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Article: Are the radical centers in peptide radical cations mobile? The generation, tautomerism, and dissociation of isomeric α-carbon-centered triglycine radical cations in the gas phase

TitleAre the radical centers in peptide radical cations mobile? The generation, tautomerism, and dissociation of isomeric α-carbon-centered triglycine radical cations in the gas phase
Authors
Issue Date2008
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
Citation
Journal Of The American Chemical Society, 2008, v. 130 n. 25, p. 7862-7872 How to Cite?
AbstractThe mobility of the radical center in three isomeric triglycine radical cations-[G •GG] +, [GG •G] +, and [GGG •] + - has been investigated theoretically via density functional theory (DFT) and experimentally via tandem mass spectrometry. These radical cations were generated by collision-induced dissociations (CIDs) of Cu(II)-containing ternary complexes that contain the tripeptides YGG, GYG, and GGY, respectively (G and Y are the glycine and tyrosine residues, respectively). Dissociative electron transfer within the complexes led to observation of [Y•GG] +, [GY •G] +, and [GGY •] +; CID resulted in cleavage of the tyrosine side chain as p-quinomethide, yielding [G •GG] +, [GG •G] +, and [GGG •] +, respectively. Interconversions between these isomeric triglycine radical cations have relatively high barriers (≥44.7 kcal/mol), in support of the thesis that isomerically pure [G •GG] +, [GG •G] +, and [GGG •] + can be experimentally produced. This is to be contrasted with barriers < 17 kcal/mol that were encountered in the tautomerism of protonated triglycine [Rodriquez C. F. et al. J. Am. Chem. Soc. 2001, 123, 3006-3012]. The CID spectra of [G •GG] +, [GG •G] +, and [GGG •] + were substantially different, providing experimental proof that initially these ions have distinct structures. DFT calculations showed that direct dissociations are competitive with interconversions followed by dissociation. © 2008 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/168311
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorChu, IKen_US
dc.contributor.authorZhao, Jen_US
dc.contributor.authorXu, Men_US
dc.contributor.authorShiu, OSen_US
dc.contributor.authorHopkinson, ACen_US
dc.contributor.authorSiu, KWMen_US
dc.date.accessioned2012-10-08T03:17:22Z-
dc.date.available2012-10-08T03:17:22Z-
dc.date.issued2008en_US
dc.identifier.citationJournal Of The American Chemical Society, 2008, v. 130 n. 25, p. 7862-7872en_US
dc.identifier.issn0002-7863en_US
dc.identifier.urihttp://hdl.handle.net/10722/168311-
dc.description.abstractThe mobility of the radical center in three isomeric triglycine radical cations-[G •GG] +, [GG •G] +, and [GGG •] + - has been investigated theoretically via density functional theory (DFT) and experimentally via tandem mass spectrometry. These radical cations were generated by collision-induced dissociations (CIDs) of Cu(II)-containing ternary complexes that contain the tripeptides YGG, GYG, and GGY, respectively (G and Y are the glycine and tyrosine residues, respectively). Dissociative electron transfer within the complexes led to observation of [Y•GG] +, [GY •G] +, and [GGY •] +; CID resulted in cleavage of the tyrosine side chain as p-quinomethide, yielding [G •GG] +, [GG •G] +, and [GGG •] +, respectively. Interconversions between these isomeric triglycine radical cations have relatively high barriers (≥44.7 kcal/mol), in support of the thesis that isomerically pure [G •GG] +, [GG •G] +, and [GGG •] + can be experimentally produced. This is to be contrasted with barriers < 17 kcal/mol that were encountered in the tautomerism of protonated triglycine [Rodriquez C. F. et al. J. Am. Chem. Soc. 2001, 123, 3006-3012]. The CID spectra of [G •GG] +, [GG •G] +, and [GGG •] + were substantially different, providing experimental proof that initially these ions have distinct structures. DFT calculations showed that direct dissociations are competitive with interconversions followed by dissociation. © 2008 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_US
dc.relation.ispartofJournal of the American Chemical Societyen_US
dc.subject.meshCarbon - Chemistryen_US
dc.subject.meshCationsen_US
dc.subject.meshFree Radicals - Chemistryen_US
dc.subject.meshGases - Chemistryen_US
dc.subject.meshOligopeptides - Chemistryen_US
dc.subject.meshPeptides - Chemistryen_US
dc.subject.meshPhase Transitionen_US
dc.subject.meshStereoisomerismen_US
dc.titleAre the radical centers in peptide radical cations mobile? The generation, tautomerism, and dissociation of isomeric α-carbon-centered triglycine radical cations in the gas phaseen_US
dc.typeArticleen_US
dc.identifier.emailChu, IK:ivankchu@hku.hken_US
dc.identifier.authorityChu, IK=rp00683en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ja801108jen_US
dc.identifier.pmid18512915-
dc.identifier.scopuseid_2-s2.0-45749143632en_US
dc.identifier.hkuros143099-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-45749143632&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume130en_US
dc.identifier.issue25en_US
dc.identifier.spage7862en_US
dc.identifier.epage7872en_US
dc.identifier.eissn1520-5126-
dc.identifier.isiWOS:000256962000038-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridChu, IK=7103327484en_US
dc.identifier.scopusauthoridZhao, J=8611619900en_US
dc.identifier.scopusauthoridXu, M=23475706200en_US
dc.identifier.scopusauthoridShiu, OS=24400196400en_US
dc.identifier.scopusauthoridHopkinson, AC=15067169300en_US
dc.identifier.scopusauthoridSiu, KWM=35312218500en_US

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