Stability test and improvement of hydrogen analyzer with trace reduction detector

We previously developed an analyzer able to detect hydrogen concentrations of less than 50 cm3/1000 m3. The analyzer uses a carrier gas purifier and a low temperature separation column to remove impurities preventing measurement of low concentrations from the carrier and sample gases. It uses a trace reduction detector with a mercuric oxide bed to detect the concentration of hydrogen based on the reduction reaction of mercuric oxide with hydrogen. We have now evaluated the performance of the analyzer by carrying out a series of tests that measured the spectrum peak and the retention time. We used three sample gases with hydrogen concentrations of 5, 20, and 50 cm3/1000 m3 in nitrogen dilution gas. The measured peak was stable (it was within a relative standard deviation of less than 10%), and there was a linear relationship between the peak and hydrogen concentration. However, the retention time gradually shortened as the measurements were repeated. The shortening was reduced by warming the low temperature separation column used in the analyzer; it was not observed when we used a hydrogen sample gas diluted by helium instead of nitrogen. Using nitrogen as a dilution gas apparently shortens the retention time. We thus added an MS-5A separation column and a thermal conductivity detector. The nitrogen and hydrogen in the sample/carrier gas are separated, and the nitrogen is efficiently removed by switching the pass line to a release line after the hydrogen has been sent to the low temperature separation column. An analyzer using this "after-cut method" was able to stably measure infinitesimal hydrogen concentrations and was not affected by nitrogen in the sample gas.     

Interfacial Interaction of Polymer/Liquid Crystal Molecules and Electrooptical Properties of their Composite Systems

Polymer/liquid crystal composite films were prepared from a solution of polymer and nematic liquid crystal (LC) by a solvent casting method. The phase-separated structure of the composite film was controlled by the solvent evaporation rate. The light-scattering profile of a poly(diisopropyl fumarate)/LC: 40/60 w/w solution during solvent evaporation exhibited a periodic structure, indicating that the phase-separated structure was formed by spinodal decomposition. The aggregation structure of the composite film was investigated with a scanning electron microscope (SEM). SEM observation of the composite film suggested the presence of periodicity and dual connectivity of polymer and LC phases. The faster the solvent was evaporated, the smaller the LC channel (domain) size in the composite film. The composite film, composed of poly(methyl methacrylate) (PMMA) and a nematic LC (E44) with a positive dielectric anisotropy, exhibited remarkable and reversible light-scattering-light-transmission switching, under the modulation of an ac electric field. The light-scattering state was dependent on such optical heterogeneities as spatial distribution of the nematic directors and/or mismatching in the refractive indices of the components. The electrooptical behavior of the composite film was strongly dependent on the LC channel (domain) size in the composite film. The transmittance increased and the rise and decay response times (τ_R and τ_D), decreased and increased, respectively, with an increase in the size of the LC channel (domain).

The electrooptical switching properties for the polymer/LC composite film should be influenced by miscibility between the polymer and the LC phases. The miscibility between both phases was evaluated from a distribution of relaxation time for interfacial polarization. The anchoring effect was also investigated by measuring the nonlinearity of the dielectric constant for the composite system.     

Blue phase stability of n-OCB homologue chiral nematic liquid crystal mixtures

Blue phase (BP) stability of a chiral nematic liquid crystal (LC) mixture is dependent upon chemical structure as well as physical properties. In this study, the blue phase temperature range dependent on alkyl chain length was investigated in order to evaluate the relationship between blue phase stability and the molecular structures of four kinds of 4-n-alkyloxy-4'-cyanobiphenyl (n-OCB) homologue chiral nematic LC mixtures composed of rod-like nematic LCs. It was confirmed that the blue phase temperature range was strongly dependent upon the molecular parity, K ₃₃/K ₁₁ and the helical twist power of the n-OCB homologues chiral nematic LC mixtures.     

