Negative ion mode evolution of potential buildup and mapping of potential gradients within the electrospray emitter

Differential electrospray emitter potential (DEEP) maps, displaying variations in potential in the electrospray (ES) capillary and in the Taylor cone, have been generated in the negative ion mode of ES operation. In all examples, measured potential was found to be the highest at the points furthest into the Taylor cone, and values descended to zero at distances beyond approximately 15 mm within the ES capillary. In agreement with results obtained previously in the positive ion mode, negative mode data show a strong influence of electrolyte concentration on measured potentials. Weakly conductive solutions exhibited the highest values, and the steepest gradients, at points furthest into the Taylor cone. However, these same low conductivity solutions did not yield nonzero measured potentials to as deep a distance into the ES capillary as was possible from their higher conductivity counterparts. Addition of a readily reducible compound lowered measured potentials at all points near the ES capillary exit, in accordance with the description of the ES device as a controlled-current electrolytic cell. The development of potential inside the ES capillary upon the onset of ES was also studied, and initial results are presented. Potential waves are observed that can require 15 min or longer, to stabilize. The slow drift to steady potentials is evidence of upstream movement of electrochemically-produced species and follow-up reaction products; low conductivity solutions require longer intervals to reach a steady state. Potentials measured along the central ES axis reflect those at the ES capillary surface, although equipotential lines can be considered to be more compressed at the latter surface. (C) 2004 American Society for Mass Spectrometry.