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
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
The efficiency and stability of catalysts for photocatalytic hydrogen evolution(PHE)are largely governed by the charge transfer behaviors across the heterojunction interfaces.In this study,CuO,a typical semiconductor ...The efficiency and stability of catalysts for photocatalytic hydrogen evolution(PHE)are largely governed by the charge transfer behaviors across the heterojunction interfaces.In this study,CuO,a typical semiconductor featuring a broad spectral absorption range,is successfully employed as the electron acceptor to combine with CdS for constructing a S-scheme heterojunction.The optimized photocatalyst(CdSCuO2∶1)delivers an exceptional hydrogen evolution rate of 18.89 mmol/(g·h),4.15-fold higher compared with bare CdS.X-ray photoelectron spectroscopy(XPS)and ultraviolet-visible diffuse reflection absorption spectroscopy(UV-vis DRS)confirmed the S-scheme band structure of the composites.Moreover,the surface photovoltage(SPV)and electron paramagnetic resonance(EPR)indicated that the photogenerated electrons and photogenerated holes of CdS-CuO2∶1 were respectively transferred to the conduction band(CB)of CdS with a higher reduction potential and the valence band(VB)of CuO with a higher oxidation potential under illumination,as expected for the S-scheme mechanism.Density-functional-theory calculations of the electron density difference(EDD)disclose an interfacial electric field oriented from CdS to CuO.This built-in field suppresses charge recombination and accelerates carrier migration,rationalizing the markedly enhanced PHE activity.This study offers a novel strategy for designing S-scheme heterojunctions with high light harvesting and charge utilization toward sustainable solar-tohydrogen conversion.展开更多
The fatigue crack growth rate of a novel Ti-6Al-4V-1Mo titanium alloy,which is developed for laser directed energy deposition technique,was investigated before and after cyclic heat treatment(CHT).Changes in microstru...The fatigue crack growth rate of a novel Ti-6Al-4V-1Mo titanium alloy,which is developed for laser directed energy deposition technique,was investigated before and after cyclic heat treatment(CHT).Changes in microstructure,fracture surfaces,and crack growth paths were analyzed before and after CHT.Results indicate that in the stable crack growth region,the growth rates for the as-deposited and cyclic heat-treated specimens follow the relationships da/dN=1.8651×10^(−8)(ΔK)^(3.2271)and da/dN=1.4112×10^(−8)(ΔK)^(3.1125),respectively.Compared with that at the as-deposited state,the microstructure after CHT is transformed from a uniform basket-weave microstructure to a dual-phase microstructure consisting of near-sphericalαandβ-transformed matrix phases.The cyclic process also disrupts the continuity of the grain boundaryα(αGB)at the primaryβ-phase grain boundary.The coarsening of primaryαand the disruption ofαGB continuity are the primary factors to release stress concentration and promote crack deflection,thereby decreasing the fatigue crack growth rate.Additionally,the increased occurrence of crack branching,secondary cracking,and crack bridging in cyclic heat-treated specimens further reduces the crack driving force and slows the fatigue crack growth rate.展开更多
Directional three-dimensional carbon-based foams are emerging as highly attractive candidates for promising electromagnetic wave absorbing materials(EWAMs)thanks to their unique architecture,but their construction usu...Directional three-dimensional carbon-based foams are emerging as highly attractive candidates for promising electromagnetic wave absorbing materials(EWAMs)thanks to their unique architecture,but their construction usually involves complex procedures and extremely depends on unidirectional freezing technique.Herein,we propose a groundbreaking approach that leverages the assemblies of salting-out protein induced by ammonium metatungstate(AM)as the precursor,and then acquire directional three-dimensional carbon-based foams through simple pyrolysis.The electrostatic interaction between AM and protein ensures well dispersion of WC_(1−x)nanoparticles on carbon frameworks.The content of WC_(1−x)nanoparticles can be rationally regulated by AM dosage,and it also affects the electromagnetic(EM)properties of final carbon-based foams.The optimized foam exhibits exceptional EM absorption performance,achieving a remarkable minimum reflection loss of−72.0 dB and an effective absorption bandwidth of 6.3 GHz when EM wave propagates parallel to the directional pores.Such performance benefits from the synergistic effects of macroporous architecture and compositional design.Although there is a directional dependence of EM absorption,radar stealth simulation demonstrates that these foams can still promise considerable reduction in radar cross section with the change of incident angle.Moreover,COMSOL simulation further identifies their good performance in preventing EM interference among different electronic components.展开更多
