Characterization of Tocochromanols in Wild Hypericum perforatum Populations in Latvia

St. John's wort (Hypericum perforatum L.) is an ornamental and medical plant, distributed worldwide, which is rich in diverse secondary metabolites. The discovery of the presence of tocotrienols (rare prenyllipids) in H. perforatum marks a new chapter demanding a deeper understanding of the accumulation of these lipophilic biomolecules. Three wild St. John's wort populations were harvested in Latvia at three different locations from 2022 to 2024 and separated into stems, leaves, flower buds, and flowers. Plant samples were freeze-dried, ground, saponified, and analyzed for tocochromanol profiles using RP-LC-FLD and confirmed by an LC-MS system. Eight tocochromanols, four tocopherols (Ts), and four tocotrienols (T3s), were identified and confirmed in H. perforatum. Leaves were dominated by alpha-T (82%), and flower buds and flowers by delta-T3 (44%); thus, the lowest concentrations of tocotrienols were recorded in leaves and the highest in flower buds. The other tocotrienols were present as follows: alpha-T3 > gamma-T3 > beta-T3. The location of H. perforatum, the year of harvest, the aerial part of the plant, and their interactions all significantly influenced the content of tocochromanols (p < 0.05). The present study demonstrates relevant discoveries regarding the accumulation of tocotrienols in various St. John's wort organs and their variability.