Light-Triggered Anti-ambipolar Transistor Based on an In-Plane Lateral Homojunction.

Currently, the construction of anti-ambipolar transistors (AATs) is primarily based on asymmetric heterostructures, which are challenging to fabricate. AATs used for photodetection are accompanied by dark currents that prove difficult to suppress, resulting in reduced sensitivity. This work presents light-triggered AATs based on an in-plane lateral WSe2 homojunction without van der Waals heterostructures. In this device, the WSe2 channel is partially electrically controlled by the back gate due to the screening effect of the bottom electrode, resulting in a homojunction that is dynamically modulated with gate voltage, exhibiting electrostatically reconfigurable and light-triggered anti-ambipolar behaviors. It exhibits high responsivity (188 A/W) and detectivity (8.94 × 1014 Jones) under 635 nm illumination with a low power density of 0.23 µW/cm2, promising a new approach to low-power, high-performance photodetectors. Moreover, the device demonstrates efficient self-driven photodetection. Furthermore, ternary inverters are realized using monolithic WSe2, simplifying the manufacturing of multivalued logic devices.

Fluorenylidene-Cyclopentadithiophene Based Asymmetric Bistricyclic Aromatic Ene Compounds: Synthesis and Substituents Effects.

Low band gap materials have always been a focus of attention due to their potential applications in various fields. In this work, a series of asymmetric bistricyclic aromatic ene (BAE) compounds with fluorenylidene-cyclopentadithiophene (FYT) skeleton were facially synthesized, which were modified with different substituents (-OMe, -SMe). The FYT core exhibit twisted C=C bond with dihedral angles around 30°, and the introduction of -SMe group can provide additional S⋅⋅⋅S interaction between molecules, which is conducive to the charge transporting. The UV-Vis spectra, electrochemistry and photoelectron spectroscopy revealed that these compounds have relatively narrow band gaps, particularly, the -SMe modified compounds have slightly lower HOMO and Fermi energy levels than that of the -OMe modified compounds. Furthermore, PSCs devices were fabricated with the three compounds as HTMs, and FYT-DSDPA exhibit the best performance among them, revealing the fine-tuning band structure could influence properties of HTMs.

Tailoring the Asymmetric Structure of NH2 -UiO-66 Metal-Organic Frameworks for Light-promoted Selective and Efficient Gold Extraction and Separation.

Designing adsorption materials with high adsorption capacities and selectivities is highly desirable for precious metal recovery. Desorption performance is also particularly crucial for subsequent precious metal recovery and adsorbent regeneration. Herein, a metal-organic framework (MOF) material (NH2 -UiO-66) with an asymmetric electronic structure of the central zirconium oxygen cluster has an exceptional gold extraction capacity of 2.04 g g-1 under light irradiation. The selectivity of NH2 -UiO-66 for gold ions is up to 98.8 % in the presence of interfering ions. Interestingly, the gold ions adsorbed on the surface of NH2 -UiO-66 spontaneously reduce in situ, undergo nucleation and growth and finally achieve the phase separation of high-purity gold particles from NH2 -UiO-66. The desorption and separation efficiency of gold particles from the adsorbent surface reaches 89 %. Theoretical calculations indicate that -NH2 functions as a dual donor of electrons and protons, and the asymmetric structure of NH2 -UiO-66 leads to energetically advantageous multinuclear gold capture and desorption. This adsorption material can greatly facilitate the recovery of gold from wastewater and can easily realize the recycling of the adsorbent.

Single-Metal-Encapsulated Double-Cage [Pt@Sn17 ]4- : An Exception from Group 14 Endohedral Clusters.

Group 14 endohedral clusters containing a metal center inside usually possess a single cage topological structure, but here an unexpected single-metal-filled double-cage cluster, [Pt@Sn17 ]4- (1 a) is reported. It can be seen as a combination of the more extended Pt-filled [Pt@Sn9 ] cage and hollow [Sn9 ] cage sharing a central Sn atom, which is offset from the central position. This double-cage species represents the largest group 14 intermetalloid cluster encapsulating a single transition metal atom. DFT calculations show that the capsule-like architecture of [Sn17 ]4- , similar to that found in [Pt2 @Sn17 ]4- , is unstable if filled with a single Pt atom and collapses to the title cluster 1 a upon geometry optimization. Deviation of the central Sn atom occurs due to the vibronic coupling as a consequence of pseudo-Jahn-Teller distortion leading to the bent Cs -symmetrical structure, in contrast to the more symmetrical D2d cage previously reported in [Ni2 @Sn17 ]4- .

