Fluorinated motifs are prevalent in both pharmaceuticals and agrochemicals.The incorporation of fluorine-containing moieties to drug candidates has emerged as a potent strategy for lead optimization in pharmaceutical ...Fluorinated motifs are prevalent in both pharmaceuticals and agrochemicals.The incorporation of fluorine-containing moieties to drug candidates has emerged as a potent strategy for lead optimization in pharmaceutical research and development.While extensive research has been devoted to constructing molecules that incorporate a trifluoromethylthio(SCF_(3)−)group on a stereogenic carbon,the synthesis of trifluoromethylthiolated alkanes featuring a SCF_(3)-substituted stereogenic carbon at non-activated site remains understudied.Herein,we report a Cu-catalyzed regio-and enantioselective hydroallylation of 1-trifluoromethylthiolated alkenes.Important to the process is the regio-and enantioselective Cu-H insertion to SCF_(3)-substituted alkene to form chiralα-SCF_(3) alkyl copper intermediates,outcompeting unproductive insertion to the coupling partner,and eventually proceed to afford optically active homoallylic trifluoromethylthiolated products.展开更多
Multilayer complex dynamical networks,characterized by the intricate topological connections and diverse hierarchical structures,present significant challenges in determining complete structural configurations due to ...Multilayer complex dynamical networks,characterized by the intricate topological connections and diverse hierarchical structures,present significant challenges in determining complete structural configurations due to the unique functional attributes and interaction patterns inherent to different layers.This paper addresses the critical question of whether structural information from a known layer can be used to reconstruct the unknown intralayer structure of a target layer within general weighted output-coupling multilayer networks.Building upon the generalized synchronization principle,we propose an innovative reconstruction method that incorporates two essential components in the design of structure observers,the cross-layer coupling modulator and the structural divergence term.A key advantage of the proposed reconstruction method lies in its flexibility to freely designate both the unknown target layer and the known reference layer from the general weighted output-coupling multilayer network.The reduced dependency on full-state observability enables more deployment in engineering applications with partial measurements.Numerical simulations are conducted to validate the effectiveness of the proposed structure reconstruction method.展开更多
The strong vertical discontinuities pose a fundamental challenge to optimizing stimulated reservoir volume(SRV)in multilayered reservoirs.This research proposes a radial borehole-assisted horizontal well fracturing te...The strong vertical discontinuities pose a fundamental challenge to optimizing stimulated reservoir volume(SRV)in multilayered reservoirs.This research proposes a radial borehole-assisted horizontal well fracturing technology,which is expected to achieve effective vertical stimulation and commingled production across multiple pay zones.Under different geological and engineering conditions,the vertical propagation behavior of hydraulic fractures guided by radial boreholes can be determined by adjusting the interlayered lithologies and radial borehole configurations in experimental samples.Experimental results reveal four fracture network patterns:passivated,cross-layer,skip-layer,and hybrid fractures in the radial borehole fracturing.The radial boreholes perform better fracture guiding performances in the high-brittleness interlayers,which form cross-layer and hybrid fracture networks to improve the growth height.Hydraulic fractures tend to propagate from high-strength to low-strength layers under radial borehole guidance.When radial boreholes interconnect multiple lithology layers,hydraulic fractures initiate preferentially in lower-strength zones rather than remaining confined to borehole root ends.Increased radial borehole length and diameter facilitate fracture skip-layer initiation and cross-layer propagation,while multiple borehole branches enhance fracture penetration across high-strength interlayers.Radial boreholes with inclination angles below 30°enhance fracture height by generating cross-layer and hybrid fracture networks.Furthermore,an inter-borehole phase angle of less than 180°facilitates single-wing fracture cross-layer propagation.Fracture height is primarily governed by radial borehole length,followed by quantity,inclination angle,and diameter.Based on the geometric similarity criteria,the recommended parameters for radial borehole-assisted fracturing in a 5 1/2-inch horizontal well include a length>15 m,an inclination angle<30°,and a diameter>52 mm to ensure effective stimulation across three or more pay zones.Finally,the field-scale numerical model was developed to simulate the optimized radial borehole fracturing and demonstrate the technical superiority.These findings are expected to provide an in-depth understanding of the effective stimulation in multilayered reservoirs.展开更多
Multi-site coupling is a promising strategy for developing highly efficient and CO-resistant hydrogen oxidation reaction(HOR)catalysts for proton exchange membrane fuel cells(PEMFCs).However,designing multifunctional ...Multi-site coupling is a promising strategy for developing highly efficient and CO-resistant hydrogen oxidation reaction(HOR)catalysts for proton exchange membrane fuel cells(PEMFCs).However,designing multifunctional synergistic schemes for single-atom sites remains a significant challenge.Herein,we propose a dual-template-confined oxophilic engineering strategy to construct well-dispersed iridium-nickel(IrNi)atomic dimers adjacent to IrNi nanoclusters on porous nitrogen-doped carbon(IrNi_(Dimer/NC1.8)-PNC).The paired IrNi dimer features an asymmetric Ir-N_(3)configuration coordinated with heteroatomic Ni-N_(3)O via an N-bridge.Remarkably,IrNi_(Dimer/NC1.8)-PNC exhibits a~23-fold enhancement in mass activity(4.36 A mg-1Ir at 20 mV)and 5-fold longer stability compared to benchmarking Pt/C toward HOR,while achieving a high rated power density of 1.18 W cm^(-2)in PEMFC anode applications.Furthermore,IrNi_(Dimer/NC1.8)-PNC demonstrates superior CO tolerance over monometallic Ir and Pt/C in both half-cell and full-cell devices.Combined experimental and density functional theory studies reveal that oxophilic Ni modulates the electronic environment of Ir through alloying and dimer interactions,thereby enhancing HOR activity.Importantly,the asymmetric IrNi dimer enables efficient CO^(*)and OH^(*)co-adsorption while facilitating CO_(2)^(*)desorption,synergistically mitigating CO poisoning and improving atom utilization efficiency.This work provides a design strategy and fundamental insights for multi-site synergistic catalysts in PEMFC anodes.展开更多
