994 resultados para 196-1173
Resumo:
Both [C4CO]−· and [C2COC2]−· are formed in the ion source of a VG ZAB 2HF mass spectrometer by the respective processes HO− + Me3Si–CC–CC–CO–CMe3 → [C4CO]−· + Me3SiOH + Me3C·, and Me3Si–CC–CO–CC–SiMe3 + SF6 + e → [C2COC2]−· + 2Me3SiF + SF4. The second synthetic pathway involves a double desilylation reaction similar to that first reported by Squires. The two radical anion isomers produce different and characteristic charge reversal spectra upon collisional activation. In contrast, following collision induced charge stripping, both radical anions produce neutral C4CO as evidenced by the identical neutralisation reionisation (−NR+) spectra. The exclusive rearrangement of C213COC2 to C413CO indicates that 12C–O bond formation is not involved in the reaction. Ab initio calculations (at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G∗ level of theory) have been used to investigate the reaction coordinates on the potential surfaces for both singlet and triplet rearrangements of neutral C2COC2. Singlet C2COC2 is less stable than singlet C4CO by 78.8 kcal mol−1 and requires only 8.5 kcal mol−1 of additional energy to effect conversion to C4CO by a rearrangement sequence involving three C–C ring opening/cyclisation steps.
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Objectives: To i) identify predictors of admission, and ii) describe outcomes for patients who arrived via ambulance to three Australian public Emergency Departments (EDs), before and after the opening of 41 additional ED beds within the area. Methods: A retrospective, comparative, cohort study using deterministically linked health data collected between 3 September 2006 and 2 September 2008. Data included ambulance offload delay, time to see doctor, ED length of stay (ED LOS), admission requirement, access block, hospital length of stay and in-hospital mortality. Logistic regression analysis was undertaken to identify predictors of hospital admission. Results: One third of all 286,037 ED presentations were via ambulance (n= 79,196) and 40.3% required admission. After increasing emergency capacity, the only outcome measure to improve was in-hospital mortality. Ambulance offload delay, time to see doctor, ED length of stay (ED LOS), admission requirement, access block, hospital length of stay did not improve. Strong predictors of admission before and after increased capacity included: age over 65 years, Australian Triage Scale (ATS) category 1-3, diagnoses of circulatory or respiratory conditions and ED LOS > 4 hours. With additional capacity the odds ratios for these predictors increased for age >65 and ED LOS > 4 hours and decreased for triage category and ED diagnoses. Conclusions: Expanding ED capacity from 81 to 122 beds within a health service area impacted favourably on mortality outcomes but not on time-related service outcomes such as ambulance offload time, time to see doctor and ED LOS. To improve all service outcomes, when altering (increasing/decreasing) ED bed numbers, the whole healthcare system needs to be considered.
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Introduction This study aimed to examine the geometric and dosimetric results when radiotherapy treatment plans are designed for prostate cancer patients with hip prostheses. Methods Ten EBRT treatment plans for localised prostate cancer, in the presence of hip prostheses, were analysed and compared with a reference set of 196 treatment plans for localised prostate cancer in patients without prostheses. Crowe et al.’s TADA code [1] was used to extract treatment plan parameters and evaluate doses to target volumes and critical structures against recommended goals [2] and constraints [3, 4]. Results The need to avoid transmitting the radiation beam through the hip prostheses limited the range of gantry angles available for use in both the rotational (VMAT) and the non-rotational (3DCRT and IMRT) radiotherapy treatments. This geometric limitation (exemplified in the VMAT data shown in Fig. 1) reduced the overall quality of the treatment plans for patients with prostheses compared to the reference plans. All plans with prostheses failed the PTV dose homogeneity requirement [2], whereas only 4 % of the plans without prostheses failed this test. Several treatment plans for patients with hip prostheses also failed the QUANTEC requirements that less than 50 % of the rectum receive 50 Gy and less than 35 % of the rectum receive 60 Gy to keep the grade 3 toxicity rate below 10 % [3], or the Hansen and Roach requirement that less than 25 % of the bladder receive 75 Gy [4]. Discussion and conclusions The results of this study exemplify the difficulty of designing prostate radiotherapy treatment plans, where beams provide adequate doses to targeted tissues while avoiding nearby organs at risk, when the presence of hip prostheses limits the available treatment geometries. This work provides qualitative evidence of the compromised dose distributions that can result, in such cases.
