Molybdenum‐Catalyzed Stereospecific Deoxygenation of Epoxides to Alkenes

Mild and simple catalytic systems consisting of molybdenum(VI) dichloride dioxide [MoO₂Cl₂] as a catalyst and a phosphine as reductant have been developed for the stereospecific deoxygenation of epoxides to alkenes. The reactions using 1,2‐bis(diphenylphosphino)ethane (dppe) and triphenylphosphine (PPh₃) proceed with retention and inversion of stereochemistry, respectively. The mild reaction tolerates the presence of various functional groups and affords stereodefined substituted olefins in good yields.

     

In-situ measurement of microwave absorption properties at 2.45 GHz for the polycondensation of lactic acid

For the construction of a microwave-assisted organic synthesis plant, it is necessary to know the dielectric properties of the reaction system. Measurements of the dielectric properties of lactic acid aqueous solution, anhydrated lactic acid, oligo(lactic acid) and water, which are constituent materials in the polycondensation of lactic acid, confirm that dielectric properties decrease as reaction progresses. Calculated microwave penetration depths, obtained from the dielectric properties, show that microwaves penetrate deeply into the reaction system. This work should be useful for the development of microwave-assisted organic syntheses in the chemical industry.     

Polybrominated diphenyl ether flame retardants in foodstuffs and human milk

Polybrominated diphenyl ethers (PBDEs) have been used worldwide as additive flame retardants in polymeric materials. Commercial products consist predominantly of deca-, octa-, and pentabromodiphenyl ether mixtures. PBDEs are resistant to degradation in the natural environment and Penta-BDE in particular accumulates in the fatty tissues of fish, birds and mammals (including humans). Several toxic effects on the thyroid system or on neurodevelopment have been reported in experimental animals exposed to PBDEs. It is likely that human exposure is predominantly through the ingestion of contaminated food and/or mother's milk. The potential health effects of dietary exposure to PBDEs have now become a great concern because of the increasing PBDE levels in the biosphere. In this review, published information on the toxicology of PBDEs, levels in foodstuffs and human milk, and analytical methods has been compiled.     

Highly reliable oxide‐semiconductor TFT for AMOLED displays

Abstract— The stability and reliability of oxide‐semiconductor TFTs were investigated. The contact material to the oxide semiconductor affected the thermal stability of the TFT, and a molybdenum‐contact source/drain showed good stability. And the passivating film and TFT structure affected the stability against bias stress and humidity stress, and dc‐sputtered Al²O³ passivation and fully covered channel structure with an etching stopper or source/drain showed good reliability. Moreover, high photo‐stability was confirmed by the bias‐enhanced photo‐irradiation stress test. An 11.7‐in.‐diagonal qHD AMOLED display was demonstrated to provide an applicable solution for a large‐sized OLED and an ultra‐high‐definition LCD‐TV mass production.     

Transport properties of undoped Cd0.9Zn0.1Te grown by high pressure bridgman technique

The electron drift mobility of undoped Cd_0.9Zn_0.1Te grown by high-pressure Bridgman method is measured by a time-of-flight technique. The sample shows a room temperature mobility and mobility lifetime product of 950 cm²/Vs and 1.6 × 10⁻⁴cm²/V, respectively. The mobility increases monotonically with decreasing temperature to 3000 cm²/Vs at 100 K. The dominant scattering mechanism for the electron transport is discussed by comparing with the theoretical mobility obtained by iterative solution of the Boltzmann equation.     

Heterogeneity in Formation of Lignin. XIII. Formation of p-Hydroxyphenyl Lignin in Various Hardwoods Visualized by Microautoradiography

The heterogeneous nature of hardwood lignin was shown by visualizing the deposition process of p-hydroxyphenyl (H) lignin in the differentiating xylem of magnolia, beech, lilac and poplar. When p-glucocoumaryl alcohol-[arom. ring-2-³H], an efficient precursor of H units in lignin, was administered to the differentiating xylem of these trees, radioactivity was incorporated in the compound middle lamella region of vessel and fiber cell walls. The deposition of H units occurs only in the early stage of cell wall formation when the outer layer of the secondary wall is formed. H lignin deposits mainly within pectic substances and hemicellulose gel to form a highly condensed structural moiety.     

