The persistent occurrence of antibiotics in aquatic environments poses significant environmental and health risks. However, conventional membrane technologies for antibiotic removal are often limited by insufficient selectivity and performance deterioration caused by membrane fouling. In this study, a novel ternary heterojunction photocatalytic membrane, BiOCl/g-C3N4@MoS2, was constructed via a hydrothermal strategy followed by vacuum-assisted filtration. The synergistic integration of BiOCl and g-C3N4 with MoS2 enhances visible-light-driven photocatalytic activity, resulting in improved antibiotic removal and enhanced operational stability. The optimized membrane exhibits high water permeability (1209.39 L & sdot;m-2 & sdot;h-1 & sdot;bar-1) and removal efficiencies of 93.2%, 93.3%, and 97.4% for tetracycline hydrochloride (TCH), ciprofloxacin (CIP), and oxytetracycline (OTC), respectively, under visible light irradiation, and maintains stable performance during repeated operation. To elucidate the underlying mechanisms, a multiscale simulation framework integrating molecular dynamics (MD), steered MD (SMD), and density functional theory (DFT) calculations was employed. MD and SMD results collectively reveal that the introduction of BiOCl regulates the interfacial environment by forming a dense and dynamic hydration layer, which weakens pollutant-surface interactions and suppresses adsorption-driven fouling. DFT calculations further demonstrate that the ternary heterojunction enables favorable band structure modulation and enhanced interfacial charge transfer, promoting efficient separation of photogenerated charge carriers and increased generation of reactive species. These coupled analyses reveal a mechanistic correlation between component-level interfacial properties, heterojunction-mediated charge transfer, and the improved cyclic stability and antibiotic removal performance of the ternary membrane. This work provides fundamental insights into the synergistic roles of interfacial regulation and electronic structure engineering in photocatalytic membranes, offering a promising strategy for high-performance antibiotic wastewater treatment.
ConspectusThe study of main-group molecules that mimic transition metal (TM) complexes in bond activation and catalysis has attracted considerable interest in recent decades. However, main-group elements lack the same electronic versatility that endows TM complexes with diverse reactivity patterns. This limitation has driven efforts to develop innovative strategies to harness and expand the reactivity of main-group compounds. Among these, leveraging cooperative effects between main-group centers has emerged as a particularly promising approach to fine-tune their reactivity, as exemplified by frustrated Lewis pairs (FLPs) and bimetallic main-group complexes. Despite these advances, examples of cooperative interactions involving multiple low-valent main-group element centers remain rare. Such cooperativity is of great interest because the presence of multiple low-valent centers facilitates enhanced multielectron transfer capabilities. Consequently, advancing the design and synthesis of multinuclear low-valent main-group compounds holds great promise for unlocking new reactivity in main-group chemistry.This Account details our studies of the synthesis of heavier tetrylene-stabilized low-valent main-group compounds and their applications in cooperative bond activation and catalysis. We describe the design of new types of multidentate silylene ligands and demonstrate their effectiveness in stabilizing boron(I) and aluminum(I) compounds, referred to as borylene and aluminylene, respectively. The cooperation between B(I)/Si(II) and Al(I)/Si(II) centers enables the cleavage of various bonds, including the N-H bond in aniline, the C=O bond in ketones and carbon dioxide, the N=O bond in nitrosoarenes, and the C≡O bond in carbon monoxide. These compounds serve as effective precatalysts for carbon dioxide reduction and the reductive coupling of nitrosoarenes to azoxyarenes, respectively. Using a bis(germylenyl)carborane ligand, we have isolated zerovalent group 14 compounds, such as stannylone and plumbylone. The cooperation between Sn(0)/Ge(II) and Pb(0)/Ge(II) centers enables multiple electron transfers to cleave the N=O bonds of nitrous oxide and nitro compounds. The stannylone acts as an efficient precatalyst for the deoxygenation of nitrous oxide and nitro compounds, leading to the formation of dinitrogen and hydrazines, respectively. These results provide a unique proof-of-concept, underscoring their potential as versatile platforms for challenging bond activation and catalysis.
