Base-catalyzed nucleophilic substitution reactions ofβ-ketonitrile with azodicarboxylates have been developed.A series of disubstituted C—N coupling products were obtained in good to excellent yields under Et_(3)N c...Base-catalyzed nucleophilic substitution reactions ofβ-ketonitrile with azodicarboxylates have been developed.A series of disubstituted C—N coupling products were obtained in good to excellent yields under Et_(3)N catalysis.Monosubstitu-tion C—N bond formation reaction catalyzed by K_(2)CO_(3) also gave novel enol-based target products.This method is simple and mild,with good chemoselectivity,excellent substrate compatibility and tolerance for various functional groups,and achieves gram-scale synthesis.The reaction is a nucleophilic substitution process without the involvement of free radicals.展开更多
In this work,Ga-doped Ce RhIn_(5) single crystals are grown by In/Ga flux method.Single-crystal X-ray diffraction,magnetic susceptibility,specific heat,and neutron diffraction measurements are utilized to characterize...In this work,Ga-doped Ce RhIn_(5) single crystals are grown by In/Ga flux method.Single-crystal X-ray diffraction,magnetic susceptibility,specific heat,and neutron diffraction measurements are utilized to characterize the sample quality and the antiferromagnetic transition temperature T_(N).By substituting In with Ga,T_(N) is slightly decreased,but the antiferromagnetic transition peaks in magnetic susceptibility and specific heat measurements are obviously broadened by external field along c-axis.By comparing with Zn-doped Ce RhIn_(5),it can be concluded that T_(N) is dominated by electron density,and the stiffness of antiferromagnetic transition is obviously reduced by Ga substitution.The substitution effects of Ga are possibly caused by forming heterogeneous local structures,which avoids quantum critical point,superconductivity,and non-Fermi liquid states.Investigations on Gadoped Ce RhIn_(5) help to comprehend the chemical substitution effects in Ce RhIn_(5),and the interaction between heterogeneous structure and long-range antiferromagnetic states.展开更多
Understanding the molecular relevance of metabolic rate(MR)is crucial for unveiling the mechanisms driving the evolution of animals.In this study,we investigated the association between mitochondrial DNA characteristi...Understanding the molecular relevance of metabolic rate(MR)is crucial for unveiling the mechanisms driving the evolution of animals.In this study,we investigated the association between mitochondrial DNA characteristics and both resting and maximal MRs in conjunction with life-history traits among 139 species of teleost fish,We gathered fish MR data from various sources and procured sequences of 13 mitochondrial protein-encoding genes.We calculated the absolute substitution rate for entire nucleotide sequences and 4-fold degenerate sites of each gene,along with encoding amino acid sequences.Using the phylogenetic comparative method,we then explored the associations between MR and mitochondrial DNA absolute substitution rate.Additionally,we screened MR-associated single nucleotide variants in mitochondrial DNA.The findings indicate no positive correlation between MRs and any substitution rate values of both combined sequences and individual mitochondrial protein-coding genes,refuting the MR hypothesis.Instead,both maximum body size and longevity correlated negatively with molecular substitution rates,suggesting their influences on both mutation and fixation within mitochondrial genes in fish.Results also revealed significant correlations between base variation at ATP6_169 and both resting MR and maximum MR,identifying the unique ATP6_169G in Scombridae fish,which results in an extremely low isoelectric point(pl)value of the ATP6 protein.Considering its functional significance,the ATP6_169G in Scombridae fish might link to their lifestyle characterized by fast locomotion and high metabolic demands alongside a slower molecular evolutionary rate.展开更多
Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such ...Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such supports has been challenging.Herein,we report an innovative strategy for the fabrication of high-density single-atoms(Rh,Ru,Pd)catalysts on CaAl-layered double hydroxides(CaAl-LDH)via isomorphous substitution.The Rh species have occupied Ca^(2+)vacancies within CaAl-LDH laminate by ion-exchange,facilitating a substantial loading of isolated Rh single-atoms.Such catalysts displayed superior performance in the selective hydrogenation to quinoline,pivotal for liquid organic hydrogen storage,and the universality for the hydrogenation of N-heterocyclic aromatic hydrocarbons was also verified.Combining the experimental results and density functional theory calculations,the pathway of quinoline hydrogenation over Rh1CaAl-LDH was proposed.This synthetic strategy marks a significant advancement in the field of single-atom catalysts,expanding their horizons in green chemical processes.展开更多
A structural conjugate(HOC)of polysaccharide,hyaluronic acid(HA)with different ratios of oleic acid(OA)via cystamine(CYS)linker as a new ocular biomaterial was developed.The HOCs with controlled degrees of substitutio...A structural conjugate(HOC)of polysaccharide,hyaluronic acid(HA)with different ratios of oleic acid(OA)via cystamine(CYS)linker as a new ocular biomaterial was developed.The HOCs with controlled degrees of substitution of OA(4.6%,8.3%and 12.2%)were synthesized to form self-assembled HA-CYS-OA nanoparticles(HONs,HON1,HON2,HON3).A poorly water-soluble cyclosporine A(CsA)to be used for the treatment of multifactorial dry eye disease(DED)was chosen as model drug.CsA-loaded HONs exhibited improved solution transparency via solubilizing capacity of HON,and increased in vitro drug permeation compared to Restasis®.The physicochemical properties of CsA-loaded HONs such as nano behaviors,solution transparency,drug release,drug permeation and ocular cytocompatibility were highly variable according to the ratios of OA substitution.Interestingly,this CsA-loaded HON1 as optimal ocular nanoformulation showed markedly augmentedmacrophage polarization into the M2 phenotype,downregulated the expression of proinflammatory cytokines levels in LPS-induced M1 macrophage,and effectively inhibited VEGF-induced endothelial cell proliferation and capillary-like tube formation by the synergistic effect of CsA and HON1 containing OA at the same time.Collectively,the current fatty acid conjugated to HA,named fattigation platform,providing the roles and physicochemical properties via structural features of HA could be a promising co-delivery strategy of drug and fatty acid for DED and other ophthalmic disease treatments.展开更多
Na_(2)FePO_(4)F is a promising sodium ion cathode due to its low cost,non-toxicity,and high stability.However,the sluggish Na^(+)diffusion kinetics and limited intrinsic electronic conductivity critically restrict its...Na_(2)FePO_(4)F is a promising sodium ion cathode due to its low cost,non-toxicity,and high stability.However,the sluggish Na^(+)diffusion kinetics and limited intrinsic electronic conductivity critically restrict its worldwide application.Herein,an anion-substitution strategy is proposed with SiO_(4)^(4-)as the dopant.SiO_(4)^(4-)substitution for PO_(4)^(3-)can apparently alter the localized electronic density and structural configuration in the lattice of Na_(2)FePO_(4)F,effectively elevating the charge transfer efficiency.As a result,the electrochemical reaction kinetics of Na_(2)FePO_(4)F is significantly enhanced,which is well demonstrated by a series of electrochemical characterizations.As-obtained Na_(2.2)Fe(PO_(4))_(0.8)(SiO_(4))_(0.2)F renders a specific capacity of 84.9 m A h g^(-1)within the region of 2.5-4.0 V at 60 mA g^(-1)(0.5 C),good rate capability,and a capacity retention of 70.0% after 1000 cycles at 1.24 A g^(-1)(10 C).Furthermore,the stabilities of the cathode-electrolyte interface and structure are strengthened,which are verified by in situ EIS and ex situ XRD analysis.These findings highlight silicate anion substitution as a promising and cost-effective strategy for overcoming the limitations of Na_(2)FePO_(4)F,contributing to the development of sustainable energy storage solutions.展开更多
