Agricultural land development is a pivotal strategy for addressing the global food security crisis.Barren grassland,especially those in mountainous regions,constitutes critical areas where cultivation can substantiall...Agricultural land development is a pivotal strategy for addressing the global food security crisis.Barren grassland,especially those in mountainous regions,constitutes critical areas where cultivation can substantially enhance land resources.This study highlights the necessity for a precise correlation between land development initiatives and constraints in order to optimize efficiency and enhance the effectiveness of such projects,with the core being the seamless integration of land development engineering and techniques to eliminate agricultural constraints.This study employs a systems engineering approach to classify improvement factors into mobile and fixed categories,elucidating the integration methods of constraint factors.Adhering to the Wooden Barrel Principle,these constraints were rigorously analyzed based on soil quality,land topography,water availability,and agricultural infrastructure.An innovative method of engineering type combination is proposed,which effectively explains the correlation between natural factors combination,project type combination,and target factors combination.It provides a convenient way for the selection of barren grassland development projects and lays a foundation for land planning,development project establishment,program selection,engineering design,and budget preparation.Taking Tang County of China as an example,it is divided into 19 factor improvement areas,a quick reference table of engineering types is established,and 14 main types of engineering combinations are obtained,which lays a foundation for the application of theoretical framework in practice.展开更多
The spinning deployment process of solar sails is analyzed in this study. A simplified model is established by considering the out-of-plane and in-plane motions of solar sails. The influences of structure parameters, ...The spinning deployment process of solar sails is analyzed in this study. A simplified model is established by considering the out-of-plane and in-plane motions of solar sails. The influences of structure parameters, initial conditions, and feedback control parameters are also analyzed.A method to build the geometric model of a solar sail is presented by analyzing the folding process of solar sails. The finite element model of solar sails is then established, which contains continuous cables and sail membranes. The dynamics of the second-stage deployment of solar sails are simulated by using ABAQUS software. The influences of the rotational speed and out-of-plane movement of the hub are analyzed by different tip masses, initial velocities, and control parameters.Compared with the results from theoretical models, simulation results show good agreements.展开更多
Self-powered flexible devices with skin-like multiple sensing ability have attracted great attentions due to their broad applications in the Internet of Things(IoT).Various methods have been proposed to enhance mechan...Self-powered flexible devices with skin-like multiple sensing ability have attracted great attentions due to their broad applications in the Internet of Things(IoT).Various methods have been proposed to enhance mechano-optic or electric performance of the flexible devices;however,it remains challenging to realize the display and accurate recognition of motion trajectories for intelligent control.Here,we present a fully self-powered mechanoluminescent-triboelectric bimodal sensor based on micronanostructured mechanoluminescent elastomer,which can patterned-display the force trajectories.The deformable liquid metals used as stretchable electrode make the stress transfer stable through overall device to achieve outstanding mechanoluminescence(with a gray value of 107 under a stimulus force as low as 0.3 N and more than 2000 cycles reproducibility).Moreover,a microstructured surface is constructed which endows the resulted composite with significantly improved triboelectric performances(voltage increases from 8 to 24 V).Based on the excellent bimodal sensing performances and durability of the obtained composite,a highly reliable intelligent control system by machine learning has been developed for controlling trolley,providing an approach for advanced visual interaction devices and smart wearable electronics in the future IoT era.展开更多
In this review,the history and outlook of gas-phase CO_(2)activation using single electrons,metal atoms,clusters(mainly metal hydride clusters),and molecules are discussed on both of the experimental and theoretical f...In this review,the history and outlook of gas-phase CO_(2)activation using single electrons,metal atoms,clusters(mainly metal hydride clusters),and molecules are discussed on both of the experimental and theoretical fronts.Although the development of bulk solid-state materials for the activation and conversion of CO_(2)into value-added products have enjoyed great success in the past several decades,this review focuses only on gas-phase studies,because isolated,well-defined gas-phase systems are ideally suited for high-resolution experiments using state-of-the-art spectrometric and spectroscopic techniques,and for simulations employing modern quantum theoretical methods.The unmatched high complementarity and comparability of experiment and theory in the case of gas-phase investigations bear an enormous potential in providing insights in the reactions of CO_(2)activation at the atomic level.In all of these examples,the reduction and bending of the inert neutral CO_(2)molecule is the critical step determined by the frontier orbitals of reaction participants.Based on the results and outlook summarized in this review,we anticipate that studies of gas-phase CO_(2)activations will be an avenue rich with opportunities for the rational design of novel catalysts based on the knowledge obtained on the atomic level.展开更多
