Electrical Power System is one of the most complex real time operating systems. It is probably one of the best examples of a large interconnected nonlinear system of varying nature. The system needs to be operated and controlled with component or system problems, often with combinatorial complexity. In addition, time scales of operation and control can vary from milliseconds to minutes to hours. It is difficult to maintain such a system at constant operating condition due to both small and large disturbances such as sudden change in loads, change in network configuration, fluctuations in turbine output, and various types of faults etc. The system is therefore affected by a variety of instability problems. Among all these instability problems one of the important modes of instability is related to dynamic instability or more precisely the small perturbation oscillatory instability. Oscillations of small magnitude and low frequency (in the range of 0.1Hz to 2.5Hz) could persist for long periods, limiting the power transfer capability of the transmission lines. Power System Stabilizers (PSS) were developed as auxiliary controllers on the excitation system to improve the system damping performance by modulating the generator excitation voltage. However, the synthesis of an effective PSS for all operating conditions still remains a difficult and challenging task. The design and tuning of PSS for robust operation is a laborious process. The existing PSS design techniques require considerable expertise, the complete system information and extensive eigenvalue calculations which increases the computational burden as the system size increases. Conventional automatic voltage regulator (AVR) and PSS designs are based on linearized models of power systems which fail to stabilize the system over a wide range of operating conditions. In the last decade or so, a variety of nonlinear control techniques have become available. In this thesis, an attempt is made to explore the suitability of some of these design techniques for designing excitation controllers to enhance small perturbation stability of power systems over a wide range of operating and system conditions. This thesis first proposes a method of designing power system stabilizers based on local measurements alone, in multi-machine systems. Next, a method has been developed to analyze and quantify the small signal performance benefits of replacing the existing AVR+PSS structure with nonlinear voltage regulators. A number of new nonlinear controller designs have been proposed subsequently. These include, (a) a new decentralized nonlinear voltage regulator for multi machine power systems with a single tunable parameter that can achieve effective trade of between both the voltage regulation and small signal objectives, (b) a decentralized Interconnection and Damping Assignment Passivity Based Controller in addition to a proportional controller that can achieve all the requirements of an excitation system and (c) a Nonlinear Quadratic Regulator PSS using Single Network Adaptive Critic architecture in the frame work of approximate dynamic programming. Performance of all the proposed controllers has been analyzed using a number of multi machine test systems over a range of operating conditions.

Background Polypharmacy is often prescribed for bipolar disorder, yet medication non-adherence remains a serious problem. This study investigated the regularity in the daily dosage taken of mood stabilizers and second generation antipsychotics. Methods Daily self-reported data on medications taken and mood were available from 241 patients with a diagnosis of bipolar disorder who received treatment as usual. Patients who took the same mood stabilizer or second generation antipsychotic for ≥ 100 days were included. Approximate entropy was used to determine serial regularity in daily dosage taken. Generalized estimating equations were used to estimate if demographic or clinical variables were associated with regularity. Results There were 422 analysis periods available from the 241 patients. Patients took drugs on 84.4% of days. Considerable irregularity was found, mostly due to single-day omissions and dosage changes. Drug holidays (missing 3 or more consecutive days) were found in 35.8% of the analysis periods. Irregularity was associated with an increasing total number of psychotropic drugs taken (p = 0.009), the pill burden (p = 0.026), and the percent of days depressed (p = 0.049). Conclusion Despite low missing percent of days, daily drug dosage may be irregular primarily due to single day omissions and dosage changes. Drug holidays are common. Physicians should expect to see partial adherence in clinical practice, especially with complex drug regimens. Daily dosage irregularity may impact the continuity of drug action, contribute to individual variation in treatment response, and needs further study.

