带有多可点击正交基团的阳离子两亲嵌段共聚物的组装：RAFT-PISA和水中的点击反应

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal Pub Date : 2025-06-06 DOI:10.1016/j.eurpolymj.2025.114062

Floriane Isselin, Laurent Fontaine, Sandie Piogé, Sagrario Pascual

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引用次数: 0

摘要

我们报道了一步水RAFT聚合诱导自组装（RAFT- pisa）策略，用于合成具有正交可点击端基的两亲性嵌段共聚物纳米结构。该方法采用聚低聚（乙二醇）甲基丙烯酸甲酯（POEGMA）宏观raft试剂的等摩尔混合物，在α-链末端用烯丙基、丙炔基或降冰片烯基基团功能化。这些混合的宏观raft剂与2-（甲基丙烯酰氧基）-N，N，N-三甲基乙基六氟磷酸铵（METAPF6）进行链扩展，生成POEGMA-b-PMETAPF6嵌段共聚物，这些共聚物在水中自组装成稳定的纳米级结构。所得到的组装体显示出表面暴露的可点击基团，与硫醇和铜催化的叠氮化物-炔环加成（CuAAC）反应兼容。序列聚合后修饰证实了在水介质中的正交反应性，通过1H NMR谱监测。该方法为嵌段共聚物组件的模块化和位点选择性功能化提供了一个通用平台，并代表了多功能纳米材料在生物偶联，药物输送和先进材料工程中的应用开发的有价值的工具。

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Assemblies of cationic amphiphilic block copolymers bearing multi-clickable orthogonal groups: RAFT-PISA and click reactions in water

We report a one-step aqueous RAFT polymerization-induced self-assembly (RAFT-PISA) strategy for the synthesis of amphiphilic block copolymer nanostructures bearing orthogonal clickable end-groups. This approach employs equimolar mixtures of poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) macro-RAFT agents functionalized with allyl, propargyl, or norbornenyl moieties at the α-chain end. These mixed macro-RAFT agents were chain-extended with 2-(methacryloyloxy)-N,N,N-trimethylethanammonium hexafluorophosphate (METAPF₆), yielding POEGMA-b-PMETAPF₆ block copolymers that self-assembled into stable nanoscale structures in water. The resulting assemblies displayed surface-exposed clickable groups compatible with thiol-ene and copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions. Sequential post-polymerization modifications confirmed orthogonal reactivity in aqueous media, as monitored by ¹H NMR spectroscopy. This method provides a versatile platform for the modular and site-selective functionalization of block copolymer assemblies and represents a valuable tool for the development of multifunctional nanomaterials for applications in bioconjugation, drug delivery, and advanced materials engineering.

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来源期刊

European Polymer Journal 化学-高分子科学

CiteScore

9.90

自引率

10.00%

发文量

691

审稿时长

23 days

期刊介绍： European Polymer Journal is dedicated to publishing work on fundamental and applied polymer chemistry and macromolecular materials. The journal covers all aspects of polymer synthesis, including polymerization mechanisms and chemical functional transformations, with a focus on novel polymers and the relationships between molecular structure and polymer properties. In addition, we welcome submissions on bio-based or renewable polymers, stimuli-responsive systems and polymer bio-hybrids. European Polymer Journal also publishes research on the biomedical application of polymers, including drug delivery and regenerative medicine. The main scope is covered but not limited to the following core research areas: Polymer synthesis and functionalization • Novel synthetic routes for polymerization, functional modification, controlled/living polymerization and precision polymers. Stimuli-responsive polymers • Including shape memory and self-healing polymers. Supramolecular polymers and self-assembly • Molecular recognition and higher order polymer structures. Renewable and sustainable polymers • Bio-based, biodegradable and anti-microbial polymers and polymeric bio-nanocomposites. Polymers at interfaces and surfaces • Chemistry and engineering of surfaces with biological relevance, including patterning, antifouling polymers and polymers for membrane applications. Biomedical applications and nanomedicine • Polymers for regenerative medicine, drug delivery molecular release and gene therapy The scope of European Polymer Journal no longer includes Polymer Physics.