On-Column Sample Enrichment for Capillary Electrophoresis Sheathless Electrospray Ionization Mass Spectrometry: Evaluation for Peptide Analysis and Protein Identification

George M. Janini*, Ming Zhou, Li Rong Yu, Josip Blonder, Michelle Gignac, Thomas P. Conrads, Haleem J. Issaq, Timothy D. Veenstra

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

62 Scopus citations

Abstract

Although several designs have been advanced for coupling sample enrichment devices to a sheathless electrospray ionization-mass spectrometry (MS) interface on a capillary electrophoresis (CE) column, most of these approaches suffer from difficulties in fabrication, and the CE separation efficiency is degraded as a result of the presence of coupling sleeves. We have developed a design that offers significant improvements in terms of ease of fabrication, durability, and maintenance of the integrity of the CE-separated analyte zones. Capillaries with different inside and outside diameters were evaluated to optimize the performance of the CE-MS system, resulting in a mass limit of detection of 500 amol for tandem MS analysis of a standard peptide using a 20-μm-i.d. capillary. The improved design incorporates an efficient method to preconcentrate a sample directly within the CE capillary followed by its electrophoretic separation and detection using a true zero dead-volume sheathless CE-MS interface. Testing of this novel CE-MS system showed its ability to characterize proteomic samples such as protein digests, in-gel-digested proteins, and hydrophobic peptides as well as to quantitate ICAT-labeled peptides.

Original languageEnglish
Pages (from-to)5984-5993
Number of pages10
JournalAnalytical Chemistry
Volume75
Issue number21
DOIs
StatePublished - 1 Nov 2003
Externally publishedYes

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