DMT-(S)-Pro-OSu derivatization UPLC/ESI-MS/MS is a powerful method for the comprehensive analysis of dipeptides

Abstract Dipeptides are important components that contribute to the characteristics of various foods; however, the dipeptide composition of foods is poorly understood. In the present study, a new, comprehensive analysis method for dipeptides, i.e., (S)-2,5-dioxopyrrolidin-1-yl-1-(4,6-dimethoxy-1,3,5-triazin-2-yl)pyrrolidine-2-carboxylate (DMT-(S)-Pro-OSu) derivatization ultra-performance liquid chromatography–electrospray ionization tandem mass spectrometry (UPLC/ESI-MS/MS), was developed. Using the method, the analytical behavior of 313 dipeptides in the UPLC/ESI-MS/MS was collected. The obtained comprehensive dataset elucidated the dipeptide profiles in fermented cocoa beans. Furthermore, the machine learning on the dataset provided the quantitative understanding of physicochemical molecular descriptors that affect the elution time of dipeptides on the reversed-phase LC analysis, namely, an in silico elution time prediction model was successfully constructed. The DMT-(S)-Pro-OSu derivatization UPLC/ESI-MS/MS method is a powerful tool for the comprehensive analysis of dipeptides.