Linearly-increasing-stress testing of carbon steel in 4 N NaNO3 and in Bayer liquor

This paper reports the application of linearly increasing stress testing (LIST) to the study of stress corrosion cracking (SCC) of carbon steel in 4 N NaNO3 and in Bayer liquor. LIST is similar to the constant extension-rate testing (CERT) methodology with the essential difference that the LIST is load controlled whereas the CERT is displacement controlled. The main conclusion is that LIST is suitable for the study of the SCC of carbon steels in 4 N NaNO3 and in Bayer liquor. The low crack velocity in Bayer liquor and a measured maximum stress close to that of the reference specimen in air both indicate that a low applied stress rate is required to study SCC in this system. (C) 1998 Chapman & Hall.

Characterization of calcium-activated chloride channels in patches excised from the dendritic knob of mammalian olfactory receptor neurons

We investigated the properties of calcium-activated chloride channels in inside-out membrane patches from the dendritic knobs of acutely dissociated rat olfactory receptor neurons. Patches typically contained large calcium-activated currents, with total conductances in the range 30-75 nS. The dose response curve for calcium exhibited an EC50 of about 26 mu M. In symmetrical NaCl solutions, the current-voltage relationship reversed at 0 mV and was linear between -80 and +70 mV. When the intracellular NaCl concentration was progressively reduced from 150 to 25 mM, the reversal potential changed in a manner consistent with a chloride-selective conductance. Indeed, modeling these data with the Goldman-Hodgkin-Katz equation revealed a P-Na/P-Cl of 0.034. The halide permeability sequence was P-Cl > P-F > P-I > P-Br indicating that permeation through the channel was dominated by ion binding sites with a high field strength. The channels were also permeable to the large organic anions, SCN-, acetate(-), and gluconate(-), with the permeability sequence P-Cl > P-SCN > gluconaie. Significant permeation to gluconate ions suggested that the channel pore had a minimum diameter of at least 5.8 Angstrom.

The kinetics of NO and N2O reduction over coal chars in fluidised-bed combustion

This paper presents a comprehensive and critical review of the mechanisms and kinetics of NO and N2O reduction reaction with coal chars under fluidised-bed combustion conditions (FBC). The heterogeneous reactions of NO and N2O with char/carbon surface have been well recognised as the most important processes in reducing both NOx and N2O in situ FBC. Compared to NO-carbon reactions in FBC, the reactions of N2O with chars have been relatively less understood and studied. Beginning with the overall reaction schemes for both NO and N2O reduction, the paper extensively discusses the reaction mechanisms including the effects of active surface sites. Generally, NO- and N2O-carbon reactions follow a series of step reactions. However, questions remain concerning the role of adsorbed phases of NO and N2O, and the behaviour of different surface sites. Important kinetics factors such as the rate expressions, kinetics parameters as well as the effects of surface area and pore structure are discussed in detail. The main factors influencing the reduction of NO and N2O in FBC conditions are the chemical and physical properties of chars, and the operating parameters of FBC such as temperature, presence of CO, O-2 and pressure. It is shown that under similar conditions, N2O is more readily reduced on the char surface than NO. Temperature was found to be a very important parameter in both NO and N2O reduction. It is generally agreed that both NO- and N2O-carbon reactions follow first-order reaction kinetics with respect to the NO and N2O concentrations. The kinetic parameters for NO and N2O reduction largely depend on the pore structure of chars. The correlation between the char surface area and the reactivities of NO/N2O-char reactions is considered to be of great importance to the determination of the reaction kinetics. The rate of NO reduction by chars is strongly enhanced by the presence of CO and O-2, but these species may not have significant effects on the rate of N2O reduction. However, the presence of these gases in FBC presents difficulties in the study of kinetics since CO cannot be easily eliminated from the carbon surface. In N2O reduction reactions, ash in chars is found to have significant catalytic effects, which must be accounted for in the kinetic models and data evaluation. (C) 1997 Elsevier Science Ltd.

Thermogravimetric determination of the carbon dioxide reactivity of char from some New Zealand coals and its association with the inorganic geochemistry of the parent coal

Thermogravimetrically-determined carbon dioxide reactivities of chars formed from New Zealand coals, ranging in rank from lignite to high volatile bituminous, vary from 0.12 to 10.63 mg/h/mg on a dry, ash-free basis. The lowest rank subbituminous coal chars have similar reactivities to the lignite coal chars. Calcium content of the char shows the strongest correlation with reactivity, which increases as the calcium content increases. High calcium per se does not directly imply a high char reactivity. Organically-bound calcium catalyses the conversion of carbon to carbon monoxide in the presence of carbon dioxide, whereas calcium present as discrete minerals in the coal matrix, e.g., calcite, fails to significantly affect reactivity. Catalytic effects of magnesium, iron, sodium and phosphorous are not as obvious, but can be recognised for individual chars. The thermogravimetric technique provides a fast, reliable analysis that is able to distinguish char reactivity differences between coals, which may be due to any of the above effects. Published by Elsevier Science B.V.

