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While aqueous zinc-ion batteries exhibit great potential, their performance is impeded by zinc dendrites. Existing literature has proposed the use of hydrogel electrolytes to ameliorate this issue. Nevertheless, the mechanical attributes of hydrogel electrolytes, particularly their modulus, are suboptimal, primarily ascribed to the substantial water content. This drawback would severely restrict the dendrite-inhibiting efficacy, especially under large mass loadings of active materials. Inspired by the structural characteristics of wood, this study endeavors to fabricate the anisotropic carboxymethyl cellulose hydrogel electrolyte through directional freezing, salting-out effect, and compression reinforcement, aiming to maximize the modulus along the direction perpendicular to the electrode surface. The heightened modulus concurrently serves to suppress the vertical deposition of the intermediate product at the cathode. Meanwhile, the oriented channels with low tortuosity enabled by the anisotropic structure are beneficial to the ionic transport between the anode and cathode. Comparative analysis with an isotropic hydrogel sample reveals a marked enhancement in both modulus and ionic conductivity in the anisotropic hydrogel. This enhancement contributes to significantly improved zinc stripping/plating reversibility and mitigated electrochemical polarization. Additionally, a durable quasi-solid-state Zn//MnO2 battery with noteworthy volumetric energy density is realized. This study offers unique perspectives for designing hydrogel electrolytes and augmenting battery performance.
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Conductive metal-organic frameworks (cMOFs) manifest great potential in modern electrical devices due to their porous nature and the ability to conduct charges in a regular network. cMOFs applied in electrical devices normally hybridize with other materials, especially a substrate. Therefore, the precise control of the interface between cMOF and a substrate is particularly crucial. However, the unexplored interface chemistry of cMOFs makes the controlled synthesis and advanced characterization of high-quality thin films, particularly challenging. Herein, we report the development of a simplified synthesis method to grow "face-on" and "edge-on" cMOF nanofilms on substrates, and the establishment of operando characterization methodology using atomic force microscopy and X-ray, thereby demonstrating the relationship between the soft structure of surface-mounted oriented networks and their characteristic conductive functions. As a result, crystallinity of cMOF nanofilms with a thickness down to a few nanometers is obtained, the possible growth mechanisms are proposed, and the interesting anisotropic softness-dependent conducting properties (over 2 orders of magnitude change) of the cMOF are also illustrated.
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Directional solidification of aqueous solutions and slurries in a temperature gradient is widely used to produce cellular materials through a phase separation of solutes or suspended particles between growing ice lamellae. While this process has analogies to the directional solidification of metallurgical alloys, it forms very different hierarchical structures. The resulting honeycomb-like porosity of freeze-cast materials consists of regularly spaced, lamellar cell walls which frequently exhibit unilateral surface features of morphological complexity reminiscent of living forms, all of which are unknown in metallurgical structures. While the strong anisotropy of ice-crystal growth has been hypothesized to play a role in shaping those structures, the mechanism by which they form has remained elusive. By directionally freezing binary water mixtures containing small solutes obeying Fickian diffusion, and phase-field modeling of those experiments, we reveal how those structures form. We show that the flat side of lamellae forms because of slow faceted ice-crystal growth along the c-axis, while weakly anisotropic fast growth in other directions, including the basal plane, is responsible for the unilateral features. Diffusion-controlled morphological primary instabilities on the solid-liquid interface form a cellular structure on the atomically rough side of the lamellae, which template regularly spaced "ridges" while secondary instabilities of this structure are responsible for the more complex features. Collating the results, we obtain a scaling law for the lamellar spacing, â[Formula: see text]â, where [Formula: see text] and [Formula: see text] are the local growth rate and temperature gradient, respectively.
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Cellular engulfment and uptake of macromolecular assemblies or nanoparticles via endocytosis can be associated to both healthy and disease-related biological processes as well as delivery of drug nanoparticles and potential nanotoxicity of pollutants. Depending on the physical and chemical properties of the system, the adsorbed particles may remain at the membrane surface, become wrapped by the membrane, or translocate across the membrane through an endocytosis-like process. In this paper, we address the question of how the wrapping of colloidal particles by lipid membranes can be controlled by the shape of the particles, the particle-membrane adhesion energy, the membrane phase behavior, and the membrane-bending rigidity. We use a model system composed of soft core-shell microgel particles with spherical and ellipsoidal shapes, together with phospholipid membranes with varying composition. Confocal microscopy data clearly demonstrate how tuning of these basic properties of particles and membranes can be used to direct wrapping and membrane deformation and the organization of the particles at the membrane. The deep-wrapped states are more favorable for ellipsoidal than for spherical microgel particles of similar volume. Theoretical calculations for fixed adhesion strength predict the opposite behavior-wrapping becomes more difficult with increasing aspect ratio. The comparison with the experiments implies that the microgel adhesion strength must increase with increasing particle stretching. Considering the versatility offered by microgels systems to be synthesized with different shapes, functionalizations, and mechanical properties, the present findings further inspire future studies involving nanoparticle-membrane interactions relevant for the design of novel biomaterials and therapeutic applications.
