Discrimination of β-1,4- and β-1,3-Linkages in Native Oligosaccharides via Charge Transfer Dissociation Mass Spectrometry

Buck-Wiese, Hagen; Fanuel, Mathieu; Liebeke, Manuel; Hoang, Kim Le Mai; Pardo-Vargas, Alonso; Seeberger, Peter H.; Hehemann, Jan‐Hendrik; Rogniaux, Hélène; Jackson, Glen P.; Ropartz, David

doi:10.1021/jasms.0c00087

Cited by 21 publications

(17 citation statements)

References 37 publications

(111 reference statements)

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“…All experiments were conducted on a modified Bruker amaZon SL 3D Ion Trap (Bruker Daltonics, Bremen, GER) 35,43 that was custom modified with a saddle‐field fast ion source (VSW/Atomtech, Oxfordshire, UK) placed directly above a 4‐mm hole in the ring electrode of the 3D ion trap. A variable leak valve controlled the amount of helium supplied to the CTD ion source, which typically raised the pressure of the main vacuum chamber to ~1.2 × 10–5 mbar (uncorrected).…”

Section: Methodsmentioning

confidence: 99%

“…Building on the fast ion/ion reactions of Zubarev's group and Schlathölter's group, 29–31 the Jackson lab developed a novel fragmentation technique called helium charge transfer dissociation (He‐CTD) 32,33 . He‐CTD has shown promising results for lipids, 34 peptides, 35 proteins, 36 and oligosaccharides 37–43 . He‐CTD has demonstrated comparable results to XUVPD for the analysis of oligosaccharides 39 and has been demonstrated to preserve labile modifications like sulfate groups 40,41 .…”

Section: Introductionmentioning

confidence: 99%

“…Recently, He‐CTD differentiated isomers in a mixture of pectin oligogalacturonans eluting from an ultrahigh‐performance liquid chromatography (UHPLC) system 42 . He‐CTD has also identified linkage patterns in β‐1,4‐ and β‐1,3‐linked oligosaccharides 43 . Until now, He‐CTD has not been used to analyze divalent metal adducted glycans or branched glycans; therefore, the goals of this project were to examine how He‐CTD would perform on various metalated species of a branched xyloglucan, XXXG, and how the fragmentation patterns compare to a traditional fragmentation technique like CID.…”

Section: Introductionmentioning

confidence: 99%

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Charge transfer dissociation of a branched glycan with alkali and alkaline earth metal adducts

et al. 2021

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Alkali and alkaline earth metal adducts of a branched glycan, XXXG, were analyzed with helium charge transfer dissociation (He‐CTD) and low‐energy collision‐induced dissociation (LE‐CID) to investigate if metalation would impact the type of fragments generated and the structural characterization of the analyte. The studied adducts included 1+ and 2+ precursors involving one or more of the cations: H+, Na+, K+, Ca2+, and Mg2+. Regardless of the metal adduct, He‐CTD generated abundant and numerous glycosidic and cross‐ring cleavages that were structurally informative and able to identify the 1,4‐linkage and 1,6‐branching patterns. In contrast, the LE‐CID spectra mainly contained glycosidic cleavages, consecutive fragments, and numerous neutral losses, which complicated spectral interpretation. LE‐CID of [M + K + H]2+ and [M + Na]+ precursors generated a few cross‐ring cleavages, but they were not sufficient to identify the 1,4‐linkage and 1,6‐branching pattern of the XXXG xyloglucan. He‐CTD predominantly generated 1+ fragments from 1+ precursors and 2+ product ions from 2+ precursors, although both LE‐CID and He‐CTD were able to generate 1+ product ions from 2+ adducts of magnesium and calcium. The singly charged fragments derive from the loss of H+ from the metalated product ions and the formation of a protonated complementary product ion; such observations are similar to previous reports for magnesium and calcium salts undergoing electron capture dissociation (ECD) activation. However, during He‐CTD, the [M + Mg]2+ precursor generated more singly charged product ions than [M + Ca]2+, either because Mg has a higher second ionization potential than Ca or because of conformational differences and the locations of the charging adducts during fragmentation. He‐CTD of the [M + 2Na]2+ and the [M + 2 K]2+ precursors generated singly charged product ions from the loss of a sodium ion and potassium ion, respectively. In summary, although the metal ions influence the mass and charge state of the observed product ions, the metal ions had a negligible effect on the types of cross‐ring cleavages observed.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Charge transfer dissociation of a branched glycan with alkali and alkaline earth metal adducts

