952 resultados para Radical scavenging activity


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Executive Summary Emergency Departments (EDs) locally, nationally and internationally are becoming increasingly busy. Within this context, it can be challenging to deliver a health service that is safe, of high quality and cost-effective. Whilst various models are described within the literature that aim to measure ED ‘work’ or ‘activity’, they are often not linked to a measure of costs to provide such activity. It is important for hospital and ED managers to understand and apply this link so that optimal staffing and financial resourcing can be justifiably sought. This research is timely given that Australia has moved towards a national Activity Based Funding (ABF) model for ED activity. ABF is believed to increase transparency of care and fairness (i.e. equal work receives equal pay). ABF involves a person-, performance- or activity-based payment system, and thus a move away from historical “block payment” models that do not incentivise efficiency and quality. The aim of the Statewide Workforce and Activity-Based Funding Modelling Project in Queensland Emergency Departments (SWAMPED) is to identify and describe best practice Emergency Department (ED) workforce models within the current context of ED funding that operates under an ABF model. The study is comprised of five distinct phases. This monograph (Phase 1) comprises a systematic review of the literature that was completed in June 2013. The remaining phases include a detailed survey of Queensland hospital EDs’ resource levels, activity and operational models of care, development of new resource models, development of a user-friendly modelling interface for ED mangers, and production of a final report that identifies policy implications. The anticipated deliverable outcome of this research is the development of an ABF based Emergency Workforce Modelling Tool that will enable ED managers to profile both their workforce and operational models of care. Additionally, the tool will assist with the ability to more accurately inform adequate staffing numbers required in the future, inform planning of expected expenditures and be used for standardisation and benchmarking across similar EDs. Summary of the Findings Within the remit of this review of the literature, the main findings include: 1. EDs are becoming busier and more congested Rising demand, barriers to ED throughput and transitions of care all contribute to ED congestion. In addition requests by organisational managers and the community require continued broadening of the scope of services required of the ED and further increases in demand. As the population live longer with more lifestyle diseases their propensity to require ED care continues to grow. 2. Various models of care within EDs exist Models often vary to account for site specific characteritics to suit staffing profile, ED geographical location (e.g. metropolitan or rural site), and patient demographic profile (e.g. paediatrics, older persons, ethnicity). Existing and new models implemented within EDs often depend on the target outcome requiring change. Generally this is focussed on addressing issues at the input, throughput or output areas of the ED. Even with models targeting similar demographic or illness, the structure and process elements underpinning the model can vary, which can impact on outcomes and variance to the patient and carer experience between and within EDs. Major models of care to manage throughput inefficiencies include: A. Workforce Models of Care focus on the appropriate level of staffing for a given workload to provide prompt, timely and clinically effective patient care within an emergency care setting. The studies reviewed suggest that the early involvement of senior medical decision maker and/or specialised nursing roles such as Emergency Nurse Practitioners and Clinical Initiatives Nurse, primary contact or extended scope Allied Health Practitioners can facilitate patient flow and improve key indicators such as length of stay and reducing the number of those who did not wait to be seen amongst others. B. Operational Models of Care within EDs focus on mechanisms for streaming (e.g. fast-tracking) or otherwise grouping patient care based on acuity and complexity to assist with minimising any throughput inefficiencies. While studies support the positive impact of these models in general, it appears that they are most effective when they are adequately resourced. 3. Various methods of measuring ED activity exist Measuring ED activity requires careful consideration of models of care and staffing profile. Measuring activity requires the ability to account for factors including: patient census, acuity, LOS, intensity of intervention, department skill-mix plus an adjustment for non-patient care time. 4. Gaps in the literature Continued ED growth calls for new and innovative care delivery models that are safe, clinically effective and cost effective. New roles and stand-alone service delivery models are often evaluated in isolation without considering the global and economic impact on staffing profiles. Whilst various models of accounting for and measuring health care activity exist, costing studies and cost effectiveness studies are lacking for EDs making accurate and reliable assessments of care models difficult. There is a necessity to further understand, refine and account for measures of ED complexity that define a workload upon which resources and appropriate staffing determinations can be made into the future. There is also a need for continued monitoring and comprehensive evaluation of newly implemented workforce modelling tools. This research acknowledges those gaps and aims to: • Undertake a comprehensive and integrated whole of department workforce profiling exercise relative to resources in the context of ABF. • Inform workforce requirements based on traditional quantitative markers (e.g. volume and acuity) combined with qualitative elements of ED models of care; • Develop a comprehensive and validated workforce calculation tool that can be used to better inform or at least guide workforce requirements in a more transparent manner.

