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Determination of ganglioside composition and structure in human brain hemangioma by chip-based nanoelectrospray ionization tandem mass spectrometry

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Abstract

We report here on a preliminary investigation of ganglioside composition and structure in human hemangioma, a benign tumor in the frontal cortex (HFC) in comparison to normal frontal cortex (NFC) tissue using for the first time advanced mass spectrometric methods based on fully automated chip-nanoelectrospray (nanoESI) high-capacity ion trap (HCT) and collision-induced dissociation (CID). The high ionization efficiency, sensitivity and reproducibility provided by the chip-nanoESI approach allowed for a reliable MS-based ganglioside comparative assay. Unlike NFC, ganglioside mixture extracted from HFC was found dominated by species of short glycan chains exhibiting lower overall sialic acid content. In HFC, only GT1 (d18:1/20:0), and GT3 (d18:1/25:1) polysialylated species were detected. Interestingly, none of these trisialylated forms was detected in NFC, suggesting that such components might selectively be associated with HFC. Unlike the case of previously investigated high malignancy gliosarcoma, in HFC one modified O-Ac-GD2 and one modified O-Ac-GM4 gangliosides were observed. This aspect suggests that these O-acetylated structures could be associated with cerebral tumors having reduced malignancy grade. Fragmentation analysis by CID in MS2 mode using as precursors the ions corresponding to GT1 (d18:1/20:0) and GD1 (d18:1/20:0) provided data corroborating for the first time the presence of the common GT1a and GT1b isomers and the incidence of unusual GT1c and GT1d glycoforms in brain hemangioma tumor.

Human brain biomarker discovery by advanced chipbased nanoelectrospray mass spectrometry

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Acknowledgments

This work was supported by Romanian National Authority for Scientific Research through the PN-II-41001/2007 project. Permission for experiments with human tissue for scientific purposes was obtained from the Ethical Commission of “Victor Babes” University of Medicine and Pharmacy Timisoara and Zagreb Medical School, under the Project no. 108120 granted by the Croatian Ministry of Science and Technology.

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Authors and Affiliations

  1. Mass Spectrometry Laboratory, National Institute for Research and Development in Electrochemistry and Condensed Matter, Str. Plautius Andronescu Nr. 1, 300224, Timisoara, Romania

    Catalin Schiopu, Corina Flangea, Alina Serb & Alina D. Zamfir

  2. “Victor Babes” University of Medicine and Pharmacy, P-ta Eftimie Murgu Nr. 2, 300041, Timisoara, Romania

    Corina Flangea, Florina Capitan, Alina Serb & Eugen Sisu

  3. Department of Chemistry and Biochemistry, University of Zagreb Medical School, Šalata 3, 10000, Zagreb, Croatia

    Željka Vukelić & Svjetlana Kalanj-Bognar

  4. Chemistry Institute of Romanian Academy, Mihai Viteazul Blvd. 24, Timisoara, 300223, Romania

    Eugen Sisu

  5. Laboratory of Analytical Chemistry and Biopolymer Structure Analysis, University of Konstanz, Universitätsstraße 10, 78464, Konstanz, Germany

    Michael Przybylski

  6. Department of Chemical and Biological Sciences, “Aurel Vlaicu” University of Arad, Revolutiei Blvd 77, Arad, 310130, Romania

    Alina D. Zamfir

Authors
  1. Catalin Schiopu
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  2. Corina Flangea
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  3. Florina Capitan
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  5. Željka Vukelić
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  6. Svjetlana Kalanj-Bognar
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  7. Eugen Sisu
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  8. Michael Przybylski
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  9. Alina D. Zamfir
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Correspondence to Alina D. Zamfir.

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Schiopu, C., Flangea, C., Capitan, F. et al. Determination of ganglioside composition and structure in human brain hemangioma by chip-based nanoelectrospray ionization tandem mass spectrometry. Anal Bioanal Chem 395, 2465–2477 (2009). https://doi.org/10.1007/s00216-009-3188-8

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  • DOI: https://doi.org/10.1007/s00216-009-3188-8

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