To overcome the limitations of traditional photocatalysts,such as inefficient separation of charge carriers and poor visible-light absorption,S-scheme g-C3N4/TiO2 heterojunction photocatalysts were synthesize...To overcome the limitations of traditional photocatalysts,such as inefficient separation of charge carriers and poor visible-light absorption,S-scheme g-C3N4/TiO2 heterojunction photocatalysts were synthesized via a combined method of thermal polymerization,hydrothermal synthesis,and calcination.The crystal structures,morphological features,and optical properties of the composites were systematically characterized,and their photocatalytic performance was evaluated through tetracycline(TC)degradation and hydrogen evolution experiments.Trapping experiments and electron paramagnetic resonance(EPR)measurements were conducted to elucidate the reaction mechanisms.The results demonstrate that the S-scheme heterojunction effectively extends the visible-light absorption range and facilitates the efficient separation of photogenerated electron-hole pairs.Under optimal conditions,the composite achieved a TC degradation rate of 94.5%and a hydrogen evolution rate of 329.1μmol·h-1·g-1 after 8 h of irradiation,both values being significantly higher than those of pristine g-C3N4 or TiO2.Moreover,the S-scheme g-C3N4/TiO2 heterojunction retained high photocatalytic activity over five consecutive cycles,confirming its excellent stability.Mechanistic investigations revealed that the S-scheme heterojunction maintained strong redox capacities,with superoxide radicals(·O2-),hydroxyl radicals(·OH),electrons(e-),and holes(h+)serving as the primary active species responsible for TC degradation and H2 production.展开更多
Neutrophils,macrophages,CD3+,CD4+,and CD8+T lymphocytes expressμ-,δ-,andκ-opioid receptors(ORs)with varying affinities for opioids.Mast cells express the atypical OR Mas-related G-protein-coupled receptor ...Neutrophils,macrophages,CD3+,CD4+,and CD8+T lymphocytes expressμ-,δ-,andκ-opioid receptors(ORs)with varying affinities for opioids.Mast cells express the atypical OR Mas-related G-protein-coupled receptor X2(MRGPRX2),which has a low affinity for morphine.Neutrophils and macrophages can synthesize and release endogenous opioid peptides.Activation of ORs enhances the synthesis of proinflammatory cytokines and the production of reactive oxygen species(ROS)in unstimulated leukocytes.Conversely,OR activation reduces proinflammatory cytokine synthesis in stimulated neutrophils and macrophages.Morphine inhibits Toll-like receptor 4(TLR4)expression in macrophages,thereby attenuating inflammation,whereas methadone induces ROS production in mast cells through TLR4 activation.Stimulation of TLR4 triggersβ-endorphin synthesis in macrophages.The production of proinflammatory cytokines and ROS contributes to cardiac reperfusion injury.Importantly,activation ofκ1-andμ-ORs suppresses proinflammatory cytokine production by leukocytes,thereby mitigating inflammatory injury to the heart and other organs.展开更多
Ferroptosis plays a key role in nerve injury in intracerebral hemorrhage and is associated with the upregulation of murine double minute 2.Investigating the mechanism underlying murine double minute 2-related ferropto...Ferroptosis plays a key role in nerve injury in intracerebral hemorrhage and is associated with the upregulation of murine double minute 2.Investigating the mechanism underlying murine double minute 2-related ferroptosis could help identify new therapies for intracerebral hemorrhage.An in vitro intracerebral hemorrhage model was established by treating BV2 microglial cells with oxygen-glucose deprivation combined with hemin.The role of murine double minute 2 in regulating ferroptosis was investigated via transduction with RNA interference and lentivirus overexpression.Furthermore,intracerebral hemorrhage mouse models were constructed with and without an murine double minute 2 inhibitor(brigimadlin),and behavioral assays were performed to assess the learning ability and cognitive function.Murine double minute 2 dysregulation was associated with oxygen-glucose deprivation combined with hemin-induced BV2 microglial cell ferroptosis and M1/M2 polarization.The results suggested that murine double minute 2 induced glutathione peroxidase 4 ubiquitination and degradation to regulate ferroptosis and inflammatory responses in BV2 microglial cells.Mechanistically,Wilms tumor 1-associated protein induced murine double minute 2 N6-methyladenosine(m6A)modification and regulated ferroptosis and inflammatory responses.In vivo analysis showed that brigimadlin improved neurological deficits and spatial memory in mice with intracerebral hemorrhage.In summary,the results indicate that Wilms tumor 1-associated protein regulates murine double minute 2 m6A modification,and murine double minute 2 induces glutathione peroxidase 4 ubiquitination and degradation.This regulation promotes ferroptosis and inflammatory responses in oxygen-glucose deprivation combined with hemin-induced BV2 microglial cells,suggesting that the murine double minute 2-glutathione peroxidase 4-ferroptosis regulatory axis exerts neurotoxic effects.These findings identify glutathione peroxidase 4 as a potential gene therapy target for intracerebral hemorrhage-related brain injury.展开更多
