426 resultados para Kyle Tuntland


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A person living in an industrialized society has almost no choice but to receive information daily with negative implications for himself or others. His attention will often be drawn to the ups and downs of economic indicators or the alleged misdeeds of leaders and organizations. Reacting to new information is central to economics, but economics typically ignores the affective aspect of the response, for example, of stress or anger. These essays present the results of considering how the affective aspect of the response can influence economic outcomes.

The first chapter presents an experiment in which individuals were presented with information about various non-profit organizations and allowed to take actions that rewarded or punished those organizations. When social interaction was introduced into this environment an asymmetry between rewarding and punishing appeared. The net effects of punishment became greater and more variable, whereas the effects of reward were unchanged. The individuals were more strongly influenced by negative social information and used that information to target unpopular organizations. These behaviors contributed to an increase in inequality among the outcomes of the organizations.

The second and third chapters present empirical studies of reactions to negative information about local economic conditions. Economic factors are among the most prevalent stressors, and stress is known to have numerous negative effects on health. These chapters document localized, transient effects of the announcement of information about large-scale job losses. News of mass layoffs and shut downs of large military bases are found to decrease birth weights and gestational ages among babies born in the affected regions. The effect magnitudes are close to those estimated in similar studies of disasters.

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This dissertation focuses on the incorporation of non-innocent or multifunctional moieties into different ligand scaffolds to support one or multiple metal centers in close proximity. Chapter 2 focuses on the initial efforts to synthesize hetero- or homometallic tri- or dinuclear metal carbonyl complexes supported by para-terphenyl diphosphine ligands. A series of [M2M’(CO)4]-type clusters (M = Ni, Pd; M’ = Fe, Co) could be accessed and used to relate the metal composition to the properties of the complexes. During these studies it was also found that non-innocent behavior was observed in dinuclear Fe complexes that result from changes in oxidation state of the cluster. These studies led to efforts to rationally incorporate central arene moieties capable managing both protons and electrons during small molecule activation.

Chapter 3 discusses the synthesis of metal complexes supported by a novel para-terphenyl diphosphine ligand containing a non-innocent 1,4-hydroquinone moiety as the central arene. A Pd0-hydroquinone complex was found to mediate the activation of a variety of small molecules to form the corresponding Pd0-quinone complexes in a formal two proton ⁄ two electron transformation. Mechanistic investigations of dioxygen activation revealed a metal-first activation process followed by subsequent proton and electron transfer from the ligand. These studies revealed the capacity of the central arene substituent to serve as a reservoir for a formal equivalent of dihydrogen, although the stability of the M-quinone compounds prevented access to the PdII-quinone oxidation state, thus hindering of small molecule transformations requiring more than two electrons per equivalent of metal complex.

Chapter 4 discusses the synthesis of metal complexes supported by a ligand containing a 3,5-substituted pyridine moiety as the linker separating the phenylene phosphine donors. Nickel and palladium complexes supported by this ligand were found to tolerate a wide variety of pyridine nitrogen-coordinated electrophiles which were found to alter central pyridine electronics, and therefore metal-pyridine π-system interactions, substantially. Furthermore, nickel complexes supported by this ligand were found to activate H-B and H-Si bonds and formally hydroborate and hydrosilylate the central pyridine ring. These systems highlight the potential use of pyridine π-system-coordinated metal complexes to reversibly store reducing equivalents within the ligand framework in a manner akin to the previously discussed 1,4-hydroquinone diphosphine ligand scaffold.

Chapter 5 departs from the phosphine-based chemistry and instead focuses on the incorporation of hydrogen bonding networks into the secondary coordination sphere of [Fe44-O)]-type clusters supported by various pyrazolate ligands. The aim of this project is to stabilize reactive oxygenic species, such as oxos, to study their spectroscopy and reactivity in the context of complicated multimetallic clusters. Herein is reported this synthesis and electrochemical and Mössbauer characterization of a series of chloride clusters have been synthesized using parent pyrazolate and a 3-aminophenyl substituted pyrazolate ligand. Efforts to rationally access hydroxo and oxo clusters from these chloride precursors represents ongoing work that will continue in the group.

