Dans le milieu interstellaire, beaucoup de molécules hydrogénées telles que CH4, NH3 ou CH3OH peuvent être dissociées, grâce à la contribution de particules cosmiques ou de photons hautement énergétiques, devenant l’une des plus importantes sources de radicaux activés. Cependant, dans le cœur de certains nuages moléculaires denses et sombres, en l’absence de ces énergies externes supplémentaires, d’autres chemins réactionnels de formation de radicaux pourraient exister sans apport d’énergie externe.Dans le travail de thèse actuel, nous avons étudié des réactions thermiquement induites impliquant de petites composés organiques et des atomes d’azote à l’état fondamental N(4S), en phase solide aux températures cryogéniques de 3 à 50 K, en utilisant une caractérisation par spectroscopie Infrarouge à Transformée de Fourier (IRTF).Nous avons montré qu’un chauffage progressif entre 3 et 10 K permet d’induire la mobilité des atomes d’azote dans l’échantillon solide, provoquant le processus de recombinaison N(4S)–N(4S). De telles recombinaisons engendrent la formation d’espèces réactives métastable d’azote moléculaire N2(A), lesquelles à travers un processus de transfert d’énergétie N2(A) → N(4S), conduit à la formation d’atomes d’azote excités N(4P/2D). La production de ces espèces azotées excitées en phase solide joue un rôle prépondérant dans la dissociation des espèces hydrogénées qui pourrait être la première étape dans l’origine de la complexification moléculaire du milieu interstellaire. / In interstellar medium, many hydrogen-containing molecules such as CH4, NH3 or CH3OH may be dissociated, with the contribution of cosmic ray particles or high-energy photons, becoming one of the most important sources of activated radicals. However, in the core of some dark and dense clouds, without those supplying external energies, other radicals formation pathways under non-energetic condition might exist.In the present Ph-D thesis, we have studied thermal reactions involving small organic compounds and ground state nitrogen atoms N(4S), in solid phase, at cryogenic temperatures from 3 to 50 K, using a Fourier Transform InfraRed Spectroscopy (FTIR) analysis. We have shown that gradual heating, between 3 and 10 K, allow to induce of the nitrogen atoms mobility in the solid sample stimulating the N(4S) – N(4S) recombination processes. Such recombinations result in the formation of a very reactive metastable molecular nitrogen N2(A) which through energetic transfer processes with N(4S) atoms can lead to the formation of excited nitrogen atoms N(4P/2D). The production of those excited nitrogen species in solid phase plays an important role in the dissociation of H-containing species which may be the first step in the origin of the molecular complexity of the interstellar medium.

Climate change is no longer imminent but eminent. To combat climate change, effective, efficient and smart energy use is imperative. Thermal energy storage (TES) with phase change materials (PCMs) is one attractive choice to realize this. Besides suitable phase change temperatures and enthalpies, the PCMs should also be robust, non-toxic, environmental-friendly and cost-effective. Cost-effective PCMs can be realized in bulk blends. Blends however do not have robust phase change unless chosen articulately. This thesis links bulk blends and robust, cost-effective PCMs via the systematic design of blends as PCMs involving phase equilibrium evaluations. The key fundamental phase equilibrium knowledge vital to accurately select robust PCMs within blends is established here. A congruent melting composition is the most PCM-ideal among blends. Eutectics are nearly ideal if supercooling is absent. Any incongruent melting composition, including peritectics, are unsuitable as PCMs. A comprehensive state-of-the-art evaluation of the phase equilibrium-based PCM design exposed the underinvestigated categories: congruent melting compositions, metal alloys, polyols and fats. Here the methods and conditions essential for a comprehensive and transparent phase equilibrium assessment for designing PCMs in blends are specified. The phase diagrams of the systems erythritol-xylitol and dodecane-tridecane with PCM potential are comprehensively evaluated. The erythritol-xylitol system contains a eutectic in a partially isomorphous system unlike in a non-isomorphous system as previous literature proposed. The dodecane-tridecane system forms a probable congruent minimum-melting solid solution, but not a maximum-melting liquidus or a eutectic as was previously proposed. The sustainability aspects of a PCM-based TES system are also investigated. Erythritol becomes cost-effective if produced using glycerol from bio-diesel production. Olive oil is cost-effective and has potential PCM compositions for cold storage. A critical need exists in the standardization of methods and transparent results reporting of the phase equilibrium investigations in the PCM-context. This can be achieved e.g. through international TES collaboration platforms. / Energi är en integrerad del av samhället men energiprocesser leder till miljöbelastning, och klimatförändringar. Därför är effektiv energianvändning, ökad energieffektivitet och smart energihantering nödvändigt. Värmeenergilagring (TES) är ett attraktivt val för att bemöta detta behov, där ett lagringsalternativ med hög densitet är s.k. fasomvandlingsmaterial (PCM). Ett exempel på ett billigt, vanligt förekommande PCM är systemet vatten-is, vilket har använts av människor i tusentals år. För att tillgodose de många värme- och kylbehov som idag uppstår inom ett brett temperaturintervall, är det viktigt med innovativ design av PCM. Förutom lämplig fasförändringstemperaturer, entalpi och andra termofysikaliska egenskaper, bör PCM också ha robust fasändring, vara miljövänlig och kostnadseffektiv. För att förverkliga storskaliga TES system med PCM, är måste kostnadseffektivitet och robust funktion under många cykler bland de viktigaste