Orientador: Percival Bueno de Araujo / Resumo: As perturbações ou variações de carga produzem oscilações eletromecânicas que devem ser amortecidas o mais rápido possível para garantir confiabilidade e estabilidade da rede. Neste trabalho apresenta-se uma análise do dispositivo FACTS Interline Power Flow Controller (IPFC) e o controlador Proporcional Integral (PI) no gerenciamento dos fluxos de potência e a influência dos Estabilizadores do Sistema de Potência (ESP) e do IPFC Power Oscillation Damping (POD) sobre a estabilidade do sistema elétrico de potência. Neste trabalho enfoca-se nos estudos de estabilidade a pequenas perturbações usando um Algoritmo Genético Adaptativo com Hiper-mutação (AGAH) para ajustar os parâmetros dos controladores suplementares de amortecimento, o Estabilizador de sistema de potência (ESPs) e o Power Oscillation Damping (POD) em forma coordenada. O AGAH tem como objetivo encontrar os parâmetros ótimos do controlador para melhorar o amortecimento fraco das oscilações de baixa frequência locais e inter-área. Neste trabalho representa-se o sistema de elétrico de potência com a inclusão do dispositivo Interline Power Flow Controller com o modelo de sensibilidade de corrente (MSC). Considera-se como sistema teste o sistema Simétrico de Duas Áreas e o sistema New England como o intuito de avaliar o algoritmo proposto. As simulações são feitas no ambiente do MatLab. Por fim, apresenta-se a comparação do algoritmo genético com o desempenho do algoritmo proposto. / Abstract: Small-magnitude disturbances happen to produce electro-mechanical oscillations which should be damped as quickly as possible to ensure reliability and stability of the network. This work presents an analysis of Interline Power Flow Controller (IPFC) FACTS device and PI controller to control and manage power flow and also how Power System Stabilizers and IPFC Power Oscillations Damping (POD) controller influence over an electric power system stability. This work focuses on small-signal stability studies using an Adaptive Genetic Algorithm with Hyper-mutation (AGAH) in order to tune controller parameters in a coordinated way ensuring proper damping. AGAH aims to find optimal controller parameters to enhance the poor damping of local and inter-area low frequency oscillations. This works represents the electric power system and Interline Power Flow Controller device by a current sensitivity model (CSM). This paper considers two areas 14 bus symmetrical power system and New England power system in order to assess proposed algorithm. Coding and Simulations take place in MatLab platform. AGAH and GA get compared by time convergence and performance. This paper shows AGAH is an interesting optimization technique which outweighs GA. / Mestre

Neste trabalho é apresentada uma abordagem fuzzy para a estabilização de uma classe de sistemas não-lineares com parâmetros descritos por saltos Markovianos. Uma nova modelagem fuzzy de sistemas é formulada para representar esta classe de sistemas na vizinhança de pontos de operação escolhidos. A estrutura deste sistema fuzzy é composta de dois níveis, um para descrição dos saltos Markovianos e outro para descrição das não-linearidades no estado do sistema. Condições suficientes para a estabilização estocástica do sistema fuzzy considerado são derivadas usando uma função de Lyapunov acoplada. O projeto de controle fuzzy é então formulado a partir de um conjunto de desigualdades matriciais lineares. Em adição, um exemplo de aplicação, envolvendo a representação da operação de um sistema elétrico de potência em esquema de co-geração por um sistema com saltos Markovianos, é construído para validação dos resultados. / This work deals with the fuzzy-model-based control design for a class of Markovian jump nonlinear systems. A new fuzzy system modeling is proposed to approximate the dynamics of this class of systems. The structure of the new fuzzy system is composed of two levels, a crisp level which describes the Markovian jumps and a fuzzy level which describes the system nonlinearities. A sufficient condition on the existence of a stochastically stabilizing controller using a Lyapunov function approach is presented. The fuzzy-model-based control design is formulated in terms of a set of linear matrix inequalities. In addition, simulation results for a single-machine infinite-bus power system in cogeneration scheme, whose operation is modeled as an Markovian jump nonlinear system, are presented to illustrate the applicability of the technique.

