Philosophiae Doctor - PhD / A phenomenological philosophy underlies this research study which attempts to understand clinicians’ perception and understanding of an electronic patient record (EPR) system currently operational at a hospital in the Western Cape Province in South Africa (SA). Healthcare is a human right, thus patient records contain critical data and mostly paper-based in many SA hospitals. Clinicians are the EPR primary users and their attitude in its use is important for its success. This study explores, identifies and determines clinicians’ cognitive attributes towards EPR with a technology use framework developed. An initial quantitative approach was applied but unsuccessful due to low sample size. A pilot study was then conducted using 11 respondents. Purposive sampling was first initiated then snowball introduced later to improve the sample size qualitatively. Interviews were administered to 15 clinicians and tape recorded. Narrative content analysis was used as the preferred analysis technique because of the advantage of gaining direct information from study participants, unobtrusive and a nonreactive way to study the phenomenon of interest. Research findings tested 12 propositions and found high impact relationships between attitude (ATT) and each listed theme namely: perceived usefulness (PU), perceived ease of use (PEOU), complexity (COM), facilitating condition (FC), use behaviour (USE). Use behaviour had high impact relationships with storage (STO) and retrieval (RET). There were moderate impact relationships between PU and USE; PEOU and PU; RA and ATT; job fit (JF) and ATT; USE and share (SHA). The implication here is that any EPR system to be implemented should be tested using this framework to ascertain its usefulness and fit with a hospital's objectives and users expectations. By so doing, anticipated problems can be mitigated against and resolved before implementation. The study contributes to the information system (IS) body of knowledge through the technology use framework. The framework is for adoption by hospital management and its use by clinicians where EPR is operational. Traditional IS frameworks can be adopted for hospitals about to implement EPR because of the relevance of the "intent to use" theme.

The quest for sustainable development has always involved the complex task of reconciling the need for socio-economic development with public health and environmental protection. This challenge has often emerged in the trade and environment debate but has most recently been evident in international trade in used electrical and electronic equipment (UEEE). While international trade in UEEE provides means for socio-economic development in the developing world, it also serves as a conduit for transboundary dumping of e-waste in the developing world giving rise to serious health and environmental concerns. This research investigates the socio-economic as well as health and environmental impacts of international trade in UEEE in two developing countries – Nigeria and Ghana. The research identifies a major loophole in the existing international legal framework as the primary factor responsible for e-waste dumping in the developing world. This loophole relates to the absence of a legal framework for differentiating between functional UEEE and junk e-waste. This has resulted in both functional UEEE and junk e-waste being concurrently shipped to the developing world as “used electrical and electronic equipment”. The research proposes two policy frameworks for addressing this problem. On the part of developing countries, the research proposes a trade policy framework crafted in line with WTO rules. This framework will entail the development of an international certification system which will serve to differentiate functional used electronics from junk e-waste. While the former may be eligible for import, the research proposes an import ban on the latter. On the part of developed countries, the research proposes the development of a policy framework which regulates the toxic and hazardous substances that go into the production of electrical and electronic equipment as well as enhance their reusability and recyclability at end-of-life. The framework should take into consideration the entire life cycle of the products from the design stage to end-of-life. The research argues that the implementation of this design framework will go a long way in reducing the health and environmental impacts of such equipment when subsequently shipped to the developing world at end-of-life.

Molecular Nanomagnets have been proposed as plausible candidates in a variety of futuristic applications. Thorough understanding of the magnetic properties of these systems is therefore necessary to develop devices that include such units. The aim of this thesis is to synthesise and structurally and magnetically characterise a range of systems that could be used as elementary units in three proposed applications such as: data storage devices, magnetic refrigerants and qubits for quantum computing. A series of mixed 3d/4f metal complexes were synthesised through solvothermal reactions and characterised by X-ray single crystal diffraction and SQUID magnetometry. Through indirect methods it was possible to obtain high magnetic entropy change for some systems. It was also possible to obtain some insight into the magnetic interactions within the systems through modelling the magnetic data. The role of the 4f-4f and 3d-4f interactions in two sets of molecules is also described. The first study is in an asymmetric dysprosium dimer, where through a range of experimental techniques and advanced theoretical methods, such ab-initio calculations we are able to explain the role of the intramolecular interactions and their effect on the SMM properties of this system. Similarly, insight into the role of the 3d-4f interactions is achieved through the observation of the magnetic behaviour of a family of 27 tetranuclear systems, though SQUID data and ab-initio calculations. Finally, chemical functionalization of a well-proposed qubits, namely {Cr7Ni} and subsequent reaction with a redox active metal ion, CoII/III, two {Cr7Ni} systems are linked. The magnitude of the exchange interaction between the {Cr7Ni}-CoII-{Cr7Ni} was determined through Electron Paramagnetic Resonance. Furthermore, by chemical oxidation/reduction of the cobalt between paramagnetic and diamagneticstates, i.e. CoII and CoIII respectively, we demonstrate that the interaction can be switched ON/OFF. This characteristic makes of these systems candidates to function as a SWAP gate.

