Transition metal selenides as sodium-ion hybrid capacitor(SIHC)anodes still suffer from amorphization difficulties and capacity degradation triggered by polyselenide dissolution.Herein,an atomistic amorphous strategy ...Transition metal selenides as sodium-ion hybrid capacitor(SIHC)anodes still suffer from amorphization difficulties and capacity degradation triggered by polyselenide dissolution.Herein,an atomistic amorphous strategy is proposed to construct adjacent Nb-Nb diatomic pairs with Se/O-coordination(Se4-Nb2-O2)in N-doped carbon-confined amorphous selenide clusters(a-Nb-Se/O@NC).Synergistic carbon confinement and hydrothermal oxygenation induce amorphization of Nb–Se bonds,eliminating crystalline rigidity while creating isotropic dual-ion transport channels and high-density active sites enriched with dangling bonds,thereby enhancing structural integrity and Na+storage capacity.The unique Se/O-coordinated Nb-Nb diatomic configuration establishes an electron-delocalized system,where the low electronegativity of Se counterbalances electron withdrawal from coordinated O at Nb centers.These strengthen d-p orbital hybridization,reduce Na+adsorption energy,and optimize charge transfer pathways and reaction kinetics in the amorphous clusters.Electrochemical tests reveal that the a-Nb-Se/O@NC anode delivers a high reversible capacity of 312.57 mAh g^(−1)and exceptional cyclic stability(103%capacity retention)after 5000 cycles at 10.0 A g^(−1).Assembled SIHCs achieve outstanding energy/power densities(207.1 Wh kg^(−1)/18966 W kg^(−1)),surpassing most amorphous and crystalline counterparts.This work provides methodological insights for the design of electrodes in high-power storage devices through atomic modulation and electronic optimization of amorphous selenides.展开更多
In order to improve the trajectory tracking precision and reduce the synchronization error of a 6-DOF lightweight robot, nonlinear proportion-deviation （N-PD） cross-coupling synchronization control strategy based on...In order to improve the trajectory tracking precision and reduce the synchronization error of a 6-DOF lightweight robot, nonlinear proportion-deviation （N-PD） cross-coupling synchronization control strategy based on adjacent coupling error analysis is presented. The mathematical models of the robot, including kinematic model, dynamic model and spline trajectory planing, are established and verified. Since it is difficult to describe the real-time contour error of the robot for complex trajectory, the adjacent coupling error is analyzed to solve the problem. Combined with nonlinear control and coupling performance of the robot, N-PD cross-coupling synchronization controller is designed and validated by simulation analysis. A servo control experimental system which mainly consists of laser tracking system, the robot mechanical system and EtherCAT based servo control system is constructed. The synchronization error is significantly decreased and the maximum trajectory error is reduced from 0.33 mm to 0.1 mm. The effectiveness of the control algorithm is validated by the experimental results, thus the control strategy can improve the robot＇s trajectory tracking precision significantly.展开更多
A chromium(II)-catalyzed reduction cross coupling reaction was reported.This reaction utilizes inexpensive and readily available chromium dichloride as a catalyst and 4,4'-di-tert-butyl-bipyridine as a ligand to a...A chromium(II)-catalyzed reduction cross coupling reaction was reported.This reaction utilizes inexpensive and readily available chromium dichloride as a catalyst and 4,4'-di-tert-butyl-bipyridine as a ligand to achieve reduction cross coupling between trifluoromethyl olefins and alkyl bromides under mild conditions,effectively synthesizing difluoroalkene derivatives.This reaction exhibits good substrate universality and is compatible with multiple important functional groups,providing a concise synthetic pathway for constructing conjugated difluoroalkenes containing allyl difluoromethylene structural units.Preliminary mechanistic experiments indicate that alkyl bromides first undergo a reduction process to generate corresponding alkyl radicals,followed by addition to trifluoromethyl olefins.After binding with Cr(II),they undergo aβ-fluorine elimination process to generate difluoroalkenes.展开更多
Chiral carbonyl compounds frequently occur in natural products and pharmaceuticals. Additionally, they serve as important intermediates in organic synthesis. Transition metal-catalyzed asymmetric carbonylative cross-c...Chiral carbonyl compounds frequently occur in natural products and pharmaceuticals. Additionally, they serve as important intermediates in organic synthesis. Transition metal-catalyzed asymmetric carbonylative cross-coupling reactions are among the most straightforward and effective methods for synthesizing chiral carbonyl compounds, including esters, amides, and ketones. The advances in asymmetric carbonylative cross-coupling reactions using various O-, N-, C-, and S-containing nucleophiles or electrophiles over the past decade are summarized.展开更多
Selective defluorinative functionalization of trifluoromethylarenes(ArCF3)to obtain the pharmaceutically commonα,α-difluorobenzylic motif is an attractive and elegant synthetic route.Over the past decade,although C(...Selective defluorinative functionalization of trifluoromethylarenes(ArCF3)to obtain the pharmaceutically commonα,α-difluorobenzylic motif is an attractive and elegant synthetic route.Over the past decade,although C(sp^(3))-F bonds functionalization have been greatly developed,catalytic cross-coupling of trifluoromethylarenes with C-H of terminal alkynes remains a challenge.Here,we report an approach to achieve Sonogashira-type cross-coupling of trifluoromethylarenes with terminal alkynes C(sp)-H bonds via photoredox and Cu/L dual catalysis.Tridentate anionic ligand is pivotal to realize this C-H sp-sp^(3) cross-coupling.Moreover,this unique catalytic system is also suitable for cross-coupling of C(sp^(3))-F bonds with azoles C(sp^(2))-H bonds.A series of trifluoromethylarenes,terminal alkynes and azoles with various functional groups are compatible with this protocol affording a variety of defluoroalkynylation or defluoroazolation products.Preliminary mechanistic studies indicated that deprotonated BINOL involved as a photocatalyst to activate ArCF3 rather than a ligand to the metal.展开更多
In most Suzuki–Miyaura carbon-carbon cross-coupling reactions,the borabicyclo[3.3.1]nonane scaffold(9-BBN)only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products.The...In most Suzuki–Miyaura carbon-carbon cross-coupling reactions,the borabicyclo[3.3.1]nonane scaffold(9-BBN)only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products.There are rare examples where the 9-BBN derivatives serve as the potentially diverse C8 building blocks in cross-coupling reactions.Herein,we report a cobalt-catalyzed migratory carboncarbon cross-coupling reaction of the in situ formed 9-BBN ate complexes to afford diverse aryl-and alkyl-functionalized cyclooctenes.Preliminary mechanistic studies suggest the oxidation-induced cisbicyclo[3.3.0]oct-1-ylborane is the key intermediate in this migratory cross-coupling reaction,which promotes the development of other diverse migratory cross-coupling of borate complexes.展开更多
