http://onlinelibrary.wiley.com/rss/journal/10.1002/(ISSN)1521-4095

Topological bosonic systems have recently aroused intense interests in exploring exotic phenomena that have no counterparts in electronic systems. The squeezed bosonic interaction in these systems is particularly interesting, because it can modify the vacuum fluctuations of topological states, drive them into instabilities, and lead to topological parametric oscillators. However, these phenomena remain experimentally elusive because of limited nonlinearities in most existing topological bosonic systems. Here, a topological parametric phonon oscillator is experimentally realized based on a nonlinear nanoelectromechanical Dirac-vortex cavity with strong squeezed interaction. Specifically, the Dirac-vortex cavity is parametrically driven to provide phase-sensitive amplification for topological phonons, leading to the observation of coherent parametric phonon oscillation above the threshold. Additionally, it is confirmed that the random frequency variation caused by fabrication disorders can be suppressed effectively by increasing the cavity size, while the free spectral range reduces at a much slower rate, which benefit the realization of large-area single-mode lasers. Our results represent an important advance in experimental investigations of topological physics with large bosonic nonlinearities and parametric gain.

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Aqueous zinc–iodine batteries (AZIBs) are attracting increasing attention because of their high safety and abundance of resources. However, the performance of AZIBs is compromised by inadequate confinement of soluble polyiodides, the undesired shuttle effect, and slow reaction kinetics. In this study, a porous aromatic framework (PAF) with abundant benzene motifs and a well-organized pore structure is adopted as the iodine host, which exhibits high iodine adsorption capacity and robust polyiodide confinement. Both experimental characterizations and theoretical simulations indicate that the interactions between iodine species and the PAF-1 facilitate the redox reaction by coupling the electronic structures of the active species in the framework. A comparison of PAF-1, PAF-5, and PAF-11 also emphasizes the structural advantages of the high surface area and interconnected three-dimensional channels of PAF-1. Consequently, the I2@PAF-1 cathode can deliver a high capacity of 328 mAh g−1 at 0.5 C, outstanding rate performance (86% retention at 10 C), and a stable cycling life of 20000 cycles. The robust polyiodide confinement and superb electrochemical performance of Zn–I2@PAF-1 provide insights into the practical application of PAFs as excellent electrode materials for AZIBs.

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We demonstrate the low-temperature operation of solid-state lithium metal batteries (LMBs) through the development of a fluorinated and plastic-crystal-embedded elastomeric electrolyte (F-PCEE). The F-PCEE is formed via polymerization-induced phase separation between the polymer matrix and plastic crystal phase, offering a high mechanical strain (∼300%) and ionic conductivity (∼0.23 mS cm−1) at -10 °C. Notably, strong phase separation between two phases leads to the selective distribution of lithium (Li) salts within the plastic crystal phase, enabling superior elasticity and high ionic conductivity at low temperatures. The F-PCEE in a Li/LiNi0.8Co0.1Mn0.1O2 full cell maintains 74.4 and 42.5% of discharge capacity at -10 and -20 °C, respectively, compared to that at 25 °C. Furthermore, the full cell exhibits 85.3% capacity retention after 150 cycles at -10 °C and a high cut-off voltage of 4.5 V, representing one of the highest cycling performances among the reported solid polymer electrolytes for low-temperature LMBs. We attribute the prolonged cycling lifetime of F-PCEE at -10 °C to the great mechanical robustness to suppress the Li-dendrite growth and ability to form superior LiF-rich interphases. This study establishes the design strategies of elastomeric electrolytes for developing solid-state LMBs operating at low temperatures and high voltages.

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Combining radiotherapy with immune checkpoint blockade therapy offers a promising approach to treat glioblastoma multiforme (GBM), yet challenges such as limited effectiveness and immune-related adverse events (irAEs) persist. These issues are largely due to the failure in targeting immunomodulators directly to the tumor microenvironment. To address this, we developed a biomimetic nanoplatform that combines a genetically modified mesenchymal stem cell (MSC) membrane with a bioactive nanoparticle core for chemokine-directed radioimmunotherapy of GBM. The CCR2-overexpressing MSC membrane acts as a tactical tentacle to achieve radiation-induced tropism toward the abundant chemokine ligand CCL2 in irradiated gliomas. The nanoparticle core, comprising diselenide-bridged mesoporous silica nanoparticles (MSNs) and PD-L1 antibodies (αPD-L1), enables X-ray-responsive drug release and radiosensitization. In two murine models with orthotopic GBM tumors, this nanoplatform reinvigorated immunogenic cell death, and augmented the efficacy and specificity of GBM radioimmunotherapy, with reduced occurrence of irAEs. This study suggests a promising radiation-induced tropism strategy for targeted drug delivery, and presents a potent nanoplatform that enhances the efficacy and safety of radio-immunotherapy.

