Network autoregression and factor model are effective methods for modeling network time series data.In this study,we propose a network autoregression model with a factor structure that incorporates a latent group stru...Network autoregression and factor model are effective methods for modeling network time series data.In this study,we propose a network autoregression model with a factor structure that incorporates a latent group structure to address nodal heterogeneity within the network.An iterative algorithm is employed to minimize a least-squares objective function,allowing for simultaneous estimation of both the parameters and the group structure.To determine the unknown number of groups and factors,a PIC criterion is introduced.Additionally,statistical inference of the estimated parameters is presented.To assess the validity of the proposed estimation and inference procedures,we conduct extensive numerical studies.We also demonstrate the utility of our model using a stock dataset obtained from the Chinese A-Share stock market.展开更多
A stochastic epidemic model with two age groups is established in this study,in which the susceptible(S),the exposed(E),the infected(I),the hospitalized(H)and the recovered(R)are involved within the total population,t...A stochastic epidemic model with two age groups is established in this study,in which the susceptible(S),the exposed(E),the infected(I),the hospitalized(H)and the recovered(R)are involved within the total population,the aging rates between two age groups are set to be constant.The existence-and-uniqueness of global positive solution is firstly showed.Then,by constructing several appropriate Lyapunov functions and using the high-dimensional Itô’s formula,the sufficient conditions for the stochastic extinction and stochastic persistence of the exposed individuals and the infected individuals are obtained.The stochastic extinction indicator and the stochastic persistence indicator are less-valued expressions compared with the basic reproduction number.Meanwhile,the main results of this study are modified into multi-age groups.Furthermore,by using the surveillance data for Fujian Provincial Center for Disease Control and Prevention,Fuzhou COVID-19 epidemic is chosen to carry out the numerical simulations,which show that the age group of the population plays the vital role when studying infectious diseases.展开更多
Lithium-ion capacitors(LICs)combine the high power dens-ity of electrical double-layer capacitors with the high energy density of lithium-ion batteries.However,they face practical limitations due to the narrow operati...Lithium-ion capacitors(LICs)combine the high power dens-ity of electrical double-layer capacitors with the high energy density of lithium-ion batteries.However,they face practical limitations due to the narrow operating voltage window of their activated carbon(AC)cathodes.We report a scalable thermal treatment strategy to develop high-voltage-tolerant AC cathodes.Through controlled thermal treatment of commer-cial activated carbon(Raw-AC)under a H_(2)/Ar atmosphere at 400-800℃,the targeted reduction of degradation-prone functional groups can be achieved while preserving the critical pore structure and increasing graph-itic microcrystalline ordering.The AC treated at 400℃(HAC-400)had a significant increase in specific capacity(96.0 vs.75.1 mAh/g at 0.05 A/g)and better rate capability(61.1 vs.36.1 mAh/g at 5 A/g)in half-cell LICs,along with an 83.5%capacity retention over 7400 cycles within an extended voltage range of 2.0-4.2 V in full-cell LICs.Scalability was demonstrated by a 120 g batch production,enabling fabrication of pouch-type LICs with commercial hard carbon anodes that delivered a higher energy density of 28.3 Wh/kg at 1 C,and a peak power density of 12.1 kW/kg compared to devices using raw AC.This simple,industry-compatible approach may be used for producing ad-vanced cathode materials for practical high-performance LICs.展开更多
This study constructs a function-private inner-product predicate encryption(FP-IPPE)and achieves standard enhanced function privacy.The enhanced function privacy guarantees that a predicate secret key skf reveals noth...This study constructs a function-private inner-product predicate encryption(FP-IPPE)and achieves standard enhanced function privacy.The enhanced function privacy guarantees that a predicate secret key skf reveals nothing about the predicate f,as long as f is drawn from an evasive distribution with sufficient entropy.The proposed scheme extends the group-based public-key function-private predicate encryption(FP-PE)for“small superset predicates”proposed by Bartusek et al.(Asiacrypt 19),to the setting of inner-product predicates.This is the first construction of public-key FP-PE with enhanced function privacy security beyond the equality predicates,which is previously proposed by Boneh et al.(CRYPTO 13).The proposed construction relies on bilinear groups,and the security is proved in the generic bilinear group model.展开更多
