A corona discharge initiated electrochemical electrospray ionization technique |
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Authors: | John R Lloyd Sonja Hess |
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Institution: | aProteomics and Mass Spectrometry Facility, National Institute of Diabetes and Digestive and Kidney Diseases, National Institutes of Health, Department of Health and Human Services, Bethesda, Maryland, USA;bProteome Exploration Laboratory, California Institute of Technology, Beckman Institute, Pasadena, California, USA |
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Abstract: | We report here the development of a corona discharge (CD) initiated electrochemical (EC) electrospray ionization (ESI) technique
using a standard electrospray ion source. This is a new ionization technique distinct from ESI, electrochemistry inherent
to ESI, APCI, and techniques using hydroxyl radicals produced under atmospheric pressure conditions. By maximizing the observable
CD at the tip of a stainless steel ESI capillary, efficient electrochemical oxidation of electrochemically active compounds
is observed. For electrochemical oxidation to be observed, the ionization potential of the analyte must be lower than Fe.
Ferrocene labeled compounds were chosen as the electrochemically active moiety. The electrochemical cell in the ESI source
was robust, and generated ions with selectivity according to the ionization potential of the analytes and up to zeptomolar
sensitivity. Our results indicate that CD initiated electrochemical ionization has the potential to become a powerful technique
to increase the dynamic range, sensitivity, and selectivity of ESI experiments. |
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Keywords: | |
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