To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects,the new anthraquinone derivatives,9‑pyridylanthrahydrazone(9‑PAH)and 9,10‑bisp...To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects,the new anthraquinone derivatives,9‑pyridylanthrahydrazone(9‑PAH)and 9,10‑bispyridylanthrahydrazone(9,10‑PAH)were designed and synthesized.Utilizing 9‑PAH and 9,10‑PAH as promising anticancer ligands,their respective copper complexes,namely[Cu(L1)Cl_(2)]Cl(1)and{[Cu_(4)(μ_(2)‑Cl)_(3)Cl_(4)(9,10‑PAH)_(2)(DMSO)_(2)]Cl_(2)}_(n)(2),were subsequently synthesized,where the new ligand L1 is formed by coupling two 9‑PAH ligands in the coordination reaction.The chemical and crystal structures of 1 and 2 were elucidated by IR,MS,elemental analysis,and single‑crystal X‑ray diffraction.Complex 1 forms a mononuclear structure.L1 coordinates with Cu through its three N atoms,together with two Cl atoms,to form a five‑coordinated square pyramidal geometry.Complex 2 constitutes a polymeric structure,wherein each structural unit centrosymmetrically encompasses two five‑coordinated binuclear copper complexes(Cu1,Cu2)of 9,10‑PAH,with similar square pyramidal geometry.A chlorine atom(Cl_(2)),located at the symmetry center,bridges Cu1 and Cu1A to connect the two binuclear copper structures.Meanwhile,the two five‑coordinated Cu2 atoms symmetrically bridge the adjacent structural units via one coordinated Cl atom,respectively,thus forming a 1D chain‑like polymeric structure.In vitro anticancer activity assessments revealed that 1 and 2 showed significant cytotoxicity even higher than cisplatin.Specifically,the IC_(50)values of 2 against HeLa‑229 and SK‑OV‑3 cancer cell lines were determined to be(5.92±0.32)μmol·L^(-1)and(6.48±0.39)μmol·L^(-1),respectively.2 could also block the proliferation of HeLa‑229 cells in S phase and significantly induce cell apoptosis.In addition,fluorescence quenching competition experiments suggested that 2 might interact with DNA by an intercalative binding mode,offering insights into its underlying anticancer mechanism.CCDC:2388918,1;2388919,2.展开更多
Two Gd_(2)complexes,namely[Gd_(2)(dbm)_(2)(HL_(1))_(2)(CH_(3)OH)_(2)]·4CH_(3)OH(1)and[Gd_(2)(dbm)_(2)(L_(2))_(2)(CH_(3)OH)_(2)]·2CH_(3)OH(2),where H_(3)L_(1)=(Z)-N'-[4-(diethylamino)-2-hydroxybenzylidene...Two Gd_(2)complexes,namely[Gd_(2)(dbm)_(2)(HL_(1))_(2)(CH_(3)OH)_(2)]·4CH_(3)OH(1)and[Gd_(2)(dbm)_(2)(L_(2))_(2)(CH_(3)OH)_(2)]·2CH_(3)OH(2),where H_(3)L_(1)=(Z)-N'-[4-(diethylamino)-2-hydroxybenzylidene]-2-hydroxyacetohydrazide,H_(2)L_(2)=(E)-N'-(5-bromo-2-hydroxy-3-methoxybenzylidene)nicotinohydrazide,Hdbm=dibenzoylmethane,have been constructed by adopting the solvothermal method.Structural characterization unveils that both complexes 1 and 2 are constituted by two Gd^(3+)ions,two dbm-ions,two CH_(3)OH molecules,and two polydentate Schiff-base ligands(HL_(1)^(2-)or L_(2)^(2-)).In addition,complex 1 contains four free methanol molecules,whereas complex 2 harbors two free methanol molecules.By investigating the interactions between complexes 1 and 2 and four types of bacteria(Bacillus subtilis,Escherichia coli,Staphylococcus aureus,Candida albicans),it was found that both complexes 1 and 2 exhibited potent antibacte-rial activities.The interaction mechanisms between the ligands H_(3)L_(1),H_(2)L_(2),complexes 1 and 2,and calf thymus DNA(CT-DNA)were studied using ultraviolet-visible spectroscopy,fluorescence titration,and cyclic voltammetry.The results demonstrated that both complexes 1 and 2 can intercalate into CT-DNA molecules,thereby inhibiting bacterial proliferation to achieve the antibacterial effects.CCDC:2401116,1;2401117,2.展开更多
Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Her...Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.展开更多
2-substituted-1-amino-o-carboranes 2-R-1-NH_(2)-o-C_(2)B_(10)H_(10)(R=CH_(3),1a;R=Ph,1b)were synthesized and the reactions of these compounds with the yttrium dialkyl complex[Y(L)(CH_(2)SiMe3)_(2)](L=[2-(2,5-Me_(2)C_(...2-substituted-1-amino-o-carboranes 2-R-1-NH_(2)-o-C_(2)B_(10)H_(10)(R=CH_(3),1a;R=Ph,1b)were synthesized and the reactions of these compounds with the yttrium dialkyl complex[Y(L)(CH_(2)SiMe3)_(2)](L=[2-(2,5-Me_(2)C_(4)H_(2)N)C_(6)H4NC(Ph)=NDipp]-,Dipp=2,6-iPr_(2)C_(6)H_(3))were investigated.The 1H NMR spectroscopy indicate that the reaction of ytrrium dialkyl complex with one equivalent of 2-R-1-NH_(2)-o-C_(2)B_(10)H_(10) produce the mixture of ytrrium alkyl-amido complex[Y(L)(2-R-1-NH-o-C_(2)B_(10)H_(10))(CH_(2)SiMe3)](R=CH_(3),2a;R=Ph,2b)and bis(amido)complex[Y(L)(2-R-1-NH-o-C_(2)B_(10)H_(10))_(2)](R=CH_(3),3a;R=Ph,3b).The yttrium bridging imido complex[Y(L)(2-CH_(3)-1-N-o-C_(2)B_(10)H_(10))]_(2)(4a)was obtained by heating the mixture at 55℃for 12 h.Complex 3a was isolated and characterized by treating the yttrium dialkyl complex with two equivalents of 1a.The structures of complexes 3a and 4a were verified by single-crystal Xray diffraction.CCDC:2424136,3a;2424137,4a.展开更多
A novel 3D metal-organic framework(MOF)[Pr_(2)(L)_(3)(H_(2)O)5·H_(2)O]n(Pr-1),(H_(2)L=4,4'-oxybis(benzoic acid))with a rare structure of broken layer net,was constructed under the condition of solvothermal sy...A novel 3D metal-organic framework(MOF)[Pr_(2)(L)_(3)(H_(2)O)5·H_(2)O]n(Pr-1),(H_(2)L=4,4'-oxybis(benzoic acid))with a rare structure of broken layer net,was constructed under the condition of solvothermal synthesis.The struc-ture and crystal net were analyzed and characterized.This rod net of Pr-1 is new to both RCSR and ToposPro data-bases,and is named as rn-12 as suggested.Due to the luminescent properties of H_(2)L and Pr(Ⅲ),the solid-state fluo-rescence property and sensing performance(solvents and metal ions)of Pr-1 were investigated.The sensing experi-ments indicated that Pr-1 could act as a fluorescence sensor to detect Cd^(2+)ions with good sensitivity.In addition,antibacterial activities show that Pr-1 exhibited stronger antibacterial activity against Escherichia coli(E.coli),Staphylococcus aureus(S.aureus),and Bacillus subtilis(B.subtilis)compared to synthetic materials.展开更多