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Microgeles , Membrana Celular/química , Endocitosis , Membranas , Lípidos/químicaRESUMEN
Natural structural materials typically feature complex hierarchical anisotropic architectures, resulting in excellent damage tolerance. Such highly anisotropic structures, however, also provide an easy path for crack propagation, often leading to catastrophic fracture as evidenced, for example, by wood splitting. Here, we describe the weakly anisotropic structure of Ginkgo biloba (ginkgo) seed shell, which has excellent crack resistance in different directions. Ginkgo seed shell is composed of tightly packed polygonal sclereids with cell walls in which the cellulose microfibrils are oriented in a helicoidal pattern. We found that the sclereids contain distinct pits, special fine tubes like a "screw fastener," that interlock the helicoidal cell walls together. As a result, ginkgo seed shell demonstrates crack resistance in all directions, exhibiting specific fracture toughness that can rival other highly anisotropic natural materials, such as wood, bone, insect cuticle, and nacre. In situ characterization reveals ginkgo's unique toughening mechanism: pit-guided crack propagation. This mechanism forces the crack to depart from the weak compound middle lamella and enter into the sclereid, where the helicoidal cell wall significantly inhibits crack growth by the cleavage and breakage of the fibril-based cell walls. Ginkgo's toughening mechanism could provide guidelines for a new bioinspired strategy for the design of high-performance bulk materials.
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Fracturas Óseas , Ginkgo biloba , Semillas , Pared Celular , MaderaRESUMEN
Solid molecular hydrogen has been predicted to be metallic and high-temperature superconducting at ultrahigh hydrostatic pressures that push current experimental limits. Meanwhile, little is known about the influence of nonhydrostatic conditions on its electronic properties at extreme pressures where anisotropic stresses are inevitably present and may also be intentionally introduced. Here we show by first-principles calculations that solid molecular hydrogen compressed to multimegabar pressures can sustain large anisotropic compressive or shear stresses that, in turn, cause major crystal symmetry reduction and charge redistribution that accelerate bandgap closure and promote superconductivity relative to pure hydrostatic compression. Our findings highlight a hitherto largely unexplored mechanism for creating superconducting dense hydrogen, with implications for exploring similar phenomena in hydrogen-rich compounds and other molecular crystals.
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Two-dimensional (2D) NbOI2 demonstrates significant second-harmonic generation (SHG) with a high conversion efficiency. To unlock its full potential in practical applications, it is desirable to modulate the SHG behavior while utilizing the intrinsic lattice anisotropy. Here, we demonstrate direction-specific modulation of the SHG response in NbOI2 by applying anisotropic strain with respect to the intrinsic lattice orientations, where more than 2-fold enhancement in the SHG intensity is achieved under strain along the polar axis. The strain-driven SHG evolution is attributed to the strengthened built-in piezoelectric field (polar axis) and the enlarged Peierls distortions (nonpolar axis). Moreover, we provide quantifications of the correlation between strain and SHG intensity in terms of the susceptibility tensor. Our results demonstrate the effective coupling of orientation-specific strain to the anisotropic SHG response through the intrinsic polar order in 2D nonlinear optical crystals, opening a new paradigm toward the development of functional devices.
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Anisotropic nanocrystals such as nanorods (NRs) display unique linearly polarized emission, which is expected to break the external quantum efficiency (EQE) limit of quantum dot-based light-emitting diodes (LEDs). However, the progress in achieving a higher EQE using NRs encounters several challenges, primarily involving a low photoluminescence quantum yield (PLQY) of NRs and imbalanced charge injection in NR-LEDs. In this work, we investigated NR-LEDs based on CdSe/CdZnS/ZnS rod-in-rod NRs with a high PLQY and higher linear polarization compared to those of dot-in-rod NRs. The balanced charge injection is achieved using ZnMgO nanoparticles as the electron transport layer and poly-TPD {poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine]} as the hole transport layer. Therefore, the NR-LEDs exhibit a maximum EQE of 21.5% and a maximum luminance of >120â¯000 cd/m2 owing to the high level of in-plane transitions with a dipole moment of 90%. The NR-LEDs also have greatly inhibited droop in EQE under a high current density as well as outstanding operation lifetime and cycle stability.
