Poly(ethylene succinate)(PES),a promising biodegradable polyester with cost advantages,suffers from inherently slow crystallization kinetics,which severely limits its processability and practical applications.To addre...Poly(ethylene succinate)(PES),a promising biodegradable polyester with cost advantages,suffers from inherently slow crystallization kinetics,which severely limits its processability and practical applications.To address this challenge,this study explored the use of commercially available,low-cost,and food-safe sugar alcohols,including Xylitol(Xy),D-sorbitol(DS),and D-mannitol(DM),as effective nucleating agents for PES.Remarkably,all three polyols significantly enhanced the nucleation and crystallization ability of PES,with DM exhibiting the most pronounced effect.DM increased the crystallization temperature by up to 23.9°C and accelerated the overall crystallization rate by more than 13-fold at only 0.5 wt%loading level.Through a combination of differential scanning calorimetry(DSC),polarized optical microscopy(POM),and wide-angle X-ray diffraction(WAXD)analyses,we revealed that DM promotes PES crystallization via a dual mechanism:epitaxial templating facilitated by excellent lattice matching,and enhanced chain adjustment through intermolecular hydrogen-bonding interactions.In contrast,Xy and DS primarily function through hydrogen-bonding interactions.This work not only identifies DM as a highly efficient,economical,and industrially viable nucleating agent for PES,but also provides fundamental insights into the role of the molecular structure and crystallization ability of nucleating agents in regulating polymer crystallization.展开更多
Cyclic olefin copolymers(COCs)are highly valuable optical resins,but their productions on industry are fully limited by the monomer norbornene.Although ethylene/dicyclopentadiene(E/DCPD)copolymers provide a cost-effec...Cyclic olefin copolymers(COCs)are highly valuable optical resins,but their productions on industry are fully limited by the monomer norbornene.Although ethylene/dicyclopentadiene(E/DCPD)copolymers provide a cost-effective alternative to commercially available COCs because of using low-cost DCPD as cyclic olefin monomer,these inherent unsaturated double bonds on E/DCPD copolymers cause low heat resistance,oxidation,and crosslinking during processing and storage.And E/DCPD copolymers usually showed lower glass-transition temperature(T_(g))compared with commercially available COCs.In this study,we studied the E-DCPD copolymerization catalyzed by a scandium complex and the sequential hydrogenation catalyzed by a nickel compound to prepare saturated copolymers H-(E/DCPD).The polymerization activities are high up to 5.86×10^(6)g/(molSc·h),and the resultant H-(E/DCPD)copolymers showed narrow polymer dispersity index(PDI=1.5–2.0).By changing the polymerization conditions,a series of H-(E/DCPD)copolymers with tunable DCPD incorporation(28.4 mol%–44.9 mol%)and a wide range of T_(g)(123–171°C)were obtained.H-(E/DCPD)copolymers exhibited excellent optical properties(transparency>90%,refractive index of 1.543),similar to those of commercial COCs,making them an alternative for high-performance optical applications.This method solves the problems of traditional E/DCPD copolymers and provides a practical way to produce stable and low-cost COCs,and is comparable with commercially available COC resins.展开更多
Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effectiv...Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.展开更多
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catal...Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.展开更多
In this study,a series of poly(ethylene succinate)-b-poly(butylene carbonate)(PES-b-PBC)multiblock copolymers were prepared through the chain-extension reaction of hydroxyl-terminated PES(PES-OH)and hydroxyl-terminate...In this study,a series of poly(ethylene succinate)-b-poly(butylene carbonate)(PES-b-PBC)multiblock copolymers were prepared through the chain-extension reaction of hydroxyl-terminated PES(PES-OH)and hydroxyl-terminated PBC(PBC-OH)prepolymers with 1,6-hexmethylene diisocyanate(HDI)as a chain extender.The effects of the prepolymer molecular weight and content on the structure and application properties of the PES-b-PBC copolymers were systematically investigated using various techniques.It was found that the compatibility of PES and PBC blocks in PES-b-PBC copolymers can be greatly enhanced by lowering the length of the prepolymers,and the amorphous phase of the PES and PBC chain