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Selective linkage detection of O-sialoglycan isomers by negative electrospray ionization ion trap tandem mass spectrometry.
Rapid Commun Mass Spectrom. 2010 Apr 15; 24(7):885-93.RC

Abstract

Sialylated O-linked oligosaccharides are involved in many biological processes, such as cell-cell interactions, cell-substance adhesion, and virus-host interactions. These activities depend on their structure, which is frequently determined by tandem mass spectrometry. However, these spectra are frequently analyzer-dependent, which makes it difficult to develop widely applicable analytical methods. In order to deepen the origin of this behavior, two couples of isomers of sialylated O-linked oligosaccharides, NeuAc alpha2-3Gal beta1-3GalNAc-ol/Gal beta1-3(NeuAc alpha2-6)GalNAc-ol and NeuGc alpha2-3Gal beta1-3GalNAc-ol/Gal beta1-3(NeuGc alpha2-6)GalNAc-ol, were analyzed by liquid chromatography/negative electrospray ionization ion trap tandem mass spectrometry (LC/ESI(-)-MS(n)) using both an ion trap and a triple quadrupole mass spectrometer. Results clearly showed that while ions obtained in the triple quadrupole instrument fitted very well with the standard fragmentation routes, in the ion trap several intense ions could not be explained by these rules, specially a fragment at m/z 597. Furthermore, this ion was observed in the mass spectrum of those isomers that sialic acid binds to GalNAc by an alpha2-6 linkage. From the MS(3) spectrum of this ion an unexpected structure was deduced, and it led to propose alternative fragmentation pathways. Molecular mechanics calculations suggested that the found atypical route could be promoted by a hydrogen bond located only in alpha2-6-linked oligosaccharides. It has also been demonstrated that this process follows a slow kinetic, explaining why it cannot be observed using an ion beam-type mass analyzer. In conclusion, ion traps seem to be more appropriate than triple quadrupoles to develop a reliable analytical method to distinguish between isomeric O-linked glycans.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Casal E
Instituto de Fermentaciones Industriales, CSIC, Madrid, Spain.
Lebrón-Aguilar R
No affiliation info available
Moreno FJ
No affiliation info available
Corzo N
No affiliation info available
Quintanilla-López JE
No affiliation info available

MeSH

Carbohydrate ConformationIsomerismN-Acetylneuraminic AcidNeuraminic AcidsOligosaccharidesSpectrometry, Mass, Electrospray IonizationTandem Mass Spectrometry

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

20196190

Citation

Casal, Enriqueta, et al. "Selective Linkage Detection of O-sialoglycan Isomers By Negative Electrospray Ionization Ion Trap Tandem Mass Spectrometry." Rapid Communications in Mass Spectrometry : RCM, vol. 24, no. 7, 2010, pp. 885-93.
Casal E, Lebrón-Aguilar R, Moreno FJ, et al. Selective linkage detection of O-sialoglycan isomers by negative electrospray ionization ion trap tandem mass spectrometry. Rapid Commun Mass Spectrom. 2010;24(7):885-93.
Casal, E., Lebrón-Aguilar, R., Moreno, F. J., Corzo, N., & Quintanilla-López, J. E. (2010). Selective linkage detection of O-sialoglycan isomers by negative electrospray ionization ion trap tandem mass spectrometry. Rapid Communications in Mass Spectrometry : RCM, 24(7), 885-93. https://doi.org/10.1002/rcm.4463
Casal E, et al. Selective Linkage Detection of O-sialoglycan Isomers By Negative Electrospray Ionization Ion Trap Tandem Mass Spectrometry. Rapid Commun Mass Spectrom. 2010 Apr 15;24(7):885-93. PubMed PMID: 20196190.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Selective linkage detection of O-sialoglycan isomers by negative electrospray ionization ion trap tandem mass spectrometry. AU - Casal,Enriqueta, AU - Lebrón-Aguilar,Rosa, AU - Moreno,Francisco Javier, AU - Corzo,Nieves, AU - Quintanilla-López,Jesús Eduardo, PY - 2010/3/3/entrez PY - 2010/3/3/pubmed PY - 2010/6/22/medline SP - 885 EP - 93 JF - Rapid communications in mass spectrometry : RCM JO - Rapid Commun Mass Spectrom VL - 24 IS - 7 N2 - Sialylated O-linked oligosaccharides are involved in many biological processes, such as cell-cell interactions, cell-substance adhesion, and virus-host interactions. These activities depend on their structure, which is frequently determined by tandem mass spectrometry. However, these spectra are frequently analyzer-dependent, which makes it difficult to develop widely applicable analytical methods. In order to deepen the origin of this behavior, two couples of isomers of sialylated O-linked oligosaccharides, NeuAc alpha2-3Gal beta1-3GalNAc-ol/Gal beta1-3(NeuAc alpha2-6)GalNAc-ol and NeuGc alpha2-3Gal beta1-3GalNAc-ol/Gal beta1-3(NeuGc alpha2-6)GalNAc-ol, were analyzed by liquid chromatography/negative electrospray ionization ion trap tandem mass spectrometry (LC/ESI(-)-MS(n)) using both an ion trap and a triple quadrupole mass spectrometer. Results clearly showed that while ions obtained in the triple quadrupole instrument fitted very well with the standard fragmentation routes, in the ion trap several intense ions could not be explained by these rules, specially a fragment at m/z 597. Furthermore, this ion was observed in the mass spectrum of those isomers that sialic acid binds to GalNAc by an alpha2-6 linkage. From the MS(3) spectrum of this ion an unexpected structure was deduced, and it led to propose alternative fragmentation pathways. Molecular mechanics calculations suggested that the found atypical route could be promoted by a hydrogen bond located only in alpha2-6-linked oligosaccharides. It has also been demonstrated that this process follows a slow kinetic, explaining why it cannot be observed using an ion beam-type mass analyzer. In conclusion, ion traps seem to be more appropriate than triple quadrupoles to develop a reliable analytical method to distinguish between isomeric O-linked glycans. SN - 1097-0231 UR - https://www.unboundmedicine.com/medline/citation/20196190/Selective_linkage_detection_of_O_sialoglycan_isomers_by_negative_electrospray_ionization_ion_trap_tandem_mass_spectrometry_ L2 - https://doi.org/10.1002/rcm.4463 DB - PRIME DP - Unbound Medicine ER -
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