The switchable cross-coupling of indoles and pyridotriazoles through carbene insertion at C_(2)-or C_(3)-positon has been developed in this paper.This highly site-selective C-H carbenoid functionalization is determine...The switchable cross-coupling of indoles and pyridotriazoles through carbene insertion at C_(2)-or C_(3)-positon has been developed in this paper.This highly site-selective C-H carbenoid functionalization is determined by both the Rh-catalyst species and auxiliary groups.[Cp∗RhCl_(2)]_(2) and coordinating pyrimidyl group direct the C-H carbenoid functionalization to occur at the C_(2)-position,while Rh2OAc4 and noncoordinating benzyl group lead the reaction to occur at the C_(3)-position of the indoles.This regioselective C−H functionalization strategy is of significant importance for the discovery of indole drugs.展开更多
An N-heterocyclic carbene(NHC)catalyzed enantioselective cyclisation and trifluoromethylation of olefins with cinnamaldehydes via radical relay cross-coupling in the presence of Togni reagent is reported andδ-lactone...An N-heterocyclic carbene(NHC)catalyzed enantioselective cyclisation and trifluoromethylation of olefins with cinnamaldehydes via radical relay cross-coupling in the presence of Togni reagent is reported andδ-lactones tolerated with stereogenic centers atβ-andγ-positions are obtained in moderate to high yields and with high enantioselectivities.Further computational studies explain that the radical crosscoupling step is the key to determining the enantioselectivity.Energy analysis of key transition states and intermediates also provides a reasonable explanation for the difficulty of diastereoselective control.DFT calculations also reveal that the hydrogen-bonding interaction plays a vital role in the promotion of this chemistry.展开更多
Urban spaces are becoming increasingly congested,and excavations are frequently performed close to existing underground structures such as tunnels.Understanding the mechanical response of proximal soil and tunnels to ...Urban spaces are becoming increasingly congested,and excavations are frequently performed close to existing underground structures such as tunnels.Understanding the mechanical response of proximal soil and tunnels to these excavations is important for efficient and safe underground construction.However,previous investigations of this issue have predominantly made assumptions of plane-strain conditions and normal gravity states,and focused on the performance of tunnels affected by excavation and unloading in sandy strata.In this study,a 3D centrifuge model test is conducted to investigate the influence of excavation on an adjacent existing tunnel in normally consolidated clay.The testing results indicate that the excavation has a significant impact on the horizontal deformation of the retaining wall and tunnel.Moreover,the settlements of the ground surface and the tunnel are mainly affected by the long-term period after excavation.The excavation is found to induce ground movement towards the pit,resulting in prolonged fluctuations in pore water pressure and lateral earth pressure.The testing results are compared with numerical simulations,achieving consistency.A numerical parametric study on the tunnel location shows that when the tunnel is closer to the retaining wall,the decreases in lateral earth pressure and pore water pressure during excavation are more pronounced.展开更多
BACKGROUND Posterior lumbar interbody fusion has good clinical results,but adjacent segment disease(ASD)affects its long-term efficacy.In patients with L4-5 fusion who were followed up for more than 10 years,the ASD i...BACKGROUND Posterior lumbar interbody fusion has good clinical results,but adjacent segment disease(ASD)affects its long-term efficacy.In patients with L4-5 fusion who were followed up for more than 10 years,the ASD incidence was 33.3%.Magnetic resonance imaging(MRI)is key for ASD diagnosis,but metal artifacts from internal fixation limit its use;therefore,removing the artifacts is crucial for ASD diagnosis and treatment.AIM To evaluate the value of WARP MRI for patients with lumbar ASD.METHODS In our hospital,the lumbar spines of patients with ASD were assessed via lumbar MRI,including conventional sequences and sequences for artifacts.A PACS workstation was used for image measurement,analysis,and assessment,which mainly included measurement of the internal fixation implant artifact area,evaluation of the visibility of the anatomical structures surrounding the implant,and diagnostic assessment of ASD in the section.Conventional MRI data sequences and artifacts to sequence the contrast analysis of the MRI data.RESULTS A total of 30 patients with ASD after lumbar fusion and internal fixation were included in the study;the patients included 13 male and 17 female patients and were aged 66.03±5.83 years.The metal artifact area of the WARP T2-tirm sequence was significantly smaller than that of the conventional STIR sequence[(20.85±6.27)cm²vs(50.56±8.55)cm²,P<0.01].The WARP T2-tirm sequence was observed around the implants,pedicles,intervertebral foramen,and vertebral bodies,and the conventional STIR sequence clearly displayed nerve roots within the intervertebral foramen.In all 30 patients,all adjacent segments of the WARP T2-tirm sequence could be clearly observed(above Grade 4),whereas it was difficult to observe these segments in the conventional STIR sequence due to the presence of more severe metal artifacts.CONCLUSION WARP sequences can significantly reduce the artifact area in the sagittal and cross-sectional images of titanium alloy spinal fixation,providing a good imaging reference for the diagnosis of ASD.展开更多
The Pd-catalyzed Suzuki-Miyaura coupling reaction is a crucial tool for constructing C-C bonds.Currently,the organic solvents employed during reaction may cause serious environmental problems.Moreover,the low solubili...The Pd-catalyzed Suzuki-Miyaura coupling reaction is a crucial tool for constructing C-C bonds.Currently,the organic solvents employed during reaction may cause serious environmental problems.Moreover,the low solubility of inorganic bases in organic solvents leads to enormous mass transfer resistance.To address this issue,the Pickering droplets reactor stabilized by Pd/g-C_(3)N_(4)at substrate-water two-phase interface is reported.Benefiting from the hydrophobic conjugated framework and hydrophilic terminal groups,Pd/g-C_(3)N_(4)can configure stable Pickering emulsion without additional functionalization.The Pd loaded catalysts exhibits excellent performance(TOF=21852 h^(-1))for the Suzuki-Miyaura coupling reaction,which is deriving from unique electronic structure of g-C_(3)N_(4)and high interfacial area of emulsion.Moreover,there is no clear decrease in reactivity after six cycles(conversion>86%).In this study,the organic solvent was replaced by reaction substrate,and the high activity can be achieved for various halogenated aromatic hydrocarbons and their derivatives.展开更多
