Voltammetric study of electrocatalysis for dioxygen reduction by trinuclear rutheniumammine complex confined in a polymer membrane

Electrocatalytic O₂ reduction was studied using a modified electrode coated with a Nafion membrane (Nf) dispersing a trinuclear ruthenium ammine complex ([(NH₃)₅Ru^IIIORu^IV(NH₃)₄ORu^III(NH₃)₅]Cl₆, Ru-red). When measuring cyclic voltammogram under O₂ atmosphere (at 0.5 mV s⁻¹), catalytic currents due to O₂ reduction were found to develop below −0.2 V (vs. Ag/AgCl). Since Ru-red undergoes irreversible decomposition into the mononuclear complexes via the reduced state (Ru^III-Ru^III-Ru^III) (∼−0.1 V), it is suggested that the electrocatalysis originates from the decomposed species (initial active species: Ru^II(NH₃)₅(OH₂) and Ru^II(NH₃)₄(OH₂)₂) rather than from the Ru-red. Although the present electrocatalyst was also applied to H₂O₂ reduction system, the catalytic activity was found to be poor from the voltammetric behavior. It appeared that the kinetics of the electrocatalysis is much faster in the O₂ reduction than in the H₂O₂ one. A selective and direct catalysis for O₂ reduction into H₂O was suggested from a ring-disk voltammogram to take place by an aggregate of the mononuclear ruthenium complexes in the polymer matrix. In addition, it was found that electrocatalytic O₂ reduction involves a slow kinetic process, so that factors affecting the overall kinetics were discussed in terms of the catalysis mechanism.     

Bubble wake visualization by using photochromic dye

Wake structure of a single “clean bubble”, rising in rectilinear, zigzagging or spiraling path, is experimentally investigated. A single nitrogen gas bubble was produced in a silicone oil pool and the wake structure development in the rear of the rising bubble was visualized by using photochromic dye. The flexibility of this visualization method enabled us to distinguish wake from drift easily. Both bubble motion and wake structure were recorded by using stereo high-speed video camera simultaneously. We present the first experimental support for the existence of the standing eddy at the rear of the clean bubble, as predicted by a previous numerical study by Ryskin and Leal [1984. Journal of Fluid Mechanics 148, 19-35], Dandy and Leal [1986. Physics of Fluids 29(5), 1360-1366] and Blanco and Magnaudet [1995. Physics of Fluids 7(6), 1265-1274]. We study motion of a pair of vortex filaments, which is called double-threaded type wake, in the case of bubble rising in an axi-asymmetric path. Visualization results of multiple formations of horse-shoe type vortices in one period of zigzag motion of rising bubble with shape oscillations, which has not been observed in previous studies are also presented.     

Structural and hydration properties of amorphous tricalcium silicate

Mechanical milling was carried out to synthesize amorphous tricalcium silicate (Ca₃SiO₅) sample, where Ca₃SiO₅ is the most principal component of Portland cement. The partial phase transformation from the crystalline to the amorphous state was observed by X-ray and neutron diffractions. Moreover, it was found that the structural distortion on the Ca-O correlation exists in the milled Ca₃SiO₅. The hydration of the milled Ca₃SiO₅ with D₂O proceeds as follows: the formation of hydration products such as Ca(OD)₂ rapidly occurs in the early hydration stage, and then proceeds slowly after about 15 h. The induction time for the hydration of the milled Ca₃SiO₅ is approximately one half shorter than that for the hydration of the unmilled one. This result means that the mechanical milling brings about the chemical activity of Ca₃SiO₅ for hydration, and may be particularly useful for increasing the reactivity in the early hydration stage.     

High-intensity multi-bunch beam generation by a photo-cathode RF gun

A multi-bunch photo-cathode RF gun system has been developed as an electron source for the production of intense quasi-monochromatic X-rays based on inverse Compton scattering. The desired multi-bunch beam is 100 bunches/pulse with a total charge of 500 nC and a bunch spacing of 2.8 ns. We modified the gun cavity of a ‘BNL-type IV’ RF gun to allow a CsTe cathode plug in the end plate. The system uses a four-dipole chicane beam line to allow the injection of laser light normal to the cathode surface. We compensate the gun cavity beam loading caused by the high-intensity multi-bunch electron beam by injecting the laser pulse before RF power has filled the cavity. We have achieved a total intensity of 220 nC in 100 bunches with a bunch-to-bunch energy spread under 1.3% (peak-to-peak). This paper concentrates on experiments to generate the high-intensity multi-bunch beam with compensation of the bunch-to-bunch energy spread due to heavy beam loading.     

