Optimization of the synthesis of non-symmetrical alkyl dimethyl sulfonium halides

This work is aimed at the optimization of the yield and purity of non-symmetrical trialkyl sulfonium halide salts. The effects of parameters such as solvent, temperature and concentration were studied. The products were carefully analyzed and the crystal structure of [{n-CH₃(CH₂)₁₅}(CH₃)₂S]Br determined. The overall aim of the present study is future syntheses of low-dimensional magnetic materials.     

Assessing contaminated hydrogen peroxide for safe storage and transportation using the FTAI

Hydrogen peroxide is a very versatile oxidizing agent, and it is also environmentally compatible considering that the products of its exothermic decomposition are oxygen and water.When kept in a clean temperature-controlled environment, the self-reaction (decomposition) rate is extremely low. However, it is well known that even a small amount of contamination will dramatically increase the reaction rate. This paper describes the use of the fast thermal activity interpreter (FTAI) instrument to examine the chemical reactivity of commercially available 50% hydrogen peroxide at two different temperatures (30 and 40°C) both with and without contamination. The results show that at 30°C a small amount of rust (330 ppm) increases the reaction rate of 50% hydrogen peroxide by a factor of 50. When the temperature is increased to 40°C, the reaction rate is further increased by almost a factor of four. The implication for reactivity management is that at this contamination level most practical vessel sizes would require emergency venting capability. An evaluation was then performed to determine the emergency venting requirement for the safe transportation or storage of the contaminated hydrogen peroxide. It was determined that for quantities of the material less than 5 gallons, conventional breather vents would be sufficient to accommodate the gas evolved. However, for larger quantities, a safety relief device would be needed. For example, for a 400-gallon tote bin at 40°C the required minimum vent area is estimated to be 4.3 in², corresponding to a minimum vent diameter of 2.3 inches.     

Spectral enhancement of Polish vowels to improve their identification by hearing impaired listeners

Abnormalities in the cochlear function usually cause broadening of the auditory filters which reduces the speech intelligibility. An attempt to apply a spectral enhancement algorithm has been undertaken to improve the identification of Polish vowels by subjects with cochlear-based hearing-impairment. The identification scores of natural (unprocessed) vowels and spectrally enhanced (processed) vowels has been measured for hearing-impaired subjects. It has been found that spectral enhancement improves vowel scores by about 10% for those subjects, however, a wide variation in individual performance among subjects has been observed. The overall vowels identification scores obtained were 85% for natural vowels and 96% for spectrally enhanced vowels.     

The magnetization behavior of nanocrystalline permanent magnets based on the Stoner–Wohlfarth Model

The magnetization behavior in nanocrystalline permanent magnets has been investigated using mean field Stoner–Wohlfarth model. The model is comparatively simple but allows the numerical treatment of extended nanostructures. The predominant intergrain exchange coupling is expressed by a mean field constant N_m in spite of no explicit relationship between N_m and the microstructure. By this model, the experimental phenomena, such as the remanence enhancement, the shape of demagnetization curve, the irreversible magnetization, the exchange bias field and their respective temperature dependence, can be well explained. The N_m dependence of magnetic properties has been extensively discussed in the present paper.     

Effect of maltodextrins on the surface activity of small-molecule surfactants

We report on the effect of commercially important polysaccharides (maltodextrins with variable dextrose equivalent (Paselli SA-2, MD-6 and MD-10) on the surface activity at the air–water interface of small-molecule surfactants (sms), possessing different hydrophobic–lipophilic balance ((SSL (Na⁺), the main component is a sodium salt of stearol–lactoyl lactic acid, and PGE (080), polyglycerol ester of C18 fatty acid), and widely used in food products. A marked change of the surface activity of sms was found in the presence of maltodextrins by tensiometry. The combined data of laser multiangle light scattering and mixing calorimetry have suggested that this result is governed by specific complex formation between maltodextrins and sms in aqueous medium. Measurements have been made of the molar mass, the second virial coefficient and the enthalpy of intermolecular interactions in aqueous solutions. The implication of a degree of polymerization of maltodextrins in this phenomenon was shown. The interrelation between the molecular parameters of the formed complexes and their surface activity at the air–water interface has been revealed and discussed.     

Effects of laser intensity on the emission direction of fast electrons in laser-solid interactions

The dependence of emission direction of fast electrons on the laser intensity has been investigated. The experimental results show that, at nonrelativistic laser intensities, the emission of fast electrons is mainly in the polarization plane. With the increase of the laser intensity, fast electrons emit towards the laser propagation direction from laser polarization direction. At relativistic laser intensities, fast electrons move away from the laser polarization plane, closely to the reflection direction of the incident laser beam.     

C2（a 3Πu）+NO 的反应机理研究

在G2 (CC ,MP2 )理论水平上研究了C2 (a3 Πu)自由基与NO分子的反应 .计算了反应体系最低二重态势能面上各驻点的构型参数、振动频率和能量 ,揭示了此反应存在两种反应机理 :由NO中的O原子进攻C2 自由基形成CCON中间体的CCON机理和NO中的N进攻C2 自由基形成CCNO中间体的CCNO机理 ,分析了对应与这两种反应机理的五个可能的反应通道 ,得出了由NO中的N原子进攻3 C2 自由基 ,生成中间体CCNO自由基 ,最终得到产物CN +CO的通道是最有利的通道 .     

Computational analysis of native and modified oligofructosides

This paper presents a quantum chemical calculation of native (2–7 fructoside residues) and chemically modified (2–4 fructoside residues) levan molecule models. A levan modification was carried out by oxidation and the following reduction or hyrdazonation of the fructoside rings. The conformational particularity and reaction ability was studied for the native and for the modified levan molecules.     

新型制冷机冷凝器壳侧的传热强化研究

针对现行制冷机冷凝器的不足 ,设计了适用于冷凝传热的新型折流杆冷凝器的壳程内部结构 ,并分析了其传热强化机理。在重力控制条件下 ,对不同内部支承结构与管束组合的冷凝器进行了传热实验研究 ,得到了水蒸汽在冷凝器壳侧的冷凝传热特性曲线。采用冷凝传热强化因子的概念 ,建立了预测该种折流杆冷凝器壳侧冷凝传热膜系数的计算公式 ,为折流杆冷疑器在制冷系统中的设计应用提供了理论依据。     

Organocatalysis: quantum chemical modeling of nucleophilic addition to α,β‐unsaturated carbonyl compounds

One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd.