On-column electrochemical reactions accompanying the electrospray process

Liu, S., Griffiths, W.J. and Sjovall, J. (2003) On-column electrochemical reactions accompanying the electrospray process. Analytical Chemistry, 75 . pp. 1022-1030. 10.1021/ac026066p.

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DOI: 10.1021/ac026066p


On-Column Electrochemical Reactions Accompanying the Electrospray Process Suya Liu, William J. Griffiths,* and Jan Sjövall Department of Medical Biochemistry and Biophysics, Karolinska Institutet, SE-171 77 Stockholm, Sweden Received for review August 22, 2002. Accepted November 15, 2002. Abstract: It is well-established that electrochemical reactions can occur within the capillary of an electrospray (ES) devise coupled to a mass spectrometer. In fact, such reactions must occur to maintain charge balance during the ES process. However, electrochemical reactions occurring distal to the capillary as a result of the high potential applied to the capillary have not been thoroughly investigated. In the present communication, we show that electrochemical processes can occur on a high performance liquid chromatography (HPLC) column coupled to an ES capillary. On-column solvent electrolysis is proposed to generate free radicals, which can subsequently initiate analyte oxidation. Oxidation of steroid sulfates possessing a reactive double bond between C-5 and C-6 is demonstrated. The possibility of similar reactions occurring within peptides possessing a site of unsaturation is also considered.

Item Type:Article
Additional Information:Full text available in print and electronically at the School of Pharmacy Library.
Departments, units and centres:Department of Pharmaceutical and Biological Chemistry > Department of Pharmaceutical and Biological Chemistry
ID Code:621
Journal or Publication Title:Analytical Chemistry
Deposited By:Library Staff
Deposited On:17 Jan 2007
Last Modified:19 Sep 2007 11:15

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