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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

Summary

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.

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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.

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.