Comparison of the Internal Energy Deposition of Venturi-Assisted Electrospray Ionization and a Venturi-Assisted Array of Micromachined UltraSonic Electrosprays (AMUSE)

The internal energy deposition of a Venturi-assisted array of micromachined ultrasonic electrosprays (AMUSE), with and without the application of a DC charging potential, is compared with equivalent experiments for Venturi-assisted electrospray ionization (ESI) using the "survival yield" method on a series of para-substituted benzylpyridinium salts. Under conditions previously shown to provide maximum ion yields for standard compounds, the observed mean internal energies were nearly identical (1.93-2.01 eV). Operation of AMUSE without nitrogen flow to sustain the air amplifier focusing effect generated energetically colder ions with mean internal energies that were up to 39% lower than those for ESI. A balance between improved ion transfer, adequate desolvation, and favorable ion energetics was achieved by selection of optimum operational ranges for the parameters that most strongly influence the ion population: the air amplifier gas flow rate and API capillary temperature. Examination of the energy landscapes obtained for combinations of these parameters showed that a low internal energy region (≤1.0 eV) was present at nitrogen flow rates between 2 and 4 L min^-1 and capillary temperatures up to 250 °C using ESI (9% of all parameter combinations tested). Using AMUSE, this region was present at nitrogen flow rates up to 2.5 L min^-1 and all capillary temperatures (13% of combinations tested). The signal-to-noise (S/N) ratio of the intact p-methylbenzylpyridinium ion obtained from a 5 μM mixture of thermometer compounds using AMUSE at the extremes of the studied temperature range was at least fivefold higher than that of ESI, demonstrating the potential of AMUSE ionization as a soft method for the characterization of labile species by mass spectrometry.