具有螺线表面的聚肽中空柱的制备与结构  

Preparation and Structure of Polypeptide Hollow Disks with Spiral Nanopattern Surface

作　　者：焦莉萍 刘艳萍 金锐琦 续文恒 蔡春华[1] 林嘉平[1] JIAO Liping;LIU Yanping;JIN Ruiqi;XU Wenheng;CAI Chunhua;LIN Jiaping(Shanghai Key Laboratory of Advanced Polymeric Materials,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学材料科学与工程学院,上海市先进聚合物材料重点实验室,上海200237

出　　处：《功能高分子学报》2022年第6期517-523,共7页Journal of Functional Polymers

基　　金：国家自然科学基金(52073095,51573049)。

摘　　要：通过聚(γ-苄基-L-谷氨酸酯)-b-聚乙二醇(PBLG-b-PEG)嵌段共聚物聚肽链段的部分酸解脱苄基及与肉桂醇的酯化反应,得到聚(γ-苄基-L-谷氨酸酯-co-肉桂基-L-谷氨酸酯)-b-聚乙二醇(P(BLG/CLG)-b-PEG)嵌段共聚物。肉桂醇基团上的C=C双键在紫外光照射下可发生环加成反应。采用溶液自组装方法,以四氢呋喃-N,N-二甲基甲酰胺(THF-DMF)混合溶剂为起始共溶剂,水为选择性溶剂,P(BLG/CLG)-b-PEG嵌段共聚物与聚苯乙烯(PS)均聚物共混自组装,形成了表面带纳米条纹的核壳型粒子,其中疏水均聚物形成球形内核,聚肽嵌段共聚物形成表面纳米条带。通过改变初始有机溶剂性质,调控了表面纳米条纹的分布形式,得到了经线球和螺线球。通过紫外照射将螺线球和经线球表面条纹中的聚肽链段交联,并用THF溶解PS内核,分别制备了具有表面有序纳米条纹图案的中空柱状和贝壳状粒子。采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和原子力显微镜(AFM)等测试方法表征聚集体形貌。研究表明:溶剂溶解可以有效去除交联螺线球和经线球的PS均聚物内核,分别制备得到新颖的纳米条纹图案化中空柱状和贝壳状粒子;这些图案化中空柱状粒子结构稳定,保持了3D结构特征;其内部空间具有良好的填充性能,可以被疏水均聚物填充。Hollow particles have attracted considerable attentions in recent years for their potential in diverse application fields.In this work,polypeptide-based hollow disk-like and conchoidal particles with surface nanostrips were prepared.For the poly(γ-benzyl-L-glutamate)-b-poly(ethylene glycol)(PBLG-b-PEG)block copolymer,through partial deprotection of the benzyl group of the PBLG block and esterification reaction between the carboxyl group and cinnamic alcohol,poly(γ-benzyl-L-glutamate-co-γ-cinnamyl-L-glutamate)-b-poly(ethylene glycol)(P(BLG/CLG)-b-PEG)block copolymers were obtained.The self-assemblies were prepared by a selective precipitation method.P(BLG/CLG)-b-PEG block copolymers and polystyrene(PS)homopolymers were first dissolved in THF-DMF mixture solvent;by adding water to the solution,core-shell particles with nanostrips on the surface were obtained,in which the hydrophobic PS homopolymer formed the spherical core and the P(BLG/CLG)-b-PEG block copolymers formed surface nanostrips.By changing the composition of THF-DMF mixture solvent,the surface patterns can be regulated.Spiral spheres were formed with V(THF)∶V(DMF)of 5∶5 as initial solvent,and meridian spheres were formed with V(THF)∶V(DMF)of 3∶7 as initial solvent.Under UV-irradiation atλ=254 nm,a cycloaddition reaction can occur on the C=C double bond of the cinnamyl group.Therefore,the P(BLG/CLG)blocks in the shell of both the spiral spheres and the meridian spheres were cross-linked.To the solution of the shell-crosslinked spiral spheres and meridian spheres,10-fold of THF was added to remove the PS homopolymers in the core.As a result,hollow nanodisks and hollow conchoidal particles were prepared,and the strip nanopatterns on the surface were retained.The morphology of the particles was characterized by scanning electron microscopy(SEM),transmission electron microscopy(TEM),and atomic force microscopy(AFM).It was found that the PS homopolymers were efficiently removed from the particles by THF solvent soaking,and the nanostrips prop up t

关 键 词：聚肽 自组装 中空柱状粒子 中空贝壳状粒子 表面纳米图案 

分 类 号：O63[理学—高分子化学]