Prediction of absolute rate coefficients and product branching ratios for the C(P-3) plus allene reaction system

Complex chemical reactions in the gas phase can be decomposed into a network of elementary (e.g., unimolecular and bimolecular) steps which may involve multiple reactant channels, multiple intermediates, and multiple products. The modeling of such reactions involves describing the molecular species and their transformation by reaction at a detailed level. Here we focus on a detailed modeling of the C(P-3)+allene (C3H4) reaction, for which molecular beam experiments and theoretical calculations have previously been performed. In our previous calculations, product branching ratios for a nonrotating isomerizing unimolecular system were predicted. We extend the previous calculations to predict absolute unimolecular rate coefficients and branching ratios using microcanonical variational transition state theory (mu-VTST) with full energy and angular momentum resolution. Our calculation of the initial capture rate is facilitated by systematic ab initio potential energy surface calculations that describe the interaction potential between carbon and allene as a function of the angle of attack. Furthermore, the chemical kinetic scheme is enhanced to explicitly treat the entrance channels in terms of a predicted overall input flux and also to allow for the possibility of redissociation via the entrance channels. Thus, the computation of total bimolecular reaction rates and partial capture rates is now possible. (C) 2002 American Institute of Physics.

Are transitions in human gait determined by mechanical, kinetic or energetic factors?

It is currently unclear whether it is the need to maintain metabolic efficiency, the need to keep skeletal loading below critical force levels, or simple mechanical factors that drive the walk-to-run (W R) and run-to-walk (R-W) transitions in human gait. Eighteen adults (9 males and 9 females) locomoted on an instrumented treadmill using their preferred gait. Each completed 2 ascending (W-R) and 2 descending (R-W) series of trials under three levels of loading (0%, 15% and 30% body weight). For each trial, participants locomoted for 60 s at each of 9 different speeds -4 speeds both above and below their preferred transition speed (PTS) plus their PTS. Evidence was sought for critical levels of key kinetic (maximum vertical force, impulse, first peak force, time to first peak force and maximum loading rate), energetic (oxygen consumption, transport cost) and mechanical variables (limb lengths, strength) predictive of the gait transition. Analyses suggested the kinetic variables of time to first peak force and loading rate as the most likely determinants of the W-R and R-W transitions. (C) 2003 Elsevier Science B.V. All rights reserved.

Cholesterol-lowering therapy with pravastatin in patients with average cholesterol levels and established ischaemic heart disease: is it cost-effective?

Objective: To measure the cost-effectiveness of cholesterol-lowering therapy with pravastatin in patients with established ischaemic heart disease and average baseline cholesterol levels. Design: Prospective economic evaluation within a double-blind randomised trial (Long-Term Intervention with Pravastatin in Ischaemic Disease [LIPID]), in which patients with a history of unstable angina or previous myocardial infarction were randomised to receive 40 mg of pravastatin daily or matching placebo. Patients and setting: 9014 patients aged 35-75 years from 85 centres in Australia and New Zealand, recruited from June 1990 to December 1992. Main outcome measures: Cost per death averted, cost per life-year gained, and cost per quality-adjusted life-year gained, calculated from measures of hospitalisations, medication use, outpatient visits, and quality of life. Results: The LIPID trial showed a 22% relative reduction in all-cause mortality (P < 0.001). Over a mean follow-up of 6 years, hospital admissions for coronary heart disease and coronary revascularisation were reduced by about 20%. Over this period, pravastatin cost $A4913 per patient, but reduced total hospitalisation costs by $A1385 per patient and other long-term medication costs by $A360 per patient. In a subsample of patients, average quality of life was 0.98 (where 0 = dead and 1 = normal good health); the treatment groups were not significantly different. The absolute reduction in all-cause mortality was 3.0% (95% CI, 1.6%-4.4%), and the incremental cost was $3246 per patient, resulting in a cost per life saved of $107730 (95% Cl, $68626-$209881) within the study period. Extrapolating long-term survival from the placebo group, the undiscounted cost per life-year saved was $7695 (and $10 938 with costs and life-years discounted at an annual rate of 5%). Conclusions: Pravastatin therapy for patients with a history of myocardial infarction or unstable angina and average cholesterol levels reduces all-cause mortality and appears cost effective compared with accepted treatments in high-income countries.

