Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(...Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(CO_(2)).With a maximal EDA conversion of 82%and EU selectivity of 99%at 160℃ for 2 h,Mn_(2)O_(3) catalysts had the best catalytic activity among them,which was superior to the reported catalysts.In the following order:Mn_(2)O_(3)>MnO_(2)>Mn_(3)O_(4),the catalytic activity for the synthesis of EU from CO_(2) and EDA decreased.Further characterization showed the Mn_(2)O_(3) catalyst possessed a greater Mn^(3+)/Mn4+ratio and more surface oxygen vacancies than the MnO_(2) and Mn_(3)O_(4),which improved its capacity to adsorb and activate CO_(2) and EDA.After four recycling runs,the EDA conversion slightly declined from 82%to 56%on Mn_(2)O_(3) catalyst,while no obvious change in EU selectivity was observed.The loss of surface Ov contents and Mn^(3+)proportion were concluded as main reasons for the decrease in catalytic activity over Mn_(2)O_(3) catalyst.This work demonstrated a metal oxide catalyst that was efficient in producing EU from CO_(2) and EDA.展开更多
Ethylene glycol(EG)is a biomass derivative of polyethylene terephthalate(PET),and its electrocatalytic conversion into high-value chemicals has sparked widespread interest.This study reviews the most recent research d...Ethylene glycol(EG)is a biomass derivative of polyethylene terephthalate(PET),and its electrocatalytic conversion into high-value chemicals has sparked widespread interest.This study reviews the most recent research development in electrocatalysis-based EG to glycolic acid(GA)conversion.Firstly,the strategies and research results of modulating the electronic structure of catalysts for efficient selective GA production from EG are reviewed.Second,by reviewing the data of in-situ Fourier transform infrared spectroscopy and in-situ electrochemically attenuated total reflection surface enhanced infrared absorption spectroscopy,the reaction pathway and catalytic mechanism of EG partial oxidation to GA were clarified.Finally,the design and regulation of catalysts for selective oxidation of EG by electrocatalysis in the future are prospected.展开更多
Although the efficiency of poly(ethylene terephthalate)(PET)degradation has been successfully improved by depolymerase engineering,mostly by using Goodfellow-PET(gf-PET)as a substrate,efforts to degrade unpretreated P...Although the efficiency of poly(ethylene terephthalate)(PET)degradation has been successfully improved by depolymerase engineering,mostly by using Goodfellow-PET(gf-PET)as a substrate,efforts to degrade unpretreated PET materials with high crystallinity remain insufficient.Here,we endeavored to improve the degradation capability of a WCCG mutant of leaf-branch compost cutinase(LCC)on a unpretreated PET substrate(crystallinity>40%)by employing iterative saturation mutagenesis.Using this method,we developed a high-throughput screening strategy appropriate for unpretreated substrates.Through extensive screening of residues around the substrate-binding groove,two variants,WCCG-sup1 and WCCG-sup2,showed good depolymerization capabilities with both high-(42%)and low-crystallinity(9%)substrates.The WCCG-sup1 variant completely depolymerized a commercial unpretreated PET product in 36 h at 72℃.In addition to enzyme thermostability and catalytic efficiency,the adsorption of enzymes onto substrates plays an important role in PET degradation.This study provides valuable insights into the structure-function relationship of LCC.展开更多
The synthesis of polyurethanes(PUs)from the reaction of low molecular weight poly(ethylene carbonate)diol(PECD)is rarely investigated.This work reports a novel PU with excellent mechanical properties from the solution...The synthesis of polyurethanes(PUs)from the reaction of low molecular weight poly(ethylene carbonate)diol(PECD)is rarely investigated.This work reports a novel PU with excellent mechanical properties from the solution polymerization of 4,4-diphenylmethane diisocyanate(MDI)with PECD that was derived from the copolymerization of carbon dioxide(CO_(2))and ethylene oxide(EO).The tensile strength,the elongation at break and 300%constant tensile strength of the PECD-PU were up to 66±2 MPa,880%±50%and 13 MPa,respectively,higher than the control PUs from the reaction of MDI with commercial polyethers or polyesters.The PECD-PU with high CO_(2) carbonate content exhibited good solvent resistance and chemical stability.Of importance,the mechanical properties and chemical resistance of PECD-PU were significantly enhanced with the increasing content of CO_(2),i.e.,the carbonate unit in PECD.This work provides comprehensive properties of PECD-derived PUs,indicating that PECD is a competitive precursor for the preparation of PU and has broad application prospects.展开更多
Polyamines(PAs)and ethylene are involved in the modulation of plant growth and development.However,their roles in fruit-set,especially in exogenous gibberellin(GA_(3))-induced grape parthenocarpic berries,and the rela...Polyamines(PAs)and ethylene are involved in the modulation of plant growth and development.However,their roles in fruit-set,especially in exogenous gibberellin(GA_(3))-induced grape parthenocarpic berries,and the related competitive action mode are poorly understood.For this,we,here performed their content determination,bioinformatics and expression pattern analysis of genes to identify the key ones in the competitive network of polyamines metabolic and ethylene biosynthesis(PMEB)pathways.The content of putrescine(Put)significantly increased;while 1-aminocyclopropanecarboxylic acid(ACC)sharply decreased during the fruit-set process of GA_(3)-induced grape parthenocarpic seedless berries.Totally,twenty-five genes in PMEB pathways,including 20 polyamines metabolic(PM)genes and 5 ethylene biosynthesis(EB)ones were identified in grape,of which 8 PM and 2 EB genes possessed the motifs responsive to phytohormone GA.The expression levels of most PMEB genes kept changing during grape fruit-set generating a competitive action mode of GA_(3)-mediated two metabolic fluxes toward PAs and ethylene synthesis.Exogenous GA_(3)might enhance grape fruit-set of parthenocarpic berries via up-regulation of VvSAMS4,VvSAMDC1/2,VvODC1,VvSPDS1,and VvPAO1 to promote PAs accumulation,whereby repressing the ethylene synthesis by down-regulation of VvACS1 and VvACO_(2).Our findings provide novel insights into GA_(3)-mediated competitive inhibition of ethylene by PAs to promote the fruit-set of parthenocarpic berries in grape,which has important implications for molecular breeding of seedless grape with high fruit-setting rate.展开更多
Upgrading carbon dioxide(CO_(2))into value-added bulk chemicals offers a dual-benefit strategy for the carbon neutrality and circular carbon economy.Herein,we develop an integrated CO_(2) valorization strategy that sy...Upgrading carbon dioxide(CO_(2))into value-added bulk chemicals offers a dual-benefit strategy for the carbon neutrality and circular carbon economy.Herein,we develop an integrated CO_(2) valorization strategy that synergizes CO_(2)-H_(2)O co-electrolysis(producing CO/O_(2) feeds)with oxidative double carbonylation of ethylene/acetylene to synthesize CO_(2)-derived C_(4) diesters(dimethyl succinate,fumarate,and maleate).A group of versatile building blocks for manufacturing plasticizers,biodegradable polymers,and pharmaceutical intermediates.Remarkably,CO_(2) exhibits dual functionality:serving simultaneously as a CO/O_(2) source and an explosion suppressant during the oxidative carbonylation process.We systematically investigated the explosion-suppressing efficacy of CO_(2) in flammable gas mixtures(CO/O_(2),C_(2)H_(4)/CO/O_(2),and C_(2)H_(2)/CO/O_(2))across varying concentrations.Notably,the mixed gas stream from CO_(2)/H_(2)O co-electrolysis at an industrial-scale current densities of 400 mA/cm^(2),enabling direct utilization in oxidative double carbonylation reactions with exceptional compatibility and inherent safety.Extended applications were demonstrated through substrate scope expansion and gram-scale synthesis.This study establishes not only a safe protocol for oxidative carbonylation processes,but also opens an innovative pathway for sustainable CO_(2) valorization,including CO surrogate and explosion suppressant.展开更多
