分别以叠氮丙胺和丙炔胺为引发剂,采用氨基酸环内酸酐开环聚合法(NCA-ROP),引发L-谷氨酸-γ-苄酯-N-羧基-环内酸酐和L-谷氨酸-γ-氯乙醇酯-N-羧基-环内酸酐聚合得到链端基为叠氮基的聚(L-谷氨酸-γ-苄酯)(PBLG)和链端基为炔基的聚(L-谷氨酸-γ-氯乙醇酯)(PCELG)均聚物.联合点击化学法(click chemistry)制备了一系列聚(L-谷氨酸-γ-苄酯)-b-聚(L-谷氨酸-γ-氯乙醇酯)(PBLG-b-PCELG),再通过对嵌段共聚物侧基氯进行化学修饰,将二代的甲基烷氧醚类亲水性树形枝化分子(G2)接枝到侧链上,形成一系列树形支化分子接枝聚肽双亲性嵌段共聚物,通过核磁(NMR)、红外光谱(IR)和凝胶渗透色谱(GPC)对其化学结构进行了表征,并采用紫外-可见光谱(UV-Vis)研究了聚合物结构及其溶液浓度对其温敏行为的影响规律.
A series of novel amphiphilic block copolypepides bearing the hydrophilic second-generation(G2) dendritic ether grafts denoted as PBLG-b-(PELG-g-G2) were designed and synthesized by a combination of ring-opening polymerization and click chemistry. First, azido-terminated poly(γ-benzyl-L-glutamate)s(PBLG) with different molecular weights were synthesized by ring-opening polymerization of γ-benzyl-L-glutamate-Ncarboxyanhydride(BLG-NCA) in DMF at room temperature using 3-azido-1-propanamine as initiator and alkyne-terminated poly(γ-2-chloroethyl-L-glutamate)(PCELG) was synthesized by ring-opening polymerization of γ-2-chloroethyl-L-glutamate-N-carboxyanhydride in DMF at room temperature using propargylamine as initiator. The block copolypeptides poly(γ-benzyl-L-glutamate)-block-poly(γ-2-chloroethyl-L-glutamate)(PBLGb-PCELG) bearing chloride side groups were synthesized by click chemistry with high efficiency from the azido-terminated PBLG and the alkyne-terminated PCELG in the presence of Cu Br and 1,1,4,7,7-pentamethyldiethylenetriamine(PMDETA) catalyst system. Then, PBLG-b-PCELG containing chloride side groups was subsequently reacted with excessive sodium azide in DMF to yield a block copolypeptide bearing azido side groups denoted as PBLG-b-(PNELG). The hydrophilic second-generation(G2) dendritic ethers were finally grafted to the side chains of the block copolypeptides PBLG-b-(PNELG) by click chemistry in the presence of Cu Br/PMDETA catalyst system and the amphiphilic dendronized block copolypepides PBLG-b-(PELG-g-G2) were successfully synthesized. Their molecular structures were further characterized by1H-NMR, FTIR and GPC. The thermo-responsive behaviour of PBLG-b-(PELG-g-G2) in water were investigated using UV-Vis and the results showed that the values of the cloud point temperatures(Tcp) of PBLG-b-(PELG-gG2) became lower with the length increase of the hydrophobic PBLG chain segment. This was explained by the fact that the amphip