目的 建立生三七Notoginseng Radix et Rhizoma与烤制三七、蒸制三七HPLC指纹图谱，并结合多元统计分析研究三七炮制前后化学成分变化，为三七炮制质量评价与质量标志物（Q-Markers）识别提供参考。方法 采用HPLC法进行测定，建立不同炮制方法下的指纹图谱；通过热图分析和层次聚类分析（hierarchical clustering analysis，HCA）、主成分分析（principal component analysis，PCA）、正交偏最小二乘法-判别分析（orthogonal partial least squares-discrimination analysis，OPLS-DA）对指纹图谱进行分析评价，同时对10个主要成分进行定量测定，阐明炮制前后差异成分，结合超高效液相色谱-串联四极杆飞行时间质谱（UPLC-Q-TOF-MS/MS）法快速预测熟三七中的化合物，对主要色谱峰进行鉴定，分析裂解规律。结果 建立三七不同炮制时间、方法的叠加指纹图谱，共匹配13个主要色谱峰，通过对照品比对指认了其中10个色谱峰。烤制230 ℃、6 h时，新生成的皂苷较蒸制转化率高且含量最大，进而把该烤制条件作为最佳的炮制方法。HCA将不同条件下炮制的三七分为2类，PCA可以明显区分不同炮制方法及时间的三七，OPLS-DA的VIP值确定了人参皂苷Rk₁、Rg₅、Rk₃、Rh₄、Rb₁、Rd这6个Q-Markers，采用UPLC-Q-TOF-MS/MS对熟三七中化合物进行预测，对其主要色谱峰进行定性分析，推测新生成皂苷可能的裂解规律。已有文献报道人参皂苷Rk₃、Rh₄均具有补血的作用，验证三七“生打熟补”的传统应用，说明建立的烤制方法具备科学依据。结论 建立的HPLC指纹图谱、含量测定、UPLC-Q-TOF-MS/MS定性分析结果指出，与传统蒸制相比，烤制法可使三七中“熟补”的化学成分转化率高；对三七及其炮制品的质量控制具有重要意义。

Objective To establish HPLC fingerprints of raw Sanqi (Notoginseng Radix et Rhizoma, NRR) with steamed NRR and baked NRR, and to study the changes of chemical constituents before and after NRR concocting by combining multivariate statistical analyses and measurements, so as to provide a reference for the evaluation of NRR concocting quality and the quality markers (Q-Markers). Methods The determination was performed by HPLC to establish the fingerprints under different concoctions; The fingerprints were analyzed and evaluated by heatmap analysis, hierarchical clustering analysis (HCA), principal component analysis (PCA), orthogonal partial least squares-discriminant analysis (OPLS-DA), and quantitative determination of the ten main components to identify the differences in components before and after processing. Ultra performance liquid chromatography-tandem quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS/MS) was used to rapidly predict the compounds in cooked NRR, and the major chromatographic peaks were analyzed qualitatively to speculate the possible cleavage pattern of the newly generated saponins. Results A total of 13 principal chromatographic peaks were matched in the superimposed fingerprints of different processing times and methods of NRR, and 10 of these peaks were identified by comparison with the control sample. At 230 ℃ for 6 h of baking, the newly generated saponins had a higher conversion rate and the largest content than that of steaming, and then 230 ℃ and 6 h of baking were taken as the optimal concoction method and concoction time. HCA classified NRR with different concoction times into two categories, and PCA could obviously distinguish NRR with different concoction times. VIP values in OPLS-DA identified six markers of quality—ginsenoside Rk₁, Rg₅, Rk₃, Rh₄, Rb₁ and Rd. UPLC-Q-TOF-MS/MS was used for the prediction of the compounds in ripe NRR. The main chromatographic peaks of raw and cooked NRR were qualitatively analyzed, and speculate on the possible cleavage pattern of the newly generated saponins. The ginsenoside Rk₃ and Rh₄ have the effect of tonifying blood, which verifies the traditional application of NRR. Conclusion The results of HPLC fingerprinting and content determination, UPLC-Q-TOF-MS/MS qualitative analyses pointed out that compared with traditional steaming, the baking method can achieve a higher conversion rate of the chemical components in NRR; which is of great significance for the quality control of NRR and its concocted products.

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国家自然科学基金项目（82360690）;云南省基础研究计划中医药联合专项-面上项目（202301AZ070001-044）;“云岭学者”支持计划;云南省重点领域科技计划项目（202303AC100025）;云南省科技厅重大科技专项计划（202402AA310027）;云南省教育厅科学研究基金项目（2024Y351）