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Scoliosis often occurs in adolescents and seriously affects physical development and health. Traditionally, medical imaging is the most common means of evaluating the corrective effect of bracing during treatment. However, the imaging approach falls short in providing real-time feedback, and the optimal corrective force remains unclear, potentially slowing the patient's recovery progress. To tackle these challenges, an all-in-one integrated array of pressure sensors and sEMG electrodes based on hierarchical MXene/chitosan/polydimethylsiloxane (PDMS)/polyurethane sponge and MXene/polyimide (PI) is developed. Benefiting from the microstructured electrodes and the modulus enhancement of PDMS, the sensor demonstrates a high sensitivity of 444.3 kPa -1 and a broad linear detection range (up to 81.6 kPa). With the help of electrostatic attraction of chitosan and interface locking of PDMS, the pressure sensor achieves remarkable stability of over 100 000 cycles. Simultaneously, the sEMG electrodes offer exceptional stretchability and flexibility, functioning effectively at 60% strain, which ensures precise signal capture for various human motions. After integrating the developed all-in-one arrays into a commercial scoliosis brace, the system can accurately categorize human motion and predict Cobb angles aided by deep learning. This study provides real-time insights into brace effectiveness and patient progress, offering new ideas for improving the efficiency of scoliosis treatment., (© 2024 Wiley‐VCH GmbH.)

Transition metal selenides (TMSs) are receiving considerable interest as improved anode materials for sodium-ion batteries (SIBs) and lithium-ion batteries (LIBs) due to their considerable theoretical capacity and excellent redox reversibility. Herein, ZIF-12 (zeolitic imidazolate framework) structure is used for the synthesis of Cu 2 Se/Co 3 Se 4 @NPC anode material by pyrolysis of ZIF-12/Se mixture. When Cu 2 Se/Co 3 Se 4 @NPC composite is utilized as an anode electrode material in LIB and SIB half cells, the material demonstrates excellent electrochemical performance and remarkable cycle stability with retaining high capacities. In LIB and SIB half cells, the Cu 2 Se/Co 3 Se 4 @NPC anode material shows the ultralong lifespan at 2000 mAg -1 , retaining a capacity of 543 mAhg -1 after 750 cycles, and retaining a capacity of 251 mAhg -1 after 200 cycles at 100 mAg -1 , respectively. The porous structure of the Cu 2 Se/Co 3 Se 4 @NPC anode material can not only effectively tolerate the volume expansion of the electrode during discharging and charging, but also facilitate the penetration of electrolyte and efficiently prevents the clustering of active particles. In situ X-ray difraction (XRD) analysis results reveal the high potential of Cu 2 Se/Co 3 Se 4 @NPC composite in building efficient LIBs and SIBs due to reversible conversion reactions of Cu 2 Se/Co 3 Se 4 @NPC for lithium-ion and sodium-ion storage., (© 2024 Wiley‐VCH GmbH.)

Nitric oxide (NO) is a crucial gaseous signaling molecules in regulating cardiovascular, immune, and nervous systems. Controlled and targeted NO delivery is imperative for treating cancer, inflammation, and cardiovascular diseases. Despite various enzyme-prodrug therapy (EPT) systems facilitating controlled NO release, their clinical utility is hindered by nonspecific NO release and undesired metabolic consequence. In this study, a novel EPT system is presented utilizing a cellobioside-diazeniumdiolate (Cel2-NO) prodrug, activated by an endocellulase (Cel5A-h38) derived from the rumen uncultured bacterium of Hu sheep. This system demonstrates nearly complete orthogonality, wherein Cel2-NO prodrug maintains excellent stability under endogenous enzymes. Importantly, Cel5A-h38 efficiently processes the prodrug without recognizing endogenous glycosides. The targeted drug release capability of the system is vividly illustrated through an in vivo near-infrared imaging assay. The precise NO release by this EPT system exhibits significant therapeutic potential in a mouse hindlimb ischemia model, showcasing reductions in ischemic damage, ambulatory impairment, and modulation of inflammatory responses. Concurrently, the system enhances tissue repair and promotes function recovery efficacy. The novel EPT system holds broad applicability for the controlled and targeted delivery of essential drug molecules, providing a potent tool for treating cardiovascular diseases, tumors, and inflammation-related disorders., (© 2024 Wiley‐VCH GmbH.)

Aqueous iron-ion batteries with reversible storage of Fe 2+ have undergone rapid development in recent years. Consistently throughout these studies, metallic iron is selected as the anode material. However, the large overpotential (250 mV) associated with the plating/stripping process of iron in aqueous solutions leads to unsatisfactory energy efficiency of the battery, although high capacity and Coulomb efficiency can be achieved. Herein, an iron-free anode material, 9,10-anthraquinone (AQ) is proposed in aqueous iron-ion batteries, which shows a low reaction potential and minimal polarization during storing iron ions. The organic anode exhibits favorable specific capacity of 106 mAh g -1 at 0.5 A g -1 and excellent cycling stability (92.6% retention after 500 cycles). In addition, an aqueous full iron-ion battery is constructed using AQ as the anode and 9,10-phenanthraquinone (PQ) as the cathode. The full battery demonstrates an enhanced energy efficiency of 72%, which is 206% higher than that of metal iron anode, and shows excellent cycling stability and Coulombic efficiency. This work provides a viable route to overcome the high polarization of metallic iron anode and promote the development of aqueous iron-ion batteries., (© 2024 Wiley‐VCH GmbH.)

Eutectic electrolytes hold promise for aqueous zinc metal batteries in sustainable energy storage chemistries, yet improvement from perspective of molecule configurational engineering are ambiguous. Herein, we propose design strategy of increasing asymmetric molecular geometry in organic ligands to regulate frustrated coordination and disordered structure for eutectic electrolytes toward enhanced zinc metal batteries. The introduced asymmetry in eutectic component gives rise to relatively weak coordination strength and configurational disorder interaction among cation-anion-ligand, leading to suppressed local aggregation, steady eutectic phase and improved Zn 2+ diffusion kinetics. Such highly frustrated coordination state also enables disruption of hydrogen bonding network and reinforcement of anion participation, which results in confined side reactions, decreased water activity and the formation of inorganic-enriched solid electrolyte interphase. In comparison to highly symmetric ligands, asymmetric ligand-involved eutectic electrolytes with configurational disorder deliver high Coulombic efficiency of 99.4 %, stabilized Zn plating/stripping of 5000 h and impressive rate capability even under harsh conditions such as small N/P, low temperature. The rationale in this work advances the deep understanding of asymmetric molecular engineering in eutectic electrolytes and showcases suitability of frustrated coordination to achieve high-performance zinc metal batteries., (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Potassium metal batteries (PMBs), with high energy density and low cost, are considered a promising option for grid-scale energy storage systems. However, challenges such as the uneven nucleation of K and instability of the solid electrolyte interphase (SEI) layer result in dendrite growth and poor cyclic performance, limiting practical application. To address them, constructing an artificial interface layer with rich defects can enhance the potassium affinity and promote the uniform nucleation of potassium, yet this can also catalyze electrolyte to decompose, leading to unstable SEI formation and poor cycle stability. Herein, a carbon layer with a locally ordered structure (SC-1600) is constructed as the artificial interface to achieve a balance between K affinity and catalytic activity. This optimized design allows for the uniform nucleation of potassium metal and the formation of a dense SEI layer. SC-1600@K symmetric cell can operate for 2000 h at 0.5 mA cm -2 with a capacity of 0.5 mAh cm -2 , and the developed full cell shows a high capacity retention of 78% after 1500 cycles at 1 A g -1 . Besides, SC-1600@Na effectively extend the life of sodium metal batteries. This work provides a new insight for the construction of efficient K metal artificial interface layer., (© 2024 Wiley‐VCH GmbH.)