The new-generation electronic components require a balance between electromagnetic interference shielding efficiency and open structure factors such as ventilation and heat dissipation.In addition,realizing the tunabl...The new-generation electronic components require a balance between electromagnetic interference shielding efficiency and open structure factors such as ventilation and heat dissipation.In addition,realizing the tunable shielding of porous shields over a wide range of wavelengths is even more challenging.In this study,the well-prepared thermoplastic polyurethane/carbon nanotubes composites were used to fabricate the novel periodic porous flexible metamaterials using fused deposition modeling 3D printing.Particularly,the investigation focuses on optimization of pore geometry,size,dislocation configuration and material thickness,thus establishing a clear correlation between structural parameters and shielding property.Both experimental and simulation results have validated the superior shielding performance of hexagon derived honeycomb structure over other designs,and proposed the failure shielding size(D_(f)≈λ/8-λ/5)and critical inclined angle(θf≈43°-48°),which could be used as new benchmarks for tunable electromagnetic shielding.In addition,the proper regulation of the material thickness could remarkably enhance the maximum shielding capability(85-95 dB)and absorption coefficient A(over 0.83).The final innovative design of the porous shielding box also exhibits good shielding effectiveness across a broad frequency range(over 2.4 GHz),opening up novel pathways for individualized and diversified shielding solutions.展开更多
^(231)Pa and ^(230)Th are two crucial isotopes in the ongoing GEOTRACES Project.However,the controversy on ^(231)Pa/^(230)Th proxy pertaining to archiving ocean circulation or recording paleoproductivity,is still unre...^(231)Pa and ^(230)Th are two crucial isotopes in the ongoing GEOTRACES Project.However,the controversy on ^(231)Pa/^(230)Th proxy pertaining to archiving ocean circulation or recording paleoproductivity,is still unresolved,partly owing to the unclear understanding of fractionation between ^(231)Pa and ^(230)Th during adsorption.In this study,controlled experiments were conducted to examine the adsorption of ^(234)Th and ^(233)Pa onto biogenic particles(SiO_(2) and CaCO_(3)),authigenic minerals(MnO_(2) and Fe_(2)O_(3)),and lithogenic minerals(kaolinite,attapulgite,montmorillonite,and aluminum oxyhydroxides),and the role of organic compounds in regulating the adsorption of ^(234)Th and ^(233)Pa in natural seawater was evaluated.The distribution coefficients(K d,presented as logK_(d))varied from 3.56 to 6.05 and from 3.27 to 5.82 for ^(234)Th and ^(233)Pa,respectively.Fe_(2)O_(3) is the strongest sorbent for both ^(234)Th and ^(233)Pa.Most of the particles showed comparable logK_(d) values for either ^(234)Th(~4.8)or ^(233)Pa(~3.9)in the presence of dextran,indicating that the adsorption of Th and Pa is likely controlled by organic coating on particle surfaces.The fractionation factors(F Th/Pa)of SiO_(2)(3±1)and CaCO_(3)(33±1)suggest in situ observed preferential scavenging of ^(230)Th to ^(231)Pa in the surface water of low-to mid-latitude regions and the nearly equal removal in the Antarctic Ocean where biogenic silica dominates the particle regime.The F Th/Pa values of the lithogenic and biogenic particles indicate that ^(230)Th is scavenged prior to ^(231)Pa in the particle-scarce ocean interior.The equal scavenging of ^(230)Th and ^(231)Pa at the ocean margins and the ridge crests is dominated by high particle fl uxes instead of particle composition control.These results imply that ^(230)Th/^(231)Pa can be used as different proxies in different oceanic settings.展开更多
Herein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process...Herein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process under mild conditions with a broad substrate scope with excellent functional group compatibilities,such as free carboxylic acid, aldehyde, halogen(including aryl iodide), amide and amino acid. The use of the nickel catalyst in combination with water provides a safe, green and economical method for oxidation of a range of molecules varying in complexity and drug derivatives, demonstrating its potential application in organic synthesis and the pharmaceutical industry. Reaction outcomes and mechanistic studies revealed the key role of the in situ Ni(Ⅱ)-dioxygen species for the subsequent oxidation of C(sp^(3))–H bonds,and short-lived reactive intermediates(aryl radical cation) was rapidly captured by the combination of a bipolar ultramicroelectrode(BUME) with nano-electrospray ionization mass spectrometry.展开更多
