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Sauter, Dominique. „Développement de nouveaux supports activateurs solides pour la polymérisation des oléfines“. Thesis, Lyon, 2016. http://www.theses.fr/2016LYSE1249.
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Bisiriyu, Muhammad Taoheed. „Préparation et Caractérisation de Nouveaux Catalyseurs Supportés à base de Rhénium pour la Metathèse des Oléfiness“. Electronic Thesis or Diss., Lyon 1, 2023. https://n2t.net/ark:/47881/m6sb45v3.
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Les catalyseurs hétérogènes à base de rhénium occupent une place unique dans la métathèse des oléfines, réaction largement utilisée dans de nombreux procédés industriels, en raison de leur capacité à catalyser cet échange de fragments oléfiniques à température ambiante. Parmi les catalyseurs décrits dans la littérature, les matériaux, obtenus par activation du méthyl-rhenium-trioxo (MTO) sur des supports munis de sites acides de Lewis, tels que l'alumine, la silice-alumine et l'alumine modifiée par ZnCl2, présentent de hautes activités initiales en métathèse des oléfines. Cependant, ces systèmes catalytiques montrent certaines limites, tels qu'une faible proportion en sites actifs et une désactivation rapide. L'objectif de la thèse est de développer une nouvelle méthode de synthèse de catalyseurs supportés qui implique un échange de ligands entre des supports activateurs et le précurseur MTO. La stratégie générale consiste à concevoir des supports activateurs portant des ligands alkyles et/ou chlorure, qui, après un transfert vers le rhénium suivi d'une α-H abstraction, permet en plus de l'augmentation de la proportion en sites actifs "Re-carbène", une activité importante en métathèse des oléfines. Ainsi, la première partie de ce travail s'est focalisée sur le développement de supports activateurs à base d'aluminium. Les supports activateurs ciblés, comprennent des fragments Al-CH2tBu ou Al-Cl, formés par le greffage par voie chimie organométallique de surface de [Al(CH2tBu)3] ou [Al(CH2tBu)2Cl]2 sur une silice ou une alumine déshydroxylées à 200-700°C. La structure des matériaux obtenus, déterminée par bilan de masse, spectroscopies DRIFT et RMN du solide, dépend de la température de déshydroxylation du support, du choix du précurseur et du solvant. Ainsi, [Al(CH2tBu)3] réagit avec la silice (SiO2-700) dans l'éther pour donner sélectivement [≡SiO-Al(CH2tBu)(Et2O)], espèce mono-podale, alors qu'avec le pentane, l'espèce majoritaire obtenue est bipodale, [(≡SiO)2Al(CH2tBu)], avec le transfert d'un ligand neopentyl vers le silicium par ouverture d'un pont siloxane. La seconde étape consiste en une activation du MTO sur ces supports activateurs. Ainsi, l'activation du MTO sur le matériau présentant des espèces [(≡SiO)2Al(CH2tBu)] donne après transfert du ligand neopentyle une espèce penta-coordonnée de structure [(≡SiO)2AlO-Re(=O)2(Me)CH2tBu)], caractérisée par bilan de masse, spectroscopies DRIFT, RMN du solide et EXAFS. Après traitement à 70 °C, cette espèce mène par α-H abstraction à un fragment rhénium-carbène supporté. Ce nouveau système catalytique présente des performances en métathèse du propylène supérieures au catalyseur classique MTO/γ-Al2O3. La meilleure activité est principalement attribuée à une plus grande proportion en sites actifs, due à cette nouvelle stratégie d'activation du MTO par échange de ligands. Ceci constitue le premier exemple de catalyseur à base de MTO supporté sur silice actif en métathèse des oléfinesRepositioned heterogeneous catalysts based on rhenium hold a unique position in olefin metathesis, a widely used reaction in various industrial processes, due to their ability to catalyze the exchange of olefinic fragments at room temperature. Among the catalysts described in the literature, materials obtained by activating methylrhenium trioxo (MTO) on supports containing Lewis acids, such as alumina, silica-alumina, and zinc chloride-modified alumina, have shown high initial activities in olefin metathesis. However, these catalytic systems have certain limitations, such as a low proportion of active sites and rapid deactivation. The aim of this thesis was to develop a new method for synthesizing supported catalysts that involves ligand exchange between activating supports and the MTO precursor. The general strategy is to design activating supports bearing alkyl and/or chloride ligands that, upon transfer to rhenium followed by α-H abstraction, not only increase the fraction of active "carbene" sites but also exhibit significant activity in olefin metathesis. Thus, the first part of this work focused on the development of aluminum-based activating supports. The targeted activating supports, comprising Al-CH2tBu or Al-Cl fragments, are formed by surface organometallic chemistry grafting of [Al(CH2tBu)3] or [Al(CH2tBu)2Cl]2 onto dehydroxylated silica or alumina at 700°C or 200°C. The structure of the resulting materials, determined by mass balance analysis, DRIFT spectroscopy, and solid-state NMR, depends on the support dehydroxylation temperature, as well as the choice of precursor and solvent. For example, [Al(CH2tBu)3] reacts with silica (SiO2-700) to selectively yield monopodal species in ether, [≡SiO-Al(CH2tBu)(Et2O)], while in pentane, the major species obtained is bipodal, [(≡SiO)2Al(CH2tBu)], with the transfer of a neopentyl ligand to silicon through siloxane bridge opening. The second step involves the activation of MTO on these activating supports. For instance, the activation of MTO on [(≡SiO)2Al(CH2tBu)] results in the transfer of a neopentyl ligand, forming a penta-coordinated species with the structure [(≡SiO)2AlO-Re(=O)2(Me)CH2tBu)]. This species is characterized by mass balance analysis, DRIFT spectroscopy, solid-state NMR and EXAFS. Upon heating to 70°C, this species undergoes a α-H abstraction to yield a supported catalyst with a rhenium-carbene fragment. This new catalytic system exhibits better catalytic performances for propylene metathesis, compared to the classical MTO/γ-Al2O3 catalyst. The better activity is primarily attributed to a higher proportion of active sites achieved through this new MTO activation strategy involving a ligand exchange. This is the first example of MTO supported on a functionalized silica that is an active catalyst for olefin metathesis
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Brimacombe, Lyn M. „Activation of methane on supported metal catalysts“. Thesis, University of Ottawa (Canada), 1991. http://hdl.handle.net/10393/7805.
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In order to obtain more information required for the catalytic conversion of methane, the interaction of methane and ethylene with various supported metal catalysts was investigated. The metals used were Ni, Fe, Co, Mo, Ru, Rh, Pd, Re, Ir, and Pt, all supported on $\rm Al\sb2O\sb3.$ Silica supported nickel was also used. The technique of temperature programmed reaction was mainly used. This method gives temperatures at which the adsorption and/or the reaction of a gas starts to occur. The present results showed wide differences in the interaction of methane or ethylene with each catalyst. The isothermal reaction of methane was also carried out in order to further investigate the behaviour of the CH$\sb{\rm n}$ species which were formed upon the chemisorption of methane. As a process for converting methane to higher hydrocarbons, the catalytic coupling of methane with ethylene (CH$\sb4$ + $\rm C\sb2H\sb4\to C\sb3H\sb8$) was examined by using the catalysts listed above. At 250 and 350$\sp\circ$C, no propane was produced on any of the catalysts, except for alumina supported platinum. A trace of propane was found in this case for the reaction at 250$\sp\circ$C. The results were discussed based on the interaction of the reactants with these metals as revealed by the temperature programmed reactions.
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Norelus, Wesley. „Etude théorique de la réaction de fischer-tropsch : l'effet du support“. Paris 6, 2013. http://www.theses.fr/2013PA066430.
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L’objectif de ce travail est d’étudier l’effet des supports dans la catalyse en prenant comme exemple la catalyse Fischer-Tropsch. Nous avons utilisé une surface TiC(100) comme support sur laquelle nous avons adsorbé un agrégat de fer, Fe4. Après adsorption, les atomes de fer ont tendance à rester agrégés et à ne pas se disperser sur la surface. L’adsorption de la molécule de monoxyde de carbone est modifiée par le support : la force de l’interaction entre CO et l’agrégat de fer est en effet plus élevée en présence du support. Dans le cas de l’agrégat supporté, la liaison C-O est plus étirée, ce qui montre une activation de CO. La barrière énergétique pour la dissociation de C-O devrait être moins élevée que pour un agrégat sans support. De plus, cette étude nous a permis de montrer que sur notre système, selon la fonctionnelle utilisée, les résultats peuvent variés mais les tendances restent les mêmesThe goal of this work is to study the well-known support effect in catalysis taking as an example the Fischer-Tropsch catalysis. We use a TiC(100) surface to support a an iron cluster, Fe4. When iron atoms are adsorbed, they tend to form a plat cluster and not to spread off along the surface. Carbon monoxide adsorption is modified by the support: the interaction strength between CO and the iron cluster is indeed larger in the presence of the support. In the case of supported cluster, C-O bound is more elongated, which shows an activation of CO. Then, the dissociation energy barrier for CO dissociation should be smaller on a supported Fe4 cluster than for free cluster. In addition, this study allows us to show that in our system, depending on the used functional, results can be different but the trends stay the same
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Xing, Junyi. „Activation of small molecules by solid-supported frustrated Lewis pairs“. Thesis, University of Oxford, 2017. https://ora.ox.ac.uk/objects/uuid:cb32a5a7-8613-413f-b47c-80674e904c3a.
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The aims of this thesis have been to develop heterogeneous frustrated Lewis pairs for the catalytic activation of small molecules. Frustrated Lewis pairs capable of H2 activation and CO2 hydrogenation based on electron-deficient tri-aryl boranes and sterically encumbered phosphines have been immobilised on silica. The reactivity of these heterogeneous systems with small molecules has been tested and compared with a variety of soluble siloxane and silsesquioxane molecular models. The use of layered double hydroxides as a potential support for the immobilisation of FLPs has also been explored. Chapter One introduces the methanol economy and provides a background to recent advances in CO2 capture and hydrogenation. The development of frustrated Lewis pairs, their reactivity with small molecules, together with theoretical studies on the mechanism of H2 cleavage and CO2 fixation by FLPs are summarised. Recent developments on heterogeneous frustrated Lewis pairs is discussed, in addition to a brief account of surface organometallic chemistry grafting procedures on silica and layered double hydroxide (LDH) supports. Chapter Two reports H2 heterolytic cleavage by [B(C6Cl5)(C6F5)2/PtBu3] FLP and the H2 reduction of CO2 to give the methoxy borate [(C6Cl5)(C6F5)2BOCH3][HPtBu3]. These results are compared with formato- and methoxy borate derivatives prepared independently via reaction of formic acid and MeOH with [B(C6Cl5)(C6F5)2/PtBu3]. The products are characterised by FTIR and NMR spectroscopy, [(C6Cl5)(C6F5)2BOCHO][HPtBu3] is characterised by single crystal X-ray structure analysis. Chapter Three details the synthesis of a group of siloxane and silsesquioxane bound Lewis acids [(tBuO)3SiOB(C6F5)2], [(tBuO)3SiOB(Fxyl)2] (Fxyl = 3,5-bis-trifluoromethylphenyl), [T8(OB(C6F5)2)2] (T8 = (C4H9)8Si8O12), [T8(OB(Fxyl)2)2], and preparation of the corresponding FLPs with Lewis bases PtBu3 and PMes3 as soluble molecular models for silica-immobilised FLPs. Their ability to activate H2 is investigated. The side-product ((tBuO)3Si)2OBC6F5 is characterised by single-crystal X-ray structure analysis. Chapter Four describes the preparation of heterogeneous Lewis acids by immobilisation of -B(C6F5)2 and -B(Fxyl)2 on the surface of thermally pretreated silica, and the subsequent formation of the corresponding solid-supported FLPs (s-FLPs) by addition of PtBu3 to the Lewis acids. s-FLPs are shown to activate H2, D2 and CD3OD. The products are characterised by FTIR and solid state NMR (SSNMR) spectroscopy. Chapter Five investigates the immobilisation of B(C6F5)2 on a thermally pretreated aqueous miscible organic layered double hydroxide (AMO-LDH) support, and formation of LDH FLP by the addition of a Lewis base, PtBu3. The B(C6F5)2 modified LDH-FLP is shown to react with H2 and D2 and the products are characterised by SSNMR and FTIR spectroscopy. Chapter Six provides experimental procedures, characterisation techniques and data for those compounds described in the preceding chapters.
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Dalle, Kristian Erwin. „Bioinspired Activation of Oxygen with Pyrazole-Supported Dinuclear Copper Complexes“. Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2014. http://hdl.handle.net/11858/00-1735-0000-002B-7C1A-B.
