Photothermal Oxidation of Cinnamyl Alcohol with Hydrogen Peroxide Catalyzed by Gold Nanoparticle/Antimony-Doped Tin Oxide Nanocrystals

Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (d_Au) at 5.3 nm≤d_Au≤8.2 nm. Light irradiation (λ_ex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs.     

Characterization and determination of linear alkylbenzenesulfonates in environmental water samples by high-performance liquid chromatography with a hydrophilic polymer column and electrospray ionization mass spectrometric detection.

A liquid chromatography-mass spectrometry (LC/MS) method was developed for the separation and determination of linear alkylbenzenesulfonates (C10-C14 LAS) in environmental water samples using a hydrophilic polymer column (Shodex Mspak GF-310 4D). This method involves a solid-phase extraction of the LAS samples with a Sep-Pak PS-2 cartridge. The LAS components were separated on the column with a mobile phase of 29% (w/v) acetonitrile-water containing 0.8 mM di-n-butylammonium acetate and 0.2 M acetic acid, and were detected by mass spectrometry with electrospray ionization. Detection limits of the developed method based on selected ion monitoring (SIM) technique for the C10-C14 LAS standards were 13-47 ng L(-1). The concentrations of the C10-C14 LAS in the environmental water samples ranged between 5-317 microg L(-1) for a river water sample and 0.4-6.4 microg L(-1) for a seawater sample. Linear relationships between the logarithms of retention factors and the alkyl chain lengths for each phenyl positional isomer of LAS could successfully be used for the identification of the isomer peaks.     

InGaAs/InAlAs Five Layer Asymmetric Coupled Quantum Well (FACQW) for Ultra-Wideband Ultrafast Optical Modulators

An InGaAs/InAlAs five-layer asymmetric coupled quantum well (FACQW) is expected to show very large electrorefractive index change. n in a wideband transparency region. Band structures of the FACQW are analyzed with Luttinger-Kohn Hamiltonian. The electrorefractive characteristics of the FACQW are discussed.     

PHOTORECEPTOR CELL TYPES IN THE RETINA OF VARIOUS VERTEBRATE SPECIES: IMMUNOCYTOCHEMISTRY WITH ANTIBODIES AGAINST RHODOPSIN AND IODOPSIN

Types of photoreceptor cells in the retinas of 36 species of vertebrates (5 classes, 14 orders) were investigated immunocytochemically with monoclonal antibodies against chicken iodopsin (Io-mAb) and antiserum against bovine rhodopsin (Rh-As). In mammals, Rh-As labeled the outer segments of some photoreceptor cells in striped squirrels (a diurnal mammal) and those of most photoreceptor cells in mice (a nocturnal mammal), while Io-mAb labeled any photoreceptor cells in either of them. In all species of birds studied, Io-mAb labeled the principal and accessory members of double cones and single cones with a red oil droplet. Rh-As labeled single cones with a yellow or clear oil droplet in addition to rods. In turtles, both Rh-As and Io-mAb labeled single cones with a red or clear oil droplet and the principal (with a yellow oil droplet) and accessory members of double cones. This suggests that the visual pigments in these cones of turtles have common epitopes with bovine rhodopsin and chicken iodopsin. In Japanese grass lizards, single cones with a yellow oil droplet and double cones were immunoreactive to both Rh-As and Io-mAb. In snakes, rods and cones could not be distinguished but both positively and negatively stained cells were observed by the use of each antibody. In geckos, however, all photoreceptor cells were immunonegative to Io-mAb. In all species studied in amphibians, Rh-As labeled rods but not cones. Neither rods nor cones reacted with Io-mAb. In fishes, almost all species studied had well developed cones, and some of these cones were labeled by Rh-As. However, Io-mAb labeled the outer segments of some cones only in loaches. Rh-As labeled photoreceptor cells in all species of fishes studied. Thus, Rh-As recognized the outer segments of rods in all species studied from fishes to mammals, whereas the epitope recognized by Io-mAb is conserved in some species of fishes, most species of reptiles and all species of birds studied.     

Determination of hexabromocyclododecane diastereoisomers and tetrabromobisphenol A in water and sediment by liquid chromatography/mass spectrometry.