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Removing organic micropollutants from water through photocatalysis is hindered by catalyst instability and substantial residuals from incomplete mineralization. Here, we present a novel water treatment paradigm, the unified heterogeneous self-Fenton process (UHSFP), which achieved an impressive 32% photon utilization efficiency at 470 nm, and a significant 94% mineralization of organic micropollutants—all without the continual addition of oxidants and iron ions. In UHSFP, the active species differs fundamentally from traditional photocatalytic processes. One electron acceptor unit of photocatalyst acquires only one photogenerated electron to convert into oxygen-centered organic radical (OCOR), then spontaneously completing subsequent processes, including pollutant degradation, hydrogen peroxide generation, activation, and mineralization of organic micropollutants. By bolstering electron-transfer capabilities and diminishing catalyst affinity for oxygen in the photocatalytic process, the generation of superoxide radicals is effectively suppressed, preventing detrimental attacks on the catalyst. This study introduces an innovative and cost-effective strategy for the efficient and stable mineralization of organic micropollutants, eliminating the necessity for continuous chemical inputs, providing a new perspective on water treatment technologies.

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Efforts to engineer high-performance protein-based materials inspired by nature have mostly focused on altering naturally occurring sequences to confer the desired functionalities, whereas de novo design lags significantly behind and calls for unconventional innovative approaches. Here, using partially disordered elastin-like polypeptides (ELPs) as initial building blocks we show that de novo engineering of protein materials can be accelerated through hybrid biomimetic design, which we achieve by integrating computational modeling, deep neural network, and recombinant DNA technology. This generalizable approach involves incorporating a series of de novo-designed sequences with α-helical conformation and genetically encoding them into biologically inspired intrinsically disordered repeating motifs. The new ELP variants maintained structural conformation and showed tunable supramolecular self-assembly out of thermal equilibrium with phase behavior in vitro. We illustrate the effective translation of the predicted molecular designs in structural and functional materials. The proposed methodology can be applied to a broad range of partially disordered biomacromolecules and potentially pave the way toward the discovery of novel structural proteins.

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Orthotopic glioblastoma (GBM) has an aggressive growth pattern and complex pathogenesis, becoming one of the most common and deadly tumors of the central nervous system (CNS). The emergence of RNA therapies offers promise for the treatment of GBM. However, the efficient and precise delivery of RNA drugs to specific tumor cells in the brain with high cellular heterogeneity remains ongoing. Here, we propose a strategy to regulate protein conformation through lipid nano-environments (RPCLN) to custom-design virus-mimicking nanoparticles (VMNs) with excellent selective cell targeting capabilities, leading to efficient and precise delivery of small interfering RNA (siRNA) for effective treatment of GBM. The optimized VMNs not only retain the ability to cross the blood-brain barrier (BBB) and release the RNA by lysosomal escape like natural viruses but also ensure precise enrichment in the GBM area. This study lays the conceptual foundation for the custom design of VMNs with superior cell-selective targeting capabilities and opens up the possibility of RNA therapies for the efficient treatment of GBM and CNS tumors.

