Dielectric properties of poly [3,3-bis(chloromethyl)oxacyclobutane] (Penton)

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STM imaging of a model surface of Ru(4,4′-dicarboxy-2,2′-bipyridine)2(NCS)2 dye-sensitized TiO2 photoelectrodes

A TiO₂(1 1 0)-(1 × 1) surface was prepared in an ultra-high vacuum, transported in laboratory air, and observed with a scanning tunneling microscope (STM) operated in a vacuum of 10⁻⁴ Pa. Empty state images showed atomically flat terraces separated by single-height steps, on which 5-fold-coordinated surface Ti atoms were observed as spots arranged in a rectangular lattice. The Ru(4,4′-dicarboxy-2,2′-bipyridine)₂(NCS)₂ (N3) dye was adsorbed on the TiO₂ surface by immersing the TiO₂ wafer into an acetonitrile solution of the dye. In the empty state images, individual N3 molecules were observed as oval particles protruding by 0.6 nm from the TiO₂ surface. The oval shape elongated to the [1  0] directions was attributed to electron tunneling from tip to unoccupied states localized at the two carboxyl groups bound to the TiO₂ surface.     

An enzyme-encapsulated microreactor for efficient theanine synthesis

A flow-type microreactor containing glutaminase-mesoporous silica composites with 10.6 nm pore diameter (TMPS10.6) was developed for the continuous synthesis of theanine, a unique amino acid. High enzymatic activity was exhibited by the local control of the reaction temperature.     

Unsteady PTV velocity field past an airfoil solved with DNS: Part 1. Algorithm of hybrid simulation and hybrid velocity field at <Emphasis Type="Italic">Re</Emphasis> ≈ 10<Superscript>3</Superscript>

We develop a hybrid unsteady-flow simulation technique combining direct numerical simulation (DNS) and particle tracking velocimetry (PTV) and demonstrate its capabilities by investigating flows past an airfoil. We rectify instantaneous PTV velocity fields in a least-squares sense so that they satisfy the equation of continuity, and feed them to the DNS by equating the computational time step with the frame rate of the time-resolved PTV system. As a result, we can reconstruct unsteady velocity fields that satisfy the governing equations based on experimental data, with the resolution comparable to numerical simulation. In addition, unsteady pressure distribution can be solved simultaneously. In this study, particle velocities are acquired on a laser-light sheet in a water tunnel, and unsteady flow fields are reconstructed with the hybrid algorithm solving the incompressible Navier–Stokes equations in two dimensions. By performing the hybrid simulation, we investigate nominally two-dimensional flows past the NACA0012 airfoil at low Reynolds numbers. In part 1, we introduce the algorithm of the proposed technique and discuss the characteristics of hybrid velocity fields. In particular, we focus on a vortex shedding phenomenon under a deep stall condition (α = 15°) at Reynolds numbers of Re = 1000 and 1300, and compare the hybrid velocity fields with those computed with two-dimensional DNS. In part 2, the extension to higher Reynolds numbers is considered. The accuracy of the hybrid simulation is evaluated by comparing with independent experimental results at various angles of attack and Reynolds numbers up to Re = 10⁴. The capabilities of the hybrid simulation are also compared with two-dimensional unsteady Reynolds-Averaged Navier–Stokes (URANS) solutions in part 2. In the first part of these twin papers, we demonstrate that the hybrid velocity field approaches the PTV velocity field over time. We find that intensive alternate vortex shedding past the airfoil, which is predicted by the two-dimensional DNS, is substantially suppressed in the hybrid simulation and the resultant flow field is similar to the PTV velocity field, which is projection of the three-dimensional velocity field on the streamwise plane. We attempt to identify the motion that originates three-dimensional flow patterns by highlighting the deviation of the PTV velocity field from the two-dimensional governing equations at each snapshot. The results indicate that the intensive spots of the deviation appear in the regions in which three-dimensional instabilities are induced in the shear layer separated from the pressure side.     

