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.     

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.     

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 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).     

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.     

Quantum chemical and topological study on the insertion reaction of dichlorcarbene with acetaldehyde

The insertion reaction mechanisms of siglet and striglet CCI2 with CH3CHO have been studied by using the DFT, NBO, CCSD（T） and AIM method. The geometries of reactions, transition state and products were completely optimized by B3LYP/6-31G（d）. All the energy of the species was obtained at the CCSD（T）/6-31G（d,p） level. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl2 can not only insert the Cα--H （reaction I） but also can react with Cβ--H （reaction ll）. There are three main existing pathways and the products are P1 （CH3COHCCl2）, P2 （CH2COHCHCl2） and P4[CHCl2CHCHOH] respectively. Reaction II happens more easily according to the energy changes and the barrier in rate-controlling step. In addition, the important geometries in domain pathways have been studied by AIM theory. And also, the energy changes of H in the inserted C--H bond have been investigated.     

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 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 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.     

Theoretical characterization of single-electron iodine-bond weak interactions in CH3…I-Y（Y=BH2,H,CH3,C2H3,C2H,CN,NC）systems

Iodine-involved single-electron halogen bonds (SEXBs) weak interactions in the systems of CH3···I-Y(Y = BH2, H, CH3, CH==CH2, C≡CH, CN, NC) were investigated for the first time using B3LYP/6-311++G(d,p) and MP2/aug-cc-pVTZ computational levels (the relativistic effective core potential basis set of Lanl2dz was used on iodine atom). The interaction energies between two moieties with basis set super-position error corrections for the seven complexes are -0.57, -1.36, -3.80, -2.17, -4.49,-6.33 and -8.64 kJ mol-1 (MP2/aug-cc-pVTZ ), respectively, which shows that SEXBs interactions are all weak. Natural bond orbital theory analysis revealed that charges flow from CH3 to the I-Y moiety. The total amount of natural bond orbital charge transfer (ΔNC) from the CH3 radical to I-Y increases in the order CH3…IBH2 < CH3…IH ≈ CH3…ICH3 ≈ CH3···IC2H3 < CH3…ICCH< CH3…ICN< CH3…INC. Atoms-in-molecules theory was used to investigate the topological properties of the bond critical points in the seven SEXB structures.     

Mechanism of Cathode Process of B(Ⅲ) in LiF-NaF-KBF4 Melt by Electrochemical Titration Technique

The mechanism of cathode process of B(Ⅲ) at molybdenum and platinum electrodes in LiF-NaF-KBF₄ melt was studied and the transferred electron number of the reaction was calculated by means of cyclic voltammetry.The effect of adsorption of electroactive component on the electrochemical response (e.g., the voltammetric i─E curves) was analyzed and discussed. The "electrochemical spectra" for linear sweep voltammetry was used to elucidate the electrode reaction accompanied by a following transform process. The results show that the reduction of B(Ⅲ) to B(0) proceeds in reversible one step three-electron reaction and the cathode process of B(Ⅲ) is affected by product adsorbed strongly at the electrode surface. It is assumed that the reduction and deposition of B(Ⅲ) at molybdenum and platinum electrodes proceed in two kinds of mechanism: (1) B(Ⅲ)+ 3e = B_ads→ B (surface diffusion deposition mechanism) and (2) B(Ⅲ) + 3e = B (direct deposition mechanism).     

DFT study on nonlinear optical properties of lithium-doped corannulene

The effects of lithium doping on the nonlinear optical properties of new electrodes (lithium-doped corannulene) were investigated in detail. Nine dynamically stable geometries of Lin-C20H10 (n=1, 2) are predicted by B3LYP/6-31G(d,p). Among these nine structures, the largest first static hyperpolarizability (β0) is computed to be 15314 au, which is dramatically larger than the β0 value of 74 au for C20H10, indicating that Li doping plays an important role in elevating the first hyperpolarizability of corannulene.     

CH(X2Ⅱ)与NH3反应机理的量子化学研究

对CH(X2Ⅱ)自由基与NH3的反应进行了量子化学研究.分别在B3LYP/6-311++G(d,p),B3LYP/6-311++G(3df,3pd),MP2/6-311++G(d,p)和MP2/6-311++G(3df,3pd)水平优化了反应势能面上各驻点的几何结构,并在QCISD(T)/6-311++G(3df,3pd)水平上计算了各驻点的能量.通过IRC计算确认了过渡态,确定了反应的机理.     

