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Chip‐nanoelectrospray quadrupole time‐of‐flight tandem mass spectrometry of meningioma gangliosides: A preliminary study
Author(s) -
Schiopu Catalin,
Vukelić Željka,
Capitan Florina,
KalanjBognar Svjetlana,
Sisu Eugen,
Zamfir Alina D.
Publication year - 2012
Publication title -
electrophoresis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.666
H-Index - 158
eISSN - 1522-2683
pISSN - 0173-0835
DOI - 10.1002/elps.201200044
Subject(s) - chemistry , chromatography , glycosphingolipid , ceramide , glycan , meningioma , mass spectrometry , tandem mass spectrometry , quadrupole time of flight , analytical chemistry (journal) , biochemistry , medicine , apoptosis , surgery , glycoprotein
A strategy combining high‐performance thin layer chromatography ( HPTLC ), laser densitometry, and fully automated chip‐based nanoelectrospray (nano ESI chip) performed on a N ano M ate robot coupled to QTOF‐MS was developed, optimized, and for the first time applied for mapping and structural identification of gangliosides (GGs) extracted and purified from a human angioblastic meningioma specimen. While HPTLC pattern indicated only seven fractions migrating as GM 3, GM 2, GM 1, GD 3, GD 1a (n LD 1, LD 1), GD 1b, GT 1b, and possibly GD 2, due to the high sensitivity, mass accuracy, and ability to ionize minor species in complex mixtures, nano ESI chip‐ QTOF MS was able to discover significantly more GG species than ever reported in meningioma. Thirty‐four distinct glycosphingolipid components of which five asialo, one GM 4, nine GM 3, two GM 2, two GD 3, nine GM 1, and six GD 1 differing in their ceramide compositions were identified. All structures presented long‐chain bases with 18 carbon atoms, while the length of the fatty acid was found to vary from C 11 to C 25. MS screening results indicated also that the diversity of the expressed GM 1 structures is higher than expected in view of the low proportions evidenced by densitometric quantification. Simultaneous fragmentation of meningioma‐associated GM 1 (d18:1/24:1) and GM 1 (d18:1/24:0) by MS / MS using CID confirmed the postulated structures of the ceramide moieties and provided data on the glycan core, which document that for each of the GM 1 (d18:1/24:1) and GM 1 (d18:1/24:0) forms both GM 1a and GM 1b isomers are expressed in the investigated meningioma tissue.