Objective:To investigate the efficacy and mechanism of Ditan Qingnao decoction(DTQND)in alleviating schizophrenia-like symptoms in a maternal immune activation(MIA)-induced rat model.Methods:DTQND components were anal...Objective:To investigate the efficacy and mechanism of Ditan Qingnao decoction(DTQND)in alleviating schizophrenia-like symptoms in a maternal immune activation(MIA)-induced rat model.Methods:DTQND components were analyzed using high-performance liquid chromatography-tandem mass spectrometry.An MIA-induced rat model was established by injecting Poly Ⅰ:C into pregnant dams on gestational day 9.Male offspring were administered DTQND(14.1 g/kg),risperidone(RIS;0.4 mg/kg),or distilled water,while the controls received only distilled water via gavage for 4 weeks.Behavioral assessments were conducted using the open-field,Y-maze,prepulse inhibition,and sucrose preference tests.Serum levels of interleukin(IL)-6,IL-18,IL-1β,and tumor necrosis factor-α(TNF-α)were measured via an enzyme-linked immunosorbent assay.Hippocampal protein levels of nuclear factor kappa B p65(NF-κB p65),phospho-NF-κB p65(p-p65),inhibitor of kappa B-alpha(IκB-α),phospho-IκB-α(p-IκB-α),and nucleotide-binding oligomerization domain-like receptor family pyrin domain-containing protein 3(NLRP3)were assessed via western blots.Immunohistochemistry detected hippocampal expression of ionized calcium-binding adapter molecule 1(Iba1)and cluster of differentiation 68(CD68).Results:Multiple DTQND compounds were identified,including stachyose,β-syringin,and isofraxidin,among others.DTQND treatment considerably enhanced spontaneous activity,reduced anxiety,improved spatial working memory,and alleviated sensory gating defects in male offspring with MIA.The DTQND group showed significantly lower serum levels of IL-1β(P=.002)and IL-18(P=.046)than the model group,with no discernible variations in IL-6 or TNF-α levels.In the hippocampus,DTQND significantly suppressed the expression of p-p65(P<.001),p-IκB-α(P=.023),and NLRP3(P<.001)compared to the model group.Additionally,DTQND modulated microglial activation markers,decreasing CD68 expression(P=.004)without affecting Iba1 levels.Conclusions:DTQND alleviated schizophrenia-like behavioral deficits and cognitive impairment by inhibiting the NF-κB/NLRP3 pathway,supporting its potential as an alternative therapy for schizophrenia.展开更多
This study focused on improving the activation property and cycling stability of V78Ti6Cr16 alloy through trace Ce doping.V78Ti6Cr16Cex(x=0,0.2,0.4)alloys were prepared by arc melting.The activati...This study focused on improving the activation property and cycling stability of V78Ti6Cr16 alloy through trace Ce doping.V78Ti6Cr16Cex(x=0,0.2,0.4)alloys were prepared by arc melting.The activation property,the kinetic and thermodynamic properties,the cycling stability and the cycling stability mechanism of the prepared alloys were investigated.The results show that trace Ce doping significantly improves the activation performance of the alloy.The kinetics changed little and the thermodynamics changed a little by trace Ce doping.Crucially,trace Ce doping remarkably improved cycling stability of the alloy.V78Ti6Cr16Ce0.2exhibited a capacity retention rate of 97.43% after 400 cycles,substantially higher than the 93.06% of undoped alloy.Even after 1000 cycles,V78Ti6Cr16Ce0.2maintained higher than 90% retention,demonstrating excellent cycling stability for practical applications.X-ray diffraction and compressing test reveal that Ce doping effectively improves the crystal structure of the alloys by increasing the cell volume and enhancing the mechanical properties of the alloy,thereby improving the structure stability of the alloy during cycling.Transmission electron microscope analysis indicated that the defect density progressively increases with cycling in undoped alloy,which is the main reason for the capacity decay.But the defect density is much less in V78Ti6Cr16Ce0.2alloy compared with undoped alloy,which contributes to its superior capacity retention rate.This work provides a new strategy for enhancing hydrogen storage properties via trace rare-earth doping.展开更多
Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C3N4)presents a promising and environmentally friendly approach.However,pristine g-...Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C3N4)presents a promising and environmentally friendly approach.However,pristine g-C3N4 suffers from limited visible-light absorption and low charge-carrier mobility.In this study,a phosphorus-doped tubular carbon nitride(5P-TCN)was synthesized via a precursor self-assembly method using phosphoric acid and melamine as raw materials,eliminating the need for organic solvents or templates.The 5P-TCN catalyst demonstrated enhanced visible-light absorption,improved charge transfer capability,and a 5.25-fold increase in specific surface area(31.092 m2/g),which provided abundant active sites to efficiently drive the PMS-assisted photocatalytic reaction.The 5P-TCN/vis/PMS system exhibited exceptional degradation performance for organic pollutants across a broad pH range(3–9),achieving over 92%degradation of Rhodamine B(RhB)within 15 min.Notably,the system retained>98%RhB degradation efficiency after three consecutive operational cycles,demonstrating robust operational stability and reusability.Moreover,key parameters influencing,active radi-cals,degradation pathways,and potential mechanisms for RhB degradation were systematically investigated.This work proposes a green and cost-effective strategy for developing high-efficiency photocatalysts,while demon-strating the exceptional capability of a PMS-assisted photocatalytic system for rapid degradation of RhB.展开更多
Machine learning(ML)is recognized as a potent tool for the inverse design of environmental functional material,particularly for complex entities like biochar-based catalysts(BCs).Thus,the tailored BCs can have a disti...Machine learning(ML)is recognized as a potent tool for the inverse design of environmental functional material,particularly for complex entities like biochar-based catalysts(BCs).Thus,the tailored BCs can have a distinct ability to trigger the nonradical pathway in advance oxidation processes(AOPs),promising a stable,rapid and selective degradation of persistent contaminants.However,due to the inherent“black box”nature and limitations of input features,results and conclusions derived from ML may not always be intuitively understood or comprehensively validated.To tackle this challenge,we linked the front-point interpretable analysis approaches with back-point density functional theory(DFT)calculations to form a chained learning strategy for deeper sight into the intrinsic activation mechanism of BCs in AOPs.At the front point,we conducted an easy-to-interpret meta-analysis to validate two strategies for enhancing nonradical pathways by increasing oxygen content and specific surface area(SSA),and prepared oxidized biochar(OBC500)and SSA-increased biochar(SBC900)by controlling pyrolysis conditions and modification methods.Subsequently,experimental results showed that OBC500 and SBC900 had distinct dominant degradation pathways for 1O2 generation and electron transfer,respectively.Finally,at the end point,DFT calculations revealed their active sites and degradation mechanisms.This chained learning strategy elucidates fundamental principles for BC inverse design and showcases the exceptional capacity to integrate computational techniques to accelerate catalyst inverse design.展开更多
The formation of peptide bonds is a crucial step in peptide synthesis and their long-term application across diverse fields.Therefore,identifying effective coupling reagents to activate carboxylic and amino acids rema...The formation of peptide bonds is a crucial step in peptide synthesis and their long-term application across diverse fields.Therefore,identifying effective coupling reagents to activate carboxylic and amino acids remains a central objective in peptide chemistry[1].Significant efforts have led to the discovery of numerous coupling agents,including both single-component and combined reagent systems.However,challenges such as high cost,limited commercial availability,un-desired racemization/epimerization,and potential safety hazards continue to hinder ideal peptide synthesis[2].展开更多
