A Symmetrically π-Expanded Carbazole Incorporating Fluoranthene Moieties

A novel doubly cyclopentannulated carbazole which is accessible through a successive π-expansion of di(1-naphthylamine) is disclosed. The carbazole moiety is generated in the final step through intramolecular oxidative coupling. The π-expansion of carbazole resulted in strongly altered optoelectronic and electrochemical properties. The solid-state structure features an interesting packing motif with alternating face-to-face π⋅⋅⋅π and edge-to-face C−H⋅⋅⋅π interactions. The experimental findings were corroborated by theoretical calculations.     

Coupled Processes in Charged Porous Media: From Theory to Applications

Charged porous media are pervasive, and modeling such systems is mathematically and computationally challenging due to the highly coupled hydrodynamic and electrochemical interactions caused by the presence of charged solid surfaces, ions in the fluid, and chemical reactions between the ions in the fluid and the solid surface. In addition to the microscopic physics, applied external potentials, such as hydrodynamic, electrical, and chemical potential gradients, control the macroscopic dynamics of the system. This paper aims to give fresh overview of modeling pore-scale and Darcy-scale coupled processes for different applications. At the microscale, fundamental microscopic concepts and corresponding mass and momentum balance equations for charged porous media are presented. Given the highly coupled nonlinear physiochemical processes in charged porous media as well as the huge discrepancy in length scales of these physiochemical phenomena versus the application, numerical simulation of these processes at the Darcy scale is even more challenging than the direct pore-scale simulation of multiphase flow in porous media. Thus, upscaling the microscopic processes up to the Darcy scale is essential and highly required for large-scale applications. Hence, we provide and discuss Darcy-scale porous medium theories obtained using the hybrid mixture theory and homogenization along with their corresponding assumptions. Then, application of these theoretical developments in clays, batteries, enhanced oil recovery, and biological systems is discussed.

     

Liquid Chromatography Analysis of Reactive Oxoammonium Cations

This study presents the first liquid chromatography method for the quantitative and qualitative analysis of highly reactive oxoammonium cations based on a simple derivatization reaction. Rapid 1,2-electrophilic addition reactions with olefins were used to transform these reactive species into analyzable derivates. Three model substances were chosen to represent each of the main application fields of oxoammonium cations and to demonstrate the versatility of the method. The measuring protocol was validated according to the ICH and USP guidelines. The method revealed an excellent linearity (R²?=?0.9980–0.9990) with a low limit of detection (0.16–0.14 mmol L^?1) and a low limit of quantification (0.55–0.43 mmol L^?1). The protocol was finally used to determine the oxoammonium cations in the presence of their corresponding radical, showing a robustness against impurity concentration of up to approx. 30%.

     

Effect of deviatoric nonassociativity on the failure prediction for elastic–plastic materials

This paper presents a theoretical study of the effect of nonassociativity of the plastic flow rule on the critical plastic modulus for discontinuous bifurcation in an elastic–plastic material. Nonassociativity in both the spherical and the deviatoric spaces are considered, with an emphasis on the effect of nonassociativity in the deviatoric space. A particular form of nonassociativity in the deviatoric space is introduced, where the projections of the plastic flow direction and the normal to the yield surface are assumed to have the same length but the projection of plastic flow direction is allowed to lag that of the normal by an angle. It is shown that even for the simple yield surface of von Mises, nonassociativity in the deviatoric space can lead to a bifurcation for a load parameter significantly lower than the value predicted with an associated flow rule.     

Comparative analysis of the structure of sterically stabilized ferrofluids on polar carriers by small-angle neutron scattering

Results of experiments on small-angle neutron scattering from ferrofluids on polar carriers (pentanol, water, methyl-ethyl-ketone), with double-layer sterical stabilization of magnetic nanoparticles, are reported. Several types of spatial structural organization are observed. The structure of highly stable pentanol-based samples is similar to that of stable ferrofluids based on organic non-polar carriers (e.g., benzene) with mono-layer covered magnetic nanoparticles. At the same time, the effect of the interparticle interaction on the scattering is stronger in polar ferrofluids because of the structural difference in the surfactant shell. The structure of the studied methyl-ethyl-ketone- and water-based ferrofluids essentially different from the previous case. The formation of large (>100 nm in size) elongated or fractal aggregates, respectively, is detected even in the absence of external magnetic field, which corresponds to weaker stability of these types of ferrofluids. The structure of the fractal aggregates in water-based ferrofluids does not depend on the particle concentration, but it is sensitive to temperature. A temperature increase results in a decrease in their fractal dimension reflecting destruction of the aggregates. In addition, in water-based ferrofluids these aggregates consist of small (radius approximately 10 nm) and temperature-stable primary aggregates.     

Data shaving: a focused screening approach

The number of compounds available for evaluation as part of the drug discovery process continues to increase. These compounds may exist physically or be stored electronically allowing screening by either actual or virtual means. This growing number of compounds has generated an increasing need for effective strategies to direct screening efforts. Initial efforts toward this goal led to the development of methods to select diverse sets of compounds for screening, methods to cluster actives into related groups of compounds, and tools to select compounds similar to actives of interest for further screening. In this work we extend these earlier efforts to exploit information about inactive compounds to help make rational decisions about which sets of compounds to include as part of a continuing screening campaign, or as part of a focused follow-up effort. This method uses the information from inactive compounds to "shave" off or deprioritize compounds similar to inactives from further consideration. This methodology can be used in two ways: first, to provide a rational means of deciding when sufficient compounds containing certain structural features have been tested and second as a tool to enhance similarity searching around known actives. Similarity searching is improved by deprioritizing compounds predicted to be inactive, due to the presence of structural features associated with inactivity.     

Trennleistung und Bodenzahlen bei gaschrcmatographischen Analysen mit Capillarkolonnen

Zusammenfassung An Hand von experimentellen und berechneten Daten von Capillarkolonnen wird die von Purnell abgeleitete Formel für die bei einer bestimmten Trennung nötige theoretische Bodenzahl diskutiert. Gleichzeitig wird der Begriff der theoretischen Bodenzahl selbst als grobe Maß-zahl für die Trennleistung einer Kolonne angezweifelt. Es wird gezeigt, daß man mit Hilfe einer einfachen Größe, des Trennwertes, wesentlich besser die Trennleistung einer Kolonne charakterisieren und auch die Möglichkeit einer gewünschten Trennung abschätzen kann.Dieser Aufsatz stellt einen Teil der Promotionsarbeit von G. Schreyer dar.