The simple homodinuclear M-M single bonds for group II and XII elements are difficult to obtain as a result of the fulfilled s2electronic configurations,consequently,a dicationic prototype is often utilized to design ...The simple homodinuclear M-M single bonds for group II and XII elements are difficult to obtain as a result of the fulfilled s2electronic configurations,consequently,a dicationic prototype is often utilized to design the M^+-M^+single bond.Existing studies generally use sterically bulky organic ligands L^-to synthesize the compounds in the L^--M^+-M^+-L-manner.However,here we report the design of Mg-Mg and Zn-Zn single bonds in two ligandless clusters,Mg2B7-and Zn2B7-,using density functional theory methods.The global minima of both of the clusters are in the form of M2^2+(B7^3-),where the M-M single bonds are positioned above a quasi-planar hexagonal B7 moiety.Chemical bonding analyses further confirm the existence of Mg-Mg and Zn-Zn single bonds in these clusters,which are driven by the unusually stable B7^3-moiety that is bothσandπaromatic.Vertical detachment energies of Mg2B7-and Zn2B7-are calculated to be 2.79 e V and 2.94 e V,respectively,for the future comparisons with experimental data.展开更多
Metal-enriched minerals have been widely observed near hydrothermal vent fields.However,the dynamics of particulate metals influenced by hydrothermal activities is poorly constrained.Here,radioactive 234Th in both dis...Metal-enriched minerals have been widely observed near hydrothermal vent fields.However,the dynamics of particulate metals influenced by hydrothermal activities is poorly constrained.Here,radioactive 234Th in both dissolved and particulate phases were used to examine the kinetics of particle-reactive metal adsorption,removal,and residence in a newly found hydrothermal plume over the Southwest Indian Ridge.The results showed a relatively low value on ^(234)Th/^(238)U ratios(i.e.,0.73-0.88)compared to the deep oceans,indicating an enhanced adsorption of particle-reactive metals onto particulate matter in the plume.Based on the 234Th-238U disequilibria,the adsorption and sinking rate constants of 234Th averaged(0.009±0.001)d^(-1) and(0.113±0.024)d^(-1) in the hydrothermal plume,corresponding to the residence times of(115±19)d and(16±5)d for dissolved and particulate 234Th,respectively.This timescale allows vent-discharged particle-reactive metals to disperse hundreds to thousands of miles away.Thus,hydrothermal activities might influence the metal distribution in deep ocean over a very large scope.Also,a high sinking flux of(36.2±5.4)B q/(m^(2)·d)for 234Th was observed for the plume,suggesting an enrichment of metal in particles deposited close to the vent.The enhancement of particle sinking could also benefit the transport of organic carbon and nitrogen and fuel the benthic ecosystems under the plume regimes.Thus,hydrothermal plumes may have an impact on both the elemental geochemistry and/or ecosystem to the deep oceans interior than previous expectation.展开更多
The influence of bread-loaf shaped magnet poles under parallel magnetization on the cogging torque of surface-mounted permanent magnet(SPM)motors is studied.For the SPM motors having magnetic poles with eccentricity a...The influence of bread-loaf shaped magnet poles under parallel magnetization on the cogging torque of surface-mounted permanent magnet(SPM)motors is studied.For the SPM motors having magnetic poles with eccentricity and sine harmonic compensation,the electromagnetic performances of integer and fractional slot motors are compared.It is found that the cogging torque and torque ripple of the integer and fractional slot motors can be reduced with the same eccentric magnet pole.The cogging torque and torque ripple of a fractional slot motor can be decreased by sine harmonic compensation,however,the same sine harmonic compensation has a small influence in integer slot motors.By varying the magnetic poles,the contribution of the field harmonics(k=(2n+1)p),which are a direct result of magnet magnetization,to the cogging torque also changes.The electromagnetic performance of a 3 kW prototype is tested,and it is found that the experimental results validate the theoretical investigation.展开更多
If a person comes into contact with pathogens on public facilities,there is a threat of contact(skin/wound)infections.More urgently,there are also reports about COVID-19 coronavirus contact infection,which once again ...If a person comes into contact with pathogens on public facilities,there is a threat of contact(skin/wound)infections.More urgently,there are also reports about COVID-19 coronavirus contact infection,which once again reminds that contact infection is a very easily overlooked disease exposure route.Herein,we propose an innovative implantation strategy to fabricate a multi-walled carbon nanotube/polyvinyl alcohol(MWCNT/PVA,MCP)interpenetrating interface to achieve flexibility,anti-damage,and non-contact sensing electronic skin(E-skin).Interestingly,the MCP E-skin had a fascinating non-contact sensing function,which can respond to the finger approaching 0−20 mm through the spatial weak field.This non-contact sensing can be applied urgently to human–machine interactions in public facilities to block pathogen.The scratches of the fruit knife did not damage the MCP E-skin,and can resist chemical corrosion after hydrophobic treatment.In addition,the MCP E-skin was developed to real-time monitor the respiratory and cough for exercise detection and disease diagnosis.Notably,the MCP E-skin has great potential for emergency applications in times of infectious disease pandemics.展开更多
