Electroneutrality coupling of electron transfer at an electrode surface and ion transfer across the interface between thin-layer of 1-octyl-3-methylimidazolium bis(perfluoroalkylsulfonyl)imide covering the electrode surface and an outer electrolyte solution.

The electrode reaction of decamethylferrocene (DMFc) dissolved in a thin layer of a room-temperature molten salt (RTMS), 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C8mimC1C1N) or 1-octyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide (C8mimC2C2N), on a self-assembled monolayer-modified gold electrode is coupled with the ion transfer across the interface between the RTMS and the outer aqueous solution (W) to give a voltammogram whose shape resembles a voltammogram of a simple one-electron transfer process. The electroneutrality of the RTMS layer during the oxidation of DMFc to decamethylferricenium ion is maintained by the concomitant dissolution of C8mim+ ion from the RTMS phase to the W phase, and the reduction of decamethylferricenium ion to DMFc is accompanied by the transfer of either C1C1N- or C2C2N- from RTMS to W. The midpoint potential of the voltammogram varies with the concentration of the salt in the aqueous phase, C8mimCl or LiCnCnN (n = 1 or 2), in a Nernstian manner, showing that the phase-boundary potential between the RTMS and the W is controlled by the partition of these ions. Although the phase-boundary potential across the RTMS / W interface is Nernstian with respect to the ions common to both phases at the equilibrium, the polarization at the RTMS / W interface under current flow distorts the shape of the voltammograms, resulting in a wider peak separation in the voltammogram.     

A simple and sensitive method for the determination of hydroxylamine in fresh-water samples using hypochlorite followed by gas chromatography.

A new and simple method for the determination of hydroxylamine in environmental water, such as fresh rivers and lakes using hypochlorite, followed by its gas choromatographic detection, has been developed. A glass vial filled with sample water was sealed by a butyl-rubber stopper and aluminum cap without head-space, and then sodium hypochlorite solution was injected into the vial through a syringe to convert hydroxylamine to nitrous oxide. The head-space in the glass vial was prepared with 99.9% grade N2 using a gas-tight syringe. After the glass vial was shaken for a few minutes, nitrous oxide in the gas-phase was measured by a gas chromatograph with an electron-capture detector. The dissolved nitrous oxide in the liquid-phase was calculated according to the solubility formula. The proposed method was applied to the analysis of fresh-water samples taken from Iu river and Hii river, flowing into brackish Lakes Nakaumi and Shinji, respectively.     

Photo-induced evolution of copper sheets from cluster molecules and its application to photolithographic copper patterning

UV photoexcitation of (t-butylethynyl copper)₂₄ cluster films induces segregation of the crystals into metallic and organic phases and leads to evolve the metallic sheets sandwiched by organic polymers. The growth of the metallic crystals in the plane of the photo-electromagnetic field is attributed due to plasmon-plasmon interaction among nanoparticles embedded in dielectric polymer matrices. The surface enhanced photochemical reaction of residual cluster molecules on the photon incident direction is expected to take an important role for joining the metal particles to produce a metallic sheet. We can apply this phenomenon for photolithographic copper pattern generation on a flexible base plate.     

Asymmetric synthesis of 2-substituted-3-aminocarbonyl propionic acid

An asymmetric synthetic route to 2-substituted-3-aminocarbonyl propionic acid, which is the significant component of low-molecular-weight renin inhibitors, is described. The key step of this synthesis is diastereoselective alkylation by using chiral oxazolidinone and benzyl bromoacetate.     

Friction coefficient and structural transition in a poly(acrylamide) gel

The friction coefficient between the polymer network of an opaque poly(acrylamide) gel and water is measured as a function of the mole fraction of cross linker. The friction coefficients of opaque gels are 4 to 5 orders of magnitude smaller than those of the transparent gels. This drastic decrease in friction occurs when the mole fraction of cross linker is 0.2. In opaque gels, the friction coefficient of gels and the mole fraction of cross linker are related by a power law. The network structure of the opaque gels used in the friction measurements is examined with a confocal laser scanning microscope. The opaque gel network consists of a fractal aggregate of colloidal particles. The radius of particles and the volume occupied by the particles depend on the mole fraction of cross linker. Both relationships are well described by the power laws. The power law of the friction coefficient is well explained in terms of the power laws of the structural parameters and the Stokes equation of the hydrodynamic friction for the spherical particle. It indicates that the friction of the opaque gel is determined simply by the structure of the polymer network.     

