New fluorescent probes applicable to aggregates of fluorocarbon surfactants

We developed new benzofurazan (NBD) labeled probes for fluorocarbon surfactant systems. The fluorescence behavior depended on the solubilization site of the fluorescent probes in the surfactant aggregates. The NBD-labeled probes suffered virtually complete reduction in the presence of Na(2)S(2)O(4) owing to the solubilization at the surface of 2-hydroxy-1,1,2,3,3-pentahydroperfluoroundecyldiethylammonium bromide (FC(8)DAB) aggregates. On the other hand, N-(3-sulfopropyl)acridinium (SPA) in FC(8)DAB aggregates showed residual fluorescence in spite of NaBH(4) addition. The large vesicles of FC(8)DAB were confirmed by DLS measurements. These facts suggest that SPA is solubilized in an inner water phase of the vesicles. The NBD labeled fluorescence probe is quite effective for the study of the aggregation behavior of fluorocarbon surfactants.     

First international two-way satellite time and frequency transfer experiment employing dual pseudo-random noise codes

Two-way satellite time and frequency transfer (TWSTFT) is one of the main techniques used to compare atomic time scales over long distances. To both improve the precision of TWSTFT and decrease the satellite link fee, a new software-defined modem with dual pseudo-random noise (DPN) codes has been developed. In this paper, we demonstrate the first international DPN-based TWSTFT experiment over a period of 6 months. The results of DPN exhibit excellent performance, which is competitive with the Global Positioning System (GPS) precise point positioning (PPP) technique in the short-term and consistent with the conventional TWSTFT in the long-term. Time deviations of less than 75 ps are achieved for averaging times from 1 s to 1 d. Moreover, the DPN data has less diurnal variation than that of the conventional TWSTFT. Because the DPN-based system has advantages of higher precision and lower bandwidth cost, it is one of the most promising methods to improve international time-transfer links.     

Grain growth prediction with inclination dependence of 〈1 1 0〉 tilt grain boundary using multi-phase-field model with penalty for multiple junctions

Multi-phase-field (MPF) model with a higher-order term representing energetic penalty for multiple junctions was proposed to predict the grain growth accompanying the inclination dependence of grain boundary (GB) energy and mobility. The inclination effect was introduced on the basis of GB energy obtained from molecular dynamics (MD) simulations. The preliminary grain growth simulation of an isolated grain surrounded by Σ3 GB certified that the analytical equilibrium shape was well reproduced. The augmented higher-order term added to conventional MPF model could improve convergence and stability of numerical calculations around triple junction (TJ) region even if there exists the large GB energy gap at the TJ. Moreover, the present MPF model can realize well the Young’s relation with no GB inclination effect and further extend to the case with that effect. For the polycrystalline grain growth simulations with the GB energy distribution according to the misorientation angle of Al 〈1 1 0〉 tilt GB, Σ3 GB inclination lead the weak anisotropy characterized by Σ3{111} twin boundary. Besides, the inclination dependence can effectively drive the GBs with low GB energy like the low-angle GB during grain growth.     

Spin doping of individual molecules by using single-atom manipulation

Being able to control the spin of magnetic molecules at the single-molecule level will make it possible to develop new spin-based nanotechnologies. Gate-field effects and electron and photon excitations have been used to achieve spin switching in molecules. Here, we show that atomic doping of molecules can be used to change the molecular spin. Furthermore, a scanning tunneling microscope was used to place or remove the atomic dopant on the molecule, allowing us to change the molecular spin in a controlled way. Bis(phthalocyaninato)yttrium (YPc(2)) molecules deposited on an Au (111) surface keep their spin-1/2 magnetic moment due to the small molecule-substrate interaction. However, when Cs atoms were carefully placed onto YPc(2) molecules, the spin of the molecule vanished as shown by our conductance measurements and corroborated by the results of density functional theory calculations.     

Nanoscale contact plasticity of crystalline metal: Experiment and analytical investigation via atomistic and discrete dislocation models

Nanoscale incipient plastic deformation in crystalline metals occurs as the result of the collective motion of dislocations. It is known as “nanoplasticity” and is recognized as the elementary process of the macroscopic deformation. Abrupt increases in indent displacements called displacement bursts were observed in recent nanoindentation experiments; that is, the specific behavior for nanoplasticity. In the present study, experimental tests are first conducted to educe the unique nature of the nanoscale deformation. Subsequently, large-scale atomistic simulations are performed to predict the incipient plastic deformation and a new discrete dislocation model combined with the boundary element analysis is constructed to capture the collective motion of the dislocations. Our results suggest that the incipient plastic deformation requires much higher critical shear stress than the theoretical shear strength due to high compressive stress distribution beneath the indenter, and that the displacement burst is induced by surface rearrangement corresponding to hundreds of dislocation dipoles.     

Bis(phthalocyaninato)yttrium grown on Au(111): Electronic structure of a single molecule and the stability of two-dimensional films investigated by scanning tunneling microscopy/spectroscopy at 4.8 K

Scanning tunneling microscopy/spectroscopy (STM/STS) at 4.8 K has been used to examine the growth of a double-decker bis(phthalocyaninato)yttrium (YPc₂) molecule on a reconstructed Au(111) substrate. Local differential conductance spectra (dI/dV) of a single YPc₂ molecule allow the characteristics of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) to be identified. Furthermore, lateral distributions of the local density of states (LDOS) have also been obtained by dI/dV mapping and confirmed by first principles simulations. These electronic feature mappings and theoretical calculations provide a basis for understanding the unique STM morphology of YPc₂, which is usually imaged as an eight-lobed structure. In addition, we demonstrate that bias-dependent STM morphologies and simultaneous dI/dV maps can provide a way of understanding the stability of two-dimensional YPc₂ films.      

