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.     

Peritectic phase growth in directionally solidified Cu-70% Sn alloy

The growth mechanism of the peritectic η phase involving the peritectic reaction and peritectic transformation in Cu-70%Sn alloy was investigated under directional solidification. The results show that a major growth mechanism in thickening of the peritectic η-layer is not the peritectic reaction but the peritectic transformation. The transformation temperature and isothermal time play crucial roles in determining the volume fraction and the thickness of the peritectic η phase. With the increase of the temperature and isothermal time, the volume fraction of the peritectic η phase increases. The regressed data show that the relationship between the thickness of η phase (Δx) and the transformation temperature (T) meets the following equation In Δx=6.5−1673 1 / T. Additionally, there exists a relationship between the thickness of the η phase (Δx) and the isothermal time (t) at the 9 mm solidification distance below the peritectic reaction interface, Δx=0.72t ^1/2, which is consistent with the theoretical model. Supported by the National Science Foundation of China (Grant No. 50395102)     

Unsteady MHD flow of a non-Newtonian fluid on a porous plate

This paper deals with the study of the MHD flow of non-Newtonian fluid on a porous plate. Two exact solutions for non-torsionally generated unsteady hydromagnetic flow of an electrically conducting second order incompressible fluid bounded by an infinite non-conducting porous plate subjected to a uniform suction or blowing have been analyzed. The governing partial differential equation for the flow has been established. The mathematical analysis is presented for the hydromagnetic boundary layer flow neglecting the induced magnetic field. The effect of presence of the material constants of the second order fluid on the velocity field is discussed.     

Amine‐blocked polyisocyanates. I. Synthesis of novel N‐methylaniline‐blocked polyisocyanates and deblocking studies using hot‐stage fourier transform infrared spectroscopy

A series of substituted N‐methylaniline‐blocked polyisocyanates based on 4,4′‐methylenebis(phenyl isocyanate) and poly(tetrahydrofuran) were prepared and characterized thoroughly with FTIR, ¹H NMR, and ¹³C NMR spectroscopy methods. Compared with unsubstituted N‐methylaniline, a blocking agent with an electron‐releasing substituent at the para position took a shorter time, whereas those with an electron‐releasing substituent at the ortho position or an electron‐withdrawing substituent at the ortho and para positions took longer times for the blocking reaction. The thermal dissociation reactions of blocked polyisocyanates were carried out with an FTIR spectrophotometer attached to hot‐stage accessories under dynamic and isothermal conditions. The dynamic method was used to determine the deblocking temperature, and the isothermal method was used to calculate the deblocking kinetics and activation parameters. The cure times of blocked polyisocyanates with hydroxyl‐terminated polybutadiene were also determined. The deblocking temperatures, the results of cure‐time studies, and the kinetic parameters revealed that the thermal dissociation of the N‐methylaniline‐blocked polyisocyanates was retarded by electron‐donating substituents and facilitated by electron‐withdrawing substituents. The action of N‐methylanilines as blocking agents for isocyanate was explained by the formation of a four‐center, intramolecularly hydrogen‐bonded ring structure during the thermal dissociation of the blocked polyisocyanates. The formation of such a hydrogen‐bonded ring structure was confirmed and supported by variable‐temperature ¹H NMR studies and entropy parameters, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1557–1570, 2007     

系综分布和它的小涨落近似

由“从正则分布出发，在小涨落近似下得出的能量涨落分布公式”求得的能量涨落的二次矩与直接由正则分布求得的二次矩完全相同，但分别由二求得的高次矩并不完全相同。     

Hyers–Ulam stability of linear differential operator with constant coefficients

Let P(z) be a polynomial of degree n with complex coefficients and consider the n–th order linear differential operator P(D). We show that the equation P(D)f = 0 has the Hyers–Ulam stability, if and only if the equation P(z) = 0 has no pure imaginary solution. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

聚醚醚酮链结构与反应的模型化合物的量子化学研究

利用ＡＭ１方法对聚醚醚酮模型化合物全优化，结果为：芳环平均相互扭转角为３３．０度，桥键角１１７．０－１１８．０度，其分子结构拓扑图形表明：所有苯环（核）为平面构型，但其内角扭曲；其氢原子对苯环构型无实质性贡献，在更长链的计算中，冻结苯核与氢原子也得出满意结果，根据Ｍｕｌｌｉｋｅｎ键序与电荷讨论了醚交换与磺化反应。     

Looking at Fokker-Planck dynamics with a noisy instrument

We consider the class of experiments which can be characterized by a Fokker-PIanck dynamics corresponding to the overdamped motion of a state point in a suitable stochastic potential. We assume that the general form of the potential is known (or can be guessed with reasonable accuracy), but that its parameters are to be determined experimentally by measurements made with a noisy instrument. This possible method for determining the potential parameters, which exploits the system's own internal stochastic motion in order to explore rapidly its available parameter space, is substantially more efficient than traditional methods involving time averages of single point measurements, and yet does not appear to have been previously considered. The method could be important when, for example, the experiment must be completed in a limited time owing either to the expense of the experimental materials or to the temporary stationarity of the preparation, situations which are commonly encountered in experimental biochemistry and biology.