960 resultados para REDUCTION REACTION
Resumo:
Capacity reduction programmes, in the form of buybacks or decommissioning, have had relatively widespread application in fisheries in the US, Europe and Australia. A common criticism of such programmes is that they remove the least efficient vessels first, resulting in an increase in average efficiency of the remaining fleet, which tends to increase the effective fishing power of the remaining fleet. In this paper, the effects of a buyback programme on average technical efficiency in Australia’s Northern Prawn Fishery are examined using a multi-output production function approach with an explicit inefficiency model. As expected, the results indicate that average efficiency of the remaining vessels was generally greater than that of the removed vessels. Further, there was some evidence of an increase in average scale efficiency in the fleet as the remaining vessels were closer, on average, to the optimal scale. Key factors affecting technical efficiency included company structure and the number of vessels fishing. In regard to fleet size, our model suggests positive externalities associated with more boats fishing at any point in time (due to information sharing and reduced search costs), but also negative externalities due to crowding, with the latter effect dominating the former. Hence, the buyback resulted in a net increase in the individual efficiency of the remaining vessels due to reduced crowding, as well as raising average efficiency through removal of less efficient vessels.
Accelerometer data reduction : a comparison of four reduction algorithms on select outcome variables
Resumo:
Purpose Accelerometers are recognized as a valid and objective tool to assess free-living physical activity. Despite the widespread use of accelerometers, there is no standardized way to process and summarize data from them, which limits our ability to compare results across studies. This paper a) reviews decision rules researchers have used in the past, b) compares the impact of using different decision rules on a common data set, and c) identifies issues to consider for accelerometer data reduction. Methods The methods sections of studies published in 2003 and 2004 were reviewed to determine what decision rules previous researchers have used to identify wearing period, minimal wear requirement for a valid day, spurious data, number of days used to calculate the outcome variables, and extract bouts of moderate to vigorous physical activity (MVPA). For this study, four data reduction algorithms that employ different decision rules were used to analyze the same data set. Results The review showed that among studies that reported their decision rules, much variability was observed. Overall, the analyses suggested that using different algorithms impacted several important outcome variables. The most stringent algorithm yielded significantly lower wearing time, the lowest activity counts per minute and counts per day, and fewer minutes of MVPA per day. An exploratory sensitivity analysis revealed that the most stringent inclusion criterion had an impact on sample size and wearing time, which in turn affected many outcome variables. Conclusions These findings suggest that the decision rules employed to process accelerometer data have a significant impact on important outcome variables. Until guidelines are developed, it will remain difficult to compare findings across studies
Resumo:
The non-8-enoate anion undergoes losses of the elements of C3H6, C4H8 and C6H12 on collisional activation, The mechanisms of these processes have been elucidated by a combination of product ion and labelling (H-2 and C-13) studies, together with a neutralisation reionisation mass spectrometric study. These studies allow the following conclusions to be made. (i) The loss of C3H6 involves cyclisation of the enolate anion of non-8-enoic acid to yield the cyclopentyl carboxylate anion and propene. (ii) The loss of 'C4H8' is a charge-remote process (one which proceeds remote from the charged centre) which yields the pent-4-enoate anion, butadiene and dihydrogen. This process co-occurs and competes with complex H scrambling. (iii) The major loss of 'C6H12' occurs primarily by a charge-remote process yielding the acrylate anion, hexa-1,5-diene and dihydrogen, but in this case no H scrambling accompanies the process. (iv) It is argued that the major reason why the two charge-remote processes occur in preference to anion-induced losses of but-l-ene and hex-l-ene from the respective 4- and 2-anions is that although these anions are formed, they have alternative and lower energy fragmentation pathways than those involving the losses of but-l-ene and hex-l-ene; viz. the transient 4-anion undergoes facile proton transfer to yield a more stable anion, whereas the 2-(enolate) anion undergoes preferential cyclisation followed by elimination of propene [see (i) above].
