Self-Assembly and Photoinduced Spindle-Toroid Morphology Transition of Macromolecular Double-Brushes with Azobenzene Pendants,ACS Macro Letters

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Self-Assembly and Photoinduced Spindle-Toroid Morphology Transition of Macromolecular Double-Brushes with Azobenzene Pendants
ACS Macro Letters ( IF 5.1 ) Pub Date : 2020-02-28 , DOI: 10.1021/acsmacrolett.0c00079
Binbin Xu ₁ , Hongyu Qian ₁ , Shaoliang Lin ₁

Affiliation

Asymmetric macromolecular double-brushes (MDBs) are composed of two different side chains grafted on a linear backbone, possessing distinct assembly behaviors in comparison with conventional amphiphiles, owing to the Janus architecture and combined effects of backbone and hetero double-brushes. Additionally, the introduction of unique functionalities and responsiveness into the self-assembly system of MDBs endows extra opportunities to pursue morphologic diversity and intriguing properties. Herein, we report the synthesis of Janus-like MDBs of polyacrylate-g-poly(6-(4-butyl-4′-oxyazobenzene) hexyl acrylate)/poly(ethylene oxide) (PA-g-PAzo/PEO), in which hydrophilic PEO and hydrophobic PAzo brushes were grafted using the combination of concurrent ATRP and click reaction. Due to the special Janus topology and inter/intramolecular association of pendant azobenzene groups, amphiphilic PA-g-PAzo/PEO self-assembled into multimolecular rod and spindle-like aggregates. It is interesting that a transition of spindle-toroid-spindle was observed upon the alternative irradiation between UV and visible light, which is ascribed to the trans-to-cis isomerization of azobenzene molecular brushes. To our best knowledge, this is the first time that azobenzene-containing MDBs enable the fabrication of distinctive self-assembled morphologies and photoinduced toroid formation. The controlled synthesis of MDBs with unique functionalities and subsequent development of their structure–property relationships would shed light on the design and optimization of bottlebrush-based nanomaterials.

中文翻译：

具有偶氮苯垂饰的大分子双刷的自组装和光诱导主轴-环形形态转变

不对称大分子双刷 (MDB) 由两个不同的侧链接枝在线性骨架上组成，由于 Janus 结构以及骨架和异质双刷的组合效应，与传统的两亲物相比具有不同的组装行为。此外，在 MDB 的自组装系统中引入独特的功能和响应能力为追求形态多样性和有趣特性提供了额外的机会。在此，我们报道了聚丙烯酸酯-g-聚（6-（4-丁基-4'-氧偶氮苯）丙烯酸己酯）/聚（环氧乙烷）（PA- g ）的 Janus 样 MDB 的合成。-PAzo/PEO)，其中亲水性 PEO 和疏水性 PAzo 刷使用并发 ATRP 和点击反应的组合进行接枝。由于特殊的 Janus 拓扑结构和偶氮苯侧基的分子间/分子内缔合，两亲性 PA- g -PAzo/PEO 自组装成多分子棒状和纺锤状聚集体。有趣的是，在紫外光和可见光交替照射时观察到纺锤-环形-纺锤的转变，这归因于反式到顺式偶氮苯分子刷的异构化。据我们所知，这是第一次含有偶氮苯的 MDB 能够制造独特的自组装形态和光诱导环形形成。具有独特功能的 MDB 的受控合成及其结构-性能关系的后续发展将为基于瓶刷的纳米材料的设计和优化提供启示。

更新日期：2020-02-28

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