Fusarium proliferatum secondary metabolism: Multi-approach metabolomics insights

Fusarium proliferatum is a toxigenic filamentous fungus that produces the harmful mycotoxins fumonisins, contaminates worldwide a broad range of crops whose products are staple food, and consequently, poses a serious threat to both human and livestock health. However, metabolomic insights into its broader secondary metabolism remain limited. In this study, liquid chromatography-traveling wave ion mobility spectrometry- highresolution mass spectrometry (LC-TWIMS-HRMS), combined with feature-based molecular networking (FBMN), was used to map F. proliferatum secondary metabolism. As a result, 111 metabolites were tentatively identified, including fumonisins their modified forms (i.e. hydrolysed, acylated, and bound derivatives), beauvericins, and other toxic metabolites, many of which are not routinely monitored, despite their putative toxicological significance. Among them, N-(deoxy-D-fructos-1-yl)-FB4 and two fumonisin A4 isomers are herein reported for the first time. Furthermore, the TWCCSN2 values of the F. proliferatum metabolites were experimentally determined, showing structural trends, and providing a valuable reference for future studies.