Based on inspection data,the authors analyze and summarize the main types and distribution characteristics of tunnel structural defects.These defects are classified into three types:surface defects,internal defects,an...Based on inspection data,the authors analyze and summarize the main types and distribution characteristics of tunnel structural defects.These defects are classified into three types:surface defects,internal defects,and defects behind the structure.To address the need for rapid detection of different defect types,the current state of rapid detection technologies and equipment,both domestically and internationally,is systematically reviewed.The research reveals that surface defect detection technologies and equipment have developed rapidly in recent years.Notably,the integration of machine vision and laser scanning technologies have significantly improved detection efficiency and accuracy,achieving crack detection precision of up to 0.1 mm.However,the non-contact rapid detection of internal and behind-the-structure defects remains constrained by hardware limitations,with traditional detection remaining dominant.Nevertheless,phased array radar,ultrasonic,and acoustic vibration detection technologies have become research hotspots in recent years,offering promising directions for detecting these challenging defect types.Additionally,the application of multisensor fusion technology in rapid detection equipment has further enhanced detection capabilities.Devices such as cameras,3D laser scanners,infrared thermal imagers,and radar demonstrate significant advantages in rapid detection.Future research in tunnel inspection should prioritize breakthroughs in rapid detection technologies for internal and behind-the-structure defects.Efforts should also focus on developing multifunctional integrated detection vehicles that can simultaneously inspect both surface and internal structures.Furthermore,progress in fully automated,intelligent systems with precise defect identification and real-time reporting will be essential to significantly improve the efficiency and accuracy of tunnel inspection.展开更多
It is of great scientific significance to construct a 3D dynamic structural color with a special color effect based on the microlens array.However,the problems of imperfect mechanisms and poor color quality need to be...It is of great scientific significance to construct a 3D dynamic structural color with a special color effect based on the microlens array.However,the problems of imperfect mechanisms and poor color quality need to be solved.A method of 3D structural color turning on periodic metasurfaces fabricated by the microlens array and self-assembly technology was proposed in this study.In the experiment,Polydimethylsiloxane(PDMS)flexible film was used as a substrate,and SiO2 microspheres were scraped into grooves of the PDMS film to form 3D photonic crystal structures.By adjusting the number of blade-coated times and microsphere concentrations,high-saturation structural color micropatterns were obtained.These films were then matched with microlens arrays to produce dynamic graphics with iridescent effects.The results showed that by blade-coated two times and SiO2 microsphere concentrations of 50%are the best conditions.This method demonstrates the potential for being widely applied in the anticounterfeiting printing and ultra-high-resolution display.展开更多
This study aimed to investigate the effect of ultrasound-assisted alkaline extraction(UAE)(at 20 kHz and different powers of 0,200,300,400,500 and 600 W for 10 min)on the yield,structure and emulsifying properties of ...This study aimed to investigate the effect of ultrasound-assisted alkaline extraction(UAE)(at 20 kHz and different powers of 0,200,300,400,500 and 600 W for 10 min)on the yield,structure and emulsifying properties of chickpea protein isolate(CPI).Compared with the non-ultrasound group,ultrasound treatment at 400 W resulted in the largest increase in CPI yield,and both the particle size and turbidity decreased with increasing ultrasound power from 0 to 400 W.The scanning electron microscope results showed a uniform structural distribution of CPI.Moreover,itsα-helix content increased,β-sheet content decreased,and total sulfhydryl group content and endogenous fluorescence intensity rose,illustrating that UAE changed the secondary and tertiary structure of CPI.At 400 W,the solubility of the emulsion increased to 63.18%,and the best emulsifying properties were obtained;the emulsifying activity index(EAI)and emulsifying stability index(ESI)increased by 85.42%and 46.78%,respectively.Furthermore,the emulsion droplets formed were smaller and more uniform.In conclusion,proper UAE power conditions increased the extraction yield and protein content of CPI,and effectively improved its structure and emulsifying characteristics.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
