Molecular distortion effect on ff-emission in a Pr(III) complex with 4,7-diphenyl-1,10-phenanthroline.

The electronic and structural behaviour of a Pr(III) complex with 4,7-diphenyl-1,10-phenanthroline, [Pr(bathophen)(2)(NO(3))(3)], is investigated with respect to the effect of configuration changes on the Pr(III) centre. [Pr(bathophen)(2)(NO(3))(3)] luminesces from the excited states of the ligand and the metal ion. The fluorescence, ff-emission ((1)D(2)-->(3)H(4)), and phosphorescence bands appear at 394, 608.2 and 482 nm, respectively, in the solid state. In acetonitrile, the complex also shows multiple emissions. From the time-resolved emission and the lifetime measurements, the excitation energy-transfer in [Pr(bathophen)(2)(NO(3))(3)] is clarified, that is, the upper excited triplet level of the ligand acts as an energy donor, while the (1)D(2) levels of Pr(III) is the acceptor. Additionally, the emission phenomena of the complex can be modified by molecular distortion, particularly by rotation of the phenyl groups in the ligand.     

Effective Synthesis of N‐Arylformamide from α‐Halo‐N‐arylacetamides

A convenient synthetic method for N‐arylformamide derivatives was successfully developed by reacting α‐iodo‐N‐arylacetamides with formamide. This method was applicable to α‐iodo‐N‐arylacetamide substrates bearing electron‐donating or electron‐withdrawing groups, N‐(benzo[d][1,3]dioxol‐5‐yl)‐2‐iodoacetamide, 2‐iodo‐N‐(pyridin‐2‐yl)acetamide, and 2‐iodo‐N‐(naphthalen‐4‐yl)acetamide to give the corresponding N‐arylformamides in moderate to excellent yields (65–94%). A plausible mechanism was proposed to account for the new transformation.     

Antimutagenic activity of ent-kaurane diterpenoids from the aerial parts of Isodon japonicus

From the methanolic extract of the aerial parts of Isodon japonicus, two new ent-kaurane diterpenes, isodonterpenes I and II, were isolated together with 10 known diterpenes. Their chemical structures were elucidated on the basis of chemical and physicochemical evidence. The absolute configuration of isodonterpene I was elucidated by Cu-Kα X-ray crystallographic analysis. Antimutagenic activities of the major diterpenes were evaluated by the Ames test. This study represents the first evaluation of the antimutagenic activities of ent-kaurane diterpenes.     

Traveling disturbance appearing in boundary layer transition in a Yawed cylinder

Boundary layers that develop over a body in fluid flow are in most cases three-dimensional owing to the spin, yaw, or surface curvature of the body. Therefore, the study of three-dimensional (3D) boundary-layer transition is essential to work in practical aerodynamics. The present investigation is concerned with the problem of 3D boundary layers over a yawed body. A yawed cylinder model that represents the leading edge portion of a swept wing and the mechanism of crossflow instability are investigated in detail using hot-wire velocimetry and a flow visualization technique. As a result, traveling disturbances having frequencies f₁ and f₂, which differ by about one order of magnitude, are detected in the transition region. The phase velocities and directions of travel of those disturbances are measured. Results for the low-frequency disturbance f₁ show qualitative coincidence with results numerically predicted for a crossflow unsteady disturbance. Nameley, F₁ travels nearly spanwise to the yawed cylinder and very close to the cylinder wall. The results for the high-frequency disturbance f₂ good agreement with the existing experimental results. The ₂ disturbance is found to be the high-frequency inflectional secondary instability that appears in 3D boundary layer transition in general. A two-stage transition process, where stationary crossflow vortices appear as the primary instability and a traveling inflectional disturbance is generated as a secondary instability, was observed. Secondary instability seems to play a major role in turbulent transition.     

Nickel-catalyzed hydrosilylation/cyclization of difluoro-substituted 1,6-enynes

Ni-catalyzed hydrosilylative cyclization of difluoro-substituted 1,6-enynes can be carried out. The presence of a geminal-difluoromethylene group at an alkene terminus in enynes is essential for the reaction to proceed.     

Highly durable Pd metal catalysts for the oxygen reduction reaction in fuel cells; coverage of Pd metal with silica

Pd cathode catalysts for polymer electrolyte fuel cells have been covered with silica layers a few nanometres thick. The silica-coated Pd catalysts showed high activity and excellent durability for the oxygen reduction under the severe cathode conditions of PEFCs, while Pd catalysts without silica-coating were seriously deactivated under the same conditions. The coverage of Pd metal with silica prevents the diffusion of Pd species out of the silica layers.     

Large‐scale SPH simulations of droplet impact onto a liquid surface up to the consequent formation of Worthington jet

In this study, the whole process of liquid droplet impact onto a liquid surface up to the consequent formation of the central column was simulated using the smoothed particle hydrodynamics method (SPH), and compared with an experiment using a high‐speed video camera. The surface tension tensor for the particle‐based expression was adequately included as the gradient of the surface tension and that enabled the simulation leading to the formations of crater and crown as well as the consequent central column. The simulated time series of the crater depth and diameter and crown height corresponded quantitatively well with the experimental result up to the rebound motion while discrepancies remained as a lower central column height in the simulation, and this seemed to be ascribed to the difficulty in realizing the complex surface structure that inevitably appeared in the fast rebound motion. Copyright © 2009 John Wiley & Sons, Ltd.     

Asymptotic distributions of regression and autoregression coefficients with martingale difference disturbances

In this paper a form of the Lindeberg condition appropriate for martingale differences is used to obtain asymptotic normality of statistics for regression and autoregression. The regression model is y_t = Bz_t + v_t. The unobserved error sequence {v_t} is a sequence of martingale differences with conditional covariance matrices {Σ_t} and satisfying sup_{t=1,…, n} {v′_tv_tI(v′_tv_t>a) |z_t, v_t−1, z_t−1, …} 0 as a → ∞. The sample covariance of the independent variables z₁, …, z_n, is assumed to have a probability limit M, constant and nonsingular; max_t=1,…,nz′_tz_t/n 0. If (1/n)Σ_t=1ⁿΣ_t Σ, constant, then √nvec( _n−B) N(0,M⁻¹Σ) and _n Σ. The autoregression model is x_t = Bx_{t − 1} + v_t with the maximum absolute value of the characteristic roots of B less than one, the above conditions on {v_t}, and (1/n)Σ_t=max(r,s)+1(Σ_tv_t−1−rv′_t−1−s) δ_rs(ΣΣ), where δ_rs is the Kronecker delta. Then √nvec( _n−B) N(0,Γ⁻¹Σ), where Γ = Σ_{s = 0}^∞B^sΣ(B′)^s.