Improved desorption electrospray ionization mass spectrometry performance using edge sampling and a rotational sample stage

The position of the surface to be analyzed relative to the sampling orifice or capillary into the mass spectrometer has been known to dramatically affect the observed signal levels in desorption electrospray ionization mass spectrometry (DESI-MS). In analyses of sample spots on planar surfaces, DESI-MS signal intensities as much as five times greater were routinely observed when the bottom of the sampling capillary was appropriately positioned beneath the surface plane ('edge sampling') compared with when the capillary just touched the surface. To take advantage of the optimum 'edge sampling' geometry and to maximize the number of samples that could be analyzed in this configuration, a rotational sample stage was integrated into a typical DESI-MS setup. The rapid quantitative determination of caffeine in two diet sport drinks spiked with an isotopically labeled internal standard demonstrated the utility of this approach.