Noncohesive particle clusters are identified and tracked in turbulent flows to determine the breakdown and time evolution of cluster statistics and their implications for interscale mass transfer,which has connections...Noncohesive particle clusters are identified and tracked in turbulent flows to determine the breakdown and time evolution of cluster statistics and their implications for interscale mass transfer,which has connections to the classical turbulent energy cascade and its mass cascade counterpart running in parallel.In particular,the formation and dynamics of sediment and larvae clusters are of interest to coral larvae settlement in coastal regions and particularly the resilience of green-gray coastal protection solutions.Analogous cluster behavior is relevant to cloud microphysics and precipitation initiation,radiation transport and light transmission through colloids and suspensions,heat and mass transfer in particle-laden flows,and viral and pollutant transmission.Following a comparison between various clustering techniques,we adopt a density-based cluster identification algorithm based on its simplicity and efficiency,where particles are clustered based on the number of neighboring particles in their individual spheres of influence.We establish parallels with lattice-based percolation theory,as evident in the power-law scaling of the cluster size distribution near the percolation threshold.The degree of discontinuity of the phase transition associated with this percolation threshold is observed to broaden with larger Stokes numbers and thereby large-scale clustering.The sensitivity of our findings to the employed clustering algorithm is discussed.A novel cluster tracking algorithm is deployed to determine the interscale transfer rate along the particle-number phase-space dimension via accounting of cluster breakup and merger events,extending previous work on the bubble breakup cascade beneath surface breaking waves.Our findings shed light on the interaction between particle clusters and their carrier turbulent flows,with an eye toward transport models incorporating cluster characteristics and dynamics.展开更多
Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated fo...Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.展开更多
Bottom-up and top-down endogenous automobile clusters exhibit distinct evolutionary traits and driving mechanisms,yet their comparative analysis remains understudied.Therefore,using Taizhou automobile industry cluster...Bottom-up and top-down endogenous automobile clusters exhibit distinct evolutionary traits and driving mechanisms,yet their comparative analysis remains understudied.Therefore,using Taizhou automobile industry cluster(TAIC)and Wuhu automobile industry cluster(WAIC)as cases,using historical statistical data and field interview data from the 1980s to 2023,combined with qualitative research methods of thematic and diachronic analysis,and quantitative research methods of social network analysis,we compare both endogenous automobile clusters’evolutionary traits and driving mechanisms.The results confirm both clusters undergo multi-scale spatial reconfiguration,organizational complexification,and intelligent networking technological transformation,yet diverge fundamentally:TAIC evolves through market-driven progressive expansion,transitioning from single to dual-core structures via private enterprise networking,with innovation following market-integrated logic and institutional thickness built on demand-driven evolution.Conversely,WAIC follows planned expansion,maintaining state-led hierarchical single-core stability through policy-driven breakthrough innovation and supply-dominated institutional construction-though both ultimately require formal-informal system synergy.Their coevolution is driven by dynamic interactions of path dependence(weakening influence),learning-innovation(strengthening influence),and relationship selection(inverted U-shaped trajectory),with divergent development paths rooted in TAIC’s grassroots self-organization genes versus WAIC’s top-level design genes,amplified by core enterprises’strategic disparities.The research findings can not only provide decision-making support for China’s industrial upgrading,but also contribute China’s insights to global economic governance.展开更多
Villager Pan Chunlin is witnessing a boom in his homestay business.More and more visitors are coming to his village,Yucun Village in Anji County,Huzhou City,Zhejiang Province.
Introduction:Chemotherapy-induced gastrointestinal symptom clusters in breast cancer impair quality of life and treatment adherence,yet lack effective interventions.While acupuncture mitigates isolated chemotherapy-in...Introduction:Chemotherapy-induced gastrointestinal symptom clusters in breast cancer impair quality of life and treatment adherence,yet lack effective interventions.While acupuncture mitigates isolated chemotherapy-induced symptoms,its mechanisms for multi-symptom clusters remain unclear.This study evaluates electroacupuncture's efficacy and explores its biological mechanisms in managing these clusters.Methods:This prospective,multicenter,block-randomized,double-blind,sham-controlled trial will enroll 388 patients with breast cancer undergoing neoadjuvant/adjuvant chemotherapy,to be randomly assigned(1:1)to electroacupuncture or sham electro-acupuncture groups.Both groups will receive the standard quadruple antiemetic regimen combined with electroacupuncture or sham intervention.The primary endpoint is the incidence of chemotherapy-induced gastrointestinal symptom clusters within 120 h after chemotherapy.Secondary endpoints include improvement in gastrointestinal symptom clusters post-first chemotherapy cycle,nausea-free rates during acute and delayed phases,vomiting-free rates during overall,acute,and delayed phases,complete response rate,complete protection rate,and quality of life.Adverse events will be documented throughout the study.Discussion:This study will assess the efficacy and safety of electroacupuncture in alleviating chemotherapy-induced gastro-intestinal symptom clusters in patients with breast cancer.By integrating multi-omics analyses,we aim to elucidate the biological mechanisms underlying its therapeutic effects.The findings may offer a robust clinical foundation for optimizing symptom cluster management in cancer care.Trial Registration:Clinical Trials ID:NCT06952920.Date of registration:April 16,2025.Prospectively registered.URL of Trial Registry Record:https://clinicaltrials.gov/study/NCT06952920cond=NCT06952920&rank=1.展开更多
In the Tianshan region,a complete textile industry chain has been established,covering the entire process from cotton cultivation and chemical fiber production,through spinning,weaving,dyeing,and finishing,and further...In the Tianshan region,a complete textile industry chain has been established,covering the entire process from cotton cultivation and chemical fiber production,through spinning,weaving,dyeing,and finishing,and further extending to apparel,home textiles,and industrial textiles.In November 2025,the first list of five characteristic textile and apparel industry clusters in Xinjiang was officially announced,marking a new stage in the clustering of Xinjiang's textile and apparel industry.Data shows that the total output value of Xinjiang's cotton and textile and apparel industry chain has exceeded 220 billion yuan.With the nation's largest cotton production,a complete industrial chain system,and strong synergistic effects,Xinjiang has become a leading and highly competitive textile industry hub in China.展开更多
