Wetting on the microscale: shape of a liquid drop on a microstructured surface at different length scales

Describing wetting of a liquid on a rough or structured surface is a challenge because of the wide range of involved length scales. Nano- and micrometer-sized textures cause pinning of the contact line, reflected in a hysteresis of the contact angle. To investigate contact angles at different length scales, we imaged water drops on arrays of 5 μm high poly(dimethylsiloxane) micropillars. The drops were imaged by laser scanning confocal microscopy (LSCM), which allowed us to quantitatively analyze the local and large-scale drop profile simultaneously. Deviations of the shape of drops from a sphere decay at two different length scales. Close to the pillars, the amplitude of deviations decays exponentially within 1-2 μm. The drop profile approached a sphere at a length scale 1 order of magnitude larger than the pillars' height. The height and position dependence of the contact angles can be understood from the interplay of pinning of the contact line, the principal curvatures set by the topography of the substrate, and the minimization of the air-water interfaces.     

Morphology evolution of Cu(2-x)S nanoparticles: from spheres to dodecahedrons

An oriented attachment and growth mechanism allows an accurate control of the size and morphology of Cu(2-x)S nanocrystals, from spheres and disks to tetradecahedrons and dodecahedrons. The synthesis conditions and the growth mechanism are detailed here.     

Klick‐Chemie. Synthesen,die gelingen

Click‐Chemistry is a concept in organic synthesis that uses a limited amount of very reliable reactions on a broad variety of substrates. This leads within a few steps to molecules of high diversity which is important to accelerate drug‐discovery. Besides favourable thermodynamic requirements, the criteria for a click‐reaction include also simple reaction conditions and a quick and easy (almost unnecessary) workup. The most successful of these click‐reactions is the copper catalysed 1, 3‐dipolar cycloaddition of azides and alkynes, which in the meantime is used in most diverse areas of chemistry. The mechanistic ideas of this reaction is looked at in more detail.     

Multilayer adsorption of water at a rutile TiO2)(110) surface: towards a realistic modeling by molecular dynamics

We present a model combining ab initio concepts and molecular dynamics simulations for a more realistic treatment of complex adsorption processes. The energy, distance, and orientation of water molecules adsorbed on stoichiometric and reduced rutile TiO(2)(110) surfaces at 140 K are studied via constant temperature molecular dynamics simulations. From ab initio calculations relaxed atomic geometries for the surface and the most probable adsorption sites were derived. The study comprises (i) large two-dimensional surface supercells, providing a realistically low concentration of surface oxygen defects, and (ii) a water coverage sufficiently large to model the onset of the growth of a bulk phase of water on the surface. By our combined approach the influence of both, the metal oxide surface, below, and the bulk water phase, above, on the water molecules forming the interface between the TiO(2) surface and the water bulk layer is taken into account. The good agreement of calculated adsorption energies with experimental temperature programmed desorption spectra demonstrates the validity of our model.     

Unspecific ligand binding yielding stable colloidal ITO-nanoparticle dispersions

Long-term stable ITO-nanoparticle dispersions are obtained using primary unbranched alkylamines with different chain lengths (C(3)-C(12)). The particles are stable despite weak interactions between the stabiliser and particle surface, which were qualitatively studied by (1)H-NMR spectroscopy and quantitatively by isothermal titration calorimetry (ITC).     

Drug delivery and imaging with polydiacetylene micelles

This concept article summarizes our recent findings regarding photopolymerized micelles obtained from the self-assembly of diacetylene-containing amphiphiles. Their synthesis and characterization are presented as well as some biomedical applications, such as tumor imaging and drug delivery. Finally, ongoing studies and future challenges are briefly discussed.     

μ-Synchrotron radiation excited X-ray fluorescence microprobe trace element studies on spherules of the Cretaceous/Tertiary boundary transitions of NE-Mexico and Haiti samples

Synchrotron radiation, collimated to a μm scale was used for the determination of trace elements in micro-tektites and spherule material for the first time. The experimental set-up of the SXRF microprobe at beamline L at HASYLAB at DESY offers a suitable method for performing non-destructive in situ multi-element analysis focusing on spatial trace element distributions and mineral phases of the melted ejecta material from the Cretaceous/Tertiary boundary. The spatial distribution of trace elements was determined in melt inclusions as well as in phase transitions in selected parts of chlorite–smectite spherules and tektite glass material by using a beam with a diameter of 15 μm collimated with a glass capillary for line- and area scans as well as for single point measurements for elements with Z between 19 and 92. The analyzed spherules show alteration features but also zonation and carbonate inclusions, originating from the Chicxulub impact event. These initial results demonstrate the potential of μ-SXRF analysis for the discrimination of alteration and primary signals of the spherules and re-construction of their genetic evolution. It could be shown that the spherules represent a complex mixture of different materials from the subsurface at the Chicxulub impact site.     

