774 resultados para sterically hindered organotellurium
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Since the Lisbon Treaty increased the legal role of the European Parliament (EP) in EU trade policy, there has been a debate about the extent to which these legal competencies have translated into actual influence over the content and outcome of EU trade negotiations. Using the case study of the on-going trade negotiations between the EU and India, this article argues that the impact of the EP has indeed been significant. Through two-level game analysis, which extends its domestic focus to include the EP as a domestic constituent, it demonstrates how the EP has affected the EU win-set in ways that have both hindered and facilitated agreement at the international level between the EU and India. It also shows how the EP has affected the negotiating dynamics and how the EU negotiators have had their preferences somewhat compromised by the EP in their attempt at reaching an agreement with India.
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Models of the air-sea transfer velocity of gases may be either empirical or mechanistic. Extrapolations of empirical models to an unmeasured gas or to another water temperature can be erroneous if the basis of that extrapolation is flawed. This issue is readily demonstrated for the most well-known empirical gas transfer velocity models where the influence of bubble-mediated transfer, which can vary between gases, is not explicitly accounted for. Mechanistic models are hindered by an incomplete knowledge of the mechanisms of air-sea gas transfer. We describe a hybrid model that incorporates a simple mechanistic view—strictly enforcing a distinction between direct and bubble-mediated transfer—but also uses parameterizations based on data from eddy flux measurements of dimethyl sulphide (DMS) to calibrate the model together with dual tracer results to evaluate the model. This model underpins simple algorithms that can be easily applied within schemes to calculate local, regional, or global air-sea fluxes of gases.
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Models of the air-sea transfer velocity of gases may be either empirical or mechanistic. Extrapolations of empirical models to an unmeasured gas or to another water temperature can be erroneous if the basis of that extrapolation is flawed. This issue is readily demonstrated for the most well-known empirical gas transfer velocity models where the influence of bubble-mediated transfer, which can vary between gases, is not explicitly accounted for. Mechanistic models are hindered by an incomplete knowledge of the mechanisms of air-sea gas transfer. We describe a hybrid model that incorporates a simple mechanistic view—strictly enforcing a distinction between direct and bubble-mediated transfer—but also uses parameterizations based on data from eddy flux measurements of dimethyl sulphide (DMS) to calibrate the model together with dual tracer results to evaluate the model. This model underpins simple algorithms that can be easily applied within schemes to calculate local, regional, or global air-sea fluxes of gases.
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A non-Markovian process is one that retains `memory' of its past. A systematic understanding of these processes is necessary to fully describe and harness a vast range of complex phenomena; however, no such general characterisation currently exists. This long-standing problem has hindered advances in understanding physical, chemical and biological processes, where often dubious theoretical assumptions are made to render a dynamical description tractable. Moreover, the methods currently available to treat non-Markovian quantum dynamics are plagued with unphysical results, like non-positive dynamics. Here we develop an operational framework to characterise arbitrary non-Markovian quantum processes. We demonstrate the universality of our framework and how the characterisation can be rendered efficient, before formulating a necessary and sufficient condition for quantum Markov processes. Finally, we stress how our framework enables the actual systematic analysis of non-Markovian processes, the understanding of their typicality, and the development of new master equations for the effective description of memory-bearing open-system evolution.
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The article covers basic inorganic chemistry of lead. As an introduction, the properties and historical uses of metallic lead are discussed, followed by aspects of lead toxicity, including the toxicity origins and effects of lead poisoning. Properties of lead as a heavy p-block element are discussed, with emphasis on the modern view of the so-called “inert pair effect”, including its origin, the influence on stability of lead oxidation states, and on the coordination chemistry of lead(II), viz., “sterically active lone pair”. This is followed by an overview of lead inorganic compounds, including halides, pseudohalides, oxides and chalcogenides, hydroxides and their chalcogenide analogs, alkoxides, oxoacids, O-donors, S- and Se-donors, Group 15 donors, compounds with lead-transition metal bonds, and finally metallic clusters (Zintl phases). This is by no means a comprehensive review, rather compounds representative for each class were presented. In most sections, structural aspects of each class of compounds are discussed, followed by applications, with the focus on modern uses in material science.
