Electronic structures of I2− and I4− ions in γ-irradiated rigid solutions

Radical-anions of iodine, bromine, and monoiodochloride are produced in γ-irradiated amorphous solids at 77 K, and their electronic and ESR spectra measured. On limited warming of the irradiated solution dimerization by the reaction I₂^? + I₂ → I₄^? occurs to produce the same species as reported by Fornier de Violet et al. The electronic structure of the dimeric anion is discussed in comparison with the monomeric anion.     

Reversible color changes in lamella hybrids of poly(diacetylenecarboxylates) incorporated in layered double hydroxide nanosheets

The present study is an investigation of a reversible thermal color change induced in lamella hybrids of poly(diacetylenecarboxylates) incorporated in layered double hydroxide (LDH) nanosheets. These poly-[m,n]/LDH hybrids prepared by the photo- or gamma-ray-induced polymerization of diacetylenecarboxylates, i.e., CH(3)(CH(2))(m)()(-)(1)CC-CC(CH(2))(n)()(-)(1)CO(2)(-) (mono-[m,n]), and intercalated in LDH lamella sheets, were observed to develop colors ranging from yellow to blue. The change in color was found to depend greatly on the alkyl carbon numbers of the mono-[m,n] (m,n = 10,11; 5,11; 10,5; 16,1) values. Moreover, the conformational alignment of the mono-[m,n] within the LDH was observed to be a crucial factor in color development, which was greatly affected by the intercalation degrees and extent of poly(ene-yne) linkage elongation of the polymers. For the poly-[m,n]/LDH hybrids investigated, a reversible color change was found to occur repeatedly and remarkably for the poly-[10,11]/LDH hybrid. This color change occurred at temperatures between ca. 20 and 80 degrees C back and forth from purple red to bright orange, in stark contrast to the irreversible color change for poly-[10,11] without LDH. Moreover, DSC and Raman spectroscopic studies of the LDH hybrids showed that the thermochromic temperature corresponded to the phase transition temperature of 80 degrees C. XRD analysis also indicated that the poly-[m,n]/LDH hybrid could retain its lamella structure during such thermochromic color changes, enabling conformational recovery in the polymer chains by a cooling down of the hybrids to temperatures lower than the transition temperature, while the nonhybrid poly-[10,11] powders exhibited an irreversible color change at 60 degrees C, above which the polymer powder turned amorphous.     

Recent progress of high-power negative ion beam development for fusion plasma heating

A negative-ion-based neutral beam injector (N-NBI) has been constructed for JT-60U. The N-NBI is designed to inject 500 keV, 10 MW neutral beams using two ion sources, each producing a 500 keV, 22 A D⁻ ion beam. In the preliminary experiment using one ion source, a D⁻ ion beam of 13.5 A has been successfully accelerated with an energy of 400 keV (5.4 MW) for 0.12 s at an operating pressure of 0.22 Pa. This is the highest D⁻ beam current and power in the world. Co-extracted electron current was effectively suppressed to the ratio of Ie/I_D⁻ < 1. The highest energy beam of 460 keV, 2.4 A, 0.44 s has also been obtained. To realize 1 MeV class NBI system for ITER (International Thermonuclear Experimental Reactor), demonstration of ampere class negative ion beam acceleration up to 1 MeV is an important mile stone. To achieve the mile stone, a prototype accelerator and a 1 MV, 1 A test facility called MeV Test Facility (MTF) were constructed. Up to now, an H⁻ ion beam was accelerated up to the energy of 805 keV with an acceleration drain current of 150 mA for 1 s in a five stage electrostatic multi-aperture accelerator.     

Distribution pattern of rare earth ions between water and montmorillonite and its relation to the sorbed species of the ions.

REE (rare earth element) distribution coefficients (Kd) between the aqueous phase and montmorillonite surface were obtained to investigate the relation between the REE distribution patterns and the species of REE sorbed on the solid-water interface. It was shown that the features in the REE patterns, such as the slope of the REE patterns, the tetrad effect, and the Y/Ho ratio, were closely related to the REE species at the montmorillonite-water interface. In a binary system (REE-montmorillonite) below pH 5, three features (a larger Kd value for a lighter REE, the absence of the tetrad effect, and the Y/Ho ratio being unchanged from its initial value) suggest that hydrated REE are directly sorbed as an outer-sphere complex at the montmorillonite-water interface. Above pH 5.5, the features in the REE patterns, the larger Kd value for heavier REE, the M-type tetrad effect, and the reduced Y/Ho ratio, showed the formation of an inner-sphere complex of REE with -OH group at the montmorillonite surface. In addition, the REE patterns in the presence of humic acid at pH 5.9 were also studied, where the REE patterns became flat, suggesting that the humate complex is dominant as both dissolved and sorbed species of REE in the ternary system. All of these results were consistent with the spectroscopic data (laser-induced fluorescence spectroscopy) showing the local structure of Eu(III) conducted in the same experimental system. The present results suggest that the features in the REE distribution patterns include information on the REE species at the solid-water interface.     

