Physics

Lysosome sequestration or drug-triggered autophagic flux curtails antitumor drug potency in hepatocellular carcinoma (HCC) and can potentially be reversed with tumor cell-specific lysosomal disruption. Here, we demonstrate that a chimeric peptide (RS-FS), consisting of HCC-targeting RS and nanostructure-forming motifs (FS), self-assembles into nanospheres at neutral pH and transforms into nanofibers under acidic and reductive conditions. These nanofibers specifically localize to tumors and disrupt tumor cell lysosomes, thus enhancing doxorubicin's activity in human HCC cells in vitro and orthotopic HCC mice in vivo after RS-FS-doxorubicin treatment. Importantly, intravenous RS-FS potentiated oral Lenvatinib's antitumor activity up to 61-fold, and eradicated tumors in orthotopic HCC mice via HCC cell-specific lysosome disruption. Potent antitumor effects were also achieved with intravenous RS-FS and oral Epimedium brevicornu Maxim. -derived extracellular vesicles in orthotopic HCC mice, with markedly reduced tumor growth and increased cytotoxic T infiltration, in which RS-FS-mediated lysosome disruption promoted drug release and autophagic flux blockade. Our study demonstrates that RS-FS self-assembles into nanospheres or nanofibers in response to stimuli and enables tumor cell-specific lysosome disruption, resulting in enhanced drug release, autophagic flux blockade, and antitumor activities of diverse therapeutics in HCC mice, and thus provides a generalizable peptide adjuvant for sensitizing HCC-targeted therapeutics.

ABSTRACT The development of multicolor room‐temperature phosphorescence (RTP) materials with tunable afterglow is crucial for advanced information encryption. Herein, we propose a synergistic strategy that integrates trap engineering and Förster resonance energy transfer (FRET) process for dynamically adjusting the emission color and lifetime. Expired rice‐derived carbon dots@Zn‐doping alumina (CDs@Zn x Al 2 O 3 ) composites with standout RTP properties are designed and fabricated using an in situ preparation strategy. In situ Zn 2+ doping is employed to engineer trap states within amorphous Al 2 O 3 , which not only optimizes the energy level structure of confined CDs but also enables precise modulation of phosphorescence color and lifetime. The optimized CDs@Zn 1.5% Al 2 O 3 composite achieves an ultralong green RTP duration of up to 22 s. Furthermore, by introducing newly synthesized red‐emissive TPA‐β‐CD‐aggregates with excellent aggregation‐induced emission (AIE) performance as an energy acceptor, efficient singlet‐to‐singlet and triplet‐to‐singlet FRET (SS‐FRET/TS‐FRET) pathways are established. Tuning the doping ratio allows dynamic control over the competition between these pathways, resulting in finely adjustable multicolor RTP emissions. This work demonstrates a versatile platform for creating color‐tunable, ultralong RTP materials and showcases their direct application in time‐gated, multilevel security encryption.

Insulin delivery systems that mimic pancreatic secretion offer promising improvements in type 1 diabetes management. However, current systems struggle with sustained and precise release. Inspired by the dynamic secretion mechanisms of the pancreas, a wearable electrically modulated semi-convertible hydrogel microneedle system for insulin delivery has been developed for long-term self-regulation in the treatment of type 1 diabetes. This system combines a non-covalent electro-responsive silk fibroin network and a polyethylene glycol/chitosan matrix, integrated with flexible electrodes that exhibit a partial gel-sol phase transition under 1.2 V electrical stimulation. In hyperglycemic conditions, the electric field induces silk fibroin phase transition, triggering insulin release through electrostatic interactions and polymer network expansion. Once blood glucose normalizes, insulin is released passively via diffusion when the electric field is turned off. In type 1 diabetic mice, a single microneedle patch provides segmented control, with a 10-min stimulation effect lasting up to 8 h, extendable to 16 h with further stimulation. This system offers a versatile, sustained, and precise drug delivery strategy with significant potential for chronic disease management.

ABSTRACT Superconductivity in manganese‐based compounds is strongly dependent on their high‐pressure phases. Consequently, capturing high‐pressure superconducting phases, particularly those that cannot be crystallized in their bulk form at ambient condition yet retain superconductivity, is of significant interest. Here, we report the capture of a superconducting high‐pressure B 31‐type MnSe 0.5 Te 0.5 phase (space group Pnma ) at ambient pressure, achieved via chemical substitution‐induced irreversible phase transitions ( Fm m ⇀ P 6 3 / mmc ⇀ Pnma ) and reversible spin‐crossover under a hydrostatic compression‐decompression cycle up to ≈40 GPa. Upon decompression, the B 31 phase exhibits structure‐borne superconductivity that persists down to ≈4 GPa, with a maximum T c of ≈7.5 K at ≈8 GPa. DFT calculations reveal that the accumulated pressure‐induced charge transfer (ligand‐to‐Mn 2+ ) causes an abrupt Jahn–Teller distortion (JTD) in MnX 6 octahedra by lifting the t 2g orbital degeneracy in low‐spin Mn 2+ ( d 5 ). The JTD triggers Peierls‐like metallic Mn–Mn dimerization, facilitating electron‐pairing by driving local electron redistribution, thereby initiating superconductivity in the orthorhombic phase. These findings demonstrate an approach to retain a superconducting phase through chemical substitution‐induced irreversible phase transition under high‐pressure.

