Photothermal Oxidation of Cinnamyl Alcohol with Hydrogen Peroxide Catalyzed by Gold Nanoparticle/Antimony-Doped Tin Oxide Nanocrystals

Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (d_Au) at 5.3 nm≤d_Au≤8.2 nm. Light irradiation (λ_ex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs.     

Numerical analysis of turbulent structure in compound meandering open channel by algebraic Reynolds stress model

The turbulent flow in a compound meandering channel with a rectangular cross section is one of the most complicated turbulent flows, because the flow behaviour is influenced by several kinds of forces, including centrifugal forces, pressure‐driven forces and shear stresses generated by momentum transfer between the main channel and the flood plain. Numerical analysis has been performed for the fully developed turbulent flow in a compound meandering open‐channel flow using an algebraic Reynolds stress model. The boundary‐fitted coordinate system is introduced as a method for coordinate transformation in order to set the boundary conditions along the complicated shape of the meandering open channel. The turbulence model consists of transport equations for turbulent energy and dissipation, in conjunction with an algebraic stress model based on the Reynolds stress transport equations. With reference to the pressure–strain term, we have made use of a modified pressure–strain term. The boundary condition of the fluctuating vertical velocity is set to zero not only for the free surface, but also for computational grid points next to the free surface, because experimental results have shown that the fluctuating vertical velocity approaches zero near the free surface. In order to examine the validity of the present numerical method and the turbulent model, the calculated results are compared with experimental data measured by laser Doppler anemometer. In addition, the compound meandering open channel is clarified somewhat based on the calculated results. As a result of the analysis, the present algebraic Reynolds stress model is shown to be able to reasonably predict the turbulent flow in a compound meandering open channel. Copyright © 2005 John Wiley & Sons, Ltd.     

Development of a “Built-in” Scanning Near Field Microscope Head for an Atomic Force Microscope System and Stress Mapping of an Al2O3/ZrO2 Eutectic Composite

We constructed a scanning near-field optical microscope (SNOM) on a commercially available atomic force microscopy (AFM) apparatus (SPM-9500J2; Shimadzu Corp.) to measure the stress distribution in ceramic composite materials. Features of our SNOM system are: (1) a compact SNOM head substituted for the original AFM head; (2) a wide scanning range (125 × 125 μm²) inherited from the original scanner; (3) use of conventional shear-force regulation; (4) an optical system for the illumination-collection (I-C) mode; (5) excitation by a 488 nm line of an Ar-ion laser, and (6) light detection by photon counting or a polychromator equipped with an electronically cooled charge coupled device (CCD). This SNOM system was used to measure the surface structure and stress distribution of an Al₂O₃/ZrO₂ eutectic composite. We simultaneously measured topographic images and fluorescence spectra of an Al₂O₃/ZrO₂ eutectic composite. We estimated its peak intensity, peak position, and peak width from the fluorescence spectrum during scanning, which respectively correspond to the abundance of Al₂O₃, stress in the grain, and the anisotropy of that stress. Mapping images showed that the stress and its anisotropy were weaker in the center of the Al₂O₃ grain than its boundary between Al₂O₃ and ZrO₂. That observation suggests that Al₂O₃ underwent intense anisotropic stress induced by volume expansion in the phase transition of ZrO₂ from the cubic phase to the monoclinic phase during preparation.     

A new Pythagorean functional equation

The purpose of this paper is to solve the following Pythagorean functional equation:(e ^p(x,y) ) ² ) = q(x,y) ² + r(x, y) ², where each ofp(x,y), q(x, y) andr(x, y) is a real-valued unknown harmonic function of the real variablesx, y on the wholexy-planeR ².The result is as follows.     

Inhibierungseffekt von 1,1,4,4-Tetraphenyl-2-tetrazen bei der radikalischen Polymerisation von Styrol

Ohne Zusammenfassung     

Photochromism of viologens included in crown ether cavity

The effect of a pi-electron-donating macrocyclic molecule on the photochromic behavior of viologen derivatives was investigated in a thin polymer film. The intermolecular interactions between the viologens and the macrocyclic molecule were investigated in a solution before photoirradiation. In acetone, benzylviologens, N,N'-dibenzyl-4,4'-bipyridinium hexafluorophosphate (1) and N,N'-dibenzyl-trans-1,2-bis(4-pyridinium)ethylene hexafluorophosphate (2) each derived from 4,4'-bipiyridine and trans-1,2-bis(4-pyridyl)ethylene, respectively, form an inclusion complex with p-benzocrown ether (3) with binding constants of ca 200 M-1, which was driven by a charge transfer interaction. The peak wavelength of the charge transfer absorption band was at 453 and 421 nm for the inclusion complexes of 1 and 2 with 3, respectively. Upon photoirradiation to the polymer film containing 1, the film changed color from colorless to blue, associated with the reduction of 1 from the dication to the radical cation. The original dication was recovered after 120 min. The addition of 3 into the film containing 1 caused not only the color change from colorless to yellow, associated with the charge transfer interaction between 1 and 3 before photoirradiation, but also an acceleration in the bleaching rate of the photoreduced 1. When p-dimethoxybenzene (4) was used as an acyclic analog of 3, a negligible change in the photochromic behavior of 1 was observed. Similar effect of 3 on the photochromic behavior of 2 was observed. These results imply that the pi-electron-donating macrocyclic molecule causes a faster bleaching of photoreduced viologens by forming the inclusion complex.