Developing strain sensors with both high sensitivity and high linearity has always been the goal of researchers.Compared to resistive strain sensors,capacitive strain sensors have incomparable linearity advantages,but...Developing strain sensors with both high sensitivity and high linearity has always been the goal of researchers.Compared to resistive strain sensors,capacitive strain sensors have incomparable linearity advantages,but have always been limited by low sensitivity.Here,we report a gradient stiffness sliding design strategy that addresses this problem,significantly improving sensitivity while maintaining high linearity.By controlling the distribution of the locally enhanced electric field and the heterogeneous deformation of the substrate,a strain sensor with excellent performance is successfully prepared,exhibiting a giant gauge factor(9.1×10^(6))and linearity(R^(2)=0.9997)over the entire sensing range,together with almost no hysteresis and fast response time(17 ms).The gradient stiffness sliding design is a general strategy expected to be applied to other types of sensors to achieve ultra-high sensitivity and ultra-high linearity at the same time.展开更多
Slide-ring structured polyrotaxanes with high molecular mobility and reversible conformational transition ability can achieve high performance and multifunctionality of the material in various applications.There have ...Slide-ring structured polyrotaxanes with high molecular mobility and reversible conformational transition ability can achieve high performance and multifunctionality of the material in various applications.There have been many reviews describing advances in the research of rotaxanes and polyrotaxanes.However,most of them typically focus on the precise synthesis of mechanically interlocked molecules and the control of microscopic molecular shuttles.In this review,we examine the effects of motion activity and conformational transition due to molecular slide on the performance of polyrotaxanes and the latest functional applications.Different designs of polyrotaxane-based functional materials are presented to improve the potential for applications including self-healing stretchable elastomers/gels,stimuli-responsive smart devices,battery electrode binders,and biomedical drug delivery.It is anticipated that this review will provide insights and guidance for future developments in the design,synthesis and application of polyrotaxane-based functional materials.展开更多
Humic-like substances(HULIS),a class of macromolecular photosensitizers,are major components of light-absorbing aerosols in the atmosphere.Due to the amphiphilic nature of HULIS,they tend to appear at the air-water in...Humic-like substances(HULIS),a class of macromolecular photosensitizers,are major components of light-absorbing aerosols in the atmosphere.Due to the amphiphilic nature of HULIS,they tend to appear at the air-water interface of atmospheric water.However,there have been limited studies on the photosensitized chemistry of HULIS at the air-water interface owing to the lack of methods with high interface selectivity.Here,a unique field-induced droplet ionization mass spectrometry(FIDI-MS)technique was used to investigate the photosensitized chemistry of several samples at the air-water interface.These samples include commercially available humic acid and the PM_(2.5)sample collected during Beijing′s severe winter haze in December 2016.Ultrahigh-resolution Fourier transform-ion cyclotron resonance mass spectrometry(FT-ICR MS)was also applied to analyze the atomic compositions,the degree of unsaturation and the aromaticity of these samples.Both TypeⅠand TypeⅡphotosensitized oxidation pathways were observed,which were postulated to be dictated by the packing density of the molecules at the air-water interface.These findings reveal that the photosensitization of HULIS at the air-water interface contributes greatly to the formation of atmospheric aerosols,further advancing our understanding of the important roles played by photosensitized chemistry in the atmosphere.展开更多
The capacity of biological tissues to undergo self-healing is crucial for the performance of functions and the continuation of life.Conventional intrinsic self-healing materials demonstrate analogous functionality dep...The capacity of biological tissues to undergo self-healing is crucial for the performance of functions and the continuation of life.Conventional intrinsic self-healing materials demonstrate analogous functionality depending on the dissociation-recombination of reversible bonds with no need of extra repair agents.However,the trade-off relationship between mechanical strength and self-healing kinetics in intrinsic self-healing systems,coupled with the lack of additional functionality,restricts their service life and practical applications.Diversified highly ordered structures in organisms significantly affect the energy dissipation mechanism,signal transmission efficiency,and molecular network reconstruction capability due to their multi-dimensional differentiated macroscopic composite constructions,microscopic orientation textures,and topologies/bonding types at molecular level.These architectures exhibit distinctive strengthening mechanisms and functionalities,which provide valuable references.This review aims at providing the current status of advanced intrinsic self-healing materials with biomimetic highly ordered internal micro/nanostructures.Through highlighting specific examples,the classifications,design inspirations,and fabrication strategies of these newly developed materials based on integrating dynamic interactions with ordered nano/microstructures are outlined.Furthermore,the strengthening and selfhealing balance mechanisms,structure–functionalization relationships,and potential application values are discussed.The review concludes with a perspective on the challenges,opportunities,and prospects for the development,application,and promotion of self-healable materials with bio-like ordered architectures.展开更多
基金funded by Science and Technology Project of Hebei Education Department[QN2023085].