We report an immobilized enzyme-catalyzed batch and continuous-flow synthesis of optically pure ethyl(R)-pantothenate((R)-PaOEt),the direct precursor of d-pantothenic acid.Firstly,a ketoreductase mutant designated as ...We report an immobilized enzyme-catalyzed batch and continuous-flow synthesis of optically pure ethyl(R)-pantothenate((R)-PaOEt),the direct precursor of d-pantothenic acid.Firstly,a ketoreductase mutant designated as M2,carrying two-point mutations of F97L and M242F relative to the wild-type SSCR,was constructed by site-directed mutagenesis,exhibited simultaneously improved activity toward ethyl 2′-ketopantothenate(K-PaOEt)and isopropanol,and could effectively catalyze the stereoselective reduction of K-PaOEt to(R)-PaOEt by using isopropanol as the sacrificial co-substrate to regenerate NADPH.After screening six commercially available carriers,an amino resin LXTE-700 was identified as the best solid support for the immobilization of M2 via the glutaraldehyde activation method.Upon optimization of the immobilization process and reaction conditions,the fabricated immobilized enzyme M2@amino resin demonstrated excellent recyclability and reusability,with the complete conversion of K-PaOEt to(R)-PaOEt being still realized after 12 cycles of reuse.Finally,M2@amino resin-catalyzed synthesis of(R)-PaOEt was successfully implemented in continuous-flow,accomplishing a 6.3 times higher space-time yield than that with the batch synthesis(529.2 versus 84 g L^(-1) d^(-1)).Our developed flow biocatalysis system also features an outstanding operational stability,as evidenced by the 100%conversion rate achieved after 15 consecutive days of operation.展开更多
A nonfused ring electron acceptor(NFREA),designated as TT-Ph-C6,has been synthesized with the aim of enhancing the power conversion efficiency(PCE)of organic solar cells(OSCs).By integrating asymmetric phenylalkylamin...A nonfused ring electron acceptor(NFREA),designated as TT-Ph-C6,has been synthesized with the aim of enhancing the power conversion efficiency(PCE)of organic solar cells(OSCs).By integrating asymmetric phenylalkylamino side groups,TT-Ph-C6 demonstrates excellent solubility and its crystal structure exhibits compact packing structures with a three-dimensional molecular stacking network.These structural attributes markedly promote exciton diffusion and charge carrier mobility,particularly advantageous for the fabrication of thick-film devices.TT-Ph-C6-based devices have attained a PCE of 18.01%at a film thickness of 100 nm,and even at a film thickness of 300 nm,the PCE remains at 14.64%,surpassing that of devices based on 2BTh-2F.These remarkable properties position TT-Ph-C6 as a highly promising NFREA material for boosting the efficiency of OSCs.展开更多
Polar two-dimensional(2D)perovskites with their excellent semiconductor properties,intrinsic anisotropy,and bulk photovoltaic effect,have emerged as promising candidates for Self-driven polarization-sensitive photodet...Polar two-dimensional(2D)perovskites with their excellent semiconductor properties,intrinsic anisotropy,and bulk photovoltaic effect,have emerged as promising candidates for Self-driven polarization-sensitive photodetectors.However,these self-driven polarized detectors typically require fabrication along the spontaneous polarization direction to maintain the device’s operation in the self-driven mode,which imposes additional limitations.Herein,we demonstrate multidirectional self-driven polarization-sensitive photodetection by constructing 2D perovskite-based asymmetric contact devices,Ag/2D perovskite/C.The built-in electric field,originating from the difference in work functions,acts as the driving force for the separation and transport of photogenerated carriers.Notably,this approach does not necessitate a specific direction,thereby enabling multidirectional self-driven photodetection.Under excitation by linearly polarized light,our devices exhibit impressive polarization-sensitive discrimination in multiple directions,achieving polarization ratios of 3.3 and 3.1 along the a and baxes,respectively.Our work enriches the approaches enabling self-driven polarization-sensitive photodetection,free from the previous limitations.展开更多
Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O cr...Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O crystal plane orientation and the corresponding adsorbed ^(*)CO species.Herein,we constructed high-index crystal planes(311) in Cu_(2)O(CO-Cu_(2)O) via a facile self-selective CO-induced strategy under a CO atmosphere,which was verified by high-resolution transmission electron microscopy(HR-TEM) and atomic force microscopy(AFM) results.By exploiting the high surface energy of the high index crystal planes,^(*)CO species are stabilized in CO-Cu_(2)O during CO_(2)RR,resulting in exceptional catalytic performance for CO_(2)-to-C_(2)products.In situ infrared spectroscopy revealed that both atop-type(^(*)CO_(atop)) and hollow-type(^(*)CO_(hollow)) adsorption of ^(*)CO species occurred on the CO-Cu_(2)O.The asymmetric C-C coupling energy barrier between ^(*)CO_(atop) and ^(*)CO_(hollow) in(311) crystal plane decreases by 47.8 % compared to the symmetric coupling of ^(*)CO_(atop) in conventional(100) crystal planes.Consequently,the Faradaic efficiency of C_(2) products generated with CO-Cu_(2)O was increased by as high as 100 % compared to that with pristine Cu_(2)O.展开更多
