Spatial arrangement of metal nanoparticles supported by porous polymer substrates studied by transmission electron microtomography

Fine metal particles (nanoparticles) stabilized on porous (polymeric) substrates can be considered as a model system of a high-performance catalyst. In the present study, the substrate was made using the periodic microphase-separated structure of a block copolymer as the template, and the Pd nanoparticles were formed inside the porous material by reduction of the Pd2+ ions with 1-propanol as the reductant. The three-dimensional morphology of such a polymer-Pd hybrid material was studied by transmission electron microtomography. The characteristic structural parameters of the hybrid, e.g., the penetration of the Pd nanoparticles into the polymer substrate, number density of the Pd nanoparticles, and size distribution of the Pd nanoparticles, were measured for the first time.     

Possibility of a non-amino acid pathway in the biosynthesis of marine-derived oxazoles

A novel avenue for oxazoles via Beckmann rearrangement of alpha-formyl ketoxime dimethyl acetals is described that indicates the possibility of a non-amino acid biosynthetic pathway in marine natural products.     

Existence and uniqueness of stabilized propagating wave segments in wave front interaction model

Recent experimental studies of photosensitive Belousov–Zhabotinskii reaction have revealed the existence of propagating wave segments. The propagating wave segments are unstable, but can be stabilized by using a feedback control to continually adjust the excitability of the medium. Experimental studies also indicate that the locus of the size of a stabilized wave segment as a function of the excitability of the medium gives the excitability boundary for the existence of 2D wave patterns with free ends in excitable media. To study the properties of this boundary curve, we use the wave front interaction model proposed by Zykov and Showalter. This is equivalent to study a first order system of three ordinary differential equations which includes a singular nonlinearity. Using two different reduced first order systems of two ordinary differential equations, we first show the existence of wave segments for any given propagating velocity. Then the wave profiles can be classified into two types, namely, convex and non-convex types. More precisely, when the normalized propagating velocity is small, we show that the wave profile is of convex type, while the wave profile is of non-convex type when the normalized velocity is close to 1.     

Global solvability for abstract semilinear evolution equations

The Cauchy problem for the abstract semilinear evolution equation u^′(t) = Au (t) + B (u (t)) + C (u (t)) is discussed in a general Banach space X. Here A is the so‐called Hille‐Yosida operator in X, B is a differentiable operator from D (A) into X, and C is a locally Lipschitz continuous operator from D (A) into itself. A vectorvalued functional defined only on X is used and appropriate conditions on the nonlinear operators B and C are imposed so that a vector‐valued functional defined on the domain of the operator A may be constructed in order to specify the growth of a global solution. The advantage of our formulation lies in the fact that it is possible to obtain a global solution by checking some energy inequalities concerning only low order derivatives (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Entire Solutions with Merging Fronts to Reaction–Diffusion Equations

We deal with a reaction–diffusion equation u _t = u _xx + f(u) which has two stable constant equilibria, u = 0, 1 and a monotone increasing traveling front solution u = φ(x + ct) (c > 0) connecting those equilibria. Suppose that u = a (0 < a < 1) is an unstable equilibrium and that the equation allows monotone increasing traveling front solutions u = ψ₁(x + c ₁ t) (c ₁ < 0) and ψ₂(x + c ₂ t) (c ₂ > 0) connecting u = 0 with u = a and u = a with u = 1, respectively. We call by an entire solution a classical solution which is defined for all . We prove that there exists an entire solution such that for t≈ − ∞ it behaves as two fronts ψ₁(x + c ₁ t) and ψ₂(x + c ₂ t) on the left and right x-axes, respectively, while it converges to φ(x + ct) as t→∞. In addition, if c > − c ₁, we show the existence of an entire solution which behaves as ψ₁( − x + c ₁ t) in and φ(x + ct) in for t≈ − ∞.     

Synthesis of S‐Aryl Arenethiosulfonates from N,N‐Di(arenesulfonyl)hydrazines: Reduction of Sulfonyl Chlorides with an Organic Reagent

N,N‐Di(arenesulfonyl)‐N′,N′‐dimethyl‐hydrazines, readily prepared from arenesulfonyl chlorides and N,N‐dimethylhydrazine, were heated at 120°C in chlorobenzene to give S‐aryl arenethiosulfonates, ArSSO₂Ar, in good yields.     