The Cooling-Storage-Ring External-target Experiment(CEE)at the Heavy Ion Research Facility in Lanzhou(HIRFL)is designed to study the properties of nuclear matter created in heavy-ion collisions at beam energies from a...The Cooling-Storage-Ring External-target Experiment(CEE)at the Heavy Ion Research Facility in Lanzhou(HIRFL)is designed to study the properties of nuclear matter created in heavy-ion collisions at beam energies from a few hundred MeV/u up to 1 GeV/u.It aims to facilitate research on the quantum chromodynamics(QCD)phase structure in the high-baryondensity region.Collective flow is a fundamental observable in heavy-ion collision experiments,providing information on the bulk properties of the produced matter.Although the standard event plane method has been widely used to measure collective flow,it is still important to validate and optimize this method for the CEE spectrometer.In this paper,we study the experimental procedures for measuring directed flow in^(238)U+^(238)U collisions at 500 MeV/u,using event planes reconstructed by Multi-Wire Drift Chamber and Zero Degree Calorimeter,respectively.Jet AA Microscopic(JAM)transport generator is used to generate events,and the detector response is simulated by the CEE Fast Simulation(CFS)package.Finally,the optimal kinematic region for proton directed flow measurements is discussed for the future CEE experiment.展开更多
Objective:To explore the interventional room nursing and its application effects in patients with ischemic stroke treated with tirofiban combined with direct thrombectomy.Methods:A total of 61 patients with ischemic s...Objective:To explore the interventional room nursing and its application effects in patients with ischemic stroke treated with tirofiban combined with direct thrombectomy.Methods:A total of 61 patients with ischemic stroke admitted to our hospital from June 2024 to June 2025 were selected and divided into two groups using the red and blue ball method:the control group(n=30,receiving routine interventional room nursing)and the observation group(n=31,receiving additional tirofiban medication-specific nursing+individualized interventional nursing on the basis of routine nursing).The cerebral hemodynamic indicators,adverse reactions,effectiveness of complication nursing,and nursing satisfaction were compared between the two groups.Results:After 7 days of treatment,the observation group had lower cerebrovascular peripheral resistance and higher mean blood flow velocity and mean blood flow volume compared to the control group(all p<0.05).The observation group had a higher effectiveness rate of complication nursing than the control group,with a statistically significant difference(p<0.05).The nursing satisfaction in the observation group(96.77%)was higher than that in the control group(80.00%),with a statistically significant difference(χ^(2)=4.223,p=0.040<0.05).Conclusion:Tirofiban combined with direct thrombectomy can significantly improve cerebral hemodynamics,enhance the effectiveness of complication nursing,and increase patient satisfaction in patients with ischemic stroke.展开更多
BACKGROUND Drug utilization research has an important role in assisting the healthcare administration to know,compute,and refine the prescription whose principal objective is to enable the rational use of drugs.Resear...BACKGROUND Drug utilization research has an important role in assisting the healthcare administration to know,compute,and refine the prescription whose principal objective is to enable the rational use of drugs.Research in developing nations relating to the cost of treatment is scarce when compared with developed countries.Thus,the drug utilization research studies from developing nations are most needed,and their number has been growing.AIM To evaluate patterns of utilization of antipsychotic drugs and direct medical cost analysis in patients newly diagnosed with schizophrenia.METHODS The present study was observational in type and based on a retrospective cohort to evaluate patterns of utilization of antipsychotic drugs using World Health Organization(WHO)core prescribing indicators and anatomical therapeutic chemical/defined daily dose indicators.We also calculated direct medical costs for a period of 6 months.RESULTS This study has found that atypical antipsychotics are the mainstay of treatment for schizophrenia in every age group and subcategories of schizophrenia.The evaluation based on WHO prescribing indicators showed a low average number of drugs per prescription and low prescribing frequency of antipsychotics from the National List of Essential Medicines 2015 and the WHO Essential Medicines List 2019.The total mean drug cost of our study was 1396 Indian rupees.The total mean cost due to the investigation in our study was 1017.34 Indian rupees.Therefore,the total mean direct medical cost incurred on patients in our study was 4337.28 Indian rupees.CONCLUSION The information from the present study can be used for reviewing and updating treatment policy at the institutional level.展开更多
