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.     

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.     

Amphidinolide X,a novel 16-membered macrodiolide from dinoflagellate Amphidinium sp

A novel cytotoxic 16-membered macrodiolide, amphidinolide X (1), has been isolated from a marine dinoflagellate Amphidinium sp. (strain Y-42). The gross structure of 1 was elucidated on the basis of spectroscopic data including one-bond and long-range (13)C-(13)C correlations. The relative and absolute stereochemistries were determined by combined analyses of NOESY data and (1)H-(1)H and (1)H-(13)C coupling constants of 1 and NMR data of the degradation products. Amphidinolide X (1) is the first macrodiolide consisting of polyketide-derived diacid and diol units from natural sources. The biosynthetic origins of 1 were investigated by means of feeding experiments with (13)C-labeled acetates.     

Solvothermal synthesis of large surface area zirconia

The reaction of zirconium n-propoxide in glycol at 300°C yielded microcrystalline tetragonal zirconia (ZrO₂). The crystallite size of the product depended on the carbon number of the glycol and increased in the following order (carbon number of glycol): 2<6<4, which suggested that the heterolytic cleavage of O-C bond of gylcoxide formed by transesterification is the prime factor for the formation of the product. In toluene, zirconium isopropoxide also gave tetragonal zirconia at 300°C, and zirconium tert-butoxide decomposed at 200°C yielding amorphous zirconia, while zirconium n-propoxide was stable at 300°C. These results suggest that the reaction in toluene depends on the structure of the alkyl group of the alkoxides. Thus-obtained tetragonal zirconias maintained large surface areas (90–160 m²/g) even after calcination at 500°C.     

Application of sequence Fourier analysis to a specific interaction in Arabidopsis thaliana

The sequence Fourier analysis reported previously seems to be applicable to elucidating a simple and concerted interaction in Arabidopsis thaliana, similar to that in Homo sapiens.     

An asymptotic approximation for EPMC in linear discriminant analysis based on two-step monotone missing samples

In this paper, we consider the expected probabilities of misclassification (EPMC) in the linear discriminant function (LDF) based on two-step monotone missing samples and derive an asymptotic approximation for the EPMC with an explicit form for the considered LDF. For this purpose, we also provide some results of the expectations for the inverted Wishart matrices in this paper. Finally, we conduct the Monte Carlo simulation for evaluating our result.     

Efficient synthesis of optically active atropisomeric anilides through catalytic asymmetric N-arylation reaction

In the presence of (R)-DTBM-SEGPHOS-Pd(OAc)2 catalyst, N-arylation of ortho-tert-butyl-NH-anilides with 4-nitroiodobenzene proceeds with high enantioselectivity (89-95% ee) to give optically active atropisomeric anilides possessing N-C chiral axis. Furthermore, the intramolecular version of the present catalytic asymmetric N-arylation gave atropisomeric lactams with high optical purity (94-96% ee).     

Rapid oligosaccharide synthesis using a fluorous protective group

The Bfp-OH, a novel fluorous protecting reagent, was able to be easily prepared. The Bfp group was readily introduced to a carbohydrate, removed in high yield, and recyclable after cleavage. The use of the Bfp group made it possible to synthesize a pentasaccharide by minimal column chromatography purification. Each synthetic intermediate was able to be easily purified only by simple fluorous-organic solvent extraction and monitored by TLC, NMR, and MS.