Structural Determinants of Chirally Selective Transport of Amino Acids through the α-Hemolysin Protein Nanopores of Free-Standing Planar Lipid Membranes.

Despite the importance of the enantioselective transport of amino acids through transmembrane protein nanopores from fundamental and practical perspectives, little has been explored to date. Here, we study the transport of amino acids through α-hemolysin (αHL) protein pores incorporated into a free-standing lipid membrane. By measuring the transport of 13 different amino acids through the αHL pores, we discover that the molecular size of the amino acids and their capability to form hydrogen bonds with the pore surface determine the chiral selectivity. Molecular dynamics simulations corroborate our findings by revealing the enantioselective molecular-level interactions between the amino acid enantiomers and the αHL pore. Our work is the first to present the determinants for chiral selectivity using αHL protein as a molecular filter.

Field-Free Spin-Orbit Torque Magnetization Switching in a Single-Phase Ferromagnetic and Spin Hall Oxide.

Current-induced spin-orbit torque (SOT) offers substantial promise for the development of low-power, nonvolatile magnetic memory. Recently, a single-phase material concurrently exhibiting magnetism and the spin Hall effect has emerged as a scientifically and technologically interesting platform for realizing efficient and compact SOT systems. Here, we demonstrate external-magnetic-field-free switching of perpendicular magnetization in a single-phase ferromagnetic and spin Hall oxide SrRuO3. We delicately altered the local lattices of the top and bottom surface layers of SrRuO3, while retaining a quasi-homogeneous, single-crystalline nature of the SrRuO3 bulk. This leads to unbalanced spin Hall effects between the top and bottom layers, enabling net SOT performance within single-layer ferromagnetic SrRuO3. Notably, our SrRuO3 exhibits the highest SOT efficiency and lowest power consumption among all known single-layer systems under field-free conditions. Our method of artificially manipulating the local atomic structures will pave the way for advances in spin-orbitronics and the exploration of new SOT materials.

Active Stratification of Colloidal Mixtures for Asymmetric Multilayers.

Stratified films offer high performance and multifunctionality, yet achieving fully stratified films remains a challenge. The layer-by-layer method, involving the sequential deposition of each layer, has been commonly utilized for stratified film fabrication. However, this approach is time-consuming, labor-intensive, and prone to leaving defects within the film. Alternatively, the self-stratification process exploiting a drying binary colloidal mixture is intensively developed recently, but it relies on strict operating conditions, typically yielding a heterogeneous interlayer. In this study, an active interfacial stratification process for creating completely stratified nanoparticle (NP) films is introduced. The technique leverages NPs with varying interfacial activity at the air-water interface. With the help of depletion pressure, the lateral compression of NP mixtures at the interface induces individual desorption of less interfacial active NPs into the subphase, while more interfacial active NPs remain at the interface. This simple compression leads to nearly perfect stratified NP films with controllability, universality, and scalability. Combined with a solvent annealing process, the active stratification process enables the fabrication of stratified films comprising a polymeric layer atop a NP layer. This work provides insightful implications for designing drug encapsulation and controlled release, as well as manufacturing transparent and flexible electrodes.

Crystallographic Pathways to Tailoring Metal-Insulator Transition through Oxygen Transport in VO2.

The metal-insulator (MI) transition of vanadium dioxide (VO2) is effectively modulated by oxygen vacancies, which decrease the transition temperature and insulating resistance. Oxygen vacancies in thin films can be driven by oxygen transport using electrochemical potential. This study delves into the role of crystallographic channels in VO2 in facilitating oxygen transport and the subsequent tuning of electrical properties. A model system is designed with two types of VO2 thin films: (100)- and (001)-oriented, where channels align parallel and perpendicular to the surface, respectively. Growing an oxygen-deficient TiO2 layer on these VO2 films prompted oxygen transport from VO2 to TiO2. Notably, in (001)-VO2 film, where oxygen ions move along the open channels, the oxygen migration deepens the depleted region beyond that in (100)-VO2, leading to more pronounced changes in metal-insulator transition behaviors. The findings emphasize the importance of understanding the intrinsic crystal structure, such as channel pathways, in controlling ionic defects and customizing electrical properties for applications.

Attojoule Hexagonal Boron Nitride-Based Memristor for High-Performance Neuromorphic Computing.