The adsorption of PMS and the associated transfer of photogenerated carriers are prerequisites for photo-Fenton activation.In this work,we constructed an S-scheme Vo-ZF@TCN heterojunction with the characteristics of i...The adsorption of PMS and the associated transfer of photogenerated carriers are prerequisites for photo-Fenton activation.In this work,we constructed an S-scheme Vo-ZF@TCN heterojunction with the characteristics of interlayer and in-plane multi-level built-in electric fields(BIEF).It was found that the BIEF amplitude of the in-plane heterojunction was~2.7 times that of a traditional heterojunction.The strong BIEF promotes the directional,rapid,and efficient transfer of photogenerated charge carriers,enabling the photostimulated synergistic activation of PMS for the degradation of organic pollutants.The rational design of redox ends promotes the formation of electron-deficient Vo-Fe,which creates Lewis acid adsorption sites.This design constructs a composite site for PMS adsorption and carrier transfer.We elucidated that the directional migration of electrons and holes causes the spatial separation of PMS radical and non-radical activation sites,regulating the activation pathways by altering the migration direction of PMS through adsorption.This study provides new insights into the regulation of PMS activation pathways and enriches the design strategies for efficient photogenerated carrier transport and transfer.展开更多
Rationale:This case report describes a couple with recurrent fertilization failure despite undergoing multiple cycles of intracytoplasmic sperm injection(ICSI).The principal clinical concern was suspected oocyte activ...Rationale:This case report describes a couple with recurrent fertilization failure despite undergoing multiple cycles of intracytoplasmic sperm injection(ICSI).The principal clinical concern was suspected oocyte activation deficiency(OAD),in which fertilization is impeded due to the oocyte’s inability to initiate embryogenesis,commonly attributed to inadequate intracellular calcium(Ca2+)release following sperm injection.Patient concerns:The couple repeatedly experienced complete or near-complete fertilization failure in previous ICSI cycles,raising suspicion of an underlying oocyte activation defect.Diagnosis:Based on the repeated absence of fertilization post-ICSI and clinical history,a diagnosis of suspected OAD leading to recurrent ICSI fertilization failure was considered.Interventions:Artificial oocyte activation(AOA)using the calcium ionophore A23187 was performed.After ICSI,unfertilized oocytes were exposed to the ionophore to induce Ca2+influx,simulating physiological calcium oscillations essential for oocyte activation.The efficacy of intervention was evaluated through subsequent embryonic development,morphological grading,and chromosomal integrity.Outcomes:Following AOA treatment,successful oocyte activation occurred,resulting in the formation of high-grade embryos with normal developmental progression.Chromosomal analysis revealed no detectable abnormalities,indicating genomic stability.Lessons:Calcium ionophore–mediated AOA may serve as an effective adjunct in cases of recurrent ICSI failure attributed to OAD.This case highlights the importance of individualized therapeutic strategies in assisted reproduction;however,further research is needed to refine protocols,validate broader clinical efficacy,and assess long-term safety,including potential epigenetic risks.展开更多
In situ chemical oxidation(ISCO)technology using peroxymonosulfate(PMS)and natural iron-bearing minerals for groundwater remediation has received increasing interest.The interaction between PMS and active Fe sites in ...In situ chemical oxidation(ISCO)technology using peroxymonosulfate(PMS)and natural iron-bearing minerals for groundwater remediation has received increasing interest.The interaction between PMS and active Fe sites in minerals significantly influences the effectiveness of groundwater remediation.Nevertheless,there has been limited research investigating the relationship between the minerals active Fe sites and PMS activation.Herein,we distinguished and quantified the active Fe sites of common natural iron-bearing minerals in groundwater aquifers.Lewis acid sites(Fe-OH)were confirmed as the reaction sites in iron oxide/hydroxide/bearing clay minerals.The activation performance of minerals is positively correlated with their Lewis acid content.In iron sulfide minerals,Fe-S sites act as electron transfer mediators,facilitating PMS adsorption and activation.The activation of PMS by Lewis acid and Fe-S sites free radical both led to the generation of free radicals(SO4·-and·OH)for CPs removal.Moreover,typical ferrihydrite/PMS and pyrite/PMS systems exhibited resistance to environmental interference and broad pH adaptability.A one-dimensional sand column experiment further proved their feasibility and long-term applicability in saturated porous media.These findings highlight the critical influence of active Fe sites of natural iron-bearing minerals and provide technical support for the application of PMS-ISCO strategies for groundwater remediation.展开更多
The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasoni...The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasonic-driven catalytic ozonation system with dynamically reconstructed CuO/Cu2O heterointerfaces,achieving unprecedented efficiency in extreme alkaline wastewater treatment.Atomic-scale interface engineering endows the catalyst with hydrophilicity(contact angle:6.1°)and 3.8–4.3 times higher oxygen vacancy density compared to single-phase catalysts.These properties facilitate efficient interfacial interactions with Bayer liquor and enable superior ozone activation through synergistic Cu(I)/Cu(II)redox cycling across the heterointerface.This interfacial synergy reduces ozone adsorption energy from 5.46 eV(Cu2O)to 1.48 eV,driving the generation of reactive oxygen species(ROS)via low-energy pathways.Under optimized conditions,the system achieves 57.82%TOC removal within 1.5 h with 2.3-fold faster kinetics than ozone–alone processes,while improving energy efficiency by 1.82–3.22 times per kWh over conventional thermal oxidation.Remarkable stability is demonstrated through 80.21%activity retention after 6 cycles,attributed to surface energy minimization(0.61 J m−2),alongside 67.91%hydroxyl radical(•OH)-mediated degradation confirmed by quenching tests.In XPS,EEMs analysis,and ECOSAR modeling further elucidate the surface reconstruction mechanism and intermediate toxicity reduction.This work establishes an atomic interface design paradigm that bridges catalytic innovation with green metallurgy applications,offering a sustainable solution for industrial wastewater remediation aligned with circular economy principles.展开更多
Photocatalytic oxidative dehydrogenation of biomass feedstocks offers the possibility for synthesizing value-added chemicals,but the sluggish transport kinetics and rapid recombination of photogenerated charge carrier...Photocatalytic oxidative dehydrogenation of biomass feedstocks offers the possibility for synthesizing value-added chemicals,but the sluggish transport kinetics and rapid recombination of photogenerated charge carriers constrain photocatalysis efficiency.Spin-polarized photocatalysts,by accelerating the separation of photogenerated electrons and holes,offer a promising strategy for selective biomass valorization.Herein,polarization unit Mo was incorporated into ZnIn2S4(ZIS)with S-vacancy through Mo-S4coordination(Mo-Vs-ZIS)to enhance hole and proton-coupled electron transfer(PCET).Mo-Vs-ZIS spin polarized photocatalyst applied to 5-hydroxymethylfurfural(HMF)afforded a 2,5-diformylfuran(DFF)selectivity of 92.3%at a production rate of 1105.3μmol gcat-1h-1,attributed to carrier transport and reaction processes.The Mo-Vs-ZIS photocatalyst efficiently(100 min)converted benzyl and furfuryl alcohols,aromatic alcohols bearing electron-rich substituents,and halogen-substituted aromatic alcohols into their corresponding aldehydes.Piezoelectric force microscopy(PFM)and Kelvin probe force microscopy analyses(KPFM)revealed that the full-space polarized electric field was formed to drive directional transfer of photogenerated carriers,facilitating bulk-to-surface charge separation.Moreover,Mo-Vs-ZIS showed high Bader charge transfer to O2,where Mo atomic sites functioned as an electron reservoir,driving the activation of O2to form•O2,a kinetically favorable step for HMF oxidation and induced transfer of holes to activate C(sp3)-H bonds,which is a rate-determining step.Then,the critical step of PCET(O2+H+→•OOH)over Mo-Vs-ZIS gave•OOH for O-H activation to complete the reaction sequence.This spin-polarized modification strategy featuring atomic-level catalytic sites enables its application to other semiconductor photocatalysts for biomass conversion.展开更多