Transition metal selenides as sodium-ion hybrid capacitor(SIHC)anodes still suffer from amorphization difficulties and capacity degradation triggered by polyselenide dissolution.Herein,an atomistic amorphous strategy ...Transition metal selenides as sodium-ion hybrid capacitor(SIHC)anodes still suffer from amorphization difficulties and capacity degradation triggered by polyselenide dissolution.Herein,an atomistic amorphous strategy is proposed to construct adjacent Nb-Nb diatomic pairs with Se/O-coordination(Se4-Nb2-O2)in N-doped carbon-confined amorphous selenide clusters(a-Nb-Se/O@NC).Synergistic carbon confinement and hydrothermal oxygenation induce amorphization of Nb–Se bonds,eliminating crystalline rigidity while creating isotropic dual-ion transport channels and high-density active sites enriched with dangling bonds,thereby enhancing structural integrity and Na+storage capacity.The unique Se/O-coordinated Nb-Nb diatomic configuration establishes an electron-delocalized system,where the low electronegativity of Se counterbalances electron withdrawal from coordinated O at Nb centers.These strengthen d-p orbital hybridization,reduce Na+adsorption energy,and optimize charge transfer pathways and reaction kinetics in the amorphous clusters.Electrochemical tests reveal that the a-Nb-Se/O@NC anode delivers a high reversible capacity of 312.57 mAh g^(−1)and exceptional cyclic stability(103%capacity retention)after 5000 cycles at 10.0 A g^(−1).Assembled SIHCs achieve outstanding energy/power densities(207.1 Wh kg^(−1)/18966 W kg^(−1)),surpassing most amorphous and crystalline counterparts.This work provides methodological insights for the design of electrodes in high-power storage devices through atomic modulation and electronic optimization of amorphous selenides.展开更多
Exploring the synthesis of novel structures is crucial for the development of functional materials.In this context,a novel and intriguing 3d-5p heterometallic cluster-substituted polyoxotungstate material,H_(29)Na_(9)...Exploring the synthesis of novel structures is crucial for the development of functional materials.In this context,a novel and intriguing 3d-5p heterometallic cluster-substituted polyoxotungstate material,H_(29)Na_(9)(H_(2)O)_(21){Ca(H_(2)O)_(2)@Sb_(12)O_(18)[Ni_(2)(OH)(A-α-Si W_(10)O_(37))]_(3)}_(2)·40H_(2)O(1),was constructed using Keggintype polyoxotungstate A-α-Si W_(10)O_(37),along with Ni and Sb elements.The structure features a Tdsymmetric Sb_(12)O_(18)({Sb_(12)})cage that encapsulates an 8-coordinate Ca^(2+)ion at its face.Additionally,the{Sb_(12)}cage forms an 18-nuclear 3d-5p heterometallic cluster by connecting with three di-nuclear nickel clusters through shared oxygen atoms.Electrochemical impedance spectra studies reveal that the single crystal of 1 achieves a proton conductivity of 1.11×10^(-1)S/cm along the[110]direction and 1.04×10^(-1)S/cm along the[100]direction at 85℃ and 98%relative humidity(RH).Furthermore,the powder form of 1 exhibits a proton conductivity of 3.00×10^(-2)S/cm.These findings suggest that compound 1 holds promise as a practical proton conducting material.展开更多
Two-dimensional metal dichalcogenides have been evidenced as potential electrocatalysts for hydrogen evolution reaction(HER);however,their application is limited by a poor oxygen evolution reaction(OER)activity due to...Two-dimensional metal dichalcogenides have been evidenced as potential electrocatalysts for hydrogen evolution reaction(HER);however,their application is limited by a poor oxygen evolution reaction(OER)activity due to insufficient number/types of multi-integrated active sites.In this study,we report a novel bifunctional catalyst developed by simultaneous engineering of single nickel atoms(Ni_(SA)) and nickel phosphate clusters(Ni_(Pi)) to synergistically trigger surface-functionalized MoS_(2) nanosheets(NSs)resulting in high reactivities for both HER and OER.The Ni_(SA)-Ni_(Pi)/MoS_(2)NSs material exhibits a fairly Pt-like HER behavior with an overpotential of 94.0 mV and a small OER overpotential of 314.0 mV to reach 10 mA cm^(-2) in freshwater containing 1.0 M KOH.Experimental results of the catalyst are well supported by theoretical study,which reveals the significant modulation of electronic structure and enrichment of electroactive site number/types with their reasonably adjusted free adsorption energy.For evaluating practicability,the Ni_(SA)-Ni_(Pi)/MoS_(2)NSs-based electrolyzer delivers effective operation voltage of 1.62,1.52,and 1.66 V at 10 mA cm^(-2) and superior long-term stability as compared to Pt/C//RuO_(2) system in freshwater,mimic seawater,and natural seawater,respectively.The present study indicates that the catalyst is a promising candidate for the practical production of green hydrogen via water electrolysis.展开更多
Objectives To identify core symptoms and symptom clusters in patients with neuromyelitis optica spectrum disorder(NMOSD)by network analysis.Methods From October 10 to 30,2023,140 patients with NMOSD were selected to p...Objectives To identify core symptoms and symptom clusters in patients with neuromyelitis optica spectrum disorder(NMOSD)by network analysis.Methods From October 10 to 30,2023,140 patients with NMOSD were selected to participate in this online questionnaire survey.The survey tools included a general information questionnaire and a self-made NMOSD symptoms scale,which included the prevalence,severity,and distress of 29 symptoms.Cluster analysis was used to identify symptom clusters,and network analysis was used to analyze the symptom network and node characteristics and central indicators including strength centrality(r_(s)),closeness centrality(r_(c))and betweeness centrality(r_(b))were used to identify core symptoms and symptom clusters.Results The most common symptom was pain(65.7%),followed by paraesthesia(65.0%),fatigue(65.0%),easy awakening(63.6%).Regarding the burden level of symptoms,pain was the most burdensome symptom,followed by paraesthesia,easy awakening,fatigue,and difficulty falling asleep.Six clusters were identified:somatosensory,motor,visual,and memory symptom clusters,bladder and rectum symptom clusters,sleep symptoms clusters,and neuropsychological symptom clusters.Fatigue(r_(s)=12.39,r_(b)=68.00,r_(c)=0.02)was the most central and prominent bridge symptom,and motor symptom cluster(r_(s)=2.68,r_(c)=0.10)was the most central symptom cluster among the six clusters.Conclusions Our study demonstrated the necessity of symptom management targeting fatigue,pain,and motor symptom cluster in patients with NMOSD.展开更多
