Printed circuit rat-race-type directional couplers for larger power-split ratio

Two different types of 5/2-wavelength rat-race-type directional couplers with a remarkably increased power-split ratio for a realizable ring-impedance, in particular which are useful for millimeter-wave circuits suffering from the severe restriction on the usable impedance range, are described. Experimental corroboration is provided in the microwave region (at 8 GHz).     

Conformational control of benzyl-o-carboranylbenzene derivatives and molecular encapsulation of acetone in the dynamically formed space of 1,3,5-tris(2-benzyl-o-carboran-1-yl)benzene

A 1,3,5-substituted benzene platform has been widely used in the fields of supramolecular chemistry and molecular recognition. Here, we show that 1,3,5-tris(2-benzyl-o-carboran-1-yl)benzene 6 exhibits solvent-dependent conformation in the crystalline state. Recrystallization from dichloromethane-n-pentane gave the anti conformation 6-anti, while recrystallization from methanol-acetone gave the syn conformation 6-syn, in which the three benzyl-o-carboranyl moieties are located to one side of the central benzene ring. Interestingly, one acetone molecule is captured in the π-rich space of 6-syn and two complexes facing each other encapsulate two acetone molecules in a π-rich container formed by the eight benzene rings. The inclusion involves several weak interactions, that is, T-shaped C-H···π interactions, and C-H···O and C-H···π interactions. Two C-H···O interactions involving benzylic C-H hydrogens activated by the electron-withdrawing character of the o-carborane cage and the oxygen atom of the acetone seem to be the most important. DFT calculations indicate that the binding energy for entrapment of acetone is 6.6 kcal/mol. Inclusion of acetone is achieved through not only multiple C-H···O interactions but also a number of C-H···π interactions. The third benzyl-o-carborane moiety is fixed in the syn conformation by intramolecular and intermolecular C-H···π interactions.     

Peierls mechanism of the metal-insulator transition in ferromagnetic hollandite K2Cr8O16

Synchrotron x-ray diffraction experiment shows that the metal-insulator transition occurring in a ferromagnetic state of a hollandite K(2)Cr(8)O(16) is accompanied by a structural distortion from the tetragonal I4/m to monoclinic P112(1)/a phase with a √2×√2×1 supercell. Detailed electronic structure calculations demonstrate that the metal-insulator transition is caused by a Peierls instability in the quasi-one-dimensional column structure made of four coupled Cr-O chains running in the c direction, leading to the formation of tetramers of Cr ions below the transition temperature. This provides a rare example of the Peierls transition of fully spin-polarized electron systems.     

Optimization of flow diverters for cerebral aneurysms

A modern technique to treat cerebral aneurysms is to insert a flow diverter in the parent artery. In order to produce an optimal design of such devices, we consider a methodology combining simulated annealing optimization and lattice Boltzmann simulations. Our results surpass, in terms of stent efficiency, those obtained in the recent literature with an other optimization method. Although our approach is still in 2D, it demonstrates the potential of the method. We give some hint on how the 3D cases can be investigated.     

Synthesis of optically active tetrahydrozerumbone

Tetrahydrozerumbone 2, which has a powerful balmy fragrance, has a stereogenic carbon at C2 and can be easily prepared from zerumbone 1, which is one of the most important materials that displays an NMRDOS character. Reduction of 2 gave two diastereomers 3 and 4; their optically active (>99% ee) alcohols were obtained by lipase-catalyzed stereoselective transesterification of each racemic alcohol. The enantioselectivity of tetrahydrozerumbol does not entirely depend on the hydroxyl position but on the 2-methyl position. Compounds (R)-2 and (S)-2 were obtained by Dess–Martin oxidation of the corresponding alcohols. Interestingly, (R)-2 showed a strong balmy fragrance while (S)-2 had hardly any fragrance.     

