Synthesis,complexation, and photochemistry of benzobisthiazole-based bis(crown ether)

Benzobisthiazole-based bis(crown ether) was synthesized and its complexation with alkali and alkaline earth cations was studied. Photochemical transformations of the free ligand and its complexes with alkaline earth cations involve E,Z-photoisomerization and [2+2] photocycloaddition. Dedicated to Academician N. S. Zefirov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2056–2065, September, 2005.     

QSPR Modeling of the Reactivity Parameters of Monomers in Radical Copolymerizations

For a series of monomers, QSPR test analysis is performed by optimizing the correlation weights of the local invariants of molecular graphs representing monomer structures in order to construct models of the reactivity parameters of monomers Q and e. This approach may be used as a tool in reactivity predictions for monomers for which no experimental data on Q and e are available.Original Russian Text Copyright © 2004 by A. A. Toropov, V. O. Kudyshkin, N. L. Voropaeva, I. N. Ruban, and S. Sh. Rashidova__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 994–998, November–December, 2004.     

工业用水中总铁含量的快速测定

介绍了以菲咯嗪－醋酸钠－醋酸缓冲溶液为显色体系、用自制的铁含量比色测定仪快速测定工业用水中总铁含量的方法。总铁含量≤０５ｍｇ／Ｌ时，标准偏差≤００３ｍｇ／Ｌ；总铁含量＞０５ｍｇ／Ｌ时，相对标准偏差≤５％。单次测定时间（包括样品处理）为１０～１５ｍｉｎ。采用单色光源及微型流动比色池，由蠕动泵和电子线路实现自动进样，直接显示测定结果。     

Synthesis of new α,α,β,β-tetrafluoroesters

Substituted phenyl iodides or diiodides reacted with ethyl iodotetrafluoroproponylate ICF₂CF₂CO₂Et, 1 in the presence of copper powder to give the coupled products 2 or 3 in good yields. Addition of 1 to ethylene and allyl acetate proceeded smoothly under thermal and radical conditions to give the corresponding adducts, which underwent elimination reaction to give β-vinyl and β-allyl α,α,β,β-tetrafluoroesters, CH₂CHCF₂CF₂CO₂Et, 4 and CH₂CHCH₂CF₂CF₂CO₂Et, 5, respectively. 1 also readily reacted with 1,5-hexadiene and 1-hexene with copper or palladium complex, followed by reduction to remove iodine to produce ω-alkenyl-α,α,β,β-tetrafluoroester CH₂CH(CH₂)₄CF₂CF₂CO₂Et 6 and α,α,β,β-tetrafluoroester C₄H₉CH₂CHICF₂CF₂CO₂Et.     

钙钛矿型CaSiO_3解压缩和重压缩过程的分子动力学模拟

用分子动力学模拟方法 (MD)研究了 3 0 0K时钙钛矿型CaSiO3 ,从高压到负压的解压缩过程 .MD模拟获得的P V关系与实验数据相近 ,与已报道的MD模拟数据基本一致 ,所得体积模量也在实验数据分布范围内 .减压缩和重压缩的MD模拟数据与实验结果相似 .钙钛矿型CaSiO3 解压缩成非晶态时 ,存在两个结构破坏阶段 :破坏硅氧八面体和破坏钙氧二十面体 .当钙氧二十面体被破坏后 ,重压缩不能得到钙钛矿型结构 .只要钙氧二十面体未被破坏 ,重压缩可恢复钙钛矿型结构 .本研究得到的结果尚未见相关报道 .由MD模拟数据计算了CaSiO3 系统的红外光谱 ,分析这些数据可知钙钛矿型CaSiO3 解压缩非晶化是一个二阶软模相变 .研究表明钙钛矿型CaSiO3 结构存在一个等容的亚稳极限 ,其解压缩非晶化是一个受动力学控制的亚稳状态 .     