In deep mining,fault activation poses a significantsafety risk due to the sudden release of stored energy.Faults capable of accumulating energy often contain heterogeneous,high-shear-strength anti-slip structures that...In deep mining,fault activation poses a significantsafety risk due to the sudden release of stored energy.Faults capable of accumulating energy often contain heterogeneous,high-shear-strength anti-slip structures that markedly alter stress transfer and slip behavior.Consequently,their activation and destabilization mechanisms differ substantially from traditional fault models.This study identifies common types of anti-slip structures through comprehensive investigation and analysis,establishes a novel fault model,and explores the relationships among structure failure,strain energy accumulation,and fault activation using combined theoretical and experimental approaches.Physical similarity simulations were conducted to analyze variations in fault slip,normal stress,shear stress,and activation degree in faults with and without anti-slip structures.Complementary three-dimensional numerical simulations further elucidated the evolution of maximum shear stress and strain energy accumulation during mining.The results show that faults with anti-slip structures initially experience reduced slippage and enhanced stability,but progressive failure of anti-slip segments leads to large-scale fault sliding.Stress concentration occurs in fault zones containing anti-slip structures,which reduce the advance abutment pressure ahead of the longwall face.In contrast,models without such structures show higher stress concentration and greater energy accumulation ahead of the face.In models with anti-slip structures,peak strain energy mainly accumulates at the structure-fault interface,indicating stronger energy storage capacity and higher instability potential.These findingsprovide new insights into dynamic hazards associated with fault activation and establish a basis for predictive modeling and risk mitigation in deep mining.展开更多
Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt ...Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt oxyhydroxide @covalent organic frameworks(CoOOH@COFs) S-scheme heterojunction was synthesized,which combined the visible-light-driven photocatalysis and peroxymonosulfate(PMS) activation to synergistically generate abundant reactive oxygen species(ROSs) for TCS degradation.The degradation efficiency of TCS reached 100 % within 8 min in the Vis-CoOOH@COFs/PMS system,and the reaction rate constant was 0.456 min-1,which was nearly 1.90 and 2.85 times that of single Co OOH and COFs,and2.36 times that under dark condition,respectively.The density functional theory(DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to Co OOH.Both experimental and theoretical analyses indicated that Co OOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation,enhanced interfacial electron transfer,accelerated PMS activation,and generated multiple ROSs.In particular,photogenerated electrons(e-)accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle,while the PMS captured the e-,which significantly decreased the charge combination of Co OOH@COFs.Radicals(O2·-,·OH,and SO4·-) and non-radicals(such as 1O2,h+,and e-) were both presented in the Vis-CoOOH@COFs/PMS system,with O2- playing a dominant role in TCS degradation.Furthermore,the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification.Importantly,the environmentally friendly CoOOH@COFs S-scheme heterojunction exhibited excellent stability and reusability.In conclusion,this study innovatively designed an S-scheme heterojunction in the photocatalytic-PMS activation system,providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.展开更多
Co based materials or peroxymonosulfate(PMS)are regarded as promising catalysts in pollutants control due to their good performance for PMS activation.Herein,a novel composite catalyst Co@POM with highly efficient act...Co based materials or peroxymonosulfate(PMS)are regarded as promising catalysts in pollutants control due to their good performance for PMS activation.Herein,a novel composite catalyst Co@POM with highly efficient active sites was synthesized via hydrothermal method,and was systematically characterized using XRD,SEM,XPS,IR,BET and TG/DTG analyses.The prepared composite was used as PMS activator for the tetracycline(TC)degradation.Effects of PMS concentration,Co@POM dosage,TC concentration,pH,temperature and anions on degradation performances were investigated systematically.The system exhibited a high TC degradation efficiency of 98.1%,with robust performance across a broad pH range and in various water matrices.Quenching experiments and EPR spectroscopy illustrated that reactive species including singlet oxygen(1O2),and superoxide radicals(O2·-)played main roles in the degradation of electron-rich TC molecules.The catalyst maintained more than 90% degradation efficiency after four cycles without any change in structural properties.The renewable active sites of Co@POM and the activation mechanism of PMS in the Co@POM/PMS system were elucidated.Overall,the present work advances the design of PMS-activating catalysts by integrating POM with transition metals,offering a scalable,eco-friendly alternative for the treatment of antibiotic-contaminated wastewater.展开更多
Catalytic hydrogenolysis offers a promising route for plastic waste upcycling.Herein,we demonstrate that oxygen vacancies(OV)in CeO2supports dramatically enhanced this process.Reduction-engineered Ru/CeO2-NH_...Catalytic hydrogenolysis offers a promising route for plastic waste upcycling.Herein,we demonstrate that oxygen vacancies(OV)in CeO2supports dramatically enhanced this process.Reduction-engineered Ru/CeO2-NH3-800 exhibits 40%higher activity at 800℃than untreated counterparts.Comprehensive characterization revealed unchanged Ru metal sites after treatment,but significantly increased oxygen vacancy content in the CeO2support.Isotopic C6-D2temperature-programmed surface reaction studies revealed that higher OVconcentrations correlate with lower C-H bond activation temperatures,directly aligning with observed activity trends.We propose a novel Ru-Ce interfacial mechanism:OV-adjacent Ce3+-O sites activate C-H bonds to form*RCCR*intermediates,while dual Ru sites cleave C-C bonds via C-Ru coordination.This work establishes an OV-driven structure-activity relationship for the first time and reveals support-mediated C-H activation as crucial for advanced catalyst design.展开更多
This study developed a monolithic Co3S4/FeOOH nanoflower(NF)-like catalyst through impregnation-boiling and mild hydrothermal methods(120°C,3 h),overcoming the drawbacks of both conventional ex-situ loading...This study developed a monolithic Co3S4/FeOOH nanoflower(NF)-like catalyst through impregnation-boiling and mild hydrothermal methods(120°C,3 h),overcoming the drawbacks of both conventional ex-situ loading techniques(uneven distribution)and powdered catalysts(difficult separation).The in-situ grown nanoflower-like Co3S4/FeOOH composite on NF demonstrated superior peroxymonosulfate(PMS)activation,achieving 87.74%norfloxacin(NOR)removal under optimized conditions(1 cm2catalyst loading with 0.2 g CoCl2·6H2O precursor,0.3 g/L PMS dose,initial pH 6.3),representing around 11-fold and 1.8-fold higher degradation rates than single-component FeOOH/NF and Co3S4/NF,respectively.Mechanistic insights of such performance enhancement revealed by electrochemical analysis and Density functional theory(DFT)calculations.Quenching experiments and Electron paramagnetic resonance(EPR)analysis confirmed the coexistence of synergistic pathways involving radical species(SO4•−)and non-radical processes((1)^O2and electron transfer).The Co3S4/FeOOH/NF&PMS system retains 84.73%NOR degradation after 3 cycles with stable morphology,while achieving broad-spectrum antibiotic removal(83.69%–99.88%).Fluorescence analysis confirms almost complete mineralization of recalcitrant humic substances from the real hospital wastewater within 40 min.展开更多
Multidrug-resistant bacterial infections are increasing globally and posing a greater threat to human health.The application of direct bactericidal agents can induce secondary infections and treatment failures.The ant...Multidrug-resistant bacterial infections are increasing globally and posing a greater threat to human health.The application of direct bactericidal agents can induce secondary infections and treatment failures.The antibacterial strategy of the innate immune system brings inspiration.Here,we developed highly stable bacterial-aggregating peptides with immunoregulatory function.These peptides were designed to capture multidrug-resistant bacteria,prevent their dissemination,and activate the antibacterial immune response of the host.Among these peptides,the central-bola amphiphile R2F4R2 highly captured bacteria without directly killing them.R2F4R2 was believed to self-assemble through the lateral connection of peptide chains.The tetra-Phe segments formed a hydrophobic core of nanoparticle,with Arg residues appearing on the surface.Notably,R2F4R2 enhanced chemotactic response and phagocytic ability of macrophages,supported a transition to M2-macrophage phenotype to combat bacterial infection.Transcriptome sequencing and molecular docking analyses revealed that R2F4R2 regulated the gene expression associated with immunoregulatory functions and modulated calcium-Rap1 signaling pathways.Finally,R2F4R2 exhibited exceptional stability against proteolytic degradation and effectively entrapped invading pathogenic bacteria Escherichia coli to alleviate skin infections and intestinal inflammation.Overall,the bacterial-aggregating peptides represent a novel and effective strategy to combat multidrug-resistant infections.展开更多