Cage plus plate(CP)and zero-profile(Zero-P)devices are widely used in anterior cervical discectomy and fusion(ACDF).This study aimed to compare adjacent segment biomechanical changes after ACDF when using Zero-P devic...Cage plus plate(CP)and zero-profile(Zero-P)devices are widely used in anterior cervical discectomy and fusion(ACDF).This study aimed to compare adjacent segment biomechanical changes after ACDF when using Zero-P device and CP in different segments.First,complete C1—C7 cervical segments were constructed and validated.Meanwhile,four surgery models were developed by implanting the Zero-P device or CP into C4—C5 or C5—C6 segments based on the intact model.The segmental range of motion(ROM)and maximum value of the intradiscal pressure of the surgery models were compared with those of the intact model.The implantation of CP and Zero-P devices in C4—C5 segments decreased ROM by about 91.6%and 84.3%,respectively,and increased adjacent segment ROM by about 8.3%and 6.82%,respectively.The implantation of CP and Zero-P devices in C5—C6 segments decreased ROM by about 93.3%and 89.9%,respectively,while increasing adjacent segment ROM by about 4.9%and 4%,respectively.Furthermore,the implantation of CP and Zero-P devices increased the intradiscal pressure in the adjacent segments of C4—C5 segments by about 4.5%and 6.7%,respectively.The implantation of CP and Zero-P devices significantly increased the intradiscal pressure in the adjacent segments of C5—C6 by about 54.1%and 15.4%,respectively.In conclusion,CP and Zero-P fusion systems can significantly reduce the ROM of the fusion implant segment in ACDF while increasing the ROM and intradiscal pressure of adjacent segments.Results showed that Zero-P fusion system is the best choice for C5—C6 segmental ACDF.However,further studies are needed to select the most suitable cervical fusion system for C4—C5 segmental ACDF.Therefore,this study provides biomechanical recommendations for clinical surgery.展开更多
This study presents a novel hybrid topology optimization and mold design framework that integrates process fitting,runner system optimization,and structural analysis to significantly enhance the performance of injecti...This study presents a novel hybrid topology optimization and mold design framework that integrates process fitting,runner system optimization,and structural analysis to significantly enhance the performance of injection-molded parts.At its core,the framework employs a greedy algorithm that generates runner systems based on adjacency and shortest path principles,leading to improvements in both mechanical strength and material efficiency.The design optimization is validated through a series of rigorous experimental tests,including three-point bending and torsion tests performed on key-socket frames,ensuring that the optimized designs meet practical performance requirements.A critical innovation of the framework is the development of the Adjacent Element Temperature-Driven Prestress Algorithm(AETDPA),which refines the prediction of mechanical failure and strength fitting.This algorithm has been shown to deliver mesh-independent accuracy,thereby enhancing the reliability of simulation results across various design iterations.The framework’s adaptability is further demonstrated by its ability to adjust optimization methods based on the unique geometry of each part,thus accelerating the overall design process while ensuring struc-tural integrity.In addition to its immediate applications in injection molding,the study explores the potential extension of this framework to metal additive manufacturing,opening new avenues for its use in advanced manufacturing technologies.Numerical simulations,including finite element analysis,support the experimental findings and confirm that the optimized designs provide a balanced combination of strength,durability,and efficiency.Furthermore,the integration challenges with existing injection molding practices are addressed,underscoring the framework’s scalability and industrial relevance.Overall,this hybrid topology optimization framework offers a computationally efficient and robust solution for advanced manufacturing applications,promising significant improvements in design efficiency,cost-effectiveness,and product performance.Future work will focus on further enhancing algorithm robustness and exploring additional applications across diverse manufacturing processes.展开更多
The cell density, species composition and distribution of phytoplankton, and their relations to environmental factors in Prydz Bay and its adjacent sea area, Antarctica (69degrees-77degrees E, 62degrees-70degrees S) d...The cell density, species composition and distribution of phytoplankton, and their relations to environmental factors in Prydz Bay and its adjacent sea area, Antarctica (69degrees-77degrees E, 62degrees-70degrees S) during the austral summer of 1998/1999 were investigated. A total of 48 taxa belonging to 21 genera of phytoplankton in the sea area were identified. The average cell density of phytoplankton was 22.46 x 10(3) cells/dm(3), of which diatoms were predominant (84.51%). The highest cell density of phytoplankton occurred in Prydz Bay and the adjacent continental shelf where the average cell density was 46.03 x 10(3) cells/dm(3). The lowest cell density (3.34 x 10(3) cells/dm(3)) occurred in deep sea area. The dominant species of phytoplankton was Fragilariopsis curta. The vertical distribution of phytoplankton density was highest in the upper part of 0-50 in depth, lower in 100 in and lowest in 150 in. The species composition and cell density of phytoplankton were influenced by water circulation. The cell density was positively correlated with water temperature and salinity, and negatively correlated with the concentration of nutrients.展开更多
Diurnal and semi-diurnal tides in the Taiwan Strait and its adjacent areas are calculated by using a two-dimensional finite-difference model. Compared with data of more than 20 observation stations around the Taiwan S...Diurnal and semi-diurnal tides in the Taiwan Strait and its adjacent areas are calculated by using a two-dimensional finite-difference model. Compared with data of more than 20 observation stations around the Taiwan Strait, the model-produced results agree quite well with those of previous researches using observational data from coastal tidal gauge stations. According to the results, the co-tidal and co-range charts are given. Furthermore, the characteristics of 8 major tidal constituents have been uminated respectively. The result shows that： （1） The tide motion can be attributed to the interaction between the degenerative rotary tidal system in the north and the progressive tidal system in the south. （2） The southward and northward tidal waves of semi-diurnal tide converge in the middle of the Taiwan Strait while the diurnal tidal waves propagate southwestward through the Taiwan Strait and the Luzon Strait. （3） The maximum amplitude of semi-diurnal tides exists at the area between the Meizhou Bay and Xinghua Bay, and that of diurnal tides appears in the region to the east of the Leizhou Peninsula, （4） The patterns of co-tidal and co-range charts of N2, K2 and P1, Q1 tidal constituents are similar to those of M2, S2 and K1 O1 tidat constituents, respectively展开更多
