含氟两亲接枝共聚物的制备及其与牛血清蛋白作用的研究  

SYNTHESIS OF AMPHIPHILIC GRAFT FLUORO-COPOLYMERS AND THEIR INTERACTION WITH BOVINE SERUM ALBUMIN

作　　者：熊圣东[1] 李玲[1] 吴水林[2,1] 易昌凤[2,1] 徐祖顺[2,1] 

机构地区：[1]湖北大学材料科学与工程学院,武汉430062 [2]湖北大学有机功能分子与应用教育部重点实验室,武汉430062

出　　处：《高分子学报》2010年第2期149-155,共7页Acta Polymerica Sinica

基　　金：湖北省杰出人才基金资助项目(基金号2004ABB003);"十一五"国家支撑计划(项目号2008BAC32B03)资助项目

摘　　要：用端基反应法合成了对乙烯基苄基的聚乙二醇大分子单体,将该大分子单体与甲基丙烯酸六氟丁酯共聚,合成了一种含氟两亲接枝共聚物.利用1H-NMR1、9F-NMR、GPC对大分子单体和两亲接枝共聚物进行了表征.表面张力法测定了两亲接枝共聚物的临界胶束浓度,发现随着共聚物中含氟链段含量的增加,其临界胶束浓度降低.采用荧光光谱研究了含氟两亲接枝共聚物与牛血清蛋白(BSA)的相互作用,结果表明由于含氟链段疏水力的作用,含氟两亲接枝共聚物能与牛血清蛋白发生相互作用使其荧光增强,随着含氟两亲接枝共聚物浓度和共聚物中含氟链段含量的增加,荧光增强幅度加大.通过透射电子显微镜(TEM)和激光光散射粒度仪(PCS)测试发现,当BSA加入到含氟两亲接枝共聚物的胶束溶液后,所得胶束的粒径和粒径分布变大,共聚物胶束由规整的实心核壳结构变为囊泡状核壳结构.A series of amphiphilic graft copolymers PHFMA-g-PEG comprising of poly（hexafluorobutyl methacrylate）（PHFMA） backbones and poly（ethylene glycol）（PEG） side chains were synthesized by copolymerization of HFMA and an SPEG macromonomer with a p-vinylbenzyl end group.The SPEG macromonomer was synthesized by reaction of PEG with p-chloromethylstyrene in THF in the presence of NaH.The resultant macromonomer and amphiphilic graft copolymers were characterized by^1H-NMR,^19F-NMR and GPC.The HFMA contents in the graft copolymers were calculated by the（—OCH2—CF2—） protons（δ = 4.19） for HFMA and（CH3O—） proton （δ = 3.38） for SPEG macromonomers from^1H-NMR spectra.The critical micelle concentration（CMC） of amphiphilic graft copolymers was measured by surface tension technique,and it showed that the CMC decreased with the increase of HFMA content in the graft copolymers.The interactions between PHFMA-g-PEG and bovine serum albumin（BSA） were studied by fluorescence spectroscopy,photon correlation spectroscopy（PCS） and transmission electron microscopy（TEM）.The fluorescence spectrum showed that the fluorescence intensity of BSA increased in PHFMA-g-PEG/BSA solution driven by hydrophobic interactions of fluorinated segments,with increasing ratio of HFMA in PHFMA-g-PEG and increasing concentration of PHFMA-g-PEG,the fluorescence emission intensity of BSA also increased.PCS showed that when BSA was added into PEG-F39 aqueous solution,the hydrodynamic diameters and distribution of micelles were increased.TEM micrographs showed that PHFMA-g-PEG mainly formed core-shell structure micelles,when BSA was added,micelles changed into vesicle like core-shell structures.This study may suggest that PHFMA-g-PEG is a potential copolymer for loading proteins or other hydrophilic bioactive drugs.

关 键 词：含氟聚合物 两亲接枝共聚物 牛血清蛋白 荧光光谱 胶束 

分 类 号：R943[医药卫生—药剂学] R96[医药卫生—药学]