Most patients with cancer are first diagnosed at an advanced disease stage, when tumors are already large and/or metastases are present. This circumstance has a negative impact on the prognosis and therapeutic effect of anticancer drugs. In this study, it is demonstrated that photosensitizer chlorin e6 and the photochemotherapy drug mitoxantrone self-assemble into relatively stable nanoassemblies (CM NAs) through hydrogen-bonding effect, π-π stacking, and hydrophobic interactions. Administration of CM NAs in combination with 660 nm laser irradiation shows chemotherapeutic, photothermal, and photodynamic effects, causing tumor cell apoptosis and pyroptosis and enabling noninvasive tumor ablation without compromising the surrounding normal tissue. More importantly, treatment with CM NAs increases tumor immunogenicity, leading to a strong and long-term antitumor immune response that eradicates large tumors and provides long-term protection against tumor recurrence on various tumor models., (© 2024 Wiley‐VCH GmbH.)

Quantum dots (QDs) are widely used, but their health impact on the visual system is little known. This study aims to elucidate the effects and mechanisms of typical metallic QDs on retinas using zebrafish. Comprehensive histology, imaging, and bulk RNA sequencing reveal that InP/ZnS QDs cause retinal degeneration. Furthermore, single-cell RNA-seq reveals a reduction in the number of retinal pigment epithelial cells (RPE) and short-wave cone UV photoreceptor cells (PR(UV)), accompanied by an increase in middle- and long-wave cone red, green, and blue photoreceptor cells [PR(RGB)]. Mechanistically, after endocytosis by RPE, InP/ZnS QDs inhibit the expression of splicing factor prpf8, resulting in gpx4b mRNA unsplicing, which finally decrease glutathione and induce ferroptosis and mitophagy. The decrease of RPE fails to engulf the damaged outer segments of PR, possibly promoting the differentiation of PR(UV) to PR(RGB). Knockout prpf8 or gpx4b with CRISPR/Cas9 system, the retinal damage is also observed. Whereas, overexpression of prpf8 or gpx4b, or supplement of glutathione can rescue the retinal degenerative damage caused by InP/ZnS QDs. In conclusion, this study illustrates the potential health risks of InP/ZnS QDs on eye development and provides valuable insights into the underlying mechanisms of InP/ZnS QDs-caused retinal degeneration., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Tin halide perovskites are the most promising candidate materials for lead-free perovskite solar cells (PSCs) thanks to their low toxicity and ideal band gap energies. The introduction of 2D/3D mixed perovskite phases in tin-based PSCs (TPSCs) has proven to be the most effective approach to improving device efficiency and stability. However, a 2D perovskite phase normally shows relatively low carrier mobility, which will be unfavorable for carrier transfer in the devices. In this work, we used a thiophene-based cation 2-(thiophen-3-yl)ethan-1-aminium (3-TEA) as a spacer to form a novel 2D perovskite phase in TPSCs, which shows the most promising effect on the performance enhancement in comparison with other cations like 2-(thiophen-2-yl)ethan-1-aminium (2-TEA) and benzene-based 2-phenylethan-1-aminium (PEA). Theoretical calculations reveal that 3-TEA enables the most compact crystal packing of [SnI 6 ] 4- octahedral layers, resulting in the lowest hole effective mass and formation energy in the 2D phase. This effect significantly enhances device efficiency and stability by facilitating more efficient carrier transfer within the 2D phase. These findings indicate that thiophene-based 2D perovskites are well-suited for high-performance TPSCs., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The practical application of solid polymer electrolyte is hindered by the small transference number of Li + , low ionic conductivity and poor interfacial stability, which are seriously determined by the microenvironment in polymer electrolyte. The introduction of functional fillers is an effective solution to these problems. In this work, based on density functional theory (DFT) calculations, it is demonstrated that the anion vacancy of filler can anchor anions of lithium salt, thereby significantly increasing the transference number of Li + in the electrolyte. Therefore, flower-like SnS 2 -based filler with abundant sulfur vacancies is prepared under the regulation of functionalized carbon dots (CDs). It is worth mentioning that the CDs dotted on the surface of SnS 2 have rich organic functional groups, which can serve as the bridging agent to enhance the compatibility of filler and polymer, leading to superior mechanical performance and fast ion transport pathway. Additionally, the in situ formed Li 2 S/Li 3 N at the interface of Li metal and electrolyte facilitate the fast Li + diffusion and uniform Li deposition, effectively mitigating the growth of lithium dendrites. As a result, the assembled lithium metal batteries exhibit excellent cycling stability, reflecting the superiority of the carbon dots derived vacancy-rich inorganic filler modification strategy., (© 2024 Wiley-VCH GmbH.)

Intracerebral hemorrhage (ICH) is a hemorrhagic disease with high mortality and disability rates. Curcumin is a promising drug for ICH treatment due to its multiple biological activities, but its application is limited by its poor watersolubility and instability. Herein, platelet membrane-coated curcumin polylactic-co-glycolic acid (PLGA) nanoparticles (PCNPs) are prepared to achieve significantly improved solubility, stability, and sustained release of curcumin. Fourier transform infrared spectra and X-ray diffraction assays indicate good encapsulation of curcumin within nanoparticles. Moreover, it is revealed for the first time that curcumin-loaded nanoparticles can not only suppress hemin-induced astrocyte proliferation but also induce astrocytes into neuron-like cells in vitro. PCNPs are used to treat rat ICH by tail vein injection, using in situ administration as control. The results show that PCNPs are more effective than curcumin-PLGA nanoparticles in concentrating on hemorrhagic lesions, inhibiting inflammation, suppressing astrogliosis, promoting neurogenesis, and improving motor functions. The treatment efficacy of intravenously administered PCNPs is comparable to that of in situ administration, indicating a good targeting effect of PCNPs on the hemorrhage site. This study provides a potent treatment for hemorrhagic injuries and a promising solution for efficient delivery of water-insoluble drugs using composite materials of macromolecules and cell membranes., (© 2024 Wiley‐VCH GmbH.)

Pain caused by lumbar disc herniation (LDH) severely compromises patients' quality of life. The combination of steroid and local anesthetics is routinely employed in clinics to alleviate LDH-induced pain. However, the approach only mediates transient efficacy and requires repeated and invasive lumbar epidural injections. Here a paravertebrally-injected multifunctional hydrogel that can efficiently co-load and controlled release glucocorticoid betamethasone and anesthetics ropivacaine for sustained anti-inflammation, reactive oxygen species (ROS)-removal and pain relief in LDH is presented. Betamethasone is conjugated to hyaluronic acid (HA) via ROS-responsive crosslinker to form amphiphilic polymer that self-assemble into particles with ropivacaine loaded into the core. Solution of drug-loaded particles and thermo-sensitive polymer rapidly forms therapeutic hydrogel in situ upon injection next to the herniated disc, thus avoiding invasive epidural injection. In a rat model of LDH, multifunctional hydrogel maintains the local drug concentration 72 times longer than free drugs and more effectively inhibits the expression of pro-inflammatory cytokines and pain-related molecules including cyclooxygenase-2 (COX-2) and prostaglandin E2 (PGE 2 ). Therapeutic hydrogel suppresses the LDH-induced pain in rats for 12 days while the equivalent dose of free drugs is only effective for 3 days. This platform is also applicable to ameliorate pain caused by other spine-related diseases., (© 2024 Wiley‐VCH GmbH.)