This paper is dedicated to fixed-time passivity and synchronization for multi-weighted spatiotemporal directed networks.First,to achieve fixed-time passivity,a type of decentralized power-law controller is developed,i...This paper is dedicated to fixed-time passivity and synchronization for multi-weighted spatiotemporal directed networks.First,to achieve fixed-time passivity,a type of decentralized power-law controller is developed,in which only one parameter needs to be adjusted in the power-law terms;this greatly decreases the inconvenience of parameter adjustment.Second,several fixed-time passivity criteria with LMI forms are derived by using a Gauss divergence theorem to deal with the spatial diffusion of nodes and by applying the Hölder’s inequality to dispose rigorously the power-law term greater than one in the designed control scheme;this improves the previous theoretical analysis.Additionally,the fixed-time synchronization of spatiotemporal directed networks with multi-weights is addressed as a direct result of fixed-time strict passivity.Finally,a numerical example is presented in order to show the validity of the theoretical analysis.展开更多
Efficient energy utilization in covert communication sustains covertness while assuring communication quality and efficiency.This paper investigates covert communication energy efficiency(EE)in direct uplink satellite...Efficient energy utilization in covert communication sustains covertness while assuring communication quality and efficiency.This paper investigates covert communication energy efficiency(EE)in direct uplink satellite-ground communications,focusing on enhancing system EE via optimized transmit beamforming and satellite orbit altitude selection.This paper first establishes an optimization problem to maximize system EE in a direct uplink satelliteground covert communication scenario.To solve this non-convex optimization problem,it is decomposed into two subproblems and solved using the successive convex approximation(SCA)method.Based on the above methods,this paper proposes an overall iterative optimization algorithm.Simulation results demonstrate that the proposed algorithm surpasses the conventional baseline algorithms in terms of system EE.Furthermore,they elucidate the correlation between the amount of information received by the receiver and the variations in the satellite’s orbital altitude.展开更多
Biopolymeric nanocomposites have attracted considerable attention because of their biocompatibility,biodegradability,and unique physicochemical properties.It is essential to manufacture three-dimensional(3D)biocompati...Biopolymeric nanocomposites have attracted considerable attention because of their biocompatibility,biodegradability,and unique physicochemical properties.It is essential to manufacture three-dimensional(3D)biocompatible micro/nanostructures using biopolymeric nanocomposites.Herein,we demonstrate the high-fidelity fabrication of biocompatible 3D features with sub-50 nm resolution using femtosecond laser direct writing(FsLDW)of a biopolymeric nanocomposite composed of egg white and sulfonated graphene(S-graphene).The biopolymer nanocomposite acts as a negative photoresist suitable for water-based lithography.The introduction of S-graphene not only dramatically lowered the laser power threshold but also significantly modulated the morphology of the 3D features constructed by FsLDW.Microstructures with porous,rough,or smooth morphologies were obtained by optimizing the S-graphene concentration and laser scanning speed.The fabricated egg-white/S-graphene microstructures exhibited biocompatibility and environmental degradability.Egg white/S-graphene was also employed to fabricate diffractive gratings with superior optical quality.This study provides a promising method to manufacture biocompatible 3D features with controllable morphology,which has potential applications in biological and photonic fields.展开更多
The rapid accumulation of spent LiFePO_(4)(LFP)cathodes from retired lithium-ion batteries necessitates the development of effective and environmental-friendly recycling strategies.In this context,direct regeneration ...The rapid accumulation of spent LiFePO_(4)(LFP)cathodes from retired lithium-ion batteries necessitates the development of effective and environmental-friendly recycling strategies.In this context,direct regeneration has emerged as a promising approach for reclaiming LFP cathode materials,offering a streamlined pathway to restore their electrochemical functionality.We report an integrated regeneration protocol that simultaneously repairs the degraded crystal structure and reconstructs the damaged carbon coating in spent LFP.The regenerated cathode material had superfast lithium-ion diffusion kinetics and a stable cathode-electrolyte interface,giving a remarkable rate capability with specific capacities of 122 m Ah g^(-1)at 5C and 106 m Ah g^(-1)at 10C(1C=170 m A g^(-1)).It also maintained capacities of 110.7 m Ah g^(-1)(5C)and 84.1 m Ah g^(-1)(10C)after 400 cycles.It could be used in harsh environments and could be stably cycled at subzero temperatures(-10 and-20°C)and in solid-state electrolyte batteries.Life cycle assessment combined with economic evaluation using the Ever Batt model reveals that this direct regeneration approach has high economic and environmental benefits.展开更多
