Effects of Raman Labeling Compounds on the Stability and Surface-Enhanced Raman Spectroscopy Performance of Ag Nanoparticle-Embedded Silica Nanoparticles as Tagging Materials.

Surface-enhanced Raman spectroscopy (SERS) tagging using silica(SiO2)@Ag nanoparticles (NPs) is easy to handle and is being studied in various fields, including SERS imaging and immunoassays. This is primarily due to its structural advantages, characterized by high SERS activity. However, the Ag NPs introduced onto the SiO2 surface may undergo structural transformation owing to the Ostwald ripening phenomenon under various conditions. As a result, the consistency of the SERS signal decreases, reducing their usability as SERS substrates. Until recently, research has been actively conducted to improve the stability of single Ag NPs. However, research on SiO2@Ag NPs used as a SERS-tagging material is still lacking. In this study, we utilized a Raman labeling compound (RLC) to prevent the structural deformation of SiO2@Ag NPs under various conditions and proposed excellent SiO2@Ag@RLC-Pre NPs as a SERS-tagging material. Using various RLCs, we confirmed that 4-mercaptobenzoic acid (4-MBA) is the RLC that maintains the highest stability for 2 months. These results were also observed for the SiO2@Ag NPs, which were unstable under various pH and temperature conditions. We believe that SERS tags using SiO2@Ag NPs and 4-MBA can be utilized in various applications on based SERS because of the high stability and consistency of the resulting SERS signal.

Dynamic mucus secretion in ventral surfaces of toe pads of the tree frog (Dryophytes japonica).

The tree frog is a prominent amphibian among terrestrial vertebrates known for its ability to adhere to various surfaces through the capillary forces of water in the microchannels between micropillars on its disc-shaped toe pads, a phenomenon known as wet adhesion. However, the secretion pattern of mucus on the attachment surface of living tree frog toe pads and the distribution of active mucus pores (AMPs) have not yet been fully elucidated. In this study, we utilized synchrotron X-ray micro-computed tomography and interference reflection microscopy to obtain the spatial distribution of the entire population of ventral mucus glands on the toe pads of living tree frogs and the real-time mucus secretion patterns from the ventral mucus pores on the contact surface under different environmental conditions. We observed that the number and secretion frequency of AMPs on the toe pad are regulated according to environmental conditions. Such dynamic mucus secretion on the tree frog's toe pad could contribute to the understanding of capillary force regulation for wet adhesion and the development of adhesive surfaces by mimicking the mucus-secreting toe pad.

Gold-Nanolayer-Derived Zincophilicity Suppressing Metallic Zinc Dendrites and Its Efficacy in Improving Electrochemical Stability of Aqueous Zinc-Ion Batteries.

Herein, an Au-coating layer adjusted on the surface of a Zn metal electrode that effectively suppresses the dendrite growth as well as the mechanisms underlying the dendrite suppression as a result of the zincophilic character of Au is introduced. For the Au-coated Zn metal symmetric cell, uniform deposition of Zn-derived compounds was revealed by operando synchrotron tomography. Microscopic studies demonstrate that the Au-coating layer is induced to form a new Zn-Au alloy during the initial Zn deposition, resulting in stabilized long-term stripping/plating of Zn via the 'embracing effect' that intimately accommodates Zn deposition for further cycles. This property supports the successful operation of symmetrical cells up to 50 mA cm-2 . According to Zn electrodeposition simulation, it is verified that the suppression of dendrite growth is responsible for the electro-conducting Au nanolayer that uniformly distributes the electric field and protects the Zn electrode from corrosion, ultimately promoting uniform Zn growth. The compatibility of the Au-coating layer for full cell configuration is verified using NaV3 O8 as a cathode material over 1 000 cycles. This finding provides a new pathway for the enhancement of the electrochemical performance of ZIBs by suppressing the dendritic growth of Zn by means of a zincophilic Au nanolayer.

Large-Area Mapping of Voids and Dislocations in Basal-Faceted Sapphire Ribbons by Synchrotron Radiation Imaging.

