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
High-sensitive quantitative determination of alpha-fetoprotein(AFP)is of crucial importance for early clinical diagnosis of cancers.Herein,an AuNPs-free electrochemical immunosensor(Ab1-Fc-COF)was prepared from a carb...High-sensitive quantitative determination of alpha-fetoprotein(AFP)is of crucial importance for early clinical diagnosis of cancers.Herein,an AuNPs-free electrochemical immunosensor(Ab1-Fc-COF)was prepared from a carboxylic group enriched COF by post-functionalization with detecting antibody(Ab1)and ferrocene(Fc),and used for electrochemical detection of AFP.Due to the small,homogeneous pore size of the COF,Ab1 with a big size was immobilized on the surface of the COF,while Fc with a small size was covalently modified both on the surface and in the pores of COF.The covalently immobilized Ab1 was quite stable and beneficial to specifically detect AFP biomarkers.Meanwhile,the enriched Fc molecules not only improved the conductivity of the COF,but also effectively transferred and amplified the electrochemical signal.This proposed immunosensor exhibited high sensitivity in detecting AFP with a detection limit of 0.39 pg/mL(S/N of 3:1)and a wide linear response range spanning from 1 pg/mL to 100 ng/mL when plotted against logarithmic concentrations.Furthermore,this immunosensor showed excellent selectivity,stability and reproducibility in the testing of real samples.This study presents an innovative prototype for construction of a precious metal-free,antibody-directly-immobilized,simple and stable electrochemical immunoprobe.展开更多
Accelerating the development of new quality productive forces(NQPF),with innovation at its core,has become essential for firm growth in the new era.Drawing on financial data from China's A-share listed companies s...Accelerating the development of new quality productive forces(NQPF),with innovation at its core,has become essential for firm growth in the new era.Drawing on financial data from China's A-share listed companies spanning the period 2010–2023,this study empirically investigates the impact of entrepreneurial spirit on firm-level NQPF.The results indicate that entrepreneurial spirit significantly promotes firm-level NQPF.Mechanism analysis indicates that entrepreneurial effort—underpinned by technological capital accumulation,effective incentive and constraint mechanisms,and a competitive market environment—plays a mediating role in this relationship.Further heterogeneity analysis reveals that,amid China's economic transition,the positive effects of entrepreneurial spirit are more pronounced in non-state-owned enterprises,high-tech firms,and newly established firms.Accordingly,systematic efforts should be pursued across the technological,organizational,and environmental(TOE)dimensions to optimize the cultivation of entrepreneurial spirit.In particular,greater emphasis should be placed on productive entrepreneurial spirit and the constructive role of entrepreneurial effort,so as to fully leverage their contribution to the advancement of firm-level NQPF.展开更多
The development of efficient photocatalysts for crucial organic transformation,such as aerobic oxidation,remains challenging.Although powdered porous materials offer abundant accessible active sites,their application ...The development of efficient photocatalysts for crucial organic transformation,such as aerobic oxidation,remains challenging.Although powdered porous materials offer abundant accessible active sites,their application in liquid-phase catalysis is often limited by insufficient light absorption and inevitable charge recombination,which are inherent drawbacks of conventional heterogeneous catalysts.Here,through rational design and nanoscale-engineering of porous aromatic frameworks(PAFs)comprising porphyrin and porous organic cage,a quasi-homogeneous porous photocatalyst with high catalytic activity and controllable dimension was developed.The interface-directed growth in oil-in-water emulsion shaped the morphology of photoactive PAFs from powders to nanoflakes,which facilitated the light absorbance and catalyst-substrate interaction.Compared with PAF powders,PAF nanoflakes exhibited superior photocatalytic activity for aerobic oxidation.For mustard gas simulant(2-chloroethyl ethyl sulfide,CEES),PAF nanoflakes exhibited ultrafast detoxification rates in room air with a half-life(t_(1/2))as fast as 26s,which even exceeded other catalysts in pure oxygen.It also completely catalyzed the aerobic oxidation of thioether within 15 min,which is almost the fastest rate among any reported organic photocatalysts.Furthermore,the efficient catalytic performance under mild conditions caused by improved light enrichment,surface charge transfer and carrier lifetime was elucidated.展开更多
