Dual-oriented thin crystals of molybdenum grown under Ar+ ion bombardment

Ar⁺ sputtering of an Cu(111) surface while simultaneously supplying Mo atoms is known to induce an oriented growth of Mo thin crystals, or seed-layers, on evolving conical Cu protrusions. The seed-layers thus formed are shown to be dual-oriented, or bicrystalline, consisting of columnar crystallites grown homo-epitaxially. The orientation relationship between the two types of crystallites was (100)_I (111)_II with [001]_I [110]_II, and this bicrystallinity probably resulted from a non-uniform charge-up of the layers' growth front. As concluded from high-resolution electron microscopy, the Mo(100) stacking is elastically converted into the Mo(111) stacking and vice versa, under the influence of tensile stress. The homo-epitaxy that the seed-layers exhibited is believed to reflect the mutual convertibility of the Mo(100) and (111) stackings.     

Magnetic properties of Pm in PrNi

A magnetic property of Pm as an impurity in PrNi single crystal was investigated by means of the low-temperature nuclear orientation of^143,144Pm. The angular distribution of -ray anisotropies revealed that the direction of hyperfine field experienced by the nuclei lie in the (a, c) plane andmade an angle of 60° (5) or 240° (5) with respect to the crystallinec-axis. From the temperature dependence of the anisotropies the strength of the hyperfine field of Pm in PrNi was deduced to be 185(22)T. The hyperfine field of Co at the Ni site of PrNi was found to be less than 4T.     

Key aspects of crystalline Mo-V-O-based catalysts active in the selective oxidation of propane

Mo-V-O-based complex metal oxide catalysts were synthesized hydrothermally for the first time, characterized structurally and tested in the selective oxidation of propane to acrylic acid, and the results obtained were compared on the basis of catalyst crystal structures in order to clarify key aspects of alkane selective oxidation over multifunctional metal oxide catalysts. The catalysts tested were black solids of rod-shaped crystals, which had a layer structure in the direction of fiber axis and various high dimensional arrangements of metal octahedra in the cross-section plane. A strong dependency on the octahedra arrangements and a facet dependency were observed, and the roles of metal elements in the course of selective oxidation of propane were clarified by comparing the catalytic performance of various Mo-V-O-based catalysts. We discuss the multi-functional character derived from high dimensional structures of the catalysts and mechanism of the selective oxidation of propane.     

Chemoselective hydrogenation method catalyzed by Pd/C using diphenylsulfide as a reasonable catalyst poison

While Pd/C is one of the most useful catalysts for hydrogenation, the high catalyst activity of Pd/C causes difficulty in its application to chemoselective hydrogenation between different types of reducible functionalities. In order to achieve chemoselective hydrogenation using Pd/C, we investigated catalyst poison as a controller of the catalyst activity. We found that the addition of Ph₂S (diphenylsulfide) to the Pd/C-catalyzed hydrogenation reaction mixture led to reasonable deactivation of Pd/C. By the use of the Pd/C-Ph₂S catalytic system, olefins, acetylenes, and azides can be selectively reduced in the coexistence of aromatic carbonyls, aromatic halides, cyano groups, benzyl esters, and N-Cbz (benzyloxycarbonyl) protecting groups. The present method is promising as a general and practical chemoselective hydrogenation process in synthetic organic chemistry.     

Production of multi-hollow polymer particles by the stepwise acid/alkali method

 Recently, we reported that multi-hollow polymer particles can be prepared from carboxylated polymer particles by the stepwise alkali/acid method. In this article, an attempt was made to prepare similar particles from acid-swellable polymer particles by the stepwise treatment with acid and alkali, which was named the stepwise acid/alkali method. The acid-swellable particles were produced by emulsion terpolymerization of styrene, butyl acrylate, and dimethyl 2-amino ethyl methacrylate. The effects of initial pH value, temperature, and time in the acid and alkali treatment processes on the multi-hollow structure were examined. Received: 18 December 1996 Accepted: 11 March 1997     

Novel [2 + 2] photocycloaddition-induced rearrangement of bichromophoric naphthalene-tethered resorcinol ethers

The first examples of sequential photocycloaddition-rearrangement reactions of naphthalene-tethered resorcinol ethers are described. Bichromophoric aromatic compounds with naphthalene and resorcinol ether moieties were irradiated in the presence/absence of a small amount of acid to give the corresponding cycloaddition-rearrangement products. From the determination of quantum yields, steady-state fluorescence spectral studies, and fluorescence lifetime measurements, the mechanism of this novel photoinduced multistep reaction was elucidated to involve the initial intramolecular exciplex formation, followed by the intramolecular [2 + 2] photocycloaddition between the two aromatic rings and the subsequent acid-catalyzed skeletal rearrangement of the resulting cyclobutane derivative leading to the final products.     

Cluster-size dependence of alloying behavior in gold clusters

Cluster-size dependence of alloying behavior in nm-sized atom clusters has been studied by transmission electron microscopy, using clusters in the Au-Cu system. It was revealed that occurrence of rapid spontaneous alloying becomes more difficult with increasing cluster size. In gold clusters of approximately 4 nm in the mean size, a rapid dissolution of copper atoms took place and homogeneously mixed Au-Cu alloy clusters were formed. In gold clusters of approximately 10 nm in the mean size, rapid alloying of copper took place only at a shell-shaped region beneath the free surface of individual clusters and pure gold was retained at the central region of clusters. In gold clusters of approximately 30 nm in the mean size, no rapid alloying of copper was induced. The ease with which spontaneous alloying takes place is discussed in terms of the lattice softening in atom clusters.