Tomato(Solanum lycopersicum)has become a model for the study of fleshy fruits.Comprehending the regulatory mechanisms of fleshy fruit ripening is important.Transcription factors(TFs),hormones,and epigenetic regulation...Tomato(Solanum lycopersicum)has become a model for the study of fleshy fruits.Comprehending the regulatory mechanisms of fleshy fruit ripening is important.Transcription factors(TFs),hormones,and epigenetic regulation mainly regulate tomato fruit ripening,and the initiation of ripening requires ethylene and ripening-related TFs,such as NAC,MADS-box,RIN,GH3,HD-ZIP,and basic helix-loop-helix.In this review,we summarize recent research progress on these TFs in the regulation of tomato fruit ripening and highlight the crosstalk mechanisms of ethylene and ripening-related TFs.By affecting ethylene synthesis and signaling,TFs regulate softening and color changes in tomato fruits,thereby influencing fruit quality.Our review contributes to a systematic understanding of the regulatory mechanisms of tomato fruit ripening and provides a basis for developing or modeling complex ripening regulatory networks.展开更多
In climacteric fruits,the role of ethylene in promoting ripening process and its molecular regulatory mechanisms have been well elucidated.However,research into ethylene's roles in non-climacteric fruits has only ...In climacteric fruits,the role of ethylene in promoting ripening process and its molecular regulatory mechanisms have been well elucidated.However,research into ethylene's roles in non-climacteric fruits has only advanced in recent years,largely because these fruits produce much less ethylene than climacteric fruits.Consequently,reports on its molecular regulatory involvement are still limited.Grape(Vitis vinifera L.),one of the most economically valuable fruits,is regarded as a classical non-climacteric fruit.In this study,an enzyme participating in the last step of ethylene biosynthesis,VvACO1,has been identified as a key enzyme controlling ethylene release in grape fruits(Vitis vinifera‘Jingyan’and‘Red Balado’)using correlation analysis and enzymatic experiments.The transcriptional regulation of VvACO1 was investigated by integrating multiple methods such as DNA pull-down assays,co-expression analysis,dual luciferase reporting system,yeast one-hybrid assays,and transgenic experiments.Our findings revealed that the upregulation of VvACO1 in grape fruits was primarily caused by the removal of transcriptional inhibition.Remarkably,seven transcription factors(TFs)were identified as inhibitors of VvACO1,including VvHY5 from bZIP family,VvWIP2 from C2H2 family,VvBLH1 from Homeobox family,VvAG1 and VvCMB1 from MADS-box family,VvASIL1 and VvASIL2 from Trihelix family.These seven TFs were located in nuclei and exhibited transcriptional inhibition activity.Notably,VvAG1 and VvASIL2 could inhibit VvACO1 expression when overexpressed in grape leaves.Our findings provided theoretical clues for differences of ethylene release regulation between climacteric and non-climacteric fruits,also the identified seven TFs could be potential targets for grape molecular breeding.展开更多
Autophagy is a universal cellular process in eukaryotes that plays a critical role in plant growth and stress response.However,the role of autophagy in fruit ripening is largely unknown.Here,we demonstrated that most ...Autophagy is a universal cellular process in eukaryotes that plays a critical role in plant growth and stress response.However,the role of autophagy in fruit ripening is largely unknown.Here,we demonstrated that most autophagy-related genes(ATGs)were up-regulated during tomato(Solanum lycopersicum L.)fruit ripening.By using mutants of different autophagy pathway genes(ATG6,ATG10,ATG18a),we revealed that the deficiency of autophagy delayed the ripening of fruit.Compared with wild-type(WT),the production of ethylene was significantly reduced and the accumulation of lycopene was delayed in atg mutants during fruit ripening.We also observed the contents of glucose and fructose were both significantly decreased in atg mutants compared with WT,while the content of organic acids showed the opposite trend.Additionally,the negative regulator of ethylene production,APETALA2a(AP2a),interacted with ATG8 through a specific ATG8-interacting motif(AIM)and could be degraded through the autophagy pathway.These results demonstrate that autophagy plays a critical role in fruit ripening by regulating ethylene production and the accumulation of pigments,sugars and organic acids in tomato.展开更多
Binuclear complexes have attracted extensive attention in fields such as catalysis because of their likely bimetallic synergistic effect;however,the mechanism and factors influencing this synergism remain unclear.In t...Binuclear complexes have attracted extensive attention in fields such as catalysis because of their likely bimetallic synergistic effect;however,the mechanism and factors influencing this synergism remain unclear.In this work,six bis-β-ketoimine binuclear titanium complexes4a-4f containing different alkylthio sidearms and configurations were synthesized and characterized by nuclear magnetic resonance hydrogen spectrum(~1H-NMR),nuclear magnetic resonance carbon spectrum(^(13)C-NMR),Fourier transform infrared spectrum(FTIR),and elemental analysis.The intermetallic distances of isomeric complexes 4a,4d,4e and 4f determined through density functional theory(DFT)optimization were in the order 4a<4d<4e<4f and were found to significantly influence the catalytic performance for ethylene(co)polymerization.These complexes could efficiently catalyze ethylene polymerization and ethylene/1-hexene or ethylene/1-octene copolymerization with high activity to produce highmolecular-weight ethylene homo-and co-polymers.Among the three binuclear titanium complexes 4a-4c with similar structures but different lengths of alkylthio sidearms,complex 4a,which contained the shortest methylthio sidearm,exhibited the highest activity for ethylene polymerization and copolymerization with 1-hexene or 1-octene.Additionally,for ethylene/1-hexene or ethylene/1-octene copolymerization,it showed the highest comonomer incorporation compared with propylthio(4b)and octylthio(4c)derivatives because of the smaller steric hindrance of the methyl group in 4a and the more open coordination space for vinyl monomers.Furthermore,among the isomeric complexes 4a,4d,4e and4f,complex 4a with the shortest bimetallic distance also exhibited the highest activity towards ethylene(co)polymerization,and the highest 1-hexene or 1-octene incorporation in comparison with its regioisomeric counterparts 4d,4e and p-phenyl-bridged analog 4f,owing to a more appropriate bimetallic distance that is conducive to a synergistic effect.展开更多
Ambient temperature affects the occurrence and prevalence of plant disease.Most bacterial diseases are damaging at high temperatures.However,kiwifruit bacterial canker caused by Pseudomonas syringae pv.actinidiae(Psa)...Ambient temperature affects the occurrence and prevalence of plant disease.Most bacterial diseases are damaging at high temperatures.However,kiwifruit bacterial canker caused by Pseudomonas syringae pv.actinidiae(Psa)has been found to be prevalent at relatively cool temperatures,and it is unclear how ambient temperature affects the development of kiwifruit bacterial canker.In this study,basal resistance to Psa was suppressed in kiwifruit at cool growth temperature(16℃)compared with at normal temperature(24℃).In addition,RNA sequence analysis and ethylene content assessment indicated that ethylene modulated kiwifruit resistance to Psa at normal growth temperature and that cool temperature inhibited ethylene accumulation and Psa-induced activation of the ethylene signaling pathway in kiwifruit.Virusmediated silencing of the kiwifruit ethylene signaling gene AcEIN2 suppressed kiwifruit resistance to Psa at normal growth temperature.Exogenous application of ethylene inhibitor 1-methylcyclopropene eliminated the difference in kiwifruit resistance to Psa at 16 and 24℃.Exogenous application of ethylene analogues ethephon induced resistance to Psa in kiwifruit.In conclusion,cool temperatures impair basal resistance to Psa by reducing the activation of ethylene biosynthesis and signaling in kiwifruit.The results provide clues for new strategies to control plant diseases in a context of global environmental change.展开更多
