Preparation of Layer Structure-Controlled Ru-Sn-Al2O3 Catalysts and Their Reactivity

In order to achieve functional group selective hydrogenation, the layer structure of Ru-Sn-Al2O3 catalysts was controlled by using sol-gel, powder impregnation and combined sol-gel impregnation methods. The properties of the catalysts and effectiveness in hydrogenation of dimethyl terephthalate were examined. The surface Sn contents of the catalysts characterized by X-ray photoelectron spectroscopy depended on the preparation method, in spite of almost the same bulk Ru and Sn compositions measured by X-ray fluorescence analyses. TPR and CO adsorption of the catalysts also depended on the preparation method. With regard to the conversion rate of dimethyl terephthalate and the rate of product conversion from methyl 4-hydroxy methylbenzoate to p-xylene via methyl p-toluate, Ru impregnation catalysts had higher rates than the other catalysts.     

Conformational Studies on Polytripeptides as a Model of Collagen

To study the role of glycine residues in stabilizing the collagen triple helix, the glycine residues in the polytripeptide (Pro-Ala-Gly)_n were partially replaced by alanine. The proline content was kept constant. The stability of the helical conformation of these polypeptides was studied by IR- and X-ray measurements in the solid state and by ORD, CD and viscometry in solution. The renaturation was followed as a function of time. All the polytripeptides studied, with the exception of (-Pro-Ala-Ala-)_n attained the polyproline II conformation. However the stability decreased with increasing alanine content. Obviously the molecules of (-Pro-Ala-Gly-) are highly associated by intermolecular hydrogen bonds and one may therefore suppose that a triple-stranded helix aggregation occurs. The results of the refolding process show that the stability of the helices seems to also affect the refolding rate in terms of the optical rotation, Two transitions appeared: the first one is responsible for a rapid reversible change in conformation and the second one for a further slow and irreversible change in the hydrodynamic shape. The latter seems to be due to the partial helical nature, leading to higher chain mobility.     

Effect of Organic Ligands Used in Sol-Gel Process on the Formation of Mullite

The preparation of mullite by the sol-gel method using organic polydentate ligands and the effect of the raw materials and organic polydentate ligands on the formation of mullite were investigated. Two series of samples were prepared using tetraethoxyorthosilicate (TEOS) and aluminum nitrate nonahydrate, or dibutoxyethylacetoacetatoaluminum (Al(OBu)₂(AcAcEt)) as the silica and alumina sources, respectively, and using ethylene glycol (EG), 1,3-propanediol (PD), 1,3-butanediol (BD), 2-methyl-2, 4-pentanediol (MPD), diethlene glycol monoethyl ether (DEME) and ethoxyethanol as the ligands. When the alumina source was aluminum nitrate nonahydrate, mullite was apt to appear in the order of EG>PD>MPD. When Al(OBu)₂(AcAcEt) was the alumina source, the tendency toward the appearance of mullite crystalline phase was EG>BD>DEME>MPD. Between the two alumina sources, aluminum nitrate nonahydrate gave mullite much easier than Al(OBu)₂(AcAcEt). These relationships were discussed from the viewpoints of the coordination ability of the ligands and the miscibility between the silica and alumina.     

A Small One-Fiber WDM Optical Ethernet PC Card for FTTD

A new generation of network interface card for fiber-to-the-desktop has been fabricated. The fabricated card is PC-card size and suitable for notebook PCs. It could become the key element in the coming optical Ethernet age.     

Preparation and Acid‐Responsive Photophysical Properties of T‐Shaped π‐Conjugated Molecules Containing a Benzimidazole Junction

T‐shaped π‐conjugated molecules with an N‐methyl‐benzimidazole junction have been synthesized and their acid‐responsive photophysical properties owing to the change in the π‐conjugation system are discussed. T‐shaped π‐conjugated molecules consist of two orthogonal π‐conjugated systems including a phenyl thiophene extended from the 2‐position and alkyl phenylenes connected through various π‐spacers from the 4,7‐positions of the N‐methyl‐benzimidazole junction. The π‐spacers, such as thiophene, ethyne, and ethane, have an effect on the acid response of photophysical properties in terms of changes in conformation, excited‐state energy and charge‐transfer (CT) characteristics. In particular, the π‐conjugated molecule with ethynyl spacers exhibited a marked redshift in the fluorescence spectrum with a large Stokes shift upon the addition of acid, whereas the other molecules showed substantial quenching. The redshift in emission was studied in detail by temperature‐dependent fluorescence measurements, which indicated the transition to a CT state over the finite activation energy at the excited state. The change in the frontier molecular orbitals upon acid addition was further discussed by means of DFT calculations.     

