Enhancement of Thermoelectric Properties in Surface Nanostructures

The thermoelectric properties of TiN/MgO surface nanostructures have been determined using first-principles calculations based on the nonequilibrium Green’s function (NEGF) method. Through structural modification of the surfaces at the atomistic level, we find that the metallic TiN thin-film layer becomes semiconducting with a small bandgap, which enhances the Seebeck coefficient, while the electrical conductivity remains high at room temperature. Hence, a much larger thermoelectric figure of merit is obtained compared with bulk. These findings indicate the possibility of designing thermoelectric devices with surface nanostructures.     

Selective hydrogenation of ethyl phenylacetate to 2-phenylethanol: a convenient catalyst preparation method

A ruthenium-tin-alumina catalyst, prepared by a combination of kneading and impregnation methods, which we have named the combination method, was able to selectively hydrogenate ethyl phenylacetate to 2-phenylethanol; tin oxide was used as a chloride-free tin source. For this combination catalyst, the optimum atomic ratio for Ru: Sn was found to be 1 4. X-ray diffraction measurements showed the presence of tin particles. It appeared that the number of the tin particles had a large effect on the hydrogenation of C=O groups. However, the catalyst prepared with ruthenium oxide had a low activity, possibly owing to the ruthenium metal or ruthenium-tin alloy, which was formed and which obstructed the reaction.     

Selective hydrolysis of polyunsaturated fatty acid-containing oil withGeotrichum candidum lipase

Polyunsaturated fatty acids (PUFA), especially docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA), can be concentrated in glycerides by hydrolyzing tuna oil withGeotrichum candidum lipase, the main components in the resulting oil being triglycerides. The reaction mechanism of this selective hydrolysis was investigated. Although the lipase acted well on the esters of oleic, linoleic, and α-linolenic acids, it did not affect the esters of γ-linolenic acid, arachidonic acid, EPA, and DHA as much. The action of PUFA-glycerides was mono-> di- > triglycerides. Furthermore, the condensation of PUFA-partial glycerides and PUFA occurred even in the presence of a large amount of water, and the partial glycerides converted to the triglycerides by transacylation. These results suggested that the PUFA-rich triglycerides were accumulated in the glyceride fraction by the following mechanism: The PUFA-partial glycerides generated by the hydrolysis were converted to PUFA-triglycerides by condensation and transacylation reactions. As the PUFA-triglycerides formed were the poor substrates of lipase, they were accumulated in the reaction mixture.     

Gas entrainment behavior of vertical plunging liquid jets in terms of changes in jet surface length

For a vertical jet system using various liquids, the shape change of liquid jets discharged from nozzles having different nozzle aspect ratios was evaluated in terms of the surface length l_m of the jet flow, and the relation between the change of l_m and the gas entrainment behavior was investigated. It was found that the way of changing of l_m with varying operating conditions or the liquids corresponded well to that of changing of the gas entrainment rate Q_g, that is, the change of l_m of the jet before plunging could be closely related to the change of Q_g.     

Liquid flow circulating within an unbaffled vessel agitated with an unsteady forward–reverse rotating impeller

Liquid‐phase mixing is a common operation, often performed in vessels using mechanically rotating impellers. To enhance axial mixing the vessels are generally equipped with baffles; however, in industries where cleaning the vessel interior is a major concern, i.e. food and pharmaceuticals, and crystallization, where baffles can disturb particle growth, unbaffled vessels are preferred. One method of agitation in unbaffled vessels is an impeller that periodically changes either the direction or rate of rotation: so‐called unsteady rotation. For use in an enhanced agitation vessel, an agitation technology using an unsteady forward–reverse rotating impeller in an unbaffled vessel was investigated. Such unsteady agitation is expected to enhance mixing. However, knowledge of the liquid flows in such an apparatus remains elusive. Thus an aim of this work was to characterize the circulation flow in such a system. Circulation by a disk turbine impeller with six flat blades was studied through examination of tracer particle trajectories. Images showing flow patterns with the forward–reverse rotating impeller resembled those obtained with a unidirectionally rotating impeller in a baffled vessel. The pattern was characterized by a circulation loop whose pathway exits from the impeller rotational region and returns to that region past the wall and bottom of the vessel. Time‐series particle tracking velocimetry (PTV) images obtained during one forward–reverse rotation of the impeller showed that the flow near the vessel wall reduced the periodic fluctuation downstream and that a flow that was almost independent of time was induced near the vessel bottom. For the flow from the bottom to the impeller, unsteadiness was provided by proximity to the impeller. Based on the intensity distribution of the unsteady flow produced by this type of forward–reverse rotating impeller within the vessel, the unsteady flow was shown to have the potential to reach the region near the vessel wall. Copyright © 2010 Society of Chemical Industry     

