(Diazoalkyl)Phosphoranes from [4 + 1]-cycloadditions of tetrahalo-orthobenzoquinones to (diazoalkyl)phosphanes [1]

The (diazoalkyl)phosphanes 4a–e undergo [4 + 1]-cycloaddition reactions with the tetrahalo-orthobenzoquinones 5a,b to furnish the previously unknown (diazoalkyl)phosphoranes 6a–h . The structure of product 6h has been investigated by X-ray crystallography.     

Swelling and fractal heterogeneities in networks

In this paper we revisit old swelling data on polymer networks that have not been interpreted theoretically on a closed molecular basis. If the osmotic pressure of the swollen network is compared to the osmotic pressure of the corresponding uncrosslinked solution unsolved problems appear, when the relative osmotic pressure is plotted against the degree of swelling, i.e. the deformation due to swelling. A significant maximum appears which cannot be explained by any of the recently derived elastic models, such as junction constraint or other entanglement models. It is suggested in this paper that the maximum is a consequence of structural heterogeneities of fractal nature. If such fractal heterogeneities are assumed a strong maximum in the relative osmotic pressure can be reproduced. The physical reason is the different thermodynamic behavior of uncrosslinked linear chains and crosslinked self-similar (non-linear) polymers. The conclusion is supported by numerical (Monte Carlo) simulations.     

Effect of filler networking on the dynamic mechanical properties of crosslinked polymer solids

The strain amplitude dependence of the viscoelastic properties of eight different carbon blacks dispersed in two different rubbery networks is investigated and evaluated within the Cole-Cole approach for the complex elastic modulus at fixed temperature and frequency. This approach is based on the Kraus model of strain-dependent filler agglomeration-deagglomeration rates. We find a non-integer universal shape exponent of the Cole-Cole process that obviously depends only on the surrounding polymer matrix but is independent of the filler grade. The exponent can be related to the fractal dimension of the carbon black surface.     

Dynamic mechanical investigations of different substituted cellulose o-silyl ethers

In contrast to many cellulose derivatives, the cellulose O-silyl ethers with bulky side groups exhibit scarcely a change in glass transition temperature by a variation of the degree of substitution (DS) or degree of polymerization (DP) or by introducing phenyl carbamate groups for the remaining hydroxyls along the main chain. However, a substitution of these hydroxyls by flexible acetate groups lowers the glass transition temperature considerably. The secondary dispersion (relaxation) behavior is strongly influenced by the various substituents and can be correlated to specific motions of the molecules. The dynamic mechanical properties are also dependent on the kind of preconditioning of the samples.     

Thermally Induced Carbohydroxylation of Styrenes with Aryldiazonium Salts

The radical carbohydroxylation of styrenes with aryldiazonium salts has been achieved under mild thermal conditions. A broad range of aryldiazonium salts was tolerated, and the reaction principle based on a radical–polar crossover mechanism could be extended to carboetherification as well as to a two‐step, metal‐free variant of the Meerwein arylation leading to stilbenes.     

Thermal relaxation times and heat conduction in β-cristobalite and α-quartz silica structures

Several studies have shown the key role of the rigid unit modes, i.e. rotational motions between neighbouring SiO₄ tetrahedra, in glass and in β-cristobalite due to the disorder generated by the large atomic amplitudes. They do not however reach a conclusion concerning heat conduction. To determine the nature of the heat carriers in the amorphous phase, we carry out an ultrashort timescale analysis of heat transfer in β-cristobalite; the behaviour is comparable to that of amorphous silica, as shown by our density of states and heat flux autocorrelation function calculations. We prove that rigid unit modes can be identified as the heat carriers by showing that the thermal relaxation time is in very good agreement with the rigid unit mode relaxation time predicted in the literature. Finally, we provide thermal conductivity data for β-cristobalite which are not available in the literature.     

Dispersion and localization of electronic states at a ferrocene/Cu(111) interface

Low-temperature scanning tunneling microscopy and spectroscopy combined with first-principles simulations reveal a nondissociative physisorption of ferrocene molecules on a Cu(111) surface, giving rise to ordered molecular layers. At the interface, a 2D-like electronic band is found, which shows an identical dispersion as the Cu(111) Shockley surface-state band. Subsequent deposition of Cu atoms forms charged organometallic compounds that localize interface-state electrons.     

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