THESIS
2020
xxxiv, 182 pages : illustrations (chiefly color) ; 30 cm
Abstract
The demand for highly efficient solid-state luminophores is continuously growing due to their potential applications in sensors, optoelectrical devices and biological applications. The discovery of luminogens with aggregation-induced emission (AIE) by our group in 2001, provides a good response to this demand. Among the exploited AIE luminogens (AIEgens), AIE-active polymers possess many advantages such as simple synthesis, convenient structure modifications and good processability and offer a creative and extensive platform for scientists and engineers. Since the first report in 2003, AIE-active polymer materials have been utilized for versatile practical applications such as fluorescent chemo-/bio-sensors, stimuli-responsive materials, fluorescence image-guided therapy, organic lighti...[
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The demand for highly efficient solid-state luminophores is continuously growing due to their potential applications in sensors, optoelectrical devices and biological applications. The discovery of luminogens with aggregation-induced emission (AIE) by our group in 2001, provides a good response to this demand. Among the exploited AIE luminogens (AIEgens), AIE-active polymers possess many advantages such as simple synthesis, convenient structure modifications and good processability and offer a creative and extensive platform for scientists and engineers. Since the first report in 2003, AIE-active polymer materials have been utilized for versatile practical applications such as fluorescent chemo-/bio-sensors, stimuli-responsive materials, fluorescence image-guided therapy, organic lighting emitting devices and smart soft materials. Based on these attractive advantages of AIE-active polymer materials, great endeavors of this thesis have been devoted to the construction of new AIE-active polymeric luminogens and exploration of their high-tech applications in the solid state.
Developing new techniques for synthesizing polymers with novel structures, broad monomer scope and unique properties is a fundamental goal of polymer science. Multicomponent polymerization (MCP) is an emerging synthesis technique for preparing functional polymers with the advantages of complicated structure, good atom economy, simple procedure and high efficiency. Thanks to the versatility of alkyne chemistry, herein two metal-free MCPs have been developed for the in-situ generation of acetylenic polymers with fused rings and heterocycles in a facile and efficient manner. The AIE-active polymers with excellent photophysical properties and diverse fascinating functionalities have been obtained by the incorporation of AIEgens along the polymer backbones. Based on their intense fluorescence in the aggregate and film state, multiple advanced applications have been realized by AIE-active polymers such as fluorescent sensors to biogenic amines and toxic chromium(VI) ion, ratiometric in vivo pH mapping, cell imaging with lysosome-targeting ability, two dimensional photopatterning and visualizing microphase separation.
As one of the intelligent materials, stimuli-responsive polymeric hydrogels have attracted intense scientific and technological interest due to their potential applications including biomimetic models for biological study, biomedical devices, soft robots and artificial tissues, etc. Smart polymeric hydrogels can adapt and alter their characteristics such as shape deformation, color and mechanical strength in response to external stimuli. Embedding AIEgens in polymer network is promising to design and construct novel stimuli-responsive hydrogels with fluorescence change. Herein, a polysaccharide-based smart hydrogel with chemically incorporated AIEgens has been synthesized through amino-yne click gelation and phenol-yne click reaction. The basic hydrolysis of the covalent bonds with AIEgens has endowed the as-prepared hydrogels with base-responsive fluorescent behavior. Meanwhile, a thermoresponsive mechanically strong hydrogel has been fabricated by the radical copolymerization with AIE-active acrylic monomers. Fluorescent technique assisted by AIE has visualized its hydrophilicity-hydrophobicity transformation and microphase separation by fluorescence change and dispersion. Additionally, a conjugated polymer has been developed with unique circularly polarized luminescence and aggregation-induced delayed fluorescence and has been employed as solution-processed emitting layers in organic light emitting diodes, indicating the potential applications in chiral optoelectronic devices.
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