Herein the use of rare-earth compounds in catalytic reduction systems for the end-group functionalization of carboxyl-terminated low-molecularweight fluoropolymers was explored.Leveraging the high catalytic activity a...Herein the use of rare-earth compounds in catalytic reduction systems for the end-group functionalization of carboxyl-terminated low-molecularweight fluoropolymers was explored.Leveraging the high catalytic activity and selectivity of rare-earth compounds along with no residual impact on polymer product's performance,highly efficient catalytic reduction systems containing sodium borohydride(NaBH_(4))and rare-earth chloride(RECl_(3))were specifically designed for a telechelic carboxyl-terminated liquid fluoroeslastomer,aiming to facilitate the conversion of chainend carboxyl groups into hydroxyl groups and improvement in end-group reactivity.To achieve this,lanthanum chloride(LaCl_(3)),cerium chloride(CeCl_(3)),and neodymium chloride(NdCl_(3))were used separately to form catalytic reduction systems with NaBH_(4).The effects of solvent dosage,reaction temperature,reaction time length,and reductant dosage on carboxylic conversion were investigated,and the molecular chain structure,molecular weight,and functional group content of the raw materials and the products were analyzed and characterized by means of infrared spectroscopy(FTIR),proton nuclear magnetic resonance(^(1)H-NMR),fluorine-19 nuclear magnetic resonance(^(19)F-NMR),gel permeation chromatography(GPC),and chemical titration.Moreover,the catalytic activity and selectivity of the rare-earth chlorides,as well as the corresponding underlying interactions were discussed.Results indicated that the rare-earth-containing catalytic reduction systems studied in this work could efficiently convert the chain-end carboxyl groups into highly active hydroxyl groups,with a highest conversion up to 87.0%and differing catalytic reduction activities ranked as NaBH_(4)/CeCl_(3)>NaBH_(4)/LaCl_(3)>NaBH_(4)/NdCl_(3).Compared with the conventional lithium aluminum hydride(LiAIH_(4))reduction system,the NaBH_(4)/RECl_(3)systems provide multiple advantages such as mild reaction conditions,high conversion ratio with good selectivity,and environmental innocuity,and are potentially applicable as new reduction-catalysis combinations for the synthesis and functionalization of polymer materials.展开更多
Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex...Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex[Pt(κ^(3)-N^C^N')(CNXyl)]Cl([A]Cl)and the molecular complex[Pt(κ^(2)-N^C^N')(CNXyl)Cl](B).Isomer B was almost the dominating product.The structures of the isomer B derivatives bearing-CF_(3)and-Cl substituents on the pyridine ring of the pinene moiety(5B and 7B,respectively)have been confirmed by single-crystal X-ray diffraction,revealing a slightly distorted square planar geometry with trans-N_(N^C^N'),CNR configuration(The terminal N atom of theκ^(2)-N^C^N'ligand is trans to the isocyanide ligand CNXyl.).Isomer B is thermodynamically more stable,as confirmed by theoretical calculations.CCDC:2416415,5B;2416414,7B.展开更多
Energetic compounds bearing the trinitromethyl group are garnering broad attraction as potential candidates for a new generation of high energy dense oxidizers.In this work,an effective dual modulation strategy involv...Energetic compounds bearing the trinitromethyl group are garnering broad attraction as potential candidates for a new generation of high energy dense oxidizers.In this work,an effective dual modulation strategy involving both molecular isomerization and crystal morphology control was employed to design and optimize trinitromethyl-oxadiazole with improved comprehensive performance.Utilizing this dual strategy,3,5-bis(trinitromethyl)-1,2,4-oxadiazole(3)was synthesized,resulting in the formation of two distinct crystal morphologies(needle and sheet)corresponding to two crystal forms(3-a and3-b).Encouragingly,while maintaining ultra-high oxygen balance(21.73%),3 achieves impressive densities(1.97-1.98 g/cm^(3)).To our knowledge,the density of 1.98 g/cm^(3)for 3-a sets a new record among that of nitrogen-rich monocyclic compounds.Notably,practical crystal morphology prediction was creatively introduced to guide the experimental crystallization conditions of 3,increasing the impact sensitivity and friction sensitivity from 1 J to 80 N(3-a)to 10 J and 240 N(3-b),respectively.Additionally,the crystal structural analyses and theoretical calculations were conducted to elucidate the reasons of differences between 3-a and 3-b in density and stability.This work provides an efficient strategy to enhance performance of trinitromethyl derivatives,broadening the path and expanding the toolbox for energetic materials.展开更多
To solve the problem of providing the best initial situation for terminal guidance when multiple missiles intercept multiple targets,a group cooperative midcourse guidance law(GCMGL)considering time-to-go is proposed....To solve the problem of providing the best initial situation for terminal guidance when multiple missiles intercept multiple targets,a group cooperative midcourse guidance law(GCMGL)considering time-to-go is proposed.Firstly,a threedimensional(3D)guidance model is established and a cooperative trajectory shaping guidance law is given.Secondly,for estimating the unknown target maneuvering acceleration,an adaptive disturbance observer(ADO)is designed,combining finitetime theory with a radial basis function(RBF)neural network,and the convergence of the estimation error is proven using Lyapunov stability theory.Then,to ensure time-to-go cooperation among missiles within the same group and across different groups,the group consensus protocols of virtual collision point mean and the inter-group cooperative consensus protocol are designed respectively.Based on the group consensus protocols,the virtual collision point cooperative guidance law is given,and the finite-time convergence is proved by Lyapunov stability theory.Simultaneously,combined with trajectory shaping guidance law,virtual collision point cooperative guidance law and the intergroup cooperative consensus protocol,the design of GCMGL considering time-to-go is given.Finally,numerical simulation results show the effectiveness and the superiority of the proposed GCMGL.展开更多
