Orbital Theory of Heterolytic Fragmentation and Remote Effects on Nitrogen Inversion Equilibria

From a molecular orbital study of model systems we derive the electronic requirements for the Grob fragmentation. The necessary condition for an allowed fragmentation in an X-C₁-C₂-C₃-N system, or the amino cation ⁺C₁-C₂-C₃-N is the level ordering A below S . This in turn is set by maximal through-bond coupling of the empty cation orbital and the nitrogen lone pair. The conformational dependence of through-bond coupling is exactly that derived by Grob, namely parallel orientation of the cation orbital (or the C-X bond), the C₂-C₃-σ-bond, and the N-lone-pair. When the C₁-C₂-C₃ and C₂-C₃-N angles are small, the through-space interaction dominates, reversing the level ordering to S below A , and consequently makes the fragmentation forbidden even though the conformational requirements for it are met. Ring closure becomes allowed. Some examples exploiting this result are presented, as well as procedures for enhancing through-bond coupling and thus fragmentation. The through-bond-effect has also kinetic consequences, allowing the definition of a new type of remote neighbouring group participation operative through bonds and not by direct overlap. The position of equilibria in nitrogen inversion processes should also be influenced by remote substituents which are π-acceptors or donors.     

Effects of upper-frequency boundary and spectral warping on speech intelligibility in electrical stimulation

Speech understanding was tested for seven listeners using 12-electrode Med-El cochlear implants (CIs) and six normal-hearing listeners using a CI simulation. Eighteen different types of processing were evaluated, which varied the frequency-to-tonotopic place mapping and the upper boundary of the frequency and stimulation range. Spectrally unwarped and warped conditions were included. Unlike previous studies on this topic, the lower boundary of the frequency and stimulation range was fixed while the upper boundary was varied. For the unwarped conditions, only eight to ten channels were needed in both quiet and noise to achieve no significant degradation in speech understanding compared to the normal 12-electrode speech processing. The unwarped conditions were often the best conditions for understanding speech; however, small changes in frequency-to-place mapping (<0.77 octaves for the most basal electrode) yielded no significant degradation in performance from the nearest unwarped condition. A second experiment measured the effect of feedback training for both the unwarped and warped conditions. Improvements were found for the unwarped and frequency-expanded conditions, but not for the compressed condition. These results have implications for new CI processing strategies, such as the inclusion of spectral localization cues.     

Preparation and characterization of core-shell latexes

Polymeric dispersions with a concentric core-shell structure of the latex particles were obtained by a two-stage emulsion polymerization technique. Conditions for the formation of shells on polymeric seeds are discussed. SANS and SAXS investigations were carried out in order to verify the core-shell structure of the particles. DSC and IR measurements indicate the existence of an interfacial layer between core and shell polymers. The results are transferred to emulsion polymers containing inorganic filler particles.     

On the computation of electronic excitations in solids

An approximation scheme is proposed for calculating electronic excitations in solids. It is described within a projection operator formalism of the Mori-Zwanzig type. The approximation consists in successively limiting the space of dynamical variables which are treated. The selection of the variables is done by making use of the local character of the correlation hole which is surrounding an electron. The method is distinct from a perturbation expansion and can be related to a variational ansatz via the Sauermann functional. The computation of the spectral density of the Green's function is reduced to the diagonalization of matrices. Their dimension depends on the required degree of accuracy of the calculations. The present method can be considered as an extension to excited states of a previously developed. Local Approach for ground state calculations.Dedicated to Prof. S. Methfessel on the occasion of his 60th birthday     

Growth and Atomic-Scale Characterization of Ultrathin Silica and Germania Films: The Crucial Role of the Metal Support

The present review reports on the preparation and atomic-scale characterization of the thinnest possible films of the glass-forming materials silica and germania. To this end state-of-the-art surface science techniques, in particular scanning probe microscopy, and density functional theory calculations have been employed. The investigated films range from monolayer to bilayer coverage where both, the crystalline and the amorphous films, contain characteristic XO₄ (X=Si,Ge) building blocks. A side-by-side comparison of silica and germania monolayer, zigzag phase and bilayer films supported on Mo(112), Ru(0001), Pt(111), and Au(111) leads to a more general comprehension of the network structure of glass former materials. This allows us to understand the crucial role of the metal support for the pathway from crystalline to amorphous ultrathin film growth.     

‘Face-to-Face’-Benzo-anellierte homologe Hypostrophene. Synthesen,Röntgenstrukturanalysen und PE-Spektren

‘Face-to-Face’ Benzo-anellated Homologous Hypostrophenes. Syntheses, X-Ray-Structure Analyses and PE Spectra ‘Face-to-face’ Benzo-anellated homologous hypostrophenes (series M ), of interest as substrates for [6 + 6]-photocycloaddition reactions, have been synthesized. From X-ray structural analyses of 13b and 13c shortest C? C distances of 2.80(2.76)/2.71 Å and interorbital angles (ω) of 129° (128°)/130° between the benzene rings have been determined. The PE spectra are discussed in the context of transannular π,π interactions.     

Ball numbers of platonic bodies

The ball number function is extended here to platonic bodies and corresponding generalized uniform distributions on platonic spheres are considered. A platonic disintegration formula of the Lebesgue measure is proved as well as a thin layers property.     

Impairment of mitochondrial calcium handling in a mtSOD1 cell culture model of motoneuron disease

Background  

Amyotrophic lateral sclerosis (ALS) is a fatal neurodegenerative disorder characterized by the selective loss of motor neurons (MN) in the brain stem and spinal cord. Intracellular disruptions of cytosolic and mitochondrial calcium have been associated with selective MN degeneration, but the underlying mechanisms are not well understood. The present evidence supports a hypothesis that mitochondria are a target of mutant SOD1-mediated toxicity in familial amyotrophic lateral sclerosis (fALS) and intracellular alterations of cytosolic and mitochondrial calcium might aggravate the course of this neurodegenerative disease. In this study, we used a fluorescence charged cool device (CCD) imaging system to separate and simultaneously monitor cytosolic and mitochondrial calcium concentrations in individual cells in an established cellular model of ALS.