The extensive transgression that occurred on the Yangtze Plate in Early Cambrian led to a massive organic carbon pool in the Niutitang Formation. A black shale core section from 3 251.08 to 3 436.08 m beneath the Eart...The extensive transgression that occurred on the Yangtze Plate in Early Cambrian led to a massive organic carbon pool in the Niutitang Formation. A black shale core section from 3 251.08 to 3 436.08 m beneath the Earth＇s surface was studied to estimate the contribution of oxygenic photosynthesis to organic carbon sink fluxes in Early Cambrian Upper Yangtze shallow sea. Results indicate that the oxygenic photosynthesis played the most important role in carbon fixation in Early Cambrian. Organic carbon sink was mainly contributed by photosynthetic microorganisms, e.g., cyanobacteria, algae and archaea. The Niutitang Formation was formed in a deep anoxic marine shelf sedimentary environment at a sedimentation rate of ~0.09±0.03 mm/yr. The initial TOC abundance in Niutitang shale ranged from 0.18% to 7.09%, with an average of 2.15%. In accordance with the sedimentation rate and initial TOC abundance, organic carbon sink fluxes were calculated and found to range from 0.21 to 8.10×10~3 kg/km^2·yr^（-1）, especially the organic carbon sink fluxes in depth between 3 385 and 3 470 m range from 3.80 to 8.10×10~3 kg/km^2·yr^（-1）, with an average of ~6.03×10~3 kg/km^2·yr^（-1）, which is much higher than that of contemporary marine sediments. The organic carbon sink fluxes of Niutitang shale are equal to 0.56 to 21.61×10~3 kg/km^2·yr^（-1） net oxygen emitted into the Early Cambrian ocean and atmosphere, this emitted oxygen may have significantly promoted the oxygen level of the Earth＇s surface and diversification of metazoans.展开更多
Constructing high-performance electrodes with both wide potential window(e.g.≥2 V in aqueous electrolyte)and excellent mechanical flexibility represents a great challenge for supercapacitors.Because of the outstandin...Constructing high-performance electrodes with both wide potential window(e.g.≥2 V in aqueous electrolyte)and excellent mechanical flexibility represents a great challenge for supercapacitors.Because of the outstanding conductivity and flexibility,carb on cloth(CC)has show n unlimited prospects for constructing flexible electrodes,but is rarely used directly as electrode material due to its electrochemical inertness and small specific surface area.To tackle these two critical limitations,we design a novel redox-etching strategy to synthesize CC-based electrode with 3D interconnecting pore structure.The sponge-like highly porous CC was further activated by strong oxidant to form abundant oxygenic groups,which occupy the interior and surface of current collector to render substantial pseudocapacitance.The as-synthesized CC electrode yielded an impressive capacitance of 4035 mF cm^(-2) at 3 mA cm^(-2) and satisfying cycling durability in a wide potential range of-1-1 V vs.SCE,which surpass the majority of reported CC-based electrodes.A symmetric supercapacitor with stable voltage of 2 V is assembled and delivers remarkable energy density of 6.57 mWh cm^(-3).Significantly,the device demonstrates an unparalleled flexibility with no capacitive decay after 100 bending cycles.This facile chemical etching and post-treatment processes are designed for large-scale manufacturing of the CC electrodes by providing high surface area and abundant electrochemically active sites,promising for industry application.The innovative synthetic strategy ope ns up new opportunities for high-performance flexible en ergy storage.展开更多
Ischemia–reperfusion injury is a common pathophysiological mechanism in retinal degeneration.PANoptosis is a newly defined integral form of regulated cell death that combines the key features of pyroptosis,apoptosis,...Ischemia–reperfusion injury is a common pathophysiological mechanism in retinal degeneration.PANoptosis is a newly defined integral form of regulated cell death that combines the key features of pyroptosis,apoptosis,and necroptosis.Oligomerization of mitochondrial voltage-dependent anion channel 1 is an important pathological event in regulating cell death in retinal ischemia–reperfusion injury.However,its role in PANoptosis remains largely unknown.In this study,we demonstrated that voltage-dependent anion channel 1 oligomerization-mediated mitochondrial dysfunction was associated with PANoptosis in retinal ischemia–reperfusion injury.Inhibition of voltage-dependent anion channel 1 oligomerization suppressed mitochondrial dysfunction and PANoptosis in retinal cells subjected to ischemia–reperfusion injury.Mechanistically,mitochondria-derived reactive oxygen species played a central role in the voltagedependent anion channel 1-mediated regulation of PANoptosis by promoting PANoptosome assembly.Moreover,inhibiting voltage-dependent anion channel 1 oligomerization protected against PANoptosis in the retinas of rats subjected to ischemia–reperfusion injury.Overall,our findings reveal the critical role of voltage-dependent anion channel 1 oligomerization in regulating PANoptosis in retinal ischemia–reperfusion injury,highlighting voltage-dependent anion channel 1 as a promising therapeutic target.展开更多
Blood-brain barrier disruption and the neuroinflammatory response are significant pathological features that critically influence disease progression and treatment outcomes.This review systematically analyzes the curr...Blood-brain barrier disruption and the neuroinflammatory response are significant pathological features that critically influence disease progression and treatment outcomes.This review systematically analyzes the current understanding of the bidirectional relationship between blood-brain barrier disruption and neuroinflammation in traumatic brain injury,along with emerging combination therapeutic strategies.Literature review indicates that blood-brain barrier disruption and neuroinflammatory responses are key pathological features following traumatic brain injury.In the acute phase after traumatic brain injury,the pathological characteristics include primary blood-brain barrier disruption and the activation of inflammatory cascades.In the subacute phase,the pathological features are characterized by repair mechanisms and inflammatory modulation.In the chronic phase,the pathological features show persistent low-grade inflammation and incomplete recovery of the blood-brain barrier.Various physiological changes,such as structural alterations of the blood-brain barrier,inflammatory cascades,and extracellular matrix remodeling,interact with each other and are influenced by genetic,age,sex,and environmental factors.The dynamic balance between blood-brain barrier permeability and neuroinflammation is regulated by hormones,particularly sex hormones and stress-related hormones.Additionally,the role of gastrointestinal hormones is receiving increasing attention.Current treatment strategies for traumatic brain injury include various methods such as conventional drug combinations,multimodality neuromonitoring,hyperbaric oxygen therapy,and non-invasive brain stimulation.Artificial intelligence also shows potential in treatment decision-making and personalized therapy.Emerging sequential combination strategies and precision medicine approaches can help improve treatment outcomes;however,challenges remain,such as inadequate research on the mechanisms of the chronic phase traumatic brain injury and difficulties with technology integration.Future research on traumatic brain injury should focus on personalized treatment strategies,the standardization of techniques,costeffectiveness evaluations,and addressing the needs of patients with comorbidities.A multidisciplinary approach should be used to enhance treatment and improve patient outcomes.展开更多