P-stereogenic compounds play pivotal roles in natural products,pharmaceuticals,bioactive molecules,and catalysts/ligands,making their synthesis a highly researched area.Current studies have predominantly concentrated ...P-stereogenic compounds play pivotal roles in natural products,pharmaceuticals,bioactive molecules,and catalysts/ligands,making their synthesis a highly researched area.Current studies have predominantly concentrated on fully carbon-substituted P-stereogenic species,despite the fact that many therapeutically relevant compounds feature P-O,P-N,or P-S bonds.The catalytic and stereoselective nucleophilic substitution at the P-center is acknowledged as a highly efficient and straightforward approach for constructing high-value P-stereogenic compounds,offering significant potential for further development.This review provides an overview of advancements in the construction of P-stereogenic centers based on Pcentered nucleophilic substitution,highlighting key challenges,breakthroughs,and future opportunities in the field.展开更多
Donor-acceptor(D-A)compounds are particularly important in optoelectronic and biological applications.However,they are normally synthesized in the presence of transition metal catalysts.Herein,we report a metal-free m...Donor-acceptor(D-A)compounds are particularly important in optoelectronic and biological applications.However,they are normally synthesized in the presence of transition metal catalysts.Herein,we report a metal-free method by a complexmediated nucleophilic aromatic substitution of aryl nitriles with amines.The method can lead to rich D-A type aggregation-induced emission luminogens(AIEgens)with tunable properties.They emit from deep-blue to yellow-green and possess high photoluminescence quantum yields up to 70.5%in the aggregate state.Interestingly,the suppression of intramolecular flapping is proved to play an indispensable role in the AIE behavior,which is different from the mechanism met in other AIEgens.Moreover,the biocompatible AIEgens possess specific staining of lipid droplets in HeLa cells and the superiority of identifying fatty liver over traditional Oil Red O staining is exhibited.展开更多
This work investigated the microstructure,magnetic properties,and crystallization kinetics of the as-spun and annealed alloy ribbons of(Fe_(40-x)Co_xNi_(40)Si_(6.33)B_(12.66)Cu_1)_(0.97)Nb_(0.03),where x=0,6,7,8,9,pre...This work investigated the microstructure,magnetic properties,and crystallization kinetics of the as-spun and annealed alloy ribbons of(Fe_(40-x)Co_xNi_(40)Si_(6.33)B_(12.66)Cu_1)_(0.97)Nb_(0.03),where x=0,6,7,8,9,prepared using the meltspinning method.The results show that adding a moderate amount of Co can improve the glass forming ability(GFA),the first peak crystallization temperature,and thermal stability of the as-spun alloy ribbons.With x=7,the two-stage crystallization temperature interval△Tx=90 exhibits optimal thermal stability,and the alloy annealed at 673 K for 10 minutes shows the favorable combined magnetic properties,with H_(c)=0.12 A/m,M_(s)=88.7 A·m^(2)/kg,andμ_(e)=13800.The magnetic domain results show that annealing removes numerous pinning points in the magnetic domains of the alloy ribbons,making the domain walls smoother and effectively reducing the pinning effect.展开更多
Low ionic conductivity is a major obstacle for polymer solid-state electrolytes.In response to this issue,a design concept of enhanced regional electric potential difference(EREPD)is proposed to modulate the interacti...Low ionic conductivity is a major obstacle for polymer solid-state electrolytes.In response to this issue,a design concept of enhanced regional electric potential difference(EREPD)is proposed to modulate the interaction of nanofillers with other components in the composite polymer solid-state electrolytes(CPSEs).While ensuring the periodic structure of the graphdiyne(GDY)backbone,methoxysubstituted GDY(OGDY)is prepared by an asymmetric substitution strategy,which increases the electric potential differences within each repeating unit of GDY.The staggered distributed electron-rich regions and electron-deficient regions on the two-dimensional plane of OGDY increase the free Li^(+)concentration through Lewis acid-base pair interaction.The adjacent ERRs and EDRs form uniformly distributed EREPDs,creating a continuous potential gradient that synergistically facilitates the efficient migration of Li^(+).Impressively,the OGDY/poly(ethylene oxide)(PEO)exhibits a high ionic conductivity(1.1×10^(-3)S cm^(−1))and ion mobility number(0.71).In addition,the accelerated Li^(+)migration promotes the formation of uniform and dense SEI layers and inhibits the growth of lithium dendrites.As a proof of concept,Li||Li symmetric cell and Li||LiFePO_(4)full cell and pouch cell assembled with OGDY/PEO exhibit good performance,highlighting the effectiveness of our EREPD design strategy for improving CPSEs performance.展开更多
Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding pro...Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding proton trap 2,6-di-tert-butylpyridine(DTBP),and the controlled initiation of DCC was confirmed by ^(1)H nuclear magnetic resonance(^(1)H-NMR)spectroscopy and matrix-assisted laser desorption ionization time-offlight mass(MALDI-TOF-MS)spectrometry.The polymerization kinetics were analyzed to for optimizing the polymerization rate.Allyl-telechelic PSTOs(allyl-PSTO-allyl)with molecular weight(Mn)range of 3540–7800 g/mol and narrow molecular weight dispersity(Mw/Mn)about 1.25 were prepared through nucleophilic substitution with allyltrimethylsilane(ATMS)at approximately 40%monomer conversion.The experimental results indicate that the substitution efficiency of ATMS increased with higher ATMS concentration,temperature,and extended reaction time.Nearly unity ally-functionality for allyl-PSTO-allyl was achieved by adding sufficient SnCl_(4) prior to the substitution.展开更多
Traditional medicine,deeply rooted in cultural practices and historical wisdom,has faced surging challenges due to the escalating demand for plant-based remedies.This comprehensive review critically emphasizes the urg...Traditional medicine,deeply rooted in cultural practices and historical wisdom,has faced surging challenges due to the escalating demand for plant-based remedies.This comprehensive review critically emphasizes the urgent need for sustainable practices within traditional medicine,with a special focus on the potential of plant part substitution.Case studies that illuminate successful instances of substituting plant parts and providing a deep insight into viable alternatives to conventional practices are presented.Opportunities and challenges inherent in plant part substitution are discussed by addressing key considerations such as phytochemical and pharmacological aspects,safety and toxicity profiles,cultural insights,standardization,clinical validation,and regulatory compliance.This review serves as a guide for navigating the delicate balance between tradition and conservation within indigenous medicine practices.It underscores the importance of embracing sustainable approaches through plant part substitution,ensuring the preservation of cultural heritage while meeting the evolving healthcare needs of society.展开更多
