Electrospray ionization quadrupole time-of-flight tandem mass spectrometric analysis of hexamethylenediamine-modified maltodextrin and dextran.
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.
Sisu
Eugen
E
Department of Biochemistry, University of Medicine and Pharmacy, RO-1900 Timişoara, Romania.
Bosker
Wouter T E
WT
Norde
Willem
W
Slaghek
Ted M
TM
Timmermans
Johan W
JW
Peter-Katalinić
Jasna
J
Cohen-Stuart
Martien A
MA
Zamfir
Alina D
AD
D003911:Dextrans / Q000032:analysis* / Q000737:chemistry*; D003959:Diamines / Q000032:analysis / Q000737:chemistry*; D011134:Polysaccharides / Q000032:analysis* / Q000737:chemistry*; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / Q000379:methods*
D003911:Dextrans; D003959:Diamines; D011134:Polysaccharides; C008315:maltodextrin; C007297:1,6-diaminohexane