Microstructural stability and age-hardening behavior of Re-added dual two-phase Ni3Al and Ni3V intermetallic alloys

The effect of Re addition on the microstructure and hardening behaviour of the dual two-phase Ni₃Al (L1₂) and Ni₃V (D0₂₂) intermetallic alloy was investigated by scanning electron microscopy, transmission electron microscopy and Vickers hardness test. The two-phase eutectoid microstructure accompanying the Re-rich precipitates were observed in the channel region of the alloys in which Re substituted for Ni but not in those in which Re substituted for Al and V. The concomitant addition of Nb (or Ta) with Re more stabilized the two-phase eutectoid microstructure and consequently more induced the fine precipitates in the channel region. The annealing at temperatures below the eutectoid temperature was necessary to induce the fine precipitates in the channel region and thereby result in the precipitation hardening. The fine precipitation in the channel region and related hardening was attributed to the alloying feature so that Re is soluble in the A1 (fcc) phase at high temperatures and becomes less soluble in the two intermetallic phases decomposed from the A1 phase at low temperatures.     

Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer

Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 ⁵⁺, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 ⁵⁺ catalyzed ethane oxidation in the presence of H₂O₂ at a relatively low temperature. The site-selective complexation of 3 ⁵⁺ with an additional anionic porphyrin (TPPS⁴⁻) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 ⁵⁺ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS⁴⁻ to 3 ⁵⁺ enhanced the catalytic activity.     

Generalized Longo–Rehren Subfactors and α-Induction

We study the recent construction of subfactors by Rehren which generalizes the Longo–Rehren subfactors. We prove that if we apply this construction to a non-degenerately braided subfactor N⊂M and α^±-induction, then the resulting subfactor is dual to the Longo–Rehren subfactor M⊗M ^opp⊂R arising from the entire system of irreducible endomorphisms of M resulting from α^plusmn;-induction. As a corollary, we solve a problem on existence of braiding raised by Rehren negatively. Furthermore, we generalize our previous study with Longo and Müger on multi-interval subfactors arising from a completely rational conformal net of factors on S ¹ to a net of subfactors and show that the (generalized) Longo–Rehren subfactors and α-induction naturally appear in this context. Received: 11 September 2001 / Accepted: 7 October 2001     

Preparation and properties of the biodegradable graded blend of poly(L‐lactic acid) and poly(ethylene oxide)

We prepared biodegradable poly(ethylene oxide) (PEO)/poly(L ‐lactic acid) (PLLA) graded blends by the dissolution–diffusion process, and discussed the biodegradability and tensile strength of the graded blends by comparing isotropic blend and PLLA only. All the graded blends were degraded more largely than the PLLA only and isotropic blend (PEO: 37.5 wt %), which had the same content as the total content of those graded blends. The graded blend having most excellent wide compositional gradient was degraded most largely with the enzyme. Thus, graded structure of the blends promoted their biodegradabilities large. It was considered that the dissolution of PEO with water increased the surface area attacked by the enzyme, while PEO caught PLLA oligomers to promote the biodegradation of PLLA. Then, the biodegradabilities of the graded blends were suppressed by the increasing crystallinity of PLLA. Furthermore, the strengths of all the graded blends were larger than those of the isotropic blend. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2972–2981, 2007     

Ion-interaction chromatography of several metallocyanide complexes stabilized by adding cyanide in a neutral mobile phase.

Standard solutions (at 10(-5) M levels) of Cu(I)- and Fe(II)-cyanide complexes were stabilized for at least 5 h using 0.5 mM cyanide solution (around pH 9) as a medium. Complexes of Cu(I)- and Fe(III)-cyanide also could be stabilized without any dissociation by adding 1 mM cyanide to an acetonitrile-water (18:82, v/v) mobile phase (pH 7.0) containing 10 mM tetra-n-propylammonium salt (TPA). Under the optimal conditions, the six complexes of Cu(I)-, Ag(I)-, Ni(II)-, Fe(II)-, Fe(III)- and Au(I)-cyanides were resolved from their mixtures within about 45 min, with well-shaped chromatographic peaks.     

Regiospecific cycloaddition reactions using functionalized isoprenylsilane and related compounds

1-Alkoxy-3-trimethylsilylmethyl- and 1-alkoxy-3-trimethylsilyl-l,3-butadienes ($\text{1}$) were newly prepared. The cycloaddition reactions of $\text{1}$ with various dienophiles including heterodienophiles were found to proceed very smoothly in a perfectly regiospecific mode.     

Solvatochromic studies of interactions between surfactants and poly(N-substituted acrylamide)s

Interactions between poly(N-substituted acrylamide)s and surfactants, such as sodium dodecyl sulfate (SDoS) and sodium decyl sulfate (SDeS), in aqueous solutions were investigated using a solvatochromic probe. The polymers used were poly(N,N-dimethylacrylamide) (PDMA), poly(N-isopropylacrylamide) (PIPA), poly(N-acryloylpyrrolidine) (PAPR), and poly(vinylpyrrolidone) (PVPy) for comparison. They were labeled with pyridinium dicyanomethylide chromophore as a solvatochromic probe, and the changes in the microenvironment polarity of the polymer upon association with surfactant micelles were investigated by monitoring the λ_max in the absorption spectra of the probe molecule. It was found that the Gibbs free energy of micelle stabilization by polymer complexation for SDoS is 7.6, 4.1, and 2.2 kJ mol⁻¹, and for SDeS 5.1, 2.9, and 0.8 kJ mol⁻¹ with PIPA, PAPR, and PDMA, respectively. These results indicate that the complexation between polymer and surfactant is influenced not only by the alkyl-chain length of the surfactant, but also by the polymer side groups.     

Rapid ruthenium-catalyzed synthesis of pyranopyrandiones by reconstructive carbonylation of cyclopropenones involving C[bond]C bond cleavage

Pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru3(CO)12 and NEt3 in THF under 15 atm of carbon monoxide at 140 degrees C for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions.     

Thermodynamic study of complex formation of benzo-18-crown-6 with K+, Tl+, and Pb2+ in water

H ⁰ and S ⁰ values of the complex formation in water of benzo-18-crown-6 (B18C6) with K⁺, Tl⁺, and Pb²⁺ were determined and compared with those of 18-crown-6. The H⁰ values of B18C6 are negative. The stability in water of the B18C6-metal ion complex at 25°C is governed largely by the magnitude of the H ⁰ value. The B18C6-metal ion complex is less stable in water than the corresponding 18C6-metal ion complex. This is due largely to a less favorable enthalpic contribution of the B18C6-metal ion complex compared with the corresponding 18C6-metal ion complex. The two aromatic ether oxygen atoms of B18C6 are responsible for the larger H ⁰ value of the B18C6-metal ion complex compared with the corresponding 18C6-metal ion complex.