Application of atmospheric pressure chemical ionisation mass spectrometry in the analysis of barbiturates by highspeed analytical countercurrent chromatography

Four barbiturates (barbital, allobarbital, phenobarbital and butalbital) were analysed using highspeed analytical countercurrent chromatography (HSACCC) and high-performance liquid chromatography (HPLC) interfaced with mass spectrometry, using negative mode atmospheric pressure chemical ionisation (APCI). The polar biphasic solvent system of butyronitrile/acetonitrile/water (1:1:1) was used, in the upper-stationary, lower-mobile mode of operation, at a flow rate of 1 mL/min and a rotational speed of 1200 rpm, equating to an applied 'g-field of 177 g. The fractional stationary phase retention (SF) was 0.58. Representative mass spectral data are presented from the HPLC and the HSACCC analyses. Structural information was obtained using source-induced fragmentation at increased source block voltages. The effect of increasing g-field on chromatographic resolution is illustrated using the binary base system of butyronitrile/water (1:1), under electrospray ionisation. Copyright (C) 2003 John Wiley Sons, Ltd.