Resumo:
We have investigated the gas-phase reaction of the alpha-aminoacetate (glycyl) radical anion (NH2(sic)CHCO2-) with O-2 using ion trap mass spectrometry, quantum chemistry, and statistical reaction rate theory. This radical is found to undergo a remarkably rapid reaction with O-2 to form the hydroperoxyl radical (HO2(sic)) and an even-electron imine (NHCHCO2-), with experiments and master equation simulations revealing that reaction proceeds at the ion molecule collision rate. This reaction is facilitated by a low-energy concerted HO2(sic) elimination mechanism in the NH2CH(OO(sic))CO2- peroxyl radical. These findings can explain the widely observed free-radical-mediated oxidation of simple amino acids to amides plus alpha-keto acids (their imine hydrolysis products). This work also suggests that imines will be the main intermediates in the atmospheric oxidation of primary and secondary amines, including amine carbon capture solvents such as 2-aminoethanol (commonly known as monoethanolamine, or MEA), in a process that avoids the ozone-promoting conversion of (sic)NO to (sic)NO2 commonly encountered in peroxyl radical chemistry.
Resumo:
Alkylperoxyl radicals are intermediates in the oxidation Of hydrocarbons. The reactive nature of these intermediates, however, has made therin elusive to direct observation and isolation. We have employed ion trap mass spectrometry to synthesize and characterize 4-carboxylatocyclohexyl radical anions ((center dot)C(6)H(10)-CO(2)(-)) and observe their reactivity in the presence of dioxygen. The resulting reaction is facile (k = 1.8 x 10(-10) cm(3) molecule(-1) s(-1) or 30% of calculated collision rate) and results in (i) the addition Of O(2) to form stabilized 4-carboxylatocyclohexylperoxyl radical anions ((center dot)OO-C(6)H(10)-CO(2)(-)), providing the first direct observation of a cyclohexylperoxyl radical, and (ii) elimination of HO(2)(center dot) and HO(center dot) radicals consistent with recent laser-induced fluorescence studies of the reaction of neutral cyclohexyl radicals with O(2). Electronic structure calculations at the B3LYP/6-31+G(d) level of theory reveal viable pathways for the observed reactions showing that formation of the peroxyl radical is exothermic by 37 kcal mol(-1) with subsequent transition states its low as -6.6 kcal mol(-1) (formation of HO(2)(center dot)) and -9.1 kcal mol(-1) (formation of HO(center dot)) with respect to the entrance channel. The combined computational and experimental data Suggest that the structures of the reaction products correspond to cyclohexenes and epoxides from HO(2)(center dot) and HO(center dot) loss, respectively, while alternative pathways leading to cyclohexanone or ring-opened isomers ate not observed, Activation of the charged peroxyl radical (center dot)OO-C(6)H(10)-CO(2)(-) by collision induced disassociation also results in the loss Of HO(2)(center dot) and HO(center dot) radicals confirming that these products are directly connected to the peroxyl radical intermediate.
Resumo:
Background Accelerometers have become one of the most common methods of measuring physical activity (PA). Thus, validity of accelerometer data reduction approaches remains an important research area. Yet, few studies directly compare data reduction approaches and other PA measures in free-living samples. Objective To compare PA estimates provided by 3 accelerometer data reduction approaches, steps, and 2 self-reported estimates: Crouter's 2-regression model, Crouter's refined 2-regression model, the weighted cut-point method adopted in the National Health and Nutrition Examination Survey (NHANES; 2003-2004 and 2005-2006 cycles), steps, IPAQ, and 7-day PA recall. Methods A worksite sample (N = 87) completed online-surveys and wore ActiGraph GT1M accelerometers and pedometers (SW-200) during waking hours for 7 consecutive days. Daily time spent in sedentary, light, moderate, and vigorous intensity activity and percentage of participants meeting PA recommendations were calculated and compared. Results Crouter's 2-regression (161.8 +/- 52.3 minutes/day) and refined 2-regression (137.6 +/- 40.3 minutes/day) models provided significantly higher estimates of moderate and vigorous PA and proportions of those meeting PA recommendations (91% and 92%, respectively) as compared with the NHANES weighted cut-point method (39.5 +/- 20.2 minutes/day, 18%). Differences between other measures were also significant. Conclusions When comparing 3 accelerometer cut-point methods, steps, and self-report measures, estimates of PA participation vary substantially.