A composite electrocatalyst,CoMoNiO-S/NF-110(NF is nickel foam),was synthesized through electrodeposition,followed by pyrolysis and then the vulcanization process.CoMoNiO-S/NF-110 exhibited a structure where Ni3S2 and...A composite electrocatalyst,CoMoNiO-S/NF-110(NF is nickel foam),was synthesized through electrodeposition,followed by pyrolysis and then the vulcanization process.CoMoNiO-S/NF-110 exhibited a structure where Ni3S2 and Mo2S3 nanoparticles were integrated at the edges of Co3O4 nanosheets,creating a rich,heterogeneous interface that enhances the synergistic effects of each component.In an alkaline electrolyte,the synthesized CoMoNiO-S/NF-110 exhibited superior electrocatalytic performance for oxygen evolution reaction(OER),achieving current densities of 100 and 200 mA·cm^(-2) with low overpotentials of 199.4 and 224.4 mV,respectively,outperforming RuO2 and several high-performance Mo and Ni-based catalysts.This excellent performance is attributed to the rich interface formed between the components and active sites exposed by the defect structure.展开更多
The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecul...The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.展开更多
About 1/3 of human life is spent sleeping.The hypoxic and cold environment in high-altitude areas leads to sleep disorders that are more prominently harmful to the human body.To improve the quality of human sleep in h...About 1/3 of human life is spent sleeping.The hypoxic and cold environment in high-altitude areas leads to sleep disorders that are more prominently harmful to the human body.To improve the quality of human sleep in high-altitude areas,this study explored the thermal and oxygen environment regulation for plateau sleep.In this study,the influencing factors of the diffusion of oxygenic–thermal coupled airflow were determined through the theoretical analysis of a thermal fluid mechanic jet.This study used computational fluid dynamics(CFD)to investigate the diffusion characteristics of the oxygenic–thermal coupled airflow with a sleeping experiment conducted on the plateau.The results showed that the influence of the thermal plume at 0.1 m near the human face was larger,and the oxygenic–thermal coupled airflow diffusion process was mainly divided into three phases over time.The size and time to stabilize the oxygen volume fraction in the inhalation zone varied between conditions and were strongly influenced by the temperature difference of the supply air.The effects of the thermal and oxygen environment were analyzed using indicators such as facial-area speed ratio,draft risk,and personal oxygen inhalation efficiency.The optimal design strategies were recommended with an outlet air velocity of 1.5 m/s,a temperature difference of 8 K between the outlet airflow and the indoor background air,and an outlet oxygen volume fraction of 30%.The results can provide implications for regulating the thermal and oxygen environment to improve human sleep quality in high-altitude areas.展开更多
Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a fo...Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a formidable challenge.Herein,we propose a dual-engineering strategy to stabilize Ru-based catalysts by synergizing the oxygen vacancy site-synergized mechanism-lattice oxygen mechanism(OVSM-LOM)with Ru-N bond stabilization.The engineered RuO_(2)@NCC catalyst exhibits exceptional OER performance in 0.5 M H2SO4,achieving an ultralow overpotential of 215 mV at 10 mA cm^(-2) and prolonged stability for over 327 h.The catalyst delivers 300 h of continuous operation at 1 A cm^(-2),with a negligible degradation rate of only 0.067 mV h-1,further demonstrating its potential for practical application.Oxygen vacancies unlock the OVSM-LOM pathway,bypassing the sluggish adsorbate evolution mechanism(AEM)and accelerating reaction kinetics,while the Ru-N bonds suppress Ru dissolution by anchoring low-valent Ru centers.Quasi-in situ X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),and isotopic labeling experiments confirm the lattice oxygen participation with *O formation as the rate-determining step.The Ru-N bonds reinforce the structural integrity by stabilizing low-valent Ru centers and inhibiting overoxidation.Theoretical calculations further verify that the synergistic interaction between OVs and Ru-O(N)active sites optimizes the Ru d-band center and stabilizes intermediates,while Ru-N coordination enhances structural integrity.This study establishes a novel paradigm for designing robust acidic OER catalysts through defect and coordination engineering,bridging the gap between activity and stability for sustainable energy technologies.展开更多
Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and of...Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.展开更多
Fenton-like technology based on peroxymonosulfate activation has shown great potential in refractory organics degradation.In this work,single Fe atom catalysts were synthesized through facile ball milling and exhibite...Fenton-like technology based on peroxymonosulfate activation has shown great potential in refractory organics degradation.In this work,single Fe atom catalysts were synthesized through facile ball milling and exhibited very high performance in peroxymonosulfate activation.The Fe single-atom filled an N vacancy on the triazine ring edge of C_(3)N_(4),as confirmed through X-ray absorption fine structure,density functional calculation and elec-tron paramagnetic resonance.The SAFe_(0.4)–C_(3)N_(4)/PMS system could completely remove phenol(20 mg/L)within 10 min and its first-order kinetic constant was 12.3 times that of the Fe_(3)O_(4)/PMS system.Under different ini-tial pH levels and in various anionic environments,SAFe_(0.4)–C_(3)N_(4) still demonstrated excellent catalytic activity,achieving a removal rate of over 90%for phenol within 12 min.In addition,SAFe_(0.4)–C_(3)N_(4) exhibited outstanding selectivity in reaction systems with different pollutants,showing excellent degradation effects on electron-rich pollutants only.Hydroxyl radicals(•OH),singlet oxygen(1O_(2))and high-valent iron oxide(Fe(Ⅳ)=O)were de-tected in the SAFe_(0.4)–C_(3)N_(4)/PMS system through free radical capture experiments.Further experiments on the quenching of active species and a methyl phenyl sulfoxide probe confirmed that 1O_(2) and Fe(Ⅳ)=O played dom-inant roles.Additionally,the change in the current response after adding PMS and phenol in succession proved that a direct electron transfer path between organic matter and the catalyst surface was unlikely to exist in the SAFe_(0.4)–C_(3)N_(4)/PMS/Phenol degradation system.This study provides a new demonstration of the catalytic mech-anism of single-atom catalysts.展开更多
