Resistivity of positive-J spin glasses: Study ofLaGd under hydrostatic pressure

Results of a new calculation of the resistivity in the noise model of spin glasses, based on the –J S interaction forpositive J, are compared with measurements of the resistivity in an fcc La-8at% Gd alloy under hydrostatic pressures up to 12 kbar, the first positive-J resistivity investigations under pressure. A positive value ofJ that decreases with increasing pressure, in accord with other experiments, leads to quantitative agreement between theory and experiment if one uses a large electronic density of states at the Fermi energy, in accord with specific heat measurements and electronic band structure calculations in fcc La. Impurity potential scattering is found to contribute significantly to the resistivity. Its size and pressure variation is determined.This work is supported in part by the Deutsche Forschungs-gemeinschaft.     

Enantioselective parallel synthesis using polymer-supported chiral Co(salen) complexes

[formula: see text] The kinetic resolution of epoxides with phenols catalyzed by a polymer-supported Co(salen) complex is applied to the first enantioselective catalytic synthesis of parallel libraries. The corresponding 1-aryloxy-2-alcohols are obtained in high yield, purity, and enantiomeric excess. Further elaboration with diversity elements provides highly efficient access to important classes of pharmacologically active compounds.     

The discovery of Kv1.5 blockers as a case study for the application of virtual screening approaches

Different virtual screening techniques are available as alternatives to high throughput screening. These different techniques have been rarely used together on the same target. We had the opportunity to do so in order to discover novel blockers of the voltage-dependent potassium channel Kv1.5, a potential target for the treatment of atrial fibrillation. Our corporate database was searched, using a protein-based pharmacophore, derived from a homology model, as query. As a result, 244 molecules were screened in vitro, 19 of them (7.8%) were found to be active. Five of them, belonging to five different chemical classes, exhibited IC50 values under 10 microM. The performance of this structure-based virtual screening protocol has been compared with those of similarity and ligand-based pharmacophore searches. The analysis of the results supports the conventional wisdom of using as many virtual screening techniques as possible in order to maximize the chance of finding as many chemotypes as possible.     

Detailed investigations of ZnO photoelectrodes preparation for dye sensitized solar cells

Wurtzite ZnO hexagonal nanopyramids were successfully synthesized in the liquid phase from homogeneous methanolic solutions of zinc acetate and tetramethylammonium hydroxide at an excess of zinc ions. The formation and properties of the nanocrystals were examined as a function of synthesis conditions. No significant influence of the [Zn(2+)]/[OH(-)] ratio was noticed on the final particle size, in spite of increased amounts of OH(-) ions, which tend to accelerate the particle nucleation and growth. Nevertheless, the reactant concentration ratio influences the surface properties of the ZnO nanocrystals. Mesoporous ZnO films were prepared by doctor blading ethanolic pastes containing ZnO nanoparticles and ethyl cellulose onto FTO conductive glass substrate followed by calcination. Additionally, the influence of a plasticizer (triacetin)-used during the paste preparation-on the film quality was investigated. A higher content of ZnO nanoparticles and plasticizer in the pastes improved the film quality. Four different temperatures (i.e., 400, 425, 450, and 475 °C) were used for the film calcination and their influence on the structural properties of the films was characterized. In principle, increasing the calcination temperature goes hand in hand with an increase of particle size, as well as the pore diameter and reduction of the surface area. Suitable mesoporous films were employed as photoanodes in dye sensitized solar cells (DSSCs). In order to assess the effect of the varied parameters on complete DSSC devices-using cis-diisothiocyanato-bis(2,2'-bipyridyl-4,4'-dicarboxylato) ruthenium(II)bis(tetrabutylammonium (N719) as a sensitizer-incident photon to current efficiency (IPCE) and current voltage measurements were carried out. The IPCE measurements confirmed photoinduced electron injection from the dye, reaching IPCE values up to 76%. Furthermore, current-voltage characteristics of complete cells emphasized the importance of the proper preparation methods and temperatures. These features are important assets for the preparation of nanocrystalline ZnO based photoelectrodes and for improving the DSSC performance.     

A group additivity methodology for predicting the thermochemistry of oxygen-containing organosilanes

A combinatorial approach was applied to devise a set of reference Si–C–O–H species that is used to derive group-additivity values (GAVs) for this class of molecules. The reference species include 62 stable single-bonded, 19 cyclic, and nine double-bonded Si–C–O–H species. The thermochemistry of these reference species, that is, the standard enthalpy of formation, entropy, and heat capacities covering the temperature range from 298 to 2000 K was obtained from quantum chemical calculations using several composite methods, including G4, G4MP2, and CBSQB3, and the isodesmic reaction approach. To calculate the GAVs from the ab initio based thermochemistry of the compounds in the training set, a multivariable linear regression analysis is performed. The sensitivity of GAVs to the different composite methods is discussed, and thermodynamics properties calculated via group additivity are compared with available ab initio calculated values from the literature.     

