高效液相色谱-串联质谱法快速测定食品中5种罂粟壳生物碱

Rapid Determination of Five Opium Poppy Husk Alkaloids in Foods by HPLC-MS/MS

建立了高效液相色谱-串联质谱法(HPLC-MS/MS)定性定量分析食品中非法添加的吗啡、可待因、蒂巴因、罂粟碱和那可丁等5种罂粟壳生物碱。采用Capcell PAK C18TYPE MGⅡ(5μm×2.0mm×150mm)色谱柱分离,以10mmol/L乙酸铵(pH 4.2)-乙腈为流动相,梯度洗脱,电喷雾离子源,多反应监测(MRM)模式检测。在优化的实验条件下,得到了较宽的线性范围和较低的定量检出限。吗啡和可待因的线性范围为1.0~20.0μg/L,蒂巴因、罂粟碱和那可丁的线性范围为0.2~4.0μg/L,相关系数均在0.999以上。食品中吗啡、可待因、蒂巴因、罂粟碱和那可丁的定量限分别为7.5、7.5、1.5、1.5、1.5μg/kg。方法的回收率和重现性较好,5种罂粟壳生物碱的回收率在72.2%~111.4%之间,相对标准偏差(RSD)在3.1%~8.8%之间。该方法操作简单、灵敏度高、准确可靠,可用于食品中5种非法添加罂粟壳生物碱的定量及确证分析。

A method of high performance liquid chromatography coupled with tandem mass spectrometry （HPLC-MS/MS） was developed for simultaneous determination of the residues of five opium poppy husk alkaloids in foods, such as morphine, codeine, tibane, papaverine and narcotinum. The samples were extracted by methanol （containing 5% ammonia acetate）, and then analyzed by HPLC-MS/MS. The separation was carried out by a Capcell PAK C18 TYPE MGⅡ（5 μm×2.0 mm×150 mm） column, with 10 mmol/L ammonium acetate （pH 4.2） and acetonitrile as mobile phases at a flow rate of 0.2 mL/min. Multiple reaction monitoring （MRM） mode was applied, with positive ion electrospray ionization （ESI）. Sample matrix-matched calibration was used to determine the residue contents by external standard. Under the optimized detection conditions, the linear ranges for morphine and codeine are 1.0-20.0 μg/L, and for tibane, papaverine and narcotinum are 0.2-4.0 μg/L, the linear correlation coefficients are all more than 0.999. The limits of quantification for morphine, codeine, tibane, papaverine and narcotinum are 7.5, 7.5, 1.5, 1.5 and 1.5 μg/kg, respectively. The recoveries of five opium poppy husk alkaloids range from 72.2% to 111.4% with the relative standard deviations （RSD） of 3.1%-8.8%. This method is simple, effective and sensitive, which is suitable for the determination and confirmation of five opium poppy husk alkaloids added in the foods illegally.