The column wicking technique was applied to estimate the surface free energy of cellulose, the importance of which is to obtain a real effective capillary radius, Reff, initially from the plot of Washburn penetration ...The column wicking technique was applied to estimate the surface free energy of cellulose, the importance of which is to obtain a real effective capillary radius, Reff, initially from the plot of Washburn penetration distance versus time. Since the cellulose sample could not be packed with good reproducibility, therefore, Reff can not be obtained readily from the slope of the plot. A method was developed in this paper by uniting all apparent packing heights with a unique value to deduce a real effective capillary radius. Based on the defined critical packing height related to the critical packing density, the surface free energy and acid-base properties of cellulose Sigma C8002 were estimated.展开更多
In this study, the contact angles of three different reference liquids (including distilled water, diiodomethane, and formamide) and PF resin on the surfaces of Chinese fir (Cunningharnia lanceolata) samples untre...In this study, the contact angles of three different reference liquids (including distilled water, diiodomethane, and formamide) and PF resin on the surfaces of Chinese fir (Cunningharnia lanceolata) samples untreated or treated with different concentrations of ACQ-D (ammoniacal copper quat Type D) solutions were measured. Then, the surface free energy was calculated by two approaches: acid-base approach and geometric mean approach. ACQ-D treatment caused higher contact angles and lower surface free energies at a retention level corresponding to the commodity treated wood products. When wood was treated with much higher concentrations of ACQ-D, the total surface free energy of wood would be higher than the untreated control. Acid-base/polar components related with the hydrogen bonding state in wood were considered to be responsible for the observed changes according to the applied approaches. The hydrophobic properties and also higher contact angles of PF resin drop on wood surfaces after ACQ-D treatment at a reasonable retention level confirms the changes on surface free energy.展开更多
Src SH3 protein domain is a typical two-state protein which has been confirmed by research of denaturant-induced unfolding dynamics.Force spectroscopy experiments by optical tweezers and atomic force microscopy have m...Src SH3 protein domain is a typical two-state protein which has been confirmed by research of denaturant-induced unfolding dynamics.Force spectroscopy experiments by optical tweezers and atomic force microscopy have measured the force-dependent unfolding rates with different kinds of pulling geometry.However,the equilibrium folding and unfolding dynamics at constant forces has not been reported.Here,using stable magnetic tweezers,we performed equilibrium folding and unfolding dynamic measurement and force-jump measurement of src SH3 domain with tethering points at its N-and C-termini.From the obtained force-dependent transition rates,a detailed two-state free energy landscape of src SH3 protein is constructed with quantitative information of folding free energy,transition state barrier height and position,which exemplifies the capability of magnetic tweezers to study protein folding and unfolding dynamics.展开更多
Jarzynski' identity (JI) method was suggested a promising tool for reconstructing free energy landscape of biomolecular interactions in numerical simulations and ex- periments. However, JI method has not yet been w...Jarzynski' identity (JI) method was suggested a promising tool for reconstructing free energy landscape of biomolecular interactions in numerical simulations and ex- periments. However, JI method has not yet been well tested in complex systems such as ligand-receptor molecular pairs. In this paper, we applied a huge number of steered molec- ular dynamics (SMD) simulations to dissociate the protease of human immunodeficiency type I virus (HIV-1 protease) and its inhibitors. We showed that because of intrinsic com- plexity of the ligand-receptor system, the energy barrier pre- dicted by JI method at high pulling rates is much higher than experimental results. However, with a slower pulling rate and fewer switch times of simulations, the predictions of JI method can approach to the experiments. These results sug- gested that the JI method is more appropriate for reconstruct- ing free energy landscape using the data taken from experi- ments, since the pulling rates used in experiments are often much slower than those in SMD simulations. Furthermore, we showed that a higher loading stiffness can produce higher precision of calculation of energy landscape because it yields a lower mean value and narrower bandwidth of work distri- bution in SMD simulations.展开更多