et al. 2021

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“…While HPAEC-PAD is a conventional tool for the analysis of food oligosaccharide composition, high-resolution mass spectrometry (e.g., MALDI-TOF-MS, LC-ESI-MS/MS) using MS and tandem MS (MS/MS) acquisition modes are becoming common methods to determine the accurate mass and linkage sequence of food oligosaccharides (Xing et al, 2015a;Jaeger et al, 2017;Roberts et al, 2018;Little et al, 2019). Notably, recently developed ESI-MS/MS fragmentation methods (e.g., charge transfer dissociation) have proven powerful for the detailed structural characterization of natural complex oligosaccharides, such as mixed linkage glucan and sulfated anions (Ropartz et al, 2016(Ropartz et al, , 2017Buck-Wiese et al, 2020). High-performance size-exclusion chromatography (HPSEC) systems coupled to multiple detectors including refractive index (RI) detector, viscometer, and multiple-angle laser light scattering detectors are used to determine molecular weight, size, intrinsic viscosity, and conformational parameters of dietary polysaccharides (Xing et al, 2013(Xing et al, , 2014(Xing et al, , 2015bYu et al, 2017).…”

Section: Current Glycomics Methods To Study Food Carbohydratesmentioning

confidence: 99%

Approaches to Investigate Selective Dietary Polysaccharide Utilization by Human Gut Microbiota at a Functional Level

et al. 2021

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The human diet is temporally and spatially dynamic, and influenced by culture, regional food systems, socioeconomics, and consumer preference. Such factors result in enormous structural diversity of ingested glycans that are refractory to digestion by human enzymes. To convert these glycans into metabolizable nutrients and energy, humans rely upon the catalytic potential encoded within the gut microbiome, a rich collective of microorganisms residing in the gastrointestinal tract. The development of high-throughput sequencing methods has enabled microbial communities to be studied with more coverage and depth, and as a result, cataloging the taxonomic structure of the gut microbiome has become routine. Efforts to unravel the microbial processes governing glycan digestion by the gut microbiome, however, are still in their infancy and will benefit by retooling our approaches to study glycan structure at high resolution and adopting next-generation functional methods. Also, new bioinformatic tools specialized for annotating carbohydrate-active enzymes and predicting their functions with high accuracy will be required for deciphering the catalytic potential of sequence datasets. Furthermore, physiological approaches to enable genotype-phenotype assignments within the gut microbiome, such as fluorescent polysaccharides, has enabled rapid identification of carbohydrate interactions at the single cell level. In this review, we summarize the current state-of-knowledge of these methods and discuss how their continued development will advance our understanding of gut microbiome function.

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“…By accelerating He ions to 6 keV, ion/ion collisions and most likely oxidation of analytes to radicals result in activated analytes prone to fragment [103]. CTD yields tandem mass spectra with a large number of fragment ions not observed with CID enabling structural characterization of GPs [104] and oligosaccharides [105]. Reactions between low-energy ions of opposite charges are currently employed by numerous groups, with the McLuckey group pioneering many of these ion/ion reactions especially in the context of lipid analysis.…”

Section: Ion/molecule and Ion/ion Reactionsmentioning

confidence: 99%

Advanced tandem mass spectrometry in metabolomics and lipidomics—methods and applications

Heiles

2021

Anal Bioanal Chem

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Metabolomics and lipidomics are new drivers of the omics era as molecular signatures and selected analytes allow phenotypic characterization and serve as biomarkers, respectively. The growing capabilities of untargeted and targeted workflows, which primarily rely on mass spectrometric platforms, enable extensive charting or identification of bioactive metabolites and lipids. Structural annotation of these compounds is key in order to link specific molecular entities to defined biochemical functions or phenotypes. Tandem mass spectrometry (MS), first and foremost collision-induced dissociation (CID), is the method of choice to unveil structural details of metabolites and lipids. But CID fragment ions are often not sufficient to fully characterize analytes. Therefore, recent years have seen a surge in alternative tandem MS methodologies that aim to offer full structural characterization of metabolites and lipids. In this article, principles, capabilities, drawbacks, and first applications of these “advanced tandem mass spectrometry” strategies will be critically reviewed. This includes tandem MS methods that are based on electrons, photons, and ion/molecule, as well as ion/ion reactions, combining tandem MS with concepts from optical spectroscopy and making use of derivatization strategies. In the final sections of this review, the first applications of these methodologies in combination with liquid chromatography or mass spectrometry imaging are highlighted and future perspectives for research in metabolomics and lipidomics are discussed. Graphical abstract

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Discrimination of β-1,4- and β-1,3-Linkages in Native Oligosaccharides via Charge Transfer Dissociation Mass Spectrometry

Cited by 21 publications

References 37 publications

Charge transfer dissociation of a branched glycan with alkali and alkaline earth metal adducts

Charge transfer dissociation of a branched glycan with alkali and alkaline earth metal adducts

Approaches to Investigate Selective Dietary Polysaccharide Utilization by Human Gut Microbiota at a Functional Level

Advanced tandem mass spectrometry in metabolomics and lipidomics—methods and applications

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