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The governance of collaboration in local public service delivery networksMoseley, Alice January 2008 (has links)
Multi-agency collaboration is often advocated as a means of tackling cross-cutting areas of public services and viewed as a solution to service fragmentation, with local agencies on the receiving end of government exhortations to collaborate. Yet there is relatively little research examining the effectiveness of policy tools and mechanisms aiming to stimulate local collaboration. This thesis examines the influence and dynamics of vertical and horizontal coordination tools, investigating their potential to enhance collaboration in local public service delivery networks and to reduce negative externalities. A theoretical framework is employed which synthesises models of policy implementation and bureaucratic decision-making. The empirical research is conducted in relation to organisations working with the homeless in England, and the research methods include a survey of Local Authorities and interviews with civil servants and frontline professionals. While governmental attempts to foster collaboration are partially effective, there are weaknesses with some of the policy tools employed, and limits to State control. Local actors’ collaborative decision-making is influenced more by ‘bottom-up’ than by ‘top-down’ factors. Moreover, the competitive context in which service providers operate leads them to pursue strategies to promote their own organisational interests rather than working towards a dominant common interest. The strategies employed are broadly in line with a bureaucratic politics perspective, and include failure to share information, possessiveness over client outcomes and projecting an image of success rather than sharing problems. Nevertheless, formal collaborative mechanisms do have the potential to alleviate externalities associated with fragmented systems. With strong local management and appropriate central facilitation, they can help to meet client needs and to counter fragmentation, ultimately leading to better services.
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Divalent iron, cobalt, nickel and palladium complexes of 1H-pyrazol-1-yl-imine and 1H-pyrazol-1-yl-ethanol ligands: coordination chemistry and evaluation as ethylene oligomerization catalysts16 May 2011 (has links)
M.Sc. / This dissertation deals with the syntheses of tridentate (O^N^N) coordination ligands [{2,4-di-tert-butyl-6-[(2-(3,5-RR-pyrazol-1-yl-ethylimino)-methyl] phenol}, R = H (L1), Me(L2), Ph(L3), t-Bu(L4)], which was reacted initially with MX2 (M = Fe, Co, Ni; X = Cl, Br). The ligands L1-L4 were also modified by functionalizing the phenol group in this ligand group to an ethoxy in L5 and L6 (L5 = [(3,5-di-tert-butyl-2-ethoxy-benzylidene)-[2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-amine, L6 = [(3,5-di-tert-butyl-2-ethoxy-benzylidene)-[2-(3,5-di-tert-butyl-pyrazol-1-yl)-ethyl]-amine)], or into a phenoxy in L7 (L7 = (3,5-di-tert-butyl-2-phenoxy-benzylidene-(2-pyrazol-1-yl-ethyl)-amine)). Another ligand L8 (L8 = [4-(4-tert-butyl-benzylidene)-[2-(3,5-dimethyl-pyrazol-1-yl)-ethyl]-amine], which was devoid of the phenoxy group was also synthesized. These modified ligands were also reacted with MX2 or PdCl(COD)Me to form bidentate (N^N) chelating complexes. Further modification of the ligand L1-L4, to replace the phenoxy pyrazolylimine unit with a source of oxygen donor other than a phenoxy led to the use of already known ligands L9, L10 (L9 = 2-(3,5-dimethyl-pyrazol-1-yl)-ethanol, L10 = 2-(3,5-di-tert-butyl-pyrazol-1yl)-ethanol and L11, where in L11, the alcohol moiety is replaced by an electron withdrawing chloro group, L11 = 1-(2-chloroethyl)-3,5-di-methyl-pyrazole). These ligands were also reacted with MX2 (M = Fe, Co, Ni, Pd; X = Cl, Br) to form complexes. The synthesized complexes were characterized by a combination of IR and NMR spectroscopy, mass spectrometry, microanalysis and in selected cases single crystal X-ray crystallography.
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Synthesis, coordination chemistry and reactivity of new diarylamido and disilylamido SeNSe pincer ligandsCharette, Bronte J. 09 June 2016 (has links)
This thesis presents advancements in the chemistry of selenium-bearing pincer ligands with respect to their synthesis, metal association and reactivity in addition to the overall nature of selenium as a donor atom.
