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

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Author: Sisu, E. · Bosker, W.T.E. · Norde, W. · Slaghek, T.M. · Timmermans, J.W. · Peter-Katalinić, J. · Cohen-Stuart, M.A. · Zamfir, A.D.
Institution: TNO Kwaliteit van Leven
Source:Rapid Communications in Mass Spectrometry, 2, 20, 209-218
Identifier: 239094
doi: doi:10.1002/rcm.2296
Keywords: Nutrition · Food technology · 1,6 hexanediamine · 1,6-diaminohexane · Dextran · Diamine · Maltodextrin · Polysaccharide · Chemistry · Electrospray mass spectrometry · Evaluation · Mass spectrometry · Methodology · Reproducibility · Sensitivity and specificity · Dextrans · Diamines · Polysaccharides · Reproducibility of Results · Sensitivity and Specificity · Spectrometry, Mass, Electrospray Ionization · Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization


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.