The understanding of structural defects in basal-faceted sapphire ribbons was improved through X-ray imaging at a synchrotron source. The combination of phase contrast and X-ray diffraction makes it possible to visualize and characterize both gas voids and dislocations in the bulk of the ribbons grown by the Stepanov-LaBelle technology. Dislocations were directly related to gas voids. X-ray diffraction topography was employed to investigate the distribution, configurations, and character of the dislocations. The formation of voids of irregular shapes was detected by large-area mapping with spatial resolution in the µm range. Computer simulations of the experimental phase contrast images of microvoids were performed. The sizes of the spherical microvoids were determined. The results are discussed with reference to the available data on the emission of dislocations from the voids. The evolution of the shape, size, and arrangement of the voids during growth provides clues on the formation of block structure in basal-faceted sapphire ribbons.

Self-array of one-dimensional GaN nanorods using the electric field on dielectrophoresis for the photonic emitters of display pixel.

Recently, high-efficiency III-nitride photonic emitters (PEs) for next-generation displays have been studied. Although micro-light-emitting diodes (µ-LEDs), one of the III-nitride PEs, have attracted considerable attention because of their high efficiency and size flexibility, they have encountered technical limitations such as high defect rate, high processing cost, and low yield. To overcome these drawbacks of µ-LEDs, a lot of research on PEs using one-dimensional (1D) gallium nitride-related nanorods (GNRs) capable of horizontally self-positioning on the electrodes has been carried out. The degree of array of GNRs on the interdigitated electrodes (IDEs) is an important factor in the efficiency of the PEs using GNRs to obtain excellent single-pixel characteristics. Therefore, in this study, we demonstrate that the improved performance of self-arrayed GNRs was realized using the dielectrophoresis technique by changing the thickness of IDEs. In addition, the shape and size of vertically aligned GNRs were controlled by the wet process, and GNR-integrated PEs (GIPEs) were driven by perfectly horizontally self-arrayed GNRs on IDEs. The electroluminescence (EL) intensity of the GIPEs was measured at 4-20 V and showed a maximum intensity value at 15 V. Over the injection voltage at 20 V, the EL intensity decreased due to the high current density of GIPEs. The external quantum efficiency (EQE) property of the GIPEs showed a similar efficiency droop as that of conventional III-nitride PEs.

Anodic Aluminum Oxide-Based Chemi-Capacitive Sensor for Ethanol Gas.

Alcohol ingested by humans can be analyzed via breath tests; however, approximately 1% can be excreted via the skin. In this paper, we present a capacitive sensor using hydrophobically treated anodic aluminum oxide (AAO) capable of detecting alcohol excreted through the epidermis. The degree of hydrophobicity based on the duration of exposure to 3-aminopropyltriethoxysilane vapor comprising a small number of Si-NH2 functional groups on the AAO surface was confirmed and the optimal exposure time was confirmed to be 60 min. The hydrophobized AAO showed a 4.8% reduction in sensitivity to moisture. Simultaneously, the sensitivity of the sensor to ethanol decreased by only 12%. Lastly, the fabricated sensor was successfully operated by attaching it to an ankle-type breathalyzer.

Four-Dimensional Visualization of Microscale Dynamics of Membrane Oil Fouling via Synchrotron Radiation Microcomputed Tomography.

Although oil-water separation technology via wettability-controlled membranes has emerged as a promising technology to treat oily wastewater, membrane fouling by faulents such as sludge flocs and colloids, and the consequent clogging of pores, severely degrades the efficiency of filtration systems. One of the main promotors of fouling by faulents is oil fouling, which is also a form of fouling itself. Despite considerable practical and academic interest in the analysis of oil-fouled membranes, direct visualization of the entire process of oil infiltration into hydrophilic membranes is still preliminary owing to (i) the similar optical contrast and physical density between oil and water, (ii) the low penetration depth of imaging methods, and (iii) the lack of 3D segmentation capability. In this study, microcomputed X-ray tomography using tunable synchrotron radiation provided direct high-speed 3D visualization of the microscale dynamics of the oil infiltration of a prewetted hydrophilic filter membrane over time. Direct visualization of the interfacial dynamics of oil infiltration opens a window into the complex liquid (water/oil)-gas-solid interface and thus helps furnish an in-depth understanding of oil fouling in the prewetted membrane.

