单次碰撞条件下，反应Ba+C2H5Br、n-C3H7Br、1,2-C2H4Br2、1,3-C3H6Br2的动力学研究

Under single-collision beam-gas scattering conditions the reactions Ba+ C_2H, Br、n-C_3H_7Br、1, 2-C_2H_4Br_2、1,3-C_3H_6Br_2 have been studied using laser induced fluore-scence to detect the BaBr X~2∑~+ product. The vibrational distributions, the fractions of the available energy going into vibrational and rotational energy of the BaBr products have been calculated by means. of computer simulation. It has been found that the average vibrationel energies of the BaBr products can be described as a linear function of the mass factors for the reactions Ba+CH_3Br、C_2H_5Br、n-C_3H_7Br、1,3-C_3H_6Br, and that the potential energy surfaces for these reactions are similar. For the reactions Ba+CH_3Br、C_2H_5Br、n-C_3H_7Br, the vibrational increae, but for the reactions Ba+CH_2Br_2、1,2-C_2H_4Br_2、1,3-C_3H_6Br_2, the vibrational excitations of the BaBr products decrease greatly when the number of the carbons increase.     

Reactions of O+4 and O+2 with methane

Rate coefficients and products were determined for the title reactions employing a drift tube mass spectrometer apparatus. The implications of these reactions for the ion chemistry of the stratosphere is discussed.     

Quantum chemistry study on the reactivity of PhOTiCl2CH2Cl and Cl3TiCH2Cl cyclopropanation reagents with olefins

In order to explore the new and efficient cyclopropanation reagents, a theoretical investigation of the cyclopropanation reactions of titanium carbenoid PhOTiCl₂CH₂Cl and Cl₃TiCH₂Cl with olefins was given at the B3LYP level of theory. All of the reactions examined displayed similar concerted mechanisms for the cyclopropanation of these reagents. The reactions are predicted to be highly chemical reactivity with low barriers and could be favored in experiment, and the cyclopropanation reaction proceed easily at lower temperature. The computational results are briefly compared to other carbenoid reactions and related species.     

Reversible Anionic Redox Activities in Conventional LiNi1/3Co1/3Mn1/3O2 Cathodes

Redox reactions of oxygen have been considered critical in controlling the electrochemical properties of lithium‐excessive layered‐oxide electrodes. However, conventional electrode materials without overlithiation remain the most practical. Typically, cationic redox reactions are believed to dominate the electrochemical processes in conventional electrodes. Herein, we show unambiguous evidence of reversible anionic redox reactions in LiNi_1/3Co_1/3Mn_1/3O₂. The typical involvement of oxygen through hybridization with transition metals is discussed, as well as the intrinsic oxygen redox process at high potentials, which is 75 % reversible during initial cycling and 63 % retained after 10 cycles. Our results clarify the reaction mechanism at high potentials in conventional layered electrodes involving both cationic and anionic reactions and indicate the potential of utilizing reversible oxygen redox reactions in conventional layered oxides for high‐capacity lithium‐ion batteries.     

Highly enantioselective aldol reactions using a tropos dibenz[c,e]azepine organocatalyst

The four-step synthesis of a chiral primary tertiary diamine salt, possessing a tropos dibenz[c,e]azepine ring is described. It is shown that 3.5-5 mol % of this salt is capable of promoting highly enantioselective crossed-aldol reactions between cyclohexanone and a series of aromatic aldehydes. In all cases, the aldol reactions proceed with high diastereoselectivity for the anti-aldol product. The outcome of crossed-aldol reactions involving other cyclic ketones and acyclic ketones are also described. All examples involving cyclic ketones result in selectivity for the anti-aldol products, whereas acyclic ketones were found to favour the syn-aldol products. A discussion on the role of the chiral primary tertiary diamine salt in the catalysis of the aldol reactions is also presented.     

Ca(1S0)+CH2Cl2、CHCl3和Ca(3P)+CH2Cl2、CHCl3反应的动态学研究

The reactions Ca(~1S_0)+ CH_2Cl_2, CHCl_3 and Ca(~3P)+ CH_2Cl_2, CHCl_3 were studied by means of the laser induced fluorescence (LIF). Systematic simulation of the observed LIF spectra revealed that change of the Ca atoms from the ~3p states to the ~1S_0 state brought about a decrease of the fraction of total energy going to the ground state CaCl product vibration and an increase of the fraction of total energy going to the ground state CaCl product rotation. Total cross sections for the reactions of Ca(~1S_0)+CH_(4-n)Cl_n(n=2, 3) and the fraction of the Ca atoms going to the ~3P states in the discharge Ca beam were estimated from the LIF indensity of the CaCl product and total cross sections for the reactions Ca(~3P)+CH_(4-n)Cl_n. They are 0.39±2 nm, 0.45±2 nm, 1.8+0.1%, respectively.     