Rational design and synthesis of low-cost trifunctional electrocatalysts with improved stability and superior electrocatalytic activity for oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen ev...Rational design and synthesis of low-cost trifunctional electrocatalysts with improved stability and superior electrocatalytic activity for oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER) are highly desirable but remain as the bottlenecks at the current state of technology.In this paper,the cobalt-iron(Co-Fe) composite supported on nitrogen-doped carbon nanotubes(CoFe composite/NCNTs) is synthesized.The intrinsic OER and HER catalytic activities of this CoFe composite/NCNTs composite are significantly improved with palladium(Pd) nanocluster decoration [Pd-coated(CoFe composite/NCNTs)].The as-prepared Pd-coated(CoFe composite/NCNTs) catalyst exhibits excellent trifunctional electrocatalytic activity and stability due to the interfacial coupling between Pd and(CoFe composite/NCNTs).This catalyst is successfully employed in the water electrolysis cell as both OER and HER electrode catalysts,flexible rechargeable Zn-air battery as the bifunctional ORR and OER electrode catalyst.The cell voltage of this catalyst-coated electrodes requires only 1.60 V to achieve 10 mA cm^(-2) current density for water electrolysis cell,which is comparable to and even better than that of Pt/C and Ir/C based cell.The primary Zn-air battery using this catalyst shows a constant high open-circuit voltage(OCV) of 1.47 V and a maximum power density of 261 mW cm^(-2) in the flooded mode configuration.Most importantly,a flexible Zn-air battery with this catalyst runs very smoothly without a change in voltage gap during flat,bending,and twisting positions.展开更多
An aluminoborate,Na_(2.5)Rb[Al{B_(5)O_(10)}{B_(3)O_(5)}]·0.5NO_(3)·H_(2)O(1),was synthesized under hydrothermal condition,which was built by mixed oxoboron clusters and AlO_(4)tetrahedra.In the structure,the...An aluminoborate,Na_(2.5)Rb[Al{B_(5)O_(10)}{B_(3)O_(5)}]·0.5NO_(3)·H_(2)O(1),was synthesized under hydrothermal condition,which was built by mixed oxoboron clusters and AlO_(4)tetrahedra.In the structure,the[B_(5)O_(10)]^(5-)and[B_(3)O_(7)]^(5-)clusters are alternately connected to form 1D[B_(8)O_(15)]_(n)^(6n-)chains,which are further linked by AlO_(4)units to form a 2D monolayer with 7‑membered ring and 10‑membered ring windows.Two adjacent monolayers with opposite orientations further form a porous‑layered structure with six channels through B—O—Al bonds.Compound 1 was characterized by single crystal X‑ray diffraction,powder X‑ray diffraction(PXRD),IR spectroscopy,UV‑Vis diffuse reflection spectroscopy,and thermogravimetric analysis(TGA),respectively.UV‑Vis diffuse reflectance analysis indicates that compound 1 shows a wide transparency range with a short cutoff edge of 201 nm,suggesting it may have potential application in UV regions.CCDC:2383923.展开更多
Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as...Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms,the obtained Pt-on-Co/C400 catalysts exhib-ited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency(TOF)value of 3022 min^(-1)at 303 K.Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability,and there were no changes in the catalyst structures and catalytic activities after 10 cycles.展开更多
Metal-doped carbon materials, as one of the most important electrocatalytic catalysts for CO_(2)reduction reaction(CO_(2)RR), have attracted increasing attention. Herein, a series of Cu cluster embedded highly porous ...Metal-doped carbon materials, as one of the most important electrocatalytic catalysts for CO_(2)reduction reaction(CO_(2)RR), have attracted increasing attention. Herein, a series of Cu cluster embedded highly porous nanofibers have been prepared through the carbonization of electro-spun MOF/PAN nanofibers.The obtained Cu cluster doped porous nanofibers possessed fibrous morphology, high porosity, conductivity, and uniformly dispersed Cu clusters, which could be applied as promising CO_(2)RR catalysts. Specifically, best of them, MCP-500 exhibited high catalytic performance for CO_(2)RR, in which the Faradaic efficiency of CO(FECO) was as high as 98% at-0.8 V and maintained above 95% after 10 h continuous electrocatalysis. The high performance might be attributed to the synergistic effect of tremendously layered graphene skeleton and uniformly dispersed Cu clusters that could largely promote the electron conductivity, mass transfer and catalytic activity during the electrocatalytic CO_(2)RR process. This attempt will provide a new idea to design highly active CO_(2)RR electrocatalyst.展开更多
Organic-inorganic hybrid clusters with strong X-ray radioluminescence have exhibited great potential in scintillator field.However,fabricating the X-ray imaging screens of the clusters without sacrificing the scintill...Organic-inorganic hybrid clusters with strong X-ray radioluminescence have exhibited great potential in scintillator field.However,fabricating the X-ray imaging screens of the clusters without sacrificing the scintillation performance is challenging.Herein,we report an effective way to prepare high-quality scintillation films of two synthesized Cu(Ⅰ)clusters through vacuum evaporation deposition.The developed Cu(Ⅰ)clusters with rigid molecular structures show excellent scintillation performance with a high light yield of up to 19356.7 photons/MeV and a low detection limit of 158 nGy/s.The scintillation film based on the Cu(Ⅰ)clusters made by vacuum evaporation deposition is highly uniform with a small surface roughness value of 1.04 nm,which can be applied to X-ray imaging for various objects.These results not only provide important guidance to develop high-performance organic-inorganic hybrid scintillators,but also pave a straightforward way to prepare non-doped scintillation screens for remarkable X-ray imaging applications.展开更多
In modern distributed systems and cloud computing architectures,high availability and high scalability are core requirements to ensure the continuous and stable operation of services.As key technologies for achieving ...In modern distributed systems and cloud computing architectures,high availability and high scalability are core requirements to ensure the continuous and stable operation of services.As key technologies for achieving these two goals,high-availability clusters and load-balancing clusters have significant differences in their design concepts and application scenarios,while also maintaining close connections.This paper aims to conduct an in-depth analysis of the core objectives,working principles,technical advantages and disadvantages,and typical application cases of high-availability clusters and load-balancing clusters.By introducing an analogical model of a“restaurant kitchen,”the differences between the two are intuitively explained,and their technical characteristics are compared in detail.Additionally,a detailed practical case is included to specifically demonstrate the collaborative work of high-availability and load-balancing technologies through the construction process of Keepalived and HAProxy.Finally,taking the architecture of a typical e-commerce website as an example,this paper demonstrates the best practice of organically combining the two cluster technologies in a production environment to build a robust and high-performance distributed system.Research shows that understanding the differences between the two and implementing collaborative deployment is the cornerstone of designing modern IT infrastructure.展开更多