The enrichment of hydrophilic nanomaterials on polymer membrane surfaces was crucial for enhancing both antifouling capability and separation efficiency. This study presented a facile strategy to drive carbon quantum dots (CQDs) directionally to the membrane surface via an electrostatic enhanced surface segregation strategy. Specifically, CQDs modified with positively charged polyethyleneimine (PEI) were added into the polyethersulfone (PES) casting solution, while negatively charged poly(sodium 4-styrenesulfonate) (PSS) was dissolved in coagulation bath. During the non-solvent induced phase separation (NIPS) process, the strong electrostatic and hydrophilic interaction between PEI@CQDs and PSS propelled PEI@CQDs to migrate and enrich towards PES membrane surface, and a composite antifouling layer was constructed in situ. The optimal membrane (MPC-P) achieved a water flux of 127.4 L•m−2•h−1, with exceptional rejection ratios of 99.35% for bovine serum albumin (BSA) and 98.80% for humic acid (HA). Accordingly, after five filtration cycles, the water flux recovery ratios (FRR) for BSA and HA remained high at 90.86% and 91.35%, while the total permeance decline ratios (DRt) were 11.01% and 6.85%, respectively. Meanwhile, it exhibited a remarkably high inhibition rate of 84.21% against S. aureus, which was approximately 5.7 times higher than that of the pure PES membrane. During a continuous filtration for model foulants lasting 400 min, the membrane exhibited outstanding sustained antifouling and permeation stability. The underlying interaction mechanisms between the pollutants and the membrane surface were successfully revealed by molecular dynamics (MD) simulations. This research offered a robust paradigm for developing high-performance antifouling membranes and promoting their practical application in water treatment.
Aerogel-based solar interfacial evaporation technology has developed into a sustainable approach for freshwater production, yet it faces difficulties like sluggish evaporation rates, inefficient thermal, water management, and salt deposition. Inspired by hierarchical structure of wood, this study fabricates aerogel evaporators with disordered (R), vertically aligned (VA), and radially oriented (VR) pore structures using quaternized cellulose nanofibers (EPTMAC-CNF), polyvinyl alcohol (PVA), and carbon black (CB) via directional freezing. Combined with Janus modification, a systematic investigation is conducted to clarify the correlation between pore topology and evaporation performance. Results show that the radial pore structure achieves optimal balance between water supply and thermal localization. The central vertical channel ensures continuous water transport, while radial pores minimize heat loss downward. The synergy between quaternized CNF and PVA reduces vaporization enthalpy, enhancing water mobility and evaporation. The Janus asymmetric configuration suppresses surface salt crystallization, and the interconnected radial network promotes internal salt redistribution, improving antifouling stability. Under 1 kW center dot m- 2, Janus radial-pore aerogel evaporator (JPCC-VR) attains an evaporation rate of 2.31 kg center dot m- 2 center dot h- 1 and keeps steady operation for 6 h in 15 % brine without salt deposition, demonstrating high efficiency and salt resistance. The research offers a feasible structural framework for superior sun-powered ocean purification within high-salt environments.
This study proposes a self-condensing water-electrode plasma device in which ambient water vapor is condensed on a cooled needle-tip electrode within a strong electric-field region, forming continuously renewed water droplets, Taylor cones, or water-film interfaces that participate in the discharge process. The effects of ambient humidity, needle-tip temperature, and applied voltage on the self-condensation behavior were investigated. The discharge modes at different applied voltages and discharge gaps, the generation of reactive species, and the inactivation efficacy against Staphylococcus aureus were also analyzed. The results showed that increasing ambient humidity, decreasing the needle-tip temperature, and increasing the applied voltage all promoted water condensation at the needle tip. The electric field shortened the droplet formation time and reduced the droplet detachment size. As the applied voltage increased, the device sequentially underwent water condensation, electrospray, stable Taylor-cone, water-film discharge, and bare-electrode discharge stages, while the boundary voltage of each stage increased with the discharge gap. The ozone concentration remained below the instrument’s limit of detection during discharge with the self-condensing water electrode, whereas hydroxyl-radical generation was significantly enhanced. Compared with a conventional metal electrode, the self-condensing water electrode exhibited greater inactivation of S. aureus at the same applied voltage, with a more pronounced advantage under low-voltage conditions. These findings demonstrate that introducing a self-condensing water interface can regulate the local discharge morphology and reactive-species composition, providing a new strategy for developing low-temperature plasma sterilization technologies with low ozone production and high bactericidal activity.