utmaningarna. Kostnadseffektiva PCM kan bäst erhållas från naturliga eller industriella material i bulkskala, vilket i huvudsak leder till materialblandningar, snarare än rena ämnen. Blandningar uppvisar dock komplexa fasförändringsförlopp, underkylning och/eller inkongruent smältprocess som leder till fasseparation. Denna doktorsavhandling ger ny kunskap som möjliggör att bulkblandningar kan bli kostnadseffektiva och robusta PCM-material, med hjälp av den systematiskutvärdering av fasjämvikt och fasdiagram. Arbetet visar att detta kräver förståelse av relevanta grundläggande fasjämviktsteorier, omfattande termiska och fysikalisk-kemiska karakteriseringar, och allmänt tillämpliga teoretiska utvärderingar. Denna avhandling specificerar befintlig fasjämviktsteori för PCM-sammanhang, men sikte på att kunna välja robusta PCM blandningar med specifika egenskaper, beroende på tillämpning. Analysen visar att blandningar med en sammansättning som leder till kongruent smältande, där faser i jämvikt har samma sammansättning, är ideala bland PCM-blandningar. Kongruent smältande fasta faser som utgör föreningar eller fasta lösningar av ingående komponenter är därför ideala. Eutektiska blandningar är nästan lika bra som PCM, så länge underkylning inte förekommer. Därmed finns en stor potential för att finna och karakterisera PCM-ideala blandningar som bildar kongruent smältande föreningar eller fasta lösningar. Därigenom kan blandningar med en skarp, reversibel fasändring och utan fasseparation erhållas – egenskaper som liknar rena materialens fasändringsprocess. Vidare kan man, via fasdiagram, påvisa de blandningar som är inkongruent smältande, inklusive peritektiska blandningar, som är direkt olämpliga som PCM. Denna avhandling ger grundläggande kunskap som är en förutsättning för att designa PCM i blandningar. Genom en omfattande state-of-the-art utvärdering av fas-jämviktsbaserad PCM-design lyfter arbetet de PCM-idealiska blandningarna som hittills inte fått någon uppmärksamhet, såsom kongruenta smältande blandningar, och materialkategorierna metallegeringar, polyoler och fetter. Resultatet av arbetet visar dessutom att vissa PCM-material som ibland föreslås är direkt olämpliga då fasdiagram undersöks, bl a pga underkylning och även peritektiska system med fasseparation och degradering av kapaciteten (t ex Glauber-salt och natriumacetat-trihydrat). Denna avhandling specificerar och upprättar grundläggande teori samt tekniker, tillvägagångssätt och förhållanden som är nödvändiga för en omfattande och genomsynlig fasjämviktsbedömning, för utformning av PCM från blandningar för energilagering. Med detta som bas har följande fasdiagramtagits fram fullständigt: för erytritol-xylitol och för dodekan-tridekan, med PCM-potential för låg temperaturuppvärmning (60-120 °C) respektive frysning (-10 °C till -20 °C) utvärderas fullständigt. Erytritol-xylitol systemet har funnits vara eutektiskt i ett delvis isomorft system, snarare än ett icke-isomorft system vilket har föreslagits tidigare litteratur. Dodekan-tridekan systemet bildar ett system med kongruent smältande fast lösning (idealisk som en PCM) vid en minimumtemperatur, till skillnad från tidigare litteratur som föreslagt en maximumtemperatur, eller ett eutektiskt system. Teoretisk modellering av fasjämvikt har också genomförts för att komplettera det experimentella fasdiagrammet för systemet erytritol-xylitol. Efter granskning av de metoder som använts tidigare i PCM-litteraturen har här valts ett generiskt tillvägagångssätt (CALPHAD-metoden). Denna generiska metod kan bedöma vilken typ av material och fasändring som helst, till skillnad från en tidigare använda metoder som är specifika för materialtyper eller kemiska egenskaper. Denna teoretiska studie bekräftar termodynamiskt solvus, solidus, eutektisk punkt och erytritol-xylitol fasdiagrammet i sin helhet. Vad gäller hållbarhetsaspekter med PCM-baserad TES, lyfter denna avhandling fokus på förnybara och kostnadseffektiva material (t.ex. polyoler och fetter) som PCM. Som exempel har här undersökts erytritol och olivolja, med förnybart ursprung. Erytritol skulle kunna bli ett kostnadseffektivt PCM (163 USD/kWh), om det produceras av glycerol vilket är en biprodukt från biodiesel/bioetanolframställning. Olivolja är ännu ett kostnadseffektivt material (144 USD/kWh), och som här har påvisats innehålla potentiella PCM sammansättningar med lämpliga fasändringsegenskaper för kylatillämpningar. En övergripande slutsats från denna avhandling är att det finns ett behov av att standardisera tekniker, metoder och transparent resultatrapportering när det gäller undersökningar av fasjämvikt och fasdiagram i PCM-sammanhang. Internationella samarbetsplattformar för TES är en väg att koordinera arbetet. / <p>QC 20170830</p>

Magister Public Health - MPH / HIV support groups have been widely adopted as part of care and support interventions in Zambia, yet there is very little research on the effectiveness of these groups in meeting the needs of the PLWHIV from the perspective of those who join them. This case study looks at a selected support group for People Living with HIV and AIDS (PLWHIV) facilitated by the Flying Angels, a faith based non-governmental organization established in 2007 by the Living Assemblies of God Church, in Ng‟ombe Township, Lusaka. The Support Group brings together around eighty young and old, married and single, men and women living with HIV and AIDS, to share experiences and find ways of coping with their situation. The qualitative case study sought to obtain a rich understanding of the experiences of members with a view to understanding the support they needed, the aspects of the support group that are relevant and effective to their situation, and which are not. In-depth interviews and focus group discussions methods were used to collect data. Discussion and interviews were audio-taped. Audio-recordings were translated during transcription, data organized, coded and thematically analysed.