Swelling-Induced Symmetry Breaking: A Versatile Approach to the Scalable Production of Colloidal Particles with a Janus Structure.

Janus particles are widely sought for applications related to colloidal assembly, stabilization of emulsions, and development of active colloids, among others. Here we report a versatile route to the fabrication of well-controlled Janus particles by simply breaking the symmetry of spherical particles with swelling. When a polystyrene (PS) sphere covered by a rigid shell made of silica or polydopamine is exposed to a good solvent for PS, a gradually increased pressure will be created inside the shell. If the pressure becomes high enough to poke a hole in the shell, the spherical symmetry will break while pushing out the swollen PS through the opening to generate a Janus particle comprised of two distinct components. One of the components is made of PS and its size is controlled by the extent of swelling. The other component is comprised of the rigid shell and remaining PS, with its overall diameter determined by the original PS sphere and the rigid shell. This solution-based route holds promises for the scalable production of complex Janus particles with a variety of compositions and in large quantities.

Controlled Asymmetric Charge Distribution of Active Centers in Conjugated Polymers for Oxygen Reduction.

Active center reconstruction is essential for high performance oxygen reduction reaction (ORR) electrocatalysts. Usually, the ORR activity stems from the electronic environment of active sites by charge redistribution. We introduce an asymmetry strategy to adjust the charge distribution of active centers by designing conjugated polymer (CP) catalysts with different degrees of asymmetry. We synthesized asymmetric backbone CP (asy-PB) by modifying B←N coordination bonds and asymmetric sidechain CP (asy-PB-A) with different alkyl chain lengths. Both CPs with backbone and sidechain asymmetry exhibit superior ORR performance to their symmetric counterparts (sy-P and sy-PB). The asy-PB with greater asymmetry shows higher catalytic activity than asy-PB-A with relatively smaller asymmetry. DFT calculations reveal that the increased dipole moment and non-uniform charge distribution caused by asymmetric structure endows the center carbon atom of bipyridine with efficient catalytic activity.

Two-Dimensional van der Waals Materials with Aligned In-Plane Polarization and Large Piezoelectric Effect for Self-Powered Piezoelectric Sensors.

Piezoelectric two-dimensional (2D) van der Waals (vdWs) materials are highly desirable for applications in miniaturized and flexible/wearable devices. However, the reverse-polarization between adjacent layers in current 2D layered materials results in decreasing their in-plane piezoelectric coefficients with layer number, which limits their practical applications. Here, we report a class of 2D layered materials with an identical orientation of in-plane polarization. Their piezoelectric coefficients (e22) increase with layer number, thereby allowing for the fabrication of flexible piezotronic devices with large piezoelectric responsivity and excellent mechanical durability. The piezoelectric outputs can reach up to 0.363 V for a 7-layer α-In2Se3 device, with a current responsivity of 598.1 pA for 1% strain, which is 1 order of magnitude higher than the values of the reported 2D piezoelectrics. The self-powered piezoelectric sensors made of these newly developed 2D layered materials have been successfully used for real-time health monitoring, proving their suitability for the fabrication of flexible piezotronic devices due to their large piezoelectric responses and excellent mechanical durability.

Thermal Drift Investigation of an SOI-Based MEMS Capacitive Sensor with an Asymmetric Structure.