Heteroatom-doped carbon is considered a promising alternative to commercial Pt/C as an efficient catalyst for the oxygen reduction reaction(ORR).This study presents the synthesis of iron-loaded,sulfur and nitrogen co-...Heteroatom-doped carbon is considered a promising alternative to commercial Pt/C as an efficient catalyst for the oxygen reduction reaction(ORR).This study presents the synthesis of iron-loaded,sulfur and nitrogen co-doped carbon(Fe/SNC)via in situ incorporation of 2-aminothiazole molecules into zeolitic imidazolate framework-8(ZIF-8)through coordination between metal ions and organic ligands.Sulfur and nitrogen doping in carbon supports effectively modulates the electronic structure of the catalyst,increases the Brunauer-Emmett-Teller surface area,and exposes more Fe-N_(x)active centers.Fe-loaded,S and N co-doped carbon with Fe/S molar ratio of 1:10(Fe/SNC-10)exhibits a half-wave potential of 0.902 V vs.RHE.After 5000 cycles of cyclic voltammetry,its half-wave potential decreases by only 20 mV vs.RHE,indicating excellent stability.Due to sulfur s lower electronegativity,the electronic structure of the Fe-N_(x)active center is modulated.Additionally,the larger atomic radius of sulfur introduces defects into the carbon support.As a result,Fe/SNC-10 demonstrates superior ORR activity and stability in alkaline solution compared with Fe-loaded N-doped carbon(Fe/NC).Furthermore,the zinc-air battery assembled with the Fe/SNC-10 catalyst shows enhanced performance relative to those assembled with Fe/NC and Pt/C catalysts.This work offers a novel design strategy for advanced energy storage and conversion applications.展开更多
Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction...Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.展开更多
Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal ...Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.展开更多
This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0...This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.展开更多
Oxygen evolution reaction(OER)is a key step in hydrogen production by water electrolysis technology.How-ever,developing efficient,stable,and low-cost OER electrocatalysts is still challenging.This article presents the...Oxygen evolution reaction(OER)is a key step in hydrogen production by water electrolysis technology.How-ever,developing efficient,stable,and low-cost OER electrocatalysts is still challenging.This article presents the preparation of a series of novel copper iridium nanocatalysts with heterostructures and low iridium content for OER.The electrochemical tests revealed higher OER of Cu@Ir_(0.3) catalyst under acidic conditions with a generated current density of 10 mA/cm^(2) at only 284 mV overpotential.The corresponding OER mass activity was estimated to be 1.057 A/mgIr,a value 8.39-fold higher than that of the commercial IrO_(2).After 50 h of endurance testing,the Cu@Ir_(0.3) catalyst preserved excellent catalytic activity with a negligible rise in overpotential and maintained a good heterostructures.Cu@Ir_(0.3) The excellent OER activity can be attributed to its heterostructure,as con-firmed by density functional theory(DFT)calculations,indicating that Cu@Ir The coupling between isoquanta causes charge redistribution,optimizing the adsorption energy of unsaturated Ir sites for oxygen intermediates and reducing the energy barrier of OER free energy determining the rate step.In summary,this method provides a new approach for designing efficient,stable,and low iridium content OER catalysts.展开更多
BACKGROUND Ulcerative colitis(UC)is a chronic and debilitating inflammatory bowel disease.Cumulative evidence indicates that excess hydrogen peroxide,a potent neutrophilic chemotactic agent,produced by colonic epithel...BACKGROUND Ulcerative colitis(UC)is a chronic and debilitating inflammatory bowel disease.Cumulative evidence indicates that excess hydrogen peroxide,a potent neutrophilic chemotactic agent,produced by colonic epithelial cells has a causal role leading to infiltration of neutrophils into the colonic mucosa and subsequent development of UC.This evidence-based mechanism identifies hydrogen peroxide as a therapeutic target for reducing agents in the treatment of UC.CASE SUMMARY Presented is a 41-year-old female with a 26-year history of refractory UC.Having developed steroid dependence and never achieving complete remission on treatment by conventional and advanced therapies,she began treatment with oral R-dihydrolipoic acid(RDLA),a lipid-soluble reducing agent with intracellular site of action.Within a week,rectal bleeding ceased.She was asymptomatic for three years until a highly stressful experience,when she noticed blood in her stool.RDLA was discontinued,and she began treatment with oral sodium thiosulfate pentahydrate(STS),a reducing agent with extracellular site of action.After a week,rectal bleeding ceased,and she resumed oral RDLA and discontinued STS.To date,she remains asymptomatic with normal stool calprotectin while on RDLA.CONCLUSION STS and RDLA are reducing agents that serve as highly effective and safe therapy for the induction and maintenance of remission in UC,even in patients refractory or poorly controlled by conventional and advanced therapies.Should preliminary findings be validated by subsequent clinical trials,the use of reducing agents could potentially prevent thousands of colectomies and represent a paradigm shift in the treatment of UC.展开更多
4-Nitrophenol(4-NP),a toxic and persistent pollutant in chemical wastewater,presents significant challenges in degradation and mineralization.Conventional ozone oxidation catalysts are hindered by low efficiency,mass ...4-Nitrophenol(4-NP),a toxic and persistent pollutant in chemical wastewater,presents significant challenges in degradation and mineralization.Conventional ozone oxidation catalysts are hindered by low efficiency,mass transfer constraints and metal leaching,necessitating the development of stable and efficient catalysts.Herein,BCn-H/MS,the derivative of Bi(Ce)-MOF,was prepared by in situ incorporation,thermal decomposition and acid etching.The resulting materials were characterized and employed in catalytic ozonation for the reduction of 4-NP.Under the specific experimental conditions of the O_(3)+BC0.3-H/MS system,the total organic carbon(TOC)and chemical oxygen demand(COD)removal rates of 4-NP were observed to reach 94.6%and 91.8%within 30 min,respectively.These two parameters were improved by raising the initial pH,reducing the pollutant concentration and increasing the catalyst dosage.The abundant oxygen vacancies(OVs)were regarded as the pivotal catalytic site of BC0.3-H/MS,which was conducive to the adsorption of O_(3) and the acceleration of the formation of reactive oxygen species(ROS).The regular hollow square structure effectively boosted the specific surface area,increased OVs exposure and accelerated the adsorption and mass transfer process.The electron paramagnetic resonance(EPR)results demonstrated that the primary ROS engaged in the degradation reaction were⋅OH and⋅O_(2)−.BC0.3-H/MS demonstrated excellent stability and reusability in cyclic experiments.Toxicity analysis revealed that the O_(3)+BC0.3-H/MS system exhibited an effective detoxification effect.Ultimately,the primary degradation pathway of 4-NP was proposed through liquid chromatography-mass spectroscopy(LC-MS)and in-situ diffuse reflectance infrared fourier-transform spectroscopy(DRIFTS)analyses at varying reaction times.展开更多
