Anomeric information obtained from a series of synthetic trisaccharides using energy resolved mass spectra

Daikoku, Shusaku; Ako, Takuro; Kurimoto, Ayako; Kanie, Osamu

doi:10.1002/jms.1196

Cited by 20 publications

(20 citation statements)

References 58 publications

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“…It is interesting that B 1 ion was observed only for the ␤-Fuc compound ( ␤ 3␤␣), even though the ␣ difference between these two (3␣␣ and 3␤␣) is the ␣ anomeric configurations of the Fuc unit only. This result is puzzling because both of the product ions, B 1 and Y 1 ions, share a similar structure; however, this may suggest that ␤Fuc-Gal had more affinity with Na ␤ ␤ ϩ compared with its counter ␣-structure because a similar ␣ tendency was observed in a previous study [27]. In the CID spectrum of 3␤␤, 2,5 X 1 ion and an unusual fragment ion with m/z 187 were observed as characteristic ions.…”

Section: Cid Analysis Of All Compoundsmentioning

confidence: 79%

“…We have analyzed isomeric oligosaccharides based on ERMS and shown that (1) the primary glycosidic linkage is more stable than the secondary glycoside linkage; and (2) ␣-glyco-␣ sides are more labile than ␤-glycosides, through inves-␤ tigation of malto (␣1¡4)-, ¡ ¡ isomalto (␣1¡6)-, and cello (␤1¡4)-oligosaccharid ¡ ¡ e [26] and trisaccharide libraries with the ␣/␤-Fuc-(1 ␤ ¡6)-␣/␤-Gal-(1 ␤ ¡6)-␣/␤-Glc-octyl ␤ sequence [27]. It is important to confirm the generality of these tendencies and at the same time to accumulate such data regarding the structure-related characteristics for future development of methods to identify novel glycoconjugates.…”

Section: Erms Analysismentioning

confidence: 99%

“…We have been attempting the extraction of an isomeric structure-oriented "parameter," based on energyresolved mass spectrometry (ERMS), and have reported that isomeric homooligomers and a series of synthetic compounds can be discriminated [26,27]. Here in this report, we describe the results of ERMS analysis of a small combinatorial library [28,29], consisting of a complete combination of compounds with a fucosyl galactose sequence and an important finding regarding anomeric structures.…”

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confidence: 99%

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Discrimination of 16 structural isomers of fucosyl galactoside based on energy-resolved mass spectrometry

Daikoku

Ako

Kato

et al. 2007

J. Am. Soc. Mass Spectrom.

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Glycans, a family of compounds often attached to proteins and ceramides, are diverse molecules involved in a wide range of biological functions. Their structural analysis is necessary and is often carried out at the microscale level. Methods based on mass spectrometry are therefore used, although they do not provide information regarding isomeric structures often found in glycan structures. If one finds "factors" characteristic of a certain isomer, this information can be used to elucidate an unknown oligosaccharide sequence. One potential technique is to use energy-resolved mass spectrometry (ERMS) that has been used to distinguish a pair of isomeric compounds. Thus, compounds in a combinatorial library might be effectively used for this purpose. We analyzed a set of 16 isomeric disaccharides, the structures of which consisted of all possible combinations of anomeric configurations and interglycosidic linkage positions. All of the compounds were distinguished based on ERMS where normal collision-induced dissociation could distinguish only seven compounds. Furthermore, it was shown that ␣-glycosidic linkages of fucose were more reactive than the ␣ ␤-isomers and the secondary glycosides were more reactive than the primary . The structural characteristics of oligosaccharides are quite different from those of other biopolymers such as nucleic acids and peptides. The diversity is generated from sequential combination in the latter two types of polymers, whereas anomers, ring size, linkage position, branching, and sequence are factors in the case of oligosaccharides [2]. Furthermore, the regulatory mechanisms for oligosaccharides still need to be clarified and synthesis, which is not template dependent, thus creates further molecular diversity called glycoforms. Despite the difficulties encountered in structural determination, there are reports on how glycosylation as a type of posttranslational modification (PTM) of protein affects glycoprotein secretion [3,4].

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Section: Cid Analysis Of All Compoundsmentioning

confidence: 79%

Section: Erms Analysismentioning

confidence: 99%

mentioning

confidence: 99%

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Discrimination of 16 structural isomers of fucosyl galactoside based on energy-resolved mass spectrometry

Daikoku

Ako

Kato

et al. 2007

J. Am. Soc. Mass Spectrom.

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“…We also acknowledge that other research groups have successfully distinguished anomers by mass spectrometry [13][14][15][16][17][18][19][20]. Among them, we are particularly interested in the report by Leavell et al [1] because they studied conformations of metal complexes of sugars.…”

Section: Discussionmentioning

confidence: 98%

Distinction of sialyl anomers on ESI- and FAB-MS/MS: Stereo-specific fragmentations

