Chondroitin 4-sulfate: comparison of the structures of the potassium and sodium salts.

Analysis of the X-ray diffraction pattern from an oriented, polycrystalline fiber of a potassium chondroitin 4-sulfate proteoglycan shows that the polysaccharide chains have a left-handed 3-fold helical secondary structure stabilized by intra- and intermolecular hydrogen bonds. Two antiparallel chains pass through each trigonal unit cell, which has dimensions a = b = 1.385 nm, c = 2.776 nm and space group symmetry P3(2)21. The cations and water molecules in the crystals are not all periodic and only one potassium ion and four water molecules per disaccharide were located by difference Fourier methods. Sodium chondroitin 4-sulfate forms an analogous structure with polyanions of similar geometry. However, the packing arrangements in the two salts are quite different, presumably because of the different co-ordination preference of K+ and Na+. Thus the relatively small differences between these two cations are greatly amplified by the idiosyncratic polymer networks they promote.