Pyramidal assemblies of colloidal particles by micromolding underneath top-gathering pillar arrays

Assemblies of colloidal particles are known to have special photonic and optical properties. Periodic pyramidal assemblies of SiO2 particles with diameters of 0.5 and 1 microm were fabricated using top-gathering pillar arrays as a new template. These top-gathering pillar arrays consisted of four pillars gathered at the top, and were fabricated by photolithography of an organic-inorganic hybrid material. The top-gathering units were obtained by controlling both the capillary and restoring forces. When a colloidal water suspension was spread on the template and the water was allowed to evaporate, the SiO2 particles were molded under the top-gathering pillars according to particle size, resulting in pyramidal assembly arrays of the particles. From in situ observation during the evaporation of water, it was found that the particles were molded underneath the top-gathering pillars by flux generated by the evaporation and by the capillary force among the particles.     

Chemisorption-induced gap states at organic-metal interfaces: benzenethiol and benzeneselenol on metal surfaces

Valence electronic states of benzenethiol (C(6)H(5)SH) and benzeneselenol (C(6)H(5)SeH) in the gas, condensed, and chemisorbed phases were examined by ultraviolet photoemission spectroscopy, metastable atom electron spectroscopy, and first-principles calculations using density functional theory. C(6)H(5)SH is chemisorbed on Pt(111) and Au(111) substrates to form a thiolate (C(6)H(5)S), and C(6)H(5)SeH is bound on Pt(111) substrate to form a selenolate (C(6)H(5)Se). In all cases, chemisorption-induced gap states (CIGSs) appear just below the Fermi level (E(F)) of the substrate, yielding a metallic character around the anchor S and Se atoms. However, the local density at E(F) decreases considerably from the anchor atom to the benzene ring, because strong coupling between benzene π(1e(1g)) and S 3p(or Se 4p) in free molecules is apparently lifted upon chemisorption. In other words, thiolates and selenolates (especially C(6)H(5)S on Au(111)) act as poor mediators of the metal wave functions at E(F), which is closely related to electric conductance in the relevant metal-organic-metal junctions at zero bias.     

Influence of an iodine treatment on the structure and physical properties of Bombyx mori silk fibroin fiber

Silk fibroin (SF) fiber from the Bombyx mori silkworm was treated with a 1.23 N iodine/potassium iodide (I₂–KI) aqueous solution, and the structure and physical properties were investigated to elucidate the effects of the iodine treatment. The SF fiber absorbed polyiodide ions such as I and I by immersion in the I₂–KI solution, and the weight gain of the SF fiber increased with the treatment time; it became saturated at about 20 wt % after 40 h. The results of the weight gain, Fourier transform infrared spectroscopy, and X‐ray diffraction measurements suggested that polyiodide ions mainly entered the amorphous region. Moreover, a new sharp reflection in the meridional direction, corresponding to a period of 7.0 Å, was observed and indicated the possibility of the formation of a mesophase structure of β‐conformation chains. Dynamic viscoelastic measurements showed that the molecular motion of the crystalline regions at about 220 °C was enhanced and shifted to lower temperature by the introduction of polyiodide ions. This indicated that the iodine component weakened the hydrogen bonding between the SF molecules forming the β‐sheet structure and caused molecular motion of the crystal to occur more easily with heating. With heating above 270 °C, the iodine component introduced intermolecular crosslinking to SF, and the melt flow of the sample was inhibited. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3418–3426, 2006     

Photodegradation of toluene over TiO(2-x)N(x) under visible light irradiation

We report the photooxidation of toluene over nitrogen doped TiO(2) (TiO(2-x)N(x)) under visible light irradiation. The photocatalytic oxidation of toluene in air over TiO(2-x)N(x) powders was studied using diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), gas chromatography (GC), ion chromatography (IC), and gas chromatography mass spectrometry (GC-MS), focusing on the photocatalytic decomposition processes of toluene. Results obtained indicate that toluene, weakly adsorbed on the catalyst surface, is initially photooxidized to benzaldehyde which adsorbs onto the TiO(2-x)N(x) surface more strongly, leading to the formation of ring-opening products such as carboxylic acids and aldehydes. No gaseous intermediates were detected during the photooxidation. Major intermediates adsorbed at the catalyst surface were oxalic acid, (COOH)(2), acetic acid, CH(3)COOH, formic acid, HCOOH, and pyruvic acid, CH(3)COCOOH, whereas more complicated carboxylic species, including propionic acid, CH(3)CH(2)COOH, isovaleric acid, (CH(3))(2)CHCH(2)COOH, and succinic acid, (CH(2)COOH)(2), were also found in the early stage of the photooxidation. These intermediate products were gradually photodegraded to CO(2) and H(2)O under visible light irradiation.     