Attributed graph clustering plays a vital role in uncovering hidden network structures,but it presents significant challenges.In recent years,various models have been proposed to identify meaningful clusters by integr...Attributed graph clustering plays a vital role in uncovering hidden network structures,but it presents significant challenges.In recent years,various models have been proposed to identify meaningful clusters by integrating both structural and attribute-based information.However,these models often emphasize node proximities without adequately balancing the efficiency of clustering based on both structural and attribute data.Furthermore,they tend to neglect the critical fuzzy information inherent in attributed graph clusters.To address these issues,we introduce a new framework,Markov lumpability optimization,for efficient clustering of large-scale attributed graphs.Specifically,we define a lumped Markov chain on an attribute-augmented graph and introduce a new metric,Markov lumpability,to quantify the differences between the original and lumped Markov transition probability matrices.To minimize this measure,we propose a conjugate gradient projectionbased approach that ensures the partitioning closely aligns with the intrinsic structure of fuzzy clusters through conditional optimization.Extensive experiments on both synthetic and real-world datasets demonstrate the superior performance of the proposed framework compared to existing clustering algorithms.This framework has many potential applications,including dynamic community analysis of social networks,user profiling in recommendation systems,functional module identification in biological molecular networks,and financial risk control,offering a new paradigm for mining complex patterns in high-dimensional attributed graph data.展开更多
[Objectives]To establish an HPLC method for the quantitative determination of multiple phenolic acid components in Tetracera asiatica medicinal material,providing a basis for establishing its quality standards.[Method...[Objectives]To establish an HPLC method for the quantitative determination of multiple phenolic acid components in Tetracera asiatica medicinal material,providing a basis for establishing its quality standards.[Methods]An Inertsil ODS-C 18 column(250 mm×4.6 mm,5μm)was used.The mobile phase consisted of acetonitrile-0.2% phosphoric acid solution(10:90).The flow rate was 1.0 mL/min.The detection wavelength was 274 nm.The column temperature was 25℃.The injection volume was 10μL.The content of three components,gallic acid,protocatechuic acid,and protocatechualdehyde,was determined in 13 batches of T.asiatica.[Results]Gallic acid showed good linearity within the range of 0.020-6.400μg/mL,protocatechuic acid within 0.201-6.432μg/mL,and protocatechualdehyde within 0.202-6.464μg/mL(r>0.9990).The average recovery rates ranged from 98.61%to 101.17%,with RSD s between 1.21%and 2.69%.[Conclusions]The quantitative determination method established in this study is simple and feasible,and can provide a basis for the quality evaluation of T.asiatica.展开更多
Chiral metal-organic clusters(MOCs)integrating lanthanide ions(Ln^(3+))and organic luminophores present a promising platform for modulating circularly polarized luminescence(CPL).However,achieving dual-wavelength CPL ...Chiral metal-organic clusters(MOCs)integrating lanthanide ions(Ln^(3+))and organic luminophores present a promising platform for modulating circularly polarized luminescence(CPL).However,achieving dual-wavelength CPL in discrete cluster systems constitutes a considerable challenge.Herein,two enantiomeric pairs of heterometallic EuSn oxo clusters,designated as Sn_(2)EuL_(2)-R/S and Sn_(2)EuL_(4)-R/S,were strategically synthesized using axially chiral binaphthol-phosphonate ligands.These hybrid clusters exhibit dual emission,characterized by a broad ligand-derived fluorescence band superimposed with sharp,characteristic Eu^(3+)f-f transitions,which enables excitation-dependent luminescence color tuning.Their emission profiles and quantum yields are found to be exquisitely adjusted by the distinct coordination environments of Sn^(4+)centers.Notably,Sn_(2)EuL_(2)-R/S demonstrates CPL activity in both near-UV(|g_(lum)|=1.7×10^(-3))and visible(|g_(lum)|=3.1×10^(-2))regions.This work not only reports the first instance of dual-wavelength CPL in a lanthanide/tin oxo complex but also establishes a robust design strategy for fabricating color-tunable chiral photonic materials.展开更多
Accurate description of noncova-lent interactions in large systems is challenging due to the require-ment of high-level electron corre-lation methods.The generalized energy-based fragmentation(GEBF)approach,in conjunc...Accurate description of noncova-lent interactions in large systems is challenging due to the require-ment of high-level electron corre-lation methods.The generalized energy-based fragmentation(GEBF)approach,in conjunc-tion with the domain-based local pair natural orbital(DLPNO)method,has been applied to assess the average binding energies(ABEs)of large benzene clus-ters,specifically(C6H6)13,at the coupled cluster singles and doubles with perturbative triples correction[CCSD(T)]level and the complete basis set(CBS)limit.Utilizing GEBF-DLPNO-CCSD(T)/CBS ABEs as benchmarks,various DFT functionals were evaluated.It was found that several functionals with empirical dispersion correction,including M06-2X-D3,B3LYP-D3(BJ),and PBE-D3(BJ),provide accurate descriptions of the ABEs for(C6H6)13 clusters.Additionally,the M06-2X-D3 functional was used to calculate the ABEs and relative stabili-ties of(C6H6)n clusters for n=11,12,13,14,and 15 revealing that the(C6H6)13 cluster ex-hibits the highest relative stability.These findings align with experimental evidence suggest-ing that n=13 is one of the magic numbers for benzene clusters(C6H6)n,with n≤30.展开更多
文摘Noncohesive particle clusters are identified and tracked in turbulent flows to determine the breakdown and time evolution of cluster statistics and their implications for interscale mass transfer,which has connections to the classical turbulent energy cascade and its mass cascade counterpart running in parallel.In particular,the formation and dynamics of sediment and larvae clusters are of interest to coral larvae settlement in coastal regions and particularly the resilience of green-gray coastal protection solutions.Analogous cluster behavior is relevant to cloud microphysics and precipitation initiation,radiation transport and light transmission through colloids and suspensions,heat and mass transfer in particle-laden flows,and viral and pollutant transmission.Following a comparison between various clustering techniques,we adopt a density-based cluster identification algorithm based on its simplicity and efficiency,where particles are clustered based on the number of neighboring particles in their individual spheres of influence.We establish parallels with lattice-based percolation theory,as evident in the power-law scaling of the cluster size distribution near the percolation threshold.The degree of discontinuity of the phase transition associated with this percolation threshold is observed to broaden with larger Stokes numbers and thereby large-scale clustering.The sensitivity of our findings to the employed clustering algorithm is discussed.A novel cluster tracking algorithm is deployed to determine the interscale transfer rate along the particle-number phase-space dimension via accounting of cluster breakup and merger events,extending previous work on the bubble breakup cascade beneath surface breaking waves.Our findings shed light on the interaction between particle clusters and their carrier turbulent flows,with an eye toward transport models incorporating cluster characteristics and dynamics.
