In-Source and Postsource Decay in Negative-Ion Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry of Neutral Oligosaccharides

Yamagaki, Tohru; Suzuki, Hiroaki; Tachibana, Kunihide

doi:10.1021/ac040150i

Cited by 48 publications

(60 citation statements)

References 36 publications

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“…This uniformity in behavior suggests a correlation between the linkage positions and fragmentation mechanisms including steric requirements for cross-ring cleavages (comprehending hydrogen transfers). The minor differences between our results and those obtained by Yamagaki et al [36] are likely to be caused by a combination of two different effects. First, the smaller size oligosaccharides employed in our study should have a higher propensity to fragment than the larger varieties used in theirs (the larger the number of monomers, the more degrees of freedom (vibrational modes) exist [54]).…”

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confidence: 83%

“…On the contrary, when subjected to PSD fragmentation in the negative ion mode, prominent cross-ring cleavages are usually produced along with glycosyl bond cleavages. PSD of both deprotonated molecules and anionic adducts of oligosaccharides has been performed and some success for differentiation of linkage positions as well as anomeric configurations in oligosaccharides has been shown [35][36][37][38][43][44][45].…”

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confidence: 99%

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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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confidence: 83%

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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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“…As glycans can be easily isolated and purified, the ISD and pMS 3 -sequencing approaches were also employed to characterize thoroughly the structures of both native [43,[54][55][56][57][58][59][60] and permethylated glycans [61][62][63][64][65][66], allowing unambiguous discrimination of isobaric species. In ref.…”

Section: Maldi-isd and Ptmsmentioning

confidence: 99%

MALDI In-Source Decay, from Sequencing to Imaging

Debois

Smargiasso

Demeure

et al. 2012

Topics in Current Chemistry

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Matrix-assisted laser desorption/ionization (MALDI) is now a mature method allowing the identification and, more challenging, the quantification of biopolymers (proteins, nucleic acids, glycans, etc). MALDI spectra show mostly intact singly charged ions. To obtain fragments, the activation of singly charged precursors is necessary, but not efficient above 3.5 kDa, thus making MALDI MS/MS difficult for large species. In-source decay (ISD) is a prompt fragmentation reaction that can be induced thermally or by radicals. As fragments are formed in the source, precursor ions cannot be selected; however, the technique is not limited by the mass of the analyzed compounds and pseudo MS3 can be performed on intense fragments. The discovery of new matrices that enhance the ISD yield, combined with the high sensitivity of MALDI mass spectrometers, and software development, opens new perspectives. We first review the mechanisms involved in the ISD processes, then discuss ISD applications like top-down sequencing and post-translational modifications (PTMs) studies, and finally review MALDI-ISD tissue imaging applications.

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“…Adduction with chloride, as used by others [37][38][39][40][45][46][47][48][49], has the disadvantage of a split signal due to the chlorine isotopes. Phosphate, which has proven to be most appropriate under electrospray conditions [32], did not form very abundant ions under MALDI conditions.…”

Section: Introductionmentioning

confidence: 99%

MALDI-MS/MS with Traveling Wave Ion Mobility for the Structural Analysis ofN-Linked Glycans

Harvey

Scarff

Crispin

et al. 2012

J. Am. Soc. Mass Spectrom.

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The preference for singly charged ion formation by MALDI makes it a better choice than electrospray ionization for profiling mixtures of N-glycans. For structural analysis, fragmentation of negative ions often yields more informative spectra than fragmentation of positive ones but such ions are more difficult to produce from neutral glycans under MALDI conditions. This work investigates conditions for the formation of both positive and negative ions by MALDI from N-linked glycans released from glycoproteins and their subsequent MS/MS and ion mobility behaviour. 2,4,6-Trihydroxyacetophenone (THAP) doped with ammonium nitrate was found to give optimal ion yields in negative ion mode. Ammonium chloride or phosphate also yielded prominent adducts but anionic carbohydrates such as sulfated N-glycans tended to ionize preferentially. Carbohydrates adducted with all three adducts (phosphate, chloride, and nitrate) produced good negative ion CID spectra but those adducted with iodide and sulfate did not yield fragment ions although they gave stronger signals. Fragmentation paralleled that seen following electrospray ionization providing superior spectra than could be obtained by PSD on MALDI-TOF instruments or with ion traps. In addition, ion mobility drift times of the adducted glycans and the ability of this technique to separate isomers also mirrored those obtained following ESI sample introduction. Ion mobility also allowed profiles to be obtained from samples whose MALDI spectra showed no evidence of such ions allowing the technique to be used in conditions where sample amounts were limiting. The method was applied to N-glycans released from the recombinant human immunodeficiency virus glycoprotein, gp120.

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In-Source and Postsource Decay in Negative-Ion Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry of Neutral Oligosaccharides

Cited by 48 publications

References 36 publications

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

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

MALDI In-Source Decay, from Sequencing to Imaging

MALDI-MS/MS with Traveling Wave Ion Mobility for the Structural Analysis ofN-Linked Glycans

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