“Internal Residue Loss”:  Rearrangements Occurring during the Fragmentation of Carbohydrates Derivatized at the Reducing Terminus

Harvey, David J.; Mattu, Taj S.; Wormald, Mark R.; Royle, Louise; Dwek, Raymond A.; Rudd, Pauline M.

doi:10.1021/ac0109321

Cited by 146 publications

(168 citation statements)

References 17 publications

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“…These ions have all lost the units H and I, and, in addition, a HN¢C¢O group (m/z 1109), the carbamate group (NH 2 COOH) from unit F (m/z 1091), a HN¢C¢O as well as the PO 3 H group (m/z 1029), or the whole uronamide-derived unit F (m/z 902). The formation of the latter ion by an internal residue loss requires a rearrangement reaction, which has been described for several compounds [42][43][44][45][46]. One possible structure of the ion at m/z 902, which is an alternative to the one proposed by Eichhorn and Aga [6], is given in Scheme observed in the intensity-range below 1% of the base peak, but still with a good S/N ratio ( Figure 2b and Scheme 2).…”

Section: Maldi-it/rtof-msmentioning

confidence: 70%

Characterization of moenomycin antibiotic complex by multistage MALDI-IT/RTOF-MS and ESI-IT-MS

Zehl

Pittenauer

Rizzi

et al. 2006

J. Am. Soc. Mass Spectrom.

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Flavomycin is a commercially available antimicrobial growth promoter and an authorized additive for feeding stuffs in the EU and in the USA. As most antibiotically active products biosynthesized by microorganisms, it contains not only a single active compound but is a complex mixture of structurally closely related substances. Multistage matrix-assisted laser desorption/ionization-ion trap/reflectron time-of-flight mass spectrometry (MALDI-IT/ RTOF-MS) and liquid chromatography-electrospray ionization-ion trap-mass spectrometry (LC-ESI-IT-MS) were utilized for a detailed analysis of the constituents of the Flavomycin complex based on low-energy collision induced dissociation (CID). An optimal sample preparation for negative ion vacuum MALDI-MS for this compound class was developed. The MALDI-IT/RTOF-MS 2 and -MS 3 analysis starting with the precursor [M Ϫ H] Ϫ ions of these interesting phosphoglycolipids, named moenomycins, yielded a large variety of product ions that facilitated the structural characterization of this class of compounds. Based on the derived CID fragmentation pathway of the five known major constituents, namely moenomycin A, moenomycin A 12 , moenomycin C 4 , moenomycin C 3 . and moenomycin C 1 , four not yet described moenomycin-type constituents could be characterized. They were assigned as 4F-demethyl-6E-O-de-␤-D-glucopyranosyl-moenomycin A, 6B-N-de(2-hydroxy-5-oxo-1-cyclopenten-1-yl)-moenomycin A, 6B-hydroxy-6B-de[N-(2-hydroxy-5-oxo-1-cyclopenten-1-yl)amino]-moenomycin A, and 6C-hydroxy-moenomycin A. In addition, a moenomycin A carrying an oxygen in the moenocinol-group was found, which is most probably a chemical degradation product. These new compounds were verified by LC-ESI-IT-MS. (J Am Soc Mass

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Section: Maldi-it/rtof-msmentioning

confidence: 70%

Characterization of moenomycin antibiotic complex by multistage MALDI-IT/RTOF-MS and ESI-IT-MS

Zehl

Pittenauer

Rizzi

et al. 2006

J. Am. Soc. Mass Spectrom.

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“…The relative labilities of fucosyl and galactosyl linkages are different, judging by the spectra, and the lability is greater for the cleavage of fucosyl glycosides. This is a commonly found phenomenon in low-energy CID analysis of oligosaccharides [30]. Thus, half of the compounds afforded Y 1 fragments associated with B 1 /Y 1 cleavages only.…”

Section: Cid Analysis Of All Compoundsmentioning

confidence: 90%

Discrimination of 16 structural isomers of fucosyl galactoside based on energy-resolved mass spectrometry

Daikoku

Ako

Kato

et al. 2007

J. Am. Soc. Mass Spectrom.

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Glycans, a family of compounds often attached to proteins and ceramides, are diverse molecules involved in a wide range of biological functions. Their structural analysis is necessary and is often carried out at the microscale level. Methods based on mass spectrometry are therefore used, although they do not provide information regarding isomeric structures often found in glycan structures. If one finds "factors" characteristic of a certain isomer, this information can be used to elucidate an unknown oligosaccharide sequence. One potential technique is to use energy-resolved mass spectrometry (ERMS) that has been used to distinguish a pair of isomeric compounds. Thus, compounds in a combinatorial library might be effectively used for this purpose. We analyzed a set of 16 isomeric disaccharides, the structures of which consisted of all possible combinations of anomeric configurations and interglycosidic linkage positions. All of the compounds were distinguished based on ERMS where normal collision-induced dissociation could distinguish only seven compounds. Furthermore, it was shown that ␣-glycosidic linkages of fucose were more reactive than the ␣ ␤-isomers and the secondary glycosides were more reactive than the primary . The structural characteristics of oligosaccharides are quite different from those of other biopolymers such as nucleic acids and peptides. The diversity is generated from sequential combination in the latter two types of polymers, whereas anomers, ring size, linkage position, branching, and sequence are factors in the case of oligosaccharides [2]. Furthermore, the regulatory mechanisms for oligosaccharides still need to be clarified and synthesis, which is not template dependent, thus creates further molecular diversity called glycoforms. Despite the difficulties encountered in structural determination, there are reports on how glycosylation as a type of posttranslational modification (PTM) of protein affects glycoprotein secretion [3,4].

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“…An alternative explanation was that these peaks were MS artifacts. It has been reported that fucose residues can rearrange during MS analysis, which can lead to misinterpretations concerning the sugar sequence of glycan moieties (30).…”

Section: Volume 286 • Number 43 • October 28 2011mentioning

confidence: 99%

Exploiting Bacterial Glycosylation Machineries for the Synthesis of a Lewis Antigen-containing Glycoprotein

Hug

Zheng

Reiz

et al. 2011

Journal of Biological Chemistry

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Background: Bacterial glycosylation systems appear to be ideal for glycoengineering purposes. Results: A Lewis x containing glycoprotein was synthesized using bacterial enzymes from four different species using in vivo and in vitro steps. Conclusion: Glycosylation systems in bacteria open new avenues for the production of engineered glycoproteins. Significance: Bacterial glycoengineering is a promising technology for the production of therapeutically valuable glycoproteins with expected high precision and low cost.

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“Internal Residue Loss”: Rearrangements Occurring during the Fragmentation of Carbohydrates Derivatized at the Reducing Terminus

Cited by 146 publications

References 17 publications

Characterization of moenomycin antibiotic complex by multistage MALDI-IT/RTOF-MS and ESI-IT-MS

Characterization of moenomycin antibiotic complex by multistage MALDI-IT/RTOF-MS and ESI-IT-MS

Discrimination of 16 structural isomers of fucosyl galactoside based on energy-resolved mass spectrometry

Exploiting Bacterial Glycosylation Machineries for the Synthesis of a Lewis Antigen-containing Glycoprotein

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