Mass spectrometry of polyaromatic sulfur compounds in the presence of palladium(II)
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Abstract
Electrospray ionization mass spectrometry (ESI-MS) and tandem MS in an ion trap were used to explore the reduction of a PdCl(2) solution and the role of the metal in the formation of organosulfur radical cations. For tandem MS experiments, a 32 Da neutral loss (M - S), was observed for dibenzothiophene, thianthrene and benzonaphthothiophene, whereas both 32 and 33 Da neutral losses were observed for 2-methyldibenzothiophene and 4,6-dimethyldibenzothiophene. The effects of several variables on the formation of molecular ions or molecular fragments were studied to optimize radical cation formation, including the concentration ratio between PdCl(2) and sulfur and the collision energy. Electrochemical and chromatographic data were used to provide an explanation for the relative sensitivity observed for a mixture of polyaromatic sulfur heterocycles.
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