文摘Agricultural land development is a pivotal strategy for addressing the global food security crisis.Barren grassland,especially those in mountainous regions,constitutes critical areas where cultivation can substantially enhance land resources.This study highlights the necessity for a precise correlation between land development initiatives and constraints in order to optimize efficiency and enhance the effectiveness of such projects,with the core being the seamless integration of land development engineering and techniques to eliminate agricultural constraints.This study employs a systems engineering approach to classify improvement factors into mobile and fixed categories,elucidating the integration methods of constraint factors.Adhering to the Wooden Barrel Principle,these constraints were rigorously analyzed based on soil quality,land topography,water availability,and agricultural infrastructure.An innovative method of engineering type combination is proposed,which effectively explains the correlation between natural factors combination,project type combination,and target factors combination.It provides a convenient way for the selection of barren grassland development projects and lays a foundation for land planning,development project establishment,program selection,engineering design,and budget preparation.Taking Tang County of China as an example,it is divided into 19 factor improvement areas,a quick reference table of engineering types is established,and 14 main types of engineering combinations are obtained,which lays a foundation for the application of theoretical framework in practice.
基金supported in part by the National Natural Science Foundation of China(Nos. 11290151 and 51075032)
文摘The spinning deployment process of solar sails is analyzed in this study. A simplified model is established by considering the out-of-plane and in-plane motions of solar sails. The influences of structure parameters, initial conditions, and feedback control parameters are also analyzed.A method to build the geometric model of a solar sail is presented by analyzing the folding process of solar sails. The finite element model of solar sails is then established, which contains continuous cables and sail membranes. The dynamics of the second-stage deployment of solar sails are simulated by using ABAQUS software. The influences of the rotational speed and out-of-plane movement of the hub are analyzed by different tip masses, initial velocities, and control parameters.Compared with the results from theoretical models, simulation results show good agreements.
基金the National Natural Science Foundation of China(52173112 and 51873123)Sichuan Provincial Natural Science Fund for Distinguished Young Scholars(2021JDJQ0017)the Program for Featured Directions of Engineering Multidisciplines of Sichuan University(No:2020SCUNG203)for financial support。
文摘Self-powered flexible devices with skin-like multiple sensing ability have attracted great attentions due to their broad applications in the Internet of Things(IoT).Various methods have been proposed to enhance mechano-optic or electric performance of the flexible devices;however,it remains challenging to realize the display and accurate recognition of motion trajectories for intelligent control.Here,we present a fully self-powered mechanoluminescent-triboelectric bimodal sensor based on micronanostructured mechanoluminescent elastomer,which can patterned-display the force trajectories.The deformable liquid metals used as stretchable electrode make the stress transfer stable through overall device to achieve outstanding mechanoluminescence(with a gray value of 107 under a stimulus force as low as 0.3 N and more than 2000 cycles reproducibility).Moreover,a microstructured surface is constructed which endows the resulted composite with significantly improved triboelectric performances(voltage increases from 8 to 24 V).Based on the excellent bimodal sensing performances and durability of the obtained composite,a highly reliable intelligent control system by machine learning has been developed for controlling trolley,providing an approach for advanced visual interaction devices and smart wearable electronics in the future IoT era.
基金National Key R&D Program of China(2018YFE0115000)the National Natural Science Foundation of China(22003027 and 22174073)+2 种基金the NSF of Tianjin City(19JCYBJC19600)the Frontiers Science Center for New Organic Matter of Nankai University(63181206)supported by the Air Force Office of Scientific Research(AFOSR)under grant number,FA9550-19-1-0077(KHB)。
文摘In this review,the history and outlook of gas-phase CO_(2)activation using single electrons,metal atoms,clusters(mainly metal hydride clusters),and molecules are discussed on both of the experimental and theoretical fronts.Although the development of bulk solid-state materials for the activation and conversion of CO_(2)into value-added products have enjoyed great success in the past several decades,this review focuses only on gas-phase studies,because isolated,well-defined gas-phase systems are ideally suited for high-resolution experiments using state-of-the-art spectrometric and spectroscopic techniques,and for simulations employing modern quantum theoretical methods.The unmatched high complementarity and comparability of experiment and theory in the case of gas-phase investigations bear an enormous potential in providing insights in the reactions of CO_(2)activation at the atomic level.In all of these examples,the reduction and bending of the inert neutral CO_(2)molecule is the critical step determined by the frontier orbitals of reaction participants.Based on the results and outlook summarized in this review,we anticipate that studies of gas-phase CO_(2)activations will be an avenue rich with opportunities for the rational design of novel catalysts based on the knowledge obtained on the atomic level.
基金supported by the National Key R&D Program of China(2023YFB4603504)the International Science&Technology Innovation Cooperation Project of Sichuan Province(2024YFHZ0232)+2 种基金the International Science&Technology Cooperation Project of Chengdu(2021-GH03-00009-HZ)the Program for Featured Directions of Engineering Multi-disciplines of Sichuan University(2020SCUNG203)the Program of Innovative Research Team for Young Scientists of Sichuan Province(22CXTD0019).