Appendix A discusses attempts to access [Fe3Ni]-type clusters as models of the enzymatic active site of [NiFe] carbon monoxide dehydrogenase. Efforts to construct tetranuclear clusters with an interstitial sulfide proved unsuccessful, although a (μ3-S) ligand could be installed through non-oxidative routes into triiron clusters. While [Fe3Ni(μ4-O)]-type clusters could be assembled, accessing an open heterobimetallic edge site proved challenging, thus prohibiting efforts to study chemical transformations, such as hydroxide attack onto carbon monoxide or carbon dioxide coordination, relevant to the native enzyme. Appendix B discusses the attempts to synthesize models of the full H-cluster of [FeFe]-hydrogenase using a bioinorganic approach. A synthetic peptide containing three cysteine donors was successfully synthesized and found to chelate a preformed synthetic [Fe4S4] cluster. However, efforts to incorporate the diiron subsite model complex proved challenging as the planned thioester exchange reaction was found to non-selectively acetylate the peptide backbone, thus preventing the construction of the full six-iron cluster.

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During the last century, the population of Pacific sardine (Sardinops sagax) in the California Current Ecosystem has exhibited large fluctuations in abundance and migration behavior. From approximately 1900 to 1940, the abundance of sardine reached 3.6 million metric tons and the “northern stock” migrated from offshore of California in the spring to the coastal areas near Oregon, Washington, and Vancouver Island in the summer. In the 1940s, the sardine stock collapsed and the few remaining sardine schools concentrated in the coastal region off southern California, year-round, for the next 50 years. The stock gradually recovered in the late 1980s and resumed its seasonal migration between regions off southern California and Canada. Recently, a model was developed which predicts the potential habitat for the northern stock of Pacific sardine and its seasonal dynamics. The habitat predictions were successfully validated using data from sardine surveys using the daily egg production method; scientific trawl surveys off the Columbia River mouth; and commercial sardine landings off Oregon, Washington, and Vancouver Island. Here, the predictions of the potential habitat and seasonal migration of the northern stock of sardine are validated using data from “acoustic–trawl” surveys of the entire west coast of the United States during the spring and summer of 2008. The estimates of sardine biomass and lengths from the two surveys are not significantly different between spring and summer, indicating that they are representative of the entire stock. The results also confirm that the model of potential sardine habitat can be used to optimally apply survey effort and thus minimize random and systematic sampling error in the biomass estimates. Furthermore, the acoustic–trawl survey data are useful to estimate concurrently the distributions and abundances of other pelagic fishes.

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The abundances and distributions of coastal pelagic fish species in the California Current Ecosystem from San Diego to southern Vancouver Island, were estimated from combined acoustic and trawl surveys conducted in the spring of 2006, 2008, and 2010. Pacific sardine (Sardinops sagax), jack mackerel (Trachurus symmetricus), and Pacific mackerel (Scomber japonicus) were the dominant coastal pelagic fish species, in that order. Northern anchovy (Engraulis mordax) and Pacific herring (Clupea pallasii) were sampled only sporadically and therefore estimates for these species were unreliable. The estimates of sardine biomass compared well with those of the annual assessments and confirmed a declining trajectory of the “northern stock” since 2006. During the sampling period, the biomass of jack mackerel was stable or increasing, and that of Pacific mackerel was low and variable. The uncertainties in these estimates are mostly the result of spatial patchiness which increased from sardine to mackerels to anchovy and herring. Future surveys of coastal pelagic fish species in the California Current Ecosystem should benefit from adaptive sampling based on modeled habitat; increased echosounder and trawl sampling, particularly for the most patchy and nearshore species; and directed-trawl sampling for improved species identification and estimations of their acoustic target stren

