Chemical Profiling of Chixiaodou Danggui San Using Liquid Chromatography–Tandem Mass Spectrometry With Data Mining Strategy

ABSTRACT Rationale 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. Methods 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. Results 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. Conclusions Our findings represent a crucial step in elucidating the active compounds in CDS for the treatment of hemorrhoids.