Electrochemical Characteristics of a Triphenylamine Derivative by Microelectrode Voltammetry

With the objective of understanding the kinetic redox properties of triphenylamine derivatives in association with chemical reactions, for their future application in functional organic semiconductor devices, the electrochemical characteristics of 4‐(2,2‐diphenylethenyl)‐N,N‐bis(4‐methylphenyl)‐benzenamine (TPA) were evaluated. Based on cyclic voltammograms of TPA on Pt disk electrodes with diameters of 300 μm and 10 μm at slow and fast scan rates in an acetonitrile solution, the TPA^.+ is stable, while the TPA²⁺ is unstable. Importantly, the unstable TPA²⁺ appears to break down by a subsequent chemical reaction. A Cottrell plot analysis from chronoamperometry of a solution containing TPA reveals that both the first and second oxidations are one‐electron reactions. Concerning the stabilization mechanism of the first oxidation state of TPA, the results of molecular orbital calculations indicate that the electrons of the HOMO level are distributed in the triphenylamine group, which induces a resonance‐stabilized TPA^.+. Based on these results, TPA/TPA^.+ is suggested to have a sufficient stability for further application in organic semiconductor devices.     

Dynamics of particles floating on liquid flowing in a semicircular open channel

The dynamic characteristics of surface-floating particles in liquids flowing in a two-dimensional, semicircular open channel is studied experimentally. For high visibility in the experiments, relatively large particles are employed whose particle-liquid density ratio is either equal to or less than unity. Particles of different size and geometry are tested in a water-glycerin mixture. A video camera traces the pathline of each particle from which the velocity and direction of particle motion are evaluated. Liquid velocity distribution is determined by hot-film anemometry. A modified dynamics (Basset-Boussinesq-Oseen) equation is derived and numerically solved by means of a finite-difference technique to determine fluid velocity. A new dimensionless parameter is disclosed which is pertinent to both particle geometry and fluid flow conditions. It correlates particle trajectory and velocity, trajectory dispersion and fluid-particle velocity ratio.Visiting Scholar on leave from Department of Mechanical Engineering, Fukuyama University, Fukujama, Japan     

Interaction of von Karman vortices and intersecting main streams in staggered tube bundles

 Flow visualization, heat transfer and pressure drop characteristics in flow through staggered tube bundles have been regarded as classical, with results well-documented. However, the mechanism of producing such results has been left untouched. Applications of staggered tube bundles are abundant in industry, for example as heat exchange devices like the shell-and-tube type and fuel bundles in nuclear reactor cores. An experimental study is recorded in the present paper which investigates the interaction of von Karman vortices and intersecting main streams in staggered tube bundles. Flow visualization by means of the particle tracing method, laser Doppler velocimetry (LDV) and pressure drop measurements using a piezometer are conducted. A modified Reynolds number appropriate to flow through a staggered tube arrangement is defined together with a pressure drop coefficient. Auto-correlation and power spectrum analyses of signals obtained from LDV measurements yield an optimum spectrum frequency which is correlated against the Reynolds number. It is concluded that flow characteristics in staggered tube bundles are determined by the interaction between the von Karman vortex street and X-shaped interacting main streams. Received: 4 August 1997 / Accepted: 3 October 1998     

Molecular chaperone-like properties of sodium caseinate to suppress the pressure-induced aggregation of β-lactoglobulin

ABSTRACT

The objective of this study was to determine whether sodium caseinate can inhibit the aggregation of whey protein induced by pressure treatment. Solutions of β-lactoglobulin (β-Lg, 0.2%, w/v) and mixtures containing 0.2% (w/v) β-Lg and 0–0.5% (w/v) sodium caseinate (NaCas) were pressurized at 400–800?MPa. NaCas suppressed the aggregation of β-Lg induced by pressure treatment, and this function was dependent on the concentration of NaCas. Furthermore, NaCas altered the aggregation process of β-Lg by suppressing the transition of the aggregate from the soluble phase to the insoluble phase and, as a result, the fraction of insoluble aggregates was decreased. During this process, NaCas formed stable complexes with the denatured β-Lg, and the formation of complexes prevented further aggregation of β-Lg. These results indicate that NaCas exhibits a chaperone-like activity under high pressure.     

A Novel Reactivity of Phosphanylalumane (>P−Al<): Reversible Addition of a Saturated Interelement Bond to Olefins

The reversible addition of olefins to a phosphanylalumane, P−Al single-bond species, was investigated. The P−Al bond added to ethylene and relatively small terminal alkenes (propylene and hex-1-ene) at room temperature to give the corresponding alkene adducts. Heating the terminal alkene adducts released the corresponding alkenes and regenerated the P−Al bond, but no release of ethylene was observed even under vacuum conditions. The reactivity of ethylene adduct as a new saturated C₂ vicinal P/Al-based FLP was also investigated. The ethylene adduct was found to undergo complexation with nitriles to give the corresponding nitrile adducts to the Al center, which retained the ethylene tether as in the case of the corresponding P/B-based FLP. However, the reactivity of ethylene toward CO₂ and benzaldehyde differed from that of the P/B system giving the corresponding adducts.     

REDUCTION OF BIS(BROMO(MESITYL)-{2,4,6-TRIS[BIS(TRIMETHYLSILYL)METHYL]- PHENYL}SILYL)BUTADIYNE WITH POTASSIUM GRAPHITE: UNEXPECTED FORMATION OF 2-ALLENYL-1-BENZOSILOLE

The reductive debromination of an very crowded bis(bromodiaryl- silyl)butadiyne 2 was performed with potassium graphite to give the corresponding 2-allenyl-1-benzosilole 3 was isolated as a main product.     

Numerical study of QCD phase diagram at high temperature and density by a histogram method

We study the QCD phase structure at high temperature and density adopting a histogram method. Because the quark determinant is complex at finite density, the Monte-Carlo method cannot be applied directly. We use a reweighting method and try to solve the problems which arise in the reweighting method, i.e. the sign problem and the overlap problem. We discuss the chemical potential dependence of the probability distribution function in the heavy quark mass region and examine the applicability of the approach in the light quark region.