三维宏观网络状囊泡薄膜的分级自组装研究  

MACROSCOPIC THREE-DIMENSIONAL SUPRAMOELCULAR NETWORKS THROUGH HIERARCHICAL SELF-ASSEMBLY OF POLYMER VESICLES

作　　者：郭美琼[1] 洪海燕[1] 孙晓毅[1] 周永丰[1] 颜德岳[1] 

机构地区：[1]上海交通大学化学化工学院,上海200240

出　　处：《高分子学报》2008年第4期303-308,共6页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号50503012;20774057;50633010);国家重点基础研究发展计划(973计划;项目号2007CB808000);上海市基础研究重大项目(项目号07DJ14004);上海市重点学科(项目号B202)资助项目

摘　　要：分别合成以疏水性超支化聚醚（HBPO）为核，以亲水性聚环氧乙烷（EO）和聚甲基丙烯酸N，N-二甲氨基乙酯（DMAEMA）为臂的两亲性超支化多臂共聚物HBPO—star—PEO和HBPO—star-PDMAEMA。通过两者在水溶液中的复合自组装制备得到具有pH响应性的巨型聚合物囊泡（1～10μm），并用zeta电位仪，激光共聚焦显微镜及光学显微镜对囊泡的自组装行为进行了研究。结果表明，在等电点以前，复合囊泡始终以单个囊泡形式存在；随着溶液pH的升高，囊泡逐步线型缔合成串珠结构；在更高的pH下，囊泡进一步二次聚集形成具有宏观尺度的三维蜘蛛网状超分子结构，这是一类新的自组装体。Synthesis and supramolecular self-assembly of hyperbranched polymers （HBPs） have received more andmore attention in recent year, and many delicate supramolecuar structures at all scales and dimensions were generated up to now. However, most of the work reported the one-step self-assembly process from HBPs to supramolecular aggregates. Herein, we report a hierarchical self-assembly of HBPs： the polymer first self-assembled into giant polymer vesicles, and then the vesicles further aggregated into macroscopic surpramolecular network. Two kinds of amphiphilic multiarm copolymers with a same hydrophobic hyperbranched poly[3-ethyl-3-（hydroxymethyl）oxetane] （HBPO） core and different hydrophilic poly （ ethylene oxide） （PEO） and poly （2- （dimethylamino） ethyl methacrylate） （DMAEMA） arms were synthesized by a ＂graft from＂ method. The obtained HBPO-star-PEO can self- assemble in water into giant vesicles, and the HBPO-star-PDMAEMA is pH-responsive and can self-assemble in water into large multimolecular micelles. However, when the two polymers were mixed together, they would co- assemble into pH-responsive giant vesicles around 1 - 10 μm in water. The self-assembly behavior of the complex vesicle was studied by zeta potential analyzer, laser scanning confocal microscope （LSCM） and optical microscope.The results show that the complex vesicles were electriferous in the solution, and the iso-electric point （IEP） was 8. 6,which indicated that PDMAEMA chains were located in the shells of the complex vesicles. At the pH below IEP, the complex vesicles were stable and could be suspended randomly in the solution because of the protonization ofPDMAEMA chains. When the solution pH was higher than IEP, the supramolecular structures like pearl necklace and the grape bunch of the vesicles. At an even higher pH, the vesicles aggregated to spider web. It is a novel supramolecular structure and belongs to vesicles gradually aggregated together to form the with the increase of pH due to the de

关 键 词：囊泡 超支化 PH响应 分级自组装 三维网络 

分 类 号：O631[理学—高分子化学]