Enhanced desorption ionization using oxidizing electrosprays.

A signal enhancement of two orders of magnitude was achieved when reactive desorption electrospray ionization (DESI) was used to investigate copper(II) dibutyl dithiocarbamate, Cu(II)(bu2dtc)2, found in a specialized polymer. Cu(II) was oxidized to Cu(III) during the DESI experiment by oxidants in the spray solvent. Such oxidants could be present or formed during electrospray (e.g., O2) or deliberately added to the spray solvent (this approach is called reactive DESI). When a strong oxidizing agent (e.g., iodine) was added to the spray solvent, the signal increased by two orders of magnitude relative to the pure solvent spray. The correlation between the standard reduction potential of the oxidant and the signal intensity and signal to noise ratio of the product ion for various reagents, was tested and discussed. The observed DESI enhancements in rates of oxidation are not observed in homogeneous solution. The major peaks in the collision induced dissociation (CID) spectrum of the complex ion Cu(III)(bu2dtc)2]+ were identified using isotopic distributions and MS3 data.