As an advanced device for observing atmospheric winds,the spaceborne Doppler Asymmetric Spatial Heterodyne(DASH)interferometer also encounters challenges associated with phase distortion,par-ticularly in limb sounding...As an advanced device for observing atmospheric winds,the spaceborne Doppler Asymmetric Spatial Heterodyne(DASH)interferometer also encounters challenges associated with phase distortion,par-ticularly in limb sounding scenarios.This paper discusses interferogram modeling and phase distortion cor-rection techniques for spaceborne DASH interferometers.The modeling of phase distortion interferograms with and without Doppler shift for limb observation was conducted,and the effectiveness of the analytical expression was verified through numerical simulation.The simulation results indicate that errors propagate layer by layer while using the onion-peeling inversion algorithm to handle phase-distorted interferograms.In contrast,the phase distortion correction algorithm can achieve effective correction.This phase correction method can be successfully applied to correct phase distortions in the interferograms of the spaceborne DASH interferometer,providing a feasible solution to enhance its measurement accuracy.展开更多
The textures and microstructures of hot-and cold-rolled sheets of an AA 5454 aluminium alloy were studied,with special attention paid to comparing the texture development for the symmetric and asymmetric cold rolling....The textures and microstructures of hot-and cold-rolled sheets of an AA 5454 aluminium alloy were studied,with special attention paid to comparing the texture development for the symmetric and asymmetric cold rolling.Scanning electron microscopy with electron-backscatter diffraction was used to monitor the development of the microstructure in the differently deformed and additionally annealed samples.Details of the formations and transformations of individual texture components occurring during the rolling processes were observed and discussed.The average grain sizes,textures and mechanical properties were correlated and explained for the symmetric and asymmetric cold-rolled samples.The asymmetric rolling is beneficial in terms of deep drawability because it reduces the planar anisotropy of the annealed material due to the decrease of the Cube,Goss,rotated-Cube and η-fibre texture components and at the same time strengthens X1-and X2-fibre texture components which are shear texture components and improve deep drawability.During the asymmetric cold rolling,the temperature increases due to friction,triggering recrystallisation processes and leading to larger grains.It is also confirmed that asymmetric cold rolling uses less rolling force and consequently less energy to produce a final material with better formability,particularly earing.展开更多
Lightweight,high-strength,and heat-resistant protective structures have consistently been crucial for applications in extreme environments,such as aerospace,semiconductors,and nuclear power industries.Multilayered TC4...Lightweight,high-strength,and heat-resistant protective structures have consistently been crucial for applications in extreme environments,such as aerospace,semiconductors,and nuclear power industries.Multilayered TC4/TB8 titanium(Ti)laminates,inspired by theheterostructures of natural biological shells,were fabricated using a hybrid diffusion bonding-hot rolling process followed by an aging treatment,resulting in an architected micro structure.The laminate achieves an ultra-high yield stress of 1020 MPa and proper uniform elongation of 4.2%at 500℃.The TB8 layers with high-density nano-precipitates and dislocations act as hard zone,contributing to high strength.The TC4 layers,with their bimodal structure consisting of coarse and fine grains characterized by equiaxed and lamellar structures,experience more plastic strain than the TB8 layers.The hetero deformation associated with the detwinning ofαgrains in the TC4 layer induces toughening at high temperatures.展开更多
Chiral pyridyl alcohols are a type of synthetically versatile building block for natural products,functional materials and bioactive molecules.Herein,a highly efficient Ir/f-amphox-catalyzed asymmetric hydrogenation o...Chiral pyridyl alcohols are a type of synthetically versatile building block for natural products,functional materials and bioactive molecules.Herein,a highly efficient Ir/f-amphox-catalyzed asymmetric hydrogenation of 1-(pyridin-2-yl)ketone derivatives to access chiral pyridyl alcohols was reported.The reaction proceeds smoothly under mild conditions,delivering excellent yields and enantioselectivities(up to>99%ee,turnover number(TON)up to 2000).A broad range of pyridyl alkyl and aryl ketones were successfully transformed,demonstrating the generality and synthetic utility of this methodology.展开更多
Isosteviol,the hydrolysate of stevioside,has attracted increasing attention from scientists because of its special molecular skeleton and extensive biological activities.In recent years,due to the continuous rise of o...Isosteviol,the hydrolysate of stevioside,has attracted increasing attention from scientists because of its special molecular skeleton and extensive biological activities.In recent years,due to the continuous rise of organocatalysis,an increasing number of organocatalysts based on isosteviol have been devised and synthesized to facilitate a range of highly enantioselective asymmetric synthesis.The isosteviol-type organocatalysts reported in the literature over the past decade and their applications in asymmetric catalysis are systematically analyzed and elaborated in order to provide assistance for the further design,synthesis,and application of organocatalysis derived from isosteviol.展开更多