Synthesis of Copper Telluride Thin Films by Electrodeposition and Their Electrical and Thermoelectric Properties.

Intermetallic copper telluride thin films, which are important in a number of electronics fields, were electrodeposited using a potentiostatic method in low-pH aqueous electrolyte baths with various ion-source concentrations, and the electrical properties of the formed films were investigated after exfoliation from the substrate. The films were electrochemically analyzed by cyclic voltammetry, while surface and cross-sectional morphologies, compositional ratios, and electrical properties were analyzed by scanning electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and Hall-effect experiments. The copper telluride thin films, which were synthesized at various potentials in each bath, exhibit different composition ratios and structures; consequently, they show a variety of electrical and thermoelectric properties, including different electrical conductivities, carrier concentrations, mobilities, and Seebeck coefficients. Among them, the thin film with a 1:1 Cu:Te ratio delivered the highest power factor due to carrier filtering at the interface between the two phases.

A novel dermal delivery system using natural spicules for cosmetics and therapeutics.

BACKGROUND: Dermal delivery is versatile in therapeutics as well as cosmetics in pursuit of enhancing safety/efficacy and alleviating pain/fear to alternate oral/injective administrations. Natural siliceous spicules offer a potential approach via simple topical medications to circumvent poor penetrations through the skin barrier by loading, carrying, and releasing the active ingredients in a highly efficient and controlled manner. AIMS: The delivery of ingredients loaded on spicules is assessed to improve the dermal efficacy compared to simple topical treatments. METHODS: First, needle-like spicules were isolated from natural freshwater sponges. Then, the active ingredient was loaded via liposome formations. Finally, the dermal efficiency was evaluated. RESULTS: Natural siliceous spicules were purified, sorted, and fully characterized to appear 250 µm of length and 12 µm of diameter on average. A model ingredient, pectolinarin, was efficiently loaded onto the internal space of spicules via lecithin-based liposome formations. The penetration was visualized using a porcine skin sample with a fluorescent dye and assessed quantitatively by a Franz diffusion cell system. Dermal absorption rate was measured 73.4%, while the percutaneous penetration rate was 2.2%. The release pattern turned out a simple diffusion analyzed by Fick's law and Higuchi model. The liposomes loaded onto spicules were further stabilized by a hydrophobic capsulation, which may benefit the overall efficacy of the ingredient. CONCLUSION: A novel dermal delivery system is beneficial to improve the topical efficacy of biologically active ingredients. The outcomes shed a light upon developing skin-protective/improving cosmetics and therapeutics with enhanced performance.

Pore-Scale Investigation of Dynamic Immiscible Displacement in Layered Media using Synchrotron X-ray Microtomography.

Understanding the dynamics of immiscible fluid in a porous media is critical in many chemical and environmental engineering processes. However, the geological heterogeneity effect on multiphase flow behavior remains unclear. Here, the dynamics of immiscible fluid displacement and entrapment were experimentally demonstrated at pore-level using time-lapse synchrotron X-ray microtomography. A drainage-imbibition experiment was designed using an unconsolidated layered sand pack that comprised coarse sand and fine sand zones. There were significant differences between the two zones, with regard to the temporal variations in fluid saturation and morphological evolution of nonwetting fluid (oil) during imbibition. Highly connected oil clusters in the coarse zone broke up into many small fragments, whereas the cluster in the fine zone remained connected while spanning multiple pores. To further understand the impacts of pore size and connectivity on multiphase fluid dynamics, a new approach that tracks the temporal variation of immiscible fluid in individual pores was conducted. The surface area at the oil-water interface increased during imbibition, which is expected to facilitate mass transfer and surface interactions. Understanding immiscible fluid displacement in layered porous media at the pore-level could lead to more effective environmental remediation.

Fabrication and Characteristics of a Conductive FeCo@Au Nanowire Alloy for Semiconductor Test Socket Connectors.

