Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated fo...Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.展开更多
Although manganese Prussian blue analogues(Mn-PBAs)offer advantages as cost-effective,high-energy-density cathode materials for sodium-ion batteries,their practical application is severely constrained by substantial c...Although manganese Prussian blue analogues(Mn-PBAs)offer advantages as cost-effective,high-energy-density cathode materials for sodium-ion batteries,their practical application is severely constrained by substantial capacity degradation during long-term cycling.This performance deterioration is closely associated with the structural instability of the material during the cycling process,which is mainly attributed to the gradual dissolution of the active material into the electrolyte and severe lattice distortion during Na+intercalation/deintercalation.Fortunately,the aforementioned challenges can be effectively addressed by fabricating an in situ engineered nickel cage(ISE-NC)on Mn-PBAs(denoted as Mn-PBAs-NC).Experimental characterization combined with theoretical calculations reveals that this spontaneously formed nickel cage not only suppresses the diffusion of Mn-PBAs into the electrolyte but also acts as a structural stabilizer,significantly alleviating lattice distortion during cycling.This dual stabilization mechanism ensures remarkable cycling stability,with Mn-PBAs-NC delivering a retained capacity of 96.4 mA h g^(−1)(80%capacity retention)over 2,300 cycles at 2 C,elevating the cycle life of Mn-PBAs to unprecedented levels.展开更多
Integration of single-atom catalysts(SACs) onto metal-organic frameworks(MOFs) with porous channels has garnered significant interest in the field of CO_(2) reduction.However,MOFs are usually bulky can impede the diff...Integration of single-atom catalysts(SACs) onto metal-organic frameworks(MOFs) with porous channels has garnered significant interest in the field of CO_(2) reduction.However,MOFs are usually bulky can impede the diffusion of intermediates with substrates and maximizing catalytic site utilization remains a challenge.In this study,we utilized firstly the post-synthetic single-atom chelation sites on zirconiumbased metal-organic cages(Zr-MOCs) to anchor cobalt(Co) atom to synthesize single-dispersible Zr T^(-1)-NH_(2)-IS-Co molecular cages for CO_(2) photoreduction.Experimental results demonstrate that Zr T^(-1)-NH_(2)-ISCo exhibits impressive catalytic performance,achieving syngas yields of up to 30.9 mmol g^(-1)h^(-1),ranking among the highest values of reported crystalline porous catalysts.Mechanistic insights reveal the newly introduced metal serving as the catalytic site and ^(*)COOH acts as a crucial intermediate in the CO_(2) reduction process.Furthermore,the successful synthesis of Zr T^(-1)-NH_(2)-IS-Ni and Zr T^(-1)-NH_(2)-IS-Mn show the universality of the modification strategies,with their CO_(2) catalytic activity surpassing that of Zr T^(-1)-NH_(2).展开更多
We report first-principles predictions of a cage-like polymeric nitrogen phase(cage-N)composed of interlocked N10 clusters stabilized by mixed sp^(2)/sp^(3) hybridization.Under high pressure,cage-N exhibits exceptiona...We report first-principles predictions of a cage-like polymeric nitrogen phase(cage-N)composed of interlocked N10 clusters stabilized by mixed sp^(2)/sp^(3) hybridization.Under high pressure,cage-N exhibits exceptional mechanical performance,including an ideal compressive strength of 343 GPa at a pressure of 300 GPa,~33% higher than that of diamond.This ultrahigh strength arises from the synergistic interplay between its three-dimensional covalent framework and hybridized bonding topology,which enables isotropic stress accommodation and dynamic electronic rearrangement.These results establish cage-N as a promising non-carbon ultrahard material and provide a bonding-driven route toward designing superhard frameworks under extreme conditions.展开更多
Grain size traits, including grain length, grain width and grain thickness, are controlled by quantitative trait loci （QTLs）. Many QTLs relating to rice grain size traits had been reported, but their control mechani...Grain size traits, including grain length, grain width and grain thickness, are controlled by quantitative trait loci （QTLs）. Many QTLs relating to rice grain size traits had been reported, but their control mechanisms have not yet been elucidated. A recombinant inbred line （RIL） population of 240 lines, deriving from a cross between TD70, an extra-large grain size japonica line with 80 g of 1000-grain weight, and Kasalath, a small grain size indica variety, were constructed and used to map grain size QTLs to a linkage map by using 141 SSR markers in 2010 and 2011. Five QTLs for grain length, six for grain width and seven for grain thickness were detected distributing over chromosomes 2, 3, 5, 7, 9 and 12. Seven QTLs, namely qGL3.1, qGW2, qGW2.2, qGW5.1, qGW5.2, qGT2.3 and qGT3.1, were detected in either of the two years and explained for 56.19%, 4.42%, 29.41%, 10.37%, 7.61%, 21.19% and 17.06% of the observed phenotypic variances on average, respectively. The marker interval RM1347-RM5699 on chromosome 2 was found common for grain length, grain width and grain thickness; qGL3.1 and qGT3.1 were mapped to the same interval RM6080-RM6832 on chromosome 3. All 18 QTL alleles were derived from the large grain parent TD70. Most of the QTLs mapped in the present study were found the same as the genes previously cloned （GW2, GS3 or qGL3, GW5 and GS5）, and several were the same as the QTLs （GS7 and qGL-7） previously mapped. Three QTLs, qGL2.2 on chromosome 2, qGW9 and qGT9 on chromosome 9, were first detected. These results laid a foundation for further fine mapping or cloning of these QTLs.展开更多