This doctoral thesis addresses in a sequence of five essays the question how fiscal policy and economic output are interrelated in emerging Europe and how this relationship is shaped by the respective politico-economic environment and the individual-level support for economic reforms. Following main findings can be highlighted: (1) Countries in Central, Eastern and Southeastern Europe (CESEE) respond to a fiscal expansion in the euro area with fiscal easing at home, while the GDP response is mixed across countries.(2)Automatic fiscal stabilizers are comparatively small and discretionary fiscal policy has been largely pro-cyclical in CESEE. (3) The public spending and revenue structure is more "growth-friendly" in CESEEthan in the EU-15. (4) In transition economies with more democratic institutions and a better quality of governance, individuals with high market-relevant skills show a significantly larger support of the privatization status quo than individuals with low market skills. (5) The society in Russia - triggered by a lack of social capital - chooses to demand more state regulationand tolerate corruption to reduce negative externalities imposed by private business.(author's abstract)

Small signal oscillation has been always a major concern in the operation of power systems. In a generator, the electromechanical coupling between the rotor and the rest of the system causes it to behave in a manner similar to a spring mass damper system. Following any disturbance, such as sudden change in loads, actuations in the output of turbine and faults etc. it exhibits an oscillatory behaviour around the equilibrium state. The use of fast acting high gain AVRs and evolution of large interconnected power systems with transfer of bulk power across weak transmission links have further aggravated the problem of these low frequency oscillations. Small oscillations in the range of about 0.1Hz to 3.5Hz can persist for long periods, limiting the power transfer capability of the transmission lines. These oscillations can be reduced by incorporating auxiliary controllers on generator excitation system. Power System Stabilizers (PSSs) were developed to produce additional damping by modulating the generator excitation voltage. Designing effective PSS for all operating conditions especially in large interconnected power systems still remains a difficult and challenging task. More and more power electronic based controllers have been and will be used in power systems. Many of these controllers such as Static Var Compensators (SVCs), Static Synchronous Compensators (STATCOMs) and Unified Power Flow Controllers (UPFCs) etc., are incorporated in power transmission networks to improve its operational capability. In addition, some of the energy storage systems such as Battery Energy Storage systems (BESS), Super conducting Magnetic Energy Storage System (SMES) as well large non-conventional energy sources are also increasingly being integrated with the power grid. With large integration of these devices, there is a significant impact on system stability, more importantly on small signal oscillatory instability of the power system. This thesis primarily focuses on impact of such devices on small signal oscillatory stability of the power systems. More specifically in this thesis small signal stability analysis of a Single Machine Infinite Bus (SMIB) system with a grid connected wind powered Permanent Magnet Synchronous Generator (PMSG) has been presented. A SMIB system has been purposely chosen so that general conclusions can be obtained on the behaviour of the embedded STATCOM/Energy Source (ES) system on system stability. With a better understanding of the impact of such a system it would be probably possible to analyze more complicated multimachine power system and their impact on system stability. Small signal model of the complete system which comprises the generator, transmission network, inter connecting STATCOM, the wind power generator and all associated controllers has been developed. The performances of the system following a small disturbance at various operating conditions have been analyzed. To obtain quantitative estimates of the damping and synchronizing torques generated in the system, expressions for damping and synchronizing torque clients have been developed. With these analyses, the relative impact of the STATCOM and STATCOM with ES on system performance have been assessed. It is shown that with active and reactive power modulation capabilities effective and efficient control of small signal oscillations in power systems can be achieved.

Neste trabalho é apresentada uma abordagem fuzzy para a estabilização de uma classe de sistemas não-lineares com parâmetros descritos por saltos Markovianos. Uma nova modelagem fuzzy de sistemas é formulada para representar esta classe de sistemas na vizinhança de pontos de operação escolhidos. A estrutura deste sistema fuzzy é composta de dois níveis, um para descrição dos saltos Markovianos e outro para descrição das não-linearidades no estado do sistema. Condições suficientes para a estabilização estocástica do sistema fuzzy considerado são derivadas usando uma função de Lyapunov acoplada. O projeto de controle fuzzy é então formulado a partir de um conjunto de desigualdades matriciais lineares. Em adição, um exemplo de aplicação, envolvendo a representação da operação de um sistema elétrico de potência em esquema de co-geração por um sistema com saltos Markovianos, é construído para validação dos resultados. / This work deals with the fuzzy-model-based control design for a class of Markovian jump nonlinear systems. A new fuzzy system modeling is proposed to approximate the dynamics of this class of systems. The structure of the new fuzzy system is composed of two levels, a crisp level which describes the Markovian jumps and a fuzzy level which describes the system nonlinearities. A sufficient condition on the existence of a stochastically stabilizing controller using a Lyapunov function approach is presented. The fuzzy-model-based control design is formulated in terms of a set of linear matrix inequalities. In addition, simulation results for a single-machine infinite-bus power system in cogeneration scheme, whose operation is modeled as an Markovian jump nonlinear system, are presented to illustrate the applicability of the technique.