Hydrogel-based biosensors offer a promising platform for designing microneedles capable of continuously tracking biomarkers in real time. However, such biosensors have been limited by the mechanical properties of hydrated hydrogels, which are generally ineffective at penetrating the skin to access interstitial fluid (ISF). As a solution, we have developed a microneedle-array biosensor (MAB) patch that enables continuous, reversible sensing by coupling fluorescent deoxyribonucleic acid (DNA) aptamer switches to a hydrated hydrogel mesh within a 3D-printed scaffold. This scaffold provides essential mechanical support for skin insertion while preserving the apatmer-hydrogel's sensing functionality in the ISF. We demonstrate this design by tuning both aptamer switch design and hydrogel mesh size to detect exogenous levels of stress hormone cortisol and the metabolite adenosine triphosphate. We subsequently incorporated our cortisol-sensing hydrogel into the MAB scaffold and coupled this system to a custom-designed portable optical detector. Following in vitro validation, we demonstrated the biocompatibility and in vivo utility of our system by conducting continuous, real-time measurements of exogenous cortisol in the ISF of live rats. These results demonstrate, for the first time, submicromolar detection using a sensor-embedded hydrogel microneedle system, highlighting the MAB platform as a versatile solution for real-time, continuous in vivo biosensing.

Balancing high performance, morphological controllability, and compatibility with non-halogenated solvent processing remains a critical bottleneck for scalable and sustainable organic solar cells (OSCs). Herein, we address this challenge via rational terpolymer design: integrating a siloxane-functionalized electron-deficient pyrazine unit (DTCPz-SiO) into the benchmark D18 backbone, with the optimized terpolymer DN1 containing 5 mol% DTCPz-SiO. DTCPz-SiO imparts two key synergies: (i) enhanced conformational rigidity and intramolecular noncovalent interactions (N···S, N···H), which improve backbone planarity, strengthen π-π stacking, and accelerate crystallization; (ii) synergistic regulation of donor-acceptor miscibility and compatibility with non-halogenated solvents. These effects collectively enable a well-optimized bulk-heterojunction morphology with enhanced molecular ordering and charge dynamics. Consequently, DN1-based binary devices deliver a significantly improved power conversion efficiency (PCE) of 20.1% compared to 18.7% for the parent polymer, together with a broadened processing window. Notably, high efficiencies of ∼19.5% are retained under common non-halogenated processing conditions. Furthermore, DN1-based ternary OSCs enhance PCE to outstanding values of 20.9% and 20.0% under chlorinated and non-halogenated processing conditions, respectively, among the highest efficiencies reported for single-junction OSCs. Overall, this work establishes siloxane-functionalized terpolymers as an effective molecular design strategy for regulating multi-scale morphology and processing tolerance, providing new insights for the development of scalable OSC systems.

The balance between excitatory and inhibitory (E/I) signaling underpins complex neural functions in biological systems. However, replicating such ion-mediated regulation with biobased materials in artificial systems remains challenging. Herein, we demonstrate two distinct light-modulated 2D nanofluidic memristors based on paper-mill waste (xylan) reinforced membranes that emulate complementary E/I synaptic signaling, enabling precise robotic motion control via ionic neural networks. The memristors were constructed using xylan-reinforced MXene membranes with asymmetric electrolytes, leveraging the interfacial interactions between the functional groups of xylan derivatives and MXene to achieve nanofluidic membrane assembly and precise control over surface charge and ion selectivity. Upon illumination, the photothermal effect of MXene induces a uniform thermal field that enables thermally activated ion transport in the interlayer spacing, allowing these biomass-based memristors to emulate key excitatory and inhibitory synaptic behaviors. These complementary memristors further implement reconfigurable Boolean logic operations and serve as foundational components for ionic circuits, as demonstrated in series and parallel configurations. As a proof-of-concept, an E/I-integrated ionic neural network achieved precise control of ten robotic motion modes by tuning light pulses, concentration gradients, and ion selectivity. This work highlights the potential of biomass-reinforced materials for nanofluidic memristors and explores new frontiers in the application of biomass materials.