In solid backfill mining without gangue removal, the gangue is separated directly underground and backfilled into goaf. This necessitates the underground construction of an extra-large section chamber for separation e...In solid backfill mining without gangue removal, the gangue is separated directly underground and backfilled into goaf. This necessitates the underground construction of an extra-large section chamber for separation equipments. For the construction of an extra-large section chamber in the Tangshan mine, we proposed an active support through a combination of bolting, anchor cables, lining, and a reinforced chamber floor by inverted arch pouring. ABAQUS software was used to analyze the surrounding rock deformation and the plastic zone development of the chamber under different excavation schemes.The best excavation scheme was determined, and the effectiveness of the combined supports was verified. In practice, the engineering installation showed good overall control of the movement of the surrounding rock, with roof-to-floor and side-to-side convergences of 154.6 and 77.5 mm, respectively,which meets the requirements for underground coal gangue separation.展开更多
1Project objective Extra-large shield tunnels have become the best choice for urban transportation tunnels due to the advantage of taking the best use of underground space.Hengqin Island in Zhuhai is a demonstration a...1Project objective Extra-large shield tunnels have become the best choice for urban transportation tunnels due to the advantage of taking the best use of underground space.Hengqin Island in Zhuhai is a demonstration area to explore a new cooperation mode among Guangzhou,Hong Kong and Macao,which is also an important pivot of the 21st Century Maritime Silk Road.Thus,it takes an important role in serving Hong Kong and Macao and driving the economic development of the Pearl River Delta.However,as typhoons are frequent in Zhuhai,Hengqin Island will be isolated to the mainland when bridges are obstructed in typhoon seasons.Therefore,the bridges cannot satisfy the traffic demand to the island.The inconvenient transportation has a neglect influence on production and live of people on the island,which also affects the long term development of Hengqin Island.Apart from the two existed bridges,Maliuzhou Traffic Tunnel in Zhuhai is the third major link of Hengqin Island to the mainland,which will put an end to the"losing connectionM problem due to obstructing the bridges in typhoon seasons.This linkage is able to promote Zhuhai tourism exploitation and the long term development of the city,and also increase the security of peopled lives.Meanwhile,the construction of the Maliuzhou Traffic Tunnel has conquered the challenges in designing and building of the extra-large shield tunnel in composite ground and undersea circumstances.The designing methods and constructing approaches used in this project will provide theoretical supports and technical guarantees to similar projects.展开更多
The extra-large scale multiple-input multiple-output(XL-MIMO)for the beyond fifth/sixth generation mobile communications is a promising technology to provide Tbps data transmission and stable access service.However,th...The extra-large scale multiple-input multiple-output(XL-MIMO)for the beyond fifth/sixth generation mobile communications is a promising technology to provide Tbps data transmission and stable access service.However,the extremely large antenna array aperture arouses the channel near-field effect,resulting in the deteriorated data rate and other challenges in the practice communication systems.Meanwhile,multi-panel MIMO technology has attracted extensive attention due to its flexible configuration,low hardware cost,and wider coverage.By combining the XL-MIMO and multi-panel array structure,we construct multi-panel XL-MIMO and apply it to massive Internet of Things(IoT)access.First,we model the multi-panel XL-MIMO-based near-field channels for massive IoT access scenarios,where the electromagnetic waves corresponding to different panels have different angles of arrival/departure(AoAs/AoDs).Then,by exploiting the sparsity of the near-field massive IoT access channels,we formulate a compressed sensing based joint active user detection(AUD)and channel estimation(CE)problem which is solved by AMP-EM-MMV algorithm.The simulation results exhibit the superiority of the AMP-EM-MMV based joint AUD and CE scheme over the baseline algorithms.展开更多
The current High-Speed Railway(HSR)communications increasingly fail to satisfy the massive access services of numerous user equipment brought by the increasing number of people traveling by HSRs.To this end,this paper...The current High-Speed Railway(HSR)communications increasingly fail to satisfy the massive access services of numerous user equipment brought by the increasing number of people traveling by HSRs.To this end,this paper investigates millimeter-Wave(mmWave)extra-large scale(XL)-MIMO-based massive Internet-of-Things(loT)access in near-field HSR communications,and proposes a block simultaneous orthogonal matching pursuit(B-SOMP)-based Active User Detection(AUD)and Channel Estimation(CE)scheme by exploiting the spatial block sparsity of the XLMIMO-based massive access channels.Specifically,we first model the uplink mmWave XL-MIMO channels,which exhibit the near-field propagation characteristics of electromagnetic signals and the spatial non-stationarity of mmWave XL-MIMO arrays.By exploiting the spatial block sparsity and common frequency-domain sparsity pattern of massive access channels,the joint AUD and CE problem can be then formulated as a Multiple Measurement Vectors Compressive Sensing(MIMV-CS)problem.Based on the designed sensing matrix,a B-SOMP algorithm is proposed to achieve joint AUD and CE.Finally,simulation results show that the proposed solution can obtain a better AUD and CE performance than the conventional CS-based scheme for massive IoT access in near-field HSR communications.展开更多