High-precision, low-temperature-sensitive microelectromechanical system (MEMS) capacitive accelerometers are widely used in aerospace, automotive, and navigation systems. An analytical study of the temperature drift of bias (TDB) and temperature drift of scale factor (TDSF) for an asymmetric comb capacitive accelerometer is presented in this paper. A five-layer model is established for the equivalent expansion ratio in the TDB and TDSF formulas, and the results calculated by the weighted average of thickness and elasticity modulus method are closest to the results of the numerical simulation. The analytical formulas of TDB and TDSF for an asymmetric structure are obtained. For an asymmetric structure, TDB is only related to thermal deformation and fabrication error. Additionally, half of the fixed electrode distance is not included in the expressions of Δ d and Δ D for asymmetric structures, thus resulting in the TDSF of the asymmetric structure being smaller compared to a symmetric structure with the same structural parameters. The TDSF of the symmetric structure is [-200.2 ppm/°C, -261.6 ppm/°C], while the results of the asymmetric structure are [-11.004 ppm/°C, -72.404 ppm/°C] under the same set of parameters. The parameters of the optimal asymmetric structure are obtained for fabrication guidance using numerical methods. In the experiment, the TDSF and TDB of the packaged structure and the non-packaged structure are compared, and a significant effect of the package on the signal output is found. The TDB is reduced from 3000 to 60 µg/°C, while the TDSF is reduced from 3000 to 140 ppm/°C.

Membrane-tethered syntaxin-4 locally abrogates E-cadherin function and activates Smad signals, contributing to asymmetric mammary epithelial morphogenesis.

Spatial and temporal epithelial-mesenchymal transition (EMT) is a critical event for the generation of asymmetric epithelial architectures. We found that only restricted cell populations in the morphogenic mammary epithelia extrude syntaxin-4, a plasmalemmal t-SNARE protein, and that epithelial cell clusters with artificial heterogenic presentation of extracellular syntaxin-4 undergo asymmetric morphogenesis. A previous study revealed that inducible expression of cell surface syntaxin-4 causes EMT-like cell behaviors in the clonal mammary epithelial cells, where laminin-mediated signals were abolished so that cells readily succumb to initiate EMT. The present study added new mechanistic insight into syntaxin-4-driven EMT-like cell behaviors. Extracellular syntaxin-4 directly perturbs E-cadherin-mediated epithelial cell-cell adhesion and activates Smad signals. We found that the epithelial cells activated Smad2/3 upon induction of expression of extracellular syntaxin-4, leading to the upregulation of certain transcriptional targets of these TGF-ß signaling mediators. Intriguingly, however, mRNA expression of canonical EMT initiators, such as Snail and Slug, was unchanged. In addition, E-cadherin protein was steeply decreased, yet its transcriptional expression remained constant for a couple of days. We found that extracellular syntaxin-4 directly bound to E-cadherin and sequestered ß-catenin from cell-cell contact sites, perturbing intercellular adhesive property. The functional ablation of E-cadherin by syntaxin-4 was further validated by L cells with stably expressing E-cadherin, in which cells shows intercellular adhesive property solely by E-cadherin. These results underline the role of local exportation of syntaxin-4 for onset of complex epithelial morphogenesis.

Improving the Electroluminescence Properties of New Chrysene Derivatives with High Color Purity for Deep-Blue OLEDs.

Two blue-emitting materials, 4-(12-([1,1':3',1″-terphenyl]-5'-yl)chrysen-6-yl)-N,N-diphenylaniline (TPA-C-TP) and 6-([1,1':3',1″-terphenyl]-5'-yl)-12-(4-(1,2,2-triphenylvinyl)phenyl)chrysene (TPE-C-TP), were prepared with the composition of a chrysene core moiety and terphenyl (TP), triphenyl amine (TPA), and tetraphenylethylene (TPE) moieties as side groups. The maximum photoluminescence (PL) emission wavelengths of TPA-C-TP and TPE-C-TP were 435 and 369 nm in the solution state and 444 and 471 nm in the film state. TPA-C-TP effectively prevented intermolecular packing through the introduction of TPA, a bulky aromatic amine group, and it showed an excellent photoluminescence quantum yield (PLQY) of 86% in the film state. TPE-C-TP exhibited aggregation-induced emission; the PLQY increased dramatically from 0.1% to 78% from the solution state to the film state. The two synthesized materials had excellent thermal stability, with a high decomposition temperature exceeding 460 °C. The two compounds were used as emitting layers in a non-doped device. The TPA-C-TP device achieved excellent electroluminescence (EL) performance, with Commission Internationale de L'Eclairage co-ordinates of (0.15, 0.07) and an external quantum efficiency of 4.13%, corresponding to an EL peak wavelength of 439 nm.

