Selected ion monitoring determination of mono- and bifunctional amines by using phosphorus-containing derivatives

Abstract

Numerous monofunctional amines have been reacted with dimethylthiophosphinic chloride to form stable derivatives. Their good gas chromatographic properties and abundant molecular ions afforded highly sensitive and specific detection by selected ion monitoring (SIM) down to the picogram level. Based upon this derivatization procedure, new methods for the determination of aniline in serum and urine by SIM were developed. The minimum detectable concentration of aniline was 500 pg ml−1. Linear response curves were obtained from 1.5 to 150 ng ml−1 using (2H5)aniline as the internal standard. Specific derivatization of a series of bifunctional amines was achieved with methyldichlorophosphine and sulfur resulting in the formation of stable phospholidine-thiones. These derivatives chromatograph well on nonpolar stationary phases, and their mass spectra exhibit abundant molecular ions. This derivatization reaction was applied to the quantification of ephedrine from urine and serum by SIM with (2H2)ephedrine as the internal standard. The detection limit of the method was 1 ng ml−1. The linearity was established in the range from 10 to 160 ng ml−1.