Application of C8 liquid chromatography-tandem mass spectrometry for the analysis of enniatins and bassianolides

•Development of a rapid LC method using a C8 chromatography for resolution of non-polar cyclodepsipeptides.•Semi-targeted LC-MS/MS analysis for the detection of all enniatin-like compounds.•Post data-acquisition product ion and neutral loss filtering resulted in the discovery of new bassianolides.•Enniatins and new bassianolides detected from naturally contaminated silage and inoculated maize.

Several moderately pathogenic Fusarium species produce enniatins, a family of cyclohexadepsipeptides with insecticidal and phytotoxic activities. A semi-targeted LC-MS/MS approach utilizing reversed-phase C8 UHPLC column chromatography that combines both product ion and neutral loss filtering was developed to detect enniatins and structurally-related compounds in a sample. Using this methodology, resolution of all major enniatins was achieved with a 6-min LC run. From extracts of F. avenaceum, F. acuminatum and F. subglutinans, 23 enniatins and 16 previously unreported bassianolide-like cyclooctadepsipeptides were detected. Enniatins B, B1, A1 and A were the most frequently detected enniatins from silage and inoculated maize. The newly discovered bassianolide compounds were also detected, in lesser amounts on inoculated maize and in naturally contaminated silage.