Fluorine(F)substitution in polymers modulates both molecular energy levels and film morphology;however,its impact on exciton–vibrational coupling and molecular reorganization energy is often neglected.Herein,we syste...Fluorine(F)substitution in polymers modulates both molecular energy levels and film morphology;however,its impact on exciton–vibrational coupling and molecular reorganization energy is often neglected.Herein,we systematically investigated F-modified polymers(PBTA-PSF,PBDB-PSF)and their nonfluorinated counterparts(PBTA-PS,PBDB-PS)through simulations and experiments.We found that F atoms effectively lower the vibrational frequency of the molecular skeleton and suppress exciton–vibration coupling,thereby reducing the nonradiative decay rate.Moreover,introducing F atoms significantly decreases the reorganization energy for the S_(0)→S_(1) and S_(0)→cation transitions while increasing the reorganization energy for the S_(1)→S_(0) and cation→S_(0) transitions.These changes facilitate exciton dissociation and reduce the energy loss caused by dissociation and nonradiative recombination of excitons.Additionally,introducing F atoms into polymers enhances theπ–πstacking strength and the crystal coherence length in both neat and blended films,ultimately resulting in improvements in the power conversion efficiency of PBTA-PSF:L8-BO and PBDB-PSF:L8-BO are 16.51%and 17.59%,respectively.This study provides valuable insights for designing organic semiconductor materials to minimize energy loss and achieve a higher power conversion efficiency.展开更多
With the rapid development of electronic technology,how to effectively eliminate electromagnetic pollu-tion has become a serious problem.Perovskite oxides have shown great potential in the field of electro-magnetic wa...With the rapid development of electronic technology,how to effectively eliminate electromagnetic pollu-tion has become a serious problem.Perovskite oxides have shown great potential in the field of electro-magnetic wave absorption due to their unique structure and excellent physicochemical properties.Herein,by rationally manipulating the A-site ion substitution strategy,the theoretically directed doping of Sr ions into La ionic sites was utilized and the layered MoS_(2) was loaded by the hydrothermal process to modify its surface.Consequently,the introduced polarization phenomenon improved the dielectric performance of the perovskite oxides,achieving a collaborative dielectric/magnetic loss mechanism.Accordingly,the prepared La0.7Sr0.3FeO3(LSFO)/MoS_(2) as coating filler in the epoxy resin coating system can obtain the minimum reflection loss of-67.09 dB at 1.9 mm and the maximum effective absorption bandwidth of 7.28 GHz at 2.3 mm.More importantly,it also exhibits excellent absorption performance for multi-band electromagnetic waves,covering a wide range of specified frequency bands.It provides inspiration for ex-ploring novel perovskite oxide-based electromagnetic wave absorbing coatings and broadens the choice of ideal candidate materials for designing highly efficient,multi-band absorbers to cope with sophisticated electromagnetic environments.展开更多
Partial substitution of inorganic fertilizers with organic amendments is an important agricultural management practice.An 11-year field experiment(22 cropping periods)was carried out to analyze the impacts of differen...Partial substitution of inorganic fertilizers with organic amendments is an important agricultural management practice.An 11-year field experiment(22 cropping periods)was carried out to analyze the impacts of different partial substitution treatments on crop yields and the transformation of nitrogen fractions in greenhouse vegetable soil.Four treatments with equal N,P_(2)O_(5),and K_(2)O inputs were selected,including complete inorganic fertilizer N(CN),50%inorganic fertilizer N plus 50%pig manure N(CPN),50%inorganic fertilizer N plus 25%pig manure N and 25%corn straw N(CPSN),and 50%inorganic fertilizer N plus 50%corn straw N(CSN).Organic substitution treatments tended to increase crop yields since the 6th cropping period compared to the CN treatment.From the 8th to the 22nd cropping periods,the highest yields were observed in the CPSN treatment where yields were 7.5-11.1%greater than in CN treatment.After 11-year fertilization,compared to CN,organic substitution treatments significantly increased the concentrations of NO_(3)^(-)-N,NH_(4)^(+)-N,acid hydrolysis ammonium-N(AHAN),amino acid-N(AAN),amino sugar-N(ASN),and acid hydrolysis unknown-N(AHUN)in soil by 45.0-69.4,32.8-58.1,49.3-66.6,62.0-69.5,34.5-100.3,and 109.2-172.9%,respectively.Redundancy analysis indicated that soil C/N and OC concentration significantly affected the distribution of N fractions.The highest concentrations of NO_(3)^(-)-N,AHAN,AAN,AHUN were found in the CPSN treatment.Organic substitution treatments increased the activities ofβ-glucosidase,β-cellobiosidase,N-acetyl-glucosamidase,L-aminopeptidase,and phosphatase in the soil.Organic substitution treatments reduced vector length and increased vector angle,indicating alleviation of constraints of C and N on soil microorganisms.Organic substitution treatments increased the total concentrations of phospholipid fatty acids(PLFAs)in the soil by 109.9-205.3%,and increased the relative abundance of G^(+)bacteria and fungi taxa,but decreased the relative abundance of G-bacteria,total bacteria,and actinomycetes.Overall,long-term organic substitution management increased soil OC concentration,C/N,and the microbial population,the latter in turn positively influenced soil enzyme activity.Enhanced microorganism numbers and enzyme activity enhanced soil N sequestration by transforming inorganic N to acid hydrolysis-N(AHN),and enhanced soil N supply capacity by activating non-acid hydrolysis-N(NAHN)to AHN,thus improving vegetable yield.Application of inorganic fertilizer,manure,and straw was a more effective fertilization model for achieving sustainable greenhouse vegetable production than application of inorganic fertilizer alone.展开更多
Metal-organic frameworks(MOFs)derived composites are extremely potential electromagnetic wave(EMW)absorbers.However,the permittivity of absorbers directly derived from MOFs with solid structure is usually relatively l...Metal-organic frameworks(MOFs)derived composites are extremely potential electromagnetic wave(EMW)absorbers.However,the permittivity of absorbers directly derived from MOFs with solid structure is usually relatively low,inevitably limiting their further applications.Cation substitution can primely overcome the problem by regulating the morphology and atomic space occupation to enhance multiple loss mechanisms and impedance matching characteristics.However,universal mechanisms of the effect on EMW absorption performance influenced by cation substitution are still comparatively inadequate,which prospectively requires further exploration.Herein,a series of imidazolic MOFs were fabricated by ultrasonic symbiosis method and tailored by subsequent cation substitution strategy to prepare target porous composites.At a low filling rate and thin thickness,the as-obtained samples reach the optimal reflection loss and effective absorption bandwidth values of–49.81 dB and 7.63 GHz,respectively.The intercoupling between multiple atoms lays a significant foundation for abundant heterogeneous interfaces and defect vacancies,which effectively ameliorate the attenuation mechanisms.Meanwhile,the porous structure introduced by cation substitution reduces the bulk density to enhance the impedance matching and multiple reflections simultaneously.This study provides a helpful idea to exceedingly improve the EMW absorbing performance of imidazolic MOFs-derived composites by cation substitution.展开更多
