An extrusion-ploughing process was presented to fabricate the integral fin function-surface. Cutting edge inclination angle and rake angle can be calculated from the tool’s geometry relationship. The description of f...An extrusion-ploughing process was presented to fabricate the integral fin function-surface. Cutting edge inclination angle and rake angle can be calculated from the tool’s geometry relationship. The description of fins’ geometry characters was standardized. The experiments show that, when the middle cutting edge’s inclination angle η is less than 35°, continuous fin will come out; when η is between 35° and 55°, the fins will be saw-tooth ones, and the fins will be torn when this angle is above 55°; when the extrusion angle θ is between 60° and 150°, the fins will appear, or else, the fins will be torn into chips from the base. Forming angle and clearance angle have little effect on fin’s formation. For continuous fin, its height is close to cutting depth when it is small, but it will become approximately constant as cutting depth grows; for saw-tooth fins, the width, the height, as well as the clearance will increase with the increase of cutting depth, but the increment of clearance is small; neither for continuous fin, nor for saw-tooth ones, cutting velocity has little influence on their structure parameters.展开更多
The formation mechanism of methane （CH4） during coal evolution has been investigated by density functional theory （DFT） of quantum chemistry. Thermogenic gas, which is generated during the thermal evolution of med...The formation mechanism of methane （CH4） during coal evolution has been investigated by density functional theory （DFT） of quantum chemistry. Thermogenic gas, which is generated during the thermal evolution of medium rank coal, is the main source of coalbed methane （CBM）. Ethylbenzene （A） and 6,7-dimethyl-5,6,7,8-tetrahydro-1-hydroxynaphthalene （B） have been used as model compounds to study the pyrolysis mechanism of highly volatile bituminous coal （R）, according to the similarity of bond orders and bond lengths. All possible paths are designed for each model. It can be concluded that the activation energies for H-assisted paths are lower than others in the process of methane formation; an H radical attacking on β-C to yield CH4 is the dominant path for the formation of CH4 from highly volatile bituminous coal. In addition, the calculated results also reveal that the positions on which H radical attacks and to which intramolecular H migrates have effects on methyl cleavage.展开更多
To screen for additional treatment targets against tongue cancer, we evaluated the contributions of extracellular signal-related kinase(ERK), AKT and ezrin in cancer development. Immunohistochemical staining showed th...To screen for additional treatment targets against tongue cancer, we evaluated the contributions of extracellular signal-related kinase(ERK), AKT and ezrin in cancer development. Immunohistochemical staining showed that ERK and ezrin expressions were significantly higher in invasive squamous cell carcinoma than in carcinoma in situ. To investigate the roles of ERK and ezrin in cancer development, we used the non-woven silica fibre sheet Cellbedwith a structure resembling the loose connective tissue morphology in a novel 3 D culture system. We confirmed that the 3 D system using CellbedTMaccurately mimicked cancer cell morphology in vivo. Furthermore, cell projections were much more apparent in 3 D-cultured tongue cancer cell lines than in 2 D cultures. Typically, under conventional 2 D culture conditions, F-actin and cortactin are colocalized in the form of puncta within cells.However, in the 3 D-cultured cells, colocalization was mainly observed at the cell margins, including the projections. Projections containing F-actin and cortactin colocalization were predicted to be invadopodia. Although suppressing ezrin expression with small interfering RNA transfection caused no marked changes in morphology, cell projection formation was decreased, and the tumour thickness in vertical sections after 3 D culture was markedly decreased after suppressing ERK activity because both the invasion ability and proliferation were inhibited. An association between cortactin activation as well as ERK activity and invadopodia formation was detected. Our novel 3 D culture systems using Cellbed? are simple and useful for in vitro studies before conducting animal experiments. ERK contributes to tongue cancer development by increasing both cancer cell proliferation and migration via cortactin activation.展开更多