Practical and economic advantages of choice feeding systems for laying poultry

Poultry can be managed under different feeding systems, depending on the husbandry skills and the feed available. These systems include the following: (1) a complete dry feed offered as a mash ad libitum; (2) the same feed offered as pellets or crumbles ad libitum; (3) a complete feed with added whole grain; (4) a complete wet feed given once or twice a day; (5) a complete feed offered on a restricted basis; (6) choice feeding. Of all these, an interesting alternative to offering complete diets is choice feeding which can be applied on both a small or large commercial scale. Under choice feeding or free-choice feeding birds are usually offered a choice between three types of feedstuffs: (a) an energy source (e.g. maize, rice bran, sorghum or wheat); (b) a protein source (e.g. soyabean meal, meat meal, fish meal or coconut meal) plus vitamins and minerals and (c), in the case of laying hens, calcium in granular form (i.e. oyster-shell grit). This system differs from the modern commercial practice of offering a complete diet comprising energy and protein sources, ground and mixed together. Under the complete diet system, birds are mainly only able to exercise their appetite for energy. When the environmental temperature varies, the birds either over- or under-consume protein and calcium. The basic principle behind practising choice feeding with laying hens is that individual hens are able to select from the various feed ingredients on offer and compose their own diet, according to their actual needs and production capacity. A choice-feeding system is of particular importance to small poultry producers in developing countries, such as Indonesia, because it can substantially reduce the cost of feed. The system is flexible and can be constructed in such a way that the various needs of a flock of different breeds, including village chickens, under different climates can be met. The system also offers a more effective way to use home-produced grain, such as maize, and by-products, such as rice bran, in developing countries. Because oyster-shell grit is readily available in developing countries at lower cost than limestone, the use of cheaper oyster-shell grit can further benefit small-holders in these countries. These benefits apart, simpler equipment suffices when designing and building a feed mixer on the farm, and transport costs are lower. If whole (unground) grain is used, the intake of which is accompanied by increased efficiency of feed utilisation, the costs of grinding, mixing and many of the handling procedures associated with mash and pellet preparation are eliminated. The choice feedstuffs can all be offered in the current feed distribution systems, either by mixing the ingredients first or by using a bulk bin divided into three compartments.

Cost comparison of hospital- and home-based treatment models for acute chronic obstructive pulmonary disease

This trial compared the cost of an integrated home-based care model with traditional inpatient care for acute chronic obstructive pulmonary disease (COPD). 25 patients with acute COPD were randomised to either home or hospital management following request for hospital admission. The acute care at home group costs per separation ($745, CI95% $595-$895, n = 13) were significantly lower (p < 0.01) than the hospital group ($2543, CI95% $1766-$3321, n = 12). There was an improvement in lung function in the hospital-managed group at the Outpatient Department review, decreased anxiety in the Emergency Department in the home-managed group and equal patient satisfaction with care delivery. Acute care at home schemes can substitute for usual hospital care for some patients without adverse effects, and potentially release resources. A funding model that allows adequate resource delivery to the community will be needed if there is a move to devolve acute care to community providers.

Opportunity cost of ad hoc marine reserve design decisions: an example from South Australia

Like many states and territories, South Australia has a legacy of marine reserves considered to be inadequate to meet current conservation objectives. In this paper we configured exploratory marine reserve systems, using the software MARXAN, to examine how efficiently South Australia's existing marine reserves contribute to quantitative biodiversity conservation targets. Our aim was to compare marine reserve systems that retain South Australia's existing marine reserves with reserve systems that are free to either ignore or incorporate them. We devised a new interpretation of irreplaceability to identify planning units selected more than could be expected from chance alone. This is measured by comparing the observed selection frequency for an individual planning unit with a predicted selection frequency distribution. Knowing which sites make a valuable contribution to efficient marine reserve system design allows us to determine how well South Australia's existing reserves contribute to reservation goals when representation targets are set at 5, 10, 15, 20, 30 and 50% of conservation features. Existing marine reserves that tail to contribute to efficient marine reserve systems constitute 'opportunity costs'. We found that despite spanning less than 4% of South Australian state waters, locking in the existing ad hoc marine reserves presented considerable opportunity costs. Even with representation targets set at 50%, more than halt of South Australia's existing marine reserves were selected randomly or less in efficient marine reserve systems. Hence, ad hoc marine reserve systems are likely to be inefficient and may compromise effective conservation of marine biodiversity.