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New technologies can be riddled with unforeseen sources of error, jeopardizing the validity and application of their advancement. Bioelectrical impedance analysis (BIA) is a new technology in fisheries research that is capable of estimating proximate composition, condition, and energy content in fish quickly, cheaply, and (after calibration) without the need to sacrifice fish. Before BIA can be widely accepted in fisheries science, it is necessary to identify sources of error and determine a means to minimize potential errors with this analysis. We conducted controlled laboratory experiments to identify sources of errors within BIA measurements. We concluded that electrode needle location, procedure deviations, user experience, time after death, and temperature can affect resistance and reactance measurements. Sensitivity analyses showed that errors in predictive estimates of composition can be large (>50%) when these errors are experienced. Adherence to a strict protocol can help avoid these sources of error and provide BIA estimates that are both accurate and precise in a field or laboratory setting.

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Abstract—Fisheries often target individuals based on size. Size-selective fishing can create selection differentials on life-history traits and, when those traits have a genetic basis, may cause evolution. The evolution of life history traits affects potential yield and sustainability of fishing, and it is therefore an issue for fishery management. Yet fishery managers usually disregard the possibility of evolution, because little guidance is available to predict evolutionary consequences of management strategies. We attempt to provide some generic guidance. We develop an individual-based model of a population with overlapping generations and continuous reproduction. We simulate model populations under size-selective fishing to generate and quantify selection differentials on growth. The analysis comprises a variety of common life-history and fishery characteristics: variability in growth, correlation between von Bertalanffy growth parameters (K and L∞), maturity rate, natural mortality rate (M), M/K ratio, duration of spawning season, fishing mortality rate (F), maximum size limit, slope of selectivity curve, age at 50% selectivity, and duration of fishing season. We found that each characteristic affected the magnitude of selection differentials. The most vulnerable stocks were those with a short spawning or fishing season. Under almost all life-history and fishery characteristics examined, selection differentials created by realistic fishing mortality rates are considerable.

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Most assessments of fish stocks use some measure of the reproductive potential of a population, such as spawning biomass. However, the correlation between spawning biomass and reproductive potential is not always strong, and it likely is weakest in the tropics and subtropics, where species tend to exhibit indeterminate fecundity and release eggs in batches over a protracted spawning season. In such cases, computing annual reproductive output requires estimates of batch fecundity and the annual number of batches—the latter subject to spawning frequency and duration of spawning season. Batch fecundity is commonly measured by age (or size), but these other variables are not. Without the relevant data, the annual number of batches is assumed to be invariant across age. We reviewed the literature and found that this default assumption lacks empirical support because both spawning duration and spawning frequency generally increase with age or size. We demonstrate effects of this assumption on measures of reproductive value and spawning potential ratio, a metric commonly used to gauge stock status. Model applications showed substantial sensitivity to age dependence in the annual number of batches. If the annual number of batches increases with age but is incorrectly assumed to be constant, stock assessment models would tend to overestimate the biological reference points used for setting harvest rates. This study underscores the need to better understand the age- or size-dependent contrast in the annual number of batches, and we conclude that, for species without evidence to support invariance, the default assumption should be replaced with one that accounts for age- or size-dependence.

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The recently revised Magnuson–Stevens Fishery Conservation and Management Act requires that U.S. fishery management councils avoid overfishing by setting annual catch limits (ACLs) not exceeding recommendations of the councils’ scientific advisers. To meet that requirement, the scientific advisers will need to know the overfishing limit (OFL) estimated in each stock assessment, with OFL being the catch available from applying the limit fishing mortality rate to current or projected stock biomass. The advisers then will derive ‘‘acceptable biological catch’’ (ABC) from OFL by reducing OFL to allow for scientific uncertainty, and ABC becomes their recommendation to the council. We suggest methodology based on simple probability theory by which scientific advisers can compute ABC from OFL and the statistical distribution of OFL as estimated by a stock assessment. Our method includes approximations to the distribution of OFL if it is not known from the assessment; however, we find it preferable to have the assessment model estimate the distribution of OFL directly. Probability-based methods such as this one provide well-defined approaches to setting ABC and may be helpful to scientific advisers as they translate the new legal requirement into concrete advice.