When stacking two-dimensional(2D)materials with a lattice mismatch and/or a small twist,moirésuperlattice emerges with fascinating electronic and optical properties.The fabrication of such stacked 2D materials us...When stacking two-dimensional(2D)materials with a lattice mismatch and/or a small twist,moirésuperlattice emerges with fascinating electronic and optical properties.The fabrication of such stacked 2D materials usually requires multiple transfer and stack processes,assisted by a certain transfer medium which needs to be removed afterwards,and it is very challenging to maintain pristine and clean surfaces/interfaces for these stacked structures.In this work,we report a facile direct bonding method for fabrication of twisted MoS_(2) bilayers with ultra-clean surfaces/interfaces.Novel interlayer interactions are revealed in the as-fabricated high-quality samples,leading to twist-angle related dispersion behavior of various Raman modes,such as layer breathing modes,shear modes and E_(2g)modes,as well as indirect bandgap excitons.Field-effect transistors(FETs)of twisted MoS_(2) bilayers also exhibit angle-dependent performance,which could be attributed to the band structure evolution.This facile method holds significance for the future integration of pre-designed multilayer 2D materials and paves a way to explore underlying physical mechanisms and potential applications.展开更多
Exercise produces a decrease in pain sensitivity via an effect called exercise-induced hypoalgesia(EIH).Transcranial direct current stimulation(tDCS),acting on similar analgesic mechanisms as EIH,represents a potentia...Exercise produces a decrease in pain sensitivity via an effect called exercise-induced hypoalgesia(EIH).Transcranial direct current stimulation(tDCS),acting on similar analgesic mechanisms as EIH,represents a potential complementary intervention that may amplify the effects of exercise on pain.This study aimed to explore if anodal tDCS could enhance the effect of exercise on pain compared to exercise alone.A total of 35 healthy participants aged 19–37 years completed a familiarisation session followed by two separate sessions where active and sham tDCS was applied in a randomised cross-over design.The familiarisation session involved familiarisation to the pain assessment and exercise tasks,while the subsequent tDCS sessions involved pain sensitivity assessment,exercise and either anodal tDCS or sham tDCS.tDCS doses were applied at 2 mA over the primary motor cortex for 10 min,with the reference electrode placed over the contralateral supraorbital area.The exercise task involved a sustained isometric grip strength contraction at 35%of maximal voluntary contraction(MVC)until volitional exhaustion.Pain sensitivity was evaluated as pressure pain threshold before tDCS,after tDCS,and after exercise.Across both tDCS conditions,pain threshold was higher after exercise when compared to pre-and post-tDCS measurement.This increase in pain threshold did not differ between active and sham tDCS conditions.Our findings suggest that the hypoalgesic effects of active anodal tDCS over the motor cortex prior to exercise are no greater than the effects of sham tDCS prior to exercise.展开更多
Enamel,the inorganic tissue covering the crowns of teeth,is known for its remarkable resilience and hardness.These properties originate from its high proportion of mineralized matrix and complex internal microarchitec...Enamel,the inorganic tissue covering the crowns of teeth,is known for its remarkable resilience and hardness.These properties originate from its high proportion of mineralized matrix and complex internal microarchitecture.On an ultrastructural level,it consists of directionally arranged enamel prisms.Continuously growing rodent incisors are an exemplary case of this phenomenon.Their enamel has a consistent decussation pattern,providing teeth with extremely high resistance and ensuring they remain constantly sharp.While the decussation pattern has been described in detail,mechanisms behind its formation have not been experimentally proven.Here,we show that the highly organized enamel micropattern is generated by directional epithelial sliding of enamel-forming ameloblasts in vivo.Our results detail how enamel micropatterning stems from individual cell cluster segregation and subsequent reciprocal interweaving.Based on this determination,we introduce and experimentally demonstrate a new model of enamel decussation pattern formation.展开更多
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.
