Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully construct...Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.展开更多
The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic ...The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic frameworks(MOFs)are ideal self-sacrificing templates for the construction of carbon-based EMW absorbers.In this work,bimetallic FeMn-MOF-derived MnFe_(2)O_(4)/C/graphene composites were fabricated via a two-step route of solvothermal reaction and the following pyrolysis treatment.The results re-veal the evolution of the microscopic morphology of carbon skeletons from loofah-like to octahedral and then to polyhedron and pomegran-ate after the adjustment of the Fe^(3+)to Mn^(2+)molar ratio.Furthermore,at the Fe^(3+)to Mn^(2+)molar ratio of 2:1,the obtained MnFe_(2)O_(4)/C/graphene composite exhibited the highest EMW absorption capacity.Specifically,a minimum reflection loss of-72.7 dB and a max-imum effective absorption bandwidth of 5.1 GHz were achieved at a low filling ratio of 10wt%.In addition,the possible EMW absorp-tion mechanism of MnFe_(2)O_(4)/C/graphene composites was proposed.Therefore,the results of this work will contribute to the construction of broadband and efficient carbon-based EMW absorbers derived from MOFs.展开更多
A thickness-controllable method for preparing metal-organic framework hollow nanofiowers on magnetic cores(Fe_(3)O_(4)@MOFs HFs)was demonstrated for the first time.The petal of magnetic core with hollow nanofiower str...A thickness-controllable method for preparing metal-organic framework hollow nanofiowers on magnetic cores(Fe_(3)O_(4)@MOFs HFs)was demonstrated for the first time.The petal of magnetic core with hollow nanofiower structure served as medium for assembling Ui O-66-NH_(2)shell with different thickness.To further improve its performance,Zr^(4+)was immobilized on the surface of Fe_(3)O_(4)@Ui O-66-NH_(2).Compared with conventional Fe_(3)O_(4)@Ui O-66-NH_(2)-Zr^(4+)nanospheres,the Fe_(3)O_(4)@Ui O-66-NH2-Zr4+HFs showed increased enrichment performance for phosphopeptides.The Fe_(3)O_(4)@Ui O-66-NH2-Zr4+HFs served as an attractive restricted-access adsorption material exhibited good selectivity(m_(β-casein):m_(BSA)=1:1000),high sensitivity(1.0 fmol)and excellent size-exclusion effect(m)((β-casein digests):m_(BSA)=1:200).Furthermore,the Fe_(3)O_(4)@Ui O-66-NH_(2)-Zr^(4+)HFs was successfully applied to the specific capture of ultratrace phosphopeptide from complex biological samples,revealing the great potential for the identification and analysis of trace phosphopeptides in clinical analysis.This work can be easily extended to the fabrication of diverse mag-MOF HFs with multifunctional and easy to post-modify properties,and open up a new avenue for the design and construction of new MOFs material.展开更多
Bridge networks are essential components of civil infrastructure,supporting communities by delivering vital services and facilitating economic activities.However,bridges are vulnerable to natural disasters,particularl...Bridge networks are essential components of civil infrastructure,supporting communities by delivering vital services and facilitating economic activities.However,bridges are vulnerable to natural disasters,particularly earthquakes.To develop an effective disaster management strategy,it is critical to identify reliable,robust,and efficient indicators.In this regard,Life-Cycle Cost(LCC)and Resilience(R)serve as key indicators to assist decision-makers in selecting the most effective disaster risk reduction plans.This study proposes an innova-tive LCC-R optimization framework to identify the most optimal retrofit strategies for bridge networks facing hazardous events during their lifespan.The proposed framework employs both single-and multi-objective opti-mization techniques to identify retrofit strategies that maximize the R index while minimizing the LCC for the under-study bridge networks.The considered retrofit strategies include various options such as different mate-rials(steel,CFRP,and GFRP),thicknesses,arrangements,and timing of retrofitting actions.The first step in the proposed framework involves constructing fragility curves by performing a series of nonlinear time-history incre-mental dynamic analyses for each case.In the subsequent step,the seismic resilience surfaces are calculated using the obtained fragility curves and assuming a recovery function.Next,the LCC is evaluated according to the pro-posed formulation for multiple seismic occurrences,which incorporates the effects of complete and incomplete repair actions resulting from previous multiple seismic events.For optimization purposes,the Non-Dominated Sorting Genetic Algorithm II(NSGA-II)evolutionary algorithm efficiently identifies the Pareto front to represent the optimal set of solutions.The study presents the most effective retrofit strategies for an illustrative bridge network,providing a comprehensive discussion and insights into the resulting tactical approaches.The findings underscore that the methodologies employed lead to logical and actionable retrofit strategies,paving the way for enhanced resilience and cost-effectiveness in bridge network management against seismic hazards.展开更多
The arbitrary discharge of tetracycline(TC)residuals has seriously influenced the ecosystem and human health.Laccase(Lac)-based biodegradation technology is considered a more effective way to remove TC due to its high...The arbitrary discharge of tetracycline(TC)residuals has seriously influenced the ecosystem and human health.Laccase(Lac)-based biodegradation technology is considered a more effective way to remove TC due to its high catalytic efficiency and less by-product.Nevertheless,free Lac suffers from poor stability,easy inactivation and difficult recovery,restricting its application.Immobilization of Lac is considered an efficient strategy for addressing these obstacles.In this study,a magnetic metal-organic framework of Fe_(3)O_(4)@SiO_(2)@UiO-66-NH_(2)(MMOF)was prepared and used as a carrier to immobilize Lac(Lac@MMOF)for TC degradation.Benefiting from the multiple binding sites,adsorption,and protection effect of MMOF,Lac@MMOF displayed a wider pH application range(2–7)and better thermal(15–85℃),repeatability,and storage stability than free Lac.Furthermore,owing to the synergism of MOF adsorption and Lac biocatalysis,the removal rate of Lac@MMOF for TC could be up to 98%at pH=7 within 1 hr,which was 1.29 and 1.24 times that of free Lac and MMOF,respectively.More importantly,Lac@MMOF could easily be separated from aqueous solution under a magnetic field and maintained good removal performance(80%)after five cycles.The degradation products were identified by applying LC-MS/MS,and possible degradation mechanisms and pathways were proposed.Finally,the antibacterial activity of intermediate products was evaluated using Escherichia coli,which revealed that the toxicity of TC was reduced effectively by the degradation of Lac@MMOF.Overall,Lac@MMOF is a green alternative for residual antibiotic removal in water.展开更多