The potent antibacterial activity of silver nanoparticles is primarily attributed to the release of silver ions,which disrupt cell membranes and inactivate essential enzymes through Ag−S bonding formation.[Objective]T...The potent antibacterial activity of silver nanoparticles is primarily attributed to the release of silver ions,which disrupt cell membranes and inactivate essential enzymes through Ag−S bonding formation.[Objective]To explore silver ion immobilization to minimize silver release.[Methods]A macrocyclic cryptand with nitrogen bridgeheads was prepared and subsequently chelated with silver ions to produce Cage silver(I),which was then coordinated with different ratios of sulfonated chitosan(SCS)to form SCS/Cage Ag(I)complexes(SCA1,SCA2,and SCA3).The antioxidant activities of the complexes were assessed by reducing power and 1,1-diphenyl-2-picrylhydrazyl(DPPH)free radical and hydrogen peroxide scavenging assays.The antibacterial activities of the complexes were evaluated based on the minimum inhibitory concentrations(MICs)and minimum bactericidal concentrations(MBCs)against Staphylococcus aureus ATCC 6538 and Escherichia coli O157:H7 and the inhibition rate on biofilm formation.[Results]Cage silver(I)exhibited strong antibacterial activity,with the MIC of 0.015 mg/mL and MBC of 0.031 mg/mL against S.aureus ATCC 6538,and the MIC of 0.031 mg/mL and MBC of 0.120 mg/mL against E.coli O157:H7.Significant antioxidant properties of Cage silver(I)were also observed,as demonstrated by the DPPH free radical scavenging rates of 42.2%and 53.1%at 326 nm and 517 nm,respectively.Cage silver(I)exhibited the highest antibacterial and antioxidant activities,followed by SCA1,SCA2,SCA3,and SCS,because the content of silver ions in Cage silver(I)was 10-fold higher than that in SCA1.The antibacterial and antioxidant activities of SCA1 were better than those of Cage silver(I),which further indicated that the sulfonic groups of SCS may intensely coordinate with silver ions to exert synergistic effects.[Conclusion]Combining the merits of silver ions and SCS improves the bioavailability of the agent at microbicidal concentrations,minimizes the accumulation in the environment,and reduces treatment costs.The method developed herein offers a sustainable approach to enhance microbial control while minimizing the impact on the environment.展开更多
An extra-large landslide occurred on June 19,2021,on the footwall slope of the Nanfen Open-pit Iron Mine in Liaoning Province,China,with a volume of approximately 1.2×107 m3.To elucidate the causative factors,dev...An extra-large landslide occurred on June 19,2021,on the footwall slope of the Nanfen Open-pit Iron Mine in Liaoning Province,China,with a volume of approximately 1.2×107 m3.To elucidate the causative factors,development process,and destructive mechanisms of this catastrophic landslide,comprehensive field tests,investigations,and laboratory experiments were conducted.Initially,the heavily weathered rock mass of the slope was intersected by faults and joint fissures,facilitating rainwater infiltration.Moreover,the landslide contained a substantial clay mineral with highly developed micro-cracks and micro-pores,exhibiting strong water-absorption properties.As moisture content increased,the rock mass underwent softening,resulting in reduced strength.Ultimately,continuous heavy rainfall infiltration amplified the slope's weight,diminishing the weak structural plane's strength,leading to fracture propagation,slip plane penetration,and extensive tensile-shear and uplift failure of the slope.The study highlights poor geological conditions as the decisive factor for this landslide,with continuous heavy rainfall as the triggering factor.Presently,adverse environmental factors persistently affect the landslide,and deformation and failure continue to escalate.Hence,it is imperative to urgently implement integrated measures encompassing slope reinforcement,monitoring,and early-warning to real-time monitor the landslide's deformation and deep mechanical evolution trends.展开更多
The design of roof frame is one of the most important parts of LNG tank design.In China,however,the calculation of roof frame system of extra-large LNG tanks is currently faced with a series of problems.For example,th...The design of roof frame is one of the most important parts of LNG tank design.In China,however,the calculation of roof frame system of extra-large LNG tanks is currently faced with a series of problems.For example,there is no united yardstick on buckling characteristic value,the calculation is based on many assumptions,and the calculation is inconsistent with domestic specifications and stipulations.In view of these problems,the material non-linearity and structural non-linearity were introduced and the initial defect was taken into consideration.Then,the large non-linear finite element calculation software ABAQUS was adopted to carry out modeling on the roof frame and liner system of extra-large LNG tanks and calculate and analyze the force applied on them and their stability.Finally,a complete set of design algorithm for the roof frame and liner system of extra-large LNG tanks was established and applied to the design of a certain LNG tank(20×10^(4)m^(3))in China.It is indicated that this design algorithm can simulate the actual situations accurately.This design algorithm is structurally composed of shell units and beam units,and it is connected in the pattern of common node.Besides,force calculation is conducted in 10 operational modes and the buckling calculation in 7 operational modes,including all operational modes in the construction process of roof frame and liner system of LNG tanks.It is also revealed that the maximum stress on the roof frame is 125.7 MPa,that on the liner is 101.4 MPa and the minimum safety coefficient used for buckling calculation is 2.57.Under this system,the force and stability of the roof frame of LNG tanks are satisfactory.The research results can be used as reference for relevant design and calculation.展开更多
