Linked Life Data

14608618

Source:http://linkedlifedata.com/resource/pubmed/id/14608618

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pubmed-article:14608618pubmed:dateCreated2003-11-10lld:pubmed
pubmed-article:14608618pubmed:abstractTextLoss of H2S is the characteristic Cys side-chain fragmentation of the [M-H]- anions of Cys-containing peptides. A combination of experiment and theory suggests that this reaction is initiated from the Cys enolate anion as follows: RNH-(-)C(CH2SH)CONHR' Ø [RNHC(=CH2)CONHR' (HS-)] Ø [RNHC(=CH2)CO-HNR'-H]-+H2S. This process is facile. Calculations at the HF/6-31G(d)//AM1 level of theory indicate that the initial anion needs only > or =20.1 kcal mol(-1) of excess energy to effect loss of H2S. Loss of CH2S is a minor process, RNHCH(CH2SH)CON(-)-R' Ø RNHCH(CH2S-)CONHR' Ø RNH -CHCONHR+CH2S, requiring an excess energy of > or =50.2 kcal mol(-1). When Cys occupies the C-terminal end of a peptide, the major fragmentation from the [M-H]- species involves loss of (H2S+CO2). A deuterium-labelling study suggests that this could either be a charge-remote reaction (a process which occurs remote from and uninfluenced by the charged centre in the molecule), or an anionic reaction initiated from the C-terminal CO2- group. These processes have barriers requiring the starting material to have an excess energy of > or =79.6 (charge-remote) or > or =67.1 (anion-directed) kcal mol(-1), respectively, at the HF/6-31G(d)//AM1 level of theory. The corresponding losses of CH2O and H2O from the [M-H]- anions of Ser-containing peptides require > or =35.6 and > or =44.4 kcal mol(-1) of excess energy (calculated at the AM1 level of theory), explaining why loss of CH2O is the characteristic side-chain loss of Ser in the negative ion mode.lld:pubmed
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pubmed-article:14608618pubmed:statusMEDLINElld:pubmed
pubmed-article:14608618pubmed:issn0951-4198lld:pubmed
pubmed-article:14608618pubmed:authorpubmed-author:BrinkworthCra...lld:pubmed
pubmed-article:14608618pubmed:authorpubmed-author:BowieJohn HJHlld:pubmed
pubmed-article:14608618pubmed:authorpubmed-author:BilusichDanie...lld:pubmed
pubmed-article:14608618pubmed:authorpubmed-author:McAnoyAndrew...lld:pubmed
pubmed-article:14608618pubmed:copyrightInfoCopyright 2003 John Wiley & Sons, Ltd.lld:pubmed
pubmed-article:14608618pubmed:issnTypePrintlld:pubmed
pubmed-article:14608618pubmed:volume17lld:pubmed
pubmed-article:14608618pubmed:ownerNLMlld:pubmed
pubmed-article:14608618pubmed:authorsCompleteYlld:pubmed
pubmed-article:14608618pubmed:pagination2488-94lld:pubmed
pubmed-article:14608618pubmed:dateRevised2006-11-15lld:pubmed
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pubmed-article:14608618pubmed:year2003lld:pubmed
pubmed-article:14608618pubmed:articleTitleThe fragmentations of [M-H]- anions derived from underivatised peptides. The side-chain loss of H2S from Cys. A joint experimental and theoretical study.lld:pubmed
pubmed-article:14608618pubmed:affiliationDepartment of Chemistry, The University of Adelaide, South Australia, 5005 Australia.lld:pubmed
pubmed-article:14608618pubmed:publicationTypeJournal Articlelld:pubmed
pubmed-article:14608618pubmed:publicationTypeResearch Support, Non-U.S. Gov'tlld:pubmed
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