This report presents a detailed density functional theory （DFT） study on the difference in regioselectivity for the copolymerization reactions of styrene oxide versus propylene oxide with CO2 utilizing binary （sale...This report presents a detailed density functional theory （DFT） study on the difference in regioselectivity for the copolymerization reactions of styrene oxide versus propylene oxide with CO2 utilizing binary （salen）cobalt（III） catalyst systems. This study focuses on the discrepancy of regioselective ring-opening of two terminal epoxides during the copolymerization with CO2. It was found that the nucleophilic ring-opening of styrene oxide occurred predominantly at the methine C a--O bond due to the election delocalization of phenyl group to stabilize the transition state for the methine C--O bond cleavage.展开更多
Ultrastable Y zeolite（USY）-supported Pt catalyst was prepared by gas-bubbling-assisted membrane reduction. The influence of reaction conditions and the metal and acid sites of catalysts on the catalytic performance ...Ultrastable Y zeolite（USY）-supported Pt catalyst was prepared by gas-bubbling-assisted membrane reduction. The influence of reaction conditions and the metal and acid sites of catalysts on the catalytic performance of catalyst in hydrogenation and selective ring opening of tetralin, 1,2,3,4-tetrahydronaphthalene（THN）, was studied. It was found that the optimal reaction conditions were at a temperature of 280 °C, hydrogen pressure of 4 MPa, liquid hourly space velocity of 2 h^-1 and H2/THN ratio of 750. Under these optimal conditions, a high conversion of almost 100% was achieved on the 0.3 Pt/USY catalyst. XRD patterns and TEM images revealed that Pt particles were highly dispersed on the USY, favorable to the hydrogenation reaction of tetralin. Ammonia temperature-programmed desorption and Py-IR results indicated that the introduction of Pt can reduce the acid sites of USY, particularly the strong acid sites of USY. Thus, the hydrocracking reaction can be suppressed.展开更多
Despite the extraordinary success has been achieved in metal catalyst-promoted stereoselective ring-opening polymerization（ROP） of rac-lactide（rac-LA）, well-controlled stereoselective rac-LA ROP by organic catalys...Despite the extraordinary success has been achieved in metal catalyst-promoted stereoselective ring-opening polymerization（ROP） of rac-lactide（rac-LA）, well-controlled stereoselective rac-LA ROP by organic catalyst still remains a scientific challenge. Here we report our investigations into organocatalytic stereoselective ROP of rac-LA by utilizing novel bulky chiral and achiral N-heterocyclic carbenes（NHC）, 1,3-bis-（1′-naphthylethyl）imidazolin-2-ylidene. The effect of polymerization conditions（e.g. solvent, temperature, alcohol initiator） on ROP behavior by these bulky NHCs has been fully studied, leading to the formation of isotactic-rich stereoblock polylactide（Pi = 0.81） under optimized conditions with high activity（Conv. = 98% in 30 min） and narrow molecular weight dispersity（D = 1.05）.展开更多
Poly(lactic-co-glycolic acid)(PLGA)copolymers exhibit exceptional biodegradability and biocompatibility,showcasing significant potential for biomedical applications.While PLG and high molecular weight PLGA emerges as ...Poly(lactic-co-glycolic acid)(PLGA)copolymers exhibit exceptional biodegradability and biocompatibility,showcasing significant potential for biomedical applications.While PLG and high molecular weight PLGA emerges as one of the most prominent PLGAs with promising thermal-mechanical performance,its utility in medical applications is limited by catalyst’s metal residue and weakened crystallinity/mechanical properties caused by increased molecular weight.Herein,we report the first high-performance metalfree alternating PLGA developed by using new highly active and selective organic catalysts and fine-tuning the PLGA crystallization.Specifically,we designed a series of guanidine-based catalysts with variable steric hindrance,facilitating high activity and suppressed side reactions:The catalyzed ring-opening polymerization of 3-methyl glycolic acid produced PLGA with high regioselectivity(up to 97%),minimal racemization,very high molecular weight(up to 168 kg/mol—ten times higher than the best previous selective organocatalytic systems),and narrow dispersity.We further efficiently reinforced the obtained PLGA materials by fine-tuning their crystallization with nucleating agents and unconventional non-stoichiometric stereocomplexation.In this way,we for the first time realize full PLLGA crystallization after melting treatment and the highest tensile strength(108.7 MPa)for alternating PLGA.This study informs the future alternating PLGA copolymers with potential applications in medical materials.展开更多
In this paper,we establish and study a single-species logistic model with impulsive age-selective harvesting.First,we prove the ultimate boundedness of the solutions of the system.Then,we obtain conditions for the asy...In this paper,we establish and study a single-species logistic model with impulsive age-selective harvesting.First,we prove the ultimate boundedness of the solutions of the system.Then,we obtain conditions for the asymptotic stability of the trivial solution and the positive periodic solution.Finally,numerical simulations are presented to validate our results.Our results show that age-selective harvesting is more conducive to sustainable population survival than non-age-selective harvesting.展开更多
To explore the formation mechanism of anisotropy in Ti-6Al-4V alloy fabricated by selective laser melting(SLM),the compressive mechanical properties,microhardness,microstructure,and crystallographic orientation of the...To explore the formation mechanism of anisotropy in Ti-6Al-4V alloy fabricated by selective laser melting(SLM),the compressive mechanical properties,microhardness,microstructure,and crystallographic orientation of the alloy across different planes were investigated.The anisotropy of SLM-fabricated Ti-6Al-4V alloys was analyzed,and the electron backscatter diffraction technique was used to investigate the influence of different grain types and orientations on the stress-strain distribution at various scales.Results reveal that in room-temperature compression tests at a strain rate of 10^(-3) s^(-1),both the compressive yield strength and microhardness vary along the deposition direction,indicating a certain degree of mechanical property anisotropy.The alloy exhibits a columnar microstructure;along the deposition direction,the grains appear equiaxed,and they have internal hexagonal close-packed(hcp)α/α'martensitic structure.α'phase has a preferential orientation approximately along the<0001>direction.Anisotropy arises from the high aspect ratio of columnar grains,along with the weak texture of the microstructure and low symmetry of the hcp crystal structure.展开更多
Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations.Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable ...Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations.Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable strategy for constructing new carbon-oxygen bonds.In comparison with traditional thermal or metal-mediated carbene transfer reactions,visible-light-promoted multi-component reaction strategy provides a mild and eco-friendly approach to access densely functionalized molecules.Recently,visible-light-induced multi-component carbene transfer reactions of diazo compounds have been rapidly developed and attracted a great deal of research interest of chemists owing to their advantages of simple operation,mild condition,high atom economy and rich structural diversity.This paper summarizes the recent research progress on the visible-light-promoted multi-component carbene transfer reactions of diazo compounds via ring-opening of cyclic ethers with various nucleophiles.The reaction patterns of different nucleophiles and their corresponding mechanism are described in this review.The future research direction and challenges in this area are also discussed.展开更多
Dear Editors,This letter,reflecting on my research career,is dedi-cated to Professor Qingshi Zhu for his 80th Birthday.Part of this letter is based on my comment“A 20-year journey on the invention of vibrational phot...Dear Editors,This letter,reflecting on my research career,is dedi-cated to Professor Qingshi Zhu for his 80th Birthday.Part of this letter is based on my comment“A 20-year journey on the invention of vibrational photothermal microscopy”published in the May 2025 Nature Meth-ods Focus Issue on Bond-Selective Imaging[1].展开更多
Selective depression of pyrite remains a major bottleneck in copper flotation,particularly when high-pyrite ores are processed and saline water is used.In such environments,conventional approaches using lime and inert...Selective depression of pyrite remains a major bottleneck in copper flotation,particularly when high-pyrite ores are processed and saline water is used.In such environments,conventional approaches using lime and inert grinding media often fail to discriminate ef-fectively between pyrite and valuable copper minerals due to strong copper activation on pyrite surfaces.This study introduced a novel approach using inorganic radicals generated from peroxymonosulfate(PMS)to selectively oxidize and depress pyrite.Flotation tests with synthetic high-pyrite ore blends showed that PMS significantly reduced pyrite recovery while maintaining or improving chalcopyrite flot-ation.Ethylenediaminetetraacetic acid(EDTA)extraction confirmed selective oxidation of pyrite,and electron paramagnetic resonance(EPR)spectroscopy identified hydroxyl(·OH)and sulfate(SO_(4)^(·-))radicals as the dominant reactive species.Iron ions from grinding me-dia and mineral surfaces were identified as key activators of PMS.A major insight was pyrite’s dual role,acting both as a radical scav-enger and an activator,which made it highly reactive and susceptible to radical-induced oxidation.This process converted surface copper-sulfur species into copper hydroxides,effectively suppressing pyrite flotation.While previous studies have applied EPR to detect radicals in simplified activator/precursor systems,this study provides the first direct mechanistic evidence of radical-driven selectivity in flotation by detecting inorganic radicals in a complex flotation slurry,thereby demonstrating their persistence under industrially relevant conditions and establishing a foundation for more effective and targeted flotation strategies.展开更多
Selective laser melting(SLM)is an advanced additive manufacturing technique that enables the fabrication of complex metal components with high density,precision,and design flexibility.A novel Sc-free Al-4.58Mg-1.17Mn-...Selective laser melting(SLM)is an advanced additive manufacturing technique that enables the fabrication of complex metal components with high density,precision,and design flexibility.A novel Sc-free Al-4.58Mg-1.17Mn-1.59Zr-1.45Ti alloy was successfully fabricated via SLM,achieving a relative density of~99.89%.The microstructure of the as-fabricated alloy was characterized by scanning electron microscopy and transmission electron microscopy,which revealed refined equiaxed grains,a high density of low-angle grain boundaries and dislocation structures,as well as Mg segregation along grain boundaries.Additionally,a variety of dispersed precipitates were identified,including Mg-containing oxides,L1_(2)-Al_(3)(Ti_(x),Zr_(1−x)),and Al_(3)Zr particles.Room-temperature tensile tests showed that the alloy exhibits an excellent combination of strength and ductility,with a yield strength of 453.2±12 MPa,an ultimate tensile strength of 515.1±8 MPa,and an elongation of 22.5%±0.3%.The high strength was attributed to the combined effects of grain boundary strengthening,solid solution strengthening,precipitation strengthening,and dislocation strengthening.The developed Sc-free Al-Mg-Mn-Zr-Ti alloy demonstrates significant potential as an economical high-strength lightweight material for SLM-based manufacturing applications.展开更多
BACKGROUND Post-stroke depression(PSD)is associated with hypothalamic-pituitary-adrenal(HPA)axis dysfunction and neurotransmitter deficits.Selective serotonin reuptake inhibitors(SSRIs)are commonly used,but their effi...BACKGROUND Post-stroke depression(PSD)is associated with hypothalamic-pituitary-adrenal(HPA)axis dysfunction and neurotransmitter deficits.Selective serotonin reuptake inhibitors(SSRIs)are commonly used,but their efficacy is limited.This study investigated whether combining SSRIs with traditional Chinese medicine(TCM)Free San could enhance their therapeutic effects.AIM To evaluate the clinical efficacy and safety of combining SSRIs with Free San in treating PSD,and to assess its impact on HPA axis function.METHODS Ninety-two patients with PSD were enrolled and randomly divided into control groups(n=46)and study groups(n=46).The control group received the SSRI paroxetine alone,whereas the study group received paroxetine combined with Free San for 4 weeks.Hamilton Depression Scale and TCM syndrome scores were assessed before and after treatment.Serum serotonin,norepinephrine,cortisol,cor-ticotropin-releasing hormone,and adrenocorticotropic hormone were measured.The treatment responses and adverse reactions were recorded.RESULTS After treatment,the Hamilton Depression Scale and TCM syndrome scores were significantly lower in the study group than in the control group(P<0.05).Serum serotonin and norepinephrine levels were significantly higher in the study group than in the control group,whereas cortisol,corticotropin-releasing hormone,and adrenocorticotropic hormone levels were significantly lower(P<0.05).The total efficacy rates were 84.78%and 65.22%in the study and control groups,respectively(P<0.05).No significant differences in adverse reactions were observed between the two groups(P>0.05).CONCLUSION Combining SSRIs with Free San can enhance therapeutic efficacy,improve depressive symptoms,and regulate HPA axis function in patients with PSD with good safety and clinical application value.展开更多
