Numerical simulation of particles movement in cellular flows under the influence of magnetic forces

A numerical model of particle motion in fluid flow under the influence of hydrodynamic and magnetic forces is presented. As computational tool, a flow solver based on the Boundary Element Method is used. The Euler-Lagrange formulation of multiphase flow is considered. In the case of a particle with a magnetic moment in a nonuniform external magnetic field, the Kelvin body force acts on a single particle. The derived Lagrangian particle tracking algorithm is used for simulation of dilute suspensions of particles in viscous flows taking into account gravity, buoyancy, drag, pressure gradient, added mass and magnetophoretic force. As a benchmark test case the magnetite particle motion in cellular flow field of water is computed with and without the action of the magnetic force. The effect of the Kelvin force on particle motion and separation from the main flow is studied for a predefined magnetic field and different values of magnetic flux density. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Reductive elimination of ArCF3 from bidentate Pd(II) complexes: a computational study

The reductive eliminations of ArCF(3) from Pd(II) complexes bearing small- and large-bite-angle phosphane ligands have been investigated using computational methods. QM/QM' and QM/MM studies were applied and complemented with CP2K molecular dynamics investigations. The ligand substituents were varied and a decomposition analysis was performed to allow us to gain insights into the steric and electronic properties of the ligands. The greater reactivity of Xantphos-derived (Xantphos=4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) complexes in the reductive elimination of ArCF(3) is primarily due to the lower repulsive effect of the phoshine substituents in the transition state than in the reactant complex, combined with the increased electronic interaction in the transition state. For DPPE (1,2-bis(diphenylphosphino)ethane), the steric effect of the ligand substituents is greater in the transition state, leading to a higher reaction barrier overall for reductive elimination. There is no direct correlation of the reactivity with the bite angle of the reactant complexes. Only for complexes with large ligand substituents may the bite angle of the Pd complexes be used as a guide for reactivity.     

Laser-ablation ICP-MS analysis of siliceous rock glasses fused on an iridium strip heater using MgO dilution

Trace element determination in rocks by fusion on an iridium strip heater followed by LA-ICP-MS analysis of the glass beads is extended here to SiO₂-rich rocks; rapid fusion of samples with >55 wt% SiO₂ is facilitated by dilution by high purity MgO. The method developed here can rapidly and accurately determine numerous trace elements in a large range of rock compositions in a short time (about 50 samples/day). Systematic evaluation for a large range of rock compositions (natural rocks and reference materials AGV-2, GSP-2, JG-1a) with SiO₂ contents between 45 and 80 wt% shows that reproducibility and accuracy within 10% can be routinely achieved for most of the 28 trace elements investigated (Rb, Sr, Cs, Ba, Ti, Zr, Hf, Nb, Ta, Sc, V, Cr, Ni, Pb, Th, U, REE). The 40 mg sample size is smaller than for XRF, INAA or solution-ICP-MS, detection limits are lower, and trace element palettes more complete than XRF and INAA. This microchemical method is thus attractive for the analysis of all natural geological materials as well as for experimental applications with small samples. Samples with SiO₂-contents >55 wt% require hot and long melting to achieve homogeneous glasses and eliminate all residual minerals, particularly refractory accessory phases. Melting conditions of 1600 °C and 20 s for samples are recommended for SiO₂ contents between 55 and 70 wt%, whereas 1800 °C and 20–30 s are often required for samples with >70 wt% SiO₂. Problems are encountered for Pb and Cs due to volatilization on the Ir strip, for Sc due to interferences, and Zr and Hf due to their sequestration in refractory accessory minerals. Correspondence: Franziska Nehring, Department of Geosciences, University of Mainz, Becherweg 21, 55099 Mainz, Germany     

Species and age determination of central nervous system tissue by fatty acid patterns

The banning of specified risk materials (SRMs) from food chain is one of the most important measures to protect the consumer against any exposition with the agent of transmissible spongiform encephalopathies (TSEs). In order to control the SRM-ban, suitable methods for the detection of SRMs have to be developed. In this study homogenized samples of central nervous system (CNS) tissue from cattle (n=38), sheep (n=38) and pig (n=40) were analyzed by gas chromatography-mass spectrometry (GC-MS). The analysis was focused on the identification of fatty acid ratios for species differentiation and age estimation. We found a novel fatty acid ratio (C24:1(n-9)/(n-7))/(2OH-C24:1(n-9)/(n-7) for species differentiation. For the first time, we used multivariate analysis for species differentiation, based on fatty acid ratios. It showed an excellent predictive ability (Q_(cum)(2))Q_(cum)(2)=0.842. For age estimation in cattle CNS we discovered a novel fatty acid ratio 2OH-C25:0/2OH-C24:1(n-7). The ratio is strongly correlated with age (coefficient of correlation (r)=0.935, Spearman-Rho). The corresponding regression analysis which allows the prediction of age by this ratio was acceptable (coefficient of determination (R(2))=0.831).     

