QuEChERS/气相色谱-质谱法同时测定砂仁中樟脑质谱法同时测定砂仁中樟脑、龙脑龙脑、乙酸龙脑酯含量乙酸龙脑酯含量

Simultaneous Determination of Camphor,Borneol and Bornyl Acetate in Amomi Fructus by QuEChERS/GC-MS

目的建立同时测定砂仁中樟脑、龙脑、乙酸龙脑酯含量的QuEChERS/气相色谱-质谱(QuEChERS/GC-MS)法。方法样品用无水乙醇提取,经N-丙基乙二胺、十八烷基硅烷键合硅胶、石墨化炭黑和硫酸镁吸附净化处理。色谱柱为HP-5 MS型色谱柱(30 m×0.25 mm,0.25μm),程序升温,流速为1.0 mL/min,分流进样,分流比为20∶1,电子轰击离子源,选择性监测、全扫描模式,定量特征离子质荷比为95。比较QuEChERS/GC-MS法和气相色谱-氢火焰离子化检测器(GC-FID)法含量测定结果的相对相差值,考察方法的可靠性。结果樟脑、龙脑、乙酸龙脑酯的质量浓度分别在50~2000μg/mL、5~200μg/mL、100~5000μg/mL范围内与峰面积线性关系良好(R2≥0.997,n=6);检测限均为0.005 mg/kg,定量限均为0.015 mg/kg;精密度、稳定性、重复性试验的RSD均低于3.0%;50%,100%,200%水平的加样回收率为93.37%~105.37%,RSD为1.38%~2.85%(n=6)。QuEChERS/GC-MS法和GC-FID法测定樟脑、龙脑、乙酸龙脑酯含量的相对相差值分别为4.76%,4.64%,3.67%。结论该方法操作简便、灵敏度高、重复性好、结果准确,可用于砂仁中樟脑、龙脑、乙酸龙脑酯的含量测定。

Objective To establish a QuEChERS/gas chromatography-mass spectrometry(GC-MS)method for simultaneous determination of camphor,borneol and bornyl acetate in Amomi Fructus.Methods The sample was extracted with anhydrous ethanol and purified by a mixed sorbent of primary secondary amine(PSA),octadecylsilane bonded silica gel(C_(18)),graphitized carbon black(GCB)and magnesium sulfate(MgSO4).The chromatographic column was HP-5 MS type chromatographic column(30 m×0.25 mm,0.25μm)with programmed heating,the flow rate was 1.0 mL/min,the split injection was adopted with the split ratio of 20∶1,electron impact ion source was adopted with selected ion monitoring,full scan mode,and the quantitative characteristic ion mass to charge ratio was 95.The relative difference of the content determined by the QuEChERS/GC-MS method and the gas chromatography hydrogen flame ionization detector(GC-FID)method was compared,and the reliability of the methods was evaluated.Results The linear ranges of camphor,borneol and bornyl acetate were 50-2000μg/mL,5-200μg/mL,and 100-5000μg/mL(R2≥0.997,n=6),respectively.The limit of detection(LOD)was 0.005 mg/kg and the limit of quantification(LOQ)was 0.015 mg/kg.The RSDs of precision,stability,and repeatability tests were all lower than 3.0%.The recoveries of samples with 50%,100%,and 200%levels were in the range of 93.37%-105.37%with RSD of 1.38%-2.85%(n=6).The relative differences in the content of camphor,borneol,and bornyl acetate determined by the QuEChERS/GC-MS method and the GC-FID method were 4.76%,4.64%,and 3.67%,respectively.Conclusion The method is simple and rapid,with good sensitivity,accuracy,and precision,which can be used for the content determination of camphor,borneol,and bornyl acetate in Amomi Fructus.