Photoactuators based on liquid crystal elastomers or networks are smart materials that show photoinduced motions. However, their crosslinked networks make their repair or reprocessing difficult. Here, a healable and reprocessable photoactuator is fabricated using entangled high‐molecular‐weight azobenzene‐containing polymers (azopolymers) that are non‐crosslinked. A series of linear liquid crystal azopolymers with different molecular weights are synthesized. The low‐molecular‐weight azopolymers (5–53 kg mol−1) cannot form freestanding photoactuators because their polymer chains lack entanglements, which makes them hard and brittle. In contrast, flexible and stretchable actuators are fabricated using high‐molecular‐weight azopolymers (80–100 kg mol−1) that exhibit good processability because of the polymer chain entanglements. The azopolymer photoactuators show photoinduced bending based on photoinduced trans–cis isomerization of the azopolymers on the irradiated side. The experiments show not only photoinduced phase transitions or changes in the order parameters but also photoinduced solid‐to‐liquid transition of the azopolymers resulting in shape changes and mechanical responses. Thus, photoinduced solid‐to‐liquid transition is a new mechanism for the design of photoactuators. Moreover, the azopolymer photoactuators are healable and reprocessable via solution processing or light irradiation. Healability and reprocessability prolong lifetimes of photoactuators are important for materials reusage and recycling, and represent a new strategy for the preparation of smart materials.
Stimuli responsive polymers have been extensively studied as nanocarriers for drug delivery systems (DDSs), especially those based on supramolecular interactions. Cyclodextrin (CD) is one kind of widely applied host molecule, and the host-guest interactions between CD and different counterparts can respond to different stimuli and thus can be applied as responsive linkers for polymeric DDSs. In this review, the polymeric nanocarriers based on the host-guest interactions between CD and ferrocene, azobenzene, and benzimidazole as DDSs are summarized, with redox, light, and pH sensitivity, respectively. The mechanisms for the stimuli responsive ability of the linkers, the application of them for construction of DDSs with different polymer structures, and the controlled release behaviors have been focused. In addition, the outlook and challenge of these systems are discussed.
Potential-stimulated Pickering emulsions, using electrochemical responsive microgels as particle stabilizers, are prepared and used for biocatalysis. The microgels are constructed from cyclodextrin functionalized 8-arm poly(ethylene glycol) (8A PEG-CD) and ferrocene modified counterparts (8A PEG-Fc) via CD/Fc host-guest chemistry. Taking advantage of the redox reaction of Fc, the formation and deformation of the microgels and corresponding Pickering emulsions can be reversibly stimulated by external potential, and have been used for the hydrolysis of triacetin and kinetic resolution reaction of (R,S)-1-phenylethanol catalyzed by lipases. Potential stimulated destabilization of the emulsion realizes an effective separation of the products and enzyme recycling.
The issue of information security is closely related to every aspect of daily life. For pursuing a higher level of security, much effort has been continuously invested in the development of information security technologies based on encryption and storage. Current approaches using single-dimension information can be easily cracked and imitated due to the lack of sufficient security. Multidimensional information encryption and storage are an effective way to increase the security level and can protect it from counterfeiting and illegal decryption. Since light has rich dimensions (wavelength, duration, phase, polarization, depth, and power) and synergy between different dimensions, light as the input is one of the promising candidates for improving the level of information security. In this review, based on six different dimensional features of the input light, we mainly summarize the implementation methods of multidimensional information encryption and storage including material preparation and response mechanisms. In addition, the challenges and future prospects of these information security systems are discussed.
Biological cyclization is highly efficient, and this can be attributed to the conformation of the backbone of the biopolymer. Taking advantage of metal-coordination geometry, we developed a method for conformation-directed polymerization cyclization through rational design of metal carbonyl monomers that could be used to produce cyclic macromolecules, even in bulk. FpR [ Fp=(PPh (CH ) Cp)Fe(CO) with the phosphine group tethered on the cyclopentadiene (Cp) ring; R=CH or (CH ) CH ] was designed and synthesized for migration insertion polymerization to generate P( FpR) with the polymer backbone containing Cp-Fe bonds. Growth of the backbone led to a cyclic conformation with close end-to-end distances, which facilitated the cyclization. This conformation-directed cyclization was attributed to the piano-stool metal-coordination geometry of the repeating units and the low rotational barrier of the Cp-Fe bonds in the backbone. The produced macrocycles, which contain a metal carbonyl coordination structure in their backbones, are rigid, unlike many organic macrocycles. The macrocycles thus have a large excluded volume. This new type of metal carbonyl macrocycle will be of interest as a building block for supramolecular chemistry and in the exploration of novel materials.
We present a new, efficient approach to achieve superior dispersibility of single-walled carbon nanotubes (SWNTs) in water by integrating reversible host-guest interaction and π-π stacking. In this approach, β-cyclodextrin (β-CD) was first modified with a pyrene group to be adsorbed onto the wall of pristine SWNTs via π-π stacking, followed by further functionalization with ferrocene (Fc)-terminated water-soluble poly(ethylene glycol) (PEG) through supramolecular host-guest interaction between β-CD and Fc. Upon alternate electrochemical oxidative/reductive stimuli, the reversible host-guest pair enabled the PEG-Fc@Py-CD@SWNTs to exhibit switchable conversion between dispersion and aggregation states. Electric field controllable PEG-Fc@Py-CD@SWNTs with good reversibility and intact nanotube structure may find potential applications in selective screening of SWNTs, biosensors, and targeted drug delivery.
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