Selective laser melting(SLM),as an additive manufacturing technology,has garnered widespread attention for its capability to fabricate components with complex geometries and to tailor the microstructure and mechanical...Selective laser melting(SLM),as an additive manufacturing technology,has garnered widespread attention for its capability to fabricate components with complex geometries and to tailor the microstructure and mechanical properties under specific conditions.However,the intrinsic influence mechanism of microstructure formation under non-equilibrium solidification conditions in SLM processes has not been clearly revealed.In the present work,the influence of Al concentration and process parameters on the microstructure forming mechanism of Al_(x)CoCrFeNi HEAs prepared by SLM is investigated by molecular dynamics simulation method.The simulation results show that the difference in Al content significantly affects the microstructure formation of HEAs,including the growth rate and morphology of columnar crystals,stress distribution at grain boundaries,and defect structure.In addition,the results show that increasing the substrate temperature improves the solidification formability,reduces microstructural defects,and helps reduce residual stress in Al_(x)CoCrFeNi HEAs.By analyzing the influence of heat and solute flow in the molten pool on the growth of columnar crystals,it is found that spatial fluctuations in Al concentration during the non-equilibrium solidification process inhibit the high cooling rates induced by steep temperature gradients.These findings promote the understanding of the forming mechanism of microstructure in HEAs prepared by SLM and provide theoretical guidance for designing high-performance SLM-fabricated HEAs.展开更多
Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via lo...Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via low-temperature coprecipitation,exhibiting excellent performance for the selective hydrogenation of 5-hydroxymethylfurfural(HMF).A linear correlation is first observed between solvent polarity(E_(T)(30))and product selectivity within both polar aprotic and protic solvent classes,suggesting that solvent properties play a vital role in directing reaction pathways.Among these,1,4-dioxane(aprotic)favors the formation of 2,5-bis(hydroxymethyl)furan(BHMF)with 97.5%selectivity,while isopropanol(iPrOH,protic)promotes 2,5-dimethylfuran production with up to 99.5%selectivity.Mechanistic investigations further reveal that beyond polarity,proton-donating ability is critical in facilitating hydrodeoxygenation.iPrOH enables a hydrogen shuttle mechanism where protons assist in hydroxyl group removal,lowering the activation barrier.In contrast,1,4-dioxane,lacking hydrogen bond donors,stabilizes BHMF and hinders further conversion.Density functional theory calculations confirm a lower activation energy in iPrOH(0.60 eV)compared to 1,4-dioxane(1.07 eV).This work offers mechanistic insights and a practical strategy for solvent-mediated control of product selectivity in biomass hydrogenation,highlighting the decisive role of solvent-catalyst-substrate interactions.展开更多
The recovery of gold from waste electronic and electric equipment(WEEE) has gained great attention with the increased number of WEEE,because it can largely alleviate the pressure on the environment and resources.Coval...The recovery of gold from waste electronic and electric equipment(WEEE) has gained great attention with the increased number of WEEE,because it can largely alleviate the pressure on the environment and resources.Covalent organic frameworks(COFs) are ideal adsorbents for gold recovery owing to their large surface area,good stability,easily functionalized ability,periodic structures,and definitive nanopores.Herein,a cyano-functionalized COF(COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold.The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance,which possesses fast adsorption kinetics,high cycling stability,and adsorption capacity up to 663.67 mg/g.Excitingly,COF-CN showed extremely high selectivity for gold ions,even in the presence of various competing cations and anions.The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE.The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.展开更多
In this article,the unit of total distance in Fig.2B was misused.In fact,the unit of total distance exported by the system was"pixels".After correction,the data in Fig.2B were not changed.The Fig.2B should h...In this article,the unit of total distance in Fig.2B was misused.In fact,the unit of total distance exported by the system was"pixels".After correction,the data in Fig.2B were not changed.The Fig.2B should have appeared as shown below.展开更多
Powder paving is an intermediate process of selective laser sintering(SLS).The dimensional accuracy and mechanical properties of sintered components are directly affected by the quality of the powder paving process,wh...Powder paving is an intermediate process of selective laser sintering(SLS).The dimensional accuracy and mechanical properties of sintered components are directly affected by the quality of the powder paving process,which is closely related to the flow characteristics of the powder and the process parameters of powder paving.This study investigated the simulation and optimization of the nylon powder paving in SLS by combining a discrete-element-method numerical simulation with a process test.A dynamic model was established to describe the flow and paving process of nylon powder at a preheating temperature considering mesoscopic van der Waals and electrostatic forces.The effects of the physical parameters and ambient temperature on the flow characteristics of nylon powder were analyzed,and the intrinsic relationship between the physical parameters of nylon powder,the process parameters of powder paving,and the quality of the powder paving were explored.A multi-objective regression model of the quality of powder paving was established using the response surface methodology,and a genetic algorithm was adopted to optimize the quality of the powder paving.A scientific and intelligent database of the nylon powder paving process in SLS was constructed by matching the process parameters of powder paving and physical parameters of the nylon powder,and the level of the SLS process was improved.展开更多
