Pulse Combustors—Performance and Control

Limited resources of fossil energy require the search for new energy conversion processes and the increase of the efficiency of power plants to ensure the energy household in the future. Basically, changing the combustion mode from steady to pulse combustion makes an enormous reduction of fuel consumption possible. Active control systems for pulse combustors installed into the inlet further improve the efficiency and extend the operating range considerably. The control algorithm including fuel rate - air rate - pressure characteristics and control strategies as well are presented.     

A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 4. Preparation parameters and impact index

The effects of the volume and pH of the impregnation solution and of the calcination conditions were examined on the physicochemical and catalytic properties of a 13 wt% MoO₃/Al₂O₃ extrudate catalyst. The Al₂O₃ support and drying procedures (static conditions without flowing air) were fixed in the preparations. In the present series of catalysts, the amount of crystalline MoO₃ was marginally small. It was found that the dispersion of Mo oxide species increased as the volume of the impregnation solution increased, gradually approaching a maximum value. The increase in pH (2–8) of the impregnation solution was found to reduce the dispersion of Mo oxide species. The Mo dispersion increased slightly for the impregnation catalysts as the calcination temperature increased (673–873 K), whereas it decreased for the equilibrium adsorption catalysts. The effects of the calcination atmosphere (with or without flowing air, or with flowing humid air) were very small on the dispersion of Mo oxide species under the present preparation conditions. On the other hand, the methanol oxidation activity of MoO₃/Al₂O₃ was sensitive to the preparation parameters examined here. It was demonstrated by means of EPMA and XPS that a considerable migration of Mo took place during the calcination.

In the present study on the preparation of a 13 wt% MoO₃/Al₂O₃ catalyst, an impact index is proposed to measure the magnitude of the effects of the respective parameter(s) on the physicochemical and catalytic properties. With the Mo dispersion, the effects of the preparation parameter decreased in the order, surface area of the support >> drying process > volume of the impregnation solution > pH, calcination temperature and atmosphere. The size of the impact index for the dispersion of Mo sulfide species is 70–75% of that for the Mo oxide species. The HDS activity of the catalyst was less affected by the preparation parameters than the Mo sulfide dispersion. The preparation parameters affected the segregation of Mo on the outer surface of extrudates in a decreasing order: drying process > volume of the impregnation solution > pH, calcination conditions. It was found that the oxidation of methanol was affected most intensely by the drying procedures. The volume of the impregnation solution, calcination conditions and pH of the impregnation solution also strongly affected the oxidation activity. The impact index suggests that the sensitivity to the preparation variables of the physicochemical and catalytic properties of MoO₃/Al₂O₃ decreases in the order, methanol oxidation activity > surface Mo segregation > Mo oxide dispersion > Mo sulfide dispersion > HDS activity.     

Batch foam separation of a soluble protein

Removal of protein dissolved in water by batch foam separation was conducted with using ovalbumin (OA) as a model protein in the light of wastewater treatment reducing organic loading. The removal efficiency had a maximum value near the i.e.p. of OA (pH 4.6); thus, most experiments were conducted at pH 4.6. Typical experimental conditions; superficial gas velocity, U(g): 1.97 x 10(-2)-5.37 x 10(-2)cm/s; initial bulk concentration of OA, C(i): ca. 0.05-0.25 g/L; liquid volume, V: 600 cm(3). A model estimating bulk concentration profile was proposed by taking into account a mass balance of the present system. The model predicted that OA could be removed perfectly, however, was not all removed experimentally. The residual OA concentration of the bulk liquid within the column reached plateau value, which correspond to ca. 18% of the initial OA concentration. The plateau value of the bulk concentration was attained for ca. 100-500 min with U(g)=1.97 x 10(-2)-5.37 x 10(-2)cm/s. Foaming ability test revealed that the foaming limit concentration of OA at pH 4.6 was 9.72 x 10(-3)g/L. These results suggested that OA molecules could be damaged by interaction of bubble surface in the dispersed phase, since there were the residual OA concentrations over the limit concentration. To take account of this phenomena and correct the model, average surface density, X(d), which should convert protein molecule into the denatured protein molecule, was introduced. The corrected model could explain well the time profile of OA bulk concentration.     

In vivo formation of mutagens by intraperitoneal administration of polycyclic aromatic hydrocarbons in animals during exposure to nitrogen dioxide