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本文主要研究了Mg2+对LHCP-II和LHCP-I在基粒膜与基质膜之间横向迁移的作用及其对激发能在两个光系统间分配的影响,进一步证实和发展了Kyle等提出的移动天线色素假说(mobile antenna hypothesis)。揭示了二价金属阳离子使激发能有利于向光系统II(PSII)分配,而不利于向光系统I(PSI)分配的生化基础。 用毛地黄皂(Digitonin)方法分离了悬浮在低渗、低浓度一价金属阳离子介质中的小麦类囊体的基粒膜与基质膜,结果发现,事先用5m MMgol2预处理过的类囊体,其基质膜比未处理的有较高的叶绿素a/b比值,基粒膜的叶绿素a/b比值变化不大。 低温荧光(77K)发射光谱表明,mg2+处理能增强类囊体膜和基粒膜的687nm荧光发射峰,降低F741/F687比值。除此以外,在对照的基质膜里还发现F687-向F688以及F741向F738的位移。 解垛叠及Mg~(2+)诱导的重垛叠实验表明,低温荧光F741/F687比值在解垛叠进程中上升,而在重垛叠过程中,F741/F687比值下降。 湿和的SDS-聚丙烯酰胺凝胶电泳分析表明,Mg2+处理使LHCP寡聚体解聚成单体,类囊体膜凝胶柱上LHCP寡聚体的含量减少,单体的含量增加。基质膜的电泳分析发现,Mg2+处理促时了LHCP从富含PSI的基质区向富含PSII的基粒膜区的迁移。同时还证明,不仅LHCP-II,LHCP-I也能向基粒膜区迁移。 进一步用梯度胶分析基粒膜与基质膜的多肽组成,发现经Mg2+处理的基质膜中相应于LHCP-II的两条多肽,25KD和27KD的量明显减少,尤其是27KD多肽变化更为显著。 此外,我们还研究了介质中pH值(H+浓度)对两个光系统间能量分配与传递的影响,发现H+的作用机理与Mg2+的不同。H+能引起膜垛叠,改变类囊体膜的低温荧光发射光谱,使F741/F687比值降低。而对基粒膜和基质膜的作用却与Mg2+作用相反。温和的SDS-聚丙烯酰胺凝胶电泳分析结果表明,pH的变化不改变类囊体膜上色素蛋白复合体的种类、组成和比例。 据此,我们比较并讨论了金属阳离子与H对光系统间能量分配与传递的影响的不同作用,认为二价金属阳离子除能引起类囊体膜垛叠、改变色素蛋白复合体的空间构象和排列,从而影响激发能在两个光系统间的分配外,还能调节和促进LHCP-II及LHCP-I从富含PSI的基质膜向富含PSII的基粒迁移,使PSII的光捕获截面增加,调节激发能有利于向PSII分配。而介质中的质子(H+)浓度的改变只能引起类囊体膜片层垛叠,可能改变光合膜中色素蛋白复合体的构象和排列,最终影响激发能在光系统间的分配。

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Studies of Erebus volcano's active lava lake have shown that many of its observable properties (gas composition, surface motion and radiant heat output) exhibit cyclic behaviour with a period of ~10 min. We investigate the multi-year progression of the cycles in surface motion of the lake using an extended (but intermittent) dataset of thermal infrared images collected by the Mount Erebus Volcano Observatory between 2004 and 2011. Cycles with a period of ~5-18 min are found to be a persistent feature of the lake's behaviour and no obvious long-term change is observed despite variations in lake level and surface area. The times at which gas bubbles arrive at the lake's surface are found to be random with respect to the phase of the motion cycles, suggesting that the remarkable behaviour of the lake is governed by magma exchange rather than an intermittent flux of gases from the underlying magma reservoir. © 2014 The Authors.