segments in the PES-b-PBC copolymer would transform from immiscibility and partial miscibility to miscibility when the number-average molecular weight(M_(n))of the PES-OH and PBC-OH prepolymers is less than 2000 g/mol.Only the crystal structure of bare PES can be observed in the wide-angle X-ray diffraction(WAXD)spectrum of the PES-b-PBC copolymers,but their crystallinity degrees were found to decrease with increasing PBC fraction.The thermal behavior,crystallization performance,rheological properties,mechanical properties,and degradation properties of the PES-b-PBC multiblock copolymers can be easily modulated by altering the block length and composition of the prepolymers,offering potential applications in biodegradable materials.展开更多
The electrocatalytic oxidation of ethylene glycol(EG)into high-value chemicals like glycolic acid(GA)is a crucial step for upcycling waste plastics.However,catalyst deactivation and low selectivity pose significant ch...The electrocatalytic oxidation of ethylene glycol(EG)into high-value chemicals like glycolic acid(GA)is a crucial step for upcycling waste plastics.However,catalyst deactivation and low selectivity pose significant challenges.This work presents the low-coordination PtBi nanosheets(LC-PtBi NSs),featuring a unique amorphous-crystalline heterostructure with a low coordination number of 2.3-2.5.They can exhibit exceptional mass activity(8.3 A mg_(Pt)^(-1))and stability(maintaining 88.7%of initial activity after running for 3600 s)of the EG oxidation reaction(EGOR).They also achieve over 90%apparent selectivity for EG-to-GA conversion at low potentials(<0.7 V vs.RHE)and even more than 100-h continuous electrolysis.Density fu nctional theory(DFT)calculations reveal that the low-coordination PtBi heterogeneous interface is responsible for the high coverage of OH_(ad) species and weakened adsorption of carbonaceous intermediates on LC-PtBi NSs,thereby promoting the direct oxidation of C_(2) intermediates to GA.This work demonstrates a strategy of doping-mediated catalytic interface regulation and electron density rearrangement,offering insights for designing efficient Pt-based electrocatalysts toward selective oxidation of small molecules.展开更多
Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardan...Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardant strategies often compromise their mechanical properties,hindering their practical applications.Herein,a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)-based comonomer(DDP)was used to synthesize flame-retardant poly(ethylene furandicarboxylate-co-phosphaphenanthrene)(PEFDn).The covalent integration of DDP confers intrinsic flame retardancy,avoiding the plasticization and migration issues associated with additive-type systems.Upon thermal decomposition,the DOPO-derived moieties release phosphoric acid and radical scavengers,promoting char formation and suppressing flame propagation.Furthermore,density functional theory(DFT)calculations combined with non-covalent interaction(NCI)analysis revealed that DOPO dimer molecules adopt a stable parallel-displaced π-π stacking configu ration,potentially facilitating microphase separation and enhancing the energy dissipation capability.PEFD_(10)achieves a UL-94 V-0 rating while simultaneously increasing impact toughness from 1.5 kJ/m^(2) to 14.7 kJ/m^(2).Im portantly,PEFDn maintained acceptable oxygen-barrier properties.PEFD10 also exhibited high transparency and UV-shielding performance.The combination of intrinsic flame safety,im pact-toughness resistance,UV shielding,and an oxygen barrier ensures reliable protection of electrical components and long-term operational stability.The integration of multiple critical properties within a single bio-based material represents a novel approach fo r enabling sustainable polymer solutions for high-pe rformance electrical applications.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
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
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
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
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
