Mechanically induced conformational switching at the single-molecule level represents a fundamental mechanism for molecular functionality, yet quantitative characterization of the underlying force and energy landscape re...Mechanically induced conformational switching at the single-molecule level represents a fundamental mechanism for molecular functionality, yet quantitative characterization of the underlying force and energy landscape remains limited. Here, we study individual TBrPP-Co(II) molecules on Au(111) using qPlus atomic force microscopy. By reconstructing interaction potentials from 3D Δ(,,) data, we determine a threshold force of ∼96 ± 8 pN and a tip-induced switching interaction energy of ∼38 ± 4 meV associate with the conformational transition. The isolated tip-molecule force follows a power law (exponent ∼6), indicating dominance of long-range van der Waals interactions. At closer distances, deviations reveal force-induced deformation preceding the transition. Validation via the inflection point test confirms measurement reliability. These findings show that long-range dispersive interactions can mechanically deform a molecule and facilitate conformational switching through a deformation-assisted pathway, providing a quantitative framework for controlling mechanically driven functionality at the single-molecule scale.
The shuttle effect of intermediate lithium polysulfides (LiPSs) and sluggish redox kinetics limit the practical application of lithium-sulfur (Li-S) batteries. Herein, RuCo alloy nanoparticles supported on N-doped mesopo...The shuttle effect of intermediate lithium polysulfides (LiPSs) and sluggish redox kinetics limit the practical application of lithium-sulfur (Li-S) batteries. Herein, RuCo alloy nanoparticles supported on N-doped mesoporous carbon spheres (RuCo/NMCS) are developed as efficient catalytic sulfur hosts. Electron transfer from Co to Ru optimizes the adsorption and catalytic conversion of LiPSs, accelerating sulfur redox reactions. Meanwhile, the dynamic changes of Ru and Co species in the RuCo/NMCS electrode demonstrate the strong Ru-S and Co-S interactions between metals and LiPSs during the discharge-charge process, corresponding to the accelerated conversions of LiS/LiS to LiPSs and LiPSs to S. Consequently, the RuCo/NMCS electrode showcases improved electrochemical performance with enhanced cycling capacity and stable reversible capacity. This work provides a feasible and rational route to construct alloy electrocatalyst-supported cathode materials with bidirectional catalysis on LiPS conversion, promoting the application of alloy electrocatalysts as kinetic regulators for high-performance Li-S batteries.
The atomic architecture of apomyoglobin amyloid fibrils, despite the protein's dual distinction as the first structurally resolved protein and the paradigmatic nondisease amyloid, has remained a decades-long puzzle. Here...The atomic architecture of apomyoglobin amyloid fibrils, despite the protein's dual distinction as the first structurally resolved protein and the paradigmatic nondisease amyloid, has remained a decades-long puzzle. Here, we identify electrostatic screening as the critical switch that enables the formation of highly ordered apomyoglobin fibrils, allowing us to determine the cryo-electron microscopy structures of three distinct polymorphs (PM1, PM2, and PM3) at 2.7 Å resolution. The structures reveal a conserved "hydrophobic-in, positively charged-out" architecture, where a charged surface surrounds a tightly packed core, providing a structural explanation for salt-dependent assembly. Structural comparisons reveal a hierarchical principle of amyloid organization, in which short sequence segments retain conserved local conformations dictated by their intrinsic folding propensities, while variations in supramolecular packing give rise to polymorphic diversity. These findings establish a molecular framework for understanding electrostatically controlled self-assembly and the structural basis of amyloid polymorphism.