The spin-forbidden effect and high bond energy of molecular oxygen(O2)pose a fundamental challenge for its activation in wastewater treatment.We address this by constructing an atomically dispersed Fe-Mn dual-site ...The spin-forbidden effect and high bond energy of molecular oxygen(O2)pose a fundamental challenge for its activation in wastewater treatment.We address this by constructing an atomically dispersed Fe-Mn dual-site catalyst(Fe0.1-Mn-350),which overcomes the sluggish O2kinetics of monometallic oxides and the aqueous instability of conventional single-atom catalysts.This catalyst enables complete degradation of 20 mg/L parachlormetaxylenol(PCMX)within 15 minutes,with a reaction rate(O.2205 min-1)25 times greater than MnO2and surpassing benchmark catalysts.Experimental and theoretical analyses reveal that the preferential side-on O2adsorption at Fe sites of Fe0.1-Mn-350 significantly reduces activation barriers by 38%(versus Fe-CNTs by 15%,Co-MnO2by 25%),and triggers a dual-pathway mechanism involving both radical(·OH,O2·-)and non-radical(1O2,Fe(IV))species.Crucially,the Fe0.1-Mn-350/O2system demonstrates robust practicality,maintaining 98%efficiency in real hospital wastewater,stable operation in a 12-h continuous-flow reactor,and a low operational cost of 0.28 USD/m3.The technology's environmental sustainability is further validated by a remarkable 8o%recovery of zebrafish embryo hatchability and a 93%reduction in developmental toxicity.This work provides a green and economically viable strategy for the destructive treatment of persistent halogenated contaminants in water.展开更多
Activation of spinal cord neural stem cells(NSCs)and subsequent neurogenesis holds a promising alternative for spinal cord injury(SCI)repair.Our previous study demonstrated that complement C3a,derived from reactive as...Activation of spinal cord neural stem cells(NSCs)and subsequent neurogenesis holds a promising alternative for spinal cord injury(SCI)repair.Our previous study demonstrated that complement C3a,derived from reactive astrocytes,inhibits NSC proliferation by suppressing protein aggregate clearance through the deubiquitinating enzyme ubiquitin carboxy-terminal hydrolase L1(UCHL1)-proteasome system post-SCI.However,the potential molecular mechanism by which C3a modulates NSC activation via this pathway remains unclear.Here,we revealed that C3a/C3a receptor(C3aR)signaling activated NF-κB p65,which in turn inhibited Nrf2 activity and UCHL1 expression,resulting in diminished proteasome activity and the accumulation of protein aggregates,and ultimately impaired NSC activation.Both knockdown of NF-κB p65 and Nrf2 upregulation restored UCHL1 expression and proteasome activity in vitro,promoting NSC activation by enhancing protein aggregate clearance.Mechanistically,we found that NF-κB p65 regulated Nrf2 activity through a dual mechanism:(1)promoting Keap1-dependent ubiquitination and proteasome degradation of Nrf2;(2)inhibiting protein kinase C-mediated Nrf2 phosphorylation and nuclear translocation.Using the dual-luciferase reporter assay and chromatin immunoprecipitation(ChIP)analysis,we further identified UCHL1 as a direct transcriptional target of Nrf2.Importantly,in vivo experiments using SCI mice confirmed that either C3aR blockade,NF-κB p65 knockdown,or Nrf2 overexpression could rescue SCI-induced UCHL1 downregulation.Together,this study uncovers the C3a-NF-κB p65-Nrf2-UCHL1-proteasome axis as a critical regulator of NSC activation after SCI.This may provide novel molecular targets and intervention strategies for SCI repair.展开更多
Peptides play important roles in chemistry,medicinal chemistry and life science,due to their high efficiency and specificity,unusual biological and therapeutic properties.As naturally occurring peptides often face wit...Peptides play important roles in chemistry,medicinal chemistry and life science,due to their high efficiency and specificity,unusual biological and therapeutic properties.As naturally occurring peptides often face with their intrinsic limitations including metabolic instability and low membrane permeability,the strategies for synthesizing unnatural amino acids and peptides are explored.Among the methods for modifying amino acids and peptides,chemo-and site-selective approaches are preferred because of the ability to fine-tuning structural features.Recently,transition metal-catalyzed C–H activation has been employed for the functionalization of amino acids and peptides.Through domino C–H activation/annulation,a series of structurally complex and diverse amino acids and peptides is constructed.This review highlights recent advances in the synthesis of unnatural amino acids and peptides via transition metal-catalyzed C–H activation/annulation.展开更多
For achieving high-power and low-platinum direct methanol fuel cell(DMFC)under proton-exchange-membrane,we introduce the oxidation-state ruthenium species as H2O-activation centers stabilized on PtZn NPs to boost m...For achieving high-power and low-platinum direct methanol fuel cell(DMFC)under proton-exchange-membrane,we introduce the oxidation-state ruthenium species as H2O-activation centers stabilized on PtZn NPs to boost methanol-oxidation reaction(MOR).The Zn-regulated Ru centers,approaching bivalent states,enhance interfacial H2O-capture/dissociation and OH-transfer,enabling rapid CO*removal from adjacent Pt sites.It exhibits an outstanding mass activity of MOR at 2.71 A mgPt-1 and powers a DMFC with 191.2 mW cm-2 peak density(382.4 W gPt-1)while maintaining 125-hour stability,higher than documented results to date,essentially different from traditional alloy catalysts.Combined ab initio molecular dynamics simulations and in-situ spectroscopy reveal a dense O-down water network around Ru centers,where intermediate RuO(OH)2 structure significantly deceases the H2O-dissociation barrier.Kinetic isotope effect tests(CH3OH/H2O vs.D2O)show J H2O/D2O=4.2 for RuOx-PtZn/C at 0.85 VRHE,versus 16.2 for RuOx-Pt/C,directly confirming superior water activation efficiency of RuOx-PtZn/C.We envision that the comprehensive understanding of high-performance MOR on RuOx-PtZn/C through experimental-theoretical approaches will contribute to the practical application of DMFC as early as possible.展开更多
基金supported by the Beijing Natural Science Foundation(7222274)the Fifth Batch of National Outstanding Talents in Clinical Chinese Medicine(20221)。
摘要Objective:To investigate the efficacy and mechanism of Ditan Qingnao decoction(DTQND)in alleviating schizophrenia-like symptoms in a maternal immune activation(MIA)-induced rat model.Methods:DTQND components were analyzed using high-performance liquid chromatography-tandem mass spectrometry.An MIA-induced rat model was established by injecting Poly Ⅰ:C into pregnant dams on gestational day 9.Male offspring were administered DTQND(14.1 g/kg),risperidone(RIS;0.4 mg/kg),or distilled water,while the controls received only distilled water via gavage for 4 weeks.Behavioral assessments were conducted using the open-field,Y-maze,prepulse inhibition,and sucrose preference tests.Serum levels of interleukin(IL)-6,IL-18,IL-1β,and tumor necrosis factor-α(TNF-α)were measured via an enzyme-linked immunosorbent assay.Hippocampal protein levels of nuclear factor kappa B p65(NF-κB p65),phospho-NF-κB p65(p-p65),inhibitor of kappa B-alpha(IκB-α),phospho-IκB-α(p-IκB-α),and nucleotide-binding oligomerization domain-like receptor family pyrin domain-containing protein 3(NLRP3)were assessed via western blots.Immunohistochemistry detected hippocampal expression of ionized calcium-binding adapter molecule 1(Iba1)and cluster of differentiation 68(CD68).Results:Multiple DTQND compounds were identified,including stachyose,β-syringin,and isofraxidin,among others.DTQND treatment considerably enhanced spontaneous activity,reduced anxiety,improved spatial working memory,and alleviated sensory gating defects in male offspring with MIA.The DTQND group showed significantly lower serum levels of IL-1β(P=.002)and IL-18(P=.046)than the model group,with no discernible variations in IL-6 or TNF-α levels.In the hippocampus,DTQND significantly suppressed the expression of p-p65(P<.001),p-IκB-α(P=.023),and NLRP3(P<.001)compared to the model group.Additionally,DTQND modulated microglial activation markers,decreasing CD68 expression(P=.004)without affecting Iba1 levels.Conclusions:DTQND alleviated schizophrenia-like behavioral deficits and cognitive impairment by inhibiting the NF-κB/NLRP3 pathway,supporting its potential as an alternative therapy for schizophrenia.