Isoflavones which mainly distributed in leguminous plants have plenty of health benefits.Isoflavone synthase(IFS)is a membrane-associated cytochrome P450 enzyme(CYP450)which carries out the unique aryl-ring migration ...Isoflavones which mainly distributed in leguminous plants have plenty of health benefits.Isoflavone synthase(IFS)is a membrane-associated cytochrome P450 enzyme(CYP450)which carries out the unique aryl-ring migration and hydroxylation.So far,few crystal structures of plant P450s have been obtained.We determined the crystal structure of IFS from Medicago truncatula at 1.9 by MAD method using a selenomethionine substituted crystal and conducted molecular docking and mutagenesis study.The structure of IFS complexed with imidazole exhibits the helix Iα-loop-helix Iβmotif which corresponds to helix I of other P 450s.Compared with structures of common P450s,IFS/imidazole structure contains an extra domain,i.e.,theγ-domain.The structure reveals a homodimer in which theγ-domain of one molecule interacts with theβ-domain of another.The plane of heme group makes an angle of approximately 40°with the helix Iα-loop-helix Iβmotif.Molecular docking combined with mutagenesis study suggested that Trp-128 and Asp-300 might play important roles in substrate binding and recognition.Phe-301,Ser-303 and Gly-305 from the helix Iα-loop-helix Iβmotif may play important roles in the aryl-ring migration.These novel structural features reveal insights into the unique reaction mechanism of IFS and provide a basis for engineering IFS in leguminous crops for health purpose.展开更多
The spatial relationship between structural planes and principal stresses significantly affects the mechanical properties of deep hard rock.This paper examines the effect of the loading angle under true triaxial compr...The spatial relationship between structural planes and principal stresses significantly affects the mechanical properties of deep hard rock.This paper examines the effect of the loading angle under true triaxial compression.While previous studies focused on the angleβbetween the maximum principal stress and the structural plane,the role of angleω,between the intermediate principal stress and the structural plane,is often overlooked.Utilizing artificially prefabricated granite specimens with a single non-penetrating structural plane,we set the loading angleβto range from 0°to 90°across seven groups,and assignedωvalues of 0°and 90°in two separate groups.The results show that the peak strength is negatively correlated withβup to 45°,beyond which it tends to stabilize.The angleωexerts a strengthening effect on the peak strength.Deformation mainly occurs post-peak,with the strain values ε_(1) and ε_(3) reaching levels 2−3 times higher than those in intact rock.The structural plane significantly influences failure mode whenω=0°,while failure localizes near the σ_(3) surface of the specimens whenω=90°.The findings enhance data on structural plane rocks under triaxial compression and inform theoretical research,excavation,and support design of rock structures.展开更多
A series of ballistic experiments were performed to investigate the damage behavior of high velocity reactive material projectiles(RMPs) impacting liquid-filled tanks,and the corresponding hydrodynamic ram(HRAM) was s...A series of ballistic experiments were performed to investigate the damage behavior of high velocity reactive material projectiles(RMPs) impacting liquid-filled tanks,and the corresponding hydrodynamic ram(HRAM) was studied in detail.PTFE/Al/W RMPs with steel-like and aluminum-like densities were prepared by a pressing/sintering process.The projectiles impacted a liquid-filled steel tank with front aluminum panel at approximately 1250 m/s.The corresponding cavity evolution characteristics and HRAM pressure were recorded by high-speed camera and pressure acquisition system,and further compared to those of steel and aluminum projectiles.Significantly different from the conical cavity formed by the inert metal projectile,the cavity formed by the RMP appeared as an ellipsoid with a conical front.The RMPs were demonstrated to enhance the radial growth velocity of cavity,the global HRAM pressure amplitude and the front panel damage,indicating the enhanced HRAM and structural damage behavior.Furthermore,combining the impact-induced fragmentation and deflagration characteristics,the cavity evolution of RMPs under the combined effect of kinetic energy impact and chemical energy release was analyzed.The mechanism of enhanced HRAM pressure induced by the RMPs was further revealed based on the theoretical model of the initial impact wave and the impulse analysis.Finally,the linear correlation between the deformation-thickness ratio and the non-dimensional impulse for the front panel was obtained and analyzed.It was determined that the enhanced near-field impulse induced by the RMPs was the dominant reason for the enhanced structural damage behavior.展开更多
