AC03CH11-Girault ARI 11 May 2010 13:26 Electrochemical Aspects of Electrospray and Laser Desorption/Ionization for Mass Spectrometry Melanie´ Abonnenc,1 Liang Qiao,1,2 BaoHong Liu,2 and Hubert H. Girault1 1Laboratoire d’Electrochimie Physique et Analytique, Station 6, Ecole Polytechnique Fed´ erale´ de Lausanne, CH-1015 Lausanne, Switzerland; email: Melanie.Abonnenc@epfl.ch, Liang.Qiao@epfl.ch, Hubert.Girault@epfl.ch 2Department of Chemistry, Institute of Biomedical Science, Fudan University, Shanghai 200433, China; email:
[email protected] Annu. Rev. Anal. Chem. 2010. 3:231–54 Key Words First published online as a Review in Advance on electrochemistry, electron-transfer reaction, emitters, ion source, peptide March 1, 2010 by Ecole Polytechnique Federal Lusanne on 12/19/11. For personal use only. analysis, proteomics The Annual Review of Analytical Chemistry is online at anchem.annualreviews.org Abstract This article’s doi: Soft-ionization methods, namely electrospray ionization and laser Annual Review of Analytical Chemistry 2010.3:231-254. Downloaded from www.annualreviews.org 10.1146/annurev.anchem.111808.073740 desorption/ionization, are widely used to transfer large molecules as in- Copyright c 2010 by Annual Reviews. tact gas-phase ions either from a solution or from a solid substrate. During All rights reserved both processes, in-source electrochemical and photoelectrochemical reac- 1936-1327/10/0719-0231$20.00 tions occur. These electrode reactions, which take place at interfaces, play important roles in influencing the ionization products, but they have re- ceived little attention. We show that having good control over both types of electrochemical reactions can lead to new analytical applications.