The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative p...The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative potential of metal-organic frameworks(MOFs)as next-generation adsorbents for PM recovery,focusing on their synthesis,functionalization,and multiscale adsorption mechanisms.We critically analyze conventional pyrometallurgical and hydrometallurgical methods and highlight their limitations in terms of selectivity,energy consumption,and secondary pollution.In contrast,MOFs offer tunable porosity,abundant active sites,and tunable surface chemistry,enabling efficient PM capture via synergistic physical and chemical adsorption.Advanced modification techniques,including direct synthesis and post-synthetic modification,are reviewed to propose strategies for enhancing the adsorption kinetics and selectivity for Au,Ag,Pt,and Pd.Key structure-property relationships are established through multiscale characterization and thermodynamic models,revealing the critical roles of hierarchical porosity,soft donor atoms,and framework stability.Industrial challenges,such as aqueous stability and scalability,are addressed via Zr-O bond strengthening,hydrophobic functionalization,and support immobilization.This study consolidates the experimental and theoretical advances in MOF-based PM recovery and provides a roadmap for translating laboratory innovations into practical applications within the circular-economy framework.展开更多
This study presents a novel polyoxometalate(POM)constructed crystalline inorganic framework,featuring a 2D layered architecture with irregular porosity and inherent proton sources.This unique configuration establishes...This study presents a novel polyoxometalate(POM)constructed crystalline inorganic framework,featuring a 2D layered architecture with irregular porosity and inherent proton sources.This unique configuration establishes an intrinsic hydrogen bonding network that facilitates proton hopping(Grotthuss mechanism),achieving a[100]directional proton conductivity of 1.75×10^(-3)S cm^(-1)under a low relative humidity(RH)of 35%at 298 K.Notably,under elevated conditions(338 K,95%RH),it attains a superprotonic conductivity of 1.61 S cm^(-1),representing one of the highest values recorded for framework materials to date.Analysis of the molecular structure,pore geometry characteristics and topological connectivity,and water vapor adsorption experiment(offering proton diffusion coefficient),indicates that the exceptional water-mediated proton dynamics stem from the interlayer S-shaped irregular pore channels,which probably induce a siphon-like effect to significantly enhance the transport of hydrated protons under the vehicle mechanism.This work not only proposes a POM strategy for constructing 2D inorganic frameworks but also reveals the irregular pore channel-enhanced proton dynamics,providing new insights into the optimization of proton conductors.展开更多
Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystall...Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystallinity and surface area of COFs,are expected to be a novel type of promising crystalline porous material with potential applications in adsorption and separation,catalysis,chemical sensing,and energy storage.Therefore,it is increasingly important to summarize polyimide-linkage in COFs and related applications and provide in-depth insight to accelerate future development.In this review,we offer a comprehensive overview of recent advancements in PI-COFs,emphasizing their synthesis methods,design principles and applications.Finally,our brief outlooks on the current challenges and future developments of PI-COFs are provided.Overall,this review aims to guide the recent and future development of PI-COFs.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
Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability...Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.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the Natural Science Foundation of ZhejiangProvince(No.LZ24B020005)the National Natural Science Foundation of China(No.22071040)for financial support.
