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

用化学方法合成了一种含有H型抗原寡糖的非还原末端三糖的新型可聚合单体5-(2-丙烯酰氧乙基氨基甲酰基)戊基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，，并与丙烯酰胺或丙烯酸甲酯进行了共聚反应。合成的糖单体与丙烯酰胺在二甲基甲酰胺中以AIBN为引发剂进行共聚，与丙烯酸甲酯在相同引发剂的苯中进行共聚。通过1H-核磁共振波谱计算得到的共聚物组成受原料中单体比例的控制。具有H型抗原寡糖的单体单元被引入到共聚物中，含量为0.005-0.54.该共聚物的数均相对分子质量在1.8×10~(-4)~8.4×10~(-4)之间。在DMF-H_2O混合溶剂中，钯-碳催化加氢脱除了共聚物的保护基团--苄基和亚苄基。尝试了用A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，证明了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.