Acidic metabolite profiling analysis of catecholamine and serotonin as O‐ethoxycarbonyl/tert‐butyldimethylsilyl derivatives by gas chromatography–mass spectrometry

A novel derivatization method was developed for the simultaneous determination of six acidic metabolites of catecholamine and serotonin by gas chromatography–mass spectrometry (GC‐MS). The metabolites were converted to O‐ethoxycarbonyl/tert‐butyldimethylsilyl (EOC/TBDMS) derivatives for the direct GC‐MS analysis in selected ion monitoring mode. Their mass spectral pattern as EOC/TBDMS derivatives showed characteristic fragment ions of M – 15]⁺ and M – 57]⁺, which permitted rapid and accurate structural confirmation of acidic metabolites. The present method was linear (r ≥ 0.998), reproducible (percentage relative standard deviation = 1.0–10.0) and accurate (% relative error = ?9.7–9.8) with detection limits of 0.001–4.7 ng/mL. When applied to human urine samples, the method allowed simultaneous determination of six acidic metabolites of catecholamine and serotonin. Copyright © 2012 John Wiley & Sons, Ltd.