Wireless Sensor Networks(WSNs)are one of the best technologies of the 21st century and have seen tremendous growth over the past decade.Much work has been put into its development in various aspects such as architectu...Wireless Sensor Networks(WSNs)are one of the best technologies of the 21st century and have seen tremendous growth over the past decade.Much work has been put into its development in various aspects such as architectural attention,routing protocols,location exploration,time exploration,etc.This research aims to optimize routing protocols and address the challenges arising from conflicting objectives in WSN environments,such as balancing energy consumption,ensuring routing reliability,distributing network load,and selecting the shortest path.Many optimization techniques have shown success in achieving one or two objectives but struggle to achieve the right balance between multiple conflicting objectives.To address this gap,this paper proposes an innovative approach that integrates Particle Swarm Optimization(PSO)with a fuzzy multi-objective framework.The proposed method uses fuzzy logic to effectively control multiple competing objectives to represent its major development beyond existing methods that only deal with one or two objectives.The search efficiency is improved by particle swarm optimization(PSO)which overcomes the large computational requirements that serve as a major drawback of existing methods.The PSO algorithm is adapted for WSNs to optimize routing paths based on fuzzy multi-objective fitness.The fuzzy logic framework uses predefined membership functions and rule-based reasoning to adjust routing decisions.These adjustments influence PSO’s velocity updates,ensuring continuous adaptation under varying network conditions.The proposed multi-objective PSO-fuzzy model is evaluated using NS-3 simulation.The results show that the proposed model is capable of improving the network lifetime by 15.2%–22.4%,increasing the stabilization time by 18.7%–25.5%,and increasing the residual energy by 8.9%–16.2% compared to the state-of-the-art techniques.The proposed model also achieves a 15%–24% reduction in load variance,demonstrating balanced routing and extended network lifetime.Furthermore,analysis using p-values obtained from multiple performance measures(p-values<0.05)showed that the proposed approach outperforms with a high level of confidence.The proposed multi-objective PSO-fuzzy model provides a robust and scalable solution to improve the performance of WSNs.It allows stable performance in networks with 100 to 300 nodes,under varying node densities,and across different base station placements.Computational complexity analysis has shown that the method fits well into large-scale WSNs and that the addition of fuzzy logic controls the power usage to make the system practical for real-world use.展开更多
Evolutionary algorithms have been extensively utilized in practical applications.However,manually designed population updating formulas are inherently prone to the subjective influence of the designer.Genetic programm...Evolutionary algorithms have been extensively utilized in practical applications.However,manually designed population updating formulas are inherently prone to the subjective influence of the designer.Genetic programming(GP),characterized by its tree-based solution structure,is a widely adopted technique for optimizing the structure of mathematical models tailored to real-world problems.This paper introduces a GP-based framework(GPEAs)for the autonomous generation of update formulas,aiming to reduce human intervention.Partial modifications to tree-based GP have been instigated,encompassing adjustments to its initialization process and fundamental update operations such as crossover and mutation within the algorithm.By designing suitable function sets and terminal sets tailored to the selected evolutionary algorithm,and ultimately derive an improved update formula.The Cat Swarm Optimization Algorithm(CSO)is chosen as a case study,and the GP-EAs is employed to regenerate the speed update formulas of the CSO.To validate the feasibility of the GP-EAs,the comprehensive performance of the enhanced algorithm(GP-CSO)was evaluated on the CEC2017 benchmark suite.Furthermore,GP-CSO is applied to deduce suitable embedding factors,thereby improving the robustness of the digital watermarking process.The experimental results indicate that the update formulas generated through training with GP-EAs possess excellent performance scalability and practical application proficiency.展开更多
The advancement of Internet of Things(IoT)technology is driving industries toward intelligent digital transformation,highlighting the crucial role of software engineering.Despite this,the integration of software engin...The advancement of Internet of Things(IoT)technology is driving industries toward intelligent digital transformation,highlighting the crucial role of software engineering.Despite this,the integration of software engineering into IoT engineering education remains underexplored.To address this gap,the School of Software at North University of China,in collaboration with QST Innovation Technology Group Co.,Ltd.(QST),has developed an innovative educational mechanism.This initiative focuses on the software engineering IoT track and optimizes the teaching process through the outcome-based education(OBE)concept.It incorporates military-industrial characteristics,introduces advanced information and technology curricula,and enhances laboratory infrastructure.The goal is to cultivate innovative talents with unique capabilities,thereby fostering the comprehensive development and application of IoT technology.展开更多
Organophosphorus pesticides(OPPs)in foods pose a serious threat to human health,motivating the development of novel analytical methods for their rapid detection and quantification.A magnetic covalent organic framework...Organophosphorus pesticides(OPPs)in foods pose a serious threat to human health,motivating the development of novel analytical methods for their rapid detection and quantification.A magnetic covalent organic framework(M-COF)adsorbent for the magnetic solid-phase extraction(MSPE)of OPPs from foods was reported.M-COF was synthesized by the Schiff base condensation reaction of 1,3,5-tris(4-aminophenyl)benzene and 4,4-biphenyldicarboxaldehyde on the surface of amino-functionalized magnetic nanoparticles.Density functional theory(DFT)calculations showed that adsorption of OPPs onto the surface of M-COF involved hydrophobic effects,van der Waals interactions,π-πinteractions,halogen-N bonding,and hydrogen bonding.Combined with gas chromatography-mass spectrometry(GC-MS)technology,the MSPE method features low limits of detection for OPPs(0.002-0.015μg/L),good reproducibility(1.45%-6.14%),wide linear detection range(0.01-1μg/L,R≥0.9935),and satisfactory recoveries(87.3%-110.4%).The method was successfully applied for the trace analysis of OPPs in spiked fruit juices.展开更多
Modulating the dipole polarization loss in the single-atom region and establishing its direct relationship with the electromagnetic wave absorption(EWA)performance remain an unmet challenge.Here,a dual-ligand modulati...Modulating the dipole polarization loss in the single-atom region and establishing its direct relationship with the electromagnetic wave absorption(EWA)performance remain an unmet challenge.Here,a dual-ligand modulation strategy,i.e.,partially changing coordination atoms in the single-metal region(sMr),is introduced to effectively break the coordination symmetry of conjugated metal-organic frameworks(cMOFs),finally enhancing EWA property of cMOFs materials.Further,the asymmetrical sMr is experimentally found to elicit the dipole polarization loss,overcoming the handicaps of other electromagnetic wave loss mechanisms,which directly contribution to enhance EWA performance of this series of cMOFs.This strategy is further confirmed by replacing metal centers.Among studied series of cMOFs,Cu_(2.25)/Co_(0.75)(HHTP1.67HITP0.33)achieves excellent EWA performance with an effective absorption bandwidth of 5.00 GHz and a reflection loss of66.03 dB.We introduce a dual-ligand modulation strategy targeting single-metal regions within cMOFs here,aiming to achieve superior EWA performance through atomic-scale dipole polarization loss modulation.We hope our study can inspire more exploration to realize high-performance EWA materials.展开更多
