Transparent poly(bisphenol A carbonate)-based nanocomposites with high refractive index nanoparticles

Transparent organic-inorganic nanocomposites were successfully synthesized from sulfonic acid-modified poly(bisphenol A carbonate) (SPC) and TiO₂ or ZrO₂ nanoparticles. The dispersibility of nanoparticles was significantly improved by both the surface treatment of nanoparticles with phosphoric acid 2-ethylhexyl esters (PAEH) and the introduction of a sulfonic acid moiety into the PC chain. It was found that in some cases, crystallization of the matrix caused a reduction in transparency. Efficient dispersion of nanoparticles and the absence of crystallization resulted in highly transparent nanocomposites with up to 42 wt% TiO₂ and 50 wt% ZrO₂ nanoparticles. The refractive indices of the nanocomposites based on SPC increased with the increasing amount of nanoparticles. Theoretical equation based on Maxwell-Garnett effective medium theory provided reasonably close estimation of the refractive indices to the experimentally observed values. The prepared nanocomposites had lower thermal stability than the host matrix polymers.     

Reaction of 2,3-diaminomaleonitrile with diones

2,3-Diaminomaleonitrile (DAMN) was allowed to react with 2,6-heptanedione to produce (2Z)-2-amino-3-[(1E)-3-methylcyclohex-2-enylideneamino]but-2-enedinitrile and (2Z)-2-amino-3-[(1Z)-3-methylcyclohex-2-enylideneamino]but-2-enedinitrile. The reaction of DAMN with 2,7-octanedione yielded trans-5,8a-dimethyl-1,5a,6,7,8,8a-hexahydrocyclopenta[e]-1,4-diazepine-2,3-dicarbonitrile. DAMN reacted with 2,8-nonanedione to afford trans- and cis-5,9a-dimethyl-5a,6,7,8,9,9a-hexahydro-1H-benzo[e]-1,4-diazepine-2,3-dicarbonitrile. These compounds were characterized by X-ray crystallography, NMR spectroscopy, and DFT calculations.     

Evidence for protein radical-mediated nuclear tunneling in fatty acid alpha-oxygenase

Rice alpha-oxygenase (RalphaO) catalyzes the insertion of O2 into the Calpha-H bond of various fatty acids. The mechanism is thought to involve a tyrosyl radical as the oxidant on the basis of comparisons to the structurally homologous cyclooxygenase enzymes. Kinetic and spectroscopic results presented here for the wild-type RalphaO and the Tyr379Phe mutant indicate an irreversible H* abstraction mechanism and support the involvement of the proposed catalytic Tyr*. In addition, very large, weakly temperature dependent deuterium kinetic isotope effects (approximately 50) are observed, consistent with extensive nuclear tunneling. RalphaO, thus, presents a novel example where such quantum effects are associated with an amino acid radical-utilizing enzyme.     

Experimental investigation on tunnel sonic boom

Upon the entrance of a high-speed train into a relatively long train tunnel, compression waves are generated in front of the train. These compression waves subsequently coalesce into a weak shock wave so that a unpleasant sonic boom is emitted from the tunnel exit. In order to investigate the generation of the weak shock wave in train tunnels and the emission of the resulting sonic boom from the train tunnel exit and to search for methods for the reduction of these sonic booms, a 1300 scaled train tunnel simulator was constructed and simulation experiments were carried out using this facility.In the train tunnel simulator, an 18 mm dia. and 200 mm long plastic piston moves along a 40 mm dia. and 25 m long test section with speed ranging from 60 to 100 m/s. The tunnel simulator was tilted 8° to the floor so that the attenuation of the piston speed was not more than 10 % of its entrance speed. Pressure measurements along the tunnel simulator and holographic interferometric optical flow visualization of weak shock waves in the tunnel simulator clearly showed that compression waves, with propagation, coalesced into a weak shock wave. Although, for reduction of the sonic boom in prototype train tunnels, the installation of a hood at the entrance of the tunnels was known to be useful for their suppression, this effect was confirmed in the present experiment and found to be effective particularly for low piston speeds. The installation of a partially perforated wall at the exit of the tunnel simulator was found to smear pressure gradients at the shock. This effect is significant for higher piston speeds. Throughout the series of train tunnel simulator experiments, the combination of both the entrance hood and the perforated wall significantly reduces shock overpressures for piston speeds ofu _p ranging from 60 to 100 m/s. These experimental findings were then applied to a real train tunnel and good agreement was obtained between the tunnel simulator result and the real tunnel measurements.     

Reinterpretation of the molecular O2 chemisorbate in the initial oxidation of the si(111)7 x 7 surface

The initial oxygen adsorption on the Si(111)7 x 7 surface was investigated by high-resolution x-ray absorption spectroscopy. Below 220 K, a molecular adsorption species is identified by distinctive absorption resonances due to the 1 pi(g) molecular orbitals. The molecular species is metastabilized to have a lifetime of 15-35 min at 135 K only with the presence of atomic adsorbates of more than 0. 1 ML (monolayer). It is thus clearly evidenced that the very initial adsorption is dissociative even at 100 K and the molecular species is not a precursor state. The molecular adsorption structures with the coadsorbed oxygen atoms are suggested.