Tuning Electrospray Ionization with Low-Frequency Sound.

Electrospray ionization (ESI) mass spectrometry (MS) is one of the key techniques used in biomolecular analysis nowadays. It relies on formation of polydisperse microdroplets, which undergo desolvation and liberate ions to the gas phase. Here we demonstrate low-frequency-sound-modulated ESI for analysis of biomolecules. By using a low-frequency (50-350 Hz) sound, it is possible to deflect electrospray microdroplets toward the mass spectrometer's orifice. Microdroplets of different sizes are deflected to a different extent leading to a partial size segregation. This effect leads to either an increase or decrease of MS signal intensity as well as signal-to-noise ratio. It also affects the selectivity of the ESI-MS analysis. The observations are rationalized by taking into account different pathways of ion formation and the likelihood of deflecting microdroplets of certain size. The online ESI-MS observations are supported with offline shadowgraphs obtained at varied sound frequencies, signal amplitudes, and phase shifts.