In next-generation neuromorphic computing applications, the primary challenge lies in achieving energy-efficient and reliable memristors while minimizing their energy consumption to a level comparable to that of biological synapses. In this work, hexagonal boron nitride (h-BN)-based metal-insulator-semiconductor (MIS) memristors operating is presented at the attojoule-level tailored for high-performance artificial neural networks. The memristors benefit from a wafer-scale uniform h-BN resistive switching medium grown directly on a highly doped Si wafer using metal-organic chemical vapor deposition (MOCVD), resulting in outstanding reliability and low variability. Notably, the h-BN-based memristors exhibit exceptionally low energy consumption of attojoule levels, coupled with fast switching speed. The switching mechanisms are systematically substantiated by electrical and nano-structural analysis, confirming that the h-BN layer facilitates the resistive switching with extremely low high resistance states (HRS) and the native SiOx on Si contributes to suppressing excessive current, enabling attojoule-level energy consumption. Furthermore, the formation of atomic-scale conductive filaments leads to remarkably fast response times within the nanosecond range, and allows for the attainment of multi-resistance states, making these memristors well-suited for next-generation neuromorphic applications. The h-BN-based MIS memristors hold the potential to revolutionize energy consumption limitations in neuromorphic devices, bridging the gap between artificial and biological synapses.

Thermodynamically Driven Tilt Grain Boundaries of Monolayer Crystals Using Catalytic Liquid Alloys.

We report a method to precisely control the atomic defects at grain boundaries (GBs) of monolayer MoS2 by vapor-liquid-solid (VLS) growth using sodium molybdate liquid alloys, which serve as growth catalysts to guide the formations of the thermodynamically most stable GB structure. The Mo-rich chemical environment of the alloys results in Mo-polar 5|7 defects with a yield exceeding 95%. The photoluminescence (PL) intensity of VLS-grown polycrystalline MoS2 films markedly exceeds that of the films, exhibiting abundant S 5|7 defects, which are kinetically driven by vapor-solid-solid growths. Density functional theory calculations indicate that the enhanced PL intensity is due to the suppression of nonradiative recombination of charged excitons with donor-type defects of adsorbed Na elements on S 5|7 defects. Catalytic liquid alloys can aid in determining a type of atomic defect even in various polycrystalline 2D films, which accordingly provides a technical clue to engineer their properties.

Observation of Hidden Polar Phases and Flux Closure Domain Topology in Bi2WO6 Thin Films.

Topological textures of ferroelectric polarizations have promise as alternative devices for future information technology. A polarization rotation inevitably deviates from the stable orientation in axial ferroelectrics, but local energy losses compromise the global symmetry, resulting in a distorted shape of the topological vortex or inhibiting the vortex. Easy planar isotropy helps to promote rotating structures and, accordingly, to facilitate access to nontrivial textures. Here, we investigate the domain structure of an epitaxial thin film of bismuth tungsten oxide (Bi2WO6) grown on a (001) SrTiO3 substrate. By using angle-resolved piezoresponse force microscopy and scanning transmission electron microscopy, we find the existence of a hidden phase with ⟨100⟩-oriented ferroelectric polarizations in the middle of the four variant ⟨110⟩-oriented polarization domains, which assists in the formation of flux closure domains. The results suggest that this material is one step closer to becoming an isotropic two-dimensional polar material.

Configurable Crack Wall Conduction in a Complex Oxide.

Mobile defects in solid-state materials play a significant role in memristive switching and energy-efficient neuromorphic computation. Techniques for confining and manipulating point defects may have great promise for low-dimensional memories. Here, we report the spontaneous gathering of oxygen vacancies at strain-relaxed crack walls in SrTiO3 thin films grown on DyScO3 substrates as a result of flexoelectricity. We found that electronic conductance at the crack walls was enhanced compared to the crack-free region, by a factor of 104. A switchable asymmetric diode-like feature was also observed, and the mechanism is discussed, based on the electrical migration of oxygen vacancy donors in the background of Sr-deficient acceptors forming n+-n or n-n+ junctions. By tracing the temporal relaxations of surface potential and lattice expansion of a formed region, we determine the diffusivity of mobile defects in crack walls to be 1.4 × 10-16 cm2/s, which is consistent with oxygen vacancy kinetics.

Rheology and dynamics of a solvent segregation driven gel (SeedGel).

Bicontinuous structures promise applications in a broad range of research fields, such as energy storage, membrane science, and biomaterials. Kinetically arrested spinodal decomposition is found responsible for stabilizing such structures in different types of materials. A recently developed solvent segregation driven gel (SeedGel) is demonstrated to realize bicontinuous channels thermoreversibly with tunable domain sizes by trapping nanoparticles in a particle domain. As the mechanical properties of SeedGel are very important for its future applications, a model system is characterized by temperature-dependent rheology. The storage modulus shows excellent thermo-reproducibility and interesting temperature dependence with the maximum storage modulus observed at an intermediate temperature range (around 28 °C). SANS measurements are conducted at different temperatures to identify the macroscopic solvent phase separation during the gelation transition, and solvent exchange between solvent and particle domains that is responsible for this behavior. The long-time dynamics of the gel is further studied by X-ray Photon Correlation Spectroscopy (XPCS). The results indicate that particles in the particle domain are in a glassy state and their long-time dynamics are strongly correlated with the temperature dependence of the storage modulus.

