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.