Quantitatively resolving mixtures of isobaric compounds using chemical ionization mass spectrometry by modulating the reactant ion composition

Acrolein (C3H4O) and 1-butene (C4H8) can both be individually detected by proton transfer chemical ionization mass spectrometry (CI-MS). However, because these compounds are isobaric, mixtures of these two compounds cannot be resolved since both compounds react with H3O+ via a proton-transfer reaction to form a protonated molecule that is detected at a nominal mass-to-charge ratio of 57 (m/z 57). While both compounds react with H3O+ only acrolein reacts to any significant extent with H3O+(H2O). Recognizing that the electrical potential applied to a drift tube reaction mass spectrometer provides a simple and effective means for varying the relative intensity of the H3O+ and H3O+(H2O) reactant ions we have developed a method whereby we make use of this reactivity difference to resolve mixtures of these two compounds. We demonstrate a technique where the individual contributions of acrolein and 1-butene within a mixture can be quantitatively resolved by systematically changing the reagent ion from H3O+ to H3O+(H2O) through control of the electric potential applied to the drift tube reaction region of a proton transfer reaction mass spectrometer. Copyright (C) 2008 John Wiley & Sons, Ltd.