Presence and origin of large amounts of d-proline in the urine of mutant mice lacking d-amino acid oxidase activity

Using a column-switching HPLC system combining a micro-ODS column and a chiral column, the amounts of d-proline (d-Pro) have been determined in 18 tissues, plasma and urine of mice. To avoid the enzymatic degradation of d-amino acids in vivo, a mutant mouse strain lacking d-amino acid oxidase activity (ddY/DAO⁻ mouse) was used. In the brain, relatively large amounts of d-Pro were observed in the anterior pituitary, posterior pituitary and pineal glands. In the peripheral tissues, the amounts of d-Pro were high in the pancreas and kidney. Above all, it is surprising that the ddY/DAO⁻ mice excreted large amounts of d-Pro in their urine (433 nmol/mL, 20 times that of l-Pro). The origin of d-Pro has also been investigated. By comparing germ-free mice and gnotobiotic mice, intestinal bacteria were shown to have no effect on the urinary d-Pro amount. Concerning the dietary origin, a notable amount of d-Pro was still excreted in the urine after starvation for 4 days, suggesting that some of the d-Pro is produced in the mice. Age-dependent changes in the urinary d-Pro amount have also been investigated from the postnatal 1st month up to 12 months, and ddY/DAO⁻ mice were found to excrete large amounts of d-Pro in the urine constantly throughout their lives. Kenji Hamase is Associate Professor in the Department of Bioanalytical Chemistry, Graduate School of Pharmaceutical Sciences at Kyushu University. His current research interests focus on the development of analytical methods for d-amino acids and the study of their physiological functions and diagnostic values. He received the Japanese Society for Analytical Chemistry Award for Young Scientists in 2003, and the PSJ Award for Young Scientists in 2006.     

New Technique for Fourier Transform Thermal Analysis

A new technique for the simultaneous measurement of higher order harmonic of temperature wave under temperature scan was proposed. The mathematical rule for the propagation of harmonies in the film shaped specimen was examined and the principle of Fourier transform thermal analysis was theoretically and experimentally justified. This principle applied to a technique called ‘Fourier transform thermal analysis’, makes it possible to determine simultaneously thermal diffusivity, heat capacity per unit volume and thermal conductivity as a function of frequency and temperature. The results on thermoplastics were shown and the glass transition and the crystallization were discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Simultaneous separation of common mono- and divalent cations on silica gel modified with aluminium by non-suppressed ion chromatography with conductimetric detection and nitric acid–15-crown-5 as eluent

The modification of silica gel with aluminium by a coating method was very effective for the preparation of silica-based stationary phases which acted as a cation exchanger under strongly acidic conditions. However, the separation of common mono- and divalent cations (Li⁺, Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺) on an aluminium-adsorbing silica (Al-Silica) column was moderate by a conductimetric detection ion chromatography (IC) with strongly acidic eluents. Then, the addition of various crown ethers (12-crown-4, 15-crown-5 and 18-crown-6) in acidic eluent was carried out. As a result, it was found that 15-crown-5 was most effective for the improvement of peak resolution. Excellent separation of these cations was achieved in 20 min by elution with 2 mM nitric acid–2 mM 15-crown-5. The proposed IC was successfully applied to the determination of major cations in various natural waters.     

Synthesis of186Re-DMSA and its biodistributions in mice

Optimum conditions were determined for high-yield synthesis of¹⁸⁶Re- and¹⁸⁸Re-meso-2, 3-dimercaptosuccinic acid complexes applicable to animal injection. The yield was more than 95% under the conditions used. The bone accumulation of the complexes was remarkable in the biodistributions in mice.