Oxygen vacancy formation and migration in La0.9Sr0.1Ga0.8Mg0.2O3-5 （LSGM） with various crystal symmetries （cubic, rhombohedral, orthorhombic, and monoclinic） are studied by employing first-principles calculations ...Oxygen vacancy formation and migration in La0.9Sr0.1Ga0.8Mg0.2O3-5 （LSGM） with various crystal symmetries （cubic, rhombohedral, orthorhombic, and monoclinic） are studied by employing first-principles calculations based on density functional theory （DFT）. It is shown that the cubic LSGM has the smallest band gap, oxygen vacancy formation energy, and migration barrier, while the other three structures give rise to much larger values for these quantities, implying the best oxygen ion conductivity of the cubic LSGM among the four crystal structures. In out calculations, one oxygen vacancy migration pathway is considered in the cubic and rhombohedral structures due to all the oxygen sites being equivalent in them, while two vacancy migration pathways with different migration barriers are found in the orthorhombic and monoclinic symmetries owing to the existence of nonequivalent O1 and 02 oxygen sites. The migration energies along the migration pathway linking the two 02 sites are obviously lower than those along the pathway linking the O1 and 02 sites. Considering the phase transitions at high temperatures, the results obtained in this paper can not only explain the experimentally observed different behaviours of the oxygen ionic conductivity of LSGM with different symmetries, but also predict the rational crystal structures of LSGM for solid oxide fuel cell applications.展开更多
Based on the double integrator mathematic model, a new kind of potential function is presented in this paper by referring to the concepts of the electric field; then a new formation control method is proposed, in whic...Based on the double integrator mathematic model, a new kind of potential function is presented in this paper by referring to the concepts of the electric field; then a new formation control method is proposed, in which the potential functions are used between agent-agent and between agent-obstacle, while state feedback control is applied for the agent and its goal. This strategy makes the whole potential field simpler and helps avoid some local minima. The stability of this combination of potential functions and state feedback control is proven. Some simulations are presented to show the rationality of this control method.展开更多
The catalytic fast pyrolysis of cellulose impregnated with phosphoric acid (H3PO4) offers a promising method for the selective production of levoglucosenone (LGO),a valuable anhydrosugar product.However,the fundamenta...The catalytic fast pyrolysis of cellulose impregnated with phosphoric acid (H3PO4) offers a promising method for the selective production of levoglucosenone (LGO),a valuable anhydrosugar product.However,the fundamental mechanism for selective LGO formation is unclear.Herein,quantum chemistry calculations and catalytic fast pyrolysis experiments were performed to reveal the formation mechanism of LGO in H3PO4-catalyzed cellulose pyrolysis.H3PO4 significantly decreased the energy barriers of the pyrolytic reactions and altered the competitiveness of the LGO formation pathways,promoting LGO formation.Through different pathways in the non-catalytic and H3P04-catalyzed conditions,LGO is mainly produced from the primary decomposition of glucose units of cellulose and secondary conversion of levoglucosan.The major catalytic formation pathways of LGO comprise similar reactions,with dehydration at the 3-OH+2-H site as the rate-determining step.Importantly,secondary conversion of 1,4;3,6-dianhydro-α-D-glucopyranose is not feasible for LGO formation,in contrast to previous reports.In addition,a high degree of polymerization is beneficial for the selectivity of LGO formation in the catalytic process,because the glycosidic bond is important for the formation of the bicyclic structure (1,5-and1,6-acetal rings).展开更多