The structural failure of Na 2 Mn[Fe(CN) 6 ] could not be alleviated with traditional modification strategies through the adjustable composition property of Prussian blue analogues (PBAs), considering that the accumulation and release of stress derived from the MnN 6 octahedrons are unilaterally restrained. Herein, a novel application of adjustable composition property, through constructing a coordination competition relationship between chelators and [Fe(CN) 6 ] 4- to directionally tune the enrichment of elements, is proposed to restrain structural degradation and induce unconventional energy coupling phenomenon. The non-uniform distribution of elements at the M 1 site of PBAs (NFM-PB) is manipulated by the sequentially precipitated Ni, Fe, and Mn according to the Irving-William order. Electrochemically active Fe is operated to accompany Mn, and zero-strain Ni is modulated to enrich at the surface, synergistically mitigating with the enrichment and release of stress and then significantly improving the structural stability. Furthermore, unconventional energy coupling effect, a fusion of the electrochemical behavior between Fe LS and Mn HS , is triggered by the confined element distribution, leading to the enhanced electrochemical stability and anti-polarization ability. Consequently, the NFM-PB demonstrates superior rate performance and cycling stability. These findings further exploit potentialities of the adjustable composition property and provide new insights into the component design engineering for advanced PBAs., (© 2024 Wiley-VCH GmbH.)

Protonic ceramic electrochemical cells (PCECs) have received considerable attention as they can directly generate electricity and/or produce chemicals. Development of the electrodes with the trifunctionalities of oxygen reduction/evolution and nonoxidative ethane dehydrogenation is yet challenging. Here these findings are reported in the design of trifunctional electrodes for PCECs with a detailed composition of Mn 0.9 Cs 0.1 Co 2 O 4-δ (MCCO) and Co 3 O 4 (CO) (MCCO-CO, 8:2 mass ratio). At 600 °C, the MCCO-CO electrode exhibits a low area-specific resistance of 0.382 Ω cm 2 and reasonable stability for ≈105 h with no obvious degradation. The single cell with the MCCO-CO electrode shows an encouraging peak power density of 1.73 W cm -2 in the fuel cell (FC) mode and a current density of -3.93 A cm -2 at 1.3 V in the electrolysis cell (EC) mode at 700 °C. Moreover, the MCCO-CO cell displays promising operational stability in FC mode (223 h), EC mode (209 h), and reversible cycling stability (52 cycles, 208 h) at 650 °C. The MCCO-CO single cell shows an encouraging ethane conversion to ethylene (with a conversion of 40.3% and selectivity of 94%) and excellent H 2 production rates of 4.65 mL min -1 cm -2 at 1.5 V and 700 °C, respectively, with reasonable Faradaic efficiencies., (© 2024 Wiley‐VCH GmbH.)

Persistent luminescence nanoparticles (PLNPs) can achieve autofluorescence-free afterglow imaging, while near-infrared (NIR) emission realizes deep tissue imaging. Nanozymes integrate the merits of nanomaterials and enzyme-mimicking activities with simple preparation. Here PLNPs are prepared of Zn 1.2 Ga 1.6 Ge 0.2 O 4 :Cr 0.0075 with NIR emission at 700 nm. The PLNPs are then incubated with IrCl 3 solution, and the nanoparticles are collected and annealed at 750 °C to obtain iridium@PLNPs. Iridium is observed on the PLNPs at the atomic level as a single-atom nanozyme with peroxidase-like catalytic activity, photothermal conversion, and computed tomography (CT) contrast capability. After coating with exosome membrane (EM), the Ir@PLNPs@EM composite exhibits long-lasting NIR luminescence, peroxidase-like catalytic activity, photothermal conversion, and CT contrast capability, with the targeting capability and biocompatibility from EM. Thus, NIR afterglow/photothermal/CT trimodal imaging-guided photothermal-chemodynamic combination therapy is realized as validated with the in vitro and in vivo inhibition of tumor growth, while toxicity and side effects are avoided as drug-free treatment. This work offers a promising avenue for advanced single-atom nanozyme@PLNPs to promote the development of nanozymes and PLNPs for clinical applications., (© 2024 Wiley‐VCH GmbH.)

In sodium-ion pouch batteries based on hard carbon, an additional source of active sodium significantly enhances the battery's initial coulombic efficiency and compensates for the loss of active sodium ions during cycling. This study investigates the interaction between metallic sodium with carbon materials and develops a composite powder material of sodium-rich lithium-aluminum using a multi-alloy grafting strategy, to replenish the initial loss of active sodium in the hard carbon materials. To enhance the stability and utilization of this highly active sodium source, a novel slurry system based on polyethylene oxide (PEO) as a binder and dimethyl carbonate (DMC) as a solvent is introduced. Furthermore, this study designs a hard carbon composite electrode structure with a stable layer and sacrificial layer (NPH), which not only accommodates current battery processing environments but also demonstrates excellent potential in practical applications. Ultimately, the soft-packed sodium-ion battery consists of NPH electrodes with composite sodium ferric pyrophosphate (NFPP) and demonstrates excellent initial coulombic efficiency (91%) and ultra-high energy density (205 Wh kg -1 ). These results indicate significant technological and application implications for future energy storage., (© 2024 Wiley‐VCH GmbH.)

Garnet solid-state electrolyte Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZTO) holds significant promise. However, the practical utilization has been seriously impeded by the poor contact of Li|garnet and electron leakage. Herein, one new type of garnet-based solid-state battery is proposed with high performance through the disparity in interfacial energy, induced by the reaction between trace fluorinated carbon dots (FCDs) and Li. The work of adhesion of Li|garnet is increased by the acquired Li-FCD composite, which facilitates an intimate Li|garnet interface with the promoted uniform Li + deposition, revealed by density functional theory (DFT) calculations. It is further validated that a concentrated C-Li 2 O-LiF component at the Li|garnet interface is spontaneously constructed, due to the significant disparity in interfacial energy between C-Li 2 O-LiF|LLZTO and C-Li 2 O-LiF|Li. Furthermore, The electron transport and Li dendrites penetration are effectively hindered by the formed Li 2 O and LiF. The Li-FCD|LLZTO|Li-FCD symmetrical cells demonstrate stable cycling performance for over 3000 hours at 0.3 mA cm -2 and 800 hours at 0.5 mA cm -2 . Furthermore, the LFP|garnet|Li-FCD full cell exhibits remarkable cycling performance (91.6 % capacity retention after 500 cycles at 1 C). Our research has revealed a novel approach to establish a dendrite-free Li|garnet interface, laying the groundwork for future advancements in garnet-based solid-state batteries., (© 2024 Wiley-VCH GmbH.)

Lithium carbon dioxide (Li-CO 2 ) batteries, noted for their high discharge voltage of approximately 2.8 V and substantial theoretical specific energy of 1876 Wh kg -1 , represent a promising avenue for new energy sources and CO 2 emission reduction. However, the practical application of these batteries faces significant hurdles, particularly at high current densities and over extended cycle lives, due to their complex reaction mechanisms and slow kinetics. This paper delves into the recent advancements in cathode catalysts for Li-CO 2 batteries, with a specific focus on the designing philosophy from composition, geometry, and homogeneity of the catalysts to the proper test conditions and real-world application. It surveys the possible catalytic mechanisms, giving readers a brief introduction of how the energy is stored and released as well as the critical exploration of the relationship between material properties and performances. Specifically, optimization and standardization of test conditions for Li-CO 2 battery research is highlighted to enhance data comparability, which is also critical to facilitate the practical application of Li-CO 2 batteries. This review aims to bring up inspiration from previous work to advance the design of more effective and sustainable cathode catalysts, tailored to meet the practical demands of Li-CO 2 batteries., (© 2024 Wiley‐VCH GmbH.)