基金supported by National Key R&D Program of China(No.2022YFB3504701)Independent and Open Research Project of State Key Laboratory of Advanced Special Steel,Shanghai Key Laboratory of Advanced Ferrometallurgy,Shanghai University(Nos.SKLASS 2023–01 and SKLASS 2023-Z02)the Science and Technology Commission of Shanghai Municipality(No.19DZ2270200)。
摘要This study focused on improving the activation property and cycling stability of V78Ti6Cr16 alloy through trace Ce doping.V78Ti6Cr16Cex(x=0,0.2,0.4)alloys were prepared by arc melting.The activation property,the kinetic and thermodynamic properties,the cycling stability and the cycling stability mechanism of the prepared alloys were investigated.The results show that trace Ce doping significantly improves the activation performance of the alloy.The kinetics changed little and the thermodynamics changed a little by trace Ce doping.Crucially,trace Ce doping remarkably improved cycling stability of the alloy.V78Ti6Cr16Ce0.2exhibited a capacity retention rate of 97.43% after 400 cycles,substantially higher than the 93.06% of undoped alloy.Even after 1000 cycles,V78Ti6Cr16Ce0.2maintained higher than 90% retention,demonstrating excellent cycling stability for practical applications.X-ray diffraction and compressing test reveal that Ce doping effectively improves the crystal structure of the alloys by increasing the cell volume and enhancing the mechanical properties of the alloy,thereby improving the structure stability of the alloy during cycling.Transmission electron microscope analysis indicated that the defect density progressively increases with cycling in undoped alloy,which is the main reason for the capacity decay.But the defect density is much less in V78Ti6Cr16Ce0.2alloy compared with undoped alloy,which contributes to its superior capacity retention rate.This work provides a new strategy for enhancing hydrogen storage properties via trace rare-earth doping.
摘要Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C3N4)presents a promising and environmentally friendly approach.However,pristine g-C3N4 suffers from limited visible-light absorption and low charge-carrier mobility.In this study,a phosphorus-doped tubular carbon nitride(5P-TCN)was synthesized via a precursor self-assembly method using phosphoric acid and melamine as raw materials,eliminating the need for organic solvents or templates.The 5P-TCN catalyst demonstrated enhanced visible-light absorption,improved charge transfer capability,and a 5.25-fold increase in specific surface area(31.092 m2/g),which provided abundant active sites to efficiently drive the PMS-assisted photocatalytic reaction.The 5P-TCN/vis/PMS system exhibited exceptional degradation performance for organic pollutants across a broad pH range(3–9),achieving over 92%degradation of Rhodamine B(RhB)within 15 min.Notably,the system retained>98%RhB degradation efficiency after three consecutive operational cycles,demonstrating robust operational stability and reusability.Moreover,key parameters influencing,active radi-cals,degradation pathways,and potential mechanisms for RhB degradation were systematically investigated.This work proposes a green and cost-effective strategy for developing high-efficiency photocatalysts,while demon-strating the exceptional capability of a PMS-assisted photocatalytic system for rapid degradation of RhB.
基金supported by Project of National and Local Joint Engineering Research Center for Biomass Energy Development and Utilization(Harbin Institute of Technology,No.2021A004).
摘要Machine learning(ML)is recognized as a potent tool for the inverse design of environmental functional material,particularly for complex entities like biochar-based catalysts(BCs).Thus,the tailored BCs can have a distinct ability to trigger the nonradical pathway in advance oxidation processes(AOPs),promising a stable,rapid and selective degradation of persistent contaminants.However,due to the inherent“black box”nature and limitations of input features,results and conclusions derived from ML may not always be intuitively understood or comprehensively validated.To tackle this challenge,we linked the front-point interpretable analysis approaches with back-point density functional theory(DFT)calculations to form a chained learning strategy for deeper sight into the intrinsic activation mechanism of BCs in AOPs.At the front point,we conducted an easy-to-interpret meta-analysis to validate two strategies for enhancing nonradical pathways by increasing oxygen content and specific surface area(SSA),and prepared oxidized biochar(OBC500)and SSA-increased biochar(SBC900)by controlling pyrolysis conditions and modification methods.Subsequently,experimental results showed that OBC500 and SBC900 had distinct dominant degradation pathways for 1O2 generation and electron transfer,respectively.Finally,at the end point,DFT calculations revealed their active sites and degradation mechanisms.This chained learning strategy elucidates fundamental principles for BC inverse design and showcases the exceptional capacity to integrate computational techniques to accelerate catalyst inverse design.
摘要The formation of peptide bonds is a crucial step in peptide synthesis and their long-term application across diverse fields.Therefore,identifying effective coupling reagents to activate carboxylic and amino acids remains a central objective in peptide chemistry[1].Significant efforts have led to the discovery of numerous coupling agents,including both single-component and combined reagent systems.However,challenges such as high cost,limited commercial availability,un-desired racemization/epimerization,and potential safety hazards continue to hinder ideal peptide synthesis[2].
基金supported by the National Natural Science Foundation of China(Grant No.22076068,22106053)the Senior Talent Fund of Jiangsu University(23JDG012).
