Unlocking the Capacity of Vanadium Oxide by Atomically Thin Graphene-Analogous V2O5·nH2O in Aqueous Zinc-Ion Batteries

Aqueous Zn-ion batteries (AZIBs) are promising due to their high theoretical energy density and intrinsic safety, and the natural abundance of Zn. Since low voltage is an intrinsic shortage of AZIBs, achieving super-high capacity of cathode materials is a vital way to realize high practical energy density, which however remains a huge challenge. Herein, the capacity increase of classical vanadium oxide cathode is predicted via designing atomic thickness of 2D structure to introduce abundant Zn²⁺ storage sites based on density functional theory (DFT) calculation; then graphene-analogous V₂O₅·nH₂O (GAVOH) with only few atomic layers is fabricated, realizing a record capacity of 714 mAh g⁻¹. Pseudocapacitive effect is unveiled to mainly contribute to the super-high capacity due to the highly exposed GAVOH external surface. In situ Raman and synchrotron X-ray techniques unambiguously uncover the Zn²⁺ storage mechanism. Carbon nanotubes (CNTs) are further introduced to design GAVOH-CNTs gel ink for large-scale cathode fabrication. The hybrid cathode demonstrates ultra-stable cycling and excellent rate capability and delivers a high energy density of 476 Wh kg⁻¹ at 76 W kg⁻¹; 228 Wh kg⁻¹ is still retained at high mass loading of 10.2 mg cm⁻². This work provides inspiration for breaking the capacity limit of cathode in AZIBs.     

Macrophage Membrane-Coated Nanoparticles Sensitize Glioblastoma to Radiation by Suppressing Proneural–Mesenchymal Transformation in Glioma Stem Cells

Radiotherapy is identified as a crucial treatment for patients with glioblastoma, but recurrence is inevitable. The efficacy of radiotherapy is severely hampered partially due to the tumor evolution. Growing evidence suggests that proneural glioma stem cells can acquire mesenchymal features coupled with increased radioresistance. Thus, a better understanding of mechanisms underlying tumor subclonal evolution may develop new strategies. Herein, data highlighting a positive correlation between the accumulation of macrophage in the glioblastoma microenvironment after irradiation and mesenchymal transdifferentiation in glioblastoma are presented. Mechanistically, elevated production of inflammatory cytokines released by macrophages promotes mesenchymal transition in an NF-κB-dependent manner. Hence, rationally designed macrophage membrane-coated porous mesoporous silica nanoparticles (MMNs) in which therapeutic anti-NF-κB peptides are loaded for enhancing radiotherapy of glioblastoma are constructed. The combination of MMNs and fractionated irradiation results in the blockage of tumor evolution and therapy resistance in glioblastoma-bearing mice. Intriguingly, the macrophage invasion across the blood-brain barrier is inhibited competitively by MMNs, suggesting that these nanoparticles can fundamentally halt the evolution of radioresistant clones. Taken together, the biomimetic MMNs represent a promising strategy that prevents mesenchymal transition and improves therapeutic response to irradiation as well as overall survival in patients with glioblastoma.     

Self-Mineralizing Dnazyme Hydrogel as a Multifaceted Bone Microenvironment Amendment for Promoting Osteogenesis in Osteoporosis

The accumulation of reactive oxygen species (ROS) and minimal osteogenic raw material in the osteoporotic bone microenvironment greatly inhibits the activity of osteoblasts. Herein, it is originally proposed to construct a biomatrix multifaceted bone microenvironment amendment -Mineralized zippered G4-Hemin DNAzyme hydrogel (MDH)-to improve osteoporotic osteogenic capacity and promote high-quality bone defect repair. The programmed design of the rolling circle amplified DNA hydrogel synthesis system allows the introduction of massive amounts of zippered G4-Hemin DNAzyme in MDH. The zippered G4-Hemin DNAzyme highly mimics the tight catalytic configuration of horseradish peroxidase and exerts excellent enzyme-like activity with considerable ROS molecule scavenging ability. In addition, the DNA amplification by-product pyrophosphate is ingeniously employed as a sufficient phosphorus source, thus constituting an autonomous mineralization system for waste reuse through the introduction of pyrophosphate hydrolase and calcium ions, which deposits in MDH as an osteogenic raw material and addresses the challenge of DNA hydrogel bio-application stability. The remarkable in vitro and in vivo outcomes demonstrate that MDH can effectively improve the oxidative stress status of osteoblasts, restore the balance of mitochondrial membrane potential, and reduce apoptosis, ultimately demonstrating superior osteogenic capacity.     

Bacteria-Responsive Self-Assembly of Antimicrobial Peptide Nanonets for Trap-and-Kill of Antibiotic-Resistant Strains

Bacterial trapping using nanonets is a ubiquitous immune defense mechanism against infectious microbes. These nanonets can entrap microbial cells, effectively arresting their dissemination and rendering them more vulnerable to locally secreted microbicides. Inspired by this evolutionarily conserved anti-infective strategy, a series of 15 to 16 residue-long synthetic β-hairpin peptides is herein constructed with the ability to self-assemble into nanonets in response to the presence of bacteria, enabling spatiotemporal control over microbial killing. Using amyloid-specific K114 assay and confocal microscopy, the membrane components lipoteichoic acid and lipopolysaccharide are shown to play a major role in determining the amyloid-nucleating capacity as triggered by Gram-positive and Gram-negative bacteria respectively. These nanonets displayed both trapping and killing functionalities, hence offering a direct improvement from the trap-only biomimetics in literature. By substituting a single turn residue of the non-amyloidogenic BTT1 peptide, the nanonet-forming BTT1-3A analog is produced with comparable antimicrobial potency. With the same sequence manipulation approach, BTT2-4A analog modified from BTT2 peptide showed improved antimicrobial potency against colistin-resistant clinical isolates. The peptide nanonets also demonstrated robust stability against proteolytic degradation, and promising in vivo efficacy and biosafety profile. Overall, these bacteria-responsive peptide nanonets are promising clinical anti-infective alternatives for circumventing antibiotic resistance.     