Characterization of a DAPI-RIT-DAPI System for Gas-Phase Ion/Molecule and Ion/Ion Reactions

The discontinuous atmospheric pressure interface (DAPI) has been developed as a facile means for efficiently introducing ions generated at atmospheric pressure to an ion trap in vacuum [e.g., a rectilinear ion trap (RIT)] for mass analysis. Introduction of multiple beams of ions or neutral species through two DAPIs into a single RIT has been previously demonstrated. In this study, a home-built instrument with a DAPI-RIT-DAPI configuration has been characterized for the study of gas-phase ion/molecule and ion/ion reactions. The reaction species, including ions or neutrals, can be introduced from both ends of the RIT through the two DAPIs without complicated ion optics or differential pumping stages. The primary reactant ions were isolated prior to reaction and the product ions were mass analyzed after controlled reaction time period. Ion/molecule reactions involving peptide radical ions and proton-transfer ion/ion reactions have been carried out using this instrument. The gas dynamic effect due to the DAPI operation on internal energy deposition and the reactivity of peptide radical ions has been characterized. The DAPI-RIT-DAPI system also has a unique feature for allowing the ion reactions to be carried out at significantly elevated pressures (in 10^–1 Torr range), which has been found to be helpful to speed up the reactions. The viability and flexibility of the DAPI-RIT-DAPI system for the study of gas-phase ion reactions have been demonstrated.

Reaction of iodobenzene dichloride with C5–C6 unsaturated steroids

Light and heat induced reactions of iodobenzene dichloride with 3β-substituted cholest-5-enes has been studied. The ratio of the isomeric 5,6-dichlorides formed was found to be nearly independent of the 3β-substituent. Radical mechanisms are proposed for these reactions. Chlorination of 3-iodocholest-5-enes may be complicated by side reactions in which iodine is liberated.     

异辛烷/正庚烷/乙醇三组分燃料着火的化学动力学模型

提出一个包括异辛烷、正庚烷和乙醇的三组分燃料的着火动力学模型, 该机理包括50 个组分和193 个反应. 通过路径分析和灵敏度分析, 给出了基础燃料在高低温条件下的不同反应路径和影响氧化过程的重要基元反应. 该机理预测的单组分(异辛烷、正庚烷、乙醇)燃料、双组分基础燃料和三组分燃料的点火延迟时间与实验值有很高一致性. 本文机理包含较少的组分数与反应数, 因而可适用汽油掺烧乙醇的多维计算流体动力学(CFD)数值模拟.     

Reduction of beta-hydroxyketones by SmI2/H2O/Et3N

Reduction of a series of beta-hydroxyketones by SmI2/H2O/Et3N provided 1,3-diols in quantitative yields. The reactions were exceedingly clean with no byproduct formation, negating the need for further purification. Most reactions provided moderate to excellent diastereoselectivity with syn-diols as the major isomer in most instances.     

Quantum Dynamics of Oxyhydrogen Complex-Forming Reactions for the HO2 and HO3 Systems

Complex-forming reactions widely exist in gas-phase chemical reactions.Various complexforming bimolecular reactions have been investigated and interesting phenomena have been discovered.The complex-forming reactions usually have small or no barrier in the entrance channel, which leads to obvious differences in kinetic and dynamic characteristics compared with direct reactions.Theoretically, quantum state-resolved reaction dynamics can provide the most detailed microscopic dynamic mechanisms and is now feasible for a direct reaction with only one potential barrier.However, it is of great challenge to construct accurate potential energy surfaces and perform accurate quantum dynamics calculations for a complex polyatomic reaction involving deep potential wells and multi-channels.This paper reviews the most recent progress in two prototypical oxyhydrogen complex-forming reaction systems, HO₂ and HO₃, which are significant in combustion, atmospheric, and interstellar chemistry.We will present a brief survey of both computational and experimental work and emphasize on some unsolved problems existing in these systems.     

Reactions of thebaine with cis- and trans-disubstituted dienophiles

Thebaine has been shown to undergo Diels-Alder reactions with trans-disubstituted ethylenes containing relatively bulky groups. These were correlated with reactions in which the corresponding cis-disubstituted dienophiles were used. Reductions, Grignard reactions and base-catalyzed rearrangements of the adducts are described.     

RADIATION ACTIVATION OF CARCINOGENS AND THE ROLE OF OH AND O2-

Abstract— Radiation-induced covalent binding of labelled carcinogens to DNA has been investigated under a variety of conditions using ultrafiltration or millipore filtration of TCA precipitable complexes. High yields of carcinogen binding at high DNA concentrations are also observed for a variety of small molecules and are not carcinogen-specific. At high carcinogen concentrations, radiation-induced unstable electrophilic carcinogenic species are produced, and undergo free-radical reactions which simulate cellular redox reactions involved in metabolic carcinogen activation, leading to the formation of covalently bound carcinogen adducts to DNA as a potential target macromolecule. The yields of carcinogen-DNA adducts increase linearly with dose and depend upon carcinogen concentration. The results of scavenger studies indicate that the oxidising species O₂^- and OH are the principal activating species. Rate constants for the selective radiation-induced oxidation reactions of various chemical carcinogens with superoxide have been measured by a competition kinetic method using pulse radiolysis. The relatively long-lived superoxide radical reacts with carcinogens at a rate which is two orders of magnitude slower than the diffusion-controlled rate for the hydroxyl radical, thus allowing a measure of O₂^- specificity in the presence of competing reactants within the cell.     