${\mathrm{Ba}}_{4}{\mathrm{SbRu}}_{3}{\mathrm{O}}_{12}$ crystallizes with a structure that consists of clusters of three face-sharing Ru-centered octahedra $({\mathrm{Ru}}_{3}{\mathrm{O}}_{12})$ connected via Sb-centered octahedra. Rietveld refinements of both x-ray and neutron powder diffraction data confirm the absence of Sb/Ru antisite mixing. Variable temperature neutron diffraction measurements reveal a phase transition on cooling below 100 K from the aristotype structure with $R\overline{3}m$ symmetry to a monoclinic structure with $\mathrm{C}2/m$ symmetry. The phase transition is driven by displacements of $\mathrm{B}{\mathrm{a}}^{2+}$ cations and, as such, only subtly perturbs the geometry of the ${\mathrm{Ru}}_{3}{\mathrm{O}}_{12}$ clusters. The Ru $4d$ orbitals overlap to form delocalized molecular orbitals that span the trioctahedral cluster. At high temperature (T \ensuremath{\ge} 200 K), the cluster adopts an $S=3/2$ intermediate spin state, but upon cooling to low temperature, susceptibility data suggest a gradual transition to an $S=1/2$ low spin state. The presence of $\mathrm{S}{\mathrm{b}}^{5+}$ ions with a [Kr] $4{d}^{10}$ electron configuration minimizes interlayer superexchange interactions between clusters, thereby maintaining the frustration of the 2D triangular network. ${\mathrm{Ba}}_{4}{\mathrm{SbRu}}_{3}{\mathrm{O}}_{12}$ shows no signs of magnetic ordering down to 0.3 K, yet Curie-Weiss fitting of high-temperature susceptibility suggests strong antiferromagnetic interactions $({\ensuremath{\theta}}_{\mathrm{CW}}=\ensuremath{-}378 \mathrm{K})$. The low-temperature specific heat evolves linearly with temperature, suggestive of a gapless quantum spin liquid. The combination of small magnetic quantum number, minimal chemical disorder, geometric frustration, and lack of long-range magnetic order makes ${\mathrm{Ba}}_{4}{\mathrm{SbRu}}_{3}{\mathrm{O}}_{12}$ an intriguing quantum spin liquid candidate that merits further study.

Relativistic spin-orbit coupling (SOC) is an important ingredient for discovering novel electronic phenomena in quantum materials. In this work, the authors investigate the consequences of strong SOC on the physical properties of the LaPn${}_{2}$ (Pn = Sb, Bi) class of layered square-net materials via the synthesis of LaBi${}_{2}$ thin films. They report a layer-by-layer growth mode, a previously mis-indexed monoclinic structure type, and classify the compound as a good metal displaying superconductivity at ~0.55 K. Compared to LaSb${}_{2}$, density functional theory calculations attribute the enhanced metallic behavior and growth dynamics of LaBi${}_{2}$ to significant relativistic corrections to its electronic band structure.

Nanoglasses (NGs) consist of amorphous grains joined by glass-glass interfaces (GGIs), yet the atomic-scale mechanisms by which these interfaces control plasticity remain unsettled. Here, we combine molecular dynamics of ${\mathrm{Cu}}_{64}{\mathrm{Zr}}_{36}$ with the activation-relaxation technique to explicitly sample thermally activated events and map the potential-energy landscape of NGs with distinct interfacial geometries. We find that Cu surface segregation in the precursors persists as a diffuse enrichment at the consolidated interfaces, creating regions of local compositional and structural heterogeneity. Spatially resolved activation-energy distributions reveal that these GGIs host a persistent population of low-barrier excitations largely absent from the bulklike cores. While external strain amplifies the low-energy tail of the distribution, the onset of plasticity is dictated by the intrinsic energetic softness of the interfaces. Macroscopically, this preexisting population of soft sites suppresses abrupt shear localization, leading to a curtailed linear regime and distributed deformation. We further show that variations in mechanical response between architectures are governed by the interfacial volume fraction, while the fundamental deformation mechanism remains invariant. These results quantitatively link interfacial structure to the potential-energy landscape, establishing GGIs as preferred nucleation sites for shear transformations and providing a physics-based foundation for tailoring the mechanical response of amorphous alloys.

Magnetic compensation in rare-earth iron garnets (REIGs) offers a unique setting in which competing sublattice moments can give rise to non-collinear (canted) magnetic configurations, where the sublattice magnetizations are not aligned with each other or with the external magnetic field. We show that this compensation regime can possibly also host nontrivial magnetic textures. To explore this behavior, we investigated (111)-oriented epitaxial ${\mathrm{Tb}}_{3}{\mathrm{Fe}}_{5}{\mathrm{O}}_{12}$/Pt heterostructures across the compensation temperature region using combined transverse magneto-transport and polar Kerr microscopy. Notably, we observe a topological Hall--like signal in the vicinity of the compensation temperature, a feature often interpreted as evidence for skyrmions in the absence of direct imaging. Here, in contrast, complementary Kerr microscopy reveals instead a non-collinear multidomain state which collapses outside the compensation regime, correlating directly with the appearance and disappearance of the spin Hall topological Hall effect (SH-THE) signal. These observations cannot be accounted for by a simple multi-anomalous-Hall-effect model, ruling out common artifacts as the origin, but indicate a topologically nontrivial contribution to the Hall response. These results establish strained REIG films as a tunable platform for exploring topological responses arising from compensation-driven non-collinear ferrimagnetic phases.