Faculty of Science, Institute of Biology and Ecology, Department of Genetics, P. J. Šafárik University in Košice, Mánesova 23, 040 01, Košice, Slovakia.
Institute of Bioorganic Chemistry, Polish Academy of Sciences, Noskowskiego 12/14, 61-704, Poznań, Poland.
Anal Bioanal Chem. 2018 Nov;410(29):7689-7699. doi: 10.1007/s00216-018-1384-0. Epub 2018 Oct 5.
A wide range of compounds that occur in the genus Hypericum are listed as effective drugs of natural origin. The main biological activities of several Hypericum representatives are due to the presence of naphthodianthrones, phloroglucinols, and other diverse groups of secondary metabolites that synergistically contribute to their therapeutic effects. The regulation of biosynthesis of hypericin as the key bioactive naphthodianthrone remains uncertain. Here, we present liquid chromatography mass spectrometry-based phenotyping of 17 Hypericum species, the results of which suggest an important role for skyrin and its derivatives in the polyketide pathway that leads to hypericin formation. Moreover, we report for the first time the presence of new metabolites in the genus Hypericum that are related to classes of anthraquinones, their derivatives, and phloroglucinols. As skyrin and other species of anthraquinones are rarely found in higher plants but frequently occur in fungal microorganisms, the obtained results suggest that further research on the synthesis pathways of hypericin and the role of anthraquinone derivatives in plant metabolism should be carried out. The fact that these compounds are commonly synthesized in endophytic fungi and perhaps there is some similarity in the metabolic pathways between these organisms should also be investigated.
许多属于贯叶连翘属的化合物被列为具有天然来源的有效药物。几种贯叶连翘代表物的主要生物活性归因于萘并二蒽酮、苯丙素醇和其他多种次生代谢物的存在，这些物质协同作用对其治疗效果有贡献。作为关键生物活性萘并二蒽酮的金丝桃素生物合成的调控仍然不确定。在这里，我们基于液相色谱-质谱法对 17 种贯叶连翘属物种进行表型分析，结果表明，在导致金丝桃素形成的聚酮途径中，色氨酸及其衍生物起着重要作用。此外，我们首次报道了贯叶连翘属中新的与蒽醌类、其衍生物和苯丙素醇有关的代谢物的存在。由于色氨酸和其他蒽醌类化合物在高等植物中很少见，但在真菌微生物中经常出现，因此获得的结果表明，应该进一步研究金丝桃素的合成途径以及蒽醌衍生物在植物代谢中的作用。这些化合物通常在内生真菌中合成，并且这些生物体之间的代谢途径可能存在一些相似性，这一事实也应该进行调查。
