Phase structure change and ER effect in liquid crystalline polymer/dimethylsiloxane blends

The mechanism of the electrorheological (ER) effect in two types of liquid crystalline polymer (LCP)/dimethylsiloxane (DMS) blends was investigated by rheological measurements and by structure observation under electric field and shear flow. The results show that the phase structures of these immiscible blends can be categorized into slipping (low viscosity) and non-slipping (high viscosity) states. In the non-slipping state, higher viscosity LCP domains connect the electrodes. In the slipping state, on the other hand, LCP domains do not connect the electrodes and the shear is mainly confined in the lower viscosity DMS domains. The ER effect (electrically induced viscosity increase) originates from the electrically induced slipping to non-slipping transition. In one of the blends, the ER effect occurs only at high shear rate, since this blend is in non-slipping state even under no field if the shear rate is low. Received: 29 April 1997 Accepted: 3 November 1997     

Unusually large magnetic anisotropy in a CuO-based semiconductor Cu5V2O10

A CuO-based material Cu(5)V(2)O(10) was successfully grown in a closed crucible using Sr(OH)(2)·8H(2)O as flux. The structure of Cu(5)V(2)O(10) can be viewed as being composed of two types of zigzag Cu-O chains running along the b- and c-axes, which shows a two-dimensional crosslike framework with 12-column square tunnels along the a-axis. Magnetic measurements show that Cu(5)V(2)O(10) exhibits unexpected large magnetic anisotropy, which is the first time magnetic anisotropy energy of ～10(7) erg/cm(3) in the CuO-based materials has been observed. The origins of large anisotropy are suggested to arise from strong anisotropic exchanges due to the particular bonding geometry and the Jahn-Teller distortion of Cu(2+) ions. Further, the band structure investigated by the GGA+U method suggests that Cu(5)V(2)O(10) is a semiconductor.     

Integrated electrochemical-chemical oxidation mediated by alkoxysulfonium ions

Generation of carbocations by the "cation pool" method followed by reaction with dimethyl sulfoxide (DMSO) gave the corresponding alkoxysulfonium ions. Alkoxysulfonium ions could also be generated by in situ DMSO trapping of electrochemically generated carbocations. The resulting alkoxysulfonium ions were transformed into carbonyl compounds by treatment with triethylamine. The present integrated electrochemical-chemical oxidation can be applied to the oxidation of diarylmethanes to diaryl ketones, toluenes to benzaldehydes, and aryl-substituted alkenes to 1,2-diketones. Moreover, the oxidation of unsaturated compounds bearing a nucleophilic group in an appropriate position gives cyclized carbonyl compounds.     

Organic reactions mediated by electrochemically generated ArS+

Low-temperature electrochemical oxidation of ArSSAr was carried out to generate a pool of "ArS(+)". Spectroscopic studies ((1)H NMR and CSI-MS) of the resulting solution revealed the accumulation of ArS(ArSSAr)(+). The resulting "ArS(+)" pool reacted with alkenes and alkynes to give diarylthio-substituted products. The "ArS(+)" pool rapidly reacted with thioacetals to give the corresponding alkoxycarbenium ion pools, which reacted with various carbon nucleophiles (indirect cation pool method). The reaction of the alkoxycarbenium ion pools with stilbene derivatives in the presence of ArSSAr gave thiochroman derivatives. In addition to such stoichiometric reactions, a catalytic amount of "ArS(+)" serves as an initiator and a chain carrier of some cationic chain reactions involving intramolecular carbon-carbon bond formation. In situ generation of "ArS(+)" by electrochemical oxidation of ArSSAr with a catalytic amount of electricity in the presence of a substrate is also effective for such cationic chain reactions.     

Aromatic character of polycyclic π systems formed by fusion of two or more rings of the same size

The sequential line plot of topological resonance energy (TRE) against the number of π electrons (N(π)) for any polycyclic aromatic hydrocarbon (PAH) is very similar with the same number of extrema to that for benzene. Thus, global aromaticity of a PAH molecular ion strongly reflects that of a benzene molecular ion. Likewise, the N(π) dependence of TRE for any polycyclic π system formed by fusion of two or more rings of the same size reflects that for a monocyclic species of the same ring size. In general, TREs for such polycyclic π systems and their molecular ions can be interpreted consistently by reference to those for neutral and charged monocyclic species of the same ring size.     

