Hydrogel coatings are a promising strategy to reduce friction and wear in biomedical implants, yet replicating the durability of natural cartilage remains a key challenge due to the inherent trade-off between low friction and high wear resistance. Here, we present a picot-fiber hydrogel coating (PFHC) that mimics the hierarchical architecture of cartilage by integrating a lubricious surface layer with a tough, fiber-reinforced core layer. The picot fibers, formed by folded peptide strands with hidden loops, endow the core layer with efficient load-bearing capacity, while the loosely packed, open-structured top layer preserves hydration lubrication. The resulting PFHC achieves both ultralow friction (~0.009) and high wear resistance under long-term sliding over 100,000 cycles, comparable to natural cartilage. By decoupling lubrication and load-bearing functionalities across distinct structural layers, PFHC overcomes the conventional limitations of hydrogel coatings, providing a generalizable strategy to integrate lubrication and mechanical durability for reliable, long-lasting implant interfaces.
Selective pollutant oxidation in complex wastewater is often limited by nonspecific consumption of reactive species by background constituents. Singlet oxygen (1O2)-mediated peroxymonosulfate (PMS) oxidation offers a promising non-radical route, but PMS activation usually generates multiple reactive species, making catalytic-site regulation essential for improving 1O2 selectivity. Here, we report an intrinsic framework-nitrogen strategy that uses embedded non-coordinated nitrogen to electronically tune Co-N4 single-atom sites, avoiding first-shell reconstruction or external heteroatom doping while preserving primary coordination environment of active center. By tuning the precursor composition, Co-N-C catalysts with similar Co loading and Co-N4 coordination but different pyridinic N/pyrrolic N ratios were obtained. Co-N-C-3 completely removed 0.1mM bisphenol A within 5min and remained active over pH 3-11 and in the presence of inorganic ions and natural organic matter. 1O2 contributed 95.4% of the oxidation pathway, with a PMS-to-1O2 conversion efficiency of 91.5%. 1O2 production increased with the pyridinic N/pyrrolic N ratio, identifying pyridinic N as the key framework regulator. In real livestock wastewater, Co-N-C-3/PMS completely removed BPA and reduced TOC and COD by 33.5-34.8% and 40.7-45.3%, respectively. This work provides a structurally preserved route for highly selective PMS oxidation and demonstrates its potential for treating complex agricultural wastewater.
Lanthanide-based upconversion aerogels (UCAs) hold considerable promise for a variety of applications, including anti-counterfeiting, temperature sensing, and photoelectric devices. However, their potential is heavily hindered by the limitations of luminescent designability and functional versatility. Herein, we demonstrate the fabrication of self-supporting UCAs with customizable components and properties through a freeze-drying method using K2YF5-based upconversion nanowires as building blocks. The UCAs can function as an optical thermometer during their applications, such as thermal insulation. Moreover, the UCAs, mainly formed through ligand-mediated assembly of the nanowires, possess sectional adjustability and can accommodate other nanomaterials as functional dopants, exhibiting potential applications in multiplexed barcoding and water-resistant phosphor. Given the high tunability of the UCAs and tremendous functional nanomaterials, these results should shed light on arbitrary UCAs for diverse applications.
ABSTRACT Electron‐transfer‐involved persulfate‐based advanced oxidation processes (ET‐AOPs) are attractive for wastewater treatment because of their high selectivity and environmental robustness. However, ET‐AOPs are intrinsically dual‐site reaction requiring efficient electron transfer between persulfate‐binding and pollutant‐binding sites. This constraint is often obscured in powder catalysts but becomes critical when reactions in integrated catalytic membranes or devices, where spatial separation of active sites and discontinuous conductive pathways can electronically isolate internal regions, substantially limiting reaction site utilization. Here we report an interfused nitrogen‐doped reduced graphene oxide fiber (N‐rGOF) membrane that overcomes this by unifying long‐range electronic continuity with internal site accessibility. Fused junctions between fibers form a continuous, low resistance conductive network, while the layered rGO structure enables persulfate entry into interlayers to activate otherwise inaccessible internal nitrogen sites through an interlayer entry‐induced site activation (IESA) mechanism. The N‐rGOF membrane degraded bisphenol A (BPA) ∼5.2 times faster than a noninterfused counterpart and maintained excellent removal of trace organic pollutants in real livestock wastewater with high ionic strength and organic loading. Furthermore, the intrinsic potential difference generated during catalysis enables a floatable, self‐powered setup that couples pollutant degradation with real‐time electrical signaling, illustrating the conceptional feasibility of integrated monitoring and remediation based on one single system.
With the rapid development of renewable energy utilization, hydrogen production by electrochemical water hydrolysis has attracted renewed research interest. The improvement of unit mass activity of low-Pt loading catalysts for hydrogen evolution reaction (HER) and the reduction of cost is attractive and challenging. Herein, the sulfide of the VIB subgroup metal (M = Cr, Mo, W) was prepared by a simple and mild electroreduction method, and Pt nanoparticles were grown on the sulphide of the VIB subgroup by Pulse electrodeposition. The MPt-S composite catalysts show excellent HER activity. Especially, Mo-Pt-S shows excellent HER performance (eta 10 = 30.12 mV) in 0.5 M H2SO4 and excellent unit mass activity of 26.63 A mg-1 at 50 mV, which is superior to the corresponding monofunctional Pt noble metal catalyst.
Direct coupling of renewable energy sources with water electrolysis for hydrogen production is critical to further reduce hydrogen costs and advance low-carbon development. To this end, a nickel foam-supported Ni3S2-2.0/NF electrocatalyst featuring amorphous-crystalline heterostructure is proposed. Ni3S2-2.0/NF demonstrates exceptional hydrogen evolution reaction (HER) performance, achieving ultralow overpotentials of 49 mV at 10 mA cm- 2 with 140 h stability. Under simulated renewable energy fluctuations (50 h accelerated degradation testing), Ni3S2-2.0/NF exhibits superior fluctuation resilience, showing the lowest 4.2 % HER current density decay. Further investigation reveals that increasing the fluctuation frequency exacerbates current density decay. Critically, a two-electrode electrolyzer assembled with Ni3S2-2.0/NF enables direct solar-driven hydrogen production without power converters.
The divergent synthesis of 2,3-fused quinazolinones via photocatalytic tandem cyclization has been disclosed. It features green reaction conditions, good functional group compatibility and applicability to gram-scale synthesis. In particular, the precursors of tertiary carbon radicals with high steric hindrance are suitable for this reaction. Mechanistic experiments indicate that a radical cascade cross-coupling/cyclization process is involved. This is an efficient example demonstrating the direct activation of inactive α-halocarbonyls to furnish alkyl radicals for the synthesis of polycyclic quinazolinones.
Near-infrared (NIR) light source technology has been integrated into mobile devices with the advantage of portability to provide efficient analysis in many fields. Among them, NIR light in the 850 nm band has attracted much attention due to its unique advantages. In this study, an ultra-broad NIR emission from 700 to 1100 nm with the peak at 839 nm and full width at half-maximum (FWHM) of 151 nm is achieved in a novel tetra-fluoride RbAlF4:Cr3+ excited by 465 nm blue light, exhibiting a relatively longer emission wavelength and wider FWHM compared with the reported Cr3+-doped fluoride phosphors. In-depth research on its crystal structure reveals that Cr3+ is in a weak crystal field with a distorted octahedral environment, coupled with a strong electron-phonon coupling effect, which prompts the phosphor to exhibit long-wavelength and broad NIR light characteristics. However, these reasons also lead to relatively moderate internal quantum efficiency and thermal stability. Finally, a NIR phosphor-converted light-emitting diode (NIR pc-LED) was fabricated by combining this phosphor with a commercial blue chip, which shows great potential in non-destructive testing, night-vision observation, and biomedical imaging. This work provides new insights into the design of long-wavelength broadband fluoride phosphors.
This study presents a novel biosensor based on TdT and CRISPR-Cas12a, which integrates the catalytic activity of terminal deoxynucleotidyl transferase (TdT) with the trans-cleavage property of CRISPR-Cas12a to achieve ultra-sensitive biomolecular detection. The biosensor exhibited a broad linear detection range from 0 to 0.2 U L-1 and a remarkably low detection limit of 1.7 × 10-3 U L-1, demonstrating high specificity and sensitivity. In practical validation, the biosensor successfully quantified alkaline phosphatase (ALP) activity in both cervical cancer cells and HeLa cell lysates, even at a dilution factor of up to 106-fold. Its sensitivity allowed precise detection at the single-cell level. This technology offers a robust, simple, and cost-effective platform for cancer diagnosis, treatment monitoring, and enzyme inhibitor screening, while maintaining excellent detection performance in complex biological samples. This breakthrough establishes a foundation for serological tumor screening and early disease diagnosis, while also opening new avenues for enhanced cancer management and clinical translation, indicating significant potential in translational medicine.