Selective Laser Melting(SLM),an advanced metal additive manufacturing technology,offers high precision and personalized customization advantages.However,selecting reasonable SLM parameters is challenging due to comple...Selective Laser Melting(SLM),an advanced metal additive manufacturing technology,offers high precision and personalized customization advantages.However,selecting reasonable SLM parameters is challenging due to complex relationships.This study proposes a method for identifying the optimal process window by combining the simulation model with an optimization algorithm.JAYA is guided by the principle of preferential behavior towards best solutions and avoidance of worst ones,but it is prone to premature convergence thus leading to insufficient global search.To overcome limitations,this research proposes a Differential Evolution-framed JAYA algorithm(DEJAYA).DEJAYA incorporates four key enhancements to improve the flexibility of the original algorithm,which include DE framework design,horizontal crossover operator,longitudinal crossover operator,and global greedy strategy.The effectiveness of DEJAYA is rigorously evaluated by a suite of 23 distinct benchmark functions.Furthermore,the numerical simulation establishes AlSi10Mg single-track formation models,and DEJAYA successfully identified the optimal process window for this problem.Experimental results validate that DEJAYA effectively guides SLM parameter selection for AlSi10Mg.展开更多
Incorporating ceramic particles into metal matrices is a proven strategy for boosting mechanical properties and wear resistance.The reinforcement potential of tungsten carbide(WC)particles in 316L stainless steel is r...Incorporating ceramic particles into metal matrices is a proven strategy for boosting mechanical properties and wear resistance.The reinforcement potential of tungsten carbide(WC)particles in 316L stainless steel is revealed,utilizing selective laser melting(SLM)to fabricate composites with 5 and 10 vol.%WC.The WC incorporation markedly alters the composite’s microstructure and mechanical attributes.Notably,5 vol.%WC-316L composite exhibits a refined submicron cellular structure,averaging 0.67μm in grain size.Elemental diffusion at WC-316L interface formed a 0.8μm gradient transition layer enriched with M_(2)C carbides(Fe,Cr,W),ensuring robust metallurgical bonding.Compared with unreinforced 316L,5%WC composite exhibits a 70%increase in tensile strength,reaching 1012.6 MPa,and a 25.3%rise in hardness,while maintaining acceptable ductility.10%WC composite achieves a 70.8%hardness enhancement,albeit with reduced elongation.Friction coefficient is reduced by up to 17.3%,and the wear mechanism shifts from adhesive to abrasive,significantly improving wear resistance.展开更多
Metal hydrides with high hydrogen density provide promising hydrogen storage paths for hydrogen transportation.However,the requirement of highly pure H_(2)for re-hydrogenation limits its wide application.Here,amorphou...Metal hydrides with high hydrogen density provide promising hydrogen storage paths for hydrogen transportation.However,the requirement of highly pure H_(2)for re-hydrogenation limits its wide application.Here,amorphous Al_(2)O_(3)shells(10 nm)were deposited on the surface of highly active hydrogen storage material particles(MgH_(2)-ZrTi)by atomic layer deposition to obtain MgH_(2)-ZrTi@Al_(2)O_(3),which have been demonstrated to be air stable with selective adsorption of H_(2)under a hydrogen atmosphere with different impurities(CH_(4),O_(2),N_(2),and CO_(2)).About 4.79 wt% H_(2)was adsorbed by MgH_(2)-ZrTi@10nmAl_(2)O_(3)at 75℃under 10%CH_(4)+90%H_(2)atmosphere within 3 h with no kinetic or density decay after 5 cycles(~100%capacity retention).Furthermore,about 4 wt%of H_(2)was absorbed by MgH_(2)-ZrTi@10nmAl_(2)O_(3)under 0.1%O_(2)+0.4%N_(2)+99.5%H_(2)and 0.1%CO_(2)+0.4%N_(2)+99.5%H_(2)atmospheres at 100℃within 0.5 h,respectively,demonstrating the selective hydrogen absorption of MgH_(2)-ZrTi@10nmAl_(2)O_(3)in both oxygen-containing and carbon dioxide-containing atmospheres hydrogen atmosphere.The absorption and desorption curves of MgH_(2)-ZrTi@10nmAl_(2)O_(3)with and without absorption in pure hydrogen and then in 21%O_(2)+79%N_(2)for 1 h were found to overlap,further confirming the successful shielding effect of Al_(2)O_(3)shells against O_(2)and N_(2).The MgH_(2)-ZrTi@10nmAl_(2)O_(3)has been demonstrated to be air stable and have excellent selective hydrogen absorption performance under the atmosphere with CH_(4),O_(2),N_(2),and CO_(2).展开更多
Developing green and efficient methods to acquire lignocellulose-based chemicals with high added value is beneficial for facilitating green chemistry and sustainable development.The goal of this study is to demonstrat...Developing green and efficient methods to acquire lignocellulose-based chemicals with high added value is beneficial for facilitating green chemistry and sustainable development.The goal of this study is to demonstrate that bio-based benzaldehyde,a noteworthy high-value chemical,is able to be directionally prepared from lignocellulosic biomass.This new control-lable transformation was materialized by uniting catalytic-pyrolysis of lignocellulose to toluene intermediate and catalytic oxidation of toluene intermediate to bio-based benzalde-hyde.This work also developed a highly active magnetic catalyst(CoFe_(2)O_(4)@Biochar(HTR)),achieving 77.1%benzaldehyde selectivity and 46.7%benzaldehyde yield using this catalyst.It was found that introducing the biochar carrier into the cobalt iron composite metal oxide cat-alyst enhanced hydroxyl radical formation and bio-based benzaldehyde synthesis.Based on catalyst characterizations and hydroxyl radical analysis,potential reaction mechanism for bio-based benzaldehyde synthesis was proposed.This strategy may provide a beneficial pathway for developing high-value bio-based chemical(benzaldehyde)using renewable lignocellulosic biomass.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.21134002 and 21174023)Program for Changjiang Scholars and Innovative Research Teams in University(No.IRT13008)the Chang Jiang Scholars Program(No.T2011056)from the Ministry of Education of China
文摘This report presents a detailed density functional theory （DFT） study on the difference in regioselectivity for the copolymerization reactions of styrene oxide versus propylene oxide with CO2 utilizing binary （salen）cobalt（III） catalyst systems. This study focuses on the discrepancy of regioselective ring-opening of two terminal epoxides during the copolymerization with CO2. It was found that the nucleophilic ring-opening of styrene oxide occurred predominantly at the methine C a--O bond due to the election delocalization of phenyl group to stabilize the transition state for the methine C--O bond cleavage.
