具有可见光响应聚合物纳米粒子的制备及性能研究  

Preparation and Characterization of Visible Light-responsive Polymer Nanoparticles

作　　者：邓飞 刘勇 马如江[1] 马飞贺 史林启[1] Fei Deng;Yong Liu;Ru-jiang Ma;Fei-he Ma;Lin-qi Shi(Institute of Polymer Chemistry,College of Chemistry,Nankai University,Tianjin 300071;School of Materials Science and Engineering,Tiangong University,Tianjin 300387;Wenzhou Institute,University of Chinese Academy of Sciences,Wenzhou 325001)

机构地区：[1]南开大学化学学院高分子化学研究所,天津300071 [2]天津工业大学材料科学与工程学院,天津300387 [3]中国科学院大学温州研究院,温州325001

出　　处：《高分子学报》2023年第5期665-674,共10页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号51933006,52103180)资助项目.

摘　　要：利用可见光响应供体-受体Stenhouse加合物(DASAs)设计并制备了2种表面含有可见光响应单元的聚合物纳米粒子,并对纳米粒子的光响应性进行了研究.首先合成了修饰DASA分子的聚合物PGMD,研究结果表明PGMD可溶于与水互溶的有机溶剂(如DMSO)中并具有良好的光响应性,PGMD链段可在可见光刺激下响应为亲水状态.因此,含有PGMD链段的嵌段共聚物PCL-b-PGMD可在水中自组装形成胶束,并能与PCL-b-PEG在水中共组装形成复合壳层胶束,但PGMD链段在水中无法可逆响应为疏水状态.为获得具有可逆响应性的聚合物纳米粒子,利用硅烷偶联剂水解修饰的方法得到表面含有疏水三烯状态DASA分子与亲水PEG短链的复合壳层二氧化硅纳米粒子,实验结果表明复合壳层二氧化硅纳米粒子在水环境中有良好的分散稳定性,并且表面修饰的DASA分子仍具有良好的响应性.本研究为设计表面性质可调的响应性聚合物纳米粒子提供了新的设计思路.In this report,we prepared two kinds of polymeric nanoparticles with visible light-responsive units on the surface by using visible light-responsive donor-acceptor Stenhouse adducts(DASAs)and studied their light responsiveness.First,we synthesized the polymer of PGMD modified with DASA molecule.The result indicates that PGMD is soluble in water-miscible organic solvents(such as DMSO)and it can convert to hydrophilic state under visible light irradiation.Therefore,the block copolymer PCL-b-PGMD with PGMD segment can selfassemble to form micelles in water,and it can co-assemble with PCL-b-PEG to form mixed-shell micelles(MSPMs)in water.However,the polymer segment PGMD modified with DASA molecules on the surface of MSPMs cannot be switched to the hydrophobic state reversibly.In order to obtain the polymer nanoparticles with reversible response,we prepared the mixed-shell silica nanoparticles with hydrophobic triene state DASA molecules and hydrophilic PEG short chains on the surface,and the mixed-shell silica nanoparticles were prepared through the silane coupling agent hydrolysis modification method.The result demonstrates that the mixed-shell silica nanoparticles can be stably dispersed in water,and the DASA molecules modified on the surface of the mixedshell silica nanoparticles still retain its great responsiveness.This work provides a great idea for designing responsive polymer nanoparticles with tunable property surface.

关 键 词：可见光响应 复合胶束 聚合物纳米粒子 供体-受体Stenhouse 加合物 

分 类 号：TB383.1[一般工业技术—材料科学与工程]