Per- and polyfluoroalkyl substances (PFAS) are persistent environmental micropollutants or emerging contaminants that resist conventional degradation, and their removal has become a hot topic worldwide in recent years. Pressure-driven membrane separation technologies such as nanofiltration (NF) and reverse osmosis (RO) are widely applied for PFAS removal and generally show higher rejection of long-chain homologues, yet they suffer from inherent drawbacks: poor removal performance toward short-chain PFAS, proneness to membrane fouling, and reliance on phase transfer rather than destructive elimination, as PFAS are merely concentrated into secondary waste streams without mineralization. These limitations collectively give rise to intractable technical bottlenecks and environmental management challenges. Herein, this review presents the “membrane as a bridge” conceptual framework, which organizes membrane separation as a preconcentration, matrix regulation, and coupling unit within integrated PFAS treatment systems that synergize with advanced destructive technologies (e.g., advanced oxidation processes (AOPs) or advanced reduction processes (ARPs)). Specifically, this work systematically elucidates how membranes act as a bridge toward PFAS separation, concentrate management, and downstream or interfacial destruction, covering the design and functional modification of high-performance membranes for selective PFAS separation, the interfacial mechanisms governing PFAS rejection and membrane fouling, the rational construction of systems that couple membrane separation with degradation, and targeted mitigation strategies for key bottlenecks including short-chain PFAS removal, fouling control, and concentrate management. Thus, this review establishes a paradigm-shifting “membrane as a bridge” framework to integrate separation and destruction, providing theoretical guidance for the design of sustainable, mineralization-oriented, and efficient PFAS removal strategies.
The photo-Fenton reaction can efficiently degrade organic pollutants and thus is applied intensively for clearing out membrane fouling. However, the pollutant removal efficiency is greatly limited by the redox cycle rate of Fe2+/Fe3+ and the rapid recombination rate of the photogenerated electrons and holes. In order to overcome these drawbacks, a sulfonated polysulfone composite membrane was designed and prepared by incorporating titanium dioxide (TiO2) nanoparticles into a sulfonated polysulfone membrane and sequentially forming beta-FeOOHs on the membrane surface. It was found that the synergy of TiO2 and beta-FeOOH enhanced the hydrophilicity and improved the pure water flux of the composite membrane. As a result, the composite membrane exhibited superior separation performance for methylene blue and rhodamine B cationic dyes. The rejection rate was larger than 99.5%, and the pure water flux was larger than 125.7 L m-2 h-1, largely surpassing that of nanofiltration membranes. Meanwhile, the composite membrane exhibited an excellent self-cleaning performance, achieving a flux recovery rate over 99.7% after visible-light driving Fenton reaction treatment. The rejection rate still remained above 97.2% after 5 cycles of filtration and recovery, indicating the strong treatment ability of the membrane for dye wastewater.
Allergic rhinitis is a non infectious chronic inflammatory disease of the nasal mucosa mediated by immunoglobulin E (IgE). It is a disease characterized by nasal itching, paroxysmal continuous sneezing, watery nasal mucus, and nasal congestion. It is a common and frequently occurring disease in clinical practice, often recurring. In recent years, the incidence rate of the disease is increasing year by year, which brings inconvenience to the life of patients. At present, there is no cure for this disease in clinical practice. But traditional Chinese medicine treatment can effectively control symptoms, improve the body’s resistance, reduce the recurrence rate after treatment, and improve the quality of life of patients.
