Structural and reaction assignments for some common polysaccharides using laser desorption ionization Fourier transform ion cyclotron resonance spectroscopy

Lam, Zamas; Comisarow, Melvin B.; Dutton, Guy G.S.

doi:10.1021/ac00171a030

Cited by 19 publications

(11 citation statements)

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“…-*• 6 linked sugars is the loss of 60 and 120 mass units(14). It can be observed in all saccharides of this type and has been observed by other groups as well(7,8,11,12). The mass losses…”

mentioning

confidence: 60%

“…Recently Coates and Wilkins have observed that (in contrast to other desorption techniques) infrared laser desorption mass spectrometry (IR-LDMS) of carbohydrates produces a unique fragmentation pattern that can be explained as two-bond ring 0003-2700/90/0362-1731$02.50/0 cleavages within the cyclic sugar units (7,8). The predominance of two-bond ring fragmentation over glycosidic bond cleavage following ionization by an infrared laser was observed as well as Cotter et al (9,10) for the phosphorylated diglucosamine known as lipid A, and its significance for the determination of substituent positions (9,10) and linkages (11,12) has been discussed. Lipid A, the anchor for the larger lipopolysaccharide (LPS) found on the outer wall of the outer membrane of Gram-negative bacteria, provided a unique opportunity to characterize the locations of the two-bond ring cleavages.…”

Section: Introductionmentioning

confidence: 92%

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Infrared laser desorption mass spectrometry of oligosaccharides: fragmentation mechanisms and isomer analysis

Spengler

Dolce

Cotter³

1990

Anal. Chem.

133

110

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Infrared laser desorptlon/lonlzatlon of oligosaccharides and their naturally occurring derivatives leads to a distinctive fragmentation pattern, which Is useful both for the analysis of functional groups (e.g., the positions of fatty acyl groups In lipid A and other glycollplds) and for distinguishing Isomers of underivatized oligosaccharides with different glycosidic linkages. The predominant mechanism of fragmentation can be understood as a perlcycllc hydrogen rearrangement of the retro-aldol reaction type, leading to fragmentation of the sugar ring. A prerequisite for this process appears to Involve opening of the hemlacetal saccharide ring to the linear saccharide form by rapid heating from the Infrared laser irradiation. Saccharides derlvatlzed at the anomerlc hydroxyl group (l.e., cyclic acetals) normally do not undergo this ring opening and thus do not exhibit ring fragmentation reactions. This fragmentation mechanism can be used to predict and Interpret fragmentation patterns of unknown oligosaccharides, glycosides, lipid A, and other glycoconjugates.

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mentioning

confidence: 60%

Section: Introductionmentioning

confidence: 92%

Infrared laser desorption mass spectrometry of oligosaccharides: fragmentation mechanisms and isomer analysis

Spengler

Dolce

Cotter³

1990

Anal. Chem.

133

110

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“…Laser desorption, with and without, matrix has been more recently developed but has been used already with great success to analyze carbohydrate structures. Extensive fragementation is observed without matrix providing numerous structurally important fragment ions. − Laser desorption without matrix (LD) is unfortunately also limited by its relatively poor detection limits. Matrix assisted laser desorption ionization (MALDI) mass spectrometry is, in contrast, a highly sensitive method but often lacks the high degree of fragmentation necessary for the structural elucidation .…”

Section: Introductionmentioning

confidence: 99%

Coordination of Alkali Metals to Oligosaccharides Dictates Fragmentation Behavior in Matrix Assisted Laser Desorption Ionization/Fourier Transform Mass Spectrometry

et al. 1996

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A correlation is found between the fragment ion yield and the degree of branching for oligosaccharides analyzed by matrix assisted laser desorption ionization/Fourier transform mass spectrometry (MALDI/FTMS). The most branched oligosaccharides produced the least amount of fragment ion. Another relationship is found between the size of the alkali metal ion and the yields of fragment ions. The smallest alkali metal ion produced the greatest amount of fragment ions. The presence of the quasimolecular ion is dependent on both the size of the metal ion and the size of the sugar. A minimum number of saccharide residues are necessary to stabilize the complex and produce a quasimolecular ion. Molecular mechanics calculations were performed and structures obtained consistent with the observed experimental behavior. The site of coordination plays a dominant role in the yield and types of fragment ions observed.