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A formidable challenge to achieve the practical applications of rechargeable lithium (Li) metal batteries (RLMBs) is to suppress the uncontrollable growth of Li dendrites. One of the most effective solutions is to fabricate Li metal anodes with specific crystal plane, but still lack of a simple and high-efficient approach. Herein, to overcome this key challenge, we report a facile and controllable way for the scalable customization of polished Li metal anodes with highly preferred (110) and (200) crystallographic orientation (donating as polished Li(110) and polished Li(200), respectively) by regulating the times of accumulative roll bonding at room temperature. In light of the inherent characteristics of polished Li(110) and polished Li(200), the influence of Li atomic structure on the electrochemical performance of RLMBs is deeply elucidated by combining theoretical calculations with relative experimental proofs. In particular, polished Li(110) crystal plane is demonstrated to induce Li+ uniform deposition, promoting the formation of flat and dense Li deposits. Impressively, the polished Li(110)||LiFePO4 full cells exhibit unprecedented cycling stability with 10000 cycles at 10 C almost without capacity degradation, indicating the great potential application prospect of such textured Li metal. More valuably, this work provides an important reference for low-cost, continued, and large-scale production of Li metal anodes with highly preferred crystal orientation through roll-to-roll manufacturability.

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The rapid growth of sensor data in the artificial intelligence often causes significant reductions in processing speed and power efficiency. Addressing this challenge, in-sensor computing has been introduced as an advanced sensor architecture that simultaneously senses, memorizes and processes images at the sensor level. However, this has rarely been reported for organic semiconductors that possess inherent flexibility and tunable bandgap. Herein, we introduce an organic heterostructure that exhibits a robust photoresponse to near-infrared (NIR) light, making it ideal for in-sensor computing applications. This heterostructure, consisting of partially overlapping p-type and n-type organic thin films, is compatible with conventional photolithography techniques, allowing for high integration density of up to 520 devices per square centimeter with a 5 µm channel length. Importantly, by modulating gate voltage, both positive and negative photoresponses to NIR light (1050 nm) are attained, which establishes a linear correlation between responsivity and gate voltage and consequently enables real-time matrix multiplication within the sensor. As a result, this organic heterostructure facilitates efficient and precise NIR in-sensor computing, including image processing and nondestructive reading and classification, achieving a recognition accuracy of 97.06%. Our work serves as a foundation for the development of reconfigurable and multifunctional NIR neuromorphic vision systems.

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A significant amount of research has been conducted in carbon dioxide (CO2) capture, particularly over the past decade, and continues to evolve. This review presents the most recent advancements in synthetic methodologies and CO2 capture capabilities of diverse polymer-based substances, which includes the amine-based polymers, porous organic polymers, and polymeric membranes, covering publications in the last five years (2019 to 2024). It aims to assist researchers with new insights and approaches to develop innovative polymer-based materials with improved capturing CO2 capacity, efficiency, sustainability, and cost-effective, thereby addressing the current obstacles in carbon capture and storage to sooner meeting the net-zero CO2 emission target.

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Ionic liquid-based thermoelectric gels become a compelling candidate for thermoelectric power generation and sensing due to their giant thermopower, good thermal stability, high flexibility, and low-cost production. However, the materials reported to date suffer from canonical trade-offs between self-healing ability, stretchability, strength and ionic conductivity. Herein, we develop a self-healing and tough ionogel (PEO/LiTFSI/EmimCl) with tunable thermoelectric properties by tailoring metal-halogen bonding interactions. Different affinities between polymer matrix and salts are exploited to induce phase separation, resulting in simultaneous enhancement of ionic conductivity and mechanical strength. Molecular dynamics simulations and spectroscopic analyses show that Cl− ions impair the lithium-ether oxygen coordination, leading to changes in chain conformation. The migration difference between cations and anions is thus widened and a transition from n-type to p-type thermoelectric ionogels is realized. Furthermore, the dynamic interactions of metal-ligand coordination and hydrogen bonding yield autonomously self-healing capability, large stretchability (2000%) and environment-friendly recyclability. Benefiting from these fascinating properties, we apply the multifunctional PEO-based ionogels in sensors, supercapacitors, and thermoelectric power generation modules. The strategy of tuning solvation dominance to address the trade-offs in thermoelectric ionogels and optimize their macroscopic properties offers new possibilities for the design of advanced ionogels.