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Kushch, S. D., N. S. Kuyunko, A. A. Arbuzov, N. N. Dremova und V. E. Muradyan. „Pt supported on reduced graphite oxide catalysts for H2 activation“. Thesis, Sumy State University, 2013. http://essuir.sumdu.edu.ua/handle/123456789/35570.
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Platinum catalysts of H2 activation with average size ≤2.0 nm were prepared in a base of reduction conversion of graphene oxide. A low few-layered carbon nanomaterial was prepared by thermoexpansion and annealing of graphene oxide. The uniformly dispersed Pt nanoparticles were supported on two-dimension graphene flat material by the use of pyridine or polyethyleneimine in alkaline (pH10) media as chelating agent modificating both metal precursor H2PtCl6 and support. Vacancies in carbon material formed as a result of thermoexpansion and annealing of graphite oxide probablly serve as anchor groups in platinum supporting.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35570
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Kessler, Phillip R. „Ready Reserve Force : West Coast activation in support of Operation Desert Shield“. Thesis, Monterey, California. Naval Postgraduate School, 1991. http://hdl.handle.net/10945/26719.
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Felgines, Avenier Priscilla. „Activation de l’azote moléculaire et activation de l’ammoniac par des hydrures de tantale supportés sur silice développées par chimie organométallique de surface“. Lyon 1, 2007. http://www.theses.fr/2007LYO10004.
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Les recherches effectuées dans cette thèse ont permis d’étendre la Chimie Organométallique de Surface à l’activation de l’azote et de l’ammoniac. Le complexe [(SiO)2Ta(=NH)(NH2)], 2, ainsi que son adduit [(SiO)2Ta(=NH)(NH2)(NH3)], 2NH3, ont été préparés par deux voies originales : l’activation de l’ammoniac à température ambiante et la réduction de l’azote moléculaire par le dihydrogène, à partir d’hydrures de tantale [(SiO)2TaH], 1a, et [(SiO)2TaH3], 1b. Ces complexes ont été totalement caractérisés par IR, EXAFS, analyse élémentaire et notamment par des techniques avancées de la RMN du solide, comme les spectroscopies 1H-15N HETCOR et 2D proton double et triple quantum. Des intermédiaires de la réduction de l’azote moléculaire ont pu être observés, ce qui a conduit à la proposition d’un mécanisme original pour cette réaction, différent de ceux établis en catalyse homogène, hétérogène ou enzymatique. Les réactions de synthèse de 2 conduisent également à la formation de silylamido, [SiNH2], à partir des silanes de surface. Le tantale promeut cette réaction d’amination. Enfin, la réactivité stœchiométrique de 2 vis-à-vis de la phénylacétylène et sa réaction catalytique vis-à-vis de SiH4 et de NH3 ont été exploréesThis thesis has focused on the development of the Surface Organometallic Chemistry of metal-imido and -amido species from ammonia and dinitrogen. The complex [(SiO)2Ta(=NH)(NH2)], 2, as well as its ammonia adduct [(SiO)2Ta(=NH)(NH2)(NH3)], 2NH3, were prepared by two original ways: by activation of ammonia at room temperature and by reduction of dinitrogen by dihydrogen on tantalum hydrides [(SiO)2TaH], 1a, and [(SiO)2TaH3], 1b. These complexes were fully characterized by IR, EXAFS, elemental analysis and by advanced solid-state NMR techniques, such as 1H-15N HETCOR and 2D proton double and triple quantum. Some intermediates of the reduction of dinitrogen were observed, that led to the proposition of an original mechanism for this reaction, different from those established in homogeneous, heterogeneous or enzymatic catalysis. Tantalum-promoted formation of silylamido, [SiNH2], by amination of surface silanes, occurs during the formation of 2. Finally, the stoichiometric reactivity of 2 toward phenylacetylene and its catalytic activity toward SiH4 and NH3 were explored
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Dodaro, Maria. „Active Cities for Activation Policies. Entrepreneurship support and young people in Milan and Barcelona“. Doctoral thesis, Universitat de Barcelona, 2019. http://hdl.handle.net/10803/668708.
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The thesis is framed in the disciplinary field of urban sociology and aims to analyse municipal entrepreneurship support policies promoted by the cities of Milan (Italy) and Barcelona (Spain), with a focus on the experiences of young people up to the age of thirty-five who have benefited from the different measures during the years 2012 to 2016. The concept of entrepreneurship, explicitly and sometimes implicitly accompanied by that of self-employment, is central in many policy agendas at many levels of government. In Europe, indeed, the growing concern about the persistence of high levels of unemployment, especially among young people, combined with the consolidation of activation as a paradigm in the reorientation of public actions for social inclusion, have made entrepreneurship a key instrument not only for economic development strategies, but also for activation policies (inclusive entrepreneurship). At the local level, European cities are particularly active in supporting inclusive entrepreneurship, being also able to count on the fact that new economic opportunities have found fertile ground in urban contexts, driven primarily by the growth of the service sector and a distinctive capacity for innovation. However, despite its relevance, this issue has been scantly addressed in the literature. In this context, the thesis proposes an interpretative framework for exploring this object of study that incorporates, on the one hand, neo-Marxist-inspired and neo-Weberian approaches to urban policy and governance and, on the other hand, the socio-economic literature and theoretically relevant institutional documentation on entrepreneurship, including within the framework of studies on the reorganization of the welfare state. The critical reading of the reference literature has led to two analytical macro-approaches. The first highlights the thesis of the convergence of urban policies towards neoliberal modes of governance, and welfare models based on market needs and competitiveness instead of social cohesion. A trend that entrepreneurship support policies seem to exemplify. The second highlights the peculiarities of the European city, identified with the resistance of the compromise between growth and social inclusion objectives, and supports the opposite thesis of the divergence between cities, the relevance of the political dimension and the local policy actors. Within this framework, the research has focused on how local political actors interpret, invalidate or reproduce the mainstream approach to entrepreneurship support policies and the role played in this respect by institutional factors and political aspects. Besides, the investigation included the analysis of the implications in terms of redistribution of risks and opportunities among the young people interviewed. To this ends, the research has availed itself of a qualitative methodology, case-based comparative analysis and the technique of the interview. The study revealed the heterogeneity of municipal entrepreneurship support policies concerning ideas and values, objectives, measures and tools, as well as the experiences of the young beneficiaries. Finally, the thesis highlights how policy orientations, local political paradigms, institutional legacies and governance arrangements interact to shape specific and different approaches to entrepreneurship support policies in the two cities, and how these influence the capacity to govern socio-economic changes.
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DODARO, MARIA. „Active Cities for Activation Policies. Entrepreneurship support and young people in Milan and Barcelona“. Doctoral thesis, Università degli Studi di Milano-Bicocca, 2019. http://hdl.handle.net/10281/241267.
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La tesi ha come oggetto di studio le politiche comunali di supporto all’imprenditorialità. In particolare, mette a confronto le politiche promosse dalle città di Milano e Barcellona e le esperienze di giovani fino a trentacinque anni di età. Il quadro interpretativo attinge, da un lato, agli studi sulle politiche e la governance urbana di impronta neo-Marxiana e neo-Weberiana e, dall’altro, alla letteratura socioeconomica e alla documentazione istituzionale teoricamente rilevante sull’imprenditorialità anche nella cornice degli studi sulla riorganizzazione del welfare. Da questa letteratura sono emersi due macro-approcci analitici. Il primo mette in evidenza la convergenza verso modelli di governance e di welfare neoliberali improntati alle esigenze del mercato e della competitività a discapito della coesione sociale. Un trend di cui le politiche per l’imprenditorialità sembrano costituire un esempio paradigmatico. Il secondo, mette a fuoco le peculiarità della città Europea e la tenuta del compromesso tra crescita e inclusione sociale che la caratterizzerebbe, sostenendo la tesi opposta della differenza tra le città e della divergenza rispetto alle logiche neoliberali. In questo quadro, la ricerca ha messo al centro dell’analisi le differenze locali, il ruolo dei governi urbani e la loro capacità di governare le trasformazioni socioeconomiche e politiche in corso, e inoltre gli effetti in termini di redistribuzione di rischi e opportunità tra i destinatari delle azioni. Per farlo, si è avvalsa di un approccio interpretativo, una metodologia basata sullo studio di caso e sulla tecnica dell’intervista, e un’analisi comparativa, che mette al centro dello studio le differenze e i relativi fattori di influenza. Dopo aver situato l’oggetto di studio all’interno delle condizioni socioeconomiche e istituzionali che caratterizzano i due contesti, e sulla base dei risultati emersi, la tesi mette a fuoco, innanzitutto, l’eterogeneità che caratterizza le diverse dimensioni di policy. Queste includono idee e valori, problemi, obiettivi, misure e strumenti, nonché le esperienze dei giovani beneficiari intervistati. Infine, mette in evidenza il modo in cui orientamenti politici, paradigmi di policy locali, eredità istituzionali e sistemi di governance interagiscono per dare forma a specifici e differenti approcci alle politiche di supporto all’imprenditorialità nelle due città, e come queste influenzano la capacità di governare i cambiamenti e alternare la distribuzione dei rischi e delle opportunità tra i partecipanti.The thesis deals with municipal entrepreneurship support policies (MESPs) through a comparison between the actions undertaken in this field by the municipalities of Milan and Barcelona and the experiences of young people up to thirty-five years of age. The theoretical framework has brought together the neo-Marxian and neo-Weberian approaches to urban policies and governance, and the socio-economic literature and theoretically valuable institutional documentation on entrepreneurship, also in the framework of welfare changes. Two analytical macro approaches emerged from this literature. The first highlights the convergence towards neoliberal governance and welfare models, oriented towards market and competitiveness at the expense of social cohesion. A trend of which the policies for entrepreneurship seem to constitute a paradigmatic example. The second one focuses on the peculiarities of the European city and on the compromise between growth and social inclusion that would characterise it, supporting the opposite thesis of the persistent difference between cities and of the divergence from the neoliberal logic. Against this background, the research focused on local differences and the role of municipal governments and their capacity to govern socio-economic and political changes. Besides, attention has been paid to the experiences of young people and policy outcomes in terms of redistribution of risks and opportunities. The analysis avails itself of an interpretative approach, a methodology based on the case study and the technique of the interview, and a comparative logic, which puts the differences and the related factors of influence at the centre of the study. After having placed MESPs within the socio-economic and institutional conditions of the two contexts, and given research findings, the thesis focused on the heterogeneity characterising different dimensions of MESPs. These include ideas and values, problems, objectives, measures and tools and outcomes. It highlighted how politics, institutional legacies, localised policy paradigms and governance arrangements interplay to shape specific and diverse local approaches to MESPs, thus affecting the capacity of city governments to govern socio-economic changes and to alter the unequal distribution of risks and opportunities for participants.
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Fiusco, Francesco. „Hemodynamics of artificial devices used in extracorporeal life support“. Licentiate thesis, KTH, Teknisk mekanik, 2021. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-301039.
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Extracorporeal Membrane Oxygenation (ECMO) is a life-saving therapy usedfor support in critical heart and/or lung failure. Patient’s blood is pumped viaan artificial lung for oxygenation outside of the body. The circuit is composedof a blood pump, cannulae for drainage and reinfusion, a membrane lung,tubing and connectors. Its use is associated with thromboembolic complicationsand hemolytic damage. Detailed numerical studies of two blood pumps anda lighthouse tip drainage cannula were undertaken to characterize the flowstructures in different scenarios and their link to platelet activation. The pumpsimulations were modelled according to manufacturer’s proclaimed use but alsoin off-design conditions with flow rates used in adult and neonatal patients.Lagrangian Particle Tracking (LPT) was used to simulate the injection ofparticles similar in size to platelets to compute platelet activation state (PAS).The results indicated that low flow rates impacted PAS similarly to high flowrates due to increased residence time leading to prolonged exposure to shearstress despite the fact that shear per se was lower at low flow rate. Regardingthe cannula, the results showed that a flow pattern similar to a jet in crossflowdeveloped at the side holes. A parameter study was conducted to quantifydrainage characteristics in terms of flow rate distribution across the holes wheninput variables of flow rate, modelled fluid, and hematocrit were altered. Thefindings showed, across all the cases, that the most proximal hole row drainedthe largest fraction of fluid. The effects due to the non-Newtonian nature ofblood were confined to regions far from the cannula holes and the flow structuresshowed very limited dependence on the hematocrit. A scaling law was found tobridge the global drainage performance of fluid between water and blood.QC 210906
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Liebnitzky, Jan. „Moral Disengagement in media and Moral Identity activation: their interactive effect on support of war“. Master's thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2015. http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-164902.
