Premium
Polysulfated Carbohydrates Analyzed as Ion‐paired Complexes with Basic Peptides and Proteins Using Electrospray Negative Ionization Mass Spectrometry
Author(s) -
Siegel Marshall M.,
Tabei Keiko,
Kagan Michael Z.,
Vlahov Ioncho R.,
Hileman Ronald E.,
Linhardt Robert J.
Publication year - 1997
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/(sici)1096-9888(199707)32:7<760::aid-jms529>3.0.co;2-r
Subject(s) - chemistry , electrospray ionization , chromatography , mass spectrometry , protein mass spectrometry , extractive electrospray ionization , electrospray , sample preparation in mass spectrometry , ion , electrospray mass spectrometry , organic chemistry
Electrospray ionization mass spectrometry was used in the negative ion mode to anlayze complexes of sucrose octasulfate, sucrose heptasulfate and sulfated α‐, β‐ and γ‐cyclodextrins with synthetically prepared basic peptides, the basic protein ubiquitin and polyamines. The spectra presented demonstrate that complexes with these basic molecules facilitate the analysis of these polysulfated oligosaccharides. Stable (1:1) complexes result from the ion pairing between the protonated basic arginine and lysine residues of the peptide and the anionic sulfate groups of the polysulfated oligosaccharides. Fragmentation of the polysulfated oligosaccharides resulting in the loss of SO 3 could be suppressed by controlling the experimental conditions, such as the nozzle–skimmer voltage, used to obtain the spectra. In the absence of fragmentation, it was possible to obtain data on the purity of sucrose octasulfate and sucrose heptasulfate as well as the distribution of the sulfated cyclodextrins. The confounding presence of sodium counter‐ions is also eliminated using this method. Complete chemical sulfation of oligosaccharides is difficult to achieve. Thus, data on sample purity are essential for the characterization of sulfated oligosaccharides used as pharmaceutical agents. © 1997 by John Wiley & Sons, Ltd.