Hydrophobic Vitamin B12. X. Steric Effect in Electrochemical Carbon-Skeleton Rearrangement Catalyzed by Hydrophobic Vitamin B12 in Nonaqueous Media

Abstract

A steric effect in the carbon-skeleton rearrangement catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C₁ester]C10₄, was investigated under electrochemical conditions. The controlled-potential electrolyses of alkyl halides having two carboxylic ester groups of different bulkiness on the same carbon atom, such as 2,2-bis(ethoxycarbonyl)-l-bromopropane, l-bromo-2-tert-butoxycarbonyl-2-ethoxy-carbonylpropane, l-bromo-2-cyclohexyloxycarbonyl-2-ethoxycarbonylpropane, and l-bromo-2-ethoxy-carbonyl-2-phenoxycarbonylpropane, were carried out in N,N-dimethylformamide, as catalyzed by [Cob(II)7C₁ester]CIO₄, to give the corresponding ester-migrated products in the dark at—1.5 V vs SCE in the presence of acetic acid and at—2.0 V vs SCE without acetic acid. As regards a correlation between bulkiness of an ester group and a migration aptitude, a smaller ester group tends to migrate to the adjacent carbon atom more readily than a larger one. The origin of such a steric effect is discussed with attention to the rate-determining step.     

On some recent proposals for testing macrorealism versus quantum mechanics

In order to evaluate its relevance, we reconsider critically the recent proposal by Leggett and Garg to test macrorealism against quantum mechanics by resorting to experiments involving noninvasive measurement processes on a SQUID. Our conclusion is that, in spite of the fact that the proposed experiment would neither constitute a test of macrorealism nor a test of macrocontextuality, a simplified form of it represents a (presumably) feasible experiment permitting a direct test of macroscopic quantum coherence. We also analyze the proposal from the point of view of the recent attempts to build up model theories allowing to take, within a purely quantum framework, a macrorealistic position about natural phenomena, i.e., the socalled dynamical reduction models and we stress that the proposed experiment has no relevance for the dynamical reduction program, as developed so far. However consideration of the SQUID system allows one to test other possible dynamical mechanisms leading to the objectification of macroproperties which could, in principle, be operative. We also briefly sketch experimental procedures to be followed to get all relevant information concerning macrocoherence.     

THE COUPLING OF NATURAL BOUNDARY ELEMENT AND FINITE ELEMENT METHOD FOR 2D HYPERBOLIC EQUATIONS

In this paper, we investigate the coupling of natural boundary element and finite element methods of exterior initial boundary value problems for hyperbolic equations. The governing equation is first discretized in time, leading to a time-step scheme, where an exterior elliptic problem has to be solved in each time step. Second, a circular artificial boundary FR consisting of a circle of radius R is introduced, the original problem in an unbounded domain is transformed into the nonlocal boundary value problem in abounded subdomain. And the natural integral equation and the Poisson integral formula are obtained in the infinite domainΩ2 outside circle of radius R. The coupled variational formulation is given. Only the function itself, not its normal derivative at artificial boundary ΓR, appears in the variational equation, so that the unknown numbers are reducedand the boundary element stiffness matrix has a few different elements. Such a coupled method is superior to the one based on direct boundary element method. This paper discusses finite element discretization for variational problem and its corresponding numerical technique, and the convergence for the numerical solutions. Finally, the numerical example is presented to illustrate feasibility and efficiency of this method.     

Three point covers with bad reduction

We study Galois covers of the projective line branched at three points with bad reduction to characteristic , under the condition that strictly divides the order of the Galois group. As an application of our results, we prove that the field of moduli of such a cover is at most tamely ramified at .

     

基于粗糙集理论的知识约简及应用实例

在保持分类能力不变的前提下 ,通过利用粗糙集理论中的知识约简方法 ,在保护知识库分类不变的条件下 ,删除其中不相关或不重要的知识 ,从而导出问题的决策 .利用基于决策表的粗糙集模型算法 ,实例分析如何数字化表示决策表 ,并对其进行属性约简和属性值的约简 ,从而提取决策规则 .     

Probabilistic Teleportation of an Arbitrary n-Particle Entangled State

A scheme for teleporting an arbitrary n-particle entangled state via n pairs of non-maximally entangled states is proposed. The probability of successful teleportation is determined only by the smaller coefficients of the partially entangled pairs. The method is very easy to be realized.     

The influence of flow-induced non-Newtonian fluid properties on turbulent drag reduction

Friction factors and velocity profiles in turbulent drag reduction can be compared to Newtonian fluid turbulence when the shear viscosity at the wall shear rate is used for the Reynolds number and the local shear viscosity is used for the non-dimensional wall distance. On this basis, an apparent maximum drag reduction asymptote is found which is independent of Reynolds number and type of drag reducing additive. However, no shear viscosity is able to account for the difference between the measured Reynolds stress and the Reynolds stress calculated from the mean velocity profile (the Reynolds stress deficit). If the appropriate local viscosity to use with the velocity fluctuation correlations includes an elongational component, the problem can be resolved. Taking the maximum drag reduction asymptote as a non-Newtonian flow, with this effective viscosity, leads to agreement with the concept of an asymptote only when the solvent viscosity is used in the non-dimensional wall distance.     

Further study on vortex shedding flow by a circular cylinder

In the present paper the mechanism involved in vortex shedding flows is investigated in detail. In the early stage of the unsteady separated flow the interaction between secondary vortices and primary vortices is quite strong. In the later stage of the flow, corresponding to the vortex shedding the recirculating flow region on each side of the aft body goes through such a cycle: growth-contraction-growth, the secondary separation occurs periodically rather than continuously. The reduction of circulation is taken into account in three cases with different decay factors to study its influence on the prediction of main flow characteristics. Results show that to simulate vortex shedding flow it is necessary to include the reduction of circulation to bring the calculated results into good agreement with experiments. An improved discrete vortex model is suggested in which both the secondary separation and the reduction are incorporated. The processes of vortex shedding, the forces prediction and other flow characteristics are given and some discussions are made. Porject is supported by National Natural Science Foundation of China.     

高光谱图像降维的判别流形学习方法

本文提出了一种高光谱图像降维的判别流形学习方法.针对获取的大量遥感对地观测数据存在大量冗余信息的特点,引入改进的流形学习方法对高光谱遥感数据进行降维处理,以提高遥感图像自动分类的总体准确度.该方法充分利用遥感图像自动分类中训练样本的判别信息,将输入样本的类别信息加入到常规流形学习方法的框架中,从本质上提高输出的特征在低维空间中的判别力.同时,引入线性化模型以解决流形学习方法中常见的小样本问题.对高光谱遥感图像自动分类的实验表明,基于判别流形学习的高光谱遥感图像自动分类方法能够显著地提高图像分类准确度.     

一种光谱分析中的降维方法

在可见/近红外光谱分析中,提取光谱数据中的有用信息是建立稳健准确模型的前提。ISOMAP是一种有效的提取数据本真维的降维方法,但对噪声和邻域参数都比较敏感。提出了一种改进的ISOMAP有监督降维方法,利用光谱数据本身的相关性指导邻域图的构建,降低对噪声和邻域参数的敏感程度,以正确表达数据的邻域结构。采用该方法对两组光谱数据降维并进行PLS建模,结果表明,改进后的算法消弱了邻域大小的影响,提取出的本真维数更小,同时提高了模型精度。