Mechanism of skeletal reorganization of 1,6-enynes catalyzed by GaCl<Subscript>3</Subscript>

The mechanism of skeletal reorganization of 1,6-enynes catalyzed by GaCI3 has been studied with the density functional method at the B3LYP/6-31G* level. The structures and energies of the stationary points were calcu-lated to identify the activation barriers. The transition stateswere testified with vibration analysis and IRC calculations.The results of calculation show that the conversion of 1,6-enynes is a step-wise reaction. The whole reaction process is formation and migration of three-membered cycle involvinga three-center and two-electron (3c-2e) bond. High stereose-lectivity of the reaction is in good agreement with experimental results.     

Density Functional Theory Study on the Addition Reactions of 4-methyl-benzaldoximes with Propene

The Michael addition reactions of Z and E 4-methyl-benzaldoximes with propene were investigated theoretically by DFT method at B3LYP/6-31G＊ level. The calculation results show that both addition reactions are concerted processes accompanied by the migration of hydrogen from the atom oxygen to carbon. Both products Z and E nitrones have dipolar charge distributions and activities. Z isomer is more favorable in the reaction due to the barrier is lower.     

Phosphonylation and aging mechanisms of mipafox and butyrylcholinesterase: A theoretical study

Phosphonylation and aging processes between butyrylcholinesterase with mipafox have been studied at the B3LYP/6-311G(d,p) level of theory. The calculated results indicate that the phosphonylation process employs a two-step addition-elimination mechanism with the addition (the first step) as the rate-limiting step. Two different calculation models revealed that the catalytic triad of butyrylcholinesterase plays an important role in accelerating the reaction. This is the same mechanism as the phosphonylation reaction of acetylcholinesterase by sarin reported by Wang et al. However, the energy barrier of the rate-limiting step in the present reaction is higher than that in phosphonylation reaction of acetylcholinesterase by sarin. This indicates the differences in the phosphonylation activity of sarin and mipafox. The aging process occurs through a two-step addition-elimination mechanism similar to the phosphonylation process with the addition as the rate-limiting step. The solvent effects have been evaluated by using a CPCM model and the results show that the stationary structures and the negative charges around some important atoms involved in the two processes are not significantly different. However, the energy barrier of the phosphonylation process is remarkably decreased, revealing that this process is feasible in solution.     

Hot deformation behavior of Super304H austenitic heat resistant steel

The hot compression tests of Super304H austenitic heat resistant steel were carried out at 800–1200℃ and 0.005–5 s-1 using a Gleeble 3500 thermal-mechanical simulator, and its deformation behavior was analyzed. The results show that the flow stress of Super304H steel decreases with the decrease of strain rate and the increase of deformation temperature; the hot deformation activation energy of the steel is 485 kJ/mol. The hot deformation equation and the relationship between the peak stress and the deformation temperature and strain rate is obtained. The softening caused by deformation heating cannot be neglected when both the deformation temperature and strain rate are higher.     

Alkylation of toluene with 1,3-pentadiene over silica supported aluminum chloride catalyst in an extracting-distilling reactor

The alkylation of toluene with 1,3-pentadiene to produce pentyltoluene is designed to obtain 2,6-dimethylnaphalene for the monomer production of 2,6-naphthalene dicarboxylic acid. The possibility of the reaction is examined by the thermodynamics of the alkylation reaction using Thinh’s group contributions method, and tested over silica supported aluminum chloride catalyst in a newly developed extracting?distilling reactor. The thermodynamics calculation results show that the alkylation reaction is exothermic and can proceed at 298?350 K under normal pressure with an equilibrium constant higher than 106. Based on the thermodynamic calculation and the properties of the reactants and product, the extracting-distilling reactor was designed to allow 1,3-pentadiene to react with toluene at much lower temperature than the boiling point of toluene at the catalyst site. The alkylation product, which has a higher boiling point than that of toluene, is transferred from the catalytic site into the toluene bath and collected. The experimental results show that the reactor functions as designed and promotes the selectivity of the alkylation reaction close to 100%. The effect of raw material ratio of toluene to 1,3-pentadiene and reaction time are discussed in this paper. The suitable catalytic reaction conditions are as follows: at reaction temperature of 338 K and ambient pressure, the reactant ratio of toluene to 1,3-pentadiene is 5:1 for a six-hour reaction.     

