Rapid Identification of Phenolics in Mixtures by Two-Dimensional Tandem Mass Spectrometry with Microdroplet Accelerated Derivatization Reactions

Complex mixtures are typically analyzed by chromatographic separation followed by mass spectrometry. Two-dimensional tandem mass spectrometry (2D MS/MS) may eliminate the need for separation and therefore significantly reduce analysis time while expanding the information space by recording the intensities of all fragment ions generated from all trapped precursor ions. Additional chemical specificity can be provided by using chemical derivatization. In this study phenolic compounds are identified after triazole click derivatization by the observation of two diagnostic features in the 2D MS/MS data domain, a mass shift of 175 Da on the precursor ion axis and a neutral loss (NL) of 119 Da. Additional NL transitions were highly correlated with particular substituents including carbonyl, ester, amino, and alkyl/phenyl groups. Substituent position information was also easily diagnosed. The derivatization reactions are accelerated in the charged electrosprayed microdroplets. Using this method, members of this single class of compounds can be identified within 1-2 minutes while structural information on the individual compounds is acquired simultaneously. Accelerated microdroplet derivatization reactions coupled with 2D MS/MS provide a rapid and convenient approach for the analysis of complex mixtures. This method selectively targets the desired compound classes within the mixture, while simultaneously providing detailed structural information for each component through 2D MS/MS.image