Toward Advanced Superomniphobicity: Hierarchical Insights from Serif-T Nanostructures to Microscale Wrinkles.

Developing a superomniphobic surface that exceeds the static and dynamic repellency observed in nature's springtails for various liquids presents a significant challenge in the realm of surface and interface science. However, progress in this field has been particularly limited when dealing with low-surface-tension liquids. This is because dynamic repellency values are typically at least 2 orders of magnitude lower than those observed with water droplets. Our study introduces an innovative hierarchical topography demonstrating exceptional dynamic repellency to low-surface-tension liquids. Inspired by the structural advantages found in springtails, we achieve a static contact angle of >160° and the complete rebound of droplet impact with a Weber number (We) of ∼104 using ethanol. These results surpass all existing benchmarks that have been reported thus far, including those of natural surfaces. The key insight from our research is the vital role of the microscale air pocket size, governed by wrinkle wavelength, in both static and dynamic repellency. Additionally, nanoscale air pockets within serif-T nanostructures prove to be essential for achieving omniphobicity. Our investigations into the wetting dynamics of ethanol droplets further reveal aspects such as the reduction in contact time and the occurrence of a fragmentation phenomenon beyond We ∼ 350, which has not been previously observed.

Effect of Feature Shape and Dimension of a Confinement Geometry on Selectivity of Electrocatalytic CO2 Reduction.

The local confinement effect, which can generate a high concentration of hydroxide ions and reaction intermediates near the catalyst surface, is an important strategy for converting CO2 into multi-carbon products in electrocatalytic CO2 reduction. Therefore, understanding how the shape and dimension of the confinement geometry affect the product selectivity is crucial. In this study, we report for the first time the effect of the shape (degree of confinement) and dimension of the confined space on the product selectivity without changing the intrinsic property of Cu. We demonstrate that geometry influences the outcomes of products, such as CH4 , C2 H4 , and EtOH, in different ways: the selectivity of CH4 and EtOH is affected by shape, while the selectivity of C2 H4 is influenced by dimension of geometry predominantly. These phenomena are demonstrated, both experimentally and through simulation, to be induced by the local confinement effect within the confined structure. Our geometry model could serve as basis for designing the confined structures tailored for the production of specific products.

Effects of natural products on polycystic ovary syndrome: From traditional medicine to modern drug discovery.

Polycystic Ovary Syndrome (PCOS) is a common endocrine disorder with a worldwide prevalence of 6-10 % of women of reproductive age. PCOS is a risk factor for cardiometabolic disorders such as type 2 diabetes, myocardial infarction, and stroke in addition to exhibiting signs of hyperandrogenism and anovulation. However, there is no known cure for PCOS, and medications have only ever been used symptomatically, with a variety of adverse effects. Drugs made from natural plant products may help treat PCOS because several plant extracts have been widely recognized to lessen the symptoms of PCOS. In light of this, 72 current studies on natural products with the potential to control PCOS were examined. By controlling the PI3K/AKT signaling pathway and decreasing NF-κB and cytokines such as tumor necrosis factor (TNF), interleukin-1 (IL-1), and interleukin-6 (IL-6), certain plant-derived chemicals might reduce inflammation. Other substances altered the HPO axis, which normalized hormones. Additionally, other plant components increased glutathione (GSH), superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase (GPx) levels to reduce radiation-induced oxidative stress. The other substances prevented autophagy by impairing beclin 1, autophagy-related 5 (ATG5), and microtubule-associated protein 1A/1B-light chain 3 - II (LC3- II). The main focus of this comprehensive review is the possibility of plant extracts as natural bio-resources of PCOS treatment by regulating inflammation, hormones, reactive oxygen species (ROS), or autophagy.

Exploring Optimal Water Splitting Bifunctional Alloy Catalyst by Pareto Active Learning.

Design of bifunctional multimetallic alloy catalysts, which are one of the most promising candidates for water splitting, is a significant issue for the efficient production of renewable energy. Owing to large dimensions of the components and composition of multimetallic alloys, as well as the trade-off behavior in terms of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) overpotentials for bifunctional catalysts, it is difficult to search for high-performance bifunctional catalysts with multimetallic alloys using conventional trial-and-error experiments. Here, an optimal bifunctional catalyst for water splitting is obtained by combining Pareto active learning and experiments, where 110 experimental data points out of 77946 possible points lead to effective model development. The as-obtained bifunctional catalysts for HER and OER exhibit high performance, which is revealed by model development using Pareto active learning; among the catalysts, an optimal catalyst (Pt0.15 Pd0.30 Ru0.30 Cu0.25 ) exhibits a water splitting behavior of 1.56 V at a current density of 10 mA cm-2 . This study opens avenues for the efficient exploration of multimetallic alloys, which can be applied in multifunctional catalysts as well as in other applications.

