Comparison of low‐energy CAD spectra of sulphonium, ammonium and phosphonium cations, propene elimination from allyl‐substituted oniums

Mestdagh, H.; Morin, Nicole; Rolando, Christian

doi:10.1002/oms.1210230405

Cited by 7 publications

(6 citation statements)

References 21 publications

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“…a reactlon which we do not observe. Alkvl radical loss from tetraalkyl ammonium ions is commonly observed in high energy CID (8,9, 11) but is not observed in low energy CID in this work nor in the work of Mesdach et al (10); this implies that alkyl radical loss has a high onset energy which is not achieved in low energy CID.…”

Section: Methodscontrasting

confidence: 68%

“…We also recorded the unimolecular fragmentation reactions occurring in the drift region between the magnetic and electric sectors; the results obtained were in good agreement with the data reported in Tables 1 and 2. The fragmentation reaction resulting in nominal elimination of C7HI6 from (C4Hg),N+ has been proposed earlier (8)(9)(10) to involve sequential elimination of C4Hg' and C3H7', viz rather than direct elimination of C7H16 (reaction [3]). …”

Section: Methodsmentioning

confidence: 99%

“…In contrast to the protonated amines, tetraalkyl ammonium ions, R4N+, show very abundant elimination of alkanes in metastable ion fragmentation reactions and in both low energy and high energy CID studies (6)(7)(8)(9)(10)(11). The nominal alkanes eliminated correspond to R H and to (R' + [R -CH,]'), the latter either as an alkane or as two alkyl radicals.…”

Section: Introductionmentioning

confidence: 99%

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An energy-resolved study of the fragmentation reactions of alkyl ammonium ions

Bosma¹,

Harrison²

1994

Can. J. Chem.

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,2205 (1994). ' The unimolecular metastable ion and low-energy collision-induced fragmentation reactions of alkyl ammonium ions R,,H,.,,Nf (tz = 2 to4, R = tz-C3H7 and n-C,H9) have been studied and breakdown graphs expressing the % fragment ion abundances as a function of the centre-of-mass collision energy have been established. The dialkyl and trialkyl ammonium ions fragment primarily by olefin ([R -HI) elimination or by formation of the alkyl ion Rf (with rearrangement to the more stable secondary structure). By contrast the tetraalkyl ammonium ions show both elimination of [R -HI and elimination of an alkane, which is C,H12 for the propyl compound C7H,6 for the butyl compound. The results are interpreted in terms of competition between heterolytic bond cleavage to form a [Rf---NH,.,,R,,.,] complex and homolytic bond cleavage to form a [R,,-,H,.,,Nf.---'R] complex. The former complex fragments either to form R+ or undergoes internal proton transfer to form R,,-,H,.,,NH+ + [R -HI, while the latter complex fragments by alkane elimination resulting from attack of R' on the a-CC bond of the alkyl group. For the propyl ammonium ions plausible potential energy profiles are established which show that the former complex is favoured for n = 2, 3 while the two complexes have similar energies for n = 4. [Traduit par la rCdaction]

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Section: Methodscontrasting

confidence: 68%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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An energy-resolved study of the fragmentation reactions of alkyl ammonium ions

Bosma¹,

Harrison²

1994

Can. J. Chem.

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“…Thus, side reactions such as charge migration via intramolecular proton transfer, alkyl group transfer, as well as breaking of bonds to give stable alkyl cations or alkenes must be avoided [92][93][94][95][96][97][98][99][100]. Proton transfer (Scheme 3, Pathway 1) would give an sulfur ylide.…”

Section: Methodsmentioning

confidence: 99%

“…The bond strengths of other breaking alkyl groups appear to be unknown in both the condensed phase and the gas phase. There have, however, been several studies on the fragmentation reactions of sulfonium ions as studied by mass spectrometry [97][98][99][100]. Scheme 3 (Pathway 3) is highly unlikely given that the least stable carbocation is formed (CH 3 ϩ ).…”

Section: Methodsmentioning

confidence: 99%

Selective identification and quantitative analysis of methionine containing peptides by charge derivatization and tandem mass spectrometry

Reid

Roberts

Simpson

et al. 2005

J. Am. Soc. Mass Spectrom.

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To enable the development of a tandem mass spectrometry (MS/MS) based methodology for selective protein identification and differential quantitative analysis, a novel derivatization strategy is proposed, based on the formation of a "fixed-charge" sulfonium ion on the side-chain of a methionine amino acid residue contained within a protein or peptide of interest. The gas-phase fragmentation behavior of these side chain fixed charge sulfonium ion containing peptides is observed to result in exclusive loss of the derivatized side chain and the formation of a single characteristic product ion, independently of charge state or amino acid composition. Thus, fixed charge containing peptide ions may be selectively identified from complex mixtures, for example, by selective neutral loss scan mode MS/MS methods. Further structural interrogation of identified peptide ions may be achieved by subjecting the characteristic MS/MS product ion to multistage MS/MS (MS3) in a quadrupole ion trap mass spectrometer, or by energy resolved "pseudo" MS3 in a triple quadrupole mass spectrometer. The general principles underlying this fixed charge derivatization approach are demonstrated here by MS/MS, MS3 and "pseudo" MS3 analysis of side chain fixed-charge sulfonium ion derivatives of peptides containing methionine formed by reaction with phenacylbromide. Incorporation of "light" and "heavy" isotopically encoded labels into the fixed-charge derivatives facilitates the application of this method to the quantitative analysis of differential protein expression, via measurement of the relative abundances of the neutral loss product ions generated by dissociation of the light and heavy labeled peptide ions. This approach, termed "selective extraction of labeled entities by charge derivatization and tandem mass spectrometry" (SELECT), thereby offers the potential for significantly improved sensitivity and selectivity for the identification and quantitative analysis of peptides or proteins containing selected structural features, without requirement for extensive fractionation or otherwise enrichment from a complex mixture prior to analysis.

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Fragmentation reactions of alkylphenylammonium ions

Harrison

1999

J. Mass Spectrom.

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Comparison of low‐energy CAD spectra of sulphonium, ammonium and phosphonium cations, propene elimination from allyl‐substituted oniums

Cited by 7 publications

References 21 publications

An energy-resolved study of the fragmentation reactions of alkyl ammonium ions

An energy-resolved study of the fragmentation reactions of alkyl ammonium ions

Selective identification and quantitative analysis of methionine containing peptides by charge derivatization and tandem mass spectrometry

Fragmentation reactions of alkylphenylammonium ions

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