Electrospray Tandem Mass Spectrometry of a Novel Series of Amphipathic Functionalized Ether-linked Di- and Trisaccharides and Cyclic Oligosaccharides

Banoub, Joseph; Thibault, Pierre; Goueth, P. Y.; Ronco, G.; Villa, Pierre

doi:10.1002/(sici)1096-9888(199701)32:1<109::aid-jms459>3.0.co;2-b

Cited by 9 publications

(6 citation statements)

References 7 publications

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“…3) show characteristic fragmentations due to the presence of the isopropylidene groups, such as loss of one acetone molecule (−58 Da), combined loss of two acetone molecules (−116 Da), combined loss of two acetone molecules plus CO (−144 Da), loss of C 10 H 16 O 4 (−200 Da), and loss of the protected galactose residue as a neutral molecule (−242 Da). These fragmentations were also observed in the ESI‐MS/MS spectra of neutral glycoporphyrins16 and of some di‐ and trisaccharides containing isopropylidene as the protecting group 24. For porphyrin 4b (Fig.…”

Section: Resultsmentioning

confidence: 57%

Characterization of cationic glycoporphyrins by electrospray tandem mass spectrometry

Silva

Serra

Ribeiro

et al. 2006

Rapid Comm Mass Spectrometry

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Novel cationic porphyrin derivatives having a galactose or a bis(isopropylidene)galactose unit linked directly to a pyridine or to an aminophenyl group were characterized by electrospray tandem mass spectrometry (ESI-MS/MS). The electrospray mass spectra (ESI-MS) show the M(+) ions, since these porphyrins are already monocharged in solution. The fragmentation of these ions under ESI-MS/MS conditions was studied and it was found that elimination of the sugar residue as a radical (-163 or -243 Da) is a common fragmentation pathway. Loss of the sugar unit as a neutral fragment (-162 or -242 Da) and cross-ring fragmentations typical of glyco-derivatives are also observed for the pyridinium glycoporphyrins, but they are absent in the case of ammonium glycoporphyrins. The cationic beta-pyridiniumvinyl porphyrins show an atypical fragmentation due to the cleavage of the C(5)-C(6) bond of the sugar unit. Overall, the different patterns of fragmentation observed in the ESI-MS/MS spectra of the sugar pyridinium porphyrins and of the sugar ammonium phenyl porphyrins can give important information about the type of spacer between the porphyrin and the sugar unit.

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Section: Resultsmentioning

confidence: 57%

Characterization of cationic glycoporphyrins by electrospray tandem mass spectrometry

Silva

Serra

Ribeiro

et al. 2006

Rapid Comm Mass Spectrometry

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“…Losses of C 2 H 4 O 2 (−60 Da), C 3 H 6 O 3 (−90 Da) and C 4 H 8 O 4 (−120 Da) are common fragmentations of hexoses linked by C‐6 in disaccharides and small oligosaccharides 20–23. The observation of these three fragmentation pathways in the tandem mass spectra of a saccharide linked by C‐6 was also observed in infrared laser desorption mass spectrometry (IR‐LD‐MS)20 and in fast atom bombardment (FAB) MS, using different dissociation conditions, such as CID19, 21 or surface‐induced dissociation (SID) 22.…”

Section: Resultsmentioning

confidence: 88%

Structural characterization of glycoporphyrins by electrospray tandem mass spectrometry

