Vacuum fusion determination of oxygen in gadolinium,terbium metal and iron-terbium alloy

The extraction conditions for the accurate determination of oxygen in gadolinium, terbium and iron-terbium alloy using vacuum fusion analysis were studied. The influence of the gettering effect, the analyzing temperature and the weight ratio of the bath metal to the sample were investigated. Oxygen values of gadolinium and terbium were measured by the graphite crucible, the graphite capsule, the tin bath, the iron-tin bath and the platinum-tin bath techniques in the temperature range of 1500–2100 °C using vacuum fusion analysis. These oxygen values were compared with those obtained by inert gas fusion analysis. In inert gas fusion analysis, the samples were analyzed with iron and tin in a tin capsule, and the samples with platinum in a tin capsule were analyzed in a graphite capsule enclosing with carbon powder. Oxygen values of both metal samples in the graphite capsule at 2000 °C, with an iron-tin bath at 1850 °C and a platinum-tin bath at 2000 °C in vacuum fusion analysis, were respectively in good agreement within their errors; the oxygen values of gadolinium were also in good agreement with that from inert gas fusion analysis in the iron-tin bath, but those of terbium were not in agreement. This agreement for gadolinium guarantees the reliability of the conditions for the accurate determination, and the difference of oxygen values for terbium suggests a need for further consideration on the conditions of the inert gas fusion analysis.     

Critical brush density for the transition between carpet-only and carpet/brush double-layered structures

The critical brush density, where transition from carpet-only structure to carpet/brush double-layered structure occurs, was estimated for a weakly ionic amphiphilic diblock copolymer, (diethylsilacyclobutane)34-b-(methacrylic acid)50, monolayer on water by an in situ X-ray reflectivity technique. The brush density in the monolayer was controlled from 0.11 to 0.60 brush chain/nm2 by changing surface pressure and mixing a poly(diethylsilacyclobutane) homopolymer separately synthesized. Only a carpet layer was formed at a low brush density condition, but a carpet and brush double layer was found for a higher brush density of more than 0.48/nm2. This brush density, which is fairly high, would be valuable for discussing the polyelectrolyte brush nanostructure.     

Significant reduction of on-site Coulomb energy U due to short-range correlation in an organic Mott insulator.

By carrying out a first-principles T-matrix calculation on multiple scatterings between electrons, we show that the intramolecular electron-electron interaction energy U, of a Mott insulator of the organic radical 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) is significantly reduced from the naive expectation value of the Coulomb interaction (7.3 eV and 5.3 eV, respectively, for the bare and screened Coulomb interactions) to 2.9 eV due to the short-range correlation. This result together with the intermolecular interaction energy D=1.3 eV explains the experimental optical gap (1.5 eV). The associated two-particle wavefunction clearly shows the Coulomb hole indicating that two electrons with antiparallel spins cannot approach because of the Coulomb repulsion. We also discuss the energetics and magnetics of this system.     

Direct EPR observations of both oxidized and reduced porphyrin dimers in the lowest excited states: a novel analysis of a homobiradical with a strong antiferromagnetic interaction

The oxidized and reduced forms of bis(tetra-tert-butyltetraazaporphinato)lutetium (III) (Lu(TAP)2) have been examined by time-resolved EPR (TREPR) spectroscopy, showing both the first EPR investigation of a homobiradical with a strong antiferromagnetic interaction and usefulness of TREPR for investigating excited-state properties of different oxidation states.     

Rapid detection of drugs in biofluids using atmospheric pressure chemi/chemical ionization mass spectrometry

We have demonstrated that, with simple pH adjustment, volatile drugs such as methamphetamine, amphetamine, 3,4‐methylenedioxymethamphetamine (MDMA), ketamine, and valproic acid could be analyzed rapidly from raw biofluid samples (e.g. urine and serum) without dilution, or extraction, using atmospheric pressure ionization. The ion source was a variant type of atmospheric pressure chemical ionization (APCI) that used a dielectric barrier discharge (DBD) to generate the metastable helium gas and reagent ions. The sample solution was loaded in a disposable glass pipette, and the volatile compounds were purged by nitrogen gas to be reacted with the metastable helium gas. The electrodes of the DBD were arranged in such a way that the generated glow discharge was confined within the discharge tube and was not exposed to the analytes. A needle held at 100–500 V was placed between the ion‐sampling orifice and the discharge tube to guide the analyte ions into the mass spectrometer. After pH adjustment of the biofluid sample, the amphiphilic drugs were in the form of a water‐insoluble oil, which could be concentrated on the liquid surface. By gentle heating of the sample to increase the evaporation rate, rapid and sensitive detection of these drugs in raw urine and serum samples could be achieved in less than 2 min for each sample. Copyright © 2009 John Wiley & Sons, Ltd.     

Development and application of an internet electron microscopy system for the outreach program in Japan.

The development of a remotely operated scanning electron microscopy (SEM) system and its use by high school students and the public as an outreach program are reported. The SEM and the server are located in the National Institute for Materials Science, Tsukuba, Japan, with client computers installed at a science museum and high schools. Using a secure virtual private network system and scheduling/management groupware, observation of SEM images and energy dispersive X-ray analysis are widely and frequently performed throughout Japan.     

Forbidden Triples Containing a Complete Graph and a Complete Bipartite Graph of Small Order

For a graph G and a set \({\mathcal{F}}\) of connected graphs, G is said be \({\mathcal{F}}\) -free if G does not contain any member of \({\mathcal{F}}\) as an induced subgraph. We let \({\mathcal{G} _{3}(\mathcal{F})}\) denote the set of all 3-connected \({\mathcal{F}}\) -free graphs. This paper is concerned with sets \({\mathcal{F}}\) of connected graphs such that \({\mathcal{F}}\) contains no star, \({|\mathcal{F}|=3}\) and \({\mathcal{G}_{3}(\mathcal{F})}\) is finite. Among other results, we show that for a connected graph T( ≠ K ₁) which is not a star, \({\mathcal{G}_{3}(\{K_{4},K_{2,2},T\})}\) is finite if and only if T is a path of order at most 6.     

Local chemical states and microstructure of photoluminescent porous silicon studied by means of EELS and TEM

Photoluminescent porous Si (PS) layers were formed on low resistivity p-type Si(100) wafers by anodization at a current density (Ia) of 100-350 mA cm(-2) at room temperature. The local chemical states and the microstructures of the PS layers were studied by means of electron energy loss spectroscopy (EELS) and transmission electron microscopy (TEM), and were correlated to the red photoluminescence (PL). The PS layer consists of sponge-like and tree-like structures. The tree-like structure becomes finer with increase of Ia. The fine tree-like structure is shown to be favorable for intensive PL. The EELS analysis reveals that the Si-4O structure, namely the basic structure of SiO2, and Si crystals coexist in the PS layers. The relative content of SiO2 to Si crystallites (R) increases with increase in Ia and decreases with the depth from the top surface of the PS layer. High R corresponds to intensive PL. These results suggest that PL may be connected with some kind of defects in SiO2 and/or defects in the boundary between Si crystallites and SiO2 structure in anodized PS layers, and that PL may be mainly emitted from the layer near the top surface of the PS layers.