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Bernal-stacked tetralayer graphene (4LG) exhibits intriguing low-energy properties, featuring two massive sub-bands and showcasing diverse features of topologically distinct, anisotropic Fermi surfaces, including Lifshitz transitions and trigonal warping. Here, we study the influence of the band structure on electron dynamics within 4LG using transverse magnetic focusing. Our analysis reveals two distinct focusing peaks corresponding to the two sub-bands. Furthermore, we uncover a pronounced dependence of the focusing spectra on crystal orientations, indicative of an anisotropic Fermi surface. Utilizing the semiclassical model, we attribute this orientation-dependent behavior to the trigonal warping of the band structure. This phenomenon leads to variations in electron trajectories based on crystal orientation. Our findings not only enhance our understanding of the dynamics of electrons in 4LG but also offer a promising method for probing anisotropic Fermi surfaces in other materials.
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Among atomically thin semiconductors, CrSBr stands out as both its bulk and monolayer forms host tightly bound, quasi-one-dimensional excitons in a magnetic environment. Despite its pivotal importance for solid-state research, the exciton lifetime has remained unknown. While terahertz polarization probing can directly trace all excitons, independently of interband selection rules, the corresponding large far-field foci substantially exceed the lateral sample dimensions. Here, we combine terahertz polarization spectroscopy with near-field microscopy to reveal a femtosecond decay of paramagnetic excitons in a monolayer of CrSBr, which is 30 times shorter than the bulk lifetime. We unveil low-energy fingerprints of bound and unbound electron-hole pairs in bulk CrSBr and extract the nonequilibrium dielectric function of the monolayer in a model-free manner. Our results demonstrate the first direct access to the ultrafast dielectric response of quasi-one-dimensional excitons in CrSBr, potentially advancing the development of quantum devices based on ultrathin van der Waals magnets.
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IV-V two-dimensional materials have emerged as key contenders for polarization-sensitive and angle-resolved devices, given their inherent anisotropic physical properties. While these materials exhibit intriguing high-pressure quasi-particle behavior and phase transition, the evolution of quasi-particles and their interactions under external pressure remain elusive. Here, employing a diamond anvil cell and spectroscopic measurements coupled with first-principles calculations, we unveil rarely observed pressure-induced phonon-phonon coupling in layered SiP flakes. This coupling manifests as an anomalous phonon hardening behavior for the A1 mode within a broad wavenumber phonon softening region. Furthermore, we demonstrate the effective tuning of exciton emissions in SiP flakes under pressure, revealing a remarkable 63% enhancement in the degree of polarization (DOP) within the pressure range of 0-3.5 GPa. These findings contribute to our understanding of high-pressure phonon evolution in SiP materials and offer a strategic approach to manipulate the anisotropic performance of in-plane anisotropic 2D materials.
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Organ morphologies are diverse but also conserved under shared developmental constraints among species. Any geometrical similarities in the shape behind diversity and the underlying developmental constraints remain unclear. Plant root tip outlines commonly exhibit a dome shape, which likely performs physiological functions, despite the diversity in size and cellular organization among distinct root classes and/or species. We carried out morphometric analysis of the primary roots of ten angiosperm species and of the lateral roots (LRs) of Arabidopsis, and found that each root outline was isometrically scaled onto a parameter-free catenary curve, a stable structure adopted for arch bridges. Using the physical model for bridges, we analogized that localized and spatially uniform occurrence of oriented cell division and expansion force the LR primordia (LRP) tip to form a catenary curve. These growth rules for the catenary curve were verified by tissue growth simulation of developing LRP development based on time-lapse imaging. Consistently, LRP outlines of mutants compromised in these rules were found to deviate from catenary curves. Our analyses demonstrate that physics-inspired growth rules constrain plant root tips to form isometrically scalable catenary curves.