A β”/β-Al_2O_3 solid electrolyte was prepared and used in a Na conentration galvanic cell: (-)O_2(in Ar),SnO_2,Na_2SnO_3|β"/β-Al_2O_3]NaCrO_2,Cr_2O_3,O_2(in Ar)(+).The emf measurements were carried out in te...A β”/β-Al_2O_3 solid electrolyte was prepared and used in a Na conentration galvanic cell: (-)O_2(in Ar),SnO_2,Na_2SnO_3|β"/β-Al_2O_3]NaCrO_2,Cr_2O_3,O_2(in Ar)(+).The emf measurements were carried out in temperature range of 912—1223 K:E=652.1— 0.2092 T+2.3(mV).Using this equation and cited free energies of formation of NaCrO_2, Cr_2O_3 and SnO_2,the molar free energy of formation of Na_2 SnO_3 may be calculated by ΔG°=-1050+0.2544 T±5.4(kJ mol^(-1)).展开更多
A dynamic free energy hysteresis model in magnetostrictive actuators is presented. It is the free energy hysteresis model coupled to an ordinary different equation in an unusual way. According to its special structure...A dynamic free energy hysteresis model in magnetostrictive actuators is presented. It is the free energy hysteresis model coupled to an ordinary different equation in an unusual way. According to its special structure, numerical implementation method of the dynamic model is provided. The resistor parameter in the dynamic model changes according to different frequency ranges. This makes numerical implementation results reasonable in the discussed operating frequency range. The validity of the dynamic free energy model is illustrated by comparison with experimental data.展开更多
The Gibbs free energy differences between the supercooled liquid and the crystalline mixture for the (Zr_(52.5)Ti_5Al_(10)-Ni_(14.6)Cu_(17.9))_((100-x)/100)Sn_x (x=0, 1, 2, 3, 4 and 5) glass forming alloys are estimat...The Gibbs free energy differences between the supercooled liquid and the crystalline mixture for the (Zr_(52.5)Ti_5Al_(10)-Ni_(14.6)Cu_(17.9))_((100-x)/100)Sn_x (x=0, 1, 2, 3, 4 and 5) glass forming alloys are estimated by introducing the equationproposed by Thompson, Spaepen and Turnbull. It can be seen that the Gibbs free energy differences decrease firstas the increases of Sn addition smaller than 3, then followed by a decrease due to the successive addition of Snlarger than 3, indicating that the thermal stabilities of these glass forming alloys increase first and then followed by adecrease owing to the excessive addition of Sn. Furthermore, the activation energy of Zr_(52.5)Ti_5Al_(10)Ni_(14.6)Cu_(17.9) and(Zr_(52.5)Ti_5Al_(10)Ni_(14.6)Cu_(17.9))_(0.97)Sn_3 was evaluated by Kissinger equation. It is noted that the Sn addition increases theactivation energies for glass transition and crystallization, implying that the higher thermal stability can be obtainedby appropriate addition of Sn.展开更多
Rare earth composite phosphate (RECP) was doped into the ceramic glazes. The contact angle and surface free energy were characterized by the OCA-30 automatism contact angle test system. Through studied the influence o...Rare earth composite phosphate (RECP) was doped into the ceramic glazes. The contact angle and surface free energy were characterized by the OCA-30 automatism contact angle test system. Through studied the influence of RECP on the surface free energy of ceramic glaze and movement modality of oil on the ceramic glaze in the water, the results show that the ceramic surface free energy increase obviously after dope RECP. Analysis and calculation show that the surface free energy increase mainly profited from the surface hydroxyl groups increase.展开更多
The conformational entropy S and free energy F were calculated by exact enumeration of polysilane chain up to 23 segments with excluded volume (EV) and long-range van der Waals (VW) interaction. A nonlinear relation b...The conformational entropy S and free energy F were calculated by exact enumeration of polysilane chain up to 23 segments with excluded volume (EV) and long-range van der Waals (VW) interaction. A nonlinear relation between SEV+VW and chain length n was found though S-EV was found to vary linearly with n. We found that the second-order transition temperature of polysilane chain with VW interaction increases with the increase of chain length, while that of polysilane chain without VW interaction is chain length independent. Moreover, the free energies FEV+VW and F-EV are both linearly related with n, and FEV+VW < F-EV for all temperatures.展开更多
The temperature dependence of standard free energy of formation of LaNi_5,CeNi_5 has been de- termined by galvanic—cell technique using 0.95LaF_3·0.05CaF_2 polycrystalline solid electrolyte.The cell used can be ...The temperature dependence of standard free energy of formation of LaNi_5,CeNi_5 has been de- termined by galvanic—cell technique using 0.95LaF_3·0.05CaF_2 polycrystalline solid electrolyte.The cell used can be expressed as: Mo|La,LaF_3|0.95LaF_3·0.05CaF2|LaNi_5,Ni,LaF_3|Mo(903~1173K) Mo|La|0.95LaF_3·0.05CaF_2|LaNi_5,Ni|Mo(903~1173K) Mo|Ce,CeF_3|0.95LaF_3·0.05CaF_2|CeNi_5,Ni,CeF_3|Mo(873~1023K) The experimental results are as follows: △G_(f,LaNi_5)~0=-152590+13.143T±150 J/mol(903~1173K) △G_(f,CeNi_5)~0=-157600+25.514T±150 J/mol(873~1023K)展开更多
