Linkage position in oligosaccharides by fast atom bombardment ionization, collision-activated dissociation, tandem mass spectrometry and molecular modeling.  L-Fucosylp-(.alpha.1.fwdarw.X)-D-N-acetyl-D-glucosaminylp-(.beta.1.fwdarw.3)-D-galactosylp-(.beta.1-O-methyl) where X = 3, 4, or 6

Laine, Roger A.; Pamidimukkala, K. M.; French, Alfred D.; Hall, Randall W.; Abbas, Saeed A.; Jain, Rakesh K.; Matta, Khushi L.

doi:10.1021/ja00229a001

Cited by 86 publications

(43 citation statements)

References 3 publications

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“…The significant difference between these values provides a reliable method for the detection of the anomeric configuration of differently linked disaccharides. Laine et al 3–5. used molecular modeling to show that steric crowding can restrict glycosidic bond rotation of the different linkage positions, and that internal energy differences based on the restricted freedom of motion can affect fragmentation; Mendonca et al 21.…”

Section: Resultsmentioning

confidence: 99%

“…It provides many advantages over traditional analytical methods, such as low sample consumption, high sensitivity, and structural information by MS/MS or MS n experiments. As early as 1988, Laine et al 3. began to use collision‐induced dissociation (CID) mass spectrometric techniques with synthetic oligosaccharides, especially the combination of early soft ionization methods such as fast atom bombardment (FAB) with CID, for linkage determination of underivatized oligosaccharides.…”

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confidence: 99%

“…However, much more information was obtained by monitoring abundances of dissociation products as a function of the energy of the precursor ion, i.e., energy‐resolved mass spectrometry (ERMS) 29,30. Laine et al 3–5. first applied incremented collision energy to discriminate among glycosidic positional isomers by taking advantage of their differing rotational freedom of motion, and subsequent ability to absorb collision energy.…”

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confidence: 99%

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Determination of linkage position and anomeric configuration in Hex‐Fuc disaccharides using electrospray ionization tandem mass spectrometry

Xue

Song

Khaja

et al. 2004

Rapid Comm Mass Spectrometry

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Fixed-energy sequential tandem mass spectrometry (MS(n)) capabilities offered by quadrupole ion trap instruments have been explored in a systematic study of six isomers of Gal-Fucalpha-OBenzyl disaccharides. Under collision-induced dissociation (CID), sodiated molecular species generated in the positive-ion electrospray ionization mode yield simple and predictable mass spectra. Information on interglycosidic linkages and configurations can be deduced from the relative intensities of the selected diagnostic fragments arising from the glycosidic bond cleavages and corroborated by the fragments arising from cross-ring cleavages. As the CID patterns are not dependent on the number of prior tandem mass spectrometric steps, structures can be unambiguously assigned by matching the spectra with a library. The rules governing the fragmentation behavior of this class of oligosaccharides were tested for a representative isomeric disaccharide, Glcbeta1,3Fucalpha-OAllyl. The findings establish a basis for using MS(n) with a quadrupole ion trap instrument to elucidate structures of hexose-fucose subunits from more complicated oligosaccharides. Energy-resolved mass spectra were also acquired by CID tandem triple-quadrupole mass spectrometry. The breakdown behavior of the molecular ions revealed patterns which could differentiate stereoisomers of Gal-Fuc disaccharides over a range of collision energy from 20 to 50 eV.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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Determination of linkage position and anomeric configuration in Hex‐Fuc disaccharides using electrospray ionization tandem mass spectrometry

Xue

Song

Khaja

et al. 2004

Rapid Comm Mass Spectrometry

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“…[7][8][9][10][11] The technique provides data related to the activation energy of a given analyte under collisioninduced dissociation (CID) conditions, which is considered to be advantageous over conventional MS/MS techniques. 12,13 In our endeavor to develop a new method based on ERMS to elucidate glycan structures, we used a series of synthetic oligosaccharides from which useful structure-related information can be extracted. 7-9 It was found that the a-anomers of individual carbohydrate units are more labile than the corresponding b-anomers for the gluco-, galacto-, and fuco-series of glycosidic linkages.…”

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confidence: 99%

Analysis of a series of isomeric oligosaccharides by energy‐resolved mass spectrometry: a challenge on homobranched trisaccharides

Daikoku

Widmalm

Kanie

2009

Rapid Comm Mass Spectrometry

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Glycans exist as part of glycoproteins and glycolipids, which are involved in a variety of biological functions. The analysis of glycan structures, particularly that of structural isomers, is fundamentally important since isomeric glycans often show distinct functions; however, a method for their structural elucidation has not yet been established. Anomeric configurations, linkage positions and branching are the major factors in glycans and their alteration results in a large diversity of glycan structures. The analysis of vicinally substituted oligosaccharides is extremely difficult because the product ions formed in tandem mass spectrometry (MS/MS) often have the same m/z values. In our endeavor to address the issue, we analyzed a series of homo-substituted trisaccharides consisting only of glucose by collision-induced dissociation (CID), especially energy-resolved mass spectrometry (ERMS). It was found that these structurally related glycans could be distinguished by taking advantage of differences in their activation energies in ERMS.

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“…[1] With no corresponding genetic code and a plethora of possible structures, [2] understanding the functions of complex oligosaccharides, as well as isolating them from natural resources, is challenging. Obtaining sufficient amounts of pure and homogenous oligosaccharides [3] and further modifying isolated oligosaccharides typically requires multiple synthetic steps and purifications.…”

Section: Introductionmentioning

confidence: 99%

Two‐Step Functionalization of Oligosaccharides Using Glycosyl Iodide and Trimethylene Oxide and Its Applications to Multivalent Glycoconjugates

Hsieh

Davis

Hoch

et al. 2014

Chemistry A European J

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Oligosaccharide conjugates, such as glycoproteins and glycolipids, are potential chemotherapeutics and also serve as useful tools for understanding the biological roles of carbohydrates. With many modern isolation and synthetic technologies providing access to a wide variety of free sugars, there is increasing need for general methodologies for carbohydrate functionalization. Herein, we report a two-step methodology for the conjugation of per-O-acetylated oligosaccharides to functionalized linkers that can be used for various displays. Oligosaccharides obtained from both synthetic and commercial sources were converted to glycosyl iodides and activated with I2 to form reactive donors that were subsequently trapped with trimethylene oxide to form iodopropyl conjugates in a single step. The terminal iodide served as a chemical handle for further modification. Conversion into the corresponding azide followed by copper-catalyzed azide–alkyne cycloaddition afforded multivalent glycoconjugates of Gb3 for further investigation as anti-cancer therapeutics.

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Linkage position in oligosaccharides by fast atom bombardment ionization, collision-activated dissociation, tandem mass spectrometry and molecular modeling. L-Fucosylp-(.alpha.1.fwdarw.X)-D-N-acetyl-D-glucosaminylp-(.beta.1.fwdarw.3)-D-galactosylp-(.beta.1-O-methyl) where X = 3, 4, or 6

Cited by 86 publications

References 3 publications

Determination of linkage position and anomeric configuration in Hex‐Fuc disaccharides using electrospray ionization tandem mass spectrometry

Determination of linkage position and anomeric configuration in Hex‐Fuc disaccharides using electrospray ionization tandem mass spectrometry

Analysis of a series of isomeric oligosaccharides by energy‐resolved mass spectrometry: a challenge on homobranched trisaccharides

Two‐Step Functionalization of Oligosaccharides Using Glycosyl Iodide and Trimethylene Oxide and Its Applications to Multivalent Glycoconjugates

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