Sugars are crucial in determining fruit quality and significantly affect the commercial value.Sucrose is the primary soluble sugar in ripe peach fruit.However,the regulatorymechanism of sucrose synthesis in peach frui...Sugars are crucial in determining fruit quality and significantly affect the commercial value.Sucrose is the primary soluble sugar in ripe peach fruit.However,the regulatorymechanism of sucrose synthesis in peach fruit,especially during natural ripening,remains largely unexplored.This study identified two structural genes of peach(Prunus persica,‘Jinlinghuanglu’),PpSUS1 and PpSPS2,whose expression was strongly correlated with sucrose accumulation.The transcription factors that regulated the expression of these two genes during peach fruit ripening were screened;and three NACs(NAM,ATAF1/2 and CUC2),whose expression also significantly correlated with sucrose accumulation,were identified.Notably,PpNAP4(NAC-like,activated by APETALA3/PISTILLATA)displayed the highest activation activity toward the PpSUS1 and PpSPS2 promoters.The direct binding activity was confirmed using luciferase imaging and electrophoretic mobility shift assays.The sucrose content and expression of sucrose synthesis-related genes significantly increased when PpNAP4 was overexpressed in peach fruit and the tomato nor mutant.Moreover,PpNAP4 functioned synergistically with PpNAP6 to modulate sucrose synthesis,and PpNAP4 targeted its own promoter and feedback-activated its own expression.This research unveils a novel regulatory mechanism controlling sucrose accumulation in peach fruit.展开更多
Efficient and sustainable photocatalytic hydrogen peroxide(H2O2)synthesis is crucial due to its role as an eco-friendly oxidant and the limitations of conventional industrial methods.Graphitic carbon nitride(g-C...Efficient and sustainable photocatalytic hydrogen peroxide(H2O2)synthesis is crucial due to its role as an eco-friendly oxidant and the limitations of conventional industrial methods.Graphitic carbon nitride(g-C3N4)is a promising photocatalyst but suffers from inefficient charge separation and limited visible light absorption.This study introduces a dual-modified g-C3N4,incorporating Na+/K+ions and cyano groups,coupled with ultrathin BiOCl nanosheets to form an S-scheme heterojunction(CN-NH-NaK/BiOCl).The modification enhances the electronic structure,visible light absorption,and charge separation.The CN-NH-NaK/BiOCl photocatalyst achieved an outstanding H2O2production rate of 33.15 mmol·g-1·h-1under visible light(λ≥400 nm),outperforming pristine g-C3N4(118-fold)and BiOCl(83-fold),and surpassing all previously reported g-C3N4-and BiOCl-based photocatalysts.Even in pure water,the production rate reached 5.18 mmol·g-1·h-1,exceeding that of most previously reported catalysts.Comprehensive characterization revealed an efficient S-scheme charge transfer mechanism,enabling selective 2e-oxygen reduction reaction(94.06%selectivity)and water oxidation.The heterojunction demonstrated excellent stability,reusability,and enhanced degradation of tetracycline hydrochloride.This work provides a promising strategy for advanced S-scheme photocatalysts in sustainable H2O2production and environmental remediation.展开更多
Transition metal sulfides(TMSs)are primitive composition of biocatalysts that are active for molecular hydrogen production.The development of non-precious TMSs with appropriate spatial ordering has great potentials to...Transition metal sulfides(TMSs)are primitive composition of biocatalysts that are active for molecular hydrogen production.The development of non-precious TMSs with appropriate spatial ordering has great potentials to contribute high-level hydrogen generation.Herein,super-hybrid transition metal sulfide nanoarrays of NiS nanoparticle/WS2nanosheet/Ni3S4nanoparticle(Super-NiS/WS2/Ni3S4)with high spatial ordering and abundant plane-and edge-type WS2-NiS and WS2-M3S4heterointerfaces were elaborately constructed though manipulating the sequential dissociation of phosphotungstic acid(PW12)as