High resolution and tandem fourier-transform mass spectrometry with californium-252 plasma desorption.

For ions formed by plasma desorption (PD) in a Fourier-transform mass spectrometer, high resolution measurements are demonstrated, such as 65,000 (FWHH) for the protonated molecularion of gramicidin S (MW 1140.7). Resolution is substantially improved by delaying measurements until a significant ion concentration has built up in the cell, and by collisionally deactivating the orbital kinetic energy of the ions. This also makes the ions available for subsequent dissociation steps, so that tandem mass spectrometry can be demonstrated for PD ions. With this for larger ions, collisionally activated dissociation (CAD) is effected with > 85% efficiency. The CAD spectra of (M + Na)(+) and of fragment ions from the PD of gramicidin S provide structurally useful information.