Chinese Angelica is a significant medical plant due to the various therapeutic constituents in its root; whereas the aerial part is considered worthless and often discarded as agricultural waste. In this work, phytochemicals from the stem were first systematically analyzed by means of GC–MS after derivatization and HPLC–MS/MS in multiple reaction monitoring (MRM) mode. Phthalides, ferulic acid, and coniferyl ferulate were detected in the stem; although their content is relatively low in comparison with the root. Some specific compounds, such as p-hydroxybenzoic acid, vanillic acid, protocatechuic acid, caffeic acid, 4-hydroxyphenyl-1, 2-ethanediol, thymol-β
-glucopyranoside, etc. and a significant amount of phytosterols (1.36 mg/g stem, mainly β-sitosterol) were detected in the stem. The extracted oil from the stem contained a considerable amount of phthalides (48.5 mg/g), β
-sitosterol (56.21 mg/g), and stigmasterol (14.03 mg/g); no other bioactive compounds were found that could be potentially used as pharmaceuticals or additives to healthcare food.
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