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      Synthesis and Photoinduced Anisotropy of Polymers Containing Nunchaku-Like Unit with an Azobenzene and a Mesogen

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          Abstract

          A series of polymers containing nunchaku-like unit with an azo chromophore and a mesogen group was successfully prepared and photoinduced anisotropy of the obtained polymers was minutely investigated. Firstly, monomers containing nunchaku-like unit with an azo chromophore and a mesogen group linked by flexible group were synthesized. The structure of the monomers was confirmed via NMR COSY spectra. Subsequently, the obtained monomers were polymerized into corresponding polymers through RAFT polymerization. The prepared polymer samples were characterized through NMR, FTIR, gel permeation chromatography (GPC), and UV-vis testing while the thermal properties of the samples were investigated through differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) measurements. The photoinduced isomerization of the polymers, which was researched in situ via measuring UV-vis spectra of the polymer solutions and spin-coated films under irradiation with 450 nm light or putting in darkness, demonstrated the rapid trans- cis- trans isomerization of the polymers. When irradiated with a linearly polarized light, significant photoinduced birefringence and dichroism were observed, suggesting photoinduced isomerization of azobenzene can drive orientation of mesogen in the system. This study blazes a way to design the optical materials with light-controllable birefringence and dichroism.

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          Most cited references43

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          Light-Driven Liquid Crystalline Materials: From Photo-Induced Phase Transitions and Property Modulations to Applications.

          Light-driven phenomena both in living systems and nonliving materials have enabled truly fascinating and incredible dynamic architectures with terrific forms and functions. Recently, liquid crystalline materials endowed with photoresponsive capability have emerged as enticing systems. In this Review, we focus on the developments of light-driven liquid crystalline materials containing photochromic components over the past decade. Design and synthesis of photochromic liquid crystals (LCs), photoinduced phase transitions in LC, and photoalignment and photoorientation of LCs have been covered. Photomodulation of pitch, polarization, lattice constant and handedness inversion of chiral LCs is discussed. Light-driven phenomena and properties of liquid crystalline polymers, elastomers, and networks have also been analyzed. The applications of photoinduced phase transitions, photoalignment, photomodulation of chiral LCs, and photomobile polymers have been highlighted wherever appropriate. The combination of photochromism, liquid crystallinity, and fabrication techniques has enabled some fascinating functional materials which can be driven by ultraviolet, visible, and infrared light irradiation. Nanoscale particles have been incorporated to widen and diversify the scope of the light-driven liquid crystalline materials. The developed materials possess huge potential for applications in optics, photonics, adaptive materials, nanotechnology, etc. The challenges and opportunities in this area are discussed at the end of the Review.
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            Photoswitching of glass transition temperatures of azobenzene-containing polymers induces reversible solid-to-liquid transitions

            Reversibly inducing solid-to-liquid transitions of polymers at room temperature represents a challenge for enhanced processability and applications of polymers. Now, three azopolymers have been shown to exhibit photoswitchable glass transition temperatures, resulting in reversible, solid-to-liquid transitions. Light exposure can heal cracks in hard azopolymers, reduce surface roughness of azopolymer films and control azopolymer adhesion.
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              A dual-responsive supra-amphiphilic polypseudorotaxane constructed from a water-soluble pillar[7]arene and an azobenzene-containing random copolymer.

              Macromolecular supra-amphiphiles refer to a kind of macromolecular amphiphiles whose hydrophlic and hydrophobic parts are connected by noncovalent forces. They have applications in various fields, such as drug delivery, sensor systems, and biomedical materials. Here we report a novel molecular recognition motif between a new thermoresponsive water-soluble pillar[7]arene (WP7) and an azobenzene derivative. Furthermore, we utilized this recognition motif to construct the first pillararene-based supra-amphiphilic polypseudorotaxane which can self-assemble to form vesicles in water. Due to the dual-responsiveness of the molecular recognition motif (the thermoresponsiveness of WP7 and photoresponsiveness of azobenzene), the reversible transformations between solid nanospheres based on the self-assembly of the polymer backbone and vesicles based on the self-assembly of the supra-amphiphilic polypseudorotaxane were achieved by adjusting the solution temperature or UV-visible light irradiation. These dual-responsive aggregation behaviors were further used in the controlled release of water-soluble dye calcein molecules.
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                Author and article information

                Journal
                Polymers (Basel)
                Polymers (Basel)
                polymers
                Polymers
                MDPI
                2073-4360
                02 April 2019
                April 2019
                : 11
                : 4
                : 600
                Affiliations
                [1 ]Research Branch of Advanced Functional Materials, School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 611731, China; wangll@ 123456std.uestc.edu.cn (L.W.); zhangyingchuan@ 123456tongji.edu.cn (Y.Z.); Zhanch@ 123456std.uestc.edu.cn (C.Z.); yourkeaib@ 123456163.com (Y.Y.); zhx78668@ 123456126.com (H.Z.); ma_jinyi163@ 123456163.com (J.M.); liuxb@ 123456uestc.edu.cn (X.L.)
                [2 ]School of Automotive Studies, Tongji University, Shanghai 201804, China
                [3 ]Department of Chemical Engineering, Laboratory of Advanced Materials (MOE), Tsinghua University, Beijing 100084, China; zhiyuan.xiong@ 123456unimelb.edu.au
                Author notes
                [* ]Correspondence: weirb10@ 123456uestc.edu.cn ; Tel.: +86-028-8320-7326
                [†]

                These authors contributed equally to this work.

                Article
                polymers-11-00600
                10.3390/polym11040600
                6523569
                30960583
                bcb58897-4f09-4a92-9437-0160da2fbe26
                © 2019 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 14 March 2019
                : 25 March 2019
                Categories
                Article

                azobenzene,mesogen,isomerization,photoinduced anisotropy

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