Production of high-purity medical radio isotope 64Cu with accelerator-based neutrons generated with 9 and 12 MeV deuterons

We conducted a feasibility study for producing a high-purity medical radioisotope ⁶⁴Cu from natural zinc with accelerator-based neutrons. ⁶⁴Cu isotopes were produced via the ⁶⁴Zn(n,p) reaction. The accelerator-based neutrons were generated via the C(d,n) reaction using low-energy deuterons of 9 and 12 MeV on a 1-mm-thick carbon target. First, the production purity was estimated using the evaluated nuclear data library JENDL-4.0 and our previously measured thick target neutron yield. We found that even when natural zinc was used as the starting material, significantly high-purity ⁶⁴Cu could be obtained. Next, irradiation experiments for producing ⁶⁴Cu using natural zinc were conducted at Kyushu University Tandem Laboratory, with the amounts of ⁶⁴Cu isotopes and other gamma-emission nuclides measured by a high-purity germanium detector. As a result, high-purity ⁶⁴Cu isotopes of 1.11(49) × 10⁰ and 3.70 (17) × 10⁰ Bq/g/μC were produced with incident deuteron energies of 9 and 12 MeV, respectively.     

Dissolution behavior of irradiated mixed oxide fuel with short stroke shearing for fast reactor reprocessing

An efficient dissolution process was established for future reprocessing in which mixed-oxide (MOX) fuels with high plutonium contents and dissolver solution with high heavy-metal (HM) concentrations (more than 500 g dm^?3) will be treated. This dissolution process involves short stroke shearing of fuels (～10 mm in length). The dissolution kinetics of irradiated MOX fuels and the effects of the Pu content, HM concentration, and fuel form on the dissolution rate were investigated. Irradiated fuel was found to dissolve as 10²–10³ times fast as non-irradiated fuel, but the rate decreased with increasing Pu content. Kinetic analysis based on the fragmentation model, which considers the penetration and diffusion of nitric acid through fuel matrices prior to chemical reaction, indicated that the dissolution rate of irradiated fuel was affected not only by the volume ratio of liquid to solid (L/S ratio) but also by the exposed surface area per unit mole of nitric acid (A/m ratio). The penetration rate of nitric acid is expected to be decreased at high HM concentrations by a reduction in the L/S ratio, but enhanced by shearing the fuel pieces with short strokes and thus enlarging the A/m ratio.     

Less Carcinogenic Chlorinated Estrogens Applicable to Hormone Replacement Therapy

Human estrogens prescribed for hormone replacement therapy (HRT) are known to be potent carcinogens. To find safer estrogens, several chlorinated estrogens were synthesized and their carcinogenic potential were determined. A pellet containing either 2-chloro-17β-estradiol (2-ClE₂) or 4-chloro-17β-estradiol (4-ClE₂) was implanted subcutaneously for 52 weeks into August Copenhagen Irish (ACI) rats, a preferred animal model for human breast cancer. 17β-Estradiol (E₂) frequently induced mammary tumors while both 2-ClE₂ and 4-ClE₂ did not. Their 17α-ethinyl forms, thought to be orally active estrogens, were also synthesized. Neither 2-chloro-17α-ethinylestradiol (2-ClEE₂) nor 4-chloro-17α-ethinylestradiol (4-ClEE₂) induced tumors. The less carcinogenic effects were supported by histological examination of mammary glands of ACI rats treated with the chlorinated estrogens. A chlorine atom positioned at the 2- or 4-position of E₂ may prevent the metabolic activation, resulting in reducing the carcinogenicity. 2-ClE₂ and 4-ClE₂ administered subcutaneously and 2-ClEE₂ and 4-ClEE₂ given orally to ovariectomized rats all showed uterotrophic potency, albeit slightly weaker than that of E₂. Our results indicate that less carcinogenic chlorinated estrogens retaining estrogenic potential could be safer alternatives to the carcinogenic estrogens now in use for HRT.     

Aqueous solution properties of disulfide-linked fluorinated gemini and cleaved monomeric thiol surfactants

We prepared a fluorinated gemini surfactant containing a disulfide bond in its spacer chain, [C?F??(CH?)?N(CH?)?CH?CH?SSCH?CH?N(CH?)?(CH?)?C?F??]2Cl, and its analogue with a hexamethylene spacer. Monomeric thiol surfactant, [C?F??(CH?)?N(CH?)?CH?CH?SH]Cl, was readily produced by the cleavage of the gemini surfactant using dithiothreitol in water. The critical micelle concentration was determined using surface tension, conductivity, and fluorescence probe methods. The critical micelle concentration of the monomeric surfactant was significantly larger than that of the gemini surfactant. The surface tension of aqueous solution for the cleaved monomeric thiol surfactant returned gradually to the original value through the formation of the disulfide bond via air oxidation.