To overcome the shortage of complex equipment,large volume,and high energy consumption in space capsule manufacturing,a novel sliding pressure Joule heat fuse additive manufacturing technique with reduced volume and l...To overcome the shortage of complex equipment,large volume,and high energy consumption in space capsule manufacturing,a novel sliding pressure Joule heat fuse additive manufacturing technique with reduced volume and low energy consumption was proposed.But the unreasonable process parameters may lead to the inferior consistency of the forming quality of single-channel multilayer in Joule heat additive manufacturing process,and it is difficult to reach the condition for forming thinwalled parts.Orthogonal experiments were designed to fabricate single-channel multilayer samples with varying numbers of layers,and their forming quality was evaluated.The influence of printing current,forming speed,and contact pressure on the forming quality of the single-channel multilayer was analyzed.The optimal process parameters were obtained and the quality characterization of the experiment results was conducted.Results show that the printing current has the most significant influence on the forming quality of the single-channel multilayer.Under the optimal process parameters,the forming section is well fused and the surface is continuously smooth.The surface roughness of a single-channel 3-layer sample is 0.16μm,and the average Vickers hardness of cross section fusion zone is 317 HV,which lays a foundation for the subsequent use of Joule heat additive manufacturing technique to form thinwall parts.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
The catalytic enantioselective electrophilic amination reaction has emerged as a highly efficient method for synthesizing diverse nitrogen-containing chiral molecules,with the development of various asymmetric catalys...The catalytic enantioselective electrophilic amination reaction has emerged as a highly efficient method for synthesizing diverse nitrogen-containing chiral molecules,with the development of various asymmetric catalysis systems.Chiral phosphoric acids(CPA)have been widely acknowledged as versatile chiral organocatalysts since it was first discovered in 2004,finding application in catalyzing diverse asymmetric reactions.A comprehensive overview of recent advances in CPA-catalyzed asymmetric electrophilic amination reactions using different N-electrophilic reagents,including azo reagents,aryldiazonium salts,and imine derivatives,is presented.Furthermore,insights into future developments in this field are offered.展开更多
Leveraging the modularity and efficiency of click chemistry,a series of chiral diamine-triazole tetradentate nitrogen donor ligands and their corresponding nonheme iron complexes were synthesized.These iron-based cata...Leveraging the modularity and efficiency of click chemistry,a series of chiral diamine-triazole tetradentate nitrogen donor ligands and their corresponding nonheme iron complexes were synthesized.These iron-based catalysts demonstrated excellent catalytic activity and enantioselectivity in the asymmetric epoxidation of electron-deficient olefins using H_(2)O_(2) as the terminal oxidant.展开更多
Chiral quaternary phosphonium salts have recently been extensively developed as robust organic catalysts for asymmetric synthesis.Asymmetric addition reactions have been dominating in the chiral phosphonium salt-catal...Chiral quaternary phosphonium salts have recently been extensively developed as robust organic catalysts for asymmetric synthesis.Asymmetric addition reactions have been dominating in the chiral phosphonium salt-catalyzed construction of stereogenic carbon centers,heteroatom centers,axes and planes.The recent achievements in the chiral phosphonium-catalyzed asymmetric addition reactions are summarized.展开更多
Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution o...Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution of remote dienes has emerged as a new route to achieve allylic C—H functionalization enantioselectively. This review provides a detailed summary of the development and advance of this strategy, introduces the related mechanistic processes, and discusses the area based on the types of catalysts and products.展开更多
The vascular network is integral to the developmental and metabolic processes of various tissues and functions as a systemic circulatory system that also interconnects organs throughout the body.In this study,we descr...The vascular network is integral to the developmental and metabolic processes of various tissues and functions as a systemic circulatory system that also interconnects organs throughout the body.In this study,we describe a multilayered microfluidic organ-on-a-chip platform designed for reproducing various three-dimensional(3D)vascularized microtissue models for biological applications.This platform utilizes a porous membrane as a physical barrier and leverages capillary action for hydrogel self-filling.Its high flow resistance mitigates the risk of gel bursting into the medium channels and facilitates the delivery of substances to generate a wide range of interstitial flow and biochemical factor concentration gradients.This study demonstrated that this platform can be used to accurately replicate 3D microenvironments for vasculogenesis,angiogenesis,and vascularized tumor modeling.We also investigated the critical role of multiple microenvironmental regulations in vascular formation on a chip.Moreover,we reproduced the process of tumor angiogenesis,including primary solid tumor features and the inhibitory effects of antitumor drugs on tumor growth and tumor vasculature before and after angiogenesis.Hence,our multilayered microfluidic platform is valuable for exploring multiple vascular mechanisms and constructing specific microtissues that closely mimic in vivo physiological conditions,providing new strategies for cancer research.Furthermore,the multilayered configuration improves design flexibility and scalability,providing the potential for a multi-organ interconnected platform for high-throughput drug screening.展开更多
基金the National Key R&D Program of China(No.2021YFF0701700)the National Natural Science Foundation of China(Nos.22271264 and 21971228)for financial support.
