Alleviation of electrochemical oxidation for peptides and proteins in electrospray ionization: obtaining more accurate mass spectra with induced high voltage.

Accurate mass spectrometry (MS) signal for peptide/protein analysis, which could be affected by various MS conditions, plays an essential role in identification and quantification of biological samples. Herein, we tried to alleviate the possible interferences from electrochemical oxidations during electrospray ionization (ESI). Three most common electrochemical oxidation reactions in ESI include oxidation of analyte, solvent, and electrode. With introduction of induced electrospray ionization (IESI) (a variant form of ESI), these interferences were significantly alleviated for peptides/proteins. That effect was also tested with flow injection experiments with different solution flow rates, electrolyte concentrations and solvent compositions, which was to simulate various chromatography conditions in conventional liquid chromatography (LC) separations. For all chromatography conditions tested, electrochemical oxidation was significantly alleviated for the absence of physical contact between spray solution and electrode.