Interrogation of spatial metabolome of <i>Ginkgo biloba</i> with high‐resolution matrix‐assisted laser desorption/ionization and laser desorption/ionization mass spectrometry imaging

Ginkgo biloba is one of the oldest extant seed plants and has a number of unique properties and uses. Numerous efforts have characterized metabolites within the ginkgo plant and their corresponding biosynthesis pathways, but spatio-chemical information on ginkgo metabolites is lacking. Mass spectrometry (MS) imaging was used to interrogate the spatio-chemical localization of metabolites with matrix-assisted laser desorption/ionization and laser desorption/ionization Fourier-transform ion cyclotron resonance MS across the ginkgo leaf. Flavonoids, particularly unexpected and rare flavonoid cyclodimers, were detected predominately from leaf epidermis; ginkgolic acids and cardanols were observed exclusively in the secretory cavities. A non-uniform distribution of flavonoids observed between the upper and lower leaf epidermis was verified by liquid chromatography-MS analyses. Other metabolites, such as saccharides, phospholipids, and chlorophylls, occurred mainly in mesophyll cells. Furthermore, organ- and tissue-specific distributions of ginkgolides were revealed in the ginkgo root, young stem, and leaf. The acquired ion images provide important information regarding biosynthesis, transportation, and accumulation of metabolites throughout the ginkgo plant and should help us to understand the physiological roles of several plant secondary metabolites.