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.     

Non-destructive rapid analysis of brominated flame retardants in electrical and electronic equipment using Raman spectroscopy.

Using Raman spectroscopy without any preparation, we analyzed the brominated flame retardant, polybromodiphenyl ethers (PBDEs), which has been prohibited by the European Union. The typical Raman bands of PBDEs, which are clearly different from those of other brominated flame retardants, are from 100 to 300 cm(-1). In our analysis, the detection limit was about 100 ppm, and the analysis took about 1 min, whereas the usual method of solvent extraction using gas chromatography/mass spectroscopy takes 50 h.     

Direct observation of chemical oscillation at a water/nitrobenzene interface with a sodium-alkyl-sulfate system.

The oscillation of the interfacial tension and electrical potential at a water/nitrobenzene interface was observed with homologous anionic surfactant molecules, sodium-alkyl-sulfates. Concerning small molecules with a short hydrophobic carbon chain, the oscillation period and amplitude decreased with a decrease of the length of the alkyl chain. On the other hand, when surfactant molecules with a long hydrophobic carbon chain were used, no remarkable periodic oscillation occurred after the first oscillation. In all systems, an interfacial flow by Marangoni convection was observed when the oscillation took place. By monitoring the movement of carbon powder scattered on the liquid/liquid interface with a CCD camera, we could observe that the liquid/liquid interface expanded outward from the area on which the surfactant molecules adsorbed when the oscillation occurred. When the small molecule was used, the speed of expansion of the interface (flow speed) was small and shrinkage followed by expansion of the interface repeatedly occurred. However, when the large molecule was used, the flow speed was large and expansion occurred only one time. These results show that hydrodynamic factors and surface activities are important in chemical oscillation systems.     

New approaches to liquid interfaces through changes in the refractive index and nonlinear susceptibility utilizing ultrashort laser pulses.

Molecules in inhomogeneous liquid environments, such as air/liquid, liquid/liquid, solid/liquid interfaces interact with each other specifically, and sometimes form characteristic structures and emerge unique properties. Here, we introduce two newly developed spectroscopic techniques, the total-internal-reflection ultrafast transient lens method (TIR-UTL) and second harmonic generation-coherent vibrational spectroscopy (SHG-CVS), to investigate the characteristic behaviors of molecules in such inhomogeneous environments. TIR-UTL probes the refractive-index change with sub-picosecond resolution and provides information on ultrafast changes in the population, density, and thermal properties, such as temperature increase and energy transfer from the solute molecules to the surrounding solvent molecules. On the other hand, SHG-CVS probes nonlinear susceptibility changes at the interfacial areas, and is expected to provide spectroscopic information on the low-frequency vibrational modes that reflect the corrective motion of the molecules in such an inhomogeneous environment. These new approaches are based on pump-probe techniques utilizing (ultra) short laser pulses. They are expected to provide further information on inhomogeneous environments from the viewpoints of solute-solvent interactions, changes in the molecular orientation, and the corrective motion of molecules at liquid interfaces.     

Two-dimensional numerical calculation of the flow field about a scoop inlet by the piecewise linear method

The piecewise linear method (PLM) based on time operator splitting is used to solve the unsteady compressible Euler equations describing the two-dimensional flow around and through a straight wall inlet placed stationary in a rapidly rotating supersonic flow. The PLM scheme is formulated as a Lagrangian step followed by an Eulerian remap. The inhomogeneous terms in the Euler equations written in cylindrical coordinates are first removed by Sod's method and the resulting set of equations is further reduced to two sets of one-dimensional Lagrangian equations, using time operator splitting. The numerically generated flow fields are presented for different values of the back pressure imposed at the downstream exit of the inlet nozzle. An oblique shock wave is formed in front of the almost whole portion of the inlet entrance, the incoming streamlines being deflected towards the higher pressure side after passing through the oblique shock wave and then bending down to the lower pressure side. A reverse flow appears inside the inlet nozzle owing to the recovery pressure of the incoming streams being lower than the back pressure of the inlet nozzle.     

Effect of core-shell micelle formation on the redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide)

Redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide) (PT-EGE_n-b-EO_m) are reversibly changed by core-shell micelle formation. In the temperature range higher than the critical micellization temperature (cmt), the anodic potential of PT group positively shifts and concomitantly its anodic current decrease, or levels off compared to those of the reference polymer PT-EO_m without the thermo-responsive EGE_n segment. The former alteration is caused by incorporation of hydrophobic PT groups into a core of the micelle and the latter by the decrease in the diffusion coefficient of PT groups due to formation of the core-shell micelles. The cmt value and the temperature-dependent alteration in the redox properties strongly depend on the polymer structure, especially the length of thermo-responsive EGE_n segment. The electrochemically determined hydrodynamic radii of the polymer aggregates seem to be overestimated, compared to the values reported for the aggregates of other thermo-responsive polymers with similar molecular weights, implying the presence of electrochemically inactive PT groups in the copolymers having longer thermo-responsive segments.