Localization of labile posttranslational modifications by electron capture dissociation: The case of γ-carboxyglutamic acid

Neil L. Kelleher, Roman A. Zubarev, Kristine Bush, Bruce Furie, Barbara C. Furie, Fred W. McLafferty*, Christopher T. Walsh

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

322 Scopus citations

Abstract

Tandem mass spectrometry (MS/MS) of 28 residue peptides harboring γ- carboxylated glutamic acid residues, a posttranslational modification of several proenzymes of the blood coagulation cascade, using either collisions or infrared photons results in complete ejection of the γ-CO2 moieties (-44 Da) before cleavage of peptide-backbone bonds. However, MS/MS using electron capture dissociation (ECD) in a Fourier transform mass spectrometer cleaves backbone bonds without ejecting CO2, allowing direct localization of this labile modification. Sulfated side chains are also retained in ECD backbone fragmentations of a 21-mer peptide, although CAD causes extensive SO3 loss. ECD thus is a unique complement to conventional methods for MS/MS, causing less undesirable loss of side-chain functionalities as well as more desirable backbone cleavages.

Original languageEnglish (US)
Pages (from-to)4250-4253
Number of pages4
JournalAnalytical Chemistry
Volume71
Issue number19
DOIs
StatePublished - Oct 1 1999

ASJC Scopus subject areas

  • Analytical Chemistry

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