Pn velocity lateral variation and anisotropy images were reconstructed by adding about 50 000 travel times from the regional seismic networks to the datum set of near 40 000 travel times from National Seismic Network ...Pn velocity lateral variation and anisotropy images were reconstructed by adding about 50 000 travel times from the regional seismic networks to the datum set of near 40 000 travel times from National Seismic Network of China used by WANG, et al. We discussed the relation of Pn velocity variation to Moho depth, Earths heat flow, distribution of Cenozoic volcanic rock and the result of rock experiment under high pressure and high temperature. The result of quantitative analysis indicates that Pn velocity is positively correlated with the crust thickness and negatively correlated with the Earths heat flow. Two linear regression equations, one between Pn velocity and crust thickness, and the other between Pn velocity and heat flow, were obtained. The rate of variation of Pn veloc-ity vP with pressure P, Pv/p, estimated from the velocity variation with crust thickness Hv/p, is close to the result obtained from the rock experiment under high pressure and high temperature. If the effect of crust thick-ness on Pn velocity is deducted from the velocity variation, then the low Pn velocity beneath Qinghai-Xizang pla-teau is more notable. The low Pn velocity regions well agree with the Cenozoic volcanic rock. In the several re-gions with significant anisotropy, the direction of fast Pn velocity is consistent with the orientation of maximum principal crustal compressive stress, and also with the direction of present-day crustal movement. It indicates that the fast Pn velocity direction may be related to the deformation or flow of top mantle material along the direction of maximum pressure.展开更多
We assembled approximately 328 seismic records. The data set was from 4 digitally recording long-period and broadband stations of CDSN. We carried out the inversion based on the partitioned waveform inversion (PWI). I...We assembled approximately 328 seismic records. The data set was from 4 digitally recording long-period and broadband stations of CDSN. We carried out the inversion based on the partitioned waveform inversion (PWI). It partitions the large-scale optimization problem into a number of independent small-scale problems. We adopted surface waveform inversion with an equal block (2((2() discretization in order to acquire the images of shear velocity structure at different depths (from surface to 430 km) in the crust and upper-mantle. The resolution of all these anomalies has been established with (check-board( resolution tests. These results show significant difference in velocity, lithosphere and asthenosphere structure between South China Sea and its adjacent regions.展开更多
In order to improve the yield and reduce the cost in the synthesis of antitumor drug vismodegib the key intermediates are prepared and the Negishi reaction step is examined.The effects of different molar ratios of rea...In order to improve the yield and reduce the cost in the synthesis of antitumor drug vismodegib the key intermediates are prepared and the Negishi reaction step is examined.The effects of different molar ratios of reactants dosages of catalyst and time for refluxing are investigated by using single factor tests.The results demonstrate that when the molar ratios of 2-bromopyridine 2-chloro-N-4-chloro-3-iodophenyl -4-methylsulfonyl benzamide zinc chloride n-butyllithium and tetrakis triphenyl phosphine palladium are changed to 1.0∶0.5∶1.5∶1.1∶0.05 and the mixture is refluxed for 24 h the production yield is improved to 72%.This reaction condition significantly enhances the synthetic efficiency avoids consuming excessive raw materials/catalysts and meanwhile prevents a prolonged reaction time.The optimization of the proportion of reactants and the heating time is proved to be important for the efficiency and economy in cross-coupling reaction to synthesize vismodegib.展开更多
A formulation of the multi degree of freedom equations of motion for damper connected adjacent multi story buildings under earthquake excitation is presented.The ground acceleration due to e...A formulation of the multi degree of freedom equations of motion for damper connected adjacent multi story buildings under earthquake excitation is presented.The ground acceleration due to earthquake is regarded as a stochastic process,and a pseudo excitation algorithm in frequency domain is implemented in a computer program to handle the non orthogonal damping properties of the system.The effectiveness of joint dampers is then investigated in terms of the reduction of displacement,acceleration and shear force responses of adjacent buildings.展开更多
A regional ocean reanalysis system for the coastal waters of China and adjacent seas has been developed by the National Marine Data and Information Service（NMDIS）.It produces a dataset package called CORA （China oc...A regional ocean reanalysis system for the coastal waters of China and adjacent seas has been developed by the National Marine Data and Information Service（NMDIS）.It produces a dataset package called CORA （China ocean reanalysis）.The regional ocean model used is based on the Princeton Ocean Model with a generalized coordinate system（POMgcs）.The model is parallelized by NMDIS with the addition of the wave breaking and tidal mixing processes into model parameterizations.Data assimilation is a sequential three-dimensional variational（3D-Var） scheme implemented within a multigrid framework.Observations include satellite remote sensing sea surface temperature（SST）,altimetry sea level anomaly（SLA）,and temperature/salinity profiles.The reanalysis fields of sea surface height,temperature,salinity,and currents begin with January 1986 and are currently updated every year. Error statistics and error distributions of temperature,salinity and currents are presented as a primary evaluation of the reanalysis fields using sea level data from tidal gauges,temperature profiles,as well as the trajectories of Argo floats.Some case studies offer the opportunity to verify the evolution of certain local circulations.These evaluations show that the reanalysis data produced provide a good representation of the ocean processes and phenomena in the coastal waters of China and adjacent seas.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.52573299)the Natural Science Foundation of Jiangxi province(No.20242BAB25223,20232BCJ23025,20232BCJ25040,20232BAB214024)the Special Funding Program for Graduate Student Innovation of Jiangxi Province(No.YC2024-S594).