Unidirectional liquid transport is critical for diverse applications, e.g., atmospheric water harvesting, integrated microfluidics, and high-efficiency heat transfer. However, existing strategies are mostly limited to na...Unidirectional liquid transport is critical for diverse applications, e.g., atmospheric water harvesting, integrated microfluidics, and high-efficiency heat transfer. However, existing strategies are mostly limited to narrow surface-tension ranges. Here, we designed bioinspired asymmetric cilia arrays (BACAs) mimicking the 45° inclined cilia of , achieving unidirectional liquid transport over an ultrabroad surface-tension range of 22.2-72.8 mN m. Systematic studies show that transport modes depend on surface tension, solid surface energy, and cilia spacing. For 0.6 mm-spaced BACAs (∼16.4 mJ m), ethanol/water mixtures exhibit reverse transport above 32.1 mN m, forward transport below 28.0 mN m, and bidirectional flow in between. These phenomena arise from the dynamic equilibrium between gravity and capillarity. We further established a theoretical predictive framework based on the bidirectional transport contact angle to quantify transport modes, which contributed to achieve programmable liquid routing and precise spatiotemporal control over liquid transport.
Chiral quasi-bound states in the continuum (q-BICs) have recently emerged in metaphotonics as resonances that combine ultra-high-quality factors with near-unity circular polarization in the far field. However, these stat...Chiral quasi-bound states in the continuum (q-BICs) have recently emerged in metaphotonics as resonances that combine ultra-high-quality factors with near-unity circular polarization in the far field. However, these states are typically confined to the Γ-point (normal incidence) due to their symmetry-protected origins. We propose a new mechanism for realizing light-cone-proximal chiral q-BICs at large oblique angles, enabled by the divergence of the radiative density of states near the light cone. Using dielectric metasurfaces with a monoclinic lattice and broken in-plane mirror symmetry, we demonstrate that tuning the lattice angle allows for robust control of these resonances. The resulting chiral q-BICs exhibit near-unity circular dichroism in transmission and fully circularly polarized emission at angles exceeding 50° from normal. Our results establish a general route to off-normal and grazing-angle chiral q-BICs, enabling directional chiral lasing and providing a versatile platform for quantum and nonlinear photonics.
Photobatteries (PBs), which integrate photoactive materials into conventional battery architectures, offer an effective strategy to enhance battery performance by utilizing photogenerated charge carriers in the energy st...Photobatteries (PBs), which integrate photoactive materials into conventional battery architectures, offer an effective strategy to enhance battery performance by utilizing photogenerated charge carriers in the energy storage medium. Herein, we report scalable synthesis of WO-WS nanosheet (NS)-based heterostructures for photoelectrodes in Li-ion PBs. These NS heterostructures enable broadband light harvesting (300-800 nm) and efficient separation of photocharge carriers. Atomically interfaced heterostructures of WO-WS NSs have demonstrated stable electrochemical performance, retaining 80% of their capacity after 300 cycles with a specific capacity of 515.94 mAh g (100-1000 mA g). Additionally, PBs exhibited enhanced kinetics under illumination (∼12 mW cm), resulting in a 35-59% increase in specific capacity. The dual-mesh current collector approach has been employed to increase the active mass loading, which further enhanced light-matter interaction and ultimately increased specific capacity. This work demonstrates a design framework for optimizing charge-carrier dynamics in PBs and establishes a viable pathway toward high-performance PBs for IoT applications.
In thin layers of the 2D magnetic semiconductor CrSBr, very recent studies identified two distinct band-edge optical resonances, believed to arise from distinguishable bulk and surface excitons. This behavior reportedly...In thin layers of the 2D magnetic semiconductor CrSBr, very recent studies identified two distinct band-edge optical resonances, believed to arise from distinguishable bulk and surface excitons. This behavior reportedly originates from the highly anisotropic nature of CrSBr─particularly in its antiferromagnetic state─where excitons are effectively confined within individual monolayers, such that excitons in the two surface layers "see" a different local dielectric environment and have a lower resonance energy. To explore this scenario, here we investigate optical absorption properties of few-layer CrSBr in magnetic fields. In addition to the fundamental exciton resonance at ∼1.36 eV, we observe an absorption resonance ∼20 meV lower in energy. Compared to the fundamental transition, this resonance redshifts only half as much in small magnetic fields that induce ferromagnetic order, while in high fields to 55 T it exhibits a smaller diamagnetic shift. Both behaviors point to distinguishable populations of bulk and surface excitons in CrSBr.
