Liquid chromatography/electrospray mass spectrometry of organoselenium compounds with postcolumn crown ether complexation

Postcolumn addition is an effective means of alleviating or solving ionization-related problems in liquid chromatography/electrospray ionization mass spectrometry (LC/ESIMS). In the current study, initial attempts to develop a direct LC/ESIMS method for an organoselenium compound, 4-hydrosyphenyl 2-methyl-2-aminoethyl selenide (HOMePAESe), were unsuccessful because of extensive fragmentation which occurred even under the mildest in-source collision-induced dissociation (CID) conditions. To reduce the extent of compound fragmentation, a crown ether, 18-crown-6, was added postcolumn to the system, forming a complex with HOMePAESe, which survived the electrospray ionization process with reduced fragmentation and hence improved sensitivity for the major ions. The general applicability of this crown ether complexation approach to clinical samples was demonstrated by the analysis of HOMePAESe in human urine, using a structural analogue, 4-fluorophenyl 2-aminoethyl selenide (FPAESe) as an internal standard. The limit of detection for HOMePAESe, based on a signal-to-noise ratio of 3:1, was estimated to be 5 pg/mu L in urine. The potential application of this approach to the general analysis of other amine-containing compounds was also evaluated.