Document Detail


Electron capture dissociation of trivalent metal ion-peptide complexes.
MedLine Citation:
PMID:  23283726     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
With electrospray ionization from aqueous solutions, trivalent metal ions readily adduct to small peptides resulting in formation of predominantly (peptide + M(T) - H)(2+), where M(T) = La, Tm, Lu, Sm, Ho, Yb, Pm, Tb, or Eu, for peptides with molecular weights below ~1000 Da, and predominantly (peptide + M(T))(3+) for larger peptides. ECD of (peptide + M(T) - H)(2+) results in extensive fragmentation from which nearly complete sequence information can be obtained, even for peptides for which only singly protonated ions are formed in the absence of the metal ions. ECD of these doubly charged complexes containing M(T) results in significantly higher electron capture efficiency and sequence coverage than peptide-divalent metal ion complexes that have the same net charge. Formation of salt-bridge structures in which the metal ion coordinates to a carboxylate group are favored even for (peptide + M(T))(3+). ECD of these latter complexes for large peptides results in electron capture by the protonation site located remotely from the metal ion and predominantly c/z fragments for all metals, except Eu(3+), which undergoes a one electron reduction and only loss of small neutral molecules and b/y fragments are formed. These results indicate that solvation of the metal ion in these complexes is extensive, which results in the electrochemical properties of these metal ions being similar in both the peptide environment and in bulk water.
Authors:
Tawnya G Flick; William A Donald; Evan R Williams
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Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural     Date:  2013-01-03
Journal Detail:
Title:  Journal of the American Society for Mass Spectrometry     Volume:  24     ISSN:  1879-1123     ISO Abbreviation:  J. Am. Soc. Mass Spectrom.     Publication Date:  2013 Feb 
Date Detail:
Created Date:  2013-02-11     Completed Date:  2013-07-22     Revised Date:  2014-02-04    
Medline Journal Info:
Nlm Unique ID:  9010412     Medline TA:  J Am Soc Mass Spectrom     Country:  United States    
Other Details:
Languages:  eng     Pagination:  193-201     Citation Subset:  IM    
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MeSH Terms
Descriptor/Qualifier:
Cations / chemistry
Coordination Complexes / chemistry*
Electrons
Lanthanoid Series Elements / chemistry*
Peptides / chemistry*
Spectrometry, Mass, Electrospray Ionization / methods*
Grant Support
ID/Acronym/Agency:
R01 GM096097/GM/NIGMS NIH HHS; R01GM096097/GM/NIGMS NIH HHS
Chemical
Reg. No./Substance:
0/Cations; 0/Coordination Complexes; 0/Lanthanoid Series Elements; 0/Peptides
Comments/Corrections

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


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