Structural development of ultra‐high strength polyethylene fibers: Transformation from kebabs to shishs through hot‐drawing process of gel‐spun fibers

Structural development of ultra‐high strength polyethylene fibers via hot‐drawing processes of as‐spun gel fibers was investigated by means of transmission electron microscopy. It is found that the shish‐kebabs developed in both the as‐spun and drawn fibers can be transformed continuously into the micro‐fibril structure composed mostly of the shish structure through the hot‐drawing process. The structure transformation involves a drastic decrease in diameter of the kebab plus the shish but almost no change in the shish diameter. This result suggests that the chains in the kebabs are incorporated into the shishs and consumed to extend the longitudinal dimension of the shishs during the drawing process. The proposed new deformation model well explains the relationship between the fiber morphology and their mechanical properties: the tensile strength and modulus of the fibers can be determined by the number of the shish in the fiber and the macroscopic diameter of the fiber, which are apriori determined at the spinning process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1861–1872, 2010     

9,9′‐spirobifluorene‐containing polycarbonates: Transparent polymers with high refractive index and low birefringence

Syntheses of 2,2′‐bisalcoholic group‐substituted 9,9′‐spirobifluorene monomers 2 were performed by the reaction of 2,2′‐dihydroxy‐9,9′‐spirobifluorene 2a with haloalcohols. Polycarbonates consisting of 9,9′‐spirobifluorene skeleton in the main chain (PC 4 ) were synthesized by the polycondensation of 2,2′‐bisalcoholic monomers 2 and triphosgene or diphenyl carbonate. PC 4 showed good thermal stability: the 5% weight loss temperature was over 330 °C under both nitrogen and air atmospheres. The glass transition temperature was in a range of 16–269 °C estimated by differential scanning calorimetry, depending on the flexibility of the alkylene or oxyethylene chains of 2 . PC 4 showed high solubility toward ordinary organic solvents such as CHCl₃, benzene, and THF, making possible the preparation of the flexible thin films. Very high refractive index in a range of 1.62–1.66 at 589 nm was observed although PC 4 consists only of C, H, and O atoms, whereas very low degree of birefringence was confirmed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3658–3667, 2010     

Room Temperature Solution ENDOR of some Super Stable Fluorocarbon Radicals

Room temperature fluorine electron nuclear double resonance (ENDOR) has been successfully observed for several superstable fluorocarbon radicals ·C(C₂F₄R)(i-C₃F₇)₂ in solution. Three radicals were employed in which CF₃, F, and O-c-C₆F₁₀SO₃C₂F₅ were introduced as R, and all the hyperfine couplings (hfcs) obtained by ENDOR were assigned with the help of ESR simulation and ab initio MO calculation. In case of ·C(i-C₃F₇)₃ large ¹³C and considerable β-fluorine couplings suggest the nonplaner arrangement for the central and three carbons at the β-position, in spite of the fact that all the methyl fluorine show the same hfc. Therefore, a rapid puckering motion along the C₃ axis together with the methyl rotation should average the hfc’s of the 18 fluorine nuclei to give the same value. When one of the CF₃ groups is substituted with an F nucleus, the five CF₃ groups give two hfc values, suggesting some dynamics still exists for the molecular frame. When a large group, O-c-C₆F₁₀SO₃C₂F₅, is substituted for CF₃, all the five CF₃ groups become nonequivalent and the ENDOR signal becomes intensive and sharp even at 290 K, indicating that the molecular frame becomes rigid. The relation between the ENDOR spectra of these systems and the intramolecular dynamics is discussed.     

Development of Polarized HD Target for Future LEPS Experiments at Spring-8

We are carrying out hadron photoproduction experiments by using polarized photon beams at SPring-8 in Japan.In 2005,we started developing a polarized HD target for future experiments using both the polarized photon beams and the polarized target.The polarized HD target is an idealistic target for experiments observing reactions with small cross sections because the HD does not include heavy nuclei which produce many background events.The measurement of double polarization asymmetries is expected to give much important information to investigate the nucleon hidden structure,hadron photoproduction dynamics,and exotic hadron property.We report on the present status of the development of the polarized HD target al RCNP.