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Desarrollo de la Planta/fisiología , Raíces de Plantas/crecimiento & desarrollo , Arabidopsis/crecimiento & desarrollo , División Celular , Meristema/anatomía & histología , Meristema/citología , Meristema/crecimiento & desarrollo , Raíces de Plantas/anatomía & histología , Raíces de Plantas/citologíaRESUMEN
A bio-inspired approach to fabricate robust superhydrophobic (SHB) surfaces with anisotropic properties replicated from a leek leaf is presented. The polydimethylsiloxane (PDMS) replica surfaces exhibit anisotropic wetting, anti-icing, and light scattering properties due to microgrooves replicated from leek leaves. Superhydrophobicity is achieved by a novel modified candle soot (CS) coating that mimics leek's epicuticular wax. The resulting surfaces show a contact angle (CA) difference of ≈30° in the directions perpendicular and parallel to the grooves, which is similar to the anisotropic properties of the original leek leaf. The coated replica is durable, withstanding cyclic bending tests (up to 10 000 cycles) and mechanical sand abrasion (up to 60 g of sand). The coated replica shows low ice adhesion (10 kPa) after the first cycle; and then, increases to ≈70 kPa after ten icing-shearing cycles; while, anisotropy in ice adhesion becomes more evident with more cycles. In addition, the candle soot-coated positive replica (CS-coated PR) demonstrates a transmittance of ≈73% and a haze of ≈65% at the wavelength of 550 nm. The results show that the properties depend on the replicated surface features of the leek leaf, which means that the leek leaf appears to be a highly useful template for bioinspired surfaces.
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Anisotropic colloidal particles with asymmetric morphology possess functionally rich heterogeneous structures, thus offering potential for intricate superstructures or nanodevices. However, it is a challenge to achieve controlled asymmetric surface partitioned growth. In this work, an innovative strategy is developed based on the selective adsorption and growth of emulsion droplets onto different regions of object which is controlled by wettability. It is found that the emulsion droplets can selectively adsorb on the hydrophilic surface but not the hydrophobic one, and further form asymmetric tentacle by the interfacial sol-gel process along its trajectory. Janus particles with an anisotropic shape and multitentacle structure are achieved via integration of emulsion droplet (soft) and seed (hard) templates. The size and number of tentacles exhibit tunability mediated by soft and hard templates, respectively. This general strategy can be expanded to a variety of planar substrates or curved particles, further confirming the correlation between tentacle growth and Brownian motion. Most interestingly, it can be employed to selectively modify one region of surface partitioned particles to achieve an ABC three-component Janus structure.
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Strong, lightweight, and shape-memory cellulose aerogels have great potential in multifunctional applications. However, achieving the integration of these features into a cellulose aerogel without harsh chemical modifications and the addition of mechanical enhancers remains challenging. In this study, a strong, lightweight, and water-stimulated shape-memory all-cellulose aerogel (ACA) is created using a combination strategy of partial dissolution and unidirectional freezing from bamboo. Benefiting from the firm architecture of cellulose microfibers bridging cellulose nanofibers /regenerated cellulose aggregated layers and the bonding of different cellulose crystal components (cellulose Iß and cellulose II), the ACA, with low density (60.74 mg cm-3 ), possesses high compressive modulus (radial section: 1.2 MPa, axial section: 0.96 MPa). Additionally, when stimulated with water, the ACA exhibits excellent shape-memory features, including highly reversible compression-resilience and instantaneous fold-expansion behaviors. As a versatile scaffold, ACA can be integrated with hydroxyapatite, carboxyl carbon nanotubes, and LiCl, respectively, via a simple impregnation method to yield functionalized cellulose composites for applications in thermal insulation, electromagnetic interference shielding, and piezoresistive sensors. This study provides inspiration and a reliable strategy for the elaborately structural design of functional cellulose aerogels endows application prospects in various multifunction opportunities.
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Polarization-sensitive broadband optoelectronic detection is crucial for future sensing, imaging, and communication technologies. Narrow bandgap 2D materials, such as Te and PdSe2, show promise for these applications, yet their polarization performance is limited by inherent structural anisotropies. In this work, a self-powered, broadband photodetector utilizing a Te/PdSe2 van der Waals (vdWs) heterojunction, with orientations meticulously tailored is introduced through polarized Raman optical spectra and tensor calculations to enhance linear polarization sensitivity. The device exhibits anisotropy ratios of 1.48 at 405 nm, 3.56 at 1550 nm, and 1.62 at 4 µm, surpassing previously-reported photodetectors based on pristine Te and PdSe2. Additionally, it exhibits high responsivity (617 mA W-1 at 1550 nm), specific detectivity (5.27 × 1010 Jones), fast response (≈4.5 µs), and an extended spectral range beyond 4 µm. The findings highlight the significance of orientation-engineered heterostructures in enhancing polarization-sensitive photodetectors and advancing optoelectronic technology.
