Electrospray ionization quadrupole time-of-flight tandem mass spectrometric analysis of hexamethylenediamine-modified maltodextrin and dextran

• Published in: Rapid communications in mass spectrometry Vol. 20; no. 2; pp. 209 - 218
• Main Authors: Sisu, Eugen, Bosker, Wouter T. E., Norde, Willem, Slaghek, Ted M., Timmermans, Johan W., Peter-Katalinić, Jasna, Cohen-Stuart, Martien A., Zamfir, Alina D.
• Format: Journal Article
• Language: English
• Published: Chichester, UK John Wiley & Sons, Ltd 01-01-2006
• Subjects: capillary-zone-electrophoresis; chromatography; copolymers; derivatives; Dextrans - analysis; Dextrans - chemistry; Diamines - analysis; Diamines - chemistry; glycoproteins; oligosaccharides; Polysaccharides - analysis; Polysaccharides - chemistry; Reproducibility of Results; resolution; Sensitivity and Specificity; Spectrometry, Mass, Electrospray Ionization - methods; Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization - methods
• ISSN: 0951-4198; 1097-0231
• DOI: 10.1002/rcm.2296

A combined methodology for obtaining at the preparative scale and characterization by nanoelectrospray ionization (nanoESI) quadrupole time‐of‐flight (QTOF) mass spectrometry (MS) and tandem MS (MS/MS) of linear polysaccharides modified at the reducing end is presented. Two polydisperse maltodextrins (1000 and 3000 Da) and a high molecular weight polydisperse dextran (6000 Da) were coupled with hexamethylenediamine (HMD). The coupling products were analyzed by nanoESI‐QTOF‐MS in the positive ion mode and MS/MS using collision‐induced dissociation (CID) at low energies. In the HMD‐M1000 mixture, the polysaccharide chains containing from 2 to 8 Glc residues were detected, while in HMD‐M3000 we identified a complete series of chains containing from 8 to 21 Glc moieties. The employed ESI conditions enhanced the detection of chains with up to 46 Glc residues in the HMD‐D6000 sample. By optimized MS/MS, HMD‐modified polysaccharides of 3, 4, 5, 12 and 46 degrees of polymerization yielded product ion spectra exhibiting the whole set of Y‐ and B‐fragment ions. The MS structural data were obtained within a few minutes of signal acquisition, with a sample consumption situating the analysis sensitivity in the picomolar range. Copyright © 2005 John Wiley & Sons, Ltd.