The synthesis of a new disilylamido ligand HN(SiMe2CH2SePh)2 2.1 and its potassium salt 2.2 is reported. The attempted metal association of these species was unsuccessful with various transition metals. Multinuclear NMR data suggests coordination to silver(I), 2.3 and copper(I), 2.4 with dπ-dπ back donation from the metal to the selenium donors. It is suggested from this data that –SePh can potentially act as a π-acceptor ligand as well as a σ- donor with heavy d metals. Another explanation for the observed shielding is conformational restrictions introduced by chelation.
The preparation of new selenium-bearing diarylamine compounds RN(C7H6SeMe)2 (R=H: 3.1; R= Me: 3.10; R= Boc 3.11) via aryllithium chemistry is reported. Unsuccessful attempts to synthesize the –SePh and –SetBu derivatives are described using: aryllithium chemistry, Buchwald-Hartwig Amination cross coupling and Pd-catalyzed C-Se cross coupling. When reacted with MCl2(COD) (M= Pd, Pt), compound 3.10 coordinates with PdII forming a bidentate complex 3.12, while 3.1 forms tridentate complexes with PdII and PtII. NMR spectroscopy suggests the formation of a silver(I) complex 3.1-Ag from 3.1 and AgOTf, but X-ray diffraction data is required to determine its coordination motif. The new ligands and complexes have been fully characterized by (1H, 13C, 77Se) NMR spectroscopy and X-ray crystal structures are reported for 3.10, 3.12, 3.3 and 3.4. The NMR spectrum of 3.1-Ag exhibits a similar effect as the complexes of disilylamido ligands with suggested potential dπ-dπ back donation from the metal to the selenium donors.
The catalytic ability of the new complex 3.3 has been tested in the Suzuki-Miyaura cross coupling reaction without notable improvements to existing catalysts. The instability of reactive intermediates may contribute to the low conversions or the size of the methyl group may decrease nanoparticle formation, a suggested active species. / October 2016
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Control over assembly and interpenetration of Pd-based coordination cagesZhu, Rongmei 24 March 2017 (has links)
No description available.
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Spectroscopie de luminescence à température et pression variables pour des complexes des lanthanides et de l'orIntissar, Mourad 11 1900 (has links)
Ce travail est axé vers la compréhension détaillée des propriétés de luminescence de composés de certains métaux lourds. La première partie de ce mémoire décrit la caractérisation spectroscopique d'un radical de type nitronyle nitroxyde, 2-(2-pyridinyl)-4,4,5,5-tétraméthyl-4,5-dihydro-1H-imidazolyl-1-oxyl-3-oxyde, abrégé (NIT2-Py), et de ses complexes avec les cations Tb(III), [Tb(hfac)3NIT2-Py], et Y(III), [Y(hfac)3NIT2-Py]. La variation de la température affecte les spectres de luminescence qui montrent de la structure vibronique résolue. Les maxima de ces transitions vibroniques se rapprochent au fur et à mesure que la température augmente. Ces variations des maxima en fonction de la température ne correspondent pas à des variations de fréquences vibrationnelles et sont de l'ordre de 200 cm-1 entre 80 K et 240 K. La variation de la température n'a pas d'influence significative sur la structure moléculaire, comme atteste la variation mineure des maxima des spectres Raman entre 80 K et 300 K. La comparaison des spectres expérimentaux à des spectres calculés montre que ces variations peuvent être reproduites par l'utilisation d'une combinaison de fréquences vibrationnelles. Le paramètre dont la variation est très significative est la résolution du spectre de luminescence, représentée par la largeur à mi-hauteur des transitions vibroniques qui forment le spectre de luminescence. La deuxième partie de ce mémoire décrit les propriétés de luminescence d'une série de complexes d’or(I). Elles sont comparées aux changements structuraux à pression et température variable. Les interactions aurophiles ont une grande influence sur la luminescence. La variation de la température et de la pression est une approche efficace pour varier la luminescence. Les effets observés dans les spectres d'émission de ces complexes dépendent des changements de structure induits par variation de la température et de la pression. Ces petites variations structurales mènent à des changements importants, à titre d'exemple à un déplacement du maximum de la bande de luminescence de 60 cm-1/ kbar vers les faibles énergies pour un des complexes de l'or(I) étudiés au cours de ce projet. / The overall goal of this work is to contribute to the understanding of luminescence properties of transition metal compounds. The first part of this thesis describes the spectroscopic characterization of a pyridine-substituted nitronyl nitroxyde radical 2-(2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-3-oxide-1-oxyl abbreviated (NIT2-Py) and its complexes with Tb(III) and Y(III), [Tb(hfac)3NIT2-Py] and [Y(hfac)3NIT2-Py], respectively. Their luminescence spectrum show resolved vibronic structure and variations with temperature The energy difference between vibronic luminescence maxima decreases with increasing temperature. This decrease is on the order of 200 cm-1 between 80 K and 240 K and is not due to decreasing Raman frequencies. The variations of temperature do not have a significant influence on the molecular structures, as illustrated by the very small variation of Raman maxima between 80 K and 300 K. Luminescence spectra were calculated using the time dependent theory of spectroscopy. Calculated luminescence spectra show that the variations with temperature are reproduced by using specific combinations of experimental frequencies and by adjusting the width of the vibronic transitions, determining the resolution of the luminescence spectrum. The second part of the thesis describes the luminescence spectroscopic properties of a series of trimetallic gold(I) complexes at variable temperature and pressure. Aurophilic interactions are very important for these compounds and influence the luminescence spectra. The spectroscopic features are compared to structural changes at variable temperature and pressure. Even small changes in structure lead to significant changes in luminescence, for example a shift of the maximum of the luminescence band by 60 cm-1/ kbar to lower energy for one of the gold(I) complexes studied.