The seedlings of Vernicia montana derived from seeds soaking with water (the first group)or 300 mg5L -1 mixed nitric_acid rare earth solution (the second group) were treated with various concentrations of mixed nitric...The seedlings of Vernicia montana derived from seeds soaking with water (the first group)or 300 mg5L -1 mixed nitric_acid rare earth solution (the second group) were treated with various concentrations of mixed nitric_acid rare earth solution by foliage spraying. The results showed that the seedling heights sprayed with 100 和 1 000 mg·L -1 of the first group and with 50 和 100 mg·L -1 of the second group were significantly higher than the controls, and the diameter at ground level sprayed with 300 mg·L -1 of the second group was significantly greater than the control, being 26.92% more than the latter; except for spraying with 0 mg5L -1 and 700～1 500 mg5L -1 of the second group, the seedling dry weight above ground of others was 29.13%～73.91% greater than the control, whereas the seedling dry weight under ground of others was 20.78%～116.88% greater than the control; the contents of chlorophyll a and chlorophyll b for all spraying seedling were 91.67%～191.67% and 87.5%～306.25% greater than the control, respectively, and soluble proteins and soluble sugars were 16.00%～179.78% and 10.73%～105.65% greater than the control, respectively. Compared with the control, the activity of SOD tended to increase, whereas the contents of MDA decreased. These indicated that spraying leaves with optimum concentration of mixed nitric_acid rare earth solution could markedly promote the growth of seedlings and improve resistance ability of V. montana seedlings to bad environment. On the whole, the effects of spraying the leaves of seedling with 50～500 mg5L -1 mixed nitric_acid rare earth solution, which were derived from seeds soaking with 300 mg·L -1 mixed nitric_acid rare earth solution, were good.展开更多
N-salicylidene-benzylamineato M(Ⅱ) complexes (ZnL2, CuL2 and CdL2) were synthesized, characterized and valued for antimicrobial activities against bacterial strands using the agar diffusion method. The crystal of ZnL...N-salicylidene-benzylamineato M(Ⅱ) complexes (ZnL2, CuL2 and CdL2) were synthesized, characterized and valued for antimicrobial activities against bacterial strands using the agar diffusion method. The crystal of ZnL2 was determined by X-ray diffraction. It crystallizes in the Monoclinic system, space group C2/c with a=2.269 1(3), b=0.918 2(1), c=1.239 5(2) nm, β=117.89(2), Z=4, R1=0.049 4, wR2=0.138 2. The complexes were found to be active against Staphylococcus aureus and Eschierichia Coli. CCDC: 249474.展开更多
A novel coordination polymer of [Co( p-CPOA)(2,2′-bipy)(H2O)]n ( p-CPOA2-=4-carboxylphenoxyacetate dianion, 2,2′-bipy=2,2′-bipyridine) was synthesized and characterized by elemental analysis, IR and X-ray single cr...A novel coordination polymer of [Co( p-CPOA)(2,2′-bipy)(H2O)]n ( p-CPOA2-=4-carboxylphenoxyacetate dianion, 2,2′-bipy=2,2′-bipyridine) was synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction. The title complex crystallizes in monoclinic space group C2/c, with a=1.424 4(3) nm, b=1.316 6(3) nm, c=1.947 7(4) nm, β=104.56(3)°. V=3.535 3(14) nm3, Z=8, R=0.028 5, wR=0.089 1. The cobalt(Ⅱ) ion displays a distorted octahedral coordination geometry, defined by three carboxyl oxygen atoms from different p-CPOA2- groups, two nitrogen atoms from 2,2′-bipyridine ligand and one water molecule. The cobalt atoms are bridged by p-CPOA2- groups, forming a one-dimensional chain structure along a axis. The adjacent Co...Co atoms distance is 0.996 8 nm. A layer supramolecular network is contrsucted by the hydrogen bonds and π-π stacking interactions. CCDC: 220039.展开更多
new coordination polymer {[Zn(CF3COO)2(C5H5ON)]·H2O}n was synthesized based on the reaction of zinc(Ⅱ) trifluoroacetate and 3-hydroxypyridine(C5H5ON) in methanol medium for the first time. The structure of the c...new coordination polymer {[Zn(CF3COO)2(C5H5ON)]·H2O}n was synthesized based on the reaction of zinc(Ⅱ) trifluoroacetate and 3-hydroxypyridine(C5H5ON) in methanol medium for the first time. The structure of the coordination polymer was confirmed by IR, 1H NMR, elemental analysis and thermal analysis. The crystal structure of the coordination polymer was also determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group P21/m, and crystallographic data of the coordination polymer are: a= 0.863 1(4) nm, b=0.717 7(3) nm, c=1.116 4(5) nm, α=γ=90°, β=107.542(6)°, V=0.659 4(5) nm3; Dc=2.037 g·cm-3; Z=2; F(000)=400; μ=1.969 mm-1. Zinc(Ⅱ) atom lies at the center of an octahedron formed by the coordination of zinc atom and six O atoms which come from four different trifluoroacetate ions and two different 3-hydroxypyridine molecules where each trifluoroacetate ion and 3-hydroxypyridine are coordinated to two different zinc ions to form coordination polymer. CCDC: 253909.展开更多
The geometric configurations of binuclear Zinc( complex Zn2[(n-Bu)2NCSS]4 and the ligand Na[(n-Bu)2 NCSS] have been optimized by B3LYP quantum chemical method. The electronic structures have been performed by density ...The geometric configurations of binuclear Zinc( complex Zn2[(n-Bu)2NCSS]4 and the ligand Na[(n-Bu)2 NCSS] have been optimized by B3LYP quantum chemical method. The electronic structures have been performed by density functional theory at B3LYP/6-31G* level. The electronic spectrums of the complex and ligand were calculated by ZINDO/S-CIS method. It is indicated from the calculation that: (1) The coordination effect of bridging ligand is bigger than that of chelating one, and the bridging ligands also translate more charge to Zn than the chelating one. (2) The calculated results about electronic spectrums are similarly to experimental measurement, and farther explain that absorption band at λ=267 nm of complex is assigned to two n → π* transitions :one arising from the bridging ligands and the another mainly arising from the chelating ligands;but absorption band at λ=236 nm of complex is assigned to π → π* transition which the electron mainly translates from the bridging ligands to the chelating ligands. (3) By consideration of delocalization and polar effects in coordination, the charge transfer from ligand to metal decreases the π-π and p-π conjugation effects in the chromophore group NCS2 and to increase the energy needed for the π → π* and n → π* transitions, and results in the absorption bands shifting towards the short wavelength direction.展开更多
Soil animal communities of Pinus koraiensis broad_leaved mixed forest were studied.The purpose was to discuss the dynamic characteristic of soil animals and relationship with environmental factors.The ecosystem geogra...Soil animal communities of Pinus koraiensis broad_leaved mixed forest were studied.The purpose was to discuss the dynamic characteristic of soil animals and relationship with environmental factors.The ecosystem geography distribution law of soil animals, soil animals’role and function in ecological system were revealed.In June,August,October each year,three plots were selected. In each plot, four layers were sampled(litter layer,0～10 cm,10～20 cm & 20～30 cm),adding up to 72 soil sample.The area for large_sized soil animals was 50 cm×50 cm,and the area for middle_small_sized soil animals was 10 cm × 10 cm.Separated soil animals through adopting hand_picking method and Tullgren method respectively.Sampled the soil animals in two continuing years.Shannon_Wiener index was adopted to analyze the diversity of soil animals.Monad liner regression was used to search the relationship between soil animals and environmental factors.The dominant groups were Oribatida, Isotomidae.There were relatively great changes in groups and individual numbers of dominant groups and rare groups when the reason changed.The individual numbers of dominant groups and the groups of rare groups changed.The number of individual and group was the most in August.Obviously it correlated with climatic factors in middle temperate zone.The evenness was low and dominance was high. The diversity index was not most.Among the annual fluctuating there was a increasing trend. The evenness was low and dominance was high.The diversity index was low.It conformed with the law of reason change.The correlation between soil animals and atmospheric temperature,rainfall,ground temperature and sunlight showed the correlation with rainfall and soil temperature was the most significant.展开更多
A one-dimensional double-chain coordination polymer [Mn(phen)(tsgluo)] was synthesized in a mixed solution and its crystal structure was determined by X-ray diffraction method. It crystallizes in orthorhombic system w...A one-dimensional double-chain coordination polymer [Mn(phen)(tsgluo)] was synthesized in a mixed solution and its crystal structure was determined by X-ray diffraction method. It crystallizes in orthorhombic system with space group P212121. The crystal data are: a=0.530 78(17) nm, b=1.723 9(5) nm, c=2.456 9(8) nm, Z=4, μ=0.729 mm-1, Dc=1.579 g·cm-3, V=2.248 1(12) nm3, R1=0.033 1, ωR2=0.078 9. In the title complex, each Mn(Ⅱ) ion presents a octahedral geometry with the coordination of two nitrogen atoms from 1,10-phenanthroline and four oxygen atoms from three different tsgluo2- ligands. The γ-carboxyl coordinates to Mn(Ⅱ) in the mode of bidentate chelate, while the α-carboxyl coordinates in a bidentate bridging mode. CCDC: 253910.展开更多
The novel copper(Ⅱ) complex with α-hydroxyphenylacetic acid (H2PHAc) and pyridine (py) ligands, [Cu(HPHAc)2(py)2], has been synthesized and characterized by elemental analysis and IR spectroscopy. Its crystal struct...The novel copper(Ⅱ) complex with α-hydroxyphenylacetic acid (H2PHAc) and pyridine (py) ligands, [Cu(HPHAc)2(py)2], has been synthesized and characterized by elemental analysis and IR spectroscopy. Its crystal structure was determined by single crystal X-ray diffraction techniques. The crystal belongs to monoclinic with space group C2/c. The cell parameters are: a=1.712 5(3) nm, b=1.533 2(2) nm, c=0.963 42(14) nm, β=111.866(2)°, V=2.347 6(6) nm3, and Dc=1.483 Mg·m-3, Z=4, F(000)=1 084. The structure was refined to final R1=0.071 4, wR2=0.166 1. The complex has a six-coordinated distorted octahedral geometry, in which copper(Ⅱ) ion coordinates with two carboxylic oxygen atoms and two hydroxyl oxygen atoms from the two α-hydroxyphenylacetic acid ligands, two nitrogen atoms from the two pyridine ligands. The analysis of the crystal structure indicates that the complex has a one-dimensional chain structure, which is formed by intermolecular hydrogen bonds. CCDC: 255346.展开更多