Effect of cation disorder on the solubility and result of doping in oxides

The quest for novel solid electrolytes and mixed ionic electronic conductors is leading us to attempt aliovalent cation substitution of new classes of oxides, but in a number of cases such doping gives no or unexpected effects. A general feature of many such systems is that they are ternary or higher oxides in which two cations of different valence are site disordered, facilitated by similar size. Examples comprise TiNb₂O₇, TiP₂O₇, ZrP₂O₇ and Ba₃La(PO₄)₃. Doping intended to create charge compensating mobile point defects may in these cases result only in shifting the ratio of the two disordered cations, as this may have a much lower energy cost. This is accompanied by the precipitation of a phase or domains rich in the expelled cation. Entropy and Gibbs energy changes by doping are calculated and compared for cation disordered and non-disordered systems for illustration.     

Transient phenomena in a PEMFC during the start-up of gas feeding observed with a 97-fold segmented cell

To measure local phenomena in a PEMFC during a transitional state induced by changing of the feeding gas, a segmented cell was fabricated and the local current and local potential distribution were measured under open-circuit conditions. The anode or cathode was divided into 97 segments of 1.5 mm each. A change in the anode gas from nitrogen or oxygen to hydrogen induced momentary internal currents among the segments. The potential distribution in the electrolyte was observed simultaneously using three quasi-reference electrodes located locally. The results supported the reverse-current decay mechanism, which is known to be a mechanism of cathode degradation. Furthermore, internal currents were observed when the cathode gas was changed from nitrogen to oxygen. While the cathode was not subjected to a harmful potential, a large potential distribution was induced in the anode.     

Unveiling Two Consecutive Hydroxylations: Mechanisms of Aromatic Hydroxylations Catalyzed by Flavin-Dependent Monooxygenases for the Biosynthesis of Actinorhodin and Related Antibiotics

Flavin-dependent monooxygenases are ubiquitous in living systems and are classified into single- or two-component systems. Actinorhodin, produced by Streptomyces coelicolor, is a representative polycyclic polyketide that is hydroxylated through the action of the two-component ActVA-5/ActVB hydroxylase system. These homologous systems are widely distributed in bacteria, but their reaction mechanisms remain unclear. This in vitro investigation has provided chemical proof of two consecutive hydroxylations via hydroxynaphthalene intermediates involved in actinorhodin biosynthesis. The ActVA-5 oxygenase component catalyzed a stepwise dihydroxylation of the substrate, whereas the ActVB flavin reductase not only supplied a reduced cofactor, but also regulated the quinone–hydroquinone interconversion of an intermediate. Our study provides clues for understanding the general biosynthetic mechanisms of highly functionalized aromatic natural products with structural diversity.     

Uplink Capacity of A Cellular System Using Multi-user Single-carrier MIMO Multiplexing Combined with Frequency-domain Equalization and Transmit Power Control

Multi-user single-carrier multiple-input multiple-output (MU SC-MIMO) multiplexing can increase the uplink capacity of a cellular system without expanding the signal bandwidth. It is practically important to make clear an extent to which the MU SC-MIMO multiplexing combined with frequency-domain equalization (FDE) and transmit power control (TPC) can increase the uplink capacity in the presence of the co-channel interference (CCI). Since the theoretical analysis is quite difficult, we resort to the computer simulation to investigate the uplink capacity. In this paper, frequency-domain zero-forcing detection (ZFD) and frequency-domain minimum mean square error detection (MMSED) are considered for MU signal detection. It is shown that ZFD and MMSED provide almost the same uplink capacity and that an advantage of fast TPC over slow TPC diminishes. As a result, MU SC-MIMO using computationally efficient ZFD can be used together with slow TPC instead of using MMSED. With 8 receive antennas and slow TPC, MU SC-MIMO multiplexing using ZFD can achieve about 1.5 times higher uplink capacity than SU SC-SIMO diversity.