W precursor and nickel foam as Ni precursor in one pot.When evaluated for the electrocatalytic hydrogen evolution reaction(HER),the Super-NiS/WS2/Ni3S4only required overpotentials of 57,95,and 151 mV to drive HER in alkaline,acid,and neutral media,respectively,and presented favorable reaction kinetics and test stability.The theoretical and experimental results verify the adsorption and dissociation of water molecules are preferential on WS2-plane-related heterointerfaces.The Gibbs free energy(ΔGH*)analysis indicated the WS2-plane-NiS interface is thermodynamically optimal for HER.Moreover,the collaborations of the abundant plane-and edge-type active interfaces,the open nanosheet-based vertical array,and the phosphorus doping in Super-NiS/WS2/Ni3S4strengthen mass transport and electron transfer in electrocatalysis.The polyoxometalates-based synthetic strategy will inspire the new vision for the rational design and construction of advanced functional materials.展开更多
Cooperative coupling of photocatalytic hydrogen generation with oxidative organic synthesis is promising in simultaneously producing sustainable energy and value-added chemicals.However,the photocatalytic activity is ...Cooperative coupling of photocatalytic hydrogen generation with oxidative organic synthesis is promising in simultaneously producing sustainable energy and value-added chemicals.However,the photocatalytic activity is constrained by restricted redox potentials and insufficient photocarrier separation and transfer.Herein,we construct S-scheme heterojunctions based on metal-doped ZnIn2S4 and covalent organic frameworks,denoted as M-ZIS/TpPa-1(M=Ni or Mo).Theoretical calculations demonstrated that Mo-ZIS possess optimum H adsorption Gibbs free energies,deeper downshift of sulfur p-band center and higher integrated crystal orbital Hamilton population(ICOHP)value than Ni-ZIS and ZIS to optimize H adsorption/desorption dynamics.Besides,metal-doping reasonably enhanced the interfacial charge transfer in heterostructures,identifying the enlarged internal electric field(IEF)in Mo-ZIS/TpPa-1 than Ni-ZIS/TpPa-1 and ZIS/TpPa-1.Moreover,experimental explorations of photoelectrochemical measurements,femtosecond transient absorption spectroscopy,in-situ irradiated X-ray photoelectron spectroscopy and electron paramagnetic resonance verified the facilitated photocarrier separation and migration in metal-doped S-scheme heterojunctions.Ultimately,Mo0.01-ZIS/TpPa-1 exhibited visible-light driven H2 evolution rate of 1648μmol g-1 h-1 and N-benzylidenebenzylamine formation rate of 1812μmol g-1 h-1,better than Ni0.048-ZIS/TpPa-1,and superior to parent ZIS/TpPa-1.This work might provide insights into the modulation of H adsorption/desorption behavior and IEF within S-scheme heterostructures via rational metal-doping strategy for efficient dual-functional photocatalysis.展开更多
摘要To overcome the limitations of traditional photocatalysts,such as inefficient separation of charge carriers and poor visible-light absorption,S-scheme g-C3N4/TiO2 heterojunction photocatalysts were synthesized via a combined method of thermal polymerization,hydrothermal synthesis,and calcination.The crystal structures,morphological features,and optical properties of the composites were systematically characterized,and their photocatalytic performance was evaluated through tetracycline(TC)degradation and hydrogen evolution experiments.Trapping experiments and electron paramagnetic resonance(EPR)measurements were conducted to elucidate the reaction mechanisms.The results demonstrate that the S-scheme heterojunction effectively extends the visible-light absorption range and facilitates the efficient separation of photogenerated electron-hole pairs.Under optimal conditions,the composite achieved a TC degradation rate of 94.5%and a hydrogen evolution rate of 329.1μmol·h-1·g-1 after 8 h of irradiation,both values being significantly higher than those of pristine g-C3N4 or TiO2.Moreover,the S-scheme g-C3N4/TiO2 heterojunction retained high photocatalytic activity over five consecutive cycles,confirming its excellent stability.Mechanistic investigations revealed that the S-scheme heterojunction maintained strong redox capacities,with superoxide radicals(·O2-),hydroxyl radicals(·OH),electrons(e-),and holes(h+)serving as the primary active species responsible for TC degradation and H2 production.
基金supported by the Russian Science Foundation(Grant No.23-65-10017 to B.K.K.and M.K.)The Ministry of Science and Higher Education of the Russian Federation(Grant No.122020300042-4 to L.N.M.)supported the preparation of the minichapter titled"Opioids reduce inflammatory injury of the heart".