Chemical looping oxidative dehydrogenation(CL‐ODH)is a promising novel method to convert ethane into higher value‐added ethylene.In this study,perovskite‐type Co_(2)O_(3)/LaCoO_(3) was prepared by the one‐step cit...Chemical looping oxidative dehydrogenation(CL‐ODH)is a promising novel method to convert ethane into higher value‐added ethylene.In this study,perovskite‐type Co_(2)O_(3)/LaCoO_(3) was prepared by the one‐step citric acid‐gel method and applied as an oxygen carrier in the CL‐ODH process of ethane to ethylene;moreover,the effects of CuO,ZnO,and MgO as additives were investigated.The properties of the oxygen carriers were characterized using XRD,BET,XPS,H_(2)‐TPR,O_(2)‐TPD,and EPR.Characterization results showed that the addition of additives into Co_(2)O_(3)/LaCoO_(3) increased the amounts of surface chemisorbed oxygen and lattice oxygen.Co_(2)O_(3)/LaCoO_(3) had a strong ability to absorb and release oxygen after adding CuO,ZnO,and MgO,respectively.The performances of the oxygen carriers for CL‐ODH of ethane to ethylene were studied at a reaction temperature of 650℃,atmospheric pressure,and GHSV of 15,000 mL/g·h in eight redox cycles.All the oxygen carriers had 100%ethane conversion,and ZnO‐Co_(2)O_(3)/LaCoO_(3) exhibited the best ethylene selectivity of more than 70%in all the oxygen carriers.It was confirmed that lattice oxygen was mainly responsible for the selectivity of ethylene,and oxygen vacancies were conducive to the migration of lattice oxygen.Most of Zn^(2+) entered into the bulk phase of Co_(2)O_(3)/LaCoO_(3),and formed lots of oxygen vacancies.展开更多
Electrocatalytic oxidation of surplus ethylene glycol(EG)to high-value glycolic acid(GA)represents a promising approach for sustainable resource utilization,though critical challenges persist in developing durable ele...Electrocatalytic oxidation of surplus ethylene glycol(EG)to high-value glycolic acid(GA)represents a promising approach for sustainable resource utilization,though critical challenges persist in developing durable electrocatalysts and achieving effective recovery of the free acid product from its salt derivatives in alkaline electrolytes.In this work,a PdNi/NF catalyst was rationally synthesized via a one-step electrodeposition method.Systematic characterization revealed that the electron transfer from Ni to Pd modulates *OH adsorption to accelerate EG oxidation reaction(EGOR)while preventing Pd deactivation through oxidation.The optimized system demonstrated exceptional alkaline performance with a glycolic acid Faraday efficiencyof 95%and a current density of 666 mA·cm^(-2).When implemented in an asymmetric EGOR||HER flowcell configuration where only the cathodic electrolyte contains alkaline,the system demonstrated exceptional operational stability by sustaining 70 mA·cm^(-2) current density at a low cell voltage of 0.9 V in neutral media for over 100 h,with product glycolic acid requiring no further acidification.This investigation provides a practical framework for designing efficientelectrocatalytic systems that simplifiesproduct separation steps.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
Aluminum(Al)alloys are widely used in aerospace,automotive,and electronics industries due to their light weight and durability.However,their poor corrosion resistance has hindered further development,especially when i...Aluminum(Al)alloys are widely used in aerospace,automotive,and electronics industries due to their light weight and durability.However,their poor corrosion resistance has hindered further development,especially when in contact with oily solutions.In this work,a simple method was adopted to superoleophobic Al alloys with hierarchical micro/nano structures,including plasma electrolytic oxidation,hydrothermal treatment,and fluorination modification.The Contact Angle(CA)and Sliding Angle(SA)of water on the surface were measured to be 164.1°and 0.6°,and those of ethylene glycol-water solutions were 157.1°and 0.7°,respectively.The surface exhibited excellent low adhesion and self-cleaning properties.The electrochemical test results showed that compared with bare Al alloy,the corrosion current density of the superoleophobic surface decreased by 2 orders of magnitude,the charge transfer resistance(R_(ct))increased by 3 orders of magnitude,and the corrosion inhibition efficiency reached 98.11%.Additionally,the superoleophobic surface still exhibited good corrosion resistance after 45 days of immersion.We believe that this work provides a novel perspective and theoretical support for the long-term durability of Al alloys in the ethylene glycol-water solution environment.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
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
基金financially supported by the National Natural Science Foundation of China(Nos.22173116 and 22473113)the Science Foundation of China University of Petroleum,Beijing(No.2462025YJRC032)for providing financial support.