Molecular adsorption of formate and carboxyl on stoichiometric CeO2（111） and CeO2（110） surfaces was studied using periodic density functional theory （DFT＋U） calculations. Two distinguishable adsorption modes （...Molecular adsorption of formate and carboxyl on stoichiometric CeO2（111） and CeO2（110） surfaces was studied using periodic density functional theory （DFT＋U） calculations. Two distinguishable adsorption modes （strong and weak） of formate are identified. The bidentate configuration is more stable than the monodentate adsorption configuration. Both formate and carboxyl bind at the more open CeO2（110） surface are stronger. The calculated vibrational frequencies of two adsorbed species are consistent with the experimental measurements. Fi- nally, the effects of U parameters on the adsorption of formate and carboxyl over both CeO2 surfaces were investigated. We found that the geometrical configurations of two adsorbed species are not affected by different U parameters （U = 0, 5, and 7）. However, the calculated ad- sorption energy of carboxyl pronouncedly increases with the U value while the adsorption energy of formate only slightly changes （〈0.2 eV）. The Bader charge analysis shows the opposite charge transfer occurs for formate and carboxyl adsorption where the adsorbed formate is neg- atively charge while the adsorbed carboxyl is positively charged. Interestingly, with the increasing U parameter, the amount of charge is also increased.展开更多
Homogeneous formation of polychlorinated dibenzothiophenes/thianthrenes（PCDT/TAs）,sulfurated compounds analogous to polychlorinated dibenzo-p-dioxin/dibenzofurans（PCDD/Fs）, has been well-documented to occur via ra...Homogeneous formation of polychlorinated dibenzothiophenes/thianthrenes（PCDT/TAs）,sulfurated compounds analogous to polychlorinated dibenzo-p-dioxin/dibenzofurans（PCDD/Fs）, has been well-documented to occur via radical–radical coupling reactions from chlorinated thiophenol precursors. However, the current understanding of the formation mechanism of PCDT/TAs is exclusively limited to the inherent point of view that chlorothiophenoxy radicals act as the only required intermediates for PCDT/TAs. This study investigates reaction pathways for the formation of PCDT/TAs involving two new types of radical species, i.e., substituted phenyl radicals and substituted thiophenoxyl diradicals. Taking 2-chlorothiophenol（2-CTP） as a model compound for chlorothiophenols,we found that apart from the mostly discussed chlorothiophenoxy radicals, substituted phenyl radicals and substituted thiophenoxyl diradicals could also be readily formed via the reaction of 2-CTP with H radicals. Furthermore, direct self-and cross-coupling of these radicals can result in the formation of PCDT/TAs, including 1-monochlorothianthrene（1-MCTA）, 1,6-dichlorothianthrene（1,6-DCTA）, 4,6-dichlorodibenzothiophene（4,6-DCDT）and 1,6-dichlorodibenzothiophene（1,6-DCDT）. The pathways proposed in this work are proven to be both thermodynamically and kinetically favorable. Particularly, comparisons were made between the formation mechanisms of sulfurated and oxygenated dioxin systems from an energetic point view, showing that replacing oxygen with sulfur atoms greatly reduces the activation barriers of the rate-controlling steps involved in the PCDT/TA formation processes compared with those involved for PCDD/Fs. The calculated results in this work may improve our understanding of the formation mechanism of PCDT/TAs from chlorothiophenol precursors and should be informative to environmental scientists.展开更多
In this paper, the strain energy function proposed by Shang and Cheng was generalized by introducing a nonlinear term. Void formation and growth in the interior of a sphere composed of compressible hyper-elastic mater...In this paper, the strain energy function proposed by Shang and Cheng was generalized by introducing a nonlinear term. Void formation and growth in the interior of a sphere composed of compressible hyper-elastic material, subjected to a prescribed uniform displacement, was examined. A parametric cavitated bifurcation solution for the radial deformed function was obtained. Stability of the solution of the cavitated bifurcation equation was discussed. With the appearance of a cavity, an interesting feature of the radial deformation near the deformed cavity wall is the transition from extension to compression.展开更多
