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.     

New layered rare-earth hydroxides with anion-exchange properties

We report the synthesis of a new series of layered hydroxides based on rare-earth elements with a composition of RE(OH)2.5Cl(0.5).0.8 H2O (RE: Eu, Tb, etc.) through the homogeneous precipitation of RECl3.x H2O with hexamethylenetetramine (HMT). Rietveld analysis combined with direct methods revealed an orthorhombic layered structure comprising a positively charged layer of [RE(OH)2.5-(H2O)0.8]0.5+ and interlayer Cl- ions. The Cl- ions were readily exchangeable for various anions (NO3-, SO4(2-), dodecylsulfonate, etc.) at ambient temperature. Photoluminescence studies showed that the compounds display typical RE3+ emission. With rare-earth-based host layers and tunable interlayer guests, the new compounds may be of interest for optoelectronic, magnetic, catalytic, and biomedical materials.     

Structural disorder and diffusional pathway of oxide ions in a doped Pr2NiO4-based mixed conductor

MEM nuclear density analysis from neutron diffraction data measured in situ at 1015.6 degrees C has indicated the two-dimensional network of curved O2-O3-O2 oxide-ion diffusion paths on the (Pr,La)-O layer in a K2NiF4-type structured oxide-ionic and electronic mixed conductor (Pr0.9La0.1)2(Ni0.74Cu0.21Ga0.05)O4+delta.     

Optical nanosensor design with uniform pore geometry and large particle morphology

Appropriate design of nanosensors for optically selective, sensitive sensing systems is needed for naked-eye detection of pollutants for environmental cleanup of toxic heavy-metal ions. Mesostructured materials with two- or three-dimensional (2D or 3D) geometries and large particle morphologies show promise as probe carriers, and can therefore be used to reproducibly fabricate uniformly packed nanosensors. This is the first report on the effects of significant key properties of the mesostructured carriers, such as morphology, geometry, and pore shape, on the functionality of optical nanosensor designs. Such mesostructured sensors with superior physical characteristics can be used as components in sensing systems with excellent stability and sensitivity, and with rapid detection response. The nanosensor design can enhance the selectivity even at low concentrations of the pollutant target ions (nanomolar level). Among the nanosensors developed here, the large pore-surface grains of highly ordered 3D monoliths (HOM) exhibited a high adsorption capability of the Pyrogallol Red probe and high accessibility to analyte ion transport, leading to possible naked-eye detection of Sb(III) ions at concentrations as low as 10(-9) mol dm(-3) and at a wide detection range of 0.5 ppb to 3 ppm. A key finding in our study was that our mesostructured nanosensor designs retained highly efficient sensitivity without a significant increase in kinetic hindrance, despite the slight decrease of the specific activity of the electron acceptor/donor strength of the probe functional group after several regeneration/reuse cycles. The results, in general, indicate that large-scale reversibility of optical nanosensors is feasible in such metal-ion sensing systems.     

Aminolysis of Y-substituted phenyl X-substituted cinnamates and benzoates: effect of modification of the nonleaving group from benzoyl to cinnamoyl

A kinetic study is reported for reactions of Y-substituted phenyl X-substituted cinnamates (1a-e and 3a-g) and benzoates (2a-e and 4a-g) with a series of alicyclic secondary amines in 80 mol % H2O/20 mol % DMSO at 25.0 +/- 0.1 degrees C. Reactions of 2,4-dinitrophenyl X-substituted cinnamates (1a-e) and benzoates (2a-e) with amines result in linear Yukawa-Tsuno plots. The rho(X) values are much smaller for the reactions of 1a-e than for those of 2a-e. A distance effect and the nature of the reaction mechanism (i.e., a concerted mechanism for 1a-e) have been suggested to be responsible for the small rho(X) values. The Br?nsted-type plots for the reactions of 2,4-dinitrophenyl X-substituted cinnamates (1a, 1c, and 1e) with amines are curved with a decreasing betanuc value from 0.65 to 0.3-0.4. The reactions of Y-substituted phenyl cinnamates (3a-g) with morpholine also result in a curved Br?nsted plot, while the corresponding reactions of Y-substituted phenyl benzoates (4a-e) exhibit a linear Br?nsted plot. It has been concluded that the curved Br?nsted plots found for the reactions of the cinnamates (1a, 1c, 1e, and 3a-g) are not due to a change in the rate-determining step (RDS) but due to a normal Hammond effect for a concerted mechanism, that is, an earlier transition state (TS) for a more reactive amine or substrate.     

Research on the algorithm of binary image cross-correlation for unsteady flow field measurement

In the present paper, the algorithm of Binary Image Cross-Correlation (BICC) was developed to measure the unsteady flow field. A vortex flow field was used to test the algorithm by numerical simulation. The results show that BICC is an effective algorithm for particle identification from consecutive images, the accurate velocity vector field can be obtained. The real velocity field in a valve chamber was measured by BICC in this study. From the full-field velocity information, the pressure and vorticity fields were also extracted by post-processing. The project supported by the National Natural Science Foundation of China     

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.     

Heat and mass transfer characteristics of organic sorbent coated on heat transfer surface of a heat exchanger

This paper describes heat and mass transfer characteristics of organic sorbent coated on heat transfer surface of a fin-tube heat exchanger. The experiments in which the moist air was passed into the heat exchanger coated with sorption material were conducted under various conditions of air flow rate (0.5–1.0 m/s) and the temperature of brine (14–20°C) that was the heat transfer fluid to cool the air flow in the dehumidifying process. It is found that the sorption rate of vapor is affected by the air flow rate and the brine temperature. Meanwhile, the attempt of clarifying the sorption mechanism is also conducted. Finally the average mass transfer coefficient of the organic sorbent coated on heat transfer surface of a fin-tube heat exchanger is non-dimensionalzed as a function of Reynolds number and non-dimensional temperature, and it is found that the effect of non-dimensional temperature on them is larger than Reynolds number .     

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.