1-Aza-2-azoniaallene salts are reactive intermediates that undergo [3+2] cycloaddition with many different types of multiple bonds. For the past several years, the Brewer group has studied the reactivity of these intermediates in intramolecular reactions, and have discovered that these cationic heteroallenes can react through a variety of other, mechanistically distinct, pathways to give different classes of nitrogen heterocycles. For example, prior work in the Brewer group revealed that 1-aza-2-azoniaallene salts could react in an intramolecular [4+2] cycloaddition reaction to give protonated azomethine imine salts containing a 1,2,3,4-tetrahydrocinnoline scaffold. Further study of the scope and limitations of this Diels-Alder-like reaction are described herein. These studies primarily focused on how varying the N-aryl ring and alkene substituents affected the reaction. We discovered that in several instances, the metal mediated reaction did not facilitate the cycloaddition very well, so we searched for alternative ways to facilitate the reaction. We discovered that a non-metallic Lewis acid (TMSOTf) provided very clean products with α-chloroazo compounds. I hypothesized that changing the leaving group adjacent to the azo might further improve the reaction. With this in mind, I developed a technique to prepare α-trifluoroacetoxyazo compounds by treating aryl hydrazones with trifluoroacetoxy dimethylsulfonium trifluoroacetate. This technique is compatible with all types of functional groups including nitro aryl compounds, which gave low yields of the corresponding chloroazo derivatives. Importantly, these α-trifluoroacetoxyazo compounds gave even better cycloaddition results when treated with TMSOTf, and this method is more practical, more environmentally friendly, and greener than the metal mediated technique. This process even returned sterically hindered products in high yield, and provide a dearomatized non-protonated azomethine imine salt, which further verified the proposed mechanism of the [4+2] cycloaddition. Azomethine imines are well known to undergo 1,3-dipolar cycloadditions with alkenes. We wondered if the protonated azomethine imine salts generated by the [4+2] cycloaddition could be used in a subsequent base-mediated [3+2] cycloaddition to generate structurally complex tetra- or pentacyclic products. We were pleased to find that the protonated azomethine imines indeed reacted smoothly with a variety of π-system in the presence of triethylamine to give the corresponding cycloadducts in high yields with moderate to high diastereoselectivities. In an attempt to understand the diastereoselectivity of these [3+2] cycloadditions better, I modeled them computationally.

The progress in device performance of modern microelectronic technology is mainly driven by down-scaling. In the near future, this road will probably reach a point where physical limits make even more down-scaling impossible. The substitution of single components materialwise over the last decades, like high-k dielectrics or metal gates, has been a suitable approach to foster performance improvements. In this scheme, the integration of high-mobility III-V compound semiconductors as channel materials into Si technology is a promising route to follow for the next one or two device generations. III-V integration, today, is conventionally performed by using techniques like molecular beam epitaxy or wafer bonding which utilize solid phase crystallization but suffer to strain due to the lattice mismatch between III-V compounds and Si. An alternative approach using sequential ion beam implantation in combination with a subsequent flash lamp annealing is presented in this work. Using this technique, nanocrystals from various III-V compounds have been successfully integrated into bulk Si and Ge as well as into thin Si layers which used either SOI substrates or were grown by plasma-enhanced chemical vapour deposition. The III-V compounds which have been fabricated are GaP, GaAs, GaSb, InP, InAs, GaSb and InxGa1-xAs with variable composition. The structural properties of these nanocrystals have been investigated by Rutherford backscattering, scanning electron microscopy and transmission electron microscopy, including bright-field, dark-field, high-resolution, high-angle annular dark-field and scanning mode imaging, electron-dispersive x-ray spectroscopy and energy-filtered element mapping. Furthermore, Raman spectroscopy and X-ray diffraction have been performed to characterise the nanocrystals optically. In Raman spectroscopy, the characteristic transversal and longitudinal optical phonon modes of the different III-V compounds have been observed. These signals proof that the nanocrystals have formed by the combination of ion implantation and flash lamp annealing. Additionally, the appearance of the typical phonon modes of the respective substrate materials verifies recrystallization of the substrate by the flash lamp after amorphisation during implantation. In the bulk Si samples, the nanocrystals have a circular or rectangular lateral