Conformational Properties of (Z,Z)-, (E,Z)-, and (E,E)-Cycloocta-1,4-dienes

Summary.  Ab initio calculations at the HF/6-31G^* level of theory for geometry optimization and the MP2/6-31G^*//HF/6-31G^* level for a single point total energy calculation are reported for (Z,Z)-, (E,Z)-, and (E,E)-cycloocta-1,4-dienes. The C ₂-symmetric twist-boat conformation of (Z,Z)-cycloocta-1,4-diene was calculated to be by 3.6 kJ·mol⁻¹ more stable than the C _S-symmetric boat-chair form; the calculated energy barrier for ring inversion of the twist-boat conformation via the C _S-symmetric boat-boat geometry is 19.1 kJ·mol⁻¹. Interconversion between twist-boat and boat-chair conformations takes place via a half-chair (C ₁) transition state which is 43.5 kJ·mol⁻¹ above the twist-boat form. The unsymmetrical twist-boat-chair conformation of (E,Z)-cycloocta-1,4-diene was calculated to be by 18.7 kJ·mol⁻¹ more stable than the unsymmetrical boat-chair form. The calculated energy barrier for the interconversion of twist-boat-chair and boat-chair is 69.5 kJ·mol⁻¹, whereas the barrier for swiveling of the trans-double bond through the bridge is 172.6 kJ·mol⁻¹. The C _S symmetric crown conformation of the parallel family of (E,E)-cycloocta-1,4-diene was calculated to be by 16.5 kJ·mol⁻¹ more stable than the C _S-symmetric boat-chair form. Interconversion of crown and boat-chair takes place via a chair (C _S) transition state which is 37.2 kJ·mol⁻¹ above the crown conformation. The axial- symmetrical twist geometry of the crossed family of (E,E)-cycloocta-1,4-diene is 5.9 kJ·mol⁻¹ less stable than the crown conformation. Corresponding author. E-mail: isayavar@yahoo.com Received March 25, 2002; accepted April 3, 2002     

A heuristic method to schedule training programs for Small and Medium Enterprises

During the life period of Small and Medium Enterprises (SMEs) in incubators they need some training programs to acquire the required knowledge in order to survive and succeed in the business environment. This paper presents a heuristic method based on an optimization model to schedule these programs at the most suitable times. Based on the proposed heuristic, each training program is implemented in a suitable time by considering the SMEs’ requirements and some other logical constraints. The proposed heuristic is described in detail, and its implementation is demonstrated via a real-life numerical example. The numerical results of the heuristic are compared with other methods.     

Medium range ordering and some magnetic properties of amorphous Fe90Zr7B3 alloy

High-resolution electron microscopy (HREM) reveals in the as-quenched Fe₉₀Zr₇B₃ alloy the existence of medium range ordered (MRO) regions 1-2 nm in size. Transmission Mössbauer spectroscopy confirms that these regions are α-Fe MRO ones. Above the Curie point of the amorphous phase (T_C=(257±2)K) they behave like non-interacting superparamagnetic particles with the magnetization decreasing linearly with the temperature. For these particles the average magnetic moment of 390μ_B and the average size of 1.7 nm, in excellent agreement with HREM observations, were estimated. The maximum of the isothermal magnetic entropy change at the maximum magnetizing field induction of 2 T occurs at the Curie temperature of the amorphous phase and equals to 1.05 Jkg⁻¹ K⁻¹. The magnetic entropy changes exhibit the linear dependence on the maximum magnetizing field induction in the range 0.5-2 T below, near and above T_C. Such correlations are attributed to superparamagnetic behavior of α-Fe MRO regions.     

Synthesis, biology, and modeling of a C-4 carbonyl C,D-seco-taxoid

A C,D-seco-paclitaxel derivative 26 was prepared from taxine and tested for biological activity. Chemical reactivity of the seco-compounds proved to be substantially modified, with respects to taxoids. The corresponding C,D-seco-taxoid does not show tubulin stabilizing activity or cytotoxicity. Explanation of these observations based on molecular modeling is provided.     

A combined isotropic-kinematic hardening model for the simulation of warm forming and subsequent loading at room temperature

A coupled isotropic-kinematic hardening material model was developed based on phenomenological observations of performed two stage experiments on a medium carbon steel – SAE 1144, where the first deformation is performed at elevated temperatures and the second deformation at room temperature. Above all, deformations with orthogonal loading at various temperatures were investigated in order to determine the influence of the loading direction as well as of the temperature. Bergström’s theory of work hardening as well as the nonlinear kinematic hardening of an Armstrong–Frederick type were used as a basis for the model development. In the proposed model a relationship between material coefficients of the classical Bergström model and temperature was investigated. The aim of the new material model was to introduce the least possible amount of new parameters as well as to facilitate the mathematical determination of parameters during the fitting of the model with experimental data. The developed model was implemented in an in-house FE-Code in order to simulate the material behavior due to the dynamic strain aging and the hardening behavior after the dynamic strain aging process. Representative simulation results were compared with the experimental data in order to validate the efficiency and the application range of the model.     

