Coherent phonon dynamics in short-period InAs/GaSb superlattices

We have performed ultrafast pump-probe spectroscopy studies on a series of InAs/GaSb-based short-period superlattice (SL) samples with periods ranging from 46 Å to 71 Å. We observe two types of oscillations in the differential reflectivity with fast (∼$\sim$1–2 ps) and slow (∼$\sim$24 ps) periods. The period of the fast oscillations changes with the SL period and can be explained as coherent acoustic phonons generated from carriers photoexcited within the SL. This mode provides an alternative method for determining the SL period. The period of the slow mode depends on the wavelength of the probe pulse and can be understood as a propagating coherent phonon wavepacket modulating the reflectivity of the probe pulse as it travels from the surface into the sample.     

Sodium methoxide: a simple but highly efficient catalyst for the direct amidation of esters

A simple NaOMe catalyst provides superior accessibility to a wide variety of functionalized amides including peptides through direct amination of esters in an atom-economical and environmentally benign way.     

Application of photoactive yellow protein as a photoresponsive module for controlling hemolytic activity of staphylococcal α-hemolysin

A chimeric protein (N-PYP-Hla), consisting of staphylococcal pore-forming toxin α-hemolysin (Hla) and photoactive yellow protein (PYP), exhibited photoresponsive hemolytic activities, where visible light irradiation gave rise to retardation of hemolysis at 25 °C.     

Theoretical verification of nonthermal microwave effects on intramolecular reactions

There have been a growing number of articles that report dramatic improvements in the experimental performance of chemical reactions by microwave irradiation compared to that under conventional heating conditions. We theoretically examined whether nonthermal microwave effects on intramolecular reactions exist or not, in particular, on Newman-Kwart rearrangements and intramolecular Diels-Alder reactions. The reaction rates of the former calculated by the transition state theory, which consider only the thermal effects of microwaves, agree quantitatively with experimental data, and thus, the increases in reaction rates can be ascribed to dielectric heating of the solvent by microwaves. In contrast, for the latter, the temperature dependence of reaction rates can be explained qualitatively by thermal effects but the possibility of nonthermal effects still remains regardless of whether competitive processes are present or not. The effective intramolecular potential energy surface in the presence of a microwave field suggests that nonthermal effects arising from potential distortion are vanishingly small in intramolecular reactions. It is useful in the elucidation of the reaction mechanisms of microwave synthesis to apply the present theoretical approach with reference to the experiments where thermal and nonthermal effects are separated by screening microwave fields.     

Catalysis of Ruthenium-Metal Oxides Mechanically Mixed with Sulfated Zirconia for Reaction of Butane to Isobutane

A highly active catalyst for the skeletal isomerization of butane to isobutane was obtained by mechanically mixing SO₄/ZrO₂ and Ru/SnO₂; Ru/SO₂ was prepared by impregnating tin hydroxide with a solution of RuCl₃ followed by calcining at 450°C (0.5 wt.% Ru). The catalyst was much more active than Ru-SO₄/ZrO₂ prepared by co-impregnation of zirconia with the Ru and sulfate materials the temperature difference to show the same conversion between both catalysts being 57°C. The effect of mixing of Ru was observed with other metal oxides as supports, Fe₂O₃, Al₂O₃, ZrO₂, TiO₂, and SiO₂; the calcination temperature of the Ru-impregnated hydroxides was 250, 300, and 400°C for the latter three, respectively.     

Trivalent Rare-Earth Metal Amide Complexes as Catalysts for the Hydrosilylation of Benzophenone Derivatives with HN(SiHMe2)2 by Amine-Exchange Reaction

The rare-earth metal complexes Ln( L¹ )[N(SiHMe₂)₂](thf) (Ln=La, Ce, Y; L¹ =N,N′′-bis(pentafluorophenyl)diethylenetriamine dianion) were synthesized by treating Ln[N(SiHMe₂)₂]₃(thf)₂ with L¹ H₂. The lanthanum and cerium derivatives are active catalysts for the hydrosilylation of benzophenone derivatives with HN(SiHMe₂)₂. An amine-exchange reaction was revealed as a key step of the catalytic cycle, in which Ln−Si−H β-agostic interactions are proposed to promote insertion of the carbonyl moiety into the Si−H bond.     

Thermoelectric properties of the Bi2−xYxRu2O7 (x=0-2) pyrochlores

Electrical conductivity and Seebeck coefficient for the Bi_2−xY_xRu₂O₇ pyrochlores with x=0.0,0.5,1.0,1.5,2.0 were measured in the temperature range of 473-1073 K in air. With increasing Bi content, the temperature dependence of the electrical conductivity changed from semiconducting to metallic. The signs of the Seebeck coefficient were positive in the measured temperature range for all the samples, indicating that the major carriers were holes. The temperature dependence of the Seebeck coefficient for the Y₂Ru₂O₇ indicated the thermal activation-type behavior of the holes, while that for the Bi_2−xY_xRu₂O₇ with x=0.0-1.5 indicated the itinerant behavior of the holes. The change in the conduction behavior from semiconductor to metal with increasing Bi content is consistent with the increase in the overlap between the Ru4d t_2g and O2p orbitals, but the mixing of Bi6s, 6p states at E_F may not be ruled out. The thermoelectric power factors for the Bi_2−xY_xRu₂O₇ with x=1.5 and 2.0 were lower than 10⁻⁵ W m⁻¹ K⁻² and those with x=0.0,0.5,1.0 were around 1-3×10⁻⁵ W m⁻¹ K⁻².     

Periodic, aperiodic and chaotic motion of drift wave vortices in a circular region

The modulated point vortex model associated with the Hasegawa-Mima equation is used to study the dynamical behavior of drift wave vortices in a bounded region. When a circle is taken as the boundary of the region, the potential for the vortices can be constructed with the aid of the circle theorem which replaces the boundary by the mirror images of the vortices inside the circle and ensures that the potential for the vortices is zero on the boundary. Periodic, aperiodic and chaotic motions are realized depending on the number of vortices and the magnitude of the value of the diamagnetic drift which breaks the rotational symmetry and has a tendency to drive vortices into chaotic motion.