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People can disengage from their internalized moral standards and self-regulation in order to perform immoral behaviour by using different Moral Disengagement mechanisms. These mechanisms within media have a positive effect on immoral behaviour. However, Moral Identity activation is said to counter arguments of Moral Disengagement. In this study, both concepts are applied to the context of war. An additional assumption took into account in how far participants’ internalized moral standards consider war as immoral. This is important since Moral Identity and Moral Disengagement are based on internalized moral standards. To test the hypotheses, this study employed a 2 x 2 RO between-subjects factorial design. The trait variable called Moral Consideration of War was supposed to reflect participants’ internalized moral standards with regard to war. It was used to operationalize the additional assumption. Factor 1 varied the activation of Moral Identity (Moral Identity activation versus control group) and factor 2 varied the depiction of the war scenario (Permissive Scenario versus Prohibitive Scenario). Scenarios were fictive newspaper articles. A Permissive Scenario comprised a higher number of arguments based on Moral Disengagement mechanisms than a Prohibitive Scenario. Main outcome measures were the support of war and war-related Moral Disengagement (questionnaire). In total 86 participants (f=45, m=41) were randomized into four cells and completed the online experiment. The Permissive Scenario failed to increase support of war and Moral Disengagement (questionnaire), on the assumption that war is considered immoral. Moral Identity activation had a negative effect on Moral Disengagement only on the assumption that war was considered moral. Moral Identity activation had no significant effect on support of war, on the premise that war was considered immoral. The interaction term of Moral Identity activation and Permissive Scenario had no significant effect neither on support of war nor on Moral Disengagement, no matter if additional assumption was taken into account or not. Results are discussed with regard to methodological limitations measuring internalized moral standards. Their measurement implied already individual Moral Disengagement. Interaction effect failed, supposedly because Moral Identity activation was not specifically targeted at immoral behaviour and because mediating effects of Moral Identity centrality were not consideredDie Mechanismen der Moralischen Entkopplung lösen das Selbst von internalisierten moralischen Standards und verhindern damit die Selbstregulierung des moralischen Verhaltens. Diese Mechanismen kommen auch in Medien vor und tragen zu unmoralischem Verhalten bei. Die Aktivierung der Moralischen Identität wirkt jedoch den Mechanismen der Moralischen Entkopplung entgegen. In dieser Studie werden beide Konzepte auf das Thema Krieg übertragen. Dabei ist wichtig zu beachten, dass internalisierte moralische Standards Krieg als unmoralisch bewerten. Schließlich basieren sowohl Moralische Entkopplung als auch die Aktivierung der Moralischen Identität auf dieser zusätzlichen Annahme. Zur Überprüfung der Hypothesen wurde ein 2 x 2 RO Between-Subjects Design verwendet. Faktor 1 variierte die Aktivierung von Moralischer Identität (Aktivierung Moralische Identität versus Kontrollgruppe). Faktor 2 variierte die Permissivität eines Kriegsszenarios in einem Zeitungsartikel (Permissives Szenario versus Prohibitives Szenario). Dabei wurde Permissivität hinsichtlich der Anzahl der Moralischen Entkopplungsmechanismen operationalisiert (Viele versus Wenig). Als Organismusvariable ist die Moralische Bewertung von Krieg zur Überprüfung der zusätzlichen Annahme notwendig gewesen. Abhängige Variablen waren die Unterstützung von Krieg und Moralische Entkopplung (Fragebogen). Teilnehmerinnen und Teilnehmer (N=86, f=45, m=41) des online Experiments wurden in vier verschiedene Versuchsbedingungen randomisiert. Die Ergebnisse zeigten, dass die Permissivität des Kriegsszenarios keinen Effekt auf Moralische Entkopplung (Fragebogen) oder die Unterstützung von Krieg hatte, unter Berücksichtigung der Zusatzannahme. Moralische Identitätsaktivierung verringerte Moralische Entkopplung (Fragebogen) aber nur unter der Bedingung, dass Krieg als moralisch bewertet wurde. Moralische Entkopplung hatte keinen Effekt auf die Unterstützung von Krieg, unter Berücksichtigung der Zusatzannahme. Die Interaktion von Moralischer Identitätsaktivierung mit der Permissivität des Kriegsszenarios war nicht signifikant, unabhängig davon ob die Zusatzannahme berücksichtigt wurde oder nicht. Die Ergebnisse werden in Bezug auf die methodischen Probleme bei der Messung internalisierter moralischer Standards diskutiert. Es fanden vermutlich Prozesse der Moralischen Entkopplung bereits während der Messung dieser Standards statt. Der fehlende Interaktionseffekt kann an der schwachen und unspezifischen Aktivierung der Moralischen Identität liegen, sowie nicht berücksichtigter Mediatoren, wie z.B. die Zentralität von Moralischer Identität
14
Al-Sayari, Saleh Abdullah. „Synthesis of active supported gold catalysts for CO oxidation and light alkane activation“. Thesis, Cardiff University, 2006. http://orca.cf.ac.uk/56051/.
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The preparation of gold catalysts supported on different metal oxides such as ZnO and Fe2O3, using two coprecipitation methods is investigated to determine important factors, such as selection of support material and preparation method, and preparation parameters, such as preparation temperature, pH, and ageing process. These factors control the synthesis of high activity catalysts for the oxidation of carbon monoxide at ambient temperature. The two preparation methods differ in the manner in which the pH is controlled during coprecipitation, either constant pH throughout or variable pH in which the pH is raised from an initial low value to a defined end point. Non- calcined Au/ZnO catalysts prepared using both methods are very sensitive to pH and ageing time. Catalysts prepared at higher pH give lower activity. However, all catalysts require a short indication period during which the oxidation activity increases. In contrast, the calcined catalysts are not sensitive to preparation conditions. Non-calcined Au/Fe203 catalysts exhibit high activity when prepared at pH > 5. Active calcined Au/Fe2O3 catalysts can be prepared when the pH is controlled at pH 6-7, 8, whereas calcined catalysts prepared using the variable pH method are inactive. The study demonstrates the immense sensitivity of catalyst preparation methods on the performance. Catalysts exhibited excellent catalytic activity and stability compared with the pure supports, ZnO and Fe2O3, and the best preparation temperature was 80 C. Use of temperatures > 80 C led to inactive catalysts. The deposition-precipitation (DP) method was also employed using four different supports in this study (ZnO, Fe2O3, MgO, and MnO2). A comparison between these catalysts was taken rather than an investigation of the effect of the preparation parameters on catalysts prepared by DP method because they have been well studied previously. Several characterization techniques including AAS, BET surface area, XRD, TPR, and XPS, were utilised to investigate the physical and chemical properties of the prepared supported gold catalysts. Characterization results were combined with catalytic results for the low temperature CO oxidation reaction of catalysts in order to study the aforementioned factors that can affect either the properties of catalysts or their activities. Subsequently, several experiments at high GHSV were conducted to study the catalytic activities of these catalysts in-depth and to correlate data with alkane activation reactions. CH4 activation reaction using supported gold catalysts at light temperatures and the effect of the preparation parameters, types of supports on catalysts activities were investigated. The Au/Fe2O3 catalyst prepared by coprecipitation method B at pH 8 showed the highest catalytic activity for CO oxidation and CH4 activation reactions. The most active catalysts were also evaluated for C2H6 and C3H8 activation at low temperature. After this, a comparison between CO oxidation and alkane activation over supported gold catalysts was undertaken to investigate the relationship between the behaviour of supported gold catalysts for these two types of reactions. Activation energies and pre-exponential factors of many catalysts were calculated based on the Arrhenius equation either for CO oxidation or for alkane activation. The preparation of gold catalysts supported on different metal oxides such as ZnO and Fe2O3, using two coprecipitation methods is investigated to determine the important factors that control the synthesis of high activity catalysts for the oxidation of carbon monoxide at ambient temperature. (Abstract shortened by UMI.)
15
Beyer, Hans [Verfasser]. „Activation of nitrogen oxides by supported noble metal catalysts: Structure-activity relationships / Hans Beyer“. München : Verlag Dr. Hut, 2010. http://d-nb.info/1009095641/34.
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Engel, Stefan Verfasser], Martin [Akademischer Betreuer] [Möller und Andrij [Akademischer Betreuer] Pich. „Functional and responsive polyglycidol based microgels as activating support for (bio)catalysts in aqueous medium / Stefan Engel ; Martin Möller, Andrij Pich“. Aachen : Universitätsbibliothek der RWTH Aachen, 2019. http://d-nb.info/1195446675/34.
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Engel, Stefan [Verfasser], Martin [Akademischer Betreuer] Möller und Andrij [Akademischer Betreuer] Pich. „Functional and responsive polyglycidol based microgels as activating support for (bio)catalysts in aqueous medium / Stefan Engel ; Martin Möller, Andrij Pich“. Aachen : Universitätsbibliothek der RWTH Aachen, 2019. http://d-nb.info/1195446675/34.
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Onesti, Riccardo. „Characterization of a ceramic monolithic support for affinity protein chromatogrophy“. Master's thesis, Alma Mater Studiorum - Università di Bologna, 2017.
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Affinity chromatography is a process for the separation of biomolecules from complex mixtures. Its versatility, high selectivity and efficiency make it the most currently used method in the final stages of purification of pharmaceutical and food industries, where a high degree of purity is required.
Conventional affinity chromatography uses packed beads as solid support and suffers of several limitations, such as high material costs, high operating costs, intraparticle diffusion as primary transport phenomenon and difficulties in column packing.
Therefore, it is necessary to develop and characterize cheaper and more efficient materials as stationary phase for chromatographic separations. From this perspective, monolithic media have shown a significant potential.
In this research project a new ceramic composite monolithic support, a cellular Al2TiO5 and Al2TiO5-Al2O3 composite monolith, has been experimentally characterized.
First, several monolithic columns have been prepared, by polishing the material to obtain cylindrical samples of the desired height and dimensions. Then the columns have been characterized by calculating the main fluid dynamic parameters that govern the motion of a fluid in a porous material: permeability, porosity and axial dispersion coefficient. To this aim permeability tests and pulse tests have been performed.
One column has been functionalized with epoxy groups, by linking 3-glycidoxypropyltrimethoxysilane (GPTMS). This step, called activation, creates active sites for the immobilization on the support of protein A, that on turn is used for the affinity adsorption of immunoglobulin-G.
The number of active epoxy groups has been estimated by measuring the ability of the column to irreversibly bind the bovine serum albumin, BSA, in chromatographic experiments.
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Ghadamgahi, Sedigheh. „Size, Shape and Support Effects on the Catalytic Activity of Immobilized Nanoparticles“. Thesis, University of Canterbury. Chemistry, 2014. http://hdl.handle.net/10092/10042.
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Abstract:
A brief overview of this PhD thesis,
The emergence of nanotechnology has stimulated both fundamental and industrially relevant
studies of the catalytic activity of noble metal nanoparticles. Palladium, ruthenium and gold
are well known catalysts when used in nanoparticle- based systems. This body of work
endeavoured to investigate the catalytic activity of these noble metal nanoparticles through
three studies as a briefly overviewed below.
Study 1:
Palladium is a well-known catalyst, even in bulk phases, but its high cost had driven industry
towards its use in nanoparticle- based systems well before nanotechnology had attracted the
attention of the media. Palladium nanoparticles often show remarkable catalytic activity and
selectivity, particularly for the hydrogenation of some unsaturated hydrocarbons, such as
alkenes, alkynes and unsaturated carbonyl compounds. The nature of supports can affect the
catalytic activity and selectivity of metal-support interaction. Natural polymeric supports,
such as wool, can be suitable for new generation of composite materials incorporating
nanosized metal nanoparticles and have the added advantage of being “environmentally
friendly”.
Catalytic hydrogenation of cyclohexene to cyclohexane by palladium nanoparticles
immobilized on wool was demonstrated by using a Parr high pressure hydrogenation set-up.
The efficiency of the process was explored over loading rates from 1.6% to 2.6% of
palladium nanoparticles (by weight) with a variety of particle sizes. Optimization of the
reaction conditions including, stirring rate, amounts of reactants, gas pressure and target
temperature, led to series of catalytic activity tests carried out for 5 or 24 hours (each) at 400psi H2 and 40 oC using a stirring rate 750 rpm. Product mixtures were analysed using gas
chromatography (GC-FID) to determine conversions. Samples S1 and S2 proved to be the
most active catalysts because the average Pd particle size was around ~5 nm and the particles
were more accessible for the reactant (i.e., Pd particles were on the surface of wool).