Wastes Treatment: Hydrothermal electrolytic oxidation of wastewater

Abstract

Electrochemical evolution of hydrogen gas, oxygen gas and chlorine at the electrodes is the usual reaction in conventional electrolysis of aqueous salt solution. However, here we demonstrate that the electrolysis governing reaction in hydrothermal solutions is different from the electrolysis performed at atmospheric pressure and temperatures up to 100°C. Experimental electrolytic reaction of aqueous salt solution carried out inside a sealed 300-mL batch autoclave showed that; accumulation of hydrogen gas, oxygen gas and chlorine is highly suppressed under hydrothermal (250°C and 7 MPa) conditions. We have also observed that, when organics are present in the aqueous salt solution being hydrothermally electrolyzed, an effective oxidation of organics is accomplished. Furthermore, for hydrothermal electrolytic oxidation (HEO) with oxygen gas added, experimentally observed TOC removal profile demonstrates apparent anodic oxidation electrical current efficiency of almost 200% for highconcentrated acetic acid solutions.     

Study of Strangeness Photoproduction on the Neutron in the Threshold Region

Photoproduction of the neutral kaon on the deuteron has been investigated at the Research Center for Electron Photon Science, Tohoku University. We constructed the Neutral Kaon Spectrometer-2 for the detection of charged particles from the decay of the neutral kaon and the hyperon. We obtained a momentum distribution of K ⁰ with the inclusive measurement. It was consistent with the previous measurement. The total cross section of γ + d → K ⁰ + Λ + p was estimated from the measured integral cross section of γ + d → Λ + X. The total cross section with respect to the photon energy was compared with the theoretical calculations. It favored the Saclay-Lyon A model calculation with the ratio of the neutral to charged coupling constants of the axial-vector meson, K ₁, as ~ ?1.5. The energy dependence and the magnitude of the total cross section were similar to the total cross section of γ + p → K ⁺ Λ.     

Structure Switching and Modulation of the Magnetic Properties in Diarylethene‐Bridged Metallosupramolecular Compounds by Controlled Coordination‐Driven Self‐Assembly

We report three self‐assembled iron complexes that comprised an anti‐parallel open form (o‐ L _anti), a parallel open form (o‐ L _syn), and a closed form (c‐ L ) of diarylethene conformers. Under kinetic control, Fe^II₂(o‐ L _anti)₃ was isolated, which exhibited a dinuclear structure with diamagnetic properties. Under light‐irradiation control, Fe^II₂(c‐ L )₃ was prepared and exhibited paramagnetism and spin‐crossover behaviour. Under thermodynamic control and in the presence of indispensable [Fe^III(Tp*)(CN)₃]^?, Fe^II₂(o‐ L _anti)₃ and Fe^II₂(c‐ L )₃ transformed into tetranuclear Fe^III₂Fe^II₂(o‐ L _syn)₂, which exhibited complete spin‐crossover behaviour at T_1/2=353 K.     

The First Study on the Reactivity of Water Vapor in Metal–Organic Frameworks with Platinum Nanocrystals

We first studied the reactivity of H₂O vapor in metal–organic frameworks (MOFs) with Pt nanocrystals (NCs) through the water–gas shift (WGS) reaction. A water‐stable MOF, UiO‐66, serves as a highly effective support material for the WGS reaction compared with ZrO₂. The origin of the high catalytic performance was investigated using in situ IR spectroscopy. In addition, from a comparison of the catalytic activities of Pt on UiO‐66, where Pt NCs are located on the surface of UiO‐66 and Pt@UiO‐66, where Pt NCs are coated with UiO‐66, we found that the competitive effects of H₂O condensation and diffusion in the UiO‐66 play important roles in the catalytic activity of Pt NCs. A thinner UiO‐66 coating further enhanced the WGS reaction activity of Pt NCs by minimizing the negative effect of slow H₂O diffusion in UiO‐66.