Radiation-Induced Emulsion Copolymerization of Tetrafluorethylene with Propylene. The Behavior of the HF Formed

The radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene was carried out at room temperature in the presence of gaseous monomers. The formation of hydrofluoric acid in the course of polymerization was observed. The amount of HF formed increased linearly with the irradiation time at various dose rates in the early stage. The tendency was similar to that of time-polymer yield curves. The rate of HF formation was proportional to the first order of the dose rate. The amount of HF formed increased in the presence of oxygen and decreased remarkably above 1 wt% emulsifier, while the polymer yield decreased in the presence of oxygen and increased with the emulsifier concentration. A remarkable decrease in the amount of HF formed in higher emulsifier concentration is mainly attributable to chemical absorption or electrostatic capture of H⁺ ion on polymer particles produced. Hydrofluoric acid is mainly formed by reaction between primary products (e _aq ^? and H) from the radiolysis of water and organic fluoride (tetrafluoroethylene and emulsifier), and is little formed by reaction between primary products and copolymer produced. The G value of HF formation was in the order of emulsifier-water system > suspension polymerization > emulsion polymerization, while the polymer yield was in the order of emulsion polymerization > suspension polymerization.     

Helix-sense controlled polymerization of a single phenyl isocyanide enantiomer leading to diastereomeric helical polyisocyanides with opposite helix-sense and cholesteric liquid crystals with opposite twist-sense

We report the unprecedented helix-sense controlled polymerization of enantiomerically pure phenyl isocyanides bearing an l- or d-alanine pendant with a long alkyl chain. The polymerization with an achiral nickel catalyst diastereoselectively proceeds, resulting in either a right- or left-handed helical polymer, whose helix-sense can be controlled by the polymerization solvent and temperature. Both the diastereomeric right- and left-handed helical polymers further self-assemble into lyotropic cholesteric liquid crystals with opposite twist-senses. Consequently, the macromolecular helicity and mesoscopic, supramolecular cholesteric twist can be controlled by the molecular chirality of the pendant of a single enantiomeric phenyl isocyanide through the polymerization under either kinetic or thermodynamic control assisted by hydrogen bonds. High-resolution atomic force microscopy revealed their helical conformations and enabled the determination of the helical sense.     

Synthesis and photochemical properties of a photochromic iron(II) complex of hexaarylbiimidazole

The photochromic ligand bis(terpyridyl)hexaarylbiimidazole (bistpy-HABI) and the Fe(II) complex of bistpy-HABI with formula [{Fe(tpy)}2.bistpy-HABI](PF6)4.4H2O were synthesized and characterized. Bistpy-HABI is readily cleaved into a pair of terpyridyltriphenylimidazolyl radicals (tpy-TPI*) on irradiation with UV light. This photochemical reaction is completely reversible, and the light-induced radicals can thermally recombine to form bistpy-HABI in the dark. [{Fe(tpy)}2.bistpy-HABI]4+ is the first example of a transition-metal complex of an HABI derivative and was found to show photochromic reaction in solution. The spin state of the light-induced radical pair in a frozen matrix was investigated by ESR spectroscopy. The triplet state of the light-induced radical pair from [{Fe(tpy)}2.bistpy-HABI]4+, as well as that from bistpy-HABI, was confirmed to be a ground state or nearly degenerated with a singlet state. Kinetic studies on the radical recombination reaction in solution elucidated the decrease in the activation energy by forming the Fe(II) complex. This is the first observation of a decrease in the activation energy of the radical recombination reaction by the formation of a metal-coordinated radical complex. The syntheses, photochemical properties, and spin states of bistpy-HABI and [{Fe(tpy)}2.bistpy-HABI](PF6)4 are discussed.     

Reverse current reduction of Ge photodiodes on Si without post-growth annealing

A new approach to reduce the reverse current of Ge pin photodiodes on Si is presented, in which an i-Si layer is inserted between Ge and top Si layers to reduce the electric field in the Ge layer. Without post- growth annealing, the reverse current density is reduced to -10 mA/cm^2 at -1 V, i.e., over one order of magnitude lower than that of the reference photodiode without i-Si layer. However, the responsivity of the photodiodes is not severely compromised. This lowered-reverse-current is explained by band-pinning at the i-Si/i-Ge interface. Barrier lowering mechanism induced by E-field is also discussed. The presented ＂non-thermal＂ approach to reduce reverse current should accelerate electronics-photonics convergence by using Oe on the Si complementary metal oxide semiconductor （CMOS） platform.     

