De novo structural determination of mannose oligosaccharides by using a logically derived sequence for tandem mass spectrometry

Hsu, Hsu Chen; Huang, Shih-Pei; Liew, Chia Yen; Tsai, Shang‐Ting; Ni, Chi-Kung

doi:10.1007/s00216-019-01817-y

Cited by 22 publications

(20 citation statements)

References 43 publications

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“…Recently, we have developed a new mass spectrometry method, namely logically derived sequence tandem mass spectrometry, for carbohydrate structural determination. [ 7–11 ] Three stereoisomers, glucose, galactose, and mannose, can be differentiated using MS 3 collision‐induced dissociation (CID) tandem mass spectrometry of lithium adducts. [ 9 ] This method is currently the only mass spectrometry method in which anomericity of glycosidic bonds and stereoisomers of monosaccharides can be identified.…”

Section: Introductionmentioning

confidence: 99%

Differentiation of aldohexoses and ketohexoses through collision‐induced dissociation

Tsai

2021

J Chinese Chemical Soc

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Mass spectrometry has high sensitivity and is widely used for carbohydrate structural determination. However, conventional mass spectrometry is not able to identify anomericity and stereoisomer. In this work, we demonstrate that aldohexose and ketohexose can be distinguished through the collision‐induced dissociation of sodium adducts in an ion trap mass spectrometer. The criterion for the differentiation is the intensity ratio of fragment ion m/z 143 to fragment ion m/z 113. Aldohexoses have an intensity ratio larger than 1.8 and ketohexoses have an intensity ratio less than 0.7. These ratios can be explained using a cross‐ring dissociation mechanism. Although the dissociation mechanism of lithium adducts is similar to that of sodium adducts, differentiation using lithium adducts is not as good as that of sodium adducts because of the large lithiation energies. In addition, a dehydration propensity rule to differentiate anomeric configuration is extended from glucose, galactose, and mannose to allose, altrose, gulose, talose, fructose, and tagatose in this work. Application of this method for the identification of aldohexoses and ketohexoses produced from the collision‐induced dissociation of oligosaccharides in tandem mass spectrometer is demonstrated.

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Section: Introductionmentioning

confidence: 99%

Differentiation of aldohexoses and ketohexoses through collision‐induced dissociation

Tsai

2021

J Chinese Chemical Soc

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“…As demonstrated in the example of disaccharide linkage determination, understanding these dissociation mechanisms is useful when applying CID mass spectrometry to the structural determination. The findings in this work can be integrated with the mass spectrometry method we recently developed ,− to determine the structures of oligosaccharide, a long-standing bottleneck in carbohydrate research.…”

Section: Resultsmentioning

confidence: 99%

“…We showed that the CID mass spectra of isomers α-arabinose pyranose (α-Ara p ), β-arabinose pyranose (β-Ara p ), α-arabinose furanose (α-Ara f ), β-arabinose furanose (β-Ara f ), α-ribose pyranose (α-Rib p ), β-ribose pyranose (β-Rib p ), α-ribose furanose (α-Rib f ), and β-ribose furanose (β-Rib f ), the structures of which are illustrated in Figure , were markedly distinct. The results of this study can be applied to current mass spectrometry methods ,− for identifying pentoses in oligosaccharides.…”

Section: Introductionmentioning

confidence: 99%

Identification of Anomericity and Linkage of Arabinose and Ribose through Collision-Induced Dissociation

Tsai

Nguan

2021

J. Phys. Chem. A

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Arabinose and ribose are two common pentoses that exist in both furanose and pyranose forms in plant and bacteria oligosaccharides. In this study, each pentose isomer, namely α-furanose, β-furanose, α-pyranose, and β-pyranose, was first separated through high-performance liquid chromatography followed by an investigation of collision-induced dissociation in an ion trap mass spectrometer. The major dissociation channels, dehydration and cross-ring dissociation, were analyzed by using high-level quantum chemistry calculations and transition state theory. The branching ratio of major dissociation channels was governed by two geometrical features: one being the cis or trans configuration of O1 and O2 atoms determining dehydration preferability and the other being the number of hydroxyl groups on the same side of the ring as the O1 atom determining the preferability of cross-ring dissociation. The relative branching ratios of the major channels were used to identify anomericity and the linkages of arabinose and ribose. Arabinose in the β-configuration and ribose in the α-configuration are predicted to have larger relative dehydration branching ratios than arabinose in the α-configuration and ribose in the β-configuration, respectively. Arabinose and ribose at the reducing end of oligosaccharides with 1 → 2 (pyranose and furanose), 1 → 3 (pyranose and furanose), 1 → 4 (pyranose only), and 1 → 5 (furanose only) linkages are predicted to undergo 0,2 X, 0,3 X, 0,2 A, and 0,2 A/ 0,3 A cross-ring dissociation, respectively. Application of the dissociation mechanism to the disaccharide linkage determination is demonstrated.

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“…Recently, a new mass spectrometry method, namely logically derived sequence (LODES) multistage tandem mass spectrometry (MS n ) was developed for the full structural determination of oligosaccharides 35 – 38 . This method can be used to determine oligosaccharide structures including linkage positions, anomericities, and monosaccharide stereoisomers.…”

Section: Introductionmentioning

confidence: 99%

Unusual free oligosaccharides in human bovine and caprine milk

Weng

Liao

Huang

et al. 2022

Sci Rep

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Free oligosaccharides are abundant macronutrients in milk and involved in prebiotic functions and antiadhesive binding of viruses and pathogenic bacteria to colonocytes. Despite the importance of these oligosaccharides, structural determination of oligosaccharides is challenging, and milk oligosaccharide biosynthetic pathways remain unclear. Oligosaccharide structures are conventionally determined using a combination of chemical reactions, exoglycosidase digestion, nuclear magnetic resonance spectroscopy, and mass spectrometry. Most reported free oligosaccharides are highly abundant and have lactose at the reducing end, and current oligosaccharide biosynthetic pathways in human milk are proposed based on these oligosaccharides. In this study, a new mass spectrometry technique, which can identify linkages, anomericities, and stereoisomers, was applied to determine the structures of free oligosaccharides in human, bovine, and caprine milk. Oligosaccharides that do not follow the current biosynthetic pathways and are not synthesized by any discovered enzymes were found, indicating the existence of undiscovered biosynthetic pathways and enzymes.

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De novo structural determination of mannose oligosaccharides by using a logically derived sequence for tandem mass spectrometry

Cited by 22 publications

References 43 publications

Differentiation of aldohexoses and ketohexoses through collision‐induced dissociation

Differentiation of aldohexoses and ketohexoses through collision‐induced dissociation

Identification of Anomericity and Linkage of Arabinose and Ribose through Collision-Induced Dissociation

Unusual free oligosaccharides in human bovine and caprine milk

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