High-entropy alloy (HEA) nanomaterials have emerged as promising electrocatalysts because of their compositional diversity and unique synergistic effects. Engineering the structure of HEAs, including facets, morphology,...High-entropy alloy (HEA) nanomaterials have emerged as promising electrocatalysts because of their compositional diversity and unique synergistic effects. Engineering the structure of HEAs, including facets, morphology, dimensions, and crystal phases, offers an effective strategy to further enhance their electrocatalytic performance. Such structural control provides a useful platform for unveiling the structure-performance relationships. This mini-review highlights recent advances in structural engineering of HEAs for electrocatalytic applications, with an emphasis on the structure formation mechanisms and structure-dependent catalytic performance. We first summarize representative synthetic strategies and discuss their advantages and limitations in the construction of well-defined HEA nanostructures. Then, we highlight the synthetic mechanisms of various HEA nanostructures and the functionalities of their unique structural characteristics in enhancing electrocatalysis. The structure-dependent performance of various HEA nanostructures in electrocatalytic reactions is reviewed from the perspectives of activity, selectivity, and durability. Finally, we discuss the current challenges and future opportunities for rationally designing next-generation HEA electrocatalysts.
The clinical application of nucleic acid aptamers is hindered by rapid degradation and poor targeting in physiological conditions. Multivalent assembly can improve their performance, yet key structural rules for stabilit...The clinical application of nucleic acid aptamers is hindered by rapid degradation and poor targeting in physiological conditions. Multivalent assembly can improve their performance, yet key structural rules for stability are not fully clarified. Here, we fabricate a symmetric tetravalent aptamer-streptavidin conjugate (Tetra-XQ@SA) for cancer theranostics with greatly enhanced stability. Thymine bases, longer sequences, and double-stranded structures collectively strengthen its nuclease resistance, enabling stable storage for 96 h in DNase I and 72 h in serum. Compared with free aptamers, Tetra-XQ@SA shows 2-fold higher binding affinity to cancer cell CD71 receptors, 7-fold greater doxorubicin loading, and improved antitumor activity. It achieves prolonged tumor retention and an ∼73% tumor inhibition rate in vivo. This study reveals the structure-stability relationship of aptamer assemblies and offers a versatile platform for targeted cancer therapy.
Pd nanoparticles are used in a variety of applications, and thus techniques that enable their high-throughput, label-free detection, as well as reaction monitoring at catalytically relevant sizes, are needed to establis...Pd nanoparticles are used in a variety of applications, and thus techniques that enable their high-throughput, label-free detection, as well as reaction monitoring at catalytically relevant sizes, are needed to establish robust structure-function relationships. Here, we introduce wavelength-resolved interferometric scattering (iSCAT) as a strategy for performing these studies, over a range of Pd nanoparticle sizes. From a sample of ∼90 nm Pd octahedra we spectroscopically discriminate structural outliers based on their scattering resonances and spectral lineshapes, using simulations to validate the structure-spectral relationships. We then demonstrate direct detection of single Pd nanocubes with <20 nm edge length and track changes occurring to them in different reactive conditions, uncovering both interparticle heterogeneity and wavelength-dependent photochemistry. The results highlight the power of wavelength-resolved iSCAT for studying Pd nanoparticle transformations and offer new insights into Pd reactivity at the nanoscale.
