Room-Temperature,Metal-Free,and One-Pot Preparation of 2H-Indazoles through a Mills Reaction and Cyclization Sequence

The Mills reaction and cyclization of readily available 2-aminobenzyl alcohols and nitrosobenzenes using thionyl bromide provided 2H-indazoles in up to 88 % yields. In the metal-free process, acetic acid played a crucial role for the both Mills reaction and cyclization. A brominated 2H-indazole could also be obtained through the one-pot sequence.     

Potential formation and high density plasma production on the tandem mirror GAMMA 10

GAMMA 10 experiments have advanced in high density experiments after the last EPS Workshop where we reported high density plasma production by using an ion cyclotron range of frequency heating at a high harmonic frequency and neutral beam injection in the central cell. Recently a high density plasma was obtained with much improved reproducibility than before and without degradation of diamagnetic signal. The high density plasma was attained by adjusting the spacing of the conducting plates installed in the anchor transition regions. Dependencies of particle confinement time, ion energy confinement time and plasma confining potential on plasma density were obtained for the first time in the high density region. Presented at 5th Workshop “Role of Electric Fields in Plasma Confinement and Exhaust”, Montreus, Switzerland, June 23–24, 2002.     

Non-destructive rapid analysis of brominated flame retardants in electrical and electronic equipment using Raman spectroscopy.

Using Raman spectroscopy without any preparation, we analyzed the brominated flame retardant, polybromodiphenyl ethers (PBDEs), which has been prohibited by the European Union. The typical Raman bands of PBDEs, which are clearly different from those of other brominated flame retardants, are from 100 to 300 cm(-1). In our analysis, the detection limit was about 100 ppm, and the analysis took about 1 min, whereas the usual method of solvent extraction using gas chromatography/mass spectroscopy takes 50 h.     

Novel UV‐induced photografting process for preparing poly(tetrafluoroethylene)‐based proton‐conducting membranes

A novel process comprising the UV‐induced photografting of styrene into poly(tetrafluoroethylene) (PTFE) films and subsequent sulfonation has been developed for preparing proton‐conducting membranes. Although under UV irradiation the initial radicals were mainly generated on the surface of the PTFE films by the action of photosensitizers such as xanthone and benzoyl peroxide, the graft chains were readily propagated into the PTFE films. The sulfonation of the grafted films was performed in a chlorosulfonic acid solution. Fourier transform infrared and scanning electron microscopy were used to characterize the grafted and sulfonated membranes. With a view to use in fuel cells, the proton conductivity, water uptake, and mechanical properties of the prepared membranes were measured. Even through the degree of grafting was lower than 10%, the proton conductivity in the thickness direction of the newly prepared membranes could reach a value similar to that of a Nafion membrane. In comparison with γ‐ray radiation grafting, UV‐induced photografting is very simple and safe and is less damaging to the membranes because significant degradation of the PTFE main chains can be avoided. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2624–2637, 2007     

Temporal analysis of products (TAP) study on oxygen storage properties over Pt−Rh/CeO2 catalyst

The oxygen storage capacity of CeO₂, Ce_0.9Pr_0.1O₂, Pt?Rh/CeO₂ and Pt?Rh/Ce_0.9Pr_0.1O₂ was investigated by conventional GC pulse method and transient pulse techniques. It is shown that incorporation of PrO_y into CeO₂ matrix strongly promotes oxygen storage capacity (OSC) measured using the transient pulse technique. The improvement of OSC at low temperature is observed in Pt?Rh loaded onto CeO₂ and Ce?Pr catalysts.     

The C-N Stretching Vibronic Bands of the MgNC ÃΠ-X?Σ Transition

We have generated MgNC in supersonic free jet expansions and measured the laser-induced fluorescence excitation spectra of the C-N stretching vibronic bands of the òΠ-X?²Σ⁺ transition. Rotational analysis yields the molecular constants of the vibronic levels, (1,0,0) and (1,0,1), in the Ã²Π state. We cannot find any anomalies in the constants of these vibronic levels, while they are predicted to lie above the barrier of the isomerization reaction pathway, MgNC↔MgCN, on the Ã²Π state. On the basis of the molecular constants obtained, we discuss the fine structures of both the ground X?²Σ⁺ and excited Ã²Π states.     

Bis(pentafluorophenyl) disulfide as a hydrogen abstractor and an electron acceptor from the resulting radical intermediate

The pentafluorobenzenethiyl radical is an efficient hydrogen abstractor from an activated methylene or methine group and bis(pentafluorophenyl) disulfide is an efficient electron acceptor from the resulting radical intermediate. Thus benzyl-OTBS ether was easily converted into the corresponding pinacol, and 2-phenyl-1,3-dioxanes are converted into the monobenzoates of diols.     

Strain analysis of Si by FEM and energy-filtering CBED.

Lattice strains around a platelet oxygen precipitate in Si wafer is studied by energy filtering convergent-beam electron diffraction (CBED) and calculations based on the finite element method (FEM). Local lattice strains are measured from CBD patterns obtained with a probe size less than 2 nm in a specimen thicker than 450 nm. Strains measured are compressive along a direction normal to a plate of the precipitation and tensile along a direction parallel to the plate. Two-dimensional stress fields near the precipitate are obtained with FEM computer analyses by fitting the measured strains. It appears that shear stresses are concentrated at the end of the precipitate edge and the maximum shear stress at an interface between the precipitate and the Si-matrix is 1.9 GPa. It is demonstrated that a combination of the energy filtering CBED and FEM is very useful for the study of local strains near interfaces in semiconductor devices, in particular for the study of stress fields that are too steep for application of the conventional CBED technique.     

Preparation and certification of the new reference materials; plastics (disk form, JSAC 0621-0625) for determination of mercury using x-ray fluorescent analysis.

The Japan Society for Analytical Chemistry has developed some new plastic certified reference materials (CRMs) for the analysis of mercury in polyester disks using XRF analysis. These CRMs (named as JSAC 0621-0625) were prepared by casting polyesters including a toluene solution of organometallic compounds as a standard. Concentrations of the five levels of mercury ranged from 0 to 250 mg/kg. Homogeneity tests of prepared disks had shown excellent results. Interlaboratory comparison study for the certification was performed by 15 laboratory participants. The z-scores in robust statistical method was applied for the evaluation of outliers. The certified values were assigned after discarding outliers. The uncertainties of certified values were determined as the confidence levels of 95%.     

Near-Field and Polarized Evanescent Field Excited Fluorescence of Self-Organized Particle Arrays of Organic Dye

A wetting/dewetting process was utilized to prepare self-organized organic dye particles of micrometer and submicrometer size. Near-field scanning optical microscopy successfully identified near-field excited near-field fluorescence from single particles. The majority of the small particles with diameters around 2 mm or less, however, did not show fluorescence under near-field observation. In contrast, far-field fluorescence, when excited by a polarized evanescent field, was observed, with the intensity depending on the excitation polarization, indicating that molecules' transition moment within dye particles was oriented parallel to the substrate surface. Single particle fluorescence spectrum consistently showed an identical sharp peak with a large redshift, indicating that the particles were composed of identical dye aggregates similar to J-aggregates. These observations suggest that the near-field at the probe tip was polarized parallel to the probe axis. Another observation, that molecules were oriented in a similar direction among adjacent particles, suggests that the dewetting process contributed to the alignment of the molecular direction among adjacent particles, which further proves that the present specimen was formed by a self-organizing mechanism.