Highly sensitive chiral shift reagent bearing two zinc porphyrins

A new type of chiral receptor (R,R)- or (S,S)-1b with C(2) symmetry was synthesized. An induced-fit type of binding behavior of 1b for diamines was revealed by CD spectroscopy. NMR studies demonstrated that 1b can function as a highly sensitive chiral shift reagent for the determination of the enantiomeric purity of chiral diamines, aziridine, and isoxazoline at the microgram level. [structure: see text]     

Discrimination of the geometrical isomers of 2,3-, 2,5-, and 2,6-dimethylpiperazines based on 1 H?Nmr spectral data

¹ H-Nmr spectra of cis and trans isomers of 2,3-, 2,5-, and 2,6-dimethylpiperazines were taken at various temperatures. The spectra of geometrical isomers bearing the ae or ea dimethyl groups showed broadening at lower temperatures. It was clarified that the measurement of the spectra at lower temperatures is useful for the discrimination of the geometrical isomers of dimethylpiperazines.     

Electronic resistivity and deffect structure of β-LiAl as a function of temperature and composition

The electrical resistivity of β-Li_xAl_1?x has been measured from 10 K to 290 K in single crystal samples for four different concentrations, x=0.480, 0.486, 0.500 and 0.525. An anomaly at 100 K is observed for the three lowest Li concentrations. This anomaly is associated with an ordering of constitutional Li vacancies. Above 100 K the temperature dependent part of the resistivity is independent of the Li concentration. However, the residual resistivity increases very rapidly with increasing Li concentration, becoming ～ 75 μΩ-cm for x=0.525. These results suggest that the two defect model of β-LiAl may be incomplete.     

Measurement of flow phenomena using the ultrasonic velocity profile method in a simulated Czochralski crystal puller

An experimental investigation of flow phenomena in a simulated Czochralski (CZ) crystal puller was conducted using an ultrasound velocity profile (UVP) probe to measure fluid velocities. To isolate the various forces that influence the fluid motion, only the crystal was rotated and a water-glycerol mixture was used as the test fluid in this experiment. Measurements of the velocity components, V_z and V_r, under the initial transient from zero rotation to a set rotation rate as well as under steady-state conditions were made. The corresponding Reynolds number based on the crystal radius and rotation varied from Re_Ω,_x ≈ 660–5000 (Ω_x ≈ 110–2000 rpm). The measured velocity profiles, V_z and V_r, were processed using a simple color image scheme based on the magnitude and direction of flow with respect to the probe. These profiles were studied to postulate flow patterns in the simulated CZ device. The measurements revealed three major regions of flow: (1) one beneath the crystal, (2) one near the free surface and crucible wall and (3) one beneath the crystal and occupying the extent of the crucible. In the initial transient, spatially symmetric outward flow beneath the crystal developed until the recirculating flow from below disturbed this pattern. At this point the apparent shear between the flow beneath the crystal and that circulating upwards from the bottom of the crucible induced flow instabilities and a non-axisymmetric flow pattern. The non-axisymmety was verified by the color-coded velocity profiles and a power spectrum analysis. The analysis revealed the critical Reynolds number for the onset of the primary instability to be Re_Ωcrit ≈ 669. The linear variation in the power of the primary peak with the Reynolds number indicates that the onset of the axisymmetry-breaking instability is due to Hopf bifurcation.     

Rhodium-Catalyzed Acrylate Synthesis from Carbon Dioxide and Ethylene by using a Guanidine-Based Pincer Ligand: Perturbing Occupied d-Orbitals by pπ-dπ Repulsion Makes a Difference

Rhodium-catalyzed acrylate synthesis from CO₂ and ethylene was accomplished by using a guanidine-based NCN pincer ligand. The repulsion between pπ-electron of guanidine sidearms and occupied dπ orbital of rhodium center raised the level of d-electrons close to those of formerly known d⁸-ruthenium catalyst, thereby promoting the metallalactone formation from carbon dioxide and ethylene. This work fills the absence of group-9 metal based catalyst for the acrylate synthesis and provides a designing approach for pincer-ligated d⁸-metal catalysts to utilize pπ-dπ interaction for promoting desirable redox processes.     