文摘The efficiency and stability of catalysts for photocatalytic hydrogen evolution(PHE)are largely governed by the charge transfer behaviors across the heterojunction interfaces.In this study,CuO,a typical semiconductor featuring a broad spectral absorption range,is successfully employed as the electron acceptor to combine with CdS for constructing a S-scheme heterojunction.The optimized photocatalyst(CdSCuO2∶1)delivers an exceptional hydrogen evolution rate of 18.89 mmol/(g·h),4.15-fold higher compared with bare CdS.X-ray photoelectron spectroscopy(XPS)and ultraviolet-visible diffuse reflection absorption spectroscopy(UV-vis DRS)confirmed the S-scheme band structure of the composites.Moreover,the surface photovoltage(SPV)and electron paramagnetic resonance(EPR)indicated that the photogenerated electrons and photogenerated holes of CdS-CuO2∶1 were respectively transferred to the conduction band(CB)of CdS with a higher reduction potential and the valence band(VB)of CuO with a higher oxidation potential under illumination,as expected for the S-scheme mechanism.Density-functional-theory calculations of the electron density difference(EDD)disclose an interfacial electric field oriented from CdS to CuO.This built-in field suppresses charge recombination and accelerates carrier migration,rationalizing the markedly enhanced PHE activity.This study offers a novel strategy for designing S-scheme heterojunctions with high light harvesting and charge utilization toward sustainable solar-tohydrogen conversion.
基金National Key Research and Development Program of China(2024YFB4610803)。
文摘The fatigue crack growth rate of a novel Ti-6Al-4V-1Mo titanium alloy,which is developed for laser directed energy deposition technique,was investigated before and after cyclic heat treatment(CHT).Changes in microstructure,fracture surfaces,and crack growth paths were analyzed before and after CHT.Results indicate that in the stable crack growth region,the growth rates for the as-deposited and cyclic heat-treated specimens follow the relationships da/dN=1.8651×10^(−8)(ΔK)^(3.2271)and da/dN=1.4112×10^(−8)(ΔK)^(3.1125),respectively.Compared with that at the as-deposited state,the microstructure after CHT is transformed from a uniform basket-weave microstructure to a dual-phase microstructure consisting of near-sphericalαandβ-transformed matrix phases.The cyclic process also disrupts the continuity of the grain boundaryα(αGB)at the primaryβ-phase grain boundary.The coarsening of primaryαand the disruption ofαGB continuity are the primary factors to release stress concentration and promote crack deflection,thereby decreasing the fatigue crack growth rate.Additionally,the increased occurrence of crack branching,secondary cracking,and crack bridging in cyclic heat-treated specimens further reduces the crack driving force and slows the fatigue crack growth rate.
基金financially supported by the National Natural Science Foundation of China(Nos.22475057 and No.52373262).
文摘Directional three-dimensional carbon-based foams are emerging as highly attractive candidates for promising electromagnetic wave absorbing materials(EWAMs)thanks to their unique architecture,but their construction usually involves complex procedures and extremely depends on unidirectional freezing technique.Herein,we propose a groundbreaking approach that leverages the assemblies of salting-out protein induced by ammonium metatungstate(AM)as the precursor,and then acquire directional three-dimensional carbon-based foams through simple pyrolysis.The electrostatic interaction between AM and protein ensures well dispersion of WC_(1−x)nanoparticles on carbon frameworks.The content of WC_(1−x)nanoparticles can be rationally regulated by AM dosage,and it also affects the electromagnetic(EM)properties of final carbon-based foams.The optimized foam exhibits exceptional EM absorption performance,achieving a remarkable minimum reflection loss of−72.0 dB and an effective absorption bandwidth of 6.3 GHz when EM wave propagates parallel to the directional pores.Such performance benefits from the synergistic effects of macroporous architecture and compositional design.Although there is a directional dependence of EM absorption,radar stealth simulation demonstrates that these foams can still promise considerable reduction in radar cross section with the change of incident angle.Moreover,COMSOL simulation further identifies their good performance in preventing EM interference among different electronic components.