基金supported by the National Natural Science Foundation of China (Nos.22064020,22364022,and 22174125)the Applied Basic Research Foundation of Yunnan Province (Nos.202101AT070101 and 202201AT070029)。
文摘Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.
基金Under the auspices of National Natural Science Foundation of China(No.42571219)Key Project of Zhejiang Province Soft Science Research Plan(No.2023C25014)。
文摘Bottom-up and top-down endogenous automobile clusters exhibit distinct evolutionary traits and driving mechanisms,yet their comparative analysis remains understudied.Therefore,using Taizhou automobile industry cluster(TAIC)and Wuhu automobile industry cluster(WAIC)as cases,using historical statistical data and field interview data from the 1980s to 2023,combined with qualitative research methods of thematic and diachronic analysis,and quantitative research methods of social network analysis,we compare both endogenous automobile clusters’evolutionary traits and driving mechanisms.The results confirm both clusters undergo multi-scale spatial reconfiguration,organizational complexification,and intelligent networking technological transformation,yet diverge fundamentally:TAIC evolves through market-driven progressive expansion,transitioning from single to dual-core structures via private enterprise networking,with innovation following market-integrated logic and institutional thickness built on demand-driven evolution.Conversely,WAIC follows planned expansion,maintaining state-led hierarchical single-core stability through policy-driven breakthrough innovation and supply-dominated institutional construction-though both ultimately require formal-informal system synergy.Their coevolution is driven by dynamic interactions of path dependence(weakening influence),learning-innovation(strengthening influence),and relationship selection(inverted U-shaped trajectory),with divergent development paths rooted in TAIC’s grassroots self-organization genes versus WAIC’s top-level design genes,amplified by core enterprises’strategic disparities.The research findings can not only provide decision-making support for China’s industrial upgrading,but also contribute China’s insights to global economic governance.
文摘Villager Pan Chunlin is witnessing a boom in his homestay business.More and more visitors are coming to his village,Yucun Village in Anji County,Huzhou City,Zhejiang Province.
基金Noncommunicable Chronic Diseases-National Science and Technology Major Project,Grant/Award Numbers:2024ZD0521400,2024ZD0521404Affiliated Hospital of Qinghai University。
文摘Introduction:Chemotherapy-induced gastrointestinal symptom clusters in breast cancer impair quality of life and treatment adherence,yet lack effective interventions.While acupuncture mitigates isolated chemotherapy-induced symptoms,its mechanisms for multi-symptom clusters remain unclear.This study evaluates electroacupuncture's efficacy and explores its biological mechanisms in managing these clusters.Methods:This prospective,multicenter,block-randomized,double-blind,sham-controlled trial will enroll 388 patients with breast cancer undergoing neoadjuvant/adjuvant chemotherapy,to be randomly assigned(1:1)to electroacupuncture or sham electro-acupuncture groups.Both groups will receive the standard quadruple antiemetic regimen combined with electroacupuncture or sham intervention.The primary endpoint is the incidence of chemotherapy-induced gastrointestinal symptom clusters within 120 h after chemotherapy.Secondary endpoints include improvement in gastrointestinal symptom clusters post-first chemotherapy cycle,nausea-free rates during acute and delayed phases,vomiting-free rates during overall,acute,and delayed phases,complete response rate,complete protection rate,and quality of life.Adverse events will be documented throughout the study.Discussion:This study will assess the efficacy and safety of electroacupuncture in alleviating chemotherapy-induced gastro-intestinal symptom clusters in patients with breast cancer.By integrating multi-omics analyses,we aim to elucidate the biological mechanisms underlying its therapeutic effects.The findings may offer a robust clinical foundation for optimizing symptom cluster management in cancer care.Trial Registration:Clinical Trials ID:NCT06952920.Date of registration:April 16,2025.Prospectively registered.URL of Trial Registry Record:https://clinicaltrials.gov/study/NCT06952920cond=NCT06952920&rank=1.
文摘In the Tianshan region,a complete textile industry chain has been established,covering the entire process from cotton cultivation and chemical fiber production,through spinning,weaving,dyeing,and finishing,and further extending to apparel,home textiles,and industrial textiles.In November 2025,the first list of five characteristic textile and apparel industry clusters in Xinjiang was officially announced,marking a new stage in the clustering of Xinjiang's textile and apparel industry.Data shows that the total output value of Xinjiang's cotton and textile and apparel industry chain has exceeded 220 billion yuan.With the nation's largest cotton production,a complete industrial chain system,and strong synergistic effects,Xinjiang has become a leading and highly competitive textile industry hub in China.