An Aqueous Analog MAC Machine.

Using ions in aqueous milieu for signal processing, like in biological circuits, may potentially lead to a bioinspired information processing platform. Studies, however, have focused on individual ionic diodes and transistors rather than circuits comprising many such devices. Here a 16 × 16 array of new ionic transistors is developed in an aqueous quinone solution. Each transistor features a concentric ring electrode pair with a disk electrode at the center. The electrochemistry of these electrodes in the solution provides the basis for the transistor operation. The ring pair electrochemically tunes the local electrolytic concentration to modulate the disk's Faradaic reaction rate. Thus, the disk current as a Faradaic reaction to the disk voltage is gated by the ring pair. The 16 × 16 array of these transistors performs analog multiply-accumulate (MAC) operations, a computing modality hotly pursued for low-power artificial neural networks. This exploits the transistor's operating regime where the disk current is a multiplication of the disk voltage and a weight parameter tuned by the ring pair gating. Such disk currents from multiple transistors are summated in a global reference electrode to complete a MAC task. This ionic circuit demonstrating analog computing is a step toward sophisticated aqueous ionics.

Atomic-Scale Homogeneous RuCu Alloy Nanoparticles for Highly Efficient Electrocatalytic Nitrogen Reduction.

Ruthenium (Ru) is the most widely used metal as an electrocatalyst for nitrogen (N2 ) reduction reaction (NRR) because of the relatively high N2 adsorption strength for successive reaction. Recently, it has been well reported that the homogeneous Ru-based metal alloys such as RuRh, RuPt, and RuCo significantly enhance the selectivity and formation rate of ammonia (NH3 ). However, the metal combinations for NRR have been limited to several miscible combinations of metals with Ru, although various immiscible combinations have immense potential to show high NRR performance. In this study, an immiscible combination of Ru and copper (Cu) is first utilized, and homogeneous alloy nanoparticles (RuCu NPs) are fabricated by the carbothermal shock method. The RuCu homogeneous NP alloys on cellulose/carbon nanotube sponge exhibit the highest selectivity and NH3 formation rate of ≈31% and -73 µmol h-1 cm-2 , respectively. These are the highest values of the selectivity and NH3 formation rates among existing Ru-based alloy metal combinations.

CMOS electrochemical pH localizer-imager.

pH controls a large repertoire of chemical and biochemical processes in water. Densely arrayed pH microenvironments would parallelize these processes, enabling their high-throughput studies and applications. However, pH localization, let alone its arrayed realization, remains challenging because of fast diffusion of protons in water. Here, we demonstrate arrayed localizations of picoliter-scale aqueous acids, using a 256-electrochemical cell array defined on and operated by a complementary metal oxide semiconductor (CMOS)-integrated circuit. Each cell, comprising a concentric pair of cathode and anode with their current injections controlled with a sub-nanoampere resolution by the CMOS electronics, creates a local pH environment, or a pH "voxel," via confined electrochemistry. The system also monitors the spatiotemporal pH profile across the array in real time for precision pH control. We highlight the utility of this CMOS pH localizer-imager for high-throughput tasks by parallelizing pH-gated molecular state encoding and pH-regulated enzymatic DNA elongation at any selected set of cells.

Searching for an Optimal Multi-Metallic Alloy Catalyst by Active Learning Combined with Experiments.