文摘Poly(ethylene succinate)(PES),a promising biodegradable polyester with cost advantages,suffers from inherently slow crystallization kinetics,which severely limits its processability and practical applications.To address this challenge,this study explored the use of commercially available,low-cost,and food-safe sugar alcohols,including Xylitol(Xy),D-sorbitol(DS),and D-mannitol(DM),as effective nucleating agents for PES.Remarkably,all three polyols significantly enhanced the nucleation and crystallization ability of PES,with DM exhibiting the most pronounced effect.DM increased the crystallization temperature by up to 23.9°C and accelerated the overall crystallization rate by more than 13-fold at only 0.5 wt%loading level.Through a combination of differential scanning calorimetry(DSC),polarized optical microscopy(POM),and wide-angle X-ray diffraction(WAXD)analyses,we revealed that DM promotes PES crystallization via a dual mechanism:epitaxial templating facilitated by excellent lattice matching,and enhanced chain adjustment through intermolecular hydrogen-bonding interactions.In contrast,Xy and DS primarily function through hydrogen-bonding interactions.This work not only identifies DM as a highly efficient,economical,and industrially viable nucleating agent for PES,but also provides fundamental insights into the role of the molecular structure and crystallization ability of nucleating agents in regulating polymer crystallization.
基金supported by the National Natural Science Foundation of China(Nos.52273017 and 52273016)Strategic Priority Program of the Chinese Academy of Sciences(No.ZDRW-CN-2023-1)Natural Science Foundation of Jilin Province(No.SKL202302033).
文摘Cyclic olefin copolymers(COCs)are highly valuable optical resins,but their productions on industry are fully limited by the monomer norbornene.Although ethylene/dicyclopentadiene(E/DCPD)copolymers provide a cost-effective alternative to commercially available COCs because of using low-cost DCPD as cyclic olefin monomer,these inherent unsaturated double bonds on E/DCPD copolymers cause low heat resistance,oxidation,and crosslinking during processing and storage.And E/DCPD copolymers usually showed lower glass-transition temperature(T_(g))compared with commercially available COCs.In this study,we studied the E-DCPD copolymerization catalyzed by a scandium complex and the sequential hydrogenation catalyzed by a nickel compound to prepare saturated copolymers H-(E/DCPD).The polymerization activities are high up to 5.86×10^(6)g/(molSc·h),and the resultant H-(E/DCPD)copolymers showed narrow polymer dispersity index(PDI=1.5–2.0).By changing the polymerization conditions,a series of H-(E/DCPD)copolymers with tunable DCPD incorporation(28.4 mol%–44.9 mol%)and a wide range of T_(g)(123–171°C)were obtained.H-(E/DCPD)copolymers exhibited excellent optical properties(transparency>90%,refractive index of 1.543),similar to those of commercial COCs,making them an alternative for high-performance optical applications.This method solves the problems of traditional E/DCPD copolymers and provides a practical way to produce stable and low-cost COCs,and is comparable with commercially available COC resins.
基金financially supported by the National Natural Science Foundation of China(No.52473338)the National Natural Science Foundation of China(Nos.52173004 and 51873055)+3 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA0540000)Advanced Materials-National Science and Technology Major Project(No.2025ZD0614000)Hebei Natural Science Foundation(No.E2022202015)Anhui Province Science and Technology Innovation Tackling Key Project(No.202423i08050025)。
文摘Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.
基金financial support from the National Natural Science Foundation of China(Nos.22401274,U23B6011)the Jilin Provincial Science and Technology Department Program(No.20250102070JC)。
文摘Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.
基金financially supported by the Science and Technology Projects of Changji Prefecture(No.2023112258)Shihezi Coal Chemical Industry Common Technology Research Institute Project(No.MGJY0104)the Program for Young Innovative Talents of Shihezi University(No.CXFZ202302).