As the second most important solid waste produced by coal-fired power plants,the improper management of coal-fired slag has the potential to result in environmental pollution.It is therefore imperative that high-value...As the second most important solid waste produced by coal-fired power plants,the improper management of coal-fired slag has the potential to result in environmental pollution.It is therefore imperative that high-value utilization pathways for coal-fired slag should be developed.In this study,modified magnesium slag(MMS),produced by a magnesium smelter,was selected as the alkali activator.The activated silica-aluminum solid wastes,namely coal-fired slag(CFS)and mineral powder(MP),were employed as pozzolanic materials in the preparation of alkali-activated cementitious materials.The alkali-activated cementitious materials prepared with 50 wt%MMS,40 wt%CFS and 10 wt%MP exhibited favorable mechanical properties,with a compressive strength of 32.804 MPa in the paste sample cured for 28 d.Then,the activated silica-aluminum solid waste consisting of CFS-MP generated a significant amount of C-S(A)-H gels,AFt,and other products,which were observed to occupy the pore structure of the specimen.In addition,the secondary hydration reaction of CFS-MP occurs in high alkalinity environments,resulting in the formation of a mutually stimulated and promoted reaction system between CFS-MP and MMS,this will subsequently accelerate the hydrolysis reaction of MMS.It is important to emphasize that the amount of MMS in alkali-activated cementitious materials must be strictly regulated to avert the potential issue of incomplete depolymerization-repolymerization of active silica-aluminum solid waste containing CFS-MP.This in turn could have a deleterious impact on the late strength of the cementitious materials.The aim of this work is to improve the joint disposal of MMS,CFS and MP and thereby provide a scientific basis for the development of environmentally friendly and low-carbon modified magnesium slag alkali-activated coal-fired slag based cementitious materials for mine backfilling.展开更多
Objective Magnetoencephalography(MEG),a non-invasive neuroimaging technique,meticulously captures the magnetic fields emanating from brain electrical activity.Compared with MEG based on superconducting quantum interfe...Objective Magnetoencephalography(MEG),a non-invasive neuroimaging technique,meticulously captures the magnetic fields emanating from brain electrical activity.Compared with MEG based on superconducting quantum interference devices(SQUID),MEG based on optically pump magnetometer(OPM)has the advantages of higher sensitivity,better spatial resolution and lower cost.However,most of the current studies are clinical studies,and there is a lack of animal studies on MEG based on OPM technology.Pain,a multifaceted sensory and emotional phenomenon,induces intricate alterations in brain activity,exhibiting notable sex differences.Despite clinical revelations of pain-related neuronal activity through MEG,specific properties remain elusive,and comprehensive laboratory studies on pain-associated brain activity alterations are lacking.The aim of this study was to investigate the effects of inflammatory pain(induced by Complete Freund’s Adjuvant(CFA))on brain activity in a rat model using the MEG technique,to analysis changes in brain activity during pain perception,and to explore sex differences in pain-related MEG signaling.Methods This study utilized adult male and female Sprague-Dawley rats.Inflammatory pain was induced via intraplantar injection of CFA(100μl,50%in saline)in the left hind paw,with control groups receiving saline.Pain behavior was assessed using von Frey filaments at baseline and 1 h post-injection.For MEG recording,anesthetized rats had an OPM positioned on their head within a magnetic shield,undergoing two 15-minute sessions:a 5-minute baseline followed by a 10-minute mechanical stimulation phase.Data analysis included artifact removal and time-frequency analysis of spontaneous brain activity using accumulated spectrograms,generating spectrograms focused on the 4-30 Hz frequency range.Results MEG recordings in anesthetized rats during resting states and hind paw mechanical stimulation were compared,before and after saline/CFA injections.Mechanical stimulation elevated alpha activity in both male and female rats pre-and post-saline/CFA injections.Saline/CFA injections augmented average power in both sexes compared to pre-injection states.Remarkably,female rats exhibited higher average spectral power 1 h after CFA injection than after saline injection during resting states.Furthermore,despite comparable pain thresholds measured by classical pain behavioral tests post-CFA treatment,female rats displayed higher average power than males in the resting state after CFA injection.Conclusion These results imply an enhanced perception of inflammatory pain in female rats compared to their male counterparts.Our study exhibits sex differences in alpha activities following CFA injection,highlighting heightened brain alpha activity in female rats during acute inflammatory pain in the resting state.Our study provides a method for OPM-based MEG recordings to be used to study brain activity in anaesthetized animals.In addition,the findings of this study contribute to a deeper understanding of pain-related neural activity and pain sex differences.展开更多
Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6...Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.展开更多
Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,t...Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,their practical use is hindered by the slow redox kinetics of sulfur and the“shuttle effect”arising from dissolved lithium polysulfides(LiPSs).In recent years,various carbon-based materials have served as sulfur hosts and catalysts for accelerating sulfur conversion redox kinetics and alleviating LiPS shuttling.However,they often suffer from irreversible passivation and structural changes that destroy their long-term performance.We consider the main problems limiting their stability,including excessive LiPS adsorption,passivation by insulating Li2S,and surface reconstruction,and clarify how these factors lead to capacity fade.We then outline effective strategies for achieving long-term sulfur catalysis,focusing on functional carbon,such as designing suitable carbon-supported catalyst interfaces,creating well-distributed active sites,adding cocatalysts to improve electron transfer,and using carbon-based protective layers to suppress unwanted side reactions.Using this information should enable the development of stable,high-activity catalysts capable of long-term operation under practical conditions in Li-S batteries.展开更多
To detect space gravitational waves in the extremely low-frequency band,the telescope and optic-al platform require high stability and reliability.However,the cantilevered design presents challenges,espe-cially in the...To detect space gravitational waves in the extremely low-frequency band,the telescope and optic-al platform require high stability and reliability.However,the cantilevered design presents challenges,espe-cially in the glass-metal hetero-bonding process.This study focuses on the analysis and experimental re-search of the bonding layer in the integrated structure.By optimizing the structural configuration and select-ing suitable bonding processes,the reliability of the telescope system is enhanced.The research indicates that using J-133 adhesive achieves the best performance,with a bonding layer thickness of 0.30 mm and a metal substrate surface roughness of Ra 0.8.These findings significantly enhance the reliability of the optical sys-tem while minimizing potential risks.展开更多
In this paper,the failure caused by HRAM loads which were generated by high-speed projectile penetration,and protection technology of the fluid-filled structure were explored.A bubble was preset on the projectile traj...In this paper,the failure caused by HRAM loads which were generated by high-speed projectile penetration,and protection technology of the fluid-filled structure were explored.A bubble was preset on the projectile trajectory in a fluid-filled structure.Based on the reflection and transmission phenomena of pressure waves at the gas-liquid interface and the compressibility characteristics of gases,a numerical analysis was conducted on the influence of preset bubble on projectile penetration and structural failure characteristics.The results indicate that the secondary water-entry impact phenomenon occurs when a preset bubble exists on the projectile trajectory,leading to the secondary water entry impact loads.The rarefaction waves reflected on the surface of the preset bubble cause the attenuation ratio of the initial impact pressure peak to reach 68.8%and the total specific impulse attenuation ratio to reach 48.6%.Furthermore,the larger the bubble,the faster the projectile,and the more obvious the attenuation effect.Moreover,due to the compressibility of the bubble,the global deformation attenuation ratio of the front and rear walls can reach over 80%.However,the larger the bubble size,the faster the projectile velocity,the smaller the local deformation attenuation effect of the rear wall,and the more severe the failure at the perforation of the rear wall.展开更多
Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions an...Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.展开更多
Five cadmium naphthalene-diphosphonates,formulated as[Cd_(1.5)(1,4-ndpaH_(2))2(4,4'-bpyH)(4,4'-bpy)0.5(H_(2)O)_(2)]2(1),[Cd(1,4-ndpaH_(2))(1,4-bib)0.5(H_(2)O)](2),[Cd(1,4-ndpaH3)2(1,2-dpe)(H_(2)O)]·(1,2-d...Five cadmium naphthalene-diphosphonates,formulated as[Cd_(1.5)(1,4-ndpaH_(2))2(4,4'-bpyH)(4,4'-bpy)0.5(H_(2)O)_(2)]2(1),[Cd(1,4-ndpaH_(2))(1,4-bib)0.5(H_(2)O)](2),[Cd(1,4-ndpaH3)2(1,2-dpe)(H_(2)O)]·(1,2-dpe)·7H_(2)O(3),(1,2-bixH)[Cd3(1,4-ndpaH)(1,4-ndpaH_(2))2(H_(2)O)_(2)](4),and[Cd(1,4-ndpaH_(2))(H_(2)O)]·H_(2)O(5),have been synthesized from the selfassembly reactions of 1,4-naphthalenediphosphonic acid(1,4-ndpaH4)with Cd(NO3)2·4H_(2)O by introducing auxiliary ligands with variation of rigidity,such as 4,4'-bipyridine(4,4'-bpy),1,4-bis(1-imidazolyl)benzene(1,4-bib),1,2-di(4-pyridyl)ethylene(1,2-dpe),1,3-di(4-pyridyl)propane(1,3-dpp),and bis(imidazol-1-ylmethyl)benzene(1,2-bix),respectively.Structure resolution by single-crystal X-ray diffraction reveals that compound 1 possesses a layered framework,in which the{Cd3(PO2)2}trimers made up of corner-sharing two{CdO4N2}and one{CdO6}octahedra are connected by phosphonate groups,forming a ribbon,which are cross-linked by 4,4'-bipy ligands,forming a 2D layer.Compound 2 shows a 3D open-framework structure,where chains of corner-sharing{CdO4N}trigonal bipyramids and{PO3C}tetrahedra are cross-linked by 1,4-bib and/or phosphonate groups.A 1D ladder-like chain structure is found in compound 3,where the ladder-like chains made up of corner-sharing{CdO5N}octahedra and{PO3C}tetra hedra are connected by 1,4-ndpaH_(2)^(2-).Both compounds 4 and 5 obtained by the introduction of flexible ligands during the synthesis show a 2D layered structure,which is formed by ligand crosslinking double metal chains.Interestingly,In 4,flexible 1,2-bix was singly protonated,as guest molecules,filled between layer and layer,while flexible ligand 1,3-dpp is absent in 5.Photophysical measurements indicate that compounds 1-5 show ligand-centered emissions.展开更多
