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.

Heat's Role in Solution Electrospinning: A Novel Approach to Nanofiber Structure Optimization.

In this study, we explored an innovative application of heat-assisted solution electrospinning, a technique that significantly advances the control of phase separation in polystyrene (PS) fibers. Our experimental approach involved the use of direct heating and a convection air sheath applied through a coaxial needle, focusing on solvents with varying vapor pressures. This method enabled a detailed investigation into how solvent evaporation rates affect the morphology of the electrospun fibers. SEM and AFM measurements revealed that the application of direct heating and a heated air sheath offered precise control over the fiber morphology, significantly influencing both the surface and internal structure of the fibers. Additionally, we observed notable changes in fiber diameter, indicating that heat-assisted electrospinning can be effectively utilized to tailor fiber dimensions according to specific application requirements. Moreover, our research demonstrated the critical role of solvent properties, particularly vapor pressure, in determining the final characteristics of the electrospun fibers. By comparing fibers produced with different solvents, we gained insights into the complex interplay between solvent dynamics and heat application in fiber formation. The implications of these findings are far-reaching, offering new possibilities for the fabrication of nanofibers with customized properties. Furthermore, this could have profound impacts on various applications, from biomedical to environmental, where specific fiber characteristics are crucial. This study not only contributes to the understanding of phase separation in electrospinning but also opens avenues for further research on the optimization of fiber properties for diverse industrial and scientific applications.

Advancing Nanofiber Research: Assessing Nonsolvent Contributions to Structure Using Coaxial Electrospinning.

In this study, we explored the influence of molecular interactions and solvent evaporation kinetics on the formation of porous structures in electrospun nanofibers, utilizing polyacrylonitrile (PAN) and polystyrene (PS) as model polymers. The coaxial electrospinning technique was employed to control the injection of water and ethylene glycol (EG) as nonsolvents into polymer jets, demonstrating its potential as a powerful tool for manipulating phase separation processes and fabricating nanofibers with tailored properties. Our findings highlighted the critical role of intermolecular interactions between nonsolvents and polymers in governing phase separation and porous structure formation. Additionally, we observed that the size and polarity of nonsolvent molecules affected the phase separation process. Furthermore, solvent evaporation kinetics were found to significantly impact phase separation, as evidenced by less distinct porous structures when using a rapidly evaporating solvent like tetrahydrofuran (THF) instead of dimethylformamide (DMF). This work offers valuable insights into the intricate relationship between molecular interactions and solvent evaporation kinetics during electrospinning, providing guidance for researchers developing porous nanofibers with specific characteristics for various applications, including filtration, drug delivery, and tissue engineering.

A Polymeric Bowl for Multi-Agent Delivery.

This paper describes a simple system for multi-agent delivery. The system consists of a biodegradable polymer particle with a hollow interior, together with a hole on its surface that can be completely or partially sealed via thermal annealing. A hydrophobic dye, Nile-red, entrapped within the shell of hollow particles presents a sustained release behavior while methylene blue, a hydrophilic model agent, encapsulated in the hollow interior shows a fast release manner. The release profiles of the probes can be further independently controlled by encapsulating methylene blue-loaded polymer nanoparticles, instead of free dye, in the hollow particle with a small hole on its surface.

Protein capsules with cross-linked, semipermeable, and enzyme-degradable surface barriers for controlled release.

This paper describes a method for fabricating protein-based capsules with semipermeable and enzyme-degradable surface barriers. It involves the use of a simple fluidic device to generate water-in-oil emulsion droplets, followed by cross-linking of proteins at the water-oil interface to generate a semipermeable surface barrier. The capsules can be readily fabricated with uniform and controllable sizes and, more importantly, show selective permeability toward molecules with different molecular weights: small molecules like fluorescein sodium salt can freely diffuse through the surface barrier while macromolecules such as proteins can not. The proteins, however, can be released by digesting the surface barrier with an enzyme such as pepsin. Taken together, the capsules hold great potential for applications in controlled release, in particular, for the delivery of protein drugs.

Emerging applications of phase-change materials (PCMs): teaching an old dog new tricks.

The nebulous term phase-change material (PCM) simply refers to any substance that has a large heat of fusion and a sharp melting point. PCMs have been used for many years in commercial applications, mainly for heat management purposes. However, these fascinating materials have recently been rediscovered and applied to a broad range of technologies, such as smart drug delivery, information storage, barcoding, and detection. With the hope of kindling interest in this incredibly versatile range of materials, this Review presents an array of aspects related to the compositions, preparations, and emerging applications of PCMs.