Mo-Modified ZnIn2S4@NiTiO3 S-Scheme Heterojunction with Enhanced Interfacial Electric Field for Efficient Visible-Light-Driven Hydrogen Evolution

Designing and developing visible-light-responsive materials for solar to chemical energy is an efficient and promising approach to green and sustainable carbon-neutral energy systems. Herein, a facile in situ growth hydrothermal strategy using Mo-modified ZnIn₂S₄ (Mo-ZIS) nanosheets coupled with NiTiO₃ (NTO) microrods to synthesize multifunctional Mo-modified ZIS wrapped NTO microrods (Mo-ZIS@NTO) photocatalyst with enhanced interfacial electric field (IEF) effect and typical S-scheme heterojunction is reported. Mo-ZIS@NTO catalyst possesses wide-spectrum light absorption properties, excellent visible light-to-thermal energy effect, electron mobility, charges transfer, and strong IEF and exhibits excellent solar-to-chemical energy conversion for efficient visible-light-driven photocatalytic hydrogen evolution. Notably, the engineered Mo_1.4-ZIS@NTO catalyst exhibits superior performance with H₂ evolution rate of up to 14.06 mmol g⁻¹ h^{− 1} and the apparent quantum efficiency of 44.1% at 420 nm. The scientific explorations provide an in-depth understanding of microstructure, S-scheme heterojunction, enhanced IEF, Mo-dopant facilitation effect. Moreover, the theoretical simulations verify the critical role of Mo element in promoting the adsorption and activation of H₂O molecules, modulating the H adsorption behavior on active S sites, and thus accelerating the overall catalytic efficiency. The photocatalytic hydrogen evolution mechanism via S-scheme heterojunction with adjustable IEF regulation over Mo_1.4-ZIS@NTO is also demonstrated.     

A Low-Hysteresis and Highly Stretchable Ionogel Enabled by Well Dispersed Slidable Cross-Linker for Rapid Human-Machine Interaction

Ionic conductive soft materials for mimicking human skin are a promising topic since they can be thought of as a possible basis for biomimetic sensing. In pursuit of devices with a long working range and low signal delay, conductive materials with low hysteresis and good stretchability are highly demanded. To overcome the challenges of highly stretchable conductive materials with good resilience, herein a chemical design is proposed where polyrotaxanes act as topological cross-linkers to enhance the stretchability by sliding-induced reduced stress concentration while the compatible ionic liquid is introduced as a dispersant for low hysteresis. The obtained ionogels exhibit versatile properties more than low hysteresis (residual strain = 7%) and good stretchability (550%), and also anti-fatigue, biocompatibility, and good adhesion. The low hysteresis is attributed to lower energy dissipation from the well-dispersed polyrotaxanes by compatible ionic liquids. The mechanism provides a new insight in fabricating highly stretchable and low-hysteresis slide-ring materials. Furthermore, the conductivity of the ionogels and their responses to strains and temperatures are measured. Benefiting from the good conductivity and low hysteresis, the ionogel is applied to develop a wireless communication system to realize rapid human-machine interactions.     

Proximity-Induced Fully Ferromagnetic Order with Eightfold Magnetic Anisotropy in Heavy Transition Metal Oxide CaRuO3

Ferromagnetic materials with a strong spin-orbit coupling (SOC) have attracted much attention in recent years because of their exotic properties and potential applications in energy-efficient spintronics. However, such materials are scarce in nature. Here, a proximity-induced paramagnetic to ferromagnetic transition for the heavy transition metal oxide CaRuO₃ in (001)-(LaMnO₃/CaRuO₃) superlattices is reported. Anomalous Hall effect is observed in the temperature range up to 180 K. Maximal anomalous Hall conductivity and anomalous Hall angle are as large as ∼15 Ω⁻¹ cm⁻¹ and ∼0.93%, respectively, by one to two orders of magnitude larger than those of the typical 3d ferromagnetic oxides such as La_0.67Sr_0.33MnO₃. Density functional theory calculations indicate the existence of avoid band crossings in the electronic band structure of the ferromagnetic CRO layer, which enhances Berry curvature thus strong anomalous Hall effects. Further evidences from polarized neutron reflectometry show that the CaRuO₃ layers are in a fully ferromagnetic state (∼0.8 μ_B/Ru), in sharp contrast to the proximity-induced canted antiferromagnetic state in 5d oxides SrIrO₃ and CaIrO₃ (∼0.1 μ_B/Ir). More than that, the magnetic anisotropy of the (001)-(LaMnO₃/CaRuO₃) superlattices is eightfold symmetric, showing potential applications in the technology of multistate data storage.     

Incomplete idempotent Schröder quasigroups and related packing designs

Summary In this paper it is proved that, for any positive integern 2, 3 (mod 4),n 7, there exists an incomplete idempotent Schröder quasigroup with one hole of size two IISQ(n, 2) except forn = 10. It is also proved that for any positive integern 0, 1 (mod 4), there exists an idempotent Schröder quasigroup ISQ(n) except forn = 5 and 9. These results completely determine the spectrum of ISQ(n) and provide an application to the packing of a class of edge-coloured block designs.Research supported by NSERC grant A-5320.Research supported by NSFC grant 19231060-2.