Catalytic activities and coking characteristics of oxides-supported Ni catalysts for CH4 reforming with carbon dioxide

Catalytic activities and deactivation characteristics of oxides-supported nickel catalysts for the reaction of methane reforming with carbon dioxide were investigated. The dynamic carbon deposition on various nickel catalysts was also studied by a thermogravimetric method. Among the catalysts prepared, Ni/La2O3, Ni/alpha-Al2O3, Ni/SiO2, and Ni/CeO2 showed very high CH4 and CO2 conversions and moderate deactivation whereas Ni/MgO and Ni/TiO2 had lower conversions when the Ni reduction was conducted at 500 degrees C. When Ni/MgO catalyst was reduced at 800 degrees C, it exhibited not only comparable conversions of CH4 and CO2 with other active catalysts but also much longer period of stability without deactivation. The amount of carbon deposited in Ni-based catalysts varied depending on the nature of support and followed the order of Ni/La2O3 > Ni/alpha-Al2O3 > Ni/SiO2 > Ni/MgO > Ni/CeO2 at 700 degrees C. The carbons formed on the catalyst surface showed different structural and chemical properties, and these in turn affected the catalytic activity of the catalysts.

Correlation between carbon isotope discrimination and transpiration efficiency in lines of the C-4 species Sorghum bicolor in the glasshouse and the field

Transpiration efficiency, W, the ratio of plant carbon produced to water transpired and carbon isotope discrimination of leaf dry matter, Delta(d)' were measured together on 30 lines of the C-4 species, Sorghum bicolor in the glasshouse and on eight lines grown in the field. In the glasshouse, the mean W observed was 4.9 mmol C mol(-1) H2O and the range was 0.8 mmol C mol(-1) H2O The mean Delta(d) was 3.0 parts per thousand and the observed range was 0.4 parts per thousand. In the field, the mean W was lower at 2.8 mmol C mol H2O and the mean Delta(d) was 4.6 parts per thousand. Significant positive correlations between W and Delta(d) were observed for plants grown in the glasshouse and in the field. The observed correlations were consistent with theory, opposite to those for C-4 species, and showed that variation in Delta(d) was an integrated measure of long-term variation in the ratio of intercellular to ambient CO2 partial pressure, p(i)/p(a). Detailed gas exchange measurements of carbon isotope discrimination during CO2 uptake, Delta(A) and p(i)/p(a) were made on leaves of eight S. bicolor lines. The observed relationship between Delta(A) and p(i)/p(a) was linear with a negative slope of 3.7 parts per thousand in Delta(A) for a unit change in p(i)/p(a). The slope of this linear relationship between Delta(A) and p(i)/p(a) in C-4 species is dependent on the leakiness of the CO2 concentrating mechanism of the C pathway, We estimated the leakiness (defined as the fraction of CO2 released in the bundle sheath by C-4 acid decarboxylations, which is lost by leakage) to be 0.2. We conclude that, although variation in Delta(d) observed in the 30 lines of S. bicolor is smaller than that commonly observed in C-4 species, it also reflects variation in transpiration efficiency, W. Among the eight lines examined in detail and in the environments used, there was considerable genotype x environment interaction.

Reforming of methane with carbon dioxide over Ni/Al2O3 catalysts: Effect of nickel precursor

The catalytic activities of Ni/gamma-Al2O3 catalysts prepared using different nickel precursor compounds were studied for the reaction of methane reforming with CO2. It is found that the nickel precursor employed in the catalyst preparation plays an important role. The catalyst based on nickel nitrate exhibited higher catalytic activity and stability over a 24-h test period than the other two catalysts derived from nickel chloride and nickel acetylacetonate. A comprehensive characterisation of the catalysts showed that the weak interaction between Ni particles and gamma-Al2O3 resulted in more active sites on Ni nitrate-derived Ni/gamma-Al2O3 catalyst. Coking studies showed that carbon deposition on Ni catalysts derived from inorganic precursors (nitrate and chloride) were more severe than on the organic precursor-derived catalyst. However, the Ni nitrate-derived catalyst was found to have the highest stability (or lowest deactivation rate) mainly due to the active carbon species (-C-C-) of the resulting graphitic structure and their close contact with the metal particles. In contrast, the carbon formed on Ni-AA catalyst (from Ni acetylacetonate) is dominated by inactive -CO-C- species, thus leading to a rapid accumulation of carbon in this catalyst and more severe deactivation. (C) 1998 Elsevier Science B.V.