The correlation relationships of apparent extraction equilibrium constant (1gK(ex)) with the electronic effect parameter( Sigma sigma(Phi)) and the steric effect parameter ( Sigma upsilon ) of the substituents in extr...The correlation relationships of apparent extraction equilibrium constant (1gK(ex)) with the electronic effect parameter( Sigma sigma(Phi)) and the steric effect parameter ( Sigma upsilon ) of the substituents in extractant molecules are investigated by linear regression analysis in the extraction of rare earths by various classes and structures of monoacidic organophosphorus extractants. The results indicate that in Linear free energy relationship formula 1gK(ex) = rho Sigma sigma(Phi) + psi Sigma upsilon + h generally follows for this kind of extraction systems. Accordingly, the quantitative structure-behaviour relationships of extractants are discussed. These relationships can be preliminarily applied to predict the 1gK(ex) values of rare earth extraction with definite structures of this class of extractants, and thus can provide some directions for the design of new RE extractants.展开更多
We build a double quantum-dot system with Coulomb coupling and aim at studying connections among the entropy production,free energy,and information flow.By utilizing concepts in stochastic thermodynamics and graph the...We build a double quantum-dot system with Coulomb coupling and aim at studying connections among the entropy production,free energy,and information flow.By utilizing concepts in stochastic thermodynamics and graph theory analysis,Clausius and nonequilibrium free energy inequalities are built to interpret local second law of thermodynamics for subsystems.A fundamental set of cycle fluxes and affinities is identified to decompose two inequalities by using Schnakenberg's network theory.Results show that the thermodynamic irreversibility has energy-related and information-related contributions.A global cycle associated with the feedback-induced information flow would pump electrons against the bias voltage,which implements a Maxwell demon.展开更多
Carboxyltransferase domain(CT) of acetyl-coenzyme A carboxylase(ACCase, EC 6.4.1.2) from a family of Poaceae is an important target of commercial herbicide APPs for controlling grass weed growth. As the abuse of A...Carboxyltransferase domain(CT) of acetyl-coenzyme A carboxylase(ACCase, EC 6.4.1.2) from a family of Poaceae is an important target of commercial herbicide APPs for controlling grass weed growth. As the abuse of APPs herbicides, the resistant ACCase due to the mutation of a single residue(Ile→Leu), which is located in CT active site, is emergent in many populations and species of Poaceae. So it is urgent to understand the resistant mechanism so as to design new effect herbicides. Herein lies the complex of CT dimmer from Lolium rigidum and herbicide haloxyfop successfully constructed for wild type enzyme and Ile/Leu mutant, respectively, providing a basis for explaining the resistance from microscopic structure. Moreover, the binding free energy difference between wild type and mutant enzymes was predicted in good agreement with the known observation, and the various contributions to it were analyzed, by Molecular mechanics-Poisson-Boltzmann surface area(MM-PBSA) method. The results indicate the van der Waals interaction difference between the protein and inhibitor, -22.94 kJ/mol of CT wild type lower than that of mutant, is the major reason for resistance. Structure analysis further suggests that van der Waals interaction difference is originated from the steric hindrance between the side chain of mutated residue Leu and the chiral methyl group of haloxyfop. All these findings enhance the understanding of resistant mechanism of ACCase to herbicide by Ile/Leu mutation and provide an important clue for the rational design of high effective herbicides.展开更多
Coiled-coils are well known protein–protein interaction motifs,with the leucine zipper region of activator protein-1(AP-1)consisting of the c-Jun and c-Fos proteins being a typical example.Molecular dynamics(MD)simul...Coiled-coils are well known protein–protein interaction motifs,with the leucine zipper region of activator protein-1(AP-1)consisting of the c-Jun and c-Fos proteins being a typical example.Molecular dynamics(MD)simulations using the MM/GBSA method have been used to predict the free energy of interaction of these proteins.The influence of force field polarisation and capping on the predicted free energy of binding of complexes with different electrostatic environments(net charge)were investigated.Although both force field polarisation and peptide capping are important for the prediction of the absolute free energy of binding,peptide capping has the largest influence on the predicted free energy of binding.Polarisable simulations appear better suited to determine structural properties of the complexes of these proteins while non-polarisable simulations seem to give better predictions of the associated free energies of binding.展开更多
