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Use of ECD and ETD Fragmentation Mechanisms for Peptide Sequencing

The use of electron capture and transfer dissociation (ECD and ETD) fragmentation mechanisms for peptide sequencing is discussed.
| 1 min read

This technical article describes how two new techniques have arisen which result in more complete fragmentation with better predictability for multiple-charge precursor ions. The techniques are electron capture dissociation (ECD) and electron transfer dissociation (ETD). The mechanism of dissociation in both cases is the same, the difference being in the source of the electrons.

The mechanism for ETD and ECD involves electron capture neutralization of a charge site on a
multiple-charge ion resulting in formation of a radical cation. Cleavage occurs at the amine bond proximal to the radical site, i.e. to the bond between the peptide bond nitrogen and the α-carbon along the peptide backbone.

In this article we'll go onto discuss the advantages of ETD and ECD vs conventional CAD for peptide sequencing.

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Meet the Author(s):

  • O. David Sparkman is currently an Adjunct Professor of Chemistry at the University of the Pacific in Stockton, California; Contractor to the National Institute of Standards and Technology Mass Spectrometry Data Center; President of ChemUserWorld.com; and a former American Chemical Society Instructor (1978–2006) and American Society for Mass Spectrometry Member-at-large for Education (2004–2006). At the University of the Pacific, Prof. Sparkman teaches courses in mass spectrometry and analytical chemistry and manages the mass spectrometry facility. Over the past 28 years, he has developed and taught five different ACS courses in mass spectrometry; he holds positions on the Editorial Advisory Boards of the European Journal of Mass Spectrometry and the HD Science GC/MS Update – Part B; and is the Book Review Editor for the European Journal of Mass Spectrometry. He is the author of Mass Spectrometry Desk Reference (Global View Publishing: Pittsburgh, PA, 1st ed. 2000; 2nd ed. 2006). Prof. Sparkman is a member of the Editorial Boards of the John Wiley Encyclopedia of Environmental Analysis and Remediation and Encyclopedia of Analytical Chemistry, Editor of and a contributor to the Mass Spectrometry Section of the Encyclopedia of Analytical Chemistry, and a contributor to the Encyclopedia of Environmental Analysis and Remediation. Along with J. Throck Watson, he developed the Mass Spectral Interpretation Quick Reference Guide. He also provides general consulting service in mass spectrometry for a number of instrument manufacturers, manufacturing companies, and government agencies.

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