Synthesis, complete 1H and 13C NMR assignment and crystal structure of novel epoxide derivatives of cytochalasin B

Five novel epoxide derivatives of cytochalasin B were synthesized. Reaction of cytochalasin B with t-BHP and BuLi led to selective epoxidation of the C-21/22 double bond to give a single monoepoxide, while reaction with m-CPBA yielded two diepoxides. Reaction of the monoepoxide with m-CPBA yielded two triepoxides. The relative configurations of the epoxides were elucidated by analogy with the natural product by means of spectroscopic methods; full assignment of NMR signals was achieved, and the absolute configuration was confirmed by X-ray crystallography.     

Wetting, drying, and layering of colloid-polymer mixtures at porous interfaces

The influence of interface porosity on the wetting properties of colloid-polymer mixtures is studied within density functional theory for the Asakura-Oosawa-Vrij model at the surface of a quenched hard-sphere matrix. While the porosity hardly changes the location of the transition from partial to complete wetting at colloidal bulk gas-liquid coexistence, the onset of wetting, as signaled by the first discontinuous layering transition, can be efficiently controlled by tailoring the porosity. We furthermore find that the penetrability of the porous interface induces complete drying into the matrix upon approaching capillary coexistence.     

Phase-noise properties of an ytterbium-doped fiber amplifier for the Laser Interferometer Space Antenna

Phase noise is a critical issue for the sensitivity of the interferometric gravitational-wave detector Laser Interferometer Space Antenna that requires laser sources with 1 W of output power. A low-power seed laser with a subsequent fiber amplifier is in discussion, and we report on spectrally resolved phase-noise measurements of an ytterbium-doped fiber amplifier emitting 1 W of output power from 10 mW of seed power. Phase-noise measurements for Fourier frequencies from 10(-4) Hz to 100 kHz show 60 rad/Hz0.5 at 10(-4) Hz and 0.2 mrad/Hz0.5 at 1 kHz. This measured excess phase noise is orders of magnitude below the free-running phase noise of nonplanar ring oscillators.     

Assignment of carbon-13 NMR spectra and sign determination of long range carbon-13—proton coupling constants with SPI

The application of selective population inversion (SPI) to the assignment of ¹³C resonances and to the determination of the relative sign of ¹³C? ¹H coupling constants is demonstrated for 1-phenyl-1,2-dibromo-2-nitroethane. A negative sign for the geminal C-2? H-1 coupling constant has been determined from the ¹³C spectra. The relationship between SPI and TSI is discussed.     

The crystal structure of Thorium(IV)tetrakis(trifluoroacetylacetonate)

The crystal structure of the compound thorium(IV)tetrakis(trifluoro-acetylacetonate) was determined by means of a threedimensional X-ray analysis. The space group is C2/c and the cell dimensions are a = 25,05 Å, b = 6.43 Å, c = 21.3 Å, β = 125.4°, with Z = 4. The thorium atom is coordinated by 8 oxygen atoms in the form of an 1111 (D₄–422) antiprism. The mean of the Th–O distances is 2.39 Å with a standard deviation ± 0.04 Å. The trifluoroacetylacetonate rings are approximately planar, except for the CH₃ and CF₃ groups which show significant deviations. The Th–O bonds form angles of approximately 72° and 50° with the theoretical 8 -axis of the antiprism. The structure is stabilized by VAN DER WAALS contacts between neighbouring molecules. The refinement of the atomic positions, the anisotropic temperature parameter of thorium and isotropic temperature parameters of all the other atoms by the least squares method, has given a reliability index of 0.148.     

Surface and interfacial structure of epitaxial SrTiO3 thin films on (0 0 1) Si grown by molecular beam epitaxy

Effects of relaxation of interfacial misfit strain and non-stoichiometry on surface morphology and surface and interfacial structures of epitaxial SrTiO₃ (STO) thin films on (0 0 1) Si during initial growth by molecular beam epitaxy (MBE) were investigated. In situ reflection high-energy electron diffraction (RHEED) in combination with X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron spectrometry (XPS) and transmission electron microscopy (TEM) techniques were employed. Relaxation of the interfacial misfit strain between STO and Si as measured by in situ RHEED indicates initial growth is not pseudomorphic, and the interfacial misfit strain is relaxed during and immediately after the first monolayer (ML) deposition. The interfacial strain up to 15 ML results from thermal mismatch strain rather than lattice mismatch strain. Stoichiometry of STO affects not only surface morphology but interfacial structure. We have identified a nanoscale Sr₄Ti₃O₁₀ second phase at the STO/Si interface in a Sr-rich film.     

Synthesis of Branched Oligonucleotides as Templates for the Assembly of Nanomaterials

Branched oligonucleotides with symmetric arms 6 – 15 , which may contain biotin as a second recognition code, were prepared. These molecules are designed to be used for the directed assembly of nanomaterials. The branched structure of the desired oligonucleotides was confirmed by mass spectrometry on small branched oliognucleotides, by gel electrophoresis, and by hybridization with complementary oligonucleotide? nanoparticle conjugates, followed by visualization of the complexes by transmission electron microscopy.     

Cosserat Parameter Identification within the Frame of the Discrete Element Method

One of the main challenges using the Discrete Element Method is that there is no direct compliance to the well known continuum parameters such as elastic moduli. In this article we show how homogenization procedures using representative volume elements composed of discrete particles lead to Cosserat continua. Simulating a shear test with discrete elements it becomes obvious, that the evolving microstructure is mainly composed of contact chains that form triangles and quadrilaterals. For these contact chains we set up contact energies in normal and shear directions and combine those to derive the effective energy of the material. By comparison of this energy to a Cosserat energy we can derive formulas for the Lamé and Cosserat parameters. They are now only dependent on the interaction energies and radii of the particles. To show the validity of our assumptions and derivations we present some discrete element simulations of shear tests. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Leptonic and charged kaon decay modes of the phi meson measured in heavy-ion collisions at the CERN super proton synchrotron

We report on results of a measurement of meson production in central Pb-Au collisions at E(lab) = 158A GeV. For the first time in the history of high energy heavy-ion collisions, phi mesons were reconstructed both in the K+K- and the dilepton decay channels in the same experiment. This measurement yields rapidity densities near midrapidity, from the two decay channels, of 2.05 +/- 0.14(stat) +/- 0.25(syst) and 2.04 +/- 0.49(stat) +/- 0.32(syst), respectively. The shape of the measured transverse momentum spectrum is also in close agreement in both decay channels. The data rule out a possible enhancement of the phi yield in the leptonic over the hadronic decay channel of a factor 1.6 or larger at the 95% C.L. This rules out the discrepancy reported in the literature between measurements of the hadronic and dimuon decay channels by two different experiments.