Self-Adhesive Polydimethylsiloxane Foam Materials Decorated with MXene/Cellulose Nanofiber Interconnected Network for Versatile Functionalities

Polydimethylsiloxanes (PDMS) foam as one of next-generation polymer foam materials shows poor surface adhesion and limited functionality, which greatly restricts its potential applications. Fabrication of advanced PDMS foam materials with multiple functionalities remains a critical challenge. In this study, unprecedented self-adhesive PDMS foam materials are reported with worm-like rough structure and reactive groups for fabricating multifunctional PDMS foam nanocomposites decorated with MXene/cellulose nanofiber (MXene/CNF) interconnected network by a facile silicone foaming and dip-coating strategy followed by silane surface modification. Interestingly, such self-adhesive PDMS foam produces strong interfacial adhesion with the hybrid MXene/CNF nano-coatings. Consequently, the optimized PDMS foam nanocomposites have excellent surface super-hydrophobicity (water contact angle of ≈159^o), tunable electrical conductivity (from 10⁻⁸ to 10 S m⁻¹), stable compressive cyclic reliability in both wide-temperature range (from −20 to 200 ^oC) and complex environments (acid, sodium, and alkali conditions), outstanding flame resistance (LOI value of >27% and low smoke production rate), good thermal insulating performance and reliable strain sensing in various stress modes and complex environmental conditions. It provides a new route for the rational design and development of advanced PDMS foam nanocomposites with versatile multifunctionalities for various promising applications such as intelligent healthcare monitoring and fire-safe thermal insulation.     

Fine-Tuning Alkyl Chains on Quinoxaline Nonfullerene Acceptors Enables High-Efficiency Ternary Organic Solar Cells with Optimizing Molecular Stacking and Reducing Energy Loss

Material design of guest acceptor is always a big challenge for improving the efficiency of ternary organic solar cells (OSCs). Here, a pair of isomeric nonfullerene acceptors based on quinoxaline core, Qx–p-C₇H₈O and Qx–m-C₇H₈O, is designed and synthesized. By moving the alkoxy chain attached on side phenyl from meta-position to para-position, both π–π stacking distance and crystallinity are enhanced simultaneously. They obtain the uplifted lowest unoccupied molecular orbital level. Compared to Qx–m-C₇H₈O, Qx–p-C₇H₈O exhibits wider absorption spectrum and higher extinction coefficient. Using D18-Cl:N3 as host materials, the addition of guest acceptor Qx–p-C₇H₈O significantly improves the power conversion efficiency (PCE) from 17.61% to 18.49% because of higher open-circuit voltage (0.875 V) and short-circuit current density (27.85 mA cm⁻²). This can be attributed to the faster exciton dissociation, more balanced carrier mobility, fine fiber morphology, and lower energy loss in the ternary devices. However, Qx–m-C₇H₈O-based ternary device achieves relatively low PCE of 17.17% because this device shows extremely low electron mobility. The results indicate that molecular stacking, film morphology, etc., can be effectively modulated by fine-tuning the side chains of guest materials, which may be an effective design rule for further improving the PCE of OSCs.     

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.     

Catalytically Induced Robust Inorganic-Rich Cathode Electrolyte Interphase for 4.5 V Li||NCM622 Batteries

Tailoring inorganic components of cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) is critical to improving the cycling performance of lithium metal batteries. However, it is challenging due to complicated electrolyte reactions on cathode/anode surfaces. Herein, the species and inorganic component content of the CEI/SEI is enriched with an objectively gradient distribution through employing pentafluorophenyl 4-nitrobenzenesulfonate (PFBNBS) as electrolyte additive guided by engineering bond order with functional groups. In addition, a catalytic effect of LiNi_0.6Mn_0.2Co_0.2O₂ (NCM622) cathode is proposed on the decomposition of PFBNBS. PFBNBS with lower highest occupied molecular orbital can be preferentially oxidized on the NCM622 surface with the help of the catalytic effect to induce an inorganic-rich CEI for superior electrochemical performance at high voltage. Moreover, PFBNBS can be reduced on the Li surface due to its lower lowest unoccupied molecular orbital , increasing inorganic moieties in SEI for inhibiting Li dendrite generation. Thus, 4.5 V Li||NCM622 batteries with such electrolyte can retain 70.4% of initial capacity after 500 cycles at 0.2 C, which is attributed to the protective effect of the excellent CEI on NCM622 and the inhibitory effect of its derived CEI/SEI on continuous electrolyte decomposition.     

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.     

Comprehensively Strengthened Metal-Oxygen Bonds for Reversible Anionic Redox Reaction

Introducing anionic redox in layered oxides is an effective approach to breaking the capacity limit of conventional cationic redox. However, the anionic redox reaction generally suffers from excessive oxidation of lattice oxygen to O₂ and O₂ release, resulting in local structural deterioration and rapid capacity/voltage decay. Here, a Na_0.71Li_0.22Al_0.05Mn_0.73O₂ (NLAM) cathode material is developed by introducing Al³⁺ into the transition metal (TM) sites. Thanks to the strong Al–O bonding strength and small Al³⁺ radius, the TMO₂ skeleton and the holistic TM–O bonds in NLAM are comprehensively strengthened, which inhibits the excessive lattice oxygen oxidation. The obtained NLAM exhibits a high reversible capacity of 194.4 mAh g^-1 at 20 mA g^-1 and decent cyclability with 98.6% capacity retention over 200 cycles at 200 mA g⁻¹. In situ characterizations reveal that the NLAM experiences phase transitions with an intermediate OP4 phase during the charge–discharge. Theoretical calculations further confirm that the Al substitution strategy is beneficial for improving the overlap between Mn 3d and O 2p orbitals. This finding sheds light on the design of layered oxide cathodes with highly reversible anionic redox for sodium storage.