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A predictive model of terrorist activity is developed by examining the daily number of terrorist attacks in Indonesia from 1994 through 2007. The dynamic model employs a shot noise process to explain the self-exciting nature of the terrorist activities. This estimates the probability of future attacks as a function of the times since the past attacks. In addition, the excess of nonattack days coupled with the presence of multiple coordinated attacks on the same day compelled the use of hurdle models to jointly model the probability of an attack day and corresponding number of attacks. A power law distribution with a shot noise driven parameter best modeled the number of attacks on an attack day. Interpretation of the model parameters is discussed and predictive performance of the models is evaluated.

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The use of graphical processing unit (GPU) parallel processing is becoming a part of mainstream statistical practice. The reliance of Bayesian statistics on Markov Chain Monte Carlo (MCMC) methods makes the applicability of parallel processing not immediately obvious. It is illustrated that there are substantial gains in improved computational time for MCMC and other methods of evaluation by computing the likelihood using GPU parallel processing. Examples use data from the Global Terrorism Database to model terrorist activity in Colombia from 2000 through 2010 and a likelihood based on the explicit convolution of two negative-binomial processes. Results show decreases in computational time by a factor of over 200. Factors influencing these improvements and guidelines for programming parallel implementations of the likelihood are discussed.

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In most radicals the singly occupied molecular orbital (SOMO) is the highest-energy occupied molecular orbital (HOMO); however, in a small number of reported compounds this is not the case. In the present work we expand significantly the scope of this phenomenon, known as SOMO-HOMO energy-level conversion, by showing that it occurs in virtually any distonic radical anion that contains a sufficiently stabilized radical (aminoxyl, peroxyl, aminyl) non-pi-conjugated with a negative charge (carboxylate, phosphate, sulfate). Moreover, regular orbital order is restored on protonation of the anionic fragment, and hence the orbital configuration can be switched by pH. Most importantly, our theoretical and experimental results reveal a dramatically higher radical stability and proton acidity of such distonic radical anions. Changing radical stability by 3-4 orders of magnitude using pH-induced orbital conversion opens a variety of attractive industrial applications, including pH-switchable nitroxide-mediated polymerization, and it might be exploited in nature.

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Nitrogen dioxide is used as a "radical scavenger" to probe the position of carbon-centered radicals within complex radical ions in the gas phase. As with analogous neutral radical reactions, this addition results in formation of an \[M + NO2](+) adduct, but the structural identity of this species remains ambiguous. Specifically, the question remains: do such adducts have a nitro-(RNO2) or nitrosoxy-(RONO) moiety, or are both isomers present in the adduct population? In order to elucidate the products of such reactions, we have prepared and isolated three distonic phenyl radical cations and observed their reactions with nitrogen dioxide in the gas phase by ion-trap mass spectrometry. In each case, stabilized \[M + NO2](+) adduct ions are observed and isolated. The structure of these adducts is probed by collision-induced dissociation and ultraviolet photodissociation action spectroscopy and a comparison made to the analogous spectra of authentic nitro-and nitrosoxy-benzenes. We demonstrate unequivocally that for the phenyl radical cations studied here, all stabilized \[M + NO2](+) adducts are exclusively nitrobenzenes. Electronic structure calculations support these mass spectrometric observations and suggest that, under low-pressure conditions, the nitrosoxy-isomer is unlikely to be isolated from the reaction of an alkyl or aryl radical with NO2. The combined experimental and theoretical results lead to the prediction that stabilization of the nitrosoxy-isomer will only be possible for systems wherein the energy required for dissociation of the RO-NO bond (or other low energy fragmentation channels) rises close to, or above, the energy of the separated reactants.

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The reaction of the aromatic distonic peroxyl radical cations N-methyl pyridinium-4-peroxyl (PyrOO center dot+) and 4-(N,N,N-trimethyl ammonium)-phenyl peroxyl (AnOO center dot+), with symmetrical dialkyl alkynes 10?ac was studied in the gas phase by mass spectrometry. PyrOO center dot+ and AnOO center dot+ were produced through reaction of the respective distonic aryl radical cations Pyr center dot+ and An center dot+ with oxygen, O2. For the reaction of Pyr center dot+ with O2 an absolute rate coefficient of k1=7.1X10-12 cm3 molecule-1 s-1 and a collision efficiency of 1.2?% was determined at 298 K. The strongly electrophilic PyrOO center dot+ reacts with 3-hexyne and 4-octyne with absolute rate coefficients of khexyne=1.5X10-10 cm3 molecule-1 s-1 and koctyne=2.8X10-10 cm3 molecule-1 s-1, respectively, at 298 K. The reaction of both PyrOO center dot+ and AnOO center dot+ proceeds by radical addition to the alkyne, whereas propargylic hydrogen abstraction was observed as a very minor pathway only in the reactions involving PyrOO center dot+. A major reaction pathway of the vinyl radicals 11 formed upon PyrOO center dot+ addition to the alkynes involves gamma-fragmentation of the peroxy O?O bond and formation of PyrO center dot+. The PyrO center dot+ is rapidly trapped by intermolecular hydrogen abstraction, presumably from a propargylic methylene group in the alkyne. The reaction of the less electrophilic AnOO center dot+ with alkynes is considerably slower and resulted in formation of AnO center dot+ as the only charged product. These findings suggest that electrophilic aromatic peroxyl radicals act as oxygen atom donors, which can be used to generate alpha-oxo carbenes 13 (or isomeric species) from alkynes in a single step. Besides gamma-fragmentation, a number of competing unimolecular dissociative reactions also occur in vinyl radicals 11. The potential energy diagrams of these reactions were explored with density functional theory and ab initio methods, which enabled identification of the chemical structures of the most important products.

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Radical-directed dissociation of gas phase ions is emerging as a powerful and complementary alternative to traditional tandem mass spectrometric techniques for biomolecular structural analysis. Previous studies have identified that coupling of 2-[(2,2,6,6-tetramethylpiperidin-1-oxyl)methyl] benzoic acid (TEMPO-Bz) to the N-terminus of a peptide introduces a labile oxygen-carbon bond that can be selectively activated upon collisional activation to produce a radical ion. Here we demonstrate that structurally-defined peptide radical ions can also be generated upon UV laser photodissociation of the same TEMPO-Bz derivatives in a linear ion-trap mass spectrometer. When subjected to further mass spectrometric analyses, the radical ions formed by a single laser pulse undergo identical dissociations as those formed by collisional activation of the same precursor ion, and can thus be used to derive molecular structure. Mapping the initial radical formation process as a function of photon energy by photodissociation action spectroscopy reveals that photoproduct formation is selective but occurs only in modest yield across the wavelength range (300-220 nm), with the photoproduct yield maximised between 235 and 225 nm. Based on the analysis of a set of model compounds, structural modifications to the TEMPO-Bz derivative are suggested to optimise radical photoproduct yield. Future development of such probes offers the advantage of increased sensitivity and selectivity for radical-directed dissociation. © 2014 the Owner Societies.

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Long lived: Carbonyloxyl radicals (RCO2 .) are reactive intermediates that play key roles in initiating polymerization reactions. This reactivity also makes their direct observation difficult. For the first time a persistent organic RCO2 . radical is detected in the gas phase, its extraordinary longevity is attributed to the high barrier towards fragmentation owing to the endothermicity of the decarboxylation products. Grant Numbers ARC/DP0986738, ARC/DP120102922, ARC/DE120100467