Ethylene(C_(2)H_(4))is a core raw material for the petrochemical industry.It is of economic and environmental significance to use C_(2)H_(6)as the fuel and proton-conducting solid oxide fuel cells(P-SOFC)as the reacto...Ethylene(C_(2)H_(4))is a core raw material for the petrochemical industry.It is of economic and environmental significance to use C_(2)H_(6)as the fuel and proton-conducting solid oxide fuel cells(P-SOFC)as the reactor to co-generate electricity and C_(2)H_(4).However,the large-sized Ni particles in the conventional Nicermet anode directly crack C_(2)H_(6);and oxide materials with a mild capability of breaking C-C bonds are generally limited to electrolyte-supported structures with high ohmic impedance.This research for the first time constructs an anode-supported cell using BZCY as the porous scaffold and impregnated double perovskite(PrBa)_(0.95)(Fe_(0.8)Ni_(0.2))_(1.8)Mo_(0.2)O_(6-δ)(PBFNM0.2)as the anode electrocatalysis.FeNi3 nanoparticles exsolve from PBFNM0.2 in H_(2) and uniformly distribute on the surface of perovskite substrate,acting as an active component for C_(2)H_(6)dehydrogenation and electrochemical performance enhancement.The cell with 30 wt%PBFNM0.2 impregnated anode showing a high power density of 508 and 386mW/cm^(2) with H_(2) and C_(2)H_(6)fuels,respectively;high C_(2)H_(6)conversion of 50.9%,C_(2)H_(4)selectivity of 92.1%,and C_(2)H_(4)yield of 46.9%are achieved at 750℃and 700mA/cm^(2),which outperforms all previously electrolyte-supported cells for co-generated electricity and ethylene.Moreover,the cell demonstrated excellent recoverability throughout three dehydrogenation-regeneration cycles.This work provides a practical way with broad application potential to create a novel anode-supported cell efficiently realizing the co-generation of electricity and C_(2)H_(4)from C_(2)H_(6).展开更多
The small punch test technique facilitates the convenient acquisition of the mechanical properties of in-service equipment materials and the assessment of their remaining service life through sampling.However,the weld...The small punch test technique facilitates the convenient acquisition of the mechanical properties of in-service equipment materials and the assessment of their remaining service life through sampling.However,the weldability of components with thin walls after small punch sampling,such as ethylene cracking furnace tubes,requires further investigation.Therefore,the weldability of in-service ethylene cracking furnace tubes following small punch sampling was investigated through nondestructive testing,microstructural characterization,and mechanical testing.Additionally,the impact of small punch sampling size and residual stress on the creep performance of the specimens was studied using an improved ductility exhaustion model.The results indicate that both the surface and interior of the weld repair areas on new furnace tubes and service-exposed furnace tubes after small-punch sampling are defect-free,exhibiting good weld quality.The strength of the specimens after weld repair was higher than that before sampling,whereas toughness decreased.Weld repair following small punch sampling of furnace tubes is both feasible and necessary.Furthermore,a linear relationship was observed between specimen thickness,diameter,and creep fracture time.The residual stress of welding affects the creep performance of the specimen under different stresses.展开更多
Controlled synthesis of two-dimensional covalent organic frameworks(2D COFs),including stoichiometric and sub-stoichiometric variations,is a topic of growing interest due to its potential in gas separation application...Controlled synthesis of two-dimensional covalent organic frameworks(2D COFs),including stoichiometric and sub-stoichiometric variations,is a topic of growing interest due to its potential in gas separation applications.In this study,we successfully synthesized three distinct 2D COFs by carefully adjusting solvent compositions and monomer ratios during the synthesis of[4+4]type COFs.These included a stoichiometric[4+4]type COF and two sub-stoichiometric[4+2]type COFs,featuring unreacted amino or formyl groups.The resulting COFs exhibit different gas adsorption and separation properties.Specifically,sub-stoichiometric COF-DA with residual amino groups shows comparable adsorption capacity for C_(2)H_(2),C_(2)H_(4),and CO_(2)to stoichiometric COF-DAPy.In contrast,sub-stoichiometric COF-Py with residual formyl groups displays enhanced adsorption selectivity for C_(2)H_(2)/C_(2)H_(4)and C_(2)H_(2)/CO_(2)separation,with the C_(2)H_(2)/C_(2)H_(4)selectivity being the highest among reported COFs,attributed to increased pore polarity resulting from the presence of formyl groups.This study not only offers an additional example of substoichiometric COF synthesis but also advocates for further exploration of sub-stoichiometric COF materials,particularly in the field of gas adsorption and separation.展开更多
BACKGROUND Ethylene glycol(EG)poisoning is often caused by the accidental ingestion of antifreeze.EG is metabolized into glycolate and oxalate and may cause metabolic acidaemia,neurotoxicity,acute kidney injury,and de...BACKGROUND Ethylene glycol(EG)poisoning is often caused by the accidental ingestion of antifreeze.EG is metabolized into glycolate and oxalate and may cause metabolic acidaemia,neurotoxicity,acute kidney injury,and death.A variety of EG poisoning case reports have been published,and we wrote this case report and literature review to summarize the clinical experience of patients who survived EG poisoning.CASE SUMMARY In this case report,a 55-year-old man developed EG poisoning after ingesting antifreeze by accident and experienced acute kidney injury,nervous system dysfunction and inhalation pneumonia.The timely use of ethanol for detoxification,initiation of haemodialysis,and protection of organ function are effective treatment methods for patients with antifreeze poisoning.The patient was discharged in the 3rd week after admission.When discharged,the patient did not report any discomfort,had stable vital signs,did not have fever or diarrhoea,and had improved liver and kidney functions.CONCLUSION A timely diagnosis,haemodialysis,and organ protection are the keys to the successful treatment of poisoned patients.展开更多
Dehydrin(DHN)enhances plant resistance to environmental stress by regulating the synthesis of osmotic adjustment substances and scavenging reactive oxygen species.However,the role of PbDHN3 under salt stress remains u...Dehydrin(DHN)enhances plant resistance to environmental stress by regulating the synthesis of osmotic adjustment substances and scavenging reactive oxygen species.However,the role of PbDHN3 under salt stress remains unclear.In this study,salt stress induced high expression of PbDHN3,and the overexpression of PbDHN3(OE-PbDHN3)enhanced plant growth under salt stress compared to wild-type(WT)plants.OE-PbDHN3 plants exhibited higher chlorophyll content and root growth capacity than WT plants under salt stress.Transcriptome analysis revealed that PbDHN3 expression is associated with ethylene signaling pathways.OE-PbDHN3 transgenic plants substantially influenced ethylene content and the expression of related genes.Following treatment with exogenous ethephon,the transgenic lines notably inhibited the processes of ethylene synthesis and signaling transduction.OE-PbDHN3 transgenic lines treated with exogenous ethylene and the ethylene inhibitor 1-MCP demonstrated significant inhibition of ethylene synthesis and signaling transduction,while promoting root development and chlorophyll content.Under salt stress,OE-PbDHN3 downregulated the expression of ethylene biosynthesis genes PbACO1-like and PbACO2,and signal transduction genes PbEIN3-like during the initial stress phase.This early regulation mitigated the adverse effects of salt stress on the plants.These findings demonstrate that PbDHN3 ameliorates the ethylene-mediated plant growth phenotype under salt stress through regulation of ethylene synthesis and signal transduction.展开更多
