Metabolomic fingerprinting and genetic discrimination of four Hypericum taxa from Greece

Hypericum perforatum has plenty of uses in traditional medicine and is the source of top-selling herbal drugs and food supplements. The secondary metabolite chemistry for most of the nearly 500 Hypericum taxa is still unknown, even though they are used interchangeably. In the present study, we characterized four Hypericum populations from Achaia, Greece, belonging to H. perforatum ssp. veronense, H. perfoliatum, H. triquetrifolium, and an uninvestigated taxon, H. empetrifolium ssp. empetrifolium, in terms of their essential oils and polar bioactives in methanolic extracts via GC-MS, LC-HRMS, LC-DAD-MS, and HPLC-DAD. We also performed sequence analysis of nrITS to explore the genetic profile of these taxa and to examine whether their genotype is correlated to the metabolome. Sixty-three non-volatile compounds, phloroglucinols in their majority, and over one hundred (113) volatiles, mostly sesqui- and mono- terpenes, were detected. The concentration of the major polar constituents varied greatly among samples. In particular, phloroglucinols' diversity and abundance in H. empetrifolium ssp. empetrifolium was remarkable. The PCA and Biplot analysis revealed the contribution of each compound to the total chemodiversity and also revealed certain compounds that contribute to the discrimination of the samples. Sequence analysis of nrITS revealed different genetic profiles and markers which can be used for the identification of the four Hypericum taxa. The Mantel test showed a relatively strong correlation between the genetic profile and the volatile compounds and low with the main polar metabolites.