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The reactions of distonic 4-(N, N, N-trimethylammonium)-2-methylphenyl and 5-(N, N, N-trimethylammonium)-2-methylphenyl radical cations (m/z 149) with O-2 are studied in the gas phase using ion-trap mass spectrometry. Photodissociation (PD) of halogenated precursors gives rise to the target distonic charge-tagged methylphenyl radical whereas collision-induced dissociation (CID) is found to produce unreactive radical ions. The PD generated distonic radicals, however, react rapidly with O-2 to form \[M + O2](center dot+) and \[M + O-2 - OH](center dot+) ions, detected at m/z 181 and m/z 164, respectively. Quantum chemical calculations using G3SX(MP3) and M06-2X theories are deployed to examine key decomposition pathways of the 5-(N, N, N-trimethylammonium)-2-methylphenylperoxyl radical and rationalise the observed product ions. The prevailing product mechanism involves a 1,5- H shift in the peroxyl radical forming a QOOH-type intermediate that subsequently eliminates (OH)-O-center dot to yield charge-tagged 2-quinone methide. Our study suggests that the analogous process should occur for the neutral methylphenyl + O-2 reaction, thus serving as a plausible source of (OH)-O-center dot radicals in combustion environments. Grants: ARC/DP0986738, ARC/DP130100862

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The anionic heterocumulene SCCCN- was generated in the gas phase by collisional activation of the radical anion of 1,2-dicyanoethylenedithiolate. The mechanism of this reaction, as well as the structures of neutral and anionic products, was investigated by hybrid density functional theory (DFT) calculations. Dissociation to form SCCCN- and SCN is proposed to occur by a radical directed cyano migration reaction, with calculations suggesting this is the lowest energy fragmentation pathway available to the precursor anion. In contrast, the even-electron protonated 1,2-dicyanoethylenedithiolate anion fragmented by loss of HCN.

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This paper reviews a wide range of literature on environmental management in the field in Queensland, and analyzes this by period and by author. An episodic pattern of activities since European settlement is evident. Periods of exploration (pre-1950) and inventory- compilation (ca. 1950-1970) were followed by two decades of media and non-government organization campaigning (ca. 1970-1990), then an era dominated by government regulatory action (ca. 1990-2010). These eras dominated public perception of what was happening in environmental practice. They were delineated by historic ‘interventions’ (summarily, the end of World War II, the 1971 inflationary crisis, and computerization respectively).

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Upon overexpression of integrin αvβ3 and its engagement by vitronectin, we previously showed enhanced adhesion, proliferation, and motility of human ovarian cancer cells. By studying differential expression of genes possibly related to these tumor biological events, we identified the epidermal growth-factor receptor (EGF-R) to be under control of αvβ3 expression levels. Thus in the present study we characterized αvβ3-dependent changes of EGF-R and found significant upregulation of its expression and activity which was reflected by prominent changes of EGF-R promoter activity. Upon disruption of DNA-binding motifs for the transcription factors p53, ETF, the repressor ETR, p50, and c-rel, respectively, we sought to identify DNA elements contributing to αvβ3-mediated EGF-R promoter induction. Both, the p53- and ETF-mutant, while exhibiting considerably lower EGF-R promoter activity than the wild type promoter, retained inducibility by αvβ3. Mutation of the repressor motif ETR, as expected, enhanced EGF-R promoter activity with a further moderate increase upon αvβ3 elevation. The p50-mutant displayed EGF-R promoter activity almost comparable to that of the wild type promoter with no impairment of induction by αvβ3. However, the activity of an EGF-R promoter mutant displaying a disrupted c-rel-binding motif did not only prominently decline, but, moreover, was not longer responsive to enhanced αvβ3, involving this DNA element in αvβ3-dependent EGF-R upregulation. Moreover, αvβ3 did not only increase the EGF-R but, moreover, also led to obvious co-clustering on the cancer cell surface. By studying αvβ3/EGF-R-effects on the focal adhesion kinase (FAK) and the mitogen activated protein kinases (MAPK) p44/42 (erk−1/erk−2), having important functions in synergistic crosstalk between integrins and growth-factor receptors, we found for both significant enhancement of expression and activity upon αvβ3/VN interaction and cell stimulation by EGF. Upregulation of the EGF-R by integrin αvβ3, both receptor molecules with a well-defined role as targets for cancer treatment, might represent an additional mechanism to adapt synergistic receptor signaling and crosstalk in response to an altered tumor cell microenvironment during ovarian cancer progression.

