Detection of the short-lived radical cation intermediate in the electrooxidation of N,N-dimethylaniline by mass spectrometry.
The N,N-dimethylaniline (DMA) radical cation DMA(.+) , a long-sought transient intermediate, was detected by mass spectrometry (MS) during the electrochemical oxidation of DMA. This was accomplished by coupling desorption electrospray ionization (DESI) MS with a waterwheel working electrode setup to sample the surface of the working electrode during electrochemical analysis. This study clearly shows that DESI-based electrochemical MS is capable of capturing electrochemically generated intermediates with half-lives on the order of microseconds, which is 4-5 orders of magnitude faster than previously reported electrochemical mass spectrometry techniques.
Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, CA 94305-5080 (USA).
Timothy A
TA
Brown
Center for Intelligent Chemical Instrumentation, Department of Chemistry & Biochemistry & Edison Biotechnology, Ohio University, Athens, OH 45701 (USA). chenh2@ohio.edu.
Hao
H
Chen
Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, CA 94305-5080 (USA). zare@stanford.edu.
Richard N
RN
Zare
DESI; dimethylaniline; electrochemistry; mass spectrometry; radical ions