基金Supported by National Natural Science Foundation of China(72222009,71991472)。
文摘Network autoregression and factor model are effective methods for modeling network time series data.In this study,we propose a network autoregression model with a factor structure that incorporates a latent group structure to address nodal heterogeneity within the network.An iterative algorithm is employed to minimize a least-squares objective function,allowing for simultaneous estimation of both the parameters and the group structure.To determine the unknown number of groups and factors,a PIC criterion is introduced.Additionally,statistical inference of the estimated parameters is presented.To assess the validity of the proposed estimation and inference procedures,we conduct extensive numerical studies.We also demonstrate the utility of our model using a stock dataset obtained from the Chinese A-Share stock market.
基金Supported by National Natural Science Foundation of China(61911530398,12231012)Consultancy Project by the Chinese Academy of Engineering(2022-JB-06,2023-JB-12)+3 种基金the Natural Science Foundation of Fujian Province of China(2021J01621)Special Projects of the Central Government Guiding Local Science and Technology Development(2021L3018)Royal Society of Edinburgh(RSE1832)Engineering and Physical Sciences Research Council(EP/W522521/1).
文摘A stochastic epidemic model with two age groups is established in this study,in which the susceptible(S),the exposed(E),the infected(I),the hospitalized(H)and the recovered(R)are involved within the total population,the aging rates between two age groups are set to be constant.The existence-and-uniqueness of global positive solution is firstly showed.Then,by constructing several appropriate Lyapunov functions and using the high-dimensional Itô’s formula,the sufficient conditions for the stochastic extinction and stochastic persistence of the exposed individuals and the infected individuals are obtained.The stochastic extinction indicator and the stochastic persistence indicator are less-valued expressions compared with the basic reproduction number.Meanwhile,the main results of this study are modified into multi-age groups.Furthermore,by using the surveillance data for Fujian Provincial Center for Disease Control and Prevention,Fuzhou COVID-19 epidemic is chosen to carry out the numerical simulations,which show that the age group of the population plays the vital role when studying infectious diseases.
文摘Lithium-ion capacitors(LICs)combine the high power dens-ity of electrical double-layer capacitors with the high energy density of lithium-ion batteries.However,they face practical limitations due to the narrow operating voltage window of their activated carbon(AC)cathodes.We report a scalable thermal treatment strategy to develop high-voltage-tolerant AC cathodes.Through controlled thermal treatment of commer-cial activated carbon(Raw-AC)under a H_(2)/Ar atmosphere at 400-800℃,the targeted reduction of degradation-prone functional groups can be achieved while preserving the critical pore structure and increasing graph-itic microcrystalline ordering.The AC treated at 400℃(HAC-400)had a significant increase in specific capacity(96.0 vs.75.1 mAh/g at 0.05 A/g)and better rate capability(61.1 vs.36.1 mAh/g at 5 A/g)in half-cell LICs,along with an 83.5%capacity retention over 7400 cycles within an extended voltage range of 2.0-4.2 V in full-cell LICs.Scalability was demonstrated by a 120 g batch production,enabling fabrication of pouch-type LICs with commercial hard carbon anodes that delivered a higher energy density of 28.3 Wh/kg at 1 C,and a peak power density of 12.1 kW/kg compared to devices using raw AC.This simple,industry-compatible approach may be used for producing ad-vanced cathode materials for practical high-performance LICs.
基金National Key Research and Development Program of China(2021YFB3101402)National Natural Science Foundation of China(62202294)。
文摘This study constructs a function-private inner-product predicate encryption(FP-IPPE)and achieves standard enhanced function privacy.The enhanced function privacy guarantees that a predicate secret key skf reveals nothing about the predicate f,as long as f is drawn from an evasive distribution with sufficient entropy.The proposed scheme extends the group-based public-key function-private predicate encryption(FP-PE)for“small superset predicates”proposed by Bartusek et al.(Asiacrypt 19),to the setting of inner-product predicates.This is the first construction of public-key FP-PE with enhanced function privacy security beyond the equality predicates,which is previously proposed by Boneh et al.(CRYPTO 13).The proposed construction relies on bilinear groups,and the security is proved in the generic bilinear group model.
