Deconstructing Desorption Electrospray Ionization: Independent Optimization of Desorption and Ionization by Spray Desorption Collection

Spray desorption collection (SDC) and reflective electrospray ionization (RESI) were used to independently study the desorption and ionization processes that together comprise desorption electrospray ionization (DESI). Both processes depend on several instrumental parameters, including the nebulizing gas flow rate, applied potential, and source geometries. Each of these parameters was optimized for desorption, as represented by the results obtained by SDC, and ionization, as represented by the results obtained by RESI. The optimized conditions were then compared to the optimization results for DESI. Our results confirm that optimal conditions for desorption and ionization are different and that in some cases the optimized DESI conditions are a compromise between both sets. The respective results for DESI, RESI, and SDC for each parameter were compared across the methods to draw conclusions about the contribution of each parameter to desorption and ionization separately and then combined within DESI. Our results indicate that desorption efficiency is (1) independent of the applied potential and (2) the impact zone to inlet distance, and that (3) gas pressure settings and (4) sprayer to impact zone distances above optimal for DESI are detrimental to desorption but beneficial for ionization. In addition, possible interpretations for the observed trends are presented.