Hierarchy in optical near-fields based on compositions of nanomaterials

Optical near-field interactions exhibit hierarchical responses in the nanometer scale allowing unique functions in nanophotonic systems. Such hierarchical properties in optical near-fields originate various physical entities in the nanometer scale. Engineering nanomaterial compositions, while maintaining geometrically equivalent conditions, leads to characteristic hierarchical responses. We experimentally demonstrate such material-dependent optical near-field hierarchy using core–shell-type nanostructures composed of gold and silver.     

Micromachining and surface processing of the super-hard nano-polycrystalline diamond by three types of pulsed lasers

Laser beam micromachining was applied to super-hard nano-polycrystalline diamond (NPD) synthesized by the direct conversion of graphite at high pressure and high temperature. Three types of pulsed lasers were tested: nanosecond near-infrared, nanosecond near-ultraviolet, and femtosecond near-infrared lasers. The latter two were also applied for synthetic single crystal of diamond to compare the results with those of the NPD. It was demonstrated that the nanosecond near-infrared laser was the most efficient device for rough shaping of the NPD, while the ultraviolet and femtosecond lasers give satisfactory results for precise surface finishing of it. The properties of the laser-processed surfaces were analyzed by scanning and transmission electron microscopy, laser scanning microscopy, and micro Raman spectroscopy. These analyses demonstrated that the three types of lasers play different and complementary roles, and that their combination is the best suitable solution for micromachining of the hardest diamond into any desired shapes.     

Morphology and size dependence of silver microstructures in fatty salts-assisted multiphoton photoreduction microfabrication

The morphology and size dependence of silver microstructures in a novel microfabrication process, fatty salts-assisted multiphoton photoreduction (MPR), were investigated by using the fatty salts with different carbon chain lengths (C _n : n=4,5,7,9) under varied powers and irradiation times of a femtosecond near-infrared laser with the wavelength of 800 nm. Not only the feature size of the silver structures was reduced but also the surface smoothness was improved by increasing the chain length of the fatty salts. The highest resolution of a silver line was obtained to be 285 nm, which exceeded the diffraction limit. The fatty salts-assisted MPR microfabrication approach would provide an efficient protocol for fabricating metallic micro/nanostructures with fine morphology and size and could play an important role in the fabrication of the metallic micro/nanostructures for applications in photonics and electronics as well as in sensors.     

The Weight-Bearing Rate on the Paretic Limb of Cerebrovascular Hemiplegic Patients Necessary for an Independent Obstacle Negotiation Gait

Purpose: The obstacle negotiation gait (ONG) is a fundamental activity of daily living. In cerebrovascular hemiplegic patients (stroke patients), the weight-bearing rate (WBR) on the paretic limb necessary for an independent ONG was studied. Methods: One hundred and seventeen stroke patients were involved. The patients'' average age at the time of the study was 67 years, and the average time from stroke onset was 102 days. There were 68 men and 49 women. Seventy patients were right hemiplegics, and 47 were left hemiplegics. The correlations between ONG and age, sex, body mass index (BMI), time from stroke onset, muscle strength of both the paretic and non-paretic limbs, Brunnstrom stage of the lower limbs, deep sensation, and the WBR on both the paretic and non-paretic limbs were studied. Patients who could perform ONG independently and safely were categorized as the independent group (IG), and those who needed observation or any assistance were categorized as the dependent group (DG). Results: The BMI, muscle strength of both the paretic and non-paretic limbs, Brunnstrom stage of the lower limbs, deep sensation and the WBR for both the paretic and non-paretic limbs were significantly different between the IG and DG groups. In particular, the WBR on the paretic limb was found to correlate significantly with the ONG, and a WBR value of 80.5% on the paretic limb gave a clear cut-off value. Conclusion: Although multiple factors influenced the ONG of stroke patients, the WBR on the paretic limb was the most influential.     

Visualization of space charge field effect on excitons in a GaAs quantum dot by near-field optical wavefunction mapping

Near-field photoluminescence (PL) imaging spectroscopy was used to investigate multi-exciton and charged-exciton states confined in a single GaAs interface fluctuation quantum dot. We determined the origin of peaks in the PL spectra by employing a wavefunction mapping technique. We observed distortion of the exciton wavefunction due to the electric field produced by an excess electron at a nearby confined state. Near-field wavefunction mapping was demonstrated to be a powerful tool for visualizing the local environment, which affects the emission properties of quantum dots.     

