Substrate binding and activation via pendant hydrogen-bonding groups as an approach to biomimetic homogeneous catalysis

In a biomimetic approach to organometallic catalysis, pendant hydrogen-bonding groups are shown to influence the chemistry of ligand binding and activation in an iridium complex. Such groups can bind a substrate by hydrogen bonding and so offer the possibility of a biomimetic approach to catalysis where binding is controlled via molecular recognition. Because catalyst design in this area may be challenging, combinatorial and rapid screening methods may be needed to assay potential catalysts and initial progress on developing these methods for hydrosilation of alkenes and imines is described. Catalysis of aldehyde imination and the origin of pK_a changes of bound H₂ are discussed.     

Enhanced ion acceleration with extremely thin foils

Enhanced backward-acceleration of ions is experimentally observed when ultra-short, high-intensity and ultra-high-contrast laser pulses interact with thin foils having thicknesses in the order of the penetration depth of the laser light. Below the experimentally observed optimum foil thickness for the maximum ion energy versus thickness, there arises a second peak. 1D simulations on foils with an initial plasma density gradient show a similar trend as the experiment. It appears that in this regime of extremely thin foils it is important to take into account the limited expansion of the plasma that is formed by ultra-high-contrast pulses.     

Observation of trielectronic recombination in Be-like Cl ions

Recombination involving the core excitation of two electrons, which may be termed trielectronic recombination, has been experimentally identified for the first time. Using Cl13+ ions circulating in the TSR heavy-ion storage ring, we have observed surprisingly strong low-energy trielectronic recombination resonances, comparable to the dielectronic process. At higher electron-ion collision energies, trielectronic recombination is suppressed due to the autoionization of the triply excited intermediate state into excited final states. The formation of the intermediate state depends sensitively on configuration mixing, making trielectronic recombination a challenge to atomic-structure calculations.     

Eine abstrakte Theorie der Kegel- und Segmentbedingungen

We develop an abstract theory of geometric regularity conditions for subsets of normed linear spaces, of the type which occurs in the theory of Sobolev spaces (cone conditions, …). The theory is to systematize the diversity of existing conditions, to replace complicated conditions by simpler ones, and to clarify the interplay between different conditions. Our main result is a very general decomposition theorem.     

Radical Protection by Differently Composed Creams in the UV/VIS and IR Spectral Ranges

Modern sunscreens are well suited to provide sufficient protection in the UV range because the filter substances absorb or scatter UV radiation. Although up to 50% of radicals are formed in the visible and infrared spectral range during solar radiation protection strategies are not provided in this range. Previous investigations of commercially available products have shown that in addition to physical filters, antioxidants (AO) are necessary to provide protective effects in the infrared range by neutralizing already formed radicals. In this study, the efficacy of filter substances and AO to reduce radical formation in both spectral ranges was investigated after UV/VIS or IR irradiation. Optical properties and radical protection were determined for the investigated creams. It was found that organic UV filters lower radical formation in the UV/VIS range to 35% compared to untreated skin, independent of the presence of AO. Further reduction to 14% was reached by addition of 2% physical filters, whereas physical filters alone were ineffective in the UV/VIS range due to the low concentration. In contrast, this filter type reduced radical formation in the IR range significantly to 65%; similar effects were aroused after application of AO. Sunscreens which contain organic UV filters, physical filters and AO ensure protection in the complete solar spectrum.     

Abstrakte Hardy-Algebren und Konjugation

Ohne Zusammenfassung     

Demonstrating the feasibility of monitoring the molecular-level structures of moving polymer/silane interfaces during silane diffusion using SFG

In this paper, the feasibility of monitoring molecular structures at a moving polymer/liquid interface by sum frequency generation (SFG) vibrational spectroscopy has been demonstrated. N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane (AATM, NH2(CH2)2NH(CH2)3Si(OCH3)3) has been brought into contact with a deuterated poly(methyl methacrylate) (d-PMMA) film, and the interfacial silane structure has been monitored using SFG. Upon initial contact, the SFG spectra can be detected, but as time progresses, the spectral intensity changes and finally disappears. Additional experiments indicate that these silane molecules can diffuse into the polymer film and the detected SFG signals are actually from the moving polymer/silane interface. Our results show that the molecular order of the polymer/silane interface exists during the entire diffusion process and is lost when the silane molecules traverse through the thickness of the d-PMMA film. The loss of the SFG signal is due to the formation of a new disordered substrate/silane interface, which contributes no detectable SFG signal. The kinetics of the diffusion of the silane into the polymer have been deduced from the time-dependent SFG signals detected from the AATM molecules as they diffuse through polymer films of different thickness.     

Comparison of chromium and nickel uptake of plants grown in different soils

The chromium and nickel uptake of ryegrass has been examined in pot experiments in extremely different soils, poor sandy and fertile black chernozem. The effect of calcium carbonate doses and nitrogen supply on heavy metal uptake of the plant has been studied for chromium and nickel loadings (0–100 mg/kg Cr³⁺ or Ni²⁺) applied as inorganic salts. The ability to uptake Cr³⁺ and Ni²⁺ differs significantly and is highly affected by the characteristics of soils, and depends on the metal investigated. The heavy metal uptake of the plant differs significantly in acid, colloid deficient sandy soils; while artificial chromium contamination did not modify the dry-matter production in the pots in either soil, a large quantity of nickel reduced the yields significantly. Nitrogen application did not change significantly the uptake of heavy metals. Lime application reduced the Ni²⁺ uptake of plants considerably, especially in sandy soil. In case of a calcium carbonate addition the dry-matter production of the plant was not affected by nickel. In chernozem soil the effect of lime application – i.e., the reduction of nickel uptake – was of a lesser degree. The significantly lesser Cr³⁺ uptake was further limited by a calcium carbonate application for both soils studied. A graphic presentation of these effects is given.     

In vitro preparation of68Ga-labelled transferrin

Systematic investigations into the practical problems of labelling transferrin with⁶⁸Gain vitro are presented. A chemical purification of the⁶⁸Ga generator eluate is described and the working conditions whereby several millicuries of⁶⁸Ga may be bound quantitatively onto a few milligrams of transferin are defined.