Porous organic cages(POCs)with permanent porosity and excellent host–vip property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testifie...Porous organic cages(POCs)with permanent porosity and excellent host–vip property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.展开更多
Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imida...Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imidazol-1-yl)phenyl]amine(tipa)ligand,whose molecular formula is(Me_(2)CH_(2))_(2)[Mg_(3)(Ti_(4)L_(6))(tipa)(H_(2)O)_(12)](PTC‑378).The Ti_(4)L_(6)tetrahedral cages serve as robust building units,while the Mg^(2+)ions and tipa ligands provide structural stability and tunable optical properties.The resulting PTC‑378 film exhibited intriguing third-order NLO property,which was systematically investigated using Z-scan techniques.Our results demonstrate that the synergistic interaction between Ti_(4)L_(6)cages andπ-conjugated ligands significantly enhances the NLO performance of the materials.CCDC:2453909.展开更多
Evaluating species composition and dynamic shifts within fouling communities is essential for developing effective strate-gies to manage biofouling in marine fish aquaculture.The coastal area in the Yellow Sea is a ke...Evaluating species composition and dynamic shifts within fouling communities is essential for developing effective strate-gies to manage biofouling in marine fish aquaculture.The coastal area in the Yellow Sea is a key area for cage aquaculture in China;however,this region faces significant challenges from biofouling organisms.Here,we employed an experimental approach in a filed mesocosm in a net cage aquaculture area in the Yellow Sea,with weekly monitoring of changes in macrofouling species on mesh nets and in the seawater,to assess the utility of water eDNA metabarcoding for identifying macrofoulers.We compared the temporal variation patterns in the composition and diversity of macrofouling communities identified through morphological method as well as COI and 18S rRNA metabarcoding.The results showed that metabarcoding detected the majority of macrofoulers identified through morphological method(64%),and revealed additional species that were overlooked by traditional monitoring approach.Furthermore,the changes in diversity and community composition over sampling dates in COI data were generally consistent with those in morphological identification,although a temporal lag existed between these two approaches.A notable shift in the fouling community occurred at the end of June with the appearance of Ectopleura crocea and Caprella sp.,marking a pivotal change in its structure.Future research could focus on developing targeted primers for these key fouling species,which would enhance the efficiency of monitoring efforts.展开更多
In recent years,stimulus-responsive metal-organic cages(MOCs)have attracted significant attention due to their dynamic structures and properties,which greatly enhance the structural diversity and functional adaptabili...In recent years,stimulus-responsive metal-organic cages(MOCs)have attracted significant attention due to their dynamic structures and properties,which greatly enhance the structural diversity and functional adaptability of these supramolecular assemblies.Among various external stimuli,light stands out as a straightforward and efficient means of modulating MOCs through the incorporation of photoresponsive units,such as azobenzene,thereby enabling precise photoresponsive behavior.Substantial progress has been made in the development of azobenzene-containing MOCs,underscoring their research significance and broad application potential across multiple fields.Given these advancements,it is timely to provide a comprehensive summary of the latest progress in azophenyl-based MOCs.This review will highlight key developments and explore their functional applications.展开更多
Background:Previously,a chronic social defeat stress(CSDS)model has been widely-adopted for assessing depressive-like behaviors in animals.However,there is still room for improvement in the CSDS model to safeguard stu...Background:Previously,a chronic social defeat stress(CSDS)model has been widely-adopted for assessing depressive-like behaviors in animals.However,there is still room for improvement in the CSDS model to safeguard study accuracy and the wel-fare of lab rodents.Our study team developed a novel,standardized apparatus to induce CSDS in rodents and assessed the model's practical adaptability.Methods:An innovative CSDS cage apparatus and water bottle was designed.To evaluate the effectiveness of the newly developed tools,a variety of animal models,including the tail suspension test(TST),sucrose preference test,forced swimming test(FST),novelty-suppressed feeding test,female urine sniffing test,and open field test(OFT),were adopted to assess depressive-like behaviors in mice.Fluoxetine treat-ment was also administered to observe the reversal effect,as part of the validation.Results:The CSDS cage apparatus resulted in the manifestation of depressive-like behaviors in the model mice.Significant reductions in sucrose preference and urine sniffing time were observed,while the OFT revealed decreased central zone total distance,residence time,and frequency of entry.Moreover,increased immobility was found in the FST and TST.Fluoxetine treatment was found to successfully reverse the modeling effect.Conclusion:The CSDS cage apparatus was validated for enhanced usability and ad-dressed the previous challenges of water bottle leakage and lab rodent welfare is-sues.The consistent results from multiple behavioral tests also supported real-world application of the apparatus,offering researchers a promising alternative to conven-tional rodent cages.展开更多
基金supported by the National Natural Science Foundation of China (Nos.22064020,22364022,and 22174125)the Applied Basic Research Foundation of Yunnan Province (Nos.202101AT070101 and 202201AT070029)。
文摘Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.