基金the National Natural Science Foundation of China (U1662103 and 21673290)the National HiTech Research and Development Program (863) of China (2015AA034603)the China National Offshore Oil Corporation Fund (LHYJYKJSA20160002)
文摘Ultrastable Y zeolite（USY）-supported Pt catalyst was prepared by gas-bubbling-assisted membrane reduction. The influence of reaction conditions and the metal and acid sites of catalysts on the catalytic performance of catalyst in hydrogenation and selective ring opening of tetralin, 1,2,3,4-tetrahydronaphthalene（THN）, was studied. It was found that the optimal reaction conditions were at a temperature of 280 °C, hydrogen pressure of 4 MPa, liquid hourly space velocity of 2 h^-1 and H2/THN ratio of 750. Under these optimal conditions, a high conversion of almost 100% was achieved on the 0.3 Pt/USY catalyst. XRD patterns and TEM images revealed that Pt particles were highly dispersed on the USY, favorable to the hydrogenation reaction of tetralin. Ammonia temperature-programmed desorption and Py-IR results indicated that the introduction of Pt can reduce the acid sites of USY, particularly the strong acid sites of USY. Thus, the hydrocracking reaction can be suppressed.
基金financially supported by the Science and Technology Commission of Shanghai Municipality(No.17JC1401200)
文摘Despite the extraordinary success has been achieved in metal catalyst-promoted stereoselective ring-opening polymerization（ROP） of rac-lactide（rac-LA）, well-controlled stereoselective rac-LA ROP by organic catalyst still remains a scientific challenge. Here we report our investigations into organocatalytic stereoselective ROP of rac-LA by utilizing novel bulky chiral and achiral N-heterocyclic carbenes（NHC）, 1,3-bis-（1′-naphthylethyl）imidazolin-2-ylidene. The effect of polymerization conditions（e.g. solvent, temperature, alcohol initiator） on ROP behavior by these bulky NHCs has been fully studied, leading to the formation of isotactic-rich stereoblock polylactide（Pi = 0.81） under optimized conditions with high activity（Conv. = 98% in 30 min） and narrow molecular weight dispersity（D = 1.05）.
基金supported by the National Key Research and Development Program of China(grant no.2021YFB3801901).
文摘Poly(lactic-co-glycolic acid)(PLGA)copolymers exhibit exceptional biodegradability and biocompatibility,showcasing significant potential for biomedical applications.While PLG and high molecular weight PLGA emerges as one of the most prominent PLGAs with promising thermal-mechanical performance,its utility in medical applications is limited by catalyst’s metal residue and weakened crystallinity/mechanical properties caused by increased molecular weight.Herein,we report the first high-performance metalfree alternating PLGA developed by using new highly active and selective organic catalysts and fine-tuning the PLGA crystallization.Specifically,we designed a series of guanidine-based catalysts with variable steric hindrance,facilitating high activity and suppressed side reactions:The catalyzed ring-opening polymerization of 3-methyl glycolic acid produced PLGA with high regioselectivity(up to 97%),minimal racemization,very high molecular weight(up to 168 kg/mol—ten times higher than the best previous selective organocatalytic systems),and narrow dispersity.We further efficiently reinforced the obtained PLGA materials by fine-tuning their crystallization with nucleating agents and unconventional non-stoichiometric stereocomplexation.In this way,we for the first time realize full PLLGA crystallization after melting treatment and the highest tensile strength(108.7 MPa)for alternating PLGA.This study informs the future alternating PLGA copolymers with potential applications in medical materials.
基金Supported by the National Natural Science Foundation of China(12261018)Universities Key Laboratory of Mathematical Modeling and Data Mining in Guizhou Province(2023013)。
文摘In this paper,we establish and study a single-species logistic model with impulsive age-selective harvesting.First,we prove the ultimate boundedness of the solutions of the system.Then,we obtain conditions for the asymptotic stability of the trivial solution and the positive periodic solution.Finally,numerical simulations are presented to validate our results.Our results show that age-selective harvesting is more conducive to sustainable population survival than non-age-selective harvesting.
基金National Natural Science Foundation of China(51504138,51674118,52271177)Hunan Provincial Natural Science Foundation of China(2023JJ50181)Supported by State Key Laboratory of Materials Processing and Die&Mould Technology,Huazhong University of Science and Technology(P2024-022)。
文摘To explore the formation mechanism of anisotropy in Ti-6Al-4V alloy fabricated by selective laser melting(SLM),the compressive mechanical properties,microhardness,microstructure,and crystallographic orientation of the alloy across different planes were investigated.The anisotropy of SLM-fabricated Ti-6Al-4V alloys was analyzed,and the electron backscatter diffraction technique was used to investigate the influence of different grain types and orientations on the stress-strain distribution at various scales.Results reveal that in room-temperature compression tests at a strain rate of 10^(-3) s^(-1),both the compressive yield strength and microhardness vary along the deposition direction,indicating a certain degree of mechanical property anisotropy.The alloy exhibits a columnar microstructure;along the deposition direction,the grains appear equiaxed,and they have internal hexagonal close-packed(hcp)α/α'martensitic structure.α'phase has a preferential orientation approximately along the<0001>direction.Anisotropy arises from the high aspect ratio of columnar grains,along with the weak texture of the microstructure and low symmetry of the hcp crystal structure.
