Living cationic polymerization of p-methoxystyrene by hydrogen iodide/zinc iodide at room temperature

Summary Cationic polymerization of p-methoxystyrene initiated by HI/ZnI₂ in toluene afforded living polymers not only at low temperature (–15°C) but at room temperature (+25°C) as well. The number-average molecular weight of the polymers was directly proportional to monomer conversion and in excellent agreement with the calculated value assuming that one polymer chain forms per unit hydrogen iodide. On addition of a fresh feed of monomer at the end of the first-stage polymerization, the added feed was smoothly polymerized at nearly the same rate as in the first stage; the polymer molecular weight further increased in direct proportion to monomer conversion and was close to the calculated value for living polymer. Throughout these reactions, the molecular weight distribution of the polymers stayed very narrow (¯M_w/¯M_n<1.1). This is the first example of living cationic polymerizations of styrene derivatives that proceed even at room temperature.     

Anodic polarization of aluminium in organic electrolytes

The polarization characteristics of aluminium anodes have been studied in various organic electrolytes containing aluminium chloride. The small amount of oxide present on the metal was dissolved by an anodic pre-treatment. The charge transfer number of the overall reaction was three. The current density supported by the electrolytes decreased in the order nitromethane>acetonitrile >propylene carbonate, formamide>tetrahydrofuran. The rest potential increased in the order formamide     

Wide-gap layered oxychalcogenide semiconductors: Materials, electronic structures and optoelectronic properties

Applying the concept of materials design for transparent conductive oxides to layered oxychalcogenides, several p-type and n-type layered oxychalcogenides were proposed as wide-gap semiconductors and their basic optical and electrical properties were examined. The layered oxychalcogenides are composed of ionic oxide layers and covalent chalcogenide layers, which bring wide-gap and conductive properties to these materials, respectively. The electronic structures of the materials were examined by normal/inverse photoemission spectroscopy and energy band calculations. The results of the examinations suggested that these materials possess unique features more than simple wide-gap semiconductors. Namely, the layered oxychalcogenides are considered to be extremely thin quantum wells composed of the oxide and chalcogenide layers or 2D chalcogenide crystals/molecules embedded in an oxide matrix. Observation of step-like absorption edges, large band gap energy and large exciton binding energy demonstrated these features originating from 2D density of states and quantum size effects in these layered materials.     

Homogeneous Strain Introduction Using Reciprocation Technique in High-Pressure Sliding

Metallurgical and Materials Transactions A - This study examines strain distribution occurring in the high-pressure sliding (HPS) processing for rods of pure Al and an AZ61 alloy. The strain...     

DNA‐Templated Synthesis of Perylenediimide Stacks Utilizing Abasic Sites as Binding Pockets and Reactive Sites

DNA is considered to be a promising biomolecule as a template and scaffold for arranging and organizing functional molecules on the nanoscale. The construction and evaluation of DNAs containing multiple functional molecules that are useful for optoelectronic devices and sensors has been studied. In this paper we report the efficient incorporation of perylenediimide (PDI) units into DNA by using abasic sites both as binding sites and as reactive sites and the construction of PDI stacks within the DNA structure, accomplished through the preorganization of the PDI units in the hydrophobic pocket within the DNA. Our approach could become a valuable method for construction of DNA/chromophore hybrid structures potentially useful for the design of DNA‐based devices and biosensors.     

Kinetic Study of the Prooxidant Effect of α-Tocopherol. Hydrogen Abstraction from Lipids by α-Tocopheroxyl Radical