As a cost-effective and acid-stable alternative to noble-metal catalysts, the rational design of high-performance metal-free electrocatalysts hinges on in-depth mechanistic insights and precise structural regulation. Gra...As a cost-effective and acid-stable alternative to noble-metal catalysts, the rational design of high-performance metal-free electrocatalysts hinges on in-depth mechanistic insights and precise structural regulation. Graphene and its derivatives hold great promise, yet their heteroatom doping often compromises lattice integrity and intrinsic electronic properties. Herein, we report highly active HER electrocatalysts with ceramic-protected graphene edges that enable N plasma functionalization while largely preserving the graphitic framework. Using in situ electrochemical characterization, we systematically investigate the catalytic role of nitrogen species in a ceramic-protected graphene edge architecture. The optimized catalyst delivers an overpotential of 46 mV at 10 mA cm, 6-fold lower than that of pristine edges even after 2000 CV cycles, outperforming most reported metal-free catalysts and approaching state-of-the-art metal-based benchmarks. Most importantly, these results propose a plausible protonation-gated mechanism: under acidic HER conditions, reversible protonation/deprotonation near-edge pyridinic N may tune α-C sites for favorable H adsorption, enhancing HER activity.
Thiolate-protected gold (Au) nanoclusters (NCs) are a well-established class of model NCs that have been extensively studied as catalysts for various reactions. However, many Au NCs feature surfaces completely passivated...Thiolate-protected gold (Au) nanoclusters (NCs) are a well-established class of model NCs that have been extensively studied as catalysts for various reactions. However, many Au NCs feature surfaces completely passivated by ligands, leaving no exposed metal sites to serve as active centers. To address this issue, researchers have searched for methods to remove the ligands. However, simply introducing weakly bound ligands often compromises the structural stability of the NCs. In this study, we identified a novel Au NC that remains stable even with relatively weakly bound thiolate ligands by reinforcing the staple motifs through the introduction of dithiolate ligands. This Au NC exhibits excellent CO oxidation activity at relatively low temperatures, because the ligands can dissociate under relatively mild conditions. These findings show that advanced ligand engineering, beyond the metal core structure, significantly affects catalytic activity, providing a robust strategy for the design of diverse metal NC catalysts.
We report vertically stacked, double-side gratings fabricated by large-area nanoimprint lithography of colloidal TiO nanocrystal inks to achieve dual-band dielectric metasurfaces with high quality factor, guided-mode res...We report vertically stacked, double-side gratings fabricated by large-area nanoimprint lithography of colloidal TiO nanocrystal inks to achieve dual-band dielectric metasurfaces with high quality factor, guided-mode resonances (GMRs). The periodicity of the top and backside gratings can be independently tailored to realize spectrally distinct GMRs. The gratings can be coupled through a shared waveguide or isolated by incorporating a spacer layer. We demonstrate differential humidity sensors by incorporating a polydimethylsiloxane blocking layer in the spacer stack to allow the backside grating to serve as an in situ optical reference and the topside grating to be sensitive to water. This work establishes a scalable and versatile strategy for fabricating monolithic, multifunctional optical devices with high accuracy and tunable performance.
The intrinsic coupling between magnetism and nontrivial band topology in magnetic topological insulators makes external magnetic fields a powerful tool for manipulating topological states. However, conventional magnetic...The intrinsic coupling between magnetism and nontrivial band topology in magnetic topological insulators makes external magnetic fields a powerful tool for manipulating topological states. However, conventional magnetic control mechanisms, such as driving magnetic phase transitions or fully reversing magnetization, typically demand large magnetic fields and lack continuous tunability. Here, we establish a symmetry framework for the reversible switching of topological states via continuous in-plane spin rotation, governed by magnetic point group constraints on the Berry curvature distribution. Using a two-dimensional kagome ferromagnetic Chern insulator as a prototype, we demonstrate that a 60° in-plane magnetization rotation reverses the sign of the Chern number, transitioning through a topologically trivial state. Crucially, micromagnetic simulations confirm that this spin-reorientation-driven switching operates under exceptionally small magnetic fields and on ultrafast time scales. This work provides a highly efficient, low-energy paradigm for the manipulation of topological states.