Engineered nanoparticles for drug delivery in cancer therapy.

In medicine, nanotechnology has sparked a rapidly growing interest as it promises to solve a number of issues associated with conventional therapeutic agents, including their poor water solubility (at least, for most anticancer drugs), lack of targeting capability, nonspecific distribution, systemic toxicity, and low therapeutic index. Over the past several decades, remarkable progress has been made in the development and application of engineered nanoparticles to treat cancer more effectively. For example, therapeutic agents have been integrated with nanoparticles engineered with optimal sizes, shapes, and surface properties to increase their solubility, prolong their circulation half-life, improve their biodistribution, and reduce their immunogenicity. Nanoparticles and their payloads have also been favorably delivered into tumors by taking advantage of the pathophysiological conditions, such as the enhanced permeability and retention effect, and the spatial variations in the pH value. Additionally, targeting ligands (e.g., small organic molecules, peptides, antibodies, and nucleic acids) have been added to the surface of nanoparticles to specifically target cancerous cells through selective binding to the receptors overexpressed on their surface. Furthermore, it has been demonstrated that multiple types of therapeutic drugs and/or diagnostic agents (e.g., contrast agents) could be delivered through the same carrier to enable combination therapy with a potential to overcome multidrug resistance, and real-time readout on the treatment efficacy. It is anticipated that precisely engineered nanoparticles will emerge as the next-generation platform for cancer therapy and many other biomedical applications.

Exploring temperature-responsive drug delivery with biocompatible fatty acids as phase change materials in ethyl cellulose nanofibers.

This study introduces a novel temperature-responsive drug delivery system using ethyl cellulose (EC) nanofibers encapsulating a eutectic mixture of lauric acid/stearic acid (LA/SA) as phase change materials (PCMs) and Rhodamine B (RhB) as a model drug. Employing blend electrospinning, the nanofibers achieved controlled drug release responsive to temperature changes. The peak shift of the carbonyl group in FTIR analysis confirmed drug-polymer compatibility, while the absence of RhB peaks in the XRD and DSC assessments revealed RhB's amorphous distribution within the fibers. Our findings demonstrate that RhB release is dependent on its loading, with a slow initial release (<2 %) for 1 % and 5 % RhB loadings and a burst release (~12 %) for 10 % loading. Notably, the release rate was tunable at 37 °C by adjusting LA/SA concentration. The optimal LA/SA loading for temperature-responsive release is identified as 10 %. Over 240 h, there is a 32 % increase in RhB release at 37 °C, and an additional 8 % increase at 40 °C, compared to 25 °C. This research illustrates the potential of PCM-integrated nanofibers in smart drug delivery, particularly for chemotherapy, antibiotics, and anti-inflammatory drugs, showcasing an innovative approach to improving therapeutic efficiency while reducing side effects.

Microscale polymer bottles corked with a phase-change material for temperature-controlled release.

Keep your wine chilled! Microscale polystyrene (PS) bottles are loaded with dye molecules and then corked with a phase-change material (PCM). When the temperature is raised beyond its melting point, the PCM quickly melts and triggers an instant release of the encapsulated dye. The release profiles can be manipulated by using a binary mixture of PCMs with different melting points.

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.

Efficient and Secure Encapsulation of a Natural Phase Change Material in Nanofibers Using Coaxial Electrospinning for Sustainable Thermal Energy Storage.

In this study, we present an ecofriendly technique for encapsulating lauric acid (LA), a natural phase change material, within polystyrene (PS) nanofibers through coaxial electrospinning. The resulting LAPS core-sheath nanofibers exhibited a melting enthalpy of up to 136.6 J/g, representing 75.8% of the heat storage capacity of pristine LA (180.2 J/g), a value surpassing all previously reported core-sheath fibers. Scanning electron microscopy revealed uniform LAPS nanofibers free of surface LA until the core LA feed rate reached 1.3 mL/h. As the core LA feed rate increased, the fiber diameter shrank from 2.24 ± 0.31 to 0.58 ± 0.45 µm. Infrared spectra demonstrated a proportional increase in the LA content with rising core LA injection rates. Thermogravimetric analysis found the maximum core LA content in core-sheath nanofibers to be 75.0%. Differential scanning calorimetry thermograms displayed a trend line shift upon LA leakage for LA1.3PS nanofibers. LAPS fibers containing 75.0% LA effectively maintained consistent cycling stability and reusability across 100 heating-cooling cycles (20-60 °C) without heat storage deterioration. The core LA remained securely within the PS sheath after 100 cycles, and the LAPS nanofibers retained an excellent structural integrity without rupture. The energy-dense and form-stable LAPS core-sheath nanofibers have great potential for various thermal energy storage applications, such as building insulation, smart textiles, and electronic cooling systems, providing efficient temperature regulation and energy conservation.