The accumulation of dense crystal layers on solar evaporators compromises the performances by reducing light absorption efficiency and obstructing water transport channels, ultimately diminishing evaporation rate. To mitigate this issue, spatially separated crystallization sites can be engineered on the evaporator surface to disrupt salt adhesion and prevent dense layers formation. In this study, a 3D column-shaped wood evaporator (KOH-activated carbon- delignified wood (KAC-DW)) is developed by coating DW with KAC. The KAC coating creates microstructured surface featuring abundant protrusions (≈144 mm-2, each 20 μm in height), which effectively inhibit salt crystal adhesion. Under 1 kW m-2 solar radiation with a 15 wt% NaCl solution, the KAC-DW evaporator achieves an impressive water evaporation rate of 8.18 kg m-2 h-1 over 96 h (0 m s-1 wind speed)-more than double the performance of uncoated DW (3.91 kg m-2 h-1). This enhancement stems from two key mechanisms: 1) the KAC protrusions prevent dense crystal layer formation, preserving open surface channels for evaporation, and 2) they promote the growth of loose salt crystals, thereby expanding the effective evaporation area and further boosting the evaporation rate.
Electro‐Fenton treatment through the two‐electron oxygen reduction reaction (2e − ORR) offers an effective approach for degrading persistent organic pollutants (POPs) in water; however, aeration is always required to overcome the low solubility of oxygen in water, ensuring adequate oxygen availability for the 2e − ORR to generate H 2 O 2 and facilitate its transport for activation into hydroxyl radicals. The aeration energy consumption can reach tens of times higher than the energy required for the electrochemical reactions themselves. To address this, we developed an aeration‐free dual‐cathode system featuring a natural oxygen‐harvesting electrode (NOHE). The NOHE's superhydrophobic and microporous structure effectively captures and utilizes anode‐generated oxygen for H 2 O 2 synthesis (957.1 mg g cat −1 ) without external aeration. By decoupling H 2 O 2 generation and activation into separate cathodes, the system optimizes both processes independently, achieving superior efficiency. This design demonstrated rapid removal of bisphenol AF (BPAF) in saline environments, achieving 98% mineralization and exhibiting excellent operational stability over 90 h continuous use. By eliminating energy‐intensive aeration, our approach may open the avenue for a scalable, sustainable solution for in situ water remediation, with broad applicability in diverse aquatic environments.
Solar-interfacial water-vapor conversion has emerged as a promising method for clean water production, particularly in water-scarce regions, but a major challenge is the volatile organic compounds (VOCs) along with water vapor, leading to polluted condensed water. This study introduces a novel design strategy that leverages surface oxygen vacancies (OVs) in photocatalysts to maximize both oxygen (O2) utilization from the air and photocarrier efficiency at the air-water interface, building upon previous research that demonstrated that oxygen concentration at the interface can be significantly higher than that in bulk water. By enhancing oxygen adsorption and facilitating charge carrier separation, OVs significantly improve reactive oxygen species (ROS, including ·O2- and ·OH) generation and overall photocatalytic activity. As a demonstration, the surface OVs-engineered BiOCl-based photocatalytic solar interfacial evaporator demonstrated a 3.41-fold increase in VOC (phenol) removal efficiency compared to a conventional system, achieving over 99.6% VOC removal in condensed water and maintaining a high water vapor generation flux of 1.90 kg/m2/h. This innovative design was further validated using ZnO-based photocatalysts, demonstrating the broad applicability of OV-engineering in interfacial systems. By fully utilizing both the high oxygen content at the air-water interface and improving photocarrier dynamics, this approach represents a significant advancement in photocatalytic water treatment technologies, offering a scalable and highly efficient solution for VOC removal and clean water production.