Ab initio research on DNA base alkylation by theβ-position me-tabolite of methylethylnitrosamine

Ab initio calculation is carried out to study the different supposed mechanisms of DNA base alkylation by [β-sulphate-nitrosamines at RHF/6-31G(d) and MP2/6-31G(d) levels. Full geometric structure optimization is done for all reactants, intermediates, products and transition states. The activation energy and IRC are obtained. The results show that the anchimeric assistant effect promotes the alkylation of DNA base by β-sulphate-nitrosamines. Solvent calculation is carried out with Onsager model of SCRF method at the same level. The results indicate that the activation energy is decreased obviously in water.     

Debating about the climate warming

Debating about the climate warming is reviewed. Discussions have focused on the validity of the temperature reconstruction for the last millennium made by Mann et al. Arguments against and for the reconstruction are introduced. Temperature reconstructions by other authors are examined, including the one carried out by Wang et al. in 1996. It is concluded that: (1) Ability of reproducing temperature variability of time scale less than 10 a is limited, so no sufficient evidence proves that the 1990s was the warmest decade, and 1998 was the warmest year over the last millennium. (2) All of the temperature reconstructions by different authors demonstrate the occurrence of the MWP (Medieval Warm Period) and LIA (Little Ice Age) in low frequency band of temperature variations, though the peak in the MWP and trough in LIA varies from one reconstruction to the others. Therefore, terms of MWP and LIA can be used in studies of climate change. (3) The warming from 1975 to 2000 was significant, but we do not know if it was the strongest for the last millennium, which needs to be proved by more evidence.     

Climate indexes of phytoliths from Homo erectus'''' cave deposits in Nanjing

Many related papers have been published since the first report on the discovery of Nanjing hominid crania by Mu et al.[1]. Mu et al.[1], Xu et al.[2—4], the Tangshan Ar-chaeological Team[5] and Dong[6] have successively stud-ied the Nanjing Homo erectus?symbiotic faunas. Mu et al. and Xu et al. considered that the nature of the fauna in the Tangshan area belongs to the Oriental Realm,and this region was usually occupied by Ailuropoda-Tapirus fauna in the Pleistocene. However, the typica…     

Oxidative Treatment of Some Reactive Dyes by Fenton Reagent

Nine kinds of reactive dye solutions: Reactive K-2RL, H-E2R, X-6B1Y, HE-4G, X-3B, K-2R,H-E7B, X-4RN and S-F3B were treated by usingFenton reagent. While the concentration of dye is 400mg/L, the FeSO_4 dosage 100-180 mg/L, H_2O_2 240～540 mg/L, that is the stoichiometric numbers of Fe~(2+)and H_2O_2. are between 1: 9～1: 12, pH=3, reaction     

Identification and significance of 3β-alkyl steranes in the Eogene lacustrine sediments and petroleum of China

The study on steranes with substitution at C-2, C-3 or C-4 positions in ring-A has become a hot field for their specific precursors in recent years[1-15]. Summons et al. firstly identified C28-C30 3β-methyl steranes in Michigan Basin and found that the p…     

Mathematical Simulation of High-Conversion Binary Copolymerization

A new model for mathematical simulation of high-conversion binary copolymerization was established by combination of the concept of the three stage polymerization model (TSPM) proposed by Qin et al. for bulk free radical homopolymerization with the North equation to describe high-conversion copolymerization reaction exhibiting a strong gel effect, and the mathematical expressions of this new model were derived. Like TSPM, the new model also assmnes that the whole course of binary copolymerization can be divided into three different stages: low conversion, gel effect and glass effect stages. In addition, the reaction rate constants and the initiator efficiency at each copolymerization stage do not vary with conversion. Based on the expressions derived, a plot method for determining the overall rate constants and critical conversions was proposed. The literature data on conversion history for styrene (St)-methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA)-MMA copolymerizations were treated to examine the model, which shows that the model is satisfactory.     

Dissolution behavior and dissolution mechanism of palygorskite in HCl solution

The 1 mol/L, 3 mol/L and 5 mol/L HCl solutions were employed to leach two palygorskites with different trioctahedral contents in their crystal structure for different period of time. The results of the dissolution experiments show that the dissolution process could be divided into three steps, and that this dissolution behavior can be attributed to its higher Mg2+ content, and is restricted by the extraction behavior of Si4+. The preferential extraction for Mg2+ promotes the extraction behavior of Si4+ from Si-O framework. Because the Si4+ in the form of amorphous SiO2 is adsorbed onto the surface of palygorskite fibre, the reaction between palygorskite and acid is obstructed. With the elapsing of time, or the increasing of the acid concentration, the amorphous SiO2 flocculates, and then the channels of chemical reaction are reopened. The ratio value of Mg2+/(Fe3++Al3+) in leaching solution tends to a fixed value, showing that the acid attacks not only the surface but also the structural channels. There are no obvious three steps observed during the acid attack on the palygorskite with a lower trioctahedral content. The differential behavior for two palygorskites is discussed.