In this paper we show that two significant phenomena of magnetospheric chorus emission can be explained by the participation of beam-like electron structures,created by Landau-resonant interaction with growing oblique...In this paper we show that two significant phenomena of magnetospheric chorus emission can be explained by the participation of beam-like electron structures,created by Landau-resonant interaction with growing oblique whistler waves.The first concerns the widely observed spectral gap near half the electron cyclotron frequency Ωe;the second is related to the observation of very obliquely propagating lower-band waves that cannot be directly generated by temperature anisotropy.Concerning the gap,kinetic dispersion theory reveals that interference of the beam-related cyclotron mode ω~Ωe-kVb with the conventional whistler mode leads to mode splitting and the appearance of a ’forbidden’ area in the ω-k space.Thereby the beam velocity appears as an essential parameter.It is directly related to the phase velocity of the most unstable whistler wave mode,which is close to VAe/2 for sufficiently hot electrons(VAe is the electron Alfven velocity).To clarify the second point,we show that Landau-resonant beams with Vb Vb<VAe/2,which arise in cold plasmas from unstable upper-band waves,are able to generate lower-band whistler mode waves at very oblique propagation(θ≥60°).Our studies demonstrate the important role of Landau-resonant electrons in nonlinear whistler wave generation in the magnetosphere.展开更多
Zr-based Zr_50Pd_40Al_10 metallic glasses has not only crystalline phases of about 5 nm in diameter but also amorphous phases. In this work, the radial distribution functions(RDFs) of amorphous structure of Zr_50Pd_40...Zr-based Zr_50Pd_40Al_10 metallic glasses has not only crystalline phases of about 5 nm in diameter but also amorphous phases. In this work, the radial distribution functions(RDFs) of amorphous structure of Zr_50Pd_40Al_10 metallic glasses were firstly measured by electron diffraction, and then Reverse Monte Carlo(RMC) optimization accompanied by density functional theory(DFT) calculations. The amorphous structure has not only short-range order but also good medium-range order. In the RDFs of its amorphous structure, the first and the second peaks are located at 2.96 ? and 4.79 ?, respectively. Partial radical distribution functions(PRDFs) show that the contributions of the first and the second nearest-neighbor distances of various atom pairs to the G(r) peak values, and the first nearest-neighbor distances of Pd–Zr and Zr–Zr atom pairs are the sources of main G(r) peak values between 2? and 6?. The competition mechanism for generating the Pd_25Zr_55 Al_20 amorphous phase and the intermetallic crystalline phase Pd_11Zr_9 is associated with the differences of atomic radius, the proportion, and the melting point of different atoms, as well as the heat of mixing between atoms, leading to an equilibrium state of the two phases. Accordingly, a composite system with intertwined nanocrystals and amorphous phases is in turn formed, and improves the stability of the material.展开更多
In this paper, the thermodynamic parameters are calculated for all gaseous Poly Chlorinat Dibenzo-p-dioxins （PCDDs） using the Density Functional Theory （DFF） method and both the enthalpy of formation （ΔfH^0） an...In this paper, the thermodynamic parameters are calculated for all gaseous Poly Chlorinat Dibenzo-p-dioxins （PCDDs） using the Density Functional Theory （DFF） method and both the enthalpy of formation （ΔfH^0） and Gibbs free energy of formation （Δf G^0） are derived, from which the order of stability of individual congeners is then predicted. All these properties, together with the calculated entropies （ S^0） and heat capacities （ Cp）, are presented as a function of the number of chlorine atoms in the various PCDD molecules. The accuracy of the method used here, is evaluated by comparing the thermodynamic parameters of gaseous chlorobenzenes with experimental values collected from literature.展开更多
It is presented the results of a long-term and intensive experiment, which models the processes of primary soil formation under controlled agro-ecosystems. The influence of mineral substrate transformation is analyzed...It is presented the results of a long-term and intensive experiment, which models the processes of primary soil formation under controlled agro-ecosystems. The influence of mineral substrate transformation is analyzed on the content of chemical elements in plants tomato, and wheat. For the first time have been established dynamic synergistic and antagonistic interrelations between the chemical elements in a various bodies of the plant (roots, reproductive bodies, stems, and leaves). Using methods of the theory of information was revealed dynamics of collective state of chemical elements in the plants. It is shown that the collective states of the chemical elements which defined by the information function is strictly differentiated for different plant bodies, and have hierarchic order. We analyzed the following chemical elements Si, Al, Fe, Mg, Ca, K, P, S, Cl, Na, Mn, Zn.展开更多