shape and they are randomly distributed at the surface. Their cross-section has either a hemispherical or triangular shape. In bulk Ge, there are two types of precipitates: one at the surface with arbitrary shape and another one buried with circular shape. For the thin film samples, the lateral shape of the nanocrystals is more or less arbitrary and they feature a block-like cross-section which is limited in height by the Si layer thickness. Regarding crystalline quality, the nanocrystals in all samples are mainly single-crystalline with only a few number of stacking faults. However, the crystalline quality in the bulk samples is slightly better than in the thin films. The X-ray diffraction measurements display the (111), (220) and (311) Bragg peaks for InAs and GaAs as well as for the InxGa1-xAs where the peaks shift with increasing In content from GaAs towards InAs. The underlying formation mechanism is identified as liquid phase epitaxy. Hereby, the ion implantation leads to an amorphisation of the substrate material which is then molten by the subsequent flash lamp annealing. This yields a homogeneous distribution of the implanted elements within the melt due to their strongly increased diffusivity in the liquid phase. Afterwards, the substrate material starts to recrystallize at first and an enrichment of the melt with group-III and group-V elements takes place due to segregation. When the temperature is low enough, the III-V compound semiconductor starts to crystallize using the recrystallized substrate material as a template for epitaxial growth. In order to gain control over the lateral nanocrystal distribution, an implantation mask of either aluminium or nickel is introduced. Using this mask, only small areas of the samples are implanted. After flash lamp treatment, nanocrystals form only in these small areas, which allows precise positioning of them. An optimal implantation window size with an edge length of around 300nm has been determined to obtain one nanocrystal per implanted area. During an additional experiment, the preparation of Si nanowires using electron beam lithography and reactive ion etching has been conducted. Hereby, two different processes have been investigated; one using a ZEP resist, a lift-off step and a Ni hard mask and another one using a hydrogen silsesquioxane resist which is used directly as a mask for etching. The HSQ-based process turned out to yield Si nanowires of better quality. Combining both, the masked implantation and the Si nanowire fabrication, it might be possible to integrate a single III-V nanocrystal into a Si nanowire to produce a III-V-in-Si-nanowire structure for electrical testing. / Der Fortschritt in der Leistungsfähigkeit der Bauelemente moderner Mikroelektroniktechnologie wird hauptsächlich durch das Skalieren vorangetrieben. In naher Zukunft wird dieser Weg wahrscheinlich einen Punkt erreichen, an dem physikalische Grenzen weiteres Herunterskalieren unmöglich machen. Der Austausch einzelner Teile auf Materialebene, wie Hoch-Epsilon-Dielektrika oder Metall-Gate-Elektroden, war während der letzten Jahrzehnte ein geeigneter Ansatz, um die Leistungsverbesserung voranzubringen. Nach diesem Schema ist die Integration von III-V-Verbindungshalbleiter mit hoher Mobilität ein vielversprechender Weg, dem man für die nächsten ein oder zwei Bauelementgenerationen folgen kann. Heutzutage erfolgt die III-V-Integration konventionell mit Verfahren wie der Molekularstrahlepitaxie oder dem Waferbonden, welche die Festphasenkristallisation nutzen, die aber aufgrund der Gitterfehlanpassung zwischen III-V-Verbindungen und Silizium an Verspannungen leiden. In dieser Arbeit wird ein alternativer Ansatz präsentiert, welcher die sequenzielle Ionenstrahlimplantation in Verbindung mit einer darauffolgenden Blitzlampentemperung ausnutzt. Mit Hilfe dieses Verfahrens wurden Nanokristalle verschiedener III-V-Verbindungshalbleiter erfolgreich in Bulksilizium- und -germaniumsubstrate sowie in dünne Siliziumschichten integriert. Für die dünnen Schichten wurden hierbei entweder SOI-Substrate verwendet oder sie wurden mittels plasmagestützer chemischer Gasphasenabscheidung gewachsen. Die hergestellten III-V-Verbindungen umfassen GaP, GaAs, GaSb, InP, InAs, InSb und InxGa1-xAs mit veränderbarer Zusammensetzung. Die strukturellen Eigenschaften dieser Nanokristalle wurden mit Rutherford-Rückstreu-Spektroskopie, Rasterelektronenmikroskopie und Transmissionselektronenmikroskopie untersucht. Bei der Transmissionelektronenmikroskopie wurden die Hellfeld-, Dunkelfeld-, hochauflösenden, “high-angle annular dark-field” und Rasteraufnahmemodi sowie die energiedispersive Röntgenspektroskopie und die energiegefilterte Elementabbildung eingesetzt. Darüber hinaus wurden Ramanspektroskopie- und Röntgenbeugungsmessungen durchgeführt, um die Nanokristalle optisch zu charakterisieren. Mittels Ramanspektroskopie wurden die charakteristischen transversal- und longitudinal-optischen Phononenmoden der verschiedenen III-V-Verbindungen beobachtet. Diese Signale beweisen, dass sich unter Verwendung