How the site of ionisation influences side-chain fragmentation in histidine radical cation

Adrià Gil, Sílvia Simon, Mariona Sodupe, Juan Bertrán

Research output: Contribution to journalArticleResearchpeer-review

12 Citations (Scopus)

Abstract

Based on MPWB1K/6-31++G(d,p) calculations, we have performed a charge and spin density analysis for the most representative structures of Hisδ(+) and Hisε(+) radical cations. This analysis shows that depending on the site where ionisation takes place, fragmentation of the side-chain can occur via R+ elimination to give the m/z 81 peak in the 70 eV EI-MS spectrum, or via the most favoured RH+ {radical dot} elimination to give the most intense m/z 82 peak. The mechanism for RH+ {radical dot} elimination involves a proton-transfer from the amino group to the free Nδ1 of the imidazole ring. © 2007 Elsevier B.V. All rights reserved.
Original languageEnglish
Pages (from-to)276-281
JournalChemical Physics Letters
Volume451
Issue number4-6
DOIs
Publication statusPublished - 21 Jan 2008

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