目的 以临床常用经典方左金丸黄连Coptidis Rhizoma-吴茱萸Evodiae Fructus药对为例，鉴定药对全局化学成分并推导药对中代表性成分的质谱碎裂规律，为黄连-吴茱萸药对后续质量控制、药效评价、机制研究提供参考。方法 运用超高效液相色谱-飞行时间质谱联用技术（UPLC-Q-TOF-MS），基于MZmine-SIRIUS质谱自动化注释工作流，辅助进行黄连-吴茱萸药对的全局化学成分解析。结果 共鉴定了包括生物碱、有机酸、黄酮、苷类、苦味素类等在内的成分144种，其中已报道成分123种，未报道的新成分21种。此外，根据SIRIUS中Fragmentation Tree推导并绘制黄连及吴茱萸中代表性成分木兰花碱、药根碱、巴马汀、小檗碱、柠檬苦素、奎宁酸、吴茱萸碱、吴茱萸次碱、去氢吴茱萸碱共9个成分的质谱裂解途径。结论 采用质谱自动化注释工作流鉴定了黄连-吴茱萸药对成分，推导药对中代表性的9种主要成分质谱裂解规律，为黄连-吴茱萸药对全成分鉴定和质量控制研究提供参考，为后续基于成分的配伍药效比较及机制考察提供研究基础。

Objective To identify the compounds ofCoptidis Rhizoma - Evodiae Fructus herbal pair from Zuojin Pills (左金丸) and to deduce the mass spectrum fragmentation law of representative components in herbal pair, providing reference for subsequent quality control, efficacy investigation, and compatibility mechanism. Methods Ultrahigh performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS) and automated annotation of mass spectrum based on the MZmine-SIRIUS workflow were used to identify global components from the Coptidis Rhizoma- Evodiae Fructus herbal pair. Results A total of 144 compounds including alkaloids, organic acids, flavonoids, glycosides and picroids were identified in this study, of which 123 were known and 21 were newly identified. In addition, fragmentations of nine typical components, including magnoflorine, jatrorrhizine, palmatine, berberine, limonin, quinic acid, rutaecarpine, evodiamine and dehydroevodiamine, were deduced and draw based on Fragmentation Tree provided by SIRIUS. Conclusion In this study, Coptidis Rhizoma - Evodiae Fructus herbal pair was globally identified by automated mass spectrometry annotation workflow, fragmentations of nine representative main components from this herbal pair were deduced, which provided reference for the study of global component identification and quality control of Coptidis Rhizoma - Evodiae Fructus herbal pair, and provided chemical basis for the subsequent therapeutic effects comparison and mechanism elucidation after herbal combination.

R284.1

国家自然科学基金青年科学基金项目（82304724）;浙江省卫生健康委临床研究应用项目（2024ZL376）;浙江中医药大学自然科学青年探索项目（2023JKZKTS06）