Adsorption of binary hydrocarbon mixtures in carbon slit pores: A density functional theory study

Adsorption of binary hydrocarbon mixtures involving methane in carbon slit pores is theoretically studied here from the viewpoints of separation and of the effect of impurities on methane storage. It is seen that even small amounts of ethane, propane, or butane can significantly reduce the methane capacity of carbons. Optimal pore sizes and pressures, depending on impurity concentration, are noted in the present work, suggesting that careful adsorbent and process design can lead to enhanced separation. These results are consistent with earlier literature studies for the infinite dilution limit. For methane storage applications a carbon micropore width of 11.4 Angstrom (based on distance between centers of carbon atoms on opposing walls) is found to be the most suitable from the point of view of lower impurity uptake during high-pressure adsorption and greater impurity retention during low-pressure delivery. The results also theoretically confirm unusual recently reported observations of enhanced methane adsorption in the presence of a small amount of heavier hydrocarbon impurity.

Spectroscopic identification of a dinuclear metal centre in manganese(II)-activated aminopeptidase P from Escherichia coli: implications for human prolidase

Electron paramagnetic resonance (EPR) spectra and X-ray absorption (EXAFS and XANES) data have been recorded for the manganese enzyme aminopeptidase P (AMPP, PepP protein) from Escherichia coli. The biological function of the protein, a tetramer of 50-kDa subunits, is the hydrolysis of N-terminal Xaa-Pro peptide bonds. Activity assays confirm that the enzyme is activated by treatment with Mn2+. The EPR spectrum of Mn2+-activated AMPP at liquid-He temperature is characteristic of an exchange-coupled dinuclear Mn(II) site, the Mn-Mn separation calculated from the zero-field splitting D of the quintet state being 3.5 (+/- 0.1) Angstrom. In the X-ray absorption spectrum of Mn2+-activated AMPP at the Mn K edge, the near-edge features are consistent with octahedrally coordinated Mn atoms in oxidation state +2. EXAFS data, limited to k less than or equal to 12 Angstrom(-1) by traces of Fe in the protein, are consistent with a single coordination shell occupied predominantly by O donor atoms at an average Mn-ligand distance of 2.15 Angstrom, but the possibility of a mixture of O and N donor atoms is not excluded. The Mn-Mn interaction at 3.5 Angstrom, is not detected in the EXAFS, probably due to destructive interference from light outer-shell atoms. The biological function, amino acid sequence and metal-ion dependence of E. coli AMPP are closely related to those of human prolidase, an enzyme that specifically cleaves Xaa-Pro dipeptides. Mutations that lead to human prolidase deficiency and clinical symptoms have been identified. Several known inhibitors of prolidase also inhibit AMPP. When these inhibitors are added to Mn2+-activated AMPP, the EPR spectrum and EXAFS remain unchanged. It can be inferred that the inhibitors either do not bind directly to the Mn centres, or substitute for existing Mn ligands without a significant change in donor atoms or coordination geometry. The conclusions from the spectroscopic measurements on AMPP have been verified by, and complement, a recent crystal structure analysis.

Thermogravimetric analysis of carbon deposition over Ni/gamma-Al2O3 catalysts in carbon dioxide reforming of methane

Carbon formation on Ni/gamma-Al2O3 catalysts and its kinetics during methane reforming with carbon dioxide was studied in the temperature range of 500-700 degrees C using a thermogravimetric analysis technique. The activation energies of methane cracking, carbon gasification in CO2, as well as carbon deposition in CO2-CH4 reforming were obtained. The results show that the activation energy for carbon gasification is larger than that of carbon formation in methane cracking and that the activation energy of coking in CO2-CH4 reforming is also larger than that of methane decomposition to carbon. The dependencies of coking rate on partial pressures of CH4 and CO2 indicate that methane decomposition is the main route for carbon deposition. A mechanism and kinetic model for carbon deposition is proposed.

Dysregulated hematopoiesis and a progressive neurological disorder induced by expression of an activated form of the human common beta chain in transgenic mice

Previously we described activating mutations of h beta(c), the common signaling subunit of the receptors for the hematopoietic and inflammatory cytokines, GM-CSF, IL-3, and IL-5. The activated mutant, h beta(c)FI Delta, is able to confer growth factor-independent proliferation on the murine myeloid cell line FDC-P1, and on primary committed myeloid progenitors. We have used this activating mutation to study the effects of chronic cytokine receptor stimulation. Transgenic mice were produced carrying the h beta(c)FI Delta cDNA linked to the constitutive promoter derived from the phosphoglycerate kinase gene, PGK-1. Transgene expression was demonstrated in several tissues and functional activity of the mutant receptor was confirmed in hematopoietic tissues by the presence of granulocyte macrophage and macrophage colony-forming cells (CFU-GM and CFU-M) in the absence of added cytokines. All transgenic mice display a myeloproliferative disorder characterized by splenomegaly, erythrocytosis, and granulocytic and megakaryocytic hyperplasia. This disorder resembles the human disease polycythemia vera, suggesting that activating mutations in h beta(c) may play a role in the pathogenesis of this myeloproliferative disorder. In addition, these transgenic mice develop a sporadic, progressive neurological disease and display bilateral, symmetrical foci of necrosis in the white matter of brain stem associated with an accumulation of macrophages. Thus, chronic h beta(c) activation has the potential to contribute to pathological events in the central nervous system.