Especially during the last hundred years, the church has become more aware of the work of the Holy Spirit. This interest has not only occurred in the holiness, pentecostal and charismatic movements, but in the church at large as well. Some have described this rediscovery as a "second great outpouring of the Holy Spirit" while others have spurned it as soulish emotionalism and ecstasy. Still others declare that the church has discovered nothing new and in a sense no new Pentecost has occurred; for to speak of the church at all one must speak of "two thousand years of Pentecost". This renewed interest in the Holy Spirit has various exponents with even still more assessments of its value, meaning and direction. All engaged in discussing the Holy Spirit today from various theological stances use biblical language concerning the Holy Spirit. Often this usage does not adequately consider the varied contextual and redactional significance of these expressions. This thesis analyzes one such phrase, "filled with/full of the Holy Spirit", in Luke-Acts and points out the significance and limitations for the phrase in a Lucan context. When other redactional and traditional points are encountered in Luke-Acts they are analyzed as well. It is apparent that Luke uses fulness of the Spirit as part of his overall programme of presenting the mission of Jesus and its expansion in the witness of the church in terms of the Holy Spirit. It is hoped that a clearer understanding of Luke's use of the concept will clarify the church's use of the phrase and reduce misunderstanding and division in the church over her greatest asset and very ground of being, the Holy Spirit.

Amines are ubiquitous in nature and serve a variety of functions in living organisms. Because of this fact amines are of great biological and pharmaceutical interest. The iridium catalyst (pentamethylcyclopentadienyl) iridium dichloride dimer ([Cp*IrCl2]2) has been used in a number of ways to synthesize new carbon-nitrogen bonds. These studies were directed toward the development of a method for the iridium catalyzed N-alkylation of alpha-amino acid esters as well as the development of a strategy for synthesis of the natural product 275A. We have optimized a method for the N-alkylation for alpha-amino acid esters. Using this method, we have N-alkylated a series of alpha-amino acid esters with a variety of alcohols. We have shown that the N-alkylation of the alpha-amino acid esters works consistently and gives the desired products in moderate to high yields. We have examined the effect of this method on the chiral center of the obtained products by analyzing their optical rotation. Evaluation of these specific rotations indicated racemization was occurring but it is believed that any loss of the chiral center is due to the reaction conditions. Amphibian alkaloids are of great interest to the pharmaceutical and academic communities due to their biological activities. Unfortunately, they are not naturally available in large quantities which makes total synthesis the most common method of generating these compounds for evaluation. One amphibian alkaloid class of interest to us are the Lehmizidines. These are bicyclic ring structures consisting of a 7-member and 5-member ring with a nitrogen bridgehead. The alkaloid, 275A, was selected as a target for a general synthetic approach. This synthetic approach required the synthesis of novel diols. The construction of these diols along with a method for the synthesis of the azepane ring is presented here.

Los beneficios laborales otorgados al sector acuícola, mediante la Ley N° 27460, Ley de Promoción y Desarrollo de la Acuicultura, de fecha 25 de mayo de 2001, consisten en un recorte marcado de algunos beneficios a los que, en principio y en una situación de empleabilidad ideal, el trabajador accedería de manera regular dentro de un régimen general. Por ello, podemos afirmar que estamos frente a normas cuyas consecuencias son claramente asumidas directamente por los trabajadores. Estos recortes de beneficios tienen un objetivo señalado expresamente en la norma: la promoción de la actividad como fuente de alimentación, empleo e ingresos; objetivos que vienen siendo claramente cumplidos, por lo que resulta necesario evaluar la continuidad del otorgamiento de los mencionados beneficios laborales, a la luz de las externalidades que vienen generando a los trabajadores. En este sentido, somos de la opinión que toda medida que restringe beneficios laborales debe estar sujeta a ciertos límites en su aplicación y/o a un plazo de vigencia concreto para su otorgamiento, situación que no ocurre actualmente con esta norma. / The work benefits given to the aquaculture sector through Law N° 27460, Law to Promote and Develop Aquaculture, dated 25 may 2001, consists of a marked limitation of some benefits that, in ideal employment circumstances, the employee would have under general regulations. In this way, these regulations have consequences are clearly borne by the employees. These limited benefits have an objective that is clearly stated in the law: promotion of the activity as a source of food, employment and income; objectives that have been clearly fulfilled given the externalities that employees bear. As such, we believe that all measures that limit work benefits should be subject to limits in their use and/or applied for a fixed period of time, measures that are not currently part of this law.