文摘In this study,a series of poly(ethylene succinate)-b-poly(butylene carbonate)(PES-b-PBC)multiblock copolymers were prepared through the chain-extension reaction of hydroxyl-terminated PES(PES-OH)and hydroxyl-terminated PBC(PBC-OH)prepolymers with 1,6-hexmethylene diisocyanate(HDI)as a chain extender.The effects of the prepolymer molecular weight and content on the structure and application properties of the PES-b-PBC copolymers were systematically investigated using various techniques.It was found that the compatibility of PES and PBC blocks in PES-b-PBC copolymers can be greatly enhanced by lowering the length of the prepolymers,and the amorphous phase of the PES and PBC chain segments in the PES-b-PBC copolymer would transform from immiscibility and partial miscibility to miscibility when the number-average molecular weight(M_(n))of the PES-OH and PBC-OH prepolymers is less than 2000 g/mol.Only the crystal structure of bare PES can be observed in the wide-angle X-ray diffraction(WAXD)spectrum of the PES-b-PBC copolymers,but their crystallinity degrees were found to decrease with increasing PBC fraction.The thermal behavior,crystallization performance,rheological properties,mechanical properties,and degradation properties of the PES-b-PBC multiblock copolymers can be easily modulated by altering the block length and composition of the prepolymers,offering potential applications in biodegradable materials.
基金supported by the National Natural Science Foundation of China(NSFC,No.22172121)the Fundamental Research Funds for the Central Universities(No.ZYN2025267)Southwest Minzu University。
文摘The electrocatalytic oxidation of ethylene glycol(EG)into high-value chemicals like glycolic acid(GA)is a crucial step for upcycling waste plastics.However,catalyst deactivation and low selectivity pose significant challenges.This work presents the low-coordination PtBi nanosheets(LC-PtBi NSs),featuring a unique amorphous-crystalline heterostructure with a low coordination number of 2.3-2.5.They can exhibit exceptional mass activity(8.3 A mg_(Pt)^(-1))and stability(maintaining 88.7%of initial activity after running for 3600 s)of the EG oxidation reaction(EGOR).They also achieve over 90%apparent selectivity for EG-to-GA conversion at low potentials(<0.7 V vs.RHE)and even more than 100-h continuous electrolysis.Density fu nctional theory(DFT)calculations reveal that the low-coordination PtBi heterogeneous interface is responsible for the high coverage of OH_(ad) species and weakened adsorption of carbonaceous intermediates on LC-PtBi NSs,thereby promoting the direct oxidation of C_(2) intermediates to GA.This work demonstrates a strategy of doping-mediated catalytic interface regulation and electron density rearrangement,offering insights for designing efficient Pt-based electrocatalysts toward selective oxidation of small molecules.
基金financially supported by the National Key Research and Development Program of China(No.2021YFB3700300)the National Natural Science Foundation of China(Nos.52573017 and U21B2093)+1 种基金Key Research and Development Program of Ningbo(No.2022Z200)the Zhejiang Provincial Natural Science Foundation(No.LY23E030005)。
文摘Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardant strategies often compromise their mechanical properties,hindering their practical applications.Herein,a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)-based comonomer(DDP)was used to synthesize flame-retardant poly(ethylene furandicarboxylate-co-phosphaphenanthrene)(PEFDn).The covalent integration of DDP confers intrinsic flame retardancy,avoiding the plasticization and migration issues associated with additive-type systems.Upon thermal decomposition,the DOPO-derived moieties release phosphoric acid and radical scavengers,promoting char formation and suppressing flame propagation.Furthermore,density functional theory(DFT)calculations combined with non-covalent interaction(NCI)analysis revealed that DOPO dimer molecules adopt a stable parallel-displaced π-π stacking configu ration,potentially facilitating microphase separation and enhancing the energy dissipation capability.PEFD_(10)achieves a UL-94 V-0 rating while simultaneously increasing impact toughness from 1.5 kJ/m^(2) to 14.7 kJ/m^(2).Im portantly,PEFDn maintained acceptable oxygen-barrier properties.PEFD10 also exhibited high transparency and UV-shielding performance.The combination of intrinsic flame safety,im pact-toughness resistance,UV shielding,and an oxygen barrier ensures reliable protection of electrical components and long-term operational stability.The integration of multiple critical properties within a single bio-based material represents a novel approach fo r enabling sustainable polymer solutions for high-pe rformance electrical applications.
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 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 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.
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.
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.