However, under the catalytic testing conditions studied, wool (Pd/wool) did not show
advantages over commercially used palladium nanoparticles on activated carbon (Pd/C).
Study 2:
Ruthenium fabricated as noble metal nanoparticles can be catalytically active for
hydrogenation of organic compounds. However, a challenging issue for researchers is that Ru
nanocatalysts can be spontaneously deactivated due to effects, such as sintering or leaching of
active components, oxidation of noble metal nanoparticles, inactive metal or metal oxide
deposition and impurities in solvents and reagents. Calcination of noble metal nanoparticles
is one option for reactivation of Ru nanoparticles immobilized on SiO2 (Ru/SiO2) utilized as
nanocatalysts in chemical reactions. In fact, the catalytic activity of noble metal nanoparticles
is known to be proportional to the active part of the surface area. The effects of calcinations
on catalytic activity of “shape- specific” 0.1 wt% Ru/SiO2 for hydrogenation of cyclohexene
to cyclohexane were investigated. Optimization of calcinations by varying temperature and
time proved to be effective on the activity of nanocatalysts retaining the Ru nanocatalysts
shapes for the hydrogenation of cyclohexene. Product mixtures were analysed using gas
chromatography (GC-FID) to determine conversions. The Ru catalysts showed the highest
activity (100%) when they were activated by calcination following protocol No.1 in a furnace
under the mildest reductive conditions studied (temperature = 200 oC for 1 hour, which was
the shortest calcination time). HRTEM study showed only minor deformation of the Ru
nanoparticles and minimal aggregation for this type of activation.
Study 3:
Supported gold nanoparticles have excited much interest owing to their unusual and
somewhat unexpected catalytic activity particularly with the selective oxidation of organic
compounds. Gold nanoparticles immobilized on Norit activated carbon (Au101/C) via
colloidal deposition gave high selectivity of benzyl alcohol oxidation. The presence of a base
(K2CO3) increased the catalytic activity of gold nanocatalysts (which was negligible in the
absence of base) through dehydrogenation of the alcohol via deprotonation of a primary OH
groups, and helped overcome the rate-limitation step of the oxidation process. The interaction
between the gold species and the support was investigated by measuring change in catalytic
activity with different activation methods (i.e., washing with a solvent at elevated
temperature, and/or followed by calcinations). A mixture of benzyl alcohol as a reactant,
methanol as a solvent, K2CO3 as a base and oxygen gas was studied by the activated gold
nanocatalysts using a mini reactor set-up. The efficiency of the process was explored by
varying the amounts of benzyl alcohol and the base, target temperature, metal loading of the
gold catalysts rate and the solvent, between 3 and 24 hours at 73 psi O2 and a stirring rate
(750 rpm). The samples of the reaction mixture were centrifuged and analysed by highperformance
liquid chromatography (HPLC) to determine conversions.
The effect of size on the catalytic activity was studied for different types of gold particles
(Au101, Aunaked and Aucitrate) and clusters (Au8 and Au9) immobilized on powder Norit
activated carbon. The highest activity of benzyl alcohol oxidation was observed for activated
1.0 wt% Au101/C catalysts (washed with toluene and followed by calcination under vacuum at
100 oC for 3 h) for ~3.5 nm gold particles. Additionally, the support effect was studied for
gold particles immobilized on different types of carbons, such as Norit activated carbon
(powder, granular and powdered) and mesoporous carbons (CMK-3, CMK-8 and NCCR-41),
granular modified carbon (–SH and –SO3H groups) and Vulcan carbon. The highest activity was observed by activated 1.0 wt% Au101/C8 catalysts (washed with toluene and followed by
calcination under vacuum at 100 oC for 3 h). Activated 1% Au101/C41 (washed with toluene
followed by calcination under vacuum at 100 oC for 3 hours) with 2.6 ± 0.1 nm gold particle
size showed the highest selectivity towards methyl benzoate as a main product (S%: 88%)
after 3 hours reaction time. However, activated 1% Au101/C (calcination in O2 -H2 at 100 oC
for 3 hours) with 6.6 ± 0.3 nm gold particle size exhibited the highest selectivity towards
benzoic acid as a main product (S: 86%) after 24 hours reaction time.Therefore, particle size
and type of carbon support can be considered as playing crucial roles in defining the catalytic
activity of gold nanocatalysts which were used for benzyl alcohol oxidation.
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Harding, Hage Brenda L. „An Examination of the Relationship Among Health Literacy, Social Support, and Patient Activation in Community Residing Older Adults“. VCU Scholars Compass, 2007. https://scholarscompass.vcu.edu/etd/5727.
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This study examined the relationships among the variables health literacy, social support, and patient activation. The subjects were 90 elderly, community residing adults meeting the inclusion criteria and who volunteered to participate in the study and completed three survey instruments: the Short Form of Functional Health Literacy (Parker, Baker, Williams & Nurss, 1995); the Medical Outcomes Survey (MOS) Social Support Survey Instrument (Sherboume & Stewart, 1991); the Patient Activation Measure (PAM) Short-Form (Hibbard, Mahoney, Stockard, & Tusler, 2005); and a demographic form.
A correlational design was used to test the hypotheses that social support and health literacy are positively related to patient activation. Health literacy was significantly and positively related to patient activation. Multiple regression analysis was used to determine whether health literacy explained a significant proportion of the variance in patient activation. Neither health literacy or social support explained a significant proportion of the variance. Demographic variables of age, level of education, gender, marital status, and self-rated health accounted for a small, but statistically significant proportion of the variance. Implications of these findings include that social support did not have significant effects on patient activation. Health professionals should continue to explore additional directions to ameliorate the negative effects of low health literacy and activate patients, including reactions to health problems.
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Ternel, Jérémy. „Nouveaux systèmes catalytiques bifonctionnels pour la silylcyanation asymétrique“. Thesis, Lille 1, 2010. http://www.theses.fr/2010LIL10071/document.
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De nouveaux complexes alkyle d’aluminium originaux comportant des ligands chiraux potentiellement tridentates hautement modulables de type phénolato-imino-sulfonamide (PISA) ont été synthétisés et caractérisés.D’autre part, dans une optique de développement de procédés plus propres, de nouveaux matériaux hybrides ont été préparés par immobilisation sur silice de complexes d’aluminium, d’ytterbium et de zinc sur silice. Ces complexes chiraux moléculaires et supportés ont été utilisés en silylcyanation énantioselective des aldéhydes et des cétones en présence d’une base de Lewis. D’excellentes conversions et sélectivités ont été obtenues pour une large gamme de substrats.Les aspects mécanistiques de ces systèmes catalytiques bifonctionnels ont également été abordésNew alkyl aluminium complexes supported by potentially tridentate, highly tunable chiral ligands of the phenolato-imino-sulfonamide type (PISA) were synthesized and characterized.In the view of developping cleaner chemical processes, new hybrid materials were prepared by immobilization of aluminum, ytterbium and zinc complexes onto silica.These molecular and supported species have been used in enantioselective silylcyanation of aldehydes and ketones in the presence of a Lewis base. Excellent conversions and selectivities were achieved for a broad scope of substrates.Mecanistic aspects of this type of bifunctional catalytic systems have also been studied
22
McAllister, Christine Horne. „The Impact of Behavioral Activation on Maternal Well-Being in Mothers of Children with Autism Spectrum Disorder“. BYU ScholarsArchive, 2016. https://scholarsarchive.byu.edu/etd/6016.
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Autism Spectrum Disorder (ASD) is a developmental disorder known for deficits in language and social skills. It is often associated with maladaptive behaviors. Studies have indicated that these behaviors in children lead to increased stress, anxiety and depression in mothers. This study examines the effects of parent-implemented Positive Behavior Support (PBS) and behavioral activation (BA) on reducing problem behaviors and increasing maternal wellness. The single subject study was conducted with three mothers (between the ages of 30 and 45) and their three children (between the ages of 5 and 7) with autism spectrum disorder. The results of this study demonstrate that while PBS implementation does reduce problem behaviors, it does not significantly impact maternal well-being. Results indicated that two of the three mothers were able to implement PBS interventions and their children demonstrated significant behavioral improvements. These mothers also engaged in high levels of valued activities both at baseline and during intervention and showed few depression symptoms. The third mother was not able to implement the interventions and her child demonstrated little behavioral progress. This mother showed signs of depression and did not make gains in this area. Further research may want to examine the relationship between behavioral activation and respite care, as well as the role of socioeconomic status.
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Pittet, Christophe. „Les pratiques artistiques dans le champ de l'insertion professionnelle comme support de construction identitaire dans le passage à la vie adulte“. Thesis, Strasbourg, 2014. http://www.theses.fr/2014STRAG020/document.
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Cette recherche a pour objectif de comprendre la place et la fonction des pratiques artistiques chez les jeunes adultes à l’aide sociale inscrits dans un processus d’insertion professionnelle. En partant des conditions de la construction de l’identité dans le passage à la vie adulte et des transformations de l’Etat social, nous nous sommes intéressé à saisir les contours des pratiques artistiques et culturelles dans le champ du travail social comme une alternative au soutien à l’accès à la formation professionnelle des jeunes adultes. A partir d’une mesure d’insertion basée à Lausanne (Suisse) qui utilise les arts de la scène comme socle central de son accompagnement psychosocial, nous avons pu observer que les pratiques artistiques favorisent le développement de l’estime personnelle, le renforcement de la confiance et l’élargissement du réseau relationnel. Les supports artistiques sont également des vecteurs de socialisation professionnelle car ils contribuent à réinscrire les jeunes adultes dans un rythme, exigent des capacités d’adaptabilité et de flexibilité, ainsi que d’amélioration de leur savoir-être. Cette dimension utilitariste réinterroge les usages de l’art à des fins de normalisation des comportements de manière à répondre aux exigences professionnelles telles que l’esprit d’initiative et le sens des responsabilitésThis research aims to understand the place and function of artistic practices among young adults receiving social assistance who are part of a work integration process. Starting from conditions linked to development of identity in the transition to adulthood and the changes of the Social State, we were interested to understand how artistic and cultural practices in the field of social work may act as an alternative to support the access to vocational training in young adults. From an integration program developed in Lausanne (Switzerland), which uses the arts as the focal point for psychosocial support, we observed that artistic practices foster the development of self-esteem, strengthening confidence and extending the interpersonal network. Artistic media are also vectors of professional socialization because they may help young adults to be re-registered in a rhythm; they require adaptability and flexibility abilities and they tend to improve self-management skills. This utilitarian dimension reexamines the uses of art for the purpose of behavior standardization to meet professional requirements such as leadership and sense of responsibility
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Walaszek, Michelle Christine. „Central and Peripheral Weight Gain Affect Trunk Kinematics and Lower-Extremity Muscle Activation Differently During Sit-To-Stand“. UKnowledge, 2016. http://uknowledge.uky.edu/khp_etds/34.
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Background: Obesity-induced alterations in biomechanics and muscle recruitment during activities of daily living, such as sit-to-stand (STS) are often attributed to increases in adipose tissue (AT) mass. Central or peripheral distribution of AT may differently affect biomechanics and muscle recruitment.
Methods: Fifteen healthy, normal weight (BMI 22.4 ± 1.9 kg/m2, 24.1 ± 4.2 years) subjects volunteered. External loads equivalent to a 5 kg/m2 BMI increase were applied in three conditions: unloaded (UN), centrally loaded (CL), and peripherally loaded (PL). Subjects completed three successful STS movements in a backless chair under each load condition in random order. Motion analysis and lower extremity surface electromyography (EMG) were measured.
Results: Compared to UN and CL, PL significantly increased support width during STS. PL also significantly increased maximum trunk flexion compared to CL. Peak and total VM EMG activity were significantly increased during CL, compared to UN and PL. During CL, peak VL EMG activity was significantly greater than UN.
Conclusions: Central and peripheral weight gain induce different biomechanical adaptations during STS. Central weight gain increases knee extensor muscle activity during STS independent of biomechanical changes. In contrast, peripheral weight gain increases support width and trunk flexion with minimal EMG changes during STS.
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Kafentzi, Maria Chrysanthi. „Reactive copper-oxygen species for C-H activation : influence of nuclearity and oxygen atom donor“. Thesis, Aix-Marseille, 2016. http://www.theses.fr/2016AIXM4355/document.