基金supported by the National Natural Science Foundation of China(Grant No.52573299)the Natural Science Foundation of Jiangxi province(No.20242BAB25223,20232BCJ23025,20232BCJ25040,20232BAB214024)the Special Funding Program for Graduate Student Innovation of Jiangxi Province(No.YC2024-S594).
文摘Transition metal selenides as sodium-ion hybrid capacitor(SIHC)anodes still suffer from amorphization difficulties and capacity degradation triggered by polyselenide dissolution.Herein,an atomistic amorphous strategy is proposed to construct adjacent Nb-Nb diatomic pairs with Se/O-coordination(Se4-Nb2-O2)in N-doped carbon-confined amorphous selenide clusters(a-Nb-Se/O@NC).Synergistic carbon confinement and hydrothermal oxygenation induce amorphization of Nb–Se bonds,eliminating crystalline rigidity while creating isotropic dual-ion transport channels and high-density active sites enriched with dangling bonds,thereby enhancing structural integrity and Na+storage capacity.The unique Se/O-coordinated Nb-Nb diatomic configuration establishes an electron-delocalized system,where the low electronegativity of Se counterbalances electron withdrawal from coordinated O at Nb centers.These strengthen d-p orbital hybridization,reduce Na+adsorption energy,and optimize charge transfer pathways and reaction kinetics in the amorphous clusters.Electrochemical tests reveal that the a-Nb-Se/O@NC anode delivers a high reversible capacity of 312.57 mAh g^(−1)and exceptional cyclic stability(103%capacity retention)after 5000 cycles at 10.0 A g^(−1).Assembled SIHCs achieve outstanding energy/power densities(207.1 Wh kg^(−1)/18966 W kg^(−1)),surpassing most amorphous and crystalline counterparts.This work provides methodological insights for the design of electrodes in high-power storage devices through atomic modulation and electronic optimization of amorphous selenides.
基金the financial support from the National Natural Science Foundation of China(Nos.22109164 and 22371046)the Key Program of the Natural Science Foundation of Fujian Province(No.2021J02007)。
文摘Exploring the synthesis of novel structures is crucial for the development of functional materials.In this context,a novel and intriguing 3d-5p heterometallic cluster-substituted polyoxotungstate material,H_(29)Na_(9)(H_(2)O)_(21){Ca(H_(2)O)_(2)@Sb_(12)O_(18)[Ni_(2)(OH)(A-α-Si W_(10)O_(37))]_(3)}_(2)·40H_(2)O(1),was constructed using Keggintype polyoxotungstate A-α-Si W_(10)O_(37),along with Ni and Sb elements.The structure features a Tdsymmetric Sb_(12)O_(18)({Sb_(12)})cage that encapsulates an 8-coordinate Ca^(2+)ion at its face.Additionally,the{Sb_(12)}cage forms an 18-nuclear 3d-5p heterometallic cluster by connecting with three di-nuclear nickel clusters through shared oxygen atoms.Electrochemical impedance spectra studies reveal that the single crystal of 1 achieves a proton conductivity of 1.11×10^(-1)S/cm along the[110]direction and 1.04×10^(-1)S/cm along the[100]direction at 85℃ and 98%relative humidity(RH).Furthermore,the powder form of 1 exhibits a proton conductivity of 3.00×10^(-2)S/cm.These findings suggest that compound 1 holds promise as a practical proton conducting material.
基金supported by the Regional Leading Research Center Program(2019R1A5A8080326)Basic Science Research Program(2020R1F1A1075921)BRL Program(2020R1A4A1018259)through the National Research Foundation(NRF)funded by the Ministry of Science and ICT of Republic of Korea.
文摘Two-dimensional metal dichalcogenides have been evidenced as potential electrocatalysts for hydrogen evolution reaction(HER);however,their application is limited by a poor oxygen evolution reaction(OER)activity due to insufficient number/types of multi-integrated active sites.In this study,we report a novel bifunctional catalyst developed by simultaneous engineering of single nickel atoms(Ni_(SA)) and nickel phosphate clusters(Ni_(Pi)) to synergistically trigger surface-functionalized MoS_(2) nanosheets(NSs)resulting in high reactivities for both HER and OER.The Ni_(SA)-Ni_(Pi)/MoS_(2)NSs material exhibits a fairly Pt-like HER behavior with an overpotential of 94.0 mV and a small OER overpotential of 314.0 mV to reach 10 mA cm^(-2) in freshwater containing 1.0 M KOH.Experimental results of the catalyst are well supported by theoretical study,which reveals the significant modulation of electronic structure and enrichment of electroactive site number/types with their reasonably adjusted free adsorption energy.For evaluating practicability,the Ni_(SA)-Ni_(Pi)/MoS_(2)NSs-based electrolyzer delivers effective operation voltage of 1.62,1.52,and 1.66 V at 10 mA cm^(-2) and superior long-term stability as compared to Pt/C//RuO_(2) system in freshwater,mimic seawater,and natural seawater,respectively.The present study indicates that the catalyst is a promising candidate for the practical production of green hydrogen via water electrolysis.
基金supported by the Specific Research Fund for Top-notch Talents of Guangdong Provincial Hospital of Chinese Medicine(No.2022KT1188).
文摘Objectives To identify core symptoms and symptom clusters in patients with neuromyelitis optica spectrum disorder(NMOSD)by network analysis.Methods From October 10 to 30,2023,140 patients with NMOSD were selected to participate in this online questionnaire survey.The survey tools included a general information questionnaire and a self-made NMOSD symptoms scale,which included the prevalence,severity,and distress of 29 symptoms.Cluster analysis was used to identify symptom clusters,and network analysis was used to analyze the symptom network and node characteristics and central indicators including strength centrality(r_(s)),closeness centrality(r_(c))and betweeness centrality(r_(b))were used to identify core symptoms and symptom clusters.Results The most common symptom was pain(65.7%),followed by paraesthesia(65.0%),fatigue(65.0%),easy awakening(63.6%).Regarding the burden level of symptoms,pain was the most burdensome symptom,followed by paraesthesia,easy awakening,fatigue,and difficulty falling asleep.Six clusters were identified:somatosensory,motor,visual,and memory symptom clusters,bladder and rectum symptom clusters,sleep symptoms clusters,and neuropsychological symptom clusters.Fatigue(r_(s)=12.39,r_(b)=68.00,r_(c)=0.02)was the most central and prominent bridge symptom,and motor symptom cluster(r_(s)=2.68,r_(c)=0.10)was the most central symptom cluster among the six clusters.Conclusions Our study demonstrated the necessity of symptom management targeting fatigue,pain,and motor symptom cluster in patients with NMOSD.
