Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

稀土甘氨酸咪唑配合物[RE(Gly)4(Im)(H2O)](ClO4)3的热化学研究

采用溶解-反应量热法在具有恒温环境的溶解-反应热量计内,测定了[Gd(Gly)4(Im)(H2O)](ClO4)3和[Y(Gly)4(Im)(H2O)](ClO4)3两种稀土甘氨酸咪唑配合物的标准生成焓分别为(-3 461.46 ±0.22) kJ·mol-1 和(-3 926.6±0.90) kJ·mol-1.     

Excess molar enthalpies of binary mixtures of 1-hexene with some cyclic and aromatic hydrocarbons at 298.15 K

Microcalorimetric measurements of excess molar enthalpies, at 298.15 K, are reported for the four binary systems formed by mixing 1-hexene with the cycloalkanes: cyclohexane and methylcyclohexane, and with the aromatic hydrocarcons: benzene and toluene. Smooth Redlich-Kister representations of the results are presented. It was found that the Liebermann-Fried model also provided good representations of the results.     

Paradigms and Paradoxes: Energetics of Aqueous Oxyanions of Nonmetals and Metalloids

The enthalpies of formation of simple nonmetal or metalloid oxyanions in aqueous solution are discussed. Archival values are cited and estimates are made. Trends prove evasive.     

Annealing behavior of gel‐spun polyethylene fibers at temperatures lower than needed for significant shrinkage

The annealing at 373 K of ultrastrong, gel‐spun polyethylene (PE) has been studied. At this temperature, the fibers show no significant shrinkage. Still, a significant decrease in the mechanical properties is observed. The fibers have been analyzed with differential scanning calorimetry (DSC), temperature‐modulated differential scanning calorimetry (TMDSC), atomic force microscopy (AFM), and small‐angle X‐ray scattering (SAXS). During the annealing, the glass transition of the intermediate phase is exceeded, as shown by DSC. When split for structure analysis by AFM, the annealed fibers undergo plastic deformation around the base fibrils instead of brittle fracture. The quasi‐isothermal TMDSC experiments are compared to the minor structural changes seen with SAXS and AFM. The loss of performance of the PE fibers at 373 K is suggested to be caused by the oriented intermediate phase, and not by major changes in the structure or morphology. The overall metastable, semicrystalline structure is shown by TMDSC to posses local regions that can melt reversibly. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 403–417, 2003     

生物小分子与铜锌超氧化物歧化酶相互作用的波谱学研究及其应用

本工作以ESR和NMR为主要手段,并结合其它生化方法,考察了氨基酸、核酸碱基、糖等生命基本物质,和抗坏血酸等生命必需物质与钢锌超氧化物歧化酶的相互作用,实验观测到氨基酸、核酸碱基和抗坏血酸在水溶液中可以与酶中的Cu²⁺作用而使其脱离活性部位,以小分子络合物形式游离在溶液中,同时使酶失活,脱离活性部位的Cu²⁺的比例和酶的失活程度取决于小分子配体的加入量及其与Cu²⁺的络合能力。此外,首次尝试使用ESR方法,并借助氨基酸与酶的作用,考察了铜锌超氧化物歧化酶在盐酸胍变性和热变性过程中的构象变化行为,结果表明这一方法是直观而有效的。     

Some results from 50 years' research on surface forces

A review is presented about research on surface forces and surface interactions conducted over the past half-century, with some emphasis on the pioneering contributions of the Department of Surface Phenomena at the Institute of Physical Chemistry of the USSR Academy of Sciences.     

Excess enthalpy of ternary mixture for diamine+heptane+cyclohexan

The excess molar enthalpy of ternary mixture for 3-diethylaminopropylamine+heptane+cyclohexane were measured using a Calvet microcalorimeter at 303.15 K. Empirical equations, Redlich-Kister, Tsao-Smith, and Kohler and group contribution models, UNIFAC (modified version) and DISQUAC have been applied. A reasonable representation of ternary data is obtained. This revised version was published online in August 2006 with corrections to the Cover Date.     

Laser spectroscopy of high spin isomers – a review

This review summarizes the experimental data on charge radii differences among ground state and high spin isomeric states determined by high-resolution laser spectroscopic methods. A comparison is presented between radii changes obtained from the isomeric shifts in the atomic spectra and from the quadrupole moments of both ground and isomeric states under the assumption that the radii changes are determined by the difference of the quadrupole deformations. Special attention is paid to isomers arising from the break-up of nucleon pairs and isomers of odd–odd nuclei. The characteristic features of the radii changes for isomeric states of different origin are discussed.     

考虑材料熔化潜热的高温高压本构

本文在修正的SCG模型基础上，提出了一种考虑了熔化潜热的高温高压本构.该本构所给出的铝的剪切模量的变化分为三个阶段：加工硬化，温度软化和熔化，并在完全熔化点处变为零.并且在前两个阶段，计算的结果与修正的SCG模型所给出的剪切模量的差别不超过4%，这一差别是在动高压实验误差范围之内的，在熔化区所给出的剪切模量与现有的实验数据相符合. 关键词： 剪切模量 熔化潜热 修正的SCG模型 动高压实验