Density functional theory calculation on the C―H bond insertion reaction of dibromocarbene with acetaldehyde

The insertion reaction mechanism of CBr_2 with CH_3CH_O has been studied by using the B3LYP/6-31G(d) method. The geometries of reactions, transition state and products were completely optimized. All the energy of the species was obtained at the CCSD(T)/6-31G(d) level. All the transition state is verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The results show that the propionaldehyde (~HP1) is the main product of CH_2 insertion with CH_3CH_O. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CBr_2 not only can insert the C_α-H [reaction I(1)]) but also can react with C_β-H [reaction II(1)]. The statistical thermodynamics and Eyring transition state theory with Wigner correc- tion are used to study the thermodynamic and kinetic characters of I(1) and II(1) in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature rang is 250 to 1750 K and 250 to 1600 K at 1.0 atm for I(1) and II(1) respectively. The rate constant and equilibrium constant are distinct in the range from 250 to 1000 K so that I(1) more easily occurs, while the reactions are not selected in the temperature range of 1000-1600 K     

Density functional theory calculation on the C―H bond insertion reaction of dibromocarbene with acetaldehyde

The insertion reaction mechanism of CBr2 with CH3CHO has been studied by using the B3LYPI6-31G（d） method. The geometries of reactions, transition state and products were completely optimized. All the energy of the species was obtained at the CCSD（T）/6-31G（d） level. All the transition state is verified by the vibrational analysis and the internal reaction coordinate （IRC） calculations. The results show that the propionaldehyde （Hp1） is the main product of CH2 insertion with CH3CHO. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CBr2 not only can insert the Cα-H [reaction I（1）]） but also can react with Cβ-H [reaction l1（1）]. The statistical thermodynamics and Eyring transition state theory with Wigner correc-tion are used to study the thermodynamic and kinetic characters of I（1） and I1（1） in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature rang is 250 to 1750 K and 250 to 1600 K at 1.0 atm for I（1） and I1（1） respectively. The rate constant and equilibrium constant are distinct in the range from 250 to 1000 K so that I（1） more easily occurs, while the reactions are not selected in the temperature range of 1000-1600 K.     

Density functional theory study on the insertion reaction mechanism of dibromocarbene with formaldehyde

The insertion reaction mechanism of CBr2 with CH3CH2O has been studied by using the B3LYP/6-311G(d) and CCSD(T)/6-311G(d) at single point. The geometries of reactions,transition state and products were completely optimized. All the transition state is verified by the vibrational analysis and the internal re-action coordinate (IRC) calculations. The results show that reaction (1) is the dominant reaction path,which proceeds via two steps: i) two reactants form an intermediate (IM1),which is an exothermal re-action of 8.62 kJ·mol?1 without energy barrier; ii) P1 is obtained via the TS1 and the H-shift,in which the energy barrier is 44.53 kJ·mol?1. The statistical thermodynamics and Eyring transition state theory with Wigner correction are used to study the thermodynamic and kinetic characters of this reaction in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature ranges from 200 to 1900 K at 1.0 atm,in which the reaction has a bigger spontaneity capability,equi-librium constant (K) and higher rate constant (k).     

Evidence for Base Substitutions and Repair of DNA Mismatch Damage Induced by Low Energy N^＋ Ion Beam Implantation in E. coli

Ever since the low energy N^ ion beam has been accepted, the mutations of ionizing radia-tion are attributable mainly to avoidance of DNA damages repair. Evidences based on in vivo proof results are limited. Using the E. coli wild type and mutator strains, the mutant frequencies suggest that base substitutions in rpoB gene are induced by the N^ implantation. A highly con-served region is selected to get the direct evidence for base substitutions by sequence of the high fi-delity PCR amplification products in mutants. Most of the mutants (90.9%, 40/44) have at least one base substitution in the amplification region. The evidences for CG to TA (55 %, 22/40), AT to GC (20%, 8/40) and TA to CG (5%, 2/40) transitions are identified. The transversions are AT to TA ( 15 %, 6/40) and GC to CG (5 %, 2/40). It is suggested that DNA cytosine methylase might play an important role in mismatch repair of DNA damage induced by N^ implantation by analysis of the mutant frequencies of mutator strains.     

Theoretic study of the reaction mechanism between (Me)_3CO· radical and trans-3-hexene

The reaction mechanism between(Me)3CO· radical and trans-3-hexene in benzene was studied for the first time at the B3LYP/6-311 G(d,p)//B3LYP/6-31G(d) ZPVE level.Two distinct elementary channels were identified as:(1) abstraction-addition;(2) addition-addition-elimination.Analysis of the potential energy surface demonstrates that for the title reaction,channels(1) and(2) have the major and minor contribution,respectively.Our calculated results can well explain the recently observed product distribution by Coseri et al.(J.Org.Chem.2005,70,4629).However,we found that the addition-abstraction channel proposed by Coseri et al.is kinetically infeasible.     