Abiotic oxygen formation predates photosynthesis,sustaining early chemical evolution,yet its elementary mechanisms remain contested.Here,we show the production pathways for molecular oxygen from doubly ionized carbon ...Abiotic oxygen formation predates photosynthesis,sustaining early chemical evolution,yet its elementary mechanisms remain contested.Here,we show the production pathways for molecular oxygen from doubly ionized carbon dioxide upon electron-impact.Through fragment ions and electron coincidence momentum imaging,we unambiguously determine the ionization mechanism by measuring the projectile energy loss in association with the C^(+) +O_(2)^(+) channel.Further potential energy and trajectory calculations enable us to elucidate the dynamical details of this fragmentation process,in which a bond rearrangement pathway is found to proceed via the structural deformation to a triangular intermediate.Moreover,we demonstrate a further roaming pathway for the formation of O_(2)^(+) from CO_(2)^(+) 2,in which a frustrated C-O bond cleavage leaves the O atom without sufficient energy to escape.The O atom then wanders around varied configuration spaces of the flat potential energy regions and forms a C-O-O_(2)^(+) intermediate prior to the final products C^(+) +O_(2)^(+).Considering the large quantities of free electrons in interstellar space,the processes revealed here are expected to be significant and should be incorporated into atmospheric evolution models.展开更多
Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-...Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-scale preparation of the“integrated”phosphorus-based precatalyst(FeP-NiP)on nickel foam(NF),which is in situ reconstructed into a highly active and corrosion-resistant(Fe)NiOOH phase for OER.The interaction between phosphate anions(PO_(x)^(y-))and iron ions(Fe^(3+))tunes the electronic structure of the catalytic phase to further enhance OER kinetics.The integrated FeP-NiP@NF electrode exhibits low overpotentials for OER in alkaline water/seawater,requiring only 275/289,320/336,and 349/358 mV to reach 0.1,0.5,and 1.0 A cm^(−2),respectively.The in situ reconstructed PO_(x)^(y-)anion electrostatically repels Cl−in seawater electrolytes,allowing stable operation for over 7 days at 1.0 A cm^(−2) in extreme electrolytes(1.0 M KOH+seawater and 6.0 M KOH+seawater),demonstrating industrial-level stability.This study overcomes the complex synthesis limitations of P-based materials through innovative material design,opening new avenues for electrochemical energy conversion.展开更多
Background:Hepatocellular carcinoma(HCC)is one of the leading causes of cancer-related mortality worldwide.This study aimed to identify key genes involved in HCC development and elucidate their molecular mechanisms,wi...Background:Hepatocellular carcinoma(HCC)is one of the leading causes of cancer-related mortality worldwide.This study aimed to identify key genes involved in HCC development and elucidate their molecular mechanisms,with a particular focus on mitochondrial function and apoptosis.Methods:Differential expression analyses were performed across three datasets—The Cancer Genome Atlas(TCGA)-Liver Hepatocellular Carcinoma(LIHC),GSE36076,and GSE95698—to identify overlapping differentially expressed genes(DEGs).A prognostic risk model was then constructed.Cysteine/serine-rich nuclear protein 1(CSRNP1)expression levels in HCC cell lines were assessed via western blot(WB)and quantitative reverse transcription polymerase chain reaction(qRT-PCR).The effects of CSRNP1 knockdown or overexpression on cell proliferation,migration,and apoptosis were evaluated using cell counting-8(CCK-8)assays,Transwell assays,and flow cytometry.Mitochondrial ultrastructure was examined by transmission electron microscopy,and intracellular and mitochondrial reactive oxygen species(mROS)levels were measured using specific fluorescent probes.WB was used to assess activation of the c-Jun N-terminal kinase(JNK)/p38 mitogen-activated protein kinase(MAPK)pathway,and pathway dependence was examined using the ROS scavenger N-Acetylcysteine(NAC)and the JNK inhibitor SP600125.Results:A six-gene prognostic model was established,comprising downregulated genes(NR4A1 and CSRNP1)and upregulated genes(CENPQ,YAE1,FANCF,and POC5)in HCC.Functional experiments revealed that CSRNP1 knockdown promoted the proliferation of HCC cells and suppressed their apoptosis.Conversely,CSRNP1 overexpression impaired mitochondrial integrity,increased both mitochondrial and cytoplasmic ROS levels,and activated the JNK/p38 MAPK pathway.Notably,treatment with NAC or SP600125 attenuated CSRNP1-induced MAPK activation and apoptosis.Conclusion:CSRNP1 is a novel prognostic biomarker and tumor suppressor in HCC.It exerts anti-tumor effects by inducing oxidative stress and activating the JNK/p38 MAPK pathway in a ROS-dependent manner.These findings suggest that CSRNP1 may serve as a potential therapeutic target in the management of HCC.展开更多
基金supported by the National Natural Science Foundation of China (No. 41302023)the Doctoral Program of Higher Education (Specialized Research Fund) of China (No. 20125121130001)+1 种基金the Science Foundation of Education Department of Sichuan Province (No. 13ZB0190)the Karst Dynamics Laboratory, MLR and GZAR (No. KDL2011-04)
文摘The extensive transgression that occurred on the Yangtze Plate in Early Cambrian led to a massive organic carbon pool in the Niutitang Formation. A black shale core section from 3 251.08 to 3 436.08 m beneath the Earth＇s surface was studied to estimate the contribution of oxygenic photosynthesis to organic carbon sink fluxes in Early Cambrian Upper Yangtze shallow sea. Results indicate that the oxygenic photosynthesis played the most important role in carbon fixation in Early Cambrian. Organic carbon sink was mainly contributed by photosynthetic microorganisms, e.g., cyanobacteria, algae and archaea. The Niutitang Formation was formed in a deep anoxic marine shelf sedimentary environment at a sedimentation rate of ~0.09±0.03 mm/yr. The initial TOC abundance in Niutitang shale ranged from 0.18% to 7.09%, with an average of 2.15%. In accordance with the sedimentation rate and initial TOC abundance, organic carbon sink fluxes were calculated and found to range from 0.21 to 8.10×10~3 kg/km^2·yr^（-1）, especially the organic carbon sink fluxes in depth between 3 385 and 3 470 m range from 3.80 to 8.10×10~3 kg/km^2·yr^（-1）, with an average of ~6.03×10~3 kg/km^2·yr^（-1）, which is much higher than that of contemporary marine sediments. The organic carbon sink fluxes of Niutitang shale are equal to 0.56 to 21.61×10~3 kg/km^2·yr^（-1） net oxygen emitted into the Early Cambrian ocean and atmosphere, this emitted oxygen may have significantly promoted the oxygen level of the Earth＇s surface and diversification of metazoans.