基金Projects(50436010 50375055) supported by the National Natural Science Foundation of China+1 种基金 Project(04105942) supported by the Natural Science Foundation of Guangdong Province, China Project(2005B10201002) supported by Scientific and Technological Project of Guangdong Province, China
文摘An extrusion-ploughing process was presented to fabricate the integral fin function-surface. Cutting edge inclination angle and rake angle can be calculated from the tool’s geometry relationship. The description of fins’ geometry characters was standardized. The experiments show that, when the middle cutting edge’s inclination angle η is less than 35°, continuous fin will come out; when η is between 35° and 55°, the fins will be saw-tooth ones, and the fins will be torn when this angle is above 55°; when the extrusion angle θ is between 60° and 150°, the fins will appear, or else, the fins will be torn into chips from the base. Forming angle and clearance angle have little effect on fin’s formation. For continuous fin, its height is close to cutting depth when it is small, but it will become approximately constant as cutting depth grows; for saw-tooth fins, the width, the height, as well as the clearance will increase with the increase of cutting depth, but the increment of clearance is small; neither for continuous fin, nor for saw-tooth ones, cutting velocity has little influence on their structure parameters.
基金supported by the Major Projects of National Science and Technology(Grant No.2011ZX05040-005-002-001)the National Natural Science Foundation of China(Grant No.21276171 and 21276003)+1 种基金the National Younger Natural Science Foundation of China(Grant No.21103120)China Postdoctoral Science Foundation(Grant No.2012M520608)
文摘The formation mechanism of methane （CH4） during coal evolution has been investigated by density functional theory （DFT） of quantum chemistry. Thermogenic gas, which is generated during the thermal evolution of medium rank coal, is the main source of coalbed methane （CBM）. Ethylbenzene （A） and 6,7-dimethyl-5,6,7,8-tetrahydro-1-hydroxynaphthalene （B） have been used as model compounds to study the pyrolysis mechanism of highly volatile bituminous coal （R）, according to the similarity of bond orders and bond lengths. All possible paths are designed for each model. It can be concluded that the activation energies for H-assisted paths are lower than others in the process of methane formation; an H radical attacking on β-C to yield CH4 is the dominant path for the formation of CH4 from highly volatile bituminous coal. In addition, the calculated results also reveal that the positions on which H radical attacks and to which intramolecular H migrates have effects on methyl cleavage.
文摘To screen for additional treatment targets against tongue cancer, we evaluated the contributions of extracellular signal-related kinase(ERK), AKT and ezrin in cancer development. Immunohistochemical staining showed that ERK and ezrin expressions were significantly higher in invasive squamous cell carcinoma than in carcinoma in situ. To investigate the roles of ERK and ezrin in cancer development, we used the non-woven silica fibre sheet Cellbedwith a structure resembling the loose connective tissue morphology in a novel 3 D culture system. We confirmed that the 3 D system using CellbedTMaccurately mimicked cancer cell morphology in vivo. Furthermore, cell projections were much more apparent in 3 D-cultured tongue cancer cell lines than in 2 D cultures. Typically, under conventional 2 D culture conditions, F-actin and cortactin are colocalized in the form of puncta within cells.However, in the 3 D-cultured cells, colocalization was mainly observed at the cell margins, including the projections. Projections containing F-actin and cortactin colocalization were predicted to be invadopodia. Although suppressing ezrin expression with small interfering RNA transfection caused no marked changes in morphology, cell projection formation was decreased, and the tumour thickness in vertical sections after 3 D culture was markedly decreased after suppressing ERK activity because both the invasion ability and proliferation were inhibited. An association between cortactin activation as well as ERK activity and invadopodia formation was detected. Our novel 3 D culture systems using Cellbed? are simple and useful for in vitro studies before conducting animal experiments. ERK contributes to tongue cancer development by increasing both cancer cell proliferation and migration via cortactin activation.
