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Article: Novel Cβ-Cγ bond cleavages of tryptophan-containing peptide radical cations

TitleNovel Cβ-Cγ bond cleavages of tryptophan-containing peptide radical cations
Authors
KeywordsC β-C γ cleavages of tryptophan
Density functional theory calculations
Low-energy collision-induced dissociation
Peptide radical cations
Issue Date2012
PublisherElsevier Inc. The Journal's web site is located at http://www.elsevier.com/locate/jasms
Citation
Journal Of The American Society For Mass Spectrometry, 2012, v. 23 n. 2, p. 264-273 How to Cite?
AbstractIn this study, we observed unprecedented cleavages of the C β-C γ bonds of tryptophan residue side chains in a series of hydrogen-deficient tryptophan-containing peptide radical cations (M •+) during low-energy collision-induced dissociation (CID). We used CID experiments and theoretical density functional theory (DFT) calculations to study the mechanism of this bond cleavage, which forms [M - 116] + ions. The formation of an α-carbon radical intermediate at the tryptophan residue for the subsequent C β-C γ bond cleavage is analogous to that occurring at leucine residues, producing the same product ions; this hypothesis was supported by the identical product ion spectra of [LGGGH - 43] + and [WGGGH - 116] +, obtained from the CID of [LGGGH] •+ and [WGGGH] •+, respectively. Elimination of the neutral 116-Da radical requires inevitable dehydrogenation of the indole nitrogen atom, leaving the radical centered formally on the indole nitrogen atom ([Ind] •-2), in agreement with the CID data for [WGGGH] •+ and [W 1-CH3GGGH] •+; replacing the tryptophan residue with a 1-methyltryptophan residue results in a change of the base peak from that arising from a neutral radical loss (116 Da) to that arising from a molecule loss (131 Da), both originating from C β-C γ bond cleavage. Hydrogen atom transfer or proton transfer to the γ-carbon atom of the tryptophan residue weakens the C β-C γ bond and, therefore, decreases the dissociation energy barrier dramatically. © 2011 The Author(s).
Persistent Identifierhttp://hdl.handle.net/10722/147139
ISSN
2015 Impact Factor: 3.031
2015 SCImago Journal Rankings: 1.322
ISI Accession Number ID
Funding AgencyGrant Number
Research Grants Council, Hong Kong Special Administrative RegionHKU 701611
HKU 701610
CityU 103110
Funding Information:

IKC and CKS thank the Research Grants Council, Hong Kong Special Administrative Region for financial support. (Project nos. HKU 701611 and HKU 701610, CityU 103110).

References

 

DC FieldValueLanguage
dc.contributor.authorSong, Ten_HK
dc.contributor.authorHao, Qen_HK
dc.contributor.authorLaw, CHen_HK
dc.contributor.authorSiu, CKen_HK
dc.contributor.authorChu, IKen_HK
dc.date.accessioned2012-05-28T08:20:51Z-
dc.date.available2012-05-28T08:20:51Z-
dc.date.issued2012en_HK
dc.identifier.citationJournal Of The American Society For Mass Spectrometry, 2012, v. 23 n. 2, p. 264-273en_HK
dc.identifier.issn1044-0305en_HK
dc.identifier.urihttp://hdl.handle.net/10722/147139-
dc.description.abstractIn this study, we observed unprecedented cleavages of the C β-C γ bonds of tryptophan residue side chains in a series of hydrogen-deficient tryptophan-containing peptide radical cations (M •+) during low-energy collision-induced dissociation (CID). We used CID experiments and theoretical density functional theory (DFT) calculations to study the mechanism of this bond cleavage, which forms [M - 116] + ions. The formation of an α-carbon radical intermediate at the tryptophan residue for the subsequent C β-C γ bond cleavage is analogous to that occurring at leucine residues, producing the same product ions; this hypothesis was supported by the identical product ion spectra of [LGGGH - 43] + and [WGGGH - 116] +, obtained from the CID of [LGGGH] •+ and [WGGGH] •+, respectively. Elimination of the neutral 116-Da radical requires inevitable dehydrogenation of the indole nitrogen atom, leaving the radical centered formally on the indole nitrogen atom ([Ind] •-2), in agreement with the CID data for [WGGGH] •+ and [W 1-CH3GGGH] •+; replacing the tryptophan residue with a 1-methyltryptophan residue results in a change of the base peak from that arising from a neutral radical loss (116 Da) to that arising from a molecule loss (131 Da), both originating from C β-C γ bond cleavage. Hydrogen atom transfer or proton transfer to the γ-carbon atom of the tryptophan residue weakens the C β-C γ bond and, therefore, decreases the dissociation energy barrier dramatically. © 2011 The Author(s).en_HK
dc.languageengen_US
dc.publisherElsevier Inc. The Journal's web site is located at http://www.elsevier.com/locate/jasmsen_HK
dc.relation.ispartofJournal of the American Society for Mass Spectrometryen_HK
dc.rightsThe Author(s)en_US
dc.rightsCreative Commons: Attribution 3.0 Hong Kong Licenseen_US
dc.subjectC β-C γ cleavages of tryptophanen_HK
dc.subjectDensity functional theory calculationsen_HK
dc.subjectLow-energy collision-induced dissociationen_HK
dc.subjectPeptide radical cationsen_HK
dc.titleNovel Cβ-Cγ bond cleavages of tryptophan-containing peptide radical cationsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://www.springerlink.com/link-out/?id=2104&code=H340157570216134&MUD=MPen_US
dc.identifier.emailChu, IK:ivankchu@hku.hken_HK
dc.identifier.authorityChu, IK=rp00683en_HK
dc.description.naturepublished_or_final_versionen_US
dc.identifier.doi10.1007/s13361-011-0295-5en_HK
dc.identifier.pmid22135037-
dc.identifier.scopuseid_2-s2.0-84856268393en_HK
dc.identifier.hkuros208682-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-84856268393&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume23en_HK
dc.identifier.issue2en_HK
dc.identifier.spage264en_HK
dc.identifier.epage273en_HK
dc.identifier.eissn1879-1123en_US
dc.identifier.isiWOS:000302467800006-
dc.publisher.placeUnited Statesen_HK
dc.description.otherSpringer Open Choice, 28 May 2012en_US
dc.identifier.scopusauthoridSong, T=36087959100en_HK
dc.identifier.scopusauthoridHao, Q=35274915300en_HK
dc.identifier.scopusauthoridLaw, CH=54922894500en_HK
dc.identifier.scopusauthoridSiu, CK=7006550712en_HK
dc.identifier.scopusauthoridChu, IK=7103327484en_HK

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