Fluorescent tetraruthenated porphyrins embedded in monolithic SiO2 gels by the sol-gel process

In this work silica gels have been prepared by a sol-gel method using tetraethylorthosilicate as gel precursor. The tetraruthenated porphyrins H2(3-TRPyP), Co(3-TRPyP), and H2(4-TRPyP) were incorporated into the systems during gel formation without problems commonly found in the process, such as aggregation. Spectroscopic studies of the resulting silica gels revealed the presence of absorption bands in the range 200-400 nm associated with the transitions of the groups ruthenium-bipyridine, along with the Soret band at the same wavelengths observed in solution. The porphyrins were found to preserve fluorescence emission properties in the range 650-700 nm even after the aging period. Study of the thermal behavior and decomposition kinetics evidenced that the porphyrin H2(4-TRPyP) is the least stable of the group and that all compounds decompose according to first-order kinetics.     

Liquid-liquid equilibria of polyrotaxane and poly(vinyl alcohol)

Liquid–liquid equillibria (LLE) of the tertiary system of hydroxypropylated polyrotaxane (HPPR)–poly(vinyl alcohol) (PVA)–solvent have been investigated by focusing on the internal structures of HPPR–PVA blend gels. The phase diagrams of the HPPR–PVA aqueous systems displayed two liquid phases at a high concentration and molecular weight of PVA. This result was consistent with the prediction of the Flory–Huggins lattice model. On the contrary, the HPPR–PVA–DMSO system exhibited only a single phase. The HPPR–PVA blend gels crosslinked in dimethylsulfoxide (DMSO) were highly transparent over a wide concentration range, while the gels prepared in water were opaque at high polymer concentrations. Spherical domains were observed in the opaque gels by laser scanning confocal microscopy, and the sizes of the domains were significantly dependent on the amount of cross-linking reagent utilized. These results indicated that the transparency of the HPPR–PVA blend gels was strongly affected by the competition between the liquid–liquid two-phase separation and the crosslinking HPPR and PVA polymers during the preparation of the blend gels.     

Dynamic processes in endocytic transformation of a raft-exhibiting giant liposome

The dynamic response of a raft-exhibiting giant liposome to external stimuli, such as the addition of Triton X-100 or osmotic stress, was studied. We observed that daughter vesicles are generated inside of the liposome through endocytic budding. It was found that the budding to generate daughter vesicles is classified into two different routes, simple budding through the invagination of a whole raft and budding from the boundary of a raft accompanied by waving motion. Smaller rafts show a preference for simple budding, whereas large rafts mainly adopt the other process. We discuss the mechanism of this difference in terms of the kinetic pathway of internalization by considering the line energy and bending energy of the membrane.     

Analysis of Off-Axial Optical Systems (1)

We have established a new method of aberration analysis for off-axial optical systems which are generalized concepts of co-axial optical systems, by introducing two kinds of newly defined 4-element vectors and expanding these vectors with the help of tensor algebra. In this method, since aberration properties are represented in tensor form, we can easily formulate the aberration relations between different azimuths. We can then evaluate the azimuth dependence of aberration properties in greater detail by separating them into inherent optical properties parts, which are independent of azimuths, and the paraxial ray-tracing part, which includes the expression of the evaluation azimuth.     

Time-Resolved Measurements of in vivo Optical Properties of Piglet Brain

The in vivo optical properties of a piglet brain were measured using a time-resolved system at three different wavelengths (759, 794, 824 nm). To separate the contribution of different head layers to the detected signals, the measurements were acquired from the surfaces of skin, skull, dura mater and brain. The source detector distance was chosen to assure a mean penetration depth within each layer. Measurements were analyzed and compared with the results of other in vivo measurements reported in literature.     

Reaction mechanism for target-like products from197Au target bombarded with12C ions of energies above 100 MeV/u

Target-like products, that is,^191–200Au,^185–200Pt, and^183–195Ir, from¹⁹⁷Au target bombarded with¹²C ions at the energies of 180, 230, and 400 MeV/u were measured by using off-line gamma-ray spectrometry combined with chemical separation procedures. Spallation systematics by Rudstam reproduces well the measured cross sections for formation of platinum and iridium isotopes. It was found that the cross sections of gold nuclides increase with increase of the incident energy in the range studied and they are enhanced if compared with the reported proton-induced reaction of gold at a similar incident energy. It is suggested that the electromagnetic dissociation process plays a role for production of such gold nuclides.     

Numerical methods for conjunctive two‐dimensional surface and three‐dimensional sub‐surface flows

Sophisticated catchment runoff problems necessitate conjunctive modeling of overland flow and sub‐surface flow. In this paper, finite difference numerical methods are studied for simulation of catchment runoff of two‐dimensional surface flow interacting with three‐dimensional unsaturated and saturated sub‐surface flows. The equations representing the flows are mathematically classified as a type of heat diffusion equation. Therefore, two‐ and three‐dimensional numerical methods for heat diffusion equations were investigated for applications to the surface and sub‐surface flow sub‐models in terms of accuracy, stability, and calculation time. The methods are the purely explicit method, Saul'yev's methods, the alternating direction explicit (ADE) methods, and the alternating direction implicit (ADI) methods. The methods are first examined on surface and sub‐surface flows separately; subsequently, 12 selected combinations of methods were investigated for modeling the conjunctive flows. Saul'yev's downstream (S‐d) method was found to be the preferred method for two‐dimensional surface flow modeling, whereas the ADE method of Barakat and Clark is a less accurate, stable alternative. For the three‐dimensional sub‐surface flow model, the ADE method of Larkin (ADE‐L) and Brian's ADI method are unconditionally stable and more accurate than the other methods. The calculations of the conjunctive models utilizing the S‐d surface flow sub‐model give excellent results and confirm the expectation that the errors of the surface and sub‐surface sub‐models interact. The surface sub‐model dominates the accuracy and stability of the conjunctive model, whereas the sub‐surface sub‐model dominates the calculation time, suggesting the desirability of using a smaller time increment for the surface sub‐model. Copyright © 2000 John Wiley & Sons, Ltd.     

Surface analysis of nitride layers formed on Fe‐based alloys through plasma nitride process

Nitriding phenomena that occur on the surfaces of pure Fe and Fe? Cr alloy (16 wt% Cr) samples were investigated. An Ar + N₂ mixture‐gas glow‐discharge plasma was used so that surface nitriding could occur on a clean surface etched by Ar⁺ ion sputtering. In addition, the metal substrates were kept at a low temperature to suppress the diffusion of nitrogen. These plasma‐nitriding conditions enabled us to characterize the surface reaction between nitrogen radicals and the metal substrates. The emission characteristics of the band heads of the nitrogen molecule ion (N₂⁺) and nitrogen molecule from the glow‐discharge plasma suggest that the active nitrogen molecule is probably the major nitriding reactant. AES and angle‐resolved XPS were used to characterize the thickness of the nitride layer and the concentration of elements and chemical species in the nitride layer. The thickness of the nitride layer did not depend on the metal substrate type. An oxide layer with a thickness of a few nanometers was formed on the top of the nitride layer during the nitriding process. The oxide layer consisted of several species of N_x‐Fe_y‐O, NO⁺, and NO₂^?. In the Fe? Cr alloy sample, these oxide species could be reduced because chromium is preferentially nitrided. Copyright © 2009 John Wiley & Sons, Ltd.