Domingues

Reis

et al. 2004

J. Mass Spectrom.

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Porphyrin derivatives having a galactose or a bis(isopropylidene)galactose structural unit, linked by ester or ether bonds, were characterized by electrospray tandem mass spectrometry (ES-MS/MS). The electrospray mass spectra of these glycoporphyrins show the corresponding [M + H](+) ions. For the glycoporphyrins with pyridyl substituents and those having a tetrafluorophenyl spacer, the doubly charged ions [M + 2H](2+) were also observed in ES-MS with high relative abundance. The fragmentation of both [M + H](+) and [M + 2H](2+) ions exhibited common fragmentation pathways for porphyrins with the same sugar residue, independently of the porphyrin structural unit and type of linkage. ES-MS/MS of the [M + H](+) ions of the galactose-substituted porphyrins gave the fragment ions [M + H - C(2)H(4)O(2)](+), [M + H - C(3)H(6)O(3)](+), [M + H - C(4)H(8)O(4)](+) and [M + H - galactose residue](+). The fragmentation of the [M + 2H](2+) ions of the porphyrins with galactose shows the common doubly charged fragment ions [porphyrin + H](2+), [M + 2H - C(2)H(4)O(2)](2+), [M + 2H - C(4)H(8)O(4)](2+), [M + 2H - galactose residue](2+) and the singly charged fragment ions [M + H - C(3)H(6)O(3)](+) and [M + H - galactose residue](+). The fragmentation of the [M + H](+) ions of glycoporphyrins with a protected galactosyl residue leads mainly to the ions [M + H - CO(CH(3))(2)](+), [M + H - 2CO(CH(3))(2)](+), [M + H - 2CO(CH(3))(2) - CO](+), [M + H - C(10)H(16)O(4)](+) and [M + H - protected galactose](+). The doubly charged ions [M + 2H](2+) fragment to give the doubly charged ions [porphyrin + H](2+) and the singly charged ions [M + H - protected galactose residue](+) and [M + H - CO(CH(3))(2)](+). For the porphyrins where the sugar structural unit is linked by an ester bond, [M + 2H](2+), ES-MS/MS showed a major and typical fragmentation corresponding to combined loss of a sugar structural unit and further loss of water, leading to the ion [M + 2H - sugar residue - H(2)O](2+), independently of the structure of the sugar structural unit. These results show that ES-MS/MS can be a powerful tool for the characterization of the sugar structural unit of glycoporphyrins, without the need for chemical hydrolysis.

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“…8 Combining ESI with collision-induced dissociation (CID) provides a powerful tool for the structural elucidation of non-volatile and thermally labile compounds, especially biological material and carbohydrate derivatives. [9][10][11][12] Fragmentation pathways of five-membered ring lactones using electrospray ionization tandem mass spectrometry (ESI-MS/MS) have previously been reported. 8,13 Knowledge of the fragmentation mechanisms of lactones and the behaviour of these compounds under ESI conditions can be extended to larger and more complex natural products that contain the a,b-unsaturated g-lactone moiety in their structure.…”

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confidence: 99%

Electrospray ionization mass spectrometric analysis of newly synthesized α,β‐unsaturated γ‐lactones fused to sugars

Madeira

Rosa

Xavier

et al. 2010

Rapid Comm Mass Spectrometry

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Knowledge of the fragmentation mechanisms of lactones and their behaviour under electrospray ionization (ESI) conditions can be extended to larger and more complex natural products that contain an alpha,beta-unsaturated gamma-lactone moiety in their structure. Moreover, little is known about the gas-phase behaviour of alpha,beta-unsaturated gamma-lactones linked or fused to sugars. Therefore, five alpha,beta-unsaturated gamma-lactones (butenolides) fused to a pyranose ring, recently synthesized compounds with potential relevance regarding their biological properties, were investigated using ESI-MS and ESI-MS/MS in both positive and negative ion modes. Their fragmentation mechanisms and product ion structures were compared. It was observed that two isomers could be unambiguously distinguished in the negative ion mode by the fragmentation pathways of their deprotonated molecules as well as in the positive ion mode by the fragmentation pathways of either the protonated or the sodiated molecule. Fragmentation mechanisms are proposed taking into account the MS/MS data and semi-empirical calculations using the PM6 Hamiltonean. The semi-empirical calculations were also very useful in determining the most probable protonation and cationization sites.

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Electrospray Tandem Mass Spectrometry of a Novel Series of Amphipathic Functionalized Ether-linked Di- and Trisaccharides and Cyclic Oligosaccharides

Cited by 9 publications

References 7 publications

Characterization of cationic glycoporphyrins by electrospray tandem mass spectrometry

Characterization of cationic glycoporphyrins by electrospray tandem mass spectrometry

Structural characterization of glycoporphyrins by electrospray tandem mass spectrometry

Electrospray ionization mass spectrometric analysis of newly synthesized α,β‐unsaturated γ‐lactones fused to sugars

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