Diphenylboron perchlorate as an efficient catalyst for self- and cross-condensation reactions of aldehydes having α-active hydrogens

Diphenylboron perchlorate very smoothly catalyzed self- and cross-condensation reactions of aldehydes at rt in nitroethane. The new catalyst provided novel behaviors owing to the characteristics of possessing a covalency in the boronoxygen bond, compared with ionic perchlorates.     

Concurrent induction of two chiral centers from symmetrical 3, 4-disubstituted and 3,3,4-trisubstituted 4-pentenals using Rh-catalyzed asymmetric cyclizations

Asymmetric cyclization of symmetrical 3,4-disubstituted and 3,3, 4-trisubstituted 4-pentenals was studied using Rh-complexes with chiral ligands. The cyclization of symmetrical 4-pentenals 4a,b by a neutral Rh[(R)-BINAP]Cl afforded cis-3,4-disubstituted (4R)-cyclopentanones 9a,b of >95% ee in 25-31% yields; on the other hand, the cyclization of 4a-c by a cationic Rh[(R)-BINAP]ClO(4) afforded trans-3,4-disubstituted (4S)-cyclopentanones 10a-c of >95% ee in 70-81% yields. All stereoisomers could be stereoselectively made by the selection of a neutral or cationic Rh-complex, and (R)- or (S)-BINAP ligand. The Rh-catalyzed cyclization could be applied to the construction of cyclopentanones 17 and 18 bearing a chiral quaternary carbon. The cyclization by the cationic Rh[(R)-BINAP]ClO(4) afforded the optically active trans-3,3, 4-trisubstituted cyclopentanones 18a-c of 92-95% ee in 75-83% yields. The catalytic cycle was also studied by using deuterium aldehyde, and the tentative mechanisms of the enantio- and diastereoselection were proposed.     

Preparation of boron-doped semiconducting diamond films using BF3 and the electrochemical behavior of the semiconducting diamond electrodes

Boron-doped semiconducting diamond films were prepared using BF₃ by microwave plasma assisted chemical vapor deposition. B-doping was confirmed by SIMS and Raman spectroscopic measurements and the B-doping levels were estimated. Electrochemical behaviors of boron-doped diamond thin-film electrodes prepared using B₂H₆ and BF₃ were studied by measuring cyclic voltammograms for anodic oxidation of 1,4-difluorobenzene in the liquid electrolyte, neat Et₄NF·4HF. The results of the direct thermal interaction of elemental fluorine with hydrogenated and oxidized diamond surfaces are also presented.     

Deoxygenation of sugar trifluoromethanesulfonates by sodium metal in liquid ammonia and by photolysis

Several trifluoromethanesulfonyl(TFMS) derivatives of sugars were prepared and treated with sodium in liquid ammonia or subjected to ultraviolet irradiation. Three 3-$\text{O}$-TFMS derivatives gave the corresponding 3-deoxy compounds, but a 2-$\text{O}$-TFMS derivative gave a branched-chain sugar.     

Effect of Solvent Diols and Ligands on the Properties of Sol-Gel Alumina-Silicas

Amorphous alumina-silicas were prepared from a tetra-alkoxysilane and anhydrous aluminum trichloride or an aluminum alkoxide by a sol-gel process using 2-methyl-2,4-pentanediol, pinacol, 1,2-propanediol, 2,3-butanediol or ethylene glycol as the solvent or complexing agent, and the effect of diols and alkoxy groups on the physical and chemical properties of the alumina-silicas was examined. When the diol or the alkoxy group was bulky, the alumina-silicas had relatively larger micropores, a larger pore volume and higher surface areas. In the conversion of methanol catalyzed by the alumina-silicas, the bulkier diols and alkoxides gave catalysts that produced dimethyl ether in higher yield and hydrocarbons in lower yield. Thus, when ethylene glycol was used as the diol, the best catalyst for the production of hydrocarbons, especially the production of olefins such as ethylene, propylene and butene, was obtained. Furthermore, in comparison with alumina-silica prepared by a traditional kneading process, it was found that the sol-gel alumina-silica could efficiently convert methanol to dimethyl ether and hydrocarbons, but the material prepared by kneading had a very low conversion of methanol to other compounds.