基金supported in part by the National Key R&D Program of China(No.2024YFA1610700)the National Natural Science Foundation of China(No.12475147)。
文摘The Cooling-Storage-Ring External-target Experiment(CEE)at the Heavy Ion Research Facility in Lanzhou(HIRFL)is designed to study the properties of nuclear matter created in heavy-ion collisions at beam energies from a few hundred MeV/u up to 1 GeV/u.It aims to facilitate research on the quantum chromodynamics(QCD)phase structure in the high-baryondensity region.Collective flow is a fundamental observable in heavy-ion collision experiments,providing information on the bulk properties of the produced matter.Although the standard event plane method has been widely used to measure collective flow,it is still important to validate and optimize this method for the CEE spectrometer.In this paper,we study the experimental procedures for measuring directed flow in^(238)U+^(238)U collisions at 500 MeV/u,using event planes reconstructed by Multi-Wire Drift Chamber and Zero Degree Calorimeter,respectively.Jet AA Microscopic(JAM)transport generator is used to generate events,and the detector response is simulated by the CEE Fast Simulation(CFS)package.Finally,the optimal kinematic region for proton directed flow measurements is discussed for the future CEE experiment.
文摘Objective:To explore the interventional room nursing and its application effects in patients with ischemic stroke treated with tirofiban combined with direct thrombectomy.Methods:A total of 61 patients with ischemic stroke admitted to our hospital from June 2024 to June 2025 were selected and divided into two groups using the red and blue ball method:the control group(n=30,receiving routine interventional room nursing)and the observation group(n=31,receiving additional tirofiban medication-specific nursing+individualized interventional nursing on the basis of routine nursing).The cerebral hemodynamic indicators,adverse reactions,effectiveness of complication nursing,and nursing satisfaction were compared between the two groups.Results:After 7 days of treatment,the observation group had lower cerebrovascular peripheral resistance and higher mean blood flow velocity and mean blood flow volume compared to the control group(all p<0.05).The observation group had a higher effectiveness rate of complication nursing than the control group,with a statistically significant difference(p<0.05).The nursing satisfaction in the observation group(96.77%)was higher than that in the control group(80.00%),with a statistically significant difference(χ^(2)=4.223,p=0.040<0.05).Conclusion:Tirofiban combined with direct thrombectomy can significantly improve cerebral hemodynamics,enhance the effectiveness of complication nursing,and increase patient satisfaction in patients with ischemic stroke.
文摘BACKGROUND Drug utilization research has an important role in assisting the healthcare administration to know,compute,and refine the prescription whose principal objective is to enable the rational use of drugs.Research in developing nations relating to the cost of treatment is scarce when compared with developed countries.Thus,the drug utilization research studies from developing nations are most needed,and their number has been growing.AIM To evaluate patterns of utilization of antipsychotic drugs and direct medical cost analysis in patients newly diagnosed with schizophrenia.METHODS The present study was observational in type and based on a retrospective cohort to evaluate patterns of utilization of antipsychotic drugs using World Health Organization(WHO)core prescribing indicators and anatomical therapeutic chemical/defined daily dose indicators.We also calculated direct medical costs for a period of 6 months.RESULTS This study has found that atypical antipsychotics are the mainstay of treatment for schizophrenia in every age group and subcategories of schizophrenia.The evaluation based on WHO prescribing indicators showed a low average number of drugs per prescription and low prescribing frequency of antipsychotics from the National List of Essential Medicines 2015 and the WHO Essential Medicines List 2019.The total mean drug cost of our study was 1396 Indian rupees.The total mean cost due to the investigation in our study was 1017.34 Indian rupees.Therefore,the total mean direct medical cost incurred on patients in our study was 4337.28 Indian rupees.CONCLUSION The information from the present study can be used for reviewing and updating treatment policy at the institutional level.
基金supported by the National Natural Science Foundation of China(62373317)the Tianshan Talent Training Program(2022TSYCCX0013)+3 种基金the Key Project of Natural Science Foundation of Xinjiang(2021D01D10)the Basic Research Foundation for Universities of Xinjiang(XJEDU2023P023)the Xinjiang Key Laboratory of Applied Mathematics(XJDX1401)the Intelligent Control and Optimization Research Platform in Xinjiang University.
