色谱

色谱 ›› 2020, Vol. 38 ›› Issue (7): 775-781.DOI: 10.3724/SP.J.1123.2020.02017

• 研究论文 • 上一篇    下一篇

分子印迹膜萃取结合高效液相色谱-串联质谱法快速检测牛奶中的痕量环丙沙星残留

田红静1,2, 刘通2, 游松1,*(), 张峰2,*()   

  1. 1 沈阳药科大学生命科学与生物制药学院, 辽宁 沈阳 110016
    2 中国检验检疫科学研究院食品安全研究所, 北京 100176
  • 收稿日期:2020-02-19 出版日期:2020-07-08 发布日期:2020-12-10
  • 通讯作者: 游松,张峰
  • 作者简介:张峰.E-mail:fengzhang@126.com
    游松.E-mail:yousong206@aliyun.com;
  • 基金资助:
    国家重点研发计划项目(2018YFC1603600);国家重点研发计划项目(2017YFC1601600);国家"万人计划"科技创新领军人才项目高层次人才特殊支持计划（张峰）

Rapid determination of trace ciprofloxacin residue in milk samples using molecularly imprinted membrane extraction-high performance liquid chromatography-tandem mass spectrometry

TIAN Hongjing1,2, LIU Tong2, YOU Song1,*(), ZHANG Feng2,*()   

  1. 1 College of Life Science and Biopharmaceutical, Shenyang Pharmaceutical University, Shenyang 110016, China
    2 Institute of Food Safety, Chinese Academy of Inspection and Quarantine, Beijing 100176, China
  • Received:2020-02-19 Online:2020-07-08 Published:2020-12-10
  • Contact: YOU Song,ZHANG Feng
  • Supported by:
    National Key Research and Development Program(2018YFC1603600);National Key Research and Development Program(2017YFC1601600);National "Ten thousand Plan" Scientific and Technological Innovation Leading Talent Project (Feng ZHANG)

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摘要：

以聚偏氟乙烯膜为载体，恩诺沙星为伪模板分子，甲基丙烯酸为功能单体，乙二醇二甲基丙烯酸酯为交联剂，在氯仿-甲醇混合体系中制备恩诺沙星分子印迹膜（MIM），并将其作为分子印迹膜萃取（MIME）材料萃取牛奶样品中的环丙沙星，结合高效液相色谱-串联质谱（HPLC-MS/MS），快速检测牛奶中痕量环丙沙星残留。环丙沙星在0.1~200 μg/L范围内线性关系良好，相关系数为0.9996，检出限（S/N=3）和定量限（S/N=10）分别为0.02和0.10 μg/L。日间和日内精密度的相对标准偏差（RSD）在3.3%~7.9%之间。将开发的MIME-HPLC-MS/MS方法用于实际牛奶样品中环丙沙星加标回收率的检测，回收率在92.6%~119.1%之间。结果表明该方法前处理简单快速灵敏，检测准确度高，可用于牛奶样品中痕量环丙沙星残留的快速检测。

关键词: 高效液相色谱-串联质谱, 环丙沙星, 牛奶, 分子印迹膜, 萃取

Abstract:

An enrofloxacin (ENR) molecularly imprinted membrane (MIM) was prepared with a polyvinylidenedifluoride (PVDF) membrane as the carrier, ENR as the dummy template molecule, α-methacrylic acid (MAA) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linker, and a chloroform-methanol mixture solvent as the porogen. The MIM showed excellent selectivity, high adsorption capacity, and high adsorption rate for ciprofloxacin. Additionally, a method combining molecularly imprinted membrane extraction (MIME) and high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed and validated for the selective analysis of trace ciprofloxacin residue in milk samples. The sample pretreatment involved only a single step of protein precipitation. Ciprofloxacin showed good linearity in mass concentration range of 0.1-200 μg/L with a high correlation coefficient (r2>0.9996). The limit of detection (LOD, S/N=3) and limit of quantification (LOQ, S/N=10) were 0.02 μg/L and 0.1 μg/L, respectively. The relative standard deviations (RSDs) of interday and intraday precisions ranged from 3.3% to 7.9%. The ciprofloxacin recovery was in the range of 92.6%-119.1%. The results showed that the proposed method is simple and fast, with high accuracy and sensitivity, thus being suitable for the rapid detection of trace ciprofloxacin residue in milk samples.

Key words: high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), ciprofloxacin, milk, molecularly imprinted membrane, extraction