Solar-driven interfacial evaporation (SDIE) has gained significant attention in seawater desalination and wastewater treatment. Inspired by natural material, various biomimetic structures are being explored in solardriven interfacial evaporation. Drawing from the hierarchical multilevel radial structure inherent in wood, polyvinyl alcohol (PVA) and cellulose nanofibers (CNF) were employed as substrates to fabricate three kinds of hydrogel evaporators (random, vertical and radial-structured) with hierarchical multilevels. The thermal management capability, evaporation enthalpy, evaporation performance and salt fouling resistance of these three different structures of hydrogel evaporators were investigated individually. Results indicated that the radial hydrogel evaporator has superior thermal management capability, lower enthalpy of evaporation and higher evaporation rate and efficiency. The radial-structured evaporator attains equilibrium between thermal regulation and water transport through meticulous optimization of the internal pore structure. Under 1 sun irradiation, the evaporation rate of radial-structured evaporator could reach to 3.01 kg center dot m- 2 center dot h- 1. Moreover, there was no salt crystals deposited on the surface of radial-structured evaporator even continuously evaporated in a high salinity (20 wt% NaCl) solution for 6 h and cyclic operation for 5 days. In addition, the hydrogel exhibits promising performance in treating seawater, dye wastewater, oil-water mixtures and domestic wastewater. The simulated outdoor seawater desalination experiment also proved the excellent evaporation performance of the graded multi-layer radial structure evaporator, and the water production per unit area can meet the daily water demand of the family. The findings offer valuable guidance for future research aimed at optimizing hydrogel design for improved hydrothermal balance. By advancing material structure design and deepening our understanding of hydrothermal equilibrium mechanisms, this work provides new perspectives and sets the foundation for further research in hydrogel-based evaporation technologies.
Parkinson's disease (PD) is exacerbated by dysfunction of inter-organelle contact, which depends on cellular responses to the mechanical microenvironment and can be regulated by external mechanical forces. Delivering dynamic mechanical forces to neural cells proves challenging due to the skull. Inspired by the effects of massage; here PEGylated black phosphorus nanosheets (PEG-BPNS), known for their excellent biocompatibility, biodegradability, specific surface area, mechanical strength, and flexibility, are introduced, which are capable of adhering to neural cell membrane and generating mechanical stimulation with their lateral size of 200 nm, exhibiting therapeutic potential in a 1-methyl-4-phenyl-1,2,3,6-te-trahydropyridine-induced PD mouse model by regulating inter-organelle contacts. Specifically, it is found that 200 nm PEG-BPNS, acting as "NanoMassage," significantly increase plasma membrane tension, as evidenced by fluorescent lipid tension reporter fluorescence lifetime analysis. This mechanical force modulates actin reorganization, subsequently regulating the contacts between actin, mitochondria, and endoplasmic reticulum, further controlling mitochondrial fission and mitigating mitochondrial dysfunction in PD, exhibiting therapeutic efficacy via intranasal administration. These findings provide a noninvasive strategy for applying mechanical stimulation to deep brain areas and elucidate the mechanism of NanoMassage mediating inter-organelle contacts, suggesting the rational design of "NanoMassage" to remodel inter-organelle communications in neurodegenerative disease treatment.
Chemodynamic therapy (CDT) has garnered significant attention in the field of tumor therapy due to its ability to convert overexpressed hydrogen peroxide (H2O2) in tumors into highly toxic hydroxyl radicals (•OH) through metal ion-mediated catalysis. However, the effectiveness of CDT is hindered by low catalyst efficiency, insufficient intra-tumor H2O2 level, and excessive glutathione (GSH). In this study, a pH/GSH dual responsive bimetallic nanocatalytic system (CuFeMOF@GOx@Mem) is developed by modifying red blood cell membranes onto glucose oxidase (GOx)-loaded Fe-Cu bimetallic MOFs, enhancing the efficacy of CDT through a triple-enhanced way by H2O2 self-supply, catalysts self-cycling, and GSH self-elimination. Upon accumulation in tumor tissues facilitated by the red blood cell membrane, the GOx initiates a reaction with glucose to generate H2O2 and gluconic acid in situ. Subsequently, the reduced pH triggers the release of Fe3+ and Cu2+ from CuFeMOF@GOx@Mem, which is immediately turned into Fe2+ and Cu+ by GSH, activating the Fe2+-mediated Fenton reaction. More importantly, Cu+ can also act as an accelerator of Fe3+/Fe2+ conversion, meanwhile, the generated Cu2+ can be further reduced to Cu+ by GSH. Consequently, sustained accumulation of H2O2 and Fe2+ as well as sustained elimination of GSH are achieved simultaneously, providing a unique approach for improving the anti-tumor ability of CDT.