Covalently Functionalized Nanopores for Highly Selective Separation of Monovalent Ions.

Biological ion channels possess prominent ion transport performances attributed to their critical chemical groups across the continuous nanoscale filters. However, it is still a challenge to imitate these sophisticated performances in artificial nanoscale systems. Herein, this work develops the strategy to fabricate functionalized graphene nanopores in pioneer based on the synergistic regulation of the pore size and chemical properties of atomically thin confined structure through decoupling etching combined with in situ covalent modification. The modified graphene nanopores possess asymmetric ion transport behaviors and efficient monovalent metal ions sieving (K+ /Li+ selectivity ≈48.6). Meanwhile, it also allows preferential transport for cations, the resulting membranes exhibit a K+ /Cl- selectivity of 76 and a H+ /Cl- selectivity of 59.3. The synergistic effects of steric hindrance and electrostatic interactions imposing a higher energy barrier for Cl- or Li+ across nanopores lead to ultra-selective H+ or K+ transport. Further, the functionalized graphene nanopores generate a power density of 25.3 W m-2 and a conversion efficiency of 33.9%, showing potential application prospects in energy conversion. The theoretical studies quantitatively match well with the experimental results. The feasible preparation of functionalized graphene nanopores paves the way toward direct investigation on ion transport mechanism and advanced design in devices.

Electrospun Biomimetic Periosteum Capable of Controlled Release of Multiple Agents for Programmed Promoting Bone Regeneration.

The effective repair of large bone defects remains a major challenge due to its limited self-healing capacity. Inspired by the structure and function of the natural periosteum, an electrospun biomimetic periosteum is constructed to programmatically promote bone regeneration using natural bone healing mechanisms. The biomimetic periosteum is composed of a bilayer with an asymmetric structure in which an aligned electrospun poly(ε-caprolactone)/gelatin/deferoxamine (PCL/GEL/DFO) layer mimics the outer fibrous layer of the periosteum, while a random coaxial electrospun PCL/GEL/aspirin (ASP) shell and PCL/silicon nanoparticles (SiNPs) core layer mimics the inner cambial layer. The bilayer controls the release of ASP, DFO, and SiNPs to precisely regulate the inflammatory, angiogenic, and osteogenic phases of bone repair. The random coaxial inner layer can effectively antioxidize, promoting cell recruitment, proliferation, differentiation, and mineralization, while the aligned outer layer can promote angiogenesis and prevent fibroblast infiltration. In particular, different stages of bone repair are modulated in a rat skull defect model to achieve faster and better bone regeneration. The proposed biomimetic periosteum is expected to be a promising candidate for bone defect healing.

Janus hydrogel loaded with a CO2-generating chemical reaction system: Construction, characterization, and application in fruit and vegetable preservation.

In this study, we inserted a dynamic chemical reaction system that can generate CO2 into Janus hydrogel (JH) to develop a multidimensional preservation platform that integrates hygroscopicity, antibacterial activity, and modified atmospheric capacity. The double gel system developed using sodium alginate/trehalose at a 1:1 ratio effectively encapsulated 90% of citric acid. Furthermore, CO2 loss was avoided by separately embedding NaHCO3/cinnamon essential oil and citric acid microcapsules into a gelatin pad to develop JH. Freeze-dried JH exhibited a porous and asymmetric structure, very strongly absorbing moisture, conducting water, and rapidly releasing CO2 and essential oils. Furthermore, when preserving various fruits and vegetables in practical settings, JH provided several preservation effects, including color protection, microbial inhibition, and antioxidant properties. Our study findings broaden the application of JH technology for developing chemical reaction systems, with the resulting JH holding substantial promise for cold chain logistics.

12.6 µm-Thick Asymmetric Composite Electrolyte with Superior Interfacial Stability for Solid-State Lithium-Metal Batteries.

