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Redox buffering in an electrospray ion source using a copper capillary emitter.

G J Van Berkel1, V Kertesz

  • 1Organic and Biological Mass Spectrometry Group, Chemical and Analytical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6365, USA. vanberkelgj@ornl.gov

Journal of Mass Spectrometry : JMS
|December 18, 2001
PubMed
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A copper capillary emitter acts as a redox buffer in electrospray mass spectrometry, controlling electrochemical reactions. This innovation prevents unwanted analyte oxidation and enables metal ion introduction for analysis.

Area of Science:

  • Analytical Chemistry
  • Electrochemistry

Background:

  • Electrospray ionization (ESI) mass spectrometry relies on electrochemical reactions at the emitter electrode for ion production.
  • Conventional stainless-steel emitters can lead to uncontrolled analyte oxidation or reduction.

Purpose of the Study:

  • To investigate the use of a copper capillary emitter as a redox buffer in positive ion mode electrospray mass spectrometry.
  • To demonstrate improved control over electrochemical reactions at the emitter electrode.

Main Methods:

  • Utilized a copper capillary emitter in a two-electrode, controlled-current electrochemical flow cell for electrospray mass spectrometry.
  • Compared the electrochemical behavior of the copper emitter with a standard stainless-steel emitter using N-phenyl-1,4-phenylenediamine.

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Main Results:

  • The copper capillary emitter maintained a stable interfacial potential near the copper corrosion equilibrium potential, acting as a redox buffer.
  • Oxidation of N-phenyl-1,4-phenylenediamine was completely avoided with the copper emitter, unlike with stainless-steel emitters.
  • Demonstrated that reduction reactions can occur at the copper emitter in positive ion mode.

Conclusions:

  • Copper capillary emitters offer superior control over electrochemical reactions in electrospray mass spectrometry by acting as redox buffers.
  • This approach prevents unwanted analyte transformations and facilitates the introduction of metal ions for analytical applications.