After many decades, macroeconomic effects of fiscal policy have returned to the centre of the economic policy debate. Both automatic fiscal stabilizers and discretionary fiscal stimuli have been used to support aggregate demand during the recent global economic crisis with a subsequent need for large-scale fiscal consolidations. In this context, a proper assessment of the size of automatic fiscal stabilizers and fiscal multipliers represents a key input for fiscal policymaking. This dissertation provides a quantitative analysis of the interactions between fiscal policy and real economy in the Czech Republic. The impact of real economy developments on public finances is assessed based on the methods of the OECD, the European Commission and the ESCB for the identification of general government structural balances, i.e. balances adjusted for effects of the economic cycle and net of one-off and other temporary transactions. I find that the underlying fiscal position, as approximated by the government structural balance, was mostly below the level stabilising the debt-to-GDP ratio since mid-1990s. An indistinct improvement in the structural balance can be identified in the period 2004--2007, which was subsequently reversed by the adverse structural impact of the world economic crisis. At the same time, dynamics of unadjusted fiscal balance was largely determined by one-off transactions in the past. The effects of fiscal policy on real economy are analysed using the structural VAR approach. I find that an increase in government spending has a temporary positive effect on output that peaks after one to two years with a multiplier of around 0.6. Tax multiplier appears to be small and, in contrast to standard Keynesian assumptions, positive. Government spending is supportive to private consumption, contradicting the hypothesis of Ricardian equivalence, but it crowds out private investment in the short run. The results should be interpreted with caution, as the analysis is complicated by rapidly changing economic environment in the period of the economic transition, relatively short available time series and a large number of one-off fiscal transactions.

[ES] La presente Tesis doctoral plantea distintas estrategias para el diseño y desarrollo de oleogeles estables, con un perfil lipídico de alta calidad nutricional y la posterior incorporación de los oleogeles en la formulación de distintos alimentos. Se pretende diseñar alimentos mediante el reemplazo de grasas sólidas, ricas en ácidos grasos saturados y trans por oleogeles, que, por un lado, mantengan las propiedades texturales y organolépticas, y, por otro lado, presenten un perfil lipídico mejorado. En una primera etapa, se desarrollaron oleogeles elaborados con 1% de hidroxipropilmetilcelulosa y 0,6% de goma xantana empleando dos condiciones de secado diferentes: secado convencional en estufa a 80 °C durante 10 h 30 min y secado a vacío a 60 °C durante 24 h. Los aceites estructurados fueron aceite de oliva, lino, girasol y girasol alto oleico. La microestructura permitió apreciar oleogeles bien estructurados cuando se utilizaron los aceites de oliva, girasol y girasol alto oleico. La estabilidad física y las propiedades reológicas corroboraron la formación de oleogeles de alta estabilidad física, a lo largo de 35 días de almacenamiento, y con un comportamiento de gel sólido. Se observó que tanto el grado de insaturación del aceite como las condiciones de secado afectaron a la estabilidad física y química del oleogel. De esta manera, se obtuvieron oleogeles poco estructurados y no homogéneos al utilizar aceite con un alto grado de insaturación, como el aceite de lino, por secado convencional, mientras que no fue factible desarrollar oleogeles de lino con secado a vacío. Además, el secado en estufa convencional a 80 °C durante 10 h 30 min generó oleogeles de girasol y de girasol alto oleico con mayor estabilidad estructural y física que el secado a 60 °C durante 24 h. Los oleogeles de oliva y de girasol alto oleico producidos por secado convencional y los oleogeles de oliva y de girasol producidos por secado a vacío presentaron valores de estabilidad oxidativa primaria y secundaria dentro de los límites de aceptabilidad establecidos por el Codex Alimentarius. En una segunda etapa se desarrollaron cremas de cacao untables y panes