摘要Neutrophils,macrophages,CD3+,CD4+,and CD8+T lymphocytes expressμ-,δ-,andκ-opioid receptors(ORs)with varying affinities for opioids.Mast cells express the atypical OR Mas-related G-protein-coupled receptor X2(MRGPRX2),which has a low affinity for morphine.Neutrophils and macrophages can synthesize and release endogenous opioid peptides.Activation of ORs enhances the synthesis of proinflammatory cytokines and the production of reactive oxygen species(ROS)in unstimulated leukocytes.Conversely,OR activation reduces proinflammatory cytokine synthesis in stimulated neutrophils and macrophages.Morphine inhibits Toll-like receptor 4(TLR4)expression in macrophages,thereby attenuating inflammation,whereas methadone induces ROS production in mast cells through TLR4 activation.Stimulation of TLR4 triggersβ-endorphin synthesis in macrophages.The production of proinflammatory cytokines and ROS contributes to cardiac reperfusion injury.Importantly,activation ofκ1-andμ-ORs suppresses proinflammatory cytokine production by leukocytes,thereby mitigating inflammatory injury to the heart and other organs.
基金the National Natural Science Foundation of China,Nos.82311530117(to RJ),82260260(to FC).
摘要Ferroptosis plays a key role in nerve injury in intracerebral hemorrhage and is associated with the upregulation of murine double minute 2.Investigating the mechanism underlying murine double minute 2-related ferroptosis could help identify new therapies for intracerebral hemorrhage.An in vitro intracerebral hemorrhage model was established by treating BV2 microglial cells with oxygen-glucose deprivation combined with hemin.The role of murine double minute 2 in regulating ferroptosis was investigated via transduction with RNA interference and lentivirus overexpression.Furthermore,intracerebral hemorrhage mouse models were constructed with and without an murine double minute 2 inhibitor(brigimadlin),and behavioral assays were performed to assess the learning ability and cognitive function.Murine double minute 2 dysregulation was associated with oxygen-glucose deprivation combined with hemin-induced BV2 microglial cell ferroptosis and M1/M2 polarization.The results suggested that murine double minute 2 induced glutathione peroxidase 4 ubiquitination and degradation to regulate ferroptosis and inflammatory responses in BV2 microglial cells.Mechanistically,Wilms tumor 1-associated protein induced murine double minute 2 N6-methyladenosine(m6A)modification and regulated ferroptosis and inflammatory responses.In vivo analysis showed that brigimadlin improved neurological deficits and spatial memory in mice with intracerebral hemorrhage.In summary,the results indicate that Wilms tumor 1-associated protein regulates murine double minute 2 m6A modification,and murine double minute 2 induces glutathione peroxidase 4 ubiquitination and degradation.This regulation promotes ferroptosis and inflammatory responses in oxygen-glucose deprivation combined with hemin-induced BV2 microglial cells,suggesting that the murine double minute 2-glutathione peroxidase 4-ferroptosis regulatory axis exerts neurotoxic effects.These findings identify glutathione peroxidase 4 as a potential gene therapy target for intracerebral hemorrhage-related brain injury.
基金supported by the earmarked fund for China Agriculture Research System(Grant No.CARS-30-Z-16)Natural Science Basic Research Program of Shaanxi(Grant No.2023-JC-QN-0186).
摘要Sugars are crucial in determining fruit quality and significantly affect the commercial value.Sucrose is the primary soluble sugar in ripe peach fruit.However,the regulatorymechanism of sucrose synthesis in peach fruit,especially during natural ripening,remains largely unexplored.This study identified two structural genes of peach(Prunus persica,‘Jinlinghuanglu’),PpSUS1 and PpSPS2,whose expression was strongly correlated with sucrose accumulation.The transcription factors that regulated the expression of these two genes during peach fruit ripening were screened;and three NACs(NAM,ATAF1/2 and CUC2),whose expression also significantly correlated with sucrose accumulation,were identified.Notably,PpNAP4(NAC-like,activated by APETALA3/PISTILLATA)displayed the highest activation activity toward the PpSUS1 and PpSPS2 promoters.The direct binding activity was confirmed using luciferase imaging and electrophoretic mobility shift assays.The sucrose content and expression of sucrose synthesis-related genes significantly increased when PpNAP4 was overexpressed in peach fruit and the tomato nor mutant.Moreover,PpNAP4 functioned synergistically with PpNAP6 to modulate sucrose synthesis,and PpNAP4 targeted its own promoter and feedback-activated its own expression.This research unveils a novel regulatory mechanism controlling sucrose accumulation in peach fruit.