The application of anaerobic digestion technology is growing worldwide, mainly because of its environmental benefits. Nevertheless, anaerobic degradation is a rather slow and sensitive process. One of the reasons is the recalcitrance nature of certain fractions of the substrate (e.g., lignocelluloses) used for microbial degradation; thus, the hydrolysis becomes the rate-limiting step. The other reason is that the degradation of organic matter is based on a highly dynamic, multi-step process of physicochemical and biochemical reactions. The reactions take place in a sequential and parallel way under symbiotic interrelation of a variety of anaerobic microorganisms, which all together make the process sensitive. The first stage of the decomposition of the organic matter is performed by fast growing (hydrolytic and acid forming) microorganisms, while in the second stage the organic acids produced are metabolized by the slow growing methanogens, which are more sensitive than the acidogens; thus, methanogenesis becomes the rate-limiting step. The first part of this work evaluates the effects of a pretreatment using an organic solvent, N-methylmorpholine-N-oxide (NMMO), on cellulose-based materials in order to overcome the challenge of biomass recalcitrance and to increase the rate of the hydrolysis. NMMO-pretreatment of straw separated from the cattle and horse manure resulted in increased methane yields, by 53% and 51%, respectively, in batch digestion tests. The same kind of pretreatment of the forest residues led to an increase by 141% in the methane production during the following batch digestion assays. The second part of this work evaluates the efficacy of a two-stage process to overcome the second challenge with methanogenesis as the rate-limiting step, by using CSTR (continuous stirred tank reactors) and UASB (up flow anaerobic sludge blanket) on a wide variety of different waste fractions in order to decrease the time needed for the digestion process. In the two-stage semi-continuous process, the NMMO-pretreatment of jeans increased the biogas yield due to a more efficient hydrolysis compared to that of the untreated jeans. The results indicated that a higher organic loading rate (OLR) and a lower retention time could be achieved if the material was easily degradable. Comparing the two-stage and the single-stage process, treating the municipal solid waste (MSW) and waste from several food processing industries (FPW), showed that the OLR could be increased from 2 gVS/l/d to 10 gVS/l /d, and at the same time the HRT could be decreased from 10 to 3 days, which is a significant improvement that could be beneficial from an industrial point of view. The conventional single stage, on the other hand, could only handle an OLR of 3 gVS/l/d and HRT of 7 days.

Changes of semimajor axes of giant planets, which took place 4 billion years ago and evolved the Solar System towards its present state, affected various populations of minor Solar-System bodies. One of these populations was a group of dynamically stable asteroids in the 2:1 mean-motion resonance with Jupiter which reside in two islands of the phase space, denoted A and B, and exhibit lifetimes comparable to the age of the Solar System. The origin of stable asteroids has not been explained so far. Our main goal is to create a viable hypothesis of their origin. We update the resonant population and its physical properties on the basis of up-to-date observational data. Using an N-body model with seven giant planets and the Yarkovsky effect included, we demonstrate that the depletion of island A is faster compared to island B. We then investigate: (i) survivability of primordial resonant asteroids and (ii) capture of the population during planetary migration, using a recently described scenario with an escaping fifth giant planet and a jumping-Jupiter instability. We employ simulations with prescribed migration, smooth late migration and we statistically evaluate the results using dynamical maps. We also model collisions during the last 4 billion years. We conclude that the long-lived group was created by a...

Flavonoids are natural compounds commonly ingested in herbs and vegetables. They are believed to have a positive impact on human organism, in particular by their antioxidant, hepatoprotective and anti-cancer effects. In these days, it is possible to consume high concentrations of these compounds in form of dietary supplements. However it is not clear, whether flavonoids in such unnaturally high concentrations are still beneficial or rather harmful. It has already been proven, that flavonoids can influence the activity of biotransformation enzymes and interfere e.g. with the process of carcinogenesis and drug metabolism. For that reason it is important to investigate the impact of an increased intake of flavonoids. The aim of this thesis was to investigate the influence of dihydromyricetin (a potential drug to cure alcohol use disorder) and its structurally similar flavonoid myricetin on the activity of enzymes, cytochrome P450 2E1 (CYP2E1) and N­acetyltransferases 1 and 2 (NAT1/2). The research included the determination of the impact of a premedication by these flavonoids on the expression and activity of CYP2E1 and NAT1/2. The inhibition capacity of myricetin and dihydromyricetin towards the activity of CYP2E1 and NAT1/2 was also investigated. After the flavonoid premedication of rats the...

