Document Detail


Electron capture dissociation product ion abundances at the X amino acid in RAAAA-X-AAAAK peptides correlate with amino acid polarity and radical stability.
MedLine Citation:
PMID:  19811930     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
We present mechanistic studies aimed at improving the understanding of the product ion formation rules in electron capture dissociation (ECD) of peptides and proteins in Fourier transform ion cyclotron resonance mass spectrometry. In particular, we attempted to quantify the recently reported general correlation of ECD product ion abundance (PIA) with amino acid hydrophobicity. The results obtained on a series of model H-RAAAAXAAAAK-OH peptides confirm a direct correlation of ECD PIA with X amino acid hydrophobicity and polarity. The correlation factor (R) exceeds 0.9 for 12 amino acids (Ile, Val, His, Asn, Asp, Glu, Gln, Ser, Thr, Gly, Cys, and Ala). The deviation of ECD PIA for seven outliers (Pro is not taken into consideration) is explained by their specific radical stabilization properties (Phe, Trp, Tyr, Met, and Leu) and amino acid basicity (Lys, Arg). Phosphorylation of Ser, Thr, and Tyr decreases the efficiency of ECD around phosphorylated residues, as expected. The systematic arrangement of amino acids reported here indicates a possible route toward development of a predictive model for quantitative electron capture/transfer dissociation tandem mass spectrometry, with possible applications in proteomics.
Authors:
Aleksey Vorobyev; Hisham Ben Hamidane; Yury O Tsybin
Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't     Date:  2009-09-03
Journal Detail:
Title:  Journal of the American Society for Mass Spectrometry     Volume:  20     ISSN:  1879-1123     ISO Abbreviation:  J. Am. Soc. Mass Spectrom.     Publication Date:  2009 Dec 
Date Detail:
Created Date:  2009-11-25     Completed Date:  2010-02-02     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9010412     Medline TA:  J Am Soc Mass Spectrom     Country:  United States    
Other Details:
Languages:  eng     Pagination:  2273-83     Citation Subset:  IM    
Affiliation:
Biomolecular Mass Spectrometry Laboratory, Ecole Polytechnique F??d??rale de Lausanne, Lausanne, Switzerland.
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MeSH Terms
Descriptor/Qualifier:
Amino Acids / analysis,  chemistry*
Computer Simulation
Free Radicals / analysis,  chemistry
Ions
Models, Chemical*
Oxidation-Reduction
Peptides / analysis,  chemistry*
Spectrometry, Mass, Electrospray Ionization / methods*
Statistics as Topic
Chemical
Reg. No./Substance:
0/Amino Acids; 0/Free Radicals; 0/Ions; 0/Peptides

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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