The development of organic frameworks with radical skeletons is desired.In this study,we report the development of a novel two-dimensional radical halogen-bonded organic framework(XOF).The radical monomer,benzimidazol...The development of organic frameworks with radical skeletons is desired.In this study,we report the development of a novel two-dimensional radical halogen-bonded organic framework(XOF).The radical monomer,benzimidazole triphenylmethyl(BTTM),was synthesized through the coupling of TTM radicals with benzimidazole.Initially,the benzimidazole units were coordinated with Ag^(+)ions to create a[N···Ag···N]^(+)framework.Subsequently,the addition of iodine led to the in situ replacement of Ag^(+)with I^(+)ions,forming[N···I···N]^(+)linkers and resulting in the creation of the XOF structure.The resulting XOF-HBTTM and XOF-BTTM structures demonstrated good-crystallinity,confirmed by PXRD,HR-TEM,SEAD,and SAXS analyses.EPR measurements confirmed the preservation of radical characteristics within the XOF framework.Furthermore,SQUID measurements indicated that XOF-BTTM exhibits spin moments of S=1/2 at 2 K,with a saturated magnetization strength peaking at 4.10 emu/g,a notable enhancement compared to 1.87 emu/g for the BTTM monomer.This improvement in magnetism is attributed to the extended spin density distribution and the presence of[N···I···N]^(+)interactions,as suggested by DFT calculations.Additionally,the radical XOF-BTTM exhibited significantly enhanced electrical conductivity,reaching up to 1.30×10^(-4)S/cm,which is two orders of magnitude higher than that of XOF-HBTTM.This increased conductivity is linked to a reduced HOMO-LUMO gap,higher carrier density,and the incorporation of triphenylmethyl radicals within the framework.This research highlights the potential of benzimidazolyl motifs in constructing functional XOFs and advances our understanding of radical organic frameworks.展开更多
Email communication plays a crucial role in both personal and professional contexts;however,it is frequently compromised by the ongoing challenge of spam,which detracts from productivity and introduces considerable se...Email communication plays a crucial role in both personal and professional contexts;however,it is frequently compromised by the ongoing challenge of spam,which detracts from productivity and introduces considerable security risks.Current spam detection techniques often struggle to keep pace with the evolving tactics employed by spammers,resulting in user dissatisfaction and potential data breaches.To address this issue,we introduce the Divide and Conquer-Generative Adversarial Network Squeeze and Excitation-Based Framework(DaC-GANSAEBF),an innovative deep-learning model designed to identify spam emails.This framework incorporates cutting-edge technologies,such as Generative Adversarial Networks(GAN),Squeeze and Excitation(SAE)modules,and a newly formulated Light Dual Attention(LDA)mechanism,which effectively utilizes both global and local attention to discern intricate patterns within textual data.This approach significantly improves efficiency and accuracy by segmenting scanned email content into smaller,independently evaluated components.The model underwent training and validation using four publicly available benchmark datasets,achieving an impressive average accuracy of 98.87%,outperforming leading methods in the field.These findings underscore the resilience and scalability of DaC-GANSAEBF,positioning it as a viable solution for contemporary spam detection systems.The framework can be easily integrated into existing technologies to enhance user security and reduce the risks associated with spam.展开更多
Enhancing the activity of fragile enzymes is greatly useful for various purposes,including fabrication of enzyme-based immunosensors.Herein,we report a defect-engineering strategy for encapsulating enzymes within cova...Enhancing the activity of fragile enzymes is greatly useful for various purposes,including fabrication of enzyme-based immunosensors.Herein,we report a defect-engineering strategy for encapsulating enzymes within covalent organic frameworks(COFs),enabling the resulting immobilized enzymes with excellent catalytic activity and stability to construct high performance immunosensors.In this design,by consciously introducing monoaldehyde ligands into the imine-linked COFs structure,we have precisely customized the structural defects to improve enzyme loading capacity and conformational stability.Defect-engineering interaction modulation between enzymes and COFs drives the enhancement of catalytic performance.Compared to the pristine COFs,the enzyme@defective COFs composites with optimally tuned catalytic performance exhibit a 4.49-fold enhancement in enzymatic activity.Furthermore,it is demonstrated that the stable skeletons of COFs provide exceptional protection for the enzymes against external perturbations.Thereafter,the optimized enzyme@defective COFs are employed to fabricate immunosensor.We have successfully established a detection method for prostate-specific antigen(PSA),achieving a low detection limit of 0.09 ng/mL.More importantly,the developed immunosensor has successfully distinguished the prostate cancer patients from healthy individuals.This work establishes a novel paradigm for enzyme immobilization,ultimately empowering the construction of a PSA immunosensor with high sensitivity,remarkable operational stability,and great clinical application potential.展开更多
Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fund...Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fundamental trade-off between haze and transparency,coupled with impractical thicknesses(≥1 mm).Inspired by squid’s skin-peeling mechanism,this work develops a peroxyformic acid(HCOOOH)-enabled precision peeling strategy to isolate intact 10-μm-thick bamboo green(BG)frameworks—100×thinner than wood-based counterparts while achieving an unprecedented optical performance(88%haze with 80%transparency).This performance surpasses delignified biomass(transparency<40%at 1 mm)and matches engineered cellulose composites,yet requires no energy-intensive nanofibrillation.The preserved native cellulose I crystalline structure(64.76%crystallinity)and wax-coated uniaxial fibril alignment(Hermans factor:0.23)contribute to high mechanical strength(903 MPa modulus)and broadband light scattering.As a light-management layer in polycrystalline silicon solar cells,the BG framework boosts photoelectric conversion efficiency by 0.41%absolute(18.74%→19.15%),outperforming synthetic anti-reflective coatings.The work establishes a scalable,waste-to-wealth route for optical-grade cellulose materials in next-generation optoelectronics.展开更多
Two-dimensional conjugated metal-organic framework(2D c-MOF)nanosheets have garnered significant research interest owing to their suite of distinctive properties.Consequently,diverse synthetic methodologies have been ...Two-dimensional conjugated metal-organic framework(2D c-MOF)nanosheets have garnered significant research interest owing to their suite of distinctive properties.Consequently,diverse synthetic methodologies have been established for the fabrication of 2D c-MOFs exhibiting welldefined nanosheet morphology.In addition,the structural engineering of 2D c-MOF nanosheets for energy storage and conversion has emerged as a prominent research focus.This review comprehensively summarizes recent advancements in 2D c-MOF nanosheets.We commence with a concise overview of diverse synthesis strategies for these materials.Subsequently,progress in their utilization as electrode materials or catalysts for batteries,supercapacitors,and electrocatalysis/photocatalysis is systematically examined.Finally,prevailing challenges and prospective research directions are discussed.Collectively,this review aims to stimulate the development of sophisticated 2D c-MOF nanosheets for high-performance energy applications.展开更多
Constructing catalysts featuring an ordered structure,stable performance,and uniformly dispersed catalytic sites is vital for the epoxidation of small-molecular olefins.Here,we design catalysts by tracing the oxidatio...Constructing catalysts featuring an ordered structure,stable performance,and uniformly dispersed catalytic sites is vital for the epoxidation of small-molecular olefins.Here,we design catalysts by tracing the oxidationprocess origin and synthesize a series of highly dispersed metal porphyrin-based covalent organic frameworks(COFs)materials.The aim is to efficiently oxidize the C-H bonds of cumene by air to in-situ generate organic peroxides at a safe concentration,and integrate the multi-step oxidation method of cumene in industry into a one-step method for olefins’epoxidation.The carbonyl-ruthenium COF(Ru-COF-1)exhibits excellent performance,with 98% epoxide selectivity,1221.77 h^(-1) productivity,and over 95% selectivity after 9 cycles for 1-hexene.Analysis of structure-properties-catalytic relationships of Ru-COF-1 shows that,compared with Ru-porphyrins and metal-free COFs,the enhanced reaction performance mainly results from Ru metal introduction,which promotes benzylic proton transfer in cumene.Besides,Ru-COF-1’s porous,ordered structure aids oxygen enrichment,forming active peroxy radicals with the cumene carboncentered radicals formed on the catalyst surface.Ru-H sites then accelerate active oxygen transfer from peroxy radicals,enabling olefin tandem epoxidation.Density functional theory(DFT)calculations verify the reaction mechanism,and this work offers a reference for the design of catalysts for the green,safe,and efficient oxidation of olefins.展开更多
