采用酶促法合成含半乳糖单体6-O-乙烯基壬二酸-D-吡喃型半乳糖酯(OVZG),采用可逆加成-链断裂转移自由基聚合法(RAFT聚合)将大分子引发剂二聚乙二醇单甲醚甲基丙烯酸甲酯(DEGMA)和OVZG有效结合,制备相对分子质量(简称分子量)分散系数(PDI)较低的温敏性含半乳糖嵌段共聚物PDEGMA-b-POVZG。通过核磁共振氢谱(1 H NMR),傅里叶变换红外光谱(FT-IR),凝胶渗透色谱(GPC)对聚合物结构进行了确认表征。通过紫外-可见光谱(UV-Vis)研究表明,共聚物的低临界溶解温度(LCST)可以通过共聚单体的比例进行调控,当PDEGMA与OVZG的物质的量之比为1∶63时,含糖共聚物的LCST值为33℃。在37℃生理温度下,PDEGMA-b-POVZG可以自组装形成纳米胶束,透射电子显微镜(TEM)显示自组装形成的聚合物胶束是结构均匀、形貌规整的球形,通过动态光散射(DLS)测得纳米微球的粒径约为167nm,该温敏性半乳糖嵌段共聚物在药物载体方面具有潜在的应用前景。
The monomer 6-O-vinyladipoyl-D-glucopyranose( VAG)was synthesized by lipase catalyzed trans-esterification of divinyladipate with D-glucopyranose. A novel double hydrophilic glycopolymer poly( diethyleneglycol methacrylate-co-6-Ovinyladipoyl-D-glucopyranose)( P( DEGMA-co-VAG)) with narrow polydispersity( PDI) and thermosensitivity was prepared by reversible addition-fragmentation chain transfer( RAFT)polymerization. P( DEGMA-co-VAG) was characterized by1 H NMR,FTIR and gel permeation chromatography( GPC). The characterization of UV-visible spectroscopy showed that the micelles from glycopolymer P( DEGMA-co-VAG) were thermo-responsive and the low critical solution temperature( LCST) could be controlled by the molar ratio of monomers. When the molar ratio of DEGMA and VAG was 2∶ 1,the LCST of P( DEGMA-co-VAG) was36 ℃ in aqueous solution,which could form nano micelles in the human body environment. It was found that P( DEGMA-co-VAG)was non-toxic at 0. 1-1 mg / m L concentrations when incubated with pig iliac endothelial cells( PIECs) for 24 h. Thus,the synthesized glycopolymers has great potential as drug delivery carriers.