文摘The new-generation electronic components require a balance between electromagnetic interference shielding efficiency and open structure factors such as ventilation and heat dissipation.In addition,realizing the tunable shielding of porous shields over a wide range of wavelengths is even more challenging.In this study,the well-prepared thermoplastic polyurethane/carbon nanotubes composites were used to fabricate the novel periodic porous flexible metamaterials using fused deposition modeling 3D printing.Particularly,the investigation focuses on optimization of pore geometry,size,dislocation configuration and material thickness,thus establishing a clear correlation between structural parameters and shielding property.Both experimental and simulation results have validated the superior shielding performance of hexagon derived honeycomb structure over other designs,and proposed the failure shielding size(D_(f)≈λ/8-λ/5)and critical inclined angle(θf≈43°-48°),which could be used as new benchmarks for tunable electromagnetic shielding.In addition,the proper regulation of the material thickness could remarkably enhance the maximum shielding capability(85-95 dB)and absorption coefficient A(over 0.83).The final innovative design of the porous shielding box also exhibits good shielding effectiveness across a broad frequency range(over 2.4 GHz),opening up novel pathways for individualized and diversified shielding solutions.
基金Supported by the National Natural Science Foundation of China(Nos.42076030,41476061)andNational Key Basic Research Special Foundation Program of China(No.2015CB452902)。
文摘^(231)Pa and ^(230)Th are two crucial isotopes in the ongoing GEOTRACES Project.However,the controversy on ^(231)Pa/^(230)Th proxy pertaining to archiving ocean circulation or recording paleoproductivity,is still unresolved,partly owing to the unclear understanding of fractionation between ^(231)Pa and ^(230)Th during adsorption.In this study,controlled experiments were conducted to examine the adsorption of ^(234)Th and ^(233)Pa onto biogenic particles(SiO_(2) and CaCO_(3)),authigenic minerals(MnO_(2) and Fe_(2)O_(3)),and lithogenic minerals(kaolinite,attapulgite,montmorillonite,and aluminum oxyhydroxides),and the role of organic compounds in regulating the adsorption of ^(234)Th and ^(233)Pa in natural seawater was evaluated.The distribution coefficients(K d,presented as logK_(d))varied from 3.56 to 6.05 and from 3.27 to 5.82 for ^(234)Th and ^(233)Pa,respectively.Fe_(2)O_(3) is the strongest sorbent for both ^(234)Th and ^(233)Pa.Most of the particles showed comparable logK_(d) values for either ^(234)Th(~4.8)or ^(233)Pa(~3.9)in the presence of dextran,indicating that the adsorption of Th and Pa is likely controlled by organic coating on particle surfaces.The fractionation factors(F Th/Pa)of SiO_(2)(3±1)and CaCO_(3)(33±1)suggest in situ observed preferential scavenging of ^(230)Th to ^(231)Pa in the surface water of low-to mid-latitude regions and the nearly equal removal in the Antarctic Ocean where biogenic silica dominates the particle regime.The F Th/Pa values of the lithogenic and biogenic particles indicate that ^(230)Th is scavenged prior to ^(231)Pa in the particle-scarce ocean interior.The equal scavenging of ^(230)Th and ^(231)Pa at the ocean margins and the ridge crests is dominated by high particle fl uxes instead of particle composition control.These results imply that ^(230)Th/^(231)Pa can be used as different proxies in different oceanic settings.
基金Financial support from National Key R&D Program of China(No.2022YFA1503200)National Natural Science Foundation of China(No.22188101)+1 种基金the Fundamental Research Funds for the Central Universities(No.63223007)Frontiers Science Center for New Organic Matter,Nankai University(No.63181206)and Nankai University.
文摘Herein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process under mild conditions with a broad substrate scope with excellent functional group compatibilities,such as free carboxylic acid, aldehyde, halogen(including aryl iodide), amide and amino acid. The use of the nickel catalyst in combination with water provides a safe, green and economical method for oxidation of a range of molecules varying in complexity and drug derivatives, demonstrating its potential application in organic synthesis and the pharmaceutical industry. Reaction outcomes and mechanistic studies revealed the key role of the in situ Ni(Ⅱ)-dioxygen species for the subsequent oxidation of C(sp^(3))–H bonds,and short-lived reactive intermediates(aryl radical cation) was rapidly captured by the combination of a bipolar ultramicroelectrode(BUME) with nano-electrospray ionization mass spectrometry.
基金supported by the National Key R&D Program of China(No.2018YFE0115000)the Natural Science Foundation of Tianjin City(No.19JCYBJC19600)。
文摘The simple homodinuclear M-M single bonds for group II and XII elements are difficult to obtain as a result of the fulfilled s2electronic configurations,consequently,a dicationic prototype is often utilized to design the M^+-M^+single bond.Existing studies generally use sterically bulky organic ligands L^-to synthesize the compounds in the L^--M^+-M^+-L-manner.However,here we report the design of Mg-Mg and Zn-Zn single bonds in two ligandless clusters,Mg2B7-and Zn2B7-,using density functional theory methods.The global minima of both of the clusters are in the form of M2^2+(B7^3-),where the M-M single bonds are positioned above a quasi-planar hexagonal B7 moiety.Chemical bonding analyses further confirm the existence of Mg-Mg and Zn-Zn single bonds in these clusters,which are driven by the unusually stable B7^3-moiety that is bothσandπaromatic.Vertical detachment energies of Mg2B7-and Zn2B7-are calculated to be 2.79 e V and 2.94 e V,respectively,for the future comparisons with experimental data.