A series of dual-extended-polyhedral metal-organic frameworks(MOFs)was constructed based on the 14-coordinated Cu_(24)-MOP-1(MOP=metal-organic polyhedron)supermolecular building blocks(SBBs)with enhanced stability and...A series of dual-extended-polyhedral metal-organic frameworks(MOFs)was constructed based on the 14-coordinated Cu_(24)-MOP-1(MOP=metal-organic polyhedron)supermolecular building blocks(SBBs)with enhanced stability and tunable functionality for high water uptake efficiency and capacity.Exceptional water stability was demonstrated by the retention of chemical integrity and crystallinity of USC-CP-5(where USC-CP stands for University of South China coordination polymer)after exposure to boiling water for 24 h.Functionalization with-Cl,-OCH_(3),-OH,and-NH_(2)groups of USC-CP-5 resulted in water uptake capacities of 450,460,490,and 590 cm^(3)·g^(-1) at relative pressure(P/P_(0))=0.9,respectively.This performance is ascribed to both the increased hydrophilicity of the ligands and stronger hydrogen bonding.Intriguingly,high-temperature activated USC-5-NH_(2)exhibits a significant water uptake of 38.5 wt.%at P/P_(0)=0.3 and releases 0.44 L·kg^(-1) water between 25 and 65℃.This water release process is reversible for at least 100 cycles with minimal weight loss of only 1.6 wt.%.Consequently,USC-5-NH_(2)holds considerable potential for harvesting and releasing atmospheric water in arid desert regions,powered by solar energy.展开更多
To meet the growing needs of flexible and wearable electronics,stretchable energy storage devices—especially supercapacitors(SCs)—have become a key focus in advanced energy storage research.However,achieving both me...To meet the growing needs of flexible and wearable electronics,stretchable energy storage devices—especially supercapacitors(SCs)—have become a key focus in advanced energy storage research.However,achieving both mechanical stretchability and high capacitance in SC still faces great challenges,and the crucial factors lie in creating superior electrode materials that exhibit high electrochemical performance as well as excellent mechanical stretchability.Covalent organic frameworks(COFs)possess considerable potential as electrode materials for SCs by virtue of stable organic frameworks,open channels and designable functional groups.Nevertheless,their applications in flexible SCs are greatly hindered by their rigid characteristics.Here a novel COFs@conductive polymer hydrogels(CPHs)@poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)complexes,which integrate the pseudocapacitance of PDITAPA COF,mechanical stretchability of hydrogels and high conductivity of PEDOT:PSS,has been developed as stretchable electrode of SCs.Physically cross-linked PEDOT nanofibers,with their interlinked and entangled architecture,collectively boost mechanical,electrical,and electrochemical performance.The COFs@CPHs@PEDOT:PSS simultaneously demonstrates outstanding mechanical stretchability,high electrical behaviors,and superior swelling characteristics.The resulting SC exhibits advantages of simple structures,facile assembly processes,high specific capacitance,excellent cycling stability,and arbitrary deformation,which holds great application prospects for wearable electronic products.Owing to its uncomplicated structure,ease of production,high energy storage capacity,robust cycling performance,and adaptability to deformation,this fabricated SC is well-suited for next-generation wearable technologies.展开更多
Photocatalytic carbon dioxide(CO_(2))reduction offers an alternative strategy for converting CO_(2)into high-value added gaseous fuels,thereby paving the way for the development of clean and renewable energy.Metal-org...Photocatalytic carbon dioxide(CO_(2))reduction offers an alternative strategy for converting CO_(2)into high-value added gaseous fuels,thereby paving the way for the development of clean and renewable energy.Metal-organic frameworks(MOFs),characterized by their highly porous structure,exceptional CO_(2)adsorption capacity,and tunable architecture,have emerged as promising candidates for photocatalytic CO_(2)reduction.This review systematically examines the recent advancement in MOFs-based photocatalysts for CO_(2)reduction to CO.It begins with the overview of the fundamental mechanisms and processes of MOFs towards photocatalytic CO_(2)reduction.Subsequently,common strategies for the modulation of MOFs-based photocatalysts are summarized,including metallic site modification,functionalized ligand incorporation,morphological control,defect engineering,and heterostructure construction.Notably,the review analyzes the critical factors contributing to the high selectivity of CO_(2)photoreduction to CO from both thermodynamic and kinetic perspectives.The conclusion addresses current challenges and future perspectives in designing highly efficient photocatalysts with abundant active sites,providing valuable insights for their continued development.展开更多
The intrinsic pressure framework,which treats self-propelling force as an external force,provides a convenient and consistent description of mechanical equilibrium in active matter.However,direct experimental evidence...The intrinsic pressure framework,which treats self-propelling force as an external force,provides a convenient and consistent description of mechanical equilibrium in active matter.However,direct experimental evidence is still lacking.To validate this framework,here we employ a programmable robotic platform,where a single light-controlled wheeled robot travels in an activity landscape.Our experiments quantitatively demonstrate that the intrinsic pressure difference across the activity interface is balanced by the emerged polarization force.This result unambiguously confirms the theoretical predictions,thus validating the intrinsic pressure framework and laying the experimental foundation for the intrinsic pressure-based mechanical description of dry active matter.展开更多
文摘Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.
基金supported by the Natural Science Research Project of the Anhui Educational Committee,China(No.2022AH050827)the Open Research Fund Program of Anhui Province Key Laboratory of Specialty Polymers,Anhui University of Science and Technology,China(No.AHKLSP23-12)the Joint National-Local Engineering Research Center for Safe and Precise Coal Mining Fund,China(No.EC2022020)。
文摘The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic frameworks(MOFs)are ideal self-sacrificing templates for the construction of carbon-based EMW absorbers.In this work,bimetallic FeMn-MOF-derived MnFe_(2)O_(4)/C/graphene composites were fabricated via a two-step route of solvothermal reaction and the following pyrolysis treatment.The results re-veal the evolution of the microscopic morphology of carbon skeletons from loofah-like to octahedral and then to polyhedron and pomegran-ate after the adjustment of the Fe^(3+)to Mn^(2+)molar ratio.Furthermore,at the Fe^(3+)to Mn^(2+)molar ratio of 2:1,the obtained MnFe_(2)O_(4)/C/graphene composite exhibited the highest EMW absorption capacity.Specifically,a minimum reflection loss of-72.7 dB and a max-imum effective absorption bandwidth of 5.1 GHz were achieved at a low filling ratio of 10wt%.In addition,the possible EMW absorp-tion mechanism of MnFe_(2)O_(4)/C/graphene composites was proposed.Therefore,the results of this work will contribute to the construction of broadband and efficient carbon-based EMW absorbers derived from MOFs.