Changes to the microstructure of a hard carbon(HC)and its solid electrolyte interface(SEI)can be effective in improving the electrode kinetics.However,achieving fast charging using a simple and inexpensive strategy wi...Changes to the microstructure of a hard carbon(HC)and its solid electrolyte interface(SEI)can be effective in improving the electrode kinetics.However,achieving fast charging using a simple and inexpensive strategy without sacrificing its initial Coulombic efficiency remains a challenge in sodium ion batteries.A simple liquid-phase coating approach has been used to generate a pitch-derived soft carbon layer on the HC surface,and its effect on the porosity of HC and SEI chemistry has been studied.A variety of structural characterizations show a soft carbon coating can increase the defect and ultra-micropore contents.The increase in ultra-micropore comes from both the soft carbon coatings and the larger pores within the HC that are partially filled by pitch,which provides more Na+storage sites.In-situ FTIR/EIS and ex-situ XPS showed that the soft carbon coating induced the formation of thinner SEI that is richer in NaF from the electrolyte,which stabilized the interface and promoted the charge transfer process.As a result,the anode produced fastcharging(329.8 mAh g^(−1)at 30 mA g^(−1)and 198.6 mAh g^(−1)at 300 mA g^(−1))and had a better cycling performance(a high capacity retention of 81.4%after 100 cycles at 150 mA g^(−1)).This work reveals the critical role of coating layer in changing the pore structure,SEI chemistry and diffusion kinetics of hard carbon,which enables rational design of sodium-ion battery anode with enhanced fast charging capability.展开更多
A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]py...A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.展开更多
Hollow multi-shelled structure(HoMS)is the novel multifunctional structural system,which are con-structed with nanoparticles as structural units,featuring two or more shells,multiple interfaces,and numerous chan-nels ...Hollow multi-shelled structure(HoMS)is the novel multifunctional structural system,which are con-structed with nanoparticles as structural units,featuring two or more shells,multiple interfaces,and numerous chan-nels and demonstrating outstanding properties in energy conversion and mass transfer.In recent years,owing to the breakthroughs in synthetic methods,the diversity of composition and structure of HoMS has been greatly enriched,showing broad application prospects in energy,catalysis,environment and other fields.This review focuses on the research status of HoMS for catalytic applications.Firstly,the new synthesis method for HoMS,namely the sequen-tial templating approach,is introduced from both practical and theoretical perspectives.Then,it summarizes and discusses the structure-performance relationship between the shell structure and catalytic performance.The unique temporal-spatial ordering property of mass transport in HoMS and the major breakthroughs it brings in catalytic applications are discussed.Finally,it looks forward to the opportunities and challenges in the development of HoMS.展开更多
The development of sustainable electrode materials for energy storage systems has become very important and porous carbons derived from biomass have become an important candidate because of their tunable pore structur...The development of sustainable electrode materials for energy storage systems has become very important and porous carbons derived from biomass have become an important candidate because of their tunable pore structure,environmental friendliness,and cost-effectiveness.Recent advances in controlling the pore structure of these carbons and its relationship between to is energy storage performance are discussed,emphasizing the critical role of a balanced distribution of micropores,mesopores and macropores in determining electrochemical behavior.Particular attention is given to how the intrinsic components of biomass precursors(lignin,cellulose,and hemicellulose)influence pore formation during carbonization.Carbonization and activation strategies to precisely control the pore structure are introduced.Finally,key challenges in the industrial production of these carbons are outlined,and future research directions are proposed.These include the establishment of a database of biomass intrinsic structures and machine learning-assisted pore structure engineering,aimed at providing guidance for the design of high-performance carbon materials for next-generation energy storage devices.展开更多
Thermally activated delayed fluorescence(TADF)molecules have outstanding potential for applications in organic light-emitting diodes(OLEDs).Due to the lack of systematic studies on the correlation between molecular st...Thermally activated delayed fluorescence(TADF)molecules have outstanding potential for applications in organic light-emitting diodes(OLEDs).Due to the lack of systematic studies on the correlation between molecular structure and luminescence properties,TADF molecules are far from meeting the needs of practical applications in terms of variety and number.In this paper,three twisted TADF molecules are studied and their photophysical properties are theoretically predicted based on the thermal vibrational correlation function method combined with multiscale calculations.The results show that all the molecules exhibit fast reverse intersystem crossing(RISC)rates(kRISC),predicting their TADF luminescence properties.In addition,the binding of DHPAzSi as the donor unit with different acceptors can change the dihedral angle between the ground and excited states,and the planarity of the acceptors is positively correlated with the reorganization energy,a property that has a strong influence on the non-radiative process.Furthermore,a decrease in the energy of the molecular charge transfer state and an increase in the kRISC were observed in the films.This study not only provides a reliable explanation for the observed experimental results,but also offers valuable insights that can guide the design of future TADF molecules.展开更多