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The objective of this study was to determine if moderate to vigorous physical activity (MVPA) of 3-5 year old preschool children varied with differences in policies/practices, and overall quality of preschools. A total of 266 children (47% males, 60% African American) from 9 preschools were observed for 1 hour on 3 different days. PA of children was observed twice per minute and scored as 1-5, with 1 for stationary/motionless and 5 for fast movement. Summary MVPA was calculated over the 3 days as percent of times observed at levels of 4 or 5, and percent of time at levels I or 2 as sedentary activity. A structured interview about PA policies was conducted with an administrator at each preschool and overall quality of the preschool was assessed using Early Childhood Environment Rating Scale-Revised Edition (ECERS-R). Preschools were divided into groups according to whether a specific policy/practice that would be logically hypothesized to promote PA was in place at the school. MVPA differences between groups of children was assessed using mixed ANOVA controlling for preschool. When preschools offered more field trips, and more college educated teachers, the children participated in more MVPA. Children who attended preschools with lower quality spent more time in sedentary activity. In conclusion, children in preschools which may have more resources and better quality appear to show both more sedentary behavior and more MVPA.
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The effect of a change of tillage and crop residue management practice on the chemical and micro-biological properties of a cereal-producing red duplex soil was investigated by superimposing each of three management practices (CC: conventional cultivation, stubble burnt, crop conventionally sown; DD: direct-drilling, stubble retained, no cultivation, crop direct-drilled; SI: stubble incorporated with a single cultivation, crop conventionally sown), for a 3-year period on plots previously managed with each of the same three practices for 14 years. A change from DD to CC or SI practice resulted in a significant decline, in the top 0-5 cm of soil, in organic C, total N, electrical conductivity, NH4-N, NO3-N, soil moisture holding capacity, microbial biomass and CO2 respiration as well as a decline in the microbial quotient (the ratio of microbial biomass C to organic C; P <0.05). In contrast, a change from SI to DD or CC practice or a change from CC to DD or SI practice had only negligible impact on soil chemical properties (P >0.05). However, there was a significant increase in microbial biomass and the microbial quotient in the top 0-5 cm of soil following the change from CC to DD or SI practice and with the change from SI to DD practice (P <0.05). Analysis of ester-linked fatty acid methyl esters (EL-FAMEs) extracted from the 0- to 5-cm and 5- to 10-cm layers of the soils of the various treatments detected changes in the FAME profiles following a change in tillage practice. A change from DD practice to SI or CC practice was associated with a significant decline in the ratio of fungal to bacterial fatty acids in the 0- to 5-cm soil (P <0.05). The results show that a change in tillage practice, particularly the cultivation of a previously minimum-tilled (direct-drilled) soil, will result in significant changes in soil chemical and microbiological properties within a 3-year period. They also show that soil microbiological properties are sensitive indicators of a change in tillage practice.
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This paper presents algebraic attacks on SOBER-t32 and SOBER-t16 without stuttering. For unstuttered SOBER-t32, two different attacks are implemented. In the first attack, we obtain multivariate equations of degree 10. Then, an algebraic attack is developed using a collection of output bits whose relation to the initial state of the LFSR can be described by low-degree equations. The resulting system of equations contains 2^69 equations and monomials, which can be solved using the Gaussian elimination with the complexity of 2^196.5. For the second attack, we build a multivariate equation of degree 14. We focus on the property of the equation that the monomials which are combined with output bit are linear. By applying the Berlekamp-Massey algorithm, we can obtain a system of linear equations and the initial states of the LFSR can be recovered. The complexity of attack is around O(2^100) with 2^92 keystream observations. The second algebraic attack is applicable to SOBER-t16 without stuttering. The attack takes around O(2^85) CPU clocks with 2^78 keystream observations.
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New ways of thinking are required in teacher education to promote beginning teachers as change agents in education. Twenty years after the Salamanca Statement (UNESCO, 1994) that called for schools to provide equitable opportunities for all children, teaching practices in many classrooms are informed by the deficit view of learning. Beginning teachers need to be prepared to challenge the ideological influences that operate in schools. Deleuze and Guattari’s (1987) model of the rhizome is used to report one beginning teacher’s journey as she learnt to negotiate structural and personal obstacles to create an inclusive learning environment. Data from reflective diaries, semi-structured interviews and classroom observations highlight contextual and personal factors in one case study that contributed to the nonlinear, complex process of becoming an inclusive educator. The paper concludes by arguing the voice of beginning teachers is essential for the ongoing movement towards the creation of just, inclusive schools.
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While economic theory acknowledges that some features of technology (e.g., indivisibilities, economies of scale and specialization) can fundamentally violate the traditional convexity assumption, almost all empirical studies accept the convexity property on faith. In this contribution, we apply two alternative flexible production technologies to measure total factor productivity growth and test the significance of the convexity axiom using a nonparametric test of closeness between unknown distributions. Based on unique field level data on the petroleum industry, the empirical results reveal significant differences, indicating that this production technology is most likely non-convex. Furthermore, we also show the impact of convexity on answers to traditional convergence questions in the productivity growth literature.