Solid-state lithium metal batteries (SSLMBs) show great promise in terms of high-energy-density and high-safety performance. However, there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes, and to minimize the electrolyte thickness to achieve high-energy-density of SSLMBs. Herein, we develop an ultrathin (12.6 µm) asymmetric composite solid-state electrolyte with ultralight areal density (1.69 mg cm-2) for SSLMBs. The electrolyte combining a garnet (LLZO) layer and a metal organic framework (MOF) layer, which are fabricated on both sides of the polyethylene (PE) separator separately by tape casting. The PE separator endows the electrolyte with flexibility and excellent mechanical properties. The LLZO layer on the cathode side ensures high chemical stability at high voltage. The MOF layer on the anode side achieves a stable electric field and uniform Li flux, thus promoting uniform Li+ deposition. Thanks to the well-designed structure, the Li symmetric battery exhibits an ultralong cycle life (5000 h), and high-voltage SSLMBs achieve stable cycle performance. The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg-1/773.1 Wh L-1. This simple operation allows for large-scale preparation, and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs.

Ultra-robust, Highly Stretchable, and Conductive Nanocomposites with Self-healable Asymmetric Structures Prepared by a Simple Green Method.

Flexible conductive polymer nanocomposites based on silver nanowires (AgNWs) have been extensively studied to develop the next generation of flexible electronic devices. Fiber materials with high strength and large stretching are an important part of high-performance wearable electronics. However, manufacturing conductive composites with both high mechanical strength and good stability remains challenging. In addition, the process of effectively dispersing conductive fillers into substrates is relatively complex, which greatly hampers its widespread application. Here, a simple green self-assembly preparation method in water is reported. The AgNW is evenly dispersed in aqueous, i.e., water-borne polyurethane (WPU) with water as the solvent, and a AgNW/WPU conductive nanocomposite film with an asymmetric structure is formed by self-assembly in one step. The film has high strength (≈49.2 MPa) and high strain (≈910%), low initial resistance (99.9 mΩ/sq), high conductivity (9968.1 S/cm), and excellent self-healing (93%) and adhesion. With good self-healing performance, fibers with a conductive filler spiral structure are formed. At the same time, the application of the conductive composite material with an asymmetric structure in intelligent wearability is demonstrated.

Asymmetric and Flexible Ag-MXene/ANFs Composite Papers for Electromagnetic Shielding and Thermal Management.

Lightweight, flexible, and electrically conductive thin films with high electromagnetic interference (EMI) shielding effectiveness and excellent thermal management capability are ideal for portable and flexible electronic devices. Herein, the asymmetric and multilayered structure Ag-MXene/ANFs composite papers (AMAGM) were fabricated based on Ag-MXene hybrids and aramid nanofibers (ANFs) via a self-reduction and alternating vacuum-assisted filtration process. The resultant AMAGM composite papers exhibit high electrical conductivity of 248,120 S m-1, excellent mechanical properties with tensile strength of 124.21 MPa and fracture strain of 4.98%, superior EMI shielding effectiveness (62 dB), ultra-high EMI SE/t (11,923 dB cm2 g-1) and outstanding EMI SE reliability as high as 96.1% even after 5000 cycles of bending deformation benefiting from the unique structure and the 3D network at a thickness of 34 µm. Asymmetric structures play an important role in regulating reflection and absorption of electromagnetic waves. In addition, the multifunctional nanocomposite papers reveal outstanding thermal management performances such as ultrafast thermal response, high heating temperatures at low operation voltage, and high heating stability. The results indicate that the AMAGM composite papers have excellent potential for high-integration electromagnetic shielding, wearable electronics, artificial intelligence, and high-performance heating devices.

Nature-Inspired Stalactite Nanopores for Biosensing and Energy Harvesting.

Nature provides a wide range of self-assembled structures from the nanoscale to the macroscale. Under the right thermodynamic conditions and with the appropriate material supply, structures like stalactites, icicles, and corals can grow. However, the natural growth process is time-consuming. This work demonstrates a fast, nature-inspired method for growing stalactite nanopores using heterogeneous atomic deposition of hafnium dioxide at the orifice of templated silicon nitride apertures. The stalactite nanostructures combine the benefits of reduced sensing region typically for 2-dimensional material nanopores with the asymmetric geometry of capillaries, resulting in ionic selectivity, stability, and scalability. The proposed growing method provides an adaptable nanopore platform for basic and applied nanofluidic research, including biosensing, energy science, and filtration technologies.