In this study, we present the synthesis and characterization of bis(silylene)-ligated plumbyliumylidene and silylene-ligated diplumbyne. Plumbyliumylidene 2 was obtained through ion-exchange reaction of the bis(silylene)amido lead(II) bromide complex 1 with one equivalent of Na[BArF 4] (ArF = 3,5-(CF3)2-C6H3). Density functional theory calculations confirmed the presence of a lone pair on the lead atom in 2. The reduction of compound 2 yielded silylene-ligated diplumbyne 3, which possesses a Pb-Pb single bond and one lone pair on each lead atom. Remarkably, compound 3 underwent single-electron oxidation to regenerate plumbyliumylidene 2, demonstrating a rare redox cycle between the Pb(I) and Pb(II) states. This study enhances the understanding of the electronic structures and redox behavior of low-valent lead compounds.
Microplastic pollution threatens sustainable agriculture. Zinc (Zn), an essential micronutrient, plays a key role in crop growth and stress responses. While zinc oxide nanoparticles (ZnO NPs) mitigate microplastic toxicity in rice, their long-term use poses environmental risks. Zinc sulfate (ZnSO₄) is a traditional Zn fertilizer, but its interaction with microplastics remains unclear. This study treated rice seedlings with polystyrene (PS) microplastics and ZnSO₄ to assess their effects on growth, Zn uptake, and stress response mechanisms. PS exposure inhibited growth, impaired photosynthesis, reduced stomatal conductance, and induced ROS accumulation, causing oxidative stress that damaged cells and disrupted metabolism, while activating antioxidant enzymes. It also reduced Zn content and altered metabolite accumulation, affecting growth regulation. Appropriate Zn levels alleviated PS toxicity via distinct mechanisms: in shoots, Zn optimized nitrogen metabolism to restore photosynthesis, while in roots, it regulated carbon metabolism to reduce ROS and enhance development. The findings indicate that zinc enhances rice tolerance to microplastic stress by revealing organspecific mechanisms through which traditional zinc fertilizers exert their alleviating effects, providing both mechanistic insight and scientific evidence to optimize their application. This study also offers a viable alternative to reduce the environmental risks associated with ZnO nanoparticles, thereby promoting greener and more sustainable agricultural development.
We report a photocatalyst-free radical cascade heptafluoroisopropylation/cyclization of unactivated alkenes with heptafluoroisopropyl iodides, facilitated by 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or N,N,N ',N '-tetrame-thylethane-1,2-diamine (TMEDA) as the electron donors. The reaction is compatible with a broad range of quinazolinones containing unactivated alkenes, producing the heptafluoroisopropylated polycyclic quinazolinones with the moderate to high yields. Preliminary mechanistic studies revealed that the reaction is initiated by the in situ generated electron donor-acceptor (EDA) complex.
Burn injuries often cause prolonged oxidative stress and inflammatory pain due to an initial increase in inflammatory responses, consequently exacerbating depressive disorders and severely impairing patients' quality of life. The primary function of traditional burn dressings is to prevent infection and facilitate tissue repair. However, these dressings are not intended for the inflammatory pain and depression that often occur during recovery. This study describes a self-healing hydrogel H@EFCP, which is designed to alleviate inflammatory pain and post-burn depression in burn injuries. This hydrogel is synthesized through the cross-linking of carboxymethyl chitosan with borate ester chelates formed from epigallocatechin gallate and 4-formylphenylboronic acid. The incorporated Prussian blue nanoparticles increase the ability of H@EFCP to regulate the inflammatory process. H@EFCP is effective in the treatment of skin burns by reducing oxidative stress and improving the microenvironment of peripheral inflammation in mice. This modulation consists of a reduction of central nervous system inflammation and the risk of post-burn depression. Behavioral assays indicate that the hydrogel significantly reduces feelings of despair and anxiety after burns. Consequently, H@EFCP provides a dual-effect solution for the care and recovery of burn patients, including both burn repair and the associated psychological effects.
