Monte Carlo simulation of hydrogen absorption in palladium and palladium–silver alloys

A modified Monte Carlo (MC) simulation was performed to investigate the hydrogen absorption behavior in Pd and Pd–Ag alloys of the composition Pd_xAg_1−x (x=0.7–0.8) under H₂ pressure (0.1 MPa) at different temperatures. The present method employed can consider the dissociative adsorption of hydrogen molecule and the subsequent absorption of hydrogen atom by formalizing the relationship between the pressure of hydrogen molecule and hydrogen atom. The potential parameters were determined to reproduce the solution enthalpy of hydrogen in pure metals. The results are in good agreement with experimental findings as well as previous theoretical studies. We confirmed that our method is useful to simulate the absorption of hydrogen in metals and alloys.     

Kinetics of the methanation of carbon dioxide over a supported Ni-La2O3 catalyst

The kinetics of the methanation of carbon dioxide was investigated using an alumina supported Ni-La₂O₂ catalyst in a differential and integral reactor. In the differential reactor the molar ratio of H₂ to CO₂ was varied from 0.6 to 30. In the integral reactor the rates were measured with up to 90% conversion. Both reactor tests were carried out at temperatures between 513 and 593 K. The experimental results were described by a Langmuir-Hinshelwood type equation. The kinetics can be explained by assuming equilibrium of dissociative carbon dioxide and hydrogen adsorption, and assuming hydrogenation of surface carbon as the rate determining step.     

The optically pumped hydrazine FIR laser: Assignments and new laser lines

Strong far-infrared (FIR) lasing action has been observed in hydrazine optically pumped with isotopic CO2lasers and the N2O laser. The wavelengths of 13 new laser lines have been determined. The results of a recent infrared-microwave double resonance study of hydrazine have been used to assign the transitions involved in the production of five of these new lines and nine of the previously observed laser lines.     

High-power operation of AlGaAs SQW-SCH broad-area laser diodes for Nd:YAG solid-state laser pumping

AlGaAs single-quantum-well separate-confinement-heterostructure (SQW-SCH) single-stripe broad-area laser diodes (LDs) for Nd:YAG solid-state laser pumping were developed. The high-power operation of the SQW-SCH LD was demonstrated. The maximum output power under continuous wave operation at room temperature was 2.6 W in the range of the Nd:YAG absorption band. Stable operation was also confirmed for over 500 h under the condition of 25 degrees C at 1 W under continuous-wave operation.<>     

Amphiphilic Poly(Amino Acid) Nanoparticles Induce Size‐Dependent Dendritic Cell Maturation

Size‐regulated amphiphilic poly(amino acid) nanoparticles (NPs) composed of poly(γ‐glutamic acid) (γ‐PGA) and the hydrophobic amino acid derivative, L ‐phenylalanine ethyl ester (Phe) are prepared to evaluate the effects of particle size on dendritic cell (DC) uptake of NPs and their immune stimulatory activities as delivery carriers and adjuvants. The size of the Phe‐conjugated γ‐PGA NPs (γ‐PGA–Phe NPs) is easily controlled by regulating the aggregated γ‐PGA–Phe numbers. Each of the differently sized γ‐PGA–Phe NPs could efficiently encapsulate ovalbumin (OVA), and the amount of encapsulated OVA per milligram of NPs is almost the same despite the differences in size. The DC uptake of small NPs is lower than for the larger NPs, but the effect of DC activation by NPs is high in the small sizes. The DC activation is significantly affected by the size of the NPs, which suggests that not only the uptake process of the NPs, but also the surface interactions between the NPs and DCs, is important for the induction of DC maturation. The precisely size‐controllable γ‐PGA–Phe NPs have significant potential as an antigen carrier and vaccine adjuvant. These results should provide guidelines for adjuvant design in the development of an effective vaccine.     

Atmospheric outflow of anthropogenic semivolatile organic compounds from East Asia in spring 2004

To estimate the emissions of anthropogenic semivolatile organic compounds (SOCs) from East Asia and to identify unique SOC molecular markers in Asian air masses, high-volume air samples were collected on the island of Okinawa, Japan between 22 March and 2 May 2004. Contributions from different source regions (China, Japan, the Koreas, Russia, and ocean/local) were estimated by use of source region impact factors (SRIFs). Elevated concentrations of hexachlorobenzene (HCB), hexachlorcyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs), and particulate-phase polycyclic aromatic hydrocarbons (PAHs) were attributed to air masses from China. A large proportion of the variation in the current-use pesticides, gas-phase PAHs, and polychlorinated biphenyl (PCB) concentrations was explained by meteorology. Chlordanes showed a technical mixture profile and similar concentrations regardless of source region. alpha/gamma HCH and trans/cis chlordane ratios did not vary significantly with different source regions and had regional averages of 2.5 +/- 1.0 and 1.2 +/- 0.3, respectively. Particulate-phase PAH concentrations were significantly correlated (p value < 0.05) with other incomplete combustion byproduct concentrations, including elemental mercury (Hg0), CO, NOx, black carbon, submicrometer aerosols, and SO2. By use of measured PAH, CO, and black carbon concentrations and estimated CO and black carbon emission inventories, the emission of six carcinogenic particulate-phase PAHs was estimated to be 1518-4179 metric tons/year for Asia and 778-1728 metric tons/year for China, respectively. These results confirm that East Asian outflow contains significant emissions of carcinogenic particulate-phase PAHs.     

