Reaction Acceleration in Electrospray Droplets: Size, Distance, and Surfactant Effects

  • Brett M. Marsh
  • Kiran Iyer
  • R. Graham CooksEmail author
Focus: Honoring Helmut Schwarzʻs Election to the National Academy of Sciences: Research Article


Phenylhydrazone formation from isatin is used to examine the effects on the reaction rate of (i) electrospray emitter distance from the mass spectrometer (MS) inlet, (ii) emitter tip diameter, and (iii) presence of surfactant. Reaction rates are characterized through measurement of conversion ratios. It is found that there is an increase in the conversion ratio as (i) the electrospray source is moved further from the inlet of the mass spectrometer, (ii) smaller sprayer diameters are used, and (iii) when surfactants are present. Each of these experimental operations is associated with an increase in reaction rate and with a decrease in average droplet sizes. The size measurements are made using super resolution microscopy from the “splash” on a collector surface produced by a fluorescent marker sprayed using conditions similar to those used for the reaction mixture. This measurement showed that droplets undergo significant evaporation as a function of distance of flight, thereby increasing their surface to volume ratios. Similarly, the effect of nanoelectrospray emitter size on conversion ratio is also found to be associated with changes in droplet size for which a 4 to 10 times increase in reaction rate is seen using tip diameters ranging from 20 μm down to 1 μm. Finally, the effects of surfactants in producing smaller droplets with corresponding large increases in reaction rate are demonstrated by splash microscopy. These findings point to reaction acceleration being strongly associated with reactions at the surfaces of microdroplets.


Microdroplets Reaction acceleration Microscopy Hydrazone Surface reactions 



This work was financially supported by the Agilent Technologies Inc. through gift no. 4212 of an Ultivo Triple Quadrupole mass spectrometer.

Supplementary material

13361_2019_2264_MOESM1_ESM.docx (22 kb)
ESM 1 (DOCX 21 kb)


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Copyright information

© American Society for Mass Spectrometry 2019

Authors and Affiliations

  1. 1.Department of ChemistryPurdue UniversityWest LafayetteUSA

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