Novel configurational structures of sodium tetrakis(3-heptafluorobutylryl-(+)-camphorato) Ln(III) complexes with a trapped Na+ by Na+...FC interactions in the solid state and in solution

For newly prepared sodium tetrakis(3-heptafluorobutylryl-(+)-camphorato) Ln(III) complexes, the X-ray crystal analysis revealed an unprecedented pseudo-achiral dodecahedron (DD-8 (D(2d))), whereas in CHCl3 solution, the exciton CD and 19F NMR spectra showed a novel chiral Delta-SAPR-8 (C4) configuration which is stereospecifically formed by a trapped Na+ ion with Na+...FC (fluorocarbon) interactions.     

Sequential reaction intermediates in aliphatic C-H bond functionalization initiated by a bis(mu-oxo)dinickel(III) complex

The reaction of [Ni2(OH)2(Me2-tpa)2]2+ (1) (Me2-tpa = bis(6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine) with H2O2 causes oxidation of a methylene group on the Me2-tpa ligand to give an N-dealkylated ligand and oxidation of a methyl group to afford a ligand-based carboxylate and an alkoxide as the final oxidation products. A series of sequential reaction intermediates produced in the oxidation pathways, a bis(mu-oxo)dinickel(III) ([Ni2(O)2(Me2-tpa)2]2+ (2)), a bis(mu-superoxo)dinickel(II) ([Ni2(O2)2(Me2-tpa)2]2+ (3)), a (mu-hydroxo)(mu-alkylperoxo)dinickel(II) ([Ni2(OH)(Me2-tpa)(Me-tpa-CH2OO)]2+ (4)), and a bis(mu-alkylperoxo)dinickel(II) ([Ni2(Me-tpa-CH2OO)2]2+ (5)), was isolated and characterized by various physicochemical measurements including X-ray crystallography, and their oxidation pathways were investigated. Reaction of 1 with H2O2 in methanol at -40 degrees C generates 2, which is extremely reactive with H2O2, producing 3. Complex 2 was isolated only from disproportionation of the superoxo ligands in 3 in the absence of H2O2 at -40 degrees C. Thermal decomposition of 2 under N2 generated an N-dealkylated ligand Me-dpa ((6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine) and a ligand-coupling dimer (Me-tpa-CH2)2. The formation of (Me-tpa-CH2)2 suggests that a ligand-based radical Me-tpa-CH2* is generated as a reaction intermediate, probably produced by H-atom abstraction by the oxo group. An isotope-labeling experiment revealed that intramolecular coupling occurs for the formation of the coupling dimer. The results indicate that the rebound of oxygen to Me-tpa-CH2* is slower than that observed for various high-valence bis(mu-oxo)dimetal complexes. In contrast, the decomposition of 2 and 3 in the presence of O2 gave carboxylate and alkoxide ligands, respectively (Me-tpa-COO- and Me-tpa-CH2O-), instead of (Me-tpa-CH2)2, indicating that the reaction of Me-tpa-CH2* with O2 is faster than the coupling of Me-tpa-CH2* to generate ligand-based peroxyl radical Me-tpa-CH2OO*. Although there is a possibility that the Me-tpa-CH2OO* species could undergo various reactions, one of the possible reactive intermediates, 4, was isolated from the decomposition of 3 under O2 at -20 degrees C. The alkylperoxo ligands in 4 and 5 can be converted to a ligand-based aldehyde by either homolysis or heterolysis of the O-O bond, and disproportionation of the aldehyde gives a carboxylate and an alkoxide via the Cannizzaro reaction.     

Simultaneous observation of CO isotopomer absorption by broadband difference-frequency generation using a direct-bonded quasi-phase-matched LiNbO3 waveguide

Rovibration absorption lines both of 12CO and 13CO are observed simultaneously with the output of a 2 microm broadband difference frequency generated in a direct-bonded quasi-phase-matched LiNbO3 waveguide, which is a 50 mm device with a single quasi-phase-matching period that is operated at a constant temperature. The wavelength conversion efficiency and the difference-frequency generation bandwidth reach 100%/W and 100 nm, respectively. The idler output bandwidth in the 2 microm region is obtained by group-velocity matching or phase-mismatch minimization when a 0.94 microm pump laser diode and a 1.55 microm tunable signal source are used.     

Strong resonance enhancement of a single harmonic generated in the extreme ultraviolet range

We report the demonstration of strong resonance enhancement of a single high-order harmonic in the extreme ultraviolet (XUV) region generated from the interaction of a femtosecond pulse with low-ionized In ablation. A strong 13th harmonic (61.2 nm) of Ti:sapphire laser radiation with output intensity almost two orders of magnitude higher than neighboring harmonics was observed in these studies. The high conversion efficiency of the 13th harmonic (8 x 10(-5)) is attributed to multiple collisions of electron trajectories with the origin due to multiphoton resonance with the In ion.     

