989 resultados para reduction chemistry


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J.W.Lindt’s Colonial man and Aborigine image from the GRAFTON ALBUM: “On chemistry and optics all does not depend, art must with these in triple union blend” (text from J.W. Lindt’s photographic backing card) In this paper, I follow an argument that Lindt held a position in his particular colonial environment where he was simultaneously both an insider and an outsider and that such a position may be considered prerequisite in stimulating exchange. A study of the transition of J.W. Lindt in Grafton, N.S.W. in the 1860s from a traveller to a migrant and subsequently to a professional photographer, as well as Lindt’s photographic career, which evolved through strategic action and technical approaches to photography, bears witness to his cultural relativity. One untitled photograph from this period of work constructs a unique commentary of Australian colonial life that illustrates a non-hegemonic position, particularly as it was included in one of the first albums of photographs of Aborigines that Lindt gifted to an illustrious person (in this case the Mayor of Grafton). As in his other studio constructions, props and backdrops were arranged and sitters were positioned with care, but this photograph is the only one in the album that includes a non-Aborigine in a relationship to an Aborigine. An analysis of the props, technical details of the album and the image suggests a reconciliatory aspect that thwarts the predominant attitudes towards Aborigines in the area at that time.

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Maize (Zea mays L.) is a chill-susceptible crop cultivated in northern latitude environments. The detrimental effects of cold on growth and photosynthetic activity have long been established. However, a general overview of how important these processes are with respect to the reduction of productivity reported in the field is still lacking. In this study, a model-assisted approach was used to dissect variations in productivity under suboptimal temperatures and quantify the relative contributions of light interception (PARc) and radiation use efficiency (RUE) from emergence to flowering. A combination of architectural and light transfer models was used to calculate light interception in three field experiments with two cold-tolerant lines and at two sowing dates. Model assessment confirmed that the approach was suitable to infer light interception. Biomass production was strongly affected by early sowings. RUE was identified as the main cause of biomass reduction during cold events. Furthermore, PARc explained most of the variability observed at flowering, its relative contributions being more or less important according to the climate experienced. Cold temperatures resulted in lower PARc, mainly because final leaf length and width were significantly reduced for all leaves emerging after the first cold occurrence. These results confirm that virtual plants can be useful as fine phenotyping tools. A scheme of action of cold on leaf expansion, light interception and radiation use efficiency is discussed with a view towards helping breeders define relevant selection criteria. This paper originates from a presentation at the 5th International Workshop on Functional–Structural Plant Models, Napier, New Zealand, November 2007.

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We examine the microchemistry of otoliths of cohorts of a fished shed population of the large catadromous fish, barramundi Lates calcarifer from the estuary of a large tropical river. Barramundi from the estuary of the large, heavily regulated Fitzroy River, north eastern Australia were analysed by making transects of 87Sr/86Sr isotope and trace metal/Ca ratios from the core to the outer edge. Firstly, we examined the Sr/Ca, Ba/Ca, Mg/Ca and Mn/Ca and 87Sr/86Sr isotope ratios in otoliths of barramundi tagged in either freshwater or estuarine habitats that were caught by the commercial fishery in the estuary. We used 87Sr/86Sr isotope ratios to identify periods of freshwater residency and assess whether trace metal/Ca ratios varied between habitats. Only Sr/Ca consistently varied between known periods of estuarine or freshwater residency. The relationships between trace metal/Ca and river flow, salinity, temperature were examined in fish tagged and recaptured in the estuary. We found weak and inconsistent patterns in relationships between these variables in the majority of fish. These results suggest that both individual movement history within the estuary and the scale of environmental monitoring were reducing our ability to detect any patterns. Finally, we examined fish in the estuary from two dominant age cohorts (4 and 7 yr old) before and after a large flood in 2003 to ascertain if the flood had enabled fish from freshwater habitats to migrate to the estuary. There was no difference in the proportion of fish in the estuary that had accessed freshwater after the flood. Instead, we found that larger individuals with each age cohort were more likely to have spent a period in freshwater. This highlights the need to maintain freshwater flows in rivers. About half the fish examined had accessed freshwater habitats before capture. Of these, all had spent at least their first two months in marine salinity waters before entering freshwater and some did not enter freshwater until four years of age. This contrasts with the results of several previous studies in other parts of the range that found that access to freshwater swamps by larval barramundi was important for enhanced population productivity and recruitment.

