Abstract
Analyte electrolysis using a repetitively pulsed high voltage ion source was investigated and compared to that using a regular, continuously operating direct current high voltage ion source in electrospray ionization mass spectrometry. The extent of analyte electrolysis was explored as a function of the length and frequency of the high voltage pulse using the model compound reserpine in positive ion mode. Using +5 kV as the maximum high voltage amplitude, reserpine was oxidized to its 2, 4, 6 and 8-electron oxidation products when direct current high voltage was employed. In contrast, when using a pulsed high voltage, oxidation of reserpine was eliminated by employing the appropriate high voltage pulse length and frequency. This effect was caused by inefficient mass transport of the analyte to the electrode surface during the duration of the high voltage pulse and the subsequent relaxation of the emitter electrode/electrolyte interface during the time period when the high voltage was turned off. This mode of ESI source operation allows for analyte electrolysis to be quickly and simply switched on or off electronically via a change in voltage pulse variables.
| Original language | English |
|---|---|
| Pages (from-to) | 206-211 |
| Number of pages | 6 |
| Journal | International Journal of Mass Spectrometry |
| Volume | 303 |
| Issue number | 2-3 |
| DOIs | |
| State | Published - Jun 1 2011 |
Funding
ESI-MS instrumentation and the PFT cell were provided through a Cooperative Research and Development Agreement with MDS SCIEX and ESA Biosciences, Inc. (CRADA No. ORNL02-0662), respectively. This work was supported by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, United States Department of Energy under Contract DE-AC05-00OR22725 with ORNL, managed and operated by UT-Battelle, LLC. This manuscript has been authored by a contractor of the U.S. Government under Contract No. DE-AC05-00OR22725. Accordingly, the U.S. Government retains a paid-up, nonexclusive, irrevocable, worldwide license to publish or reproduce the published form of this contribution, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, or allow others to do so, for U.S. Government purposes.
| Funders | Funder number |
|---|---|
| U.S. Government | |
| U.S. Department of Energy | DE-AC05-00OR22725 |
| Basic Energy Sciences | |
| Oak Ridge National Laboratory | |
| Chemical Sciences, Geosciences, and Biosciences Division |
Keywords
- Analyte electrolysis control
- Double layer relaxation
- ESI-MS
- Mass transport
- Pulsed ESI