基于UPLC-Q-Trap-MS技术的热处理前后绞股蓝中9种皂苷成分同时定量分析

Simultaneous quantitative analysis of nine saponins in Gynostemma pentaphyllum before and after heat processing based on UPLC-Q-Trap-MS

热处理绞股蓝具有更强的生物活性,其主要成分为皂苷类化合物。为进一步探究热处理前后绞股蓝皂苷成分的变化,该研究对福建漳州、广西金秀2个产地绞股蓝中的9种皂苷成分进行含量测定,超高效液相色谱-四极杆离子阱质谱联用(UPLC-Q-Trap-MS)技术,色谱柱为ACQUITY UPLC BEH C18(2.1 mm×50 mm,1.7μm),流动相为乙腈-0.1%甲酸水溶液,梯度洗脱,流速0.3 mL·min-1,柱温30℃。采用电喷雾离子源(ESI)及多反应监测模式(MRM)进行定量分析。结果显示,福建漳州产绞股蓝热处理后的皂苷活性成分gypenoside L、gypenoside LI、damulin A、damulin B及人参皂苷Rg3(S)、人参皂苷Rg3(R)的质量分数分别增加了7.369、8.289、12.155、7.587、0.929、1.068μg·g^(-1),原药材中含量较多的人参皂苷Rd、gypenoside LVI、gypenoside XLVI有所下降,分别减少了0.779、19.37、9.19μg·g^(-1);广西金秀产绞股蓝热处理后的gypenoside L、gypenoside LI、damulin A、damulin B及人参皂苷Rg3(S)、人参皂苷Rg3(R)的质量分数分别增加了0.100、0.161、0.317、0.228、3.280、3.395μg·g^(-1),原药材中的人参皂苷Rd、gypenoside LVI、gypenoside XLVI分别减少了1.661、0.014、0.010μg·g^(-1)。提示热处理方法是绞股蓝稀有皂苷转化的有效途径,同时发现不同产区绞股蓝皂苷含量存在较大差异。

Heat-processed Gynostemma pentaphyllum has strong biological activity,and saponins are the main components.To investigate the changes of saponins in G.pentaphyllum before and after heat processing,the present study determined and analyzed the content of nine saponins in G.pentaphyllum from Zhangzhou of Fujian and Jinxiu of Guangxi by ultra-high performance liquid chromatography with quadrupole ion-trap mass spectrometry(UPLC-Q-Trap-MS).The separation of the analytes was performed on an ACQUITY UPLC BEH C18 column(2.1 mm×50 mm,1.7μm)at 30℃,with acetonitrile and 0.1%formic acid in water as the mobile phase by gradient elution,and the flow rate was 0.3 mL·min-1.Quantitative analysis was performed using electrospray ionization source(ESI)in the multiple reaction-monitoring(MRM)mode.The results showed that the content of saponins with biological activities increased after heat processing.Specifically,gypenoside L,gypenoside LI,damulin A,damulin B,ginsenoside Rg3(S),and ginsenoside Rg3(R)in G.pentaphyllum produced in Zhangzhou of Fujian increased by 7.369,8.289,12.155,7.587,0.929,and 1.068μg·g^(-1),respectively,while the content of ginsenoside Rd,gypenoside LVI,and gypenoside XLVI,which were abundant in the raw materials,decreased by 0.779,19.37,and 9.19μg·g^(-1),respectively.The content of gypenoside L,gypenoside LI,damulin A,damulin B,ginsenoside Rg3(S),and ginsenoside Rg3(R)in G.pentaphyllum produced in Jinxiu of Guangxi increased by 0.100,0.161,0.317,0.228,3.280,and 3.395μg·g^(-1),respectively,while the content of ginsenoside Rd,gypenoside LVI,and gypenoside XLVI in the raw materials was reduced by 1.661,0.014,and 0.010μg·g^(-1),respectively.The results suggest that heat processing is an effective way to transform rare gypenosides.Furthermore,it is found that there are great differences in the content of gypenosides in different regions.