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.     

Synthesis of sulfonated organic–inorganic hybrids through the radical copolymerization of vinyl sulfonate esters and vinyl trialkoxysilanes

Novel organic–inorganic hybrids with sulfonic acid groups were prepared using random copolymers composed of vinyl sulfonate esters and vinyl trialkoxysilanes. Five vinyl sulfonate esters with different substituent groups were employed as protecting monomers for the production of the poly(vinyl sulfonic acid) component, and three vinyl trialkoxysilanes were used as cross-linkable monomers. Free radical and reversible addition-fragmentation chain transfer (RAFT) copolymerizations were performed for the production of random copolymers with two different functional groups. The selective deprotection of the sulfonate esters of the copolymers proceeded smoothly and resulted in the formation of copolymers with lithium vinyl sulfonate units and cross-linkable trialkoxysilane units. The co-condensation of the trialkoxysilane moieties in the deprotected copolymers with cross-linkers yielded transparent hybrid films that contained lithium sulfonate groups without aromatic rings or ester linkages.     

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.     

Secure context-sensitive authorization

There is a recent trend toward rule-based authorization systems to achieve flexible security policies. Also, new sensing technologies in pervasive computing make it possible to define context-sensitive rules, such as “allow database access only to staff who are currently located in the main office”. However, these rules, or the facts that are needed to verify authority, often involve sensitive context information. This paper presents a secure context-sensitive authorization system that protects confidential information in facts or rules. Furthermore, our system allows multiple hosts in a distributed environment to perform the evaluation of an authorization query in a collaborative way; we do not need a universally trusted central host that maintains all the context information. The core of our approach is to decompose a proof for making an authorization decision into a set of sub-proofs produced on multiple different hosts, while preserving the integrity and confidentiality policies of the mutually untrusted principals operating these hosts. We prove the correctness of our algorithm.     

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.     

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.