Surface coordination of nitric oxide to a self-assembled monolayer of a triruthenium cluster: an in situ infrared spectroscopic study

Coordination of nitric oxide (NO) to a self-assembled monolayer (SAM) of a triruthenium (Ru(3)) cluster, [Ru(3)(micro(3)-O)(micro-CH(3)COO)(6)(CO)(L(1))(L(2))] (0) (L(1) = [(NC(5)H(4))CH(2)NHC(O)(CH(2))(10)S-](2), L(2) = 4-methylpyridine), on a gold electrode surface has been studied by electrochemical and in situ infrared (IR) spectroscopic measurements. Ligand substitution reaction of NO for carbon monoxide (CO) ligands in the SAM strongly depends on the oxidation state of the terminal Ru(3) cluster. NO can be introduced into the Ru(3) cluster in the SAM with a high yield after one-electron oxidation of the Ru(3) core to a (III,III,III) oxidation state, while no coordination reaction occurs at the initial oxidation state (II,III,III) of the Ru(3) cluster. The kinetics of the NO coordination and desorption processes is also evaluated by time-resolved in situ IR spectroscopy. Finally, we demonstrate that the SAM with NO/CO randomly mixed ligands at a desired ratio can be constructed on the gold surface by tuning a suitable oxidation state of the Ru 3 cluster under electrochemical control.     

Detection of modified tyrosines as an inflammation marker in a photo-aged skin model

Reactive nitrogen species, produced during the process of inflammation induced by various factors including UV radiation, modify amino acids in crucial proteins. It is assumed that skin tissue is more likely to be modified, as it is located at the outer layer of a body that is exposed to UV radiation on a daily basis. To investigate the influence of the modified tyrosine on UV-exposed skin, we detected the nitrotyrosine or halogenated tyrosine and dityrosine in photo-aged model mice. The back skin of mice was exposed to a dose of 10 J cm(-2) day(-1) every day for 15 weeks. Samples exhibiting typical symptoms of photo aging were provided to the immunofluorescence study. The quantification of modified proteins was accomplished through a chemical analytical method known as HPLC-tandem mass spectrometry. Analysis of the irradiated skin samples showed that all modified tyrosine except nitrotyrosine demonstrated statistically significant increases. The molecular weights of major modified proteins, confirmed as 25-50 kDa, were measured using Western blot analysis with an anti-nitrotyrosine antibody. Furthermore, the immunofluorescence study verified that the localization of myeloperoxidase conformed to that of nitrotyrosine. This result suggests that the modified tyrosine was produced during the process of inflammation by UV irradiation. In this study, we used a low dose of UV irradiation to which we are exposed in daily life. Our results suggest that UV exposure in daily life may induce the production of modified tyrosines and skin aging.     

Effects of low-temperature chemistry on the wall heat flux in HCCI combustion

Direct numerical simulations of homogeneous charge compression ignition combustion are performed to investigate the behaviour of the wall heat flux, Φ, under engine relevant conditions. In laminar conditions, there are four distinctive stages where Φ evolution is affected by low-temperature chemistry (LTC), resulting in multiple local maxima with a lagged maximum value in Φ evolution. These effects are also observed in turbulence conditions locally. However, they no longer appear in the mean Φ evolution clearly, although some weak non-monotonicity in Φ due to the LTC are observed. The locality of the LTC effects may need to be addressed for near-wall pollutant prediction in future.     

Quantitative Analysis of Ozone and Nitrogen Oxides Produced by a Low Power Miniaturized Surface Dielectric Barrier Discharge: Effect of Oxygen Content and Humidity Level

Plasma Chemistry and Plasma Processing - This study presented a quantitative evaluation of the performance of a low power miniaturized SDBD source for the production of ozone and nitrogen oxides as...     

Evolving genetic code

In 1985, we reported that a bacterium, Mycoplasma capricolum, used a deviant genetic code, namely UGA, a "universal" stop codon, was read as tryptophan. This finding, together with the deviant nuclear genetic codes in not a few organisms and a number of mitochondria, shows that the genetic code is not universal, and is in a state of evolution. To account for the changes in codon meanings, we proposed the codon capture theory stating that all the code changes are non-disruptive without accompanied changes of amino acid sequences of proteins. Supporting evidence for the theory is presented in this review. A possible evolutionary process from the ancient to the present-day genetic code is also discussed.     

3D simulation and visualization of unsteady wake flow behind a cylinder

In this paper we focus on 3D simulation of unsteady wake flow behind a circular cylinder. We show that in addition to accurate formulations and sufficiently-refined meshes, efficient computing methods are essential components of an effective simulation strategy. We use the Multi-Domain Method (MDM) we developed recently in computation of two cases. At Reynolds number 300, we demonstrate how the MDM enables us to use highly-refined meshes to capture wake patterns which we otherwise cannot fully represent. At Reynolds number 140, we show that with the MDM we can extend our computations sufficiently downstream, and with sufficient accuracy, to successfully capture the second phase of the Karman vortex street, which has been observed in laboratory experiments, and which has double the spacing between the vortices compared to the first phase.     

Effect of copper compounds on the photo-degradation of polyethylene

In order to elucidate the retardation mechanism of copper compounds in the photo-degradation of polyethylene, the effects of copper stearate, butyrate, acetate and cupric chloride on the photo-degradation of the polymer were examined by infra-red spectra, emission spectra and phosphorescence lifetimes.All copper compounds examined apparently retard the photo-degradation of polyethylene. Polyethylene emits fluorescent light at around 350 nm and phosphorescent light at around 450 nm and the intensities of these emission spectra are strongly decreased by the addition of the copper compounds. The excited triplet lifetimes of the polymer are not affected. In addition, no appreciable difference in photo-degradation was observed between pure polymer samples irradiated through tetrahydrofuran solutions of copper compounds and polymer samples containing the copper compounds irradiated through pure tetrahydrofuran. From the results it is deduced that one of the main retardation functions of the copper compounds is the absorption of ultraviolet light.