摘要Efficient and sustainable photocatalytic hydrogen peroxide(H2O2)synthesis is crucial due to its role as an eco-friendly oxidant and the limitations of conventional industrial methods.Graphitic carbon nitride(g-C3N4)is a promising photocatalyst but suffers from inefficient charge separation and limited visible light absorption.This study introduces a dual-modified g-C3N4,incorporating Na+/K+ions and cyano groups,coupled with ultrathin BiOCl nanosheets to form an S-scheme heterojunction(CN-NH-NaK/BiOCl).The modification enhances the electronic structure,visible light absorption,and charge separation.The CN-NH-NaK/BiOCl photocatalyst achieved an outstanding H2O2production rate of 33.15 mmol·g-1·h-1under visible light(λ≥400 nm),outperforming pristine g-C3N4(118-fold)and BiOCl(83-fold),and surpassing all previously reported g-C3N4-and BiOCl-based photocatalysts.Even in pure water,the production rate reached 5.18 mmol·g-1·h-1,exceeding that of most previously reported catalysts.Comprehensive characterization revealed an efficient S-scheme charge transfer mechanism,enabling selective 2e-oxygen reduction reaction(94.06%selectivity)and water oxidation.The heterojunction demonstrated excellent stability,reusability,and enhanced degradation of tetracycline hydrochloride.This work provides a promising strategy for advanced S-scheme photocatalysts in sustainable H2O2production and environmental remediation.
基金supported by the financial supports from the National Natural Science Foundation of China(No.52301016)research projects from Department of Science and Technology of Shandong Province(Nos.2023HWYQ-043,ZR2023ME014,ZR2023QE033)+2 种基金The grant of Youth Innovation Team of Shandong Province(No.2022KJ030)the support of Key Technologies R&D Program of CNBM(No.2023SJYL05)the support of Ji’nan AICC。
摘要Transition metal sulfides(TMSs)are primitive composition of biocatalysts that are active for molecular hydrogen production.The development of non-precious TMSs with appropriate spatial ordering has great potentials to contribute high-level hydrogen generation.Herein,super-hybrid transition metal sulfide nanoarrays of NiS nanoparticle/WS2nanosheet/Ni3S4nanoparticle(Super-NiS/WS2/Ni3S4)with high spatial ordering and abundant plane-and edge-type WS2-NiS and WS2-M3S4heterointerfaces were elaborately constructed though manipulating the sequential dissociation of phosphotungstic acid(PW12)as W precursor and nickel foam as Ni precursor in one pot.When evaluated for the electrocatalytic hydrogen evolution reaction(HER),the Super-NiS/WS2/Ni3S4only required overpotentials of 57,95,and 151 mV to drive HER in alkaline,acid,and neutral media,respectively,and presented favorable reaction kinetics and test stability.The theoretical and experimental results verify the adsorption and dissociation of water molecules are preferential on WS2-plane-related heterointerfaces.The Gibbs free energy(ΔGH*)analysis indicated the WS2-plane-NiS interface is thermodynamically optimal for HER.Moreover,the collaborations of the abundant plane-and edge-type active interfaces,the open nanosheet-based vertical array,and the phosphorus doping in Super-NiS/WS2/Ni3S4strengthen mass transport and electron transfer in electrocatalysis.The polyoxometalates-based synthetic strategy will inspire the new vision for the rational design and construction of advanced functional materials.
摘要Cooperative coupling of photocatalytic hydrogen generation with oxidative organic synthesis is promising in simultaneously producing sustainable energy and value-added chemicals.However,the photocatalytic activity is constrained by restricted redox potentials and insufficient photocarrier separation and transfer.Herein,we construct S-scheme heterojunctions based on metal-doped ZnIn2S4 and covalent organic frameworks,denoted as M-ZIS/TpPa-1(M=Ni or Mo).Theoretical calculations demonstrated that Mo-ZIS possess optimum H adsorption Gibbs free energies,deeper downshift of sulfur p-band center and higher integrated crystal orbital Hamilton population(ICOHP)value than Ni-ZIS and ZIS to optimize H adsorption/desorption dynamics.Besides,metal-doping reasonably enhanced the interfacial charge transfer in heterostructures,identifying the enlarged internal electric field(IEF)in Mo-ZIS/TpPa-1 than Ni-ZIS/TpPa-1 and ZIS/TpPa-1.Moreover,experimental explorations of photoelectrochemical measurements,femtosecond transient absorption spectroscopy,in-situ irradiated X-ray photoelectron spectroscopy and electron paramagnetic resonance verified the facilitated photocarrier separation and migration in metal-doped S-scheme heterojunctions.Ultimately,Mo0.01-ZIS/TpPa-1 exhibited visible-light driven H2 evolution rate of 1648μmol g-1 h-1 and N-benzylidenebenzylamine formation rate of 1812μmol g-1 h-1,better than Ni0.048-ZIS/TpPa-1,and superior to parent ZIS/TpPa-1.This work might provide insights into the modulation of H adsorption/desorption behavior and IEF within S-scheme heterostructures via rational metal-doping strategy for efficient dual-functional photocatalysis.