基金financially supported by the National Natural Science Foundation of China (No. 52071171)the Liaoning Revitalization Talents Program-Pan Deng Scholars (XLYC1802005)+5 种基金the Liaoning BaiQianWan Talents Program (LNBQW2018B0048)the Natural Science Fund of Liaoning Province for Excellent Young Scholars (2019-YQ-04)the Key Project of Scientific Research of the Education Department of Liaoning Province (LZD201902)the General Project of Scientific Research of the Education Department of Liaoning Province (LJC201905)the Research Fund for the Doctoral Program of Liaoning Province (2019-BS-112)the Foundation for Young Scholars of Liaoning University (LDQN2019006).
文摘Constructing high-performance electrodes with both wide potential window(e.g.≥2 V in aqueous electrolyte)and excellent mechanical flexibility represents a great challenge for supercapacitors.Because of the outstanding conductivity and flexibility,carb on cloth(CC)has show n unlimited prospects for constructing flexible electrodes,but is rarely used directly as electrode material due to its electrochemical inertness and small specific surface area.To tackle these two critical limitations,we design a novel redox-etching strategy to synthesize CC-based electrode with 3D interconnecting pore structure.The sponge-like highly porous CC was further activated by strong oxidant to form abundant oxygenic groups,which occupy the interior and surface of current collector to render substantial pseudocapacitance.The as-synthesized CC electrode yielded an impressive capacitance of 4035 mF cm^(-2) at 3 mA cm^(-2) and satisfying cycling durability in a wide potential range of-1-1 V vs.SCE,which surpass the majority of reported CC-based electrodes.A symmetric supercapacitor with stable voltage of 2 V is assembled and delivers remarkable energy density of 6.57 mWh cm^(-3).Significantly,the device demonstrates an unparalleled flexibility with no capacitive decay after 100 bending cycles.This facile chemical etching and post-treatment processes are designed for large-scale manufacturing of the CC electrodes by providing high surface area and abundant electrochemically active sites,promising for industry application.The innovative synthetic strategy ope ns up new opportunities for high-performance flexible en ergy storage.
基金supported by the National Natural Science Foundation of China,Nos.82172196(to KX),82372507(to KX)the Natural Science Foundation of Hunan Province,China,No.2023JJ40804(to QZ)the Key Laboratory of Emergency and Trauma(Hainan Medical University)of the Ministry of Education,China,No.KLET-202210(to QZ)。
文摘Ischemia–reperfusion injury is a common pathophysiological mechanism in retinal degeneration.PANoptosis is a newly defined integral form of regulated cell death that combines the key features of pyroptosis,apoptosis,and necroptosis.Oligomerization of mitochondrial voltage-dependent anion channel 1 is an important pathological event in regulating cell death in retinal ischemia–reperfusion injury.However,its role in PANoptosis remains largely unknown.In this study,we demonstrated that voltage-dependent anion channel 1 oligomerization-mediated mitochondrial dysfunction was associated with PANoptosis in retinal ischemia–reperfusion injury.Inhibition of voltage-dependent anion channel 1 oligomerization suppressed mitochondrial dysfunction and PANoptosis in retinal cells subjected to ischemia–reperfusion injury.Mechanistically,mitochondria-derived reactive oxygen species played a central role in the voltagedependent anion channel 1-mediated regulation of PANoptosis by promoting PANoptosome assembly.Moreover,inhibiting voltage-dependent anion channel 1 oligomerization protected against PANoptosis in the retinas of rats subjected to ischemia–reperfusion injury.Overall,our findings reveal the critical role of voltage-dependent anion channel 1 oligomerization in regulating PANoptosis in retinal ischemia–reperfusion injury,highlighting voltage-dependent anion channel 1 as a promising therapeutic target.
基金supported by Open Scientific Research Program of Military Logistics,No.BLB20J009(to YZhao).
文摘Blood-brain barrier disruption and the neuroinflammatory response are significant pathological features that critically influence disease progression and treatment outcomes.This review systematically analyzes the current understanding of the bidirectional relationship between blood-brain barrier disruption and neuroinflammation in traumatic brain injury,along with emerging combination therapeutic strategies.Literature review indicates that blood-brain barrier disruption and neuroinflammatory responses are key pathological features following traumatic brain injury.In the acute phase after traumatic brain injury,the pathological characteristics include primary blood-brain barrier disruption and the activation of inflammatory cascades.In the subacute phase,the pathological features are characterized by repair mechanisms and inflammatory modulation.In the chronic phase,the pathological features show persistent low-grade inflammation and incomplete recovery of the blood-brain barrier.Various physiological changes,such as structural alterations of the blood-brain barrier,inflammatory cascades,and extracellular matrix remodeling,interact with each other and are influenced by genetic,age,sex,and environmental factors.The dynamic balance between blood-brain barrier permeability and neuroinflammation is regulated by hormones,particularly sex hormones and stress-related hormones.Additionally,the role of gastrointestinal hormones is receiving increasing attention.Current treatment strategies for traumatic brain injury include various methods such as conventional drug combinations,multimodality neuromonitoring,hyperbaric oxygen therapy,and non-invasive brain stimulation.Artificial intelligence also shows potential in treatment decision-making and personalized therapy.Emerging sequential combination strategies and precision medicine approaches can help improve treatment outcomes;however,challenges remain,such as inadequate research on the mechanisms of the chronic phase traumatic brain injury and difficulties with technology integration.Future research on traumatic brain injury should focus on personalized treatment strategies,the standardization of techniques,costeffectiveness evaluations,and addressing the needs of patients with comorbidities.A multidisciplinary approach should be used to enhance treatment and improve patient outcomes.
