Platinum Nanosheets Intercalated into Natural and Artificial Graphite Powders

Insertion of sheet-type platinum particles (platinum nanosheets) between graphite layers was achieved by a thermal treatment of a mixture of platinum chloride (IV) and graphite powder (natural graphite or artificial graphite) under 0.3 MPa of chlorine at 723 K, followed by the treatment under 40 kPa of hydrogen pressure. Similar platinum nanosheets, which were 1–3 nm in thickness and 100–500 nm in width and had a number of hexagonal holes and edges with 120° angle, were formed between the layers of both natural graphite or artificial graphite; however, their location in the graphite layers depended on the type of graphite used. A number of platinum nanosheets were observed in the edge region of natural graphite particles which have flat surface. On the other hand, a number of platinum nanosheets were found inside and away from the edge of the artificial graphite particles especially in the vicinity of the cracks. Both the platinum nanosheet-containing artificial and natural graphite samples showed high selectivity to cinnamyl alcohol in cinnamaldehyde hydrogenation under supercritical carbon dioxide conditions, while spherical platinum particles, which were located on the surface of natural and artificial graphite, showed lower selectivity.     

Enantioselective Total Synthesis of (+)‐Neostenine

A chirality transfer approach using acyclic polyol intermediates for the synthesis of (+)‐neostenine ( 1 ) has been developed. The sequential Overman/Claisen rearrangement of an allylic 1,2‐diol was especially useful, installing two contiguous stereocenters with complete diastereoselectivity in a one‐pot sequence. The SmI₂‐mediated cyclization and the subsequent chemoselective reduction of a lactam moiety accomplished the first enantioselective total synthesis of (+)‐neostenine ( 1 ).     

An artificial model of photosynthetic photosystem II: visible-light-derived O2 production from water by a di-μ-oxo-bridged manganese dimer as an oxygen evolving center

Visible-light-derived O(2) production was yielded by conjugating water oxidation catalysis by [(OH(2))(terpy)Mn(μ-O)(2)Mn(terpy)(OH(2))](3+) as an oxygen evolving center model and photo-sensitization of [Ru(bpy)(3)](2+) as a photoexcitation center model at an interlayer of mica.     

Transcutaneous immunization by a solid-in-oil nanodispersion

We have successfully achieved transcutaneous immunization without the use of any skin pre-treatment or immune-stimulant adjuvant by applying a solid-in-oil (S/O) nanodispersion: an oil-based nanodispersion of antigens coated with hydrophobic surfactant molecules. This finding indicates that the S/O nanodispersion has great promise for effective transcutaneous vaccination.     

Simultaneous tailoring of phase evolution and dopant distribution in the glassy phase for controllable luminescence

Construction of an active composite with multicolor visible and broadband near-infrared luminescence is of great technological importance for various applications, including three-dimensional (3D) display, broadband telecommunication, and tunable lasers. The major challenge is the effective management of energy transfer between different dopants in composite. Here we present an in situ strategy for controlling energy transfer between multiple active centers via simultaneous tailoring of the evolution of phases and the distribution of dopants in the glassy phase. We show that the orderly precipitation of Ga(2)O(3) and LaF(3) nanocrystals and the selective incorporation of Ni(2+) and Er(3+) into them can be achieved. The obtained composite shows unique multicolor visible and broadband near-infrared emission. Possible mechanisms for the selective doping phenomenon are proposed, based on thorough structural and optical characterizations and crystal-field calculation results. Moreover, the strategy can be successfully extended to accomplish space-selective control of multicolor luminescence by employing the modulated stimulation field. The results suggest that the strategy could be applied to fabricate a multifunctional light source with a broad range of important host/activator combinations and to construct various types of three-dimensional active microstructures.     

Modification of orientation birefringence of cellulose ester by addition of poly(lactic acid)

Effect of the addition of poly(lactic acid) (PLA) to cellulose acetate propionate (CAP) on the optical anisotropy is studied considering the morphology and molecular orientation. It is found that PLA is miscible with CAP when the amount of PLA is less than 3 wt.%. The dissolution of PLA chains having large intrinsic birefringence into CAP phase enhances the orientation birefringence of a stretched film, although the viscosity and thus the relaxation time of PLA is significantly shorter than those of CAP. The high level of orientation of PLA chains without relaxation is attained by the cooperative alignment with CAP chains. As a result, a retardation film having appropriate birefringence can be designed by polymer blends composed of biomass-based materials. When the amount of PLA is more than 3 wt.%, however, phase separation occurs. In the case of the blends with phase-separated morphology, the orientation birefringence is not greatly enhanced by blending PLA, because the molecular orientation of PLA in PLA phase relaxes immediately as compared with that of CAP.     

