Fabrication of Polymer/Cholesteric Liquid Crystal Films and Fibers Using the Nonsolvent and Phase Separation Method.

In recent years, liquid crystal materials have drawn great interest because of their wide range of applications. Among various thermochromic materials, cholesteric liquid crystalline (CLC) materials have been well studied and reported. CLC materials have the advantages of ready manipulation and multiple color transitions. For the further development of smart clothing and wearable electronics, however, the incorporation of CLC materials into polymers still remains challenging. The difficulties lie in the prevention of leakage of CLC and retention of the cholesteric liquid crystalline phase. In this work, we demonstrate a versatile nonsolvent and phase separation method using polar solvents to incorporate CLC microspheres into polymer matrix. Poly(vinyl alcohol) (PVA), a water-soluble polymer, is chosen as the polymer because of its high transparency and ease to handle. Using spin-coating and wet spinning techniques, PVA/CLC films and fibers can be fabricated. The formation of CLC microspheres in the polymer matrix is characterized through optical and polarized microscopy. Compared with the CLC films, the PVA/CLC composites demonstrate superior thermal stability. Moreover, both PVA/CLC films and fibers exhibit good color stability from the electrical tests. This work provides an effective strategy to prepare polymer/CLC composites, paving a wide avenue toward applications in smart textiles, display technologies, and medical devices.

Alkaline-Responsive, Self-Healable, and Conductive Copolymer Composites with Enhanced Mechanical Properties Tailored for Wearable Tech.

Despite significant advancements, current self-healing materials often suffer from a compromise between mechanical robustness and functional performance, particularly in terms of conductivity and responsiveness to environmental stimuli. Addressing this issue, the research introduces a self-healable and conductive copolymer, poly(ionic liquid-co-acrylic acid) (PIL-co-PAA), synthesized through free radical polymerization, and further optimized by incorporating thermoplastic polyurethane (TPU). This combination leverages the unique properties of each component, especially ion-dipole interactions and hydrogen bonds, resulting in a material that exhibits exceptional self-healing abilities and demonstrates enhanced mechanical properties and electrical conductivity. Moreover, the PIL-co-PAA/TPU films showcase alkaline-responsive behavior, a feature that broadens their applicability in dynamic environments. Through systematic characterization, including thermogravimetric analysis, tensile testing, and electrical properties measurements, the mechanisms behind the improved performance and functionality of these films are elucidated. The conductivities and ultimate tensile strength (σuts) of the PIL-co-PAA/TPU films regain 80% under 8 h healing process. To extend the applications for wearable devices, the self-healing properties of commercial cotton fabrics coated with the self-healable PIL-co-PAA are also investigated, demonstrating both self-healing and electrical properties. This study advances the understanding of self-healable conductive polymers and opens new avenues for their application in wearable technology.

Reversible Sensing Technologies Using Upcycled TPEE: Crafting pH and Light Responsive Materials towards Sustainable Monitoring.

Multiresponsive materials with reversible and durable characteristics are indispensable because of their promising applications in environmental change detections. To fabricate multiresponsive materials in mass production, however, complex reactions and impractical situations are often involved. Herein, a dual responsive (light and pH) spiropyran-based smart sensor fabricated by a simple layer-by-layer (LbL) assembly process from upcycled thermoplastic polyester elastomer (TPEE) materials derived from recycled polyethylene terephthalate (r-PET) is proposed. Positively charged chitosan solutions and negatively charged merocyanine-COOH (MC-COOH) solutions are employed in the LbL assembly technique, forming the chitosan-spiropyran deposited TPEE (TPEE-CH-SP) film. Upon UV irradiation, the spiropyran-COOH (SP-COOH) molecules on the TPEE-CH-SP film undergo the ring-opening isomerization, along with an apparent color change from colorless to purple, to transform into the MC-COOH molecules. By further exposing the TPEE-CH-MC film to hydrogen chloride (HCl) and nitric acid (HNO3 ) vapors, the MC-COOH molecules can be transformed into protonated merocyanine-COOH (MCH-COOH) with the simultaneous color change from purple to yellow.

Light-responsive MXenegel via interfacial host-guest supramolecular bridging.

Living in the global-changing era, intelligent and eco-friendly electronic components that can sense the environment and recycle or reprogram when needed are essential for sustainable development. Compared with solid-state electronics, composite hydrogels with multi-functionalities are promising candidates. By bridging the self-assembly of azobenzene-containing supramolecular complexes and MXene nanosheets, we fabricate a MXene-based composite gel, namely MXenegel, with reversible photo-modulated phase behavior. The MXenegel can undergo reversible liquefication and solidification under UV and visible light irradiations, respectively, while maintaining its conductive nature unchanged, which can be integrated into traditional solid-state circuits. The strategy presented in this work provides an example of light-responsive conducting material via supramolecular bridging and demonstrates an exciting platform for functional soft electronics.