In light of the φ-mapping method, the contribution of disclination lines to the free energy density of 2-dimensional liquid crystals is studied in the single-elastic constant approximation. It is pointed out that, co...In light of the φ-mapping method, the contribution of disclination lines to the free energy density of 2-dimensional liquid crystals is studied in the single-elastic constant approximation. It is pointed out that, compared with the previous theory, the free energy density can be divided into two parts. One is the usual distorted energy density of director field around the disclination lines. The other is the free energy density of the disclination lines themselves which is centralized at the disclination lines and topoligically quantized in a unit of 1/2kπ. The topological quantum numbers are determined by the Hopf indices and Brouwer degrees of the director field at the disclination lines, i.e., the disclination strength. From the method of Lagrangian multipliers, the equilibrium equation and the molecular field of 2-dimensional liquid crystals are also obtained. It is shown that the physical meaning of the Lagrangian multiplier is just the distorted energy density. Key words director field - disclination line - free energy - Lagrangian multiplier PASC2001 64.70.Md - 02.40.-k展开更多
Surface cell Madelung constant is firstly defined for calculating the surface free energy of nanosized crystal grains, which explains the physical performance of small crystals and may be greatly beneficial to the ana...Surface cell Madelung constant is firstly defined for calculating the surface free energy of nanosized crystal grains, which explains the physical performance of small crystals and may be greatly beneficial to the analysis of surface states and the study of the dynamics of crystal nucleation and growth. A new approximative expression of the surface energy and relevant thermodynamic data are used in this calculation. New formula and computing method for calculating the Madelung constant α of any complex crystals are proposed, and the surface free energies and surface electrostatic energies of nanosized crystal grains and the Madelung constant of some complex crystals are theoretically calculated in this paper. The surface free energy of nanosized-crystal-grain TiO2 and the surface electrostatic energy(absolute value) of nanosized-crystal-grain α-Al2O3 are found to be the biggest among all the crystal grains including those of other species.展开更多
Thermodynamic properties of 3Y_2O_3·5Al_2O_3 double compound have been determined with CaF_2 single crystal electrolyte galvanic cell at 1049 K to 1230 K.The galvanic cell used can be expressed as: Pt,O_2(g)丨Y_2...Thermodynamic properties of 3Y_2O_3·5Al_2O_3 double compound have been determined with CaF_2 single crystal electrolyte galvanic cell at 1049 K to 1230 K.The galvanic cell used can be expressed as: Pt,O_2(g)丨Y_2O_3(s),YOF_((s))丨CaF_2丨YOF_((s)), 3Y_2O_3·5Al_2O_(3(s))丨Al_2O_(3(s))丨O_2(g),Pt, of which the cell reaction is; 3Y_2O_(3(s))+SAl_2O_(3(s))=3Y_2O_3·SAl_2O_(3(s)) The following result is obtained: A_fG°(3Y_2O_3·5Al_2O_3)=-939500+765.90T±710J/mol where,△fG°(3Y_2O_3·5Al_2O_3)is the free energy of formation of 3Y_2O_3·5Al_2O_3 from Y_2O_3 and Al_2O_3.展开更多
CaO formed by decomposing CaCO3 at 1450℃ was ground in a vibrational mill, then the long-time ground sample was reheated at different temperatures. Inverse Gas Chromatography (IGC) was used to measure the variation o...CaO formed by decomposing CaCO3 at 1450℃ was ground in a vibrational mill, then the long-time ground sample was reheated at different temperatures. Inverse Gas Chromatography (IGC) was used to measure the variation of the sample’s surface free energy under grinding and reheating. It is concluded that the total surface free energy and the London dispersive component of the surface free energy increases with grinding, while the polar component first increases with grinding, and then decreases , and finally disappears. When the long-time ground sample was reheated, its total surface free energy decreases , among which the London component decreases , but the polar component appears again.展开更多
Surface cell Madelung constant is firstly defined in calculating surface free energy of nanosized crystal grains, which explains the physical performance of small crystals and may be great benefit to make surface anal...Surface cell Madelung constant is firstly defined in calculating surface free energy of nanosized crystal grains, which explains the physical performance of small crystals and may be great benefit to make surface analysis and study dynamics of crystal nucleus growth. A new approximative expression of surface energy and relevant thermodynamic data was used in this calculation. A new formula and computing method for calculating the Madelung constant a of any complex crystals is proposed, and surface free energies and surface electrostatic energies of nanosized crystal grains as well as Madelung constant of some complex crystals are theoretically calculated in this paper. The surface free energy of nanosized crystal grain TiO2 and surface electrostatic energy(absolute value) of nanosized crystal grain α-A12O3 are found to be the biggest among other crystal grains.展开更多
