A comparative study of the fragmentation of neutral lactooligosaccharides in negative-ion mode by UV-MALDI-TOF and UV-MALDI ion-trap/TOF mass spectrometry

Yamagaki, Tohru; Suzuki, Hiroaki; Tachibana, Kunihide

doi:10.1016/j.jasms.2005.09.004

Cited by 36 publications

(33 citation statements)

References 34 publications

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“…49,50) Negative-ion MALDI-PSD has been previously demonstrated to be useful int the semi-quantitative analysis of same glycans (LNDFH-I and LNDFH-II) at a concentration of 1.5 mg/mL.…”

Section: Maldi-isd Of Glycans Via "Hydrogen-de Cient" Radicalmentioning

confidence: 99%

5-Nitrosalicylic Acid as a Novel Matrix for In-Source Decay in Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

Asakawa

2013

Mass Spectrometry

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The matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) of peptides and glycans was studied using an oxidizing chemical, 5-nitrosalicylic acid (5-NSA) as the matrix. The use of 5-NSA for the MALDI-ISD of peptides and glycans promoted fragmentation pathways involving "hydrogen-deficient" radical precursors. Hydrogen abstraction from peptides resulted in the production of a "hydrogen-deficient" peptide radical that contained a radical site on the amide nitrogen in the peptide backbone with subsequent radical-induced cleavage at the C α -C bonds. Cleavage at the C α -C bond leads to the production of an a• /x fragment pair and the radical a • ions then undergo further hydrogen abstraction to form a ions after C α -C bond cleavage. Since the Pro residue does not contain a nitrogen-centered radical site, C α -C bond cleavage does not occur at this site. Alternatively, the specific cleavage of CO−N bonds leads to a b• /y fragment pair at Xxx−Pro which occurs via hydrogen abstraction from the C α −H in the Pro residue. In contrast, "hydrogen-deficient" glycan radicals were generated by hydrogen abstraction from hydroxyl groups in glycans. Both glycosidic and cross-ring cleavages occurred as the result of the degradation of "hydrogen-deficient" glycan radicals. Cross-ring cleavage ions are potentially useful in linkage analysis, one of the most critical steps in the characterization of glycans. Moreover, isobaric glycans could be distinguished by structure specific ISD ions, and the molar ratio of glycan isomers in a mixture can be estimated from their fragment ions abundance ratios. MALDI-ISD with 5-NSA could be a useful method for the sequencing of peptides including the location of post-translational modifications, identification and semi-quantitative analysis of mixtures of glycan isomers.

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“…49,50) Negative-ion MALDI-PSD has been previously demonstrated to be useful int the semi-quantitative analysis of same glycans (LNDFH-I and LNDFH-II) at a concentration of 1.5 mg/mL.…”

Section: Maldi-isd Of Glycans Via "Hydrogen-de Cient" Radicalmentioning

confidence: 99%

5-Nitrosalicylic Acid as a Novel Matrix for In-Source Decay in Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

Asakawa

2013

Mass Spectrometry

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“…These results are useful for linkage analysis [14]. The chlorideanionized molecules were stable enough to allow the measurement of their postsource decay spectra that brought us the structural information, including 3-and/or 4-linked branching and fucose-substitution positions, so that we could obtain detailed structural information for the lactooligosaccharides as well as their ESI MS measurements [15].…”

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confidence: 94%

Solid-phase fluorescence and ionization efficiency in negative-ion matrix-assisted laser desorption/ionization of neutral oligosaccharides: Interaction between β-carboline matrix and ammonium salt

Yamagaki

Suzuki

Tachibana

2007

J. Am. Soc. Mass Spectrom.

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Ammonium chloride (NH 4 Cl) with a ␤-carboline harmine (7-methoxy-1-methyl-9H-pyrido [3,4-b]indole) Matrix promotes the generation of chloride-anionized molecules of neutral oligosaccharides in negative-ion ultraviolet matrix-assisted laser/desorption ionization mass spectrometry (MALDI MS 4 Cl form a complex of the hydrochloride salt in the mixed crystal. The peak intensity at 448 nm from the harmine hydrochloride in the mixed crystal rises logarithmically with the amount of NH 4 Cl added, a result that quantitatively correlates with increases in the ion abundance ratios of the chloride-anionized molecules to that of harmine. The solid-phase spectroscopic method is useful for studying changes in the characteristics of the matrices and additives in the mixed crystal. Harmine hydrochloride, rather than harmine, works as an effective matrix. The attachment of the chloride to the matrix is essential for the generation of chlorinatedanionized molecules in MALDI. An N-acetyl glucosamine residue (GlcNAc) in lacto-N-tetraose promotes the generation of their chloride-anionized molecules, however, multi-GlcNAc residues in N-acetylchitooligosaccharides hinder it. Neutral oligosaccharides are typically examined in the positive-ion mode, whereas acidic oligosaccharides are analyzed in the negative-ion mode. In MALDI, almost all of the measurements of neutrals are made in the positiveion mode because neutral oligosaccharides readily complex to alkali metal ions [1,2]. Even contaminating amounts sodium are likely to attach to analytes in MALDI under conventional measurement conditions in ion-exchanged water. In some cases, investigators add small amounts of alkali metal chlorides to promote their ionization, but the addition of large amounts of salts suppresses ionization not only in MALDI, but also in other ionization methods. In contrast, negative-ion mode measurements of neutral oligosaccharides are rarely performed in MALDI. An unusual matrix ␤-carbolin is needed for deprotonated molecules to be generated, and anionic adducts of the whole molecules were not observed [3,4]. Both ions are labile. MALDI process imparts more than enough energy to dissociate deprotonated molecules and anionic adduct [3,4].New matrix systems, matrices, and anionic dopants themselves have been investigated for their possible use in the negative-ion mode MALDI MS of neutral oligosaccharides. Breuker et al., [5] using binary tetrabutylammonium (TBA) salt/silicon matrices, were able to generate halide ion attachment under special conditions in MALDI. Liquid TBA salts supply halide anion and silicon particulates that work as a UV-absorbing matrix. Nonami et al. [6 -8] employed ␤-carboline (9H-pyrido [3,4-b]indole) matrices and observed deprotonated carbohydrate molecules. Halide-anionized molecules were also generated through the use of matrices containing a small amount of ammonium halides [3]. Wong et al. [9,10] used hydrogen sulfate and alkylsulfonate as anion dopants for oligosaccharides in MALDI in conjunction with conventional matrices such ...

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“…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%

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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A comparative study of the fragmentation of neutral lactooligosaccharides in negative-ion mode by UV-MALDI-TOF and UV-MALDI ion-trap/TOF mass spectrometry

Cited by 36 publications

References 34 publications

5-Nitrosalicylic Acid as a Novel Matrix for In-Source Decay in Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

5-Nitrosalicylic Acid as a Novel Matrix for In-Source Decay in Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

Solid-phase fluorescence and ionization efficiency in negative-ion matrix-assisted laser desorption/ionization of neutral oligosaccharides: Interaction between β-carboline matrix and ammonium salt

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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