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Les monooxygénases à cuivre sont des systèmes enzymatiques capables de transférer un atome d'oxygène à leur substrat de manière hautement régio et stéréo-spécifique. Les complexes modèles de monooxygénases à cuivre ont fourni de précieuses informations sur la structure et la réactivité des espèces «cuivre-dioxygène» impliquées dans une telle réactivité. Cependant, la découverte récente de deux nouveaux systèmes enzymatiques (LPMO et pMMO) capables d'effectuer l'activation des liaisons C-H très énergétiques a réouvert le débat sur les espèces cuivre--oxygène capables d'une telle réactivité. Dans ce travail, nous avons choisi de préparer des complexes bio-inspirés de Cu(I) et Cu(II) avec un ligand contenant un substrat interne. Ces complexes ont été exposés à différents oxydants ou donneurs d'atome d'oxygène et nous avons étudié la régio- et stéréo-sélectivité de la réaction d'oxydation du substrat interne. De plus, nous avons évalue la capacité de ces systèmes à utiliser l'eau comme donneur d'atome d'oxygène. Pour cela, nous avons l'oxydation ou l'activation de l'eau par voie électrochimique afin de générer des intermédiaires cuivre-oxygène conduisant éventuellement à la production de dioxygène ou à l'oxydation sélective du ligand. Enfin, nous nous sommes intéressés aux propriétés d'espèces hétérobimétalliques à haute valence. Par conséquent, deux nouveaux complexes hétérobimétalliques à haute valence contenant du nickel et du cuivre ont été synthétisés. Nous avons étudié leurs propriétés électroniques et leur réactivité envers des substrats externes et internes (ligands) a été évaluée et comparée à la réactivité de leurs homologues homobimétalliquesCopper-containing monooxygenases are enzymatic systems capable of transferring an oxygen atom to their subtrates in highly regio or stereo-specific modes. Model complexes for copper-containing monooxygenases have provided valuable information on the structure and reactivity of several copper-dioxygen adducts. However, the recent discovery of two new enzymatic systems (LPMO and pMMO) able to perform activation of very strong C-H bonds has re-opened the debate on the catalytically relevant copper-dioxygen species. The use of model systems that mimic an enzyme is a simple approach to obtain a better knowledge of how nature works. For this study, Cu(I) and Cu(II) complexes containing ligand-substrate were prepared. After reaction with different oxidants or O-atom donors, we investigated the regio- and stereo-selectivity of the oxidation of the internal substrate. Based on the relatively well-known chemistry of Cu(I) with dioxygen, we, were also interested in investigating the water as an O-atom donor in C-H bond activation reactions. We have therefore investigated electrochemical water oxidation or activation to generate dioxygen and selective oxygen-insertion into the substrate-bound moiety. Finally, we explored the properties of mixed-metal dioxygen species as compared to their homometalic counter-parts. Indeed heterobimetallic active sites are found in various metalloenzymes such as cytochrome c oxidase. Therefore, two new high-valent Cu-Ni heterobimetallic complexes were synthesized. We investigated their electronic properties using various spectroscopic methods and their reactivity was evaluated towards external and internal substrates (indane)
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Laporte, Christian. „Activation de reactions supportees sur graphite et de reactions catalysees sous champ micro-onde : cycloadditions et reactions de friedel-crafts“. Toulouse 3, 1997. http://www.theses.fr/1997TOU30272.
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L'utilisation du graphite en tant que support de reactions organiques a revele toute son efficacite par couplage a la technologie micro-onde. L'obtention de niveaux thermiques eleves a permis dans un premier temps de mener des reactions pericycliques connues pour demander plusieurs heures de chauffage a temperature elevee. Des cycloadditions de diels-alder en particulier d'hetero-diels-alder et de carbonyl-diels-alder ont ainsi ete realisees en des temps de reaction considerablement reduits. Par le meme procede il a ete egalement possible d'activer la reaction d'acylation de friedel-crafts. La synthese d'arylcetones a ete realisee sur support graphite en milieu sec ainsi qu'en presence d'une faible quantite de graphite (milieu humide). Une analyse du graphite a l'echelle microscopique a permis de mettre en evidence que les impuretes presentes dans celui-ci (principalement a bases de fer) etaient a l'origine de la catalyse. Le fer sous forme d'oxydes (fe#3o#4 identifie) est responsable de l'effet catalytique du graphite par generation in situ du chlorure ferrique. Devant ce constat, l'activation de la reaction d'acylation de friedel-crafts sous micro-ondes en presence d'acides de lewis en quantites catalytiques a ete etudiee. Certains acides de lewis tels que le chlorure ferrique se sont reveles extremement actifs. L'acylation de substrats aromatiques tres desactives tels que le chlorobenzene ou le 1,3-dichlorobenzene a ete realisee. La decomplexation selective du complexe arylcetone-fecl#3 qui constituait l'etape bloquante du cycle catalytique est accomplie par une forte absorption de l'energie micro-onde au niveau de ce complexe. Le procede implique une mise en uvre simplifiee en operant en l'absence de solvant, sous la pression atmospherique, en des temps de reactions raccourcis par rapport aux conditions classiques et en utilisant une faible quantite de promoteur. Ces travaux contribuent au developpement d'une chimie moins couteuse et moins polluante.
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Bailliez, Vincent. „Nouvelle méthode de préparation de 1,6-anhydro-β-D-glucopyranose sur support solide et sans solvant sous irradiation micro-ondes : étude de réactions de substitution avec les azotures alcalins sous irradiation micro-ondes et préparation de produits polyazotés de glucose : synthèse d'analogues de la Fattiviracine“. Paris 11, 2003. http://www.theses.fr/2003PA112036.
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Lors de cette thèse, plusieurs thèmes ont été abordes. Nous avons mis au point une, nouvelle méthode de préparation d'1,6-anhydro-glycopyranose sur support solide et sans solvant en utilisant de l'alumine basique sous irradiation micro-ondes avec de bons rendements. Cette nouvelle méthode de préparation est facile a mettre en oeuvre, même a grande échelle, et économique. Une étude méthodologique a aussi été menée sur des réactions de substitution avec les azotures alcalins sous irradiation micro-ondes. Cette étude vient compléter les travaux déjà réalises au laboratoire sur des réactions classiques de la chimie des hydrates de carbone sous irradiation micro-ondes. Nous avons cherche des alternatives à l'utilisation de sels d'azoture du fait de problèmes de sécurité qu'ils peuvent engendrer. Nous nous sommes aussi intéresses à la synthèse de composes polyazotes de glucose. La synthèse de deux dérives tetra-azotes a ainsi été réalisée à partir du levoglucosane. Enfin, nous avons projette de synthétiser des analogues de la fattiviracine. Ce nouvel agent antiviral présente des activités significatives vis-à-vis des virus de l'herpes, de la grippe, de la varicelle et du hiv-1. La fattiviracine est un compose macrocyclique à 18 chaînons constitue de deux -molécules de d-glucose portant deux chaînes latérales. Il existe deux autres substances présentant des activités biologiques intéressantes qui possèdent le même type de structure, la cycloviracine et la glucolipsine. La différence se situe essentiellement au niveau des chaînes latérales. Nous avons synthétise la partie macrocyclique commune à cette famille de substances naturelles en 10 étapes à partir du levoglucosane et de l'acide s-malique. Ce nombre limite d'étapes pour obtenir ce macrocycle en fait un synthon très intéressant pour la synthèse d' analogues de la cycloviracine et de la glucolipsine. En effet, l'addition de chaînes latérales peut être envisagée à partir de ce macrocycleDuring the preparation of this doctoral dissertation, several themes have been considered and dealt with. We have elaborated a new method of preparation of 1,6- anhydro-d-glycopyranose. Satisfactory yields were obtained utilizing solid support (basic alumina), without solvent, under microwave irradiation. The new method is highly economical and can readily be extended to the preparation of large amounts of material. A methodological investigation has also been accomplished for substitution reactions in the presence of azide ions under microwave irradiation. Our study has been completing similar researches on the chemistry of carbohydrates, previously achieved in the laboratory applying classical reactions under conditions of microwave irradiation. We were also interested in the synthesis of polynitrogenated derivatives of d-glucose. Starting from levoglucosane, the synthesis of two tetra-nitrogenated derivatives have been carried out. Eventually, we have undertaken the synthesis of fattivlracine that new antiviral agent exhibits a remarkable activity against herpes virus, influenza virus, varicella virus as well as hiv-1. Fattiviracine is an eighteen-membered macrolide encompassing two molecules of d-glucose and carrying two side-chains. We are aware of two other natural products of closely related istructures cycloviracine and glucolipsine, exhibiting rather similar biological activities. The structural difference between the three compounds involve the constitution of their side-chain. Starting from levoglucosane and the readily available s-malic acid, we have synthesised, in ten steps, the common macrolide unit of this family of natural product. Our synthetic scheme, involving a limited number of steps, to obtain the macrocyclic core of these substances make it a valuable procedure for the synthesis of analogues of cyclovlracine and glucolipsine. As a matter of fact, the addition to the macrocycle of various types of side-chains may be now considered
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Schäfer, Jonas K. „Preparation and investigation of an in vitro model system for the GABAA receptor organisation machinery of inhibitory post synapses“. Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2020. http://hdl.handle.net/21.11130/00-1735-0000-0005-1426-A.
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Dalle, Kristian Erwin [Verfasser], Franc [Akademischer Betreuer] [Gutachter] Meyer und Ulf [Gutachter] Diederichsen. „Bioinspired Activation of Oxygen with Pyrazole-Supported Dinuclear Copper Complexes / Kristian Erwin Dalle ; Gutachter: Franc Meyer, Ulf Diederichsen ; Betreuer: Franc Meyer“. Göttingen : Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2016. http://d-nb.info/1116080109/34.
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Oschatz, M., Deelen T. W. van, J. L. Weber, W. S. Lamme, G. Wang, B. Goderis, O. Verkinderen, A. I. Dugulan und Jong K. P. de. „Effects of calcination and activation conditions on ordered mesoporous carbon supported iron catalysts for production of lower olefins from synthesis gas“. Royal Society of Chemistry, 2016. https://tud.qucosa.de/id/qucosa%3A30312.
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Lower C2–C4 olefins are important commodity chemicals usually produced by steam cracking of naphtha or fluid catalytic cracking of vacuum gas oil. The Fischer–Tropsch synthesis of lower olefins (FTO) with iron-based catalysts uses synthesis gas as an alternative feedstock. Nanostructured carbon materials are widely applied as supports for the iron nanoparticles due to their weak interaction with the metal species, facilitating the formation of catalytically active iron carbide. Numerous synthetic approaches towards carbon-supported FTO catalysts with various structures and properties have been published in recent years but structure-performance relationships remain poorly understood. We apply ordered mesoporous carbon (CMK-3) as a support material with well-defined pore structure to investigate the relationships between calcination/activation conditions and catalytic properties. After loading of iron and sodium/sulfur as the promoters, the structures and properties of the FTO catalysts are varied by using different calcination (300–1000 °C) and activation (350 or 450 °C) temperatures followed by FTO testing at 1 bar, 350 °C, H2/CO = 1. Carbothermal reduction of iron oxides by the support material occurs at calcination temperatures of 800 or 1000 °C, leading to a higher ratio of catalytically active iron(carbide) species but the catalytic activity remains low due to particle growth and blocking of the catalytically active sites with dense graphite layers. For the samples calcined at 300 and 500 °C, the formation of non-blocked iron carbide can be enhanced by activation at higher temperatures, leading to higher catalytic activity. Olefin selectivities of ∼60%C in the formed hydrocarbons with methane of ∼10%C are achieved for all catalysts under FTO conditions at low CO conversion. The influence of the calcination temperature is further investigated under industrially relevant FTO conditions. Promoted CMK-3-supported catalysts obtained at low calcination temperatures of 300–500 °C show stable operation for 140 h of time on stream at 10 bar, 340 °C, H2/CO = 2.
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Oschatz, M., Deelen T. W. van, J. L. Weber, W. S. Lamme, G. Wang, B. Goderis, O. Verkinderen, A. I. Dugulan und Jong K. P. de. „Effects of calcination and activation conditions on ordered mesoporous carbon supported iron catalysts for production of lower olefins from synthesis gas“. Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2017. http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-224310.
