Enantio- and diastereomerically pure threo-homoallylic alcohols via highly stereoselective reduction of α-methyl-β,γ-unsaturated ketones

Reduction of α-methyl-β,γ-unsaturated ketones with L-Selectride proceeded with high $\text{threo}$-selectivity to afford $\text{threo}$-β-methyl homoallylic alcohols of high enantio- and diastereomerical purities.     

Stereoselective hydrolysis of amino acid esters by dipeptide catalysts and by N-decanoyl-histidine in surfactant aggregate domains

The rate constants of hydrolysis of the enantiomers of amino acid nitrophenyl esters by catalytic domains composed of cationic surfactant aggregates and dipeptide catalysts or Ndecanoyl-L -histidine have been determined at pH 7.30. The dipeptide catalysts shows large rate enhancement and stereoselectivity in aggregate domains. The surfactant structural effects are examined by investigation of the rate constants and stereoselectivities, and the nature of stereoselective catalysis is discussed.     

Pockels effect of water in the electric double layer at the interface between water and transparent electrode

We have obtained the first experimental evidence for the Pockels effect of water, which is induced by a high electric field in the electric double layer (EDL) on the water-transparent electrode interface. The electric-field induced energy shift of the visible interference fringes of a 300 nm indium-tin-oxide (ITO) electrode layer is observed, indicating a negative refractive index change at the interface. Numerical calculation reproduces well the experimental observation, showing that the signal mainly originates from water in the EDL. The Pockels constants of water are estimated to be r₃₃ = 5.1 × 100 pm/V and r₁₃ = 1.7 × 100 pm/V. The large anisotropy of the Pockels effect of water is deduced from the incidence angle dependence of the p-polarization signal. At the same time, the ITO shows a blue shift of the band gap in the UV due to the band population effect in the space charge layer. The plasma frequency in the near IR is also expected to increase due to the band population effect, since the ITO has a high doped carrier population close to metal. A negative refractive index change in the ITO space charge layer is induced from both effects, but its effect on the signal is estimated to be much smaller than that of the negative refractive index change of water in the EDL.     

Destructive interference during high harmonic generation in mixed gases

We report on the first experimental evidence of the destructive and constructive interference of high harmonics generated in a mixed gas of He and Ne, which facilitates the coherent control of high harmonic generation. Theoretically, we develop an analytical model of high harmonic generation in mixed gases and succeed in reproducing the experimental results and deriving the optimization conditions for the process. The observed interference modulation is attributed to the difference between the phases of the intrinsically chirped harmonic pulses from He and Ne, which leads to a novel method for broadband measurement of the harmonic phases and for observing the underlying attosecond electron dynamics.     

Polarization imaging of a 3D object by use of on-axis phase-shifting digital holography

A polarimetric imaging method of a 3D object by use of on-axis phase-shifting digital holography is presented. The polarimetric image results from a combination of two kinds of holographic imaging using orthogonal polarized reference waves. Experimental demonstration of a 3D polarimetric imaging is presented.     

Cobalt-catalyzed cross-coupling of alkynyl Grignard reagents with alkenyl triflates

Alkenyl triflates in combination with Co(acac)(3) as a catalyst were found to be excellent coupling partners of alkynyl Grignard reagents, where no special additives (even a phosphine ligand) but a common solvent, THF, are required to obtain variously substituted enynes.     

Tuned polymer electrolyte membranes based on aromatic polyethers for fuel cell applications

Poly(arylene ether sulfone)-based ionomers containing sulfofluorenyl groups have been synthesized for applications to polymer electrolyte membrane fuel cells (PEMFCs). In order to achieve high proton conductivity and chemical, mechanical, and dimensional stability, the molecular structure of the ionomers has been optimized. Tough, flexible, and transparent membranes were obtained from a series of modified ionomers containing methyl groups with the ion-exchange capacity (IEC) ranging from 1.32 to 3.26 meq/g. Isopropylidene tetramethylbiphenylene moieties were more effective than the methyl-substituted fluorenyl groups in giving a high-IEC ionomer membrane with substantial stability to hydrolysis and oxidation. Dimensional stability was significantly improved for the methyl-substituted ionomer membranes compared to that of the non-methylated ones. This new ionomer membrane showed comparable proton conductivity to that of the perfluorinated ionomer membrane (Nafion 112) under a wide range of conditions (80-120 degrees C and 20-93% relative humidity (RH)). The highest proton conductivity of 0.3 S/cm was obtained at 80 degrees C and 93% RH. Although there is a decline of proton conductivity with time, after 10 000 h the proton conductivities were still at acceptable levels for fuel cell operation. The membranes retained their strength, flexibility, and high molecular weight after 10 000 h. Microscopic analyses revealed well-connected ionic clusters for the high-IEC membrane. A fuel cell operated using the polyether ionomer membrane showed better performance than that of Nafion at a low humidity of 20% RH and high temperature of 90 degrees C. Unlike the other hydrocarbon ionomers, the present membrane showed a lower resistance than expected from its conductivity, indicating superior water-holding capability at high temperature and low humidity.