Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time‐of‐flight mass spectrometer (Q‐TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4‐methylenedioxymethamphetamine standards and 3,4‐methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4‐methylenedioxymethamphetamine and its metabolite 3,4‐methylenedioxyamphetamine was prepared in each of these matrices again using 3,4‐methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q‐TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2–10 000 pg on‐column, r2 = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC‐fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q‐TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright © 1999 John Wiley & Sons, Ltd.