Advances in the Biosynthesis of Pyranocoumarins: Isolation and ¹³C-Incorporation Analysis by High-Performance Liquid Chromatography–Ultraviolet–Solid-Phase Extraction–Nuclear Magnetic Resonance Data

Abstract

Citrus sinensis and Citrus limonia were obtained by germination from seeds, and isotopic-labeling experiments using d-[1-13C]­glucose were performed with the seedlings. After 60 days, the seedlings were analyzed by high-performance liquid chromatography–ultraviolet–solid-phase extraction–nuclear magnetic resonance, data and the 13C enrichment patterns of xanthyletin and seselin indicated that the pyran ring was formed by the methylerythritol phosphate pathway and that the coumarin moiety was derived from the shikimate pathway in both compounds. This information regarding the biosynthetic pathway can be used to increase resistance against phytopathogens, because xanthyletin and seselin are reported to have antimicrobial activity on the growth of Xylella fastidiosa, which causes citrus variegated chlorosis in orange.

Plant Pyranocoumarins: Description, Biosynthesis, Application

“…Exposed to prenyltransferases, umbelliferone forms either osthenol, a precursor of 7,8-angular pyranocoumarins, or 7-demethylsuberosin-a precursor of linear pyranocoumarins [14]. In an experiment with carbon label conducted for orange seedlings (Citrus sinensis (L.) Osbeck) and rangpur seedlings (Citrus limonia Osbeck), it has been proven that the coumarin fragment of pyranocoumarins xanthyletin and seselin originate from the shikimate pathway (L-phenylalanine), and the pyran ring is formed via the methyl-erythrite-phosphate pathway [15]. Transformation and coupling of substitutes are most likely related to various transferases.…”

The Different Composition of Coumarins and Antibacterial Activity of Phlojodicarpus sibiricus and Phlojodicarpus villosus Root Extracts

“…Also, umbelliferone was exposed to a prenyl donor substrate (dimethylallyl pyrophosphate (DMAPP)) and transformed into demethylsuberosin or osthenol by prenyltransferase [ 47 , 48 ]. It was also shown that the biosynthesis of xanthyletin and seselin may be formed by a mevalonate-independent pathway from osthenol in Thamnosma montana [ 48 , 52 ]. Perhaps this stage is no less important for the formation of linear and angular pyranocoumarins.…”

Anti‐inflammatory and anti‐aggregating effects of rangpur in the first trimester of growth: ultra‐performance liquid chromatography–electrospray mass spectrometry profile and quantification of hesperidin

“…Studies performed on C. limonia identified coumarins (esculetin, xanthyletin, and seselin), a flavonoid (limonianin), and organic acids (tartaric, citric and ascorbic acids). [23][24][25][26] Esculetin was reported to possess anti-inflammatory, anti-oxidant, and antiproliferative activity against non-small-cell lung carcinoma (NSCLC). 25 Limonianin showed hepatoprotective effect on human hepatoma cells against D-galactosamine-induced hepatotoxicity.…”