基金financially supported by the Ten-thousand Talents Programthe K. C. Wong Pioneer Talent Program+3 种基金China Three Gorges Corporation (WWKY-2021–0027)Inner Mongolia Science and Technology Plan (2021ZD0033)the National Natural Science Foundation of China (52202121)funded by China Petroleum&Chemical Corporation (123091)
文摘Although manganese Prussian blue analogues(Mn-PBAs)offer advantages as cost-effective,high-energy-density cathode materials for sodium-ion batteries,their practical application is severely constrained by substantial capacity degradation during long-term cycling.This performance deterioration is closely associated with the structural instability of the material during the cycling process,which is mainly attributed to the gradual dissolution of the active material into the electrolyte and severe lattice distortion during Na+intercalation/deintercalation.Fortunately,the aforementioned challenges can be effectively addressed by fabricating an in situ engineered nickel cage(ISE-NC)on Mn-PBAs(denoted as Mn-PBAs-NC).Experimental characterization combined with theoretical calculations reveals that this spontaneously formed nickel cage not only suppresses the diffusion of Mn-PBAs into the electrolyte but also acts as a structural stabilizer,significantly alleviating lattice distortion during cycling.This dual stabilization mechanism ensures remarkable cycling stability,with Mn-PBAs-NC delivering a retained capacity of 96.4 mA h g^(−1)(80%capacity retention)over 2,300 cycles at 2 C,elevating the cycle life of Mn-PBAs to unprecedented levels.
基金financially supported by the NSFC of China (Nos.22175033,22371033,22371032)Jilin Provincial Department of Science and Technology (No.20230508108RC)+1 种基金the Fundamental Research Funds for the Central Universities Excellent Youth Team Program (No.2412023YQ001)the Postdoctoral Fellowship Program of CPSF (No.GZC20230939)。
文摘Integration of single-atom catalysts(SACs) onto metal-organic frameworks(MOFs) with porous channels has garnered significant interest in the field of CO_(2) reduction.However,MOFs are usually bulky can impede the diffusion of intermediates with substrates and maximizing catalytic site utilization remains a challenge.In this study,we utilized firstly the post-synthetic single-atom chelation sites on zirconiumbased metal-organic cages(Zr-MOCs) to anchor cobalt(Co) atom to synthesize single-dispersible Zr T^(-1)-NH_(2)-IS-Co molecular cages for CO_(2) photoreduction.Experimental results demonstrate that Zr T^(-1)-NH_(2)-ISCo exhibits impressive catalytic performance,achieving syngas yields of up to 30.9 mmol g^(-1)h^(-1),ranking among the highest values of reported crystalline porous catalysts.Mechanistic insights reveal the newly introduced metal serving as the catalytic site and ^(*)COOH acts as a crucial intermediate in the CO_(2) reduction process.Furthermore,the successful synthesis of Zr T^(-1)-NH_(2)-IS-Ni and Zr T^(-1)-NH_(2)-IS-Mn show the universality of the modification strategies,with their CO_(2) catalytic activity surpassing that of Zr T^(-1)-NH_(2).
基金supported by the Natural Science Foundation of China(Grant Nos.T2325013,52288102,52090024,12034009,12474004,and 12304036)the National Key R&D Program of China Grant No.2023YFA1610000+1 种基金the Fundamental Research Funds for the Central Universitiesthe Program for Jilin University and Sun Yat-sen University.
文摘We report first-principles predictions of a cage-like polymeric nitrogen phase(cage-N)composed of interlocked N10 clusters stabilized by mixed sp^(2)/sp^(3) hybridization.Under high pressure,cage-N exhibits exceptional mechanical performance,including an ideal compressive strength of 343 GPa at a pressure of 300 GPa,~33% higher than that of diamond.This ultrahigh strength arises from the synergistic interplay between its three-dimensional covalent framework and hybridized bonding topology,which enables isotropic stress accommodation and dynamic electronic rearrangement.These results establish cage-N as a promising non-carbon ultrahard material and provide a bonding-driven route toward designing superhard frameworks under extreme conditions.
基金supported by the National Natural Science Foundation of China (Grant No. 31271678)the Jiangsu Agricultural Scientific Self-Innovation Fund (Grant No. CX[11]4023)the Super Rice Breeding and Demonstration Program of the Ministry of Agriculture in China
文摘Grain size traits, including grain length, grain width and grain thickness, are controlled by quantitative trait loci （QTLs）. Many QTLs relating to rice grain size traits had been reported, but their control mechanisms have not yet been elucidated. A recombinant inbred line （RIL） population of 240 lines, deriving from a cross between TD70, an extra-large grain size japonica line with 80 g of 1000-grain weight, and Kasalath, a small grain size indica variety, were constructed and used to map grain size QTLs to a linkage map by using 141 SSR markers in 2010 and 2011. Five QTLs for grain length, six for grain width and seven for grain thickness were detected distributing over chromosomes 2, 3, 5, 7, 9 and 12. Seven QTLs, namely qGL3.1, qGW2, qGW2.2, qGW5.1, qGW5.2, qGT2.3 and qGT3.1, were detected in either of the two years and explained for 56.19%, 4.42%, 29.41%, 10.37%, 7.61%, 21.19% and 17.06% of the observed phenotypic variances on average, respectively. The marker interval RM1347-RM5699 on chromosome 2 was found common for grain length, grain width and grain thickness; qGL3.1 and qGT3.1 were mapped to the same interval RM6080-RM6832 on chromosome 3. All 18 QTL alleles were derived from the large grain parent TD70. Most of the QTLs mapped in the present study were found the same as the genes previously cloned （GW2, GS3 or qGL3, GW5 and GS5）, and several were the same as the QTLs （GS7 and qGL-7） previously mapped. Three QTLs, qGL2.2 on chromosome 2, qGW9 and qGT9 on chromosome 9, were first detected. These results laid a foundation for further fine mapping or cloning of these QTLs.
