The variability of the flavonoid content of two populations of Z. noltii from different geographical zones, i.e., the Bay of Arcachon and the Bay of Cadiz, was evaluated. Samples were collected in spring and autumn at the two sites, and extracts were prepared by maceration in water. The phenolic content was fully characterized using Nuclear Magnetic Resonance (NMR), UV and Liquid Chromatography-Mass Spectrometry (LC-MS), and the concentration of the individual phenolic was determined by quantitative High-Performance Liquid Chromatography with Diode-Array Detection (HPLC-DAD). The two populations show a strong geographical differentiation in their flavonoid content. The samples from Cadiz were dominated by apigenin 7-sulfate, which represents 71% (autumn collection) and 83% (spring collection) of the total flavonoids, whereas the samples from Arcachon were characterized by diosmetin 7-sulfate (85 and 93% of the total flavonoids). Structural elucidation of the individual phenolics was assigned using the complementary information from their spectral evidence. In addition, the results were confirmed by acid hydrolysis of the flavonoid sulfates, and comparison to synthetic standards obtained by sulfation of apigenin, diosmetin and luteolin. The results represent the first experimental evidence of the existence of chemotypes within the species Z. noltii.
Keywords: Zostera noltii; apigenin 7-sufate; chemotype; diosmetin 7-sulfate; flavonoid content; geographical chemodifferentiation.