Searching for an optimal component and composition of multi-metallic alloy catalysts, comprising two or more elements, is one of the key issues in catalysis research. Due to the exhaustive data requirement of conventional machine-learning (ML) models and the high cost of experimental trials, current approaches rely mainly on the combination of density functional theory and ML techniques. In this study, a significant step is taken toward overcoming limitations by the interplay of experiment and active learning to effectively search for an optimal component and composition of multi-metallic alloy catalysts. The active-learning model is iteratively updated using by examining electrocatalytic performance of fabricated solid-solution nanoparticles for the hydrogen evolution reaction (HER). An optimal metal precursor composition of Pt0.65 Ru0.30 Ni0.05 exhibits an HER overpotential of 54.2 mV, which is superior to that of the pure Pt catalyst. This result indicates the successful construction of the model by only utilizing the precursor mixture composition as input data, thereby improving the overpotential by searching for an optimal catalyst. This method appears to be widely applicable since it is able to determine an optimal component and composition of electrocatalyst without obvious restriction to the types of catalysts to which it can be applied.

Hierarchical Wrinkle-Structured Catalyst Layer/Membrane Interface for Ultralow Pt-Loading Polymer Electrolyte Membrane Fuel Cells (PEMFCs).

The optimal architecture of three-dimensional (3D) interface between a polymer electrolyte membrane (PEM) and catalyst layer (CL) is one of the most important issues to improve PEM fuel cells' (PEMFCs) performance. Here, we report the fabrication of hierarchical wrinkled PEM/CL interface over a large area. We fabricated the hierarchical wrinkles on a multiscale from nanometers to micrometers by bottom-up-based facile, scalable, and simple method. Notably, it allows one to go beyond the limit of the catalyst utilization by extremely enlarged interfacial area. The resulting hierarchical wrinkled PEM/CL displays a dramatically increased electrochemically active surface area (ECSA) and power performance by the enhancement factors of 89% and 67% compared with those of flat interface, which is one of the best enhancements compared to previous PEMFCs. We believe the scalability of hierarchical wrinkled interface can be exploited to design advanced 3D interfaces for high-performance PEMFCs even with ultralow Pt-loading.

Synergistic Effect of Cu2 O Mesh Pattern on High-Facet Cu Surface for Selective CO2 Electroreduction to Ethanol.

Although the electroconversion of carbon dioxide (CO2 ) into ethanol is considered to be one of the most promising ways of using CO2 , the ethanol selectivity is less than 50% because of difficulties in designing an optimal catalyst that arise from the complicated pathways for the electroreduction of CO2 to ethanol. Several approaches including the fabrication of oxide-derived structures, atomic surface control, and the Cu+ /Cu interfaces have been primarily used to produce ethanol from CO2 . Here, a combined structure with Cu+ and high-facets as electrocatalysts is constructed by creating high-facets of wrinkled Cu surrounded by Cu2 O mesh patterns. Using chemical vapor deposition graphene growth procedures, the insufficiently grown graphene is used as an oxidation-masking material, and the high-facet wrinkled Cu is simultaneously generated during the graphene growth synthesis. The resulting electrocatalyst shows an ethanol selectivity of 43% at -0.8 V versus reversible hydrogen electrode, which is one of the highest ethanol selectivity values reported thus far. This is attributed to the role of Cu+ in enhancing CO binding strength, and the high-facets, which favor C-C coupling and the ethanol pathway. This method for generating the combined structure can be widely applicable not only for electrochemical catalysts but also in various fields.

Effect of Highly Periodic Au Nanopatterns on Dendrite Suppression in Lithium Metal Batteries.

Despite the extremely high energy density of the lithium metal, dendritic lithium growth caused by nonuniform lithium deposition can result in low Coulombic efficiency and safety hazards, thereby inhibiting its practical applications. Here, we report a new strategy for adopting a nanopatterned gold (Au) seed on a copper current collector for uniform lithium deposition. We find that Au nanopatterns enhance lithium metal battery performance, which is strongly affected by the feature dimensions of Au nanopatterns (diameter and height). Ex situ scanning electron microscopy images confirm that this can be attributed to the perfectly selective lithium nucleation and uniform growth resulting from the spatial confinement effect. The spatial arrangement of Au dot seeds homogenizes the Li+ flux and electric field, and the size-controlled Au seeds prevent both seed-/substrate-induced agglomeration and interseed-induced lithium growth, leading to uniform lithium deposition. This dendrite-free lithium deposition results in the improvement of electrochemical performance, and the system showed cyclic stability over 300 cycles at 0.5 mA cm-2 and 200 cycles at 1.0 mA cm-2 (1 mA h cm-2) and a high rate capability. This study provides in-depth insights into the more complicated and diverse seed geometry control of seed materials for the development of high-performance lithium metal batteries.

Generation of high-density nanoparticles in the carbothermal shock method.

The carbothermal shock (CTS) method has attracted considerable attention in recent years because it enables the generation of finely controlled polyelemental alloy nanoparticles (NPs). However, fabricating high surface coverage of NPs with minimized exposure of the carbon substrate is essential for various electrochemical applications and has been a critical limitation in CTS method. Here, we developed a methodology for creating NPs with high surface coverage on a carbon substrate by maximizing defect sites of cellulose during CTS. Cu NPs with high surface coverage of ~85%, various single NPs and polyelemental alloy NPs were densely fabricated with high uniformity and dispersity. The synthesized Cu NPs on cellulose/carbon paper substrate were used in electrocatalytic CO2 reduction reaction showing selectivity to ethylene of ~49% and high stability for over 30 hours of reaction. Our cellulose-derived CTS method enables the greater availability of polyelemental NPs for a wide range of catalytic and electrochemical applications.

Polyelemental Nanoparticles as Catalysts for a Li-O2 Battery.

The development of highly efficient catalysts in the cathodes of rechargeable Li-O2 batteries is a considerable challenge. Polyelemental catalysts consisting of two or more kinds of hybridized catalysts are particularly interesting because the combination of the electrochemical properties of each catalyst component can significantly facilitate oxygen evolution and oxygen reduction reactions. Despite the recent advances that have been made in this field, the number of elements in the catalysts has been largely limited to two metals. In this study, we demonstrate the electrochemical behavior of Li-O2 batteries containing a wide range of catalytic element combinations. Fourteen different combinations with single, binary, ternary, and quaternary combinations of Pt, Pd, Au, and Ru were prepared on carbon nanofibers (CNFs) via a joule heating route. Importantly, the Li-O2 battery performance could be significantly improved when using a polyelemental catalyst with four elements. The cathode containing quaternary nanoparticles (Pt-Pd-Au-Ru) exhibited a reduced overpotential (0.45 V) and a high discharge capacity based on total cathode weight at 9130 mAh g-1, which was ∼3 times higher than that of the pristine CNF electrode. This superior electrochemical performance is be attributed to an increased catalytic activity associated with an enhanced O2 adsorbability by the quaternary nanoparticles.

Nanoscale Wrinkled Cu as a Current Collector for High-Loading Graphite Anode in Solid-State Lithium Batteries.

Solid-state lithium batteries have been intensively studied as part of research activities to develop energy storage systems with high safety and stability characteristics. Despite the advantages of solid-state lithium batteries, their application is currently limited by poor reversible capacity arising from their high resistance. In this study, we significantly improve the reversible capacity of solid-state lithium batteries by lowering the resistance through the introduction of a graphene and wrinkle structure on the surface of the copper (Cu) current collector. This is achieved through a process of chemical vapor deposition (CVD) facilitating graphene-growth synthesis. The modified graphene/wrinkled Cu current collector exhibits a periodic wrinkled pattern 420 nm in width and 22 nm in depth, and we apply it to a graphite composite electrode to obtain an improved areal loading average value of ∼2.5 mg cm-2. The surface-modified Cu current collector is associated with a significant increase in discharge capacity of 347 mAh g-1 at 0.2 C when used with a solid polymer electrolyte. Peel test results show that the observed enhancement is due to the improved strength of adhesion occurring between the graphite composite anode and the Cu current collector, which is attributed to mechanical interlocking. The surface-modified Cu current collector structure effectively reduces resistance by improving adhesion, which subsequently improves the performance of the solid-state lithium batteries. Our study can provide perspective and emphasize the importance of electrode design in achieving enhancements in battery performance.

Recent Progress in Simple and Cost-Effective Top-Down Lithography for ≈10 nm Scale Nanopatterns: From Edge Lithography to Secondary Sputtering Lithography.