基金Science and Technology Foundation of Guizhou Province(No.QKHJC-ZK[2024]654)Guizhou Provincial University Key Laboratory of Advanced Functional Electronic Materials(No.QJ[2023]021).
文摘Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations.Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable strategy for constructing new carbon-oxygen bonds.In comparison with traditional thermal or metal-mediated carbene transfer reactions,visible-light-promoted multi-component reaction strategy provides a mild and eco-friendly approach to access densely functionalized molecules.Recently,visible-light-induced multi-component carbene transfer reactions of diazo compounds have been rapidly developed and attracted a great deal of research interest of chemists owing to their advantages of simple operation,mild condition,high atom economy and rich structural diversity.This paper summarizes the recent research progress on the visible-light-promoted multi-component carbene transfer reactions of diazo compounds via ring-opening of cyclic ethers with various nucleophiles.The reaction patterns of different nucleophiles and their corresponding mechanism are described in this review.The future research direction and challenges in this area are also discussed.
文摘Dear Editors,This letter,reflecting on my research career,is dedi-cated to Professor Qingshi Zhu for his 80th Birthday.Part of this letter is based on my comment“A 20-year journey on the invention of vibrational photothermal microscopy”published in the May 2025 Nature Meth-ods Focus Issue on Bond-Selective Imaging[1].
基金support from the Australian Research Council(ARC)Linkage Project(No.LP230100166).
文摘Selective depression of pyrite remains a major bottleneck in copper flotation,particularly when high-pyrite ores are processed and saline water is used.In such environments,conventional approaches using lime and inert grinding media often fail to discriminate ef-fectively between pyrite and valuable copper minerals due to strong copper activation on pyrite surfaces.This study introduced a novel approach using inorganic radicals generated from peroxymonosulfate(PMS)to selectively oxidize and depress pyrite.Flotation tests with synthetic high-pyrite ore blends showed that PMS significantly reduced pyrite recovery while maintaining or improving chalcopyrite flot-ation.Ethylenediaminetetraacetic acid(EDTA)extraction confirmed selective oxidation of pyrite,and electron paramagnetic resonance(EPR)spectroscopy identified hydroxyl(·OH)and sulfate(SO_(4)^(·-))radicals as the dominant reactive species.Iron ions from grinding me-dia and mineral surfaces were identified as key activators of PMS.A major insight was pyrite’s dual role,acting both as a radical scav-enger and an activator,which made it highly reactive and susceptible to radical-induced oxidation.This process converted surface copper-sulfur species into copper hydroxides,effectively suppressing pyrite flotation.While previous studies have applied EPR to detect radicals in simplified activator/precursor systems,this study provides the first direct mechanistic evidence of radical-driven selectivity in flotation by detecting inorganic radicals in a complex flotation slurry,thereby demonstrating their persistence under industrially relevant conditions and establishing a foundation for more effective and targeted flotation strategies.
基金supported by the Jilin Scientific and Technological Development Program(No.20240302108GX)the National Natural Science Foundation of China(Nos.51974032,52174355,51874043,and 51604034).
文摘Selective laser melting(SLM)is an advanced additive manufacturing technique that enables the fabrication of complex metal components with high density,precision,and design flexibility.A novel Sc-free Al-4.58Mg-1.17Mn-1.59Zr-1.45Ti alloy was successfully fabricated via SLM,achieving a relative density of~99.89%.The microstructure of the as-fabricated alloy was characterized by scanning electron microscopy and transmission electron microscopy,which revealed refined equiaxed grains,a high density of low-angle grain boundaries and dislocation structures,as well as Mg segregation along grain boundaries.Additionally,a variety of dispersed precipitates were identified,including Mg-containing oxides,L1_(2)-Al_(3)(Ti_(x),Zr_(1−x)),and Al_(3)Zr particles.Room-temperature tensile tests showed that the alloy exhibits an excellent combination of strength and ductility,with a yield strength of 453.2±12 MPa,an ultimate tensile strength of 515.1±8 MPa,and an elongation of 22.5%±0.3%.The high strength was attributed to the combined effects of grain boundary strengthening,solid solution strengthening,precipitation strengthening,and dislocation strengthening.The developed Sc-free Al-Mg-Mn-Zr-Ti alloy demonstrates significant potential as an economical high-strength lightweight material for SLM-based manufacturing applications.
基金Supported by Open Project of Jiangsu Province Key Laboratory of Integrated Traditional Chinese and Western Medicine for the Prevention and Treatment of Geriatric Diseases,No.202232.
文摘BACKGROUND Post-stroke depression(PSD)is associated with hypothalamic-pituitary-adrenal(HPA)axis dysfunction and neurotransmitter deficits.Selective serotonin reuptake inhibitors(SSRIs)are commonly used,but their efficacy is limited.This study investigated whether combining SSRIs with traditional Chinese medicine(TCM)Free San could enhance their therapeutic effects.AIM To evaluate the clinical efficacy and safety of combining SSRIs with Free San in treating PSD,and to assess its impact on HPA axis function.METHODS Ninety-two patients with PSD were enrolled and randomly divided into control groups(n=46)and study groups(n=46).The control group received the SSRI paroxetine alone,whereas the study group received paroxetine combined with Free San for 4 weeks.Hamilton Depression Scale and TCM syndrome scores were assessed before and after treatment.Serum serotonin,norepinephrine,cortisol,cor-ticotropin-releasing hormone,and adrenocorticotropic hormone were measured.The treatment responses and adverse reactions were recorded.RESULTS After treatment,the Hamilton Depression Scale and TCM syndrome scores were significantly lower in the study group than in the control group(P<0.05).Serum serotonin and norepinephrine levels were significantly higher in the study group than in the control group,whereas cortisol,corticotropin-releasing hormone,and adrenocorticotropic hormone levels were significantly lower(P<0.05).The total efficacy rates were 84.78%and 65.22%in the study and control groups,respectively(P<0.05).No significant differences in adverse reactions were observed between the two groups(P>0.05).CONCLUSION Combining SSRIs with Free San can enhance therapeutic efficacy,improve depressive symptoms,and regulate HPA axis function in patients with PSD with good safety and clinical application value.
