The dried bulbs of Allii Macrostemonis Bulbus (AMB) are called “薤白” in China and are mainly distributed in Asia. The plant species included in the 2020 Edition of the Chinese Pharmacopoeia (ChP) are Allium macrostemon Bunge (called xiaogensuan in Chinese, A. macrostemon) and Allium chinense G. Don (called xie in Chinese, A. chinense), respectively. In the traditional Chinese medicine (TCM) theoretical system, AMB is warm in nature, acrid-bitter taste, and attributive to the heart, lung, stomach, large intestine meridian. AMB has the function of activating Yang and removing stasis, regulating Qi and eliminating stagnation. Modern pharmacological studies have shown that AMB has anti-platelet aggregation, hypolipidemic, anti-atherosclerotic, cardiomyocyte, vascular endothelial cell protection, anti-cancer, anti-bacterial, anti-asthmatic, and anti-oxidant effects. In some Asian countries, AMB is often used to treat coronary heart disease (CHD), angina pectoris (AP), asthma, and diarrhea. This review collates the botanical background, ethnopharmacology, phytochemistry, pharmacological activities, quality control, and toxicological studies of AMB, and provides an outlook on the current research deficiencies and future research priorities of AMB, intending to provide ideas for future research directions and commercial development.

• Nine spirostanol-type saponins, including five novel saponins Macrostemonoside U-Y, were found in Allium macrostemon Bunge. • All saponins were tested for DPPH, ABTS radical scavenging ability and Fe³⁺ reducing ability. • Macrostemonoside U exhibited the strongest in vitro antioxidant activity. • Twelve batches of Allium macrostemon Bunge from different origins and processing methods were examined for the content of nine saponins. • The content of Macrostemonoside W and X is influenced by factors such as its origin and whether it undergoes heating during processing.

Two new compounds named 4,4′-bis(β-D-glucopyranosyloxy)biphenyl (1) and spirostane-25(27)-en-2α,3β-diol-3-O-β-D-xylopyranosyl(1→3)-β-D-glucopyranosyl(1→4)-β-D-galactopyranoside (2) were isolated from n-butanol extraction part of 80% ethanol extract of Allii Macrostemonis Bulbus. Alongside these, ten known compounds (3–12) were also identified, including a flavonoid glycoside (3), seven steroids (4–10), a nucleoside (11), and a phenylpropanoid glycoside (12) were found. Notably, compounds 3–6 were isolated from this plant for the first time. The structures of all compounds were confirmed using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS), 1D, and 2D NMR spectroscopy. Some of these compounds showed strong antioxidant activity, and compound 1 demonstrated the most potent reduction of ferric ions (Fe³⁺) with an IC₅₀ value of 0.59 ± 0.18 mg/mL. Compounds 2 and 3 exhibited the highest scavenging activity against superoxide anion radicals (O₂⁻·) with an IC₅₀ value of 0.02 ± 0.01 mg/mL. Additionally, compound 3 displayed substantial scavenging activity against 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) with IC₅₀ values of 0.21 ± 0.17 mg/mL and 0.02 ± 0.01 mg/mL, respectively. The discovery of these two new compounds is a reference for identifying Allii Macrostemonis Bulbus quality markers. Moreover, their exceptional antioxidant activity offers a promising avenue for uncovering novel natural antioxidants.

As a traditional Chinese medicine (TCM), Allii Macrostemonis Bulbus (AMB) is a key herb for the treatment of thoracic paralytic cardiac pain, but its quality evaluation method has not yet been fully clarified. In this study, chromatographic fingerprints of AMB were developed using solid-phase extraction–high-performance liquid chromatography–evaporative light scattering detection (SPE-HPLC-ELSD) to evaluate the quality of AMB from various origins and processing methods. This was achieved by employing chemical pattern recognition techniques and verifying the feasibility and applicability of the quality evaluation of AMB through the quantitative analysis of multi-components via a single-marker (QAMS) method. Through the analysis of the fingerprints of 18 batches of AMB, 30 common peaks were screened, and 6 components (adenosine, syringin, macrostemonoside T, macrostemonoside A, macrostemonoside U, and macrostemonoside V) were identified. Moreover, three differential markers (macrostemonoside A, macrostemonoside T, and macrostemonoside U) were screened out using chemometrics techniques, including principal component analysis (PCA), hierarchical cluster analysis (HCA), and orthogonal partial least squares discriminant analysis (OPLS-DA). Subsequently, a QAMS method was established for macrostemonoside T and macrostemonoside U using macrostemonoside A as an internal reference. The results demonstrate the method’s accuracy, reproducibility, and stability, rendering it suitable for the quality evaluation of AMB. This study provides a theoretical basis for drug quality control and the discovery of quality markers for AMB.