Synthesis of Biocompatible Materials Having Blood-Group Antigenic 01 igosaccharide Chain

用化学方法合成了具有H型抗原性低聚糖非还原端三糖的5-（2-丙烯酰氧乙基氨基羰基）戊基2-乙酰氨基-4,6-0-苄基-2-脱氧-3-0-[3,4,6-三-0-苄基-2-0-(2,3,4-三-0-苄基- α - l- fucopyranosyl)- β -d -半乳糖吡喃基]- β -d -葡萄糖吡喃苷，并与丙烯酰胺或丙烯酸甲酯共聚。合成糖单体在二甲基甲酰胺中以AIBN为引发剂与丙烯酰胺共聚，在苯中以相同的引发剂与丙烯酸甲酯共聚。共聚物组成由进料中单体比例控制，通过核磁共振谱计算共聚物组成。在共聚物中引入含有H型抗原低聚糖的单体单元，其含量为0.005 ~ 0.54。共聚物的数平均分子量在1.8 × 10^4 ~ 8.4 × 10^4之间。在DMF-H_2O的混合溶剂中，通过钯碳催化加氢去除共聚物的保护基团苯基和苄基。用一种酶（GalNAc转移酶）将n -乙酰- d -半乳糖胺转移到共聚物中的半乳糖残基上，显示了GalNAc残基的转移。

A new polymerizable monomer having a nonreducing-terminal trisaccharide of an H type antigenic oligosaccharide was synthesized chemically, that is, 5-(2-acryloyloxyethylaminocarbonyl)pentyl 2-acetamido-4,6-0-benzylidene-2-deoxy-3-0-[3,4,6-tri-0-benzyl-2-0-(2,3,4- tri-0-benzyl-alpha-L-fucopyranosyl)-beta-D-galactopyranosyl]-beta-D-glucopyranoside, and was copolymerized with acrylamide or methyl acrylate. Copolymerization of the synthetic sugar monomer with acrylamide was carried out in dimethylformamide with AIBN as initiator, and copolymerization with methyl acrylate was carried out in benzene with the same initiator. The copolymer composition which was calculated by ^1H-NMR spectroscopy was controlled by the monomer ratio in the feed. The monomeric unit having an H type antigenic oligosaccharide was introduced into the copolymer in a content of 0.005 to 0.54. The number average molecular weight of the copolymer was in the range of 1.8 X 10^4 to 8.4 X 10^4. Benzyl and benzylidene groups, which were the protective groups of the copolymers, were removed by catalytic hydrogenation over palladium-carbon in the mixed solvent of DMF-H_2O. Transfer of N-acetyl-D-galactosamine to the galactose residue in the copolymer by using A enzyme (GalNAc transferase) was attempted, showing the transfer of GalNAc residue.