基金sponsored by the National Natural Science Foundation of China (Nos. 22106038, 22204171 and 22076038)the Henan Provincial Science and Technology Research Project (No. 232102310112)+2 种基金the China Postdoctoral Science Foundation (No. 2022M713299)Natural Science Foundation of Henan Province, China (No. 202300410044)Henan key scientific research programs to Universities and Colleges (No. 22ZX003)。
文摘A thickness-controllable method for preparing metal-organic framework hollow nanofiowers on magnetic cores(Fe_(3)O_(4)@MOFs HFs)was demonstrated for the first time.The petal of magnetic core with hollow nanofiower structure served as medium for assembling Ui O-66-NH_(2)shell with different thickness.To further improve its performance,Zr^(4+)was immobilized on the surface of Fe_(3)O_(4)@Ui O-66-NH_(2).Compared with conventional Fe_(3)O_(4)@Ui O-66-NH_(2)-Zr^(4+)nanospheres,the Fe_(3)O_(4)@Ui O-66-NH2-Zr4+HFs showed increased enrichment performance for phosphopeptides.The Fe_(3)O_(4)@Ui O-66-NH2-Zr4+HFs served as an attractive restricted-access adsorption material exhibited good selectivity(m_(β-casein):m_(BSA)=1:1000),high sensitivity(1.0 fmol)and excellent size-exclusion effect(m)((β-casein digests):m_(BSA)=1:200).Furthermore,the Fe_(3)O_(4)@Ui O-66-NH_(2)-Zr^(4+)HFs was successfully applied to the specific capture of ultratrace phosphopeptide from complex biological samples,revealing the great potential for the identification and analysis of trace phosphopeptides in clinical analysis.This work can be easily extended to the fabrication of diverse mag-MOF HFs with multifunctional and easy to post-modify properties,and open up a new avenue for the design and construction of new MOFs material.
文摘Bridge networks are essential components of civil infrastructure,supporting communities by delivering vital services and facilitating economic activities.However,bridges are vulnerable to natural disasters,particularly earthquakes.To develop an effective disaster management strategy,it is critical to identify reliable,robust,and efficient indicators.In this regard,Life-Cycle Cost(LCC)and Resilience(R)serve as key indicators to assist decision-makers in selecting the most effective disaster risk reduction plans.This study proposes an innova-tive LCC-R optimization framework to identify the most optimal retrofit strategies for bridge networks facing hazardous events during their lifespan.The proposed framework employs both single-and multi-objective opti-mization techniques to identify retrofit strategies that maximize the R index while minimizing the LCC for the under-study bridge networks.The considered retrofit strategies include various options such as different mate-rials(steel,CFRP,and GFRP),thicknesses,arrangements,and timing of retrofitting actions.The first step in the proposed framework involves constructing fragility curves by performing a series of nonlinear time-history incre-mental dynamic analyses for each case.In the subsequent step,the seismic resilience surfaces are calculated using the obtained fragility curves and assuming a recovery function.Next,the LCC is evaluated according to the pro-posed formulation for multiple seismic occurrences,which incorporates the effects of complete and incomplete repair actions resulting from previous multiple seismic events.For optimization purposes,the Non-Dominated Sorting Genetic Algorithm II(NSGA-II)evolutionary algorithm efficiently identifies the Pareto front to represent the optimal set of solutions.The study presents the most effective retrofit strategies for an illustrative bridge network,providing a comprehensive discussion and insights into the resulting tactical approaches.The findings underscore that the methodologies employed lead to logical and actionable retrofit strategies,paving the way for enhanced resilience and cost-effectiveness in bridge network management against seismic hazards.
基金supported by the National Natural Science Foundation of China(No.U20A20133)the National Key Research and Development Program of China(No.2022YFF0606703).
文摘The arbitrary discharge of tetracycline(TC)residuals has seriously influenced the ecosystem and human health.Laccase(Lac)-based biodegradation technology is considered a more effective way to remove TC due to its high catalytic efficiency and less by-product.Nevertheless,free Lac suffers from poor stability,easy inactivation and difficult recovery,restricting its application.Immobilization of Lac is considered an efficient strategy for addressing these obstacles.In this study,a magnetic metal-organic framework of Fe_(3)O_(4)@SiO_(2)@UiO-66-NH_(2)(MMOF)was prepared and used as a carrier to immobilize Lac(Lac@MMOF)for TC degradation.Benefiting from the multiple binding sites,adsorption,and protection effect of MMOF,Lac@MMOF displayed a wider pH application range(2–7)and better thermal(15–85℃),repeatability,and storage stability than free Lac.Furthermore,owing to the synergism of MOF adsorption and Lac biocatalysis,the removal rate of Lac@MMOF for TC could be up to 98%at pH=7 within 1 hr,which was 1.29 and 1.24 times that of free Lac and MMOF,respectively.More importantly,Lac@MMOF could easily be separated from aqueous solution under a magnetic field and maintained good removal performance(80%)after five cycles.The degradation products were identified by applying LC-MS/MS,and possible degradation mechanisms and pathways were proposed.Finally,the antibacterial activity of intermediate products was evaluated using Escherichia coli,which revealed that the toxicity of TC was reduced effectively by the degradation of Lac@MMOF.Overall,Lac@MMOF is a green alternative for residual antibiotic removal in water.
基金funded by Deanship of Graduate studies and Scientific Research at Jouf University under grant No.(DGSSR-2023-2-02038).
文摘Wireless Sensor Networks(WSNs)are one of the best technologies of the 21st century and have seen tremendous growth over the past decade.Much work has been put into its development in various aspects such as architectural attention,routing protocols,location exploration,time exploration,etc.This research aims to optimize routing protocols and address the challenges arising from conflicting objectives in WSN environments,such as balancing energy consumption,ensuring routing reliability,distributing network load,and selecting the shortest path.Many optimization techniques have shown success in achieving one or two objectives but struggle to achieve the right balance between multiple conflicting objectives.To address this gap,this paper proposes an innovative approach that integrates Particle Swarm Optimization(PSO)with a fuzzy multi-objective framework.The proposed method uses fuzzy logic to effectively control multiple competing objectives to represent its major development beyond existing methods that only deal with one or two objectives.The search efficiency is improved by particle swarm optimization(PSO)which overcomes the large computational requirements that serve as a major drawback of existing methods.The PSO algorithm is adapted for WSNs to optimize routing paths based on fuzzy multi-objective fitness.The fuzzy logic framework uses predefined membership functions and rule-based reasoning to adjust routing decisions.These adjustments influence PSO’s velocity updates,ensuring continuous adaptation under varying network conditions.The proposed multi-objective PSO-fuzzy model is evaluated using NS-3 simulation.The results show that the proposed model is capable of improving the network lifetime by 15.2%–22.4%,increasing the stabilization time by 18.7%–25.5%,and increasing the residual energy by 8.9%–16.2% compared to the state-of-the-art techniques.The proposed model also achieves a 15%–24% reduction in load variance,demonstrating balanced routing and extended network lifetime.Furthermore,analysis using p-values obtained from multiple performance measures(p-values<0.05)showed that the proposed approach outperforms with a high level of confidence.The proposed multi-objective PSO-fuzzy model provides a robust and scalable solution to improve the performance of WSNs.It allows stable performance in networks with 100 to 300 nodes,under varying node densities,and across different base station placements.Computational complexity analysis has shown that the method fits well into large-scale WSNs and that the addition of fuzzy logic controls the power usage to make the system practical for real-world use.