基金The National Natural Science Foundation of China under contract Nos 41721005,41476061China Ocean Mineral Resources R&D Association Programs under contract Nos DY135-E2-2-03,DY125-22-QY-17the Fundamental Research Funds for the Central Universities under contract No.20720190102。
文摘Metal-enriched minerals have been widely observed near hydrothermal vent fields.However,the dynamics of particulate metals influenced by hydrothermal activities is poorly constrained.Here,radioactive 234Th in both dissolved and particulate phases were used to examine the kinetics of particle-reactive metal adsorption,removal,and residence in a newly found hydrothermal plume over the Southwest Indian Ridge.The results showed a relatively low value on ^(234)Th/^(238)U ratios(i.e.,0.73-0.88)compared to the deep oceans,indicating an enhanced adsorption of particle-reactive metals onto particulate matter in the plume.Based on the 234Th-238U disequilibria,the adsorption and sinking rate constants of 234Th averaged(0.009±0.001)d^(-1) and(0.113±0.024)d^(-1) in the hydrothermal plume,corresponding to the residence times of(115±19)d and(16±5)d for dissolved and particulate 234Th,respectively.This timescale allows vent-discharged particle-reactive metals to disperse hundreds to thousands of miles away.Thus,hydrothermal activities might influence the metal distribution in deep ocean over a very large scope.Also,a high sinking flux of(36.2±5.4)B q/(m^(2)·d)for 234Th was observed for the plume,suggesting an enrichment of metal in particles deposited close to the vent.The enhancement of particle sinking could also benefit the transport of organic carbon and nitrogen and fuel the benthic ecosystems under the plume regimes.Thus,hydrothermal plumes may have an impact on both the elemental geochemistry and/or ecosystem to the deep oceans interior than previous expectation.
基金Supported by the Key Research and Development Program of Jiangsu Province(BE2018107).
文摘The influence of bread-loaf shaped magnet poles under parallel magnetization on the cogging torque of surface-mounted permanent magnet(SPM)motors is studied.For the SPM motors having magnetic poles with eccentricity and sine harmonic compensation,the electromagnetic performances of integer and fractional slot motors are compared.It is found that the cogging torque and torque ripple of the integer and fractional slot motors can be reduced with the same eccentric magnet pole.The cogging torque and torque ripple of a fractional slot motor can be decreased by sine harmonic compensation,however,the same sine harmonic compensation has a small influence in integer slot motors.By varying the magnetic poles,the contribution of the field harmonics(k=(2n+1)p),which are a direct result of magnet magnetization,to the cogging torque also changes.The electromagnetic performance of a 3 kW prototype is tested,and it is found that the experimental results validate the theoretical investigation.
基金Zhejiang Provincial Natural Science Key Foundation of China(No.LZ20E030003)National Science Foundation of China(No.51673121)+1 种基金Candidates of Young and Middle Aged Academic Leader of Zhejiang Province,the Young Elite Scientists Sponsorship Program by CAST(No.2018QNRC001)Excellent Doctoral Thesis Cultivation Fund(No.2019D01).
文摘If a person comes into contact with pathogens on public facilities,there is a threat of contact(skin/wound)infections.More urgently,there are also reports about COVID-19 coronavirus contact infection,which once again reminds that contact infection is a very easily overlooked disease exposure route.Herein,we propose an innovative implantation strategy to fabricate a multi-walled carbon nanotube/polyvinyl alcohol(MWCNT/PVA,MCP)interpenetrating interface to achieve flexibility,anti-damage,and non-contact sensing electronic skin(E-skin).Interestingly,the MCP E-skin had a fascinating non-contact sensing function,which can respond to the finger approaching 0−20 mm through the spatial weak field.This non-contact sensing can be applied urgently to human–machine interactions in public facilities to block pathogen.The scratches of the fruit knife did not damage the MCP E-skin,and can resist chemical corrosion after hydrophobic treatment.In addition,the MCP E-skin was developed to real-time monitor the respiratory and cough for exercise detection and disease diagnosis.Notably,the MCP E-skin has great potential for emergency applications in times of infectious disease pandemics.
基金supported by the Fundamental Research Funds for the Central Universities,Heilongjiang Provincial Natural Science Foundation of China(Grant No.YQ2020E009).