The most promising approach for improving the electrical performance of connectors used in semiconductor test sockets involves increasing their electrical conductivity by incorporating one-dimensional (1D) conductive materials between zero-dimensional (0D) conductive materials. In this study, FeCo nanowires were synthesized by electroplating to prepare a material in which 1D materials could be magnetically aligned. Moreover, the nanowires were coated with highly conductive Au. The magnetization per unit mass of the synthesized FeCo and FeCo@Au nanowires was 167.2 and 13.9 emu/g, respectively. The electrical performance of rubber-based semiconductor connectors before and after the introduction of synthetic nanowires was compared, and it was found that the resistance decreased by 14%. The findings reported herein can be exploited to improve the conductivity of rubber-type semiconductor connectors, thereby facilitating the development of connectors using 0D and 1D materials.

Enhanced Thermoelectric Properties of Composites Prepared With Poly(3,4-Ethylenedioxythiophene) Poly(Styrenesulfonate) and Vertically Aligned Se Wire.

Controlling the electronic transport behavior in thermoelectric composites is one of the most promising approaches to enhance their power factor because this enables decoupling of the correlation between the electrical conductivity and Seebeck coefficient. Herein, we show that the unexpected high power factor of the Se nanowire array embedded in poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) can be achieved by controlling the interfacial band structure engineering. The electrical conductivity and Seebeck coefficient simultaneously increased, confirming that the synthesis of organic/inorganic hybrid thermoelectric materials with improved performance was possible. Our exploration can be helpful for the rational design of high-performance thermoelectric composites through interface engineering.

Comprehensive Review on Thermoelectric Electrodeposits: Enhancing Thermoelectric Performance Through Nanoengineering.

Thermoelectric devices based power generation and cooling systemsystem have lot of advantages over conventional refrigerator and power generators, becausebecause of solid-state devicesdevices, compact size, good scalability, nono-emissions and low maintenance requirement with long operating lifetime. However, the applications of thermoelectric devices have been limited owingowing to their low energy conversion efficiency. It has drawn tremendous attention in the field of thermoelectric materials and devices in the 21st century because of the need of sustainable energy harvesting technology and the ability to develop higher performance thermoelectric materials through nanoscale science and defect engineering. Among various fabrication methods, electrodeposition is one of the most promising synthesis methods to fabricate devices because of its ability to control morphology, composition, crystallinity, and crystal structure of materials through controlling electrodeposition parameters. Additionally, it is an additive manufacturing technique with minimum waste materials that operates at near room temperature. Furthermore, its growth rate is significantly higher (i.e., a few hundred microns per hour) than the vacuum processes, which allows device fabrication in cost effective matter. In this paper, the latest development of various electrodeposited thermoelectric materials (i.e., Te, PbTe, Bi2Te3 and their derivatives, BiSe, BiS, Sb2Te3) in different forms including thin films, nanowires, and nanocomposites were comprehensively reviewed. Additionally, their thermoelectric properties are correlated to the composition, morphology, and crystal structure.

Metal-free high-adsorption-capacity adsorbent derived from spent coffee grounds for methylene blue.

Heavy-metal-free carbon materials were prepared from spent coffee grounds (SCG) using the coupled KOH-urea and NaOH-urea as activating agents, and these were compared with SCG activation by the alkali salts alone. SCG was impregnated with the activating agents before being pyrolyzed at 800 °C under a N2 atmosphere. Characterization of the as-pyrolyzed carbon materials was performed by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and measurement of N2 adsorption-desorption isotherms. The carbon materials were utilized for the adsorption of methylene blue (MB) in aqueous solutions. Combining KOH and urea as activating agents resulted in the generation of pertinent SCG-derived carbon material properties, including a large surface area (1665.45 m2 g-1) and excellent MB adsorption capacity. Adsorption efficiencies were studied using adsorption kinetics (pseudo-first-order and pseudo-second-order) and adsorption isotherm (Langmuir, Freundlich, and Temkin) models. The influences of pH and temperature were investigated. The results of this work raise new possibilities for synthesizing carbon materials with high MB adsorption capacities from biowastes, via less-toxic, energy-saving conventional pyrolysis methods for water-treatment applications.

