Structure of the electrical double layer on the aqueous solution side of the polarized interface between water and a room-temperature ionic liquid, tetrahexylammonium bis(trifluoromethylsulfonyl)imide

The structure of the electrical double layer on the aqueous solution side has been studied by measuring electrocapillary curves at the polarized interface between a room-temperature ionic liquid (RTIL), tetrahexylammonium bis(trifluoromethylsulfonyl)imide, and water (W) at different concentrations of LiCl. Thermodynamic analysis of the electrocapillary curves indicates that Li+ ions negatively adsorb at the point of zero charge. The adsorption of Li+ and Cl- ions in the polarized potential window of about 200 mV can be explained by the Gouy's double layer model, and the specific adsorption of Li+ and Cl- ions at the RTIL|W interface is negligible within the polarized potential window.     

Fabrication and Patterning of Submierometer-Thick Optical Polarizing Films for 800 nm Using Stretched Silver Island Multilayers

Stretched silver island multilayers have been investigated for patterned optical polarizers for the wavelength of 800 nm. Submicrometer-thick optical polarizing films are fabricated by stretching periodic multilayers consisting of silver island layers and Pyrex layers at the temperature of 660°C. As the optical anisotropy of the optical polarizing film is lost by heating at a temperature higher than the stretching temperature, the fine non-polarizing areas can be deliberately and easily formed on the optical polarizing film by laser irradiation with high power density. We have successfully formed various non-polarizing areas on the optical polarizing film with a 1 W-class carbon dioxide laser. The demonstrated fabricating techniques of deliberately patterned optical polarizing films should be useful for novel optical computing and sensing devices.     

Polymer modification of colloidal particles by spontaneous polymerization of surface active monomers

Adsorption and spontaneous polymerization of head- or tail-type surface active monomers having long methylene chains on colloidal silica and δ-alumina were investigated. Both head-type and tail-type ammonium monomers on silica in chloroform or tetrahydrofuran had the maximum adsorption on the respective adsorption isotherm. Above the monomer concentration giving the maximum adsorption, it was observed that the monomer formed micelles or clusters in bulk solution with removal of adsorbed water molecules from the silica surface. At the monomer concentration giving the maximum adsorption, heating the silica suspension containing the monomer at 40°C or 60°C in tetrahydrofuran or chloroform solution resulted in spontaneous polymerization. The composite particles formed by polymerization were observed to have many spots consisting of polymer on the surface. Therefore, it is suggested that the monomers are concentrated by micelle-like aggregation on the silica surface and consecutively spontaneous polymerization takes place. Adsorption of an anion-type monomer having a carboxyl group on δ-alumina, which exhibited a positive ζ potential in neutral aqueous solution, was higher than that on colloidal silica, but did not spontaneously polymerize on alumina. Received: 13 June 1998 Accepted in revised form: 19 August 1998     

Enantiomer separation of hydrophobic amino compounds by high-performance liquid chromatography using crown ether dynamically coated chiral stationary phase

CROWNPAK CR(+) column, which is powerful for the separation of amino acid enantiomers, must be used at a column temperature below 50°C and a mobile phase containing less than 15% methanol, because the chiral crown ether moiety of the stationary phase is dynamically coated on an ODS matrix. The second peak of the enantiomers of alanine-β-naphthylamide (Ala-β-NA) appeared at 204 min (k₂=148) by using ordinary mobile phase, that is, a mixture of 10 mM perchloric acid and 15% methanol. In this study, enantiomer separations of Ala-β-NA and 1-(1-naphthyl)ethylamine (1-NEA), both of which are hydrophobic amino compounds, were investigated through the modification of the mobile phase. Addition of crown ether, cyclodextrins (CDs), cations, etc., affected the stability of the complex between an analyte and the chiral moiety, leading to fast separation. The second peak of the enantiomers of Ala-β-NA appeared at 68 min (k₂=49) through the addition of 10 mM β-CD, or at 61 min (k₂=44) using potassium dihydrophosphate as a buffer component. This method was applied for the optical purity testing of -Ala-β-NA, which is used as one of the chiral derivatization reagents for carboxylic compounds. Validations such as reproducibility and linearity were also demonstrated and this method was found to be sufficient as a quality control method for the optical purity testing of -Ala-β-NA. As little as 0.05% -form in -Ala-β-NA could be determined.     

