Bioactive saponins and glycosides. XXVII. Structures of new cucurbitane-type triterpene glycosides and antiallergic constituents from Citrullus colocynthis

The methanolic extract from the fruit of Citrullus colocynthis showed an inhibitory effect on ear passive cutaneous anaphylaxis reactions as a type I allergic model in mice. From the methanolic extract, two new cucurbitane-type triterpene glycosides, colocynthosides A and B, were isolated together with 17 known constituents. The structures of colocynthosides A and B were elucidated on the basis of chemical and physicochemical evidence. In addition, the principal cucurbitane-type triterpene glycoside, cucurbitacin E 2-O-beta-D-glucopyranoside, and its aglycon, cucurbitacin E, exhibited the antiallergic activity at a dose of 100 and 1.25 mg/kg, p.o., respectively.     

Synthesis of gamma-hydroxybutenolides applying crossed aldol condensation in the presence of a bulky lewis acid and their anti-tumor activity

An improved synthesis of gamma-hydroxybutenolides 1a-d was achieved via crossed aldol condensation between aldehydes 2a-d and the protected gamma-hydroxy-beta-methylbutenolides 3 or 4 using the bulky Lewis acid, aluminum tris(2,6-diphenylphenoxide) (ATPH). Using this same methodology, the gamma-hydroxybutenolides 17a-d having various heteroaromatic rings were synthesized and their anti-tumor activities were evaluated.     

Interlayer water molecules in vanadium pentoxide hydrate. IX. Anisotropic translational diffusion leading to anisotropic ac conductivity

The anisotropy of the dynamic properties of interlayer water molecules along the a and b axes of vanadium pentoxide hydrate, orthorhombic V2O5.nH2O, was studied using quasielastic neutron scattering (QENS) in relation to the anisotropy of the ac conductivity. The QENS spectra were analyzed using a stretched exponential function and a Lorentzian function. Both methods showed that the double-layer water molecules along the b axis are more mobile than those along the a axis. The difference in mobility between the two axes is more pronounced using a Lorentzian function analysis. These facts suggest that the diffusion coefficient of water molecules along the b axis is larger than that along the a axis, which is closely related to the ac conductivity originating from proton hopping. The anisotropy of the dynamic motion of water molecules can be attributed to the shorter b-axis length (b=3.60 A), with respect to the longer and less regular repetition of the atomic arrangements along the a axis (42.34 A).     

Adsorption behaviors of high-valence metal ions on desferrioxamine B immobilization nylon 6,6 chelate fiber under highly acidic conditions

Adsorption behaviors of the high-valence metal ions Zr(IV), Hf(IV), Ti(IV), V(V), Nb(V), Ta(V), and Mo(IV) on desferrioxamine B (DFB) immobilization nylon 6,6 chelate fiber was investigated under highly acidic conditions. Though the complexes of DFB and the high-valence metal ions were extracted without selectivity by solvent extraction, the only zirconium ions showed higher adsorption percentages than that of other high-valence metal ions on the DFB immobilization nylon 6,6 chelate fiber. Adsorption properties were caused that limited the freedom of DFB by chemical immobilization. Especially, hafnium ions and zirconium ions, which have similar chemical properties, showed different adsorption behavior in highly acidic aqueous solutions. Zirconium ions were quantitatively adsorbed up to 13.5 micromol/g.     

Regioselective oxyfunctionalization of unactivated carbons in steroids by a model of cytochrome P-450: osmiumporphyrin complex/tert-butyl hydroperoxide system

tert-Butyl hydroperoxide catalyzed by (5,10,15,20-tetramesitylporphyrinate) osmium(II) carbonyl [Os(TMP)CO] complex was found to be a highly efficient versatile oxidant for C-H carbons in steroid substrates. When reacted with representative steroids with an estrane, pregnane, 5beta-cholane, or 5alpha-cholestane structure, regioselective oxyfunctionalization and/or oxidative degradation occurred to give a variety of novel and uncommon derivatives in one step.     