Further links between the maximum hardness principle and the hard/soft acid/base principle: insights from hard/soft exchange reactions

Ayers, Parr, and Pearson recently showed that insight into the hard/soft acid/base (HSAB) principle could be obtained by analyzing the energy of reactions in hard/soft exchange reactions, i.e., reactions in which a soft acid replaces a hard acid or a soft base replaces a hard base [J. Chem. Phys., 2006, 124, 194107]. We show, in accord with the maximum hardness principle, that the hardness increases for favorable hard/soft exchange reactions and decreases when the HSAB principle indicates that hard/soft exchange reactions are unfavorable. This extends the previous work of the authors, which treated only the "double hard/soft exchange" reaction [P. K. Chattaraj and P. W. Ayers, J. Chem. Phys., 2005, 123, 086101]. We also discuss two different approaches to computing the hardness of molecules from the hardness of the composing fragments, and explain how the results differ. In the present context, it seems that the arithmetic mean of fragment softnesses is the preferable definition.     

Beam-gas chemiluminescent reactions of Cu(2D) with Cl2, Br2, and I2

Chemiluminescent reactions involving copper and halogen molecules are shown to result from the bimolecular reaction of metastable Cu(²D) with Cl₂, Br₂, and I₂ under single-collision conditions. The collision-energy dependence of the reactions is described by a hard-sphere model with zero threshold energy. Cross sections for these reactions are compared with that for chemiluminescent reaction of Cu(²S) with F₂.     

The chemistry of uranium Part XXI. A thermogravimetric study of the decomposition of (Net4)2UCl6 and (Net4)2UBr6

The thermal decomposition reactions of (Net₄)₂UX₆, X = Cl, Br, were studied in nitrogen and oxygen atmospheres. Isothermal and dynamic techniques were used to estimate activation energies for the reactions in nitrogen. The bromo complex seems to be more resistant towards decomposition than the chloro complex.     

Microwave-assisted SNAr reaction of 2,4,6-trichloro-1,3,5-triazine for the rapid synthesis of C3-symmetrical polycarboxylate ligands

The microwave-assisted S_NAr reaction of 2,4,6-trichloro-1,3,5-triazine with various unprotected amino acids was developed for the synthesis of C₃-symmetrical polycarboxylate ligands which can be used as structural directing units in metal-organic frameworks. The reactions were performed in water using a domestic microwave oven as the heating device. In comparison to the reactions performed under conventional heating, the reactions under microwave irradiation proceeded much more rapidly within 20 min to afford the desired ligands in comparative yields to those obtained by conventional heating.     

The reaction of (SO2)2 and (CO2)2 with Ba

The reactions of (CO₂)₂ and (SO₂)₂ with Ba have been investigated using a crossed beam arrangement and the laser-induced fluorescence technique. Internal energy in the BaO product was probed in order to study differences between monomeric and dimeric reactions. The reaction cross section for the dimers of CO₂ was found to be between four and eightfold larger than that of the monomers. This can be explained by the change in the reaction mechanism due to the positive electron affinity of the dimers versus the negative electron affinity of the monomers. The product BaO from the dimeric reactions is much colder rotationally than in the monomeric case. This phenomenon can be explained based on the kinematics.     

基态和亚稳态的Ca、Ba原子与ClO2化学发光反应的动态学研究

在束-气装置上的单次碰撞条件下, 利用低压直流放电选择性地激发碱土金属到亚稳态, 观察了Ca(~1S)、Ca(~1S’~3P)、Ba(~1S)、Ba(~1S, ~3D)+ClO_2。反应的化学发光. 通过测量化学发光总包光强的空间分布, 得到这些反应的总碰撞截面为: Ca(~1S)+ClO_2, 0.97 nm; Ca(~3P)+ClO_2, 1.38 nm; Ba(~1S)+ClO_2, 13.6 nm; Ba(~3D)+ClO_2, 2.39 nm, 计算机模拟化学发光光谱, 发现新生产物MO(M=Ca, Ba)的电子激发态A~1П态的相对振动布居分布是非玻尔兹曼分布的, 求出反应Ba(~3D)+ClO_2和Ca(~3P)+ClO_2产生的MClC~П→X~2 ∑~+跃迁的化学发光截面分别为0.51 nm和0.31 nm, 计算光谱中不同成份的光强, 得到了反应产生MO、MCl的产物分支比. 最后, 讨论了这类反应的机理。     

Simultaneous propane dehydrogenation andco2hydrogenation overCrOx/SiO2catalyst

Summary Single reverse water-gas shift (RWGS) and dehydrogenation of propane with CO₂(DH-CO₂) reactions in the presence and absence of the CrO_x/SiO₂ catalyst have been studied between 673 and 873 K. It was found that the CrO_x/SiO₂ catalyst is active both in the dehydrogenation of propane and in the RWGS reactions. The obtained results suggest that the dehydrogenation of propane to propene in the presence of CO₂on CrO_x/SiO₂can be facilitated by the RWGS reaction.</o:p>