目的基于健康服务领域研究成果应用的整合性行动促进框架(integrated-promoting action on research implement action in health services framework,i-PARIHS)模式构建创伤骨科患者手术部位感染(surgical site infection,SSI)防控的...目的基于健康服务领域研究成果应用的整合性行动促进框架(integrated-promoting action on research implement action in health services framework,i-PARIHS)模式构建创伤骨科患者手术部位感染(surgical site infection,SSI)防控的审查指标,分析临床实践障碍因素并提出改进策略。方法成立循证团队、文献检索、总结最佳证据、制定审查指标,于2024年7—8月开展基线调查,调查创伤骨科医护、麻醉手术中心医护执行率及患者知晓率,从“变革、接受者、组织环境”3个要素识别障碍因素,拟定变革策略。结果根据最佳证据评估并裁剪审查指标共23项,涵盖评估与监测、内外环境优化、术中关注重点、跟踪与随访和环境因素控制5个方面,涉及创伤骨科医生的14个指标平均执行率为72.14%,涉及病房护士的14个指标平均执行率为74.11%,涉及麻醉医生的5个指标平均执行率为60.50%,涉及手术室护士的10个指标平均执行率为61.75%,涉及患者知晓的5个直接指标平均知晓率为44.54%;障碍因素分析后拟定相应促进因素8条,拟定变革策略17条。结论临床实践与循证证据存在差距,基于i-PARIHS模式构建的审查指标与障碍分析为SSI防控提供了系统化改进框架,但需进一步验证策略的临床效果。展开更多
目的基于i-PARIHS框架从变革、接受者、组织环境三个层面梳理医护人员实施临床实践指南的影响因素,为指南制订和证据转化提供参考。方法检索中国知网、万方、维普、PubMed、Web of Science数据库中的相关文献,检索时限为2014年1月1日至2...目的基于i-PARIHS框架从变革、接受者、组织环境三个层面梳理医护人员实施临床实践指南的影响因素,为指南制订和证据转化提供参考。方法检索中国知网、万方、维普、PubMed、Web of Science数据库中的相关文献,检索时限为2014年1月1日至2024年2月1日。基于i-PARIHS框架归纳影响因素。结果纳入分析的文献共23篇。变革层面影响因素包括指南的适用性、可操作性、可信度、可获得性等;接受者层面影响因素包括医护人员的态度、知识水平、技能水平、工作习惯、自我效能、工作负荷/时间缺乏等,以及团队合作程度、管理水平等;组织环境层面影响因素包括文化氛围、配套资源、监管机制、信息化建设等。结论指南、医护人员、团队及组织环境因素均会影响指南实施。应重视指南制订与传播,提升医护人员和团队指南实施能力,改善指南实施组织环境,从而促进证据顺利转化。展开更多
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
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
The separation of propylene(C_(3)H_(6))and propane(C_(3)H_(8))presents a significant industrial challenge due to their similar molecular dimensions and physicochemical properties.Among various separation methods,molec...The separation of propylene(C_(3)H_(6))and propane(C_(3)H_(8))presents a significant industrial challenge due to their similar molecular dimensions and physicochemical properties.Among various separation methods,molecular sieving emerges as the most promising approach,but it will be significantly compromised at high temperatures due to the significant thermal motion.Here,we report a thermally robust zinc-based metal-organic framework(MOF)that can be synthesized on sub-kilogram scale and achieve exceptional C_(3)H_(6)/C_(3)H_(8) separation performances across a broad temperature range(298–353 K).Unlike conventional MOFs suffering from thermal lattice expansion to give poorer selectivity,this new MOF gives the adsorption capacity of C_(3)H_(6)essentially unchanged and that of C_(3)H_(8) negligible at elevated temperatures,outperforming most state-of-the-art adsorbents,in virtue of multiple hydrogen bonds at the aperture.Column breakthrough experiments confirmed the excellent separation capability,and showed no performance degradation over multi-round adsorption-desorption cycles at 353 K.This study addresses the critical challenge of the trade-off between temperature and selectivity in adsorptive separation,which offers new insights into the design of porous structures for highly effective separation at high temperatures.展开更多