文摘Transition metal selenides as sodium-ion hybrid capacitor(SIHC)anodes still suffer from amorphization difficulties and capacity degradation triggered by polyselenide dissolution.Herein,an atomistic amorphous strategy is proposed to construct adjacent Nb-Nb diatomic pairs with Se/O-coordination(Se4-Nb2-O2)in N-doped carbon-confined amorphous selenide clusters(a-Nb-Se/O@NC).Synergistic carbon confinement and hydrothermal oxygenation induce amorphization of Nb–Se bonds,eliminating crystalline rigidity while creating isotropic dual-ion transport channels and high-density active sites enriched with dangling bonds,thereby enhancing structural integrity and Na+storage capacity.The unique Se/O-coordinated Nb-Nb diatomic configuration establishes an electron-delocalized system,where the low electronegativity of Se counterbalances electron withdrawal from coordinated O at Nb centers.These strengthen d-p orbital hybridization,reduce Na+adsorption energy,and optimize charge transfer pathways and reaction kinetics in the amorphous clusters.Electrochemical tests reveal that the a-Nb-Se/O@NC anode delivers a high reversible capacity of 312.57 mAh g^(−1)and exceptional cyclic stability(103%capacity retention)after 5000 cycles at 10.0 A g^(−1).Assembled SIHCs achieve outstanding energy/power densities(207.1 Wh kg^(−1)/18966 W kg^(−1)),surpassing most amorphous and crystalline counterparts.This work provides methodological insights for the design of electrodes in high-power storage devices through atomic modulation and electronic optimization of amorphous selenides.
基金Project(2015AA043003)supported by National High-technology Research and Development Program of ChinaProject(GY2016ZB0068)supported by Application Technology Research and Development Program of Heilongjiang Province,ChinaProject(SKLR201301A03)supported by Self-planned Task of State Key Laboratory of Robotics and System(Harbin Institute of Technology),China
文摘In order to improve the trajectory tracking precision and reduce the synchronization error of a 6-DOF lightweight robot, nonlinear proportion-deviation （N-PD） cross-coupling synchronization control strategy based on adjacent coupling error analysis is presented. The mathematical models of the robot, including kinematic model, dynamic model and spline trajectory planing, are established and verified. Since it is difficult to describe the real-time contour error of the robot for complex trajectory, the adjacent coupling error is analyzed to solve the problem. Combined with nonlinear control and coupling performance of the robot, N-PD cross-coupling synchronization controller is designed and validated by simulation analysis. A servo control experimental system which mainly consists of laser tracking system, the robot mechanical system and EtherCAT based servo control system is constructed. The synchronization error is significantly decreased and the maximum trajectory error is reduced from 0.33 mm to 0.1 mm. The effectiveness of the control algorithm is validated by the experimental results, thus the control strategy can improve the robot＇s trajectory tracking precision significantly.
文摘A chromium(II)-catalyzed reduction cross coupling reaction was reported.This reaction utilizes inexpensive and readily available chromium dichloride as a catalyst and 4,4'-di-tert-butyl-bipyridine as a ligand to achieve reduction cross coupling between trifluoromethyl olefins and alkyl bromides under mild conditions,effectively synthesizing difluoroalkene derivatives.This reaction exhibits good substrate universality and is compatible with multiple important functional groups,providing a concise synthetic pathway for constructing conjugated difluoroalkenes containing allyl difluoromethylene structural units.Preliminary mechanistic experiments indicate that alkyl bromides first undergo a reduction process to generate corresponding alkyl radicals,followed by addition to trifluoromethyl olefins.After binding with Cr(II),they undergo aβ-fluorine elimination process to generate difluoroalkenes.
文摘Chiral carbonyl compounds frequently occur in natural products and pharmaceuticals. Additionally, they serve as important intermediates in organic synthesis. Transition metal-catalyzed asymmetric carbonylative cross-coupling reactions are among the most straightforward and effective methods for synthesizing chiral carbonyl compounds, including esters, amides, and ketones. The advances in asymmetric carbonylative cross-coupling reactions using various O-, N-, C-, and S-containing nucleophiles or electrophiles over the past decade are summarized.
基金support of this work by the National Natural Science Foundation of China(Nos.22371307,21971267)the program for Guangdong Introducing Innovative and Entrepreneurial Teams(No.2017ZT07C069).
文摘Selective defluorinative functionalization of trifluoromethylarenes(ArCF3)to obtain the pharmaceutically commonα,α-difluorobenzylic motif is an attractive and elegant synthetic route.Over the past decade,although C(sp^(3))-F bonds functionalization have been greatly developed,catalytic cross-coupling of trifluoromethylarenes with C-H of terminal alkynes remains a challenge.Here,we report an approach to achieve Sonogashira-type cross-coupling of trifluoromethylarenes with terminal alkynes C(sp)-H bonds via photoredox and Cu/L dual catalysis.Tridentate anionic ligand is pivotal to realize this C-H sp-sp^(3) cross-coupling.Moreover,this unique catalytic system is also suitable for cross-coupling of C(sp^(3))-F bonds with azoles C(sp^(2))-H bonds.A series of trifluoromethylarenes,terminal alkynes and azoles with various functional groups are compatible with this protocol affording a variety of defluoroalkynylation or defluoroazolation products.Preliminary mechanistic studies indicated that deprotonated BINOL involved as a photocatalyst to activate ArCF3 rather than a ligand to the metal.