This project aimed to address the lack of research into the mechanical properties and degradation mechanisms for historical tapestries at the fabric level and understand how effective conservation support strategies can be in the preservation of these artifacts. The research incorporated a large range of techniques from diverse disciplines including weaving, ageing, computer modeling, biochemistry and conservation science. The successful manufacture and ageing of relevant samples provided an excellent opportunity to include testing of historical samples for comparison. Tensile testing of all samples provided a valuable insight into the characteristics of degraded historical samples compared to artificially aged samples. Although individual ageing processes – including UV ageing, Relative Humidity (RH) – thermal cycling and mechanical strain ageing produced a reduction in strength, the historical samples showed a far greater loss of strength due to the combination of all types of ageing in addition to handling and pollution damage. A proteomic analysis of the wool fibres resulted in a greater understanding of the degradative “dark” wool ageing process which suggests that wool yellowing and tendering can be produced not just through photo-chemical reaction. Additionally, the chemical analysis laid an important foundation for future research into linking chemical mechanisms of damage with mechanical loss of strength. Analysis using electron paramagnetic resonance spectroscopy (EPR) provided an insight into the free radical chemistry of a range of wool/wool samples. It was observed that the light aged samples produced thiyl radicals whereas thioperoxy radicals were seen in the heat-humidity aged samples. This implies separate chemical reactions occur to produce degradation in the different ageing regimes. EPR analysis of some historical samples produced a carbon-based radical peak linked to a soot calibration signal. Further research on historical samples found phenolic radicals, possibly linked to the complex dye chemistry. Further research needs to be undertaken to fully clarify these findings. A world-wide questionnaire to textile conservators has provided a useful resource in terms of a survey of methods and materials used across the world – including technical data as well as more “ethical” motivations for conservation. The results of this survey were used along with the physical data collated in the mechanical testing as information inputted into a finite element model (FEA) to undertake the digital modeling of a tapestry hanging under its own weight. Although more research is needed to fully develop this model, a preliminary investigation has been established which can be used in future research as a tool for textile conservators across the world.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21591号 / 理博第4498号 / 新制||理||1646(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 大須賀 篤弘, 教授 依光 英樹, 教授 丸岡 啓二 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Aby bylo možné charakterizovat atmosfericky citlivé vzorky ve vysokofrekvenčním elektronovém paramagnetickém rezonančním spektrometru (z angl. high-frequency electron paramagnetic resonance spectrometer, HF-EPR), je potřebné mít vakuový transportní systém. Cílem této práce je navrhnout a vyvinout tento vakuový přepravní systém, který umožní tuto přepravu. Vakuový systém, který se skládá z mobilního vakuového kufru, držáku palety a přechodové komory, byly navrženy, sestaveny a testovány. Bylo dosaženo tlaku 4,3 10^{-10}mbar, což zajistí inertní podmínky pro transport vzorků. Byl proveden transport vzorku ze systému ultravysokého vakua (UHV) do HF-EPR spektrometru. Kontaminace testovacích vzorků byla charakterizována pomocí rentgenové fotoelektronové spektroskopie. Bylo zjištěno, že nedochází téměř k žádné detekovatelné kontaminaci, pokud je vzorek přepravován pomocí vakuovém systému méně než 16 hodin. Bylo navrženo rozšíření pro přepravu vzorků z rukavicového boxu a paletky pro grafen, ale jejich výroba dosud nebyla provedena. Vyvinutý vakuový systém je plně funkční a poskytuje alternativu ke komerčně dostupným produktům, a proto bude dále používán při zkoumání vzorků citlivých na atmosféru v laboratořích CEITEC Nano.

This master thesis is focused on process of production management and scheduling in a selected company. In the first part the selected company has been described. The theoretical part contains an explanation of terms that relates to this topic. In the practical part, a process analysis of the current state of the process of production management and scheduling has been carried out, which detected certain deficiencies related to this process. The identified deficiencies are further interpreted and on the basis of the theoretical part, has been proposed a solution, which should lead to the elimination of these problems. In the final part of the thesis, the benefits of the proposed solution are determined.