Natural porous materials have exceptional properties-for example, light weight, mechanical resilience, and multi-functionality. Efforts to imitate their properties in engineered structures have limited success. This, in part, is caused by the complexity of multi-phase materials composites and by the lack of quantified understanding of each component's role in overall hierarchy. This challenge is twofold: 1) computational. because non-periodicity and defects render constructing design guidelines between geometries and mechanical properties complex and expensive and 2) experimental. because the fabrication and characterization of complex, often hierarchical and non-periodic 3D architectures is non-trivial., (© 2024 Wiley‐VCH GmbH.)

Facile evaluation of formation kinetics of key intermediate is crucial for a comprehensive understanding of electrochemical ammonia oxidation reaction (AOR) mechanisms and the design of efficient electrocatalysts. Currently, elucidating the formation kinetics of key intermediate associated with rate-determining step is still challenging. Herein, 4-phtalamide-N-(4'-methylcoumarin) naphthalimide (CF) is developed as a molecular probe to detect N 2 H 4 intermediate during AOR via electrochemiluminescence (ECL) and further investigated the formation kinetics of N 2 H 4 on Pt catalysts with different crystal planes. CF probe can selectively react with N 2 H 4 to release ECL substance luminol. Thus, N 2 H 4 intermediate as a key intermediate can be sensitively and selectively detected by ECL during AOR. For the first time, Pt(100) facet is discovered to exhibit faster N 2 H 4 formation kinetics than Pt(111) facet, which is further confirmed by Density functional theory calculation and the finite element simulation. The AOR mechanism under the framework of Gerischer and Mauerer is further validated by examining N 2 H 4 formation kinetics during the dimerization process (NH 2 coupling). The developed ECL active probe and the discovered facet-dependent formation kinetics of key intermediates provide a promising new tool and strategy for the understanding of electrochemical AOR mechanisms and the design of efficient electrocatalysts., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Matching the thickness of the graphitic carbon nitride (CN) nanolayer with the charge diffusion length is expected to compensate for the poor intrinsic conductivity and charge recombination in CN for photoelectrochemical cells (PEC). Herein, the compact CN nanolayer with tunable thickness is in situ coated on carbon fibers. The compact packing along with good contact with the substrate improves the electron transport and alleviates the charge recombination. The PEC investigation shows CN nanolayer of 93 nm-thick yields an optimum photocurrent of 116 µA cm -2 at 1.23 V versus RHE, comparable to most micrometer-thick CN layers, with a low onset potential of 0.2 V in 1 m KOH under 1 sun illumination. This optimum performance suggests the electron diffusion length matches with the thickness of the CN nanolayer. Further deposition of NiFe-layered double hydroxide enhanced the surface water oxidation kinetics, delivering an improved photocurrent of 210 µA cm -2 with IPCE of 12.8% at 400 nm. The CN nanolayer also shows extended potential in PEC organic synthesis. This work experimentally reveals the PEC behavior of the nanometer-thick CN layer, providing new insights into CN in the application of energy and environment-related fields., (© 2024 Wiley‐VCH GmbH.)

Visible light is a universal and user-friendly excitation source; however, its use to generate persistent luminescence (PersL) in materials remains a huge challenge. Herein, the concept of intermolecular charge transfer (xCT) is applied in typical host-guest molecular systems, which allows for a much lower energy requirement for charge separation, thus enabling efficient charging of near-infrared (NIR) PersL in organics by visible light (425-700 nm). Importantly, NIR PersL in organics occurs via the trapping of electrons from charge-transfer aggregates (CTAs) into constructed trap states with trap depths of 0.63-1.17 eV, followed by the detrapping of these electrons by thermal stimulation, resulting in a unique light-storage effect and long-lasting emission up to 4.6 h at room temperature. The xCT absorption range is modulated by changing the electron-donating ability of a series of acenaphtho[1,2-b]pyrazine-8,9-dicarbonitrile-based CTAs, and the organic PersL is tuned from 681 to 722 nm. This study on xCT interaction-induced NIR PersL in organic materials provides a major step forward in understanding the underlying luminescence mechanism of organic semiconductors and these findings are expected to promote their applications in optoelectronics, energy storage, and medical diagnosis., (© 2024 Wiley‐VCH GmbH.)

Integrating controllable spin states into single-molecule magnets (SMMs) enables precise manipulation of magnetic interactions at a molecular level, but remains a synthetic challenge. Herein, we developed a 3d-4f metallacrown (MC) magnet [DyNi 5 (quinha) 5 ( Cl sal) 2 (py) 8 ](ClO 4 ) ⋅ 4H 2 O (H 2 quinha=quinaldichydroxamic acid, H Cl sal=5-chlorosalicylaldehyde) wherein a square planar Ni II is stabilized by chemical stacking. Thioacetal modification was employed via post-synthetic ligand substitutions and yielded [DyNi 5 (quinha) 5 ( Cl saldt) 2 (py) 8 ](ClO 4 ) ⋅ 3H 2 O (H Cl saldt=4-chloro-2-(1,3-dithiolan-2-yl)phenol). Thanks to the additional ligations of thioacetal onto the Ni II site, coordination-induced spin state switching (CISSS) took place with spin state altering from low-spin S=0 to high-spin S=1. The synergy of CISSS effect and magnetic interactions results in distinct energy splitting and magnetic dynamics. Magnetic studies indicate prominent enhancement of reversal barrier from 57 cm -1 to 423 cm -1 , along with hysteresis opening and an over 200-fold increment in coercive field at 2 K. Ab initio calculations provide deeper insights into the exchange models and rationalize the relaxation/tunnelling pathways. These results demonstrate here provide a fire-new perspective in modulating the magnetization relaxation via the incorporation of controllable spin states and magnetic interactions facilitated by the CISSS approach., (© 2024 Wiley-VCH GmbH.)

Phase transitions in molecular solids involve synergistic changes in chemical and electronic structures, leading to diversification in physical and chemical properties. Despite the pivotal role of hydrogen bonds (H-bonds) in many phase-transition materials, it is rare and challenging to chemically regulate the dynamics and to elucidate the structure-property relationship. Here, four high-spin Co II compounds were isolated and systematically investigated by modifying the ligand terminal groups (X=S, Se) and substituents (Y=Cl, Br). S-Cl and Se-Br undergo a reversible structural phase transition near room temperature, triggering the rotation of 15-crown-5 guests and the swing between syn- and anti-conformation of NCX - ligands, accompanied by switchable magnetism. Conversely, S-Br and Se-Cl retain stability in ordered and disordered phases, respectively. H-bonds geometric analysis and ab initio calculations reveal that the electronegativity of X and Y affects the strength of N Y-ap -H⋅⋅⋅X interactions. Entropy-driven structural phase transitions occur when the H-bond strength is appropriate; otherwise, the phase stays unchanged if it is too strong or weak. This work highlights a phase transition driven by H-bond strength complementarity - pairing strong acceptor with weak donor and vice versa, which offers a straightforward and effective approach for designing phase-transition molecular solids from a chemical perspective., (© 2024 Wiley-VCH GmbH.)

