On the mechanism of the N,N‐dimethyl amination of Grignard reagents: a kinetic study

A direct kinetic study is reported for the electrophilic amination of substituted phenylmagnesium bromides with N,N‐dimethyl O‐(mesitylenesulfonyl)hydroxylamine in THF. Rate data, Hammett relationship, and activation entropy are consistent with a S_N2 displacement involving the attack of carbanions to sp³N in the amination reagent (AR). Copyright © 2007 John Wiley & Sons, Ltd.     

基于Boltzmann光谱法的焊接电弧温度场测量计算

电弧等离子体是非均匀等离子体,其内部进行着复杂的能量和质量输运过程,等离子体的温度测量具有重要意义。Boltzmann作图法测量温度较谱线绝对强度法、标准温度法等测温方法更为方便。基于Boltzmann作图法原理,对TIG电弧进行实时的空间扫描,分析了谱线的选取原则,测量计算出TIG焊电弧等离子体的温度场分布。     

Effect of substrate temperature on structural, optical and electrical properties of pulsed laser ablated nanostructured indium oxide films

Nanocrystalline indium oxide (INO) films are deposited in a back ground oxygen pressure at 0.02 mbar on quartz substrates at different substrate temperatures (T_s) ranging from 300 to 573 K using pulsed laser deposition technique. The films are characterized using GIXRD, XPS, AFM and UV-visible spectroscopy to study the effect of substrate temperature on the structural and optical properties of films. The XRD patterns suggest that the films deposited at room temperature are amorphous in nature and the crystalline nature of the films increases with increase in substrate temperature. Films prepared at T_s ≥ 473 K are polycrystalline in nature (cubic phase). Crystalline grain size calculation based on Debye Scherrer formula indicates that the particle size enhances with the increase in substrate temperature. Lattice constant of the films are calculated from the XRD data. XPS studies suggest that all the INO films consist of both crystalline and amorphous phases. XPS results show an increase in oxygen content with increase in substrate temperature and reveals that the films deposited at higher substrate temperatures exhibit better stoichiometry. The thickness measurements using interferometric techniques show that the film thickness decreases with increase in substrate temperature. Analysis of the optical transmittance data of the films shows a blue shift in the values of optical band gap energy for the films compared to that of the bulk material owing to the quantum confinement effect due to the presence of quantum dots in the films. Refractive index and porosity of the films are also investigated. Room temperature DC electrical measurements shows that the INO films investigated are having relatively high electrical resistivity in the range of 0.80-1.90 Ωm. Low temperature electrical conductivity measurements in the temperature range of 50-300 K for the film deposited at 300 K give a linear Arrhenius plot suggesting thermally activated conduction. Surface morphology studies of the films using AFM reveal the formation of nanostructured indium oxide thin films.     

Multiparameter kinetic analysis of alkaline hydrolysis of a series of aryl diphenylphosphinothioates: models for P=S neurotoxins

Alkaline hydrolysis of a series of X‐substituted‐phenyl diphenylphosphinothioates ( 2a‐i ) in 80 mol%/20 mol% DMSO at 25.0 ± 0.1°C has been studied kinetically and assessed through a multiparameter approach. Substrates 2a to 2i are approximately 12 to 22 times less reactive than their P=O analogues 1a to 1i (ie, the thio effect). The Brønsted‐type plot for the reactions of 2a to 2i is linear with β_lg = ?0.43, consistent with a concerted mechanism. Hammett plots correlated with σ^o and σ^? constants also support a concerted mechanism; the Yukawa‐Tsuno plot results in an excellent linear correlation with ρ_X = 1.26 and r = 0.30, indicating that expulsion of the leaving group occurs in the rate‐determining step (RDS). The ΔH^? value increases from 10.5 to 11.7 and 13.9 kcal/mol as substituent X in the leaving group changes from 3,4‐(NO₂)₂ to 4‐NO₂ and H, in turn, while TΔS^? remains constant at ?6.0 kcal/mol. The strong dependence of ΔH^? on the electronic nature of substituent X also indicates that the leaving group departs in the RDS. The reaction mechanism and origin of the thio effect are discussed by comparison of the current kinetic results with those reported for the reactions of 1a to 1i . The results suggest that for useful OP neurotoxins the mechanism of abiotic hydrolysis is concerted (with varying degrees of asynchronicity) when the substrate bears good leaving groups.     

Kinetic aspects of Li intercalation in mechano-chemically processed cathode materials for lithium ion batteries: Electrochemical characterization of ball-milled LiMn2O4

Micrometric LiMn₂O₄ particles are mechano-chemically modified by ball-milling to obtain a mixture of nano- and micro-scale particles. This mixture is tested as a potential active cathode material for rapid-charge Li ion batteries, and also as a model system for studying the detailed kinetics of Li intercalation/de-intercalation in such electrodes. Ragone plots recorded using galvanostatic measurements indicate enhanced power delivery characteristics of the ball-milled LiMn₂O₄ compared to its unprocessed counterpart. The processed material also exhibits improved resistance against electrolyte reactions and surface film formation. Due to these advantageous electrochemical attributes, the ball-milled LiMn₂O₄ serves as an adequately suited system for exploring certain fundamental aspects of Li intercalation in this material. Scan rate dependent slow scan cyclic voltammetry helps to identify the kinetic and diffusion controlled features of Li transport in mechano-chemically processed LiMn₂O₄. Electrochemical impedance spectroscopy substantiates these findings further and provides detailed kinetic parameters, including voltage dependent charge transfer resistance and diffusion coefficient of Li transport.     

Cole-Cole方程参数对细胞介电频谱的影响

为探讨Cole-Cole方程8个参数(Δε1,Δε2,εh,κl,f1,f2,β1,β2)对细胞介电频谱的影响,采用改变单个参数,固定其他参数的方法,观察介电频谱的变化.结果显示:Δε1影响低频介电频谱和Cole-Cole(ε′)图;Δε2影响高频介电频谱、Cole-Cole(ε′)图和Cole-Cole(κ′)图;εh影响ε′(f)、Cole-Cole(ε′)图和tgδ(f);κl对κ′(f)和Cole-Cole(κ′)图有影响;f1影响低频介电频谱;f2影响高频介电频谱;β1影响Cole-Cole(ε′)和tgδ(f);β2对高频介电频谱有影响.可见Cole-Cole方程作为细胞介电频谱的数学模型,其参数变化有规律可循.     

几种新的回归诊断图示模型及其医学应用

本文在变量选择问题的基础上，提出了一种新的图示模型──减变残差图。并给出它的两种推广形式：均值平移异常值检验图和部分影响诊断图。通过它们不但可以容易地考察一个变量在模型中的作用和检验异常值，而且可以诊断样本点对模型和变量的影响大小。     

基于Poincaré差值散点图的心率变异性分析方法研究

在心率变异性的非线性分析中, Poincaré散点图分析是一种重要手段.本文基于Poincaré差值散点图(modified Poincaré plot)提出了两个参数——区域分布熵和区域分布系数, 用于定量描述所考察区域内散点的分布趋势, 并提出对散点在4个象限中的分布进行分别计算.通过对MIT-BIH数据库中健康年轻人、健康老年人和充血性心力衰竭患者样本数据的分析, 发现两参数值均呈现显著的组间差异;同时, 不同象限的分析结果显示了四个象限具有不同的区分敏感性, 而其中尤以第一象限的区分度为最高, 反映出充血性心力衰竭患者相对健康人迷走神经调控功能的改变最为显著, 与以往的生理学研究结论相符.经验证, 该方法可用于短时数据, 更易于扩展至临床应用.