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The near-infrared (NIR) sensor technology is crucial for various applications such as autonomous driving and biometric tracking. Silicon photodetectors (SiPDs) are widely used in NIR applications; however, their scalability is limited by their crystalline properties. Organic photodetectors (OPDs) have attracted attention for NIR applications owing to their scalability, low-temperature processing, and notably low dark current density (J D), which is similar to that of SiPDs. However, the still high J D (at NIR band) and few measurements of noise equivalent powers (NEPs) pose challenges for accurate performance comparisons. This study addresses these issues by quantitatively characterizing the performance matrix and J D generation mechanism using electron-blocking layers (EBLs) in OPDs. The energy offset at an EBL/photosensitive layer interface determines the thermal activation energy and directly affects J D. A newly synthesized EBL (3PAFBr) substantially enhances the interfacial energy barrier by forming a homogeneous contact owing to the improved anchoring ability of 3PAFBr. As a result, the OPD with 3PAFBr yields a noise current of 852 aA (J D = 12.3 fA/cm2 at V → −0.1 V) and several femtowatt-scale NEPs. To the best of our knowledge, this is an ultralow magnitude of J D in NIR OPDs. This also emphasizes the necessity for quantitative performance characterization.

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The power conversion efficiencies (PCEs) of polycrystalline perovskite (PVK) solar cells (SCs) (PC-PeSCs) have been rapidly increased. However, PC-PeSCs are intrinsically unstable without encapsulation, and their efficiency drops during large-scale production; these problems hinder the commercial viability of PeSCs. Stability can be increased by using colloidal PVK nanocrystals (c-PeNCs), which have high surface strains, low defect density, and exceptional crystal quality. Use of c-PeNCs separates the crystallization process from film formation process, which is preponderant in large-scale fabrication. Consequently, use of c-PeNCs has substantial potential to overcome challenges encountered when fabricating PC-PeSCs. Research on colloidal nanocrystal-based PVK SCs (NC-PeSCs) has increased their PCEs to the level greater than those of other quantum-dot SCs, but has not reached the PCEs of PC-PeSCs; this inferiority significantly impedes widespread application of NC-PeSCs. This review at first introduces the distinctive properties of c-PeNCs, then the strategies that have been used to achieve high-efficiency NC-PeSCs. Then it discusses in detail the persisting challenges in this domain. Specifically, the major challenge and solutions for NC-PeSCs related to low short-circuit current density J sc are covered. Lastly, the article presents a perspective on future research directions and potential applications in the realm of NC-PeSCs.

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The perspective presents an overview of the array of information that can be gleaned from the characterization of single crystals of metal halide perovskites using electron spectroscopic techniques. Building on this information, the perspective then discusses the challenges that need to be addressed in order to extend these versatile techniques to include the highly heterogeneous polycrystalline perovskite thin films.

In the past years, an increasing number of experimental techniques have emerged to address the need to unveil the chemical, structural, and electronic properties of perovskite thin films with high vertical and lateral spatial resolutions. One of these is angle-resolved photoemission electron spectroscopy which can provide direct access to the electronic band structure of perovskites, with the aim of overcoming elusive and controversial information due to the complex data interpretation of purely optical spectroscopic techniques. This perspective looks at the information that can be gleaned from the direct measurement of the electronic band structure of single crystal perovskites and the challenges that remain to be overcame to extend this technique to heterogeneous polycrystalline metal halide perovskites.

Prolonging energetic hot electrons lifetimes and surface activity in the reactive site can overcome the slow kinetics and unfavorable thermodynamics of photo-activated gas sensors. However, bulk and surface recombination limit simultaneous optimization of both kinetics and thermodynamic. Here we deploy tandem electric-fields at (111)/(100)Au-CeO2 to ensure a sufficient driving force for carriers transfer and elucidate the mechanism of the relationship between charges transport and gas-sensing performance. The asymmetric structure of (111)/(100)CeO2 facet junction provide interior electric-fields, which facilitates electron transfer from (100)face to (111)face. This separation of reduction and oxidation reaction sites across different crystal faces helps inhibit surface recombination. The increased electron concentration at the (111)face intensifies the interface electric field, which promotes electron transfer to Au site. The local electric-field generated by the surface plasmon resonance effect promotes the generation of high energy hot-electrons, which maintains charge concentration in interface field by injecting into (111)/(100)CeO2, thereby provide thermodynamic contributions and inhibit bulk recombination. The tandem electric fields enable the (111)/(100)Au-CeO2 to rapidly detect 5 ppm of NO2 at room temperature with stability maintained within 20 s.