基金supported by the National Natural Science Foundation of China (Grant No.10974183)
文摘Oxygen vacancy formation and migration in La0.9Sr0.1Ga0.8Mg0.2O3-5 （LSGM） with various crystal symmetries （cubic, rhombohedral, orthorhombic, and monoclinic） are studied by employing first-principles calculations based on density functional theory （DFT）. It is shown that the cubic LSGM has the smallest band gap, oxygen vacancy formation energy, and migration barrier, while the other three structures give rise to much larger values for these quantities, implying the best oxygen ion conductivity of the cubic LSGM among the four crystal structures. In out calculations, one oxygen vacancy migration pathway is considered in the cubic and rhombohedral structures due to all the oxygen sites being equivalent in them, while two vacancy migration pathways with different migration barriers are found in the orthorhombic and monoclinic symmetries owing to the existence of nonequivalent O1 and 02 oxygen sites. The migration energies along the migration pathway linking the two 02 sites are obviously lower than those along the pathway linking the O1 and 02 sites. Considering the phase transitions at high temperatures, the results obtained in this paper can not only explain the experimentally observed different behaviours of the oxygen ionic conductivity of LSGM with different symmetries, but also predict the rational crystal structures of LSGM for solid oxide fuel cell applications.
基金the Jiangsu Province Fundamental Research Plan (Natural Science Foundation) (No.BK2006202).
文摘Based on the double integrator mathematic model, a new kind of potential function is presented in this paper by referring to the concepts of the electric field; then a new formation control method is proposed, in which the potential functions are used between agent-agent and between agent-obstacle, while state feedback control is applied for the agent and its goal. This strategy makes the whole potential field simpler and helps avoid some local minima. The stability of this combination of potential functions and state feedback control is proven. Some simulations are presented to show the rationality of this control method.
基金the National Natural Science Foundation of China(51576064,51776070)Beijing Nova Program(Z171100001117064)+2 种基金Beijing Natural Science Foundation(3172030)grants from the Fok Ying Tung Education Foundation(161051)Fundamental Research Funds for the Central Universities(2018QN057,2018ZD08)for financial support。
文摘The catalytic fast pyrolysis of cellulose impregnated with phosphoric acid (H3PO4) offers a promising method for the selective production of levoglucosenone (LGO),a valuable anhydrosugar product.However,the fundamental mechanism for selective LGO formation is unclear.Herein,quantum chemistry calculations and catalytic fast pyrolysis experiments were performed to reveal the formation mechanism of LGO in H3PO4-catalyzed cellulose pyrolysis.H3PO4 significantly decreased the energy barriers of the pyrolytic reactions and altered the competitiveness of the LGO formation pathways,promoting LGO formation.Through different pathways in the non-catalytic and H3P04-catalyzed conditions,LGO is mainly produced from the primary decomposition of glucose units of cellulose and secondary conversion of levoglucosan.The major catalytic formation pathways of LGO comprise similar reactions,with dehydration at the 3-OH+2-H site as the rate-determining step.Importantly,secondary conversion of 1,4;3,6-dianhydro-α-D-glucopyranose is not feasible for LGO formation,in contrast to previous reports.In addition,a high degree of polymerization is beneficial for the selectivity of LGO formation in the catalytic process,because the glycosidic bond is important for the formation of the bicyclic structure (1,5-and1,6-acetal rings).