Resumo:
Background A feature of epithelial to mesenchymal transition (EMT) relevant to tumour dissemination is the reorganization of actin cytoskeleton/focal contacts, influencing cellular ECM adherence and motility. This is coupled with the transcriptional repression of E-cadherin, often mediated by Snail1, Snail2 and Zeb1/δEF1. These genes, overexpressed in breast carcinomas, are known targets of growth factor-initiated pathways, however it is less clear how alterations in ECM attachment cross-modulate to regulate these pathways. EGF induces EMT in the breast cancer cell line PMC42-LA and the kinase inhibitor staurosporine (ST) induces EMT in embryonic neural epithelial cells, with F-actin de-bundling and disruption of cell-cell adhesion, via inhibition of aPKC. Methods PMC42-LA cells were treated for 72 h with 10 ng/ml EGF, 40 nM ST, or both, and assessed for expression of E-cadherin repressor genes (Snail1, Snail2, Zeb1/δEF1) and EMT-related genes by QRT-PCR, multiplex tandem PCR (MT-PCR) and immunofluorescence +/- cycloheximide. Actin and focal contacts (paxillin) were visualized by confocal microscopy. A public database of human breast cancers was assessed for expression of Snail1 and Snail2 in relation to outcome. Results When PMC42-LA were treated with EGF, Snail2 was the principal E-cadherin repressor induced. With ST or ST+EGF this shifted to Snail1, with more extreme EMT and Zeb1/δEF1 induction seen with ST+EGF. ST reduced stress fibres and focal contact size rapidly and independently of gene transcription. Gene expression analysis by MT-PCR indicated that ST repressed many genes which were induced by EGF (EGFR, CAV1, CTGF, CYR61, CD44, S100A4) and induced genes which alter the actin cytoskeleton (NLF1, NLF2, EPHB4). Examination of the public database of breast cancers revealed tumours exhibiting higher Snail1 expression have an increased risk of disease-recurrence. This was not seen for Snail2, and Zeb1/δEF1 showed a reverse correlation with lower expression values being predictive of increased risk. Conclusion ST in combination with EGF directed a greater EMT via actin depolymerisation and focal contact size reduction, resulting in a loosening of cell-ECM attachment along with Snail1-Zeb1/δEF1 induction. This appeared fundamentally different to the EGF-induced EMT, highlighting the multiple pathways which can regulate EMT. Our findings add support for a functional role for Snail1 in invasive breast cancer.
Resumo:
Aim To establish the suitability of multiplex tandem polymerase chain reaction (MT-PCR) for rapid identification of oestrogen receptor (ER) and Her-2 status using a single, formalin-fixed, paraffin-embedded (FFPE) breast tumour section. Methods Tissue sections from 29 breast tumours were analysed by immunohistochemistry (IHC) and fluorescence in situ hybridisation (FISH). RNA extracted from 10μm FFPE breast tumour sections from 24 of 29 tumours (14 ER positive and 5 Her-2 positive) was analysed by MT-PCR. After establishing a correlation between IHC and/or FISH and MT-PCR results, the ER/Her-2 status of a further 32 randomly selected, archival breast tumour specimens was established by MT-PCR in a blinded fashion, and compared to IHC/FISH results. Results MT-PCR levels of ER and Her-2 showed good concordance with IHC and FISH results. Furthermore, among the ER positive tumours, MT-PCR provided a quantitative score with a high dynamic range. Threshold values obtained from this data set applied to 32 archival tumour specimens showed that tumours strongly positive for ER and/or Her-2 expression were easily identified by MT-PCR. Conclusion MT-PCR can provide rapid, sensitive and cost-effective analysis of FFPE material and may prove useful as triage to identify patients suited to endocrine or trastuzumab (Herceptin) treatment.
Resumo:
The cotton strip assay (CSA) is an established technique for measuring soil microbial activity. The technique involves burying cotton strips and measuring their tensile strength after a certain time. This gives a measure of the rotting rate, R, of the cotton strips. R is then a measure of soil microbial activity. This paper examines properties of the technique and indicates how the assay can be optimised. Humidity conditioning of the cotton strips before measuring their tensile strength reduced the within and between day variance and enabled the distribution of the tensile strength measurements to approximate normality. The test data came from a three-way factorial experiment (two soils, two temperatures, three moisture levels). The cotton strips were buried in the soil for intervals of time ranging up to 6 weeks. This enabled the rate of loss of cotton tensile strength with time to be studied under a range of conditions. An inverse cubic model accounted for greater than 90% of the total variation within each treatment combination. This offers support for summarising the decomposition process by a single parameter R. The approximate variance of the decomposition rate was estimated from a function incorporating the variance of tensile strength and the differential of the function for the rate of decomposition, R, with respect to tensile strength. This variance function has a minimum when the measured strength is approximately 2/3 that of the original strength. The estimates of R are almost unbiased and relatively robust against the cotton strips being left in the soil for more or less than the optimal time. We conclude that the rotting rate X should be measured using the inverse cubic equation, and that the cotton strips should be left in the soil until their strength has been reduced to about 2/3.