文摘Developing strain sensors with both high sensitivity and high linearity has always been the goal of researchers.Compared to resistive strain sensors,capacitive strain sensors have incomparable linearity advantages,but have always been limited by low sensitivity.Here,we report a gradient stiffness sliding design strategy that addresses this problem,significantly improving sensitivity while maintaining high linearity.By controlling the distribution of the locally enhanced electric field and the heterogeneous deformation of the substrate,a strain sensor with excellent performance is successfully prepared,exhibiting a giant gauge factor(9.1×10^(6))and linearity(R^(2)=0.9997)over the entire sensing range,together with almost no hysteresis and fast response time(17 ms).The gradient stiffness sliding design is a general strategy expected to be applied to other types of sensors to achieve ultra-high sensitivity and ultra-high linearity at the same time.
基金The authors thank the National Natural Science Foundation of China(52173112 and 51873123)the Sichuan Provincial Natural Science Fund for Distinguished Young Scholars(2021JDJQ0017)for financial support.
文摘Slide-ring structured polyrotaxanes with high molecular mobility and reversible conformational transition ability can achieve high performance and multifunctionality of the material in various applications.There have been many reviews describing advances in the research of rotaxanes and polyrotaxanes.However,most of them typically focus on the precise synthesis of mechanically interlocked molecules and the control of microscopic molecular shuttles.In this review,we examine the effects of motion activity and conformational transition due to molecular slide on the performance of polyrotaxanes and the latest functional applications.Different designs of polyrotaxane-based functional materials are presented to improve the potential for applications including self-healing stretchable elastomers/gels,stimuli-responsive smart devices,battery electrode binders,and biomedical drug delivery.It is anticipated that this review will provide insights and guidance for future developments in the design,synthesis and application of polyrotaxane-based functional materials.
基金the National Natural Science Foundation of China(42221001)the National Natural Science Foundation of China(22325402,22174073)+4 种基金the National Key R&D Program of China(2023YFE0124200)the Natural Science Foundation of Tianjin City(21JCJQJC00010)the Natural Science Foundation of Tianjin City(23ZYJDSS00030)the Nankai Cangzhou Chemistry(NCC)Fund(NCC2022PY05)the Haihe Laboratory of Sustainable Chemical Transformations and the Frontiers Science Center for New Organic Matter at Nankai University(63181206)。
文摘Humic-like substances(HULIS),a class of macromolecular photosensitizers,are major components of light-absorbing aerosols in the atmosphere.Due to the amphiphilic nature of HULIS,they tend to appear at the air-water interface of atmospheric water.However,there have been limited studies on the photosensitized chemistry of HULIS at the air-water interface owing to the lack of methods with high interface selectivity.Here,a unique field-induced droplet ionization mass spectrometry(FIDI-MS)technique was used to investigate the photosensitized chemistry of several samples at the air-water interface.These samples include commercially available humic acid and the PM_(2.5)sample collected during Beijing′s severe winter haze in December 2016.Ultrahigh-resolution Fourier transform-ion cyclotron resonance mass spectrometry(FT-ICR MS)was also applied to analyze the atomic compositions,the degree of unsaturation and the aromaticity of these samples.Both TypeⅠand TypeⅡphotosensitized oxidation pathways were observed,which were postulated to be dictated by the packing density of the molecules at the air-water interface.These findings reveal that the photosensitization of HULIS at the air-water interface contributes greatly to the formation of atmospheric aerosols,further advancing our understanding of the important roles played by photosensitized chemistry in the atmosphere.
基金National Natural Science Foundation of China,Grant/Award Numbers:52373116,52173112。
文摘The capacity of biological tissues to undergo self-healing is crucial for the performance of functions and the continuation of life.Conventional intrinsic self-healing materials demonstrate analogous functionality depending on the dissociation-recombination of reversible bonds with no need of extra repair agents.However,the trade-off relationship between mechanical strength and self-healing kinetics in intrinsic self-healing systems,coupled with the lack of additional functionality,restricts their service life and practical applications.Diversified highly ordered structures in organisms significantly affect the energy dissipation mechanism,signal transmission efficiency,and molecular network reconstruction capability due to their multi-dimensional differentiated macroscopic composite constructions,microscopic orientation textures,and topologies/bonding types at molecular level.These architectures exhibit distinctive strengthening mechanisms and functionalities,which provide valuable references.This review aims at providing the current status of advanced intrinsic self-healing materials with biomimetic highly ordered internal micro/nanostructures.Through highlighting specific examples,the classifications,design inspirations,and fabrication strategies of these newly developed materials based on integrating dynamic interactions with ordered nano/microstructures are outlined.Furthermore,the strengthening and selfhealing balance mechanisms,structure–functionalization relationships,and potential application values are discussed.The review concludes with a perspective on the challenges,opportunities,and prospects for the development,application,and promotion of self-healable materials with bio-like ordered architectures.
