Comparison of different chiral selectors for the enantiomeric determination of amphetamine-type substances in human urine by solid-phase extraction followed by capillary electrophoresis-tandem mass spectrometry.

ABSTRACT

The present study develops a method for the enantioseparation of a group of amphetamines and their metabolites in urine by CE coupled to MS/MS (CE-MS/MS). Amphetamines present a chiral center and thus two enantiomers, which is important from a toxicological point of view because they may have different pharmacokinetic and pharmacological properties. It is therefore essential to find suitable methods to distinguish both enantiomers. Today the use of CE is becoming more important in this field since, with the simple addition of a chiral selector to the background electrolyte, the enantioseparation can easily be achieved. However, when CE is coupled to MS, the use of volatile chiral selectors and compatible background electrolytes or other strategies such as the countercurrent migration approach are required to avoid contamination of the ion source from nonvolatile species. In the present study, we use the latter strategy to evaluate six different chiral selectors using CE-MS/MS. As a sample pre-treatment, two cationic-exchange sorbents-Oasis WCX and Oasis MCX-are compared for the urine pre-treatment. Using this method, it was possible to achieve the complete chiral separation of the amphetamines under study with detection limits ranging between 0.8 and 1.5 ng/mL and method quantification limits between 2.0 and 8.0 ng/mL. Matrix-matched calibration curves up to 150 ng/mL were used to cover the usual concentration ranges at which amphetamines have generally been found in toxicological and forensic analyses.