Three decades after the approval of the first cancer nanomedicine, low (<1%) tumor delivery remains the central unsolved challenge in nanoparticle (NP)-based therapy. This barrier has prompted a research shift toward bio...Three decades after the approval of the first cancer nanomedicine, low (<1%) tumor delivery remains the central unsolved challenge in nanoparticle (NP)-based therapy. This barrier has prompted a research shift toward biologically derived delivery systems able to reduce immune clearance while preserving tumor-homing capabilities. In particular, extracellular vesicles (EVs) seem obvious candidates on account of their intrinsic biocompatibility, cell-specific tropism, and biological functionality. In this mini-review, we critically analyze EVs as nanoparticle delivery vectors in cancer therapy. We describe current EV engineering approaches, including loading methodologies, surface modification strategies, and the development of artificial or biomimetic EVs, highlighting technical, scalability, and characterization challenges. We also summarize key and results, addressing encapsulation strategy, biodistribution, and therapeutic outcomes. From this discussion, we outline research needs that must be addressed to develop EV-NP hybrids as tools to overcome the delivery challenge in cancer.
Inelastic electron tunneling (IET) provides an efficient route for electroluminescence (EL) in van der Waals (vdW) heterostructures, yet the microscopic origin of its bias-polarity dependence remains elusive due to struc...Inelastic electron tunneling (IET) provides an efficient route for electroluminescence (EL) in van der Waals (vdW) heterostructures, yet the microscopic origin of its bias-polarity dependence remains elusive due to structural asymmetry in prior devices. Here, we report a pronounced bias-polarity-selective EL in structurally symmetric graphene/hexagonal boron nitride (-BN)/graphene tunneling junctions coupled to CrSBr; light emission is observed exclusively under positive bias and is fully quenched under negative bias. We demonstrate that strong interfacial charge transfer between CrSBr and the adjacent graphene electrode induces Fermi-level pinning and asymmetric band alignment, which enhances both the IET probability and energy transfer efficiency under positive bias while suppressing them under negative bias. The control device based on monolayer WSe exhibits nearly symmetric EL, confirming this mechanism. Our results establish interfacial charge transfer as a pivotal and tunable parameter governing IET-driven light emission and provide a general framework for engineering bias-polarity-selective optoelectronic functionalities in vdW heterostructures.
Ischemia-reperfusion injury (IRI) remains a major cause of graft dysfunction following kidney transplantation, driven in large part by mitochondrial oxidative stress and subsequent apoptotic cell death. Elamipretide (SS3...Ischemia-reperfusion injury (IRI) remains a major cause of graft dysfunction following kidney transplantation, driven in large part by mitochondrial oxidative stress and subsequent apoptotic cell death. Elamipretide (SS31), a mitochondria-targeted tetrapeptide, shows robust renoprotection in preclinical models but is constrained by rapid renal elimination and limited pharmacokinetic exposure. Here, we prepared multiarm PEG-SS31 conjugates with controlled arm number and total PEG molecular weight. A ROS-cleavable thioketal linker enabled SS31 release under oxidative stress. The lead topology self-assembles into nanoparticles, produces markedly enhanced renal accumulation relative to free SS31 and alternative architectures, and yields superior renoprotection in a murine IRI model with reduced tubular injury and apoptosis. These results identify PEG topology as a key design parameter for kidney-targeted peptide therapeutics.
The dipole moment and polarizability reveal important material properties of excitons in two-dimensional materials, which can be studied through the Stark shift. However, observing excitonic Stark shift requires a device...The dipole moment and polarizability reveal important material properties of excitons in two-dimensional materials, which can be studied through the Stark shift. However, observing excitonic Stark shift requires a device design that enhances electric field coupling. Here, we demonstrate that a significant Stark shift in excitons can be observed in a back-gated field-effect transistor geometry with a specific layer stacking in rhenium disulfide (ReS). Structural stacking provides exceptional control over the excitonic response in these few-layer devices. AB-stacked ReS shows the contribution of the linear and quadratic Stark shifts, approximately 13 meV, in the off-state of the transistor. In contrast, AA-stacked samples display negligible Stark shift, highlighting the stacking-dependent dipole moment of excitons in ReS. Understanding the orientation of anisotropic excitons can be highly valuable for developing electronically tunable light-matter interactions and excitonic transport in optoelectronic devices.