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.     

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.     

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.     

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     

Three cases of Gitelman's syndrome possibly caused by different mutations in the thiazide-sensitive Na-Cl cotransporter

Three adult Japanese cases of Gitelman's syndrome were characterized by secondary aldosteronism, hypokalemic alkalosis, hypomagnesemia, and hypocalciuria. Two were revealed to be familial cases. A mutation in the thiazide-sensitive Na-Cl cotransporter gene, which had already been confirmed in one family (Takeuchi et al. J Clin Endocrinol Metab 81: 4496,1996), was not detected in the other two cases. These observations may possibly support the previous report (Simon et al. Nature Genet 12: 24, 1996) that Gitelman's syndrome is caused by a variety of mutations in the thiazide-sensitive Na-Cl cotransporter.     

Alternation in the coronary blood flow velocity pattern in patients with no reflow and reperfused acute myocardial infarction

1. The effects of fluvastatin, a new 3-hydroxy-3-methylglutaryl coenzyme A (HMG-CoA) reductase inhibitor, on the vascular angiotensin converting enzyme (ACE) activity in hyperlipidaemic rabbits were compared with those of enalapril, an ACE inhibitor. 2. Rabbits were fed a 1.5% cholesterol containing diet or normal diet for 16 weeks and treated with either fluvastatin or enalapril in the diet at the respective doses of 2 and 10 mg kg-1 day-1. The total cholesterol, triglyceride and phospholipid levels in serum were significantly increased in rabbits fed the high cholesterol diet. Treatment with fluvastatin but not enalapril resulted in a decrease in serum lipids. 3. The vascular ACE activities assessed via the cleavage rate from synthetic substrate in the aortic arches and upper thoracic aortae were increased by 8 to 10 times when the rabbits were made hyperlipidaemic. Fluvastatin as well as enalapril significantly lowered the tissue ACE in the aortae. 4. The ACE activities in serum did not alter in hyperlipidaemic rabbits either in the presence or absence of fluvastatin. The serum ACE activity was lowered by enalapril. 5. The lipid peroxide in serum as well as the plaque area in the thoracic aorta was significantly increased in the cholesterol diet-fed rabbits. Treatment with fluvastatin or enalapril reduced both serum lipid peroxide and plaque formation. The relaxant responses to acetylcoholine (ACh) were significantly suppressed in the cholesterol-fed rabbits. Treatment with fluvastatin or enalapril significantly reversed the suppression of ACh-induced relaxation. 6. It seems that the reduction of vascular ACE is not coupled to lipids and ACE activity in serum, but rather to lipid peroxidation. Thus, the decrease in vascular ACE activity by fluvastatin as well as the lipid-lowering effect may reduce the risk of atherosclerosis progression in the vasculature.     

A New Lead Identification Strategy: Screening an sp3-rich and Lead-like Compound Library Composed of 7-Azanorbornane Derivatives

Although the advantages of sp³-rich, sterically complicated molecules in drug development have been pointed out, modern screening libraries are filled with planar, sp²-rich components. Compounds that are sp³-rich are difficult to synthesize, and thus we aimed to invent an efficient method to construct sp³-rich libraries. By modifying sp³-rich 7-azanorbornane scaffolds through click chemistry, we efficiently prepared a small set of compounds. These compounds were not only sp³-rich, but also had sufficient “lead-like” properties in view of molecular weights and hydrophobicity. Screening assays of this library provided weak κ opioid receptor agonists and growth hormone secretagogue receptor agonists with high hit rates. These results indicate that the 7-azanorbornane scaffold may be a “privileged structure” for lead identification in drug discovery.     

Cross-layer selective routing for cost and delay minimization in IEEE 802.11ac wireless mesh network

Wireless Networks - A Wireless Internet-access Mesh NETwork (WIMNET) provides scalable and reliable internet access through the deployment of multiple access points (APs) and gateways (GWs). In...