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A series of secondary and tertiary amide-substituted diselenides were synthesized and studied for their GPx-like antioxidant activities using H2O2 Cum-OOH, and tBuOOH as substrates and PhSH as thiol co-substrate.The effect of substitution at the free -NH group of the amide moiety in the sec-amide-based diselenides on GPx activity was analyzed by detailed experimental and theoretical methods. It is observed that substitution at the free -NH group significantly enhances the GPx-like activities of the sec-amide-based diselenides, mainly by reducing the Se center dot center dot center dot O nonbonded interactions. The reduction in strength of the Se center dot center dot center dot O interaction upon introduction of N,N-dialkyl substituents not only prevents the undesired thiol exchange reactions, but also reduces the stability of selenenyl sulfide intermediates. This leads to a facile disproportionation of the selenenyl sulfide to the corresponding diselenide, which enhances the catalytic activity. The mechanistic investigations indicate that the reactivity of diselenides having sec-or tert-amide moieties with PhSH is extremely slow; indicating that the first step of the catalytic cycle involves the reaction between the diselenides and peroxide to produce the corresponding selenenic and seleninic acids.

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Graphene-nanocrystalline metal sulphide composites were prepared by a one-pot reaction. A dispersion of graphite oxide layers in an aqueous solution of metal ions (Cd2+/Zn2+) was reacted with H2S gas, which acts as a sulphide source as well as a reducing agent, resulting in the formation of metal sulphide nanoparticles and simultaneous reduction of graphite oxide sheets to graphene sheets. The surface defect related emissions shown by free metal sulphide particles are quenched in the composites due to the interaction of the surface of the nanoparticles with graphene sheets.

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Oxygen Consumption by alternative oxidase (AOX), present in mitochondria of many angiosperms, is known to be cyanide-resistant in contrast to cytochrome oxidase. Its activity in potato tuber (Solarium tuberosum L.) was induced following chilling treatment at 4 degrees C.About half of the total O-2 consumption of succinate oxidation in such mitochondria was found to be sensitive to SHAM, a known inhibitor of AOX activity. Addition of catalase to the reaction mixture of AOX during the reaction decreased the rate of SHAM-sensitive oxygen consumption by nearly half, and addition at the end of the reaction released nearly half of the consumed oxygen by AOX, both typical of catalase action on H2O2. These findings with catalase suggest that the product of reduction of AOX is H2O2 and not H2O, as previously Surmised. In potatoes Subjected to chill stress (4 degrees C) for periods of 3, 5 and >= 8 days the activity of AOX in mitochondria increased progressively with a corresponding increase in the AOX protein detected by immunoblot of the protein.

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The selection of an odour sampling device may influence the composition of the resulting odour sample. Limited comparison of emission rates derived from turbulent and essentially quiescent sampling devices confirms that the emission rates derived from these devices are quite different. There is therefore compelling evidence that current odour sampling practice should have greater regard for fundamental physical and chemical principles, the nature of the odour source and the conditions created by the sampling device. Such consideration may identify the most appropriate situations under which the use of these devices may or may not be correct.

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Three anaerobic ponds used to store and treat piggery wastes were fully covered with permeable materials manufactured from polypropylene geofabric, polyethylene shade cloth and supported straw. The covers were assessed in terms of efficacy in reducing odour emission rates over a 40-month period. Odour samples were collected from the surface of the covers, the surface of the exposed liquor and from the surface of an uncovered (control) pond at one of the piggeries. Relative to the emission rate of the exposed liquor at each pond, the polypropylene, shade cloth and straw covers reduced average emission rates by 76%, 69% and 66%, respectively. At the piggery with an uncovered control pond, the polypropylene covers reduced average odour emission rates by 50% and 41%, respectively. A plausible hypothesis, consistent with likely mechanisms for the odour reduction and the olfactometric method used to quantifying the efficacy of the covers, is offered.

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Replacement of deteriorated water pipes is a capital-intensive activity for utility companies. Replacement planning aims to minimize total costs while maintaining a satisfactory level of service and is usually conducted for individual pipes. Scheduling replacement in groups is seen to be a better method and has the potential to provide benefits such as the reduction of maintenance costs and service interruptions. However, developing group replacement schedules is a complex task and often beyond the ability of a human expert, especially when multiple or conflicting objectives need to be catered for, such as minimization of total costs and service interruptions. This paper describes the development of a novel replacement decision optimization model for group scheduling (RDOM-GS), which enables multiple group-scheduling criteria by integrating new cost functions, a service interruption model, and optimization algorithms into a unified procedure. An industry case study demonstrates that RDOM-GS can improve replacement planning significantly and reduce costs and service interruptions.

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In this study, reduction and desorption of oxides of nitrogen (NOx) were conducted using an electrical discharge plasma technique. The study was carried out using a simulated gas mixture to explore the possibility of re-generation of used adsorbents by a nonthermal plasma desorption technique. Three different types of corona electrodes, namely, pipe, helical wire, and straight wire, were used for analyzing their effectiveness in NOx reduction/desorption. The pipe-type corona electrode exhibited a nitric oxide (NO) conversion of 50%, which is 1.5 times that of the straight-wire-type electrode at an energy density of 175J/L. The helical-wire-type corona electrode exhibited a NOx desorption efficiency almost 4 times that of the pipe-type electrode,indicating the possibility that corona-generated species play a crucial role in desorption.