Dual-ion batteries(DIBs)usually use carbon-based materials as electrodes,showing advantages in high operating volt-age,potential low cost,and environmental friendliness.Different from conventional“rocking chair”type...Dual-ion batteries(DIBs)usually use carbon-based materials as electrodes,showing advantages in high operating volt-age,potential low cost,and environmental friendliness.Different from conventional“rocking chair”type secondary batter-ies,DIBs perform a unique working mechanism,which employ both cation and anion taking part in capacity contribution at an anode and a cathode,respectively,during electrochemical reactions.Graphite has been identified as a suitable cathode material for anion intercalation at high voltages(>4.8 V)with fast reaction kinetics.However,the development of DIBs is being hindered by dynamic mismatch between a cathode and an anode due to sluggish Li+diffusion at a high rate.Herein,we prepared phyllostachys edulis derived carbon(PEC)through microstructure regulation strategy and investigated the carbonized temperature effect,which effectively tailored the rich short-range ordered graphite microdomains and disor-dered amorphous regions,as well as a unique nano-pore hierarchical structure.The pore size distribution of nano-pores was concentrated in 0.5-5 nm,providing suitable channels for rapid Li+transportation.It was found that PEC-500(carbon-ized at 500℃)achieved a high capacity of 436 mAh·g^(-1)at 300 mA·g^(-1)and excellent rate performance(maintaining a high capacity of 231 mAh·g^(-1)at 3 A·g^(-1)).The assembled dual-carbon PEC-500||graphite full battery delivered 114 mAh·g^(-1)at 10 C with 96%capacity retention after 3000 cycles and outstanding rate capability,providing 74 mAh·g^(-1)at 50 C.展开更多
A new cobalt(Ⅱ)-radical complex:[Co(im4-py)_(2)(PNB)_(2)](im4-py=2-(4'-pyridyl)-4,4,5,5-tetramethylimidazole-1-oxyl,HPNB=p-nitrobenzoic acid)has been synthesized and characterized by X-ray diffraction analysis,el...A new cobalt(Ⅱ)-radical complex:[Co(im4-py)_(2)(PNB)_(2)](im4-py=2-(4'-pyridyl)-4,4,5,5-tetramethylimidazole-1-oxyl,HPNB=p-nitrobenzoic acid)has been synthesized and characterized by X-ray diffraction analysis,elemental analysis,IR,and magnetic properties.X-ray diffraction analysis shows that the complex exists as mononuclear molecules and Co(Ⅱ)ion is four-coordinated with two radicals and two PNB-ligands.The magnetic susceptibility study indicates the complex exhibits weak ferromagnetic interactions between cobalt(Ⅱ)and im4-py radical.The magnetic property is explained by the magnetic and structure exchange mechanism.CCDC:976028.展开更多
文摘To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects,the new anthraquinone derivatives,9‑pyridylanthrahydrazone(9‑PAH)and 9,10‑bispyridylanthrahydrazone(9,10‑PAH)were designed and synthesized.Utilizing 9‑PAH and 9,10‑PAH as promising anticancer ligands,their respective copper complexes,namely[Cu(L1)Cl_(2)]Cl(1)and{[Cu_(4)(μ_(2)‑Cl)_(3)Cl_(4)(9,10‑PAH)_(2)(DMSO)_(2)]Cl_(2)}_(n)(2),were subsequently synthesized,where the new ligand L1 is formed by coupling two 9‑PAH ligands in the coordination reaction.The chemical and crystal structures of 1 and 2 were elucidated by IR,MS,elemental analysis,and single‑crystal X‑ray diffraction.Complex 1 forms a mononuclear structure.L1 coordinates with Cu through its three N atoms,together with two Cl atoms,to form a five‑coordinated square pyramidal geometry.Complex 2 constitutes a polymeric structure,wherein each structural unit centrosymmetrically encompasses two five‑coordinated binuclear copper complexes(Cu1,Cu2)of 9,10‑PAH,with similar square pyramidal geometry.A chlorine atom(Cl_(2)),located at the symmetry center,bridges Cu1 and Cu1A to connect the two binuclear copper structures.Meanwhile,the two five‑coordinated Cu2 atoms symmetrically bridge the adjacent structural units via one coordinated Cl atom,respectively,thus forming a 1D chain‑like polymeric structure.In vitro anticancer activity assessments revealed that 1 and 2 showed significant cytotoxicity even higher than cisplatin.Specifically,the IC_(50)values of 2 against HeLa‑229 and SK‑OV‑3 cancer cell lines were determined to be(5.92±0.32)μmol·L^(-1)and(6.48±0.39)μmol·L^(-1),respectively.2 could also block the proliferation of HeLa‑229 cells in S phase and significantly induce cell apoptosis.In addition,fluorescence quenching competition experiments suggested that 2 might interact with DNA by an intercalative binding mode,offering insights into its underlying anticancer mechanism.CCDC:2388918,1;2388919,2.
文摘Two Gd_(2)complexes,namely[Gd_(2)(dbm)_(2)(HL_(1))_(2)(CH_(3)OH)_(2)]·4CH_(3)OH(1)and[Gd_(2)(dbm)_(2)(L_(2))_(2)(CH_(3)OH)_(2)]·2CH_(3)OH(2),where H_(3)L_(1)=(Z)-N'-[4-(diethylamino)-2-hydroxybenzylidene]-2-hydroxyacetohydrazide,H_(2)L_(2)=(E)-N'-(5-bromo-2-hydroxy-3-methoxybenzylidene)nicotinohydrazide,Hdbm=dibenzoylmethane,have been constructed by adopting the solvothermal method.Structural characterization unveils that both complexes 1 and 2 are constituted by two Gd^(3+)ions,two dbm-ions,two CH_(3)OH molecules,and two polydentate Schiff-base ligands(HL_(1)^(2-)or L_(2)^(2-)).In addition,complex 1 contains four free methanol molecules,whereas complex 2 harbors two free methanol molecules.By investigating the interactions between complexes 1 and 2 and four types of bacteria(Bacillus subtilis,Escherichia coli,Staphylococcus aureus,Candida albicans),it was found that both complexes 1 and 2 exhibited potent antibacte-rial activities.The interaction mechanisms between the ligands H_(3)L_(1),H_(2)L_(2),complexes 1 and 2,and calf thymus DNA(CT-DNA)were studied using ultraviolet-visible spectroscopy,fluorescence titration,and cyclic voltammetry.The results demonstrated that both complexes 1 and 2 can intercalate into CT-DNA molecules,thereby inhibiting bacterial proliferation to achieve the antibacterial effects.CCDC:2401116,1;2401117,2.
基金supported by National Natural Science Foundation of China(No.523B2070,No.52225606).
文摘Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.
