高效液相色谱-四极杆-飞行时间质谱法快速筛查保健食品中10种雄性激素类非法添加物

Rapid Screening of 10 Illegally Adulterated Androgen Drugs in Health Foods by High Performance Liquid Chromatography-Quadrupole-Time-of-flight Mass Spectrometry

建立了快速筛查保健食品中10种雄性激素类非法添加物的高效液相色谱-四极杆-飞行时间质谱(HPLC-Q-TOF MS)法。样品经直接超声或液液萃取,C18色谱柱(3.0 mm×150 mm,1.8μm)分离,以0.1%甲酸溶液(含10 mmol/L乙酸铵)-0.1%甲酸乙腈溶液梯度洗脱,采用HPLC-Q-TOF MS检测。构建10种雄性激素的一级精确质量数据库和二级谱库,通过化合物的精确质量数、保留时间、同位素比值、二级谱图等信息对检测结果进行自动检索,实现对实际样品快速准确的定性分析。结果表明,10种雄性激素在2~500 ng/mL范围内线性关系良好,相关系数(r^2)均大于0.999,在固体基质、液体基质和油性基质中的检出限为0.01~0.06 mg/kg,定量下限为0.03~0.2 mg/kg,平均回收率为74.3%~113%,相对标准偏差(RSD)为1.2%~7.7%。该方法利用自建标准谱库检索实现快速筛查,样品前处理方法简单,具有专属性好、快速、灵敏、高效等优点,适用于缓解体力疲劳类保健食品中非法添加物的快速筛查和识别。

An analytical method was established for the determination of 10 illegally adulterated androgen drugs in health foods by high performance liquid chromatography-quadrupole-time-of-flight mass spectrometry(HPLC-Q-TOF MS).The samples were extracted by ultrasonic cleaning or liquid-liquid extraction.10 androgen drugs were separated on a C18 column(3.0 mm×150 mm,1.8μm)by gradient elution with 0.1%(by volume)formic acid containing 10 mmol/L ammonium acetate and 0.1%formic acid acetonitrile,and determined by HPLC-Q-TOF MS.A data base of the accurate molecular mass and a library containing the 10 androgen drugs were established.An automatic retrieval towards the detected results was carried on according to the characteristics of the compound,such as accurate mass,retention time,isotopic ratio and MS/MS spectrum in order to carry out a rapid qualitative analysis.Results showed that 10 androgen drugs had good linear relationships in the concentration range of 2-500 ng/mL with correlation coefficients(r^2)greater than 0.999.The limits of detection(LOD)for 10 androgen drugs in three kinds of matrixes were in the range of 0.01-0.06 mg/kg,while the limits of quantitation(LOQ)were 0.03-0.2 mg/kg.The average recoveries for 10 androgen drugs ranged from 74.3%to 113%with relative standard deviations(RSD)of 1.2%-7.7%.Using library search function to rapid screen,which is efficient,sensitive and accurate,the method is suitable for rapid screening of 10 illegally adulterated androgen drugs in health foods.