Le cadmium est un métal lourd non-essentiel naturellement présent dans le sol. Il a été classé par le centre international de recherche sur le cancer (CIRC) comme un élément cancérigène de type I. Contrairement à la majorité des autres plantes, le tabac (Nicotiana tabacum) accumule le cadmium à des niveaux relativement élevés dans ses parties aériennes. Ce cadmium est ensuite retrouvé dans la fumée de cigarette. La concentration en cadmium dans les vaisseaux sanguins des fumeurs est deux à trois fois supérieure à celle que l'on rencontre chez les non-fumeurs. Pour diminuer la toxicité des cigarettes, il est souhaitable de diminuer la quantité de cadmium accumulé par le tabac dans ses feuilles. Pour parvenir à cet objectif, il est nécessaire de comprendre les mécanismes impliqués dans l'accumulation du cadmium chez le tabac.Les acteurs moléculaires impliqués dans le transport et l'accumulation du cadmium in-planta ont été principalement décrits chez l'espèce modèle Arabidopsis thaliana. Chez cette plante, le cadmium est chargé dans le xylème par AtHMA2 et AtHMA4, deux transporteurs de zinc qui partagent une redondance fonctionnelle partielle et qui sont responsables de la translocation du cadmium des parties racinaires vers les parties aériennes. Deux orthologues à AtHMA2 et AtHMA4 ont été identifiés chez N. tabacum et nommés NtHMAα et NtHMAβ. Ces deux transporteurs sont principalement exprimés dans les racines mais on en trouve également dans les feuilles. NtHMAα a été localisé plus précisément au niveau des cellules du péricycle dans les racines et dans les nervures tertiaires des feuilles. L'étude de lignées mutantes a confirmé le rôle de NtHMAα et NtHMAβ dans la translocation du cadmium des parties racinaires vers les parties aériennes. Les lignées qui expriment une version tronquée de NtHMAα ont une réduction de leur teneur en cadmium foliaire de 45%. Les lignées dans lesquelles l'expression des gènes NtHMAα et NtHMAβ est réduite sont sévèrement impactées dans leur développement. Un des phénotypes observé est une diminution drastique de la quantité de graines en raison de l'incapacité du pollen à germer à cause d'un déficit en zinc. Nous avons montré que chez ces lignées, la tolérance au cadmium était accrue. Dans l'ensemble, nos résultats montrent une grande redondance entre NtHMAα et NtHMAβ. / Cadmium is a heavy metal naturally present in the soil. It is classified as a Group 1 carcinogen by the International Agency for Research on Cancer (IARC). Unlike most other plants, tobacco (Nicotiana tabacum) translocates most of the cadmium taken up from the soil out of the roots and into the shoots. As a result, cadmium content in cigarettes is a problem for smokers who have four to five times higher blood cadmium concentrations than nonsmokers. In order to reduce cigarette toxicity it is desired to reduce cadmium accumulated in tobacco leaves. For this purpose, it is important to understand the mechanisms controlling cadmium accumulation in shoots.Molecular actors involved in cadmium repartition in plants have been well described in the model plant Arabidopsis thaliana. In Arabidopsis, cadmium is loaded into the xylem vessels by HMA2 and HMA4, two zinc transporters with partial functional redundancy. Two orthologous proteins of AtHMA2 and AtHMA4 were identified in N. tabacum and named NtHMAα and NtHMAβ. These two transporters are mainly expressed in roots but their expression was also found in shoots. NtHMAα expression was more precisely found in root pericycle cells and in shoot tertiary nerves. The analysis of mutant lines confirmed that NtHMAα and NtHMAβ are involved in cadmium translocation from roots to shoots. Lines which expressed a truncated version of NtHMAα had a 45% reduction in shoot cadmium content. Lines where both NtHMAα and NtHMAβ were silenced were severely impacted in their development. One of the phenotypes that was identified was a drastic reduction in the number of seeds due to the lack of pollen germination. We also found an enhanced tolerance to cadmium in the silenced lines. Altogether, our results show a great redundancy between NtHMAα and NtHMAβ.