Collagen microarchitecture mechanically controls myofibroblast differentiation.

Altered microarchitecture of collagen type I is a hallmark of wound healing and cancer that is commonly attributed to myofibroblasts. However, it remains unknown which effect collagen microarchitecture has on myofibroblast differentiation. Here, we combined experimental and computational approaches to investigate the hypothesis that the microarchitecture of fibrillar collagen networks mechanically regulates myofibroblast differentiation of adipose stromal cells (ASCs) independent of bulk stiffness. Collagen gels with controlled fiber thickness and pore size were microfabricated by adjusting the gelation temperature while keeping their concentration constant. Rheological characterization and simulation data indicated that networks with thicker fibers and larger pores exhibited increased strain-stiffening relative to networks with thinner fibers and smaller pores. Accordingly, ASCs cultured in scaffolds with thicker fibers were more contractile, expressed myofibroblast markers, and deposited more extended fibronectin fibers. Consistent with elevated myofibroblast differentiation, ASCs in scaffolds with thicker fibers exhibited a more proangiogenic phenotype that promoted endothelial sprouting in a contractility-dependent manner. Our findings suggest that changes of collagen microarchitecture regulate myofibroblast differentiation and fibrosis independent of collagen quantity and bulk stiffness by locally modulating cellular mechanosignaling. These findings have implications for regenerative medicine and anticancer treatments.

Anionic Flow Valve Across Oxide Heterointerfaces by Remote Electron Doping.

As an analogue of charged electron flows, the ionic flow could be controlled by the electronic band alignment due to the ambipolar nature of diffusion in the ionic crystal. Here, we demonstrate the active control of the anionic diffusion across heterointerfaces through remote electron doping in the capping layers. In contrast to the spontaneous ionic flux from the underlying VO2 layers to the undoped TiO2 capping layers, the activated Nb dopants in the TiO2 capping layers substantially restrict the ionic flux, despite identical growth conditions. The increase of Fermi level by Nb donors in TiO2 prevents electron flux from being generated across the interfaces by the heightening of a Schottky barrier; this electron shortage generates a kinetic close valve for the flow of negatively charged oxygen ions. Thus, these results demonstrate the importance of electron supply on charged ionic flow, thereby suggesting an unprecedented strategy for ionic-defect-induced emergent properties at interfaces.

Harmonious Heterointerfaces Formed on 2D-Pt Nanodendrites by Facet-Respective Stepwise Metal Deposition for Enhanced Hydrogen Evolution Reaction.

The performance of nanocrystal (NC) catalysts could be maximized by introducing rationally designed heterointerfaces formed by the facet- and spatio-specific modification with other materials of desired size and thickness. However, such heterointerfaces are limited in scope and synthetically challenging. Herein, we applied a wet chemistry method to tunably deposit Pd and Ni on the available surfaces of porous 2D-Pt nanodendrites (NDs). Using 2D silica nanoreactors to house the 2D-PtND, an 0.5-nm-thick epitaxial Pd or Ni layer (e-Pd or e-Ni) was exclusively formed on the flat {110} surface of 2D-Pt, while a non-epitaxial Pd or Ni layer (n-Pd or n-Ni) was typically deposited at the {111/100} edge in absence of nanoreactor. Notably, these differently located Pd/Pt and Ni/Pt heterointerfaces experienced distinct electronic effect to influence unequally in electrocatalytic synergy for hydrogen evolution reaction (HER). For instance, an enhanced H2 generation on the Pt{110} facet with 2D-2D interfaced e-Pd deposition and faster water dissociation on the edge-located n-Ni overpowered their facet-located counterparts in respective HER catalysis. Therefore, a feasible assembling of the valuable heterointerfaces in the optimal 2D n-Ni/e-Pd/Pt catalyst overcame the sluggish alkaline HER kinetics, with a catalytic activity 7.9 times higher than that of commercial Pt/C.

Crystal Facet-Manipulated 2D Pt Nanodendrites to Achieve an Intimate Heterointerface for Hydrogen Evolution Reactions.

Despite the Pt-catalyzed alkaline hydrogen evolution reaction (HER) progressing via oxophilic metal-hydroxide surface hybridization, maximizing Pt reactivity alongside operational stability is still unsatisfactory due to the lack of well-designed and optimized interface structures. Producing atomically flat two-dimensional Pt nanodendrites (2D-PtNDs) through our 2D nanospace-confined synthesis strategy, this study tackles the insufficient interfacial contact effect during HER catalysis by realizing an area-maximized and firmly bound lateral heterointerface with NiFe-layered double hydroxide (LDH). The well-oriented {110} crystal surface exposure of Pt promotes electronic interplay that bestows strong LDH binding. The charge-relocated interfacial bond in 2D-PtND/LDH accelerates the hydrogen generation steps and achieves nearly the highest reported Pt mass activity enhancement (∼11.2 times greater than 20 wt % Pt/C) and significantly improved long-term operational stability. This work uncovers the importance of the shape and facet of Pt to create heterointerfaces that provide catalytic synergy for efficient hydrogen production.

Soluble CCR2 gene therapy controls joint inflammation, cartilage damage, and the progression of osteoarthritis by targeting MCP-1 in a monosodium iodoacetate (MIA)-induced OA rat model.

BACKGROUND: Osteoarthritis (OA) is the most common type of degenerative arthritis and affects the entire joint, causing pain, joint inflammation, and cartilage damage. Various risk factors are implicated in causing OA, and in recent years, a lot of research and interest have been directed toward chronic low-grade inflammation in OA. Monocyte chemoattractant protein-1 (MCP-1; also called CCL2) acts through C-C chemokine receptor type 2 (CCR2) in monocytes and is a chemotactic factor of monocytes that plays an important role in the initiation of inflammation. The targeting of CCL2-CCR2 is being studied as part of various topics including the treatment of OA. METHODS: In this study, we evaluated the potential therapeutic effects the sCCR2 E3 gene may exert on OA. The effects of sCCR2 E3 were investigated in animal experiments consisting of intra-articular injection of sCCR2 E3 in a monosodium iodoacetate (MIA)-induced OA rat model. The effects after intra-articular injection of sCCR2 E3 (fusion protein encoding 20 amino acids of the E3 domain of the CCL2 receptor) in a monosodium iodoacetate-induced OA rat model were compared to those in rats treated with empty vector (mock treatment) and full-length sCCR2. RESULTS: Pain improved with expression of the sCCR2 gene. Improved bone resorption upon sCCR2 E3 gene activation was confirmed via bone analyses using micro-computed tomography. Histologic analyses showed that the sCCR2 E3 gene exerted protective effects against cartilage damage and anti-inflammatory effects on joints and the intestine. CONCLUSIONS: These results show that sCCR2 E3 therapy is effective in reducing pain severity, inhibiting cartilage destruction, and suppressing intestinal damage and inflammation. Thus, sCCR2 E3 may be a potential therapy for OA.

Removal Analysis of Residual Photoresist Particles Based on Surface Topography Affected by Exposure Times of Ultraviolet and Developer Solution.

Particle removal from the surface of a substrate has been an issue in numerous fields for a long time. In semiconductor processes, for instance, the formation of clean surfaces by removing photoresist (PR) must be followed in order to create neat patterns. Although PR removal has been intensively investigated recently, little is known about how ultraviolet (UV) and developer solutions alter the PR resin (and in what manner) near the surface. While varying the exposure times of UV and developer solution, we investigated the topographic changes on the surfaces of PR resin films and particles. The measured surface properties were then correlated with the detachment force determined using films, and eventually with the residual PR particle removal percentages obtained in a microchannel. Using a positive PR and a base developer solution, we demonstrated that UV causes the surface of PR resin to become hydrophilic and wavy, whereas the developer solution produces a surface with a larger degree of roughness by swelling and partially dissolving the resin. Ultimately, the increased roughness decreased the effective contact area between PR resins, hence decreasing the detachment force and increasing the particle removal percentages. We anticipate that our findings will help understand residual particle issues, particularly on the removal mechanism of PR resins based on surface topography.

Vapor-phase synthesis of a reagent-free self-healing polymer film with rapid recovery of toughness at room temperature and under ambient conditions.

A rapidly self-healable polymer is highly desirable but challenging to achieve. Herein, we developed an elastomeric film with instant self-healing ability within 10 s at room temperature. For this purpose, a series of copolymers of poly(glycidyl methacrylate-co-2-hydroxyethyl acrylate) (poly(GMA-co-HEA), or pGH) were synthesized in the vapor phase via an initiated chemical vapor deposition (iCVD) process. The elastomer includes a large amount of hydroxyl groups in the 2-hydroxyethyl acrylate (HEA) moiety capable of forming rapid, reversible hydrogen bonding at room temperature, while glycidyl methacrylate (GMA) with a rigid methacrylic backbone chain in the copolymer provides mechanical robustness to the elastic copolymer. With the optimized copolymer composition, pGH indeed showed instant recovery of the toughness within a minute; a completely divided specimen could be welded within a minute at room temperature and under ambient conditions simply by placing the pieces in close contact, which showed the outstanding recovery performance of elastic modulus (93.2%) and toughness (15.6 MJ m-3). The rapid toughness recovery without supplementing any external energy or reagents (e.g. light, temperature, or catalyst) at room temperature and under ambient conditions will be useful in future wearable electronics and soft robotics applications.

Visualization of Transition Metal Decoration on h-BN Surface.

Functional h-BN (hexagonal boron nitride) has been prepared via the incorporation of transition metal (TM) impurities like nanoparticles and single atoms. Herein, scanning transmission electron microscopy (STEM) combined with density functional theory (DFT) was employed to study Ta-, Co-, Ni-, and Ir-decorated h-BN monolayers to provide an overview of their preferential site occupancies and morphological evolutions on h-BN. Ta, Ni, Ir, and Co single atoms are all positioned on the nitrogen of h-BN; however DFT predicts the occupancy site can vary with their spin state. In terms of microstructural evolution, Co, Ni, and Ir atoms form 3D nanoclusters while Ta atoms are well dispersed and thus the single Ta atom can be decorated on h-BN. This study highlights on TM/h-BN interaction dynamics and presents an avenue for designing nanostructures for electrocatalytic application.

Twisted van der Waals Josephson Junction Based on a High-Tc Superconductor.

Stacking two-dimensional van der Waals (vdW) materials rotated with respect to each other show versatility for studying exotic quantum phenomena. In particular, anisotropic layered materials have great potential for such twistronics applications, providing high tunability. Here, we report anisotropic superconducting order parameters in twisted Bi2Sr2CaCu2O8+x (Bi-2212) vdW junctions with an atomically clean vdW interface, achieved using the microcleave-and-stack technique. The vdW junctions with twist angles of 0° and 90° showed the maximum Josephson coupling, comparable to that of intrinsic Josephson junctions. As the twist angle approaches 45°, Josephson coupling is suppressed, and eventually disappears at 45°. The observed twist angle dependence of the Josephson coupling can be explained quantitatively by theoretical calculation with the d-wave superconducting order parameter of Bi-2212 and finite tunneling incoherence of the junction. Our results revealed the anisotropic nature of Bi-2212 and provided a novel fabrication technique for vdW-based twistronics platforms compatible with air-sensitive vdW materials.

Identification of Point Defects in Atomically Thin Transition-Metal Dichalcogenide Semiconductors as Active Dopants.

Selective doping in semiconductors is essential not only for monolithic integrated circuity fabrications but also for tailoring their properties including electronic, optical, and catalytic activities. Such active dopants are essentially point defects in the host lattice. In atomically thin two-dimensional (2D) transition-metal dichalcogenides (TMDCs), the roles of such point defects are particularly critical in addition to their large surface-to-volume ratio, because their bond dissociation energy is relatively weaker, compared to elemental semiconductors. In this Mini Review, we review recent advances in the identifications of diverse point defects in 2D TMDC semiconductors, as active dopants, toward the tunable doping processes, along with the doping methods and mechanisms in literature. In particular, we discuss key issues in identifying such dopants both at the atomic scales and the device scales with selective examples. Fundamental understanding of these point defects can hold promise for tunability doping of atomically thin 2D semiconductor platforms.

The role of excess attractive particles in the elasticity of high internal phase Pickering emulsions.

A high internal phase emulsion (HIPE), which has a volume fraction of dispersed phase of over 74%, shows a solid-like property because of concentrated polyhedral droplets. Although many studies have proposed theoretical and empirical models to explain the rheological properties of HIPEs, most of them are only limited to the emulsions stabilized by surfactants. In the case of high internal phase Pickering emulsions (HIPPEs), much greater values of elastic modulus have been reported, compared to those of surfactant-stabilized HIPEs, but so far, there have been no clear explanations for this. In this study, we investigate how colloidal particles attribute to the significantly high elasticity of HIPPEs, specifically considering two different contributions, namely, interfacial rheological properties and bulk rheological properties. Our results reveal that the flocculated structures of colloidal particles that possess a significant elasticity can be interconnected between dispersed droplets. Furthermore, this elastic structure is a crucial factor in the high elasticity of HIPPEs, which is also supported by a simple theoretical model.