der Kombination von Ionenstrahlimplantation und Blitzlampentemperung Nanokristalle bilden. Weiterhin zeigt das Vorhandensein der typischen Phononenmoden der jeweiligen Substratmaterialien, dass die Substrate aufgrund der Blitzlampentemperung rekristallisiert sind, nachdem sie durch Ionenimplantation amorphisiert wurden. In den Bulksiliziumproben besitzen die Nanokristalle eine kreisförmige oder rechteckige Kontur und sind in zufälliger Anordnung an der Oberfläche verteilt. Ihr Querschnitt zeigt entweder eine Halbkugel- oder dreieckige Form. Im Bulkgermanium gibt es zwei Arten von Ausscheidungen: eine mit willkürlicher Form an der Oberfläche und eine andere, vergrabene mit sphärischer Form. Betrachtet man die Proben mit den dünnen Schichten, ist die laterale Form der Nanokristalle mehr oder weniger willkürlich und sie zeigen einen blockähnlichen Querschnitt, welcher in der Höhe durch die Siliziumschichtdicke begrenzt ist. Bezüglich der Kristallqualität sind die Nanokristalle in allen Proben mehrheitlich einkristallin und weisen nur eine geringe Anzahl an Stapelfehlern auf. Jedoch ist die Kristallqualität in den Bulkmaterialien ein wenig besser als in den dünnen Schichten. Die Röntgenbeugungsmessungen zeigen die (111), (220) und (311) Bragg-Reflexe des InAs und GaAs sowie des InxGa1-xAs, wobei sich hier die Signalpositionen mit steigendem Gehalt an Indium von GaAs zu InAs verschieben. Als zugrundeliegender Bildungsmechanismus wurde die Flüssigphasenepitaxie identifiziert. Hierbei führt die Ionenstrahlimplantation zu einer Amorphisierung des Substratmaterials, welches dann durch die anschließende Blitzlampentemperung aufgeschmolzen wird. Daraus resultiert eine homogene Verteilung der implantierten Elemente in der Schmelze, da diese eine stark erhöhte Diffusivität in der flüssigen Phase aufweisen. Danach beginnt zuerst das Substratmaterial zu rekristallisieren und es kommt aufgrund von Segregationseffekten zu einer Anreicherung der Schmelze mit den Gruppe-III- und Gruppe-V-Elementen. Wenn die Temperatur niedrig genug ist, beginnt auch der III-V-Verbindungshalbleiter zu kristallisieren, wobei er das rekristallisierte Substratmaterial als Grundlage für ein epitaktisches Wachstum nutzt. In der Absicht Kontrolle über die laterale Verteilung der Nanokristalle zu erhalten, wurde eine Implantationsmaske aus Aluminium beziehungsweise Nickel eingeführt. Durch die Benutzung einer solchen Maske wurden nur kleine Bereiche der Proben implantiert. Nach der Blitzlampentemperung werden nur in diesen kleinen Bereichen Nanokristalle gebildet, was eine genaue Positionierung dieser erlaubt. Es wurde eine optimale Implantationsfenstergröße mit einer Kantenlänge von ungefähr 300 nm ermittelt, damit sich nur ein Nanokristall pro implantierten Bereich bildet. Während eines zusätzlichen Experiments wurde die Präparation von Siliziumnanodrähten mit Hilfe von Elektronenstrahllithografie und reaktivem Ionenätzen durchgeführt. Hierbei wurden zwei verschiedene Prozesse getestet: einer, welcher einen ZEP-Lack, einen Lift-off-Schritt und eine Nickelhartmaske nutzt, und ein anderer, welcher einen HSQ-Lack verwendet, der wiederum direkt als Maske für die Ätzung dient. Es stellte sich heraus, dass der HSQ-basierte Prozess Siliziumnanodrähte von höherer Qualität liefert. Kombiniert man beides, die maskierte Implantation und die Siliziumnanodrahtherstellung, miteinander, sollte es möglich sein, einzelne III-V-Nanokristalle in einen Siliziumnanodraht zu integrieren, um eine III-V-in-Siliziumnanodrahtstruktur zu fertigen, welche für elektrische Messungen geeignet ist.

This thesis investigates a technique to estimate the risk of the mean-variance (MV) portfolio optimization problem. We call this technique the Scaling technique. It provides a better estimator of the risk of the MV optimal portfolio. We obtain this result for a general estimator of the covariance matrix of the returns which includes the correlated sampling case as well as the independent sampling case and the exponentially weighted moving average case. This gave rise to the paper, [CMcS]. Our result concerning the Scaling technique relies on the moments of the inverse of compound Wishart matrices. This is an open problem in the theory of random matrices. We actually tackle a much more general setup, where we consider any random matrix provided that its distribution has an appropriate invariance property (orthogonal or unitary) under an appropriate action (by conjugation, or by a left-right action). Our approach is based on Weingarten calculus. As an interesting byproduct of our study - and as a preliminary to the solution of our problem of computing the moments of the inverse of a compound Wishart random matrix, we obtain explicit moment formulas for the pseudo-inverse of Ginibre random matrices. These results are also given in the paper, [CMS]. Using the moments of the inverse of compound Wishart matrices, we obtain asymptotically unbiased estimators of the risk and the weights of the MV portfolio. Finally, we have some numerical results which are part of our future work.