A red-emitting phosphor Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) with partial Al^(3+)/P^(5+) substitution on Si^(4+) was synthesized via a simple solid-state method,and the effects of the introduction of the M^(3+/5+)(M=Al,P)...A red-emitting phosphor Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) with partial Al^(3+)/P^(5+) substitution on Si^(4+) was synthesized via a simple solid-state method,and the effects of the introduction of the M^(3+/5+)(M=Al,P)ions on the crystal structure and photoluminescence performance of Ca_(2.91)Si_(2−x)M_(x)O_(7):0.09Eu^(3+) phosphors were investigated.The X-ray diffraction(XRD),energy-dispersive X-ray spectroscopy(EDS),and X-ray photoelectron spectroscopy(XPS)results revealed that the structure of Ca_(3)Si_(2)O_(7) remained the same after the introduction of Al^(3+) and P^(5+) ions.The characteristic emission of Eu^(3+)-doped Ca_(3)Si_(2−x)M_(x)O_(7) phosphors exhibited two main peaks at 617 nm(red)and 593 nm(orange)under excitation at 394 nm,which originated from the^(5)D_(0)→^(7)F_(2)and^(5)D_(0)→^(7)F_(1) electron transitions of Eu^(3+) ions.After the partial substitution of Al^(3+) and P^(5+),the red emission intensities of the Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) phosphors were significantly enhanced by 1.88-and 1.42-fold,respectively,which is attributed to the crystal-field effect around Eu^(3+).Meanwhile,the luminescence intensities of the Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+) and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) phosphors at 210℃ were 79.36%and 77.53%of those at 30°C,respectively,indicating their excellent thermal stability.Moreover,the as-prepared Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+)and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) red-emitting phosphors were combined with a near-ultraviolet chip of 395 nm to fabricate red-light-emitting diode(LED)and white(w)-LED devices with excellent chromaticity features.In summary,Al^(3+)/P^(5+)-substituted Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) can serve as red-emitting phosphors for applications in w-LEDs.展开更多
Synthetic nitrogen(N)fertilizer has made a great contribution to the improvement of soil fertility and productivity,but excessive application of synthetic N fertilizer may cause agroecosystem risks,such as soil acidif...Synthetic nitrogen(N)fertilizer has made a great contribution to the improvement of soil fertility and productivity,but excessive application of synthetic N fertilizer may cause agroecosystem risks,such as soil acidification,groundwater contamination and biodiversity reduction.Meanwhile,organic substitution has received increasing attention for its ecologically and environmentally friendly and productivity benefits.However,the linkages between manure substitution,crop yield and the underlying microbial mechanisms remain uncertain.To bridge this gap,a three-year field experiment was conducted with five fertilization regimes:i)Control,non-fertilization;CF,conventional synthetic fertilizer application;CF_(1/2)M_(1/2),1/2 N input via synthetic fertilizer and 1/2 N input via manure;CF_(1/4)M_(3/4),1/4 N input synthetic fertilizer and 3/4 N input via manure;M,manure application.All fertilization treatments were designed to have equal N input.Our results showed that all manure substituted treatments achieved high soil fertility indexes(SFI)and productivities by increasing the soil organic carbon(SOC),total N(TN)and available phosphorus(AP)concentrations,and by altering the bacterial community diversity and composition compared with CF.SOC,AP,and the soil C:N ratio were mainly responsible for microbial community variations.The co-occurrence network revealed that SOC and AP had strong positive associations with Rhodospirillales and Burkholderiales,while TN and C:N ratio had positive and negative associations with Micromonosporaceae,respectively.These specific taxa are implicated in soil macroelement turnover.Random Forest analysis predicted that both biotic(bacterial composition and Micromonosporaceae)and abiotic(AP,SOC,SFI,and TN)factors had significant effects on crop yield.The present work strengthens our understanding of the effects of manure substitution on crop yield and provides theoretical support for optimizing fertilization strategies.展开更多
In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterpart...In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterparts.The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications.In this context,the atomic substitution method has emerged as a favorable approach.It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely,crystal structures,and inherent properties of the resulting materials.In this review,we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional,one-dimensional and two-dimensional TMC materials.The effects of substituting elements,substitution ratios,and substitution positions on the structures and morphologies of resulting material are discussed.The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided,emphasizing the role of atomic substitution in achieving these advancements.Finally,challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.展开更多
The design of advanced binders plays a critical role in stabilizing the cycling performance of large-volume-effect silicon monoxide(SiO)anodes.For the classic polyacrylic acid(PAA)binder,the self-association of-COOH g...The design of advanced binders plays a critical role in stabilizing the cycling performance of large-volume-effect silicon monoxide(SiO)anodes.For the classic polyacrylic acid(PAA)binder,the self-association of-COOH groups in PAA leads to the formation of intramolecular and intermolecular hydrogen bonds,greatly weakening the bonding force of the binder to SiO surface.However,strengthening the binder-material interaction from the perspective of binder molecular regulation poses a significant challenge.Herein,a modified PAA-Li_(x)(0.25≤x≤1)binder with prominent mechanical properties and adhesion strength is specifically synthesized for SiO anodes by quantitatively substituting the carboxylic hydrogen with lithium.The appropriate lithium substitution(x=0.25)not only effectively increases the number of hydrogen bonds between the PAA binder and SiO surface owing to charge repulsion effect between ions,but also guarantees moderate entanglement between PAA-Li_x molecular chains through the ion-dipole interaction.As such,the PAA-Li_(0.25)/SiO electrode exhibits exceptional mechanical properties and the lowest volume change,as well as the optimum cycling(1237.3 mA h g^(-1)after 100cycles at 0.1 C)and rate performance(1000.6 mA h g^(-1)at 1 C),significantly outperforming the electrode using pristine PAA binder.This work paves the way for quantitative regulation of binders at the molecular level.展开更多
文摘Base-catalyzed nucleophilic substitution reactions ofβ-ketonitrile with azodicarboxylates have been developed.A series of disubstituted C—N coupling products were obtained in good to excellent yields under Et_(3)N catalysis.Monosubstitu-tion C—N bond formation reaction catalyzed by K_(2)CO_(3) also gave novel enol-based target products.This method is simple and mild,with good chemoselectivity,excellent substrate compatibility and tolerance for various functional groups,and achieves gram-scale synthesis.The reaction is a nucleophilic substitution process without the involvement of free radicals.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFA1402203)the National Natural Science Foundations of China(Grant Nos.12174065 and 12104424)the Shanghai Municipal Science and Technology(Grant No.2019SHZDZX01)。
文摘In this work,Ga-doped Ce RhIn_(5) single crystals are grown by In/Ga flux method.Single-crystal X-ray diffraction,magnetic susceptibility,specific heat,and neutron diffraction measurements are utilized to characterize the sample quality and the antiferromagnetic transition temperature T_(N).By substituting In with Ga,T_(N) is slightly decreased,but the antiferromagnetic transition peaks in magnetic susceptibility and specific heat measurements are obviously broadened by external field along c-axis.By comparing with Zn-doped Ce RhIn_(5),it can be concluded that T_(N) is dominated by electron density,and the stiffness of antiferromagnetic transition is obviously reduced by Ga substitution.The substitution effects of Ga are possibly caused by forming heterogeneous local structures,which avoids quantum critical point,superconductivity,and non-Fermi liquid states.Investigations on Gadoped Ce RhIn_(5) help to comprehend the chemical substitution effects in Ce RhIn_(5),and the interaction between heterogeneous structure and long-range antiferromagnetic states.