Electrochemical reduction of carbon dioxide(CO_(2)RR)is a promising approach to complete the carbon cycle and potentially convert CO_(2)into valuable chemicals and fuels.Cu is unique among transition metals in its abi...Electrochemical reduction of carbon dioxide(CO_(2)RR)is a promising approach to complete the carbon cycle and potentially convert CO_(2)into valuable chemicals and fuels.Cu is unique among transition metals in its ability to catalyze the CO_(2)RR and produce multi-carbon products.However,achieving high selectivity for C2+products is challenging for copper-based catalysts,as C–C coupling reactions proceed slowly.Herein,a surface modification strategy involving grafting long alkyl chains onto copper nanowires(Cu NWs)has been proposed to regulate the electronic structure of Cu surface,which facilitates*CO-*CO coupling in the CO_(2)RR.The hydrophobicity of the catalysts increases greatly after the introduction of long alkyl chains,therefore the hydrogen evolution reaction(HER)has been inhibited effectively.Such surface modification approach proves to be highly efficient and universal,with the Faradaic efficiency(FE)of C_(2)H_(4) up to 53%for the optimized Cu–SH catalyst,representing a significant enhancement compared to the pristine Cu NWs(30%).In-situ characterizations and theoretical calculations demonstrate that the different terminal groups of the grafted octadecyl chains can effectively regulate the charge density of Cu NWs interface and change the adsorption configuration of*CO intermediate.The top-adsorbed*CO intermediates(*COtop)on Cu–SH catalytic interface endow Cu–SH with the highest charge density,which effectively lowers the reaction energy barrier for*CO-*CO coupling,promoting the formation of the*OCCO intermediate,thereby enhancing the selectivity towards C_(2)H_(4).This study provides a promising method for designing efficient Cu-based catalysts with high catalytic activity and selectivity towards C2H4.展开更多
Electrocatalytic carbon dioxide reduction(CO_(2)ER)driven by renewable energy sources to produce high-valueadded chemicals is a highly promising strategy for achieving a closed carbon cycle.Cu is the only highly activ...Electrocatalytic carbon dioxide reduction(CO_(2)ER)driven by renewable energy sources to produce high-valueadded chemicals is a highly promising strategy for achieving a closed carbon cycle.Cu is the only highly active catalyst capable of producing multi-carbon(C_(2)t)products through CO_(2)ER.However,due to the constraints of existing scaling relationships and competing hydrogen evolution reaction,it is still challenging to achieve high selectivity of a single desired product.In this work,high-entropy alloy(HEA)CuMoRuFeW surface skin on Cu nanorods was obtained by a one-pot co-reduction method.It is revealed that Fe could effectively facilitate the coreduction of Mo and W precursors and the formation of HEA surface on Cu nanorod.The Faradaic efficiency(FE)for ethylene and ethanol in CO_(2)ER reaches 49.5%and 20.4%,respectively,with a total FEC_(2)of 69.9%and current density of 250 mA cm^(-2)at-1.1 V vs.RHE.Theoretical calculations reveal that the Cu–W–Fe combination site is more active in CO_(2)activation and C–C coupling for C_(2)products than other sites.This work underscores the importance of HEA in overcoming the constraints of linear scaling relationships and improving the selectivity for C_(2)products in CO_(2)ER.展开更多
Electrocatalytic valorization of disused poly(ethylene terephthalate)(PET)plastics into value-added chemicals emerges as a potential approach to address plastic pollution and resources upgrading,but it faces challenge...Electrocatalytic valorization of disused poly(ethylene terephthalate)(PET)plastics into value-added chemicals emerges as a potential approach to address plastic pollution and resources upgrading,but it faces challenges in the development of efficient catalysts for PET-derived ethylene glycol(EG)electrooxidation.Herein,we proposed pyramid arrays on sheet Fe-doped NiO/FeNi_(3)(SPA-NiFeO_(x)/FeNi_(3))heterostructure,which is derived from the pyrolysis of MOF-on-MOF heterostructure growth triggered by graphene quantum dots(GQDs).Such SPA-NiFeO_(x)/FeNi_(3)exhibits superior catalytic performance on the electrooxidation of EG(EGOR)from PET hydrolysate,with a formic acid(FA)selectivity of 91.5%and a Faradaic efficiency of 92%.The ligand effect of GQDs in both the catalyst design and improved electrocatalytic performance was studied with combined spectroscopy analysis and theoretical calculations,which revealed that such spatially separated NiFeO_(x)and FeNi_(3)components by GQDs possess more active sites to anticipate in electrocatalytic EGOR,and the large sp2 domains in GQDs possess a strong electron-withdrawing ability to reduce the electron density of bonded Ni and Fe,resulting in high-valenced Ni^(δ+)/Fe^(δ+)in FeNi_(3)and Ni(2+δ)in NiO,respectively.Furthermore,the coordination number of Ni and Fe centers was lowered due to the steric effect of GQDs.Therefore,the adsorption of EG on Ni^(δ+)for cascade dehydrogenation and C–C bond cleavage led to adsorbed FA that transferred to adjacent Fe for desorption,which was promoted by the enrichment of OH−on nearby Ni^((2+δ))sites,along with optimized Gibbs free energy change in the multistep reaction pathway.This work provides an efficient multi-active-site catalyst for disused PET plastics valorization,thereby presenting a new approach to enhance the efficiency of PET plastics valorization reactions.展开更多
To develop an efficient electrochemical CO_(2)reduction reaction(CO_(2)RR)for the production of C_(2)chemicals,improvements in the Cu catalyst are necessary.Doping is widely used for catalyst enhancement;however,only ...To develop an efficient electrochemical CO_(2)reduction reaction(CO_(2)RR)for the production of C_(2)chemicals,improvements in the Cu catalyst are necessary.Doping is widely used for catalyst enhancement;however,only a few elements have been examined.This study proposes guidelines for the selection of Cu catalyst dopants to promote ethylene production.It was hypothesized that the dopant chemical state highly influences the CO_(2)RR catalytic activity.In the case of dopants possessing a standard reduction potential within the CO_(2)RR potential region(e.g.,Mn and Ni),low Faradaic efficiency(FE)toward ethylene production was obtained owing to the presence of a metallic dopant(10.7%for Ni dopant).In contrast,a low standard reduction potential led to a stable high oxidation state for the dopant,yielding abundant Cu^(δ+)species with modified electronic structures and enhancing the CO_(2)RR catalytic activity for ethylene production(42.1%for Hf dopant).We expected that a dopant with a low standard reduction potential is difficult to reduce,which leads to a stable Cu-O-X bond and induces a stable Cu^(δ+)species.Our study provides insights into how to select dopant for various catalyst to enhance CO_(2)RR catalytic activity.展开更多
基金supported by the National Natural Science Foundation of China(No.22278041)the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(No.2022-K78)+1 种基金Jiangsu Province Key Laboratory of Fine Petrochemical Engineering(No.KF2107)the Advanced Catalysis and Green Manufacturing Collab-orative Innovation Center(No.ACGM2022-10-07)。
文摘Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(CO_(2)).With a maximal EDA conversion of 82%and EU selectivity of 99%at 160℃ for 2 h,Mn_(2)O_(3) catalysts had the best catalytic activity among them,which was superior to the reported catalysts.In the following order:Mn_(2)O_(3)>MnO_(2)>Mn_(3)O_(4),the catalytic activity for the synthesis of EU from CO_(2) and EDA decreased.Further characterization showed the Mn_(2)O_(3) catalyst possessed a greater Mn^(3+)/Mn4+ratio and more surface oxygen vacancies than the MnO_(2) and Mn_(3)O_(4),which improved its capacity to adsorb and activate CO_(2) and EDA.After four recycling runs,the EDA conversion slightly declined from 82%to 56%on Mn_(2)O_(3) catalyst,while no obvious change in EU selectivity was observed.The loss of surface Ov contents and Mn^(3+)proportion were concluded as main reasons for the decrease in catalytic activity over Mn_(2)O_(3) catalyst.This work demonstrated a metal oxide catalyst that was efficient in producing EU from CO_(2) and EDA.