文摘This paper is dedicated to fixed-time passivity and synchronization for multi-weighted spatiotemporal directed networks.First,to achieve fixed-time passivity,a type of decentralized power-law controller is developed,in which only one parameter needs to be adjusted in the power-law terms;this greatly decreases the inconvenience of parameter adjustment.Second,several fixed-time passivity criteria with LMI forms are derived by using a Gauss divergence theorem to deal with the spatial diffusion of nodes and by applying the Hölder’s inequality to dispose rigorously the power-law term greater than one in the designed control scheme;this improves the previous theoretical analysis.Additionally,the fixed-time synchronization of spatiotemporal directed networks with multi-weights is addressed as a direct result of fixed-time strict passivity.Finally,a numerical example is presented in order to show the validity of the theoretical analysis.
基金supported in part by the National Natural Science Foundation of China under Grants 62025110,62271093sponsored by Natural Science Foundation of Chongqing,China,under Grant CSTB2023NSCQ-LZX0108.
文摘Efficient energy utilization in covert communication sustains covertness while assuring communication quality and efficiency.This paper investigates covert communication energy efficiency(EE)in direct uplink satellite-ground communications,focusing on enhancing system EE via optimized transmit beamforming and satellite orbit altitude selection.This paper first establishes an optimization problem to maximize system EE in a direct uplink satelliteground covert communication scenario.To solve this non-convex optimization problem,it is decomposed into two subproblems and solved using the successive convex approximation(SCA)method.Based on the above methods,this paper proposes an overall iterative optimization algorithm.Simulation results demonstrate that the proposed algorithm surpasses the conventional baseline algorithms in terms of system EE.Furthermore,they elucidate the correlation between the amount of information received by the receiver and the variations in the satellite’s orbital altitude.
基金financially supported by the National Key Research and Development Program of China(Nos.2024YFB4607402 and 2016YFC1100502)the National Natural Science Foundation of China(Nos.51673208 and 61975213)。
文摘Biopolymeric nanocomposites have attracted considerable attention because of their biocompatibility,biodegradability,and unique physicochemical properties.It is essential to manufacture three-dimensional(3D)biocompatible micro/nanostructures using biopolymeric nanocomposites.Herein,we demonstrate the high-fidelity fabrication of biocompatible 3D features with sub-50 nm resolution using femtosecond laser direct writing(FsLDW)of a biopolymeric nanocomposite composed of egg white and sulfonated graphene(S-graphene).The biopolymer nanocomposite acts as a negative photoresist suitable for water-based lithography.The introduction of S-graphene not only dramatically lowered the laser power threshold but also significantly modulated the morphology of the 3D features constructed by FsLDW.Microstructures with porous,rough,or smooth morphologies were obtained by optimizing the S-graphene concentration and laser scanning speed.The fabricated egg-white/S-graphene microstructures exhibited biocompatibility and environmental degradability.Egg white/S-graphene was also employed to fabricate diffractive gratings with superior optical quality.This study provides a promising method to manufacture biocompatible 3D features with controllable morphology,which has potential applications in biological and photonic fields.
基金financial support from the National Key R&D Program of China(2022YFB2402600)the National Natural Science Foundation of China(52372250,52125105,52173242)+1 种基金Shenzhen Science and Technology Planning Project(RCYX20221008092850072,JSGG20220831104004008,KJZD20230923113859006,JCYJ20220531100405012,KJZD20241122161900001)Science and Technology Planning Project of Guangdong Province(2024A1515030076)。
文摘The rapid accumulation of spent LiFePO_(4)(LFP)cathodes from retired lithium-ion batteries necessitates the development of effective and environmental-friendly recycling strategies.In this context,direct regeneration has emerged as a promising approach for reclaiming LFP cathode materials,offering a streamlined pathway to restore their electrochemical functionality.We report an integrated regeneration protocol that simultaneously repairs the degraded crystal structure and reconstructs the damaged carbon coating in spent LFP.The regenerated cathode material had superfast lithium-ion diffusion kinetics and a stable cathode-electrolyte interface,giving a remarkable rate capability with specific capacities of 122 m Ah g^(-1)at 5C and 106 m Ah g^(-1)at 10C(1C=170 m A g^(-1)).It also maintained capacities of 110.7 m Ah g^(-1)(5C)and 84.1 m Ah g^(-1)(10C)after 400 cycles.It could be used in harsh environments and could be stably cycled at subzero temperatures(-10 and-20°C)and in solid-state electrolyte batteries.Life cycle assessment combined with economic evaluation using the Ever Batt model reveals that this direct regeneration approach has high economic and environmental benefits.
