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Pregled bibliografske jedinice broj: 800263

Characterization and Modeling of the Collision Induced Dissociation Patterns of Deprotonated Glycosphingolipids: Cleavage of the Glycosidic Bond


Rožman, Marko
Characterization and Modeling of the Collision Induced Dissociation Patterns of Deprotonated Glycosphingolipids: Cleavage of the Glycosidic Bond // Journal of the American Society for Mass Spectrometry, 27 (2016), 1; 91-98 doi:10.1007/s13361-015-1247-2 (međunarodna recenzija, članak, znanstveni)


Naslov
Characterization and Modeling of the Collision Induced Dissociation Patterns of Deprotonated Glycosphingolipids: Cleavage of the Glycosidic Bond

Autori
Rožman, Marko

Izvornik
Journal of the American Society for Mass Spectrometry (1044-0305) 27 (2016), 1; 91-98

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Glycosphingolipid ; MSMS ; RRKM ; Low-energy CID ; Modeling

Sažetak
Glycosphingolipid fragmentation behavior was investigated by combining results from analysis of a series of negative ion tandem mass spectra and molecular modeling. Fragmentation patterns extracted from 75 tandem mass spectra of mainly acidic glycosphingolipid species (gangliosides) suggest prominent cleavage of the glycosidic bonds with retention of the glycosidic oxygen atom by the species formed from the reducing end (B and Y ion formation). Dominant product ions arise from dissociation of sialic acids glycosidic bonds whereas product ions resulting from cleavage of other glycosidic bonds are less abundant. Potential energy surfaces and unimolecular reaction rates of several low-energy fragmentation pathways leading to cleavage of glycosidic bonds were estimated in order to explain observed dissociation patterns. Glycosidic bond cleavage in both neutral (unsubstituted glycosyl group) and acidic glycosphingolipids was the outcome of the charge-directed intramolecular nucleophilic substitution (SN2) mechanism. According to the suggested mechanism, the nucleophile in a form of carboxylate or oxyanion attacks the carbon at position one of the sugar ring, simultaneously breaking the glycosidic bond and yielding an epoxide. For gangliosides, unimolecular reaction rates suggest that dominant product ions related to the cleavage of sialic acid glycosidic bonds are formed via direct dissociation channels. On the other hand, low abundant product ions related to the dissociation of other glycosidic bonds are more likely to be the result of sequential dissociation. Although results from this study mainly contribute to the understanding of glycosphingolipid fragmentation chemistry, some mechanistic findings regarding cleavage of the glycosidic bond may be applicable to other glycoconjugates.

Izvorni jezik
Engleski

Znanstvena područja
Kemija



POVEZANOST RADA


Ustanove
Institut "Ruđer Bošković", Zagreb

Autor s matičnim brojem:
Marko Rožman, (237562)

Citiraj ovu publikaciju

Rožman, Marko
Characterization and Modeling of the Collision Induced Dissociation Patterns of Deprotonated Glycosphingolipids: Cleavage of the Glycosidic Bond // Journal of the American Society for Mass Spectrometry, 27 (2016), 1; 91-98 doi:10.1007/s13361-015-1247-2 (međunarodna recenzija, članak, znanstveni)
Rožman, M. (2016) Characterization and Modeling of the Collision Induced Dissociation Patterns of Deprotonated Glycosphingolipids: Cleavage of the Glycosidic Bond. Journal of the American Society for Mass Spectrometry, 27 (1), 91-98 doi:10.1007/s13361-015-1247-2.
@article{article, author = {Ro\v{z}man, M.}, year = {2016}, pages = {91-98}, DOI = {10.1007/s13361-015-1247-2}, keywords = {Glycosphingolipid, MSMS, RRKM, Low-energy CID, Modeling}, journal = {Journal of the American Society for Mass Spectrometry}, doi = {10.1007/s13361-015-1247-2}, volume = {27}, number = {1}, issn = {1044-0305}, title = {Characterization and Modeling of the Collision Induced Dissociation Patterns of Deprotonated Glycosphingolipids: Cleavage of the Glycosidic Bond}, keyword = {Glycosphingolipid, MSMS, RRKM, Low-energy CID, Modeling} }

Časopis indeksira:


  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus
  • MEDLINE


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