Guard Cell-Inspired Ion Channels: Harnessing the Photomechanical Effect via Supramolecular Assembly of Cross-Linked Azobenzene/Polymers.

Stimuli-responsive ion nanochannels have attracted considerable attention in various fields because of their remote controllability of ionic transportation. For photoresponsive ion nanochannels, however, achieving precise regulation of ion conductivity is still challenging, primarily due to the difficulty of programmable structural changes in confined environments. Moreover, the relationship between noncontact photo-stimulation in nanoscale and light-induced ion conductivity has not been well understood. In this work, a versatile design for fabricating guard cell-inspired photoswitchable ion channels is presented by infiltrating azobenzene-cross-linked polymer (AAZO-PDAC) into nanoporous anodic aluminum oxide (AAO) membranes. The azobenzene-cross-linked polymer is formed by azobenzene chromophore (AAZO)-cross-linked poly(diallyldimethylammonium chloride) (PDAC) with electrostatic interactions. Under UV irradiation, the trans-AAZO isomerizes to the cis-AAZO, causing the volume compression of the polymer network, whereas, in darkness, the cis-AAZO reverts to the trans-AAZO, leading to the recovery of the structure. Consequently, the resultant nanopore sizes can be manipulated by the photomechanical effect of the AAZO-PDAC polymers. By adding ionic liquids, the ion conductivity of the light-driven ion nanochannels can be controlled with good repeatability and fast responses (within seconds) in multiple cycles. The ion channels have promising potential in the applications of biomimetic materials, sensors, and biomedical sciences.

Reversible Charge Transfer Doping in Atomically Thin In2O3 by Viologens.

Atomically thin oxide semiconductors are emerging as potential materials for their potentiality in monolithic 3D integration and sensor applications. In this study, a charge transfer method employing viologen, an organic compound with exceptional reduction potential among n-type organics, is presented to modulate the carrier concentration in atomically thin In2O3 without the need of annealing. This study highlights the critical role of channel thickness on doping efficiency, revealing that viologen charge transfer doping is increasingly pronounced in thinner channels owing to their increased surface-to-volume ratio. Upon viologen doping, an electron sheet density of 6.8 × 1012 cm-2 is achieved in 2 nm In2O3 back gate device while preserving carrier mobility. Moreover, by the modification of the functional groups, viologens can be conveniently removed with acetone and an ultrasonic cleaner, making the viologen treatment a reversible process. Based on this doping scheme, we demonstrate an n-type metal oxide semiconductor inverter with viologen-doped In2O3, exhibiting a voltage gain of 26 at VD = 5 V. This complementary pairing of viologen and In2O3 offers ease of control over the carrier concentration, making it suitable for the next-generation electronic applications.

Boosting Ion Conductivities: Light-Modulated Azobenzene-Based Ionic Liquids in Vertical Nanochannels.

Exploring stimuli-responsive ion-conductive materials is a challenging task, but it has gained increasing attention because of their enormous potential applications in actuators, sensors, and smart electronics. Here, we demonstrate a distinctive photoresponsive ion-conductive device that utilizes azobenzene-based ionic liquids ([AzoCnMIM][Br], where n = 2, 6, and 10), confined in nanochannels of anodic aluminum oxide (AAO) templates for photoisomerization. The structure of [AzoCnMIM][Br] comprises photoresponsive and hydrophobic azobenzene moieties, hydrophilic imidazolium cations, and negatively charged bromide ions. Therefore, [AzoCnMIM][Br] can form micelles and exhibit photoresponsive ion conductivities. The nanochannels of AAO templates exhibit a confinement effect on the formation of azobenzene-based ionic liquid micelles due to the pore size, thereby preventing the formation of larger micelles that could lead to a decrease in conductivity. Consequently, the ion conductivities of the azobenzene-based ionic liquids are higher in the nanochannels of the AAO templates. The effects of the length of carbon chains on the azobezene-based ionic liquids and the pore size of the AAO templates have also been investigated. Additionally, through irradiation with UV/vis light, [AzoCnMIM][Br] can undergo reversible isomerization, thereby reversibly changing the sizes of the micelles and subsequently altering the ion conductivities.

Smart Temperature-Gating and Ion Conductivity Control of Grafted Anodic Aluminum Oxide Membranes.

