Syntheses and magnetic properties of Cu(II)(hfac)2 and Mn(II)(hfac)2 complexes of 4-pyridyl-substituted thioaminyl radicals

Two types of Cu(II)(hfac)2 and Mn(II)(hfac)2 complexes of N-(4-pyridylthio)-4-ethoxycarbonyl-2,6-bis(4-chlorophenyl)phenylaminyl (1) and N-(4-pyridylthio)-2,4,6-tris(4-chlorophenyl)phenylaminyl (2) were prepared and their X-ray crystallographic and magnetic studies were performed. Mixtures of Cu(II)(hfac)2 and 1 and Mn(II)(hfac)2 and 2 in anhydrous heptane-benzene solution gave 1 : 2 complexes of M(II)(hfac)2 (M = Cu, Mn) and 1 or 2 in 73-75% yields. For Cu(II)(hfac)2(1)2 and Mn(II)(hfac)2(2)2 X-ray crystallographic analyses were successfully performed. The magnetic behaviors for the two metal complexes were investigated with a SQUID magnetometer. The analyses for the chimolTvs. T plots of Cu(II)(hfac)2(1)2 were carried out by the numerical diagonalization of the Heisenberg Hamiltonian matrix (4096 x 4096 matrix) for the four repeating units of the complex (12-spin system). The exchange interaction between the copper(II) ion and the thioaminyl radicals is ferromagnetic (J1/kB = +28 K) and the interactions between the complexes is antiferromagnetic (J2/kB = -13 K). The magnetic behavior of Mn(II)(hfac)2(2)2 complexes is well analyzed with the theoretical equation of a 1/2-5/2-1/2 three-spin system taking the intermolecular interaction (theta) into account. The exchange interaction between the Mn(II) ion and the thioaminyl radicals is antiferromagnetic (J/kB = -4.2 K) and theta = -1.0 K. These magnetic behaviors could be well explained in terms of their crystal structures.     

Viologen-modified platinum clusters acting as an efficient catalyst in photocatalytic hydrogen evolution

A highly efficient photocatalytic system for hydrogen evolution with dihydronicotinamide coenzyme (NADH) as a sacrificial agent in an aqueous solution has been constructed by using water-soluble platinum clusters functionalized with methyl viologen-alkanethiol (MVA2+) and a simple electron-donor dyad, 9-mesityl-10-methylacridinium ion (Acr+-Mes), which is capable of fast photoinduced electron transfer but extremely slow back electron transfer. The mean diameter of the platinum core was determined as R(CORE) = 1.9 nm with a standard deviation sigma = 0.5 nm by transmission electron microscopy (TEM). As a result, the hydrogen-evolution rate of the photocatalytic system with MVA2+-modified platinum clusters (MVA2+-PtC) is 10 times faster than the photocatalytic system with the mixture of the same amount of MVA2+ and platinum clusters as that of MVA2+-PtC under otherwise the same experimental conditions. The radical cation of NADH has been successfully detected by laser flash photolysis experiments. The decay of the absorbance due to NAD*, produced by the deprotonation from NADH*+, coincides with the appearance of the absorption band due to Acr*-Mes. This indicates electron transfer from NAD* to Acr+-Mes to give Acr*-Mes, which undergoes the electron-transfer reduction of MVA2+-PtC, leading to the efficient hydrogen evolution.     

In situ observation and simulation of growth process of faceted RE123 crystals

To clarify the growth mechanism of faceted REBa₂Cu₃O_7−δ (RE123, RE = Sm, Y) crystals, the growth process of the crystals was observed in situ by using a high temperature microscope. The growth rate of each faceted interface of a crystal growing from the liquid + 211 phases under an undercooling was obtained from the relationship between the position of each interface and growth time. It was observed that some of the faceted interfaces of a growing crystal stopped growing after a period of time, while other interfaces continued to grow with a growth rate approximated by a function of the undercooling. The above stoppage of the growth was observed in situ for the first time, and this fact could give powerful support to the mechanism for a similar phenomenon in REBCO films which were fabricated by the trifluoroacetates metal organic deposition method: growing microstructures of RE123 crystals in the film were revealed by transmission electron microscopy (TEM) for quenched specimens. Some very thin a-axis grains were formed by a change in c-axis growth rate. Furthermore, we showed the above growth and stop phenomena of faceted interfaces of REBCO crystal grains using numerical simulations.     

