Unveiling the distribution of chemical constituents at different body parts and maturity stages of Ganoderma lingzhi by combining metabolomics with desorption electrospray ionization mass spectrometry imaging (DESI).

Ganoderma lingzhi is an important medicinal fungus, which is widely used as dietary supplement and for pharmaceutical industries. However, the spatial distribution and dynamic accumulation pattern of active components such as ganoderic acids (GAs) among different parts of G. lingzhi fruiting body are still unclear. In this study, desorption electrospray ionization mass spectrometry imaging (DESI-MSI) with untargeted metabolomics analysis was applied to investigate the metabolites distribution within G. lingzhi fruiting body at four different maturity stages (squaring, opening, maturation and harvesting stage). A total of 132 metabolites were characterized from G. lingzhi, including 115 triterpenoids, 11 fatty acids and other component. Most of the GAs content in the cap was significantly higher than that in the stipe, with six components such as ganoderic acid B being extremely significant. GAs in the cap was mainly present in the bottom edge of the mediostratum layer, such as ganoderic A-I and ganoderic GS-1, while in the stipe, they were mainly distributed in the shell layer and the context layer, such as ganoderic A-F. Most ganoderic acids content in both the stipe and the cap of G. lingzhi was gradually decreased with the development of G. lingzhi. The GAs in the stipe was gradually transferred from the shell layer to the content layer, while the distribution of GAs among different tissues of the cap was not significantly changed. In addition, linoleic acid, 9-HODE, 9-KODE and other fatty acids were mainly accumulated in the opening and maturing stage of the caps. This study further clarifies the spatial dynamic distribution of GAs in G. lingzhi fruiting body at four different maturity stages (squaring, opening, maturation and harvesting stage), which provides a basis for the rational utilization of the medicinal parts of G. lingzhi. Furthermore, mass spectrometry imaging combined with non-target metabolome analysis provides a powerful tool for the spatial distribution of active substances in the different regions of the medicinal edible fungi.