文摘Ethylene glycol(EG)is a biomass derivative of polyethylene terephthalate(PET),and its electrocatalytic conversion into high-value chemicals has sparked widespread interest.This study reviews the most recent research development in electrocatalysis-based EG to glycolic acid(GA)conversion.Firstly,the strategies and research results of modulating the electronic structure of catalysts for efficient selective GA production from EG are reviewed.Second,by reviewing the data of in-situ Fourier transform infrared spectroscopy and in-situ electrochemically attenuated total reflection surface enhanced infrared absorption spectroscopy,the reaction pathway and catalytic mechanism of EG partial oxidation to GA were clarified.Finally,the design and regulation of catalysts for selective oxidation of EG by electrocatalysis in the future are prospected.
文摘Although the efficiency of poly(ethylene terephthalate)(PET)degradation has been successfully improved by depolymerase engineering,mostly by using Goodfellow-PET(gf-PET)as a substrate,efforts to degrade unpretreated PET materials with high crystallinity remain insufficient.Here,we endeavored to improve the degradation capability of a WCCG mutant of leaf-branch compost cutinase(LCC)on a unpretreated PET substrate(crystallinity>40%)by employing iterative saturation mutagenesis.Using this method,we developed a high-throughput screening strategy appropriate for unpretreated substrates.Through extensive screening of residues around the substrate-binding groove,two variants,WCCG-sup1 and WCCG-sup2,showed good depolymerization capabilities with both high-(42%)and low-crystallinity(9%)substrates.The WCCG-sup1 variant completely depolymerized a commercial unpretreated PET product in 36 h at 72℃.In addition to enzyme thermostability and catalytic efficiency,the adsorption of enzymes onto substrates plays an important role in PET degradation.This study provides valuable insights into the structure-function relationship of LCC.
基金financially supported by the Maoming Science and Technology Bureau(No.2022DZXHT007)。
文摘The synthesis of polyurethanes(PUs)from the reaction of low molecular weight poly(ethylene carbonate)diol(PECD)is rarely investigated.This work reports a novel PU with excellent mechanical properties from the solution polymerization of 4,4-diphenylmethane diisocyanate(MDI)with PECD that was derived from the copolymerization of carbon dioxide(CO_(2))and ethylene oxide(EO).The tensile strength,the elongation at break and 300%constant tensile strength of the PECD-PU were up to 66±2 MPa,880%±50%and 13 MPa,respectively,higher than the control PUs from the reaction of MDI with commercial polyethers or polyesters.The PECD-PU with high CO_(2) carbonate content exhibited good solvent resistance and chemical stability.Of importance,the mechanical properties and chemical resistance of PECD-PU were significantly enhanced with the increasing content of CO_(2),i.e.,the carbonate unit in PECD.This work provides comprehensive properties of PECD-derived PUs,indicating that PECD is a competitive precursor for the preparation of PU and has broad application prospects.
基金supported by grants from Jiangsu province seed industry revitalization of the leading project(JBGS[2021]086)the National Natural Science Funds(31972373,32272647,32202433)+1 种基金the Provincial Natural Science Foundation of Jiangsu(BK20200541)the Priority Academic Program Development of Jiangsu Higher Education Institutions,China(PAPD),and Postgraduate Research&Practice Innovation Program of Jiangsu Province,China(KYCX22_0754,SJCX23-0209).
文摘Polyamines(PAs)and ethylene are involved in the modulation of plant growth and development.However,their roles in fruit-set,especially in exogenous gibberellin(GA_(3))-induced grape parthenocarpic berries,and the related competitive action mode are poorly understood.For this,we,here performed their content determination,bioinformatics and expression pattern analysis of genes to identify the key ones in the competitive network of polyamines metabolic and ethylene biosynthesis(PMEB)pathways.The content of putrescine(Put)significantly increased;while 1-aminocyclopropanecarboxylic acid(ACC)sharply decreased during the fruit-set process of GA_(3)-induced grape parthenocarpic seedless berries.Totally,twenty-five genes in PMEB pathways,including 20 polyamines metabolic(PM)genes and 5 ethylene biosynthesis(EB)ones were identified in grape,of which 8 PM and 2 EB genes possessed the motifs responsive to phytohormone GA.The expression levels of most PMEB genes kept changing during grape fruit-set generating a competitive action mode of GA_(3)-mediated two metabolic fluxes toward PAs and ethylene synthesis.Exogenous GA_(3)might enhance grape fruit-set of parthenocarpic berries via up-regulation of VvSAMS4,VvSAMDC1/2,VvODC1,VvSPDS1,and VvPAO1 to promote PAs accumulation,whereby repressing the ethylene synthesis by down-regulation of VvACS1 and VvACO_(2).Our findings provide novel insights into GA_(3)-mediated competitive inhibition of ethylene by PAs to promote the fruit-set of parthenocarpic berries in grape,which has important implications for molecular breeding of seedless grape with high fruit-setting rate.
文摘Upgrading carbon dioxide(CO_(2))into value-added bulk chemicals offers a dual-benefit strategy for the carbon neutrality and circular carbon economy.Herein,we develop an integrated CO_(2) valorization strategy that synergizes CO_(2)-H_(2)O co-electrolysis(producing CO/O_(2) feeds)with oxidative double carbonylation of ethylene/acetylene to synthesize CO_(2)-derived C_(4) diesters(dimethyl succinate,fumarate,and maleate).A group of versatile building blocks for manufacturing plasticizers,biodegradable polymers,and pharmaceutical intermediates.Remarkably,CO_(2) exhibits dual functionality:serving simultaneously as a CO/O_(2) source and an explosion suppressant during the oxidative carbonylation process.We systematically investigated the explosion-suppressing efficacy of CO_(2) in flammable gas mixtures(CO/O_(2),C_(2)H_(4)/CO/O_(2),and C_(2)H_(2)/CO/O_(2))across varying concentrations.Notably,the mixed gas stream from CO_(2)/H_(2)O co-electrolysis at an industrial-scale current densities of 400 mA/cm^(2),enabling direct utilization in oxidative double carbonylation reactions with exceptional compatibility and inherent safety.Extended applications were demonstrated through substrate scope expansion and gram-scale synthesis.This study establishes not only a safe protocol for oxidative carbonylation processes,but also opens an innovative pathway for sustainable CO_(2) valorization,including CO surrogate and explosion suppressant.
