Chen Ji, Tan Ting, Luo Yun
The National Pharmaceutical Engineering Center for Solid Preparation in Chinese Herbal Medicine, Jiangxi University of Chinese Medicine, Nanchang, Jiangxi, China.
Key Laboratory of Modern Preparation of Traditional Chinese Medicine, Ministry of Education, Jiangxi University of Chinese Medicine, Nanchang, China.
Rapid Commun Mass Spectrom. 2025 Dec 15;39(23):e10134. doi: 10.1002/rcm.10134.
Chixiaodou Danggui San (CDS), composed of Vignae semen (VS) and Angelicae sinensis radix (ASR), has been utilized for the treatment of hemorrhoids in China. However, the chemical profiling of CDS remains insufficiently explored. Therefore, it is necessary to establish an accurate and rapid method for the chemical profiling of CDS.
The structure elucidation of natural products using ultra-high performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (UHPLC-QTOF-MS/MS), despite its exceptional capabilities, remains limited due to the complexity of mixtures containing hundreds of compounds. In this study, we utilized the UHPLC-QTOF-MS/MS in conjunction with data mining strategy, incorporating diagnostic fragment ions (DFIs) and neutral loss (NL), for the rapid classification and identification of compounds in CDS.
Consequently, 97 chemical compositions were tentatively characterized, comprising 31 flavonoids, 25 triterpenoid saponins, 11 fatty acids, 10 chlorogenic acids, and 20 others. Out of these, 13 were verified using authentic standards. Twenty-one triterpenoid saponins were tentatively characterized as new compounds, which need to be purified, and were identified by NMR data. It is noteworthy that flavonoids and triterpenoid saponins are exclusive to VS, chlorogenic acid is unique to ASR, while fatty acids and other compounds are present in both VS and ASR.
Our findings represent a crucial step in elucidating the active compounds in CDS for the treatment of hemorrhoids.
赤小豆当归散（CDS）由赤小豆（VS）和当归（ASR）组成，在中国已被用于治疗痔疮。然而，CDS的化学图谱仍未得到充分探索。因此，有必要建立一种准确、快速的CDS化学图谱分析方法。
使用超高效液相色谱-四极杆飞行时间串联质谱（UHPLC-QTOF-MS/MS）对天然产物进行结构解析，尽管其功能卓越，但由于含有数百种化合物的混合物的复杂性，其应用仍然有限。在本研究中，我们将UHPLC-QTOF-MS/MS与数据挖掘策略相结合，纳入诊断性碎片离子（DFIs）和中性丢失（NL），用于快速分类和鉴定CDS中的化合物。
因此，初步鉴定了97种化学成分，包括31种黄酮类化合物、25种三萜皂苷、11种脂肪酸、10种绿原酸和20种其他化合物。其中，13种通过标准品进行了验证。21种三萜皂苷初步鉴定为新化合物，需要进行纯化，并通过核磁共振数据进行鉴定。值得注意的是，黄酮类化合物和三萜皂苷是VS所特有的，绿原酸是ASR所特有的，而脂肪酸和其他化合物在VS和ASR中均有存在。
我们的研究结果是阐明CDS中治疗痔疮的活性化合物的关键一步。