Dendrite growth processes of silicon and germanium from highly undercooled melts

The crystal growth behavior of a semiconductor from a very highly undercooled melt is expected to be different from that of a metal. In the present experiment, highly pure undoped Si and Ge were undercooled by an electromagnetic levitation method, and their crystal growth velocities (V) were measured as a function of undercooling (ΔT). The value of V increased with ΔT, and V=26 m/s was observed at ΔT=260 K for Si. This result corresponds well with the predicted value based on the dendrite growth theory. The growth behaviors of Si and Ge were found to be thermally controlled in the measured range of undercooling. The microstructures of samples solidified from undercooled liquid were investigated, and the amount of dendrites immediately after recalescence increased with undercooling. The dendrite growth was also observed by a high-speed camera.     

The Chemistry of PCR Primers: Concept and Application

DNA is a typical organic compound with marked differences from other chemicals and biopolymers because DNA can be amplified by the enzyme polymerase. DNA can be, in principle, amplified from a single copy by the polymerase chain reaction (PCR). In this review, we focus our attention on the chemistry of PCR primers. Because PCR is basic technology in biology research fields, we sometimes use chemically labeled primers without any awareness of the chemistry they leave behind. We would like to emphasize that chemically labeled primers contain a lot of potential for different chemistry ideas and much study is still necessary to advance PCR for single-nucleotide polymorphism (SNP) typing, genetic diagnosis, and other fields. Two categories of primers, affinity-capture primers and signaling primers, are discussed from the viewpoints of their chemical concepts and applications. Affinity-capture primers are used for purification, isolation, and manipulation of PCR products by high specificity and affinity to the cognate molecules by molecule molecule interactions, whereas signaling primers report the hybridization and/or progress of PCR amplification by a signal change, in most cases by a fluorescence change. The content of this review may be useful for a better understanding of the chemistry of PCR primers and, more importantly, for the invention of novel PCR chemistry.     

Analysis of proton exchange membrane fuel cell catalyst layers for reduction of platinum loading at Nissan

The biggest issue that must be addressed in promoting widespread use of fuel cell vehicles (FCVs) is to reduce the cost of the fuel cell system. Especially, it is of vital importance to reduce platinum (Pt) loading of catalyst layers (CLs) in the membrane electrode assembly (MEA) of a proton exchange membrane fuel cell (PEMFC). In order to lower the Pt loading of the MEA, mass transport of reactants related to the performance in high current density should be enhanced significantly as well as kinetics of the catalyst, which can result in the better Pt utilization and effectiveness. In this study, we summarized our analytical approach and methods for reduction of Pt loading in CLs. Microstructure, mass transport properties of the reactants, and their relation in CLs were elucidated by applying experimental analyses and computational methods. A simple CL model for I–V performance prediction was then established, where experimentally elucidated parameters of the microstructure and the properties in CLs were taken into account. Finally, we revealed the impact of lowering the Pt loading on the transport properties, polarization, and the I–V performance.     

Influence of variations in creep curve on creep behavior of a high-temperature structure

It is one of the key issues for a high-temperature structural design guideline to evaluate the influence of variations in creep curve on the creep behavior of a high-temperature structure. In the present paper, a comparative evaluation was made to clarify such influence.The evaluation results showed that, in almost all cases of a creep behavior pattern in which creep strain accumulated during a stress cycle caused significant relaxation of the corresponding deformation-controlled stress in the following cycles, the variations in creep behavior with the creep curve were qualitatively similar to those in fundamental creep properties. On the other hand, in many cases of another creep behavior pattern in which creep strain accumulated during a cycle doesn't cause the significant stress-relaxation in the following cycles, the variations in creep behavior for earlier cycles are different from those in fundamental creep properties. Even in these cases, however, those get qualitatively similar after several cycles when their stress-time histories are stabilized.Additional consideration was given to the influence of the relationship between creep rupture life and minimum creep rate, i.e., the Monkman-Grant's relationship, on the creep damage evaluation.The consideration suggested that the Monkman-Grant's relationship be taken into account in evaluating the creep damage behavior, especially the creep damage variations. However, it was clarified that the application of the creep damage evaluation rule of ASME B.&P.V. Code Case N-47 to the “standard case”which was predicted from the average creep property would predict the creep damage on the safe side.