Les réactions de couplage métallocatalysées mises en avant par l'attribution du Prix Nobel de Chimie 2010 permettent la création de liaison C-C impossible par les réactions de type SN1 ou SN2. Or, les composés auxquels elles donnent accès sont très utilisés dans le domaine pharmaceutique, agrochimique ou encore dans celui de la chimie supramoléculaire. Si les réactions sont efficaces, les agents de couplages sont souvent peu accessibles et/ou peu éco(nomique/logique)-compatibles. Les triarylbismuthines lèvent en partie ces limitations, car tous les atomes de ces organométalliques participent aux processus et ces composés sont considérés comme non toxiques mais les réactions engageant ce type d'organométalliques souffrent de leur dimérisation. Afin de lever cette limitation, nous avons développé un système catalytique plus " vert" utilisant le PEPPSI comme pré-catalyseur sur une réaction test. Ces nouvelles conditions donnent généralement d'excellents rendements en série biarylique comme hétérobiarylique. La gamme des substituants sur le dérivé halogéné est très étendue mais plus limitée sur la bismuthine. Ce système catalytique a ensuite été utilisé sans modification dans les réactions domino d'élimination/couplage. Une étude cinétique comparative par GC/MS et RMN 13C a permis de montrer qu'une élimination d'ordre 2 avait lieu avant le couplage. De plus il y a un effet coopératif entre les ions fluorures et la bismuthine : celle-ci joue donc un double rôle : agent organométallique doux de couplage et base. L'ambiguïté mécanistique ainsi levée, il a été permis d'envisager une chimiosélectivité en fonction des divers états d'hybridation du carbone portant le brome au moment du couplage. Plusieurs méthodes d'accès à des molécules de structures Ar-Ar-C C-Ar à géométries variables peuvent être obtenues rapidement. Le système catalytique a également permet l'activation de liaison C-Br de bromocoumarines. Ainsi, il est possible de réaliser le couplage sur les positions 3-, 4- et 6-. L'ordre de réactivité a été déterminé ce qui a permis de réaliser des monocouplages parfaitement sélectifs sur les 3,4- ou 3,6- dibromocoumarines, dont les applications biologiques suscitent un grand intérêt. Le nouveau système catalytique a donc éliminé le problème de dimérisation des triarylbismuthines et donne potentiellement accès à des molécules intéressantes pour leurs propriétés physiques ou biologiques / Metallocatalysed crosscoupling reactions have been highlighted by the attribution of the 2010 Nobel Chemistry Price since they allow CC bond formation when classical SN1 or SN2 do not permit it. Furthermore, they give access to many pharmaceutics and agronomic compounds but also molecules used for their supramolecular properties. Nowadays, reactions are really efficient but reactants are not always readily accessible and can't be classified as green reagents. Since all its atoms act over the catalytic process and because they are not considered as toxic so far, triarylbismuthines may be a good alternative to circumvent the limitation described above. However, they suffer a main drawback, their reductive dimerisation. In order to avoid this side-reaction, a new greenest process has been developed on a benchmark reaction based on PEPPSI, an NHC/Pd catalyst. These conditions gave usually excellent yields, either for the biaryle or heterobiaryle crosscoupling reaction. The range of substituents is really wide on the aryle halide moiety but slightly more limited on the triarylbismuthine reagents. Then, this catalytic process has been applied without modification to an elimination/crosscoupling domino reaction. A GC/MS and 13C NMR supported comparative kinetic study showed that a 2nd order elimination take place before the C-C bond formation. Fluoride anion and triarylbismuthine act together. Therefore triarylbismuthine play a dual role: base and aryl transfer reagent. This mechanism study led to chimioselective reactions that allow many paths for the synthesis of Ar-Ar-C C-Ar containing compounds with a good control on geometry of this highly conjugated structure. This catalytic process allows also bromocoumarine C-Br bond activation. Thus, crosscoupling may be selectively performed at the 3-, 4- or 6- position of coumarines. The reactivity order difference of these positions even allow hightly selective mono crosscoupling reaction on 3,4- or 3,6-dibromocoumarines for further biological application. To conclude, our PEPPSI based greenest process avoid the dimerisation of bismuthines and give easy access to many compounds of great interest either for their biological or physical properties

Ce travail décrit la synthèse, l’oligomérisation et l’étude structurale de [alpha-N-amino]mères. En extrapolant une stratégie de synthèse originale d’alpha-hydrazinoacides optiquement purs développée au LCPM nous avons pu obtenir de manière satisfaisante les N-aminodipeptides, précurseurs indispensables à la suite du projet. Nous avons pu montrer que l’activation du partenaire acide impliqué dans la réaction clé de Mitsunobu, habituellement obtenue par l’utilisation du groupement phtalimide, pouvait être avantageusement réalisée par l’introduction d’une fonction hydrazone à caractère fortement électroattracteur. Une extension de cette méthode de synthèse sur résine est un résultat qui constitue une mise en œuvre efficace de la réaction de Mitsunobu en SPS. Les N-aminodipeptides obtenus ont ensuite été engagés dans des réactions d’oligomérisation. Une étude préliminaire en phase liquide a permis de démontrer la faisabilité d’un couplage peptidique classique entre deux unités pseudopeptidiques déprotégées. La suite de l’étude a été effectuée sur phase solide et nous a permis d’obtenir les tous premiers oligomères à squelette alpha-N-aminopeptidique jamais synthétisés à ce jour. Enfin, dans le troisième chapitre, ces oligomères ont été étudiés par modélisation moléculaire et par différentes méthodes spectroscopiques (RMN, IR) qui ont permis de mettre en évidence un repliement par l’établissement de liaisons hydrogène intramoléculaires / This work describes the synthesis, the oligomerization and the structural study of N-aminopeptides. By extrapolating an original strategy of hydrazinoacids synthesis developed in the LCPM we were able to obtain N-aminodipeptides in high optical purity in a satisfactory way. These compounds were the indispