Single-Crystal Ferroelectric-Based (K,Na)NbO3 Microcuboid/CuO Nanodot Heterostructures with Enhanced Photo-Piezocatalytic Activity.

Developing single-crystal-based heterostructured ferroelectrics with high-performance photo-piezocatalytic activity is highly desirable to utilize large piezopotentials and more reactive charges that can trigger the desired redox reactions. To that end, a single-crystal-based (K,Na)NbO3 (KNN) microcuboid/CuO nanodot heterostructure with enhanced photo-piezocataytic activity, prepared using a facile strategy that leveraged the synergy between heterojunction formation and an intense single-crystal-based piezoelectric effect, is reported herein. The catalytic rhodamine B degrading activity of KNN/CuO is investigated under light irradiation, ultrasonication, or co-excitation with both stimulations. Compared to polycrystalline KNN powders and bare KNN single-crystals, single-crystal-based KNN/CuO exhibits a higher piezocurrent density and an optimal energy band structure, resulting in 5.23 and 2.37 times higher piezocatalytic degradation activities, respectively. Furthermore, the maximum photo-piezocatalytic rate constant (≈0.093 min-1 ) of KNN/CuO under 25 min ultrasonication and light irradiation is superior to that of other KNN-based catalysts, and 1.6 and 48.6 times higher than individual piezocatalytic and photocatalytic reaction rate constants, respectively. The excellent photo-piezocatalytic activity is attributed to the enhanced charge-carrier separation and proper alignment of band structure to the required redox levels by the appropriate p-n heterojunction and high piezoelectric potential. This report provides useful insight into the relationships between heterojunctions, piezoelectric responses, and catalytic mechanisms for single-crystal-based heterostructured catalysts.

Contact Lens with pH Sensitivity for On-Demand Drug Release in Wearing Situation.

Drug-releasing contact lenses are emerging therapeutic systems for treating ocular diseases. However, their applicability is limited by the burst release of drugs during lens wear and premature drug leakage during packaging, rendering the precise control of release duration or dose difficult. Here, we introduce a pH-sensitive contact lens exhibiting on-demand drug release only during lens wear and negligible premature drug leakage during packaging and transportation, which is accomplished by incorporating drug-loaded mesoporous silica nanoparticles (MSNs) coated with a pH-sensitive polymer into the contact lens. The compositionally optimized pH-sensitive polymer has a lower critical solution temperature (LCST) at >45 °C at pH 7.4, whereas its LCST decreases to <35 °C under acidic conditions (pH ∼ 6.5). Consequently, the MSN-incorporated contact lens sustainably releases the loaded drugs only in the acidic state at 35 °C, which corresponds to lens-wear conditions, through the MSN pores that open because of the shrinkage of polymer chains. Conversely, negligible drug leakage is observed from the contact lens under low-temperature or neutral-pH conditions corresponding to packaging and transportation. Furthermore, compared with the plain contact lens, the pH-sensitive contact lens exhibits good biocompatibility and unchanged bulk characteristics, such as optical (transmittance in the visible-light region), mechanical (elastic modulus and tensile strength), and physical (surface roughness, oxygen permeability, and water content) properties. These findings suggest that the pH-sensitive contact lens can be potentially applied in ocular disease treatment.

Comprehensive constitutive modeling and analysis of multi-elastic polydimethylsiloxane (PDMS) for wearable device simulations.

Within the field of wearable devices, polydimethylsiloxane (PDMS) has long been one of the most prominent materials utilized. It is therefore unsurprising that demands for its usage has now extended beyond experimental works into computational simulations, particularly those involving finite element method (FEM). To replicate the mechanical properties of PDMS in FEM, an accurate constitutive model is required, preferably one that encompasses wide ranges of PDMS elasticity. In this study, we determine Mooney-Rivlin 5 parameters as the best hyperelastic model fitted against PDMS experimental data, and proceed to construct a parameter correlation plot combining PDMS of different elasticities together. Experimental validation using PDMS samples fabricated via 3D-printed molds is then performed using parameters extracted from this plot, showing good agreement between simulation and experimental result. In addition, to reflect model applicability, simulations related to basic mechanical deformations involved in flexible devices (compression, stretching, bending and twisting) are performed and analyzed. Further analysis is also performed to investigate the effect of combining different experimental datasets as input into the model. We expect our work to be potentially helpful to be applied as both framework and database for wearable device engineers and researchers who are experimenting with varying PDMS concentrations and modulus.

