High Atom Efficiency in Sc(OTf)3‐Catalyzed Allylation of Aldehydes with Tetraallyltin

The high atom efficiency was achieved through addition of Ac₂O in the Sc(OTf)₃‐catalyzed allylation of aldehyde with tetraallytin in a 4 : 1 molar ratio.     

Time flexibility to reduce climate change mitigation costs for Japanese electricity supply sector

The idea of greenhouse‐gas credit borrowing in global or national context faces severe problems such as international and intergenerational equity issues. Though the merit of cost reduction is obvious, the possibility is small for such a scheme to be massively allowed in future international negotiations. Still, there is a good chance for each specific player to use the idea of time flexibility. Through analytic and numerical model analysis, this paper demonstrates the merits of time flexibility on a sector base. First, the derived analytic solution for time paths of marginal mitigation costs gives an insight to the relation between timing and costs of mitigation action. Second, the numerical model analysis for the Japanese electricity supply sector shows that time flexibility can drastically reduce costs for mitigation in the sector. Time flexibility is important specifically to the Japanese electricity supply sector because (1) the sector is capital intensive and has long capital turnover time and (2) available mitigation option is limited for the near future. A sector like the Japanese utility sector needs some kind of mechanism to virtually realize the merits of using time flexibility. Domestic and international emission trading systems are the most promising candidate to date. © 2000 Scripta Technica, Electr Eng Jpn, 131(1): 68–77, 2000     

Hydrogen bond network in the distal site of peroxidases: spectroscopic properties of Asn70 --> Asp horseradish peroxidase mutant

The distal His in peroxidases forms a hydrogen bond with the adjacent Asn, which is highly conserved among many plant and fungal peroxidases. Our previous work [Nagano, S., Tanaka, M., Ishimori, K., Watanabe, Y., & Morishima, I. (1996) Biochemistry 35, 14251-14258] has revealed that the replacement of Asn70 in horseradish peroxidase C (HRP) by Val (N70V) and Asp (N70D) discourages the oxidation activity for guaiacol, and the elementary reaction rate constants for the mutants was decreased by 10-15-fold. In order to delineate the structure-function relationship of the His-Asn couple in peroxidase activity, heme environmental structures of the HRP mutant, N70D, were investigated by CD, 1H NMR, and IR spectroscopies as well as Fe2+/Fe3+ redox potential measurements. While N70D mutant exhibited quite similar CD spectra and redox potential to those of native enzyme, the paramagnetic NMR spectrum clearly showed that the hydrogen bond between the distal His and Asp70 is not formed in the mutant. The disappearance of the splitting in the 1H NMR signal of heme peripheral 8-methyl group observed in 50% H2O/50% D2O solution of N70D-CN suggests that the hydrogen bond between the distal His and heme-bound cyanide is also disrupted by the mutation, which was supported by the low C-N vibration frequency and large dissociation constant of the heme-bound cyanide in the mutant. Together with the results from various spectroscopies and redox potentials, we can conclude that the improper positioning of the distal His induced the cleavages of the hydrogen bonds around the distal His, resulting in the substantial decrease of the catalytic activity without large structural alterations of the enzyme. The His-Asn hydrogen bond in the distal site of peroxidases, therefore, is essential for the catalytic activity by controlling the precise location of the distal His.     

Determining the relative permeability and conductivity of thin materials

In order to determine the relative permeability and conductivity of thin materials that could not be found using traditional methods, we constructed a shield box and developed a measuring system to estimate the unknown electric parameters of exotic shielding materials such as thin cloths. Thin electromagnetic shielding sheets of both nonmagnetic materials and ferromagnetic materials were used. The shielding effectiveness of the materials was measured as a function of frequency, and the results were compared with the calculated solutions for a multilayered model that was evaluated using the Sommerfeld integral that expresses near-field spherical waves by a composition of cylindrical waves. In these calculations, the relative permeability and conductivity were varied to determine the solution closest to the measured results. The least squares method was used to determine the best fitted values. Initially the nominal values of relative permeability were assumed, and the conductivity was found using the fitting technique. Then this determined value of the conductivity was assumed, and the relative permeability was found using the fitting technique. For the nonmagnetic materials, the estimated relative permeability was the same as the nominal values. For the ferromagnetic materials, the estimated relative permeability varied 0%-30% from the nominal values. For both types of materials, the estimated conductivities were 0%-9.8% different from nominal values. This research details a new method for evaluating the attenuation of interfering electromagnetic waves for thin materials.     