文摘Evolutionary algorithms have been extensively utilized in practical applications.However,manually designed population updating formulas are inherently prone to the subjective influence of the designer.Genetic programming(GP),characterized by its tree-based solution structure,is a widely adopted technique for optimizing the structure of mathematical models tailored to real-world problems.This paper introduces a GP-based framework(GPEAs)for the autonomous generation of update formulas,aiming to reduce human intervention.Partial modifications to tree-based GP have been instigated,encompassing adjustments to its initialization process and fundamental update operations such as crossover and mutation within the algorithm.By designing suitable function sets and terminal sets tailored to the selected evolutionary algorithm,and ultimately derive an improved update formula.The Cat Swarm Optimization Algorithm(CSO)is chosen as a case study,and the GP-EAs is employed to regenerate the speed update formulas of the CSO.To validate the feasibility of the GP-EAs,the comprehensive performance of the enhanced algorithm(GP-CSO)was evaluated on the CEC2017 benchmark suite.Furthermore,GP-CSO is applied to deduce suitable embedding factors,thereby improving the robustness of the digital watermarking process.The experimental results indicate that the update formulas generated through training with GP-EAs possess excellent performance scalability and practical application proficiency.
基金supported in part by the Universityindustry Collaborative Education Program of the Ministry of Education under Grant No.202102383004。
文摘The advancement of Internet of Things(IoT)technology is driving industries toward intelligent digital transformation,highlighting the crucial role of software engineering.Despite this,the integration of software engineering into IoT engineering education remains underexplored.To address this gap,the School of Software at North University of China,in collaboration with QST Innovation Technology Group Co.,Ltd.(QST),has developed an innovative educational mechanism.This initiative focuses on the software engineering IoT track and optimizes the teaching process through the outcome-based education(OBE)concept.It incorporates military-industrial characteristics,introduces advanced information and technology curricula,and enhances laboratory infrastructure.The goal is to cultivate innovative talents with unique capabilities,thereby fostering the comprehensive development and application of IoT technology.
基金supported by Key Research and Development Project of Shandong Province(2021ZDSYS12)National Natural Science Foundation of China(22076086,21777089)+3 种基金Taishan Scholar Program of Shandong Province(ts20190948)Shandong Province Science and Technology Small and Medium Enterprises Innovation Ability Enhancement Project(2023TSGC0689,2023TSGC0055)Natural Science Foundation of Shandong Province(ZR2021MB086,ZR2023QB035)Jinan City University and Institute Innovation Team Project(2021GXRC061,20228045,202333027)。
文摘Organophosphorus pesticides(OPPs)in foods pose a serious threat to human health,motivating the development of novel analytical methods for their rapid detection and quantification.A magnetic covalent organic framework(M-COF)adsorbent for the magnetic solid-phase extraction(MSPE)of OPPs from foods was reported.M-COF was synthesized by the Schiff base condensation reaction of 1,3,5-tris(4-aminophenyl)benzene and 4,4-biphenyldicarboxaldehyde on the surface of amino-functionalized magnetic nanoparticles.Density functional theory(DFT)calculations showed that adsorption of OPPs onto the surface of M-COF involved hydrophobic effects,van der Waals interactions,π-πinteractions,halogen-N bonding,and hydrogen bonding.Combined with gas chromatography-mass spectrometry(GC-MS)technology,the MSPE method features low limits of detection for OPPs(0.002-0.015μg/L),good reproducibility(1.45%-6.14%),wide linear detection range(0.01-1μg/L,R≥0.9935),and satisfactory recoveries(87.3%-110.4%).The method was successfully applied for the trace analysis of OPPs in spiked fruit juices.
基金supported by the National Natural Science Foundation of China(52172091,52172295)Defense Industrial Technology Development Program(JCKY2023605C002)+3 种基金Basic Research Program of Jiangsu(BK20232013)the National Key Laboratory on Electromagnetic Environmental Effects and Electro-optical Engineering(NO.61422062301)The Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX23_0371,KYCX24_0571,KYCX25_0602)Opening Project of Science and Technology on Reliability Physics and Application Technology of Electronic Component Laboratory(ZHD202305).
文摘Modulating the dipole polarization loss in the single-atom region and establishing its direct relationship with the electromagnetic wave absorption(EWA)performance remain an unmet challenge.Here,a dual-ligand modulation strategy,i.e.,partially changing coordination atoms in the single-metal region(sMr),is introduced to effectively break the coordination symmetry of conjugated metal-organic frameworks(cMOFs),finally enhancing EWA property of cMOFs materials.Further,the asymmetrical sMr is experimentally found to elicit the dipole polarization loss,overcoming the handicaps of other electromagnetic wave loss mechanisms,which directly contribution to enhance EWA performance of this series of cMOFs.This strategy is further confirmed by replacing metal centers.Among studied series of cMOFs,Cu_(2.25)/Co_(0.75)(HHTP1.67HITP0.33)achieves excellent EWA performance with an effective absorption bandwidth of 5.00 GHz and a reflection loss of66.03 dB.We introduce a dual-ligand modulation strategy targeting single-metal regions within cMOFs here,aiming to achieve superior EWA performance through atomic-scale dipole polarization loss modulation.We hope our study can inspire more exploration to realize high-performance EWA materials.