文摘Fluorinated motifs are prevalent in both pharmaceuticals and agrochemicals.The incorporation of fluorine-containing moieties to drug candidates has emerged as a potent strategy for lead optimization in pharmaceutical research and development.While extensive research has been devoted to constructing molecules that incorporate a trifluoromethylthio(SCF_(3)−)group on a stereogenic carbon,the synthesis of trifluoromethylthiolated alkanes featuring a SCF_(3)-substituted stereogenic carbon at non-activated site remains understudied.Herein,we report a Cu-catalyzed regio-and enantioselective hydroallylation of 1-trifluoromethylthiolated alkenes.Important to the process is the regio-and enantioselective Cu-H insertion to SCF_(3)-substituted alkene to form chiralα-SCF_(3) alkyl copper intermediates,outcompeting unproductive insertion to the coupling partner,and eventually proceed to afford optically active homoallylic trifluoromethylthiolated products.
基金Project supported by the National Natural Science Foun-dation of China(Grant No.62373197)the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province,China(Grant No.23KJB120010)+1 种基金the Industry-University-Research Cooperation Project of Jiangsu Province,China(Grant No.BY20251038)the Cultivation and In-cubation Project of the College of Automation,Nanjing Uni-versity of Posts and Telecommunications.
文摘Multilayer complex dynamical networks,characterized by the intricate topological connections and diverse hierarchical structures,present significant challenges in determining complete structural configurations due to the unique functional attributes and interaction patterns inherent to different layers.This paper addresses the critical question of whether structural information from a known layer can be used to reconstruct the unknown intralayer structure of a target layer within general weighted output-coupling multilayer networks.Building upon the generalized synchronization principle,we propose an innovative reconstruction method that incorporates two essential components in the design of structure observers,the cross-layer coupling modulator and the structural divergence term.A key advantage of the proposed reconstruction method lies in its flexibility to freely designate both the unknown target layer and the known reference layer from the general weighted output-coupling multilayer network.The reduced dependency on full-state observability enables more deployment in engineering applications with partial measurements.Numerical simulations are conducted to validate the effectiveness of the proposed structure reconstruction method.
基金supported by the National Natural Science Foundation of China(Nos.U24B6001,52421002,52474016,and 52020105001)Research on Key Technologies for Exploration and Development of Dry Geothermal Resources(No.2022DJ5503)Deep-land National Science and Technology Major Project of China(No.2024ZD1003504).
文摘The strong vertical discontinuities pose a fundamental challenge to optimizing stimulated reservoir volume(SRV)in multilayered reservoirs.This research proposes a radial borehole-assisted horizontal well fracturing technology,which is expected to achieve effective vertical stimulation and commingled production across multiple pay zones.Under different geological and engineering conditions,the vertical propagation behavior of hydraulic fractures guided by radial boreholes can be determined by adjusting the interlayered lithologies and radial borehole configurations in experimental samples.Experimental results reveal four fracture network patterns:passivated,cross-layer,skip-layer,and hybrid fractures in the radial borehole fracturing.The radial boreholes perform better fracture guiding performances in the high-brittleness interlayers,which form cross-layer and hybrid fracture networks to improve the growth height.Hydraulic fractures tend to propagate from high-strength to low-strength layers under radial borehole guidance.When radial boreholes interconnect multiple lithology layers,hydraulic fractures initiate preferentially in lower-strength zones rather than remaining confined to borehole root ends.Increased radial borehole length and diameter facilitate fracture skip-layer initiation and cross-layer propagation,while multiple borehole branches enhance fracture penetration across high-strength interlayers.Radial boreholes with inclination angles below 30°enhance fracture height by generating cross-layer and hybrid fracture networks.Furthermore,an inter-borehole phase angle of less than 180°facilitates single-wing fracture cross-layer propagation.Fracture height is primarily governed by radial borehole length,followed by quantity,inclination angle,and diameter.Based on the geometric similarity criteria,the recommended parameters for radial borehole-assisted fracturing in a 5 1/2-inch horizontal well include a length>15 m,an inclination angle<30°,and a diameter>52 mm to ensure effective stimulation across three or more pay zones.Finally,the field-scale numerical model was developed to simulate the optimized radial borehole fracturing and demonstrate the technical superiority.These findings are expected to provide an in-depth understanding of the effective stimulation in multilayered reservoirs.
基金supported by the National Natural Science Foundation of China(22279079 and 22472101)Guangdong Science and Technology Department Program(2021QN02L252,2023A1515010021,and 2024A1515011543)Research Team Cultivation Program of Shenzhen University(2023QNT007)。
文摘Multi-site coupling is a promising strategy for developing highly efficient and CO-resistant hydrogen oxidation reaction(HOR)catalysts for proton exchange membrane fuel cells(PEMFCs).However,designing multifunctional synergistic schemes for single-atom sites remains a significant challenge.Herein,we propose a dual-template-confined oxophilic engineering strategy to construct well-dispersed iridium-nickel(IrNi)atomic dimers adjacent to IrNi nanoclusters on porous nitrogen-doped carbon(IrNi_(Dimer/NC1.8)-PNC).The paired IrNi dimer features an asymmetric Ir-N_(3)configuration coordinated with heteroatomic Ni-N_(3)O via an N-bridge.Remarkably,IrNi_(Dimer/NC1.8)-PNC exhibits a~23-fold enhancement in mass activity(4.36 A mg-1Ir at 20 mV)and 5-fold longer stability compared to benchmarking Pt/C toward HOR,while achieving a high rated power density of 1.18 W cm^(-2)in PEMFC anode applications.Furthermore,IrNi_(Dimer/NC1.8)-PNC demonstrates superior CO tolerance over monometallic Ir and Pt/C in both half-cell and full-cell devices.Combined experimental and density functional theory studies reveal that oxophilic Ni modulates the electronic environment of Ir through alloying and dimer interactions,thereby enhancing HOR activity.Importantly,the asymmetric IrNi dimer enables efficient CO^(*)and OH^(*)co-adsorption while facilitating CO_(2)^(*)desorption,synergistically mitigating CO poisoning and improving atom utilization efficiency.This work provides a design strategy and fundamental insights for multi-site synergistic catalysts in PEMFC anodes.
