Investigation of the electrochemical oxidation of 2,3′-bisindolylmethanes in positive-ion electrospray ionization mass spectrometry

Electrochemical reactions in electrospray may affect the electrospray ionization mass spectrometry (ESI-MS) detection of the analytes. During ESI-MS analysis of 2,3′-bisindolylmethanes in the positive-ion mode, when methanol or acetonitrile was used as the solvent, electrochemical oxidation products as the dehydro and radical cations were observed. Lower sample introduction rates tended to result in a higher oxidation ratio of 2,3′-bisindolylmethanes. The ESI-MS experiments of 2,3′-bisindolylmethanes in different acetonitrile/methanol solvent mixtures indicated that abundant H + , Na + or K + would facilitate the adduct formation process, and otherwise electrochemical oxidation dominated the ionization process. Additionally, when dichloromethane was used as the solvent, [M − 3H] + , [M − 2H] + &z.rad; and [M − 3H + O] + ions are the predominant ions, and the experimental results revealed that the dehydrogenation and oxidative dehydrogenation reactions of 2,3′-bisindolylmethanes in dichloromethane are electrochemical reactions. The electrochemical oxidation reactions of 2,3′-bisindolylmethanes were affected by the solvent in the positive-ion electrospray ionization mass spectrometry (ESI-MS).