Peptide-Peptide Co-Assembly: A Design Strategy for Functional Detection of C-peptide, A Biomarker of Diabetic Neuropathy.

Diabetes-related neuropathy is a debilitating condition that may be averted if it can be detected early. One possible way this can be achieved at low cost is to utilise peptides to detect C-peptide, a biomarker of diabetic neuropathy. This depends on peptide-peptide co-assembly, which is currently in a nascent stage of intense study. Instead, we propose a bead-based triple-overlay combinatorial strategy that can preserve inter-residue information during the screening process for a suitable complementary peptide to co-assemble with C-peptide. The screening process commenced with a pentapeptide general library, which revealed histidine to be an essential residue. Further screening with seven tetrapeptide focused libraries led to a table of self-consistent peptide sequences that included tryptophan and lysine at high frequencies. Three complementary nonapeptides (9mer com-peptides), wpkkhfwgq (Trp-D), kwkkhfwgq (Lys-D), and KWKKHFWGQ (Lys-L) (as a negative control) were picked from this table for co-assembly studies with C-peptide. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) and circular dichroism (CD) spectroscopies were utilized to study inter-peptide interactions and changes in secondary structures respectively. ATR-FTIR studies showed that there is indeed inter-peptide interaction between C-peptide and the tryptophan residues of the 9mer com-peptides. CD studies of unaggregated and colloidal C-peptide with the 9mer com-peptides suggest that the extent of co-assembly of C-peptide with Trp-D is greatest, followed by Lys-D and Lys-L. These results are promising and indicate that the presented strategy is viable for designing and evaluating longer complementary peptides, as well as complementary peptides for co-assembly with other polypeptides of interest and importance. We discuss the possibility of designing complementary peptides to inhibit toxic amyloidosis with this approach.

Effect of Pulse Current and Pre-annealing on Thermal Extrusion of Cu in Through-Silicon via (TSV).

Thermal stress induced by annealing the Cu filling of through-silicon vias (TSVs) requires further investigation as it can inhibit the performance of semiconductor devices. This study reports the filling behavior of TSVs prepared using direct current and pulse current Cu electrodeposition with and without pre-annealing. The thermal extrusion of Cu inside the TSVs was studied by observing the extrusion behavior after annealing and the changes in grain orientation using scanning electron microscopy and electron backscatter diffraction. The bottom-up filling ratio achieved by the direct current approach decreased because the current was used both to fill the TSV and to grow bump defects on the top surface of the wafer. In contrast, pulse current electrodeposition yielded an improved TSV bottom-up filling ratio and no bump defects, which is attributable to strong suppression and thin diffusion layer. Moreover, Cu deposited with a pulse current exhibited lesser thermal extrusion, which was attributed to the formation of nanotwins and a change in the grain orientation from random to (101). Based on the results, thermal extrusion of the total area of the TSVs could be obtained by pulse current electrodeposition with pre-annealing.

Facial Fabrication and Characterization of Novel Ag/AgCl Chloride Ion Sensor Based on Gel-Type Electrolyte.

In this study, a novel chloride ion (Cl-) sensor based on Ag wire coated with an AgCl layer was fabricated using a gel-type internal electrolyte and a diatomite ceramic membrane, which played an important role in preventing electrolyte leakage from the ion-selective electrode. The sensing performance, including reversibility, response, recovery time, low detection limit, and the long-term stability, was systemically investigated in electrolytes with different Cl- contents. The as-fabricated Cl- sensor could detect Cl- from 1 to 500 mM KCl solution with good linearity. The best response and recovery time obtained for the optimized sensor were 0.5 and 0.1 s, respectively, for 10 mM KCl solution. An exposure period of over 60 days was used to evaluate the stability of the Cl- sensor in KCl solution. A relative error of 2% was observed between the initial and final response potentials. Further, a wireless sensing system based on Arduino was also investigated to measure the response potential of Cl- in an electrolyte. The sensor exhibited high reliability with a low standard error of measurement. This type of sensor is crucial for fabricating wireless Cl- sensors for applications in reinforced concrete structures along with favorable performances.