文摘A composite electrocatalyst,CoMoNiO-S/NF-110(NF is nickel foam),was synthesized through electrodeposition,followed by pyrolysis and then the vulcanization process.CoMoNiO-S/NF-110 exhibited a structure where Ni3S2 and Mo2S3 nanoparticles were integrated at the edges of Co3O4 nanosheets,creating a rich,heterogeneous interface that enhances the synergistic effects of each component.In an alkaline electrolyte,the synthesized CoMoNiO-S/NF-110 exhibited superior electrocatalytic performance for oxygen evolution reaction(OER),achieving current densities of 100 and 200 mA·cm^(-2) with low overpotentials of 199.4 and 224.4 mV,respectively,outperforming RuO2 and several high-performance Mo and Ni-based catalysts.This excellent performance is attributed to the rich interface formed between the components and active sites exposed by the defect structure.
文摘The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.
基金supported by the National Natural Science Foundation of China(No.U20A20311,No.52378107)Shaanxi Provincial Association for Science and Technology Youth Talent Support Program(No.20230429)Research Program of Youth Innovation Team of Shaanxi Provincial Education Department(No.22JP039).
文摘About 1/3 of human life is spent sleeping.The hypoxic and cold environment in high-altitude areas leads to sleep disorders that are more prominently harmful to the human body.To improve the quality of human sleep in high-altitude areas,this study explored the thermal and oxygen environment regulation for plateau sleep.In this study,the influencing factors of the diffusion of oxygenic–thermal coupled airflow were determined through the theoretical analysis of a thermal fluid mechanic jet.This study used computational fluid dynamics(CFD)to investigate the diffusion characteristics of the oxygenic–thermal coupled airflow with a sleeping experiment conducted on the plateau.The results showed that the influence of the thermal plume at 0.1 m near the human face was larger,and the oxygenic–thermal coupled airflow diffusion process was mainly divided into three phases over time.The size and time to stabilize the oxygen volume fraction in the inhalation zone varied between conditions and were strongly influenced by the temperature difference of the supply air.The effects of the thermal and oxygen environment were analyzed using indicators such as facial-area speed ratio,draft risk,and personal oxygen inhalation efficiency.The optimal design strategies were recommended with an outlet air velocity of 1.5 m/s,a temperature difference of 8 K between the outlet airflow and the indoor background air,and an outlet oxygen volume fraction of 30%.The results can provide implications for regulating the thermal and oxygen environment to improve human sleep quality in high-altitude areas.
基金support from the National Natural Science Foundation of China(Nos.12305373 and 52276220)the Guangzhou Basic Research Program(No.SL2024A04J00234).
文摘Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a formidable challenge.Herein,we propose a dual-engineering strategy to stabilize Ru-based catalysts by synergizing the oxygen vacancy site-synergized mechanism-lattice oxygen mechanism(OVSM-LOM)with Ru-N bond stabilization.The engineered RuO_(2)@NCC catalyst exhibits exceptional OER performance in 0.5 M H2SO4,achieving an ultralow overpotential of 215 mV at 10 mA cm^(-2) and prolonged stability for over 327 h.The catalyst delivers 300 h of continuous operation at 1 A cm^(-2),with a negligible degradation rate of only 0.067 mV h-1,further demonstrating its potential for practical application.Oxygen vacancies unlock the OVSM-LOM pathway,bypassing the sluggish adsorbate evolution mechanism(AEM)and accelerating reaction kinetics,while the Ru-N bonds suppress Ru dissolution by anchoring low-valent Ru centers.Quasi-in situ X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),and isotopic labeling experiments confirm the lattice oxygen participation with *O formation as the rate-determining step.The Ru-N bonds reinforce the structural integrity by stabilizing low-valent Ru centers and inhibiting overoxidation.Theoretical calculations further verify that the synergistic interaction between OVs and Ru-O(N)active sites optimizes the Ru d-band center and stabilizes intermediates,while Ru-N coordination enhances structural integrity.This study establishes a novel paradigm for designing robust acidic OER catalysts through defect and coordination engineering,bridging the gap between activity and stability for sustainable energy technologies.
基金supported by Basic Science Research Program(Priority Research Institute)through the NRF of Korea funded by the Ministry of Education(2021R1A6A1A10039823)by the Korea Basic Science Institute(National Research Facilities and Equipment Center)grant funded by the Ministry of Education(2020R1A6C101B194)。
文摘Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.
基金supported by the National Natural Science Foundation of China(Nos.22406081,22276086,22306086)the Natural Science Foundation of Jiangxi Province(No.20232BAB213029),all of which are greatly acknowledged by the authors.
文摘Fenton-like technology based on peroxymonosulfate activation has shown great potential in refractory organics degradation.In this work,single Fe atom catalysts were synthesized through facile ball milling and exhibited very high performance in peroxymonosulfate activation.The Fe single-atom filled an N vacancy on the triazine ring edge of C_(3)N_(4),as confirmed through X-ray absorption fine structure,density functional calculation and elec-tron paramagnetic resonance.The SAFe_(0.4)–C_(3)N_(4)/PMS system could completely remove phenol(20 mg/L)within 10 min and its first-order kinetic constant was 12.3 times that of the Fe_(3)O_(4)/PMS system.Under different ini-tial pH levels and in various anionic environments,SAFe_(0.4)–C_(3)N_(4) still demonstrated excellent catalytic activity,achieving a removal rate of over 90%for phenol within 12 min.In addition,SAFe_(0.4)–C_(3)N_(4) exhibited outstanding selectivity in reaction systems with different pollutants,showing excellent degradation effects on electron-rich pollutants only.Hydroxyl radicals(•OH),singlet oxygen(1O_(2))and high-valent iron oxide(Fe(Ⅳ)=O)were de-tected in the SAFe_(0.4)–C_(3)N_(4)/PMS system through free radical capture experiments.Further experiments on the quenching of active species and a methyl phenyl sulfoxide probe confirmed that 1O_(2) and Fe(Ⅳ)=O played dom-inant roles.Additionally,the change in the current response after adding PMS and phenol in succession proved that a direct electron transfer path between organic matter and the catalyst surface was unlikely to exist in the SAFe_(0.4)–C_(3)N_(4)/PMS/Phenol degradation system.This study provides a new demonstration of the catalytic mech-anism of single-atom catalysts.