摘要The adsorption of PMS and the associated transfer of photogenerated carriers are prerequisites for photo-Fenton activation.In this work,we constructed an S-scheme Vo-ZF@TCN heterojunction with the characteristics of interlayer and in-plane multi-level built-in electric fields(BIEF).It was found that the BIEF amplitude of the in-plane heterojunction was~2.7 times that of a traditional heterojunction.The strong BIEF promotes the directional,rapid,and efficient transfer of photogenerated charge carriers,enabling the photostimulated synergistic activation of PMS for the degradation of organic pollutants.The rational design of redox ends promotes the formation of electron-deficient Vo-Fe,which creates Lewis acid adsorption sites.This design constructs a composite site for PMS adsorption and carrier transfer.We elucidated that the directional migration of electrons and holes causes the spatial separation of PMS radical and non-radical activation sites,regulating the activation pathways by altering the migration direction of PMS through adsorption.This study provides new insights into the regulation of PMS activation pathways and enriches the design strategies for efficient photogenerated carrier transport and transfer.
摘要Rationale:This case report describes a couple with recurrent fertilization failure despite undergoing multiple cycles of intracytoplasmic sperm injection(ICSI).The principal clinical concern was suspected oocyte activation deficiency(OAD),in which fertilization is impeded due to the oocyte’s inability to initiate embryogenesis,commonly attributed to inadequate intracellular calcium(Ca2+)release following sperm injection.Patient concerns:The couple repeatedly experienced complete or near-complete fertilization failure in previous ICSI cycles,raising suspicion of an underlying oocyte activation defect.Diagnosis:Based on the repeated absence of fertilization post-ICSI and clinical history,a diagnosis of suspected OAD leading to recurrent ICSI fertilization failure was considered.Interventions:Artificial oocyte activation(AOA)using the calcium ionophore A23187 was performed.After ICSI,unfertilized oocytes were exposed to the ionophore to induce Ca2+influx,simulating physiological calcium oscillations essential for oocyte activation.The efficacy of intervention was evaluated through subsequent embryonic development,morphological grading,and chromosomal integrity.Outcomes:Following AOA treatment,successful oocyte activation occurred,resulting in the formation of high-grade embryos with normal developmental progression.Chromosomal analysis revealed no detectable abnormalities,indicating genomic stability.Lessons:Calcium ionophore–mediated AOA may serve as an effective adjunct in cases of recurrent ICSI failure attributed to OAD.This case highlights the importance of individualized therapeutic strategies in assisted reproduction;however,further research is needed to refine protocols,validate broader clinical efficacy,and assess long-term safety,including potential epigenetic risks.
基金supported by the National Natural Science Foundation of China(No.U22A20591)the National Key Research and Development Program of China(No.2024YFC3712700)the Research Fund of State Key Laboratory of Geohazard Prevention and Geoenvironment Protection(No.SKLGP2020Z002)。
摘要In situ chemical oxidation(ISCO)technology using peroxymonosulfate(PMS)and natural iron-bearing minerals for groundwater remediation has received increasing interest.The interaction between PMS and active Fe sites in minerals significantly influences the effectiveness of groundwater remediation.Nevertheless,there has been limited research investigating the relationship between the minerals active Fe sites and PMS activation.Herein,we distinguished and quantified the active Fe sites of common natural iron-bearing minerals in groundwater aquifers.Lewis acid sites(Fe-OH)were confirmed as the reaction sites in iron oxide/hydroxide/bearing clay minerals.The activation performance of minerals is positively correlated with their Lewis acid content.In iron sulfide minerals,Fe-S sites act as electron transfer mediators,facilitating PMS adsorption and activation.The activation of PMS by Lewis acid and Fe-S sites free radical both led to the generation of free radicals(SO4·-and·OH)for CPs removal.Moreover,typical ferrihydrite/PMS and pyrite/PMS systems exhibited resistance to environmental interference and broad pH adaptability.A one-dimensional sand column experiment further proved their feasibility and long-term applicability in saturated porous media.These findings highlight the critical influence of active Fe sites of natural iron-bearing minerals and provide technical support for the application of PMS-ISCO strategies for groundwater remediation.
基金supported by Yunnan Major Scientific and Technological Projects (Grant No. 202402AB080004)Yunnan Provincial Education Department Universities Serve Key Industry Science and Technology Projects (Grant No: FWCY-BSPY2024043)+1 种基金Top Innovative Talents for Graduate Students of KUST (Grant No: CA24163M116A)Analysis and Testing Fund of KUST (Grant No: 2024P20233102006)
摘要The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasonic-driven catalytic ozonation system with dynamically reconstructed CuO/Cu2O heterointerfaces,achieving unprecedented efficiency in extreme alkaline wastewater treatment.Atomic-scale interface engineering endows the catalyst with hydrophilicity(contact angle:6.1°)and 3.8–4.3 times higher oxygen vacancy density compared to single-phase catalysts.These properties facilitate efficient interfacial interactions with Bayer liquor and enable superior ozone activation through synergistic Cu(I)/Cu(II)redox cycling across the heterointerface.This interfacial synergy reduces ozone adsorption energy from 5.46 eV(Cu2O)to 1.48 eV,driving the generation of reactive oxygen species(ROS)via low-energy pathways.Under optimized conditions,the system achieves 57.82%TOC removal within 1.5 h with 2.3-fold faster kinetics than ozone–alone processes,while improving energy efficiency by 1.82–3.22 times per kWh over conventional thermal oxidation.Remarkable stability is demonstrated through 80.21%activity retention after 6 cycles,attributed to surface energy minimization(0.61 J m−2),alongside 67.91%hydroxyl radical(•OH)-mediated degradation confirmed by quenching tests.In XPS,EEMs analysis,and ECOSAR modeling further elucidate the surface reconstruction mechanism and intermediate toxicity reduction.This work establishes an atomic interface design paradigm that bridges catalytic innovation with green metallurgy applications,offering a sustainable solution for industrial wastewater remediation aligned with circular economy principles.
基金National Natural Science Foundation of China(22578226,22178181 and 22508200)Natural Science Fund of Tianjin(No.25JCZDJC01000)Fundamental Research Funds for the Central Universities(Nankai University,63253204)。
摘要Photocatalytic oxidative dehydrogenation of biomass feedstocks offers the possibility for synthesizing value-added chemicals,but the sluggish transport kinetics and rapid recombination of photogenerated charge carriers constrain photocatalysis efficiency.Spin-polarized photocatalysts,by accelerating the separation of photogenerated electrons and holes,offer a promising strategy for selective biomass valorization.Herein,polarization unit Mo was incorporated into ZnIn2S4(ZIS)with S-vacancy through Mo-S4coordination(Mo-Vs-ZIS)to enhance hole and proton-coupled electron transfer(PCET).Mo-Vs-ZIS spin polarized photocatalyst applied to 5-hydroxymethylfurfural(HMF)afforded a 2,5-diformylfuran(DFF)selectivity of 92.3%at a production rate of 1105.3μmol gcat-1h-1,attributed to carrier transport and reaction processes.The Mo-Vs-ZIS photocatalyst efficiently(100 min)converted benzyl and furfuryl alcohols,aromatic alcohols bearing electron-rich substituents,and halogen-substituted aromatic alcohols into their corresponding aldehydes.Piezoelectric force microscopy(PFM)and Kelvin probe force microscopy analyses(KPFM)revealed that the full-space polarized electric field was formed to drive directional transfer of photogenerated carriers,facilitating bulk-to-surface charge separation.Moreover,Mo-Vs-ZIS showed high Bader charge transfer to O2,where Mo atomic sites functioned as an electron reservoir,driving the activation of O2to form•O2,a kinetically favorable step for HMF oxidation and induced transfer of holes to activate C(sp3)-H bonds,which is a rate-determining step.Then,the critical step of PCET(O2+H+→•OOH)over Mo-Vs-ZIS gave•OOH for O-H activation to complete the reaction sequence.This spin-polarized modification strategy featuring atomic-level catalytic sites enables its application to other semiconductor photocatalysts for biomass conversion.