Structural health monitoring is widely utilized in outdoor environments,especially under harsh conditions,which can introduce noise into the monitoring system.Therefore,designing an effective denoising strategy to enh...Structural health monitoring is widely utilized in outdoor environments,especially under harsh conditions,which can introduce noise into the monitoring system.Therefore,designing an effective denoising strategy to enhance the performance of guided wave damage detection in noisy environments is crucial.This paper introduces a local temporal principal component analysis(PCA)reconstruction approach for denoising guided waves prior to implementing unsupervised damage detection,achieved through novel autoencoder-based reconstruction.Experimental results demonstrate that the proposed denoising method significantly enhances damage detection performance when guided waves are contaminated by noise,with SNR values ranging from 10 to-5 dB.Following the implementation of the proposed denoising approach,the AUC score can elevate from 0.65 to 0.96 when dealing with guided waves corrputed by noise at a level of-5 dB.Additionally,the paper provides guidance on selecting the appropriate number of components used in the denoising PCA reconstruction,aiding in the optimization of the damage detection in noisy conditions.展开更多
By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variationa...By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variational Zn-salen ligands RZn and NADH(reduced nicotinamide adenine dinucleotide)mimic modified tridentate ligands with square-planar Pd ions.UV-Vis and luminescence spectra experiments reveal that different anions could selec-tively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound,by using the differentiated host-guest electrostatic interactions of counter ions with metal-organic hosts.Compared to other anions,the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd‑R(Zn),meanwhile,the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease,and the metal-to-ligand induced peak displayed a blue shift effect.Circular dichro-ism and ^(1)H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold.展开更多
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
Nitrogen-rich heterocyclic energetic compounds(NRHECs)and their salts have witnessed widespread synthesis in recent years.The substantial energy-density content within these compounds can lead to potentially dangerous...Nitrogen-rich heterocyclic energetic compounds(NRHECs)and their salts have witnessed widespread synthesis in recent years.The substantial energy-density content within these compounds can lead to potentially dangerous explosive reactions when subjected to external stimuli such as electrical discharge.Therefore,developing a reliable model for predicting their electrostatic discharge sensitivity(ESD)becomes imperative.This study proposes a novel and straightforward model based on the presence of specific groups(-NH_(2) or-NH-,-N=N^(+)-O^(-)and-NNO_(2),-ONO_(2) or-NO_(2))under certain conditions to assess the ESD of NRHECs and their salts,employing interpretable structural parameters.Utilizing a comprehensive dataset comprising 54 ESD measurements of NRHECs and their salts,divided into 49/5 training/test sets,the model achieves promising results.The Root Mean Square Error(RMSE),Mean Absolute Error(MAE),and Maximum Error for the training set are reported as 0.16 J,0.12 J,and 0.5 J,respectively.Notably,the ratios RMSE(training)/RMSE(test),MAE(training)/MAE(test),and Max Error(training)/Max Error(test)are all greater than 1.0,indicating the robust predictive capabilities of the model.The presented model demonstrates its efficacy in providing a reliable assessment of ESD for the targeted NRHECs and their salts,without the need for intricate computer codes or expert involvement.展开更多
In this paper,Brazilian test was performed on disk samples of analogue materials with defined structural planes.The surface strain evolution process of the disk samples during loading was analyzed via digital image co...In this paper,Brazilian test was performed on disk samples of analogue materials with defined structural planes.The surface strain evolution process of the disk samples during loading was analyzed via digital image correlation.The damage evolution process was explored from a microscopic perspective by combining discrete element numerical simulation technology.The criterion of the failure mode of the disc specimen in the split state was theoretically deduced.The influence of structural surface roughness and loading inclination angle on the stress state at the center of the specimen was explored.The results showed that the failure modes of the samples could be divided into three typical modes as matrix failure,structural plane failure and combination failure.The rough structural plane improves the failure strength of the specimen by limiting its lateral deformation,and the degree of improvement weakens continuously with the increase of the inclination angle of the structural plane.As the inclination angle of the structural plane increases,the main type of microcracks in the structural plane changes from shear microcracks to tensile microcracks.This study contributes to a better understanding of macro-and meso-failure characteristics of rock masses with structural planes under a splitting state.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
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
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
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
文摘Based on inspection data,the authors analyze and summarize the main types and distribution characteristics of tunnel structural defects.These defects are classified into three types:surface defects,internal defects,and defects behind the structure.To address the need for rapid detection of different defect types,the current state of rapid detection technologies and equipment,both domestically and internationally,is systematically reviewed.The research reveals that surface defect detection technologies and equipment have developed rapidly in recent years.Notably,the integration of machine vision and laser scanning technologies have significantly improved detection efficiency and accuracy,achieving crack detection precision of up to 0.1 mm.However,the non-contact rapid detection of internal and behind-the-structure defects remains constrained by hardware limitations,with traditional detection remaining dominant.Nevertheless,phased array radar,ultrasonic,and acoustic vibration detection technologies have become research hotspots in recent years,offering promising directions for detecting these challenging defect types.Additionally,the application of multisensor fusion technology in rapid detection equipment has further enhanced detection capabilities.Devices such as cameras,3D laser scanners,infrared thermal imagers,and radar demonstrate significant advantages in rapid detection.Future research in tunnel inspection should prioritize breakthroughs in rapid detection technologies for internal and behind-the-structure defects.Efforts should also focus on developing multifunctional integrated detection vehicles that can simultaneously inspect both surface and internal structures.Furthermore,progress in fully automated,intelligent systems with precise defect identification and real-time reporting will be essential to significantly improve the efficiency and accuracy of tunnel inspection.
文摘It is of great scientific significance to construct a 3D dynamic structural color with a special color effect based on the microlens array.However,the problems of imperfect mechanisms and poor color quality need to be solved.A method of 3D structural color turning on periodic metasurfaces fabricated by the microlens array and self-assembly technology was proposed in this study.In the experiment,Polydimethylsiloxane(PDMS)flexible film was used as a substrate,and SiO2 microspheres were scraped into grooves of the PDMS film to form 3D photonic crystal structures.By adjusting the number of blade-coated times and microsphere concentrations,high-saturation structural color micropatterns were obtained.These films were then matched with microlens arrays to produce dynamic graphics with iridescent effects.The results showed that by blade-coated two times and SiO2 microsphere concentrations of 50%are the best conditions.This method demonstrates the potential for being widely applied in the anticounterfeiting printing and ultra-high-resolution display.
文摘This study aimed to investigate the effect of ultrasound-assisted alkaline extraction(UAE)(at 20 kHz and different powers of 0,200,300,400,500 and 600 W for 10 min)on the yield,structure and emulsifying properties of chickpea protein isolate(CPI).Compared with the non-ultrasound group,ultrasound treatment at 400 W resulted in the largest increase in CPI yield,and both the particle size and turbidity decreased with increasing ultrasound power from 0 to 400 W.The scanning electron microscope results showed a uniform structural distribution of CPI.Moreover,itsα-helix content increased,β-sheet content decreased,and total sulfhydryl group content and endogenous fluorescence intensity rose,illustrating that UAE changed the secondary and tertiary structure of CPI.At 400 W,the solubility of the emulsion increased to 63.18%,and the best emulsifying properties were obtained;the emulsifying activity index(EAI)and emulsifying stability index(ESI)increased by 85.42%and 46.78%,respectively.Furthermore,the emulsion droplets formed were smaller and more uniform.In conclusion,proper UAE power conditions increased the extraction yield and protein content of CPI,and effectively improved its structure and emulsifying characteristics.
