QuEChERS-高效液相色谱-三重四极杆复合线性离子阱质谱法测定代餐食品中6种非法添加减肥药物的含量

Determination of 6 Illegally Additive Weight-Reducing Drugs in Meal Replacement Foods by High Performance Liquid Chromatography-Triple Quadrupole Composite Linear Ion Trap Mass Spectrometry with QuEChERS

代餐饼干、代餐粥或代餐奶昔样品经磨碎后,分取1.00 g,加入8.00 mL甲醇,振荡2 min,涡旋提取5 min,用甲醇稀释至10.00 mL。离心5 min,取6.00 mL上清液于含25 mg N-丙基乙二胺(PSA)、25 mg十八烷基硅烷键合硅胶(C18)和150 mg硫酸镁的净化管中,涡旋2 min,离心5 min。上清液过0.22μm有机滤膜,滤液采用高效液相色谱-三重四极杆复合线性离子阱质谱法测定。在色谱分析中,以ZORBAX Eclipse Plus C18色谱柱(50 mm×2.1 mm,1.8μm)为固定相,不同体积比的含5 mmoL·L^(-1)乙酸铵的0.1%(体积分数)甲酸溶液和甲醇的混合溶液为流动相进行梯度洗脱;在质谱分析中,以电喷雾离子源正离子模式电离,多反应监测-信息依赖采集-增强子离子(MRM-IDA-EPI)模式扫描,外标法定量。结果显示:6种非法添加减肥药物,西布曲明、N-单去甲基西布曲明、N,N-双去甲基西布曲明、麻黄碱、芬氟拉明、酚酞的质量浓度在0.5~20.0μg·L^(-1)内和峰面积呈线性关系,测定下限(10S/N)为5.0~10μg·kg^(-1);按照标准加入法进行回收试验,回收率为79.5%~102%,测定值的相对标准偏差(n=6)均小于5.0%。方法用于实际样品的分析,40批样品有3批代餐奶昔样品检出了西布曲明,检出量分别为2.60×10^(7),2.62×10^(7),1.86×10^(7)μg·kg^(-1)。

After the meal replacement biscuit,meal replacement congee or meal replacement milkshake sample was ground,an aliquot(1.00 g)was taken,and 8.00 mL of methanol was added.The mixture was shaken for 2 min,extracted by vortex for 5 min,diluted to 10.00 mL by methanol,and centrifuged for 5 min.The 6.00 mL of supernatant was taken,and placed into a purification tube containing 25 mg of N-propyletyhlenediamine(PSA),25 mg of octadecylsilane bonded silica gel(C18),and 150 mg of magnesium sulfate.The mixture was vortexed for 2 min,and centrifuged for 5 min。The supernatant was passed through a 0.22μm organic filter membrane,and the filtrate was determined by high performance liquid chromatography-triple quadrupole composite linear ion trap mass spectrometry.In the chromatographic analysis,a ZORBAX Eclipse Plus C18 column(50 mm×2.1 mm,1.8μm)was used as the stationary phase,and mixed solutions of 0.1%(volume fraction)formic acid solution containing 5 mmol·L^(−1)ammonium acetate and methanol at different volume ratios were used as the mobile phase for gradient elution.In the mass spectrometry analysis,the positive ion mode of the electrospray ion source was used for ionization,multiple reaction monitoring-information dependent acquisition-enhanced product ion(MRM-IDA-EPI)mode was used for scanning,and external standard method was used for quantitative analysis.It was shown that linear relationships between values of the mass concentration and peak area of 6 illegally additive weight-reducing drugs,including sibutramine,N-desmethyl sibutramine,N,N-didesmethyl sibutramine,ephedrine,fenflutamine,and phenolphthalein,were kept in the range of 0.5-20.0μg·L^(−1),with lower limits of determination(10S/N)in the range of 5.0-10μg·kg^(−1).Test for recovery was made according to the standard addition method,giving recoveries in the range of 79.5%-102%,and RSDs(n=6)of the determined values were less than 5.0%.The proposed method was used for the analysis of actual samples,and sibutramine was detected in 3 meal replacement milkshake samples out of 40 batches of samples,with detection amounts of 2.60×10^(7),2.62×10^(7),1.86×10^(7)μg·kg^(−1),respectively.