基金supported by the National Natural Science Foundation of China[Grant No.:32070438].
文摘Understanding the molecular relevance of metabolic rate(MR)is crucial for unveiling the mechanisms driving the evolution of animals.In this study,we investigated the association between mitochondrial DNA characteristics and both resting and maximal MRs in conjunction with life-history traits among 139 species of teleost fish,We gathered fish MR data from various sources and procured sequences of 13 mitochondrial protein-encoding genes.We calculated the absolute substitution rate for entire nucleotide sequences and 4-fold degenerate sites of each gene,along with encoding amino acid sequences.Using the phylogenetic comparative method,we then explored the associations between MR and mitochondrial DNA absolute substitution rate.Additionally,we screened MR-associated single nucleotide variants in mitochondrial DNA.The findings indicate no positive correlation between MRs and any substitution rate values of both combined sequences and individual mitochondrial protein-coding genes,refuting the MR hypothesis.Instead,both maximum body size and longevity correlated negatively with molecular substitution rates,suggesting their influences on both mutation and fixation within mitochondrial genes in fish.Results also revealed significant correlations between base variation at ATP6_169 and both resting MR and maximum MR,identifying the unique ATP6_169G in Scombridae fish,which results in an extremely low isoelectric point(pl)value of the ATP6 protein.Considering its functional significance,the ATP6_169G in Scombridae fish might link to their lifestyle characterized by fast locomotion and high metabolic demands alongside a slower molecular evolutionary rate.
文摘Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such supports has been challenging.Herein,we report an innovative strategy for the fabrication of high-density single-atoms(Rh,Ru,Pd)catalysts on CaAl-layered double hydroxides(CaAl-LDH)via isomorphous substitution.The Rh species have occupied Ca^(2+)vacancies within CaAl-LDH laminate by ion-exchange,facilitating a substantial loading of isolated Rh single-atoms.Such catalysts displayed superior performance in the selective hydrogenation to quinoline,pivotal for liquid organic hydrogen storage,and the universality for the hydrogenation of N-heterocyclic aromatic hydrocarbons was also verified.Combining the experimental results and density functional theory calculations,the pathway of quinoline hydrogenation over Rh1CaAl-LDH was proposed.This synthetic strategy marks a significant advancement in the field of single-atom catalysts,expanding their horizons in green chemical processes.
基金supported by a grant from the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(RS-2023-00208240),Republic of Korea.
文摘A structural conjugate(HOC)of polysaccharide,hyaluronic acid(HA)with different ratios of oleic acid(OA)via cystamine(CYS)linker as a new ocular biomaterial was developed.The HOCs with controlled degrees of substitution of OA(4.6%,8.3%and 12.2%)were synthesized to form self-assembled HA-CYS-OA nanoparticles(HONs,HON1,HON2,HON3).A poorly water-soluble cyclosporine A(CsA)to be used for the treatment of multifactorial dry eye disease(DED)was chosen as model drug.CsA-loaded HONs exhibited improved solution transparency via solubilizing capacity of HON,and increased in vitro drug permeation compared to Restasis®.The physicochemical properties of CsA-loaded HONs such as nano behaviors,solution transparency,drug release,drug permeation and ocular cytocompatibility were highly variable according to the ratios of OA substitution.Interestingly,this CsA-loaded HON1 as optimal ocular nanoformulation showed markedly augmentedmacrophage polarization into the M2 phenotype,downregulated the expression of proinflammatory cytokines levels in LPS-induced M1 macrophage,and effectively inhibited VEGF-induced endothelial cell proliferation and capillary-like tube formation by the synergistic effect of CsA and HON1 containing OA at the same time.Collectively,the current fatty acid conjugated to HA,named fattigation platform,providing the roles and physicochemical properties via structural features of HA could be a promising co-delivery strategy of drug and fatty acid for DED and other ophthalmic disease treatments.
基金funding support from the Beijing Natural Science Foundation(2252055)the National Natural Science Foundation of China(52072033 and 52271234)+1 种基金the State Key Laboratory of Clean Energy Utilization(Open Fund Project,ZJUCEU2024010)the BIT Research and Innovation Promoting Project(2024YCXY040,GIIP2023-34)。
文摘Na_(2)FePO_(4)F is a promising sodium ion cathode due to its low cost,non-toxicity,and high stability.However,the sluggish Na^(+)diffusion kinetics and limited intrinsic electronic conductivity critically restrict its worldwide application.Herein,an anion-substitution strategy is proposed with SiO_(4)^(4-)as the dopant.SiO_(4)^(4-)substitution for PO_(4)^(3-)can apparently alter the localized electronic density and structural configuration in the lattice of Na_(2)FePO_(4)F,effectively elevating the charge transfer efficiency.As a result,the electrochemical reaction kinetics of Na_(2)FePO_(4)F is significantly enhanced,which is well demonstrated by a series of electrochemical characterizations.As-obtained Na_(2.2)Fe(PO_(4))_(0.8)(SiO_(4))_(0.2)F renders a specific capacity of 84.9 m A h g^(-1)within the region of 2.5-4.0 V at 60 mA g^(-1)(0.5 C),good rate capability,and a capacity retention of 70.0% after 1000 cycles at 1.24 A g^(-1)(10 C).Furthermore,the stabilities of the cathode-electrolyte interface and structure are strengthened,which are verified by in situ EIS and ex situ XRD analysis.These findings highlight silicate anion substitution as a promising and cost-effective strategy for overcoming the limitations of Na_(2)FePO_(4)F,contributing to the development of sustainable energy storage solutions.