Redox-active porous aromatic frameworks(PAFs)have emerged as hopeful candidates for sodium-ion batteries(SIBs)in view of their porous structures,chemical stability and tunable architectures.Herein,we successfully synt...Redox-active porous aromatic frameworks(PAFs)have emerged as hopeful candidates for sodium-ion batteries(SIBs)in view of their porous structures,chemical stability and tunable architectures.Herein,we successfully synthesized two redox-active PAFs(PAF-305 and PAF-306)with different nitrogen-containing motifs,and demonstrated their application as cathode materials for SIBs.Density functional theory(DFT)calculations reveal that nitrogen-rich PAF-305 exhibits a lower lowest unoccupied molecular orbital(LUMO)energy level(-3.35 eV)and a narrower energy gap(E_(g))(2.40 eV)compared with nitrogen-poor PAF-306.As expected,PAF-305 displays outstanding electrochemical performance,comprising a high reversible capacity of 145.2 mAh g^(-1)at 0.05 A g^(-1)and satisfactory cycling stability with 92% capacity retention over 1000 cycles at 0.2 A g^(-1).Remarkably,PAF-305 maintains robust electrochemical properties across a wide temperature range(-20℃ to 50℃).Through a combination of experimental characterizations and theoretical calculations,the sodium-ion storage mechanism of PAF-305 is elucidated.This study not only provides a promising strategy for exploring other redox-active organic units in the design of novel PAFs,but also expands the potential applications of PAFs in energy storage systems.展开更多
Progressive skin fibrosis ultimately results in irreversible contractures,causing both joint dysfunction and cosmetic deformity.The key pathological features of skin fibrosis include persistent inflammation and abnorm...Progressive skin fibrosis ultimately results in irreversible contractures,causing both joint dysfunction and cosmetic deformity.The key pathological features of skin fibrosis include persistent inflammation and abnormal accumulation of the extracellular matrix(ECM),with epithelialmesenchymal transition(EMT)playing a critical role in disease progression.However,current therapeutic strategies for cutaneous fibrosis are largely palliative and often require repeated interventions,with limited efficacy.Celastrol(Cel)exerts anti-inflammatory and anti-fibrotic effects in skin tissue,but its clinical application is limited by poor bioavailability and a narrow therapeutic window.Tetrahedral framework nucleic acid(tFNA),a novel nanocarrier system,exhibits multiple advantages,including enhanced cellular uptake,improved cell viability,and intrinsic anti-fibrotic and anti-inflammatory properties.Therefore,this study applied tFNA-Cel complex(TCC)as an advanced nanotherapeutic agent,designed to exert a synergistic anti-fibrotic effect.In this study,an in vitro model of skin fibrosis was established using human keratinocyte(HaCaT)cells treated with 5 ng mL^(-1) transforming growth factor beta(TGF-β)for 24 h.The results showed that TCC significantly inhibited EMT progression by reducingα-smooth muscle actin(α-SMA)levels and increasing E-cadherin level.Compared to tFNA or Cel alone,TCC exhibited superior anti-fibrotic effects in the fibrosis model,as evidenced by modulation of SMAD family member 2(SMAD2)signaling and collagen I expression.Furthermore,the TCC group showed lower levels of nuclear factorκB p65(NF-κB p65),BCL-2-associated X protein(Bax),and reactive oxygen species(ROS)compared to the Cel or tFNA groups.These findings highlight TCC as a promising treatment for skin fibrosis,with its synergistic anti-fibrotic effects providing new therapeutic avenues.展开更多
CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organ...CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organic frameworks(COFs)are porous crystalline materials formed by connecting organic monomers through covalent bonds.They have the characteristics of functional diversity and rich chemical properties.Their advantages,such as high porosity,a wide range of visible light absorption,and excellent charge separation efficiency,give them good potential in CO_(2)capture,separation,and conversion.Currently,Cu is a key metal in the catalytic CO_(2)reduction reaction(CO_(2)RR)for the preparation of high-value-added chemicals.The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts.In this review,we discuss the latest advancements in this field,including the development of various Cu-based COFs and their applications as catalysts for CO_(2)RR.Here,we mainly introduce the synthesis strategies,some important characterization information,and the applications of electrocatalytic and photocatalytic CO_(2)conversion using these previously reported Cu-based COFs.展开更多
文摘目的基于健康服务领域研究成果应用的整合性行动促进框架(integrated-promoting action on research implement action in health services framework,i-PARIHS)模式构建创伤骨科患者手术部位感染(surgical site infection,SSI)防控的审查指标,分析临床实践障碍因素并提出改进策略。方法成立循证团队、文献检索、总结最佳证据、制定审查指标,于2024年7—8月开展基线调查,调查创伤骨科医护、麻醉手术中心医护执行率及患者知晓率,从“变革、接受者、组织环境”3个要素识别障碍因素,拟定变革策略。结果根据最佳证据评估并裁剪审查指标共23项,涵盖评估与监测、内外环境优化、术中关注重点、跟踪与随访和环境因素控制5个方面,涉及创伤骨科医生的14个指标平均执行率为72.14%,涉及病房护士的14个指标平均执行率为74.11%,涉及麻醉医生的5个指标平均执行率为60.50%,涉及手术室护士的10个指标平均执行率为61.75%,涉及患者知晓的5个直接指标平均知晓率为44.54%;障碍因素分析后拟定相应促进因素8条,拟定变革策略17条。结论临床实践与循证证据存在差距,基于i-PARIHS模式构建的审查指标与障碍分析为SSI防控提供了系统化改进框架,但需进一步验证策略的临床效果。
文摘目的基于i-PARIHS框架从变革、接受者、组织环境三个层面梳理医护人员实施临床实践指南的影响因素,为指南制订和证据转化提供参考。方法检索中国知网、万方、维普、PubMed、Web of Science数据库中的相关文献,检索时限为2014年1月1日至2024年2月1日。基于i-PARIHS框架归纳影响因素。结果纳入分析的文献共23篇。变革层面影响因素包括指南的适用性、可操作性、可信度、可获得性等;接受者层面影响因素包括医护人员的态度、知识水平、技能水平、工作习惯、自我效能、工作负荷/时间缺乏等,以及团队合作程度、管理水平等;组织环境层面影响因素包括文化氛围、配套资源、监管机制、信息化建设等。结论指南、医护人员、团队及组织环境因素均会影响指南实施。应重视指南制订与传播,提升医护人员和团队指南实施能力,改善指南实施组织环境,从而促进证据顺利转化。
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.
基金supported by the National Natural Science Foundation of China(22475240,22090061,22488101)the State Key Laboratory of Catalysis(2024SKL-A-010)。
文摘The separation of propylene(C_(3)H_(6))and propane(C_(3)H_(8))presents a significant industrial challenge due to their similar molecular dimensions and physicochemical properties.Among various separation methods,molecular sieving emerges as the most promising approach,but it will be significantly compromised at high temperatures due to the significant thermal motion.Here,we report a thermally robust zinc-based metal-organic framework(MOF)that can be synthesized on sub-kilogram scale and achieve exceptional C_(3)H_(6)/C_(3)H_(8) separation performances across a broad temperature range(298–353 K).Unlike conventional MOFs suffering from thermal lattice expansion to give poorer selectivity,this new MOF gives the adsorption capacity of C_(3)H_(6)essentially unchanged and that of C_(3)H_(8) negligible at elevated temperatures,outperforming most state-of-the-art adsorbents,in virtue of multiple hydrogen bonds at the aperture.Column breakthrough experiments confirmed the excellent separation capability,and showed no performance degradation over multi-round adsorption-desorption cycles at 353 K.This study addresses the critical challenge of the trade-off between temperature and selectivity in adsorptive separation,which offers new insights into the design of porous structures for highly effective separation at high temperatures.