Consumption of fossil fuels has increased indoor and outdoor concentrations of polycyclic aromatic hydrocarbons (PAHs) and nitrogen dioxide (NO2). To study the combined effect of PAH administration and NO2 exposure on mutagenicity of urine from animals we injected 400 mg/kg body wt i.p. one of five kinds of PAH (pyrene, fluoranthene, fluorene, anthracene and chrysene) into ICR mice, Wistar rats, Syrian golden hamsters or Hartley guinea pigs after exposure to 20 p.p.m. NO2 gas for 24 h and then exposed the animals to NO2 gas for an additional 24 h. During the latter 24 h we collected the urine and assayed its mutagenicity with the Ames Salmonella strains after treatment with beta-glucuronidase and arylsulfatase and extraction with dichloromethane. The urine from mice treated with both PAH and NO2 showed high mutagenicity for Salmonella typhimurium strains TA98 and TA100, whereas the urine from mice treated with PAH and air showed almost no mutagenic activity. The mutagenicity was decreased in nitroreductase- and acetyltransferase-deficient strains TA98NR and TA98/1,8-DNP6 respectively. Treatment with a mixture of 20% of each of the five kinds of PAH and NO2 augmented the urinary mutagenicity of mice 1.5-fold. The urine from hamsters treated with pyrene or fluoranthene and NO2 was also highly mutagenic, but that from rats or guinea pigs was not very mutagenic. The mutagenicity was also decreased in strains TA98NR and TA98/1,8-DNP6. These results suggest that the urine contains nitro compounds and that the nitration of PAHs occurs in the body of animals under exposure to NO2 gas. Actually, the nitrated metabolites of pyrene, 1-nitro-6/8-hydroxypyrene and 1-nitro-3-hydroxypyrene, were detected in the urine from mice treated with pyrene under exposure to NO2 gas. To elucidate the mechanism of in vivo nitration, NO2 (20 p.p.m.) was bubbled through 50 mM Tris-HCl buffer (pH 7.4) or dichloromethane solution containing pyrene or 1-hydroxypyrene (10 microg/ml). Pyrene was not nitrated by NO2 in either aqueous or organic solutions. However, 1-hydroxypyrene was changed to nitrohydroxypyrenes by NO2 in the Tris-HCl buffer, but not in the organic solution. Ascorbic acid, alpha-tocopherol, glutathione oleic acid and hemoglobin were found to inhibit the nitration of 1-hydroxypyrene in aqueous solution. The urinary mutagenicity of mice treated with both pyrene and NO2 was also decreased by oral administration of ascorbic acid and alpha-tocopherol. These results suggest that 1-hydroxypyrene is nitrated by an ionic reaction in the animal body after hydroxylation of pyrene in the liver.     

A high-density data-path generator with stretchable cells

This paper describes a newly developed module generator for cell-based design which generates a data-path layout comparable to a handcrafted one both in speed and in transistor density. The chip designer enters his schematic data-path diagram using the configurable function block library provided. There is no constraint either in the number of function blocks used, or in how to interconnect them. The data-path generator generates the function blocks, which are components of the data-path, and automatically places and routes them. The configurable function blocks were developed in 0.8-μm double metal CMOS technology. A new cell structure suitable for over the cell routing, called “stretchable cell with access free terminals,” is adopted as a bit-slice element of the data-path generator. This removes the routing region outside the cell for the wiring between function blocks, and a high density layout can be obtained. Also because of the new cell structure, there is no upper limit on the number of tracks per bit. Using this data-path generator, several data-paths were generated with high density of more than 6k Trs./mm²     

Evidence that Crystal Facet Orientation Dictates Oxygen Evolution Intermediates on Rutile Manganese Oxide

Elucidating the mechanism that differentiates the oxygen‐evolving center of photosystem II with its inorganic counterpart is crucial to develop efficient catalysts for the oxygen evolution reaction (OER). Previous studies have suggested that the larger overpotential for MnO₂ catalysts under neutral conditions may result from the instability of the Mn³⁺ intermediate to charge disproportionation. Here, by monitoring the surface intermediates of electrochemical OER on rutile MnO₂ with different facet orientations, a correlation between the stability of the intermediate species and crystal facets is confirmed explicitly for the first time. The coverage of the Mn³⁺ intermediate is found to be 11‐fold higher on the metastable (101) surfaces compared to (110) surfaces, leading to the superior OER activity of (101) surfaces. The difference in OER activity may result from the difference in surface electronic states of Mn³⁺, where interlayer charge comproportionation of Mn²⁺ and Mn⁴⁺ to generate two Mn³⁺ species is favored on (101) facets. Considering the fact that the OER enzyme accommodates Mn³⁺ stably during the Kok cycle, the enhanced OER activity of the rutile MnO₂ catalyst with a metastable surface highlights the importance of mimicking not only the crystal structure but also the electronic structure of the targeted natural enzyme.     

Site-directed mutagenesis study on the roles of evolutionally conserved aspartic acid residues in human glutathione S-transferase P1-1

The evolutionally conserved aspartyl residues (Asp57, Asp98and Asp152) in human glutathione S-transferase P1-1 were replacedwith alanine by site-directed mutagenesis to obtain the mutants(D57A, D98A and D152A). The replacement of Asp98 with alanineresulted in a decrease of the affinity for S-hexyl-GSH-agarose,a 5.5-fold increase of the K_m^GHS and a 2.9-fold increase ofthe I₅₀ of S-hexyl-GSH for GSH–CDNB conjugation. Asp98seems to participate in the binding of GSH through hydrogenbonding with the -carboxylate of the -glutamyl residue of GSH.The k_cat of D98A was 2.6-fold smaller than that of the wild-type,and the pK_a of the thiol group of GSH bound in D98A was {smalltilde}0.8 pK units higher than those in the wild-type. Asp98also seems to contribute to the activation of GSH to some extent.On the other hand, most of the kinetic parameters of D57A andD152A were similar to those of the wild-type. However, the thermostabilitiesof D57A and D152A were significantly lower than that of thewild-type. Asp57 and Asp152 seem to be important for maintainingthe proper conformation of the enzyme.     

