ABSTRACT:
The dried roots of
Angelica dahurica
(Fisch. ex Hoffm.) Benth.et Hook.f. var.
formosana
(Boiss.) Shan et Yuan, a traditional medicinal herb known as
hangbaizhi
, is significant in food and pharmaceutical applications. However, genetic diversity challenges standardized production. This study characterized the secondary metabolite profiles, particularly coumarins, in a newly bred variety of
hangbaizhi
(NAD) and compared them with traditional cultivars (TAD). Using ultra‐high‐performance liquid chromatography‐tandem mass spectrometry integrated with computational strategies, including polygonal mass defect filtering, expanded virtual formula library screening, feature‐based molecular networking, and network annotation propagation, we annotated 95 coumarins (43 simple coumarins, 45 furanocoumarins, and seven dihydrofuranocoumarins) across confidence levels. Multivariate analyses (principal component analysis, orthogonal partial least squares discriminant analysis, and volcano plot) revealed significant metabolic divergence between NAD and TAD. NAD exhibited enriched furanocoumarins and reduced dihydrofuranocoumarins compared to TAD. The newly bred variety demonstrated superior phenotypic homogeneity and distinct coumarin signatures, providing a scientific foundation for quality control and functional food applications. This study also establishes a methodological framework for secondary metabolite profiling in plant breeding programs.