The development of a simple and cost-effective method for fabricating ≈10 nm scale nanopatterns over large areas is an important issue, owing to the performance enhancement such patterning brings to various applications including sensors, semiconductors, and flexible transparent electrodes. Although nanoimprinting, extreme ultraviolet, electron beams, and scanning probe litho-graphy are candidates for developing such nanopatterns, they are limited to complicated procedures with low throughput and high startup cost, which are difficult to use in various academic and industry fields. Recently, several easy and cost-effective lithographic approaches have been reported to produce ≈10 nm scale patterns without defects over large areas. This includes a method of reducing the size using the narrow edge of a pattern, which has been attracting attention for the past several decades. More recently, secondary sputtering lithography using an ion-bombardment technique was reported as a new method to create high-resolution and high-aspect-ratio structures. Recent progress in simple and cost-effective top-down lithography for ≈10 nm scale nanopatterns via edge and secondary sputtering techniques is reviewed. The principles, technical advances, and applications are demonstrated. Finally, the future direction of edge and secondary sputtering lithography research toward issues to be resolved to broaden applications is discussed.

Facile Fabrication of High-Definition Hierarchical Wrinkle Structures for Investigating the Geometry-Sensitive Fate Commitment of Human Neural Stem Cells.

As neural stem cells (NSCs) interact with biophysical cues from their niche during development, it is important to understand the biomolecular mechanism of how the NSCs process these biophysical cues to regulate their behaviors. In particular, anisotropic geometric cues in micro-/nanoscale have been utilized to investigate the biophysical effect of the structure on NSCs behaviors. Here, a series of new nanoscale anisotropic wrinkle structures with the a range of wavelength scales (from 50 nm to 37 µm) was developed to demonstrate the effect of the anisotropic nanostructure on the fate commitment of NSCs. Intriguingly, two distinct characteristic length scales promoted the neurogenesis. Each wavelength scale showed a striking variation in terms of dependency on the directionality of the structures, suggesting the existence of at least two different ways in the processing of anisotropic geometries for neurogenesis. Furthermore, the combined effect of the two distinctive length scales was observed by employing hierarchical multiscale wrinkle structures with two characteristic neurogenesis-promoting wavelengths. Taken together, the wrinkle structure system developed in this study can serve as an effective platform to advance the understanding of how cells sense anisotropic geometries for their specific cellular behaviors. Furthermore, this could provide clues for improving nerve regeneration system of stem cell therapies.

Relationship between Hydrogen Evolution and Wettability for Multiscale Hierarchical Wrinkles.

Transition metal dichalcogenides (TMDs) are emerging two-dimensional materials with potential use for the hydrogen evolution reaction (HER) because they express a desired binding energy with protons. To date, TMD-based HER catalytic performance has been enhanced mostly by chemical modification, such as introducing defects, doping, and phase control. Herein, we enhanced the HER performance by precise control of wettability via hierarchical wrinkling. This hierarchical wrinkling confers tunability of the receding contact angle (2-30°) by controlling the wavelength of the hierarchical wrinkles. Minimization of the receding contact angle is directly related to overpotential reduction on the MoS2 wrinkles through gas detachment from the catalytic surface. Unlike in previous studies, in this work, we demonstrated the effect of wettability only without changing other parameters such as surface chemistry. We showed that our method can be applied to other TMD materials such as WS2. This study will contribute to future TMD-based catalyst applications, such as hydrogen evolution, CO2 reduction, and oxygen evolution.

Polyelemental Nanolithography via Plasma Ion Bombardment: From Fabrication to Superior H2 Sensing Application.

The development of complex nanostructures containing a homo- and heteromixture of two or more metals is a considerable challenge in nanotechnology. However, previous approaches are considerably limited to the number of combinations of metals depending on the compatibility of elements, and to the complex shape control of the nanostructure. In this study, a significant step is taken toward resolving these limitations via the utilization of a low-energy argon-ion bombardment. The multilayer films are etched and re-sputtered on the sidewall of the pre-pattern, which is a secondary sputtering phenomenon. In contrast to the precursor mixing method, most metallic combinations can be fabricated. The degree of mixing is tuned by the control of the sequence and thickness of multilayers. In addition, the feature shape and dimensions are controlled by changing the pre-pattern or by controlling the ion-beam angle. Using this method, the shortest response time (2 s to 1% H2 ) in comparison with those of Pd-based H2 sensors reported previously and a limit of detection below 1 parts per million (ppm) for Pd/Au and Pd/Pt bimetallic line arrays are achieved. This study is expected to realize a family of polyelements that can be used in various applications.

Correction: A three-dimensional metal grid mesh as a practical alternative to ITO.

Correction for 'A three-dimensional metal grid mesh as a practical alternative to ITO' by Sungwoo Jang et al., Nanoscale, 2016, 8, 14257-14263.