Near-infrared (NIR) light-driven photocatalysis provides a promising solution to the inherent limitations of conventional ultraviolet (UV) and visible-light photocatalysis, such as shallow penetration, photodamage from high-energy irradiation, and limited selectivity. However, effective strategies for achieving NIR photocatalysis remain scarce. Here, a novel strategy that achieves NIR photocatalysis with significantly enhanced selectivity is reported through lanthanide nanocrystal-mediated photosensitization. A composite nanocatalyst, comprising NaNdF4 lanthanide nanocrystals and Zn(II) phthalocyanine organic photosensitizers is designed, where the NaNdF4 absorb 808 nm NIR light and transfer energy directly to the photosensitizers via lanthanide-mediated triplet sensitization. This approach enables selective functionalization of organic substrates with increased yields and reduced side-product formation compared to UV/visible light excitation. The enhanced selectivity arises from the controlled generation of superoxide anions (O2-) as reactive oxygen species (ROS) and minimized substrate photoactivation. The approach enables targeted dehydrogenation and C & horbar;N coupling reactions of diverse N-heterocyclic substrates, including halogen-substituted compounds that are typically prone to undesired side reactions. The findings establish a versatile strategy for improving selectivity in photocatalytic transformations, opening new opportunities in light-sensitive organic synthesis and sustainable catalysis.
The development of highly sensitive and reliable gas sensors is crucial for environmental monitoring, industrial safety, and healthcare applications. We report a facile block copolymer self-assembly approach for fabricating plasmonic Au nanoparticle-decorated WO3 three-dimensional cross-stacked nanowire arrays on microchips for enhanced gas sensing. The porous nanostructure of 3D WO3 NW framework, coupled with the catalytic and surface plasmon resonance properties of Au NPs, synergistically boosts the NO2 sensing performance. The Au/WO3 sensor exhibits an exceptional response of 340.7 to 50 ppm NO2 at 150 °C in dark conditions, which further increases to 980 under white light illumination, along with rapid response/recovery times, a low detection limit, and excellent stability. To elucidate the gas sensing mechanisms, we employ environmental operando micro-spectroscopy techniques, including conductive atomic force microscopy, Kelvin probe force microscopy, and diffuse reflectance infrared Fourier transform spectroscopy. These advanced characterizations, combined with theoretical calculations, provide direct evidence for the efficient generation and transfer of hot electrons from Au NPs to the WO3 NW matrix under light irradiation, revealing their pivotal role in enhancing NO2 adsorption and expanding the electron depletion layer. In-situ measurements also unveil the dynamic modulation of the Schottky barrier height at the Au/WO3 junction, offering deeper insights into the interplay between environmental factors, hot electrons, and resistance alteration in the metal-semiconductor system. This work provides a promising strategy for designing high-performance gas sensors and paves the way for probing complex gas sensing mechanisms.
Solar-driven interfacial evaporation offers a promising sustainable approach to clean water production, leveraging its low carbon footprint and adaptability to diverse environments. Despite advancements in enhancing solar vapor generation rates, inefficient condensation heat dissipation remains a major limitation, reducing overall water collection efficiency. Here, we present a synergistic evaporative cooling and radiative cooling (SECRC) strategy that significantly boosts solar-driven clean water production by effectively dissipating condensation heat. Using a titanium dioxide nanocrystal-coated delignified wood substrate (DW-TiO2 NC) as the SECRC platform, we achieved a 2.5-fold increase in heat dissipation flux and enhanced vapor diffusion towards the condensation interface. This innovation improved water production efficiency from 0.50 to 0.80. Furthermore, the TiO2 coating provided exceptional environmental anti-fouling capabilities, maintaining a stable outdoor water collection rate with only similar to 9 % reduction after one month of exposure, compared to an 18 % decline in uncoated systems. This all-passive, single-solar-powered SECRC system delivers an efficient, stable, and practical solution to address global clean water challenges, marking a transformative advancement in solar water purification technology.
Solar-driven interfacial evaporation has shown great potential in freshwater production due to its minimal carbon footprint and adaptability to diverse water sources. However, while significant progress has been made in enhancing vapor generation rates, limited heat dissipation during condensation continues to constrain overall water production efficiency. Here, we introduce a latent heat-assisted evaporative cooling (LHEC) strategy that effectively dissipates condensation heat by harnessing water's latent heat. Using delignified wood as the demonstrating LHEC substrate, we achieved a 2.5-fold increase in heat dissipating heat flux and accelerated vapor diffusion from the evaporation region toward the condensation interface. This approach improves solar water production efficiency to 0.76 (versus 0.49 in conventional systems) and demonstrates robust salt resistance for long-term operation. Notably, the plug-and-play design of the LHEC substrate enables seamless integration into a range of solar evaporation architectures, including single/multi-stage systems, all of which benefit from its enhanced condensation performance. This universality offers a fully passive, single solar-powered solution. This LHEC strategy represents a significant step forward in scalable, efficient and environmentally sustainable freshwater production.
