目的 建立了高效液相色谱-电喷雾三重四极杆质谱法（HPLC-ESI-MS/MS）同时测定珠子参中15种皂苷类化合物（人参皂苷Rb₂、人参皂苷Re、人参皂苷Ro、人参皂苷Rd、人参皂苷Rg₁、人参皂苷Rb₃、人参皂苷Rb₁、人参皂苷Rc、人参皂苷Rh₂、人参皂苷F₂、人参皂苷Rg₃、人参皂苷Rf、三七皂苷R₁、姜状三七皂苷R₁、竹节参皂苷IVa）的检测方法。方法 采用Waters Sunfire TM C₁₈色谱柱（150 mm×1.5 mm，5 μm），以含0.05%甲酸的乙腈-水（10∶90）为流动相，梯度洗脱分离，HPLC-ESI-MS/MS多反应监测模式（MRM）检测，外标法定量。优化了色谱分离条件、质谱去簇电压（DP）、碰撞能量（CE）和碰撞池出口电压（CXP）等参数，并考察了浓缩温度、提取时间等对提取率的影响。结果 15种皂苷类化合物在0.000 9~2 952.592 3 μg/mL线性关系良好，r=0.999 6，检出限范围为0.003~626.554 ng/mL，定量限为0.075~1 762.150 ng/mL，平均加样回收率在98.15%~101.12%，RSD为0.82%~2.15%。结论 该方法操作简便、快速、准确、灵敏度高，可以对珠子参中多种皂苷类化合物进行分析鉴定。

Objective A high-performance liquid chromatography-tandem mass spectrometric method for the simultaneous determination of 15 ginsenoside compounds from Panacis Majoris Rhizoma (PMR) was developed. Methods A Waters Sunfire TM C₁₈ column (150 mm×4.6 mm, 5 μm) was used for the separation. The mobile phase consisted of A (H₂O+0.05% HCOOH) and B (CH₃CN+0.05% HCOOH) using a gradient elution. For the quantification of ginsenosides, the multiple reaction monitoring (MRM) mode of the mass spectrometer was applied and the declustering potential (DP), collision energy (CE), and collision cell exit potential (CXP) were optimized to perform automatic on-line MS/MS experiments during the chromatographic separation. Results By using the optimized method, the linearity range of 15 analytes was 0.000 9 to 2 952.592 3 μg/mL with more than 0.999 determination coefficient (r) of linear regressions, the detection limits of the 15 ginsenosides ranged from 0.003 to 626.554 ng/mL, the limits of quantitation ranged from 0.075 to 1 762.150 ng/mL, the recoveries of 15 ginsenosides in the samples were 98.15%-101.12% with relative standard deviation (RSD) that ranged from 0.82% to 2.15%. Conclusion The proposed LC-MS/MS method is accurate and reproducible in accordance with TCM guidelines, showing high sensitivity, rapidness, and recovery. This method allows the assessment of various ginsenosides in a single analytical run providing an innovative tool to control Panacis Majoris Rhizoma materials quantification.

国家自然科学基金项目（81373978，81501229）；陕西省科学技术厅协同创新计划项目（2015XT-35）；陕西省教育厅“春笋计划”项目（2011K16-03-02）；陕西省教育厅专项计划项目（320104-203010012）