基金supported by the Laboratory Directed Research and Development(LDRD) Project of the Pacific Northwest National Laboratory(PNNL)The computations were performed using the Molecular Science Computing Facility in the William R.Wiley Environmental Molecular Sciences Laboratory (EMSL)+1 种基金a U.S.Department of Energy national scientific user facility located at PNNL in Richland,WashingtonPart of the computing time was also granted by the National Energy Research Scientific Computing Center(NERSC)
文摘Molecular adsorption of formate and carboxyl on stoichiometric CeO2（111） and CeO2（110） surfaces was studied using periodic density functional theory （DFT＋U） calculations. Two distinguishable adsorption modes （strong and weak） of formate are identified. The bidentate configuration is more stable than the monodentate adsorption configuration. Both formate and carboxyl bind at the more open CeO2（110） surface are stronger. The calculated vibrational frequencies of two adsorbed species are consistent with the experimental measurements. Fi- nally, the effects of U parameters on the adsorption of formate and carboxyl over both CeO2 surfaces were investigated. We found that the geometrical configurations of two adsorbed species are not affected by different U parameters （U = 0, 5, and 7）. However, the calculated ad- sorption energy of carboxyl pronouncedly increases with the U value while the adsorption energy of formate only slightly changes （〈0.2 eV）. The Bader charge analysis shows the opposite charge transfer occurs for formate and carboxyl adsorption where the adsorbed formate is neg- atively charge while the adsorbed carboxyl is positively charged. Interestingly, with the increasing U parameter, the amount of charge is also increased.
基金supported by the National Natural Science Foundation (Nos. 21407167, 21621064, and 21607168)the Chinese Academy of Sciences (No. XDB14030500)
文摘Homogeneous formation of polychlorinated dibenzothiophenes/thianthrenes（PCDT/TAs）,sulfurated compounds analogous to polychlorinated dibenzo-p-dioxin/dibenzofurans（PCDD/Fs）, has been well-documented to occur via radical–radical coupling reactions from chlorinated thiophenol precursors. However, the current understanding of the formation mechanism of PCDT/TAs is exclusively limited to the inherent point of view that chlorothiophenoxy radicals act as the only required intermediates for PCDT/TAs. This study investigates reaction pathways for the formation of PCDT/TAs involving two new types of radical species, i.e., substituted phenyl radicals and substituted thiophenoxyl diradicals. Taking 2-chlorothiophenol（2-CTP） as a model compound for chlorothiophenols,we found that apart from the mostly discussed chlorothiophenoxy radicals, substituted phenyl radicals and substituted thiophenoxyl diradicals could also be readily formed via the reaction of 2-CTP with H radicals. Furthermore, direct self-and cross-coupling of these radicals can result in the formation of PCDT/TAs, including 1-monochlorothianthrene（1-MCTA）, 1,6-dichlorothianthrene（1,6-DCTA）, 4,6-dichlorodibenzothiophene（4,6-DCDT）and 1,6-dichlorodibenzothiophene（1,6-DCDT）. The pathways proposed in this work are proven to be both thermodynamically and kinetically favorable. Particularly, comparisons were made between the formation mechanisms of sulfurated and oxygenated dioxin systems from an energetic point view, showing that replacing oxygen with sulfur atoms greatly reduces the activation barriers of the rate-controlling steps involved in the PCDT/TA formation processes compared with those involved for PCDD/Fs. The calculated results in this work may improve our understanding of the formation mechanism of PCDT/TAs from chlorothiophenol precursors and should be informative to environmental scientists.
基金Projects （50436010, 50375055） supported by the National Natural Science Foundation of China Project （04105942） supported by the Natural Science Foundation of Guangdong Province, China
文摘In this paper, the strain energy function proposed by Shang and Cheng was generalized by introducing a nonlinear term. Void formation and growth in the interior of a sphere composed of compressible hyper-elastic material, subjected to a prescribed uniform displacement, was examined. A parametric cavitated bifurcation solution for the radial deformed function was obtained. Stability of the solution of the cavitated bifurcation equation was discussed. With the appearance of a cavity, an interesting feature of the radial deformation near the deformed cavity wall is the transition from extension to compression.