RbCl在H2O-DMF混合溶剂中活度系数的测定

应用Corning-价阳离子选择电极（M~＋－ISE）和Orion氯离子选择电极组成可逆电池，CI~－－ISE|RbCl（m），H2O（1－x），DMF（x）M~ －ISE．测量该电池标准电动势E_m，运用扩展的Debye－Hckel公式，计算RbCl在283．15至318．15K七个温度下由H2O至H2O－DMF混和溶剂的标准迁移自由能ΔG和在不同组成（H2O－DMF）混合溶剂中平均离子活度系数γ±，并对迁移自由能及活度系数随混合溶剂有机物组份的摩尔分数的变化进行了讨论。     

Kinetic studies on the formation of N-nitroso compounds

Acetic acid/acetate ion buffer acts catalytically upon the nitrosation of amines under conditions in which the only nitrosating agents are N₂O₃ and NOBr, but inhibits nitrosation by H₂NO ₂ ⁺ . The kinetic characteristics of these phenomena have been analysed quantitatively and compared with similar effects caused by the solventsTHF, DMSO and dioxane. The experimental results show that this behaviour is an effect of the medium.

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Kinetische Untersuchungen zur Bildung von N-Nitroso-Verbindungen, 8. Mitt.: Nachweis eines Medium-Effekts von Essigsäure/Acetat-Puffer auf die Geschwindigkeitskonstante der Nitrosierung

Zusammenfassung Essigsäure/Acetat-Puffer wirkt bei der Nitrosierung von Aminen katalytisch, unter Bedingungen, wo die alleinigen nitrosierenden Agentien N₂O₃ und NOBr sind; andererseits wird die Nitrosierung durch H₂NO ₂ ⁺ unterbunden. Die kinetischen Charakteristika dieses Phänomens wurden quantitativ analysiert und mit ähnlichen Effekten der LösungsmittelTHF, DMSO und Dioxan verglichen. Die experimentellen Ergebnisse zeigen, daß dieses Verhalten auf einen Mediumeffekt zurückzuführen ist.

     

Voltammetry using a dental amalgam electrode for heavy metal monitoring of wines and spirits

We have introduced a non-toxic electrode material similar to dental amalgam for use in voltammetry. Its electrochemical properties are like a silver electrode. However, it possesses a higher overvoltage towards hydrogen than silver, and therefore enables detection of metals like zinc, nickel and cobalt. As such solid electrodes are found to give stable results over several weeks, without any maintenance, and because this method greatly facilitates monitoring of heavy metals, attempts to apply such methods to various samples have been are carried out. The present paper deals with the determination of zinc and lead at nanogram per milliliter levels in wines and spirits with only minor treatment of the samples. The procedure may easily be adapted to continuous monitoring.We have previously found that audible sound may greatly increase the voltammetric signal using liquid mercury as well as silver as electrode material. This is also applied to the actual systems.Finally, model determinations of thallium in brandy with the dental amalgam electrode are compared with atomic absorption spectrometric (AAS) measurements. It was found that the electrode could be used repeatedly, without fouling, and with results close to those found by the AAS method.     

Preparation of a novel biodegradable film by co-fermentation of straw and shrimp shell with Aureobasidium pullulans and Photobacterium sp. LYM-1

The green and high-value recycling of shrimp shell and straw remains a worldwide problem. This study aimed to investigate the potential utilization of a fermentation broth (FB) which contains shrimp shell and straw as a new source for preparation of biodegradable films. Aureobasidium pullulans and Photobacterium sp. LYM-1 were used in the fermentation. The cellulase activity was 115.92 U/mL and chitinase activity was 17.89 U/mL in FB. The polysaccharides concentration in FB was 1.05 mg/mL after 7 days of fermentation. An eco-friendly PVA-reinforced FB biodegradable film (FBBF) was successfully prepared and the effect of different plasticizers and surfactants on the mechanical, structural, and impermeability properties of the film was determined. The formation of new bonds between PVA and FB was proved by FTIR spectroscopy. The FBBF containing 0.25 % (w/v) glycerol and 0.01 % (v/v) tween-20 showed better strength properties. Elongation and water-swelling properties were highly improved by adding 0.2 % (m/v) citric acid. According to FE-SEM images, the smooth and tight surface of citric acid added FBBF was observed. Interestingly, the FBBF film showed good heat/moisture capacity, antifungal, and degradation properties. This report reveals a new green, and high-value recycling of straw and shrimp shell by the co-fermentation with A. pullulans and Photobacterium sp. LYM-1. It is also a novel way for the preparation of biodegradable film.