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Different strategies for functionalization of the core region and periphery of core-shell type hyperbranched polymers (HBP) using the ``click'' reaction have been explored. For achieving periphera functionalization, an AB(2) + A-R-1 + A-R-2 type copolymerization approach was used, where A-R-1 is heptaethylene glycol monomethyl ether (HPEG-M) and A-R-2 is tetraethylene glycol monopropargyl ether (TEG-P). A very small mole fraction of the propargyl containing monomer, TEG-P, was used to ensure that the water-solubility of the hyperbranched polymer is minimally affected. Similarly, to incorporate propargyl groups in the core region, a new propargyl group bearing B-2-typ monomer was designed and utilized in an AB(2) + A(2) + B-2 + A-R-1 type copolymerization, such that the total mole fraction of B-2 + A(2) is small and their mole-ratio is 1: 1. Further, using a combination of both the above approaches, namely AB(2) + A(2) + B-2 + A-R-1 + A-R-2, hyperbranched structures that incorporate propargyl groups both at theperiphery and within the core were synthesized. Since the AB(2) monomer carries a hexamethylene spacer (C-6) and the periphery is PEGylated all the derivatized polymers form core-shell type structures in aqueous solutions. Attempts were made to ascertain and probe the location of the propargyl groups in these HBP's, by ``clicking'' azidomethylpyrene, onto them. However, the fluorescence spectra of aqueous solutions of the pyrene derivatized polymers were unable to discriminate between the various locations, possibly because the relatively hydrophobic pyrene units insert themselves into the core region to minimize exposure to water.

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Research in the field of NOx abatement has grown significantly in the past two decades. The general trend has been to develop new catalysts with complex materials in order to meet the stringent environmental regulations. This review discusses briefly about the different sources of NOx and its adverse effect on the ecosystem. The main portion of the review discusses the progress and development of various catalysts for NOx removal from exhaust by NO decomposition, NO reduction by CO or H-2 or NH3 or hydrocarbons. The importance of understanding the mechanism of NO decomposition and reduction in presence of metal ion substituted catalysts is emphasized. Some conclusions are made on the various catalytic approaches to NOx abatement.

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Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NOx, and unburned hydrocarbons-need to be fully converted to CO2, N-2, and H2O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al2O3 or SiO2 promoted by CeO2. However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce1-xMxO2-delta and Ce1-x-yTiyMxO2-delta (M = Pt, Pd, Rh; x = 0,01-0.02, delta approximate to x, y = 0.15-0.25) oxides in fluorite structure, In these oxide catalysts, pt(2+), Pd2+, or Rh3+ ions are substituted only to the extent of 1-2% of Ce4+ ion. Lower-valent noble metal ion substitution in CeO2 creates oxygen vacancies. Reducing molecules (CO, H-2, NH3) are adsorbed onto electron-deficient noble metal ions, while oxidizing (02, NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NOx reduction (with >80% N-2 selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO2 or Ce1-xTixO2 were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the more expensive Pt and Rh metals are not necessary in exhaust catalysts. We have also grown these nanocrystalline ionic catalysts on ceramic cordierite and have reproduced the results we observed in powder material on the honeycomb catalytic converter. Oxygen in a CeO2 lattice is activated by the substitution of Ti ion, as well as noble metal ions. Because this substitution creates longer Ti-O and M-O bonds relative to the average Ce-O bond within the lattice, the materials facilitate high oxygen storage and release. The interaction among M-0/Mn+, Ce4+/Ce3+, and Ti4+/Ti3+ redox couples leads to the promoting action of CeO2, activation of lattice oxygen and high oxygen storage capacity, metal support interaction, and high rates of catalytic activity in exhaust catalysis.

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A variety of materials were trialed as supported permeable covers using a series of laboratory-scale anaerobic digesters. Efficacy of cover performance was assessed in terms of impact on odour and greenhouse gas emission rate, and the characteristics of anaerobic liquor. Data were collected over a 12-month period. Initially the covers reduced the rate of odour emission 40-100 times relative to uncovered digesters. After about three months, this decreased to about a threefold reduction in odour emission rate, which was maintained over the remainder of the trial. The covers did not alter methane emission rates. Carbon dioxide emission rates varied according to cover type. Performance of the covers was attributed to the physical characteristics of the cover materials and changes in liquor composition. The reductions in odour emission indicate that these covers offer a cost-effective method for odour control.

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The efficacy of supported covers was investigated under field conditions using a series of prototypes deployed on an anaerobic pond treating typical piggery waste. Research focused on identifying effective cover support materials and deployment methods, quantifying odour reduction, and estimating the life expectancy of various permeable cover materials. Over a 10-month period, median odour emission rates were five to eight times lower from supported straw cover surfaces and a non-woven, spun fibre polypropylene weed control material than from the adjacent uncovered pond surface. While the straw covers visually appeared to degrade very rapidly, they continued to reduce odour emissions effectively. The polypropylene cover appeared to offer advantages from the perspectives of cost, reduced maintenance and ease of manufacture.