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Localization of Labile Posttranslational Modifications by Electron Capture Dissociation: The Case of γ-Carboxyglutamic Acid

1999; American Chemical Society; Volume: 71; Issue: 19 Linguagem: Inglês

10.1021/ac990684x

1520-6882

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

Analytical Chemistry and Chromatography

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.