具有“反应增强中间体活性”机制的CuAAC点击反应结合收敛法超快制备核-壳结构树形大分子  

Ultrafast Synthesis of Core-shell Dendrimers by CuAAC Click Reaction with“Reaction-enhanced Reactivity of Intermediates”Mechanism via a Convergent Strategy

作　　者：蒋希晗 周英庆 游世超 殷秀哲 侯王蒙 石毅 陈永明 Xi-han Jiang;Ying-qing Zhou;Shi-chao You;Xiu-zhe Yin;Wang-meng Hou;Yi Shi;Yong-ming Chen(School of Materials Science and Engineering,Key Laboratory of Polymeric Composite Materials and Functional Materials of Ministry of Education,Sun Yat-sen University,Guangzhou 510275)

机构地区：[1]中山大学材料科学与工程学院聚合物复合材料及功能材料教育部重点实验室,广州510275

出　　处：《高分子学报》2025年第4期575-589,共15页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号22371313,22071271);广东省自然科学基金(基金号2024A1515011133)资助.

摘　　要：树形大分子(dendrimer)是一类具有高度支化和精确结构的三维球形单分子纳米材料,实现快速、高效合成高代数树形大分子是高分子合成领域的研究难点.本研究利用具有“反应增强中间体活性(RERI)”机制的铜催化叠氮-炔基环加成反应(CuAAC)反应,开发了一种快速、高效制备树形大分子的新方法.该方法首先设计合成了一种具有1,3-三叠氮外围基团的多叠氮功能性树形分子“核”(C-9N_(3)和C-27N_(3))和一系列焦点为炔基的树形分子“壳”(ay-dendron),并结合收敛法制备核-壳结构树形大分子.C-9N_(3)和C-27N_(3)树形分子外围的1,3-三叠氮基团具有RERI效应,可以充分克服空间位阻,在ay-dendron稍过量(1.2 eq.)的情况下即可将叠氮基团定量反应.反应动力学表明:该CuAAC反应可以在几分钟内反应完全,超快制备了一系列4-7代核-壳结构树形大分子.通过核磁共振波谱(NMR)、体积排除色谱(SEC)、飞行时间质谱(MALDI-TOF)、动态光散射(DLS)和原子力显微镜(AFM)等手段对树形大分子的化学组成、分子结构、形貌和尺寸进行了系统的表征.该方法不仅可以实现超快、精准制备树形大分子,还可以通过灵活调控“核”与“壳”的化学结构,实现树形大分子的结构调控和功能化.Dendrimer is a type of three-dimensional and spherical unimolecular nanomaterials with highly branched and precise architecture,while the rapid and efficient synthesis of high-generation dendrimer has been challenging in the field of polymer chemistry.Herein,we reported a new approach for the rapid and efficient preparation of dendrimers by using the copper-catalyzed azide-alkyne cycloaddition(CuAAC)with reaction-enhanced reactivity of intermediates(RERI)mechanism.In this approach,two multi-azide functionalized molecules(C-9N_(3)and C-27N_(3))with 1,3-triazide terminal groups and a series of dendrons with alkynyl focal point(ay-dendron)were first synthesized as the core and shell,respectively,for preparing core-shell dendrimers via a convergent strategy.The C-9N_(3)and C-27N_(3)molecules with 1,3-triazide structure are capable of RERI effect,which could greatly overcome the steric effect and allow the quantitative coverage of the azide groups in the presence of a slight excess of ay-dendron(1.2 eq.).The kinetics indicated that the CuAAC reaction could finish in minutes,promoting the preparation of a series of 4-7 generation core-shell dendrimers with ultrafast rates.The chemical composition,molecular structure,morphology and size of the resultant core-shell dendrimers were systematically characterized by nuclear magnetic resonance(NMR),size exclusion chromatography(SEC),matrix assisted laser desorption ionization time of flight mass spectrometry(MALDI-TOF MS),dynamic light scattering(DLS)and atomic force microscopy(AFM).This approach can be not only used for the ultrafast preparation of dendrimers with precise architectures,but also beneficial for the structural regulation and functionalization of dendrimers by tailoring the chemical structures of the“core”and“shell”.

关 键 词：树形大分子 铜催化叠氮-炔基环加成反应 反应增强中间体活性 收敛法 

分 类 号：O631[理学—高分子化学] O631.3[理学—化学]