An Easy Synthesis of Monofluorinated Derivatives of Pyrroles from β-Fluoro-β-Nitrostyrenes

The catalyst-free conjugate addition of pyrroles to β-Fluoro-β-nitrostyrenes was investigated. The reaction was found to proceed under solvent-free conditions to form 2-(2-Fluoro-2-nitro-1-arylethyl)-1H-pyrroles. The effectiveness of this approach was demonstrated through the preparation of a series of the target products in a quantitative yield. The kinetics of a conjugate addition of pyrrole was studied in detail to reveal the substituent effect and activation parameters of the reaction. The subsequent base-induced elimination of nitrous acid afforded a series of novel 2-(2-Fluoro-1-arylvinyl)-1H-pyrroles prepared in up to an 85% isolated yield. The two-step sequence herein proposed is an indispensable alternative to a direct reaction with elusive and unstable 1-Fluoroacetylenes.     

一种计算液接电势的新方法*

依据液接电势达稳态时通过边界层的净电荷为零这一思想,提出了一种计算液接电势的新方法。对于3类液接电势的计算,特别是Lewis-Sargent公式与Henderson方程的推导,思路清晰易懂,避免了过往液接电势计算方法存在的一些问题。本文所提出的方法能够为液接电势相关内容的教学提供借鉴。     

溯源辨析“活化分子”概念在化学教材中的角色定位*

“活化分子”作为国内化学教育领域广为人知的科学概念,在各类相关化学教材中都有介绍。然而在国外多种经典化学教材中却完全没有“活化分子”的概念,反映出国内外化学教育领域对化学反应速率理论相关知识点的处理上存在明显的差异与分歧。通过溯源关键历史文献,回顾了“活化分子”概念的形成及其在化学反应速率理论发展过程中的角色演变,指出“活化分子”概念已经退出反应速率理论的舞台,在教材中应更多地呈现其在科学史方面的价值,而不是科学价值。     

物理化学混合式教学设计与实践——以“单组分系统相变热力学”为例*

以“单组分系统相变热力学”为例介绍了物理化学混合式教学设计与教学实践。围绕课程教学目标,在课前、课中、课后的每一个教学环节中践行课程教学理念,通过“问题+案例”方式突出物理化学基本方法的应用性、普适性与前沿性,让学生在教学过程中获取原理、体验探究、发展思维、生成智慧。教学评价结果显示,绝大部分学生对混合式教学模式给予了积极的评价。     

基于电磁拓扑的多腔体屏蔽效能快速算法

提出基于电磁拓扑理论计算开孔多腔体屏蔽效能的快速方法.首先给出双腔体等效电路和电磁拓扑信号流图,并推导孔缝节点处的散射矩阵,给出拓扑网络的散射矩阵方程和传输矩阵方程,获得双腔体的广义Baum-Liu-Tesche(BLT)方程.在此基础上研究了开孔三腔体,包括串型级联三腔体和串并型混合级联三腔体的广义BLT方程.对于串型级联三腔体,其电磁拓扑网络和广义BLT方程在双腔体基础上直接扩展即可获得.而对于串并型混合级联三腔体,通过将位于三腔体公共面上的孔缝等效为三端口网络节点,并根据三端口网络散射参数定义推导获得该节点的散射矩阵,最终得到串并型混合级联三腔体的广义BLT方程.本文方法对双腔体的计算结果与文献结果和实验结果相符合,对3组不同类型和尺寸开孔腔的屏蔽效能的计算结果与时域有限差分法计算结果符合较好.该算法不仅效率高,通过对所有计算结果和实验结果的误差统计分析,表明该算法具有较高的计算准确度.     