La présente thèse étudie le rôle de l'accent prosodique (accent de mot vs. accent de syntagme) lors du traitement auditif de paires minimales ambigües (mots composés vs. syntagmes) du chinois mandarin. Deux types de paires minimales ont été utilisés: 1) Mots composés avec un ton neutre (ex: dong3xi0 « chose ») vs. Syntagme avec un ton plein (ex: dong3xi1 « est et ouest ») qui se distinguent par la réalisation du ton sur la syllabe finale ; 2) Mots composés Verbe-Nom (VN) (ex: 'chaofan « riz frit ») vs. Syntagmes Verbe-Objet (VO) (ex: chao'fan « frire du riz ») se distinguant par la position de l'accent prosodique. Nos données comportementales et neurophysiologiques démontrent que : 1) la syllabe finale est plus longue et l'étendue de la F0 est plus large dans les VO que dans les VN, 2) la prosodie assiste le système de traitement pour anticiper la structure morphologique des séquences ambigües, et 3) un traitement hiérarchique « de droite-à-gauche » des informations prosodiques en complément d'un traitement séquentiel « de gauche-à-droite » prend place en chinois mandarin. Prises dans leur ensemble, nos données précisent la description fonctionnelle et structurale du modèle Prosody-Assisted-Processing (PAP) pour le chinois mandarin. / The present thesis investigates the role of prosodic stress (i.e. lexical versus phrasal stress) on the auditory processing of Mandarin Chinese ambiguous compound /phrase minimal pairs. Two types of compound/phrase minimal pairs were used: 1) Compound word with a neutral tone (e.g. dong3xi0 "thing") vs. phrase with a full tone (e.g. dong3xi1 "east and west") distinguished by the final syllable tone realization; 2) Verb-Noun (VN) compound word (e.g. 'chaofan "fried rice") and Verb-Object (VO) phrase (e.g. chao'fan "fry the rice") distinguished by the position of the prosodic stress. Combined behavioral and neurophysiological data demonstrate that 1) the final syllable was more lengthened and the F0 range was larger in VO than in VN, 2) prosodic structure does assist the processing system in anticipating morphological structure, and 3) a right-to-left hierarchical processing of prosodic information in addition to a sequential left-to-right one is involved during the processing of ambiguous spoken sequences in Mandarin Chinese. Taken together, our findings allowed us to precise the functional and structural description of the Prosody-Assisted-Processing (PAP) model for Mandarin Chinese.

La recrudescence des maladies dégénératives ces dernières décennies dans le monde a amené plusieurs chercheurs et médecins à médiatiser les antioxydants à cause des vertus qu’on leur prête: de la protection contre les maladies cardiovasculaires à la prévention de certains cancers. Le présent travail a été mené avec pour objectif principal d’évaluer le pouvoir antioxydant des épices entrant dans la préparation de la sauce en vue du développement d’un complément alimentaire nutraceutique. Pour ce faire, vingt épices largement consommées ont été choisies sur la base d’une enquête exploratoire menée au Cameroun. Les différentes épices réduites en poudres ont été analysées pour leurs teneurs en composition nutritionnelle. Le pouvoir antiradicalaire in vitro des extraits méthanoliques des différentes épices a été déterminé ainsi que le pouvoir anti-inflammatoire et antistress sur des rats adultes à stress induit. Les résultats obtenus ont montré des variations très significatives de la composition des épices. L’activité antioxydante utilisant la méthode au N’ N-diphényl-N’-picrylhydrazyl (DPPH), au « trolox equivalent antioxidant capacity » (TEAC) et le pouvoir réducteur total (PRT) ont révélé que Z. leprieurii et D. glomerata présentent les activités particulièrement élevées. Les extraits de ces deux épices ont servi de base à la préparation de mélange dont l’effet a été testé sur des rats mâles à inflammation induite. Les résultats obtenus ont montré que les épices individuelles et leur mélange à des doses de 100 mg/kg et 150 mg/kg présentent une activité anti-inflammatoire importante comparable à ceux commerciaux: inodméthacine, déxaméthasone et célécoxib. La variation de la teneur en malonaldéhyde (marqueur de l’oxydantion lipidique) a révélée l’action antioxydante in vivo des extraits, démontrant ainsi leur potentiel dans le développement de compléments alimentaires à effet antistress / Increasing evidences from current research point to the fact that certain disease conditions can be prevented through the consumption of antioxidant rich foods. The present work was carried out to evaluate the antioxidant potentials of twenty Cameroonian spices commonly used in some Cameroonian cuisine. The nutritional properties of spices, the in vitro antioxidant potential of their methanolic extracts as well as the in vivo antioxidant potential of the methanolic extracts of some selected samples were determined. The antioxidant activity brought about by N’ N-diphenyl-N’-picrylhydrazyl (DPPH), «trolox antioxidant equivalent capacity» (TEAC) and the total reduction power (PRT) methods have revealed that Z. leprieurii and D. glomerata presented the highest activities. The extracts of the two spices were used to prepare a mixture whose effect was tested on male rats with induced inflammation. The results obtained indicate that the individual spices and their mixture at 100 mg/kg and 150 mg/kg present an important anti-inflammatory activity comparable to that of commercial anti-inflammatory like indomethacin, dexamethasone and celecoxib. The variation of malondialdehyde content (a lipidic oxidant marquer) revealed the in vivo antioxidant action of extracts, thus demonstrating their potential for the development of functional foods with anti-stress effect

