Synthesis and chiroptical properties of helical poly(phenylacetylene) bearing optically active chiral oxazoline Pendants

The novel optically active (S)-4-benzyl-2-(ethynylphenyl)-oxazoline (BnEPhOx) was successfully prepared and polymerized using rhodium catalyst ([Rh(nbd)Cl]₂) to obtain the moderate molecular weight poly(phenylacetylene)s bearing chiral oxazoline derivatives with high yields (≥90%). The ¹H NMR spectra demonstrated that the resulting polymers had high stereoregular structures. Moreover, the poly(phenylacetylene)s bearing chiral oxazoline exhibited better thermal stability than poly(phenylacetylene). The resulting polymers showed higher absolute values of optical specific rotation than the monomer. The polymers also exhibited intense CD signal in the region of the π-π1 band of the conjugated polyacetylene backbone in chloroform solution. The results of specific rotation and CD spectroscopy indicated that all the polymers adopted higher-order structure with predominantly one-handed screw sense.In addition, the resulting polymers emitted fluorescence under UV irradiation.     

Current Pumping from Spin Dynamics

We show theoretically that charge and spin currents arise from spin dynamics in the presence of the spin–orbit interaction. The dominant calculation is the inverse spin Hall effect, namely the spin current pumped from precession of local spins is converted into the charge current by the spin–orbit interaction. The conversion mechanism is explained based on the conservation laws of charge and spin.     

Preliminary Study of Single Phase Preparation and Doping Effect of <Emphasis Type="Italic">β</Emphasis>-Zn<Subscript>4</Subscript>Sb<Subscript>3</Subscript>

Single phase β-Zn₄Sb₃ was prepared by the application of a two-stage heat treatment, and impurity elements were doped. The undoped and doped samples were prepared by direct melting followed by two-stage heat treatment at 450°C and 400°C after solidification of the samples in sealed quartz ampoules. Impurity doping of the samples was performed by the addition of 1 at.% of Se, In, Pb, Te, or Bi. The resulting samples were characterized by x-ray diffraction (XRD), differential thermal analysis (DTA), optical microscopy, and electron probe microanalysis, and their Seebeck coefficients were determined at room temperature. The undoped samples were determined by XRD and DTA to comprise single phase β-Zn₄Sb₃, while the doped samples were composed of multiple phases. From the measurements of the Seebeck coefficient, all samples were found to be p-type and all were found to have almost the same values. These results indicate that β-Zn₄Sb₃ has limited solubility for these impurity elements.     

TEM/STEM Observation of ZrC Coating Layer for Advanced High-Temperature Gas-Cooled Reactor Fuel, Part II

The Japan Atomic Energy Agency (JAEA) has started to study and develop zirconium carbide (ZrC)-coated fuel particles for advanced high-temperature gas-cooled reactors. The ZrC coating layer has been fabricated at JAEA by chemical vapor deposition using a pyrolytic reaction of zirconium bromide. The microstructures of the ZrC layers, whose nominal deposition temperatures could be measured and controlled during the deposition process, were characterized by means of TEM and STEM. In the present study, three batches were prepared and compared with each other as well as the previous batches. The crystallographic orientation of ZrC with regard to the growth direction in the ZrC layers deposited at a constant temperature of 1630 K was different from that deposited at varying temperatures in the 1493–1823 K range. A thin layer of turbostratic carbon was observed at the boundary between pyrolytic carbon and ZrC in particles deposited at the highest temperature among those used in this study (the nominal temperature was 1769 K); no such structure was found in a batch deposited at a lower temperature (the nominal temperature was 1632 K). Therefore, precise control of temperature is shown to be critical to the formation of good ZrC coatings.     

Motional coherency in chain dynamics of polybutadiene studied by molecular dynamics simulations

Molecular dynamics simulations of 1,4-polybutadiene in bulk amorphous state were performed. Results were compared with the recent neutron spin-echo measurements. To investigate motional coherency the relaxation rates for the collective and self-motions, the collective and self-relaxation rates, were evaluated for the short and long time regimes of the normalized intermediate scattering functions. The scattering vector dependence of the collective relaxation rates estimated for both fast and slow processes indicated a minimum at scattering vector q = 1.5 Å⁻¹, corresponding to the position of a peak in the static structure factor. The self-relaxation rates increased monotonously with q. A phenomenon known as de Gennes narrowing was reproduced well in the simulation and found to be originated from the inter-molecular correlation. The collective relaxation rate evaluated for fast process appeared to modulate around a peak of q = 2.9 Å⁻¹, corresponding to the intra-molecular correlation.     

