From fibers to micelles using point-mutated amphiphilic peptides

Biocompatible, self-assembled nanostructures are attracting ever more attention, in particular in aqueous media for biomedical applications. Here, we present the successful, solid-phase peptide synthesis (SPPS) and characterization of short amino acid sequences with amphiphilic character with the aim of gaining insight into their self-assembled, supramolecular structures. The peptide design includes three parts: (a) a charged lysine part, (b) an acetylated lysine part, and (c) a constant hydrophobic rodlike helix, based on gramicidin A (gA). By stepwise replacement of free lysine (K) with acetylated lysine (X) we generated a library of a total of 10 peptides, Ac-X(8)-gA and K(m)X(8-m)-gA (m ranging from 0 to 8). By using point mutations, we adjusted the degree of acetylation (DA) and thus the overall amphiphilicity of the peptides, which led to a change in the secondary structure in the aqueous environment from a β-sheet to an α-helix. This transition generated a significant change in the morphology of the self-assembled structures from fibers to micelles. Two different regions were observed for the conformation of the hydrophilic part of the peptide: one region, a β-sheet-like secondary structure, inducing fiber formation (high DA), the other an α-helical-like secondary structure, generating micelle formation (moderate and low DA). The micellar structures depended on the degree of acetylation, which influenced their critical micelle concentration (cmc). These morphology regions were determined by a combination of circular dichroism, dynamic light scattering, surface tension, and transmission electron microscopy, which allowed us to correlate the generated supramolecular architectures with the fine changes obtained by means of the point mutation strategy.     

Neue ternäre KäfigVerbindungen in den Systemen Barium–2B(3B)-Element-Germanium

New Ternary Clathrate Compounds in the Systems Barium–2B(3B)-Elements–Germanium In the ternary systems Barium–2B(3B) elements–germanium new ternary variants of the K₈Ge₄₆ clathrate structure and hints to clathrates of another composition have been found. Results of structure determination of Ba₈Cd₈Ge₃₈ (cubic, a = 1096.2 pm; space group Pm3n) show a prevailing ordered distribution of Cd and Ge in the sites of the structure building atoms. According to electron balance Ba₈Cd₈Ge₃₈ can be assumed to be a ternary Zintl compound.     

Diffusion of gold in silicon studied by means of neutron-activation analysis and spreading-resistance measurements

In- and out-diffusion of gold in silicon were investigated with the aid of a neutronactivation analysis in combination with mechanical sectioning or by the spreadingresistance technique. In-diffusion profiles in the range 1371–1073 K show that Au diffuses in Si mainly via the so-called kick-out mechanism. From the Au diffusion and solubility measurements the interstitialcy contributionD _I ^SD to the Si self-diffusion coefficient was determined, which shows that the self-diffusion occurs to a considerable extent via selfinterstitials. Out-diffusion profiles at 1173 K were measured on wafers homogeneously supersaturated with Au. The observed decrease of the electrical activity of Au in the bulk indicates that during the out-diffusion anneal the majority of Au atoms originally dissolved substitutionally changes its configuration.     

Synthesis of the B-seco limonoid scaffold

The underlying stereochemically complex and densely functionalized scaffold of the B-seco limonoids was synthesized employing an Ireland-Claisen rearrangement as key transformation.     

ELDONET--a decade of monitoring solar radiation on five continents

The European light dosimeter network (ELDONET) comprises more than 40 stations in 24 countries on 5 continents. The present report compares solar radiation data in the photosynthetic active radiation, UV-A (315-400 nm) and UV-B (280-315 nm) wavelength ranges for 17 stations at different latitudes on the northern and southern hemispheres for up to 10 years of monitoring. While the maximal irradiances on clear days follow a latitudinal gradient due to the cosine dependence on the solar angle, the total doses strongly depend on the local climate and atmospheric conditions as well as the day-length distribution over the year. UV-B irradiances and doses are strongly influenced by the total column ozone, which is recorded for all covered stations.