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Charge‐remote fragmentation characteristics of functionalized alkanes in high‐energy collision‐induced dissociation
Author(s) -
Denekamp Chagit,
Van den Heuvel Hilde,
Voinov Valery G.,
Claeys Magda,
Seto Carmai,
Grossert J. Stuart,
Waddell David S.,
Curtis Jonathan M.,
Boyd Robert K.
Publication year - 2000
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/1097-0231(20000630)14:12<1035::aid-rcm986>3.0.co;2-4
Subject(s) - chemistry , fragmentation (computing) , dissociation (chemistry) , ion , phosphonium , collision induced dissociation , deuterium , excited state , mass spectrometry , atomic physics , tandem mass spectrometry , organic chemistry , physics , chromatography , computer science , operating system
In this study we report on high‐energy, collision‐induced dissociation processes leading to charge‐remote fragmentations, using three alkyl cations, namely n ‐hexadecylpyridinium, n ‐hexadecyltriphenylphosphonium and n ‐hexadecyltriethylammonium, each with and without 2 H 2 ‐labelling at the C(9) position of the hexadecyl chain. The characteristic patterns corresponding to the formal elimination of alkane elements were observed, and the 2 H 2 ‐labelling at C(9) clearly affected only one charge‐remote fragment ion of the homologous series. However, in addition to the expected fragment ion containing only one deuterium atom, a significant ion retaining two deuterium atoms was observed. MS/MS/MS experiments demonstrated clearly that the latter ion showed partial deuteration around the charge site, the level of deuteration depending on the structure of the original precursor cation. These results can be interpreted in terms of two novel, distinct mechanisms, one of which involves an excited state in an aromatic ring. Mixed‐site fragmentation (MSF) ions were also observed from the phosphonium and ammonium ion precursors. We believe that the observation of the MSF process occurring at an sp 2 ‐hybridized center in the phosphonium series has not been reported previously. It thus becomes apparent that high‐energy collisions leading to charge‐remote reactions in fact lead to a broad range of pathways. © 2000 John Wiley & Sons, Ltd.