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Objectives Given increasing trends of obesity being noted from early in life and that active lifestyles track across time, it is important that children at a very young age be active to combat a foundation of unhealthy behaviours forming. This study investigated, within a theory of planned behaviour (TPB) framework, factors which influence mothers’ decisions about their child’s 1) adequate physical activity (PA) and 2) limited screen time behaviours. Methods Mothers (N = 162) completed a main questionnaire, via on-line or paper-based administration, which comprised standard TPB items in addition to measures of planning and background demographic variables. One week later, consenting mothers completed a follow-up telephone questionnaire which assessed the decisions they had made regarding their child’s PA and screen time behaviours during the previous week. Results Hierarchical multiple regression analyses revealed support for the predictive model, explaining an overall 73% and 78% of the variance in mothers’ intention and 38% and 53% of the variance in mothers’ decisions to ensure their child engages in adequate PA and limited screen time, respectively. Attitude and subjective norms predicted intention in both target behaviours, as did intentions with behaviour. Contrary to predictions, perceived behavioural control (PBC) in PA behaviour and planning in screen time behaviour were not significant predictors of intention, neither was PBC a predictor of either behaviour. Conclusions The findings illustrate the various roles that psycho-social factors play in mothers’ decisions to ensure their child engages in active lifestyle behaviours which can help to inform future intervention programs aimed at combating very young children’s inactivity.

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Background Not getting enough physical activity leads to poorer health. Regular physical activity can reduce the risk of chronic disease and improve one’s health and well-being. The lack of physical activity is a common and growing problem in many countries. We sought to evaluate the effects of community wide, multi-strategic interventions upon the physical activity patterns of populations. Method We undertook a Cochrane Systematic Review which included an extensive search of databases, including studies which met pre-determined criteria, and conducted independent risk of bias assessment and data extraction. Results After the selection process, 25 studies were included in the review. The strategies varied by the number and type of components and their intensity. No studies were identified as low risk of bias. Sixteen studies were identified as having a high risk of bias and thus untrustworthy. Nine studies were of considered to have an unclear risk of bias and some studies held back data they collected. The effects reported were inconsistent across the studies and the measures. Some of the better designed studies showed no improvement in measures of physical activity. Interventions which have an environmental change component seemed to be a promising direction. Those interventions which were primarily a mass media campaign were less likely to be successful. Conclusions Although numerous studies have been undertaken, there is considerable inconsistency in the findings of the available studies and this is confounded by serious methodological issues within the included studies. Simply combining interventions does not necessarily result in increased physical activity as many such studies, including some long term programs, failed to demonstrate efficacy. There is a clear need for well-designed studies and these studies should focus on the quality of measurement of physical activity. The review is currently being updated with newer studies.

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Background Prevention of childhood obesity is a public health priority for Malaysia and many other countries. Physical activity for children is also decreasing at an alarming rate. Both conditions are associated with non-communicable diseases and with significant morbidity and mortality in later life. Systematic reviews of public health interventions provide a useful summary to inform public health practice by combining the results of a range of research studies on a specific intervention into a single report. Systematic reviews are deemed most valuable for health program development and evidence based practice. Unfortunately, many policy makers and practitioners are simply unaware of the evidence: which strategies which are most likely to provide benefit; and which strategies are known to be harmful or useless. This presentation provides a “birds eye” overview based upon recent (since 2007 to present) high quality systematic reviews of public health interventions. Method HealthEvidece.org and the Cochrane Library were searched for systematic reviews which evaluated interventions targeting obesity prevention and increasing physical activity for children. The findings of the included reviews were themed and summarized. Results Seven reviews were identified addressing obesity in the early years, and fifteen reviews addressing obesity more broadly in childhood. Additional reviews were identified aimed at increasing physical activity. The synthesis shows several strategies to be effective, however many popular strategies clearly are not. Several of the reviews were inconclusive due to an absence of robust primary studies. Amongst the findings, interventions undertaken in the school setting appear very promising. Conclusions There is significant evidence from systematic reviews to guide public health practice and policy, and to inform future research.