基金financial support of the National Natural Science Foundation of China(No.52472271)the National Key Research and Development Program of China(No.2023YFE0115800)。
文摘Heteroatom-doped carbon is considered a promising alternative to commercial Pt/C as an efficient catalyst for the oxygen reduction reaction(ORR).This study presents the synthesis of iron-loaded,sulfur and nitrogen co-doped carbon(Fe/SNC)via in situ incorporation of 2-aminothiazole molecules into zeolitic imidazolate framework-8(ZIF-8)through coordination between metal ions and organic ligands.Sulfur and nitrogen doping in carbon supports effectively modulates the electronic structure of the catalyst,increases the Brunauer-Emmett-Teller surface area,and exposes more Fe-N_(x)active centers.Fe-loaded,S and N co-doped carbon with Fe/S molar ratio of 1:10(Fe/SNC-10)exhibits a half-wave potential of 0.902 V vs.RHE.After 5000 cycles of cyclic voltammetry,its half-wave potential decreases by only 20 mV vs.RHE,indicating excellent stability.Due to sulfur s lower electronegativity,the electronic structure of the Fe-N_(x)active center is modulated.Additionally,the larger atomic radius of sulfur introduces defects into the carbon support.As a result,Fe/SNC-10 demonstrates superior ORR activity and stability in alkaline solution compared with Fe-loaded N-doped carbon(Fe/NC).Furthermore,the zinc-air battery assembled with the Fe/SNC-10 catalyst shows enhanced performance relative to those assembled with Fe/NC and Pt/C catalysts.This work offers a novel design strategy for advanced energy storage and conversion applications.
基金funded by the Innovative Research Group Project of the National Natural Science Foundation of China(52121004)the Research Development Fund(No.RDF-21-02-060)by Xi’an Jiaotong-Liverpool University+1 种基金support received from the Suzhou Industrial Park High Quality Innovation Platform of Functional Molecular Materials and Devices(YZCXPT2023105)the XJTLU Advanced Materials Research Center(AMRC).
文摘Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.
基金funded by the National Nature Science Foundation of China(62264006,62574102)“Thousand Talents Program”of Yunnan Province for Young Talents,Innovative Research Teams(in Science and Technology)in the University of Yunnan Province(IRTSTYN),XingDian Talent Support Program for Young Talents,and Frontier Research Team of Kunming University 2023,The Basic Research Project of Yunnan Province(Nos.202201AU070022)+2 种基金Kunming University Talent Introduction Fund(Nos.YJL20024)Yunnan Province Education Department Scientific Research Fund Project(Nos.2024Y759)Undergraduate Innovation and Entrepreneurship Training Program Project of Yunnan Provincial(202411393005)。
文摘Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.
基金financially supported by the National Natural Science Foundation of China(No.22309067)the Open Project Program of the State Key Laboratory of Materials-Oriented Chemical Engineering,China(No.KL21-05)the Marine Equipment and Technology Institute,Jiangsu University of Science and Technology,China(No.XTCX202404)。
文摘This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.
基金supported by the Major Science and Technology Special Plan of Yunnan Province(Nos.202302AB080012 and 202402AB080004)the National Natural Science Foundation of China(No.22264025)+1 种基金the Basic Research Foundation of Yunnan Province(Nos.202401AS070033 and 202501AT070055)the Reserve talents for young and middleaged academic and technical leaders project of Yunnan Province(No.202405AC350071).
文摘Oxygen evolution reaction(OER)is a key step in hydrogen production by water electrolysis technology.How-ever,developing efficient,stable,and low-cost OER electrocatalysts is still challenging.This article presents the preparation of a series of novel copper iridium nanocatalysts with heterostructures and low iridium content for OER.The electrochemical tests revealed higher OER of Cu@Ir_(0.3) catalyst under acidic conditions with a generated current density of 10 mA/cm^(2) at only 284 mV overpotential.The corresponding OER mass activity was estimated to be 1.057 A/mgIr,a value 8.39-fold higher than that of the commercial IrO_(2).After 50 h of endurance testing,the Cu@Ir_(0.3) catalyst preserved excellent catalytic activity with a negligible rise in overpotential and maintained a good heterostructures.Cu@Ir_(0.3) The excellent OER activity can be attributed to its heterostructure,as con-firmed by density functional theory(DFT)calculations,indicating that Cu@Ir The coupling between isoquanta causes charge redistribution,optimizing the adsorption energy of unsaturated Ir sites for oxygen intermediates and reducing the energy barrier of OER free energy determining the rate step.In summary,this method provides a new approach for designing efficient,stable,and low iridium content OER catalysts.
文摘BACKGROUND Ulcerative colitis(UC)is a chronic and debilitating inflammatory bowel disease.Cumulative evidence indicates that excess hydrogen peroxide,a potent neutrophilic chemotactic agent,produced by colonic epithelial cells has a causal role leading to infiltration of neutrophils into the colonic mucosa and subsequent development of UC.This evidence-based mechanism identifies hydrogen peroxide as a therapeutic target for reducing agents in the treatment of UC.CASE SUMMARY Presented is a 41-year-old female with a 26-year history of refractory UC.Having developed steroid dependence and never achieving complete remission on treatment by conventional and advanced therapies,she began treatment with oral R-dihydrolipoic acid(RDLA),a lipid-soluble reducing agent with intracellular site of action.Within a week,rectal bleeding ceased.She was asymptomatic for three years until a highly stressful experience,when she noticed blood in her stool.RDLA was discontinued,and she began treatment with oral sodium thiosulfate pentahydrate(STS),a reducing agent with extracellular site of action.After a week,rectal bleeding ceased,and she resumed oral RDLA and discontinued STS.To date,she remains asymptomatic with normal stool calprotectin while on RDLA.CONCLUSION STS and RDLA are reducing agents that serve as highly effective and safe therapy for the induction and maintenance of remission in UC,even in patients refractory or poorly controlled by conventional and advanced therapies.Should preliminary findings be validated by subsequent clinical trials,the use of reducing agents could potentially prevent thousands of colectomies and represent a paradigm shift in the treatment of UC.
基金supported by the National Natural Science Foundation of China(Regional Fund)(No.51868054)the Natural Science Foundation of Inner Mongolia of China(General Program)(No.2022MS05052).