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“…Anomers and linkage isomers that have identical masses cannot be easily distinguished in mass spectrometry, but to aid in this endeavor, separation steps are often performed before mass spectrometric identification. Nevertheless, MS does have the capability to differentiate underivatized saccharide stereoisomers as demonstrated when coupled with several different desorption/ionization techniques such as field desorption (FD) [3,4], laser desorption (LD) [5,6], fast atom bombardment (FAB) [7][8][9][10][11][12][13][14][15][16][17], liquid secondary ion mass spectrometry (LSIMS) [18,19], and electrospray (ES) [20 -25].…”

mentioning

confidence: 99%

MALDI linear-field reflectron TOF post-source decay analysis of underivatized oligosaccharides: Determination of glycosidic linkages and anomeric configurations using anion attachment

Guan

Cole

2008

J. Am. Soc. Mass Spectrom.

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Six different anionic species (fluoride, chloride, bromide, iodide, nitrate, and acetate) are tested for their abilities to form anionic adducts with neutral oligosaccharides that are detectable by MALDI-TOF mass spectrometry. Fluoride and acetate cannot form anionic adducts with the oligosaccharides in significant yields. However, bromide, iodide, and nitrate anionic adducts consistently appear in higher abundances relative to [M Ϫ H] Ϫ , just like the highly stable chloride adducts. Post-source decay (PSD) decompositions of Br Ϫ , IϪ , and NO 3 Ϫ adducts of oligosaccharides provide no structural information, i.e., they yield the respective anions as the main product ions. However, determination of linkage types is achieved by analysis of structurally-informative diagnostic peaks offered by negative ion PSD spectra of chloride adducts of oligosaccharides, whereas the relative peak intensities of pairs of diagnostic fragment ions allow differentiation of anomeric configurations of glycosidic bonds. Thus, simultaneous identification of the linkage types and anomeric configurations of glycosidic bonds is achieved. Our data indicate that negative ion PSD fragmentation patterns of chloride adducts of oligosaccharides are mainly determined by the linkage types. Correlation may exist between the linkage positions and fragmentation mechanisms and/or steric requirements for both cross-ring and glycosidic bond fragmentations. PSD of the chloride adducts of saccharides containing a terminal Glc␣1-2Fru linkage also yields chlorine-containing fragment ions which appear to be specifically diagnostic for a fructose linked at the 2-position on the reducing end. This also allows differentiation from saccharides with a 1-1 linked pyranose on the same position. ollowing the advances in proteomics, there is a growing interest in the importance of glycomics, i.e., the study of the breadth of sugar forms (structure and function of glycans) in biological organisms. Carbohydrates (or saccharides) are the most abundant biological compounds found on earth. They are well known as energy reservoirs and structural materials in cell walls. However, it has become clear that oligosaccharides and glycoconjugates (e.g., glycoproteins and glycolipids) serve as crucial mediators for a wide variety of complex cellular events [1]. Carbohydrates also play an important role in specific molecular recognition, protein folding, stability, and pharmacokinetics due to their great structural diversity. Moreover, glycosylation is a ubiquitous form of post-translational modification to both proteins and lipids.Gaining a clear understanding of the crucial biological roles of oligosaccharides requires complete structural characterization of carbohydrates or glycoconjugates, which includes determinations of the numbers and types of monosaccharide units, ring substituents, sequences, branching, linkage positions, and anomeric configurations between adjacent monosaccharide units. In most cases, merely knowing the monosaccharide sequence is inadequate; thus, unam...

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Structural and reaction assignments for some common polysaccharides using laser desorption ionization Fourier transform ion cyclotron resonance spectroscopy

Cited by 19 publications

References 11 publications

Infrared laser desorption mass spectrometry of oligosaccharides: fragmentation mechanisms and isomer analysis

Infrared laser desorption mass spectrometry of oligosaccharides: fragmentation mechanisms and isomer analysis

Coordination of Alkali Metals to Oligosaccharides Dictates Fragmentation Behavior in Matrix Assisted Laser Desorption Ionization/Fourier Transform Mass Spectrometry

MALDI linear-field reflectron TOF post-source decay analysis of underivatized oligosaccharides: Determination of glycosidic linkages and anomeric configurations using anion attachment

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