文摘High-sensitive quantitative determination of alpha-fetoprotein(AFP)is of crucial importance for early clinical diagnosis of cancers.Herein,an AuNPs-free electrochemical immunosensor(Ab1-Fc-COF)was prepared from a carboxylic group enriched COF by post-functionalization with detecting antibody(Ab1)and ferrocene(Fc),and used for electrochemical detection of AFP.Due to the small,homogeneous pore size of the COF,Ab1 with a big size was immobilized on the surface of the COF,while Fc with a small size was covalently modified both on the surface and in the pores of COF.The covalently immobilized Ab1 was quite stable and beneficial to specifically detect AFP biomarkers.Meanwhile,the enriched Fc molecules not only improved the conductivity of the COF,but also effectively transferred and amplified the electrochemical signal.This proposed immunosensor exhibited high sensitivity in detecting AFP with a detection limit of 0.39 pg/mL(S/N of 3:1)and a wide linear response range spanning from 1 pg/mL to 100 ng/mL when plotted against logarithmic concentrations.Furthermore,this immunosensor showed excellent selectivity,stability and reproducibility in the testing of real samples.This study presents an innovative prototype for construction of a precious metal-free,antibody-directly-immobilized,simple and stable electrochemical immunoprobe.
基金Liaoning Provincial Social Science Fund Key Disciplines Development Project,Research on the New Supply Function of Entrepreneurs Based on Innovation Ecosystems Driven by Data(Grant No.L22ZD061)。
文摘Accelerating the development of new quality productive forces(NQPF),with innovation at its core,has become essential for firm growth in the new era.Drawing on financial data from China's A-share listed companies spanning the period 2010–2023,this study empirically investigates the impact of entrepreneurial spirit on firm-level NQPF.The results indicate that entrepreneurial spirit significantly promotes firm-level NQPF.Mechanism analysis indicates that entrepreneurial effort—underpinned by technological capital accumulation,effective incentive and constraint mechanisms,and a competitive market environment—plays a mediating role in this relationship.Further heterogeneity analysis reveals that,amid China's economic transition,the positive effects of entrepreneurial spirit are more pronounced in non-state-owned enterprises,high-tech firms,and newly established firms.Accordingly,systematic efforts should be pursued across the technological,organizational,and environmental(TOE)dimensions to optimize the cultivation of entrepreneurial spirit.In particular,greater emphasis should be placed on productive entrepreneurial spirit and the constructive role of entrepreneurial effort,so as to fully leverage their contribution to the advancement of firm-level NQPF.
基金supported by the National Natural Science Foundation of China(22075040,U21A20330,22131004)the National Key R&D Program of China(2022YFB3805900)+2 种基金the Jilin Provincial Scientific and Technological Development Program(20240602105RC)the Innovation Platform for Academicians of Hainan Provincethe Specific Research Fund of the Innovation Platform for Academicians of Hainan Province(YSPTZX202321)。
文摘The development of efficient photocatalysts for crucial organic transformation,such as aerobic oxidation,remains challenging.Although powdered porous materials offer abundant accessible active sites,their application in liquid-phase catalysis is often limited by insufficient light absorption and inevitable charge recombination,which are inherent drawbacks of conventional heterogeneous catalysts.Here,through rational design and nanoscale-engineering of porous aromatic frameworks(PAFs)comprising porphyrin and porous organic cage,a quasi-homogeneous porous photocatalyst with high catalytic activity and controllable dimension was developed.The interface-directed growth in oil-in-water emulsion shaped the morphology of photoactive PAFs from powders to nanoflakes,which facilitated the light absorbance and catalyst-substrate interaction.Compared with PAF powders,PAF nanoflakes exhibited superior photocatalytic activity for aerobic oxidation.For mustard gas simulant(2-chloroethyl ethyl sulfide,CEES),PAF nanoflakes exhibited ultrafast detoxification rates in room air with a half-life(t_(1/2))as fast as 26s,which even exceeded other catalysts in pure oxygen.It also completely catalyzed the aerobic oxidation of thioether within 15 min,which is almost the fastest rate among any reported organic photocatalysts.Furthermore,the efficient catalytic performance under mild conditions caused by improved light enrichment,surface charge transfer and carrier lifetime was elucidated.
基金supported by the National Natural Science Foundation of China(No.52304329)the Yunnan Fundamental Research Projects(No.202201BE070001-003),Guo Lin would like to acknowledge Xing Dian talent support program of Yunnan Province.
