Rapid screening of polysaccharide‐based plasma volume expanders dextran and hydroxyethyl starch in human urine by liquid chromatography–tandem mass spectrometry

Abstract The increasing number of samples and target substances in doping control requires continuously improved screening methods, combining high‐throughput analysis, simplified sample preparation, robustness and reliability. Hence, a rapid screening procedure based on liquid chromatography–electrospray ionization–tandem mass spectrometry with in‐source collision‐induced dissociation was developed. The detection of the polysaccharide‐based plasma volume expanders dextran and hydroxyethyl starch (HES) in human urine was established without further sample preparation. The in‐source fragmentation strategy of the approach represented a valuable tool in the analysis of the polysaccharide‐based compounds, allowing the use of tandem mass spectrometry. After direct injection of urine specimens, analytes were chromatographically separated on a monolithic reverse‐phase column and detected via multiple reaction monitoring of diagnostic ions at detection limits of 10 µg/mL for HES and 30 µg/mL for dextran. Validation was performed regarding the parameters specificity, linearity, precision (8–18%) and accuracy (77–105%) and the method was applied to the investigation of approximately 400 doping control samples and seven dextran and two hydroxyethyl starch post‐administration samples. The approach demonstrated its capability as a rapid screening tool for the detection of dextran and hydroxyethyl starch and represents an alternative to existing screening procedures since time consuming hydrolysis or derivatization steps were omitted. Copyright © 2008 John Wiley & Sons, Ltd.