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Efferocytosis-mediated inflammatory reversal plays a crucial role in bone repairing process. However, in refractory bone defects, the macrophage continual efferocytosis may be suppressed due to the disrupted microenvironment homeostasis, particularly the loss of apoptotic signals and overactivation of intracellular oxidative stress. In this study, we present a polydopamine-coated short fiber matrix containing biomimetic “apoptotic signals” to reconstruct the microenvironment and reactivate macrophage continual efferocytosis for inflammatory reversal and bone defect repair. The “apoptotic signals” (AM/CeO2) are prepared using CeO2 nanoenzymes with apoptotic neutrophil membrane coating for macrophage recognition and oxidative stress regulation. Additionally, a short fiber “biomimetic matrix” is utilized for loading AM/CeO2 signals via abundant adhesion sites involving π-π stacking and hydrogen bonding interactions. Ultimately, the implantable apoptosis-mimetic nanoenzyme/short-fiber matrixes (PFS@AM/CeO2), integrating apoptotic signals and biomimetic matrixes, are constructed to facilitate inflammatory reversal and reestablish pro-efferocytosis microenvironment. In vitro and in vivo data indicate that the microenvironment biomimetic short fibers could activate macrophage continual efferocytosis, leading to the suppression of overactivated inflammation. The enhanced repair of rat femoral defect further demonstrates the osteogenic potential of pro-efferocytosis strategy. We believe that the regulation of macrophage efferocytosis through microenvironment biomimetic materials could provide a new perspective for tissue repair.

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For preparing next-generation sulfide all-solid-state batteries (ASSBs), the solvent-free manufacturing process have huge potential for the advantages of economic, thick electrode, and avoidance of organic solvents. However, the dominating solvent-free process is based on the fibrillation of polytetrafluoroethylene, suffering from poor mechanical property and electrochemical instability. Herein, a continuously solvent-free paradigm of fusion bonding technique is developed. A percolation network of thermoplastic polyamide (TPA) binder with low viscosity in viscous state is constructed with Li6PS5Cl (LPSC) by thermocompression (≤5 MPa), facilitating the formation of ultrathin LPSC film (≤25 μm). This composite sulfide film (CSF) exhibits excellent mechanical properties, ionic conductivity (2.1 mS/cm), and unique stress-dissipation to promote interface stabilization. Thick LiNi0.83Co0.11Mn0.06O2 cathode can be prepared by this solvent-free method and tighly adhered to CSF by interfacial fusion of TPA for integrated battery. This integrated ASSB shows high-energy-density feasibility (>2.5 mAh·cm−2 after 1400 cycles of 9200 hours and run for more than 10 000 hours), and energy density of 390 Wh·kg−1 and 1020 Wh·L−1. More specially, high-voltage bipolar cell (≥8.5 V) and bulk-type pouch cell (326 Wh·kg−1) are facilely assembled with good cycling performance. This work inspires commercialization of ASSBs by a solvent-free method and provides beneficial guiding for stable batteries.

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Traditional lithium-ion battery (LIB) anodes, whether intercalation-type like graphite or alloying-type like silicon, which employ a single lithium storage mechanism, are often limited by modest capacity or substantial volume changes. Here, we introduce the kesterite multi-metal dichalcogenide (CZTSSe) as an anode material that harnesses a conversion-alloying hybrid lithium storage mechanism. Results unveil that during the charge-discharge processes, the CZTSSe undergoes a comprehensive phase evolution, transitioning from kesterite structure to multiple dominant phases of sulfides, selenides, metals, and alloys. The involvement of multi-components facilitates electron transport and mitigates swelling stress; meanwhile, it results in the formation of abundant defects and heterojunctions, allowing for increased lithium storage active sites and reduced lithium diffusion barrier. The CZTSSe delivers a high specific capacity of up to 2266 mA h g−1 at 0.1 A g−1 while maintaining a stable output of 116 mA h g−1 after 10000 cycles at 20 A g−1. It also demonstrates remarkable low-temperature performance, retaining 987 mA h g−1 even after 600 cycles at −40 °C. When employed in full cells, a high specific energy of 562 Wh kg−1 is achieved, rivalling many state-of-the-art LIBs. This research offers valuable insights into the design of LIB electrodes leveraging multiple lithium storage mechanisms.

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