Photogenerated radicals are an indispensable member of the state-of-the-art photochromic material family, as they can effectively modulate the photoluminescence and photothermal conversion performance of radical-induced photochromic complexes. Herein, two novel radical-induced photochromic metal-organic frameworks (MOFs), [Ag(TEPE)](AC) ⋅  7 / 4 H 2 O ⋅  5 / 4 EtOH (1) and [Ag(TEPE)](NC) ⋅ 3H 2 O ⋅ EtOH (2), are reported. Distinctly different topological networks can be obtained by judiciously introducing alternative π-conjugated anionic guests, including a new topological structure (named as sfm) first reported in this work, describing as 4,4,4,4-c net. EPR data and UV-Vis spectra prove the radical-induced photochromic mechanism. Dynamic photochromism exhibits tunability in a wide CIE color space, with a linear segment from yellow to red for 1, while a curved coordinate line for 2, resulting in colorful emission from blue to orange. Moreover, photogenerated TEPE* radicals effectively activate the near-infrared (NIR) photothermal conversion effect of MOFs. Under 1 W cm -2 808 nm laser irradiation, the surface temperatures of photoproducts 1* and 2* can reach ~160 °C and ~120 °C, respectively, with competitive NIR photothermal conversion efficiencies η=51.8 % (1*) and 36.2 % (2*). This work develops a feasible electrostatic compensation strategy to accurately introduce photoactive anionic guests into MOFs to construct multifunctional radical-induced photothermal conversion materials with tunable photoluminescence behavior., (© 2024 Wiley-VCH GmbH.)

To effectively treat osteoarthritis (OA), the existing inflammation must be reduced before the cartilage damage can be repaired; this cannot be achieved with a single type of extracellular vesicles (EVs). Here, a hydrogel complex with logic-gates function is proposed that can spatiotemporally controlled release two types of EVs: interleukin 10 (IL-10) + EVs to promote M2 polarization of macrophage, and SRY-box transcription factor 9 (SOX9) + EVs to increase cartilage matrix synthesis. Following dose-of-action screening, the dual EVs are loaded into a matrix metalloporoteinase 13 (MMP13)-sensitive self-assembled peptide hydrogel (KM13E) and polyethylene glycol diacrylate/gelatin methacryloyl-hydrogel microspheres (PGE), respectively. These materials are mixed to form a "microspheres-in-gel" KM13E@PGE system. In vitro, KM13E@PGE abruptly released IL-10 + EVs after 3 days and slowly released SOX9 + EVs for more than 30 days. In vivo, KM13E@PGE increased the CD206 + M2 macrophage proportion in the synovial tissue and decreased the tumor necrosis factor-α and IL-1β levels. The aggrecan and SOX9 expressions in the cartilage tissues are significantly elevated following inflammation subsidence. This performance is not achieved using anti-inflammatory or cartilage repair therapy alone. The present study provides an injectable, integrated delivery system with spatiotemporal control release of dual EVs, and may inspire logic-gates strategies for OA treatment., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Gel-state polymer electrolytes with superior mechanical properties, self-healing abilities and high Li + transference numbers can be obtained by in situ polymerization of monomers with hydrogen-bonding moieties. However, it is overlooked that the active hydrogen atoms in hydrogen-bond donors experience displacement reactions with lithium metal in lithium metal batteries (LMBs), leading to corrosion of the lithium metal. Herein, it is discovered that the addition of hydrogen-bond acceptors to hydrogen-bond-rich gel-state electrolytes modulates the chemical activity of the active hydrogen atoms via the formation of hydrogen-bonded intermolecular interactions. The characterizations reveal that the added hydrogen-bond acceptors encapsulate the active hydrogen atoms to suppress the interfacial chemical corrosions of lithium metals, thereby enhancing the chemical stability of the polymer structure and interphase. With the employment of this strategy, a 1.1 Ah LiNi 0.8 Co 0.1 Mn 0.1 O 2 /Li metal pouch cell achieves stable cycling with 96.3 % capacity retention at 100 cycles. This new approach indicates a feasible path for achieving in situ polymerization of highly stable gel-state-based LMBs., (© 2024 Wiley-VCH GmbH.)

Continuous monitoring of blood pressure (BP) and multiparametric analysis of cardiac functions are crucial for the early diagnosis and therapy of cardiovascular diseases. However, existing monitoring approaches often suffer from bulky and intrusive apparatus, cumbersome testing procedures, and challenging data processing, hampering their applications in continuous monitoring. Here, a heterogeneously hierarchical piezoelectric composite is introduced for wearable continuous BP and cardiac function monitoring, overcoming the rigidity of ceramic and the insensitivity of polymer. By optimizing the hierarchical structure and components of the composite, the developed piezoelectric sensor delivers impressive performances, ensuring continuous and accurate monitoring of BP at Grade A level. Furthermore, the hemodynamic parameters are extracted from the detected signals, such as local pulse wave velocity, cardiac output, and stroke volume, all of which are in alignment with clinical results. Finally, the all-day tracking of cardiac function parameters validates the reliability and stability of the developed sensor, highlighting its potential for personalized healthcare systems, particularly in early diagnosis and timely intervention of cardiovascular disease., (© 2024 Wiley‐VCH GmbH.)

In this study, a novel wide-bandgap small molecule guest material, ITOA, designed and synthesized for fabricating efficient ternary organic solar cells (OSCs) ITOA complements the absorbance of the PM6:Y6 binary system, exhibiting strong crystallinity and modest miscibility. ITOA optimizes the morphology by promoting intensive molecular packing, reducing domain size, and establishing a preferred vertical phase distribution. These features contribute to improved and well-balanced charge transport, suppressed carrier recombination, and efficient exciton dissociation. Consequently, a significantly enhanced efficiency of 18.62% for the ternary device is achieved, accompanied by increased short-circuit current density (J SC ), fill factor (FF), and open-circuit voltage (V OC ). Building on this success, replacing Y6 with BTP-eC9 leads to an outstanding PCE of 19.33% for the ternary OSCs. Notably, the introduction of ITOA expedites the formation of the optimized morphology, resulting in an impressive PCE of 18.04% for the ternary device without any postprocessing. Moreover, the ternary device exhibits enhanced operational stability under maximum power point (MPP) tracking. This comprehensive study demonstrates that a rationally designed guest molecule can optimize morphology, reduce energy loss, and streamline the fabrication process, essential for achieving high efficiency and stability in OSCs, paving the way for practical commercial applications., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

The impedance matching and high loss capabilities of composites with homogeneous distribution are limited owing to high addition and lack of structural design. Developing composites with heterogeneous distribution can achieve strong and wide electromagnetic (EM) wave absorption. However, challenges such as complex design and unclear absorption mechanisms still exist. Herein, a novel composite with a heterogeneous distribution gradient is successfully constructed via MOF derivatives Co@ nitrogen-doped carbon (Co@NC) anchored on carbon foam (CF) matrix (MDCF). Notably, the concentration of MOF can easily control the gradient structure. In particular, the morphologies of MOF derivatives on the surface of CF undergo a transition from the collapse of the inner layer to the integrity of the outer layer, accompanied by a continuous reduction in the size of Co nanoparticles. Correspondingly, enhanced interface polarization from the core-shell of Co@NC and good impedance matching of MDCF can be obtained. The optimized MDCF exhibits the minimum reflection loss of -68.18 dB at 2.01 mm and effective absorption bandwidth covering the entire X-band. Moreover, MDCF exhibits lightweight characteristics, excellent compressive strength, and low radar cross-section reduction. This work highlights the immense potential of composites with heterogeneous distribution for achieving high-performance EM wave absorption., (© 2024 Wiley‐VCH GmbH.)

