Die Einwirkung von adosrbiertem Polystyrol auf die Stabilit?t von Dispersionen von graphitierter Kohle in Toluol

Ohne Zusammenfassung     

Measurement of the oxidative stability of polyethylene by differential thermal analysis

An evaluation has been made of the experimental features critical to the evaluation of the oxidative stability of polyethylene using constant temperature DTA, with particular reference to the control and measurement of the sample temperature.     

The photoelectron spectrum and molecular geometry of bicyclo[2.1.1]hexane

The He(I) photoelectron spectrum of bicyclo[2.1.1]hexane shows excellent correlation with a theoretical spectrum based on the eigenvalues obtained in an ab initio calculation at the theoretical molecular geometry. By contrast, a calculation performed at the experimental geometry exhibits an effect of enhanced ring strain in showing a first ionization energy which is considerably lower than the experimental value. This observation offers experimental support for the recent claim that the published structure for bicyclo [2.1.1]hexane based on electron-diffraction measurements is incorrect. It also accounts for inconsistencies observed in the calculated values of some spin—spin coupling constants for substituted bicyclo[2.1.1]hexanes.     

Mode effects in second harmonic generation and their uses for laser stabilization

The influence of laser modes on second harmonic generation has been investigated using a three mode He-Ne laser operating at 633 nm as the source of the fundamental radiation. Mode locking which occurs when the laser modes are symmetrically placed relative to the centre of the gain profile enhances the second harmonic signal. This effect has been used to stabilize the frequency of the He-Ne laser to ± 1.5 MHz.     

Aluminium triflate: a remarkable Lewis acid catalyst for the ring opening of epoxides by alcohols

Al(OTf)3 was found to be an extremely effective catalyst (at ppm levels) for ring opening reactions of epoxides using a range of alcohols.     

The effects of substrate orientation on the mechanism of a phosphotriesterase

While the underlying chemistry of enzyme-catalyzed reactions may be almost identical, the actual turnover rates of different substrates can vary significantly. This is seen in the turnover rates for the catalyzed hydrolysis of organophosphates by the bacterial phosphotriesterase OpdA. We investigate the variation in turnover rates by examining the hydrolysis of three classes of substrates: phosphotriesters, phosphothionates, and phosphorothiolates. Theoretical calculations were used to analyze the reactivity of these substrates and the energy barriers to their hydrolysis. This information was then compared to information derived from enzyme kinetics and crystallographic studies, providing new insights into the mechanism of this enzyme. We demonstrate that the enzyme catalyzes the hydrolysis of organophosphates through steric constraint of the reactants, and that the equilibrium between productively and unproductively bound substrates makes a significant contribution to the turnover rate of highly reactive substrates. These results highlight the importance of correct orientation of reactants within the active sites of enzymes to enable efficient catalysis.     

Effect of sulfur coverage on Fe(110) adhesion: a DFT study

The effect of adsorbed S at different coverages on the adhesion of Fe(110) surfaces in match and mismatch is examined using density functional theory (DFT). S is adsorbed in atop, bridge, and 4-fold hollow sites on one side of the interface in c(2 x 2) and p(1 x 1) arrangements, corresponding to coverages of 1/2 and 1 monolayer, respectively. The calculated adhesion energy values at different interfacial separations are fitted to the universal binding energy relation, and the effect of the S coverages on the adhesive strength is analyzed. The effect of relaxation of the interfaces at equilibrium is also investigated, and the resulting interfacial structures and related magnetic and charge density properties are compared.     

Observation of a multiply ionized plasma with index of refraction greater than one

We present clear experimental evidence showing that the contribution of bound electrons can dominate the index of refraction of laser-created plasmas at soft x-ray wavelengths. We report anomalous fringe shifts in soft x-ray laser interferograms of Al laser-created plasmas. The comparison of measured and simulated interferograms shows that this results from the dominant contribution of low charge ions to the index of refraction. This usually neglected bound electron contribution can affect the propagation of soft x-ray radiation in plasmas and the interferometric diagnostics of plasmas for many elements.     

The preference for anti over Gauche migration in the Baeyer-Villiger reaction

Explanations for stereoselectivity in the Baeyer-Villiger reaction have relied on the assumption that the antiperiplanar (app) group migrates. However, the magnitude of the preference for app-migration over gauche migration is unknown. To investigate this, the energy differences between the two were estimated from ab initio calculations. App-migration was found to be the preferred pathway since no transition structure could be located for gauche migration. Barriers for gauche migration were estimated by performing constrained optimizations. App-migration was found to be strongly favored with a barrier that is at least 3.8 kcal/mol and as much as 58.0 kcal/mol lower in energy than the gauche migration barrier.