dulces. En las cremas se estudió la microestructura, textura, reología y atributos sensoriales. La reformulación de las cremas con un reemplazo total (100%) y parcial (50%) de grasa de coco por oleogeles de oliva o girasol obtenidos por secado a vacío permitió mantener sus propiedades estructurales. Concretamente, la sustitución parcial de grasa de coco por oleogel de girasol permitió obtener cremas con atributos sensoriales como "apariencia cremosa", "textura cremosa" y "sabor a cacao", por lo que podría ser una alternativa viable para reformular cremas untables con un perfil nutricional más saludable. Los oleogeles de oliva o girasol alto oleico obtenidos por secado convencional y previamente caracterizados, se emplearon en la formulación de panes dulces elaborados al horno o al vapor. La reformulación con oleogeles permitió obtener panes con unas características estructurales y apariencia similar a la de los panes elaborados con margarina. La realización de una prueba triangular mostró diferencias en la apariencia de la miga y el sabor, mientras que no se observaron diferencias para el atributo textura entre los panes elaborados con oleogeles y con margarina. No se encontraron diferencias en la cantidad de ácidos grasos liberados tras la digestión in vitro entre los panes dulces elaborados con oleogeles y con margarina. Sin embargo, la velocidad inicial de la digestibilidad lipídica fue diferente dependiendo del tipo de procesado, horneado o vaporización, empleado en la elaboración de los panes. El desarrollo de oleogeles a base de hidrocoloides además de ofrecer a la industria alimentaria una alternativa como sustituto de grasas plásticas, podría investigarse como estrategia para modular la digestión de lípidos y brindar beneficios para la salud. Todas las estrategias abordadas en el transcurso de esta Tesis permitieron comprender y ahondar en los conocimientos que conducen a cómo reformular un alimento para mejorar su perfil lipídico sin comprometer sus características sensoriales y fisicoquímicas. / [CA] La present Tesi doctoral planteja diferents estratègies per al disseny i desenvolupament d'oleogels estables, amb un perfil lipídic d'alta qualitat nutricional, i la posterior incorporación dels oleogels en diferents aliments. Es pretén dissenyar aliments mitjançant el reemplaçament de greixos sòlids, rics en àcids grassos saturats i trans per oleogels, que d'una banda, mantinguen les propietats texturals i organolèptiques, i d'altra banda, presenten un perfil lipídic millorat. En una primera etapa, es van desenvolupar oleogels elaborats amb un 1% de hidroxipropilmetilcel·lulosa i un 0,6% de goma xantana emprant dues condicions d'assecat diferents: assecat convencional en estufa a 80 °C durant 10 h 30 min i assecat a buit a 60 °C durant 24 h. Els olis estructurats van ser d'oliva, de lli, de gira-sol i de gira-sol alt oleic. La microestructura va permetre apreciar oleogels ben estructurats quan es van utilitzar els olis d'oliva, gira-sol i gira-sol alt oleic. L'estabilitat física i les propietats reològiques van corroborar la formació d'oleogels d'alta estabilitat física, al llarg de 35 dies d'emmagatzematge, i amb un comportament de gel sòlid. Tant el grau d'insaturació de l'oli com les condicions d'assecat van afectar l'estabilitat física i química del oleogel. D'aquesta manera, es van obtindre oleogels poc estructurats i no homogenis en utilitzar oli amb un alt grau d'insaturació, com l'oli de lli, per assecat convencional, mentre que no va ser factible desenvolupar oleogels de lli amb assecat a buit. A més, l'assecat en estufa convencional a 80 °C durant 10 h 30 min va generar oleogels de gira-sol i de gira-sol alt oleic amb major estabilitat estructural i física que l'assecat a 60 °C durant 24 h. Els oleogels d'oliva i gira-sol alt oleic, produïts per assecat convencional i els oleogels d'oliva i gira-sol produïts per assecat a buit van presentar valors d'estabilitat oxidativa primària i secundària dins dels límits d'acceptabilitat establits pel Codex Alimentarius. En una segona etapa, es van desenvolupar cremes de cacau untables i pans dolços. En aquest treball, es va estudiar la microestructura, textura, reologia i atributs sensorials de les cremes untables. La reformulació de cremes amb un reemplaçament total (100%) i parcial (50%) de greix de coco per oleogels