文摘2-substituted-1-amino-o-carboranes 2-R-1-NH_(2)-o-C_(2)B_(10)H_(10)(R=CH_(3),1a;R=Ph,1b)were synthesized and the reactions of these compounds with the yttrium dialkyl complex[Y(L)(CH_(2)SiMe3)_(2)](L=[2-(2,5-Me_(2)C_(4)H_(2)N)C_(6)H4NC(Ph)=NDipp]-,Dipp=2,6-iPr_(2)C_(6)H_(3))were investigated.The 1H NMR spectroscopy indicate that the reaction of ytrrium dialkyl complex with one equivalent of 2-R-1-NH_(2)-o-C_(2)B_(10)H_(10) produce the mixture of ytrrium alkyl-amido complex[Y(L)(2-R-1-NH-o-C_(2)B_(10)H_(10))(CH_(2)SiMe3)](R=CH_(3),2a;R=Ph,2b)and bis(amido)complex[Y(L)(2-R-1-NH-o-C_(2)B_(10)H_(10))_(2)](R=CH_(3),3a;R=Ph,3b).The yttrium bridging imido complex[Y(L)(2-CH_(3)-1-N-o-C_(2)B_(10)H_(10))]_(2)(4a)was obtained by heating the mixture at 55℃for 12 h.Complex 3a was isolated and characterized by treating the yttrium dialkyl complex with two equivalents of 1a.The structures of complexes 3a and 4a were verified by single-crystal Xray diffraction.CCDC:2424136,3a;2424137,4a.
文摘A novel 3D metal-organic framework(MOF)[Pr_(2)(L)_(3)(H_(2)O)5·H_(2)O]n(Pr-1),(H_(2)L=4,4'-oxybis(benzoic acid))with a rare structure of broken layer net,was constructed under the condition of solvothermal synthesis.The struc-ture and crystal net were analyzed and characterized.This rod net of Pr-1 is new to both RCSR and ToposPro data-bases,and is named as rn-12 as suggested.Due to the luminescent properties of H_(2)L and Pr(Ⅲ),the solid-state fluo-rescence property and sensing performance(solvents and metal ions)of Pr-1 were investigated.The sensing experi-ments indicated that Pr-1 could act as a fluorescence sensor to detect Cd^(2+)ions with good sensitivity.In addition,antibacterial activities show that Pr-1 exhibited stronger antibacterial activity against Escherichia coli(E.coli),Staphylococcus aureus(S.aureus),and Bacillus subtilis(B.subtilis)compared to synthetic materials.
基金Projects(52222404,52074212)supported by the National Natural Science Foundation of ChinaProject(2023-LL-QY-07)supported by the Two-chain Integration Key Projects in Shaanxi Province,China。
文摘As the second most important solid waste produced by coal-fired power plants,the improper management of coal-fired slag has the potential to result in environmental pollution.It is therefore imperative that high-value utilization pathways for coal-fired slag should be developed.In this study,modified magnesium slag(MMS),produced by a magnesium smelter,was selected as the alkali activator.The activated silica-aluminum solid wastes,namely coal-fired slag(CFS)and mineral powder(MP),were employed as pozzolanic materials in the preparation of alkali-activated cementitious materials.The alkali-activated cementitious materials prepared with 50 wt%MMS,40 wt%CFS and 10 wt%MP exhibited favorable mechanical properties,with a compressive strength of 32.804 MPa in the paste sample cured for 28 d.Then,the activated silica-aluminum solid waste consisting of CFS-MP generated a significant amount of C-S(A)-H gels,AFt,and other products,which were observed to occupy the pore structure of the specimen.In addition,the secondary hydration reaction of CFS-MP occurs in high alkalinity environments,resulting in the formation of a mutually stimulated and promoted reaction system between CFS-MP and MMS,this will subsequently accelerate the hydrolysis reaction of MMS.It is important to emphasize that the amount of MMS in alkali-activated cementitious materials must be strictly regulated to avert the potential issue of incomplete depolymerization-repolymerization of active silica-aluminum solid waste containing CFS-MP.This in turn could have a deleterious impact on the late strength of the cementitious materials.The aim of this work is to improve the joint disposal of MMS,CFS and MP and thereby provide a scientific basis for the development of environmentally friendly and low-carbon modified magnesium slag alkali-activated coal-fired slag based cementitious materials for mine backfilling.
文摘Objective Magnetoencephalography(MEG),a non-invasive neuroimaging technique,meticulously captures the magnetic fields emanating from brain electrical activity.Compared with MEG based on superconducting quantum interference devices(SQUID),MEG based on optically pump magnetometer(OPM)has the advantages of higher sensitivity,better spatial resolution and lower cost.However,most of the current studies are clinical studies,and there is a lack of animal studies on MEG based on OPM technology.Pain,a multifaceted sensory and emotional phenomenon,induces intricate alterations in brain activity,exhibiting notable sex differences.Despite clinical revelations of pain-related neuronal activity through MEG,specific properties remain elusive,and comprehensive laboratory studies on pain-associated brain activity alterations are lacking.The aim of this study was to investigate the effects of inflammatory pain(induced by Complete Freund’s Adjuvant(CFA))on brain activity in a rat model using the MEG technique,to analysis changes in brain activity during pain perception,and to explore sex differences in pain-related MEG signaling.Methods This study utilized adult male and female Sprague-Dawley rats.Inflammatory pain was induced via intraplantar injection of CFA(100μl,50%in saline)in the left hind paw,with control groups receiving saline.Pain behavior was assessed using von Frey filaments at baseline and 1 h post-injection.For MEG recording,anesthetized rats had an OPM positioned on their head within a magnetic shield,undergoing two 15-minute sessions:a 5-minute baseline followed by a 10-minute mechanical stimulation phase.Data analysis included artifact removal and time-frequency analysis of spontaneous brain activity using accumulated spectrograms,generating spectrograms focused on the 4-30 Hz frequency range.Results MEG recordings in anesthetized rats during resting states and hind paw mechanical stimulation were compared,before and after saline/CFA injections.Mechanical stimulation elevated alpha activity in both male and female rats pre-and post-saline/CFA injections.Saline/CFA injections augmented average power in both sexes compared to pre-injection states.Remarkably,female rats exhibited higher average spectral power 1 h after CFA injection than after saline injection during resting states.Furthermore,despite comparable pain thresholds measured by classical pain behavioral tests post-CFA treatment,female rats displayed higher average power than males in the resting state after CFA injection.Conclusion These results imply an enhanced perception of inflammatory pain in female rats compared to their male counterparts.Our study exhibits sex differences in alpha activities following CFA injection,highlighting heightened brain alpha activity in female rats during acute inflammatory pain in the resting state.Our study provides a method for OPM-based MEG recordings to be used to study brain activity in anaesthetized animals.In addition,the findings of this study contribute to a deeper understanding of pain-related neural activity and pain sex differences.
