Chemical ionisation and plasma desorption (PD) mass spectra of fumaric acid and other conjugated ketone and acid derivatives have been compared. Under plasma desorption conditions these molecules react with only one reducing hydrogen before protonation while a complete reduction of the ethylenic bond occurs under chemical ionisation conditions. Our plasma desorption results support a model that involves a preformed moiety and are consistent with a rapid energy diffusion model. Proton exchange reactions, specific fragmentations and recombinations occur in the region near the surface of the probe, possibly with water molecules adsorbed on the sample.
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