基金supported by the Science&Technology Department of Jilin Province(20230508057RC)。
文摘Redox-active porous aromatic frameworks(PAFs)have emerged as hopeful candidates for sodium-ion batteries(SIBs)in view of their porous structures,chemical stability and tunable architectures.Herein,we successfully synthesized two redox-active PAFs(PAF-305 and PAF-306)with different nitrogen-containing motifs,and demonstrated their application as cathode materials for SIBs.Density functional theory(DFT)calculations reveal that nitrogen-rich PAF-305 exhibits a lower lowest unoccupied molecular orbital(LUMO)energy level(-3.35 eV)and a narrower energy gap(E_(g))(2.40 eV)compared with nitrogen-poor PAF-306.As expected,PAF-305 displays outstanding electrochemical performance,comprising a high reversible capacity of 145.2 mAh g^(-1)at 0.05 A g^(-1)and satisfactory cycling stability with 92% capacity retention over 1000 cycles at 0.2 A g^(-1).Remarkably,PAF-305 maintains robust electrochemical properties across a wide temperature range(-20℃ to 50℃).Through a combination of experimental characterizations and theoretical calculations,the sodium-ion storage mechanism of PAF-305 is elucidated.This study not only provides a promising strategy for exploring other redox-active organic units in the design of novel PAFs,but also expands the potential applications of PAFs in energy storage systems.
基金supported by the National Natural Science Foundation of China(82101077)Sichuan Science and Technology Program(2023NSFSC1516)+2 种基金West China School/Hospital of Stomatology Sichuan University(RCDWJS2023-5)Fundamental Research Funds for the Central UniversitiesResearch and Develop Program,West China School/Hospital of Stomatology Sichuan University。
文摘Progressive skin fibrosis ultimately results in irreversible contractures,causing both joint dysfunction and cosmetic deformity.The key pathological features of skin fibrosis include persistent inflammation and abnormal accumulation of the extracellular matrix(ECM),with epithelialmesenchymal transition(EMT)playing a critical role in disease progression.However,current therapeutic strategies for cutaneous fibrosis are largely palliative and often require repeated interventions,with limited efficacy.Celastrol(Cel)exerts anti-inflammatory and anti-fibrotic effects in skin tissue,but its clinical application is limited by poor bioavailability and a narrow therapeutic window.Tetrahedral framework nucleic acid(tFNA),a novel nanocarrier system,exhibits multiple advantages,including enhanced cellular uptake,improved cell viability,and intrinsic anti-fibrotic and anti-inflammatory properties.Therefore,this study applied tFNA-Cel complex(TCC)as an advanced nanotherapeutic agent,designed to exert a synergistic anti-fibrotic effect.In this study,an in vitro model of skin fibrosis was established using human keratinocyte(HaCaT)cells treated with 5 ng mL^(-1) transforming growth factor beta(TGF-β)for 24 h.The results showed that TCC significantly inhibited EMT progression by reducingα-smooth muscle actin(α-SMA)levels and increasing E-cadherin level.Compared to tFNA or Cel alone,TCC exhibited superior anti-fibrotic effects in the fibrosis model,as evidenced by modulation of SMAD family member 2(SMAD2)signaling and collagen I expression.Furthermore,the TCC group showed lower levels of nuclear factorκB p65(NF-κB p65),BCL-2-associated X protein(Bax),and reactive oxygen species(ROS)compared to the Cel or tFNA groups.These findings highlight TCC as a promising treatment for skin fibrosis,with its synergistic anti-fibrotic effects providing new therapeutic avenues.
文摘CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organic frameworks(COFs)are porous crystalline materials formed by connecting organic monomers through covalent bonds.They have the characteristics of functional diversity and rich chemical properties.Their advantages,such as high porosity,a wide range of visible light absorption,and excellent charge separation efficiency,give them good potential in CO_(2)capture,separation,and conversion.Currently,Cu is a key metal in the catalytic CO_(2)reduction reaction(CO_(2)RR)for the preparation of high-value-added chemicals.The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts.In this review,we discuss the latest advancements in this field,including the development of various Cu-based COFs and their applications as catalysts for CO_(2)RR.Here,we mainly introduce the synthesis strategies,some important characterization information,and the applications of electrocatalytic and photocatalytic CO_(2)conversion using these previously reported Cu-based COFs.