Resumo:
The Wet Tropics region has a unique water asset and is also considered a priority region for the improvement of water quality entering the Great Barrier Reef due to a combination of high rainfall, intensive agricultural use, urban areas and the proximity of valuable reef assets to the coast. Agricultural activities are one of many identified threats to water quality and water flows in the Wet Tropics in terms of sediment and pollutant-related water quality decline. Information describing the current state of agricultural management practices across the region is patchy at best. Based on the best available information on agricultural management practices in the Wet Tropics in 2008, it is clear that opportunities exist to improve nutrient, sediment and pesticide management practice to reduce the impact on the water asset and the Great Barrier Reef. Based on current understandings of practices and the relationship between practices and reef water quality, the greatest opportunities for improved water quality are as follows: · nutrients – correct rate and the placement of fertilisers; · pesticides – improve weed control planning, herbicide rates and calibration practice; and · soil and sediment – implement new farming system practices. The 2008-09 Reef Rescue program sought to accelerate the rate of adoption of improved management practices and through Terrain invested $6.8M in the 2008-09 year for: · landholder water quality improvement incentive payments; · cross regional catchment repair of wetlands and riparian lands in areas of high sediment or nutrient loss; and · partnerships in the region to lever resources and support for on-ground practice change. The program delivered $3,021,999 in onground incentives to landholders in the Wet Tropics to improve farm practices from D or C level to B or A level. The landholder Water Quality Incentives Grants program received 300 individual applications for funding and funded 143 individual landholders to implement practice change across 36,098 ha of farm land. It is estimated that the Reef Rescue program facilitated practice change across 21% of the cane industry, and 20% of the banana industry. The program levered an additional $2,441,166 in landholder cash contributions and a further $907,653 in non-cash in-kind contributions bringing the total project value of the landholder grants program in the Wet Tropics to $6,370,819. Most funded projects targeted multiple water quality objectives with a focus on nutrient and sediment reduction. Of the 143 projects funded, 115 projects addressed nutrient management either as the primary focus or in combination with strategies that targeted other water quality objectives. Overall, 82 projects addressed two or more water quality targets. Forty-five percent of incentive funds were allocated to new farming system practices (direct drill legumes, zonal tillage equipment, permanent beds, min till planting equipment, GPS units, laser levelling), followed by 24% allocated to subsurface fertiliser applicators (subsurface application of fertiliser using a stool splitter or beside the stool, at the correct Six Easy Steps rate). As a result, Terrain estimates that the incentive grants achieved considerable reductions in nitrogen, phosphorus, sediment and pesticide loads. The program supported nutrient management training of 167 growers managing farms covering over 20% of the area harvested in 2008, and 18 industry advisors and resellers. This resulted in 115 growers (155 farms) developing nutrient management plans. The program also supported Integrated Weed Management training of 80 growers managing farms covering 8% of the area harvested in 2008, and 6 industry advisors and resellers. This report, which draws on the best available Reef Rescue Management Monitoring, Evaluation, Reporting, and Improvement (MERI) information to evaluate program performance and impact on water quality outcomes, is the first in a series of annual reports that will assess and evaluate the impact of the Reef Rescue program on agricultural practices and water quality outcomes. The assessment is predominantly focused on the cane industry because of data availability. In the next stage, efforts will expand to: · improve practice data for the banana and grazing industry; · gain a better understanding of the water quality trends and the factors influencing them in the Wet Tropics; in particular work will focus on linking the results of the Paddock to Reef monitoring program and practice change data to assess program impact; · enhance estimations of the impact of practice change on pollutant loads from agricultural land use; · gain a better understanding of the extent of ancillary practice (change not directly funded) resulting from Reef Rescue training/ education/communication programs; and · provide a better understanding of the economic cost of practice change across the Wet Tropics region. From an ecological perspective, water quality trends and the factors that may be contributing to change, require further investigation. There is a critical need to work towards an enhanced understanding of the link between catchment land management practice change and reef water quality, so that reduced nutrient, sediment, and pesticide discharge to the Great Barrier Reef can be quantified. This will also assist with future prioritisation of grants money to agricultural industries, catchments and sub catchments. From a social perspective, the program has delivered significant water quality benefits from landholder education and training. It is believed that these activities are giving landholders the information and tools to implement further lasting change in their production systems and in doing so, creating a change in attitude that is supportive and inclusive of Natural Resource Management (NRM). The program in the Wet Tropics has also considerably strengthened institutional partnerships for NRM, particularly between NRM and industry and extension organisations. As a result of the Reef Rescue program, all institutions are actively working together to collectively improve water quality. The Reef Rescue program is improving water quality entering the Great Barrier Reef Lagoon by catalysing substantial activity in the Wet Tropics region to improve land management practices and reduce the water quality impact of agricultural landscapes. The solid institutional partnerships between the regional body, industry, catchment and government organisations have been fundamental to the successful delivery of the landholder grant and catchment rehabilitation programs. Landholders have generally had a positive perception and reaction to the program, its intent, and the practical, focused nature of grant-based support. Demand in the program was extremely high in 2008-09 and is expected to increase in 2009-2010.
