Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

BPh₃ catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO₂ and PhSiH₃; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C₆F₅)₃ shows little or no activity. ¹¹B NMR spectra suggested the generation of [HBPh₃]⁻. The detailed mechanism of the BPh₃-catalyzed N-methylation of N-methylaniline ( 1 ) with CO₂ and PhSiH₃ was studied by using DFT calculations. BPh₃ promotes the conversion of two substrates (N-methylaniline and CO₂) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N⁺CO₂⁻⋅⋅⋅BPh₃]. The carbamate and BPh₃ act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH₃ to generate [HBPh₃]⁻, which is used to produce key CO₂-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh₃]⁻ species.     

A DFT study on mechanisms of CO2 coupling with propargylic alcohols using alkali carbonates

The mechanisms of CO₂ coupling with the propargylic alcohol using alkali carbonates M₂CO₃ (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs₂CO₃-mediated carboxylative cyclization of the propargylic alcohol with CO₂, and (b) the conversion of the αACC intermediate with Cs₂CO₃ to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO₃ together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO₂ with the propargylic alcohol. Compared to other alkali carbonates M₂CO₃ (M = Li, Na, K), the stronger basicity of Cs₂CO₃ and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield.     

New Exact Solutions to the Combined KdV and mKdV Equation

The modified mapping method is developed to obtain new exact solutions to the combined KdV and mKdV equation. The method is applicable to a large variety of nonlinear evolution equations, as long as odd- and even-order derivative terms do not coexist in the equation under consideration.     

含腔电大尺寸导体目标电磁散射的一体化数值模拟

应用等效原理，通过引入口面上等效磁流将含腔导电目标电磁散射简化为腔内、外两个等效 问题. 腔内问题分段求解并应用级联法获得口面等效导纳矩阵；腔内外的耦合关系应用近似 边界元方法描述并由此获得口面等效磁流；最后，这一具有混合源的腔体内外一体化散射问 题则应用所提出的广义混合场积分方程方法建立电磁模型，并用多层快速多极子方法实现高 效数值求解. 实例计算结果与测试结果具有很好的一致性. 关键词： 含腔目标 电磁散射 混合场积分方程 数值分析     

带强迫项变系数组合KdV方程的显式精确解

通过构造两个新的Riccati方程组，推广了Riccati方法，使其具有简洁的形式，丰富和发展了已有的结果，借助Mathematica软件，求出了带强迫项变系数组合KdV方程的一些精确解，包括各种类孤波解、类周期解和变速孤波解. 关键词： Riccati方程组 变系数组合KdV方程 强迫项 类孤波解     

Parking Capacity and Pricing in Park'n Ride Trips: A Continuous Equilibrium Network Design Problem

In this paper we consider the problem of designing parking facilities for park'n ride trips. We present a new continuous equilibrium network design problem to decide the capacity and fare of these parking lots at a tactical level. We assume that the parking facilities have already been located and other topological decisions have already been taken.The modeling approach proposed is mathematical programming with equilibrium constraints. In the outer optimization problem, a central Authority evaluates the performance of the transport network for each network design decision. In the inner problem a multimodal traffic assignment with combined modes, formulated as a variational inequality problem, generates the share demand for modes of transportation, and for parking facilities as a function of the design variables of the parking lots. The objective is to make optimal parking investment and pricing decisions in order to minimize the total travel cost in a subnetwork of the multimodal transportation system.We present a new development in model formulation based on the use of generalized parking link cost as a design variable.The bilevel model is solved by a simulated annealing algorithm applied to the continuous and non-negative design decision variables. Numerical tests are reported in order to illustrate the use of the model, and the ability of the approach to solve applications of moderate size.     

Extension of a combined analytical/numerical initial value problem solver for unsteady periodic flow

Here we describe analytical and numerical modifications that extend the Differential Reduced Ejector/ mixer Analysis (DREA), a combined analytical/numerical, multiple species ejector/mixing code developed for preliminary design applications, to apply to periodic unsteady flow. An unsteady periodic flow modelling capability opens a range of pertinent simulation problems including pulse detonation engines (PDE), internal combustion engine ICE applications, mixing enhancement and more fundamental fluid dynamic unsteadiness, e.g. fan instability/vortex shedding problems. Although mapping between steady and periodic forms for a scalar equation is a classical problem in applied mathematics, we will show that extension to systems of equations and, moreover, problems with complex initial conditions are more challenging. Additionally, the inherent large gradient initial condition singularities that are characteristic of mixing flows and that have greatly influenced the DREA code formulation, place considerable limitations on the use of numerical solution methods. Fortunately, using the combined analytical–numerical form of the DREA formulation, a successful formulation is developed and described. Comparison of this method with experimental measurements for jet flows with excitation shows reasonable agreement with the simulation. Other flow fields are presented to demonstrate the capabilities of the model. As such, we demonstrate that unsteady periodic effects can be included within the simple, efficient, coarse grid DREA implementation that has been the original intent of the DREA development effort, namely, to provide a viable tool where more complex and expensive models are inappropriate. Copyright © 2002 John Wiley & Sons, Ltd.     

Strength of cylinder joint adhesively bonded by coupling

Summary A method of joining two metal cylindrical shafts with adhesive coupling is proposed. Two cylindrical shafts with the same diameter are connected by bonding through a cylindrical coupling with epoxy resin. The strength of the shaft joint under tensile loading and torsional loading is investigated analytically and experimentally. The stress and strain distributions of the shaft joint is analyzed by the finite element method. The analyzed strain distributions in the joint are compared with experimental values. The joint strength is predicted by applying the strength laws of shafts, coupling, adhesive layer and adhesive interface between shaft and adhesive coupling. The effects of the coupling dimension on the joint strength are examined. It is shown that the adhesive shaft joint can transfer the load by which the cylindrical shafts are plastically deformed.This paper was refined by the author, K. Ikegami, during statying at Technische Universität München under the support of Deutscher Akademischer Austauschdients. The author is grateful to Professor Lippmann of Technische Universität München who is the host professor of the support.     

排气全燃型联合循环设计点性能简明估计公式

排气全燃型联合循环设计点性能简明估计公式蔡睿贤（中国科学院工程热物理研究所北京１０Ｏ０８０）关键词：排气全燃型联合循环，热力分析主要符号表Ｈｕ燃料热值Ｌ燃料理论空气量ｌ比功Ｐ单位能量价格Ｒ燃气轮机与蒸汽轮机的功率比α过量空气系数β摩尔燃料系数△增量η...     

承受拉-扭组合载荷的薄壁圆筒屈服时产生塑性流动的条件

提出了在无外力作功的情况下，具有Bauschinger效应的弹塑性材料处于屈服状态产生自发的塑性流动时应满足的条件．这个条件不仅与材料的力学性能有关，而且还处决于材料的具体的载荷边界条件和变形．举例说明了承受拉一扭组合的薄壁圆筒中，采用组合强化模型时，产生塑性流动的具体条件．