Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

An Integrated Two Phases Approach to Zn2+ Ions Electroreduction on Hg

The following two numerical models have been applied to zinc cations electroreduction in 1 M NaClO₄ water solution: a classical EE model describing the concentration of involved species in solution (semi infinitive diffusion region), an extended EE model describing both: the concentration of involved species in solution and the concentration of metallic zinc inside mercury drop (in limited area of diffusion). In the latter model the inner part of mercury drop and surrounding solution were treated as dynamic interrelated system. Both models were applied to experimental cyclic voltammetric CV data in 1 M NaClO₄, the results compared and discussed. The concentration profiles of all species including metallic zinc inside mercury drop were performed. The presented integrated model is essential for theoretical and analytical aspects of the electrochemistry of mercury soluble metal cations and amalgams.     

信用担保风险的模糊综合评审研究

信用担保机构是连接银行和企业的桥梁，对于改善企业融资环境和拓展银行业务具有重要意义，信用担保风险的评审是担保机构能否生存及有效运行的关键。信用风险的评审机制主观性强，对担保项目进行客观，公正的评审比较困难。本采用模糊数学中的综合判别方法，全面考虑风险评审所涵盖的各种风险指标及其重要度，建立了定性分析与定量分析方法相结合的信用担保风险综合评审模型，为担保机构提供了一种相对科学、客观的评审方法。     

Theoretical Study on the Reaction Mechanism between Dichlorocarbene and Armchair Single-walled Carbon Nanotubes

1 INTRODUCTION Carbon nanotubes have many potential applica- tions due to their unique structures and properties[1～4]. Physicists have been studying their electrical, me- chanical and other properties since their discove- ries[5, 6]. Recently, chemists are interested in carbon nanotubes because their properties can be altered by chemical functionalization[7～14], and these functiona- lized nanotubes can undergo further chemical trea- tment. So the potential application range of such na- …     

Dicyclopentadienyl complexes of titanium,niobium, and tungsten in the controlled synthesis of poly(methyl methacrylate)

Organometallic compounds Cp₂TiCl₂, (EtC₅H₄)₂NbCl₂, and (PrⁱC₅H₄)₂WCl₂ were assessed as additives that control polymer chain growth in the polymerization of methyl methacrylate. In the presence of compounds mentioned in amounts comparable with that of the initiator, a uniform process with no gel-effect occured and respective linear increase in the molecular weight of the polymer up to high degrees of the monomer conversion was observed.     

社会经济管理系统和谐性模型的构建与分析

本文从非线性自然观的视野。引用与分析了社会经济系统功能模型与效应模型。构建了系统和谐状态模型与和谐状态可信度模型，形象地说明了企业系统的和谐既是一个随机不确定状态。又是企业和谐力量与不和谐力量相互抗争干涉的过程。依据协同学原理提出了企业系统和谐演进的机制，表明企业系统的和谐发展是子系统和谐协同的过程。即子系统竞争合作的过程。文中所构建的模型，从理论上清晰地说明了企业系统和谐有序运行的机理，为如何构建和谐企业。提供了建设性的思考。     

Ultrasonic evaluation of anisotropic damage in multiaxially textile-reinforced thermoplastic composites made from hybrid yarns

The basic damage and failure models of multiaxially reinforced composites with a thermoplastic matrix are presented and verified. Within the framework of continuum damage mechanics, a phenomenological model is introduced, where the damage is defined as a change in the elasticity tensor. For damage identification, a specific ultrasonic device was developed. A combination of an immersion set-up and a contact coupling device formed a system for an efficient determination of stiffness-tensor components from convenient sets of velocity measurements. Linked to a tensile machine, it allowed us to measure the anisotropic damage of the new materials group caused by tensile loading. Russian translation published in Mekhanika Kompozitnykh Materialov, Vol. 42, No. 2, pp. 221–234, March–April, 2006.     

Organocatalysis: quantum chemical modeling of nucleophilic addition to α,β‐unsaturated carbonyl compounds

One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd.     

神经网络在大型复杂武器装备质量综合评价排序中的应用

从大型复杂武器装备系统的具体特点出发,运用基于神经网络的评价方法,构建了大型复杂武器装备质量综合评价模型。实证分析的结果表明该方法得出的结果与实际情况相符。     

On the exact distribution of linear combinations of order statistics from dependent random variables

We study the exact distribution of linear combinations of order statistics of arbitrary (absolutely continuous) dependent random variables. In particular, we examine the case where the random variables have a joint elliptically contoured distribution and the case where the random variables are exchangeable. We investigate also the particular L-statistics that simply yield a set of order statistics, and study their joint distribution. We present the application of our results to genetic selection problems, design of cellular phone receivers, and visual acuity. We give illustrative examples based on the multivariate normal and multivariate Student t distributions.