Construction of a square-planar hydroperoxo-copper(II) complex inducing a higher catalytic reactivity

A novel hydroperoxo-copper(II) complex with a square-planar geometry has been prepared, which has exhibited a higher selectivity and catalytic reactivity for dimethyl sulfide, in contrast to that with a trigonal-bipyramidal one.     

Dispersion and Confinement Loss Control in Modified Hexagonal Photonic Crystal Fibers

This paper presents a novel technique for the control of chromatic dispersion and confinement loss in hexagonal photonic crystal fibers (H-PCFs). It is demonstrated that it is possible to obtain very low chromatic dispersion of 0 ± 0:38 ps/(nm·km) in the wavelength range of 1.41 to 1.66 μm and confinement loss of less than 0.0001 dB/km from a six ring modified H-PCF (MH-PCF). The higher order dispersion at 1.55 μm is about −0.001 ps/(nm²-km).     

Thermal and photochemical reactivity of oxygen atoms on gold nanocluster surfaces

Reduction of oxidized gold nanoclusters by exposures to foreign gases and irradiation of UV photons has been investigated using X-ray photoelectron spectroscopy. Gold nanoclusters with narrow size distributions protected by alkanethiolate ligands were deposited on a TiO₂(1 1 0) surface with dip coating. Oxygen plasma etching was used for removal of alkanethiolate ligands and oxidization of gold clusters. The oxidized gold clusters were exposed to CO, C₂H₂, C₂H₄, H₂, and hydrogen atoms. Although, C₂H₄ and H₂ did not show any indications of reduction of oxidized gold clusters, CO, C₂H₂, and hydrogen atoms reduced the oxides on gold cluster surfaces. Among them, hydrogen atoms were most effective for reduction. Irradiation of UV photons around 400 nm could also reduce the oxidized gold clusters. The photochemical reduction mechanism was proposed as follows. The photo-reduction was initiated by electronic excitation of gold clusters and oxygen atoms activated reacted with carbon atoms at the surfaces of gold clusters. Carbon species were likely absorbed in gold clusters or remained at the boundaries between gold clusters when gold clusters agglomerated during oxygen plasma exposures. As the photochemical reduction progressed, carbon atoms segregated to the surfaces of gold clusters.     

22 dB all-fiber green amplifier using Er-doped fluoride fiber

We demonstrate a 22 dB all-fiber amplifier at 546 nm using Er³⁺-doped fluoride fiber by forward upconversion pumping of a 974 nm laser diode. The gain saturation effects and the power conversion efficiency of this amplifier are investigated in detail based on gain characteristics and numerical simulations.     

Synthesis and fluorescent properties of model compounds for conjugated polymer containing maleimide units at the main chain

2,3‐Diaryl substituted maleimides as model compounds of conjugated maleimide polymers [poly(RMI‐alt‐Ar) and poly(RMI‐co‐Ar)] were synthesized from 2,3‐dibromo‐N‐substituted maleimide (DBrRMI) [R= cyclohexyl (DBrCHMI) and n‐hexyl (DBrHMI)] and aryl boronic acid using palladium catalysts. To clarify structures of conjugated polymer containing maleimide units at the main chain, ¹³C NMR spectra of 2‐aryl or 2,3‐diaryl substituted maleimides were compared with those of N‐substituted maleimide polymers. Copolymers obtained with DBrRMI via Suzuki‐Miyaura cross‐coupling polymerizations or Yamamoto coupling polymerizations were dehalogenated structures at the terminal end. This dehalogenation may contribute to the low polymerizability of DBrRMIs. On the other hand, the π‐conjugated compounds showed high solubility in common organic solvents. The N‐substituents of maleimide cannot significantly affect the photoluminescence spectra of 2,3‐diaryl substituted maleimides derivatives. The fluorescence spectra of poly(RMI‐alt‐Ar) and poly(RMI‐co‐Ar) varied with N‐substituents of the maleimide ring. When exposed to ultraviolet light of wavelength 352 nm, a series of 1,4‐phenylene‐ and/or 2,5‐thienylene‐based copolymers containing N‐substituted maleimide derivatives fluoresced in a yellow to blue color. It was found that photoluminescence emissions and electronic state of π‐conjugated maleimide derivatives were controlled by aryl‐ and N‐substituents, and maleimide sequences of copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Annealing effect on performance and morphology of photovoltaic devices based on poly(3‐hexylthiophene)‐b‐poly(ethylene oxide)

Novel block copolymers, poly(3‐hexylthiophene)‐b‐poly(ethylene oxide) (P3HT‐b‐PEO) were synthesized via Suzuki coupling reaction of P3HT and PEO homopolymers. The copolymers were characterized by NMR, gel permeation chromatography, differential scanning calorimeter, and UV–vis measurements. A series of devices based on the block copolymers with a fullerene derivative were evaluated after thermal or solvent annealing. The device using P3HT‐b‐PEO showed higher efficiency than using P3HT blend after thermal annealing. Phase‐separated structures in the thin films of block copolymer blends were investigated by atomic force microscopy to clarify the relationship between morphologies constructed by annealing and the device performance. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Continuous flame oxidation in supercritical water

Abstract

Continuous flames have been observed in Supercritical water oxidation (scWO) of isopropyl alcohol (IPA), using a vertical continuous reactor with sapphire windows and a mixing nozzle. Two types of continuous flame were confirmed: the one was long pale blue colored and the other was red short cone shaped, changing blue to red at around air ratio 2.0. The flame was strongly influenced by IPA concentration, air ratio and design of the mixing nozzle. Results for decomposition of PA are presented for IPA concentrations ranging from 600 up to 28260 ppm as TOC and initial reactor temperatures, were mostly around 490°C, at 25 MPa. Decomposition rate at steady state was over 99.9%. Experimentally measured CO₂ and O₂ concentrations at the flue gas were in good agreement with theoretically calculated values. Even for low air ratio as 1.1, high decomposition rate without CO, NO, NO₂ was achieved.     

Numerical analysis of turbulent flow separation in a rectangular duct with a sharp 180‐degree turn by algebraic Reynolds stress model

Turbulent flow in a rectangular duct with a sharp 180‐degree turn is difficult to predict numerically because the flow behavior is influenced by several types of forces, including centrifugal force, pressure‐driven force, and shear stress generated by anisotropic turbulence. In particular, this type of flow is characterized by a large‐scale separated flow, and it is difficult to predict the reattachment point of a separated flow. Numerical analysis has been performed for a turbulent flow in a rectangular duct with a sharp 180‐degree turn using the algebraic Reynolds stress model. A boundary‐fitted coordinate system is introduced as a method for coordinate transformation to set the boundary conditions next to complicated shapes. The calculated results are compared with the experimental data, as measured by a laser‐Doppler anemometer, in order to examine the validity of the proposed numerical method and turbulent model. In addition, the possibility of improving the wall function method in the separated flow region is examined by replacing the log‐law velocity profile for a smooth wall with that for a rough wall. The analysis results indicated that the proposed algebraic Reynolds stress model can be used to reasonably predict the turbulent flow in a rectangular duct with a sharp 180‐degree turn. In particular, the calculated reattachment point of a separated flow, which is difficult to predict in a turbulent flow, agrees well with the experimental results. In addition, the calculation results suggest that the wall function method using the log‐law velocity profile for a rough wall over a separated flow region has some potential for improving the prediction accuracy. Copyright © 2007 John Wiley & Sons, Ltd.