Creation of Polymerizable Species in Plasma Polymerization

Plasma polymerization of trimethylsilane (TMS) was carried out and investigated in a direct current (dc) glow discharge. The formation of TMS plasma glow was carefully examined with optical photography as compared with an Ar dc glow discharge. It was found that there exists a significant difference in the nature of glow and how the glow is created in TMS glow discharge, which polymerizes or causes deposition, and that of monatomic gas such as Ar, which does not polymerize or deposit. In dc Ar discharge, the negative glow, which is the most luminous zone in the discharge, develops in a distinctive distance away from the cathode surface, and the cathode remains in the dark space. In a strong contrast to this situation, in TMS dc discharge, the primary glow that is termed as cathode-glow in this paper appears at cathode surface, while a much weaker negative glow as a secondary glow was observed at the similar location to where the Ar negative glow appears. The deposition results of plasma polymers and gas phase composition data of TMS in a closed reactor acquired by ellipsometry and residual gas analyzer (RGA) measurements clearly indicated that the cathode-glow in TMS glow discharge is mainly associated with chemically reactive species that would polymerize or form deposition, but the negative glow is related to species from simple gases that would not polymerize or deposit. Based on the glow location with respect to the cathode, it was deduced that the cathode-glow is due to photon emitting species created by molecular dissociation of the monomer that is caused by low energy electrons emanating from the cathode surface. The negative glow is due to the ionization and the formation of excited neutrals of fragmented atoms caused by high-energy electrons. Polymerizable species that would cause deposition of material (plasma polymers) are created mainly by the fragmentation of monomer molecules by low energy electrons, but not by electron-impact ionization of the monomer.     

Physicochemical properties of quaternized poly(amidoamine) dendrimers with four octyl chains

A cationic dendrimer-type tetrameric surfactant (C(8)qbG0) with four octyl chains and four ammonium groups was synthesized by the reaction of poly(amidoamine) dendrimers with generation of zero and glycidyldimethyloctylammonium bromide. The physicochemical properties of C(8)qbG0 and of their mixtures with sodium dodecyl sulfate (SDS) were characterized by investigating surface tension, electrical conductivity, fluorescence of pyrene, and dynamic light-scattering. The critical micelle concentration (cmc) of C(8)qbG0 was 13 mmol dm(-3) at the concentration of one terminal group and the surface tension at the cmc attained 34 mN m(-1). The occupied area of C(8)qbG0 was 1.94 nm(2) molecule(-1), indicating that the tetrameric dendrimers adsorb widely at the air/water interface. The fluorescence intensity ratio of the first-to-third band in the emission spectra of pyrene for C(8)qbG0 decreased from around the cmc obtained by the surface tension measurement. The hydrodynamic radius of C(8)qbG0 determined by dynamic light-scattering was about 1.3 nm. The addition of SDS to the aqueous solutions of C(8)qbG0 enhanced the surface activities; the mixtures exhibited lower cmc, lower surface tension, and higher solubilization of pyrene than SDS alone. It was found that the mixtures of C(8)qbG0 and SDS form large aggregates due to the interactions between their alkyl chains as well as hydrophilic groups.     

Effects of conformation and hydrogen bonding on the CC and NCN stretching Raman bands of N‐deuterated histidinium

Histidine is an important and versatile amino acid residue that plays a variety of structural and functional roles in proteins. Although the Raman bands of histidine are generally weak, histidine in the N‐deuterated cationic form with imidazole N_π D and N_τ D bonds (N‐deuterated histidinium) gives two strong Raman bands assignable to the C₄C₅ stretch (ν_CC) and the N_π C₂ N_τ symmetric stretch (ν_NCN) of the imidazole ring. We examined the Raman spectra of N‐deuterated histidinium in 12 crystals with known structures. The observed ν_CC and ν_NCN wavenumbers were analyzed to find empirical correlations with the conformation and hydrogen bonding. The effect of conformation on the vibrational wavenumber was expressed as a threefold cosine function of the C_α C_β C₄C₅ torsional angle. The effect of hydrogen bonding at N_π or N_τ was assumed to be proportional to the inverse sixth power of the distance between the hydrogen and acceptor atoms. Multiple linear regression analysis clearly shows that the conformational effect on the vibrational wavenumber is comparable for ν_CC and ν_NCN. The hydrogen bond at N_π weakly lowers the ν_CC wavenumber and substantially raises the ν_NCN wavenumber. On the other hand, the hydrogen bond at N_τ strongly raises the ν_CC wavenumber but does not affect the ν_NCN wavenumber. These empirical correlations may be useful in Raman spectral analysis of the conformation and hydrogen bonding states of histidine residues in proteins. Copyright © 2010 John Wiley & Sons, Ltd.     

