混合型固相萃取-UHPLC/MS/MS法测定银杏酮酯滴丸中银杏酸含量

Determination of ginkgolic acids in Yinxing Tongzhi Dropping Pills by mix-mode SPE-UHPLC/MS/MS

建立了超高效液相色谱串联三重四极杆质谱测定银杏酮酯滴丸中银杏酸的方法。采用混合型强阴离子反相吸附固相萃取净化样品, Waters Cortecs T3色谱柱(50 mm×2.1mm,2.7μm),以乙腈-甲醇-1%冰醋酸溶液(44∶44∶12)为流动相,在电喷雾离子化负离子模式下,以多反应监测方式(MRM)检测。银杏酸C13∶0、C15∶1、C17∶1分别在0.2~200、2~200和4~200μg·L^(-1)范围内成良好线性关系,相关系数均大于0.999;在50、250和600μg·kg^(-1)加标水平下的平均加样回收率为70.8%~95.1%,相对标准偏差(RSD)为0.7%~8.6%;定量限分别为1、10、20μg·kg^(-1)。本方法可应用于复杂基质样品的银杏酸测定。

An analytical method was developed for determination of ginkgolic acids in Yinxing Tongzhi Dropping Pills by ultra high performance liquid chromatography-triple quadrupole mass spectrometry. The samples were purified by mix-mode anion exchange and reversed-phase SPE. A chromatographic column, Waters Cortecs T3（50 mm × 2.1 mm, 2.7 μm）, was used with acetonitrile-methanol-1% acetic acid（44∶44∶12） as the mobile phase. The ginkgolic acids were detected by electrospray ionization mass spectrometry in negative mode with multiple reaction monitoring（MRM） mode. Ginkgolic acid C13∶0, C15∶1 and C17∶1 possessed good linear correlation in the mass concentration range from 0.2 to 200 μg·L^（-1）, 2 to 200 μg·L-1, 4 to 200 μg·L^（-1）, respectively, with the correlation coefficients more than 0.999. The mean recoveries at spiked levels of 50, 250 and 600 μg·kg^（-1） were in the range of 70.8%-95.1%, and the RSDs were 0.7%-8.6%. The limits of quantification were 1, 10, 20 μg·kg^（-1）, respectively. The method could be applied to the analysis of ginkgolic acids in complex matrix samples.