Development of ion transportation, extraction and neutralization systems for atomic beam resonance method

A device that produces a low-energy and largely spin polarized RI beam based on the atomic beam resonance method (RIABR) has been developed. We have performed measurements of stopping and drifting an incoming RI ion beam in a gas chamber, extraction of the ions into a vacuum region, and neutralization of the extracted low-energy ion beam. The drift efficiency of RI ions in a gas and the extraction efficiency at a Laval-type glass nozzle were found to be 0.72±0.04 and 0.033, respectively. The result of the experiment for the neutralization is also discussed.     

Control of peroxyoxalate chemiluminescence by nitrogen-containing ligand quenching: turning off and on by ligand-metal ion host-guest interactions

The control of peroxyoxalate chemiluminescence (PO-CL) by the coordination of nitrogen-containing ligands and metal cations was investigated. Turning the CL off and on was done by PO-CL using 15-monoazacrown-5-tethered anthracene and alkali metal ions. CL quenching and regeneration was also observed in the separated molecular system of 15-monoazacrown-5 and the fluorophores. CL quenching by a number of ligands bearing dipicolylamino groups was evaluated by these PO-CL reactions and found to be closely related to their oxidation potentials, which is dependent on the Weller rate law for electron exchange and this provides strong support for the existence of the CIEEL PO-CL process. When Zn²⁺ or Cu²⁺ are added to the PO-CL system quenched by the ligand, N-[2-(2,2′-dipicolylamino)ethyl]aniline, CL was turned on because the electron donating ability of the ligands was modulated. This was controlled by the coordination of the studied metal ions and, therefore, this system results in CL because of host-guest interactions.     

Portable formaldehyde monitoring device using porous glass sensor and its applications in indoor air quality studies

We have developed a portable device for formaldehyde monitoring with both high sensitivity and high temporal resolution, and carried out indoor air formaldehyde concentration analysis. The absorbance difference of the sensor element was measured in the monitoring device at regular intervals of, for example, one hour or 30 min, and the result was converted into the formaldehyde concentration. This was possible because we found that the lutidine derivative that was formed as a yellow product of the reaction between 1-phenyl-1,3-butandione and formaldehyde was stable in porous glass for at least six months. We estimated the reaction rate and to be 0.049 min⁻¹ and the reaction occurred quickly enough for us to monitor hourly changes in the formaldehyde concentration. The detection limit was 5 μg m⁻³ h. We achieved hourly formaldehyde monitoring using the developed device under several indoor conditions, and estimated the air exchange rate and formaldehyde adsorption rate, which we adopted as a new term in the mass balance equation for formaldehyde, in one office.     

Conductance of potassium lodide in mixed solvents

The conductance of potassium iodide has been measured in the solvents ethylene carbonate, water, methyl ethyl ketone, and pairwise mixtures of these solvents at 40°C; and ethylene carbonate-water, tetramethylene sulfone-water, dimethyl sulfoxide-water, tetrahydrofuran-water, ethylene carbonate-tetramethylene sulfone-water, ethylene carbonate-tetramethylene sulfone, and tetrahydrofuran-dimethyl sulfoxide at 25°C. For dielectric constants greater than about 60, the pairing constants K_A are in the range 0.3–2.0; no correlation between K_A and solvent properties could be established. For lower dielectric constants, K_A increases exponentially with decreasing dielectric constant. Addition of a proton, acceptor to water initially decreases K_A regardless of whether the dielectric constant of the mixture is higher or lower than that of water, suggesting that ion pairs in water may be stabilized by cage structures. The Walden product A_o is also decreased by the addition of proton acceptors.     

Beyond the standard model physics at RHIC in polarized pp collision

An polarized hadron collider experiment must have a great discovery potential for a search of physics beyond the standard model. Experimental data of various symmetry tests at RHIC are going to be obtained within a few years. The author developed a simulation tool, studying a sensitivity of hunting contact interaction at RHIC by measuring parity violating spin asymmetries.