A method to determine alpha-, beta- and gamma-hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) in water and sediments was presented using solid phase extraction (SPE) and/or solvent extraction. Recoveries from sediments were approximately 100% for all the chemicals, while recoveries of alpha-, beta- and gamma-HBCDs from water were dependent on the extraction method. In the case of dichloromethane (CH2Cl2) extraction, recoveries of alpha-, beta- and gamma-HBCD from landfill leachates were 77%, 88% and 92%, respectively. Technical difficulties in HBCD measurement are discussed in terms of the physico-chemical properties of HBCD isomers. The method was applied to landfill samples and marine sediment.     

Pressure and temperature effects on the excess deuteron and proton conductance

The limiting molar conductances ° of deuterium chloride DCl in D₂O were determined as a function of pressure and temperature in order to examine the proton-jump mechanism in detail. The excess deuteron conductances °_E(D ⁺), as estimated by the equation [°_E(D ⁺) = °(DCl/D ₂ O) – °(KCl/D ₂ O)], increases with an increase in the pressure and temperature as well as the excess proton conductance [°_E(H ⁺) = °(HCl/H ₂ O) – °(KCl/H ₂ O)]. The isotope effect on the excess conductances, however, depends on the pressure and temperature contrary to the model proposed by Conway et al.: °_E(H ⁺)/°_E(D ⁺) decreases with increasing pressure and temperature. The magnitude of the decrease with pressure becomes more prominent at lower temperature. These results are discussed in terms of the pre-rotation of adjacent water molecules, the bending of hydrogen bonds with pressure, and the difference in strength of hydrogen bonds between D₂O and H₂O.     

Efficient synthesis of CCR5 antagonist, 2,3-dihydro-1-benzothiepine derivatives by improved intramolecular Claisen type reaction using dialkylcarbonate

The efficient synthesis of 2,3-dihydro-1-benzothiepine derivatives 4 has been developed. The intramolecular Claisen type reaction of the new products, 4-(o-formylphenylthio)butyrate 9, with alcoholate in dialkylcarbonate as a solvent afforded 4 in good yields. According to this new procedure, we have accomplished the practical preparation of CCR5 antagonist 1 as a candidate for oral HIV-1 therapy.     

Electrical conducting and magnetic properties of (ethylenedithiotetrathiafulvalenothioquinone-1,3-diselenolemethide)2.FeBr4 (GaBr4) crystals with two different interlayer arrangements of donor molecules

Two donor molecules newly synthesized, dimethylthio- and ethylenedithio-tetrathiafulvalenothioquinone-1,3-diselenolemethides (1 and 2), were used to prepare their charge-transfer (CT) salts with a magnetic FeBr(4)(-) counteranion. For 1, a low electrical conducting 1:1 salt (1.FeBr(4)) was obtained, in which molecules of 1 are tightly dimerized in a one-dimensional (1D) stacking column. On the other hand, 2 gave a 2:1 salt (2(2).FeBr(4)) as two different kinds of plate crystals (I and II). Both I and II possess similar stacking structures of molecules of 2 in each 1D column with a half-cut pipelike structure along the c axis. However, for I, the stacking columns are aligned in the same direction along the a and b axes, while for II they are in the same direction along the a axis, but in the reverse direction along the b axis, resulting in the difference in the relative arrangement of molecules of 2 and FeBr(4)(-) ions between the two crystals. The room-temperature electrical conductivities of the single crystals of I and II were 13.6 and 12.7 S cm(-)(1), respectively. The electrical conducting behavior in I was metallic above 170 K but changed to be semiconducting with a very small activation energy of 7.0 meV in the temperature range 4-170 K. In contrast, II showed the semiconducting behavior in the whole temperature range 77-285 K. The corresponding nonmagnetic GaBr(4)(-) salts with almost the same crystal structure as I and II showed definitively different electrical conducting properties in the metal to semiconductor transition temperature in I as well as in the magnitude of activation energy in the semiconducting region of I and II. The interaction between the d spins of FeBr(4)(-) ions was weak and antiferromagnetic in both I and II, but the magnitude of the spin interaction was unexpectedly larger compared with that in the FeBr(4)(-) salt of the corresponding sulfur derivative of 2 with closer contact between the neighboring FeBr(4)(-) ions. These electrical conducting and magnetic results suggest a significant interaction between the conducting pi electrons and the d spins of FeBr(4)(-) ions located near the columns or layers.