Les NO-synthases sont des flavohémoprotéines responsables de la production de NO• chez les mammifères (mNOS). Elles se composent d’un domaine réductase, qui lie les cofacteurs FMN et FAD et le co-substrat NADPH, et d’un domaine oxygénase qui lie l’hème, le substrat L-arginine et le cofacteur redox essentiel tétrahydrobioptérine H4B. Ces quinze dernières années, plusieurs NOS d’origine bactérienne (bacNOS) ont été caractérisées et il a été montré qu’elles étaient semblables au domaine oxygénase de leurs homologues mammifères. Il existe cependant des différences significatives entre mNOS et bacNOS, la plus importante étant l’absence de domaine réductase chez les NOS d’origine bactérienne. De plus, le(s) mécanisme(s) catalytique(s) de ces dernières ainsi que leur(s) fonction(s) in vivo restent actuellement à déterminer. Plusieurs études publiées montrent que la substitution Val/Ile à proximité du site actif, conservée entre mNOS et bacNOS, est partiellement responsable des différences observées au niveau catalytique entre ces deux groupes. Dans le cadre de cette thèse, j’ai utilisé les spectroscopies d’absorption UV-visible et RPE, ainsi que des techniques de cinétiques rapides comme le stopped-flow et le freeze-quench, pour caractériser les deux mutants complémentaires bsNOS I224V et iNOS V346I afin de mieux comprendre l’influence de cette mutation. J’ai ainsi montré qu’il existait des différences fondamentales entre bacNOS et mNOS qui ne sont pas liées à la substitution Val/Ile et que ces deux familles d’enzymes suivent probablement des mécanismes catalytiques différents pour l’étape d’oxydation du NOHA. Ces résultats sont confirmés par l’étude de la NOS thermostable issue de Geobacillus stearothermophilus. Lorsqu’on s’intéresse au fonctionnement in vivo des bacNOS, se pose également la question de la nature du cofacteur redox puisque de nombreuses bactéries possédant une NOS n’ont pas la machinerie nécessaire à la synthèse de H4B ; c’est par exemple le cas de Deinococcus radiodurans pour qui l’utilisation du tétrahydrofolate H4F a été proposée. J’ai donc étudié et caractérisé deiNOS de manière approfondie en présence de différents cofacteurs afin de mieux comprendre leurs rôles redox et structural. Ceci a notamment permis de proposer un mécanisme catalytique légèrement différent de celui suivi par bsNOS ce qui suggère que ces enzymes pourraient avoir différentes fonctions in vivo. Enfin, la première caractérisation in vitro d’une NOS de plante, issue de l’algue verte unicellulaire Ostreococcus tauri est présentée dans ce manuscrit. Les résultats suggèrent que celle-ci aurait effectivement une activité NO-synthase in vivo. / NO-synthases are flavohemoproteins responsible for NO• production in mammals (mNOS). They are comprised of a reductase domain, that binds FMN, FAD and NADPH, and an oxygenase domain, that binds heme, the substrate L-arginine and the essential redox active tetrahydrobiopterin cofactor H4B. In the last 15 years, several bacterial NOS (bacNOS) have been characterized and shown to resemble the oxygenase domain of their mammalian counterpart. However bacNOS exhibit significant differences from mNOS, the most striking one being the lack of a reductase domain, and their catalytic mechanism(s) and in vivo function(s) are currently poorly understood. Previously published studies suggest that a conserved Val to Ile substitution near the active site is at least partially responsible for the differences in catalysis observed between mNOS and bacNOS. During my PhD I characterized the mutants on this particular position, bsNOS I224V and iNOS V346I, using UV-visible and EPR spectroscopies as well as rapid-kinetic technics such as stopped-flow spectrophotometry and rapid-freeze quench, to better understand the influence of this substitution. This showed that mammalian and bacterial enzymes are fundamentally different and probably follow different mechanisms for NOHA oxidation. Results from studying the thermostable NOS from Geobacillus stearothermophilus further confirm these observations. Another important issue regarding bacNOS functioning in vivo concerns the nature of the redox active cofactor since many NOS-containing bacteria do not have the machinery for H4B biosynthesis; this is for instance the case of Deinococcus radiodurans for which the use of tetrahydrofolate H4F has been proposed. I therefore performed an extensive characterization of deiNOS in the presence of various cofactors to better understand their redox and structural roles. This allowed proposing a slightly different mechanism for deiNOS, compared to bsNOS, suggesting different function(s) in vivo. Finally, the first in vitro characterization of a plant NOS from the unicellular green alga Ostreococcus tauri is reported in this manuscript. The results suggest that this NOS-like protein is indeed a genuine NO-synthase.

Cancer is one of the leading cause of death in modern world, so there is an emerging demand for better diagnostic tools and more specific less toxique therapeutics. Nanoparticles offers characteristics that could fullfill such perspectives. They can easily target tumor by ehanced permeation and retention effect (EPR). Nanoparticles can combine more than one imaging properties, so we can say that they are multimodal, some of them could combine diagnostic and therapeutic molecules in one nanoparticle, which is now highly popular topic of nanoparticles for theranostics . The aim of this thesis was to characterize new multimodal glycogen-based nanoparticle. Glycogen is an ideal structure for nanoparticle design. Glycogen is part of natural dendrimers group which are easily to modify. Glycogen's size is suitable for EPR effect. We have evaluated biological characteristics of five different types of modified glycogen. The in vitro experiments were carried on HepG2 cells. We have set time curve of cellular uptake of this glycogen probes, evaluated cytoplasmatic localization and for the first time we have carried MTT assay. Biodistribution studies on CD1-Nude mice were performed by using non-invasive method for measuring in vivo fluorescence. In conlusion we've provided some of the biological characteristics of new...

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