文摘Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.
文摘Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,their practical use is hindered by the slow redox kinetics of sulfur and the“shuttle effect”arising from dissolved lithium polysulfides(LiPSs).In recent years,various carbon-based materials have served as sulfur hosts and catalysts for accelerating sulfur conversion redox kinetics and alleviating LiPS shuttling.However,they often suffer from irreversible passivation and structural changes that destroy their long-term performance.We consider the main problems limiting their stability,including excessive LiPS adsorption,passivation by insulating Li2S,and surface reconstruction,and clarify how these factors lead to capacity fade.We then outline effective strategies for achieving long-term sulfur catalysis,focusing on functional carbon,such as designing suitable carbon-supported catalyst interfaces,creating well-distributed active sites,adding cocatalysts to improve electron transfer,and using carbon-based protective layers to suppress unwanted side reactions.Using this information should enable the development of stable,high-activity catalysts capable of long-term operation under practical conditions in Li-S batteries.
文摘To detect space gravitational waves in the extremely low-frequency band,the telescope and optic-al platform require high stability and reliability.However,the cantilevered design presents challenges,espe-cially in the glass-metal hetero-bonding process.This study focuses on the analysis and experimental re-search of the bonding layer in the integrated structure.By optimizing the structural configuration and select-ing suitable bonding processes,the reliability of the telescope system is enhanced.The research indicates that using J-133 adhesive achieves the best performance,with a bonding layer thickness of 0.30 mm and a metal substrate surface roughness of Ra 0.8.These findings significantly enhance the reliability of the optical sys-tem while minimizing potential risks.
文摘In this paper,the failure caused by HRAM loads which were generated by high-speed projectile penetration,and protection technology of the fluid-filled structure were explored.A bubble was preset on the projectile trajectory in a fluid-filled structure.Based on the reflection and transmission phenomena of pressure waves at the gas-liquid interface and the compressibility characteristics of gases,a numerical analysis was conducted on the influence of preset bubble on projectile penetration and structural failure characteristics.The results indicate that the secondary water-entry impact phenomenon occurs when a preset bubble exists on the projectile trajectory,leading to the secondary water entry impact loads.The rarefaction waves reflected on the surface of the preset bubble cause the attenuation ratio of the initial impact pressure peak to reach 68.8%and the total specific impulse attenuation ratio to reach 48.6%.Furthermore,the larger the bubble,the faster the projectile,and the more obvious the attenuation effect.Moreover,due to the compressibility of the bubble,the global deformation attenuation ratio of the front and rear walls can reach over 80%.However,the larger the bubble size,the faster the projectile velocity,the smaller the local deformation attenuation effect of the rear wall,and the more severe the failure at the perforation of the rear wall.
文摘Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.
文摘Five cadmium naphthalene-diphosphonates,formulated as[Cd_(1.5)(1,4-ndpaH_(2))2(4,4'-bpyH)(4,4'-bpy)0.5(H_(2)O)_(2)]2(1),[Cd(1,4-ndpaH_(2))(1,4-bib)0.5(H_(2)O)](2),[Cd(1,4-ndpaH3)2(1,2-dpe)(H_(2)O)]·(1,2-dpe)·7H_(2)O(3),(1,2-bixH)[Cd3(1,4-ndpaH)(1,4-ndpaH_(2))2(H_(2)O)_(2)](4),and[Cd(1,4-ndpaH_(2))(H_(2)O)]·H_(2)O(5),have been synthesized from the selfassembly reactions of 1,4-naphthalenediphosphonic acid(1,4-ndpaH4)with Cd(NO3)2·4H_(2)O by introducing auxiliary ligands with variation of rigidity,such as 4,4'-bipyridine(4,4'-bpy),1,4-bis(1-imidazolyl)benzene(1,4-bib),1,2-di(4-pyridyl)ethylene(1,2-dpe),1,3-di(4-pyridyl)propane(1,3-dpp),and bis(imidazol-1-ylmethyl)benzene(1,2-bix),respectively.Structure resolution by single-crystal X-ray diffraction reveals that compound 1 possesses a layered framework,in which the{Cd3(PO2)2}trimers made up of corner-sharing two{CdO4N2}and one{CdO6}octahedra are connected by phosphonate groups,forming a ribbon,which are cross-linked by 4,4'-bipy ligands,forming a 2D layer.Compound 2 shows a 3D open-framework structure,where chains of corner-sharing{CdO4N}trigonal bipyramids and{PO3C}tetrahedra are cross-linked by 1,4-bib and/or phosphonate groups.A 1D ladder-like chain structure is found in compound 3,where the ladder-like chains made up of corner-sharing{CdO5N}octahedra and{PO3C}tetra hedra are connected by 1,4-ndpaH_(2)^(2-).Both compounds 4 and 5 obtained by the introduction of flexible ligands during the synthesis show a 2D layered structure,which is formed by ligand crosslinking double metal chains.Interestingly,In 4,flexible 1,2-bix was singly protonated,as guest molecules,filled between layer and layer,while flexible ligand 1,3-dpp is absent in 5.Photophysical measurements indicate that compounds 1-5 show ligand-centered emissions.
基金National Key Research and Development Program of China(2022YFE0206300)National Natural Science Foundation of China(U21A2081,22075074,22209047)+2 种基金Guangdong Basic and Applied Basic Research Foundation(2024A1515011620)Hunan Provincial Natural Science Foundation of China(2024JJ5068)Foundation of Yuelushan Center for Industrial Innovation(2023YCII0119)。
文摘Changes to the microstructure of a hard carbon(HC)and its solid electrolyte interface(SEI)can be effective in improving the electrode kinetics.However,achieving fast charging using a simple and inexpensive strategy without sacrificing its initial Coulombic efficiency remains a challenge in sodium ion batteries.A simple liquid-phase coating approach has been used to generate a pitch-derived soft carbon layer on the HC surface,and its effect on the porosity of HC and SEI chemistry has been studied.A variety of structural characterizations show a soft carbon coating can increase the defect and ultra-micropore contents.The increase in ultra-micropore comes from both the soft carbon coatings and the larger pores within the HC that are partially filled by pitch,which provides more Na+storage sites.In-situ FTIR/EIS and ex-situ XPS showed that the soft carbon coating induced the formation of thinner SEI that is richer in NaF from the electrolyte,which stabilized the interface and promoted the charge transfer process.As a result,the anode produced fastcharging(329.8 mAh g^(−1)at 30 mA g^(−1)and 198.6 mAh g^(−1)at 300 mA g^(−1))and had a better cycling performance(a high capacity retention of 81.4%after 100 cycles at 150 mA g^(−1)).This work reveals the critical role of coating layer in changing the pore structure,SEI chemistry and diffusion kinetics of hard carbon,which enables rational design of sodium-ion battery anode with enhanced fast charging capability.
