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  1. ; ; (, Rapid Communications in Mass Spectrometry)
    RationaleIn droplet‐assisted ionization (DAI), intact molecular ions are generated from molecules in aerosol droplets by passing the droplets through a temperature‐controlled capillary inlet. Ion formation is explored through the effects of analyte mass flow, droplet solvent composition, and capillary temperature on ion signal intensity. MethodsA Waters SYNAPT G2‐S is adapted for DAI by reconfiguring the inlet with a temperature‐controlled capillary. Droplets are generated by atomization of a solution containing analyte and then sampled through the inlet. If desired, solvent can be removed from the droplets prior to analysis by sending the aerosol through a series of diffusion dryers. Size distributions of the dried aerosols allow the mass flow of analyte into the inlet to be determined. ResultsAnalyte signal intensities are orders of magnitude higher from droplets containing a protic solvent (water) than an aprotic solvent (acetonitrile). The highest signal intensities for DAI are obtained with inlet temperatures above 500°C, though the optimum temperature is analyte dependent. At elevated temperatures, droplets are thought to undergo rapid solvent evaporation and bursting to produce ions. The lowest signal intensities are generally obtained in the 100–350°C range, where slow solvent evaporation is thought to inhibit ion formation. As the temperature decreases from 100°C down to 25°C, the signal intensity increases significantly. When 3‐nitrobenzonitrile, a common matrix for solid‐state matrix‐assisted ionization (MAI), is added to droplets consisting of 50/50 v/v water and acetonitrile, the matrix enhances ion formation to produce a signal intensity comparable to DAI in 100% water. ConclusionsThe results are consistent with other inlet ionization techniques, suggesting that similar ion formation mechanisms are operative. Optimized ion yields (the combined effects of ionization probability and ion transmission) for DAI are currently in the 10−5to 10−6range, which is sufficient for many aerosol applications. 
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