文摘Herein the use of rare-earth compounds in catalytic reduction systems for the end-group functionalization of carboxyl-terminated low-molecularweight fluoropolymers was explored.Leveraging the high catalytic activity and selectivity of rare-earth compounds along with no residual impact on polymer product's performance,highly efficient catalytic reduction systems containing sodium borohydride(NaBH_(4))and rare-earth chloride(RECl_(3))were specifically designed for a telechelic carboxyl-terminated liquid fluoroeslastomer,aiming to facilitate the conversion of chainend carboxyl groups into hydroxyl groups and improvement in end-group reactivity.To achieve this,lanthanum chloride(LaCl_(3)),cerium chloride(CeCl_(3)),and neodymium chloride(NdCl_(3))were used separately to form catalytic reduction systems with NaBH_(4).The effects of solvent dosage,reaction temperature,reaction time length,and reductant dosage on carboxylic conversion were investigated,and the molecular chain structure,molecular weight,and functional group content of the raw materials and the products were analyzed and characterized by means of infrared spectroscopy(FTIR),proton nuclear magnetic resonance(^(1)H-NMR),fluorine-19 nuclear magnetic resonance(^(19)F-NMR),gel permeation chromatography(GPC),and chemical titration.Moreover,the catalytic activity and selectivity of the rare-earth chlorides,as well as the corresponding underlying interactions were discussed.Results indicated that the rare-earth-containing catalytic reduction systems studied in this work could efficiently convert the chain-end carboxyl groups into highly active hydroxyl groups,with a highest conversion up to 87.0%and differing catalytic reduction activities ranked as NaBH_(4)/CeCl_(3)>NaBH_(4)/LaCl_(3)>NaBH_(4)/NdCl_(3).Compared with the conventional lithium aluminum hydride(LiAIH_(4))reduction system,the NaBH_(4)/RECl_(3)systems provide multiple advantages such as mild reaction conditions,high conversion ratio with good selectivity,and environmental innocuity,and are potentially applicable as new reduction-catalysis combinations for the synthesis and functionalization of polymer materials.
文摘Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex[Pt(κ^(3)-N^C^N')(CNXyl)]Cl([A]Cl)and the molecular complex[Pt(κ^(2)-N^C^N')(CNXyl)Cl](B).Isomer B was almost the dominating product.The structures of the isomer B derivatives bearing-CF_(3)and-Cl substituents on the pyridine ring of the pinene moiety(5B and 7B,respectively)have been confirmed by single-crystal X-ray diffraction,revealing a slightly distorted square planar geometry with trans-N_(N^C^N'),CNR configuration(The terminal N atom of theκ^(2)-N^C^N'ligand is trans to the isocyanide ligand CNXyl.).Isomer B is thermodynamically more stable,as confirmed by theoretical calculations.CCDC:2416415,5B;2416414,7B.
基金supported by the National Natural Science Foundation of China(No.22375021,22235003,22261132516&22205021)the BIT Research and Innovation 265 Promoting Project(Grant No.2023YCXZ017)。
文摘Energetic compounds bearing the trinitromethyl group are garnering broad attraction as potential candidates for a new generation of high energy dense oxidizers.In this work,an effective dual modulation strategy involving both molecular isomerization and crystal morphology control was employed to design and optimize trinitromethyl-oxadiazole with improved comprehensive performance.Utilizing this dual strategy,3,5-bis(trinitromethyl)-1,2,4-oxadiazole(3)was synthesized,resulting in the formation of two distinct crystal morphologies(needle and sheet)corresponding to two crystal forms(3-a and3-b).Encouragingly,while maintaining ultra-high oxygen balance(21.73%),3 achieves impressive densities(1.97-1.98 g/cm^(3)).To our knowledge,the density of 1.98 g/cm^(3)for 3-a sets a new record among that of nitrogen-rich monocyclic compounds.Notably,practical crystal morphology prediction was creatively introduced to guide the experimental crystallization conditions of 3,increasing the impact sensitivity and friction sensitivity from 1 J to 80 N(3-a)to 10 J and 240 N(3-b),respectively.Additionally,the crystal structural analyses and theoretical calculations were conducted to elucidate the reasons of differences between 3-a and 3-b in density and stability.This work provides an efficient strategy to enhance performance of trinitromethyl derivatives,broadening the path and expanding the toolbox for energetic materials.
基金supported by the National Natural Science Foundation of China(62003264).
