Fast atom bombardment and fast atom bombardment collision-activated dissociation/mass-analysed ion kinetic energy analysis ofC-glycosidic flavonoids

Becchi, Michel; Fraisse, D.

doi:10.1002/bms.1200180207

Cited by 98 publications

(79 citation statements)

References 14 publications

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“…In another important fragmentation channel the ions at m/z 172 decompose even further, Le., by loss of 28 Da, due to secondary loss of CO, retaining only the C atom by which the hexose moiety is attached (Cl'). This transition is also reported as being pronounced in analogous flavone C-glycopyranosides (Becchi & Fraisse, 1989;Li et al, 1992;Prox, 1968).…”

Section: Resultsmentioning

confidence: 62%

New type of linkage between a carbohydrate and a protein: C-glycosylation of a specific tryptophan residue in human RNase Us

Hofsteenge¹,

Müller²,

Beer³

et al. 1994

Biochemistry

270

234

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We report a new type of linkage between a carbohydrate and a protein, involving the rarely modified side chain of a tryptophan residue. An aldohexopyranosyl residue was found to be linked via a C-C bond to the indole ring of the tryptophan residue at position 7 of human RNase Us. Mass spectrometric analysis of peptides containing this residue showed a molecular mass 162 Da higher than that expected for tryptophan. The fragmentation pattern of the modified amino acid side chain was reminiscent of that of aromatic C-glycosides, suggesting a direct attachment of a hexose residue to a C-position of the tryptophan indole moiety. 'H and 13C NMR spectroscopic data confirmed this inference and unequivocally demonstrated the substituent to be an aldohexopyranosyl residue, C-glycosidically linked to the C2 atom of the indole. This mode of attachment differs from the ones known so far, in which carbohydrates are linked to an amino acid side chain by N-or 0-glycosidic bonds.

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Section: Resultsmentioning

confidence: 62%

New type of linkage between a carbohydrate and a protein: C-glycosylation of a specific tryptophan residue in human RNase Us

Hofsteenge¹,

Müller²,

Beer³

et al. 1994

Biochemistry

270

234

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“…Deuterium labelling experiments indicated that hydroxyl hydrogen atoms are involved in the formation of Y n + ions [7]. Analogy exists for the MIKE/CID spectra obtained with negative ion FAB as described by Becchi and Fraisse [13]. In the spectra of the C-glycosides only the precursor …”

Section: Differentiation Between O-glycosides C-glycosides and O-c-dmentioning

confidence: 53%

Tandem mass spectral strategies for the structural characterization of flavonoid glycosides

Cuyckens¹,

L.²,

Pocsfalvi³

et al. 2000

Analusis

119

113

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IntroductionFlavonoid glycosides are predominant forms of naturally occurring flavonoids in plants, representing a large group of secondary plant metabolites [1][2][3]. They all contain a C 15 flavonoid as an aglycone, are usually divided into O-and C-glycosyl flavonoids, are of interest because they have biological activities, are useful for chemotaxonomy, and are used as tracers in medicinal plant preparations. Recently, they have also received considerable interest in foodstuffs and nutraceuticals because of their antioxidant and anticancer properties [4].During the last several years our research at the University of Antwerp has focused on the structural analysis of O-, C-and O,C-diglycosides isolated from medicinal plants using fast atom bombardment (FAB) or electrospray (ES) ionization in combination with collision-induced dissociation (CID) and tandem mass spectrometry (MS/MS) [5][6][7][8][9][10]. In this article we will review various tandem mass spectral approaches to the structural characterization of flavonoid glycosides. With regard to the structure elucidation of flavonoid O-diglycosides it will be illustrated how structural information can be obtained on (i) the carbohydrate sequence, (ii) the aglycone part, and (iii) the linkage in the diglycosidic part. Tandem mass spectral analyses have mainly been performed in the positive ion mode on protonated molecules generated by FAB or ES. In more recent work, however, which is briefly reported in the 888 ANALUSIS, 2000, 28, N°10

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“…These types of losses are well-known for C-glycosyl flavonoids, and were discussed in detail by Waridel et al [29]. The loss of one or more water molecules observed with some C-glycosyl flavonoid complexes has also been reported in mass spectral analysis of deprotonated C-glycosyl flavonoids [17,29,38] and alternate structures for these ions have been proposed [17].…”

Section: Resultsmentioning

confidence: 85%

“…Greater sensitivity has been reported in the negative ion mode than in the positive ion mode [21,30,31,38], a factor attributed to the substantial acidities of flavonoids and the ease of deprotonation due to their multiple hydroxyl groups. However, the CAD spectra of deprotonated flavonoid glycosides generally show few fragments, and are therefore not particularly useful for isomer differentiation.…”

Section: Resultsmentioning

confidence: 99%

“…The general fragmentation differences between flavonoid glycosides bonded through carbon versus oxygen atoms have been established [16], along with differentiation of 6-C-glycosyl and 8-C-glycosyl flavonoids [16,17,29,38,54]. However, to our knowledge no one has proposed a robust universal mass spectrometric method for determining five of the most common glycosylation positions encountered for the monoglucosyl flavonoids: attachment through oxygen at position 3, 4Ј, or 7; or through carbon at position 6 or 8.…”

mentioning

confidence: 99%

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Determination of the glycosylation site of flavonoid monoglucosides by metal complexation and tandem mass spectrometry

Davis

Brodbelt

2004

J. Am. Soc. Mass Spectrom.

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Metal complexation and tandem mass spectrometry were used to differentiate C-and O-bonded flavonoid monoglucoside isomers. Electrospray ionization of solutions containing a flavonoid glycoside and a metal salt led to the generation of the key [M(II) (L) (L-H)] ϩ complexes, where M is the metal ion and L is the flavonoid glycoside. Thirteen flavonoid monoglucosides were examined in combination with Ca(II), Mg(II), Co(II), Ni(II), and Cu(II). Collisional activated dissociation (CAD) of the [M(II) (L) (L-H)] ϩ complexes resulted in diagnostic mass spectra, in contrast to the CAD mass spectra of the protonated, deprotonated, and sodium-cationized flavonoid glucosides. Five common sites of glycosylation could be predicted based on the fragmentation patterns of the flavonoid glucoside/magnesium complexes, while flavonoid glucoside/calcium complexes also were effective for location of the glycosylation site when MS 3 was employed. Cobalt, nickel and copper complexation had only limited success in this application. The metal complexation methods were also applied for characterization of a flavonoid rhamnoside, and the dissociation pathways of the metal complexes indicate that flavonoid rhamnosides have distinctive dissociation features from flavonoid glucosides. (J Am Soc Mass Spectrom 2004, 15, 1287-1299

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Fast atom bombardment and fast atom bombardment collision-activated dissociation/mass-analysed ion kinetic energy analysis ofC-glycosidic flavonoids

Cited by 98 publications

References 14 publications

New type of linkage between a carbohydrate and a protein: C-glycosylation of a specific tryptophan residue in human RNase Us

New type of linkage between a carbohydrate and a protein: C-glycosylation of a specific tryptophan residue in human RNase Us

Tandem mass spectral strategies for the structural characterization of flavonoid glycosides

Determination of the glycosylation site of flavonoid monoglucosides by metal complexation and tandem mass spectrometry

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