基金supported by the National Natural Science Foundation of China(Grant Nos.32360743,32072559,31860568,31560563 and 31160398)the National Key Research and Development Program(Grant No.2018YFD1000800).
文摘Tomato(Solanum lycopersicum)has become a model for the study of fleshy fruits.Comprehending the regulatory mechanisms of fleshy fruit ripening is important.Transcription factors(TFs),hormones,and epigenetic regulation mainly regulate tomato fruit ripening,and the initiation of ripening requires ethylene and ripening-related TFs,such as NAC,MADS-box,RIN,GH3,HD-ZIP,and basic helix-loop-helix.In this review,we summarize recent research progress on these TFs in the regulation of tomato fruit ripening and highlight the crosstalk mechanisms of ethylene and ripening-related TFs.By affecting ethylene synthesis and signaling,TFs regulate softening and color changes in tomato fruits,thereby influencing fruit quality.Our review contributes to a systematic understanding of the regulatory mechanisms of tomato fruit ripening and provides a basis for developing or modeling complex ripening regulatory networks.
基金supported by grants from the National Natural Science Foundation of China(Grant Nos.32025032 and 32202415)the Agricultural Breeding Project of Ningxia Hui Autonomous Region(Grant No.NXNYYZ20210104)the National Key Research and Development Program of China(Grant No.2022YFE0116400).
文摘In climacteric fruits,the role of ethylene in promoting ripening process and its molecular regulatory mechanisms have been well elucidated.However,research into ethylene's roles in non-climacteric fruits has only advanced in recent years,largely because these fruits produce much less ethylene than climacteric fruits.Consequently,reports on its molecular regulatory involvement are still limited.Grape(Vitis vinifera L.),one of the most economically valuable fruits,is regarded as a classical non-climacteric fruit.In this study,an enzyme participating in the last step of ethylene biosynthesis,VvACO1,has been identified as a key enzyme controlling ethylene release in grape fruits(Vitis vinifera‘Jingyan’and‘Red Balado’)using correlation analysis and enzymatic experiments.The transcriptional regulation of VvACO1 was investigated by integrating multiple methods such as DNA pull-down assays,co-expression analysis,dual luciferase reporting system,yeast one-hybrid assays,and transgenic experiments.Our findings revealed that the upregulation of VvACO1 in grape fruits was primarily caused by the removal of transcriptional inhibition.Remarkably,seven transcription factors(TFs)were identified as inhibitors of VvACO1,including VvHY5 from bZIP family,VvWIP2 from C2H2 family,VvBLH1 from Homeobox family,VvAG1 and VvCMB1 from MADS-box family,VvASIL1 and VvASIL2 from Trihelix family.These seven TFs were located in nuclei and exhibited transcriptional inhibition activity.Notably,VvAG1 and VvASIL2 could inhibit VvACO1 expression when overexpressed in grape leaves.Our findings provided theoretical clues for differences of ethylene release regulation between climacteric and non-climacteric fruits,also the identified seven TFs could be potential targets for grape molecular breeding.
基金supported by the National Natural Science Foundation of China(Grant Nos.32302642,32272790)the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(Grant No.SN-ZJU-SIAS-0011)+1 种基金Collaborative Promotion Program of Zhejiang Provincial Agricultural Technology of China(Grant No.2023ZDXT05)the Fundamental Research Funds for the Central Universities(Grant No.226-2022-00122).
文摘Autophagy is a universal cellular process in eukaryotes that plays a critical role in plant growth and stress response.However,the role of autophagy in fruit ripening is largely unknown.Here,we demonstrated that most autophagy-related genes(ATGs)were up-regulated during tomato(Solanum lycopersicum L.)fruit ripening.By using mutants of different autophagy pathway genes(ATG6,ATG10,ATG18a),we revealed that the deficiency of autophagy delayed the ripening of fruit.Compared with wild-type(WT),the production of ethylene was significantly reduced and the accumulation of lycopene was delayed in atg mutants during fruit ripening.We also observed the contents of glucose and fructose were both significantly decreased in atg mutants compared with WT,while the content of organic acids showed the opposite trend.Additionally,the negative regulator of ethylene production,APETALA2a(AP2a),interacted with ATG8 through a specific ATG8-interacting motif(AIM)and could be degraded through the autophagy pathway.These results demonstrate that autophagy plays a critical role in fruit ripening by regulating ethylene production and the accumulation of pigments,sugars and organic acids in tomato.
基金financially supported by the National Natural Science Foundation of China(No.21172269)the Fundamental Research Funds for the Central Universities,SouthCentral Minzu University(No.CZH24005)。
文摘Binuclear complexes have attracted extensive attention in fields such as catalysis because of their likely bimetallic synergistic effect;however,the mechanism and factors influencing this synergism remain unclear.In this work,six bis-β-ketoimine binuclear titanium complexes4a-4f containing different alkylthio sidearms and configurations were synthesized and characterized by nuclear magnetic resonance hydrogen spectrum(~1H-NMR),nuclear magnetic resonance carbon spectrum(^(13)C-NMR),Fourier transform infrared spectrum(FTIR),and elemental analysis.The intermetallic distances of isomeric complexes 4a,4d,4e and 4f determined through density functional theory(DFT)optimization were in the order 4a<4d<4e<4f and were found to significantly influence the catalytic performance for ethylene(co)polymerization.These complexes could efficiently catalyze ethylene polymerization and ethylene/1-hexene or ethylene/1-octene copolymerization with high activity to produce highmolecular-weight ethylene homo-and co-polymers.Among the three binuclear titanium complexes 4a-4c with similar structures but different lengths of alkylthio sidearms,complex 4a,which contained the shortest methylthio sidearm,exhibited the highest activity for ethylene polymerization and copolymerization with 1-hexene or 1-octene.Additionally,for ethylene/1-hexene or ethylene/1-octene copolymerization,it showed the highest comonomer incorporation compared with propylthio(4b)and octylthio(4c)derivatives because of the smaller steric hindrance of the methyl group in 4a and the more open coordination space for vinyl monomers.Furthermore,among the isomeric complexes 4a,4d,4e and4f,complex 4a with the shortest bimetallic distance also exhibited the highest activity towards ethylene(co)polymerization,and the highest 1-hexene or 1-octene incorporation in comparison with its regioisomeric counterparts 4d,4e and p-phenyl-bridged analog 4f,owing to a more appropriate bimetallic distance that is conducive to a synergistic effect.
