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.     

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.     

Controlling Pyrene Association in DNA Duplexes by B- to Z-DNA Transitions

B- to Z-DNA transitions play a crucial role in biological systems and have attracted the interest of researchers for their applications in DNA nanotechnology. DNA and DNA analogues have also been used as templates to construct helical chromophore associations with π interactions. In this work, the B- to Z-DNA transition-induced switching of pyrene in an association manner was evaluated using DNA duplexes with non-nucleosidic pyrene residues in the middle of d(CG) repeat sequences. One of the pyrene-labeled DNAs was shown to exhibit inverted exciton coupled circular dichroism signals upon pyrene association through a B- to Z-DNA transition. This observation indicates that pyrene association switches the DNA conformation from right- to left-handed. Interestingly, the fluorescence of the pyrene-labeled DNA duplex also dynamically changed upon switching of the pyrene in an association-based manner. Taken together, these studies demonstrate that pyrene-labeled DNA shows promise as a chiroptical molecular switch.     

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.     

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.     

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...     

Layered mixed-anion compounds: Epitaxial growth,active function exploration,and device application

Optoelectronic properties and device applications of layered mixed-anion compounds such as oxychalcogenide LaCuOCh (Ch = chalcogen) and oxypnictide LaT_MOPn (T_M = 3d transition metal, Pn = pnicogen) are reviewed. Several distinctive functions have been found in these materials based on our original material exploration concept. Fabrication of high-quality epitaxial films of LaCuOCh leads to clarifying the excellent electrical and optical properties such as high hole mobility of 8 cm²/(V s) and heavy hole doping at >10²¹ cm^?3 in LaCuOSe, and sharp and tunable-wavelength photoluminescence in the solid–solution systems in LaCuOCh. In addition, a room temperature operation of a light-emitting diode is demonstrated using LaCuOSe as a light-emitting layer. These results suggest that the layered oxychalcogenides have potential for light-emitting layers as well as transparent hole-injection layers in organic/inorganic light-emitting diodes. Furthermore, by extending the material system from the copper-based oxychalcogenides to isostructural compounds, transition metal-based oxypnictides LaT_MOP (T_M = Fe, Ni), we have found novel superconductors, LaFeOP and LaNiOP.     

Odor discrimination by G protein-coupled olfactory receptors

The vertebrate olfactory system possesses a remarkable capacity to recognize and discriminate a variety of odorants by sending the coding information from peripheral olfactory sensory neurons in the olfactory epithelium to the olfactory bulb of the brain. The recognition of odorants appear to be mediated by a G protein-coupled receptor superfamily that consists of approximately 1% of total genes in vertebrates. Since the first discovery of the olfactory receptor gene superfamily in the rat, similar chemosensory receptors have been found in various species across different phyla. The functions of these receptors, however, had been uncharacterized until the recently successful functional expression and ligand screening of some olfactory receptors in various cell expression systems. The functional cloning of odorant receptors from single olfactory neurons allowed for the identification of multiple receptors that recognized a particular odorant of interest. Reconstitution of the odorant responses demonstrated that odorant receptors recognized various structurally-related odorant molecules with a specific molecular receptive range, and that odor discrimination is established based on a combinatorial receptor code model in which the identities of different odorants are encoded by a combination of odorant receptors. The receptor code for an odorant changes at different odorant concentrations, consistent with our experience that perceived quality of an odorant changes at different concentrations. The molecular bases of odor discrimination at the level of olfactory receptors appear to correlate well with the receptive field in the olfactory bulb where the input signal is further processed to create the specific odor maps.     

Buffer-trapping effects on current slump in AlGaN/GaN HEMTs

Two-dimensional transient analyses of GaN MESFETs and AlGaN/GaN HEMTs are performed in which a deep donor and a deep acceptor are considered in a semi-insulating buffer layer. Calculated transient characteristics are compared between the two FETs, and it is shown that the deep levels affect the results essentially in a similar way. Quasi-pulsed I–V curves are derived from the transient characteristics, and are compared with steady-state I–V curves. It is shown that so-called current slump is more pronounced when the deep-acceptor density in the buffer layer is higher and when an off-state drain voltage is higher, because trapping effects become more significant. It is suggested that to minimize current slump in GaN-based FETs, an acceptor density in a semi-insulating GaN layer should be made low.     

Prioritizing towards a green export portfolio for India: An environmental input–output approach

Proponents of free trade have often hailed international trade as an engine of economic growth. However, the foreign trade sector, like many other sectors in developing countries, frequently involves these countries walking a tightrope between their developmental objectives and environmental goals. In this regard, prioritizing for developing a ‘green’ yet internationally competitive export portfolio provides a quintessential win–win solution to the problem. This study factors in both environmental benignity (indicated by total CO₂ emission intensity) as well as trade competitiveness (indicated by revealed comparative advantage index) in identifying the ‘ideal’ Indian export portfolio. The analysis calculates the level of direct and indirect emissions from the foreign trade sector (exports and imports) using the environmental input–output (EIO) matrix for 2003/04 for India that has been jointly developed by researchers from Keio University, Japan, and The Energy and Resources Institute (TERI), New Delhi. The derived basket is compared to the current portfolio to estimate the potential saving from compositional changes and to suggest directions for policymaking to emphasize or de-emphasize the export of certain categories of exports.