文摘The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative potential of metal-organic frameworks(MOFs)as next-generation adsorbents for PM recovery,focusing on their synthesis,functionalization,and multiscale adsorption mechanisms.We critically analyze conventional pyrometallurgical and hydrometallurgical methods and highlight their limitations in terms of selectivity,energy consumption,and secondary pollution.In contrast,MOFs offer tunable porosity,abundant active sites,and tunable surface chemistry,enabling efficient PM capture via synergistic physical and chemical adsorption.Advanced modification techniques,including direct synthesis and post-synthetic modification,are reviewed to propose strategies for enhancing the adsorption kinetics and selectivity for Au,Ag,Pt,and Pd.Key structure-property relationships are established through multiscale characterization and thermodynamic models,revealing the critical roles of hierarchical porosity,soft donor atoms,and framework stability.Industrial challenges,such as aqueous stability and scalability,are addressed via Zr-O bond strengthening,hydrophobic functionalization,and support immobilization.This study consolidates the experimental and theoretical advances in MOF-based PM recovery and provides a roadmap for translating laboratory innovations into practical applications within the circular-economy framework.
基金supported by the National Natural Science Foundation of China(22271075,22171071)。
文摘This study presents a novel polyoxometalate(POM)constructed crystalline inorganic framework,featuring a 2D layered architecture with irregular porosity and inherent proton sources.This unique configuration establishes an intrinsic hydrogen bonding network that facilitates proton hopping(Grotthuss mechanism),achieving a[100]directional proton conductivity of 1.75×10^(-3)S cm^(-1)under a low relative humidity(RH)of 35%at 298 K.Notably,under elevated conditions(338 K,95%RH),it attains a superprotonic conductivity of 1.61 S cm^(-1),representing one of the highest values recorded for framework materials to date.Analysis of the molecular structure,pore geometry characteristics and topological connectivity,and water vapor adsorption experiment(offering proton diffusion coefficient),indicates that the exceptional water-mediated proton dynamics stem from the interlayer S-shaped irregular pore channels,which probably induce a siphon-like effect to significantly enhance the transport of hydrated protons under the vehicle mechanism.This work not only proposes a POM strategy for constructing 2D inorganic frameworks but also reveals the irregular pore channel-enhanced proton dynamics,providing new insights into the optimization of proton conductors.
基金supported by the National Key R&D Program of China(No.2023YFA1507204)National Natural Science Foundation ofChina(Nos.22475074,22171139,22225109,22302055)+4 种基金Natural Science Foundation of Guangdong Province(No.2023B1515020076)Key Scientific Research Project Plan of Colleges and Universities of Henan Province(No.24B150004)The Double Thousand Talents Plan of Jiangxi Province(No.jxsq2023102003)Project supported by the Guangdong Provincial Key Laboratory of Carbon Dioxide Resource Utilization(No.2024B121201001)Project supportedby the Major Research plan of the National Natural Science Foundation of China(No.92461310).
文摘Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystallinity and surface area of COFs,are expected to be a novel type of promising crystalline porous material with potential applications in adsorption and separation,catalysis,chemical sensing,and energy storage.Therefore,it is increasingly important to summarize polyimide-linkage in COFs and related applications and provide in-depth insight to accelerate future development.In this review,we offer a comprehensive overview of recent advancements in PI-COFs,emphasizing their synthesis methods,design principles and applications.Finally,our brief outlooks on the current challenges and future developments of PI-COFs are provided.Overall,this review aims to guide the recent and future development of PI-COFs.
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The National Natural Science Foundation of China (NSFC,Nos.92256201,52273006,22071041,92356302,and 21971052)Natural Science Foundation of Jilin Province (No.20240101181JC) are gratefully appreciated for financial the supportssupported by the User Experiment Assist System of Shanghai Synchrotron Radiation Facility (SSRF)。
文摘Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.