基金financial support from the National Natural Science Foundation of China(Nos.22171187 and 22001173)the Project of Department of Education of Guangdong Province(No.2020KTSCX116)+3 种基金the Shenzhen Science and Technology Foundation(Nos.20200812202943001 and KQJSCX20180328100401788)Frontiers Science Center for Asymmetric Synthesis and Medicinal Molecules,Department of Education,Guizhou Province(No.Qianjiaohe KY(2020)004)the Central Government Guides Local Science and Technology Development Fund Projects(Nos.Qiankehezhongyindi(2024)007,(2023)001)Singapore National Research Foundation under its NRF Competitive Research Program(No.NRFCRP22–2019–0002)。
文摘P-stereogenic compounds play pivotal roles in natural products,pharmaceuticals,bioactive molecules,and catalysts/ligands,making their synthesis a highly researched area.Current studies have predominantly concentrated on fully carbon-substituted P-stereogenic species,despite the fact that many therapeutically relevant compounds feature P-O,P-N,or P-S bonds.The catalytic and stereoselective nucleophilic substitution at the P-center is acknowledged as a highly efficient and straightforward approach for constructing high-value P-stereogenic compounds,offering significant potential for further development.This review provides an overview of advancements in the construction of P-stereogenic centers based on Pcentered nucleophilic substitution,highlighting key challenges,breakthroughs,and future opportunities in the field.
基金supported by the National Natural Science Foundation of China(22275072 and 62105184)the Natural Science Foundation of Guangdong Province(2020A1515010622)+1 种基金the Project of Science and Technology of Guangzhou(2024A04J3712)the Teli Young Scholar Program of Beijing Institute of Technology.
文摘Donor-acceptor(D-A)compounds are particularly important in optoelectronic and biological applications.However,they are normally synthesized in the presence of transition metal catalysts.Herein,we report a metal-free method by a complexmediated nucleophilic aromatic substitution of aryl nitriles with amines.The method can lead to rich D-A type aggregation-induced emission luminogens(AIEgens)with tunable properties.They emit from deep-blue to yellow-green and possess high photoluminescence quantum yields up to 70.5%in the aggregate state.Interestingly,the suppression of intramolecular flapping is proved to play an indispensable role in the AIE behavior,which is different from the mechanism met in other AIEgens.Moreover,the biocompatible AIEgens possess specific staining of lipid droplets in HeLa cells and the superiority of identifying fatty liver over traditional Oil Red O staining is exhibited.
基金Project supported by the National Natural Science Foundation of China(Grant No.52275567)the Key Research and Development Program of Shanxi Province,China(Grant No.202202050201020)+3 种基金the Doctoral Starting-up Foundation of Taiyuan University of Science and Technology(Grant No.20192016)the Research Project Supported by Shanxi Scholarship Council(Grant No.2017-085)the Graduate Education and Teaching Reform Project of Shanxi Province,China(Grant No.2023JG136)the Special Fund for Science and Technology Innovation Teams of Shanxi Province,China(Grant No.202304051001036)。
文摘This work investigated the microstructure,magnetic properties,and crystallization kinetics of the as-spun and annealed alloy ribbons of(Fe_(40-x)Co_xNi_(40)Si_(6.33)B_(12.66)Cu_1)_(0.97)Nb_(0.03),where x=0,6,7,8,9,prepared using the meltspinning method.The results show that adding a moderate amount of Co can improve the glass forming ability(GFA),the first peak crystallization temperature,and thermal stability of the as-spun alloy ribbons.With x=7,the two-stage crystallization temperature interval△Tx=90 exhibits optimal thermal stability,and the alloy annealed at 673 K for 10 minutes shows the favorable combined magnetic properties,with H_(c)=0.12 A/m,M_(s)=88.7 A·m^(2)/kg,andμ_(e)=13800.The magnetic domain results show that annealing removes numerous pinning points in the magnetic domains of the alloy ribbons,making the domain walls smoother and effectively reducing the pinning effect.
基金supported by the National Key Research and Development Project of China(2022YFA1204500,2022YFA1204503,2018YFA0703501)the National Natural Science Foundation of China(22275115,21875274,11704024)+4 种基金the Natural Science Foundation of Shandong Province(ZR2024ZD02)Natural Science Foundation of Hebei Province(B2020201006)Hebei Province Innovation Capability Enhancement Plan Project(22567620H)Young Scholarship Funding of Shandong University.Post-graduate Innovation Fund Project of Open Laboratory Project Fund of Hebei University(HBU2025SS010)Basic Research Project of Shandong University-Xin’an Group Silicon-Based High-End New Materials Institute.
文摘Low ionic conductivity is a major obstacle for polymer solid-state electrolytes.In response to this issue,a design concept of enhanced regional electric potential difference(EREPD)is proposed to modulate the interaction of nanofillers with other components in the composite polymer solid-state electrolytes(CPSEs).While ensuring the periodic structure of the graphdiyne(GDY)backbone,methoxysubstituted GDY(OGDY)is prepared by an asymmetric substitution strategy,which increases the electric potential differences within each repeating unit of GDY.The staggered distributed electron-rich regions and electron-deficient regions on the two-dimensional plane of OGDY increase the free Li^(+)concentration through Lewis acid-base pair interaction.The adjacent ERRs and EDRs form uniformly distributed EREPDs,creating a continuous potential gradient that synergistically facilitates the efficient migration of Li^(+).Impressively,the OGDY/poly(ethylene oxide)(PEO)exhibits a high ionic conductivity(1.1×10^(-3)S cm^(−1))and ion mobility number(0.71).In addition,the accelerated Li^(+)migration promotes the formation of uniform and dense SEI layers and inhibits the growth of lithium dendrites.As a proof of concept,Li||Li symmetric cell and Li||LiFePO_(4)full cell and pouch cell assembled with OGDY/PEO exhibit good performance,highlighting the effectiveness of our EREPD design strategy for improving CPSEs performance.
基金financially supported by the National Natural Science Foundation of China(No.52373011)。
文摘Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding proton trap 2,6-di-tert-butylpyridine(DTBP),and the controlled initiation of DCC was confirmed by ^(1)H nuclear magnetic resonance(^(1)H-NMR)spectroscopy and matrix-assisted laser desorption ionization time-offlight mass(MALDI-TOF-MS)spectrometry.The polymerization kinetics were analyzed to for optimizing the polymerization rate.Allyl-telechelic PSTOs(allyl-PSTO-allyl)with molecular weight(Mn)range of 3540–7800 g/mol and narrow molecular weight dispersity(Mw/Mn)about 1.25 were prepared through nucleophilic substitution with allyltrimethylsilane(ATMS)at approximately 40%monomer conversion.The experimental results indicate that the substitution efficiency of ATMS increased with higher ATMS concentration,temperature,and extended reaction time.Nearly unity ally-functionality for allyl-PSTO-allyl was achieved by adding sufficient SnCl_(4) prior to the substitution.
文摘Traditional medicine,deeply rooted in cultural practices and historical wisdom,has faced surging challenges due to the escalating demand for plant-based remedies.This comprehensive review critically emphasizes the urgent need for sustainable practices within traditional medicine,with a special focus on the potential of plant part substitution.Case studies that illuminate successful instances of substituting plant parts and providing a deep insight into viable alternatives to conventional practices are presented.Opportunities and challenges inherent in plant part substitution are discussed by addressing key considerations such as phytochemical and pharmacological aspects,safety and toxicity profiles,cultural insights,standardization,clinical validation,and regulatory compliance.This review serves as a guide for navigating the delicate balance between tradition and conservation within indigenous medicine practices.It underscores the importance of embracing sustainable approaches through plant part substitution,ensuring the preservation of cultural heritage while meeting the evolving healthcare needs of society.
