Abstract
Two simple methods for dissolving salts of acid glycosaminoglycans with inorganic cations (e.g. Li+ and Na+) in dry dimethyl sulphoxide are described. Complete n.m.r. spectra of, e.g., Na+ and Li+ salts of chondroitin sulphate and keratan sulphate were obtained on these solutions. In [2H6]dimethyl sulphoxide the NH resonance of 2-acetamido-2-deoxy hexosides is in the range 7.2-8.0 delta, but is downfield (8.3-9.3 delta) when the NH is H-bonded to -CO2-. Heparan sulphate shows two NH resonances, of which one (at 8.3 delta) is probably indicative of H-bonding. Space-filling models show that a very close approach of NH to -CO2- across the alpha-glucosaminidic bond is possible, and a solution configuration for heparan sulphate is proposed. The n.m.r. results are entirely compatible with interpretations of periodate-oxidation kinetics, based on H-bonded secondary structures present in hyaluronate and chondroitin sulphates, but not in dermatan (or keratan) sulphate.
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- Atkins E. D., Laurent T. C. X-ray-diffraction patterns from chondroitin 4-sulphate, dermatan sulphate and heparan sulphate. Biochem J. 1973 Jul;133(3):605–606. doi: 10.1042/bj1330605. [DOI] [PMC free article] [PubMed] [Google Scholar]
- DAVIDSON E., HOFFMAN P., LINKER A., MEYER K. The acid mucopolysaccharides of connective tissue. Biochim Biophys Acta. 1956 Sep;21(3):506–518. doi: 10.1016/0006-3002(56)90188-3. [DOI] [PubMed] [Google Scholar]
- Fransson L. A. Interaction between dermatan sulphate chains. I. Affinity chromatography of copolymeric galactosaminioglycans on dermatan sulphate-substituted agarose. Biochim Biophys Acta. 1976 Jun 23;437(1):106–115. doi: 10.1016/0304-4165(76)90351-2. [DOI] [PubMed] [Google Scholar]
- Fransson L. A., Nieduszynski L. A., Sheehan J. K. Interaction between heparan sulphate chains. I. A gel chromatographic, light-scattering and structural study of aggregating and non-aggregating chains. Biochim Biophys Acta. 1980 Jun 19;630(2):287–300. doi: 10.1016/0304-4165(80)90433-x. [DOI] [PubMed] [Google Scholar]
- Linker A., Hovingh P. The heparitin sulfates (heparan sulfates). Carbohydr Res. 1973 Jul;29(1):41–62. doi: 10.1016/s0008-6215(00)82069-8. [DOI] [PubMed] [Google Scholar]
- SCOTT J. E. Aliphatic ammonium salts in the assay of acidic polysaccharides from tissues. Methods Biochem Anal. 1960;8:145–197. doi: 10.1002/9780470110249.ch4. [DOI] [PubMed] [Google Scholar]
- Scott J. E., Heatley F. 1H nuclear-magnetic-resonance spectra of the methyl group of the acetamido moiety and the structure of acid glycosaminoglycans in solution. Biochem J. 1979 Aug 1;181(2):445–449. doi: 10.1042/bj1810445. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Scott J. E., Heatley F., Moorcroft D., Olavesen A. H. Secondary structures of hyaluronate and chondroitin sulphates. A 1H n.m.r. study of NH signals in dimethyl sulphoxide solution. Biochem J. 1981 Dec 1;199(3):829–832. doi: 10.1042/bj1990829. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Scott J. E., Tigwell M. J. Periodate oxidation and the shapes of glycosaminoglycuronans in solution. Biochem J. 1978 Jul 1;173(1):103–114. doi: 10.1042/bj1730103. [DOI] [PMC free article] [PubMed] [Google Scholar]