基金supported by Guangdong Major Project of Basic and Applied Basic Research(Grant No.2021B0301030002)the National Key Research and Development Program(Grant No.2021YFA1202900)the National Natural Science Foundation of China(Grant Nos.62204166 and 62404145)。
文摘When stacking two-dimensional(2D)materials with a lattice mismatch and/or a small twist,moirésuperlattice emerges with fascinating electronic and optical properties.The fabrication of such stacked 2D materials usually requires multiple transfer and stack processes,assisted by a certain transfer medium which needs to be removed afterwards,and it is very challenging to maintain pristine and clean surfaces/interfaces for these stacked structures.In this work,we report a facile direct bonding method for fabrication of twisted MoS_(2) bilayers with ultra-clean surfaces/interfaces.Novel interlayer interactions are revealed in the as-fabricated high-quality samples,leading to twist-angle related dispersion behavior of various Raman modes,such as layer breathing modes,shear modes and E_(2g)modes,as well as indirect bandgap excitons.Field-effect transistors(FETs)of twisted MoS_(2) bilayers also exhibit angle-dependent performance,which could be attributed to the band structure evolution.This facile method holds significance for the future integration of pre-designed multilayer 2D materials and paves a way to explore underlying physical mechanisms and potential applications.
文摘Exercise produces a decrease in pain sensitivity via an effect called exercise-induced hypoalgesia(EIH).Transcranial direct current stimulation(tDCS),acting on similar analgesic mechanisms as EIH,represents a potential complementary intervention that may amplify the effects of exercise on pain.This study aimed to explore if anodal tDCS could enhance the effect of exercise on pain compared to exercise alone.A total of 35 healthy participants aged 19–37 years completed a familiarisation session followed by two separate sessions where active and sham tDCS was applied in a randomised cross-over design.The familiarisation session involved familiarisation to the pain assessment and exercise tasks,while the subsequent tDCS sessions involved pain sensitivity assessment,exercise and either anodal tDCS or sham tDCS.tDCS doses were applied at 2 mA over the primary motor cortex for 10 min,with the reference electrode placed over the contralateral supraorbital area.The exercise task involved a sustained isometric grip strength contraction at 35%of maximal voluntary contraction(MVC)until volitional exhaustion.Pain sensitivity was evaluated as pressure pain threshold before tDCS,after tDCS,and after exercise.Across both tDCS conditions,pain threshold was higher after exercise when compared to pre-and post-tDCS measurement.This increase in pain threshold did not differ between active and sham tDCS conditions.Our findings suggest that the hypoalgesic effects of active anodal tDCS over the motor cortex prior to exercise are no greater than the effects of sham tDCS prior to exercise.
基金supported by the Czech Science Foundation (23-06160S)by the Faculty of Medicine of Masaryk University (MUNI/A/1738/2024)。
文摘Enamel,the inorganic tissue covering the crowns of teeth,is known for its remarkable resilience and hardness.These properties originate from its high proportion of mineralized matrix and complex internal microarchitecture.On an ultrastructural level,it consists of directionally arranged enamel prisms.Continuously growing rodent incisors are an exemplary case of this phenomenon.Their enamel has a consistent decussation pattern,providing teeth with extremely high resistance and ensuring they remain constantly sharp.While the decussation pattern has been described in detail,mechanisms behind its formation have not been experimentally proven.Here,we show that the highly organized enamel micropattern is generated by directional epithelial sliding of enamel-forming ameloblasts in vivo.Our results detail how enamel micropatterning stems from individual cell cluster segregation and subsequent reciprocal interweaving.Based on this determination,we introduce and experimentally demonstrate a new model of enamel decussation pattern formation.