We investigate the free energy relation for a system contacting with a non-Markovian heat bath and find that the validity of the relation sensitively depends on the non-Markovian memory effect, which is especially rel...We investigate the free energy relation for a system contacting with a non-Markovian heat bath and find that the validity of the relation sensitively depends on the non-Markovian memory effect, which is especially related go the initial preparation effect. This memory effect drives the statistical distribution of the system out of the initial preparation, even if the system starts from an equilibrium state. This leads to the violation of the free energy relation. A possible way of eliminating this memory effect is proposed.展开更多
基金This work is financially supported by the Chinese Education Ministry and Donghua University of China (No. 2B01).
文摘The column wicking technique was applied to estimate the surface free energy of cellulose, the importance of which is to obtain a real effective capillary radius, Reff, initially from the plot of Washburn penetration distance versus time. Since the cellulose sample could not be packed with good reproducibility, therefore, Reff can not be obtained readily from the slope of the plot. A method was developed in this paper by uniting all apparent packing heights with a unique value to deduce a real effective capillary radius. Based on the defined critical packing height related to the critical packing density, the surface free energy and acid-base properties of cellulose Sigma C8002 were estimated.
基金Supported by the Foundation for the Author of National Excellent Doctoral Dissertation of China (Grant No. 200352)
文摘In this study, the contact angles of three different reference liquids (including distilled water, diiodomethane, and formamide) and PF resin on the surfaces of Chinese fir (Cunningharnia lanceolata) samples untreated or treated with different concentrations of ACQ-D (ammoniacal copper quat Type D) solutions were measured. Then, the surface free energy was calculated by two approaches: acid-base approach and geometric mean approach. ACQ-D treatment caused higher contact angles and lower surface free energies at a retention level corresponding to the commodity treated wood products. When wood was treated with much higher concentrations of ACQ-D, the total surface free energy of wood would be higher than the untreated control. Acid-base/polar components related with the hydrogen bonding state in wood were considered to be responsible for the observed changes according to the applied approaches. The hydrophobic properties and also higher contact angles of PF resin drop on wood surfaces after ACQ-D treatment at a reasonable retention level confirms the changes on surface free energy.
基金the National Natural Science Foundation of China(Grant Nos.11874309 and 11474237)the 111 Project(Grant No.B16029)。
文摘Src SH3 protein domain is a typical two-state protein which has been confirmed by research of denaturant-induced unfolding dynamics.Force spectroscopy experiments by optical tweezers and atomic force microscopy have measured the force-dependent unfolding rates with different kinds of pulling geometry.However,the equilibrium folding and unfolding dynamics at constant forces has not been reported.Here,using stable magnetic tweezers,we performed equilibrium folding and unfolding dynamic measurement and force-jump measurement of src SH3 domain with tethering points at its N-and C-termini.From the obtained force-dependent transition rates,a detailed two-state free energy landscape of src SH3 protein is constructed with quantitative information of folding free energy,transition state barrier height and position,which exemplifies the capability of magnetic tweezers to study protein folding and unfolding dynamics.
基金supported by the National Science Foundation of China (10732050,10872115 and 11025208)Excellent Young Scholars Research Fund of Beijing Institute of Technology
文摘Jarzynski' identity (JI) method was suggested a promising tool for reconstructing free energy landscape of biomolecular interactions in numerical simulations and ex- periments. However, JI method has not yet been well tested in complex systems such as ligand-receptor molecular pairs. In this paper, we applied a huge number of steered molec- ular dynamics (SMD) simulations to dissociate the protease of human immunodeficiency type I virus (HIV-1 protease) and its inhibitors. We showed that because of intrinsic com- plexity of the ligand-receptor system, the energy barrier pre- dicted by JI method at high pulling rates is much higher than experimental results. However, with a slower pulling rate and fewer switch times of simulations, the predictions of JI method can approach to the experiments. These results sug- gested that the JI method is more appropriate for reconstruct- ing free energy landscape using the data taken from experi- ments, since the pulling rates used in experiments are often much slower than those in SMD simulations. Furthermore, we showed that a higher loading stiffness can produce higher precision of calculation of energy landscape because it yields a lower mean value and narrower bandwidth of work distri- bution in SMD simulations.