An assessment of spent nuclear fuel storage demands under uncertainty

This paper attempts to draw quantitative prospects of spent nuclear fuel (SNF) management in Japan, with emphasis on uncertainty of storage needs for SNF up to the year 2050. In a medium term up to the years 2020–2030, the storage need for SNF can be projected with relatively high accuracy as it steadily increases up to the level of 5000 tonnes of uranium (tU), which requires timely deployment of storage facilities accordingly. In a longer term up to 2050, a number of aspects may give influences on the SNF management strategy, which are analyzed in different sets of scenario assumptions. The results of quantitative simulation runs showed that the storage need for SNF will increase up to the level of 10,000 tonnes of heavy metals (tHM) in the Base Case, while it would further grow to 20,000–25,000 tHM in the Risk Management Cases. Careful attentions should be given to the point that not just quantity but characteristics of SNF to be stored will differ significantly among the simulation cases, such as from lower to higher burnup, uranium and MOX (mixed oxide) fuels. The results imply Japan's SNF management may require elaborate strategies, which consists of effective and timely measures into the future.     

Accelerated Discovery of Potent Bioactive anti-TNFα Aptamers by Microbead-Assisted Capillary Electrophoresis (MACE)-SELEX

Dysregulation of tumor necrosis factor-α (TNFα), a pro-inflammatory cytokine, causes several diseases, making it an important therapeutic target. Here, we identified a novel DNA aptamer against human TNFα using in vitro selection, which included a high exclusion pressure process against non-binding and weak binders through microbead-assisted capillary electrophoresis (MACE) in only three rounds. Among the 15 most enriched aptamers, Apt14 exhibited the highest inhibitory activity for the interaction between TNFα and its cognate receptor in mouse L929 cells. For further improving the bioactivity of the aptamer, dimerization programed by hybridization was evaluated, resulting in the Apt14 dimer exhibited a twofold higher binding affinity and stronger inhibition compared to the monomer counterpart. Rapid identification of bioactive aptamers using MACE in combination with facile dimerization by hybridization accelerates the discovery of novel bioactive aptamers, paving the way toward replacing current monoclonal antibody therapy with the less expensive and non-immunogenic aptamer therapy.     

Characterization of localized states in thin PrBa2Cu3O7−x tunnel barriers

Characteristic power-law dependence of junction conductance on temperature was confirmed at low temperatures fora,b-axis oriented Au/PrBa₂Cu₃O_7−x /YBa₂Cu₃O_7−y junctions with a PrBa₂Cu₃O_7−x layer thinner than 30 nm, indicating that current transport via a small number of localized states was predominant. The radius and the density of the localized states were estimated to be 1.1 nm and 5.0x10¹⁹ eV⁻¹ cm⁻³, respectively. Transport measurement at 1.7 K in a magnetic field of up to 6 T revealed no indication of on-site Coulomb repulsion of electrons in the localized states. These results support the possibility of resonant tunneling of Cooper pairs in superconductor-insulator-superconductor junctions with a thin PrBa₂Cu₃O_7−x tunnel barrier.     

Development of an energy-binned photon-counting detector for X-ray and gamma-ray imaging

The aim of this study is to develop an energy-binned photon-counting (EBPC) detector that enables us to provide energy information of x-rays with a reasonable count statistics. We used Al-pixel/CdTe/Pt semiconductor detectors, which had an active area of 8 mm×144 mm and consisted of 18 modules aligned linearly. The size of a CdTe detector module was 8 mm×8 mm and the thickness of the CdTe crystal was 1 mm. Each module consisted of 40×40 pixels and the pixel size was 200 μm×200 μm. We applied the bias voltage of −500 V to the Pt common electrode. The detector counted the number of x-ray photons with four different energy windows, and output four energy-binned images with pixel depths of 12, 12, 11 and 10 bits at a frame rate of 1200 Hz (300 Hz×4 energy bins). The basic performance of the detector was evaluated in several experiments. The results showed that the detector realized the photon counting rate of 0.4×10⁶ counts/sec/pixel (10⁷ counts/sec/mm²), energy resolution 4.4% FWHM at 122 keV. The integral uniformity of the detector was about 1% and the differential uniformity was about 1%. In addition, the image quality was examined with a resolution chart and step-wedge phantoms made of aluminum and polymethyl methacrylate. And we compared the quality of an acquired image with that acquired with an energy integration detector. The results of these experiments showed that the developed detector had desirable intrinsic characteristics for x-ray photon counting imaging.     

Two dimensional nano-dot array engineering of block copolymer surface micelles on water surface

When an amphiphilic block copolymer is directly spread from an organic solution, the morphology of the surface micelles is not in general controlled because the structure is rapidly frozen after the solvent evaporation. In contrast, we have developed a new versatile method to generate highly regular ordered nanopatterns of the surface micelles on water, which involves the process of two dimensional (2D) hybridization with a polar liquid crystal molecule, 4′-pentyl-4-cyanobiphenyl (5CB) [Langmuir 22 (2006) 5233]. The present work extends this approach using a family of diblock copolymers of polystyrene-block-poly(4-vinylpyridine) changing the chain length of the two polymer blocks. It is found here that the dot-to-dot distance and the dot size can be precisely controlled on-demand by the length of the polymer blocks. Such structural regulations cannot be attained without the 5CB hybridization. Due to the high reproducibility of the morphology formation, this process should be of practical significance to ‘engineer’ the 2D patterns in the range of some tens of nanometers.