Analysis of XANES for identification of highly dispersed transition metal oxides on supports

XANES of vanadium and niobium oxide on silica or alumina have been analyzed quantitatively by a deconvolution technique. Based on the results for reference compounds, local structures of supported vanadium and niobium species were identified. The composition was estimated from difference spectra for the samples which consisted of two kinds of species.     

Preparation of Aluminum Nitride Powder from Aluminum Polynuclear Complexes

AIN powder was synthesized from aluminum polynuclear complexes. Basic aluminum chloride and basic aluminum lactate were used as the aluminum polynuclear complexes. These starting materials and glucose were dissolved in water and mixed homogeneously. AIN powder was obtained by calcining after drying and precalcining at 800°C under nitrogen gas flow. Then excess carbon was removed by firing in air. Nitridation in the system was investigated and compared with that in the alumina–carbon black system. It was found that in our reaction system nitridation began and proceeded at lower calcination temperatures above 1200°C than in the alumina–carbon black system. Using aluminum polynuclear complexes, AIN was synthesized through the nitridation of γ-alumina and produced in a very fine and sharp particle size distribution.     

An Application of Silica‐Based Monolithic Membrane Emulsification Technique for Easy and Efficient Preparation of Uniformly Sized Polymer Particles

Summary: Uniformly sized polymer particles were prepared by an emulsification and polymerization technique utilizing a silica monolithic membrane, namely the “silica monolithic membrane emulsification technique”. In this paper, we utilized silica monolithic membrane as a device for the preparation of uniformly sized polymer particles. A mixture of monomers, diluents and oil‐soluble initiator was emulsified into a continuous medium through the silica monolithic membrane and polymerized. The particles obtained had a higher size uniformity than that of particles prepared by previously reported membrane emulsification techniques, such as the Shirasu Porous Glass (SPG) emulsification technique. Through the silica monolithic membrane emulsification technique, we could prepare particles having availability as a possible packing material for solid‐phase extraction (SPE) and high performance liquid chromatography (HPLC).

SEM photograph of silica particles prepared through capillary plate membrane.     

Effect of chloride ions on leaching rate of chalcopyrite

The effect of chloride on chalcopyrite leaching has been investigated by performing batch leaching tests with three kinds of leaching solutions and using Hiroyoshi’s model, which suggests that a zone of rapid leaching exists between the critical potential (E_c, equilibrium redox potential for the reduction of CuFeS₂ to Cu₂S) and the oxidation potential (E_ox, equilibrium redox potential for the oxidation of Cu₂S). The results of the leaching tests show that the leaching rate in hydrochloric acid solution is the fastest and that the relationship between the Cu leaching rate and oxidation–reduction potential (ORP) follows Hiroyoshi’s model. Thermodynamic calculations indicate that, with an increase in the chloride concentration, the concentration of cuprous ions increases as the chlorocuprate(I) complex ions are formed and the contribution of cuprous ions to the critical potential is greater than that of cupric ions, even though the concentration of cuprous ions is lower than that of cupric ions. This fact suggests that the formation of chlorocuprate(I) ions in a chloride solution may improve the chalcopyrite leaching rate by increasing the critical potential.     

Increased expression of thioredoxin/adult T-cell leukemia-derived factor in cisplatin-resistant human cancer cell lines

Thioredoxin (TRX) is a widely distributed Mr 13,000 protein with a redox-active dithiol/disulfide in the active site. The TRX system, consisting of TRX, TRX reductase, and NADPH, has an intracellular reducing capacity. Another reducing capacity, glutathione (GSH), can be associated with cis-diaminedichloroplatinum (cDDP) resistance. Therefore, we examined the involvement of TRX in cDDP resistance using two cell lines designated St/DDP and HT/DDP, which were established from the human gastric cancer cell line St-4 and the colon cancer cell line HT-29. St/DDP and HT/DDP were seven and five times as resistant to cDDP as their parental lines, and the expression of TRX in these variants was increased by 2.5- and 2-fold, respectively. The expression of TRX in the complete revertant cells of St/DDP was reduced as low as that in St-4 cells. TRX reductase activity was also increased in St/DDP and HT/DDP, suggesting that activation of the TRX system was associated with in vitro-acquired cDDP resistance. Because cDDP is the first-line drug against ovarian cancer, we examined the expression of TRX in 11 human ovarian cancer cell lines not treated with cDDP in vitro. Positive correlation between TRX expression and cDDP resistance was observed in these cell lines (r = 0.76, P = 0.007). This correlation was comparable to that between GSH content and cDDP resistance (r = 0.69, P = 0.019). These results suggest a possible involvement of TRX, as well as GSH, in cDDP resistance.     

