Catalytic transfer hydrogenation on a hydrogen-absorbing alloy (CaNi5) using hydriding–dehydriding properties

By using the characteristics of a hydrogen-absorbing alloy, the hydrogen produced by catalytic dehydrogenation of saturated compounds can be absorbed to form metal hydrides, and, vice versa, the resulting metal hydrides are able to hydrogenate efficiently unsaturated compounds upon dehydriding. Gas-phase reactions between 2-butene and 2-propanol on a hydrogen-absorbing alloy CaNi₅ have been studied in the temperature range of 393–473 K. CaNi₅ showed interesting characteristics as an active catalyst for the catalytic transfer hydrogenation of butene from propanol as a hydrogen donor. 2-propanol was effectively dehydrogenated at 423 K to yield acetone in which the dissociated hydrogen was completely absorbed by CaNi₅ to form the metal hydride. When the alloy was hydrided to some extent, butene was hydrogenated by the absorbed hydrogen in the metal hydride to produce butane. The overall reaction on CaNi₅ was expressed as catalytic transfer hydrogenation of 2-butene from 2-propanol through intermediate formation of metal hydrides, rather than the direct reaction between butene and propanol on the alloy. Thus, CaNi₅ effectively repeated hydriding–dehydriding cycles: hydriding of CaNi₅ by 2-propanol dehydrogenation with subsequent dehydriding for the hydrogenation of 2-butene. The use of hydrogen-absorbing CaNi₅ provides a novel reaction system for the catalytic transfer hydrogenation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Theoretical study of the temperature dependent hydrogen storage capacity of Pd and Ti nanoparticles

A hybrid simulation was carried out using discrete variational (DV) Xα molecular orbital and molecular dynamics methods to examine the storage of hydrogen in metal nanoparticles. The calculation load was light and therefore could be performed quickly on a generic personal computer. The simulation investigates the electronic states of hydrogen on Pd and Ti nanoparticles. The hydrogen dissociation behavior on the metal surface was reproduced, and the calculated bonding orbitals of Pd and hydrogen are consistent with other reports. The diffusion coefficient of hydrogen inside the metal displays the same temperature dependence as the theoretical results. This simplified calculation, which produces results in agreement with experimental/theoretical values, could lead to improved simulation methods for hydrogen storage materials.     

Fabrication and properties of one-mask-patterned ferroelectric integrated capacitors

A one-mask-patterned ferroelectric capacitor test structure designed with a 0.5-μm feature size was fabricated. Oxygen plasma treatment after dry etching decreased the leakage current to as low as that of as-deposited film. These one-mask-patterned ferroelectric capacitors, with switching charge almost equal to as-deposited film, were successfully fabricated. Ferroelectric memories as dense as dynamic random access memories will become possible with this technology. However, the leakage current density for micron-sized capacitors is 2 to 10 times that of large capacitors. The leakage current in small capacitors is increased due to perimeter leakage that runs through the damaged region on the capacitor sidewall. © Scripta Technica, Inc. Electr Eng Jpn, 121(1): 43–50, 1997     

Analysis of the Microstructure of Mg2Si Thermoelectric Devices

High-performance Mg₂Si thermoelectric devices have been obtained by spark plasma sintering of high-purity, pre-synthesized, all-molten Mg₂Si powder. We studied the effects of source powder particle size on thermoelectric performance. To improve the performance, further investigation of the microstructure of the devices is needed. In this work we studied the microstructure of grain boundaries and interfaces between electrodes and Mg₂Si sintered bodies to increase understanding of Mg₂Si thermoelectric devices.     

Algorithms for Extracting Correct Critical Points and Constructing Topological Graphs from Discrete Geographical Elevation Data

Researchers in the fields of computer graphics and geographical information systems (GISs) have extensively studied the methods of extracting terrain features such as peaks, pits, passes, ridges, and ravines from discrete elevation data. The existing techniques, however, do not guarantee the topological integrity of the extracted features because of their heuristic operations, which results in spurious features. Furthermore, there have been no algorithms for constructing topological graphs such as the surface network and the Reeb graph from the extracted peaks, pits, and passes. This paper presents new algorithms for extracting features and constructing the topological graphs using the features. Our algorithms enable us to extract correct terrain features; i.e., our method extracts the critical points that satisfy the Euler formula, which represents the topological invariant of smooth surfaces. This paper also provides an algorithm that converts the surface network to the Reeb graph for representing contour changes with respect to the height. The discrete elevation data used in this paper is a set of sample points on a terrain surface. Examples are presented to show that the algorithms also appeal to our visual cognition.     

A parallel method for large sparse generalized eigenvalue problems using a GridRPC system

In this paper we present a master–worker type parallel method for finding several eigenvalues and eigenvectors of a generalized eigenvalue problem , where A and B are large sparse matrices. A moment-based method that finds all of the eigenvalues that lie inside a given domain is used. In this method, a small matrix pencil that has only the desired eigenvalues is derived by solving large sparse systems of linear equations constructed from A and B. Since these equations can be solved independently, we solve them on remote servers in parallel. This approach is suitable for master–worker programming models. We have implemented and tested the proposed method in a grid environment using a grid RPC (remote procedure call) system called OmniRPC. The performance of the method on PC clusters that were used over a wide-area network was evaluated.     

Effect of Lipase Activity and Specificity on the DAG Content of Olive Oil from the Shodoshima-Produced Olive Fruits

Olive oils have a higher relative diacylglycerol (DAG) content than other plant oils. The lipase in olive fruits is involved in DAG production and is directly related to the acidity of the olive oil. However, the lipase activity and positional selectivity have not been clarified. To investigate the properties of olive fruit lipase, olive fruits of the Mission variety harvested during mid-December of 2005 on Shodoshima Island (Japan) were stored at 20, 30 or 40 °C for 4 weeks. Changes in the acidity and acylglycerol content of the oils extracted from the stored fruits were analyzed. The acidity and DAG content of the olive oils increased due to triacylglycerol (TAG) hydrolysis during storage. sn-1,2-DAGs preferentially increased during the early stages of storage, indicating that the olive fruit lipase is enantioselective for the sn-3 position, while non-enzymatic isomerization of sn-1,2-DAGs was observed throughout the entire duration of storage. Kinetic analysis revealed that the enantioselectivity of olive fruit lipase for the sn-3 position was approximately four times greater than for the sn-1 position. The lipase was gradually inactivated at temperatures of 30 °C or higher, and the ratios of the rate constant for inactivation to TAG hydrolysis at the sn-3 position was 0.2, 13, and 23 at 20, 30, and 40 °C, respectively.     

Excitons in organic-inorganic hybrid compounds (CnH2n + 1NH3)2PbBr4 (n = 4, 5, 7 and 12)

Thin films of microcrystalline (C_nH_2n + 1NH₃)₂PbBr₄ (n = 4, 5, 7 and 12) have been prepared by a modified spin-coating method, and the effect of the number of carbon atoms of the alkyl chain length (n) on optical properties has been investigated. Absorption spectra reveal that (C_nH_2n + 1NH₃)₂PbBr₄ films show stable excitons with a binding energy of a few hundred meV. The excitonic structure of (C_nH_2n + 1NH₃)₂PbBr₄ varies with the number of carbon atoms. The lowest-energy exciton splits into a few fine-structure levels at low temperature. (C_nH_2n + 1NH₃)₂PbBr₄ films (n = 5, 7 and 12) show not only singlet excitons but also triplet excitons at low temperature, while (C₄H₉NH₃)₂PbBr₄ films show only singlet excitons. The intersystem crossing from excited singlet state to triplet state plays an important role in the relaxation process of excitons.