Synthesis of Side Chain Substituted 3-Butylisocoumarins and Absolute Configurations of Natural Isocoumarins from <Emphasis Type="Italic">Artemisia dracunculus</Emphasis>

Summary. A series of 3-hydroxy- and 3-bromobutyl-substituted isocoumarins was synthesized. The absolute configurations of three isocoumarin derivatives from Artemisia dracunculus, namely (–)-epoxyartemidin, (–)-2-methoxydihydroartemidin, and (+)-3-hydroxyartemidin were determined by chemical means via derivatization, kinetic racemate resolution (Horeau method), and comparison of the circular dichroism (CD) spectra.DeceasedReceived March 17, 2003; accepted March 19, 2003 Published online August 18, 2003     

Nitrogen purity influences the occurrence of As+ ions in high-performance liquid chromatography/electrospray ionization mass spectrometric analysis of four common arsenosugars

High-performance liquid chromatography coupled to electrospray ionization mass spectrometry (HPLC/ESI-MS) can provide both elemental and molecular information and, therefore, is a very useful tool for the identification of arsenic compounds. When a method for the identification of four arsenosugars was employed in our laboratory with an HPLC/ESI-MS system equipped with a Whatman model 75-72 nitrogen generator, a signal at m/z 75 (As(+)) could not be observed. When the HPLC/ESI-MS system was operated with nitrogen 5.0 (nitrogen of a purity of at least 99.999%) all four arsenosugars gave a signal at m/z 75. Because of this observation the influence of the quality of the nitrogen drying gas on the fragmentation of the four arsenosugars was systematically investigated. Standard solutions containing the four arsenosugars (0.5 ng As each) were separated on an anion-exchange column and detected with ESI-MS in the positive ion mode by monitoring the signals for [M+H](+), m/z 237, 91, and 75. Nitrogen with defined oxygen concentrations was used as drying gas. The purity of the nitrogen ranged from 99 to 99.999% (10 400 to 10 ppm oxygen impurity). The nitrogen with 99% purity gave no signal at m/z 75, but signals were obtained at m/z 91, 237, and for [M+H](+). When higher purity nitrogen (99.9%) was used, a signal was obtained at m/z 75, which accounted for 0.8-1.1% (depending on the kind of arsenosugar) of the sum of the signals for m/z 75, 91, 237 and [M+H](+). As the level of oxygen in the nitrogen decreased, the m/z 75 signal increased to 2.0-3.1%. This was accompanied by a concomitant decrease in the m/z 91 signal from 5.2-6.6% to 0.7-1.5%, whereas the signals for [M+H](+) and m/z 237 were essentially unchanged. Signals at m/z 75 with intensities comparable with those observed for the 99.9% pure nitrogen were also obtained for all the arsenosugars when the HPLC/ESI-MS system was operated with a Domnick Hunter Nitrox UHPLCMS18 nitrogen generator. Dimethylarsinic acid, arsenobetaine, trimethylarsine oxide, arsenocholine and the tetramethylarsonium cation also gave no signal at m/z 75 when they were analyzed with the Whatman model 75-72 nitrogen generator, but clear signals at m/z 75 were observed with the Domnick Hunter Nitrox UHPLCMS18 nitrogen generator. A nitrogen quality of at least 99.9% is required to obtain elemental information (m/z 75) when arsenic compounds are investigated by HPLC/ESI-MS. Molecular and elemental information from one chromatographic run is a valuable tool for the characterization of unknown arsenic compounds.     

Zum Aufbau von RbNa5Be8O11

On RbNa₅Be₈O₁₁ For the first time RbNa₅Be₈O₁₁ was obtained by annealing intimate mixtures of the binary oxides (Rb:Na:Be = 1.1:5.5:8, Ni-cylinder, 650°C, 21d). The compound crystallizes triclinic (P 1 ) with a = 1 063.4 pm, b = 645.6 pm, c = 948.8 pm, α = 110.2º, β = 114.9º, γ = 90.8º, Z = 2. The crystal structure was solved by four-circle-diffractometer data [Siemens AED2, 3099 I₀ (hkl), R = 5.1%, R_w = 3.8%]. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, are calculated.