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This article explores the feminist critique that progress in the classification of sexual violence crimes within international criminal law has not been matched by sufficient legal enforcement. It takes the Extraordinary Chambers in the Courts of Cambodia (ECCC) as a case study, exploring the various myths, investigative failures and procedural developments that have hindered the ECCC’s effective investigation of sexual violence. The article argues that while there is a need to adopt a nuanced perspective of the many gender inequalities facing women, it remains crucial that sexual violence is adequately investigated and prosecuted, due to the normative value of such prosecutions. It concludes with some suggestions as to how the ECCC can improve accountability for such crimes, but also highlights lessons that future courts can learn from the ECCC’s failures.
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Current treatment strategies for the treatment of brain tumor have been hindered primarily by the presence of highly lipophilic insurmountable blood-brain barrier (BBB). The purpose of current research was to investigate the efficiency of engineered biocompatible polymeric nanoparticles (NPs) as drug delivery vehicle to bypass the BBB and enhance biopharmaceutical attributes of anti-metabolite methotrexate (MTX) encapsulated NPs. The NPs were prepared by solvent diffusion method using cationic bovine serum albumin (CBA), and characterized for physicochemical parameters such as particle size, polydispersity index, and zeta-potential; while the surface modification was confirmed by FTIR, and NMR spectroscopy. Developed NPs exhibited zestful relocation of FITC tagged NPs across BBB in albino rats. Further, hemolytic studies confirmed them to be non-toxic and biocompatible as compared to free MTX. In vitro cytotoxicity assay of our engineered NPs on HNGC1 tumor cells proved superior uptake in tumor cells; and elicited potent cytotoxic effect as compared to plain NPs and free MTX solution. The outcomes of the study evidently indicate the prospective of CBA conjugated poly (D,L-lactide-co-glycolide) (PLGA) NPs loaded with MTX in brain cancer bomber with amplified capability to circumvent BBB.
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The PolySMART demonstration system SP1b has been modeled in TRNSYS and calibrated against monitored data. The system is an example of distributed cooling with centralized CHP, where the driving heat is delivered via the district heating network. The system pre-cools the cooling water for the head office of Borlänge municipality, for which the main cooling is supplied by a 200 kW compression chiller. The SP1b system thus provides pre-cooling. It consists of ClimateWell TDC with nominal capacity of 10 kW together with a dry cooler for recooling and heat exchangers in the cooling and driving circuits. The cooling system is only operated from 06:00 to 17:00 during working days, and the cooling season is generally from mid May to mid September. The nominal operating conditions of the main chiller are 12/15°C. The main aims of this simulation study were to: reduce the electricity consumption, and if possible to improve the thermal COP and capacity at the same time; and to study how the system would perform with different boundary conditions such as climate and load. The calibration of the system model was made in three stages: estimation of parameters based on manufacturer data and dimensions of the system; calibration of each circuit (pipes and heat exchangers) separately using steady state point; and finally calibration of the complete model in terms of thermal and electrical energy as well as running times, for a five day time series of data with one minute average data values. All the performance figures were with 3% of the measured values apart from the running time for the driving circuit that was 4% different. However, the performance figures for this base case system for the complete cooling season of mid-May to midSeptember were significantly better than those for the monitoring data. This was attributed to long periods when the monitored system was not in operation and due to a control parameter that hindered cold delivery at certain times.
