Redox properties of CeO2 and Pt-Rh/CeO2 studied by TAP method

Redox properties of CeO₂ and Pt-Rh/CeO₂ were studied by temporal analysis of products (TAP) method using alternative pulses of CO and O₂. A portion of pulsed CO was oxidized to CO₂ and a portion of CO was adsorbed on the surface. Pulsing ¹⁸O₂ onto the catalyst which has surface species derived from CO, evolved CO₂ contained no ¹⁸O suggesting that the surface species will be carbonate ions.     

An ellipsometric study of anodic passivation of nickel in borate buffer solution

Ellipsometric and electrochemical measurements of the anodic passivation and secondary passivation films on nickel in borate buffer solution at pH 8·42 were made. The reference bare surface, obtained by cathodic reduction of electropolished nickel, gives the optical constants N₃ = 1·65?3·81 i for nickel. In the passivity region, where a little dissolution of nickel occurs, the surface film has the optical constants N₂ = 2·7?0·25 i and the film thickness as estimated by ellipsometry increases linearly with rise of the potential, from 4 to 13 Å, which is in fairly good agreement with the coulometrically estimated film thickness. In the oxygen evolution region, secondary passivation occurs with an abrupt increase in both optical constants and thickness of the surface film.The anodic passivation of nickel is compared with that of iron in terms of thickness of the surface film as a function of potential.     

Preparation and rate capability of Li4Ti5O12 hollow-sphere anode material

Spinel lithium titanate, Li₄Ti₅O₁₂, with novel hollow-sphere structure was fabricated by a sol–gel process using carbon sphere as template. The effect of the hollow-sphere structure as well as the wall thickness on the Li storage capability and high rate performance was electrochemically evaluated. High specific capacity, especially better high rate performance was achieved with this Li₄Ti₅O₁₂ hollow-sphere electrode material with thin wall thickness. It is believed that this macroporous hollow-sphere structure has shortened the Li diffusion distance, increased the contact area between Li₄Ti₅O₁₂ and electrolyte, and also led to better mixing of the active material with AB. All these factors have resulted in the good rate capability of the hollow-sphere structured Li₄Ti₅O₁₂ electrode material.     

Recent progress in the development of visible light-driven powdered photocatalysts for water splitting

Many photocatalyst materials for water splitting have been developed, particularly since the second half of the 1990s. Highly efficient water splitting on tantalate photocatalysts under UV irradiation has been achieved. Moreover, band engineering by doping, valence band formation, and synthesis of solid solutions, has led to the development of a large number of visible light-driven photocatalysts for _H2${\mathrm{H}}_2$ or _O2${\mathrm{O}}_2$ evolution from aqueous solutions containing electron donors or acceptors. Z-scheme photocatalyst systems for water splitting to _H2${\mathrm{H}}_2$ and _O2${\mathrm{O}}_2$ under visible light irradiation have been developed. This progress in the development of visible light-driven photocatalysts for water splitting is reviewed.     

吲哚荷尔蒙自由基脉冲辐解光谱及其酸基平衡和还原电位性质研究

The Absorption spectral, acid-base equilibrium potential properties and formation and decay kinetics of four kinds of radicals from natural existing indole hormones were studied by pulse radiolysis.One of the most important properties for these four indolyl hormones, melatonin, 5-methoxygramine (MTA),5-methoxy-N, N-dimethylthytrytamine (DMM TA) and 5-methoxy-N, N-diethylthytrytamine (DEMT A), which are involved in biochemical processes and play crucial roles in many neuropathy and cancer related diseases, is their facile one electron oxidation with formation of radical cations or their conjugated base, the indolyl radicals.Formation kinetics and properties of the radicals were investigated by pulse radiolysis using the Linac accelerator with fast time-resolving optical system in UTNL.In the present study, these radicals were generated through oxidation of the corresponding hormone with azide radical in radiation induced process. Their spectroscopic properties were investigated and it was found that the transient spectra in all these cases exhibit similar absorption and pH dependence: in acidic solution, the radicals are characterized with three absorption maxima around 320-350, 440-460, 520-550nm. The spectra of MTA at various pH were shown as an example. From the absorption changes as a function of pH, two pK values were determined to be around 5 and 9 for the indolyl radicals except for melatonin, in which, only one pK was distinguished to be 4.4. Formation kinetics of the radicals was measured by following the growth of their absorption peaks and it was found that these indolyl derivatives transfer an electron to N3, with different rate constants, i.e.1.2×1010, 4.5×109, 4.9×109, 1.6×109 dm3 mol-1 s-1 for melatonin, MTA, DMMTA, and DEMTA, respectively.Reduction potentials of the radicals vs their molecules were also determined and they are dependent on the pH of medium. At pH 7, the reduction potentials were estimated to be 1.10, 1.18, 1.18, 1.20eV for melatonin, MTA,DMMTA and DEMTA, respectively. Because of its relatively high contents in human brain cells, melatonin is the main antioxidant among hormones against the oxidizing species in brain cells.     

