Bestimmung von organisch gebundenem Schwefel

Ohne Zusammenfassung     

Independent component analysis of photoacoustic depth profiles

Photoacoustic spectroscopy is a powerful tool to non-destructively retrieve depth related information with minimal sample preparation from heterogeneous samples. Using a phase modulated step-scan arrangement and digital signal processing a series of spectra with effectively different modulation frequencies, probing different thermal diffusion lengths within a sample, can be collected simultaneously. In this report independent component analysis is used to analyze photoacoustic data acquired from a multilayer sample in an attempt to isolate the spectra of the constituent layers. The ICA findings are compared to the approach of eliciting this information through difference spectroscopy. The results suggest that ICA may offer substantial benefits for segmentation of PAS depth profiles without user intervention. This approach can be useful in analysis of complex heterogeneous samples when one has no prior knowledge of their constituents or their distribution in the sample.     

Self-diffusion and ‘order–order’ kinetics in B2-ordering AB binary systems with a tendency for triple-defect formation: Monte Carlo simulation

Self-diffusion of component atoms and ‘order–order’ relaxations in a B2-ordering binary system AB showing a tendency for triple-defect formation were consistently simulated by means of two Monte Carlo techniques. In view of a strict correlation between antisite-defect and vacancy concentrations the Kinetic Monte Carlo (KMC) simulations were implemented with a temperature-dependent vacancy concentration determined by means of Semi-Grand Canonical Monte Carlo (SGCMC) simulations. The Ising model of the system was completed with local-configuration-dependent saddle-point energy parameters related to vacancy mediated atomic jumps. The simulations elucidated the atomistic origin of the experimentally observed low rate of ‘order–order’ relaxations in NiAl, as well as reproduced the experimental relation between the activation energies for ‘order–order’ kinetics and Ni self-diffusion in NiAl. Higher value of the deduced activation energy for atomic migration with respect to the effective energy barriers related to individual atomic jumps indicated their high correlation.     

p‐Decyl­phenyl isocyanide and p‐decyl­benzo­nitrile: isomorphous iso­nitrile/nitrile isomers

p‐Decyl­phenyl isocyanide, p‐C₁₀H₂₁–C₆H₄–NC or C₁₇H₂₅N, and p‐decyl­benzo­nitrile, p‐C₁₀H₂₁–C₆H₄–CN or C₁₇H₂₅N, are isomorphous. The mol­ecules lie in mirror planes, with the C₆ rings perpendicular to the mirror. The packing of both mol­ecules includes an aliphatic region, with close to ideal packing of the C₁₀H₂₁ chains, and an aromatic region, with phenyl ring–CN interactions. In addition, the CN ends of the mol­ecules are also involved in a CN⋯NC dipolar interaction.     

(μ‐2,11‐Dithia­[3.3]paracyclo­phane‐κ2S:S′)bis­[(6‐carboxy­pyridine‐2‐carboxylato‐κ2N,O6)silver(I)]: a mixed‐ligand silver‐based dinuclear compound

In the title complex, [Ag₂(C₇H₄NO₄)₂(C₁₆H₁₆S₂)], each Ag^I atom is trigonally coordinated by one S atom of a 2,11‐dithia­[3.3]paracyclo­phane (dtpcp) ligand, and by one N and one O atom of a 6‐carboxy­pyridine‐2‐carboxylate ligand. Dtpcp acts as a bidentate ligand, bridging two inversion‐related Ag^I atoms to give a dinuclear silver(I) compound. The dinuclear moieties are inter­connected via O—H·O hydrogen bonds to form a two‐dimensional zigzag sheet. Two such sheets are inter­woven viaπ–π inter­actions between pyridine rings, affording an inter­woven bilayer network.     

Alkylated Aromatic Thioethers with Aggregation‐Induced Emission Properties—Assembly and Photophysics

In this contribution, we present the synthesis and self‐assembly of alkylated thioethers with interesting photophysical properties. To this end, the emission, absorption and excitation spectra in organic solvents and as aggregates in water were measured as well as the corresponding photoluminescence quantum yields and lifetimes. The aggregates in aqueous media were visualized and measured using transmission electron microscopy. Besides that, crystal structures of selected compounds allowed a detailed discussion of the structure–property relationship. Furthermore, the mesomorphic behavior was investigated using polarized optical microscopy (POM) as well as differential scanning calorimetry (DSC).     

Measurement of total decay rates of excited states in a deuterium plasma by laser-resonance fluorescence

In a deuterium plasma with an electron density of 2.8 × 10¹³ cm^-3 and an electron temperature of 1850 K, the n = 2 level is coupled to the n = 6 level by absorption of short-pulsed laser light. Due to inelastic and superelastic electron collisions, the enhanced n = 6 population density is distributed to its neighbouring levels, i.e., n = 5 and n = 7. The laser-resonance fluorescences of the Balmer lines D₅, D₆, and D₇ were measured with time resolution. The transient behaviour of the fluorescence is compared with numerical calculations, which are based on the rate equations for population densities of a system with 5 states. It is observed that the rate coefficients of Johnson cannot explain our experimental data. The coefficients of Vriens and Smeets compare favourably with the measurements within experimental errors.     

Competitive reactions among three monomers over a catalytic surface

We studied in this work a three-monomer reaction model on one- and two-dimensional lattices. We have taken different reactivity rates among pairs of monomers and the reaction between two selected monomers was forbidden. We have employed the mean field and the pair approximation to decouple the equations of motion for the densities of single and pairs of monomers. We found the stationary states and the phase diagram of the model. We have shown that, in two dimensions and within the pair approximation, there is a first-order transition line between active and poisoned steady states.