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Lower C2–C4 olefins are important commodity chemicals usually produced by steam cracking of naphtha or fluid catalytic cracking of vacuum gas oil. The Fischer–Tropsch synthesis of lower olefins (FTO) with iron-based catalysts uses synthesis gas as an alternative feedstock. Nanostructured carbon materials are widely applied as supports for the iron nanoparticles due to their weak interaction with the metal species, facilitating the formation of catalytically active iron carbide. Numerous synthetic approaches towards carbon-supported FTO catalysts with various structures and properties have been published in recent years but structure-performance relationships remain poorly understood. We apply ordered mesoporous carbon (CMK-3) as a support material with well-defined pore structure to investigate the relationships between calcination/activation conditions and catalytic properties. After loading of iron and sodium/sulfur as the promoters, the structures and properties of the FTO catalysts are varied by using different calcination (300–1000 °C) and activation (350 or 450 °C) temperatures followed by FTO testing at 1 bar, 350 °C, H2/CO = 1. Carbothermal reduction of iron oxides by the support material occurs at calcination temperatures of 800 or 1000 °C, leading to a higher ratio of catalytically active iron(carbide) species but the catalytic activity remains low due to particle growth and blocking of the catalytically active sites with dense graphite layers. For the samples calcined at 300 and 500 °C, the formation of non-blocked iron carbide can be enhanced by activation at higher temperatures, leading to higher catalytic activity. Olefin selectivities of ∼60%C in the formed hydrocarbons with methane of ∼10%C are achieved for all catalysts under FTO conditions at low CO conversion. The influence of the calcination temperature is further investigated under industrially relevant FTO conditions. Promoted CMK-3-supported catalysts obtained at low calcination temperatures of 300–500 °C show stable operation for 140 h of time on stream at 10 bar, 340 °C, H2/CO = 2.
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Amer, Jamal. „Développement de membranes métalliques de nickel déposées sur support céramiques par electroless plating : Etude des propriétés particulières de permsélectivité à l'hydrogène à hautes températures“. Université Louis Pasteur (Strasbourg) (1971-2008), 2008. https://publication-theses.unistra.fr/public/theses_doctorat/2008/AMER_Jamal_2008.pdf.
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Le principal objectif de ce travail était de synthétiser des membranes composées de nickel par electroless plating sur des supports de nature chimique (alumine-a, alumine-g, zircone) et texture diverses et de déterminer leurs propriétés de permsélectivité à l’hydrogène à haute température. La synthèse de films métalliques d’une grande pureté (>99% massique Ni) résultant du choix de l’hydrazine ayant le double rôle d’agent réducteur et complexant a permis de mettre en évidence que plus le diamètre de pores de la couche superficielle du support était élevée plus la qualité d’adhésion du métal étaient importantes. De multiples contributions au transport de l’hydrogène à travers ces membranes composites à basses (diffusion de Knudsen et de surface) et hautes températures (diffusion de Knudsen et diffusion par translation de gaz) a été établie. Lors de sa mise en oeuvre en réacteur membranaire (réaction de déshydrogénation du propane), la couche de nickel a montré une très bonne résistance au cokageThe main objective of this work was to synthesize nickel based membranes by electroless plating on materials such as alumina-a, alumina-g and zirconia with various textures and to determine their hydrogen permselectivity at high temperatures. The synthesis of metal films of high purity (> 99% mass Ni) resulting from the choice of hydrazine with its dual role of reducing and complexing agent has revealed that the diameter of pores on the surface support has an impact on the quality of metal adherence. The various contributions of hydrogen transport through these composite membranes at low temperatures (Knudsen and surface diffusion) and at high temperatures (Knudsen and activated diffusion) was established. At its implementation in a membrane reactor (reaction of propane dehydrogenation), the layer of nickel showed a very good resistance to coking
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Amer, Jamal Burgard Michel. „Développement de membranes métalliques de nickel déposées sur support céramiques par electroless plating étude des propriétés particulières de permsélectivité à l'hydrogène à hautes températures /“. Strasbourg : Université de Strasbourg, 2009. http://eprints-scd-ulp.u-strasbg.fr:8080/1046/01/AMER_Jamal_2008.pdf.
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Kili, Koffi Ani. „Preparation, activation, et caracterisation des catalyseurs de metaux de transition associes aux terres rares“. Université Louis Pasteur (Strasbourg) (1971-2008), 1988. http://www.theses.fr/1988STR13030.
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Etude de l'interaction entre les terres rares et les metaux de transition en jouant sur le mode d'impregnation, la nature des sels precurseurs des metaux de transition et des lanthanides et traitement thermique d'activation. Etude sur la dispersion et sur l'etat d'oxydation
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Bagnall, Kara Marie. „Long-term follow-up of NetmumsHWD : a feasibility randomised controlled trial of telephone supported online behavioural activation for postnatal depression at 16 months post-randomisation“. Thesis, University of Exeter, 2014. http://hdl.handle.net/10871/15289.
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Purpose: Postnatal depression has significant negative outcomes for both mother and baby. Cognitive-behavioural interventions have proven promising in its treatment, but there are a number of barriers, specific to the postnatal period, which lead to low take-up of treatment. Online interventions may circumvent some of these barriers. However, evidence of long-term follow-up is sparse, in spite of the importance of knowing how such treatments work over the longer-term. Methods: Long-term follow-up of postnatal women participating in a feasibility randomised controlled trial of NetmumsHWD, an online behavioural activation treatment with telephone support. Results: Retention rates of over 70 percent were obtained. There were small but non-significant effects of treatment on depressive symptomology and behavioural activation scores at 16 months post-randomisation. Baseline depression and behavioural activation scores predicted attrition prior to the implementation of outreach strategies for data collection; these systematic differences in attrition disappeared post-implementation. Measures of treatment adherence were not related to outcome. Conclusions: Collection of long-term follow-up data from postnatal women appears feasible. The findings demonstrate the importance of outreach in maximising retention, especially in relation to the generalizability of results. Future research should consider ways to assess treatment engagement and its relationship with outcome.
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Grelier, Gwendal. „Les réactions d'amination C(sp³)–H catalytiques par transfert de nitrènes : diversité moléculaire et éco-compatibilité“. Thesis, Université Paris-Saclay (ComUE), 2018. http://www.theses.fr/2018SACLS237.
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Cette thèse est consacrée au développement de réactions d'amination C(sp³)-H catalysées au Rhodium(ᴵᴵ) impliquant la chimie des nitrènes. La première partie décrit la valorisation des sous-produits des réactifs d'iode hypervalent comme des briques moléculaires dans des séquences Amination/Couplage croisé. Le réactif d'iode hypervalent joue alors le rôle d'oxydant pour la génération d'un nitrène, du substrat pour l'amination C(sp³)-H et de partenaire de couplage pour les réactions palladocatalysées. La seconde partie concerne le développement d'une nouvelle source de nitrène : les carbamimidates dont la structure est inspirée des précédents travaux sur les carbamates et les sulfonimidamides. La préparation de ces nouveaux réactifs ainsi que leur utilisation dans des réactions intramoléculaires est présentée. La troisième partie du manuscrit vise à combiner la chimie des nitrènes et le domaine de la catalyse hétérogène, dans le but d'obtenir un catalyseur pour l'amination C(sp³)-H immobilisé sur une matrice solide. La synthèse d'un catalyseur hétérogène et son utilisation en réaction d'amination est décrite. La quatrième partie montre les résultats obtenus lors de l'étude DFT du mécanisme d'arylation intramoléculaire de glyosides catalysée au PalladiumThis thesis describes the development of Rhodium(ᴵᴵ) catalyzed C(sp³)-H amination reactions with nitrenes. A first part will describe the recycling of hypervalent iodine reagents by-products as building-blocks in Amination/Cross Coupling sequences. The hypervalent iodine reagent is used as an oxidant to generate nitrene, a substrate for C(sp³)-H amination and a building block for palladium-catalyzed cross coupling reactions. A second part is centered on the development of a new nitrene precursor: carbamimidate, which structure is inspired from previous work on both carbamates and sulfonimidamides. Their preparation and use in intramolecular reactions will be presented. A third part of this work aim to combine the nitrene chemistry and the heterogeneous catalysis field to obtain an immobilized catalyst for C(sp³)-H amination. The preparation of the heterogeneous catalyst and its use in amination reactions is described. A last part will show the results obtained from mechanistic insights by DFT about palladium-catalyzed intramolecular arylation of glycosides
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RAPELLI, GIADA. „BATTITI DEL CUORE: UNA RICERCA DIADICA SU PAZIENTI CON MALATTIE CARDIACHE E I LORO PARTNER“. Doctoral thesis, Università Cattolica del Sacro Cuore, 2021. http://hdl.handle.net/10280/90822.
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Questa ricerca ha un approccio diadico che coinvolge sia i pazienti con malattie cardiovascolari che il loro partner durante l'ospedalizzazione. Il primo studio indaga l'effetto del coping diadico (DC) sulla soddisfazione coniugale dei partner considerando l'effetto moderatore del distress psicologico dei partner. I risultati mostrano che l'effetto benefico del DC positivo e comune sulla soddisfazione coniugale si verifica quando il distress psicologico dei partner è basso, al contrario il DC negativo diminuisce la soddisfazione coniugale tra coloro che hanno alti livelli di distress psicologico. Il secondo studio si propone di indagare la relazione tra DC, aderenza farmacologica e patient activation. La relazione è mediata dall'autoefficacia per la salute del paziente: il DC positivo e comune aumentano l'autoefficacia che a sua volta aumenta l'aderenza farmacologica e la patient activation; al contrario il DC negativo è dannoso durante il ricovero e anche dopo la dimissione. Il terzo studio indaga la relazione tra il distress psicologico e la qualità del supporto del partner (iperprotezione, ostilità e supporto al patient engagement) attraverso il ruolo moderatore del DC. I risultati mostrano che un alto distress psicologico è associato ad un peggior supporto del partner tra coloro che hanno basso DC positivo e alto DC negativo.This research has a dyadic approach involving both patients with cardiovascular disease and their partner during the hospitalization. The first study investigates the effect of dyadic coping (DC) on partners’ marital satisfaction considering the moderating effect of the partners’ psychological distress. The results show that the beneficial effect of positive and common DC on marital satisfaction occurs when the partners’ psychological distress is low, on the contrary negative DC decreases marital satisfaction among those who have high levels of psychological distress. The second study aims to investigate the relationship between DC, adherence to medications and patient activation. The relationship is mediated by the patient health self-efficacy: positive and common DC increase patient health self-efficacy which in turn increases adherence to medication and patient activation; on the contrary, the negative DC is detrimental during hospitalization and also over time after discharge. The third study investigates the relationship between psychological distress and the quality of partner support (overprotection, hostility and support for patient engagement) through the moderating role of DC. The results show that high psychological distress increases worse partner support among those with low levels of positive DC and high negative DC.
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RAPELLI, GIADA. „BATTITI DEL CUORE: UNA RICERCA DIADICA SU PAZIENTI CON MALATTIE CARDIACHE E I LORO PARTNER“. Doctoral thesis, Università Cattolica del Sacro Cuore, 2021. http://hdl.handle.net/10280/90822.
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Questa ricerca ha un approccio diadico che coinvolge sia i pazienti con malattie cardiovascolari che il loro partner durante l'ospedalizzazione. Il primo studio indaga l'effetto del coping diadico (DC) sulla soddisfazione coniugale dei partner considerando l'effetto moderatore del distress psicologico dei partner. I risultati mostrano che l'effetto benefico del DC positivo e comune sulla soddisfazione coniugale si verifica quando il distress psicologico dei partner è basso, al contrario il DC negativo diminuisce la soddisfazione coniugale tra coloro che hanno alti livelli di distress psicologico. Il secondo studio si propone di indagare la relazione tra DC, aderenza farmacologica e patient activation. La relazione è mediata dall'autoefficacia per la salute del paziente: il DC positivo e comune aumentano l'autoefficacia che a sua volta aumenta l'aderenza farmacologica e la patient activation; al contrario il DC negativo è dannoso durante il ricovero e anche dopo la dimissione. Il terzo studio indaga la relazione tra il distress psicologico e la qualità del supporto del partner (iperprotezione, ostilità e supporto al patient engagement) attraverso il ruolo moderatore del DC. I risultati mostrano che un alto distress psicologico è associato ad un peggior supporto del partner tra coloro che hanno basso DC positivo e alto DC negativo.This research has a dyadic approach involving both patients with cardiovascular disease and their partner during the hospitalization. The first study investigates the effect of dyadic coping (DC) on partners’ marital satisfaction considering the moderating effect of the partners’ psychological distress. The results show that the beneficial effect of positive and common DC on marital satisfaction occurs when the partners’ psychological distress is low, on the contrary negative DC decreases marital satisfaction among those who have high levels of psychological distress. The second study aims to investigate the relationship between DC, adherence to medications and patient activation. The relationship is mediated by the patient health self-efficacy: positive and common DC increase patient health self-efficacy which in turn increases adherence to medication and patient activation; on the contrary, the negative DC is detrimental during hospitalization and also over time after discharge. The third study investigates the relationship between psychological distress and the quality of partner support (overprotection, hostility and support for patient engagement) through the moderating role of DC. The results show that high psychological distress increases worse partner support among those with low levels of positive DC and high negative DC.