From propargylic biscarbonate to diaryl[n]dendralenes

An efficient cross-coupling reaction using a low cost carbon-supported palladium (Pd/C) catalyst for the synthesis of cross-conjugated compounds, diaryl[n]dendralenes, has been developed. The reaction of a propargylic biscarbonate with phenylboronic acid using Pd/C and phosphine ligand (S-Phos) gave 2,3-diphenyl[2]dendralene in high yield. We found that Pd/C was an effective catalyst for the synthesis of dialyl[n]dendralenes. The synthesis of various dendralenes was successfully achieved under the optimized conditions, giving dialyl [2] and [4] dendralenes in good yields.     

The formal synthesis of (+)-15-deoxy-Δ12,14-prostaglandin J2: Controlling exo-olefin geometry via SmI2-mediated cyclization

A synthetic approach of (+)-15d-PGJ₂ has been developed. The present method features a stereoselective construction of the olefin unit using SmI₂-mediated radical cyclization. The resulting cyclic compound was further utilized by efficient introduction of α and ω chains of prostaglandins to achieve enantioselective formal synthesis of (+)-15d-PGJ₂.     

Studies on the foundation and development of diagnostic ultrasound

In recent years, various types of diagnostic imaging methods, such as CT, MRI, PET and Ultrasound, have been developed rapidly and become indispensable as clinical diagnostic tools. Among these imaging modalities, CT, MRI and PET all apply electromagnetic waves like radiation rays. In contrast, an ultrasound imaging method uses a completely different mechanical pressure wave: “sound”. Ultrasound has various features, including inaudible sound at very high frequencies, which allows its use in medical diagnoses. That is, ultrasound techniques can be applied in transmission, reflection and Doppler methods. Moreover, the sharp directivity of an ultrasound beam can also improve image resolution. Another big advantage of diagnostic ultrasound is that it does not harm the human body or cause any pain to patients. Given these various advantages, diagnostic ultrasound has recently been widely used in diagnosing cancer and cardiovascular disease and scanning fetuses (Fig. 1) as well as routine clinical examinations in hospitals. In this paper, I outline my almost 50-year history of diagnostic ultrasound research, particularly that performed at the early stage from 1950–56.Open in a separate windowFig. 1.The recent ultrasonic real-time imaging diagnostic instrument by electric scan system and three dimensional images of fetus.     

Sum frequency generation spectroscopic studies on phase transitions of phospholipid monolayers containing poly(ethylene oxide) lipids at the air-water interface

Vibrational sum frequency generation (SFG) spectroscopy was applied to study the phase transitions of the mixed monolayers of l-alpha-distearoyl phosphatidylethanolamine (DSPE) and DSPE covalently coupled with poly(ethylene oxide) at the amino head group (DSPE-EO(45), DSPE with 45 ethylene oxide monomers) at the air-water interface. The SFG spectra were measured for the mixed monolayers with the mole fractions of DSPE-EO(45) of 0, 1.3, 4.5, 9.0, 12.5, and 16.7% at the surface pressures of 5, 15, and 35 mN/m. The monolayer compression isotherms indicated that the mixed monolayers at 5, 15, are 35 mN/m are mainly in the so-called "pancake", "mushroom", and "brush" states, respectively. The SFG spectra in the OH stretching vibration region give rise to SFG bands near 3200 and 3400 cm(-1). The mean molecular amplitude of the former band due to the OH stretching of the "icelike" water molecules associated mainly with the hydrophilic poly(ethylene oxide) (PEO) chains, exhibits appreciable decrease on compression of the mixed monolayers from 5 to 15 mN/m. The result corroborates the model for the pancake-mushroom transition, which presumes the dissolution of the PEO chains from the air-water interface to the water subphase. Further compression of the mixed monolayers to 35 mN/m causes a slight decrease of the line amplitude, which can be explained by considering a squeezing out of water molecules from the hydrophilic groups of DSPE-EO(45) in the brush state, where the PEO chains strongly interact with each other to form a tight binding state of the hydrophilic groups. The relative intensities of the SFG bands due to the CH3 asymmetric and symmetric vibrations were used to estimate the tilt angles of the terminal methyl group of DSPE, indicating that the angle increases with increasing the mole fraction of DSPE-EO(45). The angles almost saturate at the mole fraction larger than 10%, the saturation angle being nearly 90 degrees at 5 mN/m, ca. 60 degrees at 15 mN/m, and ca. 47 degrees at 35 mN/ m. Then, the introduction of the hydrophilic PEO head group causes a large tilting of the alkyl groups of DEPE in the mixed monolayers.