CpCo(dithiolene) complexes of highly flexible oxddt ligand with two different Z-shaped and U-shaped structures

[CpCo(oxddt)] complex (2, oxddt = o-xylenediyldithioethylene-1,2-dithiolate, Cp = η⁵-cyclopentadienyl) was obtained from o-xylenediyldithioethylene-1,3-dithiol-2-one (OC(oxddt)) (1). 2 further reacted with diazoalkanes (N₂CHR) to form some alkylidene-bridged adducts [CpCo(CHR)(oxddt)] (R = H (3a), SiMe₃ (3b)). Adduct 3a further reacted with protic acids (HX) to give some S-methylated adducts [CpCo(X)(oxddt)(S-Me)] (X = Cl (4a), OCOCF₃ (4c)), followed by the Co-C bond cleavage in the three-membered cobaltathiirane ring. Two different Z-shaped and U-shaped molecular structures were observed by X-ray diffraction studies. In the former structure (Z), the dithiolene and o-xylylene planes are located at almost parallel position each other, and in the latter structure (U), both planes are not parallel but the o-xylylene moiety is located closer to the dithiolene plane than the Z-shaped one. The Z-shaped structure involves 1 and 2. The U-shaped structure involves 3a, 3b, 4a and 4c. Complex 1 showed a one-dimensional chain through intermolecular π-π interaction in the crystal. Complex 2 had a dimeric interaction between dithioethylenedithiolate moieties (S₂C₂S₂) in the oxddt. The SiMe₃ group in 3b was placed at an exo-position with respect to the cobaltadithiolene ring due to a steric hindrance from the U-shaped oxddt ligand. In 4a, the X and Me groups are located at the opposite side of the dithiolene plane (anti-form) but in 4c, both groups are presented at the same side of the dithiolene plane (syn-form). The NMR analysis of 4a in solution indicated existence of both anti- and syn-isomers (7:1).     

An anion-exchange chromatographic study on boron isotopic fractionation at 2 MPa at 293 K

To study boron isotopic fractionation at high pressure, column chromatography operated in the breakthrough manner was performed at 2.0 MPa at 25.0 degrees C. The fractionation factor (S) between boron adsorbed onto strongly basic anion-exchange resin and boron in solution was obtained as 1.013, which was smaller than the values at 0.1 MPa (atmospheric pressure) found in literature. The pressure dependence of S was discussed based on the polymerization of boron in the solution and resin phases and on the occurrence of the pressure dependent isotope effect relating to the molar volume changes of boron species upon isotope substitution.     

Selective synthesis of 2-pyridones and pyrimidine-2,4-diones by neutral rhodium(I) complex-catalyzed cyclocotrimerization of alkynes and isocyanates

A neutral rhodium(I) complex, ‘RhCl(PPh₃)₂’ generated by the combination of [RhCl(C₂H₄)₂]₂ with a fourfold amount of PPh₃, effectively catalyzed the cyclocotrimerization of alkynes (1) and isocyanates (2) to give 2-pyridones (3) and/or pyrimidine-2,4-diones (4), selectively, by controlling the molar ratio of alkynes (1) and isocyanates (2).     

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.     

Evaluation of left ventricular function with cardiac magnetic resonance imaging using Fourier fitting

The aims of this study were to investigate the applicability of Fourier fitting in the magnetic resonance (MR) evaluation of left ventricular (LV) function and to determine the optimal number of harmonics for fitting. Cine cardiac MR imaging was performed in 10 subjects, and an LV time–volume curve was generated. Fourier fitting was applied to the original curve using 1–10 harmonics, and the qualities of the time–volume curve and first-derivative curve were evaluated. LV functional parameters were calculated from curves generated with and without fitting. The quality of the original time–volume curve was good, and Fourier fitting had no substantial effect on functional parameters obtained directly from the time–volume curve such as ejection fraction. The first-derivative curve generated without fitting showed substantial artificial fluctuation. The application of Fourier fitting depressed the fluctuation and tended to decrease estimates of peak ejection rate and peak filling rate. Five or six harmonics appeared to be appropriate for obtaining a high-quality first-derivative curve. In conclusion, Fourier fitting was indicated to aid in reducing the artificial fluctuation of the first-derivative curve generated from cine cardiac MR imaging and to contribute to the evaluation of functional parameters derived from the first-derivative curve.