Collisional activation spectra of quarternary ammonium cations produced by field desorption

Gierlich, H. H.; Röllgen, F. W.; Borchers, Friedrich; Levsen, K.

doi:10.1002/oms.1210120609

Cited by 57 publications

(20 citation statements)

References 12 publications

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“…Loss of N-methyl hydrogens in lieu of alkyl deuteriums causes the 3-u shift. The heaviest member of this series (corresponding to loss of CHaD, mlz 268) is surprisingly abundant but has precedence [21]. Its analogue for D3';; is found at mlz 271 in Figure 6a.…”

Section: A New Fragmentation Reactionmentioning

confidence: 97%

Charge-remote fragmentation in a hybrid (BEqQ) mass spectrometer to determine isotopic purity in selectively polydeuterated surfactants

Tuinrnan

Cook

Magid

1990

J. Am. Soc. Mass Spectrom.

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Section: A New Fragmentation Reactionmentioning

confidence: 97%

Charge-remote fragmentation in a hybrid (BEqQ) mass spectrometer to determine isotopic purity in selectively polydeuterated surfactants

Tuinrnan

Cook

Magid

1990

J. Am. Soc. Mass Spectrom.

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“…Note that elimination of C7H16 is observed as a minor fragmentation process at higher collision energies. 6. Breakdown graph for (n-C,H9)4N+ processes for (C4H9)4N+ correspond to elimination of C4H8, elimination of C4HI,, and elimination of C7HI6; the latter reaction (eq.…”

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%

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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“…The first is that most commonly considered in mass spectrometry for even-electron ions-the chemistry occurs at the site of protonation, and is charge-initiated. A second possibility is a charge-remote [6][7][8] mechanism. In the latter, bonds are broken far from the charge site, and are unaffected by the charge.…”

mentioning

confidence: 99%

Characterization of the primary thermal degradation processes of peptides using the mass spectrometric technique K⁺IDS, K⁺ ionization of desorbed species

Allison

1994

J. Am. Soc. Mass Spectrom.

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The mass spectrometric technique of K(+) ionization of desorbed species, K(+)IDS, is used here to characterize the primary thermal degradation chemistry of small peptides. In this technique, a small amount of a compound is rapidly heated in the condensed phase. Desorption of the intact molecule can occur. Also, thermal degradation products are formed which quickly desorb as well, rather than remain on the surface and undergo subsequent chemistry. The desorbed molecules form adducts with gas phase K(+) ions, and a mass spectrum is obtained. Deuterium labeling experiments, and the use of derivatizing reagents, allows for the thermal degradation chemistry of small peptides to be elucidated. Apparently, skeletal bond cleavages are accompanied by H-shifts, although the hydrogen atoms shift from "remote" sites, brought into close proximity with the fragmenting skeletal bond via secondary interactions. Experimental results are presented that allow for correlations between thermal degradation chemistry and the resulting K(+)IDS mass spectra to be made.

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Collisional activation spectra of quarternary ammonium cations produced by field desorption

Cited by 57 publications

References 12 publications

Charge-remote fragmentation in a hybrid (BEqQ) mass spectrometer to determine isotopic purity in selectively polydeuterated surfactants

Charge-remote fragmentation in a hybrid (BEqQ) mass spectrometer to determine isotopic purity in selectively polydeuterated surfactants

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

Characterization of the primary thermal degradation processes of peptides using the mass spectrometric technique K⁺IDS, K⁺ ionization of desorbed species

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Collisional activation spectra of quarternary ammonium cations produced by field desorption

Cited by 57 publications

References 12 publications

Charge-remote fragmentation in a hybrid (BEqQ) mass spectrometer to determine isotopic purity in selectively polydeuterated surfactants

Charge-remote fragmentation in a hybrid (BEqQ) mass spectrometer to determine isotopic purity in selectively polydeuterated surfactants

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

Characterization of the primary thermal degradation processes of peptides using the mass spectrometric technique K+IDS, K+ ionization of desorbed species

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Characterization of the primary thermal degradation processes of peptides using the mass spectrometric technique K⁺IDS, K⁺ ionization of desorbed species