Synthesis of styrene–acrylonitrile random copolymers (SAN) and polyarylate block copolymers and the control of their mechanical properties by morphology generation

The idea of repulsion in random copolymers was applied to the miscibility modification between polystyrene (PS) and polyarylate (PAr) segments of PS–PAr block copolymer (PAr–PS–PAr). Acrylonitrile (AN), which has a large positive interaction parameter against styrene, was used as a miscibility modifier toward PAr segments. AN was introduced into the carboxyl terminated telechelic‐PS at AN wt % ranging from 12 to 37 wt %. Based on these telechelic acrylonitrile–styrene random copolymers (SAN_x's where x represents AN wt %), SAN_x and PAr block copolymers (PAr–SAN_x–PAr's) were synthesized. The miscibility of SAN_x and PAr segments was estimated from the results of DSC with Fox's equation and spin–spin relaxation time measured by pulsed NMR. These results evidenced that the miscibility between PS and PAr segments can be modified by introducing AN into PS segments. The estimated volume fraction of the interfacial layer between SAN_x and PAr segments was increased as x was increased toward 24 wt %, around which the predicted miscibility reaches a maximum. Above that AN wt %, it began to decrease. The flexural strength increased as the miscibility between SAN_x and PAr segments increased. In particular, when x was between 20 and 30 wt %, PAr–SAN_x–PAr exhibited three times larger flexural strength than PAr–PS–PAr. The fracture behavior changed from brittle to ductile, even though the telechelic SAN_x by themselves exhibited almost the same fracture strength as the telechelic PS. The results of dynamic mechanical measurements and the percolation model suggested that around these AN wt % the continuum matrices in PAr–SAN_x–PAr changed from SAN_x phase to a cocontinuous phase of SAN_x and PAr. From these results, PAr–SAN_x–PAr was explained to perform such a high flexural strength by this phase change in the continuum matrices. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 127–137, 2000     

Aerosol generation and measurement of multi-wall carbon nanotubes

Mass production of some kinds of carbon nanotubes (CNT) is now imminent, but little is known about the risk associated with their exposure. It is important to assess the propensity of the CNT to release particles into air for its risk assessment. In this study, we conducted aerosolization of a multi-walled CNT (MWCNT) to assess several aerosol measuring instruments. A Palas RBG-1000 aerosol generator applied mechanical stress to the MWCNT by a rotating brush at feed rates ranging from 2 to 20 mm/h, which the MWCNT was fed to a two-component fluidized bed. The fluidized bed aerosol generator was used to disperse the MWCNT aerosol once more. We monitored the generated MWCNT aerosol concentrations based on number, area, and mass using a condensation particle counter and nanoparticle surface area monitor. Also we quantified carbon mass in MWCNT aerosol samples by a carbon monitor. The shape of aerosolized MWCNT fibers was observed by a scanning electron microscope (SEM). The MWCNT was well dispersed by our system. We found isolated MWCNT fibers in the aerosols by SEM and the count median lengths of MWCNT fibers were 4–6 μm. The MWCNT was quantified by the carbon monitor with a modified condition based on the NIOSH analytical manual. The MWCNT aerosol concentration (EC mass base) was 4 mg/m³ at 2 mm/h in this study.     