基金supported by the National Natural Science Foundation of China(Grant No.62027822)the National R&D Program of China(Grant No.2019YFA0706402).
文摘Fluorine(F)substitution in polymers modulates both molecular energy levels and film morphology;however,its impact on exciton–vibrational coupling and molecular reorganization energy is often neglected.Herein,we systematically investigated F-modified polymers(PBTA-PSF,PBDB-PSF)and their nonfluorinated counterparts(PBTA-PS,PBDB-PS)through simulations and experiments.We found that F atoms effectively lower the vibrational frequency of the molecular skeleton and suppress exciton–vibration coupling,thereby reducing the nonradiative decay rate.Moreover,introducing F atoms significantly decreases the reorganization energy for the S_(0)→S_(1) and S_(0)→cation transitions while increasing the reorganization energy for the S_(1)→S_(0) and cation→S_(0) transitions.These changes facilitate exciton dissociation and reduce the energy loss caused by dissociation and nonradiative recombination of excitons.Additionally,introducing F atoms into polymers enhances theπ–πstacking strength and the crystal coherence length in both neat and blended films,ultimately resulting in improvements in the power conversion efficiency of PBTA-PSF:L8-BO and PBDB-PSF:L8-BO are 16.51%and 17.59%,respectively.This study provides valuable insights for designing organic semiconductor materials to minimize energy loss and achieve a higher power conversion efficiency.
基金National Natural Science Foundation of China(No.52301192)Natural Science Foundation of Shandong Province(No.ZR2019YQ24)+2 种基金Taishan Scholars and Young Experts Program of Shandong Province(No.tsqn202103057)Qingchuang Talents Induction Program of Shandong Higher Education Institution(Research and Innovation Team of Structural Functional Polymer Composites)Special Financial of Shandong Province(Structural Design of High-efficiency Electromag-netic Wave-absorbing Composite Materials and Construction of Shandong Provincial Talent Teams).
文摘With the rapid development of electronic technology,how to effectively eliminate electromagnetic pollu-tion has become a serious problem.Perovskite oxides have shown great potential in the field of electro-magnetic wave absorption due to their unique structure and excellent physicochemical properties.Herein,by rationally manipulating the A-site ion substitution strategy,the theoretically directed doping of Sr ions into La ionic sites was utilized and the layered MoS_(2) was loaded by the hydrothermal process to modify its surface.Consequently,the introduced polarization phenomenon improved the dielectric performance of the perovskite oxides,achieving a collaborative dielectric/magnetic loss mechanism.Accordingly,the prepared La0.7Sr0.3FeO3(LSFO)/MoS_(2) as coating filler in the epoxy resin coating system can obtain the minimum reflection loss of-67.09 dB at 1.9 mm and the maximum effective absorption bandwidth of 7.28 GHz at 2.3 mm.More importantly,it also exhibits excellent absorption performance for multi-band electromagnetic waves,covering a wide range of specified frequency bands.It provides inspiration for ex-ploring novel perovskite oxide-based electromagnetic wave absorbing coatings and broadens the choice of ideal candidate materials for designing highly efficient,multi-band absorbers to cope with sophisticated electromagnetic environments.
基金supported by the earmarked fund for China Agriculture Research System(CARS-23-B04)the National Key Research and Development Program of China(2016YFD0201001)HAAFS Science and Technology Innovation Special Project,China(2022KJCXZX-ZHS-2).
文摘Partial substitution of inorganic fertilizers with organic amendments is an important agricultural management practice.An 11-year field experiment(22 cropping periods)was carried out to analyze the impacts of different partial substitution treatments on crop yields and the transformation of nitrogen fractions in greenhouse vegetable soil.Four treatments with equal N,P_(2)O_(5),and K_(2)O inputs were selected,including complete inorganic fertilizer N(CN),50%inorganic fertilizer N plus 50%pig manure N(CPN),50%inorganic fertilizer N plus 25%pig manure N and 25%corn straw N(CPSN),and 50%inorganic fertilizer N plus 50%corn straw N(CSN).Organic substitution treatments tended to increase crop yields since the 6th cropping period compared to the CN treatment.From the 8th to the 22nd cropping periods,the highest yields were observed in the CPSN treatment where yields were 7.5-11.1%greater than in CN treatment.After 11-year fertilization,compared to CN,organic substitution treatments significantly increased the concentrations of NO_(3)^(-)-N,NH_(4)^(+)-N,acid hydrolysis ammonium-N(AHAN),amino acid-N(AAN),amino sugar-N(ASN),and acid hydrolysis unknown-N(AHUN)in soil by 45.0-69.4,32.8-58.1,49.3-66.6,62.0-69.5,34.5-100.3,and 109.2-172.9%,respectively.Redundancy analysis indicated that soil C/N and OC concentration significantly affected the distribution of N fractions.The highest concentrations of NO_(3)^(-)-N,AHAN,AAN,AHUN were found in the CPSN treatment.Organic substitution treatments increased the activities ofβ-glucosidase,β-cellobiosidase,N-acetyl-glucosamidase,L-aminopeptidase,and phosphatase in the soil.Organic substitution treatments reduced vector length and increased vector angle,indicating alleviation of constraints of C and N on soil microorganisms.Organic substitution treatments increased the total concentrations of phospholipid fatty acids(PLFAs)in the soil by 109.9-205.3%,and increased the relative abundance of G^(+)bacteria and fungi taxa,but decreased the relative abundance of G-bacteria,total bacteria,and actinomycetes.Overall,long-term organic substitution management increased soil OC concentration,C/N,and the microbial population,the latter in turn positively influenced soil enzyme activity.Enhanced microorganism numbers and enzyme activity enhanced soil N sequestration by transforming inorganic N to acid hydrolysis-N(AHN),and enhanced soil N supply capacity by activating non-acid hydrolysis-N(NAHN)to AHN,thus improving vegetable yield.Application of inorganic fertilizer,manure,and straw was a more effective fertilization model for achieving sustainable greenhouse vegetable production than application of inorganic fertilizer alone.
基金supported by the Natural Science Foundation of Sichuan Province(No.2023NSFSC0435)Sichuan Agricultural University College Student Innovation Training Program Project Funding(No.202210626019)Sichuan Agricultural University double support(035–2221993150).