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Quiroga, Espitia Lenny Maritza. „Isomérisation du lactose en lactulose en solution modèle de lactose et dans du perméat de lactosérum par électro-activation supportée par échange ionique sur résine“. Master's thesis, Université Laval, 2016. http://hdl.handle.net/20.500.11794/26958.
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L'isomérisation alcaline du lactose en lactulose a été effectuée électro-chimiquement à l’aide d’un réacteur d'électro-activation en combinaison avec des résines échangeuses d'anions de polystyrène de trois types; à savoir Lewatit VP-OC-1065 faible-acide, Lewatit MP-64 moyenne-acide et Lewatit Monoplus M500 forte-acide. Les paramètres opératoires qui ont fait l’objet de cette étude ont été étudiés sur trois blocs expérimentaux pour optimiser le système. Dans le Premier bloc, les paramètres étudiés sont : (1) ratio lactose-5%(p/v) : résine échangeuse d'anions (1:0.5, 1:1 et 1:2), (2) intensité du champ électrique : 50 mA, 100 mA et 200 mA et (3) type de résines : faible, moyenne et forte. Dans le Deuxième bloc, les paramètres mis à l’étude comprenaient : (1) l’intensité du champ électrique : 300 mA, 450 mA et 550 mA, (2) le débit de la solution traitée : 25 ml / min, 50 ml/ min et 100 ml/min et (3) la surface active de la membrane adjacente au compartiment cathodique : 0.78 cm2, 7.06 cm2 et 18.1 cm2. Le Troisième bloc expérimental a été effectué sur la base de la distance entre la membrane et l'électrode : 3.1 cm, 5.6 cm et 9 cm. Le même modèle expérimental a était également réalisé avec du perméat du lactosérum d’une concentration de 7% (p/v). Les résultats obtenus ont révélé que le meilleur rendement de l’isomérisation du lactose en lactulose était obtenu après 30 minutes d’électroactivation en utilisant une solution modèle de lactose-5% avec une valeur d’environ 20.1%. Les conditions opératoires qui ont permis d’avoir ce taux de conversion sont une intensité du courant de 550 mA, un débit de la solution de 25 ml/min, une surface active de la membrane de 7.06 cm2 et une distance de 9 cm entre la cathode et la membrane qui lui y est adjacente. En utilisant le perméat de lactosérum-7%, un taux de conversion de lactose en lactulose de 8.34% a était obtenu avec une intensité du courant de 200 mA, un débit de 120 ml/min, une surface active de de 18.1cm2 et une distance de 9 cm entre la membrane et l’électrode dans le compartiment cathodique. Les analyses de variance ont indiqué un effet catalytique significatif du type de la résine. En effet, la résine-forte a permis d’avoir les plus hauts rendements de la réaction d’isomérisation par électro-activation. La résistance électrique globale du système d’électroactivation dépendait de la valeur de l’intensité du courant. Le produit final était d’une grande pureté, car il ne présentait que quelques traces de galactose (< 4%).The isomerization of lactose to lactulose in alkaline conditions was carried out electrochemically using an electro-activation reactor in combination with three types of anion-exchange polystyrene resins, namely Lewatit VPOC 1065 weak acid, Lewatit MP-64 medium acid, and Lewatit Monoplus M500 strong acid. The operational parameters evaluated in this study have been adjusted to three blocks to optimize the system: first block: a) ratio lactose- 5% (w /v): anionexchange resin (1:0.5, 1:1 and 1:2), b) electric field intensity of 50 mA, 100 mA, and 200 mA, and c) resin type; second block: a) electric field intensity of 300 mA, 450 mA, and 550 mA, b) flow rate (25 ml / min, 50 ml / min, and 100 ml / min); and c) area of the membrane adjacent to the cathode compartment (0.78 cm2,7.06 cm2, and 18.1 cm2); and third block: distance between the membrane and the electrode (3.1 cm, 5.6 cm, and 9 cm). The same experimental model was used with whey permeat at a concentration of 7% (w/v). Obtained results revealed that the best yield was obtained after 30 minutes of electro-activation using a typical solution based on 20.1% of lactose-5% under a current intensity of 550 mA, a flow rate of 25 ml / min, a membrane area of 7.06 cm2, and a distance of 9 cm between the membrane and the electrode. The use of whey permeate-7% resulted in 8.34% of lactulose under a current intensity of 200 mA, a flow rate of 120 ml / min, a membrane area of 18.1 cm2, and a distance of 9 cm in the cathodic compartment. The analysis of variance indicated a significant catalytic effect on the resin type since the strong acid resin allowed obtaining the highest yields of the isomerization reaction by electro-activation. The overall electrical resistance of the electro-activation system depends on the current intensity. The final product was of high purity since it contains only few traces of galactose (< 4%).
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Kaya, Yasemin. „Bifunctional activation and heterolytic cleavage of ammonia and dihydrogen by silica-supported tantalum imido amido complexes and relevance to the dinitrogen cleavage mechanism by tantalum hydrides“. Thesis, Lyon 1, 2013. http://www.theses.fr/2013LYO10054/document.
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L'activation de petites molécules azotées telles que l'azote et l'ammoniac a été développé dans notre laboratoire via la chimie organométallique de surface (COMS). Les recherches effectuées durant cette thèse ont permis d'établir la réactivité de complexe de tantale imido amido supporté sur silice, [(SiO)2Ta(=NH)(NH2)] vis-à-vis de l'hydrogène et de l'ammoniac. Des étapes élémentaires de clivage hétérolytique de liaison H-H ou N-H ont été établies. En particulier, l'importance d'une molécule d'ammoniac dans la deuxième sphère de coordination (outer sphere assistance) du système s'est avérée cruciale pour la diminution des barrières d'énergie des états de transition pendant le transfert de protons. Les études ont été faites pour déterminer et expliquer le mécanisme de réduction de N2 par les complexes d'hydrures de tantale. La compréhension du mécanisme a été établie grâce aux études avec N2, N2H4 et N2H2 pour trouver les intermédiaires de cette réduction suivis par in-situ infrarouge, RMN et l'analyse élémentaire, et à l'aide de calcul DFT. Un mécanisme de clivage de N2 par des complexes dihydrogènes de Ta(V) est proposé. Enfin, la réactivité du complexe [(SiO)2Ta(=NH)(NH2)] vers l'activation de liaison C-H de C6H6, C6H5-CH3, t-Bu-Ethylène et CH4 a été étudié par la spectroscopie infrarougeThe activation of small molecules such as nitrogen and ammonia was already developed in our laboratory using the surface organometallic chemistry (SOMC) approach. This thesis focused on understanding the reactivity of tantalum imido amido complex [(SiO)2Ta(=NH)(NH2)], under hydrogen and/ or ammonia atmosphere. Heterolytic H-H and N-H cleavage across Ta-NH2 and Ta=NH bonds appeared crucial. The assistance of an additional ammonia molecule in the outer sphere of the d0 tantalum(v) imido amido ammonia model complex in order to reduce the energy barriers of the transition states during proton transfer was also shown. Studies were done to identify the mechanism of N2 reduction by tantalum hydride complexes. Studies with N2, N2H4 and N2H2 allowed identifying the intermediaries via in situ IR, NMR and elemental analysis. Combined with DFT calculations, these experiments led to the proposal of a novel mechanism for N2 cleavage based on the central role of Ta(H2) adducts. Finally, the reactivity of imido amido complex toward C-H bond activation was studied with C6H6, C6H5-CH3, t-Bu-Ethylene and CH4
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Dehou, Saint-Charles. „Etude des propriétés d'adsorption des oxyhydroxydes de fer déposés sur un support naturel (la brique) : « application à l'élimination du fer dans les eaux de forages en République Centrafricaine »“. Thesis, Lille 1, 2011. http://www.theses.fr/2011LIL10127/document.
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Si la République Centrafricaine, ne manque pas d’eau, de nombreux forages sont abandonnés, en raison de teneurs en fer trop élevées. Parmi les techniques d’élimination des polluants métalliques utilisables en vue de rendre l’eau propre à la consommation humaine, l’adsorption par l’hydroxyde de fer déposé sur un support semble être une méthode bien adaptée, en raison de son faible coût d’utilisation et de la non génération d’autres polluants. En vue d’optimiser cette technique et de la rendre exploitable dans les pays en voie de développement, nous avons remplacé le support sable par un matériau naturel présent dans la plupart des pays, la brique, et nous avons choisi parmi les oxyhydroxydes de fer, la ferrihydrite qui possède l’aire spécifique la plus élevée. Deux méthodes d’activation du support constitué par des grains de brique ont été optimisées : HCl 1M durant 24h et HCl 6M 6h à 90°C. La composition de la brique et son état de surface ont été étudiés par les techniques FTIR, ESEM/EDS, RX, RMN du solide (27Al et 28Si), ATG /MS, ATG/ATD, mesure d’aire spécifique, ICP-AES. Des études cinétiques sur l’adsorption des ions ferreux ont été réalisées sur la ferrihydrite déposée sur la brique modifiée par les deux traitements chimiques. Le traitement des données cinétiques expérimentales nous a permis d’estimer l’énergie d’activation des systèmes étudiés et les paramètres thermodynamiques résultants. La gamme optimale du pH des eaux à traiter a été établie par la mesure du point de charge nulle (PZNPC). Une approche théorique des phénomènes mis en jeu a été abordée par des expériences sur colonne. La possibilité de régénérer l’adsorbant par l’utilisation d’eau de Javel, comme éluant, a été examinée, en vue de rendre le système opérationnel sur le terrainIn developing countries, freshwaters contain frequently undesirable and naturally occurring inorganic, microbial contaminants. Thus, ground waters in Bangui regions (Central Africa Republic) _ that serve as sole source of drinking water in the rural communities of the country _ are known to contain elevated amounts of soluble iron (up to 10 mg/liter). This metal precipitates easily in the presence of air oxygen, this becoming undrinkable and even inappropriate to be used for washing / … the laundry. To eliminate this pollutant, there is evidence in the literature that ….with iron oxides / hydroxides can be used as an adsorbent for cations / anions removal from waters. In the present work, we are poured our attention on the use of a new low-cost material, brick _ that is commonly made by local craftsmen in Central African Republic_ which is mainly composed of sand and metakaolinite. To enhance the efficiency of water purification process with the brick, this adsorbent had however to be improved in its chemical nature, crystalline surface properties and preparation methods thermal and acid treatments by using several techniques: FTIR, ESEM/EDS, RX, Solid- RMN (27Al et 28Si), ATG /MS, ATG/ATD, Specific surface, ICP-AES. In this thesis, we have poured our attention on the determination of the chemical composition and crystalline / morphological characteristics of the raw brick and its various modified forms obtained by acid activation. Some kinetic aspects of Fe (II) adsorption onto FeOOH coated brick were further … in this work and activated energy and thermodynamic parameters were evaluated and discussed. Finally, the adsorption of iron (II) onto brick pellets from aqueous solutions was investigate by using a …glass column and performances when filling of the various composites prepared in this work were compared each other : Thomas model was applied to our experimental data to assess the characteristic parameters of the column. Furthermore the possibility to regenerate the adsorbent by the use of bleach as an elute and to use it directly in the field was raised
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Feghali, Khalil. „Dinitrogen activation promoted by medium valent vanadium, strategies for the preparation of complexes containing medium-valent vanadium supported by sulfur containing ligands : a synthetic and theoretical study“. Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp01/MQ36692.pdf.
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Escudero, Vasconez Maria Veronica. „Design and Delivery of Effective Activation Measures : what Works and for Whom?“ Thesis, Paris Sciences et Lettres (ComUE), 2018. http://www.theses.fr/2018PSLEH122.