基金supported by the National Natural Science Foundation of China (No. 51304206)the Project of National Scientific and Technical Supporting Programs Foundation of China (No. 2012BAB13B03)the Program for New Century Excellent Talents in University of Ministry of Education of China (No. NCET-11-0728)
文摘In solid backfill mining without gangue removal, the gangue is separated directly underground and backfilled into goaf. This necessitates the underground construction of an extra-large section chamber for separation equipments. For the construction of an extra-large section chamber in the Tangshan mine, we proposed an active support through a combination of bolting, anchor cables, lining, and a reinforced chamber floor by inverted arch pouring. ABAQUS software was used to analyze the surrounding rock deformation and the plastic zone development of the chamber under different excavation schemes.The best excavation scheme was determined, and the effectiveness of the combined supports was verified. In practice, the engineering installation showed good overall control of the movement of the surrounding rock, with roof-to-floor and side-to-side convergences of 154.6 and 77.5 mm, respectively,which meets the requirements for underground coal gangue separation.
文摘1Project objective Extra-large shield tunnels have become the best choice for urban transportation tunnels due to the advantage of taking the best use of underground space.Hengqin Island in Zhuhai is a demonstration area to explore a new cooperation mode among Guangzhou,Hong Kong and Macao,which is also an important pivot of the 21st Century Maritime Silk Road.Thus,it takes an important role in serving Hong Kong and Macao and driving the economic development of the Pearl River Delta.However,as typhoons are frequent in Zhuhai,Hengqin Island will be isolated to the mainland when bridges are obstructed in typhoon seasons.Therefore,the bridges cannot satisfy the traffic demand to the island.The inconvenient transportation has a neglect influence on production and live of people on the island,which also affects the long term development of Hengqin Island.Apart from the two existed bridges,Maliuzhou Traffic Tunnel in Zhuhai is the third major link of Hengqin Island to the mainland,which will put an end to the"losing connectionM problem due to obstructing the bridges in typhoon seasons.This linkage is able to promote Zhuhai tourism exploitation and the long term development of the city,and also increase the security of peopled lives.Meanwhile,the construction of the Maliuzhou Traffic Tunnel has conquered the challenges in designing and building of the extra-large shield tunnel in composite ground and undersea circumstances.The designing methods and constructing approaches used in this project will provide theoretical supports and technical guarantees to similar projects.
基金supported by National Key Research and Development Program of China under Grants 2021YFB1600500,2021YFB3201502,and 2022YFB3207704Natural Science Foundation of China(NSFC)under Grants U2233216,62071044,61827901,62088101 and 62201056+1 种基金supported by Shandong Province Natural Science Foundation under Grant ZR2022YQ62supported by Beijing Nova Program,Beijing Institute of Technology Research Fund Program for Young Scholars under grant XSQD-202121009.
文摘The extra-large scale multiple-input multiple-output(XL-MIMO)for the beyond fifth/sixth generation mobile communications is a promising technology to provide Tbps data transmission and stable access service.However,the extremely large antenna array aperture arouses the channel near-field effect,resulting in the deteriorated data rate and other challenges in the practice communication systems.Meanwhile,multi-panel MIMO technology has attracted extensive attention due to its flexible configuration,low hardware cost,and wider coverage.By combining the XL-MIMO and multi-panel array structure,we construct multi-panel XL-MIMO and apply it to massive Internet of Things(IoT)access.First,we model the multi-panel XL-MIMO-based near-field channels for massive IoT access scenarios,where the electromagnetic waves corresponding to different panels have different angles of arrival/departure(AoAs/AoDs).Then,by exploiting the sparsity of the near-field massive IoT access channels,we formulate a compressed sensing based joint active user detection(AUD)and channel estimation(CE)problem which is solved by AMP-EM-MMV algorithm.The simulation results exhibit the superiority of the AMP-EM-MMV based joint AUD and CE scheme over the baseline algorithms.
基金supported in part by the Natural Science Foundation of China(NSFC)under Grant 62071044 and Grant 62088101in part by the Shandong Province Natural Science Foundation under Grant ZR2022YQ62in part by the Beijing Nova Program.
文摘The current High-Speed Railway(HSR)communications increasingly fail to satisfy the massive access services of numerous user equipment brought by the increasing number of people traveling by HSRs.To this end,this paper investigates millimeter-Wave(mmWave)extra-large scale(XL)-MIMO-based massive Internet-of-Things(loT)access in near-field HSR communications,and proposes a block simultaneous orthogonal matching pursuit(B-SOMP)-based Active User Detection(AUD)and Channel Estimation(CE)scheme by exploiting the spatial block sparsity of the XLMIMO-based massive access channels.Specifically,we first model the uplink mmWave XL-MIMO channels,which exhibit the near-field propagation characteristics of electromagnetic signals and the spatial non-stationarity of mmWave XL-MIMO arrays.By exploiting the spatial block sparsity and common frequency-domain sparsity pattern of massive access channels,the joint AUD and CE problem can be then formulated as a Multiple Measurement Vectors Compressive Sensing(MIMV-CS)problem.Based on the designed sensing matrix,a B-SOMP algorithm is proposed to achieve joint AUD and CE.Finally,simulation results show that the proposed solution can obtain a better AUD and CE performance than the conventional CS-based scheme for massive IoT access in near-field HSR communications.