Structure-activity relationship (SAR) studies on oxazolidinone antibacterial agents. 1. Conversion of 5-substituent on oxazolidinone

A structure-activity relationship (SAR) study on 5-substituted oxazolidinones as an antibacterial agent is described. The oxazolidinones, of which 5-acetylaminomethyl moiety was converted into other functions, were prepared and evaluated for antibacterial activity. Elongation of the methylene chain (8) and conversion of the acetamido moiety into guanidino moiety (12) decreased the antibacterial activity. The replacement of carbonyl oxygen (=O) by thiocarbonyl sulfur (=S) enhanced in vitro antibacterial activity. Especially, compound 16, which had the 5-thiourea group, showed 4-8 stronger in vitro activity than linezolid. Our SAR study revealed that the antibacterial activity was greatly affected by the conversion of 5-substituent.     

Liquid crystalline gel with refractive index gradient of curdlan

Curdlan dissolved in aqueous sodium hydroxide was dialyzed to aqueous calcium chloride to form a gel. Transparent and turbid concentric layers observed in the gel cross section perpendicular to the long axis of the dialysis tube were identified as liquid crystalline gels with refractive index gradient and amorphous gels, respectively. The thickness of each layer was proportional to the diameter of the dialysis tube, and the gelation proceeded in proportion to the root of time. The unique pattern formation was attributed to the change of curdlan conformation and calcium-induced cross-linking resulting from a diffusion of calcium cations and hydroxide anions through the dialysis tube. It is suggested that the orderedness of the curdlan molecules decreases by the increase of the curvature of the concentric liquid crystal layers as the layer comes toward the center of the dialysis tube.     

High modulus polyimide/polyimide molecular composite films that utilize acetylene unit as a crosslink site

Polyimide/polyimide molecular composite (MC) films comprised of a rigid polyimide derived from biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA) and a flexible polyimide derived from BPDA and bis (3,3'-diaminodiphenyl) acetylene (intA) and/or oxydianiline (ODA) were prepared by blending the polyamic acid solutions in 7 : 3 weight ratio, and then imidizing the blend films. Acetylene content in the flexible polyimide backbone was controlled by the ratio of intA and ODA. Cold-drawing of the blend polyamic acid films, followed by imidization, gives high modulus polyimide/polyimide MC films. The modulus of the MC films increased almost linearly with the draw ratio, reaching 25.5 GPa for the 40% drawn film. Acetylene groups in the flexible polyimide can be thermally cured to crosslink. The onset of exotherm appeared at 340°C on DSC, reaching maximum at 398°C. After the thermal crosslinking, the MC films maintained the high modulus, though elongation became small. Taking advantage of the crosslinkable acetylene units, two MC films were laminated and processed at 400°C for 20 min under 100 kg/cm² to give a good-quality laminate film. The interface of the two films was strongly bonded through the crosslinking of acetylene groups. Laminate films maintained the high modulus afforded by the cold-drawing. © 1994 John Wiley & Sons, Inc.     

Stark and Zeeman spectroscopies of 4f 66s6p 7G1-6 levels in Sm I under external electric and magnetic fields

Systematic study of hyperfine structures, Zeeman and Stark effects in Sm I is performed for the lowest ⁷G_1-6 levels belonging to the configuration 4f ⁶6s6p by atomic-beam laser spectroscopy with fluorescence detection. The hyperfine coupling constants of ⁷G_2-6 levels are determined. From the Zeeman splittings for the 4f ⁶6s ^{2 7}F_2-6 ? 4f ⁶6s6p ⁷G_2-6 transitions, g-values are determined for the ⁷G_2.6 levels and the precision is improved by several orders of magnitude. From the Stark splittings for the ⁷F_0-3 ? ⁷G_1-3 transitions, tensor polarizabilities α ₂(J) are determined for the upper ⁷G_1-3 levels. Particularly for the ⁷G₁ level (15 650.55 cm^?1) which has close-lying opposite-parity level, the isotope dependence of α ₂(J) is clearly observed for the first time.     

Polymerization of vinylcyclopropanes. III. Cationic polymerization of stereoisomers of 1-halo-2-vinylcyclopropanes

Vinylcyclopropane derivatives, 1-chloro- and 1-bromo-2-vinylcyclopropane, have respectively two stereoisomers, and radical polymerizations of both isomers gave 1,5-type polymers. On the other hand, only the cis isomers gave a polymer which had mainly 1,2-type structural units in cationic polymerizations with Lewis acids. The difference between the cationic polymerizabilities of the cis and trans isomers is interpreted in terms of steric conformation of monomers.