基金supported by the National Natural Science Foundation of China(Grant No.12102133).
文摘Selective laser melting(SLM),as an additive manufacturing technology,has garnered widespread attention for its capability to fabricate components with complex geometries and to tailor the microstructure and mechanical properties under specific conditions.However,the intrinsic influence mechanism of microstructure formation under non-equilibrium solidification conditions in SLM processes has not been clearly revealed.In the present work,the influence of Al concentration and process parameters on the microstructure forming mechanism of Al_(x)CoCrFeNi HEAs prepared by SLM is investigated by molecular dynamics simulation method.The simulation results show that the difference in Al content significantly affects the microstructure formation of HEAs,including the growth rate and morphology of columnar crystals,stress distribution at grain boundaries,and defect structure.In addition,the results show that increasing the substrate temperature improves the solidification formability,reduces microstructural defects,and helps reduce residual stress in Al_(x)CoCrFeNi HEAs.By analyzing the influence of heat and solute flow in the molten pool on the growth of columnar crystals,it is found that spatial fluctuations in Al concentration during the non-equilibrium solidification process inhibit the high cooling rates induced by steep temperature gradients.These findings promote the understanding of the forming mechanism of microstructure in HEAs prepared by SLM and provide theoretical guidance for designing high-performance SLM-fabricated HEAs.
基金the National Nature Science Foundation of China for Excellent Young Scientists Fund(32222058)Fundamental Research Foundation of CAF(CAFYBB2022QB001).
文摘Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via low-temperature coprecipitation,exhibiting excellent performance for the selective hydrogenation of 5-hydroxymethylfurfural(HMF).A linear correlation is first observed between solvent polarity(E_(T)(30))and product selectivity within both polar aprotic and protic solvent classes,suggesting that solvent properties play a vital role in directing reaction pathways.Among these,1,4-dioxane(aprotic)favors the formation of 2,5-bis(hydroxymethyl)furan(BHMF)with 97.5%selectivity,while isopropanol(iPrOH,protic)promotes 2,5-dimethylfuran production with up to 99.5%selectivity.Mechanistic investigations further reveal that beyond polarity,proton-donating ability is critical in facilitating hydrodeoxygenation.iPrOH enables a hydrogen shuttle mechanism where protons assist in hydroxyl group removal,lowering the activation barrier.In contrast,1,4-dioxane,lacking hydrogen bond donors,stabilizes BHMF and hinders further conversion.Density functional theory calculations confirm a lower activation energy in iPrOH(0.60 eV)compared to 1,4-dioxane(1.07 eV).This work offers mechanistic insights and a practical strategy for solvent-mediated control of product selectivity in biomass hydrogenation,highlighting the decisive role of solvent-catalyst-substrate interactions.
基金financially supported by the National Natural Science Foundation of China (No.51972302)。
文摘The recovery of gold from waste electronic and electric equipment(WEEE) has gained great attention with the increased number of WEEE,because it can largely alleviate the pressure on the environment and resources.Covalent organic frameworks(COFs) are ideal adsorbents for gold recovery owing to their large surface area,good stability,easily functionalized ability,periodic structures,and definitive nanopores.Herein,a cyano-functionalized COF(COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold.The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance,which possesses fast adsorption kinetics,high cycling stability,and adsorption capacity up to 663.67 mg/g.Excitingly,COF-CN showed extremely high selectivity for gold ions,even in the presence of various competing cations and anions.The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE.The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.
文摘In this article,the unit of total distance in Fig.2B was misused.In fact,the unit of total distance exported by the system was"pixels".After correction,the data in Fig.2B were not changed.The Fig.2B should have appeared as shown below.
基金Supported by National Natural Science Foundation of China(Grant Nos.52375466,51975504)Guangdong Provincial Basic and Applied Basic Research Foundation(Grant No.2022A1515110862)+1 种基金Jiangsu Provincial Key Laboratory of Precision and Micro-Manufacturing Technology(Grant No.JSKL2223K06)Hunan Provincial Excellent Youth Project of Education Department(Grant No.22B0109).
文摘Powder paving is an intermediate process of selective laser sintering(SLS).The dimensional accuracy and mechanical properties of sintered components are directly affected by the quality of the powder paving process,which is closely related to the flow characteristics of the powder and the process parameters of powder paving.This study investigated the simulation and optimization of the nylon powder paving in SLS by combining a discrete-element-method numerical simulation with a process test.A dynamic model was established to describe the flow and paving process of nylon powder at a preheating temperature considering mesoscopic van der Waals and electrostatic forces.The effects of the physical parameters and ambient temperature on the flow characteristics of nylon powder were analyzed,and the intrinsic relationship between the physical parameters of nylon powder,the process parameters of powder paving,and the quality of the powder paving were explored.A multi-objective regression model of the quality of powder paving was established using the response surface methodology,and a genetic algorithm was adopted to optimize the quality of the powder paving.A scientific and intelligent database of the nylon powder paving process in SLS was constructed by matching the process parameters of powder paving and physical parameters of the nylon powder,and the level of the SLS process was improved.