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Isoflavones which mainly distributed in leguminous plants have plenty of health benefits.Isoflavone synthase(IFS)is a membrane-associated cytochrome P450 enzyme(CYP450)which carries out the unique aryl-ring migration and hydroxylation.So far,few crystal structures of plant P450s have been obtained.We determined the crystal structure of IFS from Medicago truncatula at 1.9 by MAD method using a selenomethionine substituted crystal and conducted molecular docking and mutagenesis study.The structure of IFS complexed with imidazole exhibits the helix Iα-loop-helix Iβmotif which corresponds to helix I of other P 450s.Compared with structures of common P450s,IFS/imidazole structure contains an extra domain,i.e.,theγ-domain.The structure reveals a homodimer in which theγ-domain of one molecule interacts with theβ-domain of another.The plane of heme group makes an angle of approximately 40°with the helix Iα-loop-helix Iβmotif.Molecular docking combined with mutagenesis study suggested that Trp-128 and Asp-300 might play important roles in substrate binding and recognition.Phe-301,Ser-303 and Gly-305 from the helix Iα-loop-helix Iβmotif may play important roles in the aryl-ring migration.These novel structural features reveal insights into the unique reaction mechanism of IFS and provide a basis for engineering IFS in leguminous crops for health purpose.
基金Projects(51979268,52279117,52309146)supported by the National Natural Science Foundation of ChinaProject(SKLGME-JBGS2401)supported by the Fund of State Key Laboratory of Geomechanics and Geotechnical Engineering,China。
文摘The spatial relationship between structural planes and principal stresses significantly affects the mechanical properties of deep hard rock.This paper examines the effect of the loading angle under true triaxial compression.While previous studies focused on the angleβbetween the maximum principal stress and the structural plane,the role of angleω,between the intermediate principal stress and the structural plane,is often overlooked.Utilizing artificially prefabricated granite specimens with a single non-penetrating structural plane,we set the loading angleβto range from 0°to 90°across seven groups,and assignedωvalues of 0°and 90°in two separate groups.The results show that the peak strength is negatively correlated withβup to 45°,beyond which it tends to stabilize.The angleωexerts a strengthening effect on the peak strength.Deformation mainly occurs post-peak,with the strain values ε_(1) and ε_(3) reaching levels 2−3 times higher than those in intact rock.The structural plane significantly influences failure mode whenω=0°,while failure localizes near the σ_(3) surface of the specimens whenω=90°.The findings enhance data on structural plane rocks under triaxial compression and inform theoretical research,excavation,and support design of rock structures.
基金supported by the Youth Foundation of State Key Laboratory of Explosion Science and Technology (Grant No.QNKT22-12)the State Key Program of National Natural Science Foundation of China (Grant No.12132003)。
文摘A series of ballistic experiments were performed to investigate the damage behavior of high velocity reactive material projectiles(RMPs) impacting liquid-filled tanks,and the corresponding hydrodynamic ram(HRAM) was studied in detail.PTFE/Al/W RMPs with steel-like and aluminum-like densities were prepared by a pressing/sintering process.The projectiles impacted a liquid-filled steel tank with front aluminum panel at approximately 1250 m/s.The corresponding cavity evolution characteristics and HRAM pressure were recorded by high-speed camera and pressure acquisition system,and further compared to those of steel and aluminum projectiles.Significantly different from the conical cavity formed by the inert metal projectile,the cavity formed by the RMP appeared as an ellipsoid with a conical front.The RMPs were demonstrated to enhance the radial growth velocity of cavity,the global HRAM pressure amplitude and the front panel damage,indicating the enhanced HRAM and structural damage behavior.Furthermore,combining the impact-induced fragmentation and deflagration characteristics,the cavity evolution of RMPs under the combined effect of kinetic energy impact and chemical energy release was analyzed.The mechanism of enhanced HRAM pressure induced by the RMPs was further revealed based on the theoretical model of the initial impact wave and the impulse analysis.Finally,the linear correlation between the deformation-thickness ratio and the non-dimensional impulse for the front panel was obtained and analyzed.It was determined that the enhanced near-field impulse induced by the RMPs was the dominant reason for the enhanced structural damage behavior.