A kinetic study of the prooxidant effect of α-tocopherol was performed. The rates of allylic hydrogen abstraction from various unsaturated fatty acid esters (ethyl stearate 1, ethyl oleate 2, ethyl linoleate 3, ethyl linolenate 4, and ethyl arachidonate 5) by α-tocopheroxyl radical in toluene were determined, using a double-mixing stopped-flow spectrophotometer. The second-order rate constants (k _p) obtained are <1 × 10⁻² M⁻¹ s⁻¹ for 1, 1.90 × 10⁻² M⁻¹ s⁻¹ for 2, 8.33 × 10⁻² M⁻¹ s⁻¹ for 3, 1.92 × 10⁻¹ M⁻¹ s⁻¹ for 4, and 2.43 × 10⁻¹ M⁻¹ s⁻¹ for 5 at 25.0 °C. Fatty acid esters 3, 4, and 5 contain two, four, and six –CH₂– hydrogen atoms activated by two π-electron systems (–C=C–CH₂–C=C–). On the other hand, fatty acid ester 2 has four –CH₂– hydrogen atoms activated by a single π-electron system (–CH₂–C=C–CH₂–). Thus, the rate constants, k _abstr/H, given on an available hydrogen basis are k _p/4 = 4.75 × 10⁻³ M⁻¹ s⁻¹ for 2, k _p/2 = 4.16 × 10⁻² M⁻¹ s⁻¹ for 3, k _p/4 = 4.79 × 10⁻² M⁻¹ s⁻¹ for 4, and k _p/6 = 4.05 × 10⁻² M⁻¹ s⁻¹ for 5. The k _abstr/H values obtained for 3, 4, and 5 are similar to each other, and are by about one order of magnitude higher than that for 2. From these results, it is suggested that the prooxidant effect of α-tocopherol in edible oils, fats, and low-density lipoproteins may be induced by the above hydrogen abstraction reaction.     

Effect of blending on liquefaction of coals

After solvent extraction of Taiheiyo, Miike and Balmer coals using wash oil under nitrogen atmosphere at 370 °C for 30 min, the extraction yield is always within the additivity law. Further studies used Yallourn, Soyakoishi, Taiheiyo, Horonai, Miike, Shin Yubari, Balmer coals and their blends which were hydrogenated in tetralin, wash oil or creosote oil, with or without catalyst, at 400–450 °C under 10 or 3 MPa of initial hydrogen pressure. When hydrogen is available, the additivity law exists for blended coals, but when the hydrogen supply is deficient, the experimental conversion of blended coals is always lower than calculated conversions. This may be due to the faster consumption of the hydrogen by more reactive coals and thus the less reactive coals were unable to react with hydrogen.     

Correlation of reactivity to hydrogenation and chemical structure of lignites

Three North Dakota lignites with almost the same percentage carbon have been used to determine the relation between chemical structure and reactivity to hydrogenation. Average structural indices of the lignites were estimated using the pyridine-soluble products after alcohol-alkali treatment, the structural indices obtained at various reaction times being extrapolated to zero reaction time. Hydrogenation was influenced by the average structure, with the lignite having higher aromaticity, higher molecular weight of the pyridine extract from the alcohol-alkali reaction product, larger aromatic ring size and lower content of aliphatic structure, showing a smaller degree of conversion.     

Effects of water chemistry and potential distribution on electrochemical corrosion potential measurements in 553 K pure water

The effects of water chemistry distribution on the potential of a reference electrode and of the potential distribution on the measured potential should be known qualitatively to obtain accurate electrochemical corrosion potential (ECP) data in BWRs. First, the effects of oxygen on a platinum reference electrode were studied in 553 K pure water containing dissolved hydrogen (DH) concentration of 26–105 μg kg^?1 (ppb). The platinum electrode worked in the same way as the theoretical hydrogen electrode under the condition that the molar ratio of DH to dissolved oxygen (DO) was more than 10 and that DO was less than 100 ppb. Second, the effects of potential distribution on the measured potential were studied by using the ECP measurement part without platinum deposition on the surfaces connected to another ECP measurement part with platinum deposition on the surfaces in 553 K pure water containing 100–130 ppb of DH or 100–130 ppb of DH plus 400 ppb of hydrogen peroxide. Measured potentials for each ECP measurement part were in good agreement with literature data for each surface condition. The lead wire connecting point did not affect the measured potential. Potential should be measured at the nearest point from the reference electrode in which case it will be not affected by either the potential distribution or the connection point of the lead wire in pure water.     

Modification of Shockley surface state by long-chain n-alkane: Photoemission study on tetratetracontane/Au(111) interface

Modification of quasi two-dimensional surface electron system on Au(111) with adsorption of long-chain n-alkane molecule n-CH₃(CH₂)₄₂CH₃ (tetratetracontane: TTC) was investigated by angle-resolved photoemission spectroscopy. Significant modification of the energy band structure of the Shockley surface state was induced by the adsorption of TTC monolayer with “flat-on” structure. The energy shift of the Shockley surface state toward the Fermi level reaches about 160 meV at Γ? point (k = 0 Å^− 1). The possible origin of the stabilization of the surface electron system with TTC monolayer is discussed.