Does low‐energy collision‐induced dissociation of lithiated and sodiated carbohydrates always occur at anomeric carbon of the reducing end?

Tsai, Shang‐Ting; Chen, Jien-Lian; Ni, Chi-Kung

doi:10.1002/rcm.7961

Cited by 25 publications

(23 citation statements)

References 32 publications

(70 reference statements)

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“…However, in the process of LODES, the first step is to generate the fragment by dehydration or cross‐ring dissociation at the reducing end, such that B (or C) ions can be differentiated from Z (or Y) ions in subsequent dissociation. Our previous study showed that dehydration and cross‐ring dissociation from the nonreducing end of oligosaccharide lithium adducts were not negligible, compared with sodium adducts; therefore, labeling of the O1 atom of the sugar at the reducing end by 18 O is necessary for some oligosaccharides if lithium adducts are used.…”

Section: Resultsmentioning

confidence: 99%

Automatic Full Glycan Structural Determination through Logically Derived Sequence Tandem Mass Spectrometry

et al. 2019

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Glycans have diverse functions and play vital roles in many biological systems, such as influenza, vaccines, and cancer biomarkers. However, full structural identification of glycans remains challenging. The glycan structure was conventionally determined by chemical methods or NMR spectroscopy, which require a large amount of sample and are not readily applicable for glycans extracted from biological samples. Although it has high sensitivity and is widely used for structural determination of molecules, current mass spectrometry can only reveal parts of the glycan structure. Herein, the full structures of glycans, including diastereomers, the anomericity of each monosaccharide, and the linkage position of each glycosidic bond, which can be determined by using tandem mass spectrometry guided by a logically derived sequence (LODES), are shown. This new method provides de novo oligosaccharide structural identification with high sensitivity and has been applied to automatic in situ structural determination of oligosaccharides eluted by means of HPLC. It is shown that the structure of a given trisaccharide from a trisaccharide mixture and bovine milk were determined from nearly 3000 isomers by using 6–7 logically selected collision‐induced dissociation spectra. The entire procedure for mass spectrometry measurement guided by LODES can be programmed in a computer for automatic full glycan structure identification.

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Section: Resultsmentioning

confidence: 99%

Automatic Full Glycan Structural Determination through Logically Derived Sequence Tandem Mass Spectrometry

et al. 2019

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“…In positive ionization mode, adduct ions formed with cations may have different origins and may result from: the protonation of a basic site of an entity already existing as a salt; the charge solvation of a metal cation by the lone‐pair(s) of heteroatom(s) of either (A) a molecule or (B) a salt. Representative examples of such adduct ions possibly formed with glucose and sodium cations are depicted in Figure as well as the corresponding proposed annotation.…”

Section: Illustrative Examples and Discussionmentioning

confidence: 99%

“…In positive mode, adduct ions such as [M + Na] + in their charge‐solvated form usually dissociate with regeneration of the alkali cation . In contrast, the ionized salts are much more stable species and can only dissociate under higher desolvation conditions.…”

Section: Illustrative Examples and Discussionmentioning

confidence: 99%

Proposal for a chemically consistent way to annotate ions arising from the analysis of reference compounds under ESI conditions: A prerequisite to proper mass spectral database constitution in metabolomics

et al. 2019

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Nowadays, high‐resolution mass spectrometry is widely used for metabolomic studies. Thanks to its high sensitivity, it enables the detection of a large range of metabolites. In metabolomics, the continuous quest for a metabolite identification as complete and accurate as possible has led during the last decade to an ever increasing development of public MS databases (including LC‐MS data) concomitantly with bioinformatic tool expansion. To facilitate the annotation process of MS profiles obtained from biological samples, but also to ease data sharing, exchange, and exploitation, the standardization and harmonization of the way to describe and annotate mass spectra seemed crucial to us. Indeed, under electrospray (ESI) conditions, a single metabolite does not produce a unique ion corresponding to its protonated or deprotonated form but could lead to a complex mixture of signals. These MS signals result from the existence of different natural isotopologues of the same compound and also to the potential formation of adduct ions, homomultimeric and heteromultimeric ions, fragment ions resulting from “prompt” in‐source dissociations. As a joint reflection process within the French Infrastructure for Metabolomics and Fluxomics (MetaboHUB) and with the purpose of developing a robust and exchangeable annotated MS database made from pure reference compounds (chemical standards) analysis, it appeared to us that giving the metabolomics community some clues to standardize and unambiguously annotate each MS feature was a prerequisite to data entry and further efficient querying of the mass spectral database. The use of a harmonized notation is also mandatory for interlaboratory MS data exchange. Additionally, thorough description of the variety of MS signals arising from the analysis of a unique metabolite might provide greater confidence on its annotation.

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“…The new method involves the sequential low-energy resonance excitation CID experiments of sodiated oligosaccharides in a typical ion trap mass spectrometer. However, the sequence of the tandem CID experiment is specially designed according to the dissociation mechanism we found recently 38 , 39 , and the measured CID spectra are compared with our specially prepared database. In the following sections, we first describe the dissociation mechanism, followed by a description of the database and the scheme of the procedure to determine the structures of oligosaccharides.…”

Section: The Approach Of De Novo Structural Determinationmentioning

confidence: 99%

“…Recent high-level quantum chemistry calculations 12 , 38 , 39 have indicated that glycosidic bond cleavage, cross-ring dissociation and dehydration reactions on the reducing sugar are dissociation channels with low barrier heights for sodiated carbohydrates. By contrast, cross-ring dissociation and dehydration reactions on the nonreducing sugar are dissociation channels with high barrier heights.…”

Section: The Approach Of De Novo Structural Determinationmentioning

confidence: 99%

Simple Method for De Novo Structural Determination of Underivatised Glucose Oligosaccharides

Hsu

Liew

Huang

et al. 2018

Sci Rep

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Carbohydrates have various functions in biological systems. However, the structural analysis of carbohydrates remains challenging. Most of the commonly used methods involve derivatization of carbohydrates or can only identify part of the structure. Here, we report a de novo method for completely structural identification of underivatised oligosaccharides. This method, which can provide assignments of linkages, anomeric configurations, and branch locations, entails low-energy collision-induced dissociation (CID) of sodium ion adducts that enable the cleavage of selective chemical bonds, a logical procedure to identify structurally decisive fragment ions for subsequent CID, and the specially prepared disaccharide CID spectrum databases. This method was first applied to determine the structures of four underivatised glucose oligosaccharides. Then, high-performance liquid chromatography and a mass spectrometer with a built-in logical procedure were established to demonstrate the capability of the in situ CID spectrum measurement and structural determination of the oligosaccharides in chromatogram. This consolidation provides a simple, rapid, sensitive method for the structural determination of glucose oligosaccharides, and applications to oligosaccharides containing hexoses other than glucose can be made provided the corresponding disaccharide databases are available.

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Does low‐energy collision‐induced dissociation of lithiated and sodiated carbohydrates always occur at anomeric carbon of the reducing end?

Abstract: Our data shows that dehydration reactions and cross ring dissociation do not always occur at the anomeric carbon atom of the reducing monomer.

Cited by 25 publications

References 32 publications

Automatic Full Glycan Structural Determination through Logically Derived Sequence Tandem Mass Spectrometry

Automatic Full Glycan Structural Determination through Logically Derived Sequence Tandem Mass Spectrometry

Proposal for a chemically consistent way to annotate ions arising from the analysis of reference compounds under ESI conditions: A prerequisite to proper mass spectral database constitution in metabolomics

Simple Method for De Novo Structural Determination of Underivatised Glucose Oligosaccharides

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