Refraction effect of scattered X-ray fluorescence at surface

The angular distribution of X-ray fluorescence shows anisotropic radiation. We proved that the origin of the anisotropic radiation is X-ray refraction by using a scattered X-ray fluorescence model. Utilizing the refraction effect of X-ray fluorescence, we can obtain much information: for example, surface density, chemical condition, surface roughness, and particle diameter of element, as a new tool of studying surfaces and interfaces. We introduce a new X-ray dispersive system utilizing X-ray refraction.     

Use of ESCA for a convenient and semi-quantitative state analysis of copper-nickel alloy surfaces

Summary A semi-quantitative technique by means of ESCA was applied to the surface state analysis of copper-nickel alloys. With area integrated intensity of peaks at the L₃M_{4, 5}M_{4, 5} region of copper and 2 p 3/2 region of nickel, cuprous state and nickel oxide state on alloys could be semi-quantitatively determined. As to oxygen states on alloy surfaces, interstitial (Cu₂O and NiO states), non-stoichiometric (represents -OH) and molecular states (adsorbed) were estimated. Further, the surface composition of alloys after heating under high vacuum was discussed.

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Einsatz von ESCA für die einfache halbquantitative Zustandsanalyse von Oberflächen von Kupfer-Nickel-Legierungen

Zusammenfassung Das ESCA-Verfahren wurde für die Untersuchung des Oberflächenzustandes von KupferNickel-Legierungen eingesetzt. Mit Hilfe der flächenintegrierten Peakintensitäten (L₃ M_{4, 5} M_{4, 5} für Kupfer, 2 p 3/2 für Nickel) konnten Kupfer(II) und Nickeloxid auf den Legierungen halbquantitativ bestimmt werden. Sauerstoff wurde im interstitiellen (Cu₂O, NiO) nichtstöchiometrischen (-OH) und molekularen (adsorbierten) Zustand gefunden. Weiterhin wurde die Oberflächenzusammensetzung der Legierungen nach Erhitzen im Hochvakuum diskutiert.

     

Study of a novel sample injection method (floating electrokinetic supercharging) for high-performance microchip electrophoresis of DNA fragments

Aiming to achieve high-performance analysis of DNA fragments using microchip electrophoresis, we developed a novel sample injection method, which was given the name of floating electrokinetic supercharging (FEKS). In the method, electrokinetic injection (EKI) and ITP preconcentration of samples was performed in a separation channel, connecting two reservoir ports (P3 and P4) on a cross-geometry microchip. At these two stages, side channels, crossing the separation channel, and their ports (P1 and P2) were electrically floated. After the ITP-stacked zones passed the cross-part, they were eluted for detection by using leading ions from P1 and P2 that enabled electrophoresis mode changing rapidly from ITP to zone electrophoresis (ZE). Possible sample leakage at the cross-part toward P1 and P2 was studied in detail on the basis of computer simulation using a CFD-ACE+ software and real experiments, through which it was validated that the analyte recovery to the separation channel was almost complete. The FEKS method successfully contributed to higher resolution and shorter analysis time of DNA fragments on the cross-microchip owing to more rapid switching from ITP status to ZE separation in comparison with our previous EKS procedure realized on a single-channel microchip. Without any degradation of resolution, the achieved LODs were on average ten times better than using conventional pinched injection.     

Temperature-swing adsorption of aromatic compounds in water using polyampholyte gel

The adsorption property of the polyampholyte gel composed of sodium styrene sulfate (SSS) and vinylbenzyl trimethylammonium chloride (VBTA) has been investigated with several hydrophobic aromatic compounds as adsorbate. Using the N-isopropylacrylamide (NIPA) gel, the corresponding experiments were also performed for comparison. At room temperature, the NIPA gel hardly adsorbed the aromatic compounds, while it adsorbed them at higher temperatures. As for the SSS-VBTA gel, the adsorption amounts of the polyaromatic compounds decreased with increasing temperature, while the adsorption amounts of the monoaromatic compounds were almost independent of temperature and smaller than those of the polyaromatic compounds. These results indicate that the aromatic rings in the SSS-VBTA gel may play an important role in the adsorption of the aromatic compounds. Also, it has been demonstrated that the SSS-VBTA gel can repeatedly adsorb bisphenol-A at room temperature and desorb it at higher temperature by the temperature-swing operation: this behavior is diametrically opposite to that of the NIPA gel. This shows that the SSS-VBTA gel is much more suitable for the adsorption removal of the hydrophobic aromatic compounds from very dilute aqueous solutions, because a vast amount of energy is required for heating a large amount of water when using the NIPA gel.     

Uptake of gas-phase nitrous acid by pH-controlled aqueous solution studied by a wetted wall flow tube

Uptake kinetics of gas phase nitrous acid (HONO) by a pH-controlled aqueous solution was investigated by using a wetted wall flow tube. The gas phase concentration of HONO after exposure to the aqueous solution was measured selectively by the chemical ionization mass spectrometer in a high sensitive manner. The uptake rate of the gaseous HONO was found to depend on the pH of the solution. For the uptake by neutral and alkaline solutions, the gas phase concentration was observed to decay exponentially, suggesting that the uptake was fully limited by the gas phase diffusion. On the other hand, the uptake by the acidic solution was found to be determined by both the gas phase diffusion and the liquid phase processes such as physical absorption and reversible acid dissociation reaction. The decay was analyzed by the rate equations using the time dependent uptake coefficient involving the saturation of the liquid surface. While the uptake processes by the solution at pH = 2-3 were well described by those calculated using the physical and chemical parameters reported for the bulk, the uptake rates by the solution at 4 < pH < 7 deviate from the calculated ones. The present result can suggest that the pH at the liquid surface is lower than that in the bulk liquid, which is responsible for the additional resistance of mass transfer from the gas to the liquid phase.     

Synthesis of 5,10,15-triazaporphyrins--effect of benzo-annulation on the electronic structures

Novel triazaporphyrins were synthesized using 1,9-dibromodipyrromethene as a key starting material. These triazaporphyrins exhibit comparatively intense Soret and Q bands in the UV/vis region due to their hybrid properties between porphyrins and phthalocyanines.     

Direct meso-alkynylation of porphyrins doubly assisted by pyridyl coordination

Direct meso-alkynylation of β,β'-dipyridylporphyrin with various alkynyllithium reagents has been achieved, in which the β,β'-dipyridyl groups play an important role in facilitating the nucleophilic addition of the reagents through double coordination. This method enabled the synthesis of a meso-ethynylene-bridged diporphyrin.