QuEChERS-超高效液相色谱-串联质谱法快速测定凉茶中非法添加的12种化学药物

建立了凉茶中马来酸氯苯那敏、吡罗昔康、α-细辛脑等12种非法添加的化学药物的QuEChERS结合超高效液相色谱-串联质谱(UPLC-MS/MS)的检测方法。样品经乙腈提取,应用QuEChERS技术净化,经0.22 μm微孔滤膜过滤后进行UPLC-MS/MS测定,以乙腈-0.1%(v/v)乙酸水溶液为流动相梯度洗脱,在XBridge BEH C₁₈柱(100 mm×2.1 mm, 3.5 μm)上实现12种化学药物的基线分离。该方法采用多反应监测(MRM)正离子模式扫描,标准曲线外标法定量。12种待测物在各自的质量浓度范围内线性关系良好,相关系数均大于0.997,检出限为0.1~2.1 μg/L,定量限为0.4~8.0 μg/L。在3个不同添加水平下的平均回收率为62.7%~95.2%, RSD为1.3%~10.8%。应用该方法对市面上销售的74批次凉茶进行了筛查测定,部分样品的测定结果为阳性。该方法操作简单,净化效果好,灵敏度高,适用于凉茶中12种非法添加的化学药物的快速分析。

Determination of twelve chemical drugs illegally added in herbal tea by ultra high performance liquid chromatography-tandem mass spectrometry coupled with modified QuEChERS

An ultra high performance liquid chromatography-tandem mass spectrometry method with modified QuEChERS procedure for sample preparation was developed for the simultaneous determination of 12 chemical drugs (chlorpheniramine, piroxicam, α-asarone etc) illegally added in herbal tea. The samples were extracted with acetonitrile, purified with QuEChERS procedure and filtrated by 0.22 μm microporous filters. The separation was carried on an XBridge BEH C₁₈ column (100 mm×2.1 mm, 3.5 μm) by a gradient elution using acetonitrile/0.1%(v/v) formic acid aqueous solution as mobile phases. The analytes were detected by tandem mass spectrometry with positive electrospray ionization (ESI⁺) in multiple reaction monitoring (MRM) mode, and quantified by external standard calibration method. The correlation coefficients of the standard calibration curves for the 12 analytes were all above 0.997. The limits of detection ranged from 0.1 μg/L to 2.1 μg/L, and the limits of quantification ranged from 0.4 μg/L to 8.0 μg/L. The average recoveries of the 12 analytes spiked at three levels in blank samples ranged from 62.7% to 95.2% with the RSDs from 1.3% to 10.8%. The samples bought from markets were screened, and some of the samples showed positive for these analytes. The method developed is easy to operate, sensitive, and with good purification effect. It can be applied to the rapid determination of the 12 chemical drugs illegally added in herbal tea.