Phytochemical characterization of the berry like fruits of tutsan (Hypericum Andrsaemun L.).

Hypericum androsaemum L. (family Hypericaceae, Fig. 1) is a small evergreen shrub, fairly common in damp woods and hedgerows within the Mediterranean Basin, mainly in Western and Southern Europe, South-Western Asia, North Africa, while it has been introduced elsewhere. [1,2]. Among Hypericum species, H. androsaemum has the peculiarity to produce fleshy ‘berry-like’ fruits that ripen from red to shiny black. The plant is also known as ‘tutsan’, meaning ‘tout-saine’, i.e. ‘all-heal’, name given for its supposed medicinal properties. In fact, it has been used for its diuretic effect and infusions of the leaves were used for liver, kidney and bladder ailments[3]. In the present work, we reported a comprehensive analysis on the chemical composition, secretory structures, nutritional values and antioxidant potential of the ‘berry-like’ fruits of H. androsaemum collected both from wild and cultivated plants in central Italy. The phenolic profile of methanolic extracts and infusions of red and black fruits was obtained by HPLC-DAD, and correlated with their antioxidant properties which were evaluated by the DPPH, β-Carotene/linoleic acid and hypochlorous acid tests. Moreover, the main polar compounds of the berries were isolated by column chromatography and structurally elucidated by NMR. The red berries showed higher levels of phenolic compounds such as shikimic and chrlorogenic acids with respect to black berries. In addition, the infusion obtained from red berries gave the highest values of antioxidant activity. The composition of the essential oil and aroma components of the fruits were investigated by GC-FID, GC-MS, and HS-SPME-GC-MS. It was found that red fruits have higher content of essential oil and of monoterpene hydrocarbons with respect to black fruits (0.3 vs 0.1%, and 84.0 vs 78.8%, respectively). To complete the work, we performed a morphological and histochemical study on H. androsaemum berries to provide new insights on fruit anatomy, and on the histolocalization of the complex metabolite mixture produced. References [1]Allen, D. A., & Hatfield, G. (2004). Medicinal plants in folk tradition. An ethnobotany of Britain and Ireland. Portland, Oregon, USA: Timber Press, Inc. [2]Valentão, P., Carvalho, M., Fernandes, E., Carvalho, F., Andrade, P. B., Seabra, R. M., & Bastos, M. d. L. (2004). Protective activity of Hypericum androsaemum infusion against tert-butyl hydroperoxide-induced oxidative damage in isolated rat hepatocytes. Journal of Ethnopharmacology, 92, 79-84. [3]Valentão, P., Fernandes, E., Carvalho, F., Andrade, P. B., Seabra, R. M., & Bastos, M. d. L. (2002). Antioxidant Activity of Hypericum androsaemum Infusion: Scavenging Activity against Superoxide Radical, Hydroxyl Radical and Hypochlorous Acid. Biological and Pharmaceutical Bulletin, 25, 1320-1323.