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People’s ability to change their social and economic circumstances may be constrained by various forms of social, cultural and political domination. Thus to consider a social actor’s particular lifeworld in which the research is embedded assists in the understanding of how and why different trajectories of change occur or are hindered and how those changes fundamentally affect livelihood opportunities and constraints. In seeking to fulfill this condition this thesis adopted an actor-oriented approach to the study of rural livelihoods. A comprehensive livelihoods study requires grasping how social reality is being historically constituted. That means to understand how the interaction of modes of production and symbolical reproduction produces the socio-space. Research is here integrated to action through the facilitation of farmer groups. The overall aim of the groups was to prompt agency, as essential conditions to build more resilient livelihoods. The smallholder farmers in the Mabalane District of Mozambique are located in a remote semi-arid area. Their livelihoods customarily depend at least as much on livestock as on (mostly) rain-fed food crops. Increased climate variability exerts pressure on the already vulnerable production system. An extensive 10-month duration of participant observation divided into 3 periods of fieldwork structured the situated multi-method approach that drew on a set of interview categories. The actor-oriented appraisal of livelihoods worked in building a mutually shared definition of the situation. This reflection process was taken up by the facilitation of the farmer groups, one in Mabomo and one in Mungazi, which used an inquiry iteratively combining individual interviews and facilitated group meetings. Integration of action and reflection was fundamental for group constitution as spaces for communicative action. They needed to be self-organized and to achieve understanding intersubjectively, as well as to base action on cooperation and coordination. Results from this approach focus on how learning as collaboratively generated was enabled, or at times hindered, in (a) selecting meaningful options to test; (b) in developing mechanisms for group functioning; and (c) in learning from steering the testing of options. The study of livelihoods looked at how the different assets composing livelihoods are intertwined and how the increased severity of dry spells is contributing to escalated food insecurity. The reorganization of the social space, as households moved from scattered homesteads to form settlements, further exerts pressure on the already scarce natural resource-based livelihoods. Moreover, this process disrupted a normative base substantiating the way that the use of resources is governed. Hence, actual livelihood strategies and response mechanisms turn to diversification through income-generating activities that further increase pressure on the resource-base in a rather unsustainable way. These response mechanisms are, for example, the increase in small-livestock keeping, which has easier conversion to cash, and charcoal production. The latter results in ever more precarious living and working conditions. In the majority of the cases such responses are short-term and reduce future opportunities in a downward spiral of continuously decreasing assets. Thus, by indicating the failure of institutions in the mediation of smallholders’ adaptive capabilities, the livelihood assessment in Mabomo and Mungazi sheds light on the complex underlying structure of present day social vulnerability, linking the macro-context to the actual situation. To assist in breaking this state of “subordination”, shaped by historical processes, weak institutions and food insecurity, the chosen approach to facilitation of farmer groups puts farmer knowledge at the center of an evolving process of intersubjective co-construction of knowledge towards emancipation.
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Chronic Obstructive Pulmonary Disease (COPD) phenotypes have become increasingly recognized as important for grouping patients with similar presentation and/or behavior, within the heterogeneity of the disease. The primary aim of identifying phenotypes is to provide patients with the best health care possible, tailoring the therapeutic approach to each patient. However, the identification of specific phenotypes has been hindered by several factors such as which specific attributes are relevant, which discriminant features should be used for assigning patients to specific phenotypes, and how relevant are they to the therapeutic approach, prognostic and clinical outcome. Moreover, the definition of phenotype is still not consensual. Comorbidities, risk factors, modifiable risk factors and disease severity, although not phenotypes, have impact across all COPD phenotypes. Although there are some identified phenotypes that are fairly consensual, many others have been proposed, but currently lack validation. The on-going debate about which instruments and tests should be used in the identification and definition of phenotypes has contributed to this uncertainty. In this paper, the authors review present knowledge regarding COPD phenotyping, discuss the role of phenotypes and comorbidities on the severity of COPD, propose new phenotypes and suggest a phenotype-based pharmacological therapeutic approach. The authors conclude that a patient-tailored treatment approach, which takes into account each patient's specific attributes and specificities, should be pursued.