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Background Increasing prevalence of overweight and obesity represents a global pandemic. As the largest occupational group in international healthcare systems nurses are at the forefront of health promotion to address this pandemic. However, nurses own health behaviours are known to influence the extent to which they engage in health promotion and the public's confidence in advice offered. Estimating the prevalence of overweight and obesity among nurses is therefore important. However, to date, prevalence estimates have been based on non-representative samples and internationally no studies have compared prevalence of overweight and obesity among nurses to other healthcare professionals using representative data. Objectives To estimate overweight and obesity prevalence among nurses in Scotland, and compare to other healthcare professionals and those working in non-heath related occupations. Design Cross-sectional study using a nationally representative sample of five aggregated annual rounds (2008-2012) of the Scottish Health Survey. Setting Scotland. Participants: 13,483 adults aged 17 to 65 indicating they had worked in the past 4 weeks, classified in four occupational groups: nurses (n = 411), other healthcare professionals (n = 320), unqualified care staff (n = 685), and individuals employed in non-health related occupations (n = 12,067). Main outcome measures: Prevalence of overweight and obesity defined as Body Mass Index ≥ 25.0. Methods Estimates of overweight and obesity prevalence in each occupational group were calculated with 95% confidence intervals (CI). A logistic regression model was then built to compare the odds of being overweight or obese with not being overweight or obese for nurses in comparison to the other occupational categories. Data were analysed using SAS 9.1.3. Results 69.1% (95% CI 64.6,73.6) of Scottish nurses were overweight or obese. Prevalence of overweight and obesity was higher in nurses than other healthcare professionals (51.3%, CI 45.8,56.7), unqualified care staff (68.5%, CI 65.0,72.0) and those in non-health related occupations (68.9%, CI 68.1,69.7). A logistic regression model adjusted for socio-demographic composition indicated that, compared to nurses, the odds of being overweight or obese was statistically significantly lower for other healthcare professionals (Odds Ratio [OR] 0.45, CI 0.33,0.61) and those in non-health related occupations (OR 0.78, CI 0.62,0.97). Conclusions Prevalence of overweight and obesity among Scottish nurses is worryingly high, and significantly higher than those in other healthcare professionals and non-health related occupations. High prevalence of overweight and obesity potentially harms nurses’ own health and hampers the effectiveness of nurses’ health promotion role. Interventions are therefore urgently required to address overweight and obesity among the Scottish nursing workforce.

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The evolution of pharmaceutical competition since Congress passed the Hatch-Waxman Act in 1984 raises questions about whether the act's intended balance of incentives for cost savings and continued innovation has been achieved. Generic drug usage and challenges to brand-name drugs' patents have increased markedly, resulting in greatly increased cost savings but also potentially reduced incentives for innovators. Congress should review whether Hatch-Waxman is achieving its intended purpose of balancing incentives for generics and innovation. It also should consider whether the law should be amended so that some of its provisions are brought more in line with recently enacted legislation governing approval of so-called biosimilars, or the corollary for biologics of generic competition for small-molecule drugs.

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© 2012 by Oxford University Press. All rights reserved.This article considers the determinants and effects of M&As in the pharmaceutical industry, with a particular focus on innovation and R&D productivity. As is the case in other industries, mergers in the pharmaceutical field are driven by a variety of company motives and conditions. These include defensive responses to industry shocks as well as more proactive rationales, such as economies of scale and scope, access to new technologies, and expansion to new markets. It is important to take account of firms' characteristics and motivations in evaluating merger performance, rather than using a broad aggregate brushstroke. Research to date on pharmaceuticals suggests considerable variation in both motivation and outcomes. From an antitrust policy standpoint, the larger horizontal mergers in pharmaceuticals have run into few challenges from regulatory authorities in the United States and the European Union, given the option to spin off competing therapeutic products to other drug firms.

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Gemstone Team SnowMelt