Optimizing PET Glycolysis with an Oyster Shell-Derived Catalyst Using Response Surface Methodology.

Polyethylene terephthalate (PET) waste was depolymerized into bis(2-hydroxyethyl) terephthalate (BHET) through glycolysis with the aid of oyster shell-derived catalysts. The equilibrium yield of BHET was as high as 68.6% under the reaction conditions of mass ratios (EG to PET = 5, catalyst to PET = 0.01) at 195 °C for 1 h. Although biomass-derived Ca-based catalysts were used for PET glycolysis to obtain BHET monomers, no statistical analysis was performed to optimize the reaction conditions. Thus, in this study, we applied response surface methodology (RSM) based on three-factor Box-Behnken design (BBD) to investigate the optimal conditions for glycolysis by analyzing the independent and interactive effects of the factors, respectively. Three independent factors of interest include reaction time, temperature, and mass ratio of catalyst to PET under a fixed amount of ethylene glycol (mass ratio of EG to PET = 5) due to the saturation of the yield above the mass ratio. The quadratic regression equation was calculated for predicting the yield of BHET, which was in good agreement with the experimental data (R2 = 0.989). The contour and response surface plots showed the interaction effect between three variables and the BHET yield with the maximum average yield of monomer (64.98%) under reaction conditions of 1 wt% of mass ratio (catalyst to PET), 195 °C, and 45 min. Both the experimental results and the analyses of the response surfaces revealed that the interaction effects of reaction temperature vs. time and temperature vs. mass ratio of the catalyst to the PET were more prominent in comparison to reaction time vs. mass ratio of the catalyst to the PET.

Magnetic polymer bowl for enhanced catalytic activity and recyclability.

This work introduces the fabrication of a magnetic polymer bowl for enhanced catalytic activity and recyclability, which involves the synthesis of silica-coated Fe3O4 magnetic clusters, seeded dispersion polymerization using the magnetic clusters, and transformation into a bowl-like structure via a phase separation route. The additional treatment with tannic acid (TA) on the bowls allows the in situ formation of silver nanoparticles (AgNPs) on their surfaces. The openness and larger surface area of the bowls, as compared with those of other structured particles, such as spheres and flowers, enable a considerably higher immobilization of AgNPs, thus leading to an excellent catalytic reduction for 4-nitrophenol (4-NP), methylene blue (MB), and rhodamine B. Furthermore, the strong magnetic response originating from the magnetic clusters inside the bowls endows a good magnetic recovery and an excellent reusability for the repeated reduction of the organic dyes without loss of catalytic activity.

Yolk-Shell Nanostructures: Syntheses and Applications for Lithium-Ion Battery Anodes.

Yolk-shell nanostructures have attracted tremendous research interest due to their physicochemical properties and unique morphological features stemming from a movable core within a hollow shell. The structural potential for tuning inner space is the focal point of the yolk-shell nanostructures in a way that they can solve the long-lasted problem such as volume expansion and deterioration of lithium-ion battery electrodes. This review gives a comprehensive overview of the design, synthesis, and battery anode applications of yolk-shell nanostructures. The synthetic strategies for yolk-shell nanostructures consist of two categories: templating and self-templating methods. While the templating approach is straightforward in a way that the inner void is formed by removing the sacrificial layer, the self-templating methods cover various different strategies including galvanic replacement, Kirkendall effect, Ostwald ripening, partial removal of core, core injection, core contraction, and surface-protected etching. The battery anode applications of yolk-shell nanostructures are discussed by dividing into alloying and conversion types with details on the synthetic strategies. A successful design of yolk-shell nanostructures battery anodes achieved the improved reversible capacity compared to their bare morphologies (e.g., no capacity retention in 300 cycles for Si@C yolk-shell vs. capacity fading in 10 cycles for Si@C core-shell). This review ends with a summary and concluding remark yolk-shell nanostructures.