Mechanism of antioxidative activity of fluvastatin-determination of the active position

In order to clarify the mechanism of action for the antioxidative activity of fluvastatin sodium (FLV, (+/-)-sodium (3RS, 5RS, 6E)-7-[3-(4-fluorophenyl)-1-(1-methylethyl)-1H-indol-2-yl]-3, 5-dihydroxy-6-heptanoate) and its derivatives, reaction of the corresponding methyl ester of FLV with di-tert-butyl diperoxyoxalate was examined, and the corresponding keto derivative was isolated from the reaction mixture. On the basis of this result, it was concluded that the active site is the allylic carbon conjugated with the indole ring.     

Syntheses and biological activities of renin inhibitors containing statine analogues

Syntheses and biological activities of dipeptide renin inhibitors that contain statine analogues are described. The key steps of the synthetic approach to dipeptide renin inhibitors are the asymmetric synthesis of 2(R)-substituted-3-aminocarbonylpropionic acids and the diastereoselective syntheses of (3S,4S)-statine analogues. These inhibitors (2,14-40) inhibited human renin in the 3-140 nM range. Inhibitor ES 6864 (2) was found to be a highly potent inhibitor of human renin (IC50: 4.6 x 10(-9) M) and showed high enzyme specificity. Oral administration of ES 6864 at 3 mg/kg to conscious, sodium-depleted marmosets inhibited plasma renin activity (PRA) more than 80% after 1 h.     

Phylogenetic analysis of picoplankton in Lake Biwa and application to legal medicine

Three strains of picoplankton designated as brown, green, and pink belonging to the Synechococcus genus in cyanobacteria (approximately 1 microm in size) are found ubiquitously in Lake Biwa, Japan. However, they could not be morphologically discriminated from other bacteria such as Proteobacteria and Bacillus by microscopy. In this study, we attempted to use the polymerase chain reaction (PCR) analysis of the 16S ribosomal DNA (rDNA) from picoplankton for the diagnosis of death by drowning. A segment of 16S rDNA was sequenced in order to investigate their phylogenetic relationships and to design the specific primers. The PCR products from three picoplanktons were compared with those from five other cyanobacteria, Melosira (diatom), Staurastrum (green alga), bacteria from Lake Baikal, and humans. The picogram order of template DNA from picoplankton was specifically amplified by the primers. When the template of picoplankton was mixed with human tissue, at least 10 ng of template DNA was needed to obtain a PCR product. The efficiency of PCR was increased more than hundredfold by isolating the picoplankton from human lung tissue. The specific PCR products of the picoplankton were obtained from a formalin-fixed drowning body (lung and liver) that was found in a downstream river and Lake Biwa. The PCR analysis of the picoplanktion 16S rDNA is considered useful for the diagnosis of death by drowning.     

Chemo-enzymatic Synthesis of Novel Oligo-N-acetyllactosamine Derivatives having a β(1-4)–β(1-6) Repeating Unit by Using Transition State Analogue Substrate

Chitinase-catalyzed hydrolytic and transglycosylating behavior of 1,2-oxazoline derivative of N-acetyllactosamine (LacNAc-oxa) 1 has been investigated. An extremely rapid hydrolysis (ring-opening of the oxazoline moiety) could be observed, suggesting that 1 behaves as a transition state analogue substrate for chitinase A1 (Bacillus circulans WL-12). This disaccharide monomer 1 was found to polymerize under basic conditions, giving rise to novel oligosaccharides having a β(1-4)–β(1-6) repeating unit in the main chain. The degree of polymerization of the resulting oligosaccharides was up to 5. This is the first example of enzymatic glycosylation reaction forming a β(1-6) bond catalyzed by chitinase.