基金supported by grants from the National Key Research and Development Program of China(Grant No.2022YFD1400200)the Special Support Plan for High-Level Talent of Shaanxi Province。
文摘Ambient temperature affects the occurrence and prevalence of plant disease.Most bacterial diseases are damaging at high temperatures.However,kiwifruit bacterial canker caused by Pseudomonas syringae pv.actinidiae(Psa)has been found to be prevalent at relatively cool temperatures,and it is unclear how ambient temperature affects the development of kiwifruit bacterial canker.In this study,basal resistance to Psa was suppressed in kiwifruit at cool growth temperature(16℃)compared with at normal temperature(24℃).In addition,RNA sequence analysis and ethylene content assessment indicated that ethylene modulated kiwifruit resistance to Psa at normal growth temperature and that cool temperature inhibited ethylene accumulation and Psa-induced activation of the ethylene signaling pathway in kiwifruit.Virusmediated silencing of the kiwifruit ethylene signaling gene AcEIN2 suppressed kiwifruit resistance to Psa at normal growth temperature.Exogenous application of ethylene inhibitor 1-methylcyclopropene eliminated the difference in kiwifruit resistance to Psa at 16 and 24℃.Exogenous application of ethylene analogues ethephon induced resistance to Psa in kiwifruit.In conclusion,cool temperatures impair basal resistance to Psa by reducing the activation of ethylene biosynthesis and signaling in kiwifruit.The results provide clues for new strategies to control plant diseases in a context of global environmental change.
基金financially supported by the National Natural Science Foundation of China(Nos.52072134,52272205)Hubei Province(Nos.2021BCA149,2021CFA072,2022BAA087)the special fund for Science and Technology Innovation Teams of Shanxi Province(No.202304051001007)。
文摘Ethylene(C_(2)H_(4))is a core raw material for the petrochemical industry.It is of economic and environmental significance to use C_(2)H_(6)as the fuel and proton-conducting solid oxide fuel cells(P-SOFC)as the reactor to co-generate electricity and C_(2)H_(4).However,the large-sized Ni particles in the conventional Nicermet anode directly crack C_(2)H_(6);and oxide materials with a mild capability of breaking C-C bonds are generally limited to electrolyte-supported structures with high ohmic impedance.This research for the first time constructs an anode-supported cell using BZCY as the porous scaffold and impregnated double perovskite(PrBa)_(0.95)(Fe_(0.8)Ni_(0.2))_(1.8)Mo_(0.2)O_(6-δ)(PBFNM0.2)as the anode electrocatalysis.FeNi3 nanoparticles exsolve from PBFNM0.2 in H_(2) and uniformly distribute on the surface of perovskite substrate,acting as an active component for C_(2)H_(6)dehydrogenation and electrochemical performance enhancement.The cell with 30 wt%PBFNM0.2 impregnated anode showing a high power density of 508 and 386mW/cm^(2) with H_(2) and C_(2)H_(6)fuels,respectively;high C_(2)H_(6)conversion of 50.9%,C_(2)H_(4)selectivity of 92.1%,and C_(2)H_(4)yield of 46.9%are achieved at 750℃and 700mA/cm^(2),which outperforms all previously electrolyte-supported cells for co-generated electricity and ethylene.Moreover,the cell demonstrated excellent recoverability throughout three dehydrogenation-regeneration cycles.This work provides a practical way with broad application potential to create a novel anode-supported cell efficiently realizing the co-generation of electricity and C_(2)H_(4)from C_(2)H_(6).
基金supports provided by the National Natural Science Foundation of China(No.52372330).
文摘The small punch test technique facilitates the convenient acquisition of the mechanical properties of in-service equipment materials and the assessment of their remaining service life through sampling.However,the weldability of components with thin walls after small punch sampling,such as ethylene cracking furnace tubes,requires further investigation.Therefore,the weldability of in-service ethylene cracking furnace tubes following small punch sampling was investigated through nondestructive testing,microstructural characterization,and mechanical testing.Additionally,the impact of small punch sampling size and residual stress on the creep performance of the specimens was studied using an improved ductility exhaustion model.The results indicate that both the surface and interior of the weld repair areas on new furnace tubes and service-exposed furnace tubes after small-punch sampling are defect-free,exhibiting good weld quality.The strength of the specimens after weld repair was higher than that before sampling,whereas toughness decreased.Weld repair following small punch sampling of furnace tubes is both feasible and necessary.Furthermore,a linear relationship was observed between specimen thickness,diameter,and creep fracture time.The residual stress of welding affects the creep performance of the specimen under different stresses.
基金supported by the National Key Research and Development Project of China(No.2022YFE0113800)the National Natural Science Foundation of China(No.22375179)+1 种基金the startup grant(No.2019125016829)in Zhejiang University of Technologypartially supported by the National Innovation and Entrepreneurship Training Program(No.202310337063)。
文摘Controlled synthesis of two-dimensional covalent organic frameworks(2D COFs),including stoichiometric and sub-stoichiometric variations,is a topic of growing interest due to its potential in gas separation applications.In this study,we successfully synthesized three distinct 2D COFs by carefully adjusting solvent compositions and monomer ratios during the synthesis of[4+4]type COFs.These included a stoichiometric[4+4]type COF and two sub-stoichiometric[4+2]type COFs,featuring unreacted amino or formyl groups.The resulting COFs exhibit different gas adsorption and separation properties.Specifically,sub-stoichiometric COF-DA with residual amino groups shows comparable adsorption capacity for C_(2)H_(2),C_(2)H_(4),and CO_(2)to stoichiometric COF-DAPy.In contrast,sub-stoichiometric COF-Py with residual formyl groups displays enhanced adsorption selectivity for C_(2)H_(2)/C_(2)H_(4)and C_(2)H_(2)/CO_(2)separation,with the C_(2)H_(2)/C_(2)H_(4)selectivity being the highest among reported COFs,attributed to increased pore polarity resulting from the presence of formyl groups.This study not only offers an additional example of substoichiometric COF synthesis but also advocates for further exploration of sub-stoichiometric COF materials,particularly in the field of gas adsorption and separation.
文摘BACKGROUND Ethylene glycol(EG)poisoning is often caused by the accidental ingestion of antifreeze.EG is metabolized into glycolate and oxalate and may cause metabolic acidaemia,neurotoxicity,acute kidney injury,and death.A variety of EG poisoning case reports have been published,and we wrote this case report and literature review to summarize the clinical experience of patients who survived EG poisoning.CASE SUMMARY In this case report,a 55-year-old man developed EG poisoning after ingesting antifreeze by accident and experienced acute kidney injury,nervous system dysfunction and inhalation pneumonia.The timely use of ethanol for detoxification,initiation of haemodialysis,and protection of organ function are effective treatment methods for patients with antifreeze poisoning.The patient was discharged in the 3rd week after admission.When discharged,the patient did not report any discomfort,had stable vital signs,did not have fever or diarrhoea,and had improved liver and kidney functions.CONCLUSION A timely diagnosis,haemodialysis,and organ protection are the keys to the successful treatment of poisoned patients.
基金funded by the Earmarked Fund for CARS(CARS-28-07)the Agricultural Variety Improvement Project of Shandong Province,China(2022LZGC011)the Qingdao Agricultural University Doctoral Start-Up Fund,China.
文摘Dehydrin(DHN)enhances plant resistance to environmental stress by regulating the synthesis of osmotic adjustment substances and scavenging reactive oxygen species.However,the role of PbDHN3 under salt stress remains unclear.In this study,salt stress induced high expression of PbDHN3,and the overexpression of PbDHN3(OE-PbDHN3)enhanced plant growth under salt stress compared to wild-type(WT)plants.OE-PbDHN3 plants exhibited higher chlorophyll content and root growth capacity than WT plants under salt stress.Transcriptome analysis revealed that PbDHN3 expression is associated with ethylene signaling pathways.OE-PbDHN3 transgenic plants substantially influenced ethylene content and the expression of related genes.Following treatment with exogenous ethephon,the transgenic lines notably inhibited the processes of ethylene synthesis and signaling transduction.OE-PbDHN3 transgenic lines treated with exogenous ethylene and the ethylene inhibitor 1-MCP demonstrated significant inhibition of ethylene synthesis and signaling transduction,while promoting root development and chlorophyll content.Under salt stress,OE-PbDHN3 downregulated the expression of ethylene biosynthesis genes PbACO1-like and PbACO2,and signal transduction genes PbEIN3-like during the initial stress phase.This early regulation mitigated the adverse effects of salt stress on the plants.These findings demonstrate that PbDHN3 ameliorates the ethylene-mediated plant growth phenotype under salt stress through regulation of ethylene synthesis and signal transduction.
