Abstract
The first observation of organic dications formed by multiple electron loss in electrospray mass spectra is reported. The dications of β-carotene, canthaxanthine, cobalt(II) octaethylporphyrin, and nicke(II) octaethylporphyrin were created in solution via chemical electrontransfer reactions and detected in the gas phase by electrospray ionization mass spectrometry (ES-MS) using a flow-injection experiment. The analytes were injected into a flowing solvent-oxidant stream (10 μL/min) composed of dried methylene chloride containing ≈ 0.1% by volume trifluoroacetic acid and 0.1% by volume antimony pentafluoride (SbF5). The dications created in this oxidizing solvent system were preserved for detection by rapidly transferring them from the reactive solvent-oxidant system to the gas phase, where, in the absence of the solvent system, they were “long-lived” and amenable to mass analysis. This work demonstrates means to produce ions novel to ES-MS and means to detect and study by ES-MS species that are short-lived in solution. In addition, this work shows that electrospray ionization can potentially be used to generate gas-phase dications for mass spectrometric study that are difficult to produce directly from gas-phase neutrals by other ionization techniques (e.g., M2+ from β-carotene).
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Van Berkel, G.J., Asano, K.G. & McLuckey, S.A. Observation of gas-phase molecular dications formed from neutral organics in solution via qemical electron-transfer reactions by using electrospray Ionization Mass Spectrometry. J Am Soc Mass Spectrom 5, 689–692 (1994). https://doi.org/10.1016/1044-0305(94)85009-7
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DOI: https://doi.org/10.1016/1044-0305(94)85009-7