Metrodorea A. St.-Hil. é um gênero neotropical de Rutaceae, com espécies que apresentam folhas compostas ou unifolioladas e heterofilia, além de uma intrigante estrutura protetora de gemas em sua base. Filogenias moleculares disponíveis para a família apontam para uma necessidade de revisão de sua classificação tradicional, que deve encontrar respaldo em sinapomorfias morfológicas adequadas para os novos grupos estabelecidos. Foi realizado um estudo da morfanatomia e ontogênese foliar de Metrodorea e grupos relacionados, observadas sob uma perspectiva filogenética, com dados disponíveis na literatura e obtidos de técnicas usuais em anatomia vegetal. No primórdio de folha ocorre formação da base seguida de diferenciação acrópeta de primórdios de folíolos, sendo dois proximais pareados e um terminal nas folhas trifolioladas, mas apenas o terminal nas folhas simples e unifolioladas. Rudimentos de folíolos foram observados em espécies heterofilas de Metrodorea. Na base foliar das espécies deste gênero a estrutura protetora inicia-se como apêndices pareados, revelando uma condição estipular. A quantidade de folíolos é dependente de uma maior ou menor determinação do primórdio foliar e sua redução pode ter sido favorecida pela perda de folíolos durante uma restrição do espaço necessário para o desenvolvimento. Metrodorea tem como sinapomorfias a presença de aborto de folíolos, estípula intrapeciolar vascularizada, tricomas glandulares proximais adaxiais no pecíolo, folíolos evidentemente peciolulados, duas sementes por lóculo no fruto e estivação valvar da corola. Suas relações infragenéricas são debatidas de acordo com a localização dos cristais, forma de aderência da base das folhas e presença ou não de tricomas na lâmina foliar. A proximidade do gênero com Raulinoa é sustentada por uma maior quantidade de sinapomorfias morfológicas do que com outros gêneros. A monofilia de Esenbeckia não encontra apoio em nossos dados e Helietta + Balfourodendron (outrora de outra subfamília) são mais relacionados a Esenbeckia, Raulinoa e Metrodorea (antigas Pilocarpinae) do que com Pilocarpus, relação sustentada pela presença de tricomas glandulares no pecíolo, cristais prismáticos romboédricos, carpelos conatos e apófises dorsais do fruto / Metrodorea A. St.-Hil. is a Neotropical genus of Rutaceae, with species that have compound or 1-foliolated leaves and heterophylly, in addition to an intriguing bud-protecting structure on its basis. Available molecular phylogenies for the family indicate a need in reviewing its traditional classification, which must find support in appropriate morphological synapomorphies that support the new established groups. We conducted a study of leaf ontogeny and morphoanatomy of Metrodorea and related groups, under a phylogenetic framework, with data available in the literature and obtained from standard techniques in plant anatomy. In leaf primordia, the base formation is followed by acropetal differentiation of leaflet primordia, two paired proximal and one terminal on 3-foliated leaves, but only the terminal one on simple and 1-foliolated leaves. Leaflets rudiments were observed in heterophyllous species of Metrodorea. In species of this genus, at the base of the leaf, the protective structure emerges as paired appendages, revealing a stipular condition. The number of leaflets is dependent upon a greater or lesser determination of leaf primordium and its reduction may have been favored by the loss of leaflets as consequence of a restriction of the space required for development. Metrodorea synapomorphies found were: aborted leaflets, vascularized intrapeciolar stipules, glandular hairs in the proximal and adaxial region of the petiole, petiolulated leaflets, two seeds per locule in the fruit and valvar aestivation of the corolla. Their infrageneric relations are discussed according to the location of the crystals, adherence of the base of the leaves and the presence or absence of trichomes on the leaf blade. The close-relationship of the genus with Raulinoa is supported by a greater number of morphological synapomorphies than with other genera. The monophyly of Esenbeckia finds no support in our data and Helietta + Balfourodendron (formerly of another subfamily) are more related to Esenbeckia, Raulinoa and Metrodorea (former Pilocarpinae) than Pilocarpus, and such relationship is sustained by the presence of glandular hairs on the petiole, rhombohedral prismatic crystals, conate carpels and dorsal apophysis of the fruit

