QuEChERS/高效液相色谱-四极杆-飞行时间质谱法测定巧克力中的18种合成大麻素

Determination of 18 Synthetic Cannabinoids in Chocolate by QuEChERS/High Performance Liquid Chromatography-Quadrupole-Time of Flight Mass Spectrometry

建立了检测巧克力中18种合成大麻素的QuEChERS/高效液相色谱-四极杆-飞行时间质谱方法。通过优化提取溶剂种类、提取条件和净化条件,确定200.0 mg巧克力采用1 mL甲醇超声提取10 min,取上层清液加入0.05 g C_(18)和0.05 g PSA净化后,以乙腈和0.1%甲酸水溶液为流动相进行梯度洗脱,采用ZORBAX Eclipse Plus C_(18)(3.0 mm×100 mm,1.8μm)色谱柱进行色谱分离,利用四极杆-飞行时间质谱检测。18种合成大麻素在11 min内实现了分离,5F-EMB-PICA与5F-MDMB-PICA同分异构体通过色谱保留时间和二级质谱碎片实现分辨;5F-EMB-PINACA与5F-ADB同分异构体通过二级质谱碎片实现分辨。18种合成大麻素在1~200μg/L范围内呈良好线性关系,相关系数均不小于0.9970,检出限为0.02~0.20μg/L,定量下限为0.07~0.66μg/L,在50、100、150μg/kg加标水平下样品的回收率为86.2%~104%,仪器的相对标准偏差(RSD)为0.040%~2.0%,方法的日内RSD为0.32%~3.0%,日间RSD为1.3%~3.6%。该方法灵敏度高、稳定性强、分析速度快,可为巧克力产品的安全监管和打击合成大麻素类毒品犯罪提供技术支持。

A method for the determination of 18 synthetic cannabinoids in chocolate based on QuEChERS/high performance liquid chromatography-quadrupole-time of flight mass spectrometry was established.By optimization the type of extraction solvent,sample extraction and purification conditions,it was determined that 200.0 mg of chocolate was extracted by ultrasonic extraction with 1 mL of methanol for 10 min,and then the supernatant was purified by adding 0.05 g of C_(18) and 0.05 g of PSA.The separation was achieved on ZORBAX Eclipse Plus C_(18)(3.0 mm×100 mm,1.8μm)column with gradient elution of acetonitrile and 0.1%formic acid aqueous solution as the mobile phase.Quadrupole-time of flight high resolution mass spectrometry was used for detection.Eighteen synthetic cannabinoids were separated and detected within 11 min.Two pairs of isomers:5F-EMBPICA and 5F-MDMB-PICA were resolved by chromatographic retention time and secondary mass spectrum fragments;5F-EMB-PINACA and 5F-ADB are resolved by secondary mass spectrometry fragments.18 synthetic cannabinoids obtained good linear relations in concentration ranges of 1-200μg/L with correlation coefficients not less than 0.9970.The limits of detection were between 0.02μg/L and 0.20μg/L,and the limits of quantitation were between 0.07μg/L and 0.66μg/L.The recoveries of samples at spiked levels of 50,100 and 150μg/kg were between 86.2%and 104%.The relative standard deviations(RSDs)of instrument was between 0.040%and 2.0%,the intra-day RSDs of method was between 0.32%and 3.0%and the inter-day RSDs of method was between 1.3%and 3.6%.This method has the advantages of high sensitivity,strong stability and fast analysis speed,and provide technical support for the safety supervision of chocolate products and the fight against synthetic cannabinoid drug crimes.