文摘Metal-organic frameworks(MOFs)derived composites are extremely potential electromagnetic wave(EMW)absorbers.However,the permittivity of absorbers directly derived from MOFs with solid structure is usually relatively low,inevitably limiting their further applications.Cation substitution can primely overcome the problem by regulating the morphology and atomic space occupation to enhance multiple loss mechanisms and impedance matching characteristics.However,universal mechanisms of the effect on EMW absorption performance influenced by cation substitution are still comparatively inadequate,which prospectively requires further exploration.Herein,a series of imidazolic MOFs were fabricated by ultrasonic symbiosis method and tailored by subsequent cation substitution strategy to prepare target porous composites.At a low filling rate and thin thickness,the as-obtained samples reach the optimal reflection loss and effective absorption bandwidth values of–49.81 dB and 7.63 GHz,respectively.The intercoupling between multiple atoms lays a significant foundation for abundant heterogeneous interfaces and defect vacancies,which effectively ameliorate the attenuation mechanisms.Meanwhile,the porous structure introduced by cation substitution reduces the bulk density to enhance the impedance matching and multiple reflections simultaneously.This study provides a helpful idea to exceedingly improve the EMW absorbing performance of imidazolic MOFs-derived composites by cation substitution.
基金This work was financially supported by the Department of Science and Technology of Sichuan Province(No.2020YJ0157).
文摘A red-emitting phosphor Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) with partial Al^(3+)/P^(5+) substitution on Si^(4+) was synthesized via a simple solid-state method,and the effects of the introduction of the M^(3+/5+)(M=Al,P)ions on the crystal structure and photoluminescence performance of Ca_(2.91)Si_(2−x)M_(x)O_(7):0.09Eu^(3+) phosphors were investigated.The X-ray diffraction(XRD),energy-dispersive X-ray spectroscopy(EDS),and X-ray photoelectron spectroscopy(XPS)results revealed that the structure of Ca_(3)Si_(2)O_(7) remained the same after the introduction of Al^(3+) and P^(5+) ions.The characteristic emission of Eu^(3+)-doped Ca_(3)Si_(2−x)M_(x)O_(7) phosphors exhibited two main peaks at 617 nm(red)and 593 nm(orange)under excitation at 394 nm,which originated from the^(5)D_(0)→^(7)F_(2)and^(5)D_(0)→^(7)F_(1) electron transitions of Eu^(3+) ions.After the partial substitution of Al^(3+) and P^(5+),the red emission intensities of the Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) phosphors were significantly enhanced by 1.88-and 1.42-fold,respectively,which is attributed to the crystal-field effect around Eu^(3+).Meanwhile,the luminescence intensities of the Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+) and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) phosphors at 210℃ were 79.36%and 77.53%of those at 30°C,respectively,indicating their excellent thermal stability.Moreover,the as-prepared Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+)and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) red-emitting phosphors were combined with a near-ultraviolet chip of 395 nm to fabricate red-light-emitting diode(LED)and white(w)-LED devices with excellent chromaticity features.In summary,Al^(3+)/P^(5+)-substituted Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) can serve as red-emitting phosphors for applications in w-LEDs.
基金supported by the National Key Research and Development Program of China(2022YFD2301403-2)the Major Special Project of Anhui Province,China(2021d06050003)+2 种基金the Postdoctoral Foundation of Anhui Province,China(2022B638)the Special Project of Zhongke Bengbu Technology Transfer Center,China(ZKBB202103)the Grant of the President Foundation of Hefei Institutes of Physical Science of Chinese Academy of Sciences(YZJJ2023QN37)。
文摘Synthetic nitrogen(N)fertilizer has made a great contribution to the improvement of soil fertility and productivity,but excessive application of synthetic N fertilizer may cause agroecosystem risks,such as soil acidification,groundwater contamination and biodiversity reduction.Meanwhile,organic substitution has received increasing attention for its ecologically and environmentally friendly and productivity benefits.However,the linkages between manure substitution,crop yield and the underlying microbial mechanisms remain uncertain.To bridge this gap,a three-year field experiment was conducted with five fertilization regimes:i)Control,non-fertilization;CF,conventional synthetic fertilizer application;CF_(1/2)M_(1/2),1/2 N input via synthetic fertilizer and 1/2 N input via manure;CF_(1/4)M_(3/4),1/4 N input synthetic fertilizer and 3/4 N input via manure;M,manure application.All fertilization treatments were designed to have equal N input.Our results showed that all manure substituted treatments achieved high soil fertility indexes(SFI)and productivities by increasing the soil organic carbon(SOC),total N(TN)and available phosphorus(AP)concentrations,and by altering the bacterial community diversity and composition compared with CF.SOC,AP,and the soil C:N ratio were mainly responsible for microbial community variations.The co-occurrence network revealed that SOC and AP had strong positive associations with Rhodospirillales and Burkholderiales,while TN and C:N ratio had positive and negative associations with Micromonosporaceae,respectively.These specific taxa are implicated in soil macroelement turnover.Random Forest analysis predicted that both biotic(bacterial composition and Micromonosporaceae)and abiotic(AP,SOC,SFI,and TN)factors had significant effects on crop yield.The present work strengthens our understanding of the effects of manure substitution on crop yield and provides theoretical support for optimizing fertilization strategies.
基金supported by the Teli Fellowship from Beijing Institute of Technology,the National Natural Science Foundation of China(Nos.52303366,22173109).
文摘In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterparts.The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications.In this context,the atomic substitution method has emerged as a favorable approach.It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely,crystal structures,and inherent properties of the resulting materials.In this review,we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional,one-dimensional and two-dimensional TMC materials.The effects of substituting elements,substitution ratios,and substitution positions on the structures and morphologies of resulting material are discussed.The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided,emphasizing the role of atomic substitution in achieving these advancements.Finally,challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.
基金supported by the National Natural Science Foundation of China (Grant Nos.92372101,52162036 and 21875155)the Fundamental Research Funds for the Central Universities (Grant Nos.20720220010)the National Key Research and Development Program of China (Grant Nos.2021YFA1201502)。
文摘The design of advanced binders plays a critical role in stabilizing the cycling performance of large-volume-effect silicon monoxide(SiO)anodes.For the classic polyacrylic acid(PAA)binder,the self-association of-COOH groups in PAA leads to the formation of intramolecular and intermolecular hydrogen bonds,greatly weakening the bonding force of the binder to SiO surface.However,strengthening the binder-material interaction from the perspective of binder molecular regulation poses a significant challenge.Herein,a modified PAA-Li_(x)(0.25≤x≤1)binder with prominent mechanical properties and adhesion strength is specifically synthesized for SiO anodes by quantitatively substituting the carboxylic hydrogen with lithium.The appropriate lithium substitution(x=0.25)not only effectively increases the number of hydrogen bonds between the PAA binder and SiO surface owing to charge repulsion effect between ions,but also guarantees moderate entanglement between PAA-Li_x molecular chains through the ion-dipole interaction.As such,the PAA-Li_(0.25)/SiO electrode exhibits exceptional mechanical properties and the lowest volume change,as well as the optimum cycling(1237.3 mA h g^(-1)after 100cycles at 0.1 C)and rate performance(1000.6 mA h g^(-1)at 1 C),significantly outperforming the electrode using pristine PAA binder.This work paves the way for quantitative regulation of binders at the molecular level.
