Isomerization Of Azobenzene Moieties Research Articles

Light-Induced Reversible Hierarchical Self-Assembly of Amphiphilic Diblock Copolymers into Microscopic Vesicles with Tunable Optical and Nanocarrier Properties.

In contrast to the conventional hierarchical self-assembly process, effective methods to enable reversible hierarchical self-assembly of block copolymers are comparatively few and limited in scope. Herein, we report, for the first time, a simple yet robust strategy for light-induced reversible hierarchical self-assembly of an amphiphilic diblock copolymer, poly(4-vinylpyridine)-block-poly[6-[4-(4-butyloxyphenylazo)phenoxy]hexyl methacrylate] (denoted P4VP-b-PAzoMA). The hierarchical structures are constructed via a two-step self-assembly process (first-level reverse micelles, second-level compound micelles, and rearrangement into micrometer-sized vesicles) driven by use of solvent. Intriguingly, because of reversible photoinduced trans-to-cis isomerization of azobenzene moieties in PAzoMA, the vesicles could disassemble into subunits upon UV light and then recover the nearly identical vesicular morphology upon visible light. Such a reversible hierarchical self-assembly process is accompanied by reversible fluorescence, encapsulation, and controlled release of dyes and can be used as a template for the synthesis of nanoparticles. Clearly, the ability to render the light-enabled reversible hierarchical self-assembly provides a unique platform for smart delivery vehicles and templates for nanomaterials.

Photoalignment in Polysiloxane Liquid‐Crystalline Elastomers with Rearrangeable Networks

AbstractMolecular alignment in liquid‐crystalline elastomers with polysiloxane backbone is controlled with the aid of photoalignment and exchangeable links to enhance performance as photoactuators. The photoalignment is triggered by trans‐cis‐trans isomerization of azobenzene moieties, which are introduced at crosslinking points, upon irradiation with linearly polarized UV (LPUV) light under heating. The induced alignment is memorized by rearrangement of network structures through exchange reactions of covalent bonds. When irradiated with LPUV light, freestanding films show bending along with the alignment change in surface regions. Macroscopic shapes are also rememorized by exchange reactions at crosslinks. Combination of photoalignment and network rearrangement allows continuous deformation of freestanding films upon exposure to LPUV light with varying polarization directions. This approach enhances the degree of freedom in alignment control, photoactuation, and reshaping of polysiloxane‐based liquid‐crystalline elastomers, which are feasible as soft actuators.

Light-powered and transient peptide two-dimensional assembly driven by trans-to-cis isomerization of azobenzene side chains.

Transient nanosheets were fabricated based on the ionic self-assembly of anionic polyoxometalates and cationic peptides appended with azobenzene side chains. The two-dimensional (2D) nanostructures are initiated through ultraviolet (UV) light-actuated trans-to-cis isomerization of azobenzene moieties.

Synthesis of Crosslinked Liquid-Crystalline Polymer Brushes on Flexible Polymer Films Toward Photomobile Materials

We prepared crosslinked azobenzene liquid-crystalline polymer brushes on flexible polymer films by surface-initiated atom transfer radical polymerization and a subsequent crosslinking reaction. Reversible isomerization of azobenzene moieties was observed in the crosslinked films upon irradiation with UV and visible light. Upon exposure to linearly polarized UV light, the films bent slightly along the polarization direction of light toward an actinic light source. After turning off the UV light, the films maintained the bent shape, and then reverted to the initial form by irradiation with visible light. We have successfully developed a novel photomobile material with crosslinked azobenzene liquid-crystalline polymer brushes.

Photoresponsive Release from Azobenzene-Modified Single Cubic Crystal NaCl/Silica Particles

Azobenzene ligands were uniformly anchored to the pore surfaces of nanoporous silica particles with single crystal NaCl using 4-(3-triethoxysilylpropylureido)azobenzene (TSUA). The functionalization delayed the release of NaCl significantly. The modified particles demonstrated a photocontrolled release by trans/cis isomerization of azobenzene moieties. The addition of amphiphilic solvents, propylene glycol (PG), propylene glycol propyl ether (PGPE), and dipropylene glycol propyl ether (DPGPE) delayed the release in water, although the wetting behavior was improved and the delay is the most for the block molecules with the longest carbon chain. The speedup by UV irradiation suggests a strong dependence of diffusion on the switchable pore size. TGA, XRD, FTIR, and NMR techniques were used to characterize the structures.

Methacrylate copolymers with substituted azobenzene side groups: synthesis, characterization and photo-induced birefringence properties

AbstractWell-defined copolymer of methyl methacrylate (MMA) and 2-methylacrylic- acid-2-{ethyl-[4-(4-methoxy-phenylazo)-3-methyl-phenyl]-amino}-ethyl ester (MAMP) bearing pendent azobenzene groups, was synthesized via reversible addition-fragmentation chain transfer polymerization (RAFT). Copolymers with different contents of azobenzene moieties, e. g. from 12 mol % to 100 mol %, were obtained by varying the feed molar ratios of MAMP and MMA. The reactivity ratios of these two monomers were measured and calculated via the modified Kelen- Tüdos method. Glass transition temperature of the copolymers was measured by differential scanning calorimetry (DSC). Photoinduced trans-cis isomerization of azobenzene moieties in the copolymer was studied at room temperature. Films cast from the functional copolymers were characterized by photo-induced birefringence and surface relief grating (SRG).