Self-regulated Ni cluster formation on the TiO2(1 1 0) terrace studied using scanning tunneling microscopy

We have studied the growth mode and morphology of Ni clusters on a TiO₂(1 1 0) surface with a wide terrace using scanning tunneling microscopy (STM) at a low coverage (less than 3 atoms nm⁻²). The Ni clusters are formed on the terrace at the low coverage of 0.2 atoms nm⁻². Their average dimensions are constant in three directions up to 1 atoms nm⁻². The Ni clusters have an oval shape with average sizes of 1.8 nm (along [0 0 1]) × 1.4 nm (along (in the [1 1 0] directions). Above the coverage of 1.0 atoms nm⁻², an increase in the cluster height occurs, retaining an almost constant lateral size. It is proposed that the interaction of the Ni cluster and the support surface regulates the Ni cluster size.     

Combined volumetric T1, T2 and secular-T2 quantitative MRI of the brain: age-related global changes (preliminary results)

The combined T1, T2 and secular-T2 pixel frequency distributions of 24 adult human brains were studied in vivo using a technique based on the mixed-TSE pulse sequence, dual-space clustering segmentation and histogram gaussian decomposition. Pixel frequency histograms of whole brains and the four principal brain compartments were studied comparatively and as function of age. For white matter, the position of the T1 peak correlates with age (R2 =.7868) when data are fitted to a quadratic polynomial. For gray matter, a weaker age correlation is found (R2 =.3687). T2 and secular-T2 results are indicative of a weaker correlation with age. The technique and preliminary results presented herein may be useful for characterizing normal as well as abnormal aging of the brain, and also for comparison with the results obtained with alternative quantitative MRI methodologies.     

Turbulence kinetic energy budget in bubbly flows in a vertical duct

Understanding turbulence kinetic energy (TKE) budget in gas–liquid two-phase bubbly flows is indispensable to develop and improve turbulence models for the bubbly flows. In this study, a molecular tagging velocimetry based on photobleaching reaction was applied to turbulent bubbly flows with sub-millimeter bubbles in a vertical square duct to examine the applicability of the k–ε models to the bubbly flows. Effects of bubbles on TKE budget are discussed and a priori tests of the standard and low Reynolds number k–ε models are carried out to examine the applicability of these models to the bubbly flows. The conclusions obtained are as follows: (1) The photobleaching molecular tagging velocimetry is of use for validating turbulence models. (2) The bubbles increase the liquid velocity gradient in the near wall region, and therefore, enhance the production and dissipation rates of TKE. (3) The k–ε models can reasonably evaluate the production rate of TKE in the bubbly flows. (4) The modulations of diffusion due to the bubbles have different characteristics from the diffusion enhancement due to shear-induced turbulence. Hence, the k–ε models fail in evaluating the diffusion rate in the near wall region in the bubbly flows. (5) The k–ε models represent the trends of the production, dissipation, and diffusion rates of ε in the bubbly flow, although more accurate experimental data are required for quantitative validation of the ε equation.     

Interactions between clusters of self-interstitial atoms via a conservative climb in BCC–Fe

We conduct kinetic Monte Carlo simulations for the conservative climb motion of a cluster of self-interstitial atoms (SIAs) towards another SIA cluster in BCC–Fe; the conservative climb velocity is inversely proportional to the fourth power of the distance between them, as per the prediction based on Einstein’s equation. The size of the climbing cluster significantly affects its conservative climb velocity, while the size of the cluster that originates the stress field does not. The activation energy for the conservative climb is considerably greater than that derived in previous studies and strongly dependent on the climbing cluster size. The results presented in this study are the atomistic evaluation of the behaviour of SIA clusters through three-dimensional motion, which cannot be achieved using molecular dynamics techniques alone.     

Wavelet processing and digital interferometric contrast to improve reconstructions from X‐ray Gabor holograms

In this work, the application of an undecimated wavelet transformation together with digital interferometric contrast to improve the resulting reconstructions in a digital hard X‐ray Gabor holographic microscope is shown. Specifically, the starlet transform is used together with digital Zernike contrast. With this contrast, the results show that only a small set of scales from the hologram are, in effect, useful, and it is possible to enhance the details of the reconstruction.     

Direct structural observation of the alignment and elongation in lyotropic chromonic liquid crystals under shear flow

The structural characterization of the orientation and elongation under shear flow in Lyotropic Chromonic Liquid Crystals (LCLCs) molecules, Sunset Yellow FCF (SSY), was performed by in situ rheological small/wide angle X-ray scattering (Rheo-SAXS/WAXS). The X-ray measurement results clearly demonstrated that the stacked aggregates were oriented and elongated to the shear direction under shear flow. Further shear rate increase caused the enhancement in the orientation and elongation with the inter-aggregate distance constant, and then the structural change decreased implying the onset of the orientation saturation at high shear rates.