基金the support of the National Nature Science Foundation of China (21908124)Zhaoqing Xijiang Talent Program。
文摘Rational design and synthesis of low-cost trifunctional electrocatalysts with improved stability and superior electrocatalytic activity for oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER) are highly desirable but remain as the bottlenecks at the current state of technology.In this paper,the cobalt-iron(Co-Fe) composite supported on nitrogen-doped carbon nanotubes(CoFe composite/NCNTs) is synthesized.The intrinsic OER and HER catalytic activities of this CoFe composite/NCNTs composite are significantly improved with palladium(Pd) nanocluster decoration [Pd-coated(CoFe composite/NCNTs)].The as-prepared Pd-coated(CoFe composite/NCNTs) catalyst exhibits excellent trifunctional electrocatalytic activity and stability due to the interfacial coupling between Pd and(CoFe composite/NCNTs).This catalyst is successfully employed in the water electrolysis cell as both OER and HER electrode catalysts,flexible rechargeable Zn-air battery as the bifunctional ORR and OER electrode catalyst.The cell voltage of this catalyst-coated electrodes requires only 1.60 V to achieve 10 mA cm^(-2) current density for water electrolysis cell,which is comparable to and even better than that of Pt/C and Ir/C based cell.The primary Zn-air battery using this catalyst shows a constant high open-circuit voltage(OCV) of 1.47 V and a maximum power density of 261 mW cm^(-2) in the flooded mode configuration.Most importantly,a flexible Zn-air battery with this catalyst runs very smoothly without a change in voltage gap during flat,bending,and twisting positions.
文摘An aluminoborate,Na_(2.5)Rb[Al{B_(5)O_(10)}{B_(3)O_(5)}]·0.5NO_(3)·H_(2)O(1),was synthesized under hydrothermal condition,which was built by mixed oxoboron clusters and AlO_(4)tetrahedra.In the structure,the[B_(5)O_(10)]^(5-)and[B_(3)O_(7)]^(5-)clusters are alternately connected to form 1D[B_(8)O_(15)]_(n)^(6n-)chains,which are further linked by AlO_(4)units to form a 2D monolayer with 7‑membered ring and 10‑membered ring windows.Two adjacent monolayers with opposite orientations further form a porous‑layered structure with six channels through B—O—Al bonds.Compound 1 was characterized by single crystal X‑ray diffraction,powder X‑ray diffraction(PXRD),IR spectroscopy,UV‑Vis diffuse reflection spectroscopy,and thermogravimetric analysis(TGA),respectively.UV‑Vis diffuse reflectance analysis indicates that compound 1 shows a wide transparency range with a short cutoff edge of 201 nm,suggesting it may have potential application in UV regions.CCDC:2383923.
文摘Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms,the obtained Pt-on-Co/C400 catalysts exhib-ited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency(TOF)value of 3022 min^(-1)at 303 K.Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability,and there were no changes in the catalyst structures and catalytic activities after 10 cycles.
基金financially supported by the National Natural Science Foundation of China (Nos. 21471003, 21871141, 21871142,21701085 and 21901122)Natural Science Foundation of Educational Commission of Anhui Province of China (No. KJ2020A0240)+1 种基金the Natural Science Research of Jiangsu Higher Education Institutions of China (No. 19KJB150011)Project funded by China Postdoctoral Science Foundation (No. 2019M651873)。
文摘Metal-doped carbon materials, as one of the most important electrocatalytic catalysts for CO_(2)reduction reaction(CO_(2)RR), have attracted increasing attention. Herein, a series of Cu cluster embedded highly porous nanofibers have been prepared through the carbonization of electro-spun MOF/PAN nanofibers.The obtained Cu cluster doped porous nanofibers possessed fibrous morphology, high porosity, conductivity, and uniformly dispersed Cu clusters, which could be applied as promising CO_(2)RR catalysts. Specifically, best of them, MCP-500 exhibited high catalytic performance for CO_(2)RR, in which the Faradaic efficiency of CO(FECO) was as high as 98% at-0.8 V and maintained above 95% after 10 h continuous electrocatalysis. The high performance might be attributed to the synergistic effect of tremendously layered graphene skeleton and uniformly dispersed Cu clusters that could largely promote the electron conductivity, mass transfer and catalytic activity during the electrocatalytic CO_(2)RR process. This attempt will provide a new idea to design highly active CO_(2)RR electrocatalyst.
文摘Organic-inorganic hybrid clusters with strong X-ray radioluminescence have exhibited great potential in scintillator field.However,fabricating the X-ray imaging screens of the clusters without sacrificing the scintillation performance is challenging.Herein,we report an effective way to prepare high-quality scintillation films of two synthesized Cu(Ⅰ)clusters through vacuum evaporation deposition.The developed Cu(Ⅰ)clusters with rigid molecular structures show excellent scintillation performance with a high light yield of up to 19356.7 photons/MeV and a low detection limit of 158 nGy/s.The scintillation film based on the Cu(Ⅰ)clusters made by vacuum evaporation deposition is highly uniform with a small surface roughness value of 1.04 nm,which can be applied to X-ray imaging for various objects.These results not only provide important guidance to develop high-performance organic-inorganic hybrid scintillators,but also pave a straightforward way to prepare non-doped scintillation screens for remarkable X-ray imaging applications.