Sequencing batch reactor technology: the key to a BP refinery (Bulwer Island) upgraded environmental protection system - a low cost lagoon based retro-fit

BP Refinery (Bulwer Island) Ltd (BP) located on the eastern Australian coast is currently undergoing a major expansion as a part of the Queensland Clean Fuels Project. The associated wastewater treatment plant upgrade will provide a better quality of treated effluent than is currently possible with the existing infrastructure, and which will be of a sufficiently high standard to meet not only the requirements of imposed environmental legislation but also BP's environmental objectives. A number of challenges were faced when considering the upgrade, particularly; cost constraints and limited plot space, highly variable wastewater, toxicity issues, and limited available hydraulic head. Sequencing Batch Reactor (SBR) Technology was chosen for the lagoon upgrade based on the following; SBR technology allowed a retro-fit of the existing earthen lagoon without the need for any additional substantial concrete structures, a dual lagoon system allowed partial treatment of wastewaters during construction, SBRs give substantial process flexibility, SBRs have the ability to easily modify process parameters without any physical modifications, and significant cost benefits. This paper presents the background to this application, an outline of laboratory studies carried out on the wastewater and details the full scale design issues and methods for providing a cost effective, efficient treatment system using the existing lagoon system.

Effects of heat treatment on the nutritional value of raw soybean selected for low trypsin inhibitor activity

1. Two broiler experiments and a layer experiments were conducted on Kunitz trypsin inhibitor (Kti) soybeans (SB) of low trypsin inhibitor (TI) activity to determine their nutritive value when included as mash in least-cost poultry diets. 2. Experiment 1 compared chick performance on the Kti or raw SB using a commercial full-fat SB meal (FFSBM) and a solvent extracted SB meal (SBM) as controls during a 20 d experimental period. Broiler experiment 2 compared Kti and raw SB, non-steamed, or steam-pelleted with and without DL-methionine supplementation added to every treatment containing 170 g SB/kg. For each broiler experiment the levels of each SB were 70, 120 and 170 g/kg with the control birds fed only 170 g SB/kg. 3. The layer experiment, compared steam-pelleted Kti and raw SB against a non-steamed Kti and raw SB each fed at two levels (70 and 110 g/kg) x 30 replicates from 29 weeks of age for 19 weeks in a completely randomised design. Production parameters were measured when diets were formulated to contain minimum required specifications and calculated apparent metabolisable energy (AME). At the completion of each trial, 2 broiler birds from each cage and 5 layer birds per treatment were killed, weighed, and their liver and pancreas weighed. 4. Both broiler experiments indicated that production parameters on the Kti SB treatments were significantly lower (P < 0.05) than on the two commercial control SB treatments. However, the Kti treatments were superior to the raw SB treatments. 5. Pancreas weight increased with increasing inclusion of both raw and Kti SB, suggesting that a TI was causing the depression in performance. The AME of the Kti SB was similar to that of commercial FFSB meal. After steam conditioning, the raw SB meal AME value of 9.5 MJ/kg dry matter (DM) was improved to 14.1 MJ/kg DM by reduced TI activity, but this AME improvement with TI activity reduction, plus the supplementation with DL-methionine on birds fed the raw SB had no effect (P > 0.05) on any parameter evaluated in experiment 2. 6. The layer experiment showed that hens on the Kti SB treatments had significantly greater live weight gain (LWG), egg weight and daily egg mass than birds given raw SB. A reduced food intake (FI) was observed in the Kti treatments but egg mass was generally similar to that on the FFSB control diet, indicating that Kti SB supported excellent egg production at an inclusion of 110 g/kg. The depressed performance observed for broiler chicks suggest that younger birds are more susceptible to the effects of SB TI.

