Vapor phase hydroformylation of ethene over Co/SiO2 promoted by noble metals: dynamic in situ diffuse reflectance FT-IR study of surface species

An in situ diffuse reflectance FT-IR technique was employed to investigate the active surface species and the reaction mechanism of the oxygenate formation in the vapor phase hydroformylation of ethene on Co/SiO₂ promoted with various noble metals such as Ir, Rh, Pt, Re, Ru, and Pd. Co(A)/SiO₂ and Ir(CO)/SiO₂ which were derived from cobalt(II) acetate and Ir₄(CO)₁₂, respectively, were quite inactive in the reaction, and showed only quite small peaks of adsorbed CO under the conditions of 1.1 MPa of C₂H₄/CO/H₂ at 298 K. In contrast, Co(A)-Ir(CO)/SiO₂, which were very active in the reaction, exhibited strong absorption bands of linear and bridged CO species. At 423–463 K, propanal adsorbed on the catalyst and acyl species which is suggested as the intermediate for the formation of propanal were also observed on this catalyst. By exposing CO preadsorbed on this catalyst to C₂H₄/H₂ at 289 K and 0.1 MPa, the intensity of the linear CO band decreased, and the bands of propanal and acyl species emerged simultaneously, whereas that of the bridged CO band remained constant after the initial drop. These results suggested that the oxygenates are formed via the CO insertion into adsorbed ethyl species, and linear CO species plays a major role in the CO insertion on these noble metal-promoted cobalt catalysts.     

Cathode properties of metal trifluorides in Li and Na secondary batteries

Fluorine compounds have high discharge voltage due to its highly ionic metal-ligand bonds. In them, perovskite-type metal trifluorides with corner sharing matrix have large bottlenecks of diffusion pathways for intercalants. Iron trifluoride composites (FeF₃-C) prepared by planetary ball milling with carbon showed reversible charge/discharge behavior not only for Li, but also for Na anodes. X-ray diffraction and ⁵⁷Fe Mössbauer spectroscopy were applied to characterize the electrochemical properties of FeF₃ vs. Li and Na anodes. The cathode performances of the other commercially available transition metal trifluorides such as MF₃ (M = Ti, V, Mn, Co) have been also investigated.     

The measurement of hydrogen activities in molten copper using an oxide protonic conductor

We have developed a hydrogen sensor for in situ measurements of hydrogen activities in molten copper. The sensor consists of a concentration cell utilizing a proton conductor, CaZr_0.9In_0.1O_3-δ, as the solid electrolyte. The electromotive force (emf) of the cell was generated by both hydrogen and oxygen activity gradients across the cell in a high-temperature region simulating the fire refining processes of copper. However, accurate hydrogen activity in molten copper could be evaluated from the emf if oxygen activity in molten copper was determined simultaneously by another concentration cell and if the hydrogen and the oxygen activities at the reference electrode were known. The performance of the sensor was studied under various conditions. The observed good response and reliability of the sensor show that it should be a powerful tool for improvement of the fire refining process of the molten copper. Theoretical treatment of the calculation of the emf of the concentration cells using a mixed ionic conductor, i.e., protonic and oxide ionic conductor, as solid electrolytes is also discussed briefly.     

Symmetric lithium-ion cell based on lithium vanadium fluorophosphate with ionic liquid electrolyte

Lithium vanadium fluorophosphate, LiVPO₄F, was utilized as both cathode and anode for fabrication of a symmetric lithium-ion LiVPO₄F//LiVPO₄F cell. The electrochemical evolution of the LiVPO₄F//LiVPO₄F cell with the commonly used organic electrolyte LiPF₆/EC-DMC has shown that this cell works as a secondary battery, but exhibits poor durability at room temperature and absolutely does not work at increased operating temperatures. To improve the performance and safety of this symmetric battery, we substituted a non-flammable ionic liquid (IL) LiBF₄/EMIBF₄ electrolyte for the organic electrolyte. The symmetric battery using the IL electrolyte was examined galvanostatically at different rates and operating temperatures within the voltage range of 0.01–2.8 V. It was demonstrated that the IL-based symmetric cell worked as a secondary battery with a Coulombic efficiency of 77% at 0.1 mA cm⁻² and 25 °C. It was also found that the use of the IL electrolyte instead of the organic one resulted in the general reduction of the first discharge capacity by about 20–25% but provided much more stable behavior and a longer cycle life. Moreover, an increase of the discharge capacity of the IL-based symmetric battery up to 120 mA h g⁻¹ was observed when the operating temperature was increased up to 80 °C at 0.1 mA cm⁻². The obtained electrochemical behavior of both symmetric batteries was confirmed by complex-impedance measurements at different temperatures and cycling states. The thermal stability of LiVPO₄F with both the IL and organic electrolytes was also examined.     

Isolation, inoculation to insect host, and molecular phylogeny of an entomogenous fungus Paecilomyces tenuipes

BACKGROUND: To improve the poor prognosis of patients with advanced incurable gastric cancer, intensive chemotherapy combined with radical surgery was used. PATIENTS AND METHODS: Thirty patients with incurable gastric cancer were treated with a combination of 5-fluorouracil (370 mg/m2) and leucovorin (30 mg/person), given intravenously for five consecutive days, followed by cisplatinum (70 mg/m2) and etoposide (70 mg/m2) on days 6 and 20, delivered through a catheter placed either in the aorta with its tip at the level of the ninth thoracic vertebra or in the celiac artery. This treatment (FLEP therapy) was repeated twice every 5 weeks. Radical or palliative surgery followed chemotherapy. RESULTS: The overall response rate to the chemotherapy was 50.0% (15 of 30 patients, 95% confidence limit 0.305-0.671). Nineteen patients (15 with a partial response, three showing no change, and one with progressive disease) underwent surgery. Of these, nine underwent curative surgery and 10 palliative surgery. The median survival time was 6.5 months overall, 12.7 months for responders, and 4.7 months for nonresponders. Long-term survivors were exclusively found among patients with distant lymph node metastasis treated by curative surgery (55.6% at 5 years). CONCLUSIONS: Favorable results of this small phase II study justify a phase III trial.     