d'oliva o gira-sol obtinguts per assecat a buit, va permetre mantindre les propietats estructurals de les cremes untables. Concretament, la substitució parcial de greix de coco per oleogel de gira-sol va ser descrita amb atributs sensorials com a "aparença cremosa", "textura cremosa" i "sabor de cacau", la qual cosa podria ser una alternativa viable per a reformular cremes per a untar amb un perfil nutricional més saludable. Els oleogels d'oliva o gira-sol alt oleic obtinguts per assecat convencional i prèviament caracteritzats, es van empra en la formulació de pans dolços cuinats al forn o al vapor. Es van estudiar les propietats estructurals, i la digestibilitat lipídica in vitro del producte final. La reformulació amb oleogels va permetre obtindre pans amb unes característiques estructurals i aparença similar a la dels pans elaborats amb margarina. La realització d'una prova triangular va mostrar diferències en l'aparença de la molla i el sabor, mentre que no es van observar diferències per a l'atribut textura, entre els pans elaborats amb oleogels i amb margarina. No es van trobar diferències en la quantitat d'àcids grassos alliberats després de la digestió in vitro entre els pans dolços elaborats amb oleogels i amb margarina. No obstant això, la velocitat inicial de la digestibilitat lipídica va ser diferent depenent de la mena de processament, enfornat o vaporatge, emprat en l'elaboració dels pans. El desenvolupament d’oleogels a base de hidrocol∙loides, a més d ́oferir a la indústria alimentària una alternativa com a substitut de greixos plàstics, podria investigar-se com a estratègia per modular la digestió de lípids i brindar beneficis per la salut. Totes les estratègies abordades en el transcurs d'aquesta Tesi van permetre comprendre i aprofundir en els coneixements que condueixen a com reformular un aliment per a millorar el seu perfil lipídic sense comprometre les seues característiques sensorials i fisicoquímiques. / [EN] The research of this doctoral thesis proposes different strategies for the design and development of stable oleogels, with high nutritional lipid profile and the subsequent incorporation of the oleogels in the formulation of different . It aims to design foods by replacing solid fats, rich in saturated and trans fatty acids with oleogels, which, on the one hand, maintain the textural and organoleptic properties, and on the other hand, present an improved lipid profile. In a first stage, oleogels made with 1% hydroxypropylmethylcellulose and 0.6% xanthan gum were developed using two different drying conditions: conventional drying in an oven at 80 ° C for 10 h 30 'and vacuum drying at 60 ° C for 24 h. The structured oils were olive, flaxseed, sunflower and high oleic sunflower oil. The microstructure showed the oleogels structured, when olive, sunflower or high oleic sunflower oils were used. Physical stability and rheological properties corroborated the formation of oleogels with high physical stability, over 35 days of storage, and with a solid gel behaviour. Both the degree of unsaturation of the oil and the drying conditions affected the physical and chemical stability of the oleogel. In this way, unstructured non-homogeneous oleogels were obtained by using oil with a high degree of unsaturation, such as flaxseed oil, by conventional drying, while it was not feasible to develop flaxseed oleogels with vacuum drying. Furthermore, drying in a conventional oven at 80 ° C for 10 h 30 min generated sunflower and high oleic sunflower oleogels with more structural and physical stability than drying at 60 ° C for 24 h. Olive and high oleic sunflower oleogels, produced by conventional drying, and olive and sunflower oleogels produced by vacuum drying, presented primary and secondary oxidative values within the acceptability limits established by the Codex Alimentarius. In a second stage, spreadable cocoa creams and sweet breads were developed. The microstructure, texture, rheology and sensory attributes of spreadable creams were studied. The reformulation of cocoa creams with a total (100%) and partial (50%) replacement of coconut fat by olive or sunflower oleogels obtained by vacuum drying allowed to maintain the structural properties of spreadable creams. Specifically, the partial substitution of coconut fat for sunflower oleogel gave place to