Amphiphilic treelike rods at interfaces: layered stems and circular aggregation

Amphiphilic dendron-rod molecules with three hydrophilic poly(ethylene oxide) (PEO) branches attached to a hydrophobic octa-p-phenylene rod stem were investigated for their ability to form two-dimensional micellar structures on a solid surface. A treelike shape of the molecules was reported to be a major factor in the formation of nonplanar micellar structures in solution and in the bulk state (cylindrical and spherical). We observed that in these treelike amphiphilic molecules the hydrophilic terminated dendron branches assemble themselves in surface monolayers with the formation of two-dimensional layered or circular micellar structures. We suggested the formation of the planar ribbon-like structures with interdigitated layering within the loosely packed monolayers and circular, ringlike structures (2D circular aggregates) in the precollapsed state.     

From a monomer to a protein-sized, doughnut-shaped coordination oligomer-the influence of side chains of C3-symmetric ligands in supramolecular chemistry

Herein we describe the importance of side chains in C3-symmetric ligands in supramolecular chemistry. The reaction of the new ligand tris(5-bromo-2-methoxybenzylidene)triaminoguanidinium chloride [H3Me3Br3L]Cl (1) with ZnCl2 results in the formation of the monomeric complex (Et3NH)2[(ZnCl2)3Me3Br3L] (2), in which the ligand remains in a conformation less favourable for the coordination of metal centres. The use of the related tris(5-bromo-2-hydroxybenzylidene)triaminoguanidinium chloride, [H6Br3L]Cl, under similar conditions, results in the formation of two different dimeric compounds (NH4)[{[Zn(NH3)]3Br3L}2{mu-(OH)}3]1/4MeOH (3) and [Zn{Zn2(OH2)3(NH3)Br3L}2] (4), depending on the solvent mixture used. The comparable reaction of the ligand tris(5-bromo-2-hydroxy-3-methoxybenzylidene)triaminoguanidinium chloride [H6(OMe)3Br3L]Cl (5), leads to the formation of a doughnut-shaped, protein-sized coordination oligomer (Et3NH)18[{Zn[Zn2Cl{(OMe)3Br3L}]2}6(mu-Cl)6(OH2)6]x CH3CN (6), which comprises six dimeric [Zn5{(OMe)3Br3L}2] units. Whereas 3 and 4 decompose in DMSO solution, 6 is surprisingly stable in the same solvent.     

Study of metal containing hydrogenated carbon films by STM/AFM and SAXS

Metal-containing amorphous hydrogenated carbon films are of high interest for industrial applications because of their excellent frictional properties, their high abrasive wear resistance and their electrical conductivity, which can be adjusted in a range of 10–12 orders of magnitude. In order to get insight into the mechanical and electrical properties it is necessary to study the nanostructure of the films. The structure consists of small nanometer sized metallic or carbidic particles, which are embedded in a three dimensional amorphous hydrogen-carbon matrix. Anomalous small angle X-ray scattering (ASAXS) and scanning tunneling microscopy (STM) have been used to determine size- and distance-distributions of the particles as a function of metal content. Problems and restrictions of both methods will be discussed. Furthermore the capabilities of scanning probe techniques to distinguish different materials on a nanometer scale (material contrast) have been studied employing barrier height imaging (dI/dz) and friction force microscopy.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday     

Anthracene-Porphyrin Nanoribbons

π-Conjugated nanoribbons attract interest because of their unusual electronic structures and charge-transport behavior. Here, we report the synthesis of a series of fully edge-fused porphyrin-anthracene oligomeric ribbons (dimer and trimer), together with a computational study of the corresponding infinite polymer. The porphyrin dimer and trimer were synthesized in high yield, via oxidative cyclodehydrogenation of singly linked precursors, using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and trifluoromethanesulfonic acid (TfOH). The crystal structure of the dimer shows that the central π-system is flat, with a slight S-shaped wave distortion at each porphyrin terminal. The extended π-conjugation causes a dramatic red-shift in the absorption spectra: the absorption maxima of the fused dimer and trimer appear at 1188 nm and 1642 nm, respectively (for the nickel complexes dissolved in toluene). The coordinated metal in the dimer was changed from Ni to Mg, using p-tolylmagnesium bromide, providing access to free-base and Zn complexes. These results open a versatile avenue to longer π-conjugated nanoribbons with integrated metalloporphyrin units.     

Massenspektrometrischer Nachweis von ββ-Zerfallsprodukten

The principles and methods of mass-spectrometric detection ofββ-decay products and the theoretical purposes for such studies are discussed in detail. We report also the results of our new measurements on two tellurides, one native tellurium sample and one selenide. Concerning the decay\(Te^{130} \underrightarrow {\beta - \beta - }Xe^{130} \), we have found that Xe¹³⁰ in a native tellurium sample amounts to 67% of the total xenon with an absence of any other anomaly, which is an important improvement over previous measurements. —For the first time the decay\(Se^{82} \underrightarrow {\beta - \beta - }Kr^{82} \) was studied by massspectrometry. A Kr⁸²-excess was positively found in an copper selenide. A detailed discussion of all processes other than doubleβ-decay which might contribute to the Xe¹³⁰ and Kr⁸²-anomalies is undertaken. It can be shown that these effects are small compared to theββ-decay process. It can be said now positively thatββ-decay occurs in nature. Discussing all available data we obtained the effective half-life of Te¹³⁰ to be 6×10^20±0.3 y and that of Se⁸² equals to 6 × 10^19±0.3 y. The results are in agreement with the theoretical predictions for the 2ν-ββ-decay. Nevertheless, no-neutrinoββ-decay is still possible. However, from the data we calculated that the leptonnonconservation is at most 0.7%.     

A tandem Diels–Alder/Mannich approach to the synthesis of AE and ABE ring analogues of Delphinium alkaloids

The one-pot TiCl₄ catalysed Diels–Alder/Mannich reaction of α-cyanoaminoacrylates with 2-silyloxy-1,4-butadienes gives 6-keto-3-azabicyclo[3.3.1]nonane-1-carboxylates. Reduction of the ketone and alkylation of the resultant alcohol gives 6-alkoxy-3-azabicyclo[3.3.1]nonanes mimicking the AE rings of a number of Delphinium and Aconitum alkaloids, with the same stereochemistry as the natural products.