基金supported by National Natural Science Foundation of China(Nos.22371218,21702153,52270070 and21801194)Natural Science Foundation of Zhejiang Province(No.LR22B020001)+1 种基金Wuhan Science and Technology Bureau(No.whkxjsj009)the support of the Core Facility of Wuhan University and the Large-scale Instrument and Equipment Sharing Foundation of Wuhan University。
文摘The development of organic frameworks with radical skeletons is desired.In this study,we report the development of a novel two-dimensional radical halogen-bonded organic framework(XOF).The radical monomer,benzimidazole triphenylmethyl(BTTM),was synthesized through the coupling of TTM radicals with benzimidazole.Initially,the benzimidazole units were coordinated with Ag^(+)ions to create a[N···Ag···N]^(+)framework.Subsequently,the addition of iodine led to the in situ replacement of Ag^(+)with I^(+)ions,forming[N···I···N]^(+)linkers and resulting in the creation of the XOF structure.The resulting XOF-HBTTM and XOF-BTTM structures demonstrated good-crystallinity,confirmed by PXRD,HR-TEM,SEAD,and SAXS analyses.EPR measurements confirmed the preservation of radical characteristics within the XOF framework.Furthermore,SQUID measurements indicated that XOF-BTTM exhibits spin moments of S=1/2 at 2 K,with a saturated magnetization strength peaking at 4.10 emu/g,a notable enhancement compared to 1.87 emu/g for the BTTM monomer.This improvement in magnetism is attributed to the extended spin density distribution and the presence of[N···I···N]^(+)interactions,as suggested by DFT calculations.Additionally,the radical XOF-BTTM exhibited significantly enhanced electrical conductivity,reaching up to 1.30×10^(-4)S/cm,which is two orders of magnitude higher than that of XOF-HBTTM.This increased conductivity is linked to a reduced HOMO-LUMO gap,higher carrier density,and the incorporation of triphenylmethyl radicals within the framework.This research highlights the potential of benzimidazolyl motifs in constructing functional XOFs and advances our understanding of radical organic frameworks.
基金funded by the Deanship of Scientific Research(DSR)at King Abdulaziz University,Jeddah,Saudi Arabia under Grant No.(GPIP:71-829-2024).
文摘Email communication plays a crucial role in both personal and professional contexts;however,it is frequently compromised by the ongoing challenge of spam,which detracts from productivity and introduces considerable security risks.Current spam detection techniques often struggle to keep pace with the evolving tactics employed by spammers,resulting in user dissatisfaction and potential data breaches.To address this issue,we introduce the Divide and Conquer-Generative Adversarial Network Squeeze and Excitation-Based Framework(DaC-GANSAEBF),an innovative deep-learning model designed to identify spam emails.This framework incorporates cutting-edge technologies,such as Generative Adversarial Networks(GAN),Squeeze and Excitation(SAE)modules,and a newly formulated Light Dual Attention(LDA)mechanism,which effectively utilizes both global and local attention to discern intricate patterns within textual data.This approach significantly improves efficiency and accuracy by segmenting scanned email content into smaller,independently evaluated components.The model underwent training and validation using four publicly available benchmark datasets,achieving an impressive average accuracy of 98.87%,outperforming leading methods in the field.These findings underscore the resilience and scalability of DaC-GANSAEBF,positioning it as a viable solution for contemporary spam detection systems.The framework can be easily integrated into existing technologies to enhance user security and reduce the risks associated with spam.
基金supported by the Nanjing Second Hospital talent lifting project(No.RCZD23001)the Jiangsu Province traditional Chinese medicine science and technology development general program(No.MS2023063)+1 种基金Medical Science and Technology Development Foundation,Nanjing Department of Health(No.ZKX20033)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX25_0240).
文摘Enhancing the activity of fragile enzymes is greatly useful for various purposes,including fabrication of enzyme-based immunosensors.Herein,we report a defect-engineering strategy for encapsulating enzymes within covalent organic frameworks(COFs),enabling the resulting immobilized enzymes with excellent catalytic activity and stability to construct high performance immunosensors.In this design,by consciously introducing monoaldehyde ligands into the imine-linked COFs structure,we have precisely customized the structural defects to improve enzyme loading capacity and conformational stability.Defect-engineering interaction modulation between enzymes and COFs drives the enhancement of catalytic performance.Compared to the pristine COFs,the enzyme@defective COFs composites with optimally tuned catalytic performance exhibit a 4.49-fold enhancement in enzymatic activity.Furthermore,it is demonstrated that the stable skeletons of COFs provide exceptional protection for the enzymes against external perturbations.Thereafter,the optimized enzyme@defective COFs are employed to fabricate immunosensor.We have successfully established a detection method for prostate-specific antigen(PSA),achieving a low detection limit of 0.09 ng/mL.More importantly,the developed immunosensor has successfully distinguished the prostate cancer patients from healthy individuals.This work establishes a novel paradigm for enzyme immobilization,ultimately empowering the construction of a PSA immunosensor with high sensitivity,remarkable operational stability,and great clinical application potential.
基金supported by National Natural Science Foundation of China(32494793).
文摘Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fundamental trade-off between haze and transparency,coupled with impractical thicknesses(≥1 mm).Inspired by squid’s skin-peeling mechanism,this work develops a peroxyformic acid(HCOOOH)-enabled precision peeling strategy to isolate intact 10-μm-thick bamboo green(BG)frameworks—100×thinner than wood-based counterparts while achieving an unprecedented optical performance(88%haze with 80%transparency).This performance surpasses delignified biomass(transparency<40%at 1 mm)and matches engineered cellulose composites,yet requires no energy-intensive nanofibrillation.The preserved native cellulose I crystalline structure(64.76%crystallinity)and wax-coated uniaxial fibril alignment(Hermans factor:0.23)contribute to high mechanical strength(903 MPa modulus)and broadband light scattering.As a light-management layer in polycrystalline silicon solar cells,the BG framework boosts photoelectric conversion efficiency by 0.41%absolute(18.74%→19.15%),outperforming synthetic anti-reflective coatings.The work establishes a scalable,waste-to-wealth route for optical-grade cellulose materials in next-generation optoelectronics.
基金supported by the National Natural Science Foundation of China(Nos.22205196 and 52371240)the Natural Science Foundation of Jiangsu Province(No.BK20210790)the start-up fundings from Yangzhou University.
文摘Two-dimensional conjugated metal-organic framework(2D c-MOF)nanosheets have garnered significant research interest owing to their suite of distinctive properties.Consequently,diverse synthetic methodologies have been established for the fabrication of 2D c-MOFs exhibiting welldefined nanosheet morphology.In addition,the structural engineering of 2D c-MOF nanosheets for energy storage and conversion has emerged as a prominent research focus.This review comprehensively summarizes recent advancements in 2D c-MOF nanosheets.We commence with a concise overview of diverse synthesis strategies for these materials.Subsequently,progress in their utilization as electrode materials or catalysts for batteries,supercapacitors,and electrocatalysis/photocatalysis is systematically examined.Finally,prevailing challenges and prospective research directions are discussed.Collectively,this review aims to stimulate the development of sophisticated 2D c-MOF nanosheets for high-performance energy applications.
基金financially supported by the National Natural Science Foundation of China(No.22508360)Zhejiang Provincial Natural Science Foundation of China(No.QN26B060028)+1 种基金the National Key Research and Development Program Nanotechnology Specific Project(No.2020YFA0210900)Innovative Team Project of Guang-dong Ordinary University(No.2019KCXTD002).
