高效液相色谱-串联质谱法同时测定中药中的玉米赤酶烯酮和α-玉米赤霉烯醇

Simultaneous determination of zearalenone and α-zearalenol in traditional Chinese medicines by high performance liquid chromatography-tandem mass spectrometry

目的：建立同时测定中药中真菌毒素玉米赤酶烯酮（ZON）和α-玉米赤霉烯醇（α-ZOL）的高效液相色谱-串联质谱法,对市售中药材及其制品中的ZON和α-ZOL进行检测。方法：样品经甲醇-水溶液（80∶20,v/v）提取,免疫亲和柱净化,C18分析色谱柱分离,以0.1%（v/v）甲酸-水/0.1%（v/v）甲酸-乙腈为流动相,采用梯度洗脱方式进行液相色谱分离,多反应监测模式,以染料木素为内标进行定量。结果：在0.1 ng.m l-1~500 ng.m l-1范围内,ZON和α-ZOL的线性相关系数分别为0.9981和0.9988。通过添加回收试验,两种毒素的定量限（S/N=10）均为0.12μg.kg-1,ZON三个添加水平的回收率为74.4%~96.5%,相对标准偏差为1.7%~5.0%;α-ZOL三个添加水平的回收率为89.3%~98.3%,相对标准偏差为1.5%~8.1%。结论：该方法简单快速、灵敏度和选择性高,适用于中药中微量真菌毒素ZON和α-ZOL的检测。

Objective：To evaluate a method for the determination of zearalenone and α-zearalenol by HPLC-MS/MS in 25 widely consumed Chinese medicinal herbs and related products（CMHRP） samples collected from different regions of China.Methods： The samples were extracted by methanol-water（80∶ 20,v/v）,cleaned up by immunoaffinity column.The HPLC separation was performed on a C18 column with a linear gradient elution program of 0.1%（v/v） formic acid solution and 0.1%（v/v） formic acid-acetonitrile as the mobile phase.Multiple reaction monitoring（MRM） was used for the selective detection of ZON and α-ZOL.Results： The linearity of ZON and α-ZOL in the range from 0.1 to 500 ng·ml-1 was 0.9981 and 0.9988,respectively.In the detection of spiked samples,the quantification limit of the method was 0.12 μg/kg for the two toxins.The recoveries of ZON were 74.4%~96.5% with the relative standard deviations of 1.7%~5.0%,and the recoveries of α-ZOL were 89.3%~98.3% with the relative standard deviations of 1.5%~8.1%.Internal standard calibration was used for the quantitative analysis.Conclusion： This method was simple,fast,highly sensitive and selective for the detection of ZON and α-ZOL in traditional Chinese medicinals.