太赫兹波段Smith-Purcell辐射的介质加载光栅高频特性

提出了一种用于Smith-Purcell效应器件的介质加载光栅慢波结构,通过研究该结构的注-波互作用过程,推导出带电子注的色散方程,并数值求解出波的线性增长率.利用色散方程,结合电磁场传播的边界条件,推导出Smith-Purcell效应振荡器工作所需的起振电流.详细研究了高频结构长度、电子注主要参数和介质相对介电常数对起振电流的影响,并与普通金属光栅结构进行了比较.结果表明:保持其他参数不变时,高频结构长度越短,起振电流越大;保持高频结构参数不变时,起振电流随电子注厚度和注-栅距离的增大而增大,随电子注电压的增大而减小;与金属光栅相比,介质的引入提高了注-波互作用的增长率,有效减小了振荡器的起振电流.理论计算结果与软件CHIPIC的模拟结果比较符合.     

球形Dirac方程的空间格点求解及假态问题

本文在空间格点上利用虚时间步长方法求解了球形Dirac方程, 着重研究了出现的假态问题. 利用三点数值导数公式离散方程中一阶导数项, 可以证明对于量子数为 κ 和 -κ的单粒子能级能量是完全相同的, 其中一个为物理解, 另一个为假态. 通过在径向Dirac方程中引入Wilson 项, 可以解决假态问题, 得到全部物理解. 文章以 Woods-Saxon 势为例, 考虑 Wilson 项后, 得到与打靶法一致的结果.     

An investigation on surface tensions of Pb-free solder materials

Surface tensions of some Pb-free solder systems such as Ag–Bi–Sn with cross-sections Ag/Bi = 1/1, Ag/Bi = 1/2, Ag/Bi = 2/1, In–Sn–Zn with cross-sections Sn/In = 1/1, Sn/In = 1/3 and (Ag₇Cu₃)_100?x Sn_x with cross-section Ag/Cu = 7/3 are calculated from the sub-binary surface tension data using the models, such as the Muggianu, Kohler, Toop models, Butler’s equation and Chou’s General Solution Model (GSM) at 873, 923 and 1073 K, respectively. The surface tension of In–Sn–Zn increases wavily with increasing amount of Zn and it is found that the best models are the GSM for both cross-sections in question while GSM becomes the best model for (Ag₇Cu₃)_100?x Sn_x alloy in the whole experimental range. Moreover, the surface tension of (Ag₇Cu₃)_100?x Sn_x decreases slightly with increasing amount of Sn. The Muggianu, Butler and Butler models are determined as the best models for the cross-sections in the order given above for entire measurement range, respectively, and the surface tension of Ag–Bi–Sn decreases slightly with an increasing amount of Bi and Ag but increases with increasing Sn in liquid alloys.     

Some insights in superdiffusive transport

In a wide range of systems, the relaxation in response to an initial pulse has been experimentally found to follow a nonlinear relationship for the mean squared displacement, of the kind 〈x²(t)〉∝t^α$〈x^2(t)〉\propto t^{\alpha }$, where α$\alpha$ may be greater or smaller than 1. Such phenomena have been described under the generic term of anomalous diffusion. “Lévy flights” stochastic processes lead to superdiffusive behaviour (1<α<2)$(1<\alpha <2)$ and have been recently proposed to model—among the others—the subsurface contaminant spread in highly heterogeneous media under the effects of water flow. In this paper, within the continuous-time random walk (CTRW) approach to anomalous diffusion, we compare the analytical solution of the approximated fractional diffusion equation (FDE) with the Monte Carlo one, obtained by simulating the superdiffusive behaviour of an ensemble of particle in a medium. We show that the two are neatly different as the process approaches the standard diffusive behaviour. We argue that this is due to a truncation in the Fourier space expansion introduced by the FDE approach. We propose a second-order correction to this expansion and numerically solve the CTRW model under this hypothesis: the accuracy of the results thus obtained is validated through Monte Carlo simulation over all the superdiffusive range. The same kind of discrepancy is shown to occur also in the derivation of the fractional moments of the distribution: analogous corrections are proposed and validated through the Monte Carlo approach.