Effects of hydrogen bonding on metal ion-promoted intramolecular electron transfer and photoinduced electron transfer in a ferrocene-quinone dyad with a rigid amide spacer

A ferrocene-quinone dyad (Fc-Q) with a rigid amide spacer and Fc-(Me)Q dyad, in which the amide proton acting as a hydrogen-bonding acceptor is replaced by the methyl group, are employed to examine the effects of hydrogen bonding on both the thermal and the photoinduced electron-transfer reactions. The hydrogen bonding of the semiquinone radical anion with the amide proton in Fc-Q(.-) produced by the electron-transfer reduction of Fc-Q is indicated by the significant positive shift of the one-electron reduction potential of Fc-Q. The hyperfine coupling constants of Fc-Q(.-) also indicate the existence of hydrogen bonding, agreeing with those predicted by the density functional calculation. The hydrogen-bonding dynamics in the photoinduced electron transfer from the ferrocene (Fc) to the quinone moiety (Q) in Fc-Q have been successfully detected in the femtosecond laser flash photolysis experiments. Thermal intramolecular electron transfer from Fc to Q in Fc-Q and Fc-(Me)Q also occurs efficiently in the presence of metal ions in acetonitrile at 298 K. The hydrogen bond formed between the semiquinone radical anion and the amide proton in Fc-Q results in remarkable acceleration of the rate of metal ion-promoted electron transfer as compared to the rate of Fc-(Me)Q in which hydrogen bonding is prohibited. The metal ion-promoted electron-transfer rates are well correlated with the binding energies of superoxide ion-metal ion complexes, which are derived from the g(zz) values of the ESR spectra.     

基于任意形状颗粒集合二值图像的体积估算模型

基于任意形状颗粒集合的二值图像,提出了估计其体积(或质量)的方法.首先利用发光背景台面获取的颗粒灰度图像变换为相应的二值图像,得到颗粒的边界轮廓.然后再基于其边界信息,定义与颗粒形状特征相关的描述量,并将其无量纲化.将由此定义的无量纲参变量作为回归变量建立一个多元线性回归(multiple linear regression)模型用以估计颗粒集合的扁平度,进而估算颗粒体积.回归变量的系数由随机采样的501个样本颗粒(尺寸范围为4.75～25 mm)用误差最小平方和求得.将模型应用于由具有相似统计分布特征的其他颗粒集合,并将得到的体积估计值与其体积真实值相比较,实验结果显示模型的相对误差在±2%以内.     

一种基于新型小波包阈值的图像去噪方法

提出了一种基于小波包理论去除图像噪声的方法,用小波包把图像分解为高频分量和低频分量,根据高频分量估计噪声的标准差,并利用该标准差以及Birge-Massart惩罚函数计算阈值.鉴于传统软硬阈值的缺陷,采用一种新型阈值量化方法,用三次多项式在硬阈值的基础上插值,使新的阈值函数保持了连续性和可导性.通过这种方法既消除了图像的振铃现象,又保留了细节成分.实验表明：与传统方法相比,新方法使图像视觉效果和峰值信噪比均获得提高.     

Effect of an electric field on defects in a nematic liquid crystal with variable surface anchoring

We report experimental studies on defects in a nematic liquid crystal with negative dielectric anisotropy mounted in a cell with perfluoropolymer-coated surfaces. The sample exhibits a discontinuous anchoring transition from planar to homeotropic on cooling at zero or a small electric field, and above a cross-over voltage a continuous ‘inverse Freedericksz transition’, at which the director starts tilting in opposite directions at the two surfaces. Defects of strength ±1/2 are either annihilated or expelled when the director tilts. On the other hand, disclination lines of ±1 which end in partial point defects (boojums) at the surfaces in the planar alignment regime acquire point defects of strength ±1 at the midplane of the cell when the director tilts. At a low enough temperature, the homeotropic anchoring becomes strong, and an electric field above the Freedericksz threshold generates the usual umbilic defects, which follow the dynamic scaling laws found in earlier studies.     

Biodegradable Polyurethanes from Plant Components

Abstract

Polyurethane (PU) sheets and foams having plant components in their network were prepared by using the following procedure. Polyethylene glycol (PEG) was mixed with one of the following; molasses, lignin, woodmeal, or coffee grounds. The mixture obtained was reacted with diphenylmethane diisocyanate (MDI) at room temperature, and precured PUs were prepared. The precured PUs were heat-pressed and PU sheets were obtained. In order to make PU foam, the above mixture was reacted with MDI after the addition of plasticizer, surfactant (silicone oil), catalyst (di-n-butyltin dilaurate), and droplets of water under vigorous stirring. The glass transition temperature, tensile and compression strengths, and Young's modulus of the PU sheets and foams increased with an increasing amount of plant components. This suggests that saccharide and lignin residues act as hard segments in PUs. It was found that the PUs obtained were biodegradable in soil. The rate of biodegradation of the PUs derived from molasses and coffee grounds was between that of cryptomeria (Cryptomeria japonica) and beech (Fagus sieboldi).     

A new product construction for partial difference sets

Relatively few constructions are known of negative Latin square type Partial Difference Sets (PDSs), and most of the known constructions are in elementary abelian groups. We present a product construction that produces negative Latin square type PDSs, and we apply this product construction to generate examples in p-groups of exponent bigger than p.