Bit-dependent degradation caused by stimulated Brillouin scatteringin CPFSK coherent optical repeaterless systems with booster amplifiers

An interesting phenomenon due to stimulated Brillouin scattering (SBS) is experimentally found in a CPFSK heterodyne system with a booster amplifier. We find that the demodulated waveform amplitudes of just a few distinguished bits are strongly suppressed leading to a significant increase in BER. It is confirmed that the BER degradation can be reduced by adjusting the threshold voltage bias of the receiver decision circuit     

Phase and magnetic properties of iron oxide clusters in 20CaO·20SiO2·7Fe2O3·6FeO glasses

The annealing of 20CaO·20SiO₂·7Fe₂O₃·6FeO glasses at 973K in vacuo produced clusters of iron oxide, the shape of which was nearly spherical and the diameter distributed in the narrow range 25–115Å. The phase of clusters was identified to be Fe³⁺(Fe³⁺ _{poststagger|1.30}Fe²⁺ _{poststagger|0.55}V_0.15)·O₄ in the inverse spinel structure based upon the Mössbauer spectra and x-ray diffraction profiles. The clusters exhibited superparamagnetism and their effective anisotropy energy constant was inversely proportional to the cluster diameter. The magnetization of the glasses measured by a vibrating sample magnetometer was 7.2 × 10^-6 Wbmkg^-1 at 10 kOe at room temperature and smaller than the value calculated assuming that the whole clusters have superparamagnetism. These results suggest the pinning of spins near the cluster surface.     

Cloning and heterologous expression of a beta-fructofuranosidase gene from Arthrobacter globiformis IFO 3062, and site-directed mutagenesis of the essential aspartic acid and glutamic acid of the active site

We have cloned the gene encoding a beta-fructofuranosidase from Arthrobacter globiformis IFO 3062, and subsequently, the gene was heterologously expressed in Escherichia coli. This beta-fructofuranosidase gene encodes a protein of 548 amino acid residues with a calculated molecular mass of 60,519 Da. We have examined the roles of three residues of A. globiformis IFO 3062 beta-fructofuranosidase by site-directed mutagenesis, and found that aspartic acid 130 and glutamic acid 392, which are two of the apparent catalytic residues, are essential for hydrolase activity. This study provides the first experimental evidence showing that these two amino acid residues of beta-fructofuranosidase play a critical role in hydrolyzing sucrose.     

Fluorogenic derivatization reagents suitable for isolation and identification of cysteine-containing proteins utilizing high-performance liquid chromatography-tandem mass spectrometry

The fluorogenic derivatization reagents with a positive charge, 4-(dimethylaminoethylaminosulfonyl)-7-chloro-2,1,3-benzoxadiazole (DAABD-Cl) and 7-chloro-2,1,3-benzoxadiazole-4-sulfonylaminoethyltrimethylammonium chloride (TAABD-Cl), are proposed for use in proteomics studies. Following derivatization of protein mixtures with these reagents, a series of standard processes of isolation, digestion, and identification of the proteins were performed utilizing high-performance liquid chromatography-fluorescence detection and tandem mass spectrometry with the probability-based protein identification algorithm. Both DAABD and TAABD derivatives were detected fluorometrically at the femtomole level and showed more than 100-fold improvement in sensitivity compared to the underivatized original compounds with an electrospray ionization ion trap mass spectrometer analysis. The modification of the MASCOT database search system memorized with the fragment information of a DAABD-attached Cys residue allowed the identification of the proteolytic peptide fragments of the derivatized bovine serum albumin (BSA) with an estimated 38% sequence coverage of BSA. Utilizing DAABD-Cl as a derivatization reagent, identification of several proteins was also possible in a soluble extract of Caenorhabditis elegans (10 microg of protein). Consequently, for identification of proteins in the complex matrixes of proteins, DAABD-Cl could be a more appropriate reagent than ammonium 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate as reported previously.