Modular synthesis of the ClickFerrophos ligand family and their use in rhodium- and ruthenium-catalyzed asymmetric hydrogenation

A series of diphosphine ClickFerrophos ligands (CF), based on a triazoleferrocene backbone, was synthesized in a four-step sequence via click chemistry methodology. In addition to the four previously synthesized ligands CF1, CF4, CF7 and CF10, six novel CF ligands CF2–3 and CF5–8 were prepared. Hydrogenation reactions of alkenes and ketones were significantly improved upon by using CF ligands as rhodium- or ruthenium-complexes in which the % ee values can be optimized by choosing the appropriate CF ligand depending on the substrate.     

A Thermal And Structural Study on Lanthanum Hexacyanocobaltate(III) Pentahydrate. Part II

The thermal dehydration of La[Co(CN)₆]⋅5H₂O proceeded through at least three stages from the temperature range of30~230°C, and an abrupt mass loss occurred around 350°C and the perovskite type oxide,LaCoO₃ was obtained at 1000°C. After dehydration, the color of the anhydride changed from white to pale blue around 230°C and furthermore, the color changed to blue around 290°C. These color changes were discussed on the basis of the changes of coordination structures around Co ions. In La[Co(CN)₆]⋅5H₂O, Co³⁺ ions lie at the center of the O_h crystal field consisted of six CN^– ions. However, in the pale blue specimen, Co³⁺ ions were situated in the center of D_4h crystal field which was distorted the O_h one by lengthening of the trans CN^– ions along z-axis. In the blue specimen, Co³⁺ ions were reduced to Co²⁺ ions which were situated in the T_d crystal field formed by four CN^–ions as [Co(CN)₄]^2–. This revised version was published online in July 2006 with corrections to the Cover Date.     

Printed circuit rat-race-type directional couplers for larger power-split ratio

Two different types of 5/2-wavelength rat-race-type directional couplers with a remarkably increased power-split ratio for a realizable ring-impedance, in particular which are useful for millimeter-wave circuits suffering from the severe restriction on the usable impedance range, are described. Experimental corroboration is provided in the microwave region (at 8 GHz).     

Effect of suspended particles on spreading of volatile droplet on solid substrate

Abstract  

We have been interested in behaviors of suspended particles in a volatile droplet placed on a smooth substrate. It is known that the particles gather and deposit in the vicinity of the macroscopic contact line of the droplet, which is generally called ‘coffee stain problem’. A convective flow induced by non-uniform evaporation through the interface brings suspended particles toward the pinned contact line in the drying droplet, which forms a ring stain. We have focused on the dynamics of the droplet with/without suspended particles spreading on the solid substrate and on the behaviors of particles in the evaporating droplet. Spreading process of the droplet is significantly affected by the suspended particles. We indicate flow patterns in the droplet, in which the flow exhibits a modal structure with a mode number in the azimuthal direction, and indicate particles depositions after the dryout of the droplet. Three-dimensional particle tracking velocimetry is applied to reconstruct such unique flow patterns in the spreading process of the droplet. Resultant patterns of the particles depositing on the substrate are introduced.     

Gasification characteristics of woody biomass in the packed bed reactor

Gasification technology is recognized as one of the possibilities for utilizing biomass effectively. This study focused on woody biomass gasification fundamentals, using a bench-scale packed-bed reactor. In this experiment, pellets of black pine were gasified, using air as the oxidizing agent. Gasification tests were carried out under both updraft and downdraft conditions. Temperature distributions and compositions of syngas inside the gasifier were continuously monitored during gasification experiments at several ports on the wall of the reactor. The syngas at the exit of the gasifier was also sampled to estimate the amount of tar. Lower heating values of the syngas under updraft and downdraft conditions were 4.8 and 3.8 MJ/m³N, respectively. It was easier to control the height of the packed bed under the downdraft condition than under the updraft condition. Under the updraft condition, a bridging phenomenon occurred. Tar generation under the downdraft condition was lower than that under the updraft condition. This is because tar passes through a partial combustion zone or higher temperature zone in the downdraft gasifier.     

Czochralski-growth of germanium crystals containing high concentrations of oxygen impurities

Oxygen-containing germanium (Ge) single crystals with low density of grown-in dislocations were grown by the Czochralski (CZ) technique from a Ge melt, both with and without a covering by boron oxide (B₂O₃) liquid. Interstitially dissolved oxygen concentrations in the crystals were determined by the absorption peak at 855 cm⁻¹ in the infrared absorption spectra at room temperature. It was found that oxygen concentration in a Ge crystal grown from melt partially or fully covered with B₂O₃ liquid was about 10¹⁶ cm⁻³ and was almost the same as that in a Ge crystal grown without B₂O₃. Oxygen concentration in a Ge crystal was enhanced to be greater than 10¹⁷ cm⁻³ by growing a crystal from a melt fully covered with B₂O₃; with the addition of germanium oxide powder, the maximum oxygen concentration achieved was 5.5×10¹⁷ cm⁻³. The effective segregation coefficients of oxygen in the present Ge crystal growth were roughly estimated to be between 1.0 and 1.4.     

Anatomy of a laminar starting thermal plume at high Prandtl number

We present an experimental study of the dynamics of a plume generated from a small heat source in a high Prandtl number fluid with a strongly temperature-dependent viscosity. The velocity field was determined with particle image velocimetry, while the temperature field was measured using differential interferometry and thermochromic liquid crystals. The combination of these different techniques run simultaneously allows us to identify the different stages of plume development, and to compare the positions of key-features of the velocity field (centers of rotation, maximum vorticity locations, stagnation points) respective to the plume thermal anomaly, for Prandtl numbers greater than 10³. We further show that the thermal structure of the plume stem is well predicted by the constant viscosity model of Batchelor (Q J R Met Soc 80: 339–358, 1954) for viscosity ratios up to 50.     

Sensitivity analysis incorporating fuzzy evaluation for scaling constants of multiattribute utility functions

A multiattribute utility function can be represented by a function of single-attribute utility functions if the decision maker’s preference satisfies additive independence or mutually utility independence. Additive independence is a preference condition stronger than mutually utility independence, and the multiattribute utility function is in the additive form if the former condition is satisfied, otherwise it is in the multiplicative form. In this paper, we propose a method for sensitivity analysis of multiattribute utility functions in multiplicative form, taking into account the imprecision of the decision maker’s judgment in the procedures for determining scaling constants (attribute weights).     

High resolution‐HMBC (HR‐HMBC), a new method for measuring heteronuclear long‐range coupling constants

A useful pulse sequence for measuring long‐range C? H coupling constants (J_{C? H}) named high resolution‐HMBC (HR‐HMBC) has been developed. In this pulse sequence, the J‐scaling pulse [(nt₁)/2? 180° (H/C) ? (nt₁)/2] is incorporated after the spin evolution period, and then followed by an ¹H 180° pulse to reverse the magnetization of J_{C? H} couplings. As a result, splittings of the cross peaks due to the long‐range J_{C? H} are realigned with separations of nJ_{C? H} along the F₁ dimension, and thus even the small long‐range J_{C? H} values can easily be determined. The efficiency of measuring the long‐range J_{C? H} using the proposed pulse sequences has been demonstrated in application to the complicated natural product, portmicin. Copyright © 2010 John Wiley & Sons, Ltd.