文摘Constructing catalysts featuring an ordered structure,stable performance,and uniformly dispersed catalytic sites is vital for the epoxidation of small-molecular olefins.Here,we design catalysts by tracing the oxidationprocess origin and synthesize a series of highly dispersed metal porphyrin-based covalent organic frameworks(COFs)materials.The aim is to efficiently oxidize the C-H bonds of cumene by air to in-situ generate organic peroxides at a safe concentration,and integrate the multi-step oxidation method of cumene in industry into a one-step method for olefins’epoxidation.The carbonyl-ruthenium COF(Ru-COF-1)exhibits excellent performance,with 98% epoxide selectivity,1221.77 h^(-1) productivity,and over 95% selectivity after 9 cycles for 1-hexene.Analysis of structure-properties-catalytic relationships of Ru-COF-1 shows that,compared with Ru-porphyrins and metal-free COFs,the enhanced reaction performance mainly results from Ru metal introduction,which promotes benzylic proton transfer in cumene.Besides,Ru-COF-1’s porous,ordered structure aids oxygen enrichment,forming active peroxy radicals with the cumene carboncentered radicals formed on the catalyst surface.Ru-H sites then accelerate active oxygen transfer from peroxy radicals,enabling olefin tandem epoxidation.Density functional theory(DFT)calculations verify the reaction mechanism,and this work offers a reference for the design of catalysts for the green,safe,and efficient oxidation of olefins.
基金supported by the National Natural Science Foundation of China(Nos.11375082,22271189,12405385,92356301,and 21522105)the Hunan Provincial Natural Science Foundation of China(No.2021JJ30565)+5 种基金the Science and Technology Commission of Shanghai Municipality(Nos.21XD1402300,21JC1401700,and 21DZ2260400)the supports by the Double First-Class Initiative Fund of ShanghaiTech University(No.SYLDX0052022)the Analytical Instrumentation Center(No.SPST-AIC10112914)for adsorption measurementthe staff at BL17B1 beamline of the National Facility for Protein Science in Shanghai(NFPS),Shanghai Advanced Research Institute,CAS,for providing beamtime for single-crystal X-ray diffraction data collectionthe project CICECO-Aveiro Institute of Materials,Grants(Nos.UIDB/50011/2020,UIDP/50011/2020,and LA/P/0006/2020)financed by national funds through the FCT/MEC(PIDDAC).
文摘A series of dual-extended-polyhedral metal-organic frameworks(MOFs)was constructed based on the 14-coordinated Cu_(24)-MOP-1(MOP=metal-organic polyhedron)supermolecular building blocks(SBBs)with enhanced stability and tunable functionality for high water uptake efficiency and capacity.Exceptional water stability was demonstrated by the retention of chemical integrity and crystallinity of USC-CP-5(where USC-CP stands for University of South China coordination polymer)after exposure to boiling water for 24 h.Functionalization with-Cl,-OCH_(3),-OH,and-NH_(2)groups of USC-CP-5 resulted in water uptake capacities of 450,460,490,and 590 cm^(3)·g^(-1) at relative pressure(P/P_(0))=0.9,respectively.This performance is ascribed to both the increased hydrophilicity of the ligands and stronger hydrogen bonding.Intriguingly,high-temperature activated USC-5-NH_(2)exhibits a significant water uptake of 38.5 wt.%at P/P_(0)=0.3 and releases 0.44 L·kg^(-1) water between 25 and 65℃.This water release process is reversible for at least 100 cycles with minimal weight loss of only 1.6 wt.%.Consequently,USC-5-NH_(2)holds considerable potential for harvesting and releasing atmospheric water in arid desert regions,powered by solar energy.
基金granted by the National Natural Science Foundation of China(Nos.52533008,21835003,62274097,and 62004106)National Key Research and Development Program of China(Nos.2024YFB3612500,2024YFB3612600,and 2023YFB3608900)+2 种基金Basic Research Program of Jiangsu Province(No.BK20243057)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX25_1213)the Natural Science Foundation of Nanjing Universityof Posts and Telecommunications(No.NY225135).
文摘To meet the growing needs of flexible and wearable electronics,stretchable energy storage devices—especially supercapacitors(SCs)—have become a key focus in advanced energy storage research.However,achieving both mechanical stretchability and high capacitance in SC still faces great challenges,and the crucial factors lie in creating superior electrode materials that exhibit high electrochemical performance as well as excellent mechanical stretchability.Covalent organic frameworks(COFs)possess considerable potential as electrode materials for SCs by virtue of stable organic frameworks,open channels and designable functional groups.Nevertheless,their applications in flexible SCs are greatly hindered by their rigid characteristics.Here a novel COFs@conductive polymer hydrogels(CPHs)@poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)complexes,which integrate the pseudocapacitance of PDITAPA COF,mechanical stretchability of hydrogels and high conductivity of PEDOT:PSS,has been developed as stretchable electrode of SCs.Physically cross-linked PEDOT nanofibers,with their interlinked and entangled architecture,collectively boost mechanical,electrical,and electrochemical performance.The COFs@CPHs@PEDOT:PSS simultaneously demonstrates outstanding mechanical stretchability,high electrical behaviors,and superior swelling characteristics.The resulting SC exhibits advantages of simple structures,facile assembly processes,high specific capacitance,excellent cycling stability,and arbitrary deformation,which holds great application prospects for wearable electronic products.Owing to its uncomplicated structure,ease of production,high energy storage capacity,robust cycling performance,and adaptability to deformation,this fabricated SC is well-suited for next-generation wearable technologies.
基金supported by the National Key Research and Development Program of China(No.2021YFC2901100)the National Natural Science Foundation of China(No.22478425).
文摘Photocatalytic carbon dioxide(CO_(2))reduction offers an alternative strategy for converting CO_(2)into high-value added gaseous fuels,thereby paving the way for the development of clean and renewable energy.Metal-organic frameworks(MOFs),characterized by their highly porous structure,exceptional CO_(2)adsorption capacity,and tunable architecture,have emerged as promising candidates for photocatalytic CO_(2)reduction.This review systematically examines the recent advancement in MOFs-based photocatalysts for CO_(2)reduction to CO.It begins with the overview of the fundamental mechanisms and processes of MOFs towards photocatalytic CO_(2)reduction.Subsequently,common strategies for the modulation of MOFs-based photocatalysts are summarized,including metallic site modification,functionalized ligand incorporation,morphological control,defect engineering,and heterostructure construction.Notably,the review analyzes the critical factors contributing to the high selectivity of CO_(2)photoreduction to CO from both thermodynamic and kinetic perspectives.The conclusion addresses current challenges and future perspectives in designing highly efficient photocatalysts with abundant active sites,providing valuable insights for their continued development.
基金supported by the National Natural Science Foundation of China (Grant Nos.T2325027,12274448,T2350007,12404239,12174041,12325405,12090054,and T2221001)the National Key R&D Program of China (Grant No.2022YFF0503504)。
文摘The intrinsic pressure framework,which treats self-propelling force as an external force,provides a convenient and consistent description of mechanical equilibrium in active matter.However,direct experimental evidence is still lacking.To validate this framework,here we employ a programmable robotic platform,where a single light-controlled wheeled robot travels in an activity landscape.Our experiments quantitatively demonstrate that the intrinsic pressure difference across the activity interface is balanced by the emerged polarization force.This result unambiguously confirms the theoretical predictions,thus validating the intrinsic pressure framework and laying the experimental foundation for the intrinsic pressure-based mechanical description of dry active matter.
