Sequential and Exhaustive Ionization of Analytes with Different Surface Activity by Probe Electrospray Ionization

The probe electrospray ionization (PESI) is an ESI-based ionization technique that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for the single-shot PESI were measured as a function of time for a mixture of several analytes with different surface activity values. It was found that the analytes were elecrosprayed in the order of their surface activity. For example, detergent and protein were detected separately and respectively at the first and last stages of electrospray, for a mixed sample of 10(-3) M Triton X100 and 10(-5) M cytochrome c. For human breast cancer tissue, at first proteins such as alpha and beta chains of hemoglobin, were observed as the dominant ions, but just before the liquid droplet on the needle was depleted only lipids were observed, meaning that PESI has the advantage of the suppression effect with analytes being detected separately in the order of their surface activity values.