Enzyme-mediated enantioselective hydrolysis of soluble polymer-supported carboxylates

The enzyme-mediated enantioselective hydrolysis of water-soluble polymer-supported carboxylates is disclosed. The representative monomethoxy poly(ethylene glycol) (MPEG, av MW 5000)-supported substrate was synthesized by immobilization of (±)-1-phenylethanol onto the modified MPEG (MPEG/NH₂) through an carboxylate linker with a succinate spacer. For the screening of the hydrolytic enzymes, the substrate was enantioselectively hydrolyzed by lipase from Candida antarctica (Novozym 435) in a mixed solvent (hexane/buffer=9/1) at 30 °C to afford the remaining (S)-substrate and the resulting (R)-alcohol (E value>200). The products were easily separated by a simple procedure without any laborious column chromatography. The substrate was hydrolyzed with NaOH in MeOH/H₂O to afford the corresponding (S)-alcohol. We also found that the structure of the spacer between the MPEG moiety and the carboxylate linker strongly affected both the reactivity and enantioselectivity, and the substrate bearing a glutarate spacer gave the best result. Our procedure was applicable for the preparation of several optically active alcohols.     

A note on the relationship between the sound absorption by microperforated panels and panel/membrane-type absorbers

The sound absorption mechanism of microperforated panel (MPP) absorbers and panel/membrane-type absorbers is both based on a certain resonance system and utilising its resonance effect. However, the relationship between the absorption mechanisms of MPPs and panel/membrane-type absorbers has not been discussed: it is not clarified whether they can occur simultaneously, or how they interfere each other. On the other hand, in a previous study there is an attempt to cause both absorption mechanisms simultaneously. In this paper, using an electro-acoustical equivalent circuit model, their sound absorption mechanisms and their relationship are discussed. In this study, three cases are considered: (1) the case in which only the mass reactance of the MPP is considered, (2) the case in which the losses of the panel is considered, and (3) the case in which the sound absorption of the back wall surface is considered. The results suggest that the microperforated panel absorption, which is Helmhotz-type resonance, and the panel/membrane-type absorption can be regarded as phenomena of the same kind which can be smoothly transformed into each other by changing a parameter, and can be consistently modelled and comprehensively discussed.     

Ultra fast melting process in femtosecond laser crystallization of thin a-Si layer

In this paper, we investigated the mechanism of crystallization induced by femtosecond laser irradiation for an amorphous Si (a-Si) thin layer on a crystalline Si (c-Si) substrate. The fundamental, SHG, THG wavelength of a Ti:Sapphire laser was used for the crystallization process. To investigate the processed areas we performed Laser Scanning Microscopy (LSM), Transmission Electron Microscopy (TEM) and Imaging Pump-Probe measurements. Except for 267 nm femtosecond laser irradiation, the crystallization occurred well. The threshold fluences for the crystallization using 800 nm and 400 nm femtosecond laser irradiations were 100 mJ/cm² and 30 mJ/cm², respectively. TEM observation revealed that the crystallization occurred by epitaxial growth from the boundary surface between the a-Si layer and c-Si substrate. The melting depths estimated by Imaging Pump-Probe measurements became shallower when the shorter wavelength was used.     

Photochemical welding of silica microspheres to silicone rubber by ArF excimer laser

Transparent fused silica (SiO₂) microspheres 2.5 μm in diameter were photochemically welded to transparent, flexible silicone rubber ([SiO(CH₃)₂]_n) substrate by 193 nm ArF excimer laser induced photochemical modification of silicone into silicon oxide. Single layer of silica microspheres was easily formed on an adhesive silicone rubber before laser irradiation after dropping of silica microspheres dispersed in ethanol and subsequent tape peeling. The welding rate, the percentage of welded microspheres tested by ultrasonic cleaning with ethanol, was examined by varying the single pulse fluence and irradiation time of ArF excimer laser. The welding layer underneath microsphere, silicon oxide, was also found to emit white light of strong intensity under UV light illumination.