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Self-organising network management for heterogeneous LTE-advanced networksBehjati, Mohammadreza January 2015 (has links)
Since 2004, when the Long Term Evolution (LTE) was first proposed to be publicly available in the year 2009, a plethora of new characteristics, techniques and applications have been constantly enhancing it since its first release, over the past decade. As a result, the research aims for LTE-Advanced (LTE-A) have been released to create a ubiquitous and supportive network for mobile users. The incorporation of heterogeneous networks (HetNets) has been proposed as one of the main enhancements of LTE-A systems over the existing LTE releases, by proposing the deployment of small-cell applications, such as femtocells, to provide more coverage and quality of service (QoS) within the network, whilst also reducing capital expenditure. These principal advantages can be obtained at the cost of new challenges such as inter-cell interference, which occurs when different network applications share the same frequency channel in the network. In this thesis, the main challenges of HetNets in LTE-A platform have been addressed and novel solutions are proposed by using self-organising network (SON) management approaches, which allows the cooperative cellular systems to observe, decide and amend their ongoing operation based on network conditions. The novel SON algorithms are modelled and simulated in OPNET modeler simulation software for the three processes of resource allocation, mobility management and interference coordination in multi-tier macro-femto networks. Different channel allocation methods based on cooperative transmission, frequency reuse and dynamic spectrum access are investigated and a novel SON sub-channel allocation method is proposed based on hybrid fractional frequency reuse (HFFR) scheme to provide dynamic resource allocation between macrocells and femtocells, while avoiding co-tier and cross-tier interference. Mobility management is also addressed as another important issue in HetNets, especially in hand-ins from macrocell to femtocell base stations. The existing research considers a limited number of methods for handover optimisation, such as signal strength and call admission control (CAC) to avoid unnecessary handovers, while our novel SON handover management method implements a comprehensive algorithm that performs sensing process, as well as resource availability and user residence checks to initiate the handover process at the optimal time. In addition to this, the novel femto over macro priority (FoMP) check in this process also gives the femtocell target nodes priority over the congested macrocells in order to improve the QoS at both the network tiers. Inter-cell interference, as the key challenge of HetNets, is also investigated by research on the existing time-domain, frequency-domain and power control methods. A novel SON interference mitigation algorithm is proposed, which is based on enhanced inter-cell interference coordination (eICIC) with power control process. The 3-phase power control algorithm contains signal to interference plus noise ratio (SINR) measurements, channel quality indicator (CQI) mapping and transmission power amendments to avoid the occurrence of interference due to the effects of high transmission power. The results of this research confirm that if heterogeneous systems are backed-up with SON management strategies, not only can improve the network capacity and QoS, but also the new network challenges such as inter-cell interference can also be mitigated in new releases of LTE-A network.