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Property optimization through orientation control of metal-organic framework (MOF) crystals that exhibit anisotropic crystal structures continues to garner tremendous interest. Herein, an electric field is utilized to post-synthetically control the orientation of conductive layered Cu3(HHTP)2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) crystals dispersed in an electronically insulating poly(ethylene glycol) diacrylate (PEGDA) oligomer matrix. Optical and electrical measurements are performed to investigate the impact of the electric field on the alignment of Cu3(HHTP)2 crystals and the formation of aggregated microstructures, which leads to an ≈5000-fold increase in the conductivity of the composite. Notably, the composite thin-films containing aligned Cu3(HHTP)2 crystals exhibit significant conductivity of ≈10-3 S cm-1 despite the low concentration (≈1 wt.%) of conductive Cu3(HHTP)2. The use of an electric field to align Cu3(HHTP)2 crystals can rapidly generate various desired patterns that exhibit on-demand tunable collective charge transport anisotropy. The findings provide valuable insights toward the manipulation and utilization of conductive MOFs with anisotropic crystal structures for various applications such as adhesive electrical interconnects and microelectronics.
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Using nanoparticle surfactants to stabilize the liquid-liquid interface has attracted significant attention for developing all-liquid constructs including emulsions and liquid devices. Here, an efficient strategy is demonstrated to stabilize complex emulsions that consist of multiphase droplets by using the co-assembly between the cellulose nanocrystal and amine-functionalized polystyrene. Cellulose nanocrystal surfactants (CNCSs) form and assembly in situ at the specified area of emulsion interface, showing a unique pH responsiveness due to their dynamic nature and allowing the reconfiguration of complex emulsion from encapsulated to Janus structures. Such complex emulsions can be further used as the templates to fabricate polymeric particles with hollow, semi-spherical, and spherical shapes on large scale. These findings establish a promising platform for designing intelligent soft matter that can be used in microreactors, sensors, and anisotropic materials.
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Droplet well-controlled directional motion being an essential function has attracted much interest in academic and industrial applications, such as self-cleaning, micro-/nano-electro-mechanical systems, drug delivery, and heat-transferring. Conventional understanding has it that a droplet impacted on an anisotropic surface tends to bounce along the microstructural direction, which is mainly dictated by surface properties rather than initial conditions. In contrast to previous findings, it demonstrates that the direction of a droplet's rebound on an anisotropic surface can be switched by designing the initial impacting velocity. With an increase in impacting height from 2 to 10 cm, the droplet successively shows a backward, vertical, and forward motion on anisotropic surfaces. Theoretical demonstrations establish that the transition of droplet bouncing on the anisotropic surface is related to its dynamic wettability during impacting process. Characterized by the liquid-solid interaction, it is demonstrated that the contact state at small and large impacting heights induces an opposite resultant force in microstructures. Furthermore, energy balance analysis reveals that the energy conversion efficiency of backward motion is almost three times as that of traditional bouncing. This work, including experiments, theoretical models, and energy balance analysis provides insight view in droplet motions on the anisotropic surfaces and opens a new way for the droplet transport.
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Na2 Ti3 O7 is considered one of the most promising anode materials for sodium ion batteries due to its superior safety, environmental friendliness, and low manufacturing cost. However, its structural stability and reaction mechanism still have not been fully explored. As the electron beam irradiation introduces a similar impact on the Na2 Ti3 O7 anode as the extraction of Na+ ions during the battery discharge process, the microstructure evolution of the materials is investigated by advanced electron microscopy techniques at the atomic scale. Anisotropic amorphization is successfully observed. Through the integrated differential phase contrast-scanning transmission electron microscopy technique and density functional theory calculation, a phase transition pathway involving a new phase, Na2 Ti24 O49 , is proposed with the reduction of Na atoms. Additionally, it is found that the amorphization is dominated by the surface energy and electron dose rate. These findings will deepen the understanding of structural stability and deintercalation mechanism of the Na2 Ti3 O7 anode, providing new insight into exploring the failure mechanism of electrode materials.