Integrated dual-split high capacity sorptive extraction and chemometrics reveal extraction-dependent volatile signatures in Hypericum perforatum

• CWR/PDMS HiSorb maximises VOC extraction, enabling broad and sensitive volatilome profiling. • Dual‑split GC‑MS workflow captures high‑ and low‑abundance VOCs from a single sample. • Processing methods shape VOC diversity of H. perforatum profiles for different applications. Hypericum perforatum (L.), commonly known as St. John’s Worth, is a medicinal plant rich in bioactive compounds including volatile organic ones, which contribute to its antimicrobial, anti-inflammatory, and wound-healing properties. Optimising the extraction and analysis of these compounds is essential for their application in pharmaceutical, cosmetic and nutraceutical industries. This study employed high-capacity extraction (HiSorb) probes and Gas Chromatography-Mass Spectrometry (GC-MS) to profile volatile organic compounds (VOCs) from hypericum flowering aerial parts. Four HiSorb phases were evaluated, with the double-phase CWR/PDMS demonstrating superior performance by capturing the broadest range of compounds and yielding the highest total peak area. A dual-split strategy was implemented to prevent detector saturation and ensure retention of low-abundance analytes, enabling comprehensive VOC profiling from a single sample. VOCs were analysed across various extract types, including alcoholic, water infused and oil-based preparations. A total of 108 VOCs were putatively identified, including terpenes, alcohols, and aldehydes, which contribute to the plant’s aromatic and therapeutic properties. Chemometric analyses, including Principal Component Analysis (PCA), hierarchical clustering and Partial least square-discriminant analysis (PLS-DA), identified shared and discriminatory components across extract types. These findings support the selection of optimal extraction strategies tailored to specific industrial applications and highlight the chemical diversity and functional potential of Hypericum perforatum .