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.

New Autonomous Water-Enabled Self-Healing Coating Material with Antibacterial-Agent-Releasing Properties.

A new autonomous water-enabled self-healing coating with antibacterial-agent-releasing capability was developed for the first time by precipitating an aqueous solution of hydrogen-bonded tannic acid (TA) and polyethylene glycol (PEG) (TA: 5 mg/mL; PEG: 5 mg/mL with MW = 100 kDa) to form a smooth, uniform coating layer with an average roughness of 0.688 nm and thickness of 22.3 µm on a polymethyl methacrylate (PMMA) substrate after 10 min of incubation. Our method is cost- and time-efficient, as the hydrophilic coating (water contact angle = 65.1°) forms rapidly, binding strongly to the PMMA substrate (adhesive energy = 83 mJ/m2), without the need for pretreatment or surface modification, and is capable of rapid self-repair (approximately 5 min) through hydrogen bonding in aqueous media. Furthermore, adding 0.5 mg/mL of chlorhexidine acetate (CHX), a commonly used antibacterial agent in dentistry, into the TA-PEG emulsion allowed the release of 2.89 µg/mL of the drug from the coating layer, which is promising for actively inhibiting the vitality and growth of bacteria around PMMA dental restorations. The use of CHX-loaded TA-PEG hydrogen-bonded complexes is highly favorable for the fabrication of an autonomous self-healing biocoating with active antibacterial-agent-releasing capability, which can be applied not only in dentistry but also in other medical fields.

Characterization of Silver Nanowire-Based Transparent Electrodes Obtained Using Different Drying Methods.

Metal-based transparent top electrodes allow electronic devices to achieve transparency, thereby expanding their application range. Silver nanowire (AgNW)-based transparent electrodes can function as transparent top electrodes, owing to their excellent conductivity and transmittance. However, they require a high-temperature drying process, which damages the bottom functional layers. Here, we fabricated two types of AgNW-based electrodes using the following three drying methods: thermal, room-temperature, and vacuum. Thereafter, we investigated the variation in their morphological, electrical, and optical characteristics as a function of the drying method and duration. When the AgNW-exposed electrode was dried at room temperature, it exhibited a high surface roughness and low conductivity, owing to the slow solvent evaporation. However, under vacuum, it exhibited a similar electrical conductivity to that achieved by thermal drying because of the decreased solvent boiling point and fast solvent evaporation. Conversely, the AgNW-embedded electrodes exhibited similar roughness values and electrical conductivities regardless of the drying method applied. This was because the polymer shrinkage during the AgNW embedding process generated capillary force and improved the interconnectivity between the nanowires. The AgNW-based electrodes exhibited similar optical properties regardless of the drying method and electrode type. This study reveals that vacuum drying can afford transparent top electrodes without damaging functional layers.

Continuous production of functionalized polymer particles employing the phase separation in polymer blend films.

This study reports a continuous prepartion of spherical or hemispherical polymer particles simply utilizing the phase separation in polymer blend films during the coating process. We took an advantage of the strong phase separation between a water-soluble crystalline polymer as a matrix and hydrophobic polymers as minor components. We demonstrated the prepartion of water-soluble polystyrene (PS) particles, nitrilotriacetic acid (NTA)-functionalized PS particles for protein separation, and semiconducting poly(3-hexylthiophene) (P3HT) particles. The sizes of the particles could be controlled by adjusting the film thickness and weight fraction of the minor component polymers in the blend film. It provides a simple facile way to prepare polymer particles in a continous process.

Characterization of optical manipulation using microlens arrays depending on the materials and sizes in organic photovoltaics.