creams described with sensory attributes such as "creamy appearance", "creamy texture" and "cocoa flavor"; therefore, it could be a viable alternative to reformulate spreads with a healthier nutritional profile. The olive or sunflower oleogels obtained by conventional drying and previously characterized, were used in the formulation of sweet breads made in the oven or steamed. Replacement of margarine for oleogels produced breads with similar structural characteristics and appearance that those made with margarine. A triangular discriminatory test showed differences in the appearance of the crumb and the flavor, while no differences were observed for the texture attribute, between the breads made with oleogels or with margarine. No differences were found in the amount of fatty acids released after in vitro digestion between sweet breads made with oleogels and margarine. However, the initial rate of lipid digestibility was different depending on the type of processing, baking or steaming, used in the preparation of the breads. In addition to offering the food industry an alternative as a substitute for plastic fats, the debe lopment of hydrocolloid-based oleogels could be investigated as a strategy to modulate lipid digestion and provide health benefits. / Bascuas Véntola, SM. (2021). Estructuración de aceites mediante el uso de hidrocoloides para sustituir grasas plásticas en los alimentos [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/174797

Ce travail de thèse rentre dans le cadre d’un projet de recherche appliquée mené à l’Institut National de Criminalistique et de Criminologie s’intitulant « développement d’un système intégral de détection et d’identification de résidus de tir » visant à doter le laboratoire de balistique chimique d’un outil performant pour la recherche et la caractérisation des résidus de tir aussi bien inorganiques qu’organiques. Comme nous l’expliquons dans le chapitre 1, l’analyse des résidus de tir est aujourd’hui essentiellement basée sur la mise en évidence par microscopie électronique à balayage des particules métalliques provenant de l’amorce. Cette pratique a des limites. Introductif, ce chapitre met en lumière la relation entre criminologie et criminalistique, donne un aperçu de la classification des armes et décrit les relations entre les armes de poing, les munitions, les résidus de tir et la criminalistique. La motivation de l’analyse de résidus organiques et plus particulièrement des stabilisants pour poudres propulsives y est aussi expliquée. Le but principal de ce travail étant le développement d’une méthode d’analyse des stabilisants par spectrométrie de masse en tandem couplée à la chromatographie liquide à haute performance (LC-MS/MS), ce premier chapitre aborde de façon détaillée le principe de fonctionnement d’un spectromètre de masse quadripolaire, qu’il soit avec simple quadripôle ou en tandem, et traite avec une attention particulière les aspects relatifs à la production d’ions, l’acquisition des données et la détection des ions. Le chapitre 2 est consacré aux résultats et discussions. Comme point de départ de tous les travaux ultérieurs, l’optimisation du fonctionnement du spectromètre et plus particulièrement la détermination des « ions précurseurs » et des « ions produits » y est traitée en détails. De plus, l’étude de la fragmentation des ions précurseurs y occupe une place prépondérante et conditionne l’établissement d’une méthode de détection et d’acquisition des données. Dans ce même chapitre sont successivement traités la mise au point de la méthode chromatographique pour l’analyse des stabilisants par LC-MS/MS, le couplage LC-MS/MS, la collecte et préparation des échantillons, dont l’extraction sur phase solide (SPE). Disposant des procédures de traitement des échantillons et d’une méthode LC-MS/MS, il nous a été possible de mener l’étude de faisabilité de l’analyse des stabilisants dans les échantillons prélevés sur les mains d’un tireur. Cette étude fait l’objet d’une proposition de publication jointe en annexe. Pour être exploitable en criminalistique, ce travail est complété par une étude sur les fréquences d’observation des stabilisants pour poudres propulsives sur les mains des non-tireurs. L’ensemble des résultats nous permet de dresser un bilan et proposer des perspectives décrites dans le chapitre 3. A