Preparation of cerium-loaded Y-zeolites for removal of organic sulfur compounds from hydrodesulfurizated gasoline and diesel oil

Ce(IV)-loaded Y-zeolites (CeY) were prepared for selective removal of the trace amount of organic sulfur compounds from hydrodesulfurization (HDS)-treated diesel oil. The CeY samples can be obtained from NH4-Y-zeolite (NH4Y) using liquid-phase ion-exchange and solid-state ion-exchange methods. The ion-exchange reactions, structures, and selective adsorptions of organic sulfur compounds of the CeY samples were investigated using XRD, IR, XPS, TEM, and GC sulfur analyzer. The organic sulfur compound uptakes strongly depend on the amount and the valency of Ce in the zeolite structure. Ce(IV) shows much higher adsorptive ability than Ce(III). A CeY-S sample prepared by solid-state ion-exchange reaction of NH4Y and Ce(NO3)3 with Ce/NH4 mole ratio of 0.63 at 250 degrees C showed a maximum sulfur uptake from a model solution of HDS-treated gasoline containing thiophene [S = 5 ppm (ppm = mg/L)]. A desulfurization from a HDS-treated diesel oil containing organic sulfur compounds (S = 1.87 ppm) and H2S (S = 0.73 ppm) was investigated with a combination of the CeY-S and a CuO adsorbent for removal of H2S by a batch method. The sulfur content was reduced to below 0.01 ppm for the first time. This method provides a promising desulfurization process to prepare a clean fuel for fuel cells.     

New hybrid [2]catenanes based on a 4,4'-bipyridinium ligand

The self-assembly-mediated synthesis of metallomacrocycles 4a and 4b from (en)M(NO3)2 (M = Pd, Pt) and bipyridinium ligand 3 is described. The reaction is templated by disodium p-phenyldiacetic dicarboxylate, which is inserted into the macrocyclic cavity. Similarly, the self-assembly process between ligand 3, (en)M(NO3)2 (M = Pd, Pt), and the macrocyclic polyether 6 resulted in the formation of hybrid catenanes 7a and 7b. In the [2]catenanes, the circumrotation of the macrocyclic polyether through the cavity of the metallocycle is slow on the 1H NMR time scale.     

Optical Devices for Optical Access Networks Recent Progress in Semiconductor Optical Devices and Optical Modules

Cost-effectiveness is essential in developing optical access network systems. To reduce system costs, both improved system and component technologies are required. Reducing the costs of optical devices and modules in an optical network unit is especially necessary. In this paper, the requirements for optical devices in optical access networks and modules are clarified. Moreover, we also review the recent progress in technologies for semiconductor optical devices and hybrid integration for low-cost optical modules in access networks.     

Electrochemical and guest binding properties of Frechet- and Newkome-type dendrimers with a single viologen unit located at their apical positions

Several new series of dendrimers containing a single redox-active 4,4'-bipyridinium (viologen) residue were synthesized and characterized. In these dendrimers, the viologen group is covalently attached to the apical position of a Newkome- or Frechet-type dendron, ranging in size from first to third generation of growth. The half-wave potentials corresponding to the two consecutive one-electron reductions of the viologen residue are affected by the size of the dendritic component. The size effects are more pronounced in the Newkome-type dendrimers and seem to result from the polarity contrast between the microenvironments provided by the solution and the internal phase of the dendrimer. Unlike in many other dendrimers having a redox-active core, the voltammetric behavior remains fast (reversible) even in third generation dendrimers. Pulse gradient stimulated echo NMR diffusion coefficient measurements on the Newkome-type dendrimers reveal that their hydrodynamic radii are relatively invariant in solvents of widely different polarities (dichloromethane to dimethyl sulfoxide). The host-guest binding interactions between the viologen residue in these dendrimers and the crown ether host bis-p-phenylene-34-crown-8 were also investigated. While in Newkome-type dendrimers the growth of the dendron caused a substantial attenuation of the binding constant values, this size effect was not observed in the Frechet-type dendrimers. These electrochemical and binding measurements underscore some of the structural differences between these two common types of dendritic architectures.     

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.