Photocatalytic Property and Electronic Structure of Lanthanide-based Oxysulfides

Lanthanide-based oxysulfides and sulfide, LnTaO_3.5S_0.5, Ln₁₀OS₁₄ (Ln = La, Pr, Nd, Sm) and La₄In₅S₁₃, were successively synthesized by sulfurization in a flowing H₂S. The sulfurization decreased the band-gap energies from >4 eV to <3eV, because of the formation of occupied S3p orbitals on the top of valence band. In accordance with the small band gap, the H₂ evolution from a 0.01 M Na₂S and 0.01 M Na₂SO₃ solution system was observed under irradiation of light up to >500 nm. The rate of H₂ evolution under light irradiation of >500 nm increased in the order of Ni/LaTaO_3.5S_0.5 < Ru/La₁₀OS₁₄ < Pt/La₄In₅S₁₃.     

Neoadjuvant intra-arterial chemotherapy based on chemosensitivity tests for locally invasive bladder cancer

We investigated the clinical usefulness of individualization of chemotherapeutic regimen in neoadjuvant intra-arterial chemotherapy for locally invasive bladder cancer. Anticancer drugs were selected according to the results of an in vitro chemosensitivity test (collagen matrix assay or succinic dehydrogenase inhibition test). Nine patients with locally invasive bladder cancer received 1 to 4 courses of neoadjuvant intra-arterial chemotherapy, followed by radical cystectomy. Histopathological responses in the cystectomized specimens were grade 3 in 3 cases, grade 2 in 2, grade 1b in 2 and no response in 2. Pathologically, a complete response and downstaging were observed in 3 and 4 cases, respectively. Seven of the 9 patients were alive no evidence of disease with a mean follow-up period of 38.9 months, whereas 2 patients died of metastasis within 2 years. Six of the 7 patients who showed a complete response or down staging have been free of recurrence. These findings suggest that our chemotherapeutic strategy may improve the prognosis for locally invasive bladder cancer.     

NiCoFe/C cathode electrocatalysts for direct ethanol fuel cells

A direct ethanol fuel cell (DEFC), which is less prone to ethanol crossover, is reported. The cell consists of PtRu/C catalyst as the anode, Nafion^® 117 membrane, and Ni–Co–Fe (NCF) composite catalyst as the cathode. The NCF catalyst was synthesized by mixing Ni, Co, and Fe complexes into a polymer matrix (melamine-formaldehyde resins), followed by heating the mixture at 800 °C under inert atmosphere. TEM and EDX experiments suggest that the NCF catalyst has alloy structures of Ni, Co and Fe. The catalytic activity of the NCF catalyst for the oxygen reduction reaction (ORR) was compared with that of commercially available Pt/C (CAP) catalyst at different ethanol concentrations. The decrease in open circuit voltage (V_oc) of the DEFC equipped with the NCF catalysts was less than that of CAP catalyst at higher ethanol concentrations. The NCF catalyst was less prone to ethanol oxidation at cathode even when ethanol crossover occurred through the Nafion^®117 film, which prevents voltage drop at the cathode. However, the CAP catalyst did oxidize ethanol at the cathode and caused a decrease in voltage at higher ethanol concentrations.     

Fabrication of damascene Cu wirings using solid acidic catalyst

The copper damascene process is one of the most promising technologies for fabricating Cu wirings for electronic devices such as LSIs. In this research, the fabrication of damascene Cu wirings was conducted using solid acidic catalyst. When a Cu-plated wafer, whose oxide is a basic oxide is dipped into a mixture of oxidizing solution and acidic solution, surface atoms are ionized and etched off into the solution. However, because conventional nonelectrolytic etching does not have a reference surface, it is difficult to utilize for planarization. Therefore, a new nonelectrolytic machining method using a cation-exchange fabric instead of an acidic solution was developed. To be more precise, the planarization of a Cu-plated wafer was carried out by rubbing with the cation-exchange fabric in ozone water. Basically, this method exploits chemical reactions so that the physical properties of the workpiece surface are not deteriorated. Furthermore, this method uses no chemicals except for ozone water, which easily dissociates into water and oxygen molecules; thus, this method is a low-cost, environmentally friendly process. In this paper, as a preliminary experiment, the nonelectrolytic etching of a Cu sample using solutions of O₃ and CO₂ was carried out to inspect the dependence of the etching rate on [O₃] and [H⁺]. The results indicate that the etching rate increased as [O₃] and [H⁺] increased. When [H⁺] was high relative to [O₃], a smooth etch-pit-free surface was achieved. Next, nonelectrolytic etching using a cation-exchange fabric was carried out, and properties similar to those in the case of etching using solutions were obtained. Finally, damascene Cu wirings were fabricated using ozone water and a cation-exchange catalyst.     