Curing Reaction Kinetics of Epoxy Resin Using Dicyandiamide Modified by Aromatic Amines

The curing reaction and reaction mechanism of epoxy resin E-44, for which aromatic amine modified dicyandiamide was used as a curing reagent, were investigated by means of differential scanning calorimetry （DSC）. The results showed that the modified dicyandiamide had better curing characteristic than unmodified dicyandiamide for epoxy resin E-44, and the curing reaction could be carried out at moderate temperature. Apparent activation energy of the curing reaction was decreased appreciably from 123.829 kJ/mol to 61.550-64.405 kJ/mol, and reaction order was decreased from 0.941 to 0.896-0.900. Curing reaction mechanism also was discussed.     

Hydrometallurgical application for treating a Nigerian chalcopyrite ore in chloride medium: Part I. Dissolution kinetics assessment

The dissolution kinetics of a Nigerian chalcopyrite ore in hydrochloric acid was studied in this article. Acid concentration, reaction temperature, and ore particle size were chosen as experimental parameters. The chemical and morphological studies of the ore before and after leaching at optimal conditions were carried out by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It is revealed that increasing the acid concentration and system temperature and decreasing the ore particle size greatly enhances the dissolution rate. The dissolution kinetics was found to follow the shrinking core model for the diffusion control mechanism where the activation energy (E_a) of 32.92 kJ·mol?1 was obtained for the process and supported by morphological changes at a higher dissolution of 91.33%.     

Theoretical study on the mechanism of cycloaddition between dimethyl methylene carbene and acetone

The mechanism of the cycloaddition reaction of singlet dimethyl methylene carbene and acetone has been studied by using second-order Moller-Plesset perturbation and density functional theory. The geometrical parameters, harmonic vibrational frequencies and energy of stationary points on the potential energy surface are calculated by MP2/6-31G and B3LYP/6-31G methods. The results show that path b of the cycloaddition reaction （1） would be the major reactive channel of the cycloaddition reaction between singlet dimethyl methylene carbene and acetone, which proceeds in two steps： i） The two reactants form an energy-rich intermediate （INT1b）, which is an exothermic reaction of 23.3 kJ/mol with no energy barrier. ii） The intermediate INT1b isomerizes to a three.membered ring product （P1） via transition state TS1b with energy barrier of 22.2 kJ/mol. The reaction rate of this reaction and its competitive reactions do greatly differ, with excellent selectivity. In view of dynamics and thermodynamics, this reaction is suitable for occurring at 1 atm and temperature range of 300-800 K, in which the reaction will have not only the larger spontaneous tendency and equilibrium constant but also the faster reaction rate.     

A new extraction process of refractory gold arsenosulfide concentrates

A new hydrometallurgical process for the refractory gold arsenosulfide concentrates under normal temperature and pressure was presented. The experimental results of a refractory gold concentrate show that the total consumption of NaOH in alkaline leaching is only 40% of those theoretically calculated under the conditions of full oxidization at the same oxidation of arsenic to arsenate and sulfur to sulfate. After alkaline leaching, cyanidation and adsorption were carried out for 24 h. The dissolution of gold by NaCN is increased to 95.3% from 12.8% before pretreatment, and meanwhile 99.3% of the adsorption of gold by activated charcoal.The consumption of NaCN for one ton ore is 10 kg, which is 1.2 times less than that before pretreatment. As it is carried out under normal temperature and pressure, the investment of installations is also decreased.     

Mechanical properties and kinetics of thermally aged Z3CN20.09M cast duplex stainless steel

Cast stainless steels used in nuclear power plants suffer from fracture toughness losses owing to thermal aging after long-term service at temperatures ranging from 280-320℃. To study the thermal aging embrittlement of Z3CN20.09M duplex stainless steel produced in China, accelerated thermal aging experiments were carried out at 350, 380, and 400℃ for up to 10000 h. Microhardness and Charpy impact energies were measured at different aging times. The microhardness of ferrite increased drastically over the initial aging time of 2000 h at 380 and 400℃ and then slowly reached HV_0.01 560. In contrast to this observed change in microhardness, Charpy impact energies sharply decreased after initial aging and then gradually reached a minimum value. Taking the microhardness of the ferrite phase as the parameter describing the thermal kinetics of the stainless steel samples, the activation energy of thermal aging was calculated to be 51 kJ/mol. Correlations between the thermal aging parameter, P, and ferrite microhardness and between P and Charpy impact energy were also analyzed. The results showed that the activation energy calculated from the ferrite microhardness is much more reasonable than that obtained using other parameters, such as chemical composition and impact energy.     

