文献类型：期刊文献

中文题名：两亲刚性三嵌段聚多肽的合成及其自组装行为

英文题名：Synthesis and Self-assembly of Amphiphilic Rigid Triblock Copolypeptides

作者：陈智[1];姚远[1];唐颂超[1]

机构：[1]华东理工大学材料科学与工程学院,上海200237

年份：2018

卷号：31

期号：3

起止页码：225

中文期刊名：功能高分子学报

外文期刊名：Journal of Functional Polymers

收录：CSTPCD;;北大核心:【北大核心2017】；CSCD:【CSCD2017_2018】；

基金：国家自然科学基金(51573088)

语种：中文

中文关键词：三嵌段聚多肽;α-螺旋;刚性;自组装

外文关键词：triblock copolypeptides;a-helix;rigid;sef-assembly

摘要：通过胱胺三甲基硅氮烷(N-TMS)引发N-羧基内酸苷(NCA)开环聚合,合成了2种两亲刚性三嵌段聚多肽聚(L-赖氨酸-ε-端甲基二缩乙二醇酰胺)-b-聚(L-谷氨酸-γ-苄酯)-b-聚(L-赖氨酸-ε-端甲基二缩乙二醇酰胺)(P[Lys-(EG)_2]-b-PBLG-b-P[Lys-(EG)_2])和聚(L-谷氨酸-γ-苄酯)-b-聚(L-赖氨酸-端甲基二缩乙二醇酰胺)-b-聚(L-谷氨酸-γ-苄酯)(PBLG-b-P[Lys-(EG)_2]-bPBLG),并用其在N,N-二甲基甲酰胺(DMF)-水的混合溶液中制备了三嵌段聚多肽的自组装体。采用核磁共振氢谱(1 H-NMR)和凝胶渗透色谱(GPC)表征了三嵌段聚多肽的结构,通过透射电子显微镜(TEM)研究了三嵌段聚多肽在混合溶液中的自组装行为。结果表明:通过N-TMS引发NCA开环聚合得到的三嵌段聚多肽的分子量与其理论值基本一致,且分子量分布窄;聚多肽在DMF-水的混合溶液中分别形成了球状胶束、大复合胶束、棒状大复合胶束等组装体;其自组装行为与特殊的全刚性嵌段结构有关。
Triblock copolypeptides poly（L-lysine-Nε-2-[2-（2-methoxyethoxy）ethoxy]acetyl）-b-poly（Lglutamate-γ-benzyl）-b-poly（L-lysine-Nε-2-[2-（2-methoxyethoxy）ethoxy]acetyl）（P[Lys-（EG）2]-b-PBLGb-P[Lys-（EG）2]）and poly（L-glutamate-γ-benzyl）-b-poly（L-lysine-Nε-2-[2-（2-methoxyethoxy）ethoxy]acetyl）-b-poly（L-glutamate-γ-benzyl）（PBLG-b-P [Lys-（EG）2]-b-PBLG） were synthesized via N-carboxyanhydride（NCA）ring opening polymerization using N,N′-（disulfanediylbis（ethane-2,1-diyl））bis（1,1,1-trimethylsilanamine）（N-TMS）as the initiator.The hydrophilic block poly（L-lysine-Nε-2-[2-（2-methoxyethoxy）ethoxy]acetyl）（P[Lys-（EG）2]）and hydrophobic block poly（L-glutamate-γ-benzyl）（PBLG）maintained stableα-helix conformation in water and N,N-dimethylformamide（DMF）mixture.The a-helices were in rigid rod-like constellation and inflexible in self-assembly. Therefore,the amphiphilic copolypeptides were expected to show distinct self-assembly behavior in selective solutions.Herein,DMF-water mixture was adopted as the media and copolypeptides were allowed self-assembly through traditional strategies.1 H-Nuclear Magnetic Resonance（^1H-NMR） and Gel Permeation Chromatography（GPC）confirmed the formation of desired copolypeptides.The assemblies were observed with Transmission Electron Microscope（TEM）.Results demonstrated that the obtained polypeptides showed controllable molecular weights（Mw）and narrow polydispersity index（PDI）.P[Lys-（EG）2]-bPBLG-b-P[Lys-（EG）2]self-assembled into small micelles while containing long hydrophilic P[Lys-（EG）2]blocks,otherwise only spherical and rod-like large compound micelles with different dimensions were observed.In contrast,PBLG-b-P[Lys-（EG）2]-b-PBLG self-assembled into larger micelles while containing long hydrophilic blocks,which showed unstableness while the hydrophobic blocks turned longer.The unusual all-rigid skeletons and the confined conformation of the amphiphilic triblock copolypeptides might be the reason of these results.