基金supported by the Research Fund of the National Natural Science Foundation of China(Grant No.51504128)the Research Fund of the State Key Laboratory of Coal Resources and Safe Mining,CUMT(Grant No.YJY-XD-2024-A-016)the Fundamental Research Project of the Educational Department of Liaoning Province,China(Grant No.JYTMS20230793).
摘要In deep mining,fault activation poses a significantsafety risk due to the sudden release of stored energy.Faults capable of accumulating energy often contain heterogeneous,high-shear-strength anti-slip structures that markedly alter stress transfer and slip behavior.Consequently,their activation and destabilization mechanisms differ substantially from traditional fault models.This study identifies common types of anti-slip structures through comprehensive investigation and analysis,establishes a novel fault model,and explores the relationships among structure failure,strain energy accumulation,and fault activation using combined theoretical and experimental approaches.Physical similarity simulations were conducted to analyze variations in fault slip,normal stress,shear stress,and activation degree in faults with and without anti-slip structures.Complementary three-dimensional numerical simulations further elucidated the evolution of maximum shear stress and strain energy accumulation during mining.The results show that faults with anti-slip structures initially experience reduced slippage and enhanced stability,but progressive failure of anti-slip segments leads to large-scale fault sliding.Stress concentration occurs in fault zones containing anti-slip structures,which reduce the advance abutment pressure ahead of the longwall face.In contrast,models without such structures show higher stress concentration and greater energy accumulation ahead of the face.In models with anti-slip structures,peak strain energy mainly accumulates at the structure-fault interface,indicating stronger energy storage capacity and higher instability potential.These findingsprovide new insights into dynamic hazards associated with fault activation and establish a basis for predictive modeling and risk mitigation in deep mining.
摘要Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt oxyhydroxide @covalent organic frameworks(CoOOH@COFs) S-scheme heterojunction was synthesized,which combined the visible-light-driven photocatalysis and peroxymonosulfate(PMS) activation to synergistically generate abundant reactive oxygen species(ROSs) for TCS degradation.The degradation efficiency of TCS reached 100 % within 8 min in the Vis-CoOOH@COFs/PMS system,and the reaction rate constant was 0.456 min-1,which was nearly 1.90 and 2.85 times that of single Co OOH and COFs,and2.36 times that under dark condition,respectively.The density functional theory(DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to Co OOH.Both experimental and theoretical analyses indicated that Co OOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation,enhanced interfacial electron transfer,accelerated PMS activation,and generated multiple ROSs.In particular,photogenerated electrons(e-)accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle,while the PMS captured the e-,which significantly decreased the charge combination of Co OOH@COFs.Radicals(O2·-,·OH,and SO4·-) and non-radicals(such as 1O2,h+,and e-) were both presented in the Vis-CoOOH@COFs/PMS system,with O2- playing a dominant role in TCS degradation.Furthermore,the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification.Importantly,the environmentally friendly CoOOH@COFs S-scheme heterojunction exhibited excellent stability and reusability.In conclusion,this study innovatively designed an S-scheme heterojunction in the photocatalytic-PMS activation system,providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
基金supported by the National Natural Science Foundation of China(No.52166001)the Analytical Testing Fund of Kunming University of Science and Technology(No.2023M20222111092)。
摘要Co based materials or peroxymonosulfate(PMS)are regarded as promising catalysts in pollutants control due to their good performance for PMS activation.Herein,a novel composite catalyst Co@POM with highly efficient active sites was synthesized via hydrothermal method,and was systematically characterized using XRD,SEM,XPS,IR,BET and TG/DTG analyses.The prepared composite was used as PMS activator for the tetracycline(TC)degradation.Effects of PMS concentration,Co@POM dosage,TC concentration,pH,temperature and anions on degradation performances were investigated systematically.The system exhibited a high TC degradation efficiency of 98.1%,with robust performance across a broad pH range and in various water matrices.Quenching experiments and EPR spectroscopy illustrated that reactive species including singlet oxygen(1O2),and superoxide radicals(O2·-)played main roles in the degradation of electron-rich TC molecules.The catalyst maintained more than 90% degradation efficiency after four cycles without any change in structural properties.The renewable active sites of Co@POM and the activation mechanism of PMS in the Co@POM/PMS system were elucidated.Overall,the present work advances the design of PMS-activating catalysts by integrating POM with transition metals,offering a scalable,eco-friendly alternative for the treatment of antibiotic-contaminated wastewater.
摘要Catalytic hydrogenolysis offers a promising route for plastic waste upcycling.Herein,we demonstrate that oxygen vacancies(OV)in CeO2supports dramatically enhanced this process.Reduction-engineered Ru/CeO2-NH3-800 exhibits 40%higher activity at 800℃than untreated counterparts.Comprehensive characterization revealed unchanged Ru metal sites after treatment,but significantly increased oxygen vacancy content in the CeO2support.Isotopic C6-D2temperature-programmed surface reaction studies revealed that higher OVconcentrations correlate with lower C-H bond activation temperatures,directly aligning with observed activity trends.We propose a novel Ru-Ce interfacial mechanism:OV-adjacent Ce3+-O sites activate C-H bonds to form*RCCR*intermediates,while dual Ru sites cleave C-C bonds via C-Ru coordination.This work establishes an OV-driven structure-activity relationship for the first time and reveals support-mediated C-H activation as crucial for advanced catalyst design.
基金supported by the Key Research and Development Program Project of Gansu Province,China(No.25YFFA003)the Youth Science and Technology Talent Innovation Project of Lanzhou City,China(No.2023-QN-80)the Fundamental Research Funds for the Central Universities,China(No.lzujbky-2023-ey14).
摘要This study developed a monolithic Co3S4/FeOOH nanoflower(NF)-like catalyst through impregnation-boiling and mild hydrothermal methods(120°C,3 h),overcoming the drawbacks of both conventional ex-situ loading techniques(uneven distribution)and powdered catalysts(difficult separation).The in-situ grown nanoflower-like Co3S4/FeOOH composite on NF demonstrated superior peroxymonosulfate(PMS)activation,achieving 87.74%norfloxacin(NOR)removal under optimized conditions(1 cm2catalyst loading with 0.2 g CoCl2·6H2O precursor,0.3 g/L PMS dose,initial pH 6.3),representing around 11-fold and 1.8-fold higher degradation rates than single-component FeOOH/NF and Co3S4/NF,respectively.Mechanistic insights of such performance enhancement revealed by electrochemical analysis and Density functional theory(DFT)calculations.Quenching experiments and Electron paramagnetic resonance(EPR)analysis confirmed the coexistence of synergistic pathways involving radical species(SO4•−)and non-radical processes((1)^O2and electron transfer).The Co3S4/FeOOH/NF&PMS system retains 84.73%NOR degradation after 3 cycles with stable morphology,while achieving broad-spectrum antibiotic removal(83.69%–99.88%).Fluorescence analysis confirms almost complete mineralization of recalcitrant humic substances from the real hospital wastewater within 40 min.
基金supported by the National Natural Science Foundation of China(32472956)Heilongjiang Provincial Natural Science Foundation of China(BS2025C007)+1 种基金China Postdoctoral Science Foundation(2021M690576,2024T170116)Heilongjiang Postdoctoral Science Foundation(LBHZ21003 and LBH-TZ2305).
