A direct electrochemical route to construct a polymer/manganese oxide layered structure

A layered nanocomposite with poly(diallyldimethylammonium), PDDA, intercalated between manganese oxide layers can be formed on a platinum electrode in a thin film form through a direct electrochemical route. The process involves a potentiostatic oxidation of aqueous Mn(2+) precursors in the presence of PDDA by applying a constant potential (+1.0 V vs Ag/AgCl).     

Characterization of preformed plasmas with an interferometer for ultra-short high-intensity laser-plasma interactions

The evolution of an Al preformed plasma produced by a prepulse was observed before and after the arrival of the main pulse by an interferometer using a femtosecond probe pulse. A central density depression due to the ponderomotive force of the main laser pulse in the preformed plasma with a 100 m scale length was clearly visible after the main pulse irradiation at an intensity of 5×10¹⁶ W/cm². The temporal profiles of the prepulse, characterized by a cross-correlation in conjunction with a precise density profile measurement by an interferometer, contribute to the better understanding of femtosecond laser-matter interactions. PACS 52.38.-r; 52.50.Jm; 52.70.-m     

Magnetically recoverable osmium catalysts for dihydroxylation of olefins

We prepared magnetically recoverable osmium catalysts by use of magnetite, quaternary ammonium salts, and potassium osmate(VI), and applied them to the dihydroxylation of olefins. By employing 2 mol% of the magnetic osmium catalyst, the dihydroxylation reaction proceeded smoothly to provide the corresponding vicinal diol in a good chemical yield. The osmium catalyst was readily recovered by use of an external magnet, and was reused repeatedly.     

Towards Realization of a Micro- and Mesoporous Composite Silicate Catalyst

A composite silicate material, which possesses the characteristics of both microporous zeolite and mesoporous silica materials, is developed by top–down and bottom–up synthesis techniques. In order to realize a micro- and mesoporous composite material, several essential points must be clarified, since each porous material is synthesized under very different metastable conditions: zeolite is a silicate crystal, while the wall of mesoporous material is composed of amorphous silicate. Here, some aspects of the realization of a micro- and mesocomposite porous material are described, as are our experimental results regarding the successful production of composite catalyst.     

Tactile impression and friction of water on human skin

Water has a unique touch as well as characteristic physical properties. However, nobody knows the real identity of its touch. Here, we show that water creates a stick-slip feel when a small amount is rubbed using fingertip on an artificial skin that mimics the structure of human skin. The results of frictional analyses predict that this stick-slip feel is caused by a drastic change in frictional resistance. The present result is valuable for biologists and robot engineers as well as cognitive scientists and tribologists, because it is a new example of stick-slip phenomena on biological surfaces. The tactile texture of this most familiar material could also be applied to consumer products or virtual reality systems.     

Direct patterning of poly(amic acid) and low‐temperature imidization using a crosslinker,a photoacid generator,and a thermobase generator

A positive‐type photosensitive polyimide (PSPI) based on poly(amic acid) (PAA), a crosslinker 1,1,1‐tris{4‐[2‐(vinyloxy)ethoxy]phenyl}ethane (TVPE), a photoacid generator (PAG) (5‐propylsulfonyloxyimino‐5H‐thiophen‐2‐ylidene)‐2‐(methylphenyl)acetonitrile (PTMA), and a thermobase generator (TBG) t‐butyl 2,6‐dimethylpiperidine‐1‐carboxylate (BDPC) has been developed as a promising material in microelectronics. The PAA was prepared from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐oxydianiline (ODA) in dimethyl sulfoxide (DMSO). The PSPI, consisting of PAA (69 wt %), TPVE (21 wt %), PTMA (3 wt %), and BDPC (7 wt %), showed high sensitivity of 21 mJ/cm² and a high contrast of 6.8 when it was exposed to a 436‐nm line (g‐line), postbaked at 90 °C for 5 min, and developed with 1.69 wt % TMAHaq. A clear positive image of 8 μm line and space pattern was printed on film, which was exposed to 50 mJ/cm² of g‐line by a contact printing mode and fully converted to the corresponding polyimide (PI) pattern on heating at 200 °C, confirmed by FTIR spectroscopy. Thus, this system will be a good candidate for next generation PSPIs. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3362–3369, 2009     

