文献类型：期刊文献

中文题名：基于Ugi多组分聚合的偶氮苯聚类肽合成与自组装

英文题名：Synthesis and Self-assembly of Azobenzene-Functionalized Polypeptoids Based on Ugi Multicomponent Polymerization

作者：李妙川[1];金圣[1];冯伟胜[1];陶鑫峰[1];林绍梁[1]

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

年份：2025

卷号：56

期号：10

起止页码：1716

中文期刊名：高分子学报

外文期刊名：Acta Polymerica Sinica

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001584552400018)】；北大核心:【北大核心2023】；

基金：国家自然科学基金(基金号52325308);上海市自然科学基金(基金号24ZR1416500)资助。

语种：中文

中文关键词：聚类肽;Ugi反应;偶氮苯;自组装;光响应

外文关键词：Polypeptoids;Ugi reaction;Azobenzene;Self-assembly;Photo-responsiveness

摘要：设计合成了4-异氰基偶氮苯(Azo-NC)单体和4-((2,5,8,11-四氧杂十三烷-13-基)氧基)苯甲醛(EG4-CHO)单体,并以4-氨基丁酸(AA_(4))、5-氨基戊酸(AA_(5))、6-氨基己酸(AA_(6))为氨基酸单体,通过Ugi多组分聚合成功制备了新型主链结构的偶氮苯功能化聚(γ-类肽)、聚(δ-类肽)和聚(ε-类肽),即P(AA_(x)-Azo/EG_(4))(x=4、5和6).通过核磁共振氢谱(^(1)H-NMR)、红外光谱(FTIR)和体积排除色谱(SEC)表征了偶氮苯聚类肽的化学结构、分子量和分子量分布.系统研究了P(AA_(x)-Azo/EG_(4))的自组装行为,利用透射电子显微镜(TEM)对组装体的形貌进行了详细表征,获得了“松针”状和“竹叶”状等形貌的组装体.紫外-可见光谱(UV-Vis)测试表明,随着氨基酸重复单元长度的增加,组装体中偶氮苯基团从H-型排列向J-型排列转变,且光致异构化速率加快.P(AA_(x)-Azo/EG_(4))组装体具有良好的光响应性和温度响应性,“竹叶”形片状组装体在365 nm紫外光照后转变为纺锤形聚集体,在45℃热处理后转变为球形大复合胶束.
Azobenzene-functionalized polypeptoids represent a significant class of photo-responsive smart materials,exhibiting remarkable application potential in biomimetics,medicine,and other fields because of their excellent biocompatibility,remotely controllable structure,and non-contact variable performance.However,reported azobenzene-functionalized polypeptoids are mainly poly(α-peptoid)synthesized by solid-phase synthesis and ring-opening polymerization of N-substituted glycine N-carboxyanhydride(NNCA)or N-substituted glycine N-thiocarboxyanhydride(NNTA).Azobenzene-functionalized polypeptoids with alternative main-chain structures have rarely been explored.In this study,novel azobenzene-functionalized polypeptoids were synthesized through Ugi multicomponent polymerization.First,4-isocyanoazobenzene(Azo-NC)and 4-((2,5,8,11-tetraoxatridecan-13-yl)oxy)benzaldehyde(EG4-CHO)were designed and synthesized,which could endow polypeptoids with photoresponsiveness and thermo-responsiveness.Azo-NC and EG4-CHO were polymerized with 4-aminobutyric acid(AA_(4)),5-aminovaleric acid(AA_(5)),and 6-aminocaproic acid(AA_(6))respectively in trifluoroethanol at 50℃ for 96 h,yielding azobenzene-functionalized poly(γ-peptoid)(P(AA_(4)-Azo/EG4)),poly(δ-peptoid)(P(AA_(5)-Azo/EG_(4))),and poly(ε-peptoid)(P(AA_(6)-Azo/EG_(4)))with high yields(>86%).The chemical structures,molecular weights(MWs),and MW distributions of P(AAx-Azo/EG4)were confirmed using proton nuclear magnetic resonance(^(1)H-NMR)spectroscopy,Fourier transform infrared(FTIR)spectroscopy,and size-exclusion chromatography(SEC).The selfassembly behavior of P(AA_(x)-Azo/EG_(4))in an aqueous solution was systematically investigated,and the resulting morphologies were characterized by TEM.At an initial water At an initial water content of 33%in volume,P(AA_(4)-Azo/EG_(4))formed“pine leaf”-like assemblies,whereas P(AA_(5)-Azo/EG_(4))and P(AA_(6)-Azo/EG_(4))formed“bamboo leaf”-like assemblies,which indicated that aspect ratio of the assemblies decreased with increasing lengths of the amino acid repeat unit.As the initial water content was increased,spherical composite micelles gradually appeared.UV-Vis spectroscopy measurements revealed that P(AA_(x)-Azo/EG_(4))and its assemblies showed excellent photo-isomerization properties.Notably,with longer amino acid repeat units,the azobenzene groups within the assemblies changed from an H-type to a J-type arrangement,accompanied by an accelerated rate of photo-induced trans-to-cis isomerization.The P(AA_(x)-Azo/EG_(4))assemblies exhibited excellent photoresponsiveness and thermo-responsiveness.Specifically,the“bamboo leaf”-like assemblies of P(AA_(6)-Azo/EG_(4))transformed into spindle-shaped aggregates after 6 h irradiation of 365 nm ultraviolet light.The“bamboo leaf”-like assemblies of P(AA_(5)-Azo/EG_(4))reorganized into spherical composite micelles after 4 h heat treatment at 45℃.