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超高效液相色谱-串联质谱法测定水果中的甲氧基丙烯酸酯类杀菌剂及其质谱裂解途径

[Determination of strobilurin fungicides in fruits and their mass fragmentation routes by ultra performance liquid chromatography-tandem mass spectrometry].

作者信息

Zhou Yao, Yang Huiqin, Shi Yiyin, Chen Jiaxian, Zhu Jian, Deng Xiaojun, Guo Dehua

机构信息

Shanghai Entry-Exit Inspection and Quarantine Bureau, Shanghai 200135, China.

出版信息

Se Pu. 2017 Sep 8;35(9):970-979. doi: 10.3724/SP.J.1123.2017.05009.

DOI:10.3724/SP.J.1123.2017.05009
PMID:29048855
Abstract

A method was developed for the simultaneous determination of six strobilurin fungicide (-metominostrobin, azoxystrobin, kresoxim-methyl, picoxystrobin, pyraclostrobin and trifloxystrobin) residues in orange, banana, apple and pineapple samples by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The fragmentation routes of all the compounds were explained by the aid of a fragment predicting software ACD Lab/MS Fragmenter. The samples were extracted by acetonitrile, then cleaned up by amino solid phase extraction cartridges (SupelClean LC-NH). The extracts were separated on a ACQUITY UPLC BEH C column (50 mm×2.1 mm, 1.7 μm) with gradient elution. Acetonitrile containing 0.1% (v/v) formic acid and 10 mmol/L ammonium acetate containing 0.1% (v/v) formic acid were used as mobile phases. The samples were detected by electrospray ionization (ESI)-MS/MS in positive ion and multiple reaction monitoring (MRM) mode, quantified by external standard method. Good linearities were obtained in the range of 5-100 μg/L (for pyraclostrobin, 1-20 μg/L) with correlation coefficients () greater than 0.999. The recoveries ranged from 60.4% to 120% with the relative standard deviations between 2.15% and 15.1% (=6). The developed method can meet the inspection of the six strobilurin residues in the orange, banana, apple and pineapple samples.

摘要

建立了一种超高效液相色谱-串联质谱法(UPLC-MS/MS)同时测定橙子、香蕉、苹果和菠萝样品中6种甲氧基丙烯酸酯类杀菌剂(甲氨基阿维菌素苯甲酸盐、嘧菌酯、醚菌酯、啶氧菌酯、吡唑醚菌酯和肟菌酯)残留量的方法。借助碎片预测软件ACD Lab/MS Fragmenter对所有化合物的裂解途径进行了解释。样品用乙腈提取,然后用氨基固相萃取柱(SupelClean LC-NH)净化。提取物在ACQUITY UPLC BEH C柱(50 mm×2.1 mm,1.7 μm)上进行梯度洗脱分离。以含0.1%(v/v)甲酸的乙腈和含0.1%(v/v)甲酸的10 mmol/L醋酸铵为流动相。样品采用电喷雾电离(ESI)-MS/MS在正离子和多反应监测(MRM)模式下进行检测,外标法定量。在5-100 μg/L范围内(吡唑醚菌酯为1-20 μg/L)获得了良好的线性关系,相关系数()大于0.999。回收率在60.4%至120%之间,相对标准偏差在2.15%至15.1%之间(n=6)。所建立的方法能够满足橙子、香蕉、苹果和菠萝样品中6种甲氧基丙烯酸酯类残留量的检测要求。

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