Development and applications of paper-based electrospray ionization-mass spectrometry for monitoring of sequentially generated droplets

In this work, sub-microlitre droplets were generated by gravity and electrostatic attraction using a capillary tube. The parameters affecting the sizes and frequency of the droplets were investigated. The volume of droplets could be controlled in the range from 0.7 mu L to 2.4 mu L and the time interval from 15 s to 60 s with appropriate parameters. Combining the droplets with on-line mass spectrometry (MS) via paper-based electrospray ionization (ESI), a steady flow of solvent was delivered by the capillary tube to the base-side of the paper, which maintained the consistent state of the electrospray. With this approach, each droplet produced a peak in the ion chromatogram. Relative standard deviations (RSDs) not higher than 9% for both the intensities and the time intervals were achieved when using rhodamine 6G and L-phenylalanine as model analytes. The present method was utilized for the monitoring of the amine-aldehyde condensation reaction of butylamine and benzaldehyde. Direct analysis and distribution of molecules in fruits were also performed, which demonstrated the potential application of this approach.