基金the Science and Technology R&D Major Project of Jiangxi Province(No.20244AFI92001)the National Natural Science Foundation of China(Nos.22071033 and 21801047)for the financial supports.
文摘We report an immobilized enzyme-catalyzed batch and continuous-flow synthesis of optically pure ethyl(R)-pantothenate((R)-PaOEt),the direct precursor of d-pantothenic acid.Firstly,a ketoreductase mutant designated as M2,carrying two-point mutations of F97L and M242F relative to the wild-type SSCR,was constructed by site-directed mutagenesis,exhibited simultaneously improved activity toward ethyl 2′-ketopantothenate(K-PaOEt)and isopropanol,and could effectively catalyze the stereoselective reduction of K-PaOEt to(R)-PaOEt by using isopropanol as the sacrificial co-substrate to regenerate NADPH.After screening six commercially available carriers,an amino resin LXTE-700 was identified as the best solid support for the immobilization of M2 via the glutaraldehyde activation method.Upon optimization of the immobilization process and reaction conditions,the fabricated immobilized enzyme M2@amino resin demonstrated excellent recyclability and reusability,with the complete conversion of K-PaOEt to(R)-PaOEt being still realized after 12 cycles of reuse.Finally,M2@amino resin-catalyzed synthesis of(R)-PaOEt was successfully implemented in continuous-flow,accomplishing a 6.3 times higher space-time yield than that with the batch synthesis(529.2 versus 84 g L^(-1) d^(-1)).Our developed flow biocatalysis system also features an outstanding operational stability,as evidenced by the 100%conversion rate achieved after 15 consecutive days of operation.
基金Financial support from the National Natural Science Foundation of China(22375024,21975031,21734009,51933001,22109080,and 52173174)the Natural Science Foundation of Shandong Province(No.ZR2022YQ45)+2 种基金the Taishan Scholars Program(Nos.tstp20221121 and tsqnz20221134)The Beijing Natural Science Foundation(No.2244073)supported by State Key Laboratory of Bio-Fibers and Eco-Textiles(Qingdao University)(RZ2200002821)is acknowledged.
文摘A nonfused ring electron acceptor(NFREA),designated as TT-Ph-C6,has been synthesized with the aim of enhancing the power conversion efficiency(PCE)of organic solar cells(OSCs).By integrating asymmetric phenylalkylamino side groups,TT-Ph-C6 demonstrates excellent solubility and its crystal structure exhibits compact packing structures with a three-dimensional molecular stacking network.These structural attributes markedly promote exciton diffusion and charge carrier mobility,particularly advantageous for the fabrication of thick-film devices.TT-Ph-C6-based devices have attained a PCE of 18.01%at a film thickness of 100 nm,and even at a film thickness of 300 nm,the PCE remains at 14.64%,surpassing that of devices based on 2BTh-2F.These remarkable properties position TT-Ph-C6 as a highly promising NFREA material for boosting the efficiency of OSCs.
基金supported by the National Natural Science Foundation of China(22435005,22193042,52202194,21833010,21921001,22175177,21971238,22201284)the Natural Science Foundation of Fujian Province(2023J05076)+1 种基金the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(ZDBS-LY-SLH024)the China Postdoctoral Science Foundation(2022M713152,2023M733501,2023T160646)。
文摘Polar two-dimensional(2D)perovskites with their excellent semiconductor properties,intrinsic anisotropy,and bulk photovoltaic effect,have emerged as promising candidates for Self-driven polarization-sensitive photodetectors.However,these self-driven polarized detectors typically require fabrication along the spontaneous polarization direction to maintain the device’s operation in the self-driven mode,which imposes additional limitations.Herein,we demonstrate multidirectional self-driven polarization-sensitive photodetection by constructing 2D perovskite-based asymmetric contact devices,Ag/2D perovskite/C.The built-in electric field,originating from the difference in work functions,acts as the driving force for the separation and transport of photogenerated carriers.Notably,this approach does not necessitate a specific direction,thereby enabling multidirectional self-driven photodetection.Under excitation by linearly polarized light,our devices exhibit impressive polarization-sensitive discrimination in multiple directions,achieving polarization ratios of 3.3 and 3.1 along the a and baxes,respectively.Our work enriches the approaches enabling self-driven polarization-sensitive photodetection,free from the previous limitations.
