Synthetic studies on the taxane skeleton: construction of eight-membered carbocyclic rings by the intramolecular B-alkyl Suzuki-Miyaura cross-coupling reaction

Construction of eight-membered carbocyclic rings via the intramolecular B-alkyl Suzuki-Miyaura cross-coupling reaction has been studied. This protocol proved its potency through the formation of the eight-membered ring possessing a quaternary carbon on its ring in high yield, affording promise of a new access to the eight-membered ring of Taxol. [reaction: see text]     

Phonon density of states and compression behavior in iron sulfide under pressure

We report the partial phonon densities of states (DOS) of iron sulfide, a possible component of the rocky planet's core, measured by the 57Fe nuclear resonant inelastic x-ray scattering and calculate the total phonon DOS under pressure. From the phonon DOS, we drive thermodynamic parameters. A comparison of the observed and estimated compressibilities makes it clear that there is a large pure electronic contribution in the observed compressibility in the metallic state. Our results present the observation of thermodynamic parameters of iron sulfide with the low-spin state of an Fe2+ ion at the high density, which is similar to the condition of the Martian core.     

LambdaN spin-orbit splittings in (9)(Lambda)Be and (13)(Lambda)C studied with one-boson-exchange LambdaN interactions

Parametric x rays (PXR) produced by bombarding silicon and diamond crystals with electrons of 30 to 87 MeV were detected at 180 degrees relative to the direction of the electron beam. It was found that the dependence of the intensity on the orientation of the crystal agrees with the predictions of the kinematical theory of PXR. The absolute intensity is twice as large as predicted. These findings can be explained considering dynamical effects that govern the x-ray crystal interaction. Additionally, x rays caused by self-diffracted transition radiation have been observed.     

Raman spectroscopy of SWNTs produced by a XeCl excimer laser ablation at high temperatures

Synthesis of single-wall carbon nanotubes (SWNTs) was carried out by an ablation method using a XeCl excimer laser. It was irradiated onto a graphite target containing Co and Ni at the temperatures of 1073, 1173, 1273, 1373, 1473, 1523 and 1623 K under the atmosphere (0.1 MPa) of Ar gas with the flow rate of 12 ml/min. The measurement by a scanning/transmission electron microscope and Raman spectroscopy found the formation of SWNTs with the diameter of about 1.3 nm and the length of about 2 μm in ablated carbonaceous soot. The ratio of peak intensity of 1590 cm⁻¹ (G band) to that of 1335 cm⁻¹ (D band) in the high frequency Raman spectra increased with increasing the ambient temperature. The radial breathing mode (RBM) in the low frequency Raman spectra shows that the mean diameter of SWNTs increased with increasing the ambient temperature.     

Spin-freezing processes around the tricritical point in Mn1−xTixSb

Transitions related to the spin-glass phase in Mn_1−xTi_xSb are revisited from the nonlinear ac susceptibility. Near the tricritical point (x≈0.8), the transition between ferromagnetic and reentrant spin-glass states is sharp. At x0.8, an anomally is found slightly above the temperature of usual spin-glass freezing.     

A simple HPLC-fluorescence detection of nitric oxide in cultivated plant cells by in situ derivatization with 2,3-diaminonaphthalene.

An HPLC method with fluorescence detection for the determination of nitric oxide (NO) in cultivated plant cells (Agave pacifica, Agavaceae) was developed. NO was derivatized in situ with 2,3-diaminonaphthalene (DAN) as a labeling reagent and converted to 1(H)-naphthotriazole. The maximum peak height of the derivative was observed by incubation for 3 h at 25 degrees C with 0.2 mM DAN. Excess reagent in cells was removed by washing 3 times with 5 ml of water. The calibration curve for authentic standard of DAN-NO spiked to cultivated plant cells showed a good linearity (r = 0.995) in the range of 5.0 to 50 pmol/g cell. The detection limit at a signal-to-noise ratio of 3 was 3.4 pmol/g cells. The proposed method was successfully applied to the monitoring of NO concentration with cell growth. The effect of thermal treatment on the concentration of NO in plant cells was also examined. The concentration of NO in cells treated at 5 degrees C for 1 h was significantly higher than that treated at 25 degrees C and 35 degrees C for 1 h (n = 3, p < 0.05).     

Rheo-optical properties of polyethylene films in the nonlinear viscoelastic region

A new apparatus was designed to investigate the dynamic viscoelastic properties of solid polymer materials in the nonlinear viscoelastic region. The apparatus was combined with a birefringence apparatus in such a way that birefringence could be measured simultaneously with stress under oscillatory deformation. The nonlinear viscoelastic behavior of bulk-crystallized high-density polyethylene films was examined. Nonlinearity of mechanical properties became evident around 30°C, while optical properties became markedly nonlinear around 50°C. The nonlinearity of viscoelastic properties changes very little when the films are swollen with tetrachloroethane. It is proposed that disruption of lamellae to crystallites in the drawing process is one of the most important causes of the nonlinear behavior of high-density polyethylene films.     

An efficient and selective conversion of sorbitol in ionic liquids: Use of ion exchange resin as a solid acid catalyst

Sorbitol was readily converted by heating in hydrophobic ionic liquids by the presence of ion exchange resins. Chemoseletivity of the dehydration depended on the choice of ion exchange resin; Nafion selectively produced isosorbide while Amberlite gave 1,5-anhydrosorbitol along with unreacted sorbitol. Ionic liquids used in the reaction were readily recovered by simple extraction procedure. With these procedures, we succeeded to prepare isosorbide in pure form, not contaminated with either ionic liquids or acid catalyst, by simple experimental procedure.     

Cobalt-catalyzed regioselective [3+2] annulation of ortho-formyl and acetyl substituted phenylboronic acids with alkynes

Treatment of alkynes with ortho-formyl and acetyl phenylboronic acids in the presence of a cobalt catalyst resulted in the formation of 2,3-disubstituted indenols in good yields. When aryl silyl alkynes were used, 2-aryl-3-silyl indenols were obtained regioselectively in good yields.