基金supported by the National Natural Science Foundation of China(No.22171046)the Hundred-Talent Project of Fujian(No.50021113)Fuzhou University(No.0480-00489503)。
文摘In most Suzuki–Miyaura carbon-carbon cross-coupling reactions,the borabicyclo[3.3.1]nonane scaffold(9-BBN)only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products.There are rare examples where the 9-BBN derivatives serve as the potentially diverse C8 building blocks in cross-coupling reactions.Herein,we report a cobalt-catalyzed migratory carboncarbon cross-coupling reaction of the in situ formed 9-BBN ate complexes to afford diverse aryl-and alkyl-functionalized cyclooctenes.Preliminary mechanistic studies suggest the oxidation-induced cisbicyclo[3.3.0]oct-1-ylborane is the key intermediate in this migratory cross-coupling reaction,which promotes the development of other diverse migratory cross-coupling of borate complexes.
基金CAMS Innovation Fund for Medical Sciences(CIFMS)(Nos.2022-I2M-1-013,2022-I2M-1-014,2022-I2M-2-002).
文摘The switchable cross-coupling of indoles and pyridotriazoles through carbene insertion at C_(2)-or C_(3)-positon has been developed in this paper.This highly site-selective C-H carbenoid functionalization is determined by both the Rh-catalyst species and auxiliary groups.[Cp∗RhCl_(2)]_(2) and coordinating pyrimidyl group direct the C-H carbenoid functionalization to occur at the C_(2)-position,while Rh2OAc4 and noncoordinating benzyl group lead the reaction to occur at the C_(3)-position of the indoles.This regioselective C−H functionalization strategy is of significant importance for the discovery of indole drugs.
基金financial supports for this work are provided by the National Natural Science Foundation of China(Nos.21871160,21672121,22071130)。
文摘An N-heterocyclic carbene(NHC)catalyzed enantioselective cyclisation and trifluoromethylation of olefins with cinnamaldehydes via radical relay cross-coupling in the presence of Togni reagent is reported andδ-lactones tolerated with stereogenic centers atβ-andγ-positions are obtained in moderate to high yields and with high enantioselectivities.Further computational studies explain that the radical crosscoupling step is the key to determining the enantioselectivity.Energy analysis of key transition states and intermediates also provides a reasonable explanation for the difficulty of diastereoselective control.DFT calculations also reveal that the hydrogen-bonding interaction plays a vital role in the promotion of this chemistry.
基金supported by the National Natural Science Foundation of China(Nos.52378341,51938005,and 52090082).
文摘Urban spaces are becoming increasingly congested,and excavations are frequently performed close to existing underground structures such as tunnels.Understanding the mechanical response of proximal soil and tunnels to these excavations is important for efficient and safe underground construction.However,previous investigations of this issue have predominantly made assumptions of plane-strain conditions and normal gravity states,and focused on the performance of tunnels affected by excavation and unloading in sandy strata.In this study,a 3D centrifuge model test is conducted to investigate the influence of excavation on an adjacent existing tunnel in normally consolidated clay.The testing results indicate that the excavation has a significant impact on the horizontal deformation of the retaining wall and tunnel.Moreover,the settlements of the ground surface and the tunnel are mainly affected by the long-term period after excavation.The excavation is found to induce ground movement towards the pit,resulting in prolonged fluctuations in pore water pressure and lateral earth pressure.The testing results are compared with numerical simulations,achieving consistency.A numerical parametric study on the tunnel location shows that when the tunnel is closer to the retaining wall,the decreases in lateral earth pressure and pore water pressure during excavation are more pronounced.
基金Supported by Shanghai Tongren Hospital Scientific Research Funds,No.TRKYRC-xx202203Shanghai Municipal Health Commission,No.2022YQ006Science and Technology Commission of Shanghai Municipality,No.22ZR1457200.
文摘BACKGROUND Posterior lumbar interbody fusion has good clinical results,but adjacent segment disease(ASD)affects its long-term efficacy.In patients with L4-5 fusion who were followed up for more than 10 years,the ASD incidence was 33.3%.Magnetic resonance imaging(MRI)is key for ASD diagnosis,but metal artifacts from internal fixation limit its use;therefore,removing the artifacts is crucial for ASD diagnosis and treatment.AIM To evaluate the value of WARP MRI for patients with lumbar ASD.METHODS In our hospital,the lumbar spines of patients with ASD were assessed via lumbar MRI,including conventional sequences and sequences for artifacts.A PACS workstation was used for image measurement,analysis,and assessment,which mainly included measurement of the internal fixation implant artifact area,evaluation of the visibility of the anatomical structures surrounding the implant,and diagnostic assessment of ASD in the section.Conventional MRI data sequences and artifacts to sequence the contrast analysis of the MRI data.RESULTS A total of 30 patients with ASD after lumbar fusion and internal fixation were included in the study;the patients included 13 male and 17 female patients and were aged 66.03±5.83 years.The metal artifact area of the WARP T2-tirm sequence was significantly smaller than that of the conventional STIR sequence[(20.85±6.27)cm²vs(50.56±8.55)cm²,P<0.01].The WARP T2-tirm sequence was observed around the implants,pedicles,intervertebral foramen,and vertebral bodies,and the conventional STIR sequence clearly displayed nerve roots within the intervertebral foramen.In all 30 patients,all adjacent segments of the WARP T2-tirm sequence could be clearly observed(above Grade 4),whereas it was difficult to observe these segments in the conventional STIR sequence due to the presence of more severe metal artifacts.CONCLUSION WARP sequences can significantly reduce the artifact area in the sagittal and cross-sectional images of titanium alloy spinal fixation,providing a good imaging reference for the diagnosis of ASD.