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The Cyprus dispute accurately portrays the evolution of the conflict from ‘warfare to lawfare’ enriched in politics; this research has proven that the Cyprus problem has been and will continue to be one of the most judicialised disputes across the globe. Notwithstanding the ‘normalisation’ of affairs between the two ethno-religious groups on the island since the division in 1974, the Republic of Cyprus’ (RoC) European Union (EU) membership in 2004 failed to catalyse reunification and terminate the legal, political and economic isolation of the Turkish Cypriot community. So the question is; why is it that the powerful legal order of the EU continuously fails to tame the tiny troublesome island of Cyprus? This is a thesis on the interrelationship of the EU legal order and the Cyprus problem. A literal and depoliticised interpretation of EU law has been maintained throughout the EU’s dealings with Cyprus, hence, pre-accession and post-accession. The research has brought to light that this literal interpretation of EU law vis-à-vis Cyprus has in actual fact deepened the division on the island. Pessimists outnumber optimists so far as resolving this problem is concerned, and rightly so if you look back over the last forty years of failed attempts to do just that, a diplomatic combat zone scattered with the bones of numerous mediators. This thesis will discuss how the decisions of the EU institutions, its Member States and specifically of the European Court of Justice, despite conforming to the EU legal order, have managed to disregard the principle of equality on the divided island and thus prevent the promised upgrade of the status of the Turkish Cypriot community since 2004. Indeed, whether a positive or negative reading of the Union’s position towards the Cyprus problem is adopted, the case remains valid for an organisation based on the rule of law to maintain legitimacy, democracy, clarity and equality to the decisions of its institutions. Overall, the aim of this research is to establish a link between the lack of success of the Union to build a bridge over troubled waters and the right of self-determination of the Turkish Cypriot community. The only way left for the EU to help resolve the Cyprus problem is to aim to broker a deal between the two Cypriot communities which will permit the recognition of the Turkish Republic of Northern Cyprus (TRNC) or at least the ‘Taiwanisation’ of Northern Cyprus. Albeit, there are many studies that address the impact of the EU on the conflict or the RoC, which represents the government that has monopolised EU accession, the argument advanced in this thesis is that despite the alleged Europeanisation of the Turkish Cypriot community, they are habitually disregarded because of the EU’s current legal framework and the Union’s lack of conflict transformation strategy vis-à-vis the island. Since the self-declared TRNC is not recognised and EU law is suspended in northern Cyprus in accordance with Protocol No 10 on Cyprus of the Act of Accession 2003, the Turkish-Cypriots represent an idiomatic partner of Brussels but the relations between the two resemble the experience of EU enlargement: the EU’s relevance to the community has been based on the prospects for EU accession (via reunification) and assistance towards preparation for potential EU integration through financial and technical aid. Undeniably, the pre-accession and postaccession strategy of Brussels in Cyprus has worsened the Cyprus problem and hindered the peace process. The time has come for the international community to formally acknowledge the existence of the TRNC.
Estimating the effect of state-level gun purchasing policy on county-level firearm suicide mortality
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Thesis (Master's)--University of Washington, 2016-08
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In many product categories, unit prices facilitate price comparisons across brands and package sizes; this enables consumers to identify those products that provide the greatest value. However in other product categories, unit prices may be confusing. This is because there are two types of unit pricing, measure-based and usage-based. Measure-based unit prices are what the name implies; price is expressed in cents or dollars per unit of measure (e.g. ounce). Usage-based unit prices, on the other hand, are expressed in terms of cents or dollars per use (e.g., wash load or serving). The results of this study show that in two different product categories (i.e., laundry detergent and dry breakfast cereal), measure-based unit prices reduced consumers’ ability to identify higher value products, but when a usage-based unit price was provided, their ability to identify product value was increased. When provided with both a measure-based and a usage-based unit price, respondents did not perform as well as when they were provided only a usage-based unit price, additional evidence that the measure-based unit price hindered consumers’ comparisons. Finally, the presence of two potential moderators, education about the meaning of the two measures and having to rank order the options in the choice set in terms of value before choosing, did not eliminate these effects.
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Cubane is a peculiar cube-shaped alkane molecule with a rigid, regular structure. This makes it a good scaffold, i.e. a molecular platform to which the substituents are arranged in a specific and fixed orientation. Moreover, cubane has a body diagonal of 2.72 Å, very similar to the distance across the benzene ring, i.e. 2.79 Å. Thus, it would be possible to use cubane as a scaffold in medicinal and material chemistry as a benzene isostere 1,2. This could lead to advantages in terms of solubility and toxicity and could provide novel properties. For this purpose, the possibility of performing “modern organic chemistry” on the cubane scaffold has to be studied. This project was entirely carried out in the framework of the Erasmus+ mobility programme at the Trinity College (Dublin, IRL) under the supervision of prof. M. O. Senge. The main goal of this project was to widen the knowledge on cubane chemistry. In particular, it was decided to test reactions that were never applied to the scaffold before, such as metathesis of 4-iodo-1-vinylcubane and Stetter reaction of 1-iodocubane-4-carboxaldehyde. These two molecules were synthesized in 10 and 9 steps respectively from commercially available cyclopentanone, following a known procedure. Unfortunately, metathesis with different olefins, such as styrene, α,β unsaturated compounds and linear α-olefins failed under different conditions, highlighting cubane behaves as a Type IV, challenging olefin under metathesis conditions. Even the employment of a specific catalyst for hindered olefins failed in the cross-coupling with linear α-olefins. On the other hand, two new molecules were synthesized via Stetter reaction and benzoin condensation respectively. Even if the majority of the reactions were not successful, this work can be seen as an inspiration for further investigation on cubane chemistry, as new questions were raised and new opportunities were envisioned.
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Thesis (Ph.D.)--University of Washington, 2016-08