Thioridazine induces immediate and delayed erythema in photopatch test

Thioridazine is a phenothiazine derivative that has been used as an antipsychotic; it rarely causes photosensitization. However, we noticed that this drug induced an erythematous reaction in a photopatch test. Six volunteers were patch tested with various concentrations of thioridazine and irradiated with a range of UVA doses, and the time courses of the color of and blood flow to the test sites were monitored. The free-radical metabolites of thioridazine generated under UVA irradiation and its effects on ascorbate radical formation were examined with an electron paramagnetic resonance (EPR) spectrometer in vitro. As a result, immediate erythema developed during UVA irradiation in most subjects when 1% thioridazine was applied for 48 h and irradiation doses were higher than 4 J cm(-2). Another peak of erythematous reaction was observed 8-12 h after irradiation. The in vitro examination detected an apparent EPR signal, which appeared when 2 mM thioridazine in air-saturated phosphate buffer was irradiated with UVA, whereas this reaction was attenuated under anaerobic conditions. The EPR signal of the ascorbate radical was augmented under both aerobic and anaerobic conditions. Thioridazine-derived oxidants and/or thioridazine radicals generated during UVA irradiation seem to play an important role in this unique phototoxic reaction.     

Synthesis and heteronuclear inclusion properties of a novel thiacalix[4]arene-based hard-soft receptor with 1,3-alternate conformation

A novel thiacalix[4]arene ditopic receptor with 1,3-alternate conformation and possessing two complexation sites for hard and soft cations, 5,11,17,23-tetra-tert-butyl-25,27-bis[(N,N-diethylaminocarbonyl)methoxy]-26,28-bis[(pyridylmethyl)oxy]-2,8,14,20-tetrathiacalix[4]arene is prepared. Regioselective synthesis of distal-bis[(N,N-diethylaminocarbonyl)methoxy]thiacalix[4]arene is accomplished by a protection-deprotection method using benzyl groups as a protecting group. The deprotection of benzyl group was succeeded in the presence of solid superacid (Nafion-H) under refluxing benzene. Its complexation behavior is examined by ¹H-NMR titration experiments. The formation of 1:2 homo- and heteronuclear complexes demonstrates that the preorganization, subtle conformational changes and affinity have a pronounced effect on the complexation of the receptor.     

Relation between electrical and optical gaps of amorphous semiconductors in the SiAsTe system

Electrical and optical properties of semiconducting SiAsTe glasses have been investigated. Compositional dependences of the properties in the Si_xAs_yTe_z system are examined as a function of atomic percentage x (or y, z) of one element with parameters of constant atomic ratio y/z (or x/z, x/y) of the other two elements. A pre-exponential factor σ₀ in the dc conductivity formula is estimated to be $\text{(2.1 ± 0.6) × 10}{}^4\text{(Ω ·}\text{cm}\text{)}{}^{\mathrm{?1}}$, inependently of the compositions. A systematic relationship between the compositional changes in the electrical gap E_g(el) and optical gap E_g(op) has been found. The energy gaps increase linearly with increasing Si content and decreasing Te content, but are almost independent of As content. The relation between E_g(el) and E_g(op) is expressed by E_g(el) = 1.60 E_g(op) ? 0.15 in eV. On the other hand, the optical absorption coefficient α(Ω) near the band edge follows the empirical formula, $\text{α(Ω) = α}{}_0$ exp ($\text{h}\text{?}\text{Ω/E}{}_{\mathrm{<mtext>s</mtext>}}$). The experimentally determined factor E_s increases linearly with E_g(op) and is closely related to the energy difference between the two gaps. A tentative model to explain these experimental results is proposed by taking into account of the effect of the potential fluctuations in such disordered materials.