Stereochemical Dichotomy in Two Competing Cascade Processes: Total Syntheses of Both Enantiomers of Spiroxin A

The first total synthesis of the marine antibiotic spiroxin A has been achieved for both enantiomeric forms. The discovery of two competing cascade processes triggered by two orthogonal stimuli, photo‐irradiation or acid/base treatment, enabled the divergent conversion of a single chiral, nonracemic bis‐quinone into both enantiomers of an advanced intermediate en route to both (?)‐ and (+)‐spiroxin A. The mechanism of the enantiodivergence is discussed.     

Molecular understanding of the adhesive interactions between silica surface and epoxy resin: Effects of interfacial water

The molecular mechanism of the adhesion between silica surface and epoxy resin under atmospheric conditions is investigated by periodic density-functional-theory (DFT) calculations. Slab models of the adhesion interface were built by integrating a fragment of epoxy resin and hydroxylated (0 0 1) surface of α-cristobalite in the presence of adsorbed water molecules. Effects of adsorbed water on the adhesion interaction are evaluated on the basis of geometry-optimized structures, adhesion energies, and forces. Calculated results demonstrate that adsorbed water molecules significantly reduce both the adhesion energies and forces of the silica surface–epoxy resin interface. The reduction of adhesion properties can be associated with structural deformation of water molecules confined in the tight space between the adhesive and adherend as well as structural flexibility of the hydrogen-bonding network in the interfacial region during detachment of the epoxy resin from the hydrophilic silica surface. © 2018 Wiley Periodicals, Inc.     

Synthesis,Structures, and Near‐IR Absorption of Heterole‐Fused Earring Porphyrins

A reaction sequence of regioselective peripheral bromination, Suzuki–Miyaura coupling with 2‐borylated thiophene or pyrrole, and oxidative ring‐closure with FeCl₃ allowed the synthesis of heterole‐fused earring porphyrins 4Pd and 9Pd from the parent earring porphyrin 1 . Differently pyrrole‐fused porphyrins 5H and 6H and their Pd^II complexes 5Pd and 6Pd were also synthesized. The structures of 4Pd , 5H, 6Pd , and 8Pd have been revealed by X‐ray analysis to be slightly twisted owing to constraints imposed by heterole‐fused structures. 5Pd exhibits an intensified band at 1505 nm, while 4Pd and 9Pd display small but remarkably red‐shifted absorption bands reaching around 2200 nm.     

Long-Range Lateral Correlation between Self-Assembled Domains of Fluorocarbon-Hydrocarbon Tetrablocks by Quantitative GISAXS

The structure and lateral correlation of fluorocarbon-hydrocarbon tetrablock di(F10Hm) domains at the air/water interface have been determined by quantitative analysis of grazing incidence small-angle X-ray scattering (GISAXS) data. The measured GISAXS signals can be well represented by the full calculation of the form and structure factors. The form factor suggests that di(F10Hm) domains take a hemiellipsoid shape. Both major and minor axes of the hemiellipsoids monotonically increased in response to the elongation of the hydrocarbon blocks, which can be explained by the concominant increase in van der Waals interaction. The structure factor calculated from the GISAXS signals suggests that the domains take an orthorhombic lattice. Remarkably, the lateral correlation can reach over a distance that is more than 14 times longer than the distance to the nearest neighbors. Our data suggest that quantitative GISAXS enables the optimal design of mesoscopic self-assemblies at the air/water interface by fine-tuning of the structures of molecular building blocks.     

Far‐ and Deep‐Ultraviolet Surface Plasmon Resonance Sensor

Plasmonics in the UV region has been widely focused because of the higher energy and the abundant electronic resonances compared to the conventional visible plasmonics. Recently, we have investigated the surface plasmon resonance (SPR) properties of the Al film, aiming for the application as refractive index sensors. Utilizing the UV lights, we expect three advantages: high sensitivity, material selectivity, and surface selectivity. By using an original attenuated total reflectance spectroscopic instrument, Al‐SPR angle and wavelength were investigated with changing environments on the Al film. Al film thickness and materials of prisms on which Al was evaporated were also important factors for the SPR properties. By optimizing the conditions, the Al film worked as a sensor both in air and in liquids. In addition, our established system expands the plasmonics into an even higher energy region than 200 nm, while the UV‐plasmonics have been studied in the wavelength region longer than 200 nm.     

Nature of magnetic coupling between Mn ions in As-grown Ga1-xMnxAs studied by X-ray magnetic circular dichroism

The magnetic properties of as-grown Ga1-xMnxAs have been investigated by the systematic measurements of temperature and magnetic field dependent soft x-ray magnetic circular dichroism (XMCD). The intrinsic XMCD intensity at high temperatures obeys the Curie-Weiss law, but a residual spin magnetic moment appears already around 100 K, significantly above the Curie temperature (T_{C}), suggesting that short-range ferromagnetic correlations are developed above T_{C}. The present results also suggest that the antiferromagnetic interaction between the substitutional and interstitial Mn (Mn_{int}) ions exists and that the amount of the Mn_{int} affects T_{C}.     

Structure and stability of a homologous series of tin oxides

The structures and stabilities of a series of nonstoichiometric SnO2-x compounds, which are yet unknown experimentally, are predicted using the cluster expansion technique combined with first-principles calculations. A homologous series of Sn(n+1)O(2n) in which oxygen vacancies are layered on (101) planes of the rutile lattice is discovered. The homologous crystals are composed of divalent and quadrivalent Sn atoms. No trivalent Sn atoms are formed.     

Effect of laser intensity on fast-electron-beam divergence in solid-density plasmas

Metal foil targets were irradiated with 1 mum wavelength (lambda) laser pulses of 5 ps duration and focused intensities (I) of up to 4x10;{19} W cm;{-2}, giving values of both Ilambda;{2} and pulse duration comparable to those required for fast ignition inertial fusion. The divergence of the electrons accelerated into the target was determined from spatially resolved measurements of x-ray K_{alpha} emission and from transverse probing of the plasma formed on the back of the foils. Comparison of the divergence with other published data shows that it increases with Ilambda;{2} and is independent of pulse duration. Two-dimensional particle-in-cell simulations reproduce these results, indicating that it is a fundamental property of the laser-plasma interaction.     

Electronic state on the surface in the strongly correlated electron systems

In order to clarify the tunneling spectroscopy in high-T_c cuprates, we study electronic state of the surface in the strongly correlated electron systems. First, we obtain Green's function of strongly correlated normal bulk system using the fluctuation exchange (FLEX) approximation. Next, we insert infinite potential into the bulk system and obtain Green's function of surface. We find that the density of states (DOS) in strongly correlated bulk systems are different from that on the surface, and the difference decreases as the magnitude of Coulomb interaction (U) increases.     

Chirality sensitive effect on surface states in chiral p-wave superconductors

We study the local density of states at the surface of a chiral p-wave superconductor in the presence of a weak magnetic field. As a result, the formation of low-energy Andreev bound states is either suppressed or enhanced by an applied magnetic field, depending on its orientation with respect to the chirality of the p-wave superconductor. Similarly, an Abrikosov vortex, which is situated not too far from the surface, leads to a zero-energy peak of the density of states, if its chirality is the same as that of the superconductor, and to a gap structure for the opposite case. We explain the underlying principle of this effect and propose a chirality sensitive test on unconventional superconductors.