Simple and comprehensive two-dimensional reversed-phase HPLC using monolithic silica columns

Simple and comprehensive two-dimensional (2D)-HPLC was studied in a reversed-phase mode using monolithic silica columns for second-dimension (2nd-D) separation. Every fraction from the first column, 15 cm long (4.6-mm i.d.), packed with fluoroalkylsilyl-bonded (FR) silica particles, was subjected to the separation in the 2nd-D using one or two octadecylsilylated (C(18)) monolithic silica columns (4.6-mm i.d., 3 cm). Monolithic silica columns in the 2nd-D were eluted at a flow rate of up to 10 mL/min with separation time of 30 s that meets the fractionation every 15-30 s at the first dimension (1st-D) operated at a flow rate of 0.4-0.8 mL/min. Three cases were studied. (1) In the simplest scheme of 2D-HPLC, effluent of the 1st-D was directly loaded into an injector loop of 2nd-D HPLC for 28 s, and 2 s was allowed for injection. (2) Two six-port valves each having a sample loop were used to hold the effluent of the 1st-D alternately for 30 s for one 2nd-D column to effect comprehensive 2D-HPLC without the loss of 1st-D effluent. (3) Two monolithic silica columns were used for 2nd-D by using a switching valve and two sets of 2nd-D chromatographs separating each fraction of the 1st-D effluent with the two 2nd-D columns alternately. In this case, two columns of the same stationary phase (C(18)) or different phases, C(18) and (pentabromobenzyloxy)propylsilyl-bonded (PBB), could be employed at the 2nd-D, although the latter needed two complementary runs. The systems produced peak capacity of approximately 1000 in approximately 60 min in cases 1 and 2 and in approximately 30 min in case 3. The three stationary phases, FR, C(18), and PBB, showed widely different selectivity from each other, making 2D separations possible. The simple and comprehensive 2D-HPLC utilizes the stability and high efficiency at high linear velocities of monolithic silica columns.     

Enhanced path smoothing based on conjugate gradient descent for firefighting robots in petrochemical complexes*

The firefighting robot system (FFRS) comprises several autonomous robots that can be deployed to fire disasters in petrochemical complexes. For autonomous navigation, the path planner should consider the robot constraints and characteristics. Specifically, three requirements should be satisfied for a path to be suitable for the FFRS. First, the path must satisfy the maximum curvature constraint. Second, it must be smooth for robots to easily execute the trajectory. Third, it must allow reaching the target location in a specific heading. We propose a path planner that provides smooth paths, satisfy the maximum curvature constraint, and allows a suitable robot heading. The path smoother is based on the conjugate gradient descent, and three approaches are proposed for this path planner to meet all the FFRS requirements. The effectiveness of these approaches is qualitatively and quantitatively evaluated by examining the generated paths. Finally, the path planner is applied to an actual robot to verify the suitability of the generated paths for the FFRS, and planning is applied to another type of robot to demonstrate the wide applicability of the proposed planner.     

Peel Test Using Nonstationary Peel Method

The cohesive peel spectra of pressure-sensitive adhesive (PSA) tapes have been measured using a non-stationary peel tester. The experimental evidence and a viscoelastic analysis based on a peel model indicate that there are no significant effects of acceleration in the normal rate region. The nonstationary peel tester can be regarded as a useful tool for testing and evaluating PSA tapes.     

In Situ Observation of Deformation in Semi-solid Fe-C Alloys at High Shear Rate

Synchrotron X-ray radiography at 125 frames per second was used to study deformation mechanisms in semi-solid Fe-C alloys at high solid fraction and shear strain rates of 10^?1/s. An image correlation approach was also used to quantify the shear strain fields and study shear-induced dilation and the origin of shear cracking. It was shown that, at high solid fraction (90 to 93 pct solid), rearrangement including rotation and translation of solid particles became restricted and shear strain localized into narrow liquid-filled channels/fissures. Shear cracking was shown to originate from inadequate liquid flow into the expanding spaces between solid particles caused by shear-induced dilation. At lower solid fraction (~85 pct solid), solid particles rearranged with a significantly higher component of rotation leading to more shear-induced dilation and a wider shear band.     

XPS and IR study of electrochemically or chemically redoped poly(3-methylthienylene) films

XPS (X-ray photoemission spectroscopy) and IR (infrared) analyses of poly(3-methylthienylene) films, electrochemically or chemically redoped0 with various chemical species at varying doping levels, have been investigated. On the basis of these results, the major chemical species of dopants have been identified. As a results, the dopant content was determined and the poly(3-methylthienylene) films were classified as light or heavy by doping level. The conductivity ranged from about 10^?12 to 10₂ S cm^?1 for all the films investigated. The conductivity and the activation energy of conduction for the heavily-doped films vary as a function of the dopant content, independent of the different chemical species of dopants. In particular, a sudden change is observed in the dependence of activation energy on dopant content. This sudden change may be associated with the semi-conductor-metal transition. Furthermore, it is shown that the specific absorption bands in the infrared are induced by the doping, intensified with increasing dopant uptake and accompanied by an increase in conductivity.