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

Journal Article · · Rapid Communications in Mass Spectrometry
DOI:https://doi.org/10.1002/rcm.4014· OSTI ID:959443

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