文摘4-Nitrophenol(4-NP),a toxic and persistent pollutant in chemical wastewater,presents significant challenges in degradation and mineralization.Conventional ozone oxidation catalysts are hindered by low efficiency,mass transfer constraints and metal leaching,necessitating the development of stable and efficient catalysts.Herein,BCn-H/MS,the derivative of Bi(Ce)-MOF,was prepared by in situ incorporation,thermal decomposition and acid etching.The resulting materials were characterized and employed in catalytic ozonation for the reduction of 4-NP.Under the specific experimental conditions of the O_(3)+BC0.3-H/MS system,the total organic carbon(TOC)and chemical oxygen demand(COD)removal rates of 4-NP were observed to reach 94.6%and 91.8%within 30 min,respectively.These two parameters were improved by raising the initial pH,reducing the pollutant concentration and increasing the catalyst dosage.The abundant oxygen vacancies(OVs)were regarded as the pivotal catalytic site of BC0.3-H/MS,which was conducive to the adsorption of O_(3) and the acceleration of the formation of reactive oxygen species(ROS).The regular hollow square structure effectively boosted the specific surface area,increased OVs exposure and accelerated the adsorption and mass transfer process.The electron paramagnetic resonance(EPR)results demonstrated that the primary ROS engaged in the degradation reaction were⋅OH and⋅O_(2)−.BC0.3-H/MS demonstrated excellent stability and reusability in cyclic experiments.Toxicity analysis revealed that the O_(3)+BC0.3-H/MS system exhibited an effective detoxification effect.Ultimately,the primary degradation pathway of 4-NP was proposed through liquid chromatography-mass spectroscopy(LC-MS)and in-situ diffuse reflectance infrared fourier-transform spectroscopy(DRIFTS)analyses at varying reaction times.
基金supported by the National Natural Science Foundation of China (Grant Nos.12325406,92261201,12404305,and W2512072)the Shaanxi Province Natural Science Fundamental Research Project (Grant Nos.2023JC-XJ-03 and23JSQ013)the China Postdoctoral Science Foundation (Grant Nos.BX20240286 and 2024M7625)。
文摘Abiotic oxygen formation predates photosynthesis,sustaining early chemical evolution,yet its elementary mechanisms remain contested.Here,we show the production pathways for molecular oxygen from doubly ionized carbon dioxide upon electron-impact.Through fragment ions and electron coincidence momentum imaging,we unambiguously determine the ionization mechanism by measuring the projectile energy loss in association with the C^(+) +O_(2)^(+) channel.Further potential energy and trajectory calculations enable us to elucidate the dynamical details of this fragmentation process,in which a bond rearrangement pathway is found to proceed via the structural deformation to a triangular intermediate.Moreover,we demonstrate a further roaming pathway for the formation of O_(2)^(+) from CO_(2)^(+) 2,in which a frustrated C-O bond cleavage leaves the O atom without sufficient energy to escape.The O atom then wanders around varied configuration spaces of the flat potential energy regions and forms a C-O-O_(2)^(+) intermediate prior to the final products C^(+) +O_(2)^(+).Considering the large quantities of free electrons in interstellar space,the processes revealed here are expected to be significant and should be incorporated into atmospheric evolution models.
基金funding support from Natural Science Foundation of Shanghai(Grant No.23ZR1443900)the National Natural Science Foundation of China(Grant Nos.22178309,22476131 and 22176127)。
文摘Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-scale preparation of the“integrated”phosphorus-based precatalyst(FeP-NiP)on nickel foam(NF),which is in situ reconstructed into a highly active and corrosion-resistant(Fe)NiOOH phase for OER.The interaction between phosphate anions(PO_(x)^(y-))and iron ions(Fe^(3+))tunes the electronic structure of the catalytic phase to further enhance OER kinetics.The integrated FeP-NiP@NF electrode exhibits low overpotentials for OER in alkaline water/seawater,requiring only 275/289,320/336,and 349/358 mV to reach 0.1,0.5,and 1.0 A cm^(−2),respectively.The in situ reconstructed PO_(x)^(y-)anion electrostatically repels Cl−in seawater electrolytes,allowing stable operation for over 7 days at 1.0 A cm^(−2) in extreme electrolytes(1.0 M KOH+seawater and 6.0 M KOH+seawater),demonstrating industrial-level stability.This study overcomes the complex synthesis limitations of P-based materials through innovative material design,opening new avenues for electrochemical energy conversion.
基金funded by Shanghai Yangpu District Science and Technology Commission(Grant No.YPQ202303(Xuejing Lin))Shanghai Yangpu Hospital Foundation(Grant No.Se1202420(Wenchao Wang)and Ye1202423(Juan Huang)).
文摘Background:Hepatocellular carcinoma(HCC)is one of the leading causes of cancer-related mortality worldwide.This study aimed to identify key genes involved in HCC development and elucidate their molecular mechanisms,with a particular focus on mitochondrial function and apoptosis.Methods:Differential expression analyses were performed across three datasets—The Cancer Genome Atlas(TCGA)-Liver Hepatocellular Carcinoma(LIHC),GSE36076,and GSE95698—to identify overlapping differentially expressed genes(DEGs).A prognostic risk model was then constructed.Cysteine/serine-rich nuclear protein 1(CSRNP1)expression levels in HCC cell lines were assessed via western blot(WB)and quantitative reverse transcription polymerase chain reaction(qRT-PCR).The effects of CSRNP1 knockdown or overexpression on cell proliferation,migration,and apoptosis were evaluated using cell counting-8(CCK-8)assays,Transwell assays,and flow cytometry.Mitochondrial ultrastructure was examined by transmission electron microscopy,and intracellular and mitochondrial reactive oxygen species(mROS)levels were measured using specific fluorescent probes.WB was used to assess activation of the c-Jun N-terminal kinase(JNK)/p38 mitogen-activated protein kinase(MAPK)pathway,and pathway dependence was examined using the ROS scavenger N-Acetylcysteine(NAC)and the JNK inhibitor SP600125.Results:A six-gene prognostic model was established,comprising downregulated genes(NR4A1 and CSRNP1)and upregulated genes(CENPQ,YAE1,FANCF,and POC5)in HCC.Functional experiments revealed that CSRNP1 knockdown promoted the proliferation of HCC cells and suppressed their apoptosis.Conversely,CSRNP1 overexpression impaired mitochondrial integrity,increased both mitochondrial and cytoplasmic ROS levels,and activated the JNK/p38 MAPK pathway.Notably,treatment with NAC or SP600125 attenuated CSRNP1-induced MAPK activation and apoptosis.Conclusion:CSRNP1 is a novel prognostic biomarker and tumor suppressor in HCC.It exerts anti-tumor effects by inducing oxidative stress and activating the JNK/p38 MAPK pathway in a ROS-dependent manner.These findings suggest that CSRNP1 may serve as a potential therapeutic target in the management of HCC.
