Synthesis and characterization of benzo[1,2-b:3,4-b':5,6-b']trithiophene (BTT) oligomers

Two dimers (2 and 3), dendritic tetramer (4), hexamer (5), and decamer (6) of benzo[1,2-b:3,4-b':5,6-b']trithiophene (BTT), a potential π-core unit with C(3h) symmetry, were synthesized, characterized, and evaluated for possible use as organic semiconductors. Single crystal X-ray analyses of the dimers (2 and 3) revealed that they have planar molecular structures with dihedral angles of almost 180° between two BTT units. In accordance with the rigid and planar molecular structure, the unsubstituted dimer (2) is poorly soluble, whereas the octyl-substituted dimer (3) has improved solubility. Although the solubility of the dendritic tetramer (4) is decreased, further extended systems, i.e., the dendritic hexamer (5) and decamer (6), have solubilities better than that of 4. With increasing numbers of BTT units in the molecule, the experimentally determined energy levels of HOMO shift upward slightly and the HOMO-LUMO energy gaps become smaller, but the extent of HOMO destabilization and reduction of the HOMO-LUMO gap are not significant. Taking into account the energy levels of the frontier orbitals, 3-6 could be useful as p-channel organic semiconductors rather than n-channel. In fact, the spin-coated thin film of 3 with edge-on molecular orientation acted as an active channel of field-effect transistors that showed hole mobilities as high as 0.14 cm(2) V(-1) s(-1), indicating that the BTT core is a useful π-conjugated system for application to organic semiconductors, although 4-6 gave FET characteristics rather inferior to those of 3, owing to their amorphous nature in the thin film state.     

First acid dissociation at an aqueous H2SO4 interface with sum frequency generation spectroscopy

The vibrational sum frequency generation (SFG) spectra of the air-liquid interface of H2SO4-H2O solutions over a wide range of concentrations are measured in the SO stretching region (1000-1300 cm(-1)). The analogy of the concentration dependence of Raman and SFG is indicative of a nearly identical behavior of the first acid dissociation at the air-liquid interface as in the bulk.     

Reversible mechanochromic luminescence of [(C6F5Au)2(mu-1,4-diisocyanobenzene)

Reversible mechanochromic luminescence of [(C6F5Au)2(mu-1,4-diisocyanobenzene)] is reported. Grinding of the complex induced a photoluminescent color change, which was restored by exposure to a solvent. This cycle was repeated 20 times with no color degradation in the emissions. Their optical properties, X-ray crystallographic analysis, IR, and XRD measurements strongly suggested that the change in the molecular arrangement is responsible for this mechanochromic property. Intermolecular aurophilic bondings presumably play a key role in the altered emission.     

Fluorescence imaging of intracellular cadmium using a dual-excitation ratiometric chemosensor

We described here a coumarin-based dual-excitation ratiometric probe for cadmium, CadMQ. This fluorescence sensor has high quantum yields of 0.59 and 0.70 in the metal-free and Cd2+-bound forms, respectively, and has a dissociation constant of 0.16 nM for Cd2+. CadMQ is cell permeable and locates within the acidic compartments of the cells. We further show that CadMQ is a useful tool to ratiometrically probe the change in the intracellular Cd2+ levels with the use of two excited wavelengths.     

Dipyrrolyldiketone difluoroboron complexes: novel anion sensors with C-H...X- interactions

1,3-Dipyrrolyl-1,3-propanediones, synthesized from pyrroles and malonyl chloride, form BF2 complexes, which represent a new class of naked-eye sensors for halide and oxoanions. The association mode for the interactions of both the pyrrolyl NH and bridging CH protons with anions was confirmed by 1H NMR chemical shifts in CD2Cl2 and supported by theoretical studies. The binding constants (Ka) were estimated as 8.1x10(4), 2.0x10(3), 3.3x10(2), 1.3x10(4), and 80 M(-1) for F-, Cl-, Br-, H2PO4(-), and HSO4(-) by UV/Vis absorption spectral changes in CH2Cl2. Augmentation of Ka compared with dipyrrolylquinoxaline for H2PO4(-) is much larger than those for other anions. Contrary to other anions, F- quenches the emission almost completely, which was detected by the fluorescence spectrum as well as the naked-eye. In the case of the chloride anion complex, the formation of Cl(-)-bridged 1D networks, in which anion is associated with two BF2 complexes, is observed in the solid state.     

Analytical model of longitudinal tire traction in snow

An analytical model to estimate longitudinal traction of a tire in snow was developed and verified to have good predictability in comparison with measurements. Snow traction of a tire is composed of four kinds of forces in this model: braking force attributable to snow compression, shear force of snow in void (space between tread blocks), frictional force, and digging force (edge effect generated by sipes and blocks). The mechanical characteristics of snow were considered in the prediction of braking force and shear force, but were not considered in the prediction of other forces. The contribution of shear force of snow in void and the frictional force was large in static traction (traction just before a tire slips). On the other hand, the contributions of digging force and frictional force were large in situations involving high slip ratios.     

Topological superconductivity in bilayer Rashba system

We theoretically study a possible topological superconductivity in the interacting two layers of Rashba systems, which can be fabricated by the heterostructures of semiconductors and oxides. The hybridization, which induces the gap in the single particle dispersion, and the electron-electron interaction between the two layers leads to the novel phase diagram of the superconductivity. It is found that the topological superconductivity without breaking time-reversal symmetry is realized when (i) the Fermi energy is within the hybridization gap, and (ii) the interlayer interaction is repulsive, both of which can be satisfied in realistic systems. Edge channels are studied in a tight-binding model numerically, and the several predictions on experiments are also given.     

Magnetic circular dichroism of [Co/Pd] and [CoB/Pd] multilayered films

Magnetic circular dichroism (MCD) and X-ray absorption spectra (XAS) at the Co L_2,3-edge of [Co/Pd]₂₀ and [CoB/Pd]₂₀ multilayered films, which were fabricated at 260 °C with different magnetic layer thicknesses (δ), have been measured. The lineshapes of XAS–MCD show that the electronic state of Co 3d of the films hardly changes even when sputtered at higher temperatures. The expectation values of orbital and spin angular momentum (〈L_z〉 and 〈S_z〉) are estimated using the sum rule, and it is found that 〈L_z〉/〈S_z〉 in δ<0.5 nm is larger than that in δ>0.5 nm.     

Automatic Deformation Analysis in Electronic Speckle Pattern Interferometry Using One Speckle Interferogram of Deformed Object

We propose a new fringe analysis method that uses only one speckle interferogram of a deformed object to obtain phase change distribution by deformation. This method uses cos^-1 operations to extract absolute, not signed, values of new phase after deformation. Considering the phase changes in a small local area, true phase changes retain almost the same value by assuming a continuous deformation in the area. This retention determines the sign of the new phase. From the new phase and the initial phase, the phase change distribution by the deformation can be obtained. Experimental results show the usefulness of this method.