文摘In modern distributed systems and cloud computing architectures,high availability and high scalability are core requirements to ensure the continuous and stable operation of services.As key technologies for achieving these two goals,high-availability clusters and load-balancing clusters have significant differences in their design concepts and application scenarios,while also maintaining close connections.This paper aims to conduct an in-depth analysis of the core objectives,working principles,technical advantages and disadvantages,and typical application cases of high-availability clusters and load-balancing clusters.By introducing an analogical model of a“restaurant kitchen,”the differences between the two are intuitively explained,and their technical characteristics are compared in detail.Additionally,a detailed practical case is included to specifically demonstrate the collaborative work of high-availability and load-balancing technologies through the construction process of Keepalived and HAProxy.Finally,taking the architecture of a typical e-commerce website as an example,this paper demonstrates the best practice of organically combining the two cluster technologies in a production environment to build a robust and high-performance distributed system.Research shows that understanding the differences between the two and implementing collaborative deployment is the cornerstone of designing modern IT infrastructure.
基金supported by the National Natural Science Foundation of China(Grant No.72571150)Beijing Natural Science Foundation(Grant No.9182015)。
文摘Attributed graph clustering plays a vital role in uncovering hidden network structures,but it presents significant challenges.In recent years,various models have been proposed to identify meaningful clusters by integrating both structural and attribute-based information.However,these models often emphasize node proximities without adequately balancing the efficiency of clustering based on both structural and attribute data.Furthermore,they tend to neglect the critical fuzzy information inherent in attributed graph clusters.To address these issues,we introduce a new framework,Markov lumpability optimization,for efficient clustering of large-scale attributed graphs.Specifically,we define a lumped Markov chain on an attribute-augmented graph and introduce a new metric,Markov lumpability,to quantify the differences between the original and lumped Markov transition probability matrices.To minimize this measure,we propose a conjugate gradient projectionbased approach that ensures the partitioning closely aligns with the intrinsic structure of fuzzy clusters through conditional optimization.Extensive experiments on both synthetic and real-world datasets demonstrate the superior performance of the proposed framework compared to existing clustering algorithms.This framework has many potential applications,including dynamic community analysis of social networks,user profiling in recommendation systems,functional module identification in biological molecular networks,and financial risk control,offering a new paradigm for mining complex patterns in high-dimensional attributed graph data.
基金Supported by Regional Science Foundation of China,National Natural Science Foundation(No.82160820)General Program of Guizhou Provincial Natural Science Foundation[QianKeHe Foundation-ZK(2023)General153].
文摘[Objectives]To establish an HPLC method for the quantitative determination of multiple phenolic acid components in Tetracera asiatica medicinal material,providing a basis for establishing its quality standards.[Methods]An Inertsil ODS-C 18 column(250 mm×4.6 mm,5μm)was used.The mobile phase consisted of acetonitrile-0.2% phosphoric acid solution(10:90).The flow rate was 1.0 mL/min.The detection wavelength was 274 nm.The column temperature was 25℃.The injection volume was 10μL.The content of three components,gallic acid,protocatechuic acid,and protocatechualdehyde,was determined in 13 batches of T.asiatica.[Results]Gallic acid showed good linearity within the range of 0.020-6.400μg/mL,protocatechuic acid within 0.201-6.432μg/mL,and protocatechualdehyde within 0.202-6.464μg/mL(r>0.9990).The average recovery rates ranged from 98.61%to 101.17%,with RSD s between 1.21%and 2.69%.[Conclusions]The quantitative determination method established in this study is simple and feasible,and can provide a basis for the quality evaluation of T.asiatica.
基金financially supported by the National Natural Science Foundation of China(22471268)the National Key Research and Development Project(2022YFA1503900)+2 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB1170000)the Natural Science Foundation of Fujian Province(2022J05090,2024T3003)the Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(CXZX-2022-GH03,CXZX-2024-JQ08).
文摘Chiral metal-organic clusters(MOCs)integrating lanthanide ions(Ln^(3+))and organic luminophores present a promising platform for modulating circularly polarized luminescence(CPL).However,achieving dual-wavelength CPL in discrete cluster systems constitutes a considerable challenge.Herein,two enantiomeric pairs of heterometallic EuSn oxo clusters,designated as Sn_(2)EuL_(2)-R/S and Sn_(2)EuL_(4)-R/S,were strategically synthesized using axially chiral binaphthol-phosphonate ligands.These hybrid clusters exhibit dual emission,characterized by a broad ligand-derived fluorescence band superimposed with sharp,characteristic Eu^(3+)f-f transitions,which enables excitation-dependent luminescence color tuning.Their emission profiles and quantum yields are found to be exquisitely adjusted by the distinct coordination environments of Sn^(4+)centers.Notably,Sn_(2)EuL_(2)-R/S demonstrates CPL activity in both near-UV(|g_(lum)|=1.7×10^(-3))and visible(|g_(lum)|=3.1×10^(-2))regions.This work not only reports the first instance of dual-wavelength CPL in a lanthanide/tin oxo complex but also establishes a robust design strategy for fabricating color-tunable chiral photonic materials.
基金supported by the National Key R&D Program of China(No.2023YFB3712504)the National Natural Science Foundation of China(Nos.22273038,22073043,and 22033004)。
文摘Accurate description of noncova-lent interactions in large systems is challenging due to the require-ment of high-level electron corre-lation methods.The generalized energy-based fragmentation(GEBF)approach,in conjunc-tion with the domain-based local pair natural orbital(DLPNO)method,has been applied to assess the average binding energies(ABEs)of large benzene clus-ters,specifically(C6H6)13,at the coupled cluster singles and doubles with perturbative triples correction[CCSD(T)]level and the complete basis set(CBS)limit.Utilizing GEBF-DLPNO-CCSD(T)/CBS ABEs as benchmarks,various DFT functionals were evaluated.It was found that several functionals with empirical dispersion correction,including M06-2X-D3,B3LYP-D3(BJ),and PBE-D3(BJ),provide accurate descriptions of the ABEs for(C6H6)13 clusters.Additionally,the M06-2X-D3 functional was used to calculate the ABEs and relative stabili-ties of(C6H6)n clusters for n=11,12,13,14,and 15 revealing that the(C6H6)13 cluster ex-hibits the highest relative stability.These findings align with experimental evidence suggest-ing that n=13 is one of the magic numbers for benzene clusters(C6H6)n,with n≤30.