In-situ wastewater treatment has gained popularity due to cost and energy savings tailored to water sources and user needs. However, this treatment, particularly through advanced oxidation processes (AOPs), poses ecological risks due to the need for strong oxidizing agents. Here, we present a decoupled oxidation process (DOP) using single-atom copper-modified graphite felt electrodes. This process creates a positive potential difference (ΔE ~ 0.5 V) between spatially isolated oxidants and organics and drives electron transfer-based redox reactions. The approach avoids the drawbacks of conventional AOPs, while being capable of treating various recalcitrant electron-rich organics. A floating water treatment device designed based on the DOP approach can degrade organic molecules in large bodies of water with oxidants stored separately in the device. We demonstrate that over 200 L of contaminated water can be treated with a floating device containing only 40 mL of oxidant (10 mM peroxysulphate). The modular device can be used in tandem structures on demand, maximizing water remediation per unit area. Our result provides a promising, eco-friendly method for in-situ water treatment that is unattainable with existing techniques.
AbstractTraditional high‐dose antibiotic treatments of intracellular methicillin‐resistant staphylococcus aureus (MRSA) are highly inefficient and associated with a high rate of infection relapse. As an effective antibacterial technology, sonodynamic therapy (SDT) may be able to break the dilemma. However, indiscriminate reactive oxygen species (ROS) release leads to potential side effects. This study incorporates Staphylococcal Protein A antibody‐modified Cu2+/tetracarboxyphenylporphyrin nanoparticles (Cu(II)NS‐SPA) into hydrogel microspheres (HAMA@Cu(II)NS‐SPA) to achieve precise eradication of intracellular bacteria. This eradication is under bioorthogonal activation mediated by bacillithiol (BSH) (internally) and ultrasound (US) (externally). To specify, the US responsiveness of Cu(II)NS‐SPA is restored when it is reduced to Cu(I)NS‐SPA by the BSH secreted characteristically by intracellular MRSA, thus forming a bioorthogonal activation with the external US, which confines ROS production within the infected MΦ. Under external US activation at 2 W cm−2, over 95% of intracellular MRSA can be cleared. In vivo, a single injection of HAMA@Cu(II)NS‐SPA achieves up to two weeks of antibacterial sonodynamic therapy, reducing pro‐inflammatory factor expression by 90%, and peri‐implant bone trabeculae numbers exceed the control group by five times. In summary, these micro/nano hydrogel microspheres mediated by internal and external bioorthogonal activation can precisely eliminate intracellular MRSA, effectively treating multi‐drug resistant intracellular bacterial infections.
Multidrug resistance (MDR) is an incidental trouble post-chemotherapy, necessitating innovative therapeutic strategies. This study explores the potential of chloroquine (CQ) as a sensitizer for mitoxantrone hydrochloride (MitH) in drug-resistant tumors and introduces a novel pH-responsive drug-induced self-assembly nanovesicle (DIV) based on an amphiphilic polyphosphonitrile (PPAP) for the co-delivery of MitH and CQ. PPAP cannot self-assemble into nanovesicles alone, but when a certain amount of MitH was added, the multiple non-covalent interactions between PPAP and MitH contributed to the formation of DIV, which exactly improved the co-loading content of MitH and CQ to a large extent. CQ prevents MitH efflux and autophagy to reverse MitH resistance. Given the synergy between MitH and CQ at a 1:2 mass ratio with a combination index of 0.40 in K562/ADR cells, MitH and CQ co-loaded DIV (MC-DIV) is constructed and demonstrates a sensitivity index of 7.1 on cytotoxicity compared to free MitH. Furthermore, MC-DIV achieves extended circulation time, synchronous dual-drug delivery, and improved tumor targeting following systemic administration, resulting in exceptional antitumor efficacy in K562/ADR xenograft models with a tumor inhibition rate of 83.0 %. Overall, MC-DIV provides a viable method to maximize the loading capacity of nanocarriers, and potentially serves as a promising formulation for various MitH-resistant tumors.