The Huggins band of ozone: unambiguous electronic and vibrational assignment

The Huggins band of ozone is investigated by means of exact dynamics calculations using a new (diabatic) potential energy surface for the (1)B(2) state. The remarkable agreement with the measured spectrum strongly suggests that the Huggins band is due to the two C(s) potential wells of the (1)B(2) state. The vibrational assignment, based on the nodal structure of wave functions, supports the most recent experimental assignment.     

Amphidinolide Y, a novel 17-membered macrolide from dinoflagellate Amphidinium sp.: plausible biogenetic precursor of amphidinolide X

A novel cytotoxic 17-membered macrolide, amphidinolide Y (1), has been isolated from a marine dinoflagellate Amphidinium sp., and it was elucidated to exist as a 9:1 equilibrium mixture of 6-keto- and 6(9)-hemiacetal forms (1a and 1b, respectively) on the basis of 2D NMR data and chemical means. The feeding experiments with (13)C-labeled acetates suggested that amphidinolide Y (1) may be a biogenetic precursor of 16-membered macrodiolide, amphidinolide X (2).     

Plakevulin A, a new oxylipin inhibiting DNA polymerases α and γ from sponge Plakortis species

A new cytotoxic oxylipin, plakevulin A (1), possessing a cyclopentene ring and a levulinyl ester has been isolated from an Okinawan marine sponge Plakortis sp. The structure was elucidated on the basis of spectroscopic data, and the absolute configurations at three chiral centers were assigned by spectroscopic data of the reductive product of 1 and a modified Mosher's method. Plakevulin A (1) exhibited inhibitory activity against DNA polymerases α and γ.     

A novel action of terpendole E on the motor activity of mitotic Kinesin Eg5

To reveal the mechanism of mitosis, the development of M phase-specific inhibitors is an important strategy. We have been screening microbial products to find specific M phase inhibitors that do not directly target tubulins, and rediscovered terpendole E (TerE) as a novel Eg5 inhibitor. TerE did not affect microtubule integrity in interphase, but induced formation of a monoastral spindle in M phase. TerE inhibited both motor and microtubule-stimulated ATPase activities of human Eg5, but did not affect conventional kinesin from either Drosophila or bovine brain. Although terpendoles have been reported as inhibitors of acyl-CoA:cholesterol O-acyltransferase (ACAT), the Eg5 inhibitory activity of TerE was independent of ACAT inhibition. Taken together, we demonstrate that TerE is a novel Eg5 inhibitor isolated from a fungal strain.     

High-pressure elastic properties of solid argon to 70 GPa

The acoustic velocities, adiabatic elastic constants, bulk modulus, elastic anisotropy, Cauchy violation, and density in an ideal solid argon (Ar) have been determined at high pressures up to 70 GPa in a diamond anvil cell by making new approaches of Brillouin spectroscopy. These results place the first complete study for elastic properties of dense Ar and provide an improved basis for making the theoretical calculations of rare-gas solids over a wide range of compression.     

Effects of fine fuel droplets on a laminar flame stabilized in a partially prevaporized spray stream

A partially prevaporized spray burner was developed to investigate the interaction between fuel droplets and a flame. Monodispersed partially prevaporized ethanol sprays with narrow diameter distribution were generated by the condensation method using rapid pressure reduction of a saturated ethanol vapor–air mixture. A tilted flat flame was stabilized at the nozzle exit using a hot wire. Particle tracking velocimetry (PTV) was applied to measurements of the droplet velocity; the laminar burning velocity was obtained from gas velocity derived from the droplet velocity. Observations were made of flames in partially prevaporized spray streams with mean droplet diameters of 7 μm and the liquid equivalence ratios of 0.2; the total equivalence ratio was varied. In all cases, a sharp vaporization plane was observed in front of the blue flame. Flame oscillation was observed on the fuel-rich side. At strain rates under 50 s⁻¹, the change in the burning velocity with the strain rate is small in fuel-lean spray streams. In spray streams of 0.7 and 0.8 in the total equivalence ratio, burning velocity increases with strain rates of greater than 50 s⁻¹. However, in spray streams with 0.9 and 1.0 in the total equivalence ratio, burning velocity decreases as the strain rate increases. At strain rates greater than 80 s⁻¹, burning velocity decreases with an increased gas equivalence ratio. The effect of mean droplet diameter, and the entry length of droplets into a flame on the laminar burning velocity, were also investigated to interpret the effect of the strain rate on the laminar burning velocity of partially prevaporized sprays.     

Investigation of structural changes related to temperature: An understanding of H-bond based proton transfer in 4(5)-vinylimidazole and acrylic acid copolymer membrane

An attempt to understand how proton transfer proceeds in poly (acrylic acid-co-4(5)-vinylimidazole) has been carried out based on the temperature dependent characterization techniques, i.e., Fourier transform infrared spectroscopy (FTIR), wide angle X-ray diffraction (WAXD), Raman spectroscopy, including the atomic distance calculations. Systematical studies are achieved from a series of poly (acrylic acid-co-4(5)-vinylimidazole) with different acrylic acid content. When the copolymer is almost an ideal in equimolar ratio of an alternating structure, the hydrogen bond between carboxylic acid and imidazole is maintained and initiates the proton conductivity even at 120 °C. Whereas when the copolymer is carboxylic acid rich, the dehydration to form anhydride proceeds resulting in the decrease in proton conductivity at high temperature. The radial distribution function (RDF) calculated from the WAXD pattern shows that the inter-atomic distances reflect how the increase in temperature induces a favorable packing structure under the hydrogen bond network and the chain mobility to enhance the proton transfer at high temperature, especially in the case of the copolymer with an ideal alternating structure.     

Stress distribution in poly‐p‐phenylenebenzobisoxazole (PBO) fiber estimated from vibrational spectroscopic measurement under tension. II. Analysis of inhomogeneous stress distribution in PBO fiber

Fourier transform Raman spectra were measured for poly‐p‐phenylenebenzobisoxazole (PBO) fiber subjected to a tensile stress, and the Raman shift factor (the frequency shift caused by 1 GPa tensile stress) depended strongly on the sample‐preparation condition. To clarify the reasons of this dependency, a mechanical series parallel model was adopted that could successfully and quantitatively explain the observed Raman shift factors and gave a concreate heterogeneous stress distribution in the PBO fibers. As a result, a mechanical series model was reasonable for PBO fiber. Broadening of Raman bands, which was observed when the PBO fiber was tensioned, could also be interpreted on the basis of an idea of heterogeneous stress distribution. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1281–1287, 2002