Studies on polyyne polymers containing transition metals in the main chain. VII. Synthesis and characterization of palladium-polyyne polymers

Metal-polyyne polymers consisting of palladium and conjugated acetylenic systems, where P_D and R represent the —Pd(PBu₃)₂—moiety and alkyl groups, respectively, were prepared by polycondensation between palladium chlorides and α,ω-diethynyl compounds in amines using a catalytic amount of cuprous iodide. The molecular weights of the polymers formed were greatly affected by the basicity of the amines and the addition of free phosphines to the polymerization system. Under the optimum conditions, i.e., in the presence of CuI and PBu₃ (in molar ratio 1/4) in piperidine at room temperature, polymer Ia (R¹ = R² = H) having M?_w = 29,000 was obtained.     

Multidynamic Crystalline Molecular Rotors Comprising an N-Heterocyclic Carbene Binuclear Au(I) Complex Bearing Multiple Rotators

We report multidynamic molecular rotations in crystals using a concave-shape N-heterocyclic carbene (NHC) binuclear Au(I) complex rotor bearing pyrazine and tetrahydrofuran (THF) molecules as multicomponent rotators. Single-crystal X-ray diffraction (XRD) measurements revealed that two THF molecules are located near the central pyrazine encapsulated by two bulky NHC ligands. From ²H solid-state NMR analysis, it was observed that the pyrazine rotated in a 2-fold site exchange with a 180° rotational angle and a 31 kJ mol⁻¹ energy barrier, while the THF molecules showed a 23°-38° libration with a lower energy barrier (14 kJ mol⁻¹). Interestingly, the pyrazine rotation was accelerated when the THF molecules rotated in fast site exchange with a large angle of libration, suggesting that the rotators exhibit multidynamics in a correlated manner.     

James-Stein estimators for time series regression models

The least squares (LS) estimator seems the natural estimator of the coefficients of a Gaussian linear regression model. However, if the dimension of the vector of coefficients is greater than 2 and the residuals are independent and identically distributed, this conventional estimator is not admissible. James and Stein [Estimation with quadratic loss, Proceedings of the Fourth Berkely Symposium vol. 1, 1961, pp. 361-379] proposed a shrinkage estimator (James-Stein estimator) which improves the least squares estimator with respect to the mean squares error loss function. In this paper, we investigate the mean squares error of the James-Stein (JS) estimator for the regression coefficients when the residuals are generated from a Gaussian stationary process. Then, sufficient conditions for the JS to improve the LS are given. It is important to know the influence of the dependence on the JS. Also numerical studies illuminate some interesting features of the improvement. The results have potential applications to economics, engineering, and natural sciences.     

Initiation and propagation of detonation waves in combustible high speed flows

The initiation and propagation of detonation waves in combustible high speed flows were studied experimentally. A planar detonation wave traveling in an initiation tube was transmitted into a test section where a combustible high speed flow was induced by an incident shock wave generated in a shock tube. In this study, the flow Mach numbers were obtained as 0.9 and 1.2. The experimental results show that depending on the flow velocity, the apparent propagation velocity of a detonation wave is higher in the upstream and lower in the downstream direction than the CJ velocity. Smoked plate records reveal cellular patterns deformed in the flow direction, and the calculated aspect ratios of the cell were found to agree well with the experimental ones on the basis of the assumption that the velocity of the transverse wave is not affected by the flowing mixture. By analyzing the shock-wave diffraction at the position where there is an abrupt change in the area, on the basis of Whitham’s theory, it was deduced that in the present experimental set-up, the detonation was initiated by the reflection of the diffracted shock waves on the sidewalls of the test section. The agreement between the experimental and calculated results regarding the position of the cellular patterns on the smoked plate record indicated that the position of detonation initiation in high speed flows is shifted downstream due to the flow velocity.     

Visible-light photocatalysis of ZnO deposited on nanoporous Au

ZnO deposited on nanoporous Au showed photocatalytic decomposition toward methyl orange under visible light, unlike ZnO sputtered on flat Au without a nanoporous structure. First-principles calculations suggested that the surface lattice disorder in nanoporous Au induced a band gap narrowing and a large built-in electric field in the adjacent ZnO, resulting in the visible-light photocatalytic response.     

Kondo effect in a quantum antidot

We report Kondo-like behavior in a quantum antidot (a submicron depleted region in a two-dimensional electron gas) in the quantum-Hall regime. When both spins of the lowest Landau level are present all around the antidot, the resonances between extended edge states via antidot bound states show an abnormal feature in alternate Coulomb-blockaded regions. The feature becomes suppressed when the temperature or source-drain bias is raised as for Kondo resonances in quantum dots. Although the exact mechanism is unknown, Kondo-like correlated tunneling may arise from a Skyrmion-type edge reconstruction. This observation demonstrates the generality of the Kondo phenomenon.     

New bis- and tris-annulation reagents for the syntheses of CD rings of steroids,bearing a functionalized 18-methyl group,by the palladium-catalyzed cyclization

2-Substituted 2-alkoxycarbonyl-3-vinylcyclopentanones (2), easily prepared by the palladium-catalyzed cyclization of 2-substituted 3-oxo-8-phenoxy-6-octenoates (1), are very suitable building blocks for CD rings of steroids, bearing particularly a functionalized 18-methyl group.     

Transverse instability of solitary waves in the generalized kadomtsev-petviashvili equation

The linear stability of planar solitary waves with respect to long-wavelength transverse perturbations is studied in the framework of the generalized Kadomtsev-Petviashvili equation. It is newly discovered that for some nonlinearities in this family, the solitary waves could be transversely unstable even in a medium with negative dispersion. In the case of positive dispersion, they are found to be always unstable.