Gas-Phase Fragmentation of Cyclic Oligosaccharides in Tandem Mass Spectrometry

Chizhov, Alexander O.; Tsvetkov, Yury E.; Nifantiev, Nikolay E.

doi:10.3390/molecules24122226

Cited by 15 publications

(9 citation statements)

References 82 publications

(144 reference statements)

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“…β-Cyclodextrin is a cyclic heptasaccharide, which finds many applications in food, biotechnology, pharmacy, textiles, medicine, and cosmetics. , β-Cyclodextrin (MW 1135 Da) is composed of seven glucose subunits joined together by α(1 → 4) glycosidic bonds. The noncontact nESI analysis of β-cyclodextrin in methanol/chloroform solution produced a peak at m / z 1170 formed by its adduction with chloride.…”

Section: Resultsmentioning

confidence: 99%

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Mass Spectrometry Approach for Differentiation of Positional Isomers of Saccharides: Toward Direct Analysis of Rare Sugars

et al. 2023

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Rare sugars have gained popularity in recent years due to their use in antiaging treatments, their ability to sweeten with few calories, and their ability to heal infections. Rare sugars are found in small quantities in nature, and they exist typically as isomeric forms of traditional sugars, rendering some challenges in their isolation, synthesis, and characterization. In this work, we present the first direct mass spectrometric approach for differentiating structural isomers of sucrose that differ only by their glycosidic linkages. The method employed a noncontact nanoelectrospray (nESI) platform capable of analyzing minuscule volumes (5 μL) of saccharides via the formation of halide adducts ([M+X]−; X = Cl and Br). Tandem mass spectrometry analysis of the five structural isomers of sucrose afforded diagnostic fragment ions that can be used to distinguish each isomer. Detailed mechanisms showcasing the distinct fragmentation pattern for each isomer are discussed. The method was applied to characterize and confirm the presence of all five selected rare sugars in raw honey complex samples. Aside from the five natural α isomers of sucrose, the method was also suitable for differentiating some β isomers of the same glycosidic linkages, provided the monomeric sugar units are different. The halide adduct formation via the noncontact nESI source was also proven to be effective for oligosaccharides such as raffinose, β-cyclodextrin, and maltoheptaose. The results from this study encourage the future development of methods that function with simple operation to enable straightforward characterization of small quantities of rare sugars.

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Section: Resultsmentioning

confidence: 99%

“…54,55 β-Cyclodextrin (MW 1135 Da) is composed of seven glucose subunits joined together by α(1 → 4) glycosidic bonds. The noncontact nESI analysis of βcyclodextrin in methanol/chloroform solution produced a peak at m/z 1170 formed by its adduction with chloride.…”

mentioning

confidence: 99%

Mass Spectrometry Approach for Differentiation of Positional Isomers of Saccharides: Toward Direct Analysis of Rare Sugars

et al. 2023

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“…MS/MS fragmentation studies were further employed to confirm the structures of CDCL main products. The fragmentation of CDCL derivatives proceeds similarly to other CD-oligoester derivatives [ 19 , 20 , 45 , 46 ], having two main pathways: the cleavage of the 1,4-glycosidic bond of β-CD [ 53 , 54 , 55 ] and the cleavage of the ester bonds from the CL attached to the β-CD molecule [ 56 , 57 , 58 ]. Oligocaprolactone fragmentation can occur either on the acyl side through 1-3 hydrogen rearrangements ( Scheme 2 A— a series ) or on the alkyl side through 1-4 hydrogen rearrangements of the ester bond ( Scheme 2 A— b series ).…”

Section: Resultsmentioning

confidence: 99%

Cyclodextrin-Oligocaprolactone Derivatives—Synthesis and Advanced Structural Characterization by MALDI Mass Spectrometry