Location of [60]fullerene incorporation in lipid membranes

We confirmed that most C(60) fullerene units are located in the hydrophobic core of the lipid bilayer membrane in water-soluble lipid membrane incorporated C(60) (LMIC(60)) complexes using differential scanning calorimetry (DSC) and (13)C NMR spectra in the presence of radical labels.     

Photoresponsive liposomal nanohybrid cerasomes

An innovative photoresponsive cerasome is fabricated by sol-gel process in combination of self-assembly technique from a molecularly designed organoalkoxysilylated lipid containing an azobenzene unit, which is able to operate as a "valve" with an "on-off" function under specific stimuli to control the release of loaded guest molecules from the liposomal membrane.     

Physicochemical properties and plastic crystal structures of phosphonium fluorohydrogenate salts

Fluorohydrogenate salts of quaternary phosphonium cations with alkyl and methoxy groups (tetraethylphosphonium (P(2222)(+)), triethyl-n-pentylphosphonium (P(2225)(+)), triethyl-n-octylphosphonium (P(2228)(+)), and triethylmethoxymethylphosphonium (P(222(101))(+))) have been synthesized by the metatheses of anhydrous hydrogen fluoride and the corresponding phosphonium bromide or chloride precursors. The three salts with asymmetric cations, P(222m)(FH)(2.1)F (m = 5, 8, and 101), are room temperature ionic liquids (ILs) and are characterized by differential scanning calorimetry, density, viscosity, and conductivity measurements. Linear sweep voltammetry using a glassy carbon working electrode shows these phosphonium fluorohydrogenate ILs have wide electrochemical windows (>4.9 V) with the lowest viscosity and highest conductivity in the known phosphonium-based ILs. Thermogravimetry shows their thermal stabilities are also improved compared to previously reported alkylammonium cation-based fluorohydrogenate salts. Differential scanning calorimetry and X-ray diffraction revealed that tetraethylphosphonium fluorohydrogenate salt, P(2222)(FH)(2)F, exhibits two plastic crystal phases. The high temperature phase has a hexagonal lattice, which is the first example of a plastic crystal phase with an inverse nickel arsenide-type structure, and the low-temperature phase has an orthorhombic lattice. The high-temperature plastic crystal phase exhibits a conductivity of 5 mS cm(-1) at 50 °C, which is the highest value for the neat plastic crystals.     

Effects of sub-millimeter-bubble injection on transition to turbulence in natural convection boundary layer along a vertical plate in water

Temperature and velocity measurements are performed to clarify the effects of sub-millimeter-bubble injection on the transition to turbulence in the natural convection boundary layer along a vertical plate in water. In particular, we focus on the relationship between the bubble injection position L and the transition to turbulence in the natural convection boundary layer. The bubble injection positions used in our experiments are L = 1.6 and 3.6 mm. Bubble injection at L = 1.6 mm delays the transition to turbulence in the natural convection boundary layer, while that at L = 3.6 mm accelerates the transition to turbulence in the boundary layer. In the case of L = 1.6 mm, the appearance region of the liquid velocity fluctuation in the bubble-induced upward flow in the upstream unheated section is restricted to near the wall, although the peak of the liquid velocity fluctuation is high. In contrast, in the case of L = 3.6 mm, the relatively large liquid velocity fluctuation is distributed widely over the laminar boundary layer width. These results suggest that the effect of the liquid velocity fluctuation on the laminar boundary layer is quite different between L = 1.6 and 3.6 mm. It is therefore expected that the transition to turbulence in the natural convection boundary layer for the case with bubble injection is dependent on the magnitude and appearance region of the liquid velocity fluctuation in the bubble-induced upward flow in the upstream unheated section.     

All-Fiber Optical Add-Drop Multiplexer Using a Pair of Fiber Grating Couplers

A new all-fiber optical add-drop multiplexer (ADM) using a pair of fiber grating couplers (FGCs) was proposed and first demonstrated. It was theoretically and experimentally shown that both drop and add efficiencies could be maximized in the proposed ADM. It was also clarified that the crosstalk between dropped and added signals could be improved in the proposed ADM compared with that in the single FGC. Drop and add operations in the ADM for 3-channel WDM signals with 1.6 nm wavelength spacing were confirmed. The ADM with signal amplification ability, which consists of a pair of FGCs, an EDF, and a pump-LD, was proposed and demonstrated. It was confirmed that the dropped and transmitted optical signals could be amplified in the ADM, and would be able to expand fiber routing spans.