Poly(ε-caprolactone) (PCL) Hollow Nanoparticles with Surface Sealability and On-Demand Pore Generability for Easy Loading and NIR Light-Triggered Release of Drug.

A new system for the easy loading and NIR light-triggered release of drugs is introduced. It consists of poly(ε-caprolactone) (PCL) hollow nanoparticles with surface openings containing a biodegradable fatty acid with phase-change ability and a biocompatible photothermal agent. These openings, which can enhance the connectivity between the interior and the exterior, enable the easy loading of drug molecules into the interior voids, and their successive sealing ensures a stable encapsulation of the drug. Upon exposure to an external NIR light irradiation, the photothermal agent generates heat that raises the local temperature of the hollow particles above the melting point of the fatty acid, leading to the formation of nanopores on their shells, and consequently, the instant release of the encapsulated drug molecules through the pores. The synergistic activity of the hyperthermia effect from the photothermal agent and the NIR-triggered release of the drug molecules results in noticeable anticancer efficacy.

Gold Nanocage-Incorporated Poly(ε-Caprolactone) (PCL) Fibers for Chemophotothermal Synergistic Cancer Therapy.

This paper introduces a new fibrous system for synergistic cancer therapy, which consists of gold nanocage (AuNC)-loaded poly(ε-caprolactone) (PCL) fibers with encapsulation of a chemotherapeutic anticancer drug in their core and loading of a phase-changeable fatty acid in their sheath. Under on⁻off switching of near-infrared (NIR) light irradiation, the excellent photothermal ability and photostability of AuNCs allows repeated, significant heating of the fibers to a temperature available to hyperthermia. Simultaneously, the NIR light-induced heat generation enables the melting out of the loaded fatty acid, leading to a rapid release of the drug molecules from the fibers. The combination of this NIR light-triggered drug release with the repeated hyperthermia treatment exhibits excellent anticancer efficacy.

Poly(d,l-lactic-co-glycolic acid) (PLGA) hollow fiber with segmental switchability of its chains sensitive to NIR light for synergistic cancer therapy.

This work introduces a new fibrous system for synergistic cancer therapy. The system consists of poly(d,l-lactic-co-glycolic acid) (PLGA) fibers with a core encapsulating an anticancer drug and a shell entrapping gold nanorods (AuNRs) as a photothermal agent. On exposure to NIR light, the photothermal agent generates heat to raise the local temperature of the fibers. If the temperature is above a glass transition (Tg) of the polymer, the polymer chains will be mobile, increasing free volume in size within the shell. As a result, a rapid release of the drug can be achieved. When NIR light is turned off, the release will stop with inactivity of the photothermal agent, followed by freezing the segmental motion of the polymer chains. The on-off switching of NIR light in a time-controllable manner allows a repeated and accurate release of the drug, leading to the significant enhancement of anticancer activity in combination with the hyperthermia effect arising from the photothermal agent.

Dimensional and compositional change of 1D chalcogen nanostructures leading to tunable localized surface plasmon resonances.

As part of the oxygen family, chalcogen (Se, Te) nanostructures have been considered important elements for various practical fields and further exploited to constitute metal chalcogenides for each targeted application. Here, we report a controlled synthesis of well-defined one-dimensional chalcogen nanostructures such as nanowries, nanorods, and nanotubes by controlling reduction reaction rate to fine-tune the dimension and composition of the products. Tunable optical properties (localized surface plasmon resonances) of these chalcogen nanostructures are observed depending on their morphological, dimensional, and compositional variation.