cet égard, nous proposons de poursuivre les essais relatifs aux tests de persistance des résidus de stabilisant sur les mains des tireurs et d’entamer une étude sur la caractérisation des résidus de tir de la nitrocellulose. Du point de vue de l’exploitation des acquis de ce travail, nous suggérons que les méthodes et procédures développées soient mises à l’épreuve dans les affaires nécessitant l’analyse des prélèvements effectués sur les vêtements d’un suspect ou d’une victime. Cette mise à l’épreuve permettra de comparer l’efficacité de la méthode LC-MS/MS à celle de la technique SEM/EDX habituellement utilisée. Le chapitre 4 est consacré aux matériels et méthodes détaillant notamment les procédures de collectes et de traitement des échantillons, les paramètres de fonctionnement du spectromètre de masse et les méthodes analytiques. <br> <br> This thesis deals with a research project entitled "Development of an integral system of detection and identification of gunshot residues”, carried out at the Belgian National Institute of Criminalistics and Criminology (NICC). This project aims at providing the Laboratory of Chemical Ballistics, a powerful tool to detect and identify organic gunshot residues. For instance, the analyses of gunshot residues is presently performed mainly for characterizing metallic particles originating from the primer, using scanning electron microscopy coupled to energy dispersive X-ray microanalysis (SEM-EDX). However this technique has its limits and the goal of the thesis was the development of a method for the analysis of the stabilizers (and their derivatives) present in propellant powders with the use of tandem mass spectrometry coupled to high performance liquid chromatography (LC-MS/MS). The introduction highlights the relations between Criminology and Criminalistics; it gives an outline of the classification of weapons, and describes how handguns, ammunitions, gunshot residues and Criminalistics can be linked when investigating criminal cases. The motivation of the analysis of organic gunshot residues and in particular the propellant powder stabilizers is also explained. Chapter 1 deals in detail with the working principle of a quadrupole mass spectrometer, whether it is with a single quadrupole or composed of a tandem mass spectrometer. Important aspects connected with the ion production, the data acquisition and the ion detection are also considered. Chapter 2 presents the results and discussions. It begins with the optimization of the operating conditions of the spectrometer, and focuses more specifically on the determination of “precursor ions" and "daughter ions”. The study of the precursor ion is more important because it is required for the choice of parameters involved in the data acquisition mode. The development of a liquid chromatography (LC) method and the procedures for collecting and preparing the samples are explained. Moreover, Chapter 2 summarizes the results of a feasibility study of the analyses of stabilizers in samples collected from the hands of a shooter. This study was published in a peer reviewed journal [1]. A complementary study on the frequencies of observation of stabilizers on the hands of non-shooter persons is reported at the end the Chapter. The results allow also proposing perspectives which are described in Chapter 3. In this respect, the characterization of nitrocellulose residues and the study of the persistence of stabilizer residues on the hands of shooters should be undertaken. From the practical point of view, the developed methods and procedures should be tested in real cases which involve the analyses of the samples taken from the clothing of suspects and/or victims. These tests should allow an assessment of the LC-MS/MS method compared to the efficiency of the SEM/EDX technique currently used. Chapter 4 is dedicated to the materials and methods; the sample collection and treatment procedures, as well as the working parameters of the mass spectrometer and the analytical methods are explained in detail. [1]. Désiré Laza, Ph.D.; Bart Nys, Ph.D.; Jan De Kinder, Ph.D.; Andrée Kirsch - De Mesmaeker, Ph.D.; and Cécile Moucheron, Ph.D. Development of a Quantitative LC-MS/MS Method for the Analysis of Common Propellant Powder Stabilizers in Gunshot Residue. J. Forensic Sci, July 2007, Vol. 52, N° 4, 842-850.