Sulfated oligosaccharides isolated from the deamination products of heparins.

Porcine heparin, whale heparin, and a solvolyzed porcine heparin were deaminated, and sulfated oligosaccharides, compounds 3f, 4f, 3s, 4s, 5, 6, 7s, 10, 11f, 11s, and 13 were isolated from the deamination products by Dowex 1 x 2 (Cl- form) column chromatography and high voltage paper electrophoresis and/or gel filtration on Sephadex G-25. Based on the results of chemical, 1H and 13C NMR spectral analyses, and of Smith degradation, together with previous observations, the structures of these sulfated oligosaccharides are proposed to be as follows: compound 3f, IdUA(2S)alpha 1 leads to GlcNAc alpha 1 leads to 4GlcUA; compound 4f, IdUA alpha 1 leads to 4GlcNAc(6S) alpha 1 leads to 4GlcUA; compound 3s, IdUA(2S) alpha 1 leads to 4GlcNAc alpha 1 leads to 4 GlcUA beta 1 leads to 4a Man; compound 4s, IdUA alpha 1 leads to 4Glc NAc(6S) alpha 1 leads to 4 GlcUA beta 1 leads to 4aMan; compound 5, IdUA(2S) alpha 1 leads to 4aMan; compound 6, GlcUA beta 1 leads to aMan(6S); compound 7s, IdUA alpha 1 leads to 4aMan(6S); compound 10, IdUA(2S)alpha 1 leads 4GlcNAc(6S)alpha 1 leads to 4 GlcUA beta 1 leads to 4aMan; compound 11f, IdUA(2S) alpha 1 leads 4GlcNAc alpha 1 leads to 4GlcUA beta 1 leads to 4a Man (6S); compound 11s, IdUA alpha 1 leads to GlcNAc(6S) alpha 1 leads to 4GlcUA beta 1 leads to 4aMan(6S); compound 13, IdUA(2S) alpha 1 leads to 4aMan(6S). For ths sulfated disaccharides, the same results as those reported in our previous papers were obtained. On the other hand, the proportion of total sulfated tri- and tetrasaccharides from whale heparin was 1.9 times higher than that from porcine heparine, reflecting a higher content of GlcNAc in the former. Also, the yields of compound 11s from these two heparins were comparable to their anticoagulant activities. In addition, certain 2-O-sulfates on IdUA flanked with GlcNS(6X) (X=H or S) in the heparin molecule are suggested to be important for the activity.