Desenvolvimento e avaliação da acurácia do sistema de filtração (BacFil 6.0) na detecção de bacilos álcool-ácido resistentes em amostras de lavado broncoalveolar de pacientes com suspeita de tuberculose

A baciloscopia é o principal método diagnóstico da tuberculose (TB) em razão do seu baixo custo, rapidez e facilidade de execução. Porém sua sensibilidade é baixa, principalmente nas formas paucibacilares da doença. Nesse sentido, novas metodologias que resultem no aumento da sensibilidade da baciloscopia tornam-se absolutamente necessárias. Neste estudo, nos propusemos a aprimorar e padronizar o sistema de filtração BacFil e avaliar sua performance e acurácia em amostras paucibacilares (lavado broncoalveolar). Para alcançar esses objetivos desenvolvemos o estudo em duas fases. Na primeira fase, foram realizados ensaios para definir: 1) utilização de membranas brancas para visualização de BAAR corados por Auramina-O; 2) aumento do volume de NALC, utilização de pérolas de vidro no processo de digestão das amostras e mudança no sistema do suporte do pré-filtro; 3) meios de fixação da membrana de filtração na lâmina de microscopia; 4) limite de detecção da técnica; 5) aumento do volume de NaOCl e a influência desse aumento na visualização de BAAR na membrana. Verificou-se que: a membrana de policarbonato branca tem a mesma eficiência da membrana de policarbonato preta na visualização de BAAR fluorescentes; o método modificado utilizando maior concentração de NALC, pérolas de vidro e sistema de pré-filtro baseado em orifícios obteve 98% de passagem das amostras pelo sistema; a melhor forma de fixação da membrana na lâmina foi obtida por intermédio da utilização de fita dupla face; o limite de detecção da técnica de filtração utilizando o sistema BacFil versão 6.0 foi de 2 a 9 BAAR por mililitro de suspensão bacteriana com D.O de 0,250 ± 0,01 a 625nm; o aumento da concentração de NaOCl para 10% ajuda na passagem de um maior volume de amostra pelo sistema, porém ocasiona a diminuição da quantidade BAAR na membrana de filtração após o período necessário para todo o processo. Na segunda fase foi avaliado acurácia da técnica padronizada em 101 amostras de lavado broncoalveolar (LBA) de pacientes com suspeita de TB provenientes do Hospital Universitário Cassiano Antônio de Moraes. Observou-se que a sensibilidade da técnica de filtração (BacFil versão 6.0) foi de 76% e especificidade de 95%. A sensibilidade obtida foi significativamente maior do que a observada na baciloscopia após centrifugação que foi de 59% (p = 0,001). No entanto, constatou-se uma diminuição de especificidade na técnica de filtração (95%) em relação a técnica de 8 centrifugação (99%). Concluímos que as modificações realizadas nos sistema de filtração permitiu sanar os problemas técnicos apresentados nas versões anteriores e aumentar a sensibilidade da baciloscopia de amostras paucibacilares (lavado broncoalveolar) para o diagnóstico da TB pulmonar.

Nitrogen fertilizer (15N) leaching in a central pivot fertigated coffee crop

Nitrogen has a complex dynamics in the soil-plant-atmosphere system. N fertilizers are subject to chemical and microbial transformations in soils that can result in significant losses. Considering the cost of fertilizers, the adoption of good management practices like fertigation could improve the N use efficiency by crops. Water balances (WB) were applied to evaluate fertilizer N leaching using 15N labeled urea in west Bahia, Brazil. Three scenarios (2008/2009) were established: i) rainfall + irrigation the full year, ii) rainfall only; and iii) rainfall + irrigation only in the dry season. The water excess was considered equal to the deep drainage for the very flat area (runoff = 0) with a water table located several meters below soil surface (capillary rise = 0). The control volume for water balance calculations was the 0 - 1 m soil layer, considering that it involves the active root system. The water drained below 1 m was used to estimate fertilizer N leaching losses. WB calculations used the mathematic model of Penman-Monteith for evapotranspiration, considering the crop coefficient equal to unity. The high N application rate associated to the high rainfall plus irrigation was found to be the main cause for leaching, which values were 14.7 and 104.5 kg ha-1 for the rates 400 and 800 kg ha-1 of N, corresponding to 3.7 and 13.1 % of the applied fertilizer, respectively.