Dynamic Study of Gemini Surfactant and Single-chain Surfactant at Air／Water Interface

Molecular dynamics (MD) simulation are used to study the properties of gemini surfactant of ethyl-α,ω-bis(dodecyldimethylammonium bromide) (C12C2C12) and dodecyl-trimethylammonium bromide (DTAB) at the air/water interface, respectively. In the two systems,t he surfactant concentrations are both 28 wt.%, and other conditions are also the same. After reaching the thermodynamic equilibrium, the concentration profiles, the radial distributions functions (RDF) and the mean squared displacement (MSD) are investigated. The results reveal that the surface activity of C12C2C12 surfactant is higher than DTAB surfactant.     

Wittig-Olefinierung zu neuen donor- und akzeptor-substituierten 3-Vinylindolen: Optimierte Syntheseverfahren

Summary The optimized Wittig reaction of selectively functionalized 3-acylindoles yield new, and for Diels-Alder reactions highly reactive donor- and acceptor substituted 3-vinylindoles, respectively.

     

Impact of electron-electron interaction on the electron energy distribution function in molecular plasmas under rf field action

Calculations of the electron energy distribution and of relevant macroscopic quantities of collision-dominated, weakly ionized plasmas under rf field action have been performed with increasing degrees of ionization, and the impact of the electron-electron interaction on these quantities was determined. The investigations were performed for the gas plasmas in CO and H₂ as representatives of molecular plasmas The energy distribution and macroscopic quantities are obtained by solving the nonstationary Bolizmann equation for a given rf field and degree of ionization taking into accoung and additional Fokker-Planck term besides the collision integrals for the elastic and the main inelastic collision processes. In these molecular plasmas a remarkable impact of the electron-electron interaction connected with increasing Maxwellization is observed for degrees of ionization greater than 10.     

Effects of Amplitude of the Radiofrequency Electromagnetic Radiation on Aqueous Suspensions and Solutions

The effects of radiofrequency (RF) (1–4) and magnetic fields (5–9) on the behavior of aqueous solutions and suspensions have been a popular subject in recent years. The mechanism of the magnetic “water memory” effect, though, is still largely unknown (5). In this work, we present evidence that the primary “receptor” of the electromagnetic radiation is a gas/liquid interface. Gas can be either already present in water or produced by the effects of electromagnetic fields. Perturbed gas/liquid interfaces require hours to equilibrate. Certain RF and magnetic signals also produce reactive oxygen and hydrogen species (superoxide, hydrogen peroxide, hydrogen, atomic hydrogen). The perturbed gas/liquid interface modifies the hydrogen bonding networks in water and also the hydration of ions and interfaces. Careful outgassing removes all of the effects of the electromagnetic fields, including the magnetic memory effect. The amplitude of the applied field influences the observed effects. Different amplitudes of RF radiation perturb the interfacial water in different ways and consequently affect the behavior of colloids and ions in specific manners. For instance, the bulk and template precipitation of calcium carbonate, zeta potentials of suspended colloids, rate of dissolution of colloidal silica, and attachment of colloidal silica to metal surfaces are modified in specific ways with the low amplitude or high amplitude RF treatments described in this paper. The solubility/diffusivity of gas species is also modified in a different manner, and it is probably at the core of the specificity of the RF amplitude effects.     

Vibrational spectra and structure of zirconium and hafnium cyclopentadienyl hydrides

Raman and IR spectra (4000-50 cm^–1) of solid cyclopentadienyl zirconium and hafnium hydrides Cp₂MH₂, Cp₂MD₂, Cp₂Zr(H)X, and Cp₂Zr(D)X (Cp = ⁵-C₅H₅; M = Zr, Hf; X = Cl, Br) have been studied. The vibrational modes of MH groups, Cp-rings, and metal-ligand bonds are discussed and the band assignments are proposed. In the solid state, these complexes form polymers with linear hydride bridges of the M-H-M type. The force constants of the M-H and M-Cp bonds increase on going from Zr to Hf.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1604–1609, September, 1994.