Structural determination of novel lacto-N-decaose and its monofucosylated analogue from human milk by electrospray tandem mass spectrometry and 1H NMR spectroscopy

Chai, Wengang; Piskarev, V. E.; Zhang, Yibing; Lawson, A. M.; Kogelberg, Heide

doi:10.1016/j.abb.2004.09.035

Cited by 42 publications

(44 citation statements)

References 23 publications

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“…A D-type ion results from cleavage of the 1-and 3-substituents of the core Man residue. As such, its m/z value determines the mass of the 6-branch [23,[32][33][34][35]. Deprotonated, neutral, Nlinked oligosaccharides have been observed to produce in-source fragmentation during ESI in some cases [11].…”

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confidence: 99%

The influence of sialylation on glycan negative ion dissociation and energetics

Seymour

Costello

Zaia

2006

J. Am. Soc. Mass Spectrom.

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For the analysis of native glycans using tandem mass spectrometry (MS), it is desirable to choose conditions whereby abundances of cross-ring cleavages indicative of branch positions are maximized. Recently, negative ion tandem mass spectrometry has been shown to produce significantly higher abundances of such ions in glycans compared to the positive ion mode. Much of this prior work has concerned fragmentation patterns in asialo glycans. The present work compares the abundances of critical cross-ring cleavage ions using negative mode tandem mass spectrometry for milk oligosaccharides and N-linked glycans. For comparison, product ion formation was studied for deprotonated and nitrated ions formed from asialo glycans and deprotonated ions from sialylated glycans. Breakdown profiles demonstrate clearly that more energy was required to fragment sialylated compounds to the same extent as either their asialo or nitrate adducted counterparts. The extraction of a proton from a ring hydroxyl group during the ionization process may be viewed, qualitatively, as imparting significantly more energy to the ion than would that from a molecule bearing an acidic group, so that acidic glycans are more stable in the gas phase, as the negative charge resides on the carboxyl group. These results have strong practical implications because a major portion of glycans released from mammalian proteins will be sialylated. T he most information-rich tandem mass spectra of oligosaccharides are those in which a combination of abundant glycosidic bond and cross-ring cleavages is observed. Cross-ring cleavages at branching residues and those where linkages are known to vary in the given oligosaccharide or glycoconjugate class provide particularly valuable information. Although abundant A-type and X-type cross-ring cleavages are observed using high-energy collisionalinduced dissociation (CID) [1,2], most modern mass analyzers operate in the low-energy regime. Thus, positive ion CID MS using triple quadrupole, ion trap, quadrupole orthogonal time-of-flight, and FT-ICR analyzers results in low-energy fragmentation in which Band Y-type ions and only those cross-ring cleavage ions that result from particularly facile processes are abundant [3]. Recently, high-energy CID fragmentation, including X-type cross-ring cleavage ions, has been observed for a variety of nonacidic oligosaccharides using matrix-assisted laser desorption/ionization (MALDI) tandem time-of-flight analyzers [4,5]. However, since fragile oligosaccharides, particularly polysialylated [6], and polysulfated molecules [7,8] have been observed to undergo prompt fragmentation in the vacuum MALDI source and metastable decomposition in the analyzer, they are more amenable to electrospray ionization. Negatively charged neutral oligosaccharides undergo fragmentation at very low collision energies [9 -11], and such ions are also more amenable to electrospray ionization than MALDI. Now, there remains no commercial instrument option for producing high-energy CID for fragile molecules. Introdu...

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confidence: 99%

The influence of sialylation on glycan negative ion dissociation and energetics

Seymour

Costello

Zaia

2006

J. Am. Soc. Mass Spectrom.

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“…For instance, a double glycosidic D-type cleavage [23,24] is unique to 3-linked GlcNAc and Glc residues, whereas 0,2 A-type cleavages (nomenclature used to define the cleavage based on that introduced previously [32]), only occur with 4-linked GlcNAc [23], Glc [24] and unsubstituted glucosamine [25]. These fragmentations were used for identification of important structural features on underivatized neutral and sialylated oligosaccharides, including differentiation of type 1 and type 2 chains [23,24] or blood-group types [23,[26][27][28][29] (e.g. Lewisa or Lewis×determinants).…”

