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Electrochemical aspects of electrospray

Conference ·
OSTI ID:210636
;  [1]
  1. Oak Ridge National Lab., TN (United States)

Electrospray mass spectrospray (ES-MS) has proven especially useful in the molecular weight determination and structural analysis of involatile, polar and thermally labile compounds. However, the mechanism(s) involved in the generation of gas-phase ions from species in solution during the ES process is not well understood. In this study, attention is given to the electrochemical processes that occur at the metal/solution interface in the ES capillary. Kebarle and co-workers postulated that the mechanism responsible for charge balance in the ES capillary was electrochemical in nature and that the ES source was in fact {open_quotes}an electrolytic cell of a somewhat special kind.{close_quotes} The authors demonstrated that the radical cations observed in the ES mass spectra of some easily oxidized organic compounds were formed via electrochemical oxidation in the ES capillary. Recently, similar data from an ES-MS study of various metallocenes was also presented. A better understanding about the electrochemical processes in ES is desirable because it might lead to means for improving ES-MS performance (e.g., improving dynamic range and detection limits), means to expand the range of analytes amenable to analysis and possibly the means to control or alter the ionic species observed in the gas-phase.

OSTI ID:
210636
Report Number(s):
CONF-9505261--
Country of Publication:
United States
Language:
English

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