基金the National Natural Science Foundation of China(22178243).
文摘The Pd-catalyzed Suzuki-Miyaura coupling reaction is a crucial tool for constructing C-C bonds.Currently,the organic solvents employed during reaction may cause serious environmental problems.Moreover,the low solubility of inorganic bases in organic solvents leads to enormous mass transfer resistance.To address this issue,the Pickering droplets reactor stabilized by Pd/g-C_(3)N_(4)at substrate-water two-phase interface is reported.Benefiting from the hydrophobic conjugated framework and hydrophilic terminal groups,Pd/g-C_(3)N_(4)can configure stable Pickering emulsion without additional functionalization.The Pd loaded catalysts exhibits excellent performance(TOF=21852 h^(-1))for the Suzuki-Miyaura coupling reaction,which is deriving from unique electronic structure of g-C_(3)N_(4)and high interfacial area of emulsion.Moreover,there is no clear decrease in reactivity after six cycles(conversion>86%).In this study,the organic solvent was replaced by reaction substrate,and the high activity can be achieved for various halogenated aromatic hydrocarbons and their derivatives.
基金the National Natural Science Foundation of China(Nos.32260235 and 82260446)。
文摘Cage plus plate(CP)and zero-profile(Zero-P)devices are widely used in anterior cervical discectomy and fusion(ACDF).This study aimed to compare adjacent segment biomechanical changes after ACDF when using Zero-P device and CP in different segments.First,complete C1—C7 cervical segments were constructed and validated.Meanwhile,four surgery models were developed by implanting the Zero-P device or CP into C4—C5 or C5—C6 segments based on the intact model.The segmental range of motion(ROM)and maximum value of the intradiscal pressure of the surgery models were compared with those of the intact model.The implantation of CP and Zero-P devices in C4—C5 segments decreased ROM by about 91.6%and 84.3%,respectively,and increased adjacent segment ROM by about 8.3%and 6.82%,respectively.The implantation of CP and Zero-P devices in C5—C6 segments decreased ROM by about 93.3%and 89.9%,respectively,while increasing adjacent segment ROM by about 4.9%and 4%,respectively.Furthermore,the implantation of CP and Zero-P devices increased the intradiscal pressure in the adjacent segments of C4—C5 segments by about 4.5%and 6.7%,respectively.The implantation of CP and Zero-P devices significantly increased the intradiscal pressure in the adjacent segments of C5—C6 by about 54.1%and 15.4%,respectively.In conclusion,CP and Zero-P fusion systems can significantly reduce the ROM of the fusion implant segment in ACDF while increasing the ROM and intradiscal pressure of adjacent segments.Results showed that Zero-P fusion system is the best choice for C5—C6 segmental ACDF.However,further studies are needed to select the most suitable cervical fusion system for C4—C5 segmental ACDF.Therefore,this study provides biomechanical recommendations for clinical surgery.
文摘This study presents a novel hybrid topology optimization and mold design framework that integrates process fitting,runner system optimization,and structural analysis to significantly enhance the performance of injection-molded parts.At its core,the framework employs a greedy algorithm that generates runner systems based on adjacency and shortest path principles,leading to improvements in both mechanical strength and material efficiency.The design optimization is validated through a series of rigorous experimental tests,including three-point bending and torsion tests performed on key-socket frames,ensuring that the optimized designs meet practical performance requirements.A critical innovation of the framework is the development of the Adjacent Element Temperature-Driven Prestress Algorithm(AETDPA),which refines the prediction of mechanical failure and strength fitting.This algorithm has been shown to deliver mesh-independent accuracy,thereby enhancing the reliability of simulation results across various design iterations.The framework’s adaptability is further demonstrated by its ability to adjust optimization methods based on the unique geometry of each part,thus accelerating the overall design process while ensuring struc-tural integrity.In addition to its immediate applications in injection molding,the study explores the potential extension of this framework to metal additive manufacturing,opening new avenues for its use in advanced manufacturing technologies.Numerical simulations,including finite element analysis,support the experimental findings and confirm that the optimized designs provide a balanced combination of strength,durability,and efficiency.Furthermore,the integration challenges with existing injection molding practices are addressed,underscoring the framework’s scalability and industrial relevance.Overall,this hybrid topology optimization framework offers a computationally efficient and robust solution for advanced manufacturing applications,promising significant improvements in design efficiency,cost-effectiveness,and product performance.Future work will focus on further enhancing algorithm robustness and exploring additional applications across diverse manufacturing processes.
文摘The cell density, species composition and distribution of phytoplankton, and their relations to environmental factors in Prydz Bay and its adjacent sea area, Antarctica (69degrees-77degrees E, 62degrees-70degrees S) during the austral summer of 1998/1999 were investigated. A total of 48 taxa belonging to 21 genera of phytoplankton in the sea area were identified. The average cell density of phytoplankton was 22.46 x 10(3) cells/dm(3), of which diatoms were predominant (84.51%). The highest cell density of phytoplankton occurred in Prydz Bay and the adjacent continental shelf where the average cell density was 46.03 x 10(3) cells/dm(3). The lowest cell density (3.34 x 10(3) cells/dm(3)) occurred in deep sea area. The dominant species of phytoplankton was Fragilariopsis curta. The vertical distribution of phytoplankton density was highest in the upper part of 0-50 in depth, lower in 100 in and lowest in 150 in. The species composition and cell density of phytoplankton were influenced by water circulation. The cell density was positively correlated with water temperature and salinity, and negatively correlated with the concentration of nutrients.