Effect of metal-sulfide additives on electrochemical properties of nano-sized Fe2O3-loaded carbon for Fe/air battery anodes

In the present study, K₂S and Bi₂S₃ were used as additives in electrolytes and electrodes, respectively. The effects of these additives on the electrochemical properties of nano-sized Fe₂O₃-loaded carbon electrodes were investigated using cyclic voltammetry (CV), galvanostatic cycling performance and scanning electron microscopy (SEM), along with electron dispersive spectroscopy (EDS). The results showed that both K₂S and Bi₂S₃ significantly reduced hydrogen evolution and benefited the Fe₂O₃-loaded carbon electrode, such as by retarding passivation and improving the discharge capacity. The effects of metal sulfide additives depended on the carbon used. For Bi₂S₃ additive, all carbons provided larger capacities than acetylene black (AB) while AB gave greater capacity than other carbons when K₂S was used.     

Male fertility in rats treated with etretinate for 4 weeks

The toxicity of Etretinate, a retinoid compound, on the male reproductive system was studied in male rats. The drug was administered for four weeks at the dose levels of 0 (control: Vehicle, Peanut oil), 5 and 25 mg/kg/day. The animals were then allowed to mate, and their male reproductive functions and organs were examined in detail. No significant changes due to toxicity were observed in male reproductive functions and organs in the 5 mg/kg/day group after the 4-week treatment. In contrast, males in the 25 mg/kg/day group showed drug-related changes in their reproductive performance (decrease of mating ability and fertility rate), testosterone blood level, sperm head counts, sperm viability and number in the caudal epididymis, organ weight and in the histopathology of their reproductive organs (atrophy of seminiferous tubules, necrosis of spermatocytes and spermatids, vacuolation of nuclei of spermatocytes and spermatids). Even though Etretinate belong to the retinoid group of compounds, the changes seen in the 25 mg/kg/day group were almost the same as those observed in Vitamin A-deficient animals. In conclusion, there is a correlation between changes due to toxicity observed for parameters of male fertility and for histopathological evaluation of the testis of rats that receiving high dose, treatment with Etretinate for 4 weeks.     

High frequency model of transformer winding

A high frequency model of transformer winding is used to analyze the voltage oscillations due to various excitations such as the very fast transient overvoltage which occurs at the time of disconnecting switch operations. Usually, a circuit of interlinked inductances and capacitances is used for this purpose, in which circuit parameters have to be properly determined. Previously, those constants have been estimated taking the coil section pair as a unit. In the method proposed here, the section pair can be further subdivided. The time‐domain calculation is conducted combining the frequency analysis and FFT technique. The voltage oscillations of the winding subjected to the lightning impulse are calculated. The correspondence with the experimental results is satisfactory. The response to a chopped impulse shows this method's applicability to high frequency analysis. Since the constants are calculated directly from the design parameters of transformer winding, this technique is particularly useful in developing and designing transformers. © 2003 Wiley Periodicals, Inc. Electr Eng Jpn, 146(3): 8–16, 2004; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.10280     

Advanced glycation end products in Alzheimer's disease and other neurodegenerative diseases

Advanced glycation end products (AGEs) have been implicated in the chronic complications of diabetes mellitus and have been reported to play an important role in the pathogenesis of Alzheimer's disease. In this study, we examined the immunohistochemical localization of AGEs, amyloid beta protein (A beta), apolipoprotein E (ApoE), and tau protein in senile plaques, neurofibrillary tangles (NFTs), and cerebral amyloid angiopathy (CAA) in Alzheimer's disease and other neurodegenerative diseases (progressive supranuclear palsy, Pick's disease, and Guamanian amyotrophic lateral sclerosis/Parkinsonism-dementia complex). In most senile plaques (including diffuse plaques) and CAA from Alzheimer's brains, AGE and ApoE were observed together. However, approximately 5% of plaques were AGE positive but A beta negative, and the vessels without CAA often showed AGE immunoreactivity. In Alzheimer's disease, AGEs were mainly present in intracellular NFTs, whereas ApoE was mainly present in extracellular NFTs. Pick's bodies in Pick's disease and granulovacuolar degeneration in various neurodegenerative diseases were also AGE positive. In non-Alzheimer neurodegenerative diseases, senile plaques and NFTs showed similar findings to those in Alzheimer's disease. These results suggest that AGE may contribute to eventual neuronal dysfunction and death as an important factor in the progression of various neurodegenerative diseases, including Alzheimer's disease.     

Influence of CRT workstation on observer's performance.

The effects of the operability of the prototype CRT workstation and room illumination upon observer's performance were studied. In the experiment of reading CT images as a routine daily work at the CRT workstation, the average time required to analyse one CT image under a room illuminance of 100 lux was longer than that on the film viewbox. Prolongation occurred due mainly to the longer time required to retrieve and to arrange images as observers desired, and the limitation to the number of images simultaneously displayed on two CRT monitors. In the ROC studies to detect small pulmonary nodules on CRT images of computed radiography with imaging plate, illuminance around 170 lux showed the best result and a statistically significant difference (P less than 0.05) as compared with that of 480 lux. In addition to the radiologist's visual performance, room illumination must also be taken into consideration as it influences the observer's performance and diagnostic efficiency.