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Les politiques actives du marché du travail (PAMT) sont considérées de plus en plus comme nécessaires pour renforcer le lien entre protection sociale et création de sources de revenu plus durables dans l’objectif d’améliorer la qualité de l’emploi mais aussi, de façon plus générale, les conditions de vie. En conséquence, ces mesures jouent un rôle essentiel aujourd’hui dans les programmes de politique publique de la plupart des économies avancées et voient leur importance augmenter fortement dans les pays émergents et dans les pays en développement, où elles ne sont pas encore aussi bien établies. Il reste toutefois encore beaucoup à apprendre sur l’impact de ces mesures, en particulier sur le rôle des caractéristiques de leur mise en œuvre. Cette thèse entend contribuer à ce débat en étudiant l’efficacité des PAMT et le rôle des systèmes de mise en œuvre pour ce qui est de leur impact à la fois dans les pays développés et dans les pays émergents et en développement.Le premier chapitre examine sous un angle macroéconomique l’efficacité des PAMT à améliorer les résultats sur le marché du travail au sein des pays de l’OCDE, en particulier pour les travailleurs peu qualifiés. Il est capital de saisir de façon empirique l’effet net global des PAMT sur l’ensemble du marché du travail, car ces politiques entraînent souvent des phénomènes de substitution, de déplacement et d’autres conséquences indirectes. Les deux chapitres suivants cherchent à déterminer si les PAMT doivent être encore étendues dans les pays émergents et en développement. Pour ce faire, les effets au niveau individuel de deux types de PAMT en Amérique latine sont étudiés, en s’appuyant sur la présence de règles d’attribution intéressantes et de données de qualité au niveau individuel. Ainsi, le deuxième chapitre s’intéresse plus particulièrement aux conséquences à moyen et long terme d’un programme de workfare péruvien, l’une des mesures d’activation les moins étudiées, bien que fréquemment mise en œuvre dans la région, afin d’évaluer la durabilité de ses effets. Le troisième chapitre s’intéresse à l’introduction d’un ensemble complet de PAMT en Argentine, dans le but d’aider les bénéficiaires éligibles d’un programme de transfert de fonds sous conditions à trouver des sources de revenus plus stables. Dans les deux cas, l’accent est mis sur les effets sur la qualité de l’emploi et sur la manière dont la mise en œuvre des mesures conditionne leur impact.Ces travaux montrent que les PAMT sont utiles mais à condition qu’elles s’accompagnent d’une conception et d’une mise en œuvre appropriées. Les résultats confirment l’importance de ces facteurs pour ce qui est de l’efficacité des mesures tant dans les pays de l’OCDE que dans ceux d’Amérique latine étudiés. L’ampleur des effets dépend du type de mesure étudiée et de la catégorie de bénéficiaires viséeToday, active labor market policies (ALMPs) are increasingly seen as a necessary tool to strengthen the link between social protection and the creation of more sustainable sources of income with a view to increasing work quality but also improving living conditions more broadly. As a result, the role of ALMPs in policy agendas remains high in most advanced economies and has increased dramatically in emerging and developing countries, where ALMPs are still less established. Despite this, there is still a lot to be learned regarding the impact of these policies, particularly with regards to the role of implementation characteristics. My dissertation aims to contribute to this debate by looking at the effectiveness of ALMPs and the role of delivery systems in shaping their impact in both, developed and emerging and developing countries.It starts by examining the effectiveness of ALMPs in OECD countries in improving labor market outcomes, especially for low-skilled individuals, from a macroeconomic perspective (Chapter 1). Capturing empirically the overall net effect of ALMPs on the wide labor market is of upmost importance, since the role of ALMPs frequently involves substitution, displacement and other indirect effects. Then, the following two chapters aim to assess whether ALMPs should be leveraged further in emerging and developing countries, by investigating the individual-level effects of two different types of ALMPs in Latin America, exploiting the availability of interesting assignment rules and good-quality individual-level data. Chapter 2 focuses on the medium- to long-term effects of a Peruvian workfare program, one of the least studied ALMPs in the region albeit commonly implemented, to assess the sustainability of these type of programs’ effects. Chapter 3 then looks at the provision of a comprehensive package of ALMPs in Argentina, implemented to support eligible beneficiaries of a conditional cash transfer program in finding more stable income opportunities. In both cases, the focus is placed on the effects on work quality and on the role of design and implementation in shaping the effects.My research suggests that ALMPs are relevant but mostly through appropriate design and implementation aspects. The results confirm the importance of these factors in ensuring effectiveness both in OECD and the Latin American countries assessed. The size of effects depends on the type of policy assessed and on the beneficiary group
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Hynaux, Amélie. „Synthèse et caractérisation de carbures de molybdène supportés sur composite de noir de carbone mésoporeux : application en hydrodésulfuration du dibenzothiophène et en hydrodésazotation de l'indole“. Paris 6, 2005. http://www.theses.fr/2005PA066096.
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Kube, Pierre [Verfasser], Robert [Akademischer Betreuer] Schlögl, Robert [Gutachter] Schlögl, Reinhard [Gutachter] Schomäcker und Klaus [Gutachter] Rademann. „Comparison of alkane activation over supported and bulk transition metal oxide catalysts and transition metal free carbon nano structures / Pierre Kube ; Gutachter: Robert Schlögl, Reinhard Schomäcker, Klaus Rademann ; Betreuer: Robert Schlögl“. Berlin : Technische Universität Berlin, 2018. http://d-nb.info/1166752380/34.
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Alouche, Adel. „Propriétés du nickel déposé sur oxydes de terre rare dans la réaction de conversion d'oxydes de carbone“. Poitiers, 1988. http://www.theses.fr/1988POIT2260.
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Mise en evidence du role du support dans l'activation des reactifs. Les proprietes particulieres de ces catalyseurs seraient dues a la reduction partielle du support a proximite des particules metalliques et a la modification locale des proprietes electroniques du metal
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Rick, Robert Steven. „Marketplace Clinics Complementing Community-Based Diabetes Care for Urban Residing American Indians“. ScholarWorks, 2015. https://scholarworks.waldenu.edu/dissertations/1210.
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The American Indians population in Minneapolis, Minnesota has experienced limited health care access and threefold diabetes health disparity. The purpose of this study was to measure the extent to which collaborating marketplace clinics and community-based support groups expanded diabetes care and provided self-management education for this largely urban Indian neighborhood. The marketplace clinics located in nearby CVS, Walmart, Target, and Supervalu stores committed financial support, certified educators, and pharmacy staff for the community-based support group. The study was conducted within the patient activation measure (PAM) analytical framework to assess the participants' acquired knowledge, skills, and confidence for diabetes self-management. A case-control study and 3 years retrospective analysis of secondary data were used to test whether the Minneapolis marketplace clinics and the Phillips community diabetes support group participants (n = 48) had improved diabetes health outcomes relative to the control group (n = 87). The intervention group employed motivational interviewing and PAM in coaching diabetes self-care and behavioral modification. The control group received only basic self-management education. T test and Cohen's d effect size measurements were used to quantify the size of the health outcome variables' difference between the study intervention and comparison groups. The positive effects of marketplace clinics and community-based complementation were shown through improved blood sugar control (A1C), weight loss (BMI), and healthful lifestyle changes. Social change progress could be realized by incorporating PAM with diabetes prevention programs for 33 Urban Indian Health Organizations that are located in large cities throughout the United States.
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Han, Kilsoo. „Professionalitetens gränser : Socialsekreterares erfarenheter av unga vuxna klienter med komplexa behov inom socialtjänst–ekonomiskt bistånd“. Thesis, Uppsala universitet, Centrum för socialt arbete - CESAR, 2020. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-422371.
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This study explores the experiences of the Swedish front-line social workers (socialsekreterare) in the municipal income support unit, Young Adults, monthly assessing the income support applications as well as daily processing the activation programs for young adult clients with mental ill-health combined with social-medicinal vulnerabilities, also referred to as young adults with complex needs. Furthermore, this study aims to illuminate the ever changing conditions of the Swedish welfare state and its underlying driving forces through the lens of the social workers. 9 Semi-structured distance interviews with 11 social workers from 6 municipalities belonging to 5 regions in Sweden, were conducted for the collection of qualitative data. It has been analyzed by the inductive-deductive coding as well as a theoretical frame consisting of concepts such as discretiona and advocacy of M. Lipsky, and reciprocal interaction (Wechselwirkung), form and contents, and call of G.Simmel. The result and analysis show that the rehabilitative approach based on the interactions and relations with the clients, is prevalent through the social workers’ processing of the activation program. It seems to be effective in a dyad, between the social workers and the client while the social workers’ discretion is maximized for the utilization of the agency (unit) activation resources. However, it proved not to be as effective in a triad or more when an extern agent outside of the unit, Young Adults begins to be involved. The tension is a fact and the social workers’ discretion is minimized when they have to process the activation program for the clients who are neither “active enough” to have a job in the ordinary labor market, nor “sick enough” to be eligible for the stately activity compensation (aktivitetsersättning) from the Social Insurance Agency (Försäkringskassan) which heavily relies on the medicinal expertise for its decision making. The social workers’ experience to fail to deliver the best possible results out of the activation programs, and the client relationship built on the rehabilitative approach turns out to be unsustainable, which can indicate the discrepancy between the rehabilitative approach as well as the activation programs, as content, and the unit, Young Adults, as form. Even though the social workers daily carry the ideological as well as the social-political tensions between the medicalization and the activation through the ever changing reality of the Swedish welfare state, their mandate to make an impact on the decision making of the activity compensation program, is rather limited, reflecting the Swedish welfare state’s expectation for the professionalism of the social workers. Rather striking that the social workers, however, confess that they in spite of the pressure of organizational efficiency as well as socio-economic discourse of digitalization undermining the concept of the unit, Young Adults, are not willing to give up the rehabilitative approach for the client’s sake but also to protect their unit, Young Adults, which postulate that they are not the gatekeepers in the agency but the advocate for the clients. In this moment, they also seem to know, and even have the call, the essential, if not mandatory, element needed to be landed in the perfect society of G. Simmel.
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Menke, Katrin. „Familienpolitik“. Universität Leipzig, 2018. https://ul.qucosa.de/id/qucosa%3A23360.
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Familienpolitik bezeichnet ein Politikfeld im Wohlfahrtsstaat, dessen Ziel es ist, das Zusammenleben in Familien im Lebensverlauf mit Hilfe von Zeit, Geld und Infrastruktur zu unterstützen. Die Definition von Familie hat sich ebenso wie das Politikfeld stetig gewandelt. Aus Perspektive der (intersektionalen) Geschlechterforschung lassen sich verschiedene historische Phasen seit Gründung der Bundesrepublik beschreiben. Von besonderer Bedeutung ist der paradigmatische Wandel der Familienpolitik seit der Jahrtausendwende: Im Zuge dessen etablierten sich zunehmend ein volkswirtschaftlicher Begründungszusammenhang für Familienpolitik und die Verknüpfung von Elternschaft mit Erwerbstätigkeit.
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Mervin, Lewis. „Improved in silico methods for target deconvolution in phenotypic screens“. Thesis, University of Cambridge, 2018. https://www.repository.cam.ac.uk/handle/1810/283004.
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Target-based screening projects for bioactive (orphan) compounds have been shown in many cases to be insufficiently predictive for in vivo efficacy, leading to attrition in clinical trials. Phenotypic screening has hence undergone a renaissance in both academia and in the pharmaceutical industry, partly due to this reason. One key shortcoming of this paradigm shift is that the protein targets modulated need to be elucidated subsequently, which is often a costly and time-consuming procedure. In this work, we have explored both improved methods and real-world case studies of how computational methods can help in target elucidation of phenotypic screens. One limitation of previous methods has been the ability to assess the applicability domain of the models, that is, when the assumptions made by a model are fulfilled and which input chemicals are reliably appropriate for the models. Hence, a major focus of this work was to explore methods for calibration of machine learning algorithms using Platt Scaling, Isotonic Regression Scaling and Venn-Abers Predictors, since the probabilities from well calibrated classifiers can be interpreted at a confidence level and predictions specified at an acceptable error rate. Additionally, many current protocols only offer probabilities for affinity, thus another key area for development was to expand the target prediction models with functional prediction (activation or inhibition). This extra level of annotation is important since the activation or inhibition of a target may positively or negatively impact the phenotypic response in a biological system. Furthermore, many existing methods do not utilize the wealth of bioactivity information held for orthologue species. We therefore also focused on an in-depth analysis of orthologue bioactivity data and its relevance and applicability towards expanding compound and target bioactivity space for predictive studies. The realized protocol was trained with 13,918,879 compound-target pairs and comprises 1,651 targets, which has been made available for public use at GitHub. Consequently, the methodology was applied to aid with the target deconvolution of AstraZeneca phenotypic readouts, in particular for the rationalization of cytotoxicity and cytostaticity in the High-Throughput Screening (HTS) collection. Results from this work highlighted which targets are frequently linked to the cytotoxicity and cytostaticity of chemical structures, and provided insight into which compounds to select or remove from the collection for future screening projects. Overall, this project has furthered the field of in silico target deconvolution, by improving the performance and applicability of current protocols and by rationalizing cytotoxicity, which has been shown to influence attrition in clinical trials.