文摘A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.
文摘Hollow multi-shelled structure(HoMS)is the novel multifunctional structural system,which are con-structed with nanoparticles as structural units,featuring two or more shells,multiple interfaces,and numerous chan-nels and demonstrating outstanding properties in energy conversion and mass transfer.In recent years,owing to the breakthroughs in synthetic methods,the diversity of composition and structure of HoMS has been greatly enriched,showing broad application prospects in energy,catalysis,environment and other fields.This review focuses on the research status of HoMS for catalytic applications.Firstly,the new synthesis method for HoMS,namely the sequen-tial templating approach,is introduced from both practical and theoretical perspectives.Then,it summarizes and discusses the structure-performance relationship between the shell structure and catalytic performance.The unique temporal-spatial ordering property of mass transport in HoMS and the major breakthroughs it brings in catalytic applications are discussed.Finally,it looks forward to the opportunities and challenges in the development of HoMS.
文摘The development of sustainable electrode materials for energy storage systems has become very important and porous carbons derived from biomass have become an important candidate because of their tunable pore structure,environmental friendliness,and cost-effectiveness.Recent advances in controlling the pore structure of these carbons and its relationship between to is energy storage performance are discussed,emphasizing the critical role of a balanced distribution of micropores,mesopores and macropores in determining electrochemical behavior.Particular attention is given to how the intrinsic components of biomass precursors(lignin,cellulose,and hemicellulose)influence pore formation during carbonization.Carbonization and activation strategies to precisely control the pore structure are introduced.Finally,key challenges in the industrial production of these carbons are outlined,and future research directions are proposed.These include the establishment of a database of biomass intrinsic structures and machine learning-assisted pore structure engineering,aimed at providing guidance for the design of high-performance carbon materials for next-generation energy storage devices.
文摘Thermally activated delayed fluorescence(TADF)molecules have outstanding potential for applications in organic light-emitting diodes(OLEDs).Due to the lack of systematic studies on the correlation between molecular structure and luminescence properties,TADF molecules are far from meeting the needs of practical applications in terms of variety and number.In this paper,three twisted TADF molecules are studied and their photophysical properties are theoretically predicted based on the thermal vibrational correlation function method combined with multiscale calculations.The results show that all the molecules exhibit fast reverse intersystem crossing(RISC)rates(kRISC),predicting their TADF luminescence properties.In addition,the binding of DHPAzSi as the donor unit with different acceptors can change the dihedral angle between the ground and excited states,and the planarity of the acceptors is positively correlated with the reorganization energy,a property that has a strong influence on the non-radiative process.Furthermore,a decrease in the energy of the molecular charge transfer state and an increase in the kRISC were observed in the films.This study not only provides a reliable explanation for the observed experimental results,but also offers valuable insights that can guide the design of future TADF molecules.
基金supported by the National Natural Science Foundation of China(Grant Nos.52272208,22309057)the Natural Science Foundation of Hubei Province(Grant No.2023AFB355)the Fundamental Research Funds for the Central Universities of China(Grant No.2662022LXQD001).
文摘Dual-ion batteries(DIBs)usually use carbon-based materials as electrodes,showing advantages in high operating volt-age,potential low cost,and environmental friendliness.Different from conventional“rocking chair”type secondary batter-ies,DIBs perform a unique working mechanism,which employ both cation and anion taking part in capacity contribution at an anode and a cathode,respectively,during electrochemical reactions.Graphite has been identified as a suitable cathode material for anion intercalation at high voltages(>4.8 V)with fast reaction kinetics.However,the development of DIBs is being hindered by dynamic mismatch between a cathode and an anode due to sluggish Li+diffusion at a high rate.Herein,we prepared phyllostachys edulis derived carbon(PEC)through microstructure regulation strategy and investigated the carbonized temperature effect,which effectively tailored the rich short-range ordered graphite microdomains and disor-dered amorphous regions,as well as a unique nano-pore hierarchical structure.The pore size distribution of nano-pores was concentrated in 0.5-5 nm,providing suitable channels for rapid Li+transportation.It was found that PEC-500(carbon-ized at 500℃)achieved a high capacity of 436 mAh·g^(-1)at 300 mA·g^(-1)and excellent rate performance(maintaining a high capacity of 231 mAh·g^(-1)at 3 A·g^(-1)).The assembled dual-carbon PEC-500||graphite full battery delivered 114 mAh·g^(-1)at 10 C with 96%capacity retention after 3000 cycles and outstanding rate capability,providing 74 mAh·g^(-1)at 50 C.
文摘A new cobalt(Ⅱ)-radical complex:[Co(im4-py)_(2)(PNB)_(2)](im4-py=2-(4'-pyridyl)-4,4,5,5-tetramethylimidazole-1-oxyl,HPNB=p-nitrobenzoic acid)has been synthesized and characterized by X-ray diffraction analysis,elemental analysis,IR,and magnetic properties.X-ray diffraction analysis shows that the complex exists as mononuclear molecules and Co(Ⅱ)ion is four-coordinated with two radicals and two PNB-ligands.The magnetic susceptibility study indicates the complex exhibits weak ferromagnetic interactions between cobalt(Ⅱ)and im4-py radical.The magnetic property is explained by the magnetic and structure exchange mechanism.CCDC:976028.