Chloride‐based CVD of 3C‐SiC epitaxial layers on 6H(0001) SiC

The heteroepitaxial growth of 3C‐SiC on 6H‐SiC(0001) on‐axis substrates is demonstrated in this study. A hot‐wall CVD reactor working at a reduced pressure was used to perform growth experiments at temperatures between 1300 °C and 1500 °C. The addition of hydrogen chloride to standard precursors allowed a wide window of operating parameters, which resulted in the growth of very high quality and purity 3C‐SiC layers, with a morphology characterized largely by single‐domains, especially when nitrogen was intentionally added. Growth rate of 10 µm/h and n‐type background doping in the low 10¹⁵ cm^–3 range were achieved. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Reactivity and stability of dinuclear Pd(I) complexes: studies on the active catalytic species, insights into precatalyst activation and deactivation, and application in highly selective cross-coupling reactions

The catalysis derived from the dinuclear Pd(I)-Pd(I) complex, {[PtBu(3)]PdBr}(2), has been studied with experimental, computational, and spectroscopic techniques. Experimental selectivity studies were performed, and the reactivity was subsequently investigated with density functional theory (B3LYP-D and M06L) to deduce information on the likely active catalytic species. The reactivity with aryl chlorides and bromides was found to be inconsistent with direct catalytic involvement of the Pd(I) dimer but consistent with mononuclear Pd(0) catalysis. Computational studies suggest that precatalyst transformation to the active catalytic species does not proceed via a direct disproportionation mechanism; a reductive pathway is the most likely scenario instead. Through (31)P NMR investigations it was identified that the combination of ArB(OH)(2), KF, and water triggers the conversion of the precatalyst to Pd(PtBu(3))(2) and, most likely, Pd-black as a competing side process, explaining the incomplete conversions of aryl chlorides in Suzuki cross-coupling reactions under Pd(I) dimer conditions. New applications in highly regio- and chemoselective transformations in short reaction times at room temperature are also demonstrated.     

Catalytic activity of macroion-porphyrin nanoassemblies

A new type of catalytically active self-assembled nanostructures in aqueous solution is presented. Polyelectrolyte-porphyrin nanoscale assemblies consisting of anionic cylindrical poly(styrene sulfonate) brush molecules and cationic tetravalent meso-tetrakis(4-N-methyl-pyridinium)porphyrin (TMPyP) or meso-tetrakis(4-(trimethyl-ammonium)phenyl)-porphyrin (TAPP), respectively, exhibit up to 8-fold higher catalytic activity with regard to light induced iodide oxidation than the corresponding porphyrins without polymeric template. This is particularly interesting because a general concept rather than a specific binding motif is exploited. The approach introduced here hence is attractive due to its facility and versatility and bears potential, for example, in light harvesting and energy conversion.     

SERS enhancement of gold nanospheres of defined size

Monodisperse, citrate‐stabilized gold nanoparticles of sizes ranging from 15 to 40 nm were synthesized and characterized by small angle X‐ray scattering and UV‐vis experiments. Identical surface properties of nanoparticles of different sizes to avoid variation in the chemical surface‐enhanced Raman scattering (SERS) enhancement, as well as selection of experimental conditions so that no aggregation took place, enabled the investigation of enhancement of individual nanospheres. Enhancement factors (EFs) for SERS were determined using the dye crystal violet (CV). EFs for individual gold nanospheres ranged from 10² to 10³, in agreement with theoretical predictions. An increase of the EFs of individual spheres with size can be correlated to changes in the extinction spectra of nanoparticle solutions. This confirms that the increase in enhancement with increasing size results from an increase in electromagnetic enhancement. Beyond this dependence of EFs of isolated gold spheres on their size, EFs were shown to vary with analyte concentration as a result of analyte‐induced aggregation. This has implications for the application of nanoparticle solutions as SERS substrates in quantitative analytical tasks. Copyright © 2011 John Wiley & Sons, Ltd.