ABSTRACTStar anise has been used for a long time in improving human health and curing diseases, owing to its unlimited components with complex chemical structures and a wide range of bioactivities. This study is aimed to investigate the influence of extraction methods (steam distillation, ethanol Soxhlet extraction, supercritical carbon dioxide extraction, subcritical n‐butane extraction) on the yield, aroma properties, chemical composition, and bioactivity of star anise essential oils. Electronic nose detection revealed the essential oils from subcritical extraction exhibited the most intense aroma, while the essential oils from ethanol Soxhlet extraction had a more complex aroma profile. Fourier‐transform infrared analysis showed the presence of benzene rings, carbonyl groups, C=C, and aromatic ether bonds in the essential oils extracted through different methods. The major components were heterocyclic olefins, heterocyclic oxygenates, and aromatic oxygenates, as well as certain amounts of flavonoids and polyphenols. Correlation analysis revealed the relative contents of volatile trans‐anethole, wormwood, d‐limonene, cineole, and trans‐α‐citronelene were strongly associated with the antibacterial activity of the essential oils. Similarly, the contents of volatile components (d‐limonene, cineole) and non‐volatile components (total flavonoids and total polyphenols) were strongly correlated with the DPPH scavenging activity of the essential oils. These results confirm the effectiveness of the ethanol Soxhlet extraction method in retaining the bioactivity of the essential oils. Finally, with a Box–Behnken central composite design of response surface and single‐factor experiments, the optimal extraction conditions for the ethanol Soxhlet method were determined: ultrasonic frequency of 80 kHz, crushing particle size of 60 meshes, liquid–material ratio of 8:1 (mL:g), and ultrasonic time of 35 min. Under these conditions, the essential oil yield was 25.51% ± 0.21%. Overall, these findings highlight the significance of extraction methods in obtaining high‐quality star anise essential oils with desirable aroma properties and potent bioactivities.
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