基金the financial support from the National Natural Science Foundation of China (Nos.U23A20677,22022610 and 52400137)"Pioneer" and "Leading Goose" R&D Program of Zhejiang (Nos.2022C03146 and 2023C03017)+2 种基金China Postdoctoral Science Foundation (No.2024T170805)Zhejiang Provincial Natural Science Foundation of China (No.LDT23E06015B06)the support of the Research Computing Center in College of Chemical and Biological Engineering at Zhejiang University for assistance with the calculations。
文摘Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O crystal plane orientation and the corresponding adsorbed ^(*)CO species.Herein,we constructed high-index crystal planes(311) in Cu_(2)O(CO-Cu_(2)O) via a facile self-selective CO-induced strategy under a CO atmosphere,which was verified by high-resolution transmission electron microscopy(HR-TEM) and atomic force microscopy(AFM) results.By exploiting the high surface energy of the high index crystal planes,^(*)CO species are stabilized in CO-Cu_(2)O during CO_(2)RR,resulting in exceptional catalytic performance for CO_(2)-to-C_(2)products.In situ infrared spectroscopy revealed that both atop-type(^(*)CO_(atop)) and hollow-type(^(*)CO_(hollow)) adsorption of ^(*)CO species occurred on the CO-Cu_(2)O.The asymmetric C-C coupling energy barrier between ^(*)CO_(atop) and ^(*)CO_(hollow) in(311) crystal plane decreases by 47.8 % compared to the symmetric coupling of ^(*)CO_(atop) in conventional(100) crystal planes.Consequently,the Faradaic efficiency of C_(2) products generated with CO-Cu_(2)O was increased by as high as 100 % compared to that with pristine Cu_(2)O.
文摘As an advanced device for observing atmospheric winds,the spaceborne Doppler Asymmetric Spatial Heterodyne(DASH)interferometer also encounters challenges associated with phase distortion,par-ticularly in limb sounding scenarios.This paper discusses interferogram modeling and phase distortion cor-rection techniques for spaceborne DASH interferometers.The modeling of phase distortion interferograms with and without Doppler shift for limb observation was conducted,and the effectiveness of the analytical expression was verified through numerical simulation.The simulation results indicate that errors propagate layer by layer while using the onion-peeling inversion algorithm to handle phase-distorted interferograms.In contrast,the phase distortion correction algorithm can achieve effective correction.This phase correction method can be successfully applied to correct phase distortions in the interferograms of the spaceborne DASH interferometer,providing a feasible solution to enhance its measurement accuracy.
文摘The textures and microstructures of hot-and cold-rolled sheets of an AA 5454 aluminium alloy were studied,with special attention paid to comparing the texture development for the symmetric and asymmetric cold rolling.Scanning electron microscopy with electron-backscatter diffraction was used to monitor the development of the microstructure in the differently deformed and additionally annealed samples.Details of the formations and transformations of individual texture components occurring during the rolling processes were observed and discussed.The average grain sizes,textures and mechanical properties were correlated and explained for the symmetric and asymmetric cold-rolled samples.The asymmetric rolling is beneficial in terms of deep drawability because it reduces the planar anisotropy of the annealed material due to the decrease of the Cube,Goss,rotated-Cube and η-fibre texture components and at the same time strengthens X1-and X2-fibre texture components which are shear texture components and improve deep drawability.During the asymmetric cold rolling,the temperature increases due to friction,triggering recrystallisation processes and leading to larger grains.It is also confirmed that asymmetric cold rolling uses less rolling force and consequently less energy to produce a final material with better formability,particularly earing.
基金financially supported by the Natural Science Foundation of Changsha,China(No.kq2402015)the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIP)(Nos.NRF-2021R1A2C3006662 and NRF-2022R1A5A1030054)supported by Brain Pool Program through the NRF of Korea,funded by the Ministry of Science and ICT(No.NRF-RS_(2)02300263999)
文摘Lightweight,high-strength,and heat-resistant protective structures have consistently been crucial for applications in extreme environments,such as aerospace,semiconductors,and nuclear power industries.Multilayered TC4/TB8 titanium(Ti)laminates,inspired by theheterostructures of natural biological shells,were fabricated using a hybrid diffusion bonding-hot rolling process followed by an aging treatment,resulting in an architected micro structure.The laminate achieves an ultra-high yield stress of 1020 MPa and proper uniform elongation of 4.2%at 500℃.The TB8 layers with high-density nano-precipitates and dislocations act as hard zone,contributing to high strength.The TC4 layers,with their bimodal structure consisting of coarse and fine grains characterized by equiaxed and lamellar structures,experience more plastic strain than the TB8 layers.The hetero deformation associated with the detwinning ofαgrains in the TC4 layer induces toughening at high temperatures.
文摘Chiral pyridyl alcohols are a type of synthetically versatile building block for natural products,functional materials and bioactive molecules.Herein,a highly efficient Ir/f-amphox-catalyzed asymmetric hydrogenation of 1-(pyridin-2-yl)ketone derivatives to access chiral pyridyl alcohols was reported.The reaction proceeds smoothly under mild conditions,delivering excellent yields and enantioselectivities(up to>99%ee,turnover number(TON)up to 2000).A broad range of pyridyl alkyl and aryl ketones were successfully transformed,demonstrating the generality and synthetic utility of this methodology.
