色谱 ›› 2017, Vol. 35 ›› Issue (9): 970-979.DOI: 10.3724/SP.J.1123.2017.05009

• 研究论文 • 上一篇    下一篇

超高效液相色谱-串联质谱法检测水果中6种甲氧基丙烯酸酯类杀菌剂及其质谱裂解规律

周瑶, 杨惠琴, 时逸吟, 陈佳娴, 朱坚, 邓晓军, 郭德华   

  1. 上海出入境检验检疫局, 上海 200135
  • 收稿日期:2017-05-09 出版日期:2017-09-08 发布日期:2017-09-15
  • 通讯作者: 周瑶,Tel:(021)38620521,E-mail:zhouyao@shciq.gov.cn.
  • 基金资助:

    上海市科委科研项目(15142201700).

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

ZHOU Yao, YANG Huiqin, SHI Yiyin, CHEN Jiaxian, ZHU Jian, DENG Xiaojun, GUO Dehua   

  1. Shanghai Entry-Exit Inspection and Quarantine Bureau, Shanghai 200135, China
  • Received:2017-05-09 Online:2017-09-08 Published:2017-09-15
  • Supported by:

    Shanghai Science and Technology Committee Fund (No. 15142201700).

摘要:

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)同时测定橙子、香蕉、苹果、菠萝中E-苯氧菌胺、嘧菌酯、醚菌酯、啶氧菌酯、吡唑醚菌酯和肟菌酯6种甲氧基丙烯酸酯类杀菌剂残留的方法。采用计算机辅助谱图解析软件ACD Lab/MS Fragmenter对质谱裂解路径进行了分析。样品经乙腈提取,氨基固相萃取柱(SupelClean LC-NH2)净化,采用ACQUITY UPLC BEH C18色谱柱(50 mm×2.1 mm, 1.7 μm)进行分离,以含0.1%(v/v)甲酸的10 mmol/L乙酸铵溶液和含0.1%(v/v)甲酸的乙腈溶液为流动相进行梯度洗脱,在电喷雾正离子模式下,采用多反应监测(MRM)模式监测,外标法定量。结果显示,6种甲氧基丙烯酸酯类杀菌剂在5~100 μg/L(其中吡唑醚菌酯在1~20 μg/L)范围内的相关系数(r2)均大于0.999。6种杀菌剂的加标回收率为60.4%~120%,相对标准偏差(RSD)为2.15%~15.1%(n=6)。该法能满足橙子、香蕉、苹果和菠萝中6种甲氧基丙烯酸酯类杀菌剂残留量的检测要求。

关键词: 超高效液相色谱-串联质谱, 固相萃取, 计算机辅助谱图解析软件, 甲氧基丙烯酸酯类杀菌剂, 水果

Abstract:

A method was developed for the simultaneous determination of six strobilurin fungicide (E-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-NH2). The extracts were separated on a ACQUITY UPLC BEH C18 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 (r2) greater than 0.999. The recoveries ranged from 60.4% to 120% with the relative standard deviations between 2.15% and 15.1% (n=6). The developed method can meet the inspection of the six strobilurin residues in the orange, banana, apple and pineapple samples.

Key words: fragment predicting software, fruits, solid phase extraction (SPE), strobilurin fungicides, ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)

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