title: Identification of fleeting electrochemical reaction intermediates using desorption electrospray ionization mass spectrometry.
abstract: We report a new method for the mass spectrometric detection of fleeting reaction intermediates in electrochemical reactions utilizing a "waterwheel" working electrode setup. This setup takes inspiration from desorption electrospray ionization (DESI) mass spectrometry, where the sampling time is on the order of milliseconds, to sample directly from the surface of a working electrode for mass spectrometric analysis. We present data that show the formation of a diimine intermediate of the electrochemical oxidation of uric acid that has a lifetime in solution of 23 ms as well as data that provide evidence for the formation of a similar diimine species from the electrooxidation of xanthine, which has not been previously observed.
authors.affiliation: ‡Department of Chemistry, Stanford University, Stanford, California 94305-5080, United States.
authors.forename: Timothy A
authors.initials: TA
authors.lastname: Brown
authors.affiliation: †Center for Intelligent Chemical Instrumentation, Department of Chemistry and Biochemistry, and Edison Biotechnology Institute, Ohio University, Athens, Ohio 45701-2979, United States.
authors.forename: Hao
authors.initials: H
authors.lastname: Chen
authors.affiliation: ‡Department of Chemistry, Stanford University, Stanford, California 94305-5080, United States.
authors.forename: Richard N
authors.initials: RN
authors.lastname: Zare