文摘To solve the problem of providing the best initial situation for terminal guidance when multiple missiles intercept multiple targets,a group cooperative midcourse guidance law(GCMGL)considering time-to-go is proposed.Firstly,a threedimensional(3D)guidance model is established and a cooperative trajectory shaping guidance law is given.Secondly,for estimating the unknown target maneuvering acceleration,an adaptive disturbance observer(ADO)is designed,combining finitetime theory with a radial basis function(RBF)neural network,and the convergence of the estimation error is proven using Lyapunov stability theory.Then,to ensure time-to-go cooperation among missiles within the same group and across different groups,the group consensus protocols of virtual collision point mean and the inter-group cooperative consensus protocol are designed respectively.Based on the group consensus protocols,the virtual collision point cooperative guidance law is given,and the finite-time convergence is proved by Lyapunov stability theory.Simultaneously,combined with trajectory shaping guidance law,virtual collision point cooperative guidance law and the intergroup cooperative consensus protocol,the design of GCMGL considering time-to-go is given.Finally,numerical simulation results show the effectiveness and the superiority of the proposed GCMGL.
文摘The seedlings of Vernicia montana derived from seeds soaking with water (the first group)or 300 mg5L -1 mixed nitric_acid rare earth solution (the second group) were treated with various concentrations of mixed nitric_acid rare earth solution by foliage spraying. The results showed that the seedling heights sprayed with 100 和 1 000 mg·L -1 of the first group and with 50 和 100 mg·L -1 of the second group were significantly higher than the controls, and the diameter at ground level sprayed with 300 mg·L -1 of the second group was significantly greater than the control, being 26.92% more than the latter; except for spraying with 0 mg5L -1 and 700～1 500 mg5L -1 of the second group, the seedling dry weight above ground of others was 29.13%～73.91% greater than the control, whereas the seedling dry weight under ground of others was 20.78%～116.88% greater than the control; the contents of chlorophyll a and chlorophyll b for all spraying seedling were 91.67%～191.67% and 87.5%～306.25% greater than the control, respectively, and soluble proteins and soluble sugars were 16.00%～179.78% and 10.73%～105.65% greater than the control, respectively. Compared with the control, the activity of SOD tended to increase, whereas the contents of MDA decreased. These indicated that spraying leaves with optimum concentration of mixed nitric_acid rare earth solution could markedly promote the growth of seedlings and improve resistance ability of V. montana seedlings to bad environment. On the whole, the effects of spraying the leaves of seedling with 50～500 mg5L -1 mixed nitric_acid rare earth solution, which were derived from seeds soaking with 300 mg·L -1 mixed nitric_acid rare earth solution, were good.
文摘N-salicylidene-benzylamineato M(Ⅱ) complexes (ZnL2, CuL2 and CdL2) were synthesized, characterized and valued for antimicrobial activities against bacterial strands using the agar diffusion method. The crystal of ZnL2 was determined by X-ray diffraction. It crystallizes in the Monoclinic system, space group C2/c with a=2.269 1(3), b=0.918 2(1), c=1.239 5(2) nm, β=117.89(2), Z=4, R1=0.049 4, wR2=0.138 2. The complexes were found to be active against Staphylococcus aureus and Eschierichia Coli. CCDC: 249474.
文摘A novel coordination polymer of [Co( p-CPOA)(2,2′-bipy)(H2O)]n ( p-CPOA2-=4-carboxylphenoxyacetate dianion, 2,2′-bipy=2,2′-bipyridine) was synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction. The title complex crystallizes in monoclinic space group C2/c, with a=1.424 4(3) nm, b=1.316 6(3) nm, c=1.947 7(4) nm, β=104.56(3)°. V=3.535 3(14) nm3, Z=8, R=0.028 5, wR=0.089 1. The cobalt(Ⅱ) ion displays a distorted octahedral coordination geometry, defined by three carboxyl oxygen atoms from different p-CPOA2- groups, two nitrogen atoms from 2,2′-bipyridine ligand and one water molecule. The cobalt atoms are bridged by p-CPOA2- groups, forming a one-dimensional chain structure along a axis. The adjacent Co...Co atoms distance is 0.996 8 nm. A layer supramolecular network is contrsucted by the hydrogen bonds and π-π stacking interactions. CCDC: 220039.
文摘new coordination polymer {[Zn(CF3COO)2(C5H5ON)]·H2O}n was synthesized based on the reaction of zinc(Ⅱ) trifluoroacetate and 3-hydroxypyridine(C5H5ON) in methanol medium for the first time. The structure of the coordination polymer was confirmed by IR, 1H NMR, elemental analysis and thermal analysis. The crystal structure of the coordination polymer was also determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group P21/m, and crystallographic data of the coordination polymer are: a= 0.863 1(4) nm, b=0.717 7(3) nm, c=1.116 4(5) nm, α=γ=90°, β=107.542(6)°, V=0.659 4(5) nm3; Dc=2.037 g·cm-3; Z=2; F(000)=400; μ=1.969 mm-1. Zinc(Ⅱ) atom lies at the center of an octahedron formed by the coordination of zinc atom and six O atoms which come from four different trifluoroacetate ions and two different 3-hydroxypyridine molecules where each trifluoroacetate ion and 3-hydroxypyridine are coordinated to two different zinc ions to form coordination polymer. CCDC: 253909.
