Detection of the 1H and 15N NMR resonances of sulfamate groups in aqueous solution: A new tool for heparin and heparan sulfate characterization

Abstract

Sulfamate (NHSO3-) groups are critically important structural elements of the glycosaminoglycans heparin and heparan sulfate (HS). Experimental conditions are presented for detection of the sulfamate 1H NMR resonances in aqueous solution. NMR spectra reported for N-sulfoglucosamine (GlcNS) and the synthetic pentasaccharide drug fondaparinux demonstrate the broad utility of the sulfamate group 1H chemical shifts to reflect differences in molecular structure. The sulfamate protons also provide an efficient route for detection of 15N chemical shifts through proton-nitrogen correlations measured with the heteronuclear single quantum coherence (HSQC) experiment. The HSQC spectra of GlcNS, fondaparinux, and the low-molecular weight heparin enoxaparin illustrate the power of the 1H and 15N chemical shifts of the sulfamate NH groups for the structural characterization of heparin and HS. © 2011 American Chemical Society.