Contrasting diurnal variations in fossil and nonfossil secondary organic aerosol in urban outflow, Japan

Diurnal variations of fossil secondary organic carbon (SOC) and nonfossil SOC were determined for the first time using a combination of several carbonaceous aerosol measurement techniques, including radiocarbon (1?C) determinations by accelerator mass spectrometry, and a receptor model (chemical mass balance, CMB) at a site downwind of Tokyo during the summer of 2007. Fossil SOC showed distinct diurnal variation with a maximum during daytime, whereas diurnal variation of nonfossil SOC was relatively small. This behavior was reproduced by a chemical transport model (CTM). However, the CTM underestimated the concentration of anthropogenic secondary organic aerosol (ASOA) by a factor of 4-7, suggesting that ASOA enhancement during daytime is not explained by production from volatile organic compounds that are traditionally considered major ASOA precursors. This result suggests that unidentified semivolatile organic compounds or multiphase chemistry may contribute largely to ASOA production. As our knowledge of production pathways of secondary organic aerosol (SOA) is still limited, diurnal variations of fossil and nonfossil SOC in our estimate give an important experimental constraint for future development of SOA models.     

Scavenging effect of tea catechins and their epimers on superoxide anion radicals generated by a hypoxanthine and xanthine oxidase system

Catechins are a major group of polyphenolic compounds contained in abundance in green tea. Using electron spin resonance spectroscopy along with a spin‐trapping agent, the scavenging effect of tea catechins and their corresponding epimers against superoxide anion radicals generated by a hypoxanthine and xanthine oxidase reaction system was evaluated. The presence of 3′,4′,5′‐trihydroxyl groups attached to the B‐ring of the flavan skeleton of tea catechins elevated their radical‐scavenging efficiency in comparison to those with 3′,4′‐dihydroxyl groups. There were no significant differences between the four dominant tea catechins and their corresponding epimers with regard to radical‐scavenging ability. Under the different spin‐trapping agent concentrations, the sigmoid curves of reducing spin‐trapping adducts produced by tea catechins were shifted leftward, suggesting that a likely possible action of tea catechins is to scavenge superoxide anion radicals directly, not to inhibit the function of xanthine oxidase. Although caffeine is also known as a major ingredient of tea, its superoxide anion radical‐scavenging effect was much weaker than that of the catechin family. It is concluded that tea catechins and their epimers serve as powerful antioxidants for directly eliminating superoxide anion radicals, and may be useful in the prevention of diseases relating to in vivo oxidative stress. © 2000 Society of Chemical Industry     

Design of new catalysts for ecological high-quality transportation fuels by combinatorial computational chemistry and tight-binding quantum chemical molecular dynamics approaches

Recently, we introduced a concept of combinatorial chemistry to computational chemistry and proposed a new method called “combinatorial computational chemistry”, which enables us to perform a theoretical high-throughput screening of catalysts. In the present paper, we reviewed our recent application of our combinatorial computational chemistry approach to the design of new catalysts for high-quality transportation fuels. By using our combinatorial computational chemistry techniques, we succeeded to predict new catalysts for methanol synthesis and Fischer–Tropsch synthesis. Moreover, we have succeeded in the development of chemical reaction dynamics simulator based on our original tight-binding quantum chemical molecular dynamics method. This program realizes more than 5000 times acceleration compared to the regular first-principles molecular dynamics method. Electronic- and atomic-level information on the catalytic reaction dynamics at reaction temperatures significantly contributes the catalyst design and development. Hence, we also summarized our recent applications of the above quantum chemical molecular dynamics method to the clarification of the methanol synthesis dynamics in this review.     

Effects of acid strength and micro pore size on -caprolactam selectivity and catalyst deactivation in vapor phase Beckmann rearrangement over acid solid catalysts

The vapor phase Beckmann rearrangement of cyclohexanone oxime (CHO) over solid acid catalysts including zeolites was carried out to elucidate the effects of the acid strength and the micropore size of the catalysts on the selectivity of -caprolactam (CL) and the catalyst deactivation rate. It was found that the catalyst deactivation rate was strongly dependent on the acid strength of the acid catalysts. The improvement of catalyst life was achieved by using MFI-type metallosilicates having weak acid sites. The CL selectivity decreased over the acid catalysts with micropores larger than those of the MFI zeolites. Furthermore, using methanol and carbon dioxide as the diluent solvent and diluent gas improved CL selectivity and catalyst life, respectively.