基金National Science Foundation of Zhejiang under Contract(LY23E010001)。
文摘Structural health monitoring is widely utilized in outdoor environments,especially under harsh conditions,which can introduce noise into the monitoring system.Therefore,designing an effective denoising strategy to enhance the performance of guided wave damage detection in noisy environments is crucial.This paper introduces a local temporal principal component analysis(PCA)reconstruction approach for denoising guided waves prior to implementing unsupervised damage detection,achieved through novel autoencoder-based reconstruction.Experimental results demonstrate that the proposed denoising method significantly enhances damage detection performance when guided waves are contaminated by noise,with SNR values ranging from 10 to-5 dB.Following the implementation of the proposed denoising approach,the AUC score can elevate from 0.65 to 0.96 when dealing with guided waves corrputed by noise at a level of-5 dB.Additionally,the paper provides guidance on selecting the appropriate number of components used in the denoising PCA reconstruction,aiding in the optimization of the damage detection in noisy conditions.
文摘By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variational Zn-salen ligands RZn and NADH(reduced nicotinamide adenine dinucleotide)mimic modified tridentate ligands with square-planar Pd ions.UV-Vis and luminescence spectra experiments reveal that different anions could selec-tively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound,by using the differentiated host-guest electrostatic interactions of counter ions with metal-organic hosts.Compared to other anions,the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd‑R(Zn),meanwhile,the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease,and the metal-to-ligand induced peak displayed a blue shift effect.Circular dichro-ism and ^(1)H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold.
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Nitrogen-rich heterocyclic energetic compounds(NRHECs)and their salts have witnessed widespread synthesis in recent years.The substantial energy-density content within these compounds can lead to potentially dangerous explosive reactions when subjected to external stimuli such as electrical discharge.Therefore,developing a reliable model for predicting their electrostatic discharge sensitivity(ESD)becomes imperative.This study proposes a novel and straightforward model based on the presence of specific groups(-NH_(2) or-NH-,-N=N^(+)-O^(-)and-NNO_(2),-ONO_(2) or-NO_(2))under certain conditions to assess the ESD of NRHECs and their salts,employing interpretable structural parameters.Utilizing a comprehensive dataset comprising 54 ESD measurements of NRHECs and their salts,divided into 49/5 training/test sets,the model achieves promising results.The Root Mean Square Error(RMSE),Mean Absolute Error(MAE),and Maximum Error for the training set are reported as 0.16 J,0.12 J,and 0.5 J,respectively.Notably,the ratios RMSE(training)/RMSE(test),MAE(training)/MAE(test),and Max Error(training)/Max Error(test)are all greater than 1.0,indicating the robust predictive capabilities of the model.The presented model demonstrates its efficacy in providing a reliable assessment of ESD for the targeted NRHECs and their salts,without the need for intricate computer codes or expert involvement.
基金Project(52274148)supported by the National Natural Science Foundation of ChinaProject(2022XJLJ01)supported by the Fundamental Research Funds for the Central Universities,China。
文摘In this paper,Brazilian test was performed on disk samples of analogue materials with defined structural planes.The surface strain evolution process of the disk samples during loading was analyzed via digital image correlation.The damage evolution process was explored from a microscopic perspective by combining discrete element numerical simulation technology.The criterion of the failure mode of the disc specimen in the split state was theoretically deduced.The influence of structural surface roughness and loading inclination angle on the stress state at the center of the specimen was explored.The results showed that the failure modes of the samples could be divided into three typical modes as matrix failure,structural plane failure and combination failure.The rough structural plane improves the failure strength of the specimen by limiting its lateral deformation,and the degree of improvement weakens continuously with the increase of the inclination angle of the structural plane.As the inclination angle of the structural plane increases,the main type of microcracks in the structural plane changes from shear microcracks to tensile microcracks.This study contributes to a better understanding of macro-and meso-failure characteristics of rock masses with structural planes under a splitting state.
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.