Ultrathin silver telluride nanowire films and gold nanosheet electrodes for a flexible resistive switching device.

We demonstrated a flexible resistive switching device based on ultrathin Ag2Te nanowire (NW) films and Au nanosheet (NS) electrodes by exploiting a monolayer assembly on the water surface for macroscale two-dimensional structures. Firstly, ultrathin TeNWs (diameter ≈ 10 nm) are rapidly assembled on the water surface as a form of monolayer and transferred to fabricate TeNW films on various substrates with any available size. An assembled TeNW film was used as a template to produce a Ag2TeNW film through chemical transformation. A well-aligned Ag2TeNW film device showed reversible resistive switching properties when the Ag composition of the silver telluride NW becomes stoichiometric Ag2Te. Additionally, a non-stoichiometric Ag2+δTeNW film shows an increased On/Off ratio. For a flexible memory device, ultrathin AuNSs (thickness ≤20 nm) were adopted as working electrodes, since thermally deposited gold electrodes tend to crack under strain, which can fail to maintain the electrical properties. A paper-like flexibility of AuNS proved its capability as optimal electrodes of ultrathin Ag2TeNW film-based resistive memory devices.

Decoration of size-tunable CuO nanodots on TiO2 nanocrystals for noble metal-free photocatalytic H2 production.

We report a simple yet effective approach for the decoration of the TiO2 nanocrystal surface with size-tunable CuO nanodots for high-performance noble metal-free photocatalytic H2 production. Modification with polyacrylic acid enables the surface of TiO2 nanocrystals to be selectively deposited with Cu(OH)2 nanodots, which can be subsequently converted to CuO through dehydration without changing their morphologies. UV irradiation of the nanocomposite solution in the presence of a hole scavenger produces photogenerated electrons which reduce CuO to metallic Cu nanodots, making them effective co-catalysts in a role similar to Pt for promoting photocatalytic H2 production. Due to the considerably high work function of Cu, the formation of a metal-semiconductor Schottky junction induces efficient charge separation and transfer. As a result, the TiO2 nanocrystals decorated with an optimal amount of CuO nanodots (1.7 wt%) could reach ∼50% of the photocatalytic activity achievable by the Pt-TiO2 counterparts (1 wt%), clearly demonstrating the great potential of such composite catalysts for efficient noble metal-free photocatalytic H2 production.

Stacked multilayers of alternating reduced graphene oxide and carbon nanotubes for planar supercapacitors.

A simple layer-by-layer approach has been developed for constructing 2D planar supercapacitors of multi-stacked reduced graphene oxide and carbon nanotubes. This sandwiched 2D architecture enables the full utilization of the maximum active surface area of rGO nanosheets by using a CNT layer as a porous physical spacer to enhance the permeation of a gel electrolyte inside the structure and reduce the agglomeration of rGO nanosheets along the vertical direction. As a result, the stacked multilayers of rGO and CNTs are capable of offering higher output voltage and current production.

Highly stretchable patterned gold electrodes made of Au nanosheets.

Multilayered Au nanosheets are suggested as a novel class of material for fabricating stretchable electrodes suitable for organic-based electronic devices. The electrodes show no difference in resistivity during repeated stretching cycles of up to ϵ = 40%.

Quick, controlled synthesis of ultrathin Bi2Se3 nanodiscs and nanosheets.

Ultrathin (4-6 nm) single-crystal Bi(2)Se(3) nanodiscs and nanosheets were synthesized through a simple and quick solution process. The growth mechanism was investigated in detail. Crystal seeds grew via 2D self-attachment of small nanoparticles followed by epitaxial recrystallization into single crystals. The lateral dimension of the nanodiscs increased and their shape changed from circles to hexagons as the reaction temperature increased. Positively charged polymer surfactants greatly enlarged the lateral dimension to produce nanosheets with uniform thickness.