Advanced organic electronic technologies have put forward a pressing demand for cost-effective and high-throughput fabrication of organic single-crystal films (OSCFs). However, solution-printed OSCFs are typically plagued by the existence of abundant structural defects, which pose a formidable challenge to achieving large-scale and high-performance organic electronics. Here, it is elucidated that these structural defects are mainly originated from printing flow-induced anisotropic growth, an important factor that is overlooked for too long. In light of this, a surfactant-additive printing method is proposed to effectively overcome the anisotropic growth, enabling the deposition of uniform OSCFs over the wafer scale at a high speed of 1.2 mm s -1 at room temperature. The resulting OSCF exhibits appealing performance with a high average mobility up to 10.7 cm 2 V -1 s -1 , which is one of the highest values for flexible organic field-effect transistor arrays. Moreover, large-scale OSCF-based flexible logic circuits, which can be bent without degradation to a radius as small as 4.0 mm and over 1000 cycles are realized. The work provides profound insights into breaking the limitation of flow-induced anisotropic growth and opens new avenues for printing large-scale organic single-crystal electronics., (© 2024 Wiley‐VCH GmbH.)

With alkyl halides (I, Br, Cl) as a coupling partner, an electrochemically driven strategy for para-selective C(sp 2 )-H alkylation of electron-deficient arenes (aryl esters, aldehydes, nitriles, and ketones) has been achieved to access diverse alkylated arenes in one step. The reaction enables the activation of alkyl halides in the absence of sacrificial anodes, achieving the formation of C(sp 2 )-C(sp 3 ) bonds under mild electrolytic conditions. The utility of this protocol is reflected in high site selectivity, broad substrate scope, and scalable., (© 2024 Wiley-VCH GmbH.)

A family of hexagonal in-plane chemical ordering (Mo 2/3 R 1/3 ) 2 AlB 2 (R = Tb, Dy, Ho, Er, Tm, and Lu) i-MAB phases are synthesized with R-3m hexagonal structure. The i-MAB phases with R = Tb to Tm are considered to have a nonlinear ferromagnetic-like coupling magnetic ground state with gradually weakened magnetocrystalline anisotropy due to variant R-R distances and 4f electrons. Their 2D derivatives (2D-MBene) with rare-earth (R) atom vacancies are obtained by chemical etching. The delamination solvent, surface functional terminations, and chemical bond of 2D-MBene can be modified by one-step nitridation in environment-friendly nitrogen instead of ammonia. A phase conversion is caused by nitridation at 973 K from 2D-MBene to Mo 2 N, leading to the optimized specific capacitance of 229 F g -1 . Besides exploring more rare-earth-containing laminated boride systems, this work also demonstrates the promising application of their 2D derivatives with R vacancies in supercapacitors., (© 2023 Wiley‐VCH GmbH.)

Recently, nonmetal NH 4 + ions have attracted extensive attention for use as charge carries in the field of energy storage due to their abundant resources, environmental friendliness, and low cost. However, the development of aqueous ammonium-ion batteries (AAIBs) is constrained by the absence of high-voltage and long-life materials. Herein, different tunnel-structure MnO 2 materials (α-, β-, and γ-MnO 2 ) are utilized as cathodes for AAIBs and hybrid-ion batteries and compared, and α-MnO 2 is demonstrated to exhibit the most remarkable electrochemical performance. The α-MnO 2 cathode material delivers the highest discharge capacity of 219 mAh g -1 at a current density of 0.1 A g -1 and the best cyclability with a capacity retention of 95.4% after 10 000 cycles at 1.0 A g -1 . Moreover, aqueous ammonium-ion and hybrid-ion (ammonium/sodium ions) full batteries are successfully constructed using α-MnO 2 cathodes. This work provides a novel direction for the development of aqueous energy storage for practical applications., (© 2023 Wiley‐VCH GmbH.)

Intelligent vision necessitates the deployment of detectors that are always-on and low-power, mirroring the continuous and uninterrupted responsiveness characteristic of human vision. Nonetheless, contemporary artificial vision systems attain this goal by the continuous processing of massive image frames and executing intricate algorithms, thereby expending substantial computational power and energy. In contrast, biological data processing, based on event-triggered spiking, has higher efficiency and lower energy consumption. Here, this work proposes an artificial vision architecture consisting of spiking photodetectors and artificial synapses, closely mirroring the intricacies of the human visual system. Distinct from previously reported techniques, the photodetector is self-powered and event-triggered, outputting light-modulated spiking signals directly, thereby fulfilling the imperative for always-on with low-power consumption. With the spiking signals processing through the integrated synapse units, recognition of graphics, gestures, and human action has been implemented, illustrating the potent image processing capabilities inherent within this architecture. The results prove the 90% accuracy rate in human action recognition within a mere five epochs utilizing a rudimentary artificial neural network. This novel architecture, grounded in spiking photodetectors, offers a viable alternative to the extant models of always-on low-power artificial vision system., (© 2024 Wiley‐VCH GmbH.)

VO 2 material, as a promising intercalation host, is widely investigated not only in aqueous lithium-ion batteries, but also in aqueous zinc-ion batteries (AZIBs) owing to its stable tunnel-like framework and multivalence of vanadium. Different from lithium-ion storage, VO 2 can provide higher capacity when storing zinc ions, even exceeding its theoretical capacity (323 mAh g -1 ), but the specific reason for this unconventional performance in AZIBs is still unclear. The present study proposes a catalytic oxygen evolution reaction (OER) coupled with an interface oxidation mechanism of VO 2 during the initial charging to a high voltage. This coupling induces a phase transformation of VO 2 into a high oxidation state of V 5 O 12 ∙6H 2 O, enabling a nearly two-electron reaction and providing additional zinc storage sites to achieve super-theoretical capacity. Furthermore, it is demonstrated that these vanadium oxide cathodes (V 2 O 3 , VO 2 , and V 2 O 5 ) will all undergo phase change after the first charge or short cycle. Notably, water molecules participate in the final formation of layered vanadium-based hydrate, highlighting their crucial role as "pillars" for stabilizing the structure. This work significantly enhances the understanding of vanadium-based oxide cathodes., (© 2023 Wiley‐VCH GmbH.)

The induction of cuproptosis, a recently identified form of copper-dependent immunogenic cell death, is a promising approach for antitumor therapy. However, sufficient accumulation of intracellular copper ions (Cu 2+ ) in tumor cells is essential for inducing cuproptosis. Herein, an intelligent cuproptosis-inducing nanosystem is constructed by encapsulating copper oxide (CuO) nanoparticles with the copper ionophore elesclomol (ES). After uptake by tumor cells, ES@CuO is degraded to release Cu 2+ and ES to synergistically trigger cuproptosis, thereby significantly inhibiting the tumor growth of murine B16 melanoma cells. Moreover, ES@CuO further promoted cuproptosis-mediated immune responses and reprogrammed the immunosuppressive tumor microenvironment by increasing the number of tumor-infiltrating lymphocytes and secreted inflammatory cytokines. Additionally, combining ES@CuO with programmed cell death-1 (PD-1) immunotherapy substantially increased the antitumor efficacy in murine melanoma. Overall, the findings of this study can lead to the use of a novel strategy for cuproptosis-mediated antitumor therapy, which may enhance the efficacy of immune checkpoint inhibitor therapy., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Detecting short-wavelength infrared (SWIR) light has underpinned several emerging technologies. However, the development of highly sensitive organic photodetectors (OPDs) operating in the SWIR region is hindered by their poor external quantum efficiencies (EQEs) and high dark currents. Herein, the development of high-sensitivity SWIR-OPDs with an efficient photoelectric response extending up to 1.3 µm is reported. These OPDs utilize a new ultralow-bandgap molecular semiconductor featuring a quinoidal tricyclic electron-deficient central unit and multiple non-covalent conformation locks. The SWIR-OPD achieves an unprecedented EQE of 26% under zero bias and an even more impressive EQE of up to 41% under a -4 V bias at 1.10 µm, effectively pushing the detection limit of silicon photodetectors. Additionally, the low energetic disorder and trap density in the active layer lead to significant suppression of thermal-generation carriers and dark current, resulting in excellent detectivity (D sh * ) exceeding 10 13 Jones from 0.50 to 1.21 µm and surpassing 10 12 Jones even at 1.30 µm under zero bias, marking the highest achievements for OPDs beyond the silicon limit to date. Validation with photoplethysmography measurements, a spectrometer prototype in the 0.35-1.25 µm range, and image capture under 1.20 µm irradiation demonstrate the extensive applications of this SWIR-OPD., (© 2024 Wiley‐VCH GmbH.)