Electronic structures of imidazolium-based ionic liquids

Electronic structures of ionic liquids formed by 1-buthyl-3-alkylimidazolium ion [C_nmim]⁺ (n = 4 and 8) with various inorganic and organic anions have been investigated by ultraviolet photoemission, X-ray photoemission, inverse photoemission and soft X-ray emission spectroscopies (SXES). The comparison of the calculated density of states with the observed spectra revealed that the molecular orbital energies of these ionic liquids are significantly affected by the electrostatic Madelung potential among the ions. The SXES results clearly show that the both highest occupied and lowest unoccupied states of [C₄mim]⁺PF₆⁻ are derived from the cation as a result of strong Madelung potential. On the other hand, the SXES results show the valence electronic structures of ionic liquids with larger anion molecules, [C_nmim]⁺Tf₂N⁻ and [C_nmim]⁺OTf⁻ are contributed from the both cation and anion.     

Structural scaffold of 18-crown-6 tetracarboxylic Acid for optical resolution of chiral amino acid: x-ray crystal analyses of complexes of D- and L-isomers of serine and glutamic acid

(+)-18-crown-6 tetracarboxylic acid (18C6H4) has been used as a chiral selector for D/L-amino acids in HPLC, where L-isomer is usually eluted prior to D-isomer, except for the case of serine. To clarify why serine exhibits the reverse order for the elusion, the chiral interactions of D- and L-serines with (+)-18C6H4 were investigated by the X-ray single crystal analyses, together with the case of D- and L-glutamic acids, which exhibit the usual elution order in HPLC. The backbone structures (amino, Calpha-H and carboxyl groups) of these four amino acids showed the nearly same interaction with (+)-18C6H4 despite their different chirality. In contrast, the hydroxyl group of L-serine side chain formed a hydrogen bond with the carboxyl group of (+)-18C6H4, whereas such a interaction was not formed for the side chain of D-serine and D- and L-glutamic acids. Thus, it was shown that the exception of D/L-serine from the first elution rule of L-isomer in HPLC is due to the presence and absence of a hydrogen bond formation of its side chain OH group.     

DNA functionalization of carbon nanotubes for ultrathin atomic layer deposition of high kappa dielectrics for nanotube transistors with 60 mV/decade switching

For single-walled carbon nanotube (SWNT) field effect transistors, vertical scaling of high kappa dielectrics by atomic layer deposition (ALD) currently stands at approximately 8 nm with a subthreshold swing S approximately 70-90 mV/decade at room temperature. ALD on as-grown pristine SWNTs is incapable of producing a uniform and conformal dielectric layer due to the lack of functional groups on nanotubes and because nucleation of an oxide dielectric layer in the ALD process hinges upon covalent chemisorption on reactive groups on surfaces. Here, we show that by noncovalent functionalization of SWNTs with poly-T DNA molecules (dT40-DNA), one can impart functional groups of sufficient density and stability for uniform and conformal ALD of high kappa dielectrics on SWNTs with thickness down to 2-3 nm. This enables approaching the ultimate vertical scaling limit of nanotube FETs and reliably achieving S approximately 60 mV/decade at room temperature, and S approximately 50 mV/decade in the band-to-band tunneling regime of ambipolar transport. We have also carried out microscopy investigations to understand ALD processes on SWNTs with and without DNA functionalization.     

Power extraction using flow-induced vibration of a circular cylinder placed near another fixed cylinder

We conducted an experiment in a towing tank to investigate the performance of an energy extraction system using the flow-induced vibration of a circular cylinder. This experiment tested three different cases involving the following arrangements of cylinder(s) of identical diameter: the upstream fixed–downstream movable arrangement (case F); the upstream movable–downstream fixed arrangement (case R); and a movable isolated cylinder (case I). In cases F and R, the separation distance (ratio of the distance between the centers of the two cylinders to their diameters) is fixed at 1.30. Measurement results show that while cases F and I generate vortex-induced vibration (VIV) resonance responses, case R yields wake-induced vibration (WIV) at reduced velocity over 9.0, which is significantly larger than that of the VIV response, leading to the induction of higher electronic power in a generator. Accordingly, primary energy conversion efficiency is higher in the case involving WIV.