Ohashi

Kubota²,

Hatase

et al. 2009

J. Am. Soc. Mass Spectrom.

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An anomeric pair of the lysoglyceroganglioside 1-O-octadecyl-3-O-(N-acetyl)neuraminyl-N N snglycerol sodium salt was studied to see if sialic anomers were distinguishable by mass spectra. It was evident that, in the electrospray ionization and fast-atom bombardment product-ion spectra: (1) in the positive MS 2 product-ion spectrum, the ␤-anomer showed an unexpected ␤ aglycone-side sodiated sodium alkoxide ion, which was absent for the ␣-anomer; (2) in both ␣ polarities the ␤-anomer showed dehydration much more easily than the ␤ ␣-anomer; and (3) in ␣ the negative MS 2 product-ion spectrum, the ␤-anomer also readily showed decarboxylation. ␤ Our hypothesis is that, although several easily interconvertible conformations may be allowed, the one having the large aglycone in the equatorial orientation affects the collision-induced dissociation fragmentations. and MS 3 product-ion spectra of lysoglyceroganglioside anomers and seek to elucidate the differences based on stereochemical considerations. Such differences also apply to fast-atom bombardment mass spectrometry (FABMS).Sialic acid is one of the most important sugars for mammals. In normal life events, its conjugates, particularly gangliosides, are deeply involved in fertilization, development, cell-cell recognition, cell differentiation, and even in the programmed cell death. Gangliosides are also heavily related to cancer and other diseases. Studies of sialyl compounds are rapidly expanding these days in particular to meet the imminent threat of avian influenza infection, in which sialic acid may play a critical role.To study the structure-activity relationships, detailed structural information has to be clarified. Nuclear magnetic resonance (NMR) has served that purpose for years. However, soft ionization mass spectrometry often provides structural information parallel to or even exceeding what can be provided by NMR.Indeed, positional isomers and even linkage isomers in the same branching sugar unit are distinguishable by using mass spectrometry [5][6][7][8][9]. Among all, the most difficult isomer analysis is the distinction of stereoisomers. We previously reported the epimer distinction on N-acetyllactosamine-6,6 N N =-disulfate [10]. Here we report mass spectrometry of an anomeric pair of lysoglycerotype ganglioside. We selected product-ion mass spectrometry applying both ESI-and FAB-ionization methods, and we found that they showed similar tendencies with respect to their major fragmentation. However, ESI modes with high mass resolving power definitely produced more differences in the fragmentations and consumed less sample. We show here that mass spectrometric differences between anomers are not peculiar, but can be reasonably explained through stereochemical rationalizations.Yu and Ledeen reported in 1969, using an anomeric pair of methylketosides of N-acetylneuraminic acid N N that, on dehydration with dicyclohexylcarbodiimide in hot pyridine, the neuraminidase-resistant isomer gave two lactones, whereas the enzyme-susceptible anomer did not [11]. The...

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“…The dissociation of Fuc residues from a pair of precursor ions in the above case can be identified by ERMS (Figure 6). Since the method is very sensitive to the structural differences, it has been used to distinguish structurally closely related glycans [71][72][73][74][75].…”

Section: New Parameter For Use In Structural Analysismentioning

confidence: 99%

Addressing the glycan complexity by using mass spectrometry: In the pursuit of decoding glycologic

Kanie¹,

Kanie²

2017

Bio Chem Comp

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Biomolecules often contain carbohydrates. Such molecules, namely glycoconjugates, play central roles in cell adhesion, tumor migration, and attachment of pathogens. The conjugation of "natural products" with glycans is not a template-dependent process but is achieved by multiple enzymatic reactions. Because of the nature of the synthetic process, glycans exist as a complex mixture creating a glycoform and thus, the analysis becomes inevitably difficult. Mass spectrometry is one of the most informative, and thus important, tools for the structural analysis of glycans. The obvious advantage of mass spectrometry is the high sensitivity at low femtomole detection levels. A variety of ions can be obtained depending on the adducted cationic species. In order to obtain sequential information, the gas-phase dissociation reaction is used. Among the various techniques, collision-induced dissociation (CID) has been frequently used in the past. Although the technique is proven useful, there are cases that normal CID process is not suitable. This review highlights an emerging technique that focuses on the activation-energy difference between the isomeric glycans, and will complement the current methods. Furthermore, the possible source and the methodology for obtaining useful structural information are discussed.

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Anomeric information obtained from a series of synthetic trisaccharides using energy resolved mass spectra

Cited by 20 publications

References 58 publications

Discrimination of 16 structural isomers of fucosyl galactoside based on energy-resolved mass spectrometry

Discrimination of 16 structural isomers of fucosyl galactoside based on energy-resolved mass spectrometry

Distinction of sialyl anomers on ESI- and FAB-MS/MS: Stereo-specific fragmentations

Addressing the glycan complexity by using mass spectrometry: In the pursuit of decoding glycologic

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