Oxidation behavior of artificial magnetite pellets

The oxidation behavior of artificial magnetite pellets was investigated through measurements of the oxidation degree and mineralogical analysis. The results show that artificial magnetite pellets are much easier to oxidize than natural magnetite. The oxidation is controlled through two different reaction mechanisms. The oxidation of artificial magnetite is dominated by internal diffusion, with an activation energy of 8.40 kJ/mol, at temperatures less than 800℃, whereas it is controlled by chemical reaction, with a reaction activation energy of 67.79 kJ/mol, at temperatures greater than 800℃. In addition, factors such as the oxygen volume fraction and the pellet diameter strongly influence the oxidation of artificial magnetite:a larger oxygen volume fraction and a smaller pellet diameter result in a much faster oxidation process.     

Nonlinear Finite Element Analysis of Mechanical Performance of Reinforced Concrete Short.Limb Shear Wall

On the basis of test, nonlinear finite element analysis of reinforced concrete (R. C) short-limb shear walls under monotonic horizontal load are carried out by ANSYS program in order to understand the evolution of cracking, deformation and failure course of the specimens. At the same time, the results of numerical calculation are compared with the results of test. The results indicate that, under monotonic horizontal load the failures of the specimens with flange wall and without flange wall all occur at the intersections of lintel bottom and limb of wall, the failures also occur at the bottom of limb; the load-displacement curve of wall without flange is steeper than that of wall with flange, and the ductility is worse than that of wall with flange; the results, such as cracking, deformation, yield load and ,so on of finite element analysis agree well with the results of test. These results provide theoretical basis of study and application of R. C shortlimb shear wall.     

Hydrometallurgical application for treating a Nigerian chalcopyrite ore in chloride medium:Part I.Dissolution kinetics assessment

The dissolution kinetics of a Nigerian chalcopyrite ore in hydrochloric acid was studied in this article.Acid concentration,reaction temperature,and ore particle size were chosen as experimental parameters.The chemical and morphological studies of the ore before and after leaching at optimal conditions were carried out by X-ray difraction(XRD)and scanning electron microscopy(SEM).It is revealed that increasing the acid concentration and system temperature and decreasing the ore particle size greatly enhances the dissolution rate.The dissolution kinetics was found to follow the shrinking core model for the difusion control mechanism where the activation energy(Ea)of 32.92 kJ·mol 1was obtained for the process and supported by morphological changes at a higher dissolution of 91.33%.     

Clustered DNA damage induced by protons radiation in plasmid DNA

Clustered DNA damage is considered as a critical type of lesions induced by ionizing radiation, which can be converted into the fatal or strong mutagenic complex double strand breaks (DSBs) during damage processing in the cells. The new data show that high energy protons produce more potentially lethal DSBs than low LET radiation. In this study, plasmid DNA were used to in-vestigate and re-evaluate the biological effects induced by the protons with the LET of ～3.6 keV/μm at the molecular level in vitro, including single strand breaks (SSBs), DSBs, isolated and clustered base damages. The results of complex DNA damage detections indicated that protons at the given LET value induce about 1.6 fold more non-DSB clustered DNA damages than the prompt DSB. The DNA damage yields by protons were greater than that by γ-rays, specifically by 6 fold for the isolated type of DNA damage and 14 fold for the clustered damage. Furthermore, the spectrum of damages was also demonstrated to be depended on the radiation quality, with protons producing more DSBs relative to clusters than do γ-rays.     

Deformation behavior and microstructure of an Al-Zn-Mg-Cu-Zr alloy during hot deformation

The hot deformation behavior and microstructures of Al-7055 commercial alloy were investigated by axisymmetric hot compression at temperatures ranging from 300℃ to 450℃ and strain rates from 10-2 to 10 s-1, respectively. Microstructures of deformed 7055 alloy were investigated by transmission electron microscopy (TEM). The dependence of peak stress on deformation temperature and strain rate can be expressed by the hyperbolic-sine type equation. The hot deformation activation energy of the alloy is 146 kJ/mol. Moreover, the flow stress curves predicted by the modified constitutive equations are reasonably consistent with the experimental results, which confirms that the proposed deformation constitutive equations can provide evidence for the selection of hot forming parameters. TEM results indicate that dynamic recovery is the main softening mechanism during hot deformation.