Various physical structures have improved light-harvesting and power-conversion efficiency in organic photovoltaic devices, and optical simulations have supported the improvement of device characteristics. Herein, we experimentally investigated how microlens arrays manipulate light propagation in microlens films and material stacks for organic photovoltaics to understand the influence of the constituent materials and sizes of the microlens. As materials to fabricate a microlens array, poly(dimethylsiloxane) and Norland Optical Adhesive 63 were adopted. The poly(dimethylsiloxane) microlens array exhibited higher total transmittance and higher diffuse transmittance, further enhancing the effective optical path and light extinction in material stacks for organic photovoltaics. This resulted in more current generation in an organic photovoltaic device with a poly(dimethylsiloxane) microlens array than in a Norland Optical Adhesive 63 microlens array. The sizes of the microlenses were controlled from 0.5 to 10 µm. The optical characteristics of microlens array films and material stacks with microlenses generally increased with size of the microlens, leading to a 10.6% and 16.0% improvement in the light extinction and power-conversion efficiency, respectively. In addition, electron and current generation in material stacks for organic photovoltaics were calculated from light extinction. The theoretical current generation matched well with experimental values derived from organic photovoltaic devices. Thus, the optical characterization of physical structures helps to predict how much more current can be generated in organic photovoltaic cells with a certain physical structure; it can also be used for screening the physical structures of organic photovoltaic cells.

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.

Enhancing the conductivity of PEDOT:PSS films for biomedical applications via hydrothermal treatment.

This paper reports a new biocompatible conductivity enhancement of poly (3,4-ethylenedioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) films for biomedical applications. Conductivity of PEDOT:PSS layer was reproducibly from 0.495 to 125.367 S cm-1 by hydrothermal (HT) treatment. The HT treatment employs water (relative humidity > 80%) and heat (temperature > 61 °C) instead of organic solvent doping and post-treatments, which can leave undesirable residue. The treatment can be performed using the sterilizing conditions of an autoclave. Additionally, it is possible to simultaneously reduce the electrical resistance, and sterilize the electrode for practical use. The key to conductivity enhancement was the structural rearrangement of PEDOT:PSS, which was determined using atomic force microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and ultraviolet-visible spectroscopy. It was found that PEDOT inter-bridging occurred as a result of the structural rearrangement. Therefore, the conductivity increased on account of the continuous conductive pathways of the PEDOT chains. To test the biocompatible enhancement technique for biomedical applications, certain demonstrations, such as the monitoring of joint movements and skin temperature, and measuring electrocardiogram signals were conducted with the hydrothermal-treated PEDOT:PSS electrode. This simple, biocompatible treatment exhibited significant potential for use in other biomedical applications as well.

In situ Localization of Molecules in Crosslinked Particles during Electrohydrodynamic Process: Simple Route to Produce Microcapsules and Fibers with Controlled Release.

This study reports a spontaneous selective localization of molecules in crosslinked particles during electrospraying and electrospinning polymer solutions containing the particles. It provides a facile way of preparing microcapsules and fibers with controlled release. The dye molecules were phase separated from the crystalline polymer matrix during the electrohydrodynamic process and moved to the solvent-rich crosslinked particles. The position of the particles in the microcapsules and fibers could be controlled by adjusting compatibility of the particles with the matrix polymer. The microcapsules and fibers did not show the initial burst release of the molecules and gave considerably prolonged release behavior.

Effect of Low-Pressure Plasma Treatment Parameters on Wrinkle Features.

Wrinkles attract significant attention due to their ability to enhance the mechanical and optical characteristics of various optoelectronic devices. We report the effect of the plasma gas type, power, flow rate, and treatment time on the wrinkle features. When an optical adhesive was treated using a low-pressure plasma of oxygen, argon, and nitrogen, the oxygen and argon plasma generated wrinkles with the lowest and highest wavelengths, respectively. The increase in the power of the nitrogen and oxygen plasma increased the wavelengths and heights of the wrinkles; however, the increase in the power of the argon plasma increased the wavelengths and decreased the heights of the wrinkles. Argon molecules are heavier and smaller than nitrogen and oxygen molecules that have similar weights and sizes; moreover, the argon plasma comprises positive ions while the oxygen and nitrogen plasma comprise negative ions. This resulted in differences in the wrinkle features. It was concluded that a combination of different plasma gases could achieve exclusive control over either the wavelength or the height and allow a thorough analysis of the correlation between the wrinkle features and the characteristics of the electronic devices.