摘要Multidrug-resistant bacterial infections are increasing globally and posing a greater threat to human health.The application of direct bactericidal agents can induce secondary infections and treatment failures.The antibacterial strategy of the innate immune system brings inspiration.Here,we developed highly stable bacterial-aggregating peptides with immunoregulatory function.These peptides were designed to capture multidrug-resistant bacteria,prevent their dissemination,and activate the antibacterial immune response of the host.Among these peptides,the central-bola amphiphile R2F4R2 highly captured bacteria without directly killing them.R2F4R2 was believed to self-assemble through the lateral connection of peptide chains.The tetra-Phe segments formed a hydrophobic core of nanoparticle,with Arg residues appearing on the surface.Notably,R2F4R2 enhanced chemotactic response and phagocytic ability of macrophages,supported a transition to M2-macrophage phenotype to combat bacterial infection.Transcriptome sequencing and molecular docking analyses revealed that R2F4R2 regulated the gene expression associated with immunoregulatory functions and modulated calcium-Rap1 signaling pathways.Finally,R2F4R2 exhibited exceptional stability against proteolytic degradation and effectively entrapped invading pathogenic bacteria Escherichia coli to alleviate skin infections and intestinal inflammation.Overall,the bacterial-aggregating peptides represent a novel and effective strategy to combat multidrug-resistant infections.
基金supported by the National Natural Science Foundation of China(No.52370168)the Jiangxi Provincial Natural Science Foundation,China(No.20253BAC280127)the Key Laboratory of Functional Biology and Pollution Control in red soil regions of Jiangxi Province,China(No.2023SSY02051).
摘要The spin-forbidden effect and high bond energy of molecular oxygen(O2)pose a fundamental challenge for its activation in wastewater treatment.We address this by constructing an atomically dispersed Fe-Mn dual-site catalyst(Fe0.1-Mn-350),which overcomes the sluggish O2kinetics of monometallic oxides and the aqueous instability of conventional single-atom catalysts.This catalyst enables complete degradation of 20 mg/L parachlormetaxylenol(PCMX)within 15 minutes,with a reaction rate(O.2205 min-1)25 times greater than MnO2and surpassing benchmark catalysts.Experimental and theoretical analyses reveal that the preferential side-on O2adsorption at Fe sites of Fe0.1-Mn-350 significantly reduces activation barriers by 38%(versus Fe-CNTs by 15%,Co-MnO2by 25%),and triggers a dual-pathway mechanism involving both radical(·OH,O2·-)and non-radical(1O2,Fe(IV))species.Crucially,the Fe0.1-Mn-350/O2system demonstrates robust practicality,maintaining 98%efficiency in real hospital wastewater,stable operation in a 12-h continuous-flow reactor,and a low operational cost of 0.28 USD/m3.The technology's environmental sustainability is further validated by a remarkable 8o%recovery of zebrafish embryo hatchability and a 93%reduction in developmental toxicity.This work provides a green and economically viable strategy for the destructive treatment of persistent halogenated contaminants in water.
基金supported by the National Natural Science Foundation of China(82071362 and 82270669)Key Project of the Regional Joint Fund of Guangdong Province(2023B1515120077)+3 种基金Basic Research Program of Shenzhen Science and Technology Innovation Commission(JCYJ20210324123001003 and JCYJ20220530144801003)Shenzhen Key Laboratory of Bone Tissue Repair and Translational Research(ZDSYS20230626091402006)the Innovation and Entrepreneurship Training Program for College Students,Sun Yat-sen University(20242150)the Leading Innovation and Entrepreneurship Team Program of Zhejiang Province,China(2023R01005).
摘要Activation of spinal cord neural stem cells(NSCs)and subsequent neurogenesis holds a promising alternative for spinal cord injury(SCI)repair.Our previous study demonstrated that complement C3a,derived from reactive astrocytes,inhibits NSC proliferation by suppressing protein aggregate clearance through the deubiquitinating enzyme ubiquitin carboxy-terminal hydrolase L1(UCHL1)-proteasome system post-SCI.However,the potential molecular mechanism by which C3a modulates NSC activation via this pathway remains unclear.Here,we revealed that C3a/C3a receptor(C3aR)signaling activated NF-κB p65,which in turn inhibited Nrf2 activity and UCHL1 expression,resulting in diminished proteasome activity and the accumulation of protein aggregates,and ultimately impaired NSC activation.Both knockdown of NF-κB p65 and Nrf2 upregulation restored UCHL1 expression and proteasome activity in vitro,promoting NSC activation by enhancing protein aggregate clearance.Mechanistically,we found that NF-κB p65 regulated Nrf2 activity through a dual mechanism:(1)promoting Keap1-dependent ubiquitination and proteasome degradation of Nrf2;(2)inhibiting protein kinase C-mediated Nrf2 phosphorylation and nuclear translocation.Using the dual-luciferase reporter assay and chromatin immunoprecipitation(ChIP)analysis,we further identified UCHL1 as a direct transcriptional target of Nrf2.Importantly,in vivo experiments using SCI mice confirmed that either C3aR blockade,NF-κB p65 knockdown,or Nrf2 overexpression could rescue SCI-induced UCHL1 downregulation.Together,this study uncovers the C3a-NF-κB p65-Nrf2-UCHL1-proteasome axis as a critical regulator of NSC activation after SCI.This may provide novel molecular targets and intervention strategies for SCI repair.
基金supported by the Natural Science Foundation of Jiangsu Province(No.BK20220409)the National Natural Science Foundation of China(No.22401153)+2 种基金the FWO[Fund for Scientific Research-Flanders(Belgium)]for financial support(recipient Erik V.Van der Eycken)the Research Council of the KU Leuven(recipient Erik V.Van der Eycken)the support of the"RUDN University Strategic Academic Leadership Program"(recipient Erik V.Van der Eycken).
摘要Peptides play important roles in chemistry,medicinal chemistry and life science,due to their high efficiency and specificity,unusual biological and therapeutic properties.As naturally occurring peptides often face with their intrinsic limitations including metabolic instability and low membrane permeability,the strategies for synthesizing unnatural amino acids and peptides are explored.Among the methods for modifying amino acids and peptides,chemo-and site-selective approaches are preferred because of the ability to fine-tuning structural features.Recently,transition metal-catalyzed C–H activation has been employed for the functionalization of amino acids and peptides.Through domino C–H activation/annulation,a series of structurally complex and diverse amino acids and peptides is constructed.This review highlights recent advances in the synthesis of unnatural amino acids and peptides via transition metal-catalyzed C–H activation/annulation.
摘要For achieving high-power and low-platinum direct methanol fuel cell(DMFC)under proton-exchange-membrane,we introduce the oxidation-state ruthenium species as H2O-activation centers stabilized on PtZn NPs to boost methanol-oxidation reaction(MOR).The Zn-regulated Ru centers,approaching bivalent states,enhance interfacial H2O-capture/dissociation and OH-transfer,enabling rapid CO*removal from adjacent Pt sites.It exhibits an outstanding mass activity of MOR at 2.71 A mgPt-1 and powers a DMFC with 191.2 mW cm-2 peak density(382.4 W gPt-1)while maintaining 125-hour stability,higher than documented results to date,essentially different from traditional alloy catalysts.Combined ab initio molecular dynamics simulations and in-situ spectroscopy reveal a dense O-down water network around Ru centers,where intermediate RuO(OH)2 structure significantly deceases the H2O-dissociation barrier.Kinetic isotope effect tests(CH3OH/H2O vs.D2O)show J H2O/D2O=4.2 for RuOx-PtZn/C at 0.85 VRHE,versus 16.2 for RuOx-Pt/C,directly confirming superior water activation efficiency of RuOx-PtZn/C.We envision that the comprehensive understanding of high-performance MOR on RuOx-PtZn/C through experimental-theoretical approaches will contribute to the practical application of DMFC as early as possible.