Over the past few decades, stimuli-responsive materials have been widely applied to porous surfaces. Permeability and conductivity control of ions confined in nanochannels modified with stimuli-responsive materials, however, have been less investigated. In this work, the permeability and conductivity control of ions confined in nanochannels of anodic aluminum oxide (AAO) templates modified with thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) brushes are demonstrated. By surface-initiated atom transfer radical polymerization (SI-ATRP), PNIPAM brushes are successfully grafted onto the hexagonally packed cylindrical nanopores of AAO templates. The surface hydrophilicities of the membranes can be reversibly altered because of the lower critical solution temperature (LCST) behavior of the PNIPAM polymer brushes. From electrochemical impedance spectroscopy (EIS) analysis, the temperature-gating behaviors of the AAO-g-PNIPAM membranes exhibit larger impedance changes than those of the pure AAO membranes at higher temperatures because of the aggregation of the grafted PNIPAM chains. The reversible surface properties caused by the extended and collapsed states of the polymer chains are also demonstrated by dye release tests. The smart thermo-gated and ion-controlled nanoporous membranes are suitable for future smart membrane applications.

Photoswitchable and Solvent-Controlled Directional Actuators: Supramolecular Assembly and Crosslinked Polymers.

Untethered small actuators have drawn tremendous interest owing to their reversibility, flexibility, and widespread applications in various fields. For polymer actuators, however, it is still challenging to achieve programmable structural changes under different stimuli caused by the intractability and single-stimulus responses of most polymer materials. Herein, multi-stimuli-responsive polymer actuators that can respond to light and solvent via structural changes are developed. The actuators are based on bilayer films of polydimethylsiloxane (PDMS) and azobenzene chromophore (AAZO)-crosslinked poly(diallyldimethylammonium chloride) (PDAC). Upon UV light irradiation, the AAZO undergoes trans-cis-trans photoisomerization, causing the bending of the bilayer films. When the UV light is off, a shape recovery toward an opposite direction occurs spontaneously. The reversible deformation can be repeated at least 20 cycles. Upon solvent vapor annealing, one of the bilayer films can be selectively swollen, causing the bending of the bilayer films with the directions controlled by the solvent vapors. The effects of different parameters, such as the weight ratios of AAZO and film thicknesses, on the bending angles and curvatures of the polymer films are also analyzed. The results demonstrate that multi-stimuli-responsive actuators with fast responses and high reproducibility can be fulfilled.

Laser-Induced NanoKneading (LINK): Deformation of Patterned Azopolymer Nanopillar Arrays via Photo-Fluidization.

Ordered arrays of polymer nanostructures have been widely investigated because of their promising applications such as solar-cell devices, sensors, and supercapacitors. It remains a great challenge, however, to manipulate the shapes of individual nanostructures in arrays for tailoring specific properties. In this study, an effective strategy to prepare anisotropic polymer nanopillar arrays via photo-fluidization is presented. Azobenzene-containing polymers (azopolymers) are first infiltrated into the nanopores of ordered anodic aluminum oxide (AAO) templates. After the removal of the AAO templates using weak bases, azopolymer nanopillar arrays can be prepared. Upon exposure of linearly polarized lights, azobenzene groups in the azopolymers undergo trans-cis-trans photoisomerization, causing mass migration and elongation of the nanopillar along with the polarization directions. As a result, anisotropic nanopillar arrays can be fabricated, of which the deformation degrees are controlled by the illumination times. Furthermore, patterned nanopillar arrays can also be constructed with designed photomasks. This work presents a practical and versatile strategy to fabricate arrays of anisotropic nanostructures for future technical applications.

Hierarchical Polymer Structures Using Templates and the Modified Breath Figure Method.

Hierarchical structures are commonly observed in nature and possess unique properties. The fabrication of hierarchical structures with well-controlled sizes in different length scales, however, is still a great challenge. To further understand the morphologies and properties of the hierarchical structures, here we present a novel strategy to prepare hierarchical polymer structures by combining the modified breath figure method and the template method. Poly(methyl methacrylate) (PMMA) honeycomb films with regular micropores are first prepared using the modified breath figure method by dipping PMMA films into mixtures of chloroform and methanol. The polymer chains on the honeycomb films are then annealed and wetted into the nanopores of anodic aluminum oxide templates via capillary forces, resulting in the formation of hierarchical polymer structures. The morphologies of the polymer structures, which can be controlled by the molecular weights of the polymers and the concentrations of the polymer solutions, are characterized by scanning electron microscopy. The surface wettabilities of the polymer structures are also examined by water contact angle measurements, and the hierarchical structures are observed to be more hydrophobic than the flat films and honeycomb films. This work not only provides a feasible approach to fabricate hierarchical polymer structures with controlled sizes but also gives a better understanding of the relationship between surface morphologies and properties.