Two-dimensional, pyrazine-based nonlinear optical chromophores with ruthenium(II) ammine electron donors

Six new nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by complexing a known pro-ligand with electron donating {Ru(II)(NH(3))(5)}(2+) or trans-{Ru(II)(NH(3))(4)(py)}(2+) (py = pyridine) centers. These cationic complexes have been characterized as their PF(6)(-) salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible d → π* metal-to-ligand charge-transfer (MLCT) absorptions gain intensity on increasing the number of Ru(II) centers from one to two, but remain at constant energy. One or two Ru(III/II) redox processes are observed which are reversible, quasi-reversible, or irreversible, while all of the ligand-based reductions are irreversible. Molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) at 1064 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly two-dimensional (2D) in character, with dominant "off-diagonal" β(zyy) components. Stark (electroabsorption) spectroscopic measurements on the MLCT bands also allow the indirect determination of estimated static first hyperpolarizabilities β(0). Both the HRS and the Stark-derived β(0) values increase on moving from mono- to bimetallic complexes, and substantial enhancements in NLO response are achieved when compared with one-dimensional (1D) and 2D monometallic Ru(II) ammine complexes reported previously.     

Einführung in prädikatives und funktionales Denken

A particular interest for invariances on the one hand and variability on the other hand as seen in sationary and moving objects respectively has often led people to more or less severe disagreements. The notions of «predicative thinking» versus «functional thinking» describe a cognitive pattern that tries to explain the preference or even special capability for either one of the two view points. Meanwhile, there are not only numerous qualitative experimental results that prove the usefulness of this theoretical construct, but also an EEG-study and several studies involving eye-movement analysis that emphasise quantitative evidence. As aspects of predicative thinking have been studied quite frequently in cognitive psychology, there is an accumulated need for studies of functional thinking. Primary school education shows that functional approaches have been neglected in spite of advocates of the operational principle. Anyhow, there are didactical materials like the Addition-, Multiplication-Landscape, the spiral staircase for calculating or the Dynamic Labyrinths that are very well suited to demand and promote functional thinking.     

Immobilized β-cyclodextrin on surface-modified carbon-coated cobalt nanomagnets: reversible organic contaminant adsorption and enrichment from water

Surface-modified magnetic nanoparticles can be used in extraction processes as they readily disperse in common solvents and combine high saturation magnetization with excellent accessibility. Reversible and recyclable adsorption and desorption through solvent changes and magnetic separation provide technically attractive alternatives to classical solvent extraction. Thin polymer layered carbon-coated cobalt nanoparticles were tagged with β-cyclodextrin. The resulting material reversibly adsorbed organic contaminants in water within minutes. Isolation of the immobilized inclusion complex was easily carried out within seconds by magnetic separation due to the strong magnetization of the nanomagnets (metal core instead of hitherto used iron oxide). The trapped molecules were fully and rapidly recovered by filling the cyclodextrin cavity with a microbiologically well accepted substitute, e.g., benzyl alcohol. Phenolphthalein was used as a model compound for organic contaminants such as polychlorinated dibenzodioxins (PCDDs) or bisphenol A (BPA). Fast regeneration of nanomagnets (compared to similar cyclodextrin-based systems) under mild conditions resulted in 16 repetitive cycles (adsorption/desorption) at full efficiency. The high removal and regeneration efficiency was examined by UV-vis measurements at chemical equilibrium conditions and under rapid cycling (5 min). Experiments at ultralow concentrations (160 ppb) underline the high potential of cyclodextrin modified nanomagnets as a fast, recyclable extraction method for organic contaminants in large water streams or as an enrichment tool for analytics.     

The porosity, acidity, and reactivity of dealuminated zeolite ZSM-5 at the single particle level: the influence of the zeolite architecture

A combination of atomic force microscopy (AFM), high‐resolution scanning electron microscopy (HR‐SEM), focused‐ion‐beam scanning electron microscopy (FIB‐SEM), X‐ray photoelectron spectroscopy (XPS), confocal fluorescence microscopy (CFM), and UV/Vis and synchrotron‐based IR microspectroscopy was used to investigate the dealumination processes of zeolite ZSM‐5 at the individual crystal level. It was shown that steaming has a significant impact on the porosity, acidity, and reactivity of the zeolite materials. The catalytic performance, tested by the styrene oligomerization and methanol‐to‐olefin reactions, led to the conclusion that mild steaming conditions resulted in greatly enhanced acidity and reactivity of dealuminated zeolite ZSM‐5. Interestingly, only residual surface mesoporosity was generated in the mildly steamed ZSM‐5 zeolite, leading to rapid crystal coloration and coking upon catalytic testing and indicating an enhanced deactivation of the zeolites. In contrast, harsh steaming conditions generated 5–50 nm mesopores, extensively improving the accessibility of the zeolites. However, severe dealumination decreased the strength of the Brønsted acid sites, causing a depletion of the overall acidity, which resulted in a major drop in catalytic activity.