10.1016/j.chroma.2017.07.080.
[13]Qin Y,Zhang J,Li Y,et al.Automated multi-filtration cleanup with nitrogen-enriched activated carbon material as pesticide multi-residue analysis method in representative crop commodities[J].J Chromatogr A,2017,doi:10.1016/j.chroma.2017.08.009.
[14]Trevisan M T,Owen R W,Calatayud-Vernich P,et al.Pesticide analysis in coffee leaves using a quick,easy,cheap,effective,rugged and safe approach and liquid chromatography tandem mass spectrometry:Optimization of the clean-up step[J].J Chromatogr A,2017,doi:10.1016/j.chroma.2017.07.033.
[15]Moreno-González D,Alcántara-Durán J,Gilbert-López B,et al.Matrix-effect free quantitative liquid chromatography mass spectrometry analysis in complex matrices using nanoflow LC with integrated emitter tip and high dilution factors[J].J Chromatogr A,2017,doi:10.1016/j.chroma.2017.09.006.
[16]贺利民,刘祥国,曾振灵.气相色谱分析农药残留的基质效应及其解决方法[J].色谱,2008,26(1):98-104.
[17]盛静,管健,吴永江,等.气相色谱-质谱联用法测定杭白菊中32种残留农药[J].中草药,2008,39(10):1568-1572.