Real-time tracking of drug release from nanomedicine in vivo is crucial for optimizing its therapeutic efficacy in clinical settings, particularly in dosage control and determining the optimal therapeutic window. However, most current real-time tracking systems require a tedious synthesis and purification process. Herein, a supramolecular nano-tracker (SNT) capable of real-time tracking of drug release in vivo based on non-covalent host-guest interactions is presented. By integrating multiple cavities into a single nanoparticle, SNT achieves co-loading of drugs and probes while efficiently quenching the photophysical properties of the probe through host-guest complexation. Moreover, SNT is readily degraded under hypoxic tumor tissues, leading to the simultaneous release of drugs and probes and the fluorescence recovery of probes. With this spatial and temporal consistency in drug loading and fluorescence quenching, as well as drug release and fluorescence recovery, SNT successfully achieves real-time tracking of drug release in vivo (Pearson r = 0.9166, R2 = 0.8247). Furthermore, the released drugs can synergize effectively with fluorescent probes upon light irradiation, achieving potent chemo-photodynamic combination therapy in 4T1-bearing mice with a significantly improved survival rate (33%), providing a potential platform to significantly advance the development of nanomedicine and achieve optimal therapeutic effects in the clinic.
Organic fouling causes the filtration property and serve life decrease of the PVDF membrane and is the challenge for filtration applications. Therefore, it is an urgency desire to construct a PVDF membrane with good filtration and antifouling for researchers. To this end, a based PVDF and poly(N-isopropyl acrylamide)(PNIPA) semiinterpenetrating network polymer was synthesized and used as membrane matrix for preparing semiinterpenetrating network/block copolymers blend membrane. The membrane composition, structure and performance were systematically characterized and investigated by FTIR spectrum, XPS, SEM, contact angle instrument and the other experimental techniques etc. Results indicate that the prepared membrane contains PVDF, PNIPA and block copolymer poly(ethylene oxide)-b-poly(propylene oxide)-b- poly(ethylene oxide) (F127) components, shows a porous cross section comprising a thin top surface layer with small pores, a finger-shape lower layer and a sponge-shape pore bottom layer. When the membrane are used for the filtration of bovine serum albumin(BSA) in aqueous solution at 25 celcius, the rejection can exceed 95.0% at a high flux of 307 L/ (m2 & sdot;h & sdot;bar). Simply raising filtration temperature to 60 degrees C, the flux can reach 606 L/(m2 & sdot;h & sdot;bar) while the rejection barely changes, significantly improving the filtration ability of the membrane. Furthermore, the flux can recover above 93% of the original value after a BSA filtration and a subsequent water washing. Undoubtedly, the prepared membrane displays great potential for filtering BSA aqueous solution and the reason can be ascribed to the synergy between PNIPA and F127 of the membrane.
Membrane as a support for metal nanocatalysts, can greatly enhance the catalytic activity of metal nanoparticles and promote the efficient production and separation of products. In this study, a novel sandwich-structured composite membrane was designed and facilely fabricated by using palladium nanocatalysts as the core catalytic layer and two different structured PVDF layers as the outer layers. The composite membrane was used as a reaction interface as well as a separation barrier between reactants and products, efficiently realizing the catalytic oxidation of benzyl alcohol and convenient separation of the product benzaldehyde. The membrane was characterized in detailed and the effects of the membrane structure and various reaction conditions on the catalytic oxidation were systematically investigated. The results indicated that the reaction could be conveniently carried out under very mild experimental conditions, obtaining the product benzaldehyde at as high selectivity as 93.17%. The successful implementation of the sandwich membrane for the production of chlorine-free benzaldehyde provides a new method for the interface reaction.
Intelligent hydrogel actuators that can display stimuli-responsive shape transformations have attracted tremendous interest and shown promising potential applications in many fields. However, it remains a significant challenge to accomplish remotely controllable actuating performance. Herein, an untethered hydrogel actuator fabricated through an interfacial diffusion reaction toward pick-and-place tasks is presented. The anisotropic structures are obtained by generating Fe3O4 nanoparticles in the local regions of a poly(N-isopropylacrylamide) (PNIPAm) hydrogel, leading to complex shape transformation behaviors. The presence of Fe3O4 nanoparticles endows the hydrogel with magnetically responsive navigation and photothermal conversion capacity. Therefore, untethered soft robots capable of realizing pick-and-place tasks were developed. This presented strategy is expected to promote the development of untethered soft robotics toward pick-and-place tasks.