PMID: 11924969Apr 2, 2002Paper

Enhancement of ionization efficiency by electrochemical reaction products in on-line electrochemistry/electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Analytical Chemistry
Tianyi ZhangAnna Brajter-Toth

Abstract

A miniaturized two-electrode electrochemical (EC) cell was developed and was coupled on-line with an electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer (ESI-FTICR MS). Electrochemistry on-line with mass spectrometry, EC/ESI-FTICR MS, of triphenylamine (TPA), which undergoes one-electron oxidation to form a radical cation (TPA*+), demonstrates a significant sensitivity enhancement compared to ESI-FTICR MS. The on-line EC cell configuration with a stainless steel ES needle as the working electrode produces the highest sensitivity in EC/ESI-MS. The results provide evidence that, during the ES ionization, electrolytic reactions occur mainly in the ES tip region, as previously predicted. The results demonstrate that ESI-MS signal suppression by tetrabutylammonium perchlorate electrolyte, which can be a problem, is minimized in EC/ESI-MS. TPA*+ dimer tetraphenylbenzidine (TPB) can be detected by EC/ESI-MS, together with TPA*+, as TPB*+ and TPB2+. The high mass resolving power of FTICR MS was exploited to identify TPB2+ dication in the presence of [TPA*+ - H*]+ ions of the same m/z, from their respective isotopic distributions. The dimer dication TPB2+ can be detected only in EC/ESI-MS.

Citations

May 16, 2006·Journal of the American Society for Mass Spectrometry·Vilmos Kertesz, Gary J Van Berkel
Mar 4, 2008·Journal of the American Society for Mass Spectrometry·Michel Prudent, Hubert H Girault
Feb 18, 2016·Analytical and Bioanalytical Chemistry·Wen Donq LooiAnna Brajter-Toth
Aug 28, 2015·Journal of the American Society for Mass Spectrometry·Yao-Min Liu, Richard H Perry
Dec 18, 2013·Mass Spectrometry Reviews·Herbert OberacherSabine Plattner
Jul 19, 2002·Journal of Mass Spectrometry : JMS
Oct 20, 2009·The Analyst·Michel Prudent, Hubert H Girault
Dec 31, 2005·Journal of Mass Spectrometry : JMS·Marina V KosevichLudwik Adamowicz
Jul 31, 2013·The Analyst·Pengyuan LiuHao Chen

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