Turbulent flow past a bubble and an ellipsoid using shadow-image and PIV techniques

An experimental investigation on flow around an oscillating bubble and solid ellipsoid with a flat bottom was conducted. A single air bubble (equivalent diameter D_e=9.12 mm) was attached to a small disk (1 mm) at the end of a needle and suspended across a vertical square channel (100 mm) by wire wherein water flowed downward at a constant flowrate. The solid ellipsoid (D_e9.1 mm) was suspended across the square channel in the same manner. The equivalent diameter-based Reynolds and Eotvos number range, 1950<Re<2250 and 11<Eo<11.5, placed the bubble in the ‘wobbly’ regime while the flow in its wake was turbulent. A constant flowrate and one bubble size was used such that flow in the wake was turbulent. Velocity measurements of the flow field around the bubble or solid were made using a one CCD camera Digital Particle Image Velocimetry (DPIV) system enhanced by Laser Induced Fluorescence (LIF). The shape of the bubble or solid was simultaneously recorded along with the velocity using a second CCD camera and an Infrared Shadow Technique (IST). In this way both the flow-field and the boundary of the bubble (solid) were measured. The velocity vector plots of flow around and in the wake of a bubble/solid, supplemented by profiles and contours of the average and root-mean-square velocities, vorticity, Reynolds stress and turbulent kinetic energy, revealed differences in the wake flow structure behind a bubble and solid. One of the significant differences was in the inherent, oscillatory motion of the bubble which not only produced vorticity in the near-wake, but as a result of apparent vorticity stretching distributed the turbulent kinetic energy associated with this flow more uniformly on its wake, in contrast to the solid.     

Frequency dependence of intermolecular proton spin-lattice relaxation rate and pair-diffusion constant in neat acetonitrile -d2

Frequency dependence of intermolecular proton spin-lattice relaxation rate [(1/T₁)inter(ω)] in neat acetonitrile-d₂ was studied. From (1/T₁)inter(ω) pair-diffusion constants were determined to be 0.281 × 10^?5 and 0.237 × 10^?5 cm² s^?1 at 22 and ?32.6°C, respectively. These values differ greatly from the self-diffusion constants.     

Lipoproteins modulate growth and differentiation of cultured human epidermal keratinocytes

The effects of various lipoproteins on the growth and the differentiation of cultured normal human keratinocytes were investigated. Primary cultures of human epidermal keratinocytes were obtained from neonatal foreskin, and then added with lipoproteins, very low density lipoprotein (VLDL), low density lipoprotein (LDL), and high density lipoprotein (HDL). Cell growth potential was examined using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay. VLDL and LDL enhanced keratinocytes growth and LDL receptor expression at the plasma membrane level. These effects were more remarkably observed in cells cultured with VLDL than in cells cultured with LDL. Apolipoprotein E (ApoE) was highly increased in VLDL treated cells. These results suggest that VLDL binds with high affinity to cell surface receptors and induces cell proliferation.     

Convenient syntheses of 3,6-dialkyl-1,4-dihydroxy-2,5-dioxopiperazines

Some 3,6-dialkyl-1,4-dihydroxy-2,5-dioxopiperazines were conveniently prepared from the corresponding 3,6-dialkyl-2,5-dichloropyrazines via their 1,4-dioxides and 3,6-dialkyl-2,5-dihydroxypyrazine 1,4-dioxides. On the basis of the examination of pmr, tlc, and glc of the 2,5-dioxopiperazines derived from the products, it was clarified that all the products were cis-diastereomers.     

Metabolic engineering of Saccharomyces cerevisiae for efficient production of pure l−(+)−lactic acid

We developed a metabolically engineered Saccharomyces cerevisiae, which produces optically pure L-lactic acid efficiently using cane juice-based medium. In this recombinant, the coding region of pyruvate decarboxylase (PDC)1 was completely deleted, and six copies of the bovine L-lactate dehydrogenase (L-LDH) genes were introduced on the genome under the control of the PDC1 promoter. To confirm optically pure lactate production in low cost medium, cane juice-based medium was used in fermentation with neutralizing conditions. L-lactate production reached 122 g/L, with 61% of sugar being transformed into L-lactate finally. The optical purity of this L-lactate, that affects the physical characteristics of poly-L-lactic acid, was extremely high, 99.9% or over.