QuEChERS-UPLC-MS/MS-内标法测定肉制餐饮食品中5种罂粟壳生物碱

建立改进的QuEChERS（quick, easy, cheap, effective, rugged, safe）方法，以内标法结合超高效液相色谱-串联质谱法（ultra high performance liquid chromatography-tandem mass spectrometry，UPLC-MS/MS）测定肉制餐饮食品中吗啡、可待因、那可丁、罂粟碱、蒂巴因5 种罂粟壳生物碱。样品经乙腈-体积分数0.1%氨水提取，净化包（2 g无水硫酸镁、50 mg N-丙基乙二胺，100 mg C18E）净化，选择含10 mmol/L甲酸铵的体积分数0.1%甲酸-水溶液和体积分数0.1%甲酸-乙腈溶液作为流动相，采用等度洗脱，使净化液中5 种罂粟壳生物碱经HILIC Core-shell色谱柱（50.0 mm×2.1 mm，1.7 μm）分离，在多反应监测模式下利用电喷雾电离源正离子模式扫描获得质谱数据，内标法定量。结果表明：5 种罂粟壳生物碱可在8 min内有效分离，且罂粟碱、那可丁、蒂巴因在0.2～20.0 ng/mL质量浓度范围内线性良好，吗啡、可待因在1.0～100.0 ng/mL范围内线性良好，r均大于0.999，方法检出限为0.3～2.5 ng/mL，定量限为1.0～7.5 ng/mL，5 种罂粟壳生物碱的平均回收率为85.8%～107.4%，相对标准偏差为0.5%～4.7%。该方法操作简单、净化效果好、检测效率高，适用于餐饮肉制食品中5 种罂粟壳生物碱的快速检测。

Determination of Five Poppy Husk Alkaloids in Meat Products Used in the Catering Industry by QuEChERS Combined with Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry Using Internal Standard Method

An analytical method using a modified QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction procedure combined with ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with an internal standard was developed for the determination of five poppy husk alkaloids in meat products used in the catering industry, including morphine, codeine, nocictin, papaverine and thibaine. Samples were extracted with acetonitrile-0.1% (V/V) aqueous ammonia solution and the extract was purified with a mixture of sorbents: 2 g of anhydrous magnesium sulfate, 50 mg of primary secondary amine (PSA), and 100 mg of C18E. Complete separation of the poppy husk alkaloids was achieved on an ACQUITY UPLC? HILIC Core-shell chromatographic column (50.0 mm × 2.1 mm, 1.7 μm) using a mobile phase composed of 10 mmol/L ammonium formate and 0.1% formic acid in acetonitrile by gradient elution. Mass spectrometric data were acquired using an electrospray ionization (ESI) source in the positive ion mode with multi-reaction monitoring (MRM). The analytes were quantified by an internal standard method. The results showed that the five poppy husk alkaloids could be separated effectively within eight minutes and good linearity were obtained for morphine and codeine in the range of 0.2–20.0 ng/mL and for the other amines in the range of 1.0–100.0 ng/mL (r > 0.999). The limits of detection (LOD) and limits of quantification (LOQ) were in the range from 0.3 to 1.5 ng/mL and from 1.0 to 5.0 ng/mL, respectively. Satisfactory recoveries for spiked samples were obtained in the range of 85.8%–107.4% with relative standard deviation (RSD) lower than 4.7%. In summary, the method is easy to operate and has good purification effect and high detection efficiency. It can be applied to the rapid determination of the five poppy husk alkaloids in meat products used in the catering industry.