基金supported by the National Natural Science Foundation of China under contract Nos. 40576015, 40810069004 and 40821063by the key research project of Fujian Province under contract No. 2004N203by the Fujian demonstrating region of the "863" Project of the Ministry of Science and Technology of China
文摘Diurnal and semi-diurnal tides in the Taiwan Strait and its adjacent areas are calculated by using a two-dimensional finite-difference model. Compared with data of more than 20 observation stations around the Taiwan Strait, the model-produced results agree quite well with those of previous researches using observational data from coastal tidal gauge stations. According to the results, the co-tidal and co-range charts are given. Furthermore, the characteristics of 8 major tidal constituents have been uminated respectively. The result shows that： （1） The tide motion can be attributed to the interaction between the degenerative rotary tidal system in the north and the progressive tidal system in the south. （2） The southward and northward tidal waves of semi-diurnal tide converge in the middle of the Taiwan Strait while the diurnal tidal waves propagate southwestward through the Taiwan Strait and the Luzon Strait. （3） The maximum amplitude of semi-diurnal tides exists at the area between the Meizhou Bay and Xinghua Bay, and that of diurnal tides appears in the region to the east of the Leizhou Peninsula, （4） The patterns of co-tidal and co-range charts of N2, K2 and P1, Q1 tidal constituents are similar to those of M2, S2 and K1 O1 tidat constituents, respectively
基金State Key Basic Research Project of Development and Programming Mechanism and Prediction of Continental Strong Earthquakes (G1998040700).
文摘Pn velocity lateral variation and anisotropy images were reconstructed by adding about 50 000 travel times from the regional seismic networks to the datum set of near 40 000 travel times from National Seismic Network of China used by WANG, et al. We discussed the relation of Pn velocity variation to Moho depth, Earths heat flow, distribution of Cenozoic volcanic rock and the result of rock experiment under high pressure and high temperature. The result of quantitative analysis indicates that Pn velocity is positively correlated with the crust thickness and negatively correlated with the Earths heat flow. Two linear regression equations, one between Pn velocity and crust thickness, and the other between Pn velocity and heat flow, were obtained. The rate of variation of Pn veloc-ity vP with pressure P, Pv/p, estimated from the velocity variation with crust thickness Hv/p, is close to the result obtained from the rock experiment under high pressure and high temperature. If the effect of crust thick-ness on Pn velocity is deducted from the velocity variation, then the low Pn velocity beneath Qinghai-Xizang pla-teau is more notable. The low Pn velocity regions well agree with the Cenozoic volcanic rock. In the several re-gions with significant anisotropy, the direction of fast Pn velocity is consistent with the orientation of maximum principal crustal compressive stress, and also with the direction of present-day crustal movement. It indicates that the fast Pn velocity direction may be related to the deformation or flow of top mantle material along the direction of maximum pressure.
基金State Natural Scientific Foundation (49734150) and National High Performance Computation Foundation.
文摘We assembled approximately 328 seismic records. The data set was from 4 digitally recording long-period and broadband stations of CDSN. We carried out the inversion based on the partitioned waveform inversion (PWI). It partitions the large-scale optimization problem into a number of independent small-scale problems. We adopted surface waveform inversion with an equal block (2((2() discretization in order to acquire the images of shear velocity structure at different depths (from surface to 430 km) in the crust and upper-mantle. The resolution of all these anomalies has been established with (check-board( resolution tests. These results show significant difference in velocity, lithosphere and asthenosphere structure between South China Sea and its adjacent regions.
基金The National Basic Research Program of China(973Program)(No.2011CB933503)China Postdoctoral Science Foundation(No.2013M541592)
文摘In order to improve the yield and reduce the cost in the synthesis of antitumor drug vismodegib the key intermediates are prepared and the Negishi reaction step is examined.The effects of different molar ratios of reactants dosages of catalyst and time for refluxing are investigated by using single factor tests.The results demonstrate that when the molar ratios of 2-bromopyridine 2-chloro-N-4-chloro-3-iodophenyl -4-methylsulfonyl benzamide zinc chloride n-butyllithium and tetrakis triphenyl phosphine palladium are changed to 1.0∶0.5∶1.5∶1.1∶0.05 and the mixture is refluxed for 24 h the production yield is improved to 72%.This reaction condition significantly enhances the synthetic efficiency avoids consuming excessive raw materials/catalysts and meanwhile prevents a prolonged reaction time.The optimization of the proportion of reactants and the heating time is proved to be important for the efficiency and economy in cross-coupling reaction to synthesize vismodegib.
文摘A formulation of the multi degree of freedom equations of motion for damper connected adjacent multi story buildings under earthquake excitation is presented.The ground acceleration due to earthquake is regarded as a stochastic process,and a pseudo excitation algorithm in frequency domain is implemented in a computer program to handle the non orthogonal damping properties of the system.The effectiveness of joint dampers is then investigated in terms of the reduction of displacement,acceleration and shear force responses of adjacent buildings.
文摘A regional ocean reanalysis system for the coastal waters of China and adjacent seas has been developed by the National Marine Data and Information Service（NMDIS）.It produces a dataset package called CORA （China ocean reanalysis）.The regional ocean model used is based on the Princeton Ocean Model with a generalized coordinate system（POMgcs）.The model is parallelized by NMDIS with the addition of the wave breaking and tidal mixing processes into model parameterizations.Data assimilation is a sequential three-dimensional variational（3D-Var） scheme implemented within a multigrid framework.Observations include satellite remote sensing sea surface temperature（SST）,altimetry sea level anomaly（SLA）,and temperature/salinity profiles.The reanalysis fields of sea surface height,temperature,salinity,and currents begin with January 1986 and are currently updated every year. Error statistics and error distributions of temperature,salinity and currents are presented as a primary evaluation of the reanalysis fields using sea level data from tidal gauges,temperature profiles,as well as the trajectories of Argo floats.Some case studies offer the opportunity to verify the evolution of certain local circulations.These evaluations show that the reanalysis data produced provide a good representation of the ocean processes and phenomena in the coastal waters of China and adjacent seas.