文摘A β”/β-Al_2O_3 solid electrolyte was prepared and used in a Na conentration galvanic cell: (-)O_2(in Ar),SnO_2,Na_2SnO_3|β"/β-Al_2O_3]NaCrO_2,Cr_2O_3,O_2(in Ar)(+).The emf measurements were carried out in temperature range of 912—1223 K:E=652.1— 0.2092 T+2.3(mV).Using this equation and cited free energies of formation of NaCrO_2, Cr_2O_3 and SnO_2,the molar free energy of formation of Na_2 SnO_3 may be calculated by ΔG°=-1050+0.2544 T±5.4(kJ mol^(-1)).
文摘A dynamic free energy hysteresis model in magnetostrictive actuators is presented. It is the free energy hysteresis model coupled to an ordinary different equation in an unusual way. According to its special structure, numerical implementation method of the dynamic model is provided. The resistor parameter in the dynamic model changes according to different frequency ranges. This makes numerical implementation results reasonable in the discussed operating frequency range. The validity of the dynamic free energy model is illustrated by comparison with experimental data.
文摘The Gibbs free energy differences between the supercooled liquid and the crystalline mixture for the (Zr_(52.5)Ti_5Al_(10)-Ni_(14.6)Cu_(17.9))_((100-x)/100)Sn_x (x=0, 1, 2, 3, 4 and 5) glass forming alloys are estimated by introducing the equationproposed by Thompson, Spaepen and Turnbull. It can be seen that the Gibbs free energy differences decrease firstas the increases of Sn addition smaller than 3, then followed by a decrease due to the successive addition of Snlarger than 3, indicating that the thermal stabilities of these glass forming alloys increase first and then followed by adecrease owing to the excessive addition of Sn. Furthermore, the activation energy of Zr_(52.5)Ti_5Al_(10)Ni_(14.6)Cu_(17.9) and(Zr_(52.5)Ti_5Al_(10)Ni_(14.6)Cu_(17.9))_(0.97)Sn_3 was evaluated by Kissinger equation. It is noted that the Sn addition increases theactivation energies for glass transition and crystallization, implying that the higher thermal stability can be obtainedby appropriate addition of Sn.
文摘Rare earth composite phosphate (RECP) was doped into the ceramic glazes. The contact angle and surface free energy were characterized by the OCA-30 automatism contact angle test system. Through studied the influence of RECP on the surface free energy of ceramic glaze and movement modality of oil on the ceramic glaze in the water, the results show that the ceramic surface free energy increase obviously after dope RECP. Analysis and calculation show that the surface free energy increase mainly profited from the surface hydroxyl groups increase.
文摘The conformational entropy S and free energy F were calculated by exact enumeration of polysilane chain up to 23 segments with excluded volume (EV) and long-range van der Waals (VW) interaction. A nonlinear relation between SEV+VW and chain length n was found though S-EV was found to vary linearly with n. We found that the second-order transition temperature of polysilane chain with VW interaction increases with the increase of chain length, while that of polysilane chain without VW interaction is chain length independent. Moreover, the free energies FEV+VW and F-EV are both linearly related with n, and FEV+VW < F-EV for all temperatures.