Basal-like breast cancer (BLBC) is the most aggressive molecular subtype of breast cancer with worse prognosis and fewer treatment options. The underlying mechanisms upon BLBC transcriptional dysregulation and its upstream transcription factors (TFs) remain unclear. Here, among the hyperactive candidate TFs of BLBC identified by bioinformatic analysis, POU4F1 is uniquely upregulated in BLBC and is associated with poor prognosis. POU4F1 is necessary for the tumor growth and malignant phenotypes of BLBC through regulating G1/S transition by direct binding at the promoter of CDK2 and CCND1. More importantly, POU4F1 maintains BLBC identity by repressing ERα expression through CDK2-mediated EZH2 phosphorylation and subsequent H3K27me3 modification in ESR1 promoter. Knocking out POU4F1 in BLBC cells reactivates functional ERα expression, rendering BLBC sensitive to tamoxifen treatment. In-depth epigenetic analysis reveals that the subtype-specific re-configuration and activation of the bivalent chromatin in the POU4F1 promoter contributes to its unique expression in BLBC, which is maintained by DNA demethylase TET1. Together, these results reveal a subtype-specific epigenetically activated TF with critical role in promoting and maintaining BLBC, suggesting that POU4F1 is a potential therapeutic target for BLBC., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Ni/Mn-based oxide cathode materials have drawn great attention due to their high discharge voltage and large capacity, but structural instability at high potential causes rapid capacity decay. How to moderate the capacity loss while maintaining the advantages of high discharge voltage remains challenging. Herein, the replacement of Mn ions by Ga ions is proposed in the P2-Na 2/3 Ni 0.2 Mn 0.8 O 2 cathode for improving their cycling performances without sacrificing the high discharge voltage. With the introduction of Ga ions, the relative movement between the transition metal ions is restricted and more Na ions are retained in the lattice at high voltage, leading to an enhanced redox activity of Ni ions, validated by ex situ synchrotron X-ray absorption spectrum and X-ray photoelectron spectroscopy. Additionally, the P2-O2 phase transition is replaced by a P2-OP4 phase transition with a smaller volume change, reducing the lattice strain in the c-axis direction, as detected by operando/ex situ X-ray diffraction. Consequently, the Na 2/3 Ni 0.21 Mn 0.74 Ga 0.05 O 2 electrode exhibits a high discharge voltage close to that of the undoped materials, while increasing voltage retention from 79% to 93% after 50 cycles. This work offers a new avenue for designing high-energy density Ni/Mn-based oxide cathodes for sodium-ion batteries., (© 2023 Wiley‐VCH GmbH.)

The simultaneous improvement of efficiency and stability of organic solar cells (OSCs) for commercialization remains a challenging task. Herein, we designed asymmetric acceptors DT-C8Cl and DT-C8BTz with functional haloalkyl chains, in which the halogen atoms could induce noncovalent interactions with heteroatoms like O, S, and Se, etc., thus leading to appropriately manipulated film morphology. Consequently, binary devices based on D18: DT-C8Cl achieved a champion power conversion efficiency (PCE) of 19.40 %. The higher PCE of D18: DT-C8Cl could be attributed to the enhanced π-π stacking, improved charge transport, and reduced recombination losses. In addition, the noncovalent interactions induced by haloalkyl chains could effectively suppress unfavorable morphology evolutions and thereby reduce trap density of states, leading to improved thermal and storage stability. Overall, our findings reveal that the rational design of asymmetric acceptors with functional haloalkyl chains is a novel and powerful strategy for simultaneously enhancing the efficiency and stability of OSCs., (© 2024 Wiley-VCH GmbH.)

Multifunction superhydrophobic coatings that facilitate water harvesting are attractive for addressing the daunting water crisis, yet, they are caught in a double bind when their durability is considered, as durable coatings will require both tough micro-textures to survive concentrated stress and high-surface-energy chemistry to form chemical bonds within the matrix. To date, a universal bulk-phase coating that combines multifunctionality, ultra-durability, and fabrication feasibility remains challenging. Here, a binary cooperative cell design is reported that can solve the contradiction between the multifunctionality and durability requirements of superhydrophobic coatings. In this strategy, mechanochemically tailored cells with releasable nanoseeds are infused in the common matrix, which serves both as a versatile chemical bridge to achieve strong bonds within the coating building blocks, and as an instantaneous self-repairing generator to improve durability. Such a strategy significantly boosted the wear resistance and outdoor stability of the coatings by over 30-100 and 18 folds, respectively, compared with conventional coatings. The coating is applied to the sustainable application, i.e., enhancing the water collection efficiency by at least 1000% even after harsh abrasion. The strategy will broaden the vision in handling the dilemma properties among functional coatings and promote the application of superhydrophobic coatings in extreme environments., (© 2023 Wiley‐VCH GmbH.)

Rechargeable zinc-based batteries are finding their niche in energy storage applications where cost, safety, scalability matter, yet they are plagued by rapid performance degradation due to the lack of suitable electrolytes to stabilize Zn anode. Herein, we report a competitive coordination structure to form unique quaternary hydrated eutectic electrolyte with ligand-cation-anion cluster. Unraveled by experiment and calculation results, the competing component can enter initial primary coordination shell of Zn 2+ ion, partially substituting Lewis basic eutectic ligands and reinforcing cation-anion interaction. The hydration-deficient complexes induced between competing eutectic as hydrogen bond donor-accepter and water also broaden the electrochemical window and confine free water activity. The altered coordination further leads to robust hybrid organic-inorganic enriched solid electrolyte interphase, enabling passivated surface and suppressed dendrite growth. Noticeably, stable Zn plating/stripping for 8000 cycles with high Coulombic efficiencies of 99.6 % and long cycling life of 10000 cycles for Zn-organic batteries are obtained. Even under harsh conditions (small N/P ratio, low temperature), the profits brought by the competitive eutectic electrolyte are still very prominent. This design principle leveraged by eutectic electrolytes with competitive coordination offers a new approach to improve battery performance., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Although the research on aqueous batteries employing metal as the anode is still mainly focused on the aqueous zinc-ion battery, aqueous iron-ion batteries are considered as promising aqueous batteries owing to the lower cost, higher specific capacity, and better stability. However, the sluggish Fe 2+ (de)intercalation leads to unsatisfactory specific capacity and poor electrochemical stability, which makes it difficult to find cathode materials with excellent electrochemical properties. Herein, phenylamine (PA)-intercalated VOPO 4 materials with expanded interlayer spacing are synthesized and applied successfully in aqueous iron-ion batteries. Owing to enough diffusion space from the expanded interlayer, which can boost fast Fe 2+ diffusion, the aqueous iron-ion battery shows a high specific capacity of 170 mAh g -1 at 0.2 A g -1 , excellent rate performance, and cycle stability (96.2% capacity retention after 2200 cycles). This work provides a new direction for cathode material design in the development of aqueous iron-ion batteries., (© 2023 Wiley-VCH GmbH.)