Allylation of methylenecyclopropanes with allylindium reagents

Methylenecyclopropanes carrying a hydroxymethyl group at the ring underwent stereoselective allylindation with allylindium sesquiiodide to afford the allylated products, in which the allyl group was delivered at the external sp² carbon via cyclopropylindium intermediates. The reaction of ethyl 2-cyclopropylideneacetate and triallylindium afforded the 1,4-adduct along with dimeric products.     

The theoretical study for the perovskite-type manganese fluorides of KMnF3, RbMnF3 and K1−xLixMnF3

We performed the hybrid-density functional theory (DFT) calculations for the strongly correlated perovskite-type manganese fluorides of KMnF₃, RbMnF₃ and K_1?xLi_xMnF₃ In both solids, UBHHLYP, which contains 50% Hartree–Fock exchange term, provided the reasonable effective exchange integral (J_ab) values, in comparison with the experimental ones. In order to investigate the intrinsic roles of counter cations precisely, we examined the variations of the total energy and J_ab value, assuming the displacement of counter cation toward <1 0 0> direction. In KMnF₃ (RbMnF₃), it was found that the steric repulsion between potassium (rubidium) and bottleneck is large, while that between lithium and bottleneck is negligible in K_1?xLi_xMnF₃. Finally, we also showed the possibility of the lithium ion conduction in the antiferromagnetic K_1?xLi_xMnF₃. It was concluded that the lithium ion conduction in RMnF₃ is possible, if the vacancy at R site exists.     

Influence of wall heat loss on the emission characteristics of premixed ammonia-air swirling flames interacting with the combustor wall

The influence of wall heat loss on the emission characteristics of ammonia-air swirling flames has been investigated employing Planar Laser-Induced Fluorescence imaging of OH radicals and Fourier Transform Infrared spectrometry of the exhaust gases in combustors with insulated and uninsulated walls over a range of equivalence ratios, ?, and pressures up to 0.5 MPa. Strong influence of wall heat loss on the flames led to quenching of the flame front near the combustor wall at 0.1 MPa, resulting in large unburned NH₃ emissions, and inhibited the stabilization of flames in the outer recirculating zone (ORZ). A decrease in heat loss effects with an increase in pressure promoted extension of the fuel-rich stabilization limit owing to increased recirculation of H₂ from NH₃ decomposition in the ORZ. The influence of wall heat loss resulted in emission trends that contradict already reported trends in literature. NO emissions were found to be substantially low while unburned NH₃ and N₂O emissions were high at fuel-lean conditions during single-stage combustion, with values such as 55 ppmv of NO, 580 ppmv of N₂O and 4457 ppmv of NH₃ at ? = 0.8. In addition, the response of the flame to wall heat loss as pressure increased was more important than the effects of pressure on fuel-NO emission, thereby leading to an increase in NO emission with pressure. It was found that a reduction in wall heat loss or a sufficiently long fluid residence time in the primary combustion zone is necessary for efficient control of NH₃ and N₂O emissions in two-stage rich-lean ammonia combustors, the latter being more effective for N₂O in addition to NO control. This study demonstrates that the influence of wall heat loss should not be ignored in emissions measurements in NH₃-air combustion, and also advances the understanding of previous studies on ammonia micro gas turbines.     

Enantioselective total synthesis of sacrolide A

An enantioselective total synthesis of sacrolide A, an antimicrobial and cytotoxic fourteen-membered macrolactonic oxylipin isolated from an edible freshwater cyanobacterium, has been accomplished from a known carboxylic acid in 20% overall yield by a concise ten-step sequence. The key transformations include chiral oxazolidinone-based diastereoselective installation of two hydroxy-bearing stereocenters, the Horner–Wadsworth–Emmons olefination to construct the full carbon skeleton, and the Shiina macrolactonization to establish the fourteen-membered macrolide structure.