Section: Introductionmentioning

confidence: 99%

“…Using the negative-ion ES-CID-MS/MS strategy eight novel oligosaccharide sequences, including six neutral [26,27,29], one sialylated [28] and a glucuronic acid-containing [25,33] oligosaccharides, have been determined, and the structural assignments completed by NMR analysis.…”

Section: Introductionmentioning

confidence: 99%

“…The rapid advancement in electrospray (ES) ionization and matrix-assisted laser desorption/ionization has allowed MS to be used not only to measure the molecular mass for profiling but also to provide sequence, branching pattern, and partial linkage information of oligosaccharides [18][19][20][21][22][23][24][25][26][27][28][29][30][31]. Negative-ion electrospray mass spectrometry (ES-MS) with collision-induced dissociation tandem mass spectrometry (ES-CID-MS/MS) has been successfully used for sequence determination of various types of carbohydrate molecules [19][20][21][22].…”

Section: Introductionmentioning

confidence: 99%

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Sequence determination of a non-sulfated glycosaminoglycan-like polysaccharide from melanin-free ink of the squid Ommastrephes bartrami by negative-ion electrospray tandem mass spectrometry and NMR spectroscopy

Chen

Xue

et al. 2008

Glycoconj J

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A non-sulfated polysaccharide was isolated from the ink sac of squid Ommastrephes bartrami after removal of the melanin granules. The carbohydrate sequence of this polysaccharide was assigned by negative-ion electrospray tandem mass spectrometry with collision-induced dissociation of the oligosaccharide fractions produced by partial acid hydrolysis of the polysaccharide. The structural determination was completed by NMR for assignment of anomeric configuration and confirmation of linkage information and it was unambiguously identified as a glycosaminoglycan-like polysaccharide containing a glucuronic acid-fucose (GlcA-Fuc) disaccharide repeat in the main chain and a N-acetylgalactosamine (GalNAc) branch at Fuc position 3: -[3GlcAbeta1-4(GalNAcalpha1-3)Fucalpha1](n)-. Partial hydrolysis of the polysaccharide to obtain several oligosaccharide fractions with different numbers of the repeating unit assisted the assignment. In the negative-ion tandem mass spectrometric analysis, the unique (0,2)A type fragmentation was important to establish the presence of a 4-linked fucose in the main polysaccharide chain and a GalNAc branch at the Fuc position-3 of the disaccharide repeat.

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“…Compared with LC-MS and GC-MS, one of the advantages of NMR spectroscopy is the direct and quantitative relationship between the molar concentration and the intensity of the NMRs. For instance, NMR has played an important role in the structural characterization of free oligosaccharides in human milk [114][115][116][117]. Monakhova et al [118] suggest the use of NMR spectroscopy as screening tool to validate nutrition labeling of lactose-free milk, reporting a detection limit of 30 mg/L.…”

Section: Nuclear Magnetic Resonance (Nmr)mentioning

confidence: 99%

Advances in Fractionation and Analysis of Milk Carbohydrates

Nagaraj¹,

Upadhyay²,

Nath³

et al. 2018

Technological Approaches for Novel Applications in Dairy Processing

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Lactose is a principal component of the milk obtained from the mammals. Milk also contains several other sugars such as monosaccharides and oligosaccharides in low concentrations. Lactose has reactive functional groups and can be converted to valuable food-grade derivatives for commercial applications through chemical and/or enzymatic reactions. Physical and chemical properties of carbohydrates determine the methods that can be used for their fractionation and purification. In this chapter, the advanced extraction techniques for fractionation and analytical methodologies applied for the determination of different carbohydrates of milk (lactose, lactulose, and oligosaccharides) are summarized.The main aim of this contribution is to provide the reader with a broad view on the recent fractionation and analytical techniques employed for the analysis of carbohydrates in dairy foods and their applications in food and pharmaceutical industry.

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Structural determination of novel lacto-N-decaose and its monofucosylated analogue from human milk by electrospray tandem mass spectrometry and 1H NMR spectroscopy

Cited by 42 publications

References 23 publications

The influence of sialylation on glycan negative ion dissociation and energetics

The influence of sialylation on glycan negative ion dissociation and energetics

Sequence determination of a non-sulfated glycosaminoglycan-like polysaccharide from melanin-free ink of the squid Ommastrephes bartrami by negative-ion electrospray tandem mass spectrometry and NMR spectroscopy

Advances in Fractionation and Analysis of Milk Carbohydrates

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