文摘The geometric configurations of binuclear Zinc( complex Zn2[(n-Bu)2NCSS]4 and the ligand Na[(n-Bu)2 NCSS] have been optimized by B3LYP quantum chemical method. The electronic structures have been performed by density functional theory at B3LYP/6-31G* level. The electronic spectrums of the complex and ligand were calculated by ZINDO/S-CIS method. It is indicated from the calculation that: (1) The coordination effect of bridging ligand is bigger than that of chelating one, and the bridging ligands also translate more charge to Zn than the chelating one. (2) The calculated results about electronic spectrums are similarly to experimental measurement, and farther explain that absorption band at λ=267 nm of complex is assigned to two n → π* transitions :one arising from the bridging ligands and the another mainly arising from the chelating ligands;but absorption band at λ=236 nm of complex is assigned to π → π* transition which the electron mainly translates from the bridging ligands to the chelating ligands. (3) By consideration of delocalization and polar effects in coordination, the charge transfer from ligand to metal decreases the π-π and p-π conjugation effects in the chromophore group NCS2 and to increase the energy needed for the π → π* and n → π* transitions, and results in the absorption bands shifting towards the short wavelength direction.
文摘Soil animal communities of Pinus koraiensis broad_leaved mixed forest were studied.The purpose was to discuss the dynamic characteristic of soil animals and relationship with environmental factors.The ecosystem geography distribution law of soil animals, soil animals’role and function in ecological system were revealed.In June,August,October each year,three plots were selected. In each plot, four layers were sampled(litter layer,0～10 cm,10～20 cm & 20～30 cm),adding up to 72 soil sample.The area for large_sized soil animals was 50 cm×50 cm,and the area for middle_small_sized soil animals was 10 cm × 10 cm.Separated soil animals through adopting hand_picking method and Tullgren method respectively.Sampled the soil animals in two continuing years.Shannon_Wiener index was adopted to analyze the diversity of soil animals.Monad liner regression was used to search the relationship between soil animals and environmental factors.The dominant groups were Oribatida, Isotomidae.There were relatively great changes in groups and individual numbers of dominant groups and rare groups when the reason changed.The individual numbers of dominant groups and the groups of rare groups changed.The number of individual and group was the most in August.Obviously it correlated with climatic factors in middle temperate zone.The evenness was low and dominance was high. The diversity index was not most.Among the annual fluctuating there was a increasing trend. The evenness was low and dominance was high.The diversity index was low.It conformed with the law of reason change.The correlation between soil animals and atmospheric temperature,rainfall,ground temperature and sunlight showed the correlation with rainfall and soil temperature was the most significant.
文摘A one-dimensional double-chain coordination polymer [Mn(phen)(tsgluo)] was synthesized in a mixed solution and its crystal structure was determined by X-ray diffraction method. It crystallizes in orthorhombic system with space group P212121. The crystal data are: a=0.530 78(17) nm, b=1.723 9(5) nm, c=2.456 9(8) nm, Z=4, μ=0.729 mm-1, Dc=1.579 g·cm-3, V=2.248 1(12) nm3, R1=0.033 1, ωR2=0.078 9. In the title complex, each Mn(Ⅱ) ion presents a octahedral geometry with the coordination of two nitrogen atoms from 1,10-phenanthroline and four oxygen atoms from three different tsgluo2- ligands. The γ-carboxyl coordinates to Mn(Ⅱ) in the mode of bidentate chelate, while the α-carboxyl coordinates in a bidentate bridging mode. CCDC: 253910.
文摘The novel copper(Ⅱ) complex with α-hydroxyphenylacetic acid (H2PHAc) and pyridine (py) ligands, [Cu(HPHAc)2(py)2], has been synthesized and characterized by elemental analysis and IR spectroscopy. Its crystal structure was determined by single crystal X-ray diffraction techniques. The crystal belongs to monoclinic with space group C2/c. The cell parameters are: a=1.712 5(3) nm, b=1.533 2(2) nm, c=0.963 42(14) nm, β=111.866(2)°, V=2.347 6(6) nm3, and Dc=1.483 Mg·m-3, Z=4, F(000)=1 084. The structure was refined to final R1=0.071 4, wR2=0.166 1. The complex has a six-coordinated distorted octahedral geometry, in which copper(Ⅱ) ion coordinates with two carboxylic oxygen atoms and two hydroxyl oxygen atoms from the two α-hydroxyphenylacetic acid ligands, two nitrogen atoms from the two pyridine ligands. The analysis of the crystal structure indicates that the complex has a one-dimensional chain structure, which is formed by intermolecular hydrogen bonds. CCDC: 255346.