Surfactant-free CuInSe2 nanocrystals transformed from In2Se3 nanoparticles and their application for a flexible UV photodetector.

In(2)Se(3) nanoparticles were synthesized in an aqueous solution without using any surfactant and then chemically transformed into CuInSe(2) nanocrystals. The transformation was thermodynamically favorable and fast. The 93% production yield in mild reaction conditions allowed mass production of the CuInSe(2) nanocrystals. By the virtue of the surface charges, the CuInSe(2) nanocrystals were well dispersed in polar solvents. The surfactant-free nanocrystals enabled the formation of semiconducting CuInSe(2) films on a flexible polymer substrate without any thermal treatment. We took advantage of this to fabricate a flexible UV photodetector. The current and sensitivity of the devices could be improved by utilizing CuInSe(2) nanocrystals annealed at 160 °C in the reaction batch. On bending test, the detection sensitivity remained the same until the bending radius was reduced down to 4 mm. The dynamic response of the film device was stable and reproducible during light illumination (350 nm).

Assembled monolayers of hydrophilic particles on water surfaces.

A facile and quick approach to prepare self-assembled monolayers of water-dispersible particles on the water surface is presented. Particle suspensions in alcohols were dropped on a water reservoir to form long-range ordered monolayers of various particles, including spherical solid particles, soft hydrogel particles, metal nanoparticles, quantum dots, nanowires, single-wall carbon nanotubes (SWCNTs), nanoplates, and nanosheets. A systematic study was conducted on the variables affecting the monolayer assembly: the solubility parameter of spreading solvents, particle concentration, zeta potential of the particles in the suspension, surface tension of the water phase, hardness of the particles, and addition of a salt in the suspension. This method requires no hydrophobic surface treatment of the particles, which is useful to exploit these monolayer films without changing the native properties of the particles. The study highlights a quick 2D colloidal assembly without cracks in the wafer scale as well as transparent conductive thin films made of SWCNTs and graphenes.

Shape control of cadmium hydroxides (Cd(OH)2) sensitive to pH quenching depth and massive production of CdSe nanocrystals by their chemical transformation.

This study demonstrates that the structure of cadmium hydroxides (Cd(OH)(2)) precipitated from a basic cadmium nitrate solution can be finely controlled by adjusting the pH of the precursor solution. The synthesis process involves only pouring the saturated solution into pure water to quench the pH and the total process is finished within 30 s. At a shallow pH quenching, the unstable nanoparticles turned into microparticles via a ripening process. Cd(OH)(2) was precipitated in the form of one-dimensional nanowires and then two-dimensional plates as the pH quenching was increased. At a large pH quenching, porous aggregates of Cd(OH)(2) were obtained due to the too fast precipitation. The ultrafine Cd(OH)(2) nanowires were readily transformed into CdSe chain-like nanocrystals. The transformation was quick and gave 100% yield, facilitating massive production of CdSe nanocrystals in an aqueous condition. The Cd(OH)(2) nanowires were directly grown on Si nanowires and transformed into CdSe chain-like nanocrystals, decorating the surface of each Si nanowire.

A new theranostic system based on gold nanocages and phase-change materials with unique features for photoacoustic imaging and controlled release.

This communication reports a new theranostic system with a combination of capabilities to both enhance the contrast of photoacoustic (PA) imaging and control the release of a chemical or biological effector by high-intensity focused ultrasound (HIFU). The fabrication of this system simply involves filling the hollow interiors of gold nanocages with a phase-change material (PCM) such as 1-tetradecanol that has a melting point of 38-39 °C. The PCM can be premixed and thus loaded with a dye, as well as other chemical or biological effectors. When exposed to direct heating or HIFU, the PCM will melt and escape from the interiors of nanocages through small pores on the surface, concurrently releasing the encapsulated molecules into the surrounding medium. We can control the release profile by varying the power of HIFU, the duration of exposure to HIFU, or both.