文摘In this paper we show that two significant phenomena of magnetospheric chorus emission can be explained by the participation of beam-like electron structures,created by Landau-resonant interaction with growing oblique whistler waves.The first concerns the widely observed spectral gap near half the electron cyclotron frequency Ωe;the second is related to the observation of very obliquely propagating lower-band waves that cannot be directly generated by temperature anisotropy.Concerning the gap,kinetic dispersion theory reveals that interference of the beam-related cyclotron mode ω~Ωe-kVb with the conventional whistler mode leads to mode splitting and the appearance of a ’forbidden’ area in the ω-k space.Thereby the beam velocity appears as an essential parameter.It is directly related to the phase velocity of the most unstable whistler wave mode,which is close to VAe/2 for sufficiently hot electrons(VAe is the electron Alfven velocity).To clarify the second point,we show that Landau-resonant beams with Vb Vb<VAe/2,which arise in cold plasmas from unstable upper-band waves,are able to generate lower-band whistler mode waves at very oblique propagation(θ≥60°).Our studies demonstrate the important role of Landau-resonant electrons in nonlinear whistler wave generation in the magnetosphere.
基金supported by National Science Fund for Excellent Young Scholars of China (No. 51422203)the National Natural Science Foundation of China (Nos. 51572091 and 51372001)+4 种基金the Natural Science Foundation of Guangdong Province, China (No. 2018A030313395)the China Postdoctoral Science Foundation (No. 2017M610522)the Science and Technology Program of Guangzhou, China (No. 201604046027)the Fundamental Research Funds for the Central Universities (No. 2017BQ035)the fund of the State Key Laboratory of Solidification Processing in NWPU (No. SKLSP201716)
文摘Zr-based Zr_50Pd_40Al_10 metallic glasses has not only crystalline phases of about 5 nm in diameter but also amorphous phases. In this work, the radial distribution functions(RDFs) of amorphous structure of Zr_50Pd_40Al_10 metallic glasses were firstly measured by electron diffraction, and then Reverse Monte Carlo(RMC) optimization accompanied by density functional theory(DFT) calculations. The amorphous structure has not only short-range order but also good medium-range order. In the RDFs of its amorphous structure, the first and the second peaks are located at 2.96 ? and 4.79 ?, respectively. Partial radical distribution functions(PRDFs) show that the contributions of the first and the second nearest-neighbor distances of various atom pairs to the G(r) peak values, and the first nearest-neighbor distances of Pd–Zr and Zr–Zr atom pairs are the sources of main G(r) peak values between 2? and 6?. The competition mechanism for generating the Pd_25Zr_55 Al_20 amorphous phase and the intermetallic crystalline phase Pd_11Zr_9 is associated with the differences of atomic radius, the proportion, and the melting point of different atoms, as well as the heat of mixing between atoms, leading to an equilibrium state of the two phases. Accordingly, a composite system with intertwined nanocrystals and amorphous phases is in turn formed, and improves the stability of the material.
文摘In this paper, the thermodynamic parameters are calculated for all gaseous Poly Chlorinat Dibenzo-p-dioxins （PCDDs） using the Density Functional Theory （DFF） method and both the enthalpy of formation （ΔfH^0） and Gibbs free energy of formation （Δf G^0） are derived, from which the order of stability of individual congeners is then predicted. All these properties, together with the calculated entropies （ S^0） and heat capacities （ Cp）, are presented as a function of the number of chlorine atoms in the various PCDD molecules. The accuracy of the method used here, is evaluated by comparing the thermodynamic parameters of gaseous chlorobenzenes with experimental values collected from literature.
文摘It is presented the results of a long-term and intensive experiment, which models the processes of primary soil formation under controlled agro-ecosystems. The influence of mineral substrate transformation is analyzed on the content of chemical elements in plants tomato, and wheat. For the first time have been established dynamic synergistic and antagonistic interrelations between the chemical elements in a various bodies of the plant (roots, reproductive bodies, stems, and leaves). Using methods of the theory of information was revealed dynamics of collective state of chemical elements in the plants. It is shown that the collective states of the chemical elements which defined by the information function is strictly differentiated for different plant bodies, and have hierarchic order. We analyzed the following chemical elements Si, Al, Fe, Mg, Ca, K, P, S, Cl, Na, Mn, Zn.