Made available in DSpace on 2016-05-02T13:53:48Z (GMT). No. of bitstreams: 1 Mario Viana Paredes FilhoDissertacao.pdf: 2880775 bytes, checksum: 811c5430de6e51adbac8bc361dd36a3d (MD5) Previous issue date: 2013-08-26 / The waste without proper treatment constitute an environmental problem and its management should be conducted appropriately, either it be for its final disposal or recycling. Among the conventional alternatives to the waste treatment are the landfill, incineration, use of biodigesters and composting. The composting is a controlled aerobic decomposition process, where through this, we obtain a final product stable, sanitized, rich in humic compounds and whose use in soil offer no hazard to the environment and public health. The efficiency of the composting process is directly related to techniques that can provide great conditions in wich the microorganisms can multiply and work in the degradation of organic matter, such as the use of effective microorganisms (EM). This present study had as aimed to evaluate the reduction of the period of composting and the influence of the use of effective microorganisms in compost quality of the organic compound. The work was developed in the composting plant called Nutriorg Manufacture of Organic Fertilizers LTDA, located in São Sebastião da Bela Vista, MG, from March 2013 to July 2013. The preparation of the EM was performed using 4 m3 yogurt, 40 kg of wheat flour, 30 kg of sugar, 0,2 kg of bread yeast and 1 m3 of water. 5 windrows without EM where the same presented 1.5 m in height, 3m of base and 100 m of length, resulting in a volume of 225 m3. For the application of the EM in the windrows, the same was previously diluted in a proportion of 1:20, where it was applied in approximately 110 tons of waste mass. The collected data were subjected to Student's t test at the level of 5% significance to compare the averages of the obtained samples in the samples without and with EM, where the physical and chemical parameters were evaluated. Also were evaluated samples without and with EM to the biological agents and heavy metals to determine the quality of the compost produced. That was proved the reduction in the period of composting through the framing elements of CTC, pH and C / N ratio, indicating if the decomposition of organic matter reached desirable levels to be accorded to the status of the compound and for the "hand test". The performed statistical analyzes indicated a non-significant (P> 0.05) for the physico-chemical parameters without and with EM. Regarding biological agents and heavy metals, the same fell into the legislation and there was a significant reduction in the parameters of the compound with the use of EM. It is concluded that EM reduced composting period, however the effect was not justified the use of effective microorganisms in the composting process because without the compound EM, it was observed that the concentration of nutrients in the compound with EM were similar. / Os resíduos, sem o devido tratamento, constituem um problema ambiental e o seu gerenciamento deve ser conduzido de forma adequada, seja pela sua disposição final ou pela reciclagem. Entre as alternativas convencionais para o tratamento de resíduos estão: o aterro sanitário, a incineração, o uso de biodigestores e a compostagem. A compostagem é um processo de decomposição aeróbia controlada, onde através deste, obtêm-se um produto final estável, higienizado, rico em compostos húmicos e cuja utilização no solo não oferece riscos ao meio ambiente e à saúde pública. A eficiência do processo de compostagem está diretamente relacionada a técnicas que podem proporcionar condições ótimas para que os micro-organismos possam se multiplicar e atuar na degradação da matéria orgânica, como a utilização de micro-organismos eficazes (EM). O presente trabalho teve como objetivo avaliar a redução do período de compostagem e a influência do uso de micro-organismos eficazes na qualidade do composto orgânico. O trabalho foi desenvolvido na usina de compostagem denominada Nutriorg Fabricação de Adubos Orgânicos LTDA, situada no município de São Sebastião da Bela Vista, MG, no período de março de 2013 a julho de 2013. Foi realizado o preparo do EM utilizando-se 4 m3 de iogurte, 40 kg de farinha de trigo, 30 kg de açúcar, 0,2 kg de fermento de pão e 1 m3 de água. Foram montadas 5 leiras sem EM e 5 leiras com EM, onde as mesmas apresentaram 1,5 m de altura, 3 m de base e 100 m de comprimento,obtendo-se um volume de 225 m3. Para a aplicação do EM nas leiras, o mesmo foi previamente diluído numa proporção de 1:20, onde foi aplicado em cerca de 110 toneladas de massa de resíduos. Os dados coletados foram submetidos ao teste t de Student ao nível de 5 % de significância para comparar as médias das amostras obtidas nas amostras sem EM e com EM, onde se avaliaram os parâmetros físico-químicos. Foram avaliadas amostras sem EM e com EM para os agentes biológicos e metais pesados para determinar a qualidade do composto produzido. Comprovou-se a redução no período de compostagem através do enquadramento dos elementos CTC, pH e relação C/N, que indicam se a decomposição da matéria orgânica atingiu níveis desejáveis para que seja atribuída a qualidade do composto e pelo teste da mão . As análises estatísticas realizadas indicaram uma não significância (P>0,05) para os parâmetros físico-químicos sem EM e com EM. Quanto aos agentes biológicos e metais pesados, os mesmos enquadraram-se na legislação e ocorreu uma redução expressiva nos parâmetros do composto com o uso do EM. Conclui-se que o EM reduziu o período de compostagem, entretanto não se justificou a influência no uso de micro-organismos eficazes no processo de compostagem, pois no composto sem EM, observou-se que a concentração de nutrientes no composto com EM foram semelhantes.