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Regulating the self-assembly of rigid 2D ribbon-like amphiphilic homopolymer via tailoring its holistic conformation

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Science China Chemistry 2023年第8期66卷 2339-2346页

作者： Yumeng Gao Weisheng Feng Yao Sun Yuan Yao Liquan Wang Shaoliang Lin Shanghai Key Laboratory of Advanced Polymeric Materials Frontiers Science Center for Materiobiology and Dynamic Chemistry of Ministry of EducationSchool of Materials Science and EngineeringEast China University of Science and TechnologyShanghai200237China

Amphiphilic rigid backbone polymers are traditionally seemed as one-dimensional(1D)rods and show distinct self-assembly behavior to flexible polymers,but they could hardly adapt morphology-tunable self-assembly by changing their holistic conformation upon external *** this study,we synthesized a series of amphiphilic homopolymers poly(acetylene azobenzene oligoethylene glycol)(P(AAzo-EGx))containing conjugated polyacetylene mainchain,azobenzene pendants and oligo ethylene glycol tails in each *** comb-like amphiphilic polymer could be treated as two-dimensional(2D)nanoribbons with tunable holistic conformation via meticulous tailoring intrastrand repulsion and interchainπ-πinteraction of azobenzene pendants by light,temperature,and solvent swelling.P(AAzo-EG_(2))could self-assemble into large vesicles in ambient,whereas transformed to supramolecular helix bundles(SHBs)at 65℃as well as depicted by dissipative particle dynamics(DPD)simulation,and then turned into grass leaf-like micelles upon sequential ultraviolet(UV)and blue light *** three assemblies featured different stacking mode of PAAzo skeletons although showed similar aggregate induce emission(AIE)*** this holistic macromolecular chain conformation-induced self-assembly and morphology transformation,temperature influenced the stacking of hydrophobic parts mainly by tuning the torsion of PAAzo *** amount of good solvent played a vital role by swelling of hydrophobic PAAzo skeleton,and helping the movement and rearrangement of azobenzene pendants and polyacetylene mainchains like a *** length and diameter of SHBs could be tuned by changing *** work uncovered a facile strategy to tailor the self-assembly of rigid backbone polymers for fabrication of functional nanodevices.

关键词： self-assembly tunable conformation rigid skeleton two-dimensional nanoribbon stimuli response

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