A novel chromatographic separation technique using tertiary pyridine resin for the partitioning of trivalent actinides and lanthanides

A novel chromatographic separation technique using a tertiary pyridine type resin has been applied to the partitioning of the trivalent actinides (An) and lanthanides (Ln) and several successful results have been shown. In an alcoholic hydrochloric acid system, the trivalent An were clearly separated from the Ln, while no such group separation was achieved in an alcoholic nitric acid system. On the other hand, the nitric acid system was more effective for the intragroup (i.e. individual) separation of the trivalent An and the Ln than the hydrochloric acid system. On the basis of these results, a novel concept for the partitioning of the trivalent An and Ln using the present separation technique and its flowchart have been proposed with its advantages and disadvantages.     

A fast and compact elimination method of empty elements from a double‐array structure

A double‐array is a well‐known data structure to implement the trie. However, the space efficiency of the double‐array degrades with the number of key deletions because the double‐array keeps empty elements produced by the key deletion. This paper presents a fast and compact elimination method of empty elements using properties of the trie nodes that have no siblings. The present elimination method is implemented by C language. From simulation results for large sets of keys, the present elimination method is about 30–330 times faster than the conventional elimination method and maintains high space efficiency. Copyright © 2003 John Wiley & Sons, Ltd.     

Visualization of oscillating flow in a double-inlet pulse tube refrigerator with a diaphragm inserted in a bypass-tube

The double-inlet pulse tube refrigerator that has a diaphragm inserted in a bypass-tube, which enabled it to transmit a pressure oscillation whereas to obstruct a DC gas flow, was manufactured and tested. The oscillating flow behavior inside of the refrigerator was studied by using a smoke-wire flow visualization technique. It was found that if the diaphragm was optimized, the performance would be improved more than that of the refrigerator with a bypass valve due to the increase in the P–V work of the gas and the decrease in the convective heat loss caused by a secondary flow.     

Anthocyanins,but not Anthocyanidins,from Bilberry (Vaccinium myrtillus L.) Alleviate Pruritus via Inhibition of Mast Cell Degranulation

Abstract: We have previously reported that bilberry anthocyanins exhibit an anti‐pruritic effect in a mouse model of allergic contact dermatitis. It has been reported that anthocyanins are particularly sensitive to thermal treatment and are easily hydrolyzed to anthocyanidins when exposed to high temperatures. The objective of this study was to compare the anti‐pruritic effect of anthocyanin‐rich quality‐controlled bilberry extract and anthocyanidin‐rich degraded extract using a mouse model of allergic contact dermatitis. BALB/c mice with allergic contact dermatitis induced by 4 weeks of repeated application of 2,4,6‐trinitro‐1‐chlorobenzene (TNCB) were administered Bilberon‐25 orally for 4 weeks after sensitization with TNCB. The effect of Bilberon‐25 on pruritus was evaluated by measurement of scratching behavior. RBL‐2H3 mast cells were used to investigate the effect of Bilberon‐25 on degranulation in 48/80‐stimulated mast cells. Compared with nonheated Bilberon‐25, the proportion of anthocyanins in heated Bilberon‐25 decreased, and the proportion of anthocyanidins was increased in heated‐time dependent manner. Treatment with non‐heated Bilberon‐25 significantly attenuated the TNCB‐induced increase in scratching behavior, whereas treatment with 2 h‐heated Bilberon‐25 did not. Moreover, 300 μg/mL nonheated Bilberon‐25 showed significant inhibition of degranulation in RBL‐2H3 mast cells, whereas 2 h‐heated Bilberon‐25 had no effect at any concentration studied. It is assumed that the inhibitory effect of bilberry anthocyanins on pruritus might be mediated, at least in part, by its inhibitory effect on mast cell degranulation. In conclusion, the anthocyanin‐rich but not anthocyanidin‐rich bilberry extract may be a useful dietary supplement for skin diseases involving pruritic symptoms, such as chronic allergic contact dermatitis, atopic dermatitis, and rhinitis.     

Simultaneous Quantification of Secoisolariciresinol Diglucoside and Cyanogenic Glycosides in Flaxseed Products by Various Processing Methods

Two cyanogenic glycosides (linustatin and neolinustatin) and sucrose were isolated from defatted flaxseed, and their structures were determined by NMR spectral analysis and comparison with existing data. Using secoisolariciresinol diglucoside (SDG) and the cyanogenic glycosides as standards, we developed a method to quantify the three compounds simultaneously by ultrahigh-performance liquid chromatography (UHPLC)-MS in selected reaction monitoring (SRM) mode. Using this tool, flaxseed powder—processed by various methods—was analyzed with regard to the contents of the beneficial compound, SDG, and the toxic compounds, cyanogenic glycosides. The levels of SDG in samples treated with alkaline solution are much higher than in samples without treatment, and in general, the levels of linustatin and neolinustatin in flaxseed powder decreased progressively as heating time is prolonged after treatment with alkaline solutions.     

Detection of Buckminsterfullerene in Usual Soots and Commercial Charcoals

Abstract

It was confirmed that soot produced by free burning of small hydrocarbons like benzene and cyclohexane generally contains less than 0.1 ppm of C₆₀. Small, but measurable amounts of C₆₀ were found in two samples of charcoal, providing the first indication of fullerene formation in the solid state.