Stereoselective vinylogous Mukaiyama aldol reaction of α-haloenals

We have developed a high-yielding and stereoselective vinylogous Mukaiyama aldol reaction (VMAR) of α-haloenals. Contrary to the simple α,β-unsaturated aldehyde, α-haloenals were found to be reactive affording the corresponding VMAR adducts in excellent yields. Some transformations of VMAR adducts by Pd-mediated cross-coupling were also examined in order to demonstrate the synthetic utility of VMAR of α-haloenals.     

Fluorous solvent for cell culture

Incubation of mouse melanoma B16 cells in fluorous solvents with low boiling point such as perfluoromethylcyclohexane, 1,1,1,3,3,3-hexafluoro-2-propanol, ethylpentafluoropropionate resulted in cell death. However, cells lived up to 2 days in fluorous alcohols such as 2,2,3,3,4,4,5,5-octafluoro-1-pentanol and 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexanol with relatively higher fluorine content. Remarkably, cells survived deprived of nutrition up to 4 days when incubated in 2,2,3,3,4,4,5,5,6,6,6-undecafluoro-1-hexanol or in 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptanol that have the most number of fluorine atoms (11 and 12, respectively) among the perfluoroalkyl alcohols used, and with boiling points of 128 °C and 169 °C, respectively.     

Analytic Bethe ansatz for fundamental representations of Yangians

We study the analytic Bethe, ansatz in solvable vertex models associated with the YangianY(X _r ) or its quantum affine analogueU _q (X _r ⁽¹⁾ ) forX _r =B _r ,C _r andD _r . Eigenvalue formulas are proposed for the transfer matrices related to all the fundamental representations ofY(X _r ). Under the Bethe ansatz equation, we explicitly prove that they are pole-free, a crucial property in the ansatz. Conjectures are also given on higher representation cases by applying theT-system, the transfer matrix functional relations proposed recently. The eigenvalues are neatly described in terms of Yangian analogues of the semi-standard Young tableaux.     

Changes in light scattering from poly(ethylene terephthalate) and nylon 6 films upon stretching in relation to the deformation mechanism

Unoriented T-die flat films of nylon 6 and PET films annealed at 90°C were stretched in water at 80°C. Amorphous PET films were stretched in water at 65–75°C. Changes in the light scattering patterns from these samples upon stretching were investigated. One of the observed LS patterns from the stretched samples is the H_v eight-leaf pattern consisting of four lobes and streaks. In the nylon 6 and heat-treated PET showing this pattern, spherulitic patterns can be seen in polarization microscopy. The microscopic spherulitic superstructure may possibly be the factor responsible for producing the lobe-and-streak pattern. On the other hand, many microscopic eight-leaf patterns can be observed in amorphous unannealed PET showing the lobe-and-streak pattern. These microscopic patterns are due to retardation at stress concentrations around impurities and nuclei. The superstructure giving these microscopic patterns must be the origin of the lobe-and-streak pattern from unannealed PET. Another scattering pattern, the V_v cruciform pattern, was observed in both stretched nylon 6 and unannealed PET. This pattern is due to an orientation change across the slip lines observed under a polarizing microscope. It is noted (1) that the appearance of the slip lines in PET coincides with the occurrence of oriented crystallization on stretching, (2) that the lobe-and-streak pattern from PET in which orientation crystallization has taken place is fairly stable to heat treatment and does not disappear until just before melting, and (3) that the superstructures produced at low stretching seem to be deformed on further stretching, in accordance with affine deformation theory.     

Effective 4ƒ energy level in virtual excitation and in photoemission processes in Ce-pnictides

Effects of relaxation of occupied band electrons to the ?-hole state through the hybridization between ? and band states are studied based on a detailed model for Ce-monopnictides. The effective 4? level is shifted about 1–2 eV to shallow energy side from the unrenormalized bare level in processes in which the 4? electron is only virtually excited, such as in excitation to the vacant p band states through the p-? mixing. Photoemission spectra show two peaks, one near the Fermi energy and the other about 3 eV below it. The latter is shifted to deep energy side about 0.5–1 eV from the bare level when it lies near the bottom of the valence band. The discrepancy between the 4? level estimated from the low energy phenomena and that from photoemission is resolved.     

Quantitative determination of methyltestosterone and methyltestosterone-d3 in serum by gas chromatography-mass spectrometry

A method for the quantitative estimation of methyltestosterone and methyltestosterone-d3 in biological fluids has been developed using gas chromatography-mass spectrometry-selected-ion monitoring. Methyltestosterone-d6 was used as an internal standard. Methyltestosterone and methyltestosterone-d3 in serum were determined based on the peak height ratios of the molecular ions of methyltestosterone, methyltestosterone-d3 and methyltestosterone-d6. Sensitivity, specificity, precision, accuracy and reproducibility of the present method were demonstrated to be satisfactory for application to pharmacokinetic and bioavailability studies.     

Proton spin-lattice relaxation study of polymer solutions

Proton spin-lattice relaxation times of solvent molecules were measured on ternary mixtures of a polymer and two solvents by the adiabatic rapid-passage method. The selective adsorption of a good solvent was verified by this experimental technique for the systems benzene—cyclohexane—polystyrene(PS), benzene—carbon tetrachloride—poly(methyl methacrylate)(PMMA), and chloroform—carbon tetrachloride—PMMA. The number of molecules of adsorbed benzene per monomeric unit of PS was estimated to be about four, which is almost identical with that determined previously by thermodynamic measurements. The number of molecules of benzene and chloroform adsorbed on PMMA were also determined to be about five and four, respectively. It was found that the interaction between chloroform and PMMA has the greatest effect on the molecular motion of the solvent, whereas the benzene—PS interaction is weak.     

Anomalous resistivity near curie temperature due to the critical scattering

Critical behavior of the temperature derivative of the electrical resistivity at the Curie temperature is treated in general. It is shown by treating the sum rule in the correlation function rigorously that, for a large Fermi wave vector, the divergence is similar to that of specific heat both below and above the Curie temperature, but for a small Fermi wave vector, the de Gennes—Friedel region appears at higher temperatures. Comparison with other divergent mechanisms are also done.     

Stability condition for molecular magnetic polaron

It is shown that under suitable conditions a short range attractive interaction is expected for two magnetic polarons which causes formation of molecular magnetic polaron. For many valley band structures, the attractive molecular magnetic polaron. For many valley band structures, the attractive potential is enhanced and several electrons may form a giant magnetic polaron. Application for bubble domain is also proposed.