文摘The potent antibacterial activity of silver nanoparticles is primarily attributed to the release of silver ions,which disrupt cell membranes and inactivate essential enzymes through Ag−S bonding formation.[Objective]To explore silver ion immobilization to minimize silver release.[Methods]A macrocyclic cryptand with nitrogen bridgeheads was prepared and subsequently chelated with silver ions to produce Cage silver(I),which was then coordinated with different ratios of sulfonated chitosan(SCS)to form SCS/Cage Ag(I)complexes(SCA1,SCA2,and SCA3).The antioxidant activities of the complexes were assessed by reducing power and 1,1-diphenyl-2-picrylhydrazyl(DPPH)free radical and hydrogen peroxide scavenging assays.The antibacterial activities of the complexes were evaluated based on the minimum inhibitory concentrations(MICs)and minimum bactericidal concentrations(MBCs)against Staphylococcus aureus ATCC 6538 and Escherichia coli O157:H7 and the inhibition rate on biofilm formation.[Results]Cage silver(I)exhibited strong antibacterial activity,with the MIC of 0.015 mg/mL and MBC of 0.031 mg/mL against S.aureus ATCC 6538,and the MIC of 0.031 mg/mL and MBC of 0.120 mg/mL against E.coli O157:H7.Significant antioxidant properties of Cage silver(I)were also observed,as demonstrated by the DPPH free radical scavenging rates of 42.2%and 53.1%at 326 nm and 517 nm,respectively.Cage silver(I)exhibited the highest antibacterial and antioxidant activities,followed by SCA1,SCA2,SCA3,and SCS,because the content of silver ions in Cage silver(I)was 10-fold higher than that in SCA1.The antibacterial and antioxidant activities of SCA1 were better than those of Cage silver(I),which further indicated that the sulfonic groups of SCS may intensely coordinate with silver ions to exert synergistic effects.[Conclusion]Combining the merits of silver ions and SCS improves the bioavailability of the agent at microbicidal concentrations,minimizes the accumulation in the environment,and reduces treatment costs.The method developed herein offers a sustainable approach to enhance microbial control while minimizing the impact on the environment.
基金supported by the National Natural Science Foundation of China(Grant No.52074295)the State Key Laboratory for GeoMechanics and Deep Underground Engineering,China University of Mining&Technology,Beijing(Grant No.SKLGDUEK202217).
文摘An extra-large landslide occurred on June 19,2021,on the footwall slope of the Nanfen Open-pit Iron Mine in Liaoning Province,China,with a volume of approximately 1.2×107 m3.To elucidate the causative factors,development process,and destructive mechanisms of this catastrophic landslide,comprehensive field tests,investigations,and laboratory experiments were conducted.Initially,the heavily weathered rock mass of the slope was intersected by faults and joint fissures,facilitating rainwater infiltration.Moreover,the landslide contained a substantial clay mineral with highly developed micro-cracks and micro-pores,exhibiting strong water-absorption properties.As moisture content increased,the rock mass underwent softening,resulting in reduced strength.Ultimately,continuous heavy rainfall infiltration amplified the slope's weight,diminishing the weak structural plane's strength,leading to fracture propagation,slip plane penetration,and extensive tensile-shear and uplift failure of the slope.The study highlights poor geological conditions as the decisive factor for this landslide,with continuous heavy rainfall as the triggering factor.Presently,adverse environmental factors persistently affect the landslide,and deformation and failure continue to escalate.Hence,it is imperative to urgently implement integrated measures encompassing slope reinforcement,monitoring,and early-warning to real-time monitor the landslide's deformation and deep mechanical evolution trends.
基金Project supported by the Special and Significant Project of China National Offshore Oil Corporation“Study on the design of full-containment large LNG storage tank and engineering applications”(No.:CNOOC-KJ125ZDXM14QD-04QD11).
文摘The design of roof frame is one of the most important parts of LNG tank design.In China,however,the calculation of roof frame system of extra-large LNG tanks is currently faced with a series of problems.For example,there is no united yardstick on buckling characteristic value,the calculation is based on many assumptions,and the calculation is inconsistent with domestic specifications and stipulations.In view of these problems,the material non-linearity and structural non-linearity were introduced and the initial defect was taken into consideration.Then,the large non-linear finite element calculation software ABAQUS was adopted to carry out modeling on the roof frame and liner system of extra-large LNG tanks and calculate and analyze the force applied on them and their stability.Finally,a complete set of design algorithm for the roof frame and liner system of extra-large LNG tanks was established and applied to the design of a certain LNG tank(20×10^(4)m^(3))in China.It is indicated that this design algorithm can simulate the actual situations accurately.This design algorithm is structurally composed of shell units and beam units,and it is connected in the pattern of common node.Besides,force calculation is conducted in 10 operational modes and the buckling calculation in 7 operational modes,including all operational modes in the construction process of roof frame and liner system of LNG tanks.It is also revealed that the maximum stress on the roof frame is 125.7 MPa,that on the liner is 101.4 MPa and the minimum safety coefficient used for buckling calculation is 2.57.Under this system,the force and stability of the roof frame of LNG tanks are satisfactory.The research results can be used as reference for relevant design and calculation.
