基于氮掺杂碳纳米管净化的QuEChERS-HPLC-MS/MS法同步检测植物源性食品中异丁乙氧喹啉及其代谢物残留

Simultaneous determination of isobutoxyquinoline and its metabolites in plant-derived foods by QuEChERS-HPLC-MS/MS method based on purification of nitrogen-doped carbon nanotubes purification

摘要:

为了同时测定植物源性食品中异丁乙氧喹啉（Tebufloquin）及其代谢物（Tebufloquin-defacetyl）的残留，建立了一种基于改良QuEChERS前处理技术结合高效液相色谱-串联质谱（HPLC-MS/MS）的分析方法。样品经柠檬酸盐-乙腈提取后，采用C18、PAX及新型吸附剂XFM64（氮掺杂多壁碳纳米管）进行净化。色谱分离在C18柱上以甲醇-含0.1%甲酸的2 mmol·L-1乙酸铵水溶液梯度洗脱完成，采用电喷雾正离子（ESI+）和多反应监测（MRM）模式进行检测，用基质匹配外标法定量。方法在葡萄、黄瓜、梨等8种基质中验证结果表明：目标物线性关系良好（r2>0.9977），检出限（LOD）为0.03~0.30 μg·kg-1，定量限（LOQ）为0.10~1.00 μg·kg?1。在1.0、2.0、10.0 μg·kg-1三个添加水平下，平均回收率为80.04%～115.02%，相对标准偏差为0.76%～13.37%。结果各项性能指标符合欧盟、日本等对植物源性食品中农药残留的检测要求，为我国植物源性食品中该类农药的进出口检验提供了理论基础。

Abstract:

An analytical method based on a modified QuEChERS sample preparation technique combined with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed for the simultaneous determination of tebufloquin and its metabolite (tebufloquin-desacetyl) residues in plant-derived foods. Following extraction with a citrate-acetonitrile solution, the sample extract was purified using C18, PAX, and a novel adsorbent, XFM64 (nitrogen-doped multi-walled carbon nanotubes). Chromatographic separation was performed on a C18 column with a gradient elution of methanol and an aqueous solution containing 0.1% formic acid and 2 mmol·L-1 ammonium acetate. Detection was carried out in electrospray positive ionization (ESI+) and multiple reaction monitoring (MRM) modes, and quantification was achieved using a matrix-matched external standard method.Validation results in eight matrices including grape, cucumber, and pear demonstrated satisfactory performance: good linearity was observed for the target compounds (r2>0.9977), with limits of detection (LOD) ranging from 0.03 to 0.30 μg·kg-1 and limits of quantification (LOQ) from 0.10 to 1.00 μg·kg?1. At three fortified levels of 1.0, 2.0, and 10.0 μg·kg?1, the average recoveries ranged from 80.04% to 115.02%, with relative standard deviations (RSDs) between 0.76% and 13.37%. All performance indicators met the detection requirements for pesticide residues in plant-derived foods stipulated by regulations such as those of the European Union and Japan. This study provides a theoretical foundation for the import and export inspection of such pesticides in plant-derived foods in China.