Direct identification of intramolecular disulfide links in peptides using negative ion electrospray mass spectra of underivatised peptides. A joint experimental and theoretical study

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dc.contributor.authorBilusich, D.
dc.contributor.authorMaselli, V.
dc.contributor.authorBrinkworth, C.
dc.contributor.authorSamguina, T.
dc.contributor.authorLebedev, A.
dc.contributor.authorBowie, J.
dc.date.issued2005
dc.descriptionThe definitive version may be found at www.wiley.com
dc.description.abstract[M--H]- parent anions of underivatised peptides containing an intramolecular disulfide bridge undergo characteristic loss of the elements of H2S2, a process diagnostic of the presence of the disulfide moeity. This facile process is initiated from a side-chain enolate anion. Theoretical calculations (at the HF/6-31G(d)//AM1 level of theory) indicate that the process is exothermic with a small barrier. When the disulfide link involves a C-terminal Cys, the negative ion spectrum shows an [(M--H)--(H2S2+CO2)] fragment anion which is usually the main peak of the spectrum. This process is also directed by an enolate anion: theoretical calculations suggest a stepwise sequence with loss of CO2 preceding loss of H2S2. Both [(M--H)--H2S2] and [(M--H)--(H2S2+CO2)] anions undergo backbone cleavage allowing identification of the amino acid sequence of the peptide.
dc.description.statementofresponsibilityDaniel Bilusich, Vita M. Maselli, Craig S. Brinkworth, Tatiana Samguina, Albert T. Lebedev, John H. Bowie
dc.identifier.citationRapid Communications in Mass Spectrometry, 2005; 19(21):3063-3074
dc.identifier.doi10.1002/rcm.2149
dc.identifier.issn0951-4198
dc.identifier.issn1097-0231
dc.identifier.urihttp://hdl.handle.net/2440/17807
dc.language.isoen
dc.provenancePublished Online: 3 Oct 2005
dc.publisherJohn Wiley & Sons Ltd
dc.source.urihttp://www3.interscience.wiley.com/cgi-bin/fulltext/112098770/PDFSTART
dc.subjectAnimals
dc.subjectRana ridibunda
dc.subjectPeptides
dc.subjectAntimicrobial Cationic Peptides
dc.subjectAmphibian Proteins
dc.subjectPeptide Mapping
dc.subjectSpectrometry, Mass, Electrospray Ionization
dc.subjectAmino Acid Sequence
dc.subjectMolecular Sequence Data
dc.titleDirect identification of intramolecular disulfide links in peptides using negative ion electrospray mass spectra of underivatised peptides. A joint experimental and theoretical study
dc.typeJournal article
pubs.publication-statusPublished

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