文摘Selective Laser Melting(SLM),an advanced metal additive manufacturing technology,offers high precision and personalized customization advantages.However,selecting reasonable SLM parameters is challenging due to complex relationships.This study proposes a method for identifying the optimal process window by combining the simulation model with an optimization algorithm.JAYA is guided by the principle of preferential behavior towards best solutions and avoidance of worst ones,but it is prone to premature convergence thus leading to insufficient global search.To overcome limitations,this research proposes a Differential Evolution-framed JAYA algorithm(DEJAYA).DEJAYA incorporates four key enhancements to improve the flexibility of the original algorithm,which include DE framework design,horizontal crossover operator,longitudinal crossover operator,and global greedy strategy.The effectiveness of DEJAYA is rigorously evaluated by a suite of 23 distinct benchmark functions.Furthermore,the numerical simulation establishes AlSi10Mg single-track formation models,and DEJAYA successfully identified the optimal process window for this problem.Experimental results validate that DEJAYA effectively guides SLM parameter selection for AlSi10Mg.
基金supported by Opening funding of National Key Laboratory of Aerospace Liquid Propulsion(HTKJ2024KL011004)Aeronautical Science Fund of China(ASFC-20240042070001)+2 种基金Opening funding of State Key Laboratory of Metal Forming Technology and Heavy Equipment(B2408100.W05)National Key R&D Program of China(2022YFB4601804)National Natural Science Foundation of China(52250287,52275375).
文摘Incorporating ceramic particles into metal matrices is a proven strategy for boosting mechanical properties and wear resistance.The reinforcement potential of tungsten carbide(WC)particles in 316L stainless steel is revealed,utilizing selective laser melting(SLM)to fabricate composites with 5 and 10 vol.%WC.The WC incorporation markedly alters the composite’s microstructure and mechanical attributes.Notably,5 vol.%WC-316L composite exhibits a refined submicron cellular structure,averaging 0.67μm in grain size.Elemental diffusion at WC-316L interface formed a 0.8μm gradient transition layer enriched with M_(2)C carbides(Fe,Cr,W),ensuring robust metallurgical bonding.Compared with unreinforced 316L,5%WC composite exhibits a 70%increase in tensile strength,reaching 1012.6 MPa,and a 25.3%rise in hardness,while maintaining acceptable ductility.10%WC composite achieves a 70.8%hardness enhancement,albeit with reduced elongation.Friction coefficient is reduced by up to 17.3%,and the wear mechanism shifts from adhesive to abrasive,significantly improving wear resistance.
基金supported by the National Natural Science Foundation of China(22175136)the State Key Laboratory of Electrical Insulation and Power Equipment(EIPE23127)the Fundamental Research Funds for the Central Universities(xtr052024009).
文摘Metal hydrides with high hydrogen density provide promising hydrogen storage paths for hydrogen transportation.However,the requirement of highly pure H_(2)for re-hydrogenation limits its wide application.Here,amorphous Al_(2)O_(3)shells(10 nm)were deposited on the surface of highly active hydrogen storage material particles(MgH_(2)-ZrTi)by atomic layer deposition to obtain MgH_(2)-ZrTi@Al_(2)O_(3),which have been demonstrated to be air stable with selective adsorption of H_(2)under a hydrogen atmosphere with different impurities(CH_(4),O_(2),N_(2),and CO_(2)).About 4.79 wt% H_(2)was adsorbed by MgH_(2)-ZrTi@10nmAl_(2)O_(3)at 75℃under 10%CH_(4)+90%H_(2)atmosphere within 3 h with no kinetic or density decay after 5 cycles(~100%capacity retention).Furthermore,about 4 wt%of H_(2)was absorbed by MgH_(2)-ZrTi@10nmAl_(2)O_(3)under 0.1%O_(2)+0.4%N_(2)+99.5%H_(2)and 0.1%CO_(2)+0.4%N_(2)+99.5%H_(2)atmospheres at 100℃within 0.5 h,respectively,demonstrating the selective hydrogen absorption of MgH_(2)-ZrTi@10nmAl_(2)O_(3)in both oxygen-containing and carbon dioxide-containing atmospheres hydrogen atmosphere.The absorption and desorption curves of MgH_(2)-ZrTi@10nmAl_(2)O_(3)with and without absorption in pure hydrogen and then in 21%O_(2)+79%N_(2)for 1 h were found to overlap,further confirming the successful shielding effect of Al_(2)O_(3)shells against O_(2)and N_(2).The MgH_(2)-ZrTi@10nmAl_(2)O_(3)has been demonstrated to be air stable and have excellent selective hydrogen absorption performance under the atmosphere with CH_(4),O_(2),N_(2),and CO_(2).
基金supported by the National Natural Sci-ence Foundation of China(Nos.U21A20288 and 21978280).
文摘Developing green and efficient methods to acquire lignocellulose-based chemicals with high added value is beneficial for facilitating green chemistry and sustainable development.The goal of this study is to demonstrate that bio-based benzaldehyde,a noteworthy high-value chemical,is able to be directionally prepared from lignocellulosic biomass.This new control-lable transformation was materialized by uniting catalytic-pyrolysis of lignocellulose to toluene intermediate and catalytic oxidation of toluene intermediate to bio-based benzalde-hyde.This work also developed a highly active magnetic catalyst(CoFe_(2)O_(4)@Biochar(HTR)),achieving 77.1%benzaldehyde selectivity and 46.7%benzaldehyde yield using this catalyst.It was found that introducing the biochar carrier into the cobalt iron composite metal oxide cat-alyst enhanced hydroxyl radical formation and bio-based benzaldehyde synthesis.Based on catalyst characterizations and hydroxyl radical analysis,potential reaction mechanism for bio-based benzaldehyde synthesis was proposed.This strategy may provide a beneficial pathway for developing high-value bio-based chemical(benzaldehyde)using renewable lignocellulosic biomass.