基金The project supported by the National Natural Science Foundation of China
文摘The temperature dependence of standard free energy of formation of LaNi_5,CeNi_5 has been de- termined by galvanic—cell technique using 0.95LaF_3·0.05CaF_2 polycrystalline solid electrolyte.The cell used can be expressed as: Mo|La,LaF_3|0.95LaF_3·0.05CaF2|LaNi_5,Ni,LaF_3|Mo(903~1173K) Mo|La|0.95LaF_3·0.05CaF_2|LaNi_5,Ni|Mo(903~1173K) Mo|Ce,CeF_3|0.95LaF_3·0.05CaF_2|CeNi_5,Ni,CeF_3|Mo(873~1023K) The experimental results are as follows: △G_(f,LaNi_5)~0=-152590+13.143T±150 J/mol(903~1173K) △G_(f,CeNi_5)~0=-157600+25.514T±150 J/mol(873~1023K)
文摘The correlation relationships of apparent extraction equilibrium constant (1gK(ex)) with the electronic effect parameter( Sigma sigma(Phi)) and the steric effect parameter ( Sigma upsilon ) of the substituents in extractant molecules are investigated by linear regression analysis in the extraction of rare earths by various classes and structures of monoacidic organophosphorus extractants. The results indicate that in Linear free energy relationship formula 1gK(ex) = rho Sigma sigma(Phi) + psi Sigma upsilon + h generally follows for this kind of extraction systems. Accordingly, the quantitative structure-behaviour relationships of extractants are discussed. These relationships can be preliminarily applied to predict the 1gK(ex) values of rare earth extraction with definite structures of this class of extractants, and thus can provide some directions for the design of new RE extractants.
基金Project supported by the National Natural Science Foundation(Grant No.11805159)the First Batch of National First-class Undergraduate Courses of China(2020)+1 种基金the Natural Science Foundation of Fujian Province,China(Grant No.2019J05003)Teaching Research Program of Thermodynamics and Statistical Physics in the Institution of Higher Education of China(2019).
文摘We build a double quantum-dot system with Coulomb coupling and aim at studying connections among the entropy production,free energy,and information flow.By utilizing concepts in stochastic thermodynamics and graph theory analysis,Clausius and nonequilibrium free energy inequalities are built to interpret local second law of thermodynamics for subsystems.A fundamental set of cycle fluxes and affinities is identified to decompose two inequalities by using Schnakenberg's network theory.Results show that the thermodynamic irreversibility has energy-related and information-related contributions.A global cycle associated with the feedback-induced information flow would pump electrons against the bias voltage,which implements a Maxwell demon.
基金Supported by the National Natural Science Foundation of China(Nos.20802025, 30870539, 20432010 and 20672045)
文摘Carboxyltransferase domain(CT) of acetyl-coenzyme A carboxylase(ACCase, EC 6.4.1.2) from a family of Poaceae is an important target of commercial herbicide APPs for controlling grass weed growth. As the abuse of APPs herbicides, the resistant ACCase due to the mutation of a single residue(Ile→Leu), which is located in CT active site, is emergent in many populations and species of Poaceae. So it is urgent to understand the resistant mechanism so as to design new effect herbicides. Herein lies the complex of CT dimmer from Lolium rigidum and herbicide haloxyfop successfully constructed for wild type enzyme and Ile/Leu mutant, respectively, providing a basis for explaining the resistance from microscopic structure. Moreover, the binding free energy difference between wild type and mutant enzymes was predicted in good agreement with the known observation, and the various contributions to it were analyzed, by Molecular mechanics-Poisson-Boltzmann surface area(MM-PBSA) method. The results indicate the van der Waals interaction difference between the protein and inhibitor, -22.94 kJ/mol of CT wild type lower than that of mutant, is the major reason for resistance. Structure analysis further suggests that van der Waals interaction difference is originated from the steric hindrance between the side chain of mutated residue Leu and the chiral methyl group of haloxyfop. All these findings enhance the understanding of resistant mechanism of ACCase to herbicide by Ile/Leu mutation and provide an important clue for the rational design of high effective herbicides.
基金the State Key Laboratory of Phytochemistry and Plant Resources in West China,Kunming Institute of Botany,Chinese Academy of Sciences(P2013-ZZ05).
文摘Coiled-coils are well known protein–protein interaction motifs,with the leucine zipper region of activator protein-1(AP-1)consisting of the c-Jun and c-Fos proteins being a typical example.Molecular dynamics(MD)simulations using the MM/GBSA method have been used to predict the free energy of interaction of these proteins.The influence of force field polarisation and capping on the predicted free energy of binding of complexes with different electrostatic environments(net charge)were investigated.Although both force field polarisation and peptide capping are important for the prediction of the absolute free energy of binding,peptide capping has the largest influence on the predicted free energy of binding.Polarisable simulations appear better suited to determine structural properties of the complexes of these proteins while non-polarisable simulations seem to give better predictions of the associated free energies of binding.