PARTICLE PROPERTIES—PROMISE AND NEGLECT

We see two major trends in Particle Technology. First, the focus is shifted from unit operations towards functional products, i.e. towards product engineering. Second, modeling will become more and more important. Processes cannot yet be designed from basic molecular understanding. Nanotechnology, however, begins to bridge this gap between molecules and particles and may thus open new ways not only for the production and handling of particulate matter but also for the engineered design of advanced material properties. Starting from the concept of product engineering we investigate the basic preconditions for tailoring nanoparticulate properties, i.e. the control of the particle interactions. Nanotechnology can only be transferred to industrial production if the interactions are effectively controlled. Material and particle properties are essential for predictive models. Although strong tools like MD, DEM or population balance models are available, these models are only predictive if realistic material and particle properties are available which is often not the case. We show for selected examples how particle properties can be obtained by studying the physically relevant elementary processes. The impact breakage behavior of many different materials is described by a master curve. Particle adhesion can be modeled if the roughness of particle and substrate and the Hamaker constant are known. The latter is obtained from adsorption studies.     

The low Reynolds number turbulent flow and mixing in a confined impinging jet reactor

Turbulent mixing takes an important role in chemical engineering, especially when the chemical reaction is fast compared to the mixing time. In this context a detailed knowledge of the flow field, the distribution of turbulent kinetic energy (TKE) and its dissipation rate is important, as these quantities are used for many mixing models. For this reason we conduct a direct numerical simulation (DNS) of a confined impinging jet reactor (CIJR) at Re = 500 and Sc = 1. The data is compared with particle image velocimetry (PIV) measurements and the basic flow features match between simulation and experiment. The DNS data is analysed and it is shown that the flow is dominated by a stable vortex in the main mixing duct. High intensities of turbulent kinetic energy and dissipation are found in the impingement zone which decrease rapidly towards the exit of the CIJR. In the whole CIJR the turbulence is not in equilibrium. The strong mixing in the impingement zone leads to a rapid development of a monomodal PDF. Due to the special properties of the flow field, a bimodal PDF is generated in cross-sections downstream the impingement zone, that slowly relaxes under relaminarising conditions. The time required for meso-mixing is dominating the overall mixing performance.     

Influence of particle size and concentration on the second-harmonic signal generated at colloidal surfaces

Second harmonic generation (SHG) spectroscopy is a recently developed technique for the investigation of surface properties of particles. To apply the method to technical colloidal systems, the dependences of several experimental parameters on the signal have to be studied. In this work the influence of particle concentration on the SHG signal from the surfaces of colloids (polystyrene beads in a size range of 0.1 μm to 2.9 μm) is investigated. A simple model, based on Lambert–Beer’s law, to describe the measured dependences is derived. The model agrees with the experimental observations for particles smaller 1.1 μm and with a small modification also for larger particles. Based on the new model an analytical equation for determining the optimum concentration, where highest signals in colloidal SHG spectroscopy measurements are obtained, is derived. PACS 42.25.Fx; 42.65.-k; 82.70.Dd     

Mechano-chemical radical formation and polymerization initiation during wet grinding of alumina

The formation of free radicals during wet grinding of alumina in a stirred media mill was studied by using the test radical 2,2-diphenyl-1-picrylhydracyl (DPPH). The kinetics of mechano-chemical radical formation follows a zeroth-order rate law. Particle breakage as well as mechanical activation of the surface of the alumina particles contributes to the radical formation. The rate constants of the radical formation due to mechanical activation of the particle surface k(A) and due to particle breakage k(B) depend on the milling process parameters. The radical formation during wet grinding of alumina was exploited to initiate mechano-chemical polymerization reactions of acrylic acid and acryl amide, respectively. In this way nanoparticles functionalized with polyacrylic acid and polyacryl amide, respectively, are obtained. The influence of the milling process parameters on the kinetics of mechano-chemical radical formation and on the grafted amount of polymer is discussed on the basis of stress energy and number of stress events in the mill. A correlation between the grafted amount of polyacryl amide on the alumina particles and the total radical formation rate was found showing that the concentration of mechano-chemically formed free radicals governs the efficacy of a chemical reaction at activated particle surfaces.