Resumo:
This article elucidates and analyzes the fundamental underlying structure of the renormalization group (RG) approach as it applies to the solution of any differential equation involving multiple scales. The amplitude equation derived through the elimination of secular terms arising from a naive perturbation expansion of the solution to these equations by the RG approach is reduced to an algebraic equation which is expressed in terms of the Thiele semi-invariants or cumulants of the eliminant sequence { Zi } i=1 . Its use is illustrated through the solution of both linear and nonlinear perturbation problems and certain results from the literature are recovered as special cases. The fundamental structure that emerges from the application of the RG approach is not the amplitude equation but the aforementioned algebraic equation. © 2008 The American Physical Society.
Resumo:
Sub-oxide-to-metallic highly-crystalline nanowires with uniformly distributed nanopores in the 3 nm range have been synthesized by a unique combination of the plasma oxidation, re-deposition and electron-beam reduction. Electron beam exposure-controlled oxide → sub-oxide → metal transition is explained using a non-equilibrium model.
Resumo:
The mechanisms and the reaction products for the oxidation of sulfide ions in the presence of pyrite have been established. When the leach solution contains free sulfide ions, oxidation occurs via electron transfer from the sulfide ion to dissolved oxygen on the pyrite mineral surface, with polysulfides being formed as an intermediate oxidation product. In the absence of cyanide, the polysulfides are further oxidised to thiosulfate, whilst with cyanide present, thiocyanate and sulfite are also formed from the reaction of polysulfides with cyanide and dissolved oxygen. Polysulfide chain length has been shown to affect the final reaction products of polysulfide oxidation by dissolved oxygen. The rate of pyrite catalysed sulfide ion oxidation was found to be slower in cyanide solutions compared to cyanide free solutions. Mixed potential measurements indicated that the reduction of oxygen at the pyrite surface is hindered in the presence of cyanide. The presence of sulfide ions was also found to activate the pyrite surface, increasing its rate of oxidation by oxygen. This effect was particularly evident in the presence of cyanide; in the presence of sulfide the increase in total sulfur from pyrite oxidation was 2.3 mM in 7 h, compared to an increase of <1 mM in the absence of sulfide over 24 h.
Resumo:
Using density functional theory, we have investigated the catalytic properties of bimetallic complex catalysts PtlAum(CO)n (l + m = 2, n = 1–3) in the reduction of SO2 by CO. Due to the strong coupling between the C-2p and metal 5d orbitals, pre-adsorption of CO molecules on the PtlAum is found to be very effective in not only reducing the activation energy, but also preventing poisoning by sulfur. As result of the coupling, the metal 5d band is broadened and down-shifted, and charge is transferred from the CO molecules to the PtlAum. As SO2 is adsorbed on the catalyst, partial charge moves to the anti-σ bonding orbitals between S and O in SO2, weakening the S–O bond strength. This effect is enhanced by pre-adsorbing up to three CO molecules, therefore the S–O bonds become vulnerable. Our results revealed the mechanism of the excellent catalytic properties of the bimetallic complex catalysts.
Resumo:
The catalytic activities, to the reduction of SO2 by CO, of clusters PtlAum (l + m = 2) with or without preadsorbing CO molecules are investigated using first-principles density functional theory. We find that the PtAu(CO)n (n = 1–3) clusters show more excellent catalytic properties than either pure metallic catalysts. Preadsorption of CO to the catalysts could effectively avoid platinum-based catalyst sulfur poisoning; as more CO molecules preadsorbed to the catalysts, the energy barriers for the carbonyl sulfide (COS) molecule’s desorption from the catalyst are remarkably decreased. We propose an ideal catalytic cycle to simultaneously get rid of SO2 and CO over the catalysts PtAu(CO)3.