The fragmentation mechanism of five-membered lactones by electrospray ionisation tandem mass spectrometry

Crotti, Antônio Eduardo Miller; Fonseca, Tatiana; Hong, Hui; Staunton, James; Galembeck, Sérgio E.; Lopes, Norberto Peporine; Gates, Paul J.

doi:10.1016/j.ijms.2004.02.009

Cited by 61 publications

(76 citation statements)

References 12 publications

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“…[25 -27,30] For all these reasons, the theoretical approach can be useful for the understanding of the dissociation process and stability of each species during the fragmentation. [18,24,25,27,30] Mass spectrometry fragmentation processes are routinely analyzed using quantum mechanics, in order to postulate plausible structures for unstable intermediate species, such as radicals, carbocations, carbanions, and other species, whose lifetime is often limited to within mass spectrometers. [31,32] As part of our ongoing project on the use of ESI-MS/MS in the structural elucidation of natural products and new products from organic synthesis, we report here the gasphase dissociation of a set of 2-acylamino-1,4-naphthoquinone derivatives ( Fig.…”

Section: Introductionmentioning

confidence: 99%

Gas‐phase dissociation of 1,4‐naphthoquinone derivative anions by electrospray ionization tandem mass spectrometry

et al. 2009

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Gas-phase dissociation pathways of deprotonated 1,4-naphthoquinone (NQ) derivatives have been investigated by electrospray ionization tandem mass spectrometry (ESI-MS/MS). The major decomposition routes have been elucidated on the basis of quantum chemical calculations at the B3LYP/6-31 + G(d,p) level. Deprotonation sites have been indicated by analysis of natural charges and gas-phase acidity. NQ anions underwent an interesting reaction under collision-induced dissociation conditions, which resulted in the radical elimination of the lateral chain, in contrast with the even-electron rule. Possible pathways have been suggested, and their mechanisms have been elucidated on the basis of Gibbs energy and enthalpy values for the anions previously described at each pathway.

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Section: Introductionmentioning

confidence: 99%

Gas‐phase dissociation of 1,4‐naphthoquinone derivative anions by electrospray ionization tandem mass spectrometry

et al. 2009

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“…[5] A. E. M. Crotti's group analyzed a series of five-membered lactones (both saturated and unsaturated) and lactam by ESI-MS/MS and electrospray ionization multi-stage mass spectrometry (ESI-MS n ). [10] It was observed that the main fragment ions of their protonated molecules are derived from neutral losses of CO and/or H 2 O (NH 3 for the lactam). Recently, they used ESI-MS/MS to investigate the fragmentation of a series of DKPs previously isolated from Aspergillus fumigatus and found that losing CO directly from the protonated molecule was a fragmentation process common to all the compounds analyzed.…”

Section: Introductionmentioning

confidence: 99%

Fragmentation of deprotonated cyclic dipeptides by electrospray ionization mass spectrometry

et al. 2009

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The fragmentation pathways of deprotonated cyclic dipeptides have been studied by electrospray ionization multi-stage mass spectrometry (ESI-MSn) in negative mode. The results showed that the fragmentation pathways of deprotonated cyclic dipeptides depended significantly on the different substituents, the side chains of amino acid residues at the diketopiperazine ring. In the spectra of deprotonated cyclic dipeptides, the ion [M-H-substituent radical]- was firstly observed in the ESI mode. The characteristic fragment ions [M-H-substituent radical]- and [M-H-(substituent-H)]- could be used as the symbols of particular cyclic dipeptides. The hydrogen/deuterium (H/D) exchange experiment, the high-resolution mass spectrometry (Q-TOF) and theoretical calculations were used to rationalize the proposed fragmentation pathways and to verify the differences between the fragmentation pathways. The relative Gibbs free energies (DeltaG) of the product ions and possible fragmentation pathways were estimated using the B3LYP/6-31++G(d, p) model. The results have some potential applications in the structural elucidation and interpretation of the mass spectra of homologous compounds and will enrich the gas-phase ESI-MS ion chemistry of cyclic dipeptides.

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“…[16 -18] It produces highly abundant protonated/cationized molecules mainly due to the low residual energy of the ionization process. [19] The combination of ESI with collision induced dissociation (CID) results in a powerful tool for structure elucidation of non-volatile and thermally labile compounds, especially biological material and carbohydrate derivatives. [20 -23] The fragmentation pathways of five-membered ring lactones using electrospray ionization mass spectrometry have already been reported.…”

Section: Introductionmentioning

confidence: 99%

“…[20 -23] The fragmentation pathways of five-membered ring lactones using electrospray ionization mass spectrometry have already been reported. [19,24] Recently we reported the gas-phase behaviour of α,β-unsaturated γ -lactones fused to pyranose rings, [25] nevertheless, studies on the gas-phase behaviour of monosaccharide derivatives of this type are still lacking. In fact, studies that deal with the gas-phase behaviour of monosaccharides are scarce.…”

Section: Introductionmentioning

confidence: 99%

Furanose C—C‐linked γ‐lactones: a combined ESI FTICR MS and semi‐empirical calculations study

Madeira¹,

Xavier²,

Rauter³

et al. 2010

J. Mass Spectrom.

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Sugars that incorporate the unsaturated carbonyl motif have become important synthetic targets not only as a result of their potential biological properties but also as precursors in the synthesis of many bioactive products. Moreover, little is known about the influence of the γ-lactone moiety in the fragmentation pattern of furanose rings. Therefore, two α,β-unsaturated γ-lactones (butenolides) and two β-hydroxy γ-lactones, C-C linked to a furanose ring were studied using electrospray ionization FTICR mass spectrometry. The behaviour of the protonated and sodiated forms of the compounds under study has been compared considering their structural features. Fragmentation mechanisms were established and ion structures were proposed taking into account the MS(2) and MS(3) experiments, accurate mass measurements and semi-empirical calculations. These inexpensive methods proved to be a valuable resource for proposing protonation sites and for the establishment of fragmentation pathways.

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The fragmentation mechanism of five-membered lactones by electrospray ionisation tandem mass spectrometry

Cited by 61 publications

References 12 publications

Gas‐phase dissociation of 1,4‐naphthoquinone derivative anions by electrospray ionization tandem mass spectrometry

Gas‐phase dissociation of 1,4‐naphthoquinone derivative anions by electrospray ionization tandem mass spectrometry

Fragmentation of deprotonated cyclic dipeptides by electrospray ionization mass spectrometry

Furanose C—C‐linked γ‐lactones: a combined ESI FTICR MS and semi‐empirical calculations study

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