文摘Electrochemical reduction of carbon dioxide(CO_(2)RR)is a promising approach to complete the carbon cycle and potentially convert CO_(2)into valuable chemicals and fuels.Cu is unique among transition metals in its ability to catalyze the CO_(2)RR and produce multi-carbon products.However,achieving high selectivity for C2+products is challenging for copper-based catalysts,as C–C coupling reactions proceed slowly.Herein,a surface modification strategy involving grafting long alkyl chains onto copper nanowires(Cu NWs)has been proposed to regulate the electronic structure of Cu surface,which facilitates*CO-*CO coupling in the CO_(2)RR.The hydrophobicity of the catalysts increases greatly after the introduction of long alkyl chains,therefore the hydrogen evolution reaction(HER)has been inhibited effectively.Such surface modification approach proves to be highly efficient and universal,with the Faradaic efficiency(FE)of C_(2)H_(4) up to 53%for the optimized Cu–SH catalyst,representing a significant enhancement compared to the pristine Cu NWs(30%).In-situ characterizations and theoretical calculations demonstrate that the different terminal groups of the grafted octadecyl chains can effectively regulate the charge density of Cu NWs interface and change the adsorption configuration of*CO intermediate.The top-adsorbed*CO intermediates(*COtop)on Cu–SH catalytic interface endow Cu–SH with the highest charge density,which effectively lowers the reaction energy barrier for*CO-*CO coupling,promoting the formation of the*OCCO intermediate,thereby enhancing the selectivity towards C_(2)H_(4).This study provides a promising method for designing efficient Cu-based catalysts with high catalytic activity and selectivity towards C2H4.
基金supported by the National Natural Science Foundation of China(No.22272059)the Natural Science Foundation of Guangdong Province(No.2024A1515010030)。
文摘Electrocatalytic carbon dioxide reduction(CO_(2)ER)driven by renewable energy sources to produce high-valueadded chemicals is a highly promising strategy for achieving a closed carbon cycle.Cu is the only highly active catalyst capable of producing multi-carbon(C_(2)t)products through CO_(2)ER.However,due to the constraints of existing scaling relationships and competing hydrogen evolution reaction,it is still challenging to achieve high selectivity of a single desired product.In this work,high-entropy alloy(HEA)CuMoRuFeW surface skin on Cu nanorods was obtained by a one-pot co-reduction method.It is revealed that Fe could effectively facilitate the coreduction of Mo and W precursors and the formation of HEA surface on Cu nanorod.The Faradaic efficiency(FE)for ethylene and ethanol in CO_(2)ER reaches 49.5%and 20.4%,respectively,with a total FEC_(2)of 69.9%and current density of 250 mA cm^(-2)at-1.1 V vs.RHE.Theoretical calculations reveal that the Cu–W–Fe combination site is more active in CO_(2)activation and C–C coupling for C_(2)products than other sites.This work underscores the importance of HEA in overcoming the constraints of linear scaling relationships and improving the selectivity for C_(2)products in CO_(2)ER.
基金support from the National Natural Science Foundation of China(Grant No.22102140the Natural Science Foundation of Jiangsu Province(Grant No.BK20211602)+1 种基金the Qing Lan Project of Yangzhou Universitythe Postgraduate Research&Practice Innovation Program of Jiangsu Province(Yangzhou University,Grant No.SJCX23_1911).
文摘Electrocatalytic valorization of disused poly(ethylene terephthalate)(PET)plastics into value-added chemicals emerges as a potential approach to address plastic pollution and resources upgrading,but it faces challenges in the development of efficient catalysts for PET-derived ethylene glycol(EG)electrooxidation.Herein,we proposed pyramid arrays on sheet Fe-doped NiO/FeNi_(3)(SPA-NiFeO_(x)/FeNi_(3))heterostructure,which is derived from the pyrolysis of MOF-on-MOF heterostructure growth triggered by graphene quantum dots(GQDs).Such SPA-NiFeO_(x)/FeNi_(3)exhibits superior catalytic performance on the electrooxidation of EG(EGOR)from PET hydrolysate,with a formic acid(FA)selectivity of 91.5%and a Faradaic efficiency of 92%.The ligand effect of GQDs in both the catalyst design and improved electrocatalytic performance was studied with combined spectroscopy analysis and theoretical calculations,which revealed that such spatially separated NiFeO_(x)and FeNi_(3)components by GQDs possess more active sites to anticipate in electrocatalytic EGOR,and the large sp2 domains in GQDs possess a strong electron-withdrawing ability to reduce the electron density of bonded Ni and Fe,resulting in high-valenced Ni^(δ+)/Fe^(δ+)in FeNi_(3)and Ni(2+δ)in NiO,respectively.Furthermore,the coordination number of Ni and Fe centers was lowered due to the steric effect of GQDs.Therefore,the adsorption of EG on Ni^(δ+)for cascade dehydrogenation and C–C bond cleavage led to adsorbed FA that transferred to adjacent Fe for desorption,which was promoted by the enrichment of OH−on nearby Ni^((2+δ))sites,along with optimized Gibbs free energy change in the multistep reaction pathway.This work provides an efficient multi-active-site catalyst for disused PET plastics valorization,thereby presenting a new approach to enhance the efficiency of PET plastics valorization reactions.
基金supported by Research Project for‘Carbon Upcycling Project for Platform Chemicals’of the National Research Foundation(NRF)funded by the Ministry of Science and ICT,Republic of Korea(grant number:2022M3J3A1050053)supported by the National Research Council of Science&Technology(NST)grant by the Korean government(MSIT)(No.CAP21011-100)+1 种基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(RS-2023-00302697)institutional program grants from the Korea Institute of Science and Technology。
文摘To develop an efficient electrochemical CO_(2)reduction reaction(CO_(2)RR)for the production of C_(2)chemicals,improvements in the Cu catalyst are necessary.Doping is widely used for catalyst enhancement;however,only a few elements have been examined.This study proposes guidelines for the selection of Cu catalyst dopants to promote ethylene production.It was hypothesized that the dopant chemical state highly influences the CO_(2)RR catalytic activity.In the case of dopants possessing a standard reduction potential within the CO_(2)RR potential region(e.g.,Mn and Ni),low Faradaic efficiency(FE)toward ethylene production was obtained owing to the presence of a metallic dopant(10.7%for Ni dopant).In contrast,a low standard reduction potential led to a stable high oxidation state for the dopant,yielding abundant Cu^(δ+)species with modified electronic structures and enhancing the CO_(2)RR catalytic activity for ethylene production(42.1%for Hf dopant).We expected that a dopant with a low standard reduction potential is difficult to reduce,which leads to a stable Cu-O-X bond and induces a stable Cu^(δ+)species.Our study provides insights into how to select dopant for various catalyst to enhance CO_(2)RR catalytic activity.