Asymmetric Epoxidation of α,β‐Unsaturated Aldehydes in Aqueous Media Catalyzed by Resin‐Supported Peptide‐ Containing Unnatural Amino Acids

The enantio‐ and diastereoselective epoxidation of α,β‐unsaturated aldehydes in aqueous media was realized using a resin‐supported peptide catalyst. Introducing the hydrophobic and bulky unnatural amino acid 3‐(1‐pyrenyl)alanine into the peptide sequence was effective for enhancing the reaction rate and enantioselectivity.     

Antibacterial action on pathogenic bacterial spore by green tea catechins

Antibacterial effects of catechins, the major green tea polyphenols, were studied using Clostridium and Bacillus spores. Incubation with crude catechins decreased the number of C botulinum and C butyricum spores but not B cereus spores. Furthermore, the effects of six catechin derivatives on spores were investigated. (−)‐Epicatechin gallate (ECg), (−)‐epigallocatechin (EGC), (−)‐epigallocatechin gallate (EGCg) and (+)‐gallocatechin gallate (GCg) were more effective in decreasing C botulinum and C butyricum spore numbers than (+)‐catechin (C) and (−)‐epicatechin (EC). The vegetative growth of C botulinum and B cereus was inhibited by crude extracts of the catechins. Specifically, purified GCg and EGCg inhibited the vegetative growth of C botulinum and B cereus. The inhibitory effect of ECg on B cereus was similar to that of GCg. However, toxin‐production by B cereus was not inhibited by catechin. Damage to the membrane of C butyricum spores by catechin derivatives was shown using fluorescent microscopy. This study shows that low concentrations of catechins, although requiring a long exposure time, inhibited the growth of bacterial spores. However, the effects of the purified derivatives of the catechins were not the same and GCg and EGCg were found to be the most potent. Spores that are generally resistant to many disinfectants were sensitive to catechins. Copyright © 2005 Society of Chemical Industry     

THz-wave absorption by field-induced carriers in pentacene thin-film transistors for THz imaging sensors

Innovative sensing systems based on THz electromagnetic waves have been attracting a great deal of attention. Although many THz detectors have been developed over the years, it is currently difficult to manufacture low-cost THz sensing/imaging devices. In the present study, we propose to use organic field-effect transistors (OFETs) and small potential fluctuation against the carriers within them (N. Ohashi, H. Tomii, R. Matsubara, M. Sakai, K. Kudo, M. Nakamura, Appl. Phys. Lett. 91 (2007) 162105). We use THz time-domain spectroscopy for OFETs in which the carrier density in the pentacene active layer is modulated by the gate bias. We found evidence that the accumulated free holes in pentacene films can be excited by THz photons to overcome the surrounding barriers in the fluctuating potential. The Drude–Lorentz model could not account for the shape of the absorption spectra, which suggests that the holes are weakly restricted by the potential fluctuation. The integrated absorption intensity was proportional to the transfer characteristics of the OFETs. The present findings represent an important step toward developing a new class of THz-wave sensors.     

Increased Lipid Synthesis and Decreased β-Oxidation in the Liver of SHR/NDmcr-cp (cp/cp) Rats, an Animal Model of Metabolic Syndrome

SHR/NDmcr-cp (cp/cp) rats (SHR/NDcp) are an animal model of metabolic syndrome. A previous study of ours revealed drastic increases in the mass of palmitic (16:0), oleic (18:1n-9), palmitoleic (16:1n-7), cis-vaccenic (18:1n-7) and 5,8,11-eicosatrienoic acids in the liver of SHR/NDcp. However, detailed information on the class of lipid accumulated and the mechanism responsible for the overproduction of the accumulated lipid in the liver was not obtained. This study aimed to characterize the class of lipid accumulated and to explore the mechanism underlying the lipid accumulation in the liver of SHR/NDcp, in comparison with SHR/NDmcr-cp (+/+) (lean hypertensive littermates of SHR/NDcp) and Wistar Kyoto rats. In the liver of SHR/NDcp, de novo synthesis of fatty acids (16:0, 18:1n-9 and 16:1n-7) and triacylglycerol (TAG) synthesis were up-regulated and fatty acid β-oxidation was down-regulated. These perturbations of lipid metabolism caused fat accumulation in hepatocytes and accumulation of TAG, which were enriched with 16:0, 18:1n-9 and 16:1n-7, in the liver of SHR/NDcp. On the other hand, no changes were found in hepatic contents of diacylglycerol and unesterified fatty acid (FFA); among FFA, there were no differences in the hepatic concentrations of unesterified 16:0 and stearic acid between SHR/NDcp and two other groups of rats. Moreover, little change was brought about in the expression of genes responsive to endoplasmic reticulum stress in the liver of SHR/NDcp. These results may reinforce the pathophysiological role of stearoyl-CoA desaturase 1 and fatty acid elongase 6 in the liver of SHR/NDcp.