Sex Pheromone of the Persimmon Fruit Moth, Stathmopoda masinissa: Identification and Laboratory Bioassay of (4E, 6Z)-4,6-Hexadecadien-1-ol Derivatives

Three electroantennogram (EAG)-active components were detected by gas chromatography coupled to an electroantennographic detector (GC–EAD) analysis of a hexane extract of the pheromone glands of the persimmon fruit moth, Stathmopoda masinissa. These compounds were identified as (4E,6Z)-4,6-hexadecadienal (E4,Z6-16:Ald) and the corresponding acetate (E4,Z6-16: OAc) and alcohol (E4,Z6-16:OH) by mass spectral, GC retention time (RT), and microchemical test data. The characteristic base peak of the aldehyde at m/z 84 provided a crucial piece of information suggesting the possibility of a 4,6-diene structure. The (4E,6Z)-isomer elicited the strongest EAG responses among the four geometrical isomers of each synthetic 4,6-hexadecadienyl compound. In a laboratory bioassay, only E4,Z6-16:OAc elicited male moth behavioral activity significantly different from the control; the activity of the acetate was not affected by addition of the aldehyde and alcohol. A preliminary field trial confirmed that E4,Z6-16:OAc as a single component attracted male moths. The possible roles of E4,Z6-16:Ald and E4,Z6-16:OH as components of lures for field use remain to be determined.     

Identification of the Sex Pheromone Secreted by a Nettle Moth, Monema flavescens, Using Gas Chromatography/Fourier Transform Infrared Spectroscopy

The nettle moth Monema flavescens (Limacodidae) is a defoliator of fruit trees, such as Chinese plum and persimmon. The larvae of this species have spines containing a poison that causes serious irritation and inflammation in humans. Coupled gas chromatography-electroantennogram detection and gas chromatography/mass spectrometry analyses of a crude pheromone extract, combined with derivatization, indicated that female moths produced 8-decen-1-ol and 7,9-decadien-1-ol at a ratio of approximately 9:1. The E configuration of the double bonds was assigned for both components from infrared spectra, recorded on a gas chromatograph/Fourier transform-infrared spectrophotometer equipped with a zinc selenide disk cooled to ?30 °C. The monoenyl and dienyl alcohols had absorptions characteristic of E geometry at 966 and 951 cm^?1, respectively. A band chromatogram at 951 cm^?1 was useful for distinguishing geometric isomers, because terminal conjugated diene are difficult to resolve, even on high polarity columns. Furthermore, we identified the Z configuration of the same 7,9-dienyl alcohol secreted by another nettle moth, Parasa lepida lepida, through the absence of this absorption. In field trials, lures baited with a 9:1 mixture of (E)-8-decen-1-ol and (E)-7,9-decadien-1-ol attracted M. flavescens males. Furthermore, the field trials indicated that contamination with the (Z)-diene reduced catches to the pheromone mixture more than did contamination with the (Z)-monoene.     

Kinetics study of hydrogen adsorption over Pt/MoO3

The rate controlling step and the energy barrier involved in the hydrogen adsorption over Pt/MoO₃ were studied. Rates of hydrogen adsorption on Pt/MoO₃ were measured at the adsorption temperature range of 323–573 K and at the initial hydrogen pressure of 6.7 kPa. The rate of hydrogen uptake was very high for the initial few minutes for adsorption at and above 473 K, and reached equilibrium within 2 h. At and below 423 K, the hydrogen uptake still continued and did not reach equilibrium after 10 h. The hydrogen uptake exceeded the H/Pt ratio of unity for adsorption at and above 423 K, indicating that hydrogen adsorption involves hydrogen atom spillover and surface diffusion of the spiltover hydrogen atom over the bulk surface of MoO₃ followed by formation of H_xMoO₃. The hydrogen uptake was scarcely appreciable for Pt-free MoO₃. The rate controlling step of the hydrogen adsorption on Pt/MoO₃ was the surface diffusion of the spiltover hydrogen with the activation energy of 83.1 kJ/mol. The isosteric heats of hydrogen adsorption on Pt/MoO₃ were 18.1–16.9 kJ/mol for the hydrogen uptake range 2.4–2.8 × 10¹⁹ H-atom/g-cat. Similarities and differences in hydrogen adsorption on Pt/SO₄^2?–ZrO₂, Pt/WO₃–ZrO₂ and Pt/MoO₃ catalysts are discussed.