基金The funding of this submission came from our laboratory sponsored by the college
文摘Chemical looping oxidative dehydrogenation(CL‐ODH)is a promising novel method to convert ethane into higher value‐added ethylene.In this study,perovskite‐type Co_(2)O_(3)/LaCoO_(3) was prepared by the one‐step citric acid‐gel method and applied as an oxygen carrier in the CL‐ODH process of ethane to ethylene;moreover,the effects of CuO,ZnO,and MgO as additives were investigated.The properties of the oxygen carriers were characterized using XRD,BET,XPS,H_(2)‐TPR,O_(2)‐TPD,and EPR.Characterization results showed that the addition of additives into Co_(2)O_(3)/LaCoO_(3) increased the amounts of surface chemisorbed oxygen and lattice oxygen.Co_(2)O_(3)/LaCoO_(3) had a strong ability to absorb and release oxygen after adding CuO,ZnO,and MgO,respectively.The performances of the oxygen carriers for CL‐ODH of ethane to ethylene were studied at a reaction temperature of 650℃,atmospheric pressure,and GHSV of 15,000 mL/g·h in eight redox cycles.All the oxygen carriers had 100%ethane conversion,and ZnO‐Co_(2)O_(3)/LaCoO_(3) exhibited the best ethylene selectivity of more than 70%in all the oxygen carriers.It was confirmed that lattice oxygen was mainly responsible for the selectivity of ethylene,and oxygen vacancies were conducive to the migration of lattice oxygen.Most of Zn^(2+) entered into the bulk phase of Co_(2)O_(3)/LaCoO_(3),and formed lots of oxygen vacancies.
基金financially supported by the National Key Research and Development Program of China(2022YFA1504200)the National Natural Science Foundation of China(22178033 and 22090030)the Fundamental Research Funds for the Central Universities(2024CDJXY010).
文摘Electrocatalytic oxidation of surplus ethylene glycol(EG)to high-value glycolic acid(GA)represents a promising approach for sustainable resource utilization,though critical challenges persist in developing durable electrocatalysts and achieving effective recovery of the free acid product from its salt derivatives in alkaline electrolytes.In this work,a PdNi/NF catalyst was rationally synthesized via a one-step electrodeposition method.Systematic characterization revealed that the electron transfer from Ni to Pd modulates *OH adsorption to accelerate EG oxidation reaction(EGOR)while preventing Pd deactivation through oxidation.The optimized system demonstrated exceptional alkaline performance with a glycolic acid Faraday efficiencyof 95%and a current density of 666 mA·cm^(-2).When implemented in an asymmetric EGOR||HER flowcell configuration where only the cathodic electrolyte contains alkaline,the system demonstrated exceptional operational stability by sustaining 70 mA·cm^(-2) current density at a low cell voltage of 0.9 V in neutral media for over 100 h,with product glycolic acid requiring no further acidification.This investigation provides a practical framework for designing efficientelectrocatalytic systems that simplifiesproduct separation steps.
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supported by the National Defense Basic Scientific Research Project(No.JCKY2020210B001)the Jilin Province Scientific and Technological Development Program(No.YDZJ202101ZYTS025).
文摘Aluminum(Al)alloys are widely used in aerospace,automotive,and electronics industries due to their light weight and durability.However,their poor corrosion resistance has hindered further development,especially when in contact with oily solutions.In this work,a simple method was adopted to superoleophobic Al alloys with hierarchical micro/nano structures,including plasma electrolytic oxidation,hydrothermal treatment,and fluorination modification.The Contact Angle(CA)and Sliding Angle(SA)of water on the surface were measured to be 164.1°and 0.6°,and those of ethylene glycol-water solutions were 157.1°and 0.7°,respectively.The surface exhibited excellent low adhesion and self-cleaning properties.The electrochemical test results showed that compared with bare Al alloy,the corrosion current density of the superoleophobic surface decreased by 2 orders of magnitude,the charge transfer resistance(R_(ct))increased by 3 orders of magnitude,and the corrosion inhibition efficiency reached 98.11%.Additionally,the superoleophobic surface still exhibited good corrosion resistance after 45 days of immersion.We believe that this work provides a novel perspective and theoretical support for the long-term durability of Al alloys in the ethylene glycol-water solution environment.
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.