Electrically driven heartbeat effect of gallium-based liquid metal on a ratchet.

The realization of the liquid metal heartbeat effect shows better controllability under non-periodic stimuli than spontaneous oscillation or periodic stimuli. However, adjusting the liquid metal heartbeat performance, drop spreading area, and frequency, solely by the magnitude of the voltage, has great limitations. Here, we demonstrate that the eGaIn drop can beat inside graphite ring electrodes under DC voltage in alkaline solutions on ratchet substrates. These sawtooth structures provide asymmetric textures which influence liquid metal deformation during the beating of the heart. We achieved heartbeat frequencies from 2.7 to 4.8 Hz, a 100% increase in the tunable frequency range compared to that on a flat surface. The oxidative spreading of the eGaIn drop on the ratchet substrate shows that the drop penetrates into the grooves of the sawtooth structure. Moreover, we investigated the physical mechanisms affecting the eGaIn heartbeat frequency and the influence on the spreading area of the eGaIn drop at various sawtooth sizes and orientations. These findings not only enhance our understanding of droplet manipulation on sawtooth-structured surfaces but also facilitate the design of microfluidic pump systems.

Proton Donor-Regulated Mechanically Robust Aramid Nanofiber Aerogel Membranes for High-Temperature Thermal Insulation.

High-performance thermal insulators are urgently desired for energy-saving and thermal protection applications. However, the creation of such materials with synchronously ultralow thermal conductivity, lightweight, and mechanically robust properties still faces enormous challenges. Herein, a proton donor-regulated assembly strategy is presented to construct asymmetric aramid nanofiber (ANF) aerogel membranes with a dense skin layer and a high-porous nanofibrous body part. The asymmetric structure originates from the otherness of the structural restoration of deprotonated ANFs and the resulting ANF assembly due to the diversity of available proton concentrations. Befitting from the synergistic effect of the distinct architectures, the resulting aerogel membranes exhibit excellent overall performance in terms of a low thermal conductivity of 0.031 W·m-1·K-1, a low density of 19.2 mg·cm-3, a high porosity of 99.53%, a high tensile strength of 11.8 MPa (16.5 times enhanced), high heat resistance (>500 °C), and high flame retardancy. Furthermore, a blade-scraping process is further proposed to fabricate the aerogel membrane in a continuous and scalable manner, as it is believed to have potential applications in civil and military fields.

Silicon Distribution-Induced Actuation Film with Bidirectional Bending Deformation and Versatile Bionic Applications.

As an important branch of intelligent materials, the research and development of stimulus-responsive flexible intelligent actuation materials is of great significance to promote the industrialization of intelligent materials. In this study, the asymmetric PVA-co-PE/silicon nanoparticle (PPSN) composite films and PVA-co-PE/silicon sol (PPSS) composite film with different silicon distributions were prepared by a simple spraying method. The silicon nanoparticle layer in the PPSN composite film was similar to the sand-like water-absorbing layer, which can quickly absorb water and permeate it into the interior region, leading to the hygroscopic expansion behavior on one side of the nanofiber film. Then, the PPSN composite film would quickly bend and deform to the silicon nanoparticle side. However, in the PPSS composite film, due to the excellent hygroscopicity and swelling characteristics of the silica sol layer, the composite film can be rapidly deformed to the PVA-co-PE nanofiber film side under moisture stimulation. The above results subvert the traditional asymmetric actuation film, which mainly depends on the hydrophilicity difference to determine the hygroscopic responsiveness and deformation direction, and ignore that the swelling degree is the main factor determining the bending direction of actuator. In addition, both the composite films can quickly respond to moisture stimulation (<1 s) and produce large-scale bending deformation (180°). Furthermore, due to the excellent interface adhesion formed by the continuity structure in the PPSS composite film, it has better actuation stability than the PPSN composite film. The excellent actuation characteristics and different bending directions of the PPSN and PPSS composite films make it a great application prospect in the field of bionics in the future.