Investigation of Small-Molecule Constituents in Seeds and Mapping of Their Spatial Distributions Using Laser Ablation Direct Analysis in Real-Time Imaging-Mass Spectrometry (LADI-MS).

Plant seeds are a renewable resource that can furnish access to medicinal natural products that can only otherwise be isolated from aerial or root parts, the harvest of which may be destructive to the plant or threaten its viability. However, optimization of the isolation of such compounds from seeds would be greatly assisted if the spatial distribution of the molecules of interest within the plant tissue were known. For example, iboga alkaloids that hold promise for the treatment of opioid use disorder are typically isolated from the leaves, bark, or roots of or spp. trees, but it would be more environmentally sustainable to isolate such compounds from their seeds. Here, we leveraged the unique capabilities of the ambient mass spectral imaging technique termed laser ablation direct analysis in real-time imaging-mass spectrometry (LADI-MS) to reveal the spatial distributions of a range of molecules, including alkaloids within seeds. In addition to six compounds previously reported in these seeds, namely, tetradecanoic acid, -hexadecanoic acid, (,)-9,12-octadecadienoic acid, ()-9-octadecenoic acid, octadecanoic acid, and Δ-vincamine, an additional 31 compounds were newly identified in seeds. The compound classes included alkaloids, terpenes, and fatty acids. The ion images showed that the fatty acids were localized in the embryo of the seed. The alkaloids, which were mainly localized in the seed endosperm, included strictamine, akuammidine, polyneruidine, vobasine, and Δ-vincamine. This information can be exploited to enhance the efficiency of secondary metabolite isolation from seeds while eliminating the destruction of other plant parts.