Direct Measurement of Contact Angle Change in Capillary Rise.

Capillary rise is important in many aspects of physical phenomena from transport in porous media to biotechnology. It is typically described by the Lucas-Washburn-Rideal equation (LWRE), but discrepancy between some experiments and the model still remains elusive. In this paper, we show that the discrepancy is simply from the contact angle change during the capillary rise with no help of any specific models, such as dynamic contact angle (DCA) models. To demonstrate this, we directly measure the contact angle change in the capillary rise for glycerol and carboxymethyl cellulose solutions as examples of Newtonian and non-Newtonian liquids. Unlike previous studies that used DCA models to explain the discrepancy, when the contact angle change is directly applied to the LWRE for all four tested fluids, the model agrees well with experimental data. The estimated contact angle from the capillary rise as a function of time is in good agreement with the directly measured contact angle within a narrow margin of error. To pinpoint the conditions for the discrepancy, we propose a new time scale when contact angle dynamics dominates. The contact angle dynamics that can be obtained from the macroscopic capillary rise may provide useful information for capillary flow in a more complicated geometry such as porous media.

Template-Free Electrochemical Deposition of t-Se Nano- and Sub-micro Structures With Controlled Morphology and Dimensions.

Selenium, depending on its crystal structure, can exhibit various properties and, as a result, be used in a wide range of applications. However, its exploitation has been limited due to the lack of understanding of its complex growth mechanism. In this work, template-free electrodeposition has been utilized for the first time to synthesize hexagonal-selenium (t-Se) microstructures of various morphologies at 80°C. Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) revealed 5 reduction peaks, which were correlated with possible electrochemical or chemical reaction related to the formation of selenium. Potentiostatic electrodeposition using 100 mM SeO2 showed selenium nanorods formed at-0.389 V then increased in diameter up to -0.490 V, while more negative potentials (-0.594 V) induced formation of sub-micron wires with average diameter of 708 ± 116 nm. Submicron tubes of average diameter 744 ± 130 nm were deposited at -0.696 V. Finally, a mixture of tubes, wires, and particles was observed at more cathodic potential due to a combination of nucleation, growth, dissolution of structures as well as formation of amorphous selenium via comproportionation reaction. Texture coefficient as a function of applied potential described the preferred orientation of the sub-microstructures changed from (100) direction to more randomly oriented as more cathodic potentials were applied. Lower selenium precursor concentration lead to formation of nanowires only with smaller average diameters (124 ± 42 nm using 1 mM, 153 ± 46 nm using 10 mM SeO2 at -0.389 V). Time-dependent electrodeposition using 100 mM selenium precursor at -0.696 V explained selenium was formed first as amorphous, on top of which nucleation continued to form rods and wires, followed by preferential dissolution of the wire core to form tubes.

Fabrication of PEDOT: PSS-PVP Nanofiber-Embedded Sb2Te3 Thermoelectric Films by Multi-Step Coating and Their Improved Thermoelectric Properties.

Antimony telluride thin films display intrinsic thermoelectric properties at room temperature, although their Seebeck coefficients and electrical conductivities may be unsatisfactory. To address these issues, we designed composite films containing upper and lower Sb2Te3 layers encasing conductive poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)- polyvinylpyrrolidone(PVP) nanowires. Thermoelectric Sb2Te3/PEDOT:PSS-PVP/Sb2Te3(ED) (STPPST) hybrid composite films were prepared by a multi-step coating process involving sputtering, electrospinning, and electrodeposition stages. The STPPST hybrid composites were characterized by field-emission scanning electron microscopy, X-ray diffraction, ultraviolet photoelectron spectroscopy, and infrared spectroscopy. The thermoelectric performance of the prepared STPPST hybrid composites, evaluated in terms of the power factor, electrical conductivity and Seebeck coefficient, demonstrated enhanced thermoelectric efficiency over a reference Sb2Te3 film. The performance of the composite Sb2Te3/PEDOT:PSS-PVP/Sb2Te3 film was greatly enhanced, with σ = 365 S/cm, S = 124 µV/K, and a power factor 563 µW/mK.