Infrared vibrational autodetachment spectroscopy of microsolvated benzonitrile radical anions

Vibrational spectra of microsolvated benzonitrile radical anions (C6H5CN- -S; S = H2O and CH3OH) were measured by probing the electron detachment efficiency in the 3 microm region, representing resonance bands of autodetachment via OH stretching vibrations of the solvent molecules. The hydrogen-bonded OH band for both the cluster anions exhibited a large shift to the lower energy side with approximately 300 cm-1 compared to those for the corresponding neutral clusters. The solvent molecules are bound collinearly to the edge of the CN group of the benzonitrile anion in the cluster structures optimized with the density functional theory, in which the simulated vibrational energies are in good agreement with the observed band positions. Natural population analyses were performed for a qualitative implication in changes of solvent orientation upon electron attachment. Asymmetric band shapes depending on the vibrational modes are discussed with respect to dynamics of the autodetachment process from a theoretical aspect incorporated with density functional calculations.     

A new technique to examine individual pollutant particle and fibre deposition and transit behaviour in live mouse trachea

During respiration, particles suspended in the air are inhaled and unless cleared by airway defences they can remain and affect lung health. Their size precludes the use of standard imaging modalities so we have developed synchrotron phase-contrast X-ray imaging (PCXI) methods to non-invasively monitor the behaviour of individual particles in live mouse airways. In this study we used these techniques to examine post-deposition particle behaviour in the trachea. PCXI was used to monitor the deposition and subsequent behaviour of particles of quarry dust and lead ore; fibres of asbestos and fibreglass; and hollow glass micro-spheres. Visibility was examined in vitro and ex vivo to avoid the complicating effects of surrounding tissue and respiratory or cardiac motion. Particle behaviour was then examined after deposition onto the tracheal airway surfaces of live mice. Each particle and fibre looked and behaved differently on the airway surface. Particles lodged on the airway shortly after deposition, and the rate at which this occurred was dependent on the particle type and size. After the live-imaging experiments, excised airway samples were examined using light and electron microscopy. Evidence of particle capture into the airway surface fluids and the epithelial cell layer was found. PCXI is a valuable tool for examining post-deposition particulate behaviour in the tracheal airway. These first indications that the interaction between airways and individual particles may depend on the particle type and size should provide a novel approach to studying the early effects of respired particles on airway health.     

Degradation characteristics of YBCO coated conductors due to fault-current in power cable applications

In high temperature superconductor applications used in electric power devices, YBCO coated conductors may be subjected to short-circuit fault-currents that are 10–30 times the normal operating current. These over-currents cause heat generation, resulting in I_c degradation of the YBCO coated conductor. Therefore, it is necessary to fully investigate the degradation characteristics of YBCO coated conductors. We previously conducted preliminary experiments on the degradation of YBCO sample tapes resulting from the over-current pulse drive.     

Insights into adsorption of uncharged macrocyclic complexes into a Nafion Film: Adsorption characteristics and analysis of tetraphenylporphyrine zinc(II)

Tetraphenylporphine zinc(II) (ZnTPP) was found to be adsorbed from its CH2Cl2 solution into a Nafion (Nf) film. The characteristics of the adsorption of ZnTPP into the Nf film were studied using a visible absorption spectroscopic technique. The initial rate (v0, mol cm(-2) s(-1)) for uptake of ZnTPP was saturated with increasing ZnTPP concentration (c0, M) in the solution. This kinetic profile was analyzed in terms of a Michaelis-Menten model considering preequilibrium of ZnTPP adsorption between the solution and the outer layer of the Nf film, followed by diffusion to an inner bulk region, giving a maximum diffusion reflux of v(max) = (2.2 +/- 0.2) x 10(-13) mol cm(-2) s(-1). This is different from the kinetics for the Nf/phthalocyanine zinc(II) (ZnPc) film, which gives a linear plot of v(0) vs c(0). This can be explained by the relatively slow diffusion of ZnTPP in the film compared to that of ZnPc because of steric factors: ZnTPP contains bulky tetraphenyl moieties attached perpendicular to a porphyrin ring, whereas ZnPc has higher planarity. The isotherm for the adsorption of ZnTPP into the Nf film was analyzed using a Langmuir isotherm equation, yielding an equilibrium constant of (3.6 +/- 1.1) x 10(6) M(-1) and a saturated amount of adsorbed ZnTPP of (1.8 +/- 0.1) x 10(-9) mol cm(-2), suggesting monolayer adsorption of ZnTPP on the hydrophobic polymer network interfacial with hydrophilic transport channels without significant intermolecular overlap. This is in contrast to the multilayer adsorption mode suggested for the ZnPc adsorption. The tetraphenyl moieties could prevent the stacking of ZnTPP for multilayer adsorption.     

Global tuning of local molecular phenomena: an alternative approach to bionanoelectronics

We have applied simultaneous horizontal and vertical bias to a single molecule (2 nm(2)) in an ordered and disordered matrix to virtually isolate and tune its property without taking it out physically from its environment. Using a dedicated electrode system, we have locally tuned nanoscale properties vertically by STM, while stabilizing its environment by applying a global electric field horizontally. Using this technique, we report tuning of molecular conformations in room temperature, whose evolution of states has been statistically investigated. We have also shown control on switching of a few selected conformations by applying dual bias simultaneously. As we avoid any direct injection of charge into the system via electrode contact, this technique could be used as a generalized method to tune phenomena evolved in an environment of weak interaction from a large distance without destroying the property.     

Master-oscillator power-amplifier scheme for efficient green-light generation in a planar MgO:PPLN waveguide

We developed a new master-oscillator power-amplifier scheme consisting of a tapered semiconductor amplifier and a fiber-grating-stabilized laser diode for efficient green-light generation in a planar MgO:PPLN waveguide, and demonstrated cw green-light generation of 346 mW.     

Diode-pumped 65 fs Kerr-lens mode-locked Yb(3+):Lu(2)O(3) and nondoped Y(2)O(3) combined ceramic laser

Diode-pumped Kerr-lens mode-locked laser operation of Yb(3+):Lu(2)O(3) and nondoped Y(2)O(3) combined ceramics has been achieved; 65 fs pulses with an average power of 320 mW under 5 W of pump power were obtained at the center wavelength of 1032 nm. The spectral bandwidth and the time bandwidth product were 18.9 and 0.345 nm, respectively. To our knowledge, this is the first demonstration of a Kerr-lens mode-locked laser operation based on Yb(3+):Lu(2)O(3) ceramic.     

CaCrO3: an anomalous antiferromagnetic metallic oxide

Combining infrared reflectivity, transport, susceptibility, and several diffraction techniques, we find compelling evidence that CaCrO3 is a rare case of a metallic and antiferromagnetic transition-metal oxide with a three-dimensional electronic structure. Local spin density approximation calculations correctly describe the metallic behavior as well as the anisotropic magnetic ordering pattern of C type: The high Cr valence state induces via sizable pd hybridization remarkably strong next-nearest-neighbor interactions stabilizing this ordering. The subtle balance of magnetic interactions gives rise to magnetoelastic coupling, explaining pronounced structural anomalies observed at the magnetic ordering transition.