Non-Hermitian (NH) physics describes novel phenomena in open systems that allow generally complex spectra. Introducing NH physics into topological metamaterials, which permits explorations of topological wave phenomena in artificially designed structures, not only enables the experimental verification of exotic NH phenomena in these flexible platforms, but also enriches the manipulation of wave propagation beyond the Hermitian cases. Here, a perspective on the advances in the research of NH topological phononic metamaterials is presented, which covers the exceptional points and their topological geometries, the skin effect related to the topology of complex spectra, the interplay of NH effects and topological states in phononic metamaterials, etc., (© 2023 Wiley-VCH GmbH.)

The immune response in cancer reflects a series of carefully regulated events; however, current tumor immunotherapies typically address a single key aspect to enhance anti-tumor immunity. In the present study, a nanoplatform (Fe 3 O 4 @IR820@CpG)-based immunotherapy strategy that targets the multiple key steps in cancer-immunity cycle is developed: 1) promotes the release of tumor-derived proteins (TDPs), including tumor-associated antigens and pro-immunostimulatory factors), in addition to the direct killing effect, by photothermal (PTT) and photodynamic therapy (PDT); 2) captures the released TDPs and delivers them, together with CpG (a Toll-like receptor 9 agonist) to antigen-presenting cells (APCs) to promote antigen presentation and T cell activation; 3) enhances the tumor-killing ability of T cells by combining with anti-programmed death ligand 1 antibody (α-PD-L1), which collectively advances the outstanding of the anti-tumor effects on colorectal, liver and breast cancers. The broad-spectrum anti-tumor activity of Fe 3 O 4 @IR820@CpG with α-PD-L1 demonstrates that optimally manipulating anti-cancer immunity not singly but as a group provides promising clinical strategies., (© 2023 Wiley-VCH GmbH.)

Detecting and distinguishing light polarization states, one of the most basic elements of optical fields, have significant importance in both scientific studies and industry applications. Artificially fabricated structures, e.g., metasurfaces with anisotropic absorptions, have shown the capabilities of detecting polarization light and controlling. However, their operations mainly rely on resonant absorptions based on structural designs that are usually narrow bands. Here, a mid-infrared (MIR) broadband polarization photodetector with high PRs and wavelength-dependent polarities using a 2D anisotropic/isotropic Nb 2 GeTe 4 /MoS 2 van der Waals (vdWs) heterostructure is demonstrated. It is shown that the photodetector exhibits high PRs of 48 and 34 at 4.6  and 11.0 µm wavelengths, respectively, and even a negative PR of -3.38 for 3.7 µm under the zero bias condition at room temperature. Such interesting results can be attributed to the superimposed effects of a photovoltaic (PV) mechanism in the Nb 2 GeTe 4 /MoS 2 hetero-junction region and a bolometric mechanism in the MoS 2 layer. Furthermore, the photodetector demonstrates its effectiveness in bipolar and unipolar polarization encoding communications and polarization imaging enabled by its unique and high PRs., (© 2023 Wiley-VCH GmbH.)

Hematogenous metastasis is the main approach for colorectal cancer liver metastasis (CRCLM). However, as the gatekeepers in the tumor vessels, the role of TPCs in hematogenous metastasis remains largely unknown, which may be attributed to the lack of specific biomarkers for TPC isolation. Here, microdissection combined with a pericyte medium-based approach is developed to obtain TPCs from CRC patients. Proteomic analysis reveals that TRP channel-associated factor 2 (TCAF2), a partner protein of the transient receptor potential cation channel subfamily M member 8 (TRPM8), is overexpressed in TPCs from patients with CRCLM. TCAF2 in TPCs is correlated with liver metastasis, short overall survival, and disease-free survival in CRC patients. Gain- and loss-of-function experiments validate that TCAF2 in TPCs promotes tumor cell motility, epithelial-mesenchymal transition (EMT), and CRCLM, which is attenuated in pericyte-conditional Tcaf2-knockout mice. Mechanistically, TCAF2 inhibits the expression and activity of TRPM8, leading to Wnt5a secretion in TPCs, which facilitates EMT via the activation of the STAT3 signaling pathway in tumor cells. Menthol, a TRPM8 agonist, significantly suppresses Wnt5a secretion in TPCs and CRCLM. This study reveals the previously unidentified pro-metastatic effects of TPCs from the perspective of cold-sensory receptors, providing a promising diagnostic biomarker and therapeutic target for CRCLM., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The high-throughput scalable production of low-cost and high-performance electrode materials that work well under high power densities required in industrial application is full of challenges for the large-scale implementation of electrochemical technologies. Here, motivated by theoretical calculation that Mo-S-C heterojunction and sulfur vacancies can reduce the energy band gap, decrease the migration energy barrier, and improve the mechanical stability of MoS 2 , the scalable preparation of inexpensive MoS 2-x @CN is contrived by employing natural molybdenite as precursor, which is characteristic of high efficiency in synthesis process and energy conservation and the calculated costs are four orders of magnitude lower than MoS 2 /C in previous work. More importantly, MoS 2- x @CN electrode is endowed with impressive rate capability even at 5 A g -1 , and ultrastable cycling stability during almost 5000 cycles, which far outperform chemosynthesis MoS 2 @CN anode and carbon cathode, the energy/power output is high up to 265.3 W h kg 2- at 250 W kg x @CN anode and carbon cathode, the energy/power output is high up to 265.3 W h kg -1 at 250 W kg -1 . These advantages indicate the huge potentials of the designed MoS 2- x @CN and of mineral-based cost-effective and abundant resources as anode materials in high-performance AICs., (© 2023 Wiley-VCH GmbH.)

High-voltage aqueous rechargeable energy storage devices with safety and high specific energy are hopeful candidates for the future energy storage system. However, the electrochemical stability window of aqueous electrolytes is a great challenge. Herein, inspired by density functional theory (DFT), polyethylene glycol (PEG) can interact strongly with water molecules, effectively reconstructing the hydrogen bond network. In addition, N, N-dimethylformamide (DMF) can coordinate with Zn 2+ , assisting in the rapid desolvation of Zn 2+ and stable plating/stripping process. Remarkably, by introducing PEG400 and DMF as co-solvents into the electrolyte, a wide electrochemical window of 4.27 V can be achieved. The shift in spectra indicate the transformation in the number and strength of hydrogen bonds, verifying the reconstruction of hydrogen bond network, which can largely inhibit the activity of water molecule, according well with the molecular dynamics simulations (MD) and online electrochemical mass spectroscopy (OEMS). Based on this electrolyte, symmetric Zn cells survived up to 5000 h at 1 mA cm -2 , and high voltage aqueous zinc ion supercapacitors assembled with Zn anode and activated carbon cathode achieved 800 cycles at 0.1 A g -1 . This work provides a feasible approach for constructing high-voltage alkali metal ion supercapacitors through reconstruction strategy of hydrogen bond network., (© 2023 Wiley-VCH GmbH.)