Electrochemically Initiated Tagging of Thiols Using an Electrospray Ionization-Based Liquid Microjunction Surface Sampling Probe Two-Electrode Cell

Journal Article · Thu Jan 01 04:00:00 EST 2009 · Rapid Communications in Mass Spectrometry

DOI:https://doi.org/10.1002/rcm.4014· OSTI ID:959443

Van Berkel, Gary J ^[1]; Kertesz, Vilmos ^[1]

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1. ORNL

This paper reports on the conversion of a liquid microjunction surface sampling probe (LMJ-SSP) into a two electrode electrochemical cell using a conductive sample surface and the probe as the two electrodes with an appropriate battery powered circuit. With this LMJ-SSP, two-electrode cell arrangement, tagging of analyte thiol functionalities (in this case peptide cysteine residues) with hydroquinone tags was initiated electrochemically using a hydroquinone doped solution when the analyte either was initially in solution or was sampled from a surface. Efficient tagging (~90%), at flow rates of 5-10 L/min, could be achieved for up to at least two cysteines on a peptide. The high tagging efficiency observed was explained with a simple kinetic model. In general, the incorporation of a two-electrode electrochemical cell, or other multiple electrode arrangement, into the LMJ-SSP is expected to add to the versatility of this approach for surface sampling and ionization coupled with mass spectrometric detection.

• Research Organization: Oak Ridge National Laboratory (ORNL)
• Sponsoring Organization: SC USDOE - Office of Science (SC)
• DOE Contract Number: AC05-00OR22725
• OSTI ID: 959443
• Journal Information: Rapid Communications in Mass Spectrometry, Journal Name: Rapid Communications in Mass Spectrometry Journal Issue: 9 Vol. 23; ISSN RCMSEF; ISSN 0951-4198
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CYSTEINE
DETECTION
EFFICIENCY
ELECTROCHEMICAL CELLS
ELECTRODES
Electrospray Ionization
FLOW RATE
IONIZATION
KINETICS
PEPTIDES
RESIDUES
SAMPLING
THIOLS
liquid microjunction
surface sampling probe