Isomeric differentiation and quantification of alpha, beta-amino acid-containing tripeptides by the kinetic method: alkali metal-bound dimeric cluster ions

dc.creatorWu, LM
dc.creatorMeurer, EC
dc.creatorYoung, B
dc.creatorYang, PX
dc.creatorEberlin, MN
dc.creatorCooks, RG
dc.date2004
dc.dateFEB
dc.date2014-11-17T12:17:51Z
dc.date2015-11-26T16:42:52Z
dc.date2014-11-17T12:17:51Z
dc.date2015-11-26T16:42:52Z
dc.date.accessioned2018-03-28T23:27:37Z
dc.date.available2018-03-28T23:27:37Z
dc.identifierInternational Journal Of Mass Spectrometry. Elsevier Science Bv, v. 231, n. 41700, n. 103, n. 111, 2004.
dc.identifier1387-3806
dc.identifierWOS:000188970900003
dc.identifier10.1016/j.ijms.2003.09.017
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/60863
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/60863
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/60863
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1273412
dc.descriptionThe kinetic method is applied to differentiate and quantify mixtures of isomeric tripeptides by generating and mass-selecting alkali metal ion-bound dimeric clusters and examining their competitive dissociations in an ion trap mass spectrometer. This methodology readily distinguishes the pairs of isomers examined here: (alpha-A)GG/(beta-A)GG, G(alpha-A)G/G(beta-A)G, and GG(alpha-A)/GG(beta-A). The isomeric selectivity increases with decreasing size of the metal ion, viz. from Cs to Rb to K to Na to Li. When alanine is at the N-terminus, as in the case of (alpha-A)GG/(beta-A)GG, the isomeric selectivity can exceed 10(3). The corresponding proton-bound dimers behave similarly to the Li clusters. Structural features that favor zwitterionic versus charge-solvated forms of the alkali metal-bound clusters are reflected in the b(n) and y(n) fragment ion abundances recorded by tandem mass spectrometry, and the propensities to form the charge-solvated or zwitterionic structures play a key role in promoting isomeric differentiation. The zwitterionic forms favor intramolecular interactions in the cluster and hence isomeric distinction. There is no discrimination in the formation of the alkali metal-bound dimers, so isomeric quantification is based entirely on dissociation kinetics. Previous kinetic method-based isomeric analyses have used the trimeric clusters and shown linear correlations between composition of the mixture of isomers and the logarithm of the branching ratio for competitive fragmentation. A similar relationship is found for the dimeric clusters examined here. As used here, the kinetic method provides a possible way for future quantitative analysis of mixtures of larger peptides such as those generated in combinatorial synthesis of peptides and peptide mimics. (C) 2004 Elsevier B.V. All rights reserved.
dc.description231
dc.description41700
dc.description103
dc.description111
dc.languageen
dc.publisherElsevier Science Bv
dc.publisherAmsterdam
dc.publisherHolanda
dc.relationInternational Journal Of Mass Spectrometry
dc.relationInt. J. Mass Spectrom.
dc.rightsfechado
dc.rightshttp://www.elsevier.com/about/open-access/open-access-policies/article-posting-policy
dc.sourceWeb of Science
dc.subjectkinetic method
dc.subjectdissociation
dc.subjectquantification
dc.subjectisomeric tripeptides
dc.subjectcomplexes
dc.subjectcentral ion effects
dc.subjectMass-spectrometry
dc.subjectGas-phase
dc.subjectChiral Analysis
dc.subjectThermochemical Determinations
dc.subjectEnantiomeric Quantification
dc.subjectAmino-acids
dc.subjectPeptides
dc.subjectComplexes
dc.subjectDissociation
dc.subjectMixtures
dc.titleIsomeric differentiation and quantification of alpha, beta-amino acid-containing tripeptides by the kinetic method: alkali metal-bound dimeric cluster ions
dc.typeArtículos de revistas


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