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L'aide à la santé : mobilisation et coordination. Une analyse économique / Assistance to health : mobilization and coordination. An economic analysisBarry, Mamadou I 07 March 2012 (has links)
La coopération internationale pour la santé a connu, cette dernière décennie, une des périodes les plus dynamiques de son histoire. Les ressources disponibles ont augmenté, une pléthore d’organismes de santé a été créée, et la société civile et le secteur privé ont été mobilisés. Des approches plus participatives ont émergé dans la façon de lever les fonds et de livrer l’assistance. Cependant, l’enthousiasme suscité par ces changements a été accompagné par un malaise croissant, un sentiment que les actions sur le terrain sont « dispersées », faiblement articulées et que les « gaspillages » continuent. Le nombre croissant d’acteurs aurait donc compliqué la gestion de l’aide pour les bénéficiaires, alourdi les coûts de transaction et augmenté les coûts fixes dans l’aide globale. En conséquence, la littérature indique qu’une amélioration de l’efficacité de l’aide internationale passe par une coordination accrue des acteurs de l’aide, notamment les donateurs. Notre thèse vise à montrer que, s’il est fondé de remettre de l’ordre dans l’architecture chaotique de l’aide, notamment celle de la santé, l’entente des donateurs sur des objectifs limités sur la base de critères coût-efficacité est irréaliste. En nous appuyant sur l’abondante littérature consacrée à l’aide, sur les rapports d’évaluation, sur des entretiens qualitatifs et sur une exploitation de données empiriques, nous soulignons pourquoi l’agenda actuel de coordination ne permet pas une réduction de la dispersion de l’aide. / International cooperation in health has experienced over the last decade, one of the most dynamic periods in its history. The resources available have increased, a plethora of health agencies have been established, and civil society and the private sector have been mobilized. More participatory approaches have emerged in how to raise funds and deliver assistance. However, enthusiasm for these changes was accompanied by a growing unease, a feeling that the actions in the field are "scattered", loosely connected and that the "waste" continue. The increasing number of players would thus have complicated the management of aid to recipients, increased the transaction costs and increased fixed costs in total aid. As a result, the literature indicates that improving the efficiency of international assistance has to go through increased coordination of aid actors, including donors. Our thesis aims to show that if it is justified to restore order in the chaotic architecture of aid, including that of health, donor agreement on limited objectives on the basis of cost- effectiveness criterias is unrealistic. Based on the extensive literature on aid, on the evaluation reports, interviews and qualitative operation of empirical data, we emphasize why the current agenda of coordination does not allow a reduction in the dispersion of aid.
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Rozvoj koordinačních schopností ve fotbale žen / The development of coordination abilities in women's footballKrálíčková, Lucie January 2015 (has links)
Aimes: The dissertation examines the development of coordination abilities in women's football. At first, problems of fitness training, planning of training macrocycle and the issue of women's and young ladies' training are analysed. A considerable part of the theoretical section is devoted to coordination abilities. Second part and testing follow. To find out the level of coordination abilities, these testing disciplines were used: Agility test, run with a somersault, two-footed jump on target and vertical jump with the rotation of torso. The results of this testing informed us about the level of coordination abilities of both observed players and the whole group. Methods:Literary researches, descriptive and illustrative examples used in order to acquaint probands with particular motor tests, the observation of probands during testing, testing and evaluation of performance in motor tests, a method of test-retest, qualitative and quantitative statistical methods, logical methods (analysis, synthesis, inductive and deductive reasoning. Results: From the point of view of the long-term conception of sports training, the coordination skills seem to be an essential element of a successful mastering of motor skills, more or less dependent on the coordination. If the particular skills are not developed during so...
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Koordinační schopnosti u fotbalového brankáře v mládežnických kategoriích / Coordination abilities of soccer goalkeeper in youth categoriesKumšta, Martin January 2011 (has links)
Název: Koordinační schopnosti u fotbalového brankáře v mládežnických kategoriích Anotace: Tato diplomová práce se zabývá porovnáním úrovně koordinačních schopností žáků různých věkových kategoriích a specializovaně trénujících brankářů stejného věku. Klíčová slova: Koordinace, schopnosti, brankář, fotbal
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Weekly Two-Stage Robust Generation Scheduling for Hydrothermal Power SystemsDashti, Hossein, Conejo, Antonio J., Jiang, Ruiwei, Wang, Jianhui 11 1900 (has links)
As compared to short-term forecasting (e.g., 1 day), it is often challenging to accurately forecast the volume of precipitation in a medium-term horizon (e.g., 1 week). As a result, fluctuations in water inflow can trigger generation shortage and electricity price spikes in a power system with major or predominant hydro resources. In this paper, we study a two-stage robust scheduling approach for a hydrothermal power system. We consider water inflow uncertainty and employ a vector autoregressive (VAR) model to represent its seasonality and accordingly construct an uncertainty set in the robust optimization approach. We design a Benders' decomposition algorithm to solve this problem. Results are presented for the proposed approach on a real-world case study.
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