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Should the firm move successfully into a growth or expansion phase the owner manager will be required to increase the scale and scope of its operations. Part of this expansion will involve hiring additional employees, and increasing the overall complexity of the firm's activities. It is likely that the need for greater levels of professional management will be required to operate the firm, along with the need for enhanced planning and the introduction of systems to support the new levels of complexity. The transition from a small, owner-managed firm to a large systems-managed business will require the development of a team-based management approach with greater specialisation within the management team. Corporate governance is also likely to change as the growth cycle takes place. As it grows, the business will become more formalised in its accounting, management and other systems. The need for greater quantities of capital is likely to lead the business towards equity finance. As new equity partner are taken into the company the original owner managers may find their level of control diminished. The larger the firm becomes the more likely its management structure will become decentralised with greater separation between the owner and the firm in terms of operational and financial matters.
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The chlamydiae are obligate intracellular parasites that have evolved specific interactions with their various hosts and host cell types to ensure their successful survival and consequential pathogenesis. The species Chlamydia pneumoniae is ubiquitous, with serological studies showing that most humans are infected at some stage in their lifetime. While most human infections are asymptomatic, C. pneumoniae can cause more-severe respiratory disease and pneumonia and has been linked to chronic diseases such as asthma, atherosclerosis, and even Alzheimer's disease. The widely dispersed animal-adapted C. pneumoniae strains cause an equally wide range of diseases in their hosts. It is emerging that the ability of C. pneumoniae to survive inside its target cells, including evasion of the host's immune attack mechanisms, is linked to the acquisition of key metabolites. Tryptophan and arginine are key checkpoint compounds in this host-parasite battle. Interestingly, the animal strains of C. pneumoniae have a slightly larger genome, enabling them to cope better with metabolite restrictions. It therefore appears that as the evolutionarily more ancient animal strains have evolved to infect humans, they have selectively become more "susceptible" to the levels of key metabolites, such as tryptophan. While this might initially appear to be a weakness, it allows these human C. pneumoniae strains to exquisitely sense host immune attack and respond by rapidly reverting to a persistent phase. During persistence, they reduce their metabolic levels, halting progression of their developmental cycle, waiting until the hostile external conditions have passed before they reemerge.
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Purpose To examine macular retinal thickness and retinal layer thickness with spectral domain optical coherence tomography (OCT) in a population of children with normal ocular health and minimal refractive errors. Methods High resolution macular OCT scans from 196 children aged from 4 to 12 years (mean age 8 ± 2 years) were analysed to determine total retinal thickness and the thickness of 6 different retinal layers across the central 5 mm of the posterior pole. Automated segmentation with manual correction was used to derive retinal thickness values. Results The mean total retinal thickness in the central 1 mm foveal zone was 255 ± 16 μm, and this increased significantly with age (mean increase of 1.8 microns per year) in childhood (p<0.001). Age-related increases in thickness of some retinal layers were also observed, with changes of highest statistical significance found in the outer retinal layers in the central foveal region (p<0.01). Significant topographical variations in thickness of each of the retinal layers were also observed (p<0.001). Conclusions Small magnitude, statistically significant increases in total retinal thickness and retinal layer thickness occur from early childhood to adolescence. The most prominent changes appear to occur in the outer retinal layers of the central fovea.
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Amoebic gill disease (AGD) is a parasite-mediated proliferative gill disease capable of affecting a range of teleost hosts. While a moderate heritability for AGD resistance in Atlantic salmon has been reported previously, the mechanisms by which individuals resist the proliferative effects remain poorly understood. To gain more knowledge of this commercially important trait, we compared gill transcriptomes of two groups of Atlantic salmon, one designated putatively resistant, and one designated putatively susceptible to AGD. Utilising a 17k Atlantic salmon cDNA microarray we identified 196 transcripts that were differentially expressed between the two groups. Expression of 11 transcripts were further examined with real-time quantitative RT-PCR (qPCR) in the AGD-resistant and AGD-susceptible animals, as well as non-infected naïve fish. Gene expression determined by qPCR was in strong agreement with the microarray analysis. A large number of differentially expressed genes were involved in immune and cell cycle responses. Resistant individuals displayed significantly higher expression of genes involved in adaptive immunity and negative regulation of the cell cycle. In contrast, AGD-susceptible individuals showed higher expression of acute phase proteins and positive regulators of the cell cycle. Combined with the gill histopathology, our results suggest AGD resistance is acquired rather than innately present, and that this resistance is for the most part associated with the dysregulation of immune and cell cycle pathways. © 2008 Elsevier Ltd. All rights reserved.