Phase control of iron silicides using femtosecond laser irradiation

Phase control of Fe–Si amorphous thin film in micro area is demonstrated using femtosecond laser irradiation. A femtosecond laser beam with a high repetition rate over 200 kHz and tightly focused through an objective lens promotes both crystallization and phase transformation from an amorphous phase into crystalline β-FeSi₂, α-FeSi₂, or ε-FeSi phases. Formation of each crystalline phase is possible by changing the pulse energy or the scanning speed of the incident laser beam.     

Spectrophotometric determination of sulfide in the presence of sulfite and thiosulfate via the precipitation of bismuth(III) sulfide.

A photometric method has been developed for the determination of sulfide at 10(-5) mol dm(-3) levels, which is based on the reaction of sulfide with a given excess amount of bismuth(III) to form a precipitate of bismuth(III) sulfide and on the spectrophotometric measurement of the residual bismuth(III) at 335 nm after extracting with bismuthiol II reagent from an aqueous solution containing acetate buffer into benzene. The presence of sulfite and thiosulfate up to 0.002 mol dm(-3) did not cause any interference in the determination of sulfide, because both sulfite and thiosulfate do not produce any precipitate with bismuth(III). A linear calibration plot with a negative slope was obtained for sulfide over the range of 5.00 x 10(-7) - 3.00 x 10(-5) mol dm(-3) (16.0 - 960 ppb). An experimental calibration plot was in accord with the theoretical plot, taking into account the known excess of bismuth(III), showing that the reaction of sulfide with bismuth(III) proceeded to completion. The relative standard deviation of results from 10 replicate determinations of standard sulfide (2.00 x 10(-5) mol dm(-3)) was 0.44%. The proposed method was successfully applied to the determination of sulfide in hotspring water samples without any pretreatment.     

Dependence of NO2 sensitivity on thickness of oxide-sensing electrodes for mixed-potential-type sensor using stabilized zirconia

The effect of thickness of oxide-sensing electrode (SE) on NO₂ sensitivity of the planar sensor based on yttria-stabilized zirconia (YSZ) was examined at high temperatures. The sensitivity of the sensor increased with decreasing thickness of SE, and the highest sensitivity was obtained by using the thinnest layer of Cr₂O₃–SE (2.7 μm) at 700 °C. In the case of NiO–SE, the highest sensitivity was observed for the sensor using the 4-μm-thick SE even at a high temperature of 850 °C. Based on the results of the measurements for the complex impedances, the polarization curves, and the gas-phase NO₂ decomposition catalysis, it was confirmed that the catalytic activity to the gas-phase NO₂ decomposition on the oxide–SE matrix played an important role in determining the NO₂ sensitivity of the present sensors.     

Bifurcation in an inverted pendulum with tilted high-frequency excitation: analytical and experimental investigations on the symmetry-breaking of the bifurcation

In this study, we investigate the dynamics of an inverted pendulum subjected to high-frequency excitation. In particular, we focus on bifurcation phenomena in the dynamics and analyze the effect of the tilt of the excitation direction with respect to gravity direction on the bifurcation. It is analytically clarified that the tilt produces stable equilibrium states different from the directions of the gravity and the excitation. The stability of the stable equilibrium states under the effect of the tilt is discussed non-locally. Also, an analogy of the bifurcation of the inverted pendulum to that of the buckling phenomenon is presented. The theoretically predicted effects of the tilt are qualitatively confirmed by performing some experiments.     

H2 dissociative adsorption at the armchair edges of graphite

We investigate and discuss how hydrogen behaves at the edges of a graphite sheet, in particular the armchair edge. Our density functional theory-based calculations results show that, in contrast to the zigzag edge [W.A. Diño, H. Nakanishi, H. Kasai, T. Sugimoto, T. Kondoe, e-J. Surf. Sci. Nanotech. 2 (2004) 77. [25]], regardless of orientation, there is an activation barrier hindering H₂ dissociation at the armchair edges. And once they do get dissociatively adsorbed at the armchair edges, we find that it would be extremely hard to desorb the H from their adsorption sites at the armchair edges. Furthermore, we also found that, consistent with our earlier conclusions [W.A. Diño, Y. Miura, H. Nakanishi, H. Kasai, T. Sugimoto, J. Phys. Soc. Jpn. 72 (2003) 1867. [24]], it is unlikely that we would find a whole H₂ in between plain graphite sheets.