Kosakai M, Yosizawa Z
J Biochem. 1981 Jun;89(6):1933-44. doi: 10.1093/oxfordjournals.jbchem.a133395.
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.
对猪肝素、鲸肝素和一种溶剂分解的猪肝素进行脱氨处理，然后通过Dowex 1×2（Cl-型）柱色谱法、高压纸电泳和/或Sephadex G-25凝胶过滤，从脱氨产物中分离出硫酸化寡糖，即化合物3f、4f、3s、4s、5、6、7s、10、11f、11s和13。基于化学分析、1H和13C NMR光谱分析以及Smith降解的结果，并结合先前的观察结果，提出这些硫酸化寡糖的结构如下：化合物3f，IdUA(2S)α1→GlcNAcα1→4GlcUA；化合物4f，IdUAα1→4GlcNAc(6S)α1→4GlcUA；化合物3s，IdUA(2S)α1→4GlcNAcα1→4GlcUAβ1→4aMan；化合物4s，IdUAα1→4GlcNAc(6S)α1→4GlcUAβ1→4aMan；化合物5，IdUA(2S)α1→4aMan；化合物6，GlcUAβ1→aMan(6S)；化合物7s，IdUAα1→4aMan(6S)；化合物10，IdUA(2S)α1→4GlcNAc(6S)α1→4GlcUAβ1→4aMan；化合物11f，IdUA(2S)α1→4GlcNAcα1→4GlcUAβ1→4aMan(6S)；化合物11s，IdUAα1→GlcNAc(6S)α1→4GlcUAβ1→4aMan(6S)；化合物13，IdUA(2S)α1→4aMan(6S)。对于硫酸化二糖，得到了与我们先前论文中报道的相同结果。另一方面，鲸肝素中总硫酸化三糖和四糖的比例比猪肝素中的高1.9倍，这反映出前者中GlcNAc的含量更高。此外，这两种肝素中化合物11s的产率与其抗凝活性相当。另外，肝素分子中IdUA上某些与GlcNS(6X)（X = H或S）相邻的2-O-硫酸盐被认为对活性很重要。