文摘In light of the φ-mapping method, the contribution of disclination lines to the free energy density of 2-dimensional liquid crystals is studied in the single-elastic constant approximation. It is pointed out that, compared with the previous theory, the free energy density can be divided into two parts. One is the usual distorted energy density of director field around the disclination lines. The other is the free energy density of the disclination lines themselves which is centralized at the disclination lines and topoligically quantized in a unit of 1/2kπ. The topological quantum numbers are determined by the Hopf indices and Brouwer degrees of the director field at the disclination lines, i.e., the disclination strength. From the method of Lagrangian multipliers, the equilibrium equation and the molecular field of 2-dimensional liquid crystals are also obtained. It is shown that the physical meaning of the Lagrangian multiplier is just the distorted energy density. Key words director field - disclination line - free energy - Lagrangian multiplier PASC2001 64.70.Md - 02.40.-k
文摘Surface cell Madelung constant is firstly defined for calculating the surface free energy of nanosized crystal grains, which explains the physical performance of small crystals and may be greatly beneficial to the analysis of surface states and the study of the dynamics of crystal nucleation and growth. A new approximative expression of the surface energy and relevant thermodynamic data are used in this calculation. New formula and computing method for calculating the Madelung constant α of any complex crystals are proposed, and the surface free energies and surface electrostatic energies of nanosized crystal grains and the Madelung constant of some complex crystals are theoretically calculated in this paper. The surface free energy of nanosized-crystal-grain TiO2 and the surface electrostatic energy(absolute value) of nanosized-crystal-grain α-Al2O3 are found to be the biggest among all the crystal grains including those of other species.
文摘Thermodynamic properties of 3Y_2O_3·5Al_2O_3 double compound have been determined with CaF_2 single crystal electrolyte galvanic cell at 1049 K to 1230 K.The galvanic cell used can be expressed as: Pt,O_2(g)丨Y_2O_3(s),YOF_((s))丨CaF_2丨YOF_((s)), 3Y_2O_3·5Al_2O_(3(s))丨Al_2O_(3(s))丨O_2(g),Pt, of which the cell reaction is; 3Y_2O_(3(s))+SAl_2O_(3(s))=3Y_2O_3·SAl_2O_(3(s)) The following result is obtained: A_fG°(3Y_2O_3·5Al_2O_3)=-939500+765.90T±710J/mol where,△fG°(3Y_2O_3·5Al_2O_3)is the free energy of formation of 3Y_2O_3·5Al_2O_3 from Y_2O_3 and Al_2O_3.
基金Jointly funded by the National Excellent Young Scientists Foundation of China( No. 59925207) and the Natural Science Foun-dation of China (No.59872024)
文摘CaO formed by decomposing CaCO3 at 1450℃ was ground in a vibrational mill, then the long-time ground sample was reheated at different temperatures. Inverse Gas Chromatography (IGC) was used to measure the variation of the sample’s surface free energy under grinding and reheating. It is concluded that the total surface free energy and the London dispersive component of the surface free energy increases with grinding, while the polar component first increases with grinding, and then decreases , and finally disappears. When the long-time ground sample was reheated, its total surface free energy decreases , among which the London component decreases , but the polar component appears again.
文摘Surface cell Madelung constant is firstly defined in calculating surface free energy of nanosized crystal grains, which explains the physical performance of small crystals and may be great benefit to make surface analysis and study dynamics of crystal nucleus growth. A new approximative expression of surface energy and relevant thermodynamic data was used in this calculation. A new formula and computing method for calculating the Madelung constant a of any complex crystals is proposed, and surface free energies and surface electrostatic energies of nanosized crystal grains as well as Madelung constant of some complex crystals are theoretically calculated in this paper. The surface free energy of nanosized crystal grain TiO2 and surface electrostatic energy(absolute value) of nanosized crystal grain α-A12O3 are found to be the biggest among other crystal grains.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 10875011 and 11075016)the National Basic Research Program of China (Grant No. 2007CB814805)+1 种基金the Fundamental Research Funds for the Central Universities of China(Grant No. 201001)the Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20100003110007)
文摘We investigate the free energy relation for a system contacting with a non-Markovian heat bath and find that the validity of the relation sensitively depends on the non-Markovian memory effect, which is especially related go the initial preparation effect. This memory effect drives the statistical distribution of the system out of the initial preparation, even if the system starts from an equilibrium state. This leads to the violation of the free energy relation. A possible way of eliminating this memory effect is proposed.