Peptu¹,

Blaj²,

Balan-Porcăraşu³

et al. 2022

Polymers

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Cyclodextrins have previously been proven to be active in the catalysis of cyclic ester ring-opening reactions, hypothetically in a similar way to lipase-catalyzed reactions. However, the way they act remains unclear. Here, we focus on β-cyclodextrin’s involvement in the synthesis and characterization of β-cyclodextrin-oligocaprolactone (CDCL) products obtained via the organo-catalyzed ring-opening of ε-caprolactone. Previously, bulk or supercritical carbon dioxide polymerizations has led to inhomogeneous products. Our approach consists of solution polymerization (dimethyl sulfoxide and dimethylformamide) to obtain homogeneous CDCL derivatives with four monomer units on average. Oligomerization kinetics, performed by a matrix-assisted laser desorption ionization mass spectrometry (MALDI MS) optimized method in tandem with 1H NMR, revealed that monomer conversion occurs in two stages: first, the monomer is rapidly attached to the secondary OH groups of β-cyclodextrin and, secondly, the monomer conversion is slower with attachment to the primary OH groups. MALDI MS was further employed for the measurement of the ring-opening kinetics to establish the influence of the solvents as well as the effect of organocatalysts (4-dimethylaminopyridine and (–)-sparteine). Additionally, the mass spectrometry structural evaluation was further enhanced by fragmentation studies which confirmed the attachment of oligoesters to the cyclodextrin and the cleavage of dimethylformamide amide bonds during the ring-opening process.

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“…For illustration (Figure 1), the MS/MS spectrum obtained for the mono-grafted species highlighted two fragmentation pathways. On the one hand, six successive losses of glucopyranose unit (−162 Da) were observed [19] leading to the characteristic fragment ion at m/z 497.31, which was attributed to a sodiated mono grafted dehydro glucose unit. On the other hand, a loss of 312 Da corresponding to the methyl oleate chain occurred first and was then followed by six successive losses of 162 Da.…”

Section: Scheme 2 Opening Reaction Of Methyl Oleate Epoxide By Cds Umentioning

confidence: 99%

“…Indeed, electrospray ionization (ESI) either in direct introduction [17] or coupled with liquid chromatography (LC/ESI-MS) [18] and matrix assisted laser desorption ionization (MALDI) [16] are frequently used in that context. To go deeper in the structural analysis of cyclic oligosaccharides tandem mass spectrometry (MS/MS) [19] and more recently ion mobility spectrometry (IMS) [20] are described. In this study, in addition to classical NMR and mass spectrometry experiments, we focus on an original approach based on ion mobility measurements for a better structural characterization of L-CDs isomers.…”

Section: Introductionmentioning

confidence: 99%

New Lipidyl-Cyclodextrins Obtained by Ring Opening of Methyl Oleate Epoxide Using Ball Milling

et al. 2020

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Bearing grafts based on fatty esters derivatives, lipidyl-cyclodextrins (L-CDs) are compounds able to form water-soluble nano-objects. In this context, bicatenary biobased lipidic-cyclodextrins of low DS were easily synthesized from a fatty ester epoxide by means of alternative methods (ball-milling conditions, use of enzymes). The ring opening reaction of methyl oleate epoxide needs ball-milling and is highly specific of cyclodextrins in solventless conditions. L-CDs are thus composed of complex mixtures that were deciphered by an extensive structural analysis using mainly mass spectrometry and NMR spectroscopy. In addition, as part of their potential use as vectors of active drugs, these products were submitted to an integrity study on in vitro model of the blood-brain-barrier (BBB) and the intestinal epithelium. No toxicity has been observed, suggesting that applications for the vectorization of active ingredients can be expected.

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Gas-Phase Fragmentation of Cyclic Oligosaccharides in Tandem Mass Spectrometry

Cited by 15 publications

References 82 publications

Mass Spectrometry Approach for Differentiation of Positional Isomers of Saccharides: Toward Direct Analysis of Rare Sugars

Mass Spectrometry Approach for Differentiation of Positional Isomers of Saccharides: Toward Direct Analysis of Rare Sugars

Cyclodextrin-Oligocaprolactone Derivatives—Synthesis and Advanced Structural Characterization by MALDI Mass Spectrometry

New Lipidyl-Cyclodextrins Obtained by Ring Opening of Methyl Oleate Epoxide Using Ball Milling

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