Detection of the ~(1)H and ~(15)N NMR Resonances of Sulfamate Groups in Aqueous Solution: A New Tool for Heparin and Heparan Sulfate Characterization

摘要

Sulfamate (NHSO_(3)~(-)) groups are critically important structural elements of the glycosaminoglycans heparin and heparan sulfate (HS). Experimental conditions are presented for detection of the sulfamate ~(1)H 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 ~(1)H chemical shifts to reflect differences in molecular structure. The sulfamate protons also provide an efficient route for detection of ~(15)N 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 ~(1)H and ~(15)N chemical shifts of the sulfamate NH groups for the structural characterization of heparin and HS.