Catalytic hydrodechlorination of 1-chlorooctadecane, 9,10-dichlorostearic acid, and 12,14-dichlorodehydroabietic acid in supercritical carbon dioxide

Kinetic and thermodynamic analyses of catalytic hydrodechlorinations in supercritical carbon dioxide (SC-CO₂) were performed using 5% Pd supported on γ-Al₂O₃. The selected standard compounds used for the study represented chlorinated wood resins commonly found in pitch deposits; 1-chlorooctadecane (C₁₈-Cl), 9,10-dichlorostearic acid (Stearic-Cl₂), and 12,14-dichlorodehydroabietic acid (DHA-Cl₂). The reaction utilized isopropanol as a hydrogen donor. Pressure, temperature, and the concentrations of isopropanol and palladium were varied to study the effect of each parameter and to optimize the dechlorination yield. The reaction in SC-CO₂ was compared to the one in liquid solvents at atmospheric pressure. By applying a Langmuir–Hinshelwood kinetic model, the rate-determining step of the reaction was deduced to be adsorption of the chlorinated molecules on the palladium surface. The apparent activation energies of the reactions for C₁₈-Cl, Stearic-Cl₂, DHA-Cl₂ were 43±5, 40±7, and 135±7 kJ mol⁻¹, respectively, in SC-CO₂. The relatively high activation energy for DHA-Cl₂ was apparently due to structural differences from the other two compounds. The apparent activation energy of dechlorination of C₁₈-Cl in liquid isopropanol at atmospheric pressure was determined to be 35±3 kJ mol⁻¹, leading to the conclusion that the rate-determining step is the same for this compound in both fluid systems. The enthalpies of desorption of stearic acid and dehydroabietic acid were determined to be 18±2 and 12±2 kJ mol⁻¹, respectively. These values being less than half of the apparent activation energies of dechlorination of their corresponding chlorinated compounds indicates that desorption of the dechlorinated products is not the rate-determining step of the reaction. This was consistent with the conclusion that the rate-determining step is adsorption, on the understanding that the reaction mechanism is same in both fluid systems.     

Revolving Vernier Mechanism Controls Size of Linear Homomultimer

A new kind of the Vernier mechanism that is able to control the size of linear assembly of DNA origami nanostructures is proposed. The mechanism is realized by mechanical design of DNA origami, which consists of a hollow cylinder and a rotatable shaft in it connected through the same scaffold. This nanostructure stacks with each other by the shape complementarity at its top and bottom surfaces of the cylinder, while the number of stacking is limited by twisting angle of the shaft. Experiments have shown that the size distribution of multimeric assembly of the origami depends on the twisting angle of the shaft; the average lengths of the multimer are decamer, hexamer, and tetramer for 0°, 10°, and 20° twist, respectively. In summary, it is possible to affect the number of polymerization by adjusting the precise shape and movability of a molecular structure.     

Ergonomic design and evaluation of the handle for an endoscopic dissector

The purpose of this study was to design an endoscopic dissector handle and objectively assess its usability. The handles were designed with increased contact area between the fingers and thumb and the eye rings, and the eye rings were modified to have a more perpendicular insertion angle to the finger midline. Four different handle models were compared, including a conventional product. Subjects performed dissection, exclusion, grasping, precision manipulation and precision handling tasks. Electromyography and subjective evaluations were measured. Compared to conventional handles, the designated handle reduced the muscle load in the extensor and flexor muscles of the forearm and increased subjective stability. The activity of the first dorsal interosseous muscle was sometimes influenced by the shape of the other parts. The ergonomically designed endoscopic dissector handle used in this study achieved high usability. Medical instrument designs based on ergonomic concepts should be assessed with objective indices.

Practitioner Summary: The endoscopic dissector handles were designed with increased contact area and more suitable insertion angle between the fingers and thumb and the eye rings. Compared to conventional handles, the designated handle reduced the muscle load in the extensor and flexor muscles of the forearm and increased subjective stability.