基金supported by the National Natural Science Foundation of China(No.92372123)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515012057,2022B1515020005,2023B1515130004)Guangzhou Basic and Applied Basic Research Foundation(No.202201011342).
文摘Porous organic cages(POCs)with permanent porosity and excellent host–vip property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.
文摘Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imidazol-1-yl)phenyl]amine(tipa)ligand,whose molecular formula is(Me_(2)CH_(2))_(2)[Mg_(3)(Ti_(4)L_(6))(tipa)(H_(2)O)_(12)](PTC‑378).The Ti_(4)L_(6)tetrahedral cages serve as robust building units,while the Mg^(2+)ions and tipa ligands provide structural stability and tunable optical properties.The resulting PTC‑378 film exhibited intriguing third-order NLO property,which was systematically investigated using Z-scan techniques.Our results demonstrate that the synergistic interaction between Ti_(4)L_(6)cages andπ-conjugated ligands significantly enhances the NLO performance of the materials.CCDC:2453909.
基金supported by grants from the National Key Research and Development Program of China(No.2023YFD2401103)the Fundamental Research Funds for the Central Universities.
文摘Evaluating species composition and dynamic shifts within fouling communities is essential for developing effective strate-gies to manage biofouling in marine fish aquaculture.The coastal area in the Yellow Sea is a key area for cage aquaculture in China;however,this region faces significant challenges from biofouling organisms.Here,we employed an experimental approach in a filed mesocosm in a net cage aquaculture area in the Yellow Sea,with weekly monitoring of changes in macrofouling species on mesh nets and in the seawater,to assess the utility of water eDNA metabarcoding for identifying macrofoulers.We compared the temporal variation patterns in the composition and diversity of macrofouling communities identified through morphological method as well as COI and 18S rRNA metabarcoding.The results showed that metabarcoding detected the majority of macrofoulers identified through morphological method(64%),and revealed additional species that were overlooked by traditional monitoring approach.Furthermore,the changes in diversity and community composition over sampling dates in COI data were generally consistent with those in morphological identification,although a temporal lag existed between these two approaches.A notable shift in the fouling community occurred at the end of June with the appearance of Ectopleura crocea and Caprella sp.,marking a pivotal change in its structure.Future research could focus on developing targeted primers for these key fouling species,which would enhance the efficiency of monitoring efforts.
基金supported by the National Nature Science Foundation of China(No.22401096)the Fundamental Research Funds for the Central Universities(East China Normal University)。
文摘In recent years,stimulus-responsive metal-organic cages(MOCs)have attracted significant attention due to their dynamic structures and properties,which greatly enhance the structural diversity and functional adaptability of these supramolecular assemblies.Among various external stimuli,light stands out as a straightforward and efficient means of modulating MOCs through the incorporation of photoresponsive units,such as azobenzene,thereby enabling precise photoresponsive behavior.Substantial progress has been made in the development of azobenzene-containing MOCs,underscoring their research significance and broad application potential across multiple fields.Given these advancements,it is timely to provide a comprehensive summary of the latest progress in azophenyl-based MOCs.This review will highlight key developments and explore their functional applications.
基金National Natural Science Foundation of China,Grant/Award Number:82204958 and 82305065Natural Science Foundation of Shandong Province,Grant/Award Number:ZR2020ZD17+2 种基金Traditional Chinese Medicine Emotional Disease and Brain Steady State Regulation Innovation Team,Grant/Award Number:2023KJ191Medical and Health Science and Technology Development Plan Project of Shandong Province,Grant/Award Number:202105010467Traditional Chinese Medicine Science and Technology Project of Shandong Province,Grant/Award Number:Q-2022059。
文摘Background:Previously,a chronic social defeat stress(CSDS)model has been widely-adopted for assessing depressive-like behaviors in animals.However,there is still room for improvement in the CSDS model to safeguard study accuracy and the wel-fare of lab rodents.Our study team developed a novel,standardized apparatus to induce CSDS in rodents and assessed the model's practical adaptability.Methods:An innovative CSDS cage apparatus and water bottle was designed.To evaluate the effectiveness of the newly developed tools,a variety of animal models,including the tail suspension test(TST),sucrose preference test,forced swimming test(FST),novelty-suppressed feeding test,female urine sniffing test,and open field test(OFT),were adopted to assess depressive-like behaviors in mice.Fluoxetine treat-ment was also administered to observe the reversal effect,as part of the validation.Results:The CSDS cage apparatus resulted in the manifestation of depressive-like behaviors in the model mice.Significant reductions in sucrose preference and urine sniffing time were observed,while the OFT revealed decreased central zone total distance,residence time,and frequency of entry.Moreover,increased immobility was found in the FST and TST.Fluoxetine treatment was found to successfully reverse the modeling effect.Conclusion:The CSDS cage apparatus was validated for enhanced usability and ad-dressed the previous challenges of water bottle leakage and lab rodent welfare is-sues.The consistent results from multiple behavioral tests also supported real-world application of the apparatus,offering researchers a promising alternative to conven-tional rodent cages.