基金Project supported by the National Natural Science Foundation of China(No.51403053)the University Scientific Innovation Team of Henan Province(No.24IRTSTHN017)。
文摘Isosteviol,the hydrolysate of stevioside,has attracted increasing attention from scientists because of its special molecular skeleton and extensive biological activities.In recent years,due to the continuous rise of organocatalysis,an increasing number of organocatalysts based on isosteviol have been devised and synthesized to facilitate a range of highly enantioselective asymmetric synthesis.The isosteviol-type organocatalysts reported in the literature over the past decade and their applications in asymmetric catalysis are systematically analyzed and elaborated in order to provide assistance for the further design,synthesis,and application of organocatalysis derived from isosteviol.
基金Shaanxi Province Qin Chuangyuan“Scientist+Engineer”Team Construction Project(2022KXJ-071)2022 Qin Chuangyuan Achievement Transformation Incubation Capacity Improvement Project(2022JH-ZHFHTS-0012)+1 种基金Shaanxi Province Key Research and Development Plan-“Two Chains”Integration Key Project-Qin Chuangyuan General Window Industrial Cluster Project(2023QCY-LL-02)Xixian New Area Science and Technology Plan(2022-YXYJ-003,2022-XXCY-010)。
文摘To overcome the shortage of complex equipment,large volume,and high energy consumption in space capsule manufacturing,a novel sliding pressure Joule heat fuse additive manufacturing technique with reduced volume and low energy consumption was proposed.But the unreasonable process parameters may lead to the inferior consistency of the forming quality of single-channel multilayer in Joule heat additive manufacturing process,and it is difficult to reach the condition for forming thinwalled parts.Orthogonal experiments were designed to fabricate single-channel multilayer samples with varying numbers of layers,and their forming quality was evaluated.The influence of printing current,forming speed,and contact pressure on the forming quality of the single-channel multilayer was analyzed.The optimal process parameters were obtained and the quality characterization of the experiment results was conducted.Results show that the printing current has the most significant influence on the forming quality of the single-channel multilayer.Under the optimal process parameters,the forming section is well fused and the surface is continuously smooth.The surface roughness of a single-channel 3-layer sample is 0.16μm,and the average Vickers hardness of cross section fusion zone is 317 HV,which lays a foundation for the subsequent use of Joule heat additive manufacturing technique to form thinwall parts.
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.
文摘The catalytic enantioselective electrophilic amination reaction has emerged as a highly efficient method for synthesizing diverse nitrogen-containing chiral molecules,with the development of various asymmetric catalysis systems.Chiral phosphoric acids(CPA)have been widely acknowledged as versatile chiral organocatalysts since it was first discovered in 2004,finding application in catalyzing diverse asymmetric reactions.A comprehensive overview of recent advances in CPA-catalyzed asymmetric electrophilic amination reactions using different N-electrophilic reagents,including azo reagents,aryldiazonium salts,and imine derivatives,is presented.Furthermore,insights into future developments in this field are offered.
文摘Leveraging the modularity and efficiency of click chemistry,a series of chiral diamine-triazole tetradentate nitrogen donor ligands and their corresponding nonheme iron complexes were synthesized.These iron-based catalysts demonstrated excellent catalytic activity and enantioselectivity in the asymmetric epoxidation of electron-deficient olefins using H_(2)O_(2) as the terminal oxidant.
文摘Chiral quaternary phosphonium salts have recently been extensively developed as robust organic catalysts for asymmetric synthesis.Asymmetric addition reactions have been dominating in the chiral phosphonium salt-catalyzed construction of stereogenic carbon centers,heteroatom centers,axes and planes.The recent achievements in the chiral phosphonium-catalyzed asymmetric addition reactions are summarized.
文摘Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution of remote dienes has emerged as a new route to achieve allylic C—H functionalization enantioselectively. This review provides a detailed summary of the development and advance of this strategy, introduces the related mechanistic processes, and discusses the area based on the types of catalysts and products.
基金supported by grants from the Interdisciplinary Program of Shanghai Jiao Tong University(No.YG2023LC04)the National Natural Science Foundation of China(Nos.32471473,62231025,and 82171011)+1 种基金the Research Program of Shanghai Science and Technology Committee(Nos.24141900900 and 25JC3201100)Chongqing Natural Science Foundation(No.CSTB2022NSCQ-MSX0767)
文摘The vascular network is integral to the developmental and metabolic processes of various tissues and functions as a systemic circulatory system that also interconnects organs throughout the body.In this study,we describe a multilayered microfluidic organ-on-a-chip platform designed for reproducing various three-dimensional(3D)vascularized microtissue models for biological applications.This platform utilizes a porous membrane as a physical barrier and leverages capillary action for hydrogel self-filling.Its high flow resistance mitigates the risk of gel bursting into the medium channels and facilitates the delivery of substances to generate a wide range of interstitial flow and biochemical factor concentration gradients.This study demonstrated that this platform can be used to accurately replicate 3D microenvironments for vasculogenesis,angiogenesis,and vascularized tumor modeling.We also investigated the critical role of multiple microenvironmental regulations in vascular formation on a chip.Moreover,we reproduced the process of tumor angiogenesis,including primary solid tumor features and the inhibitory effects of antitumor drugs on tumor growth and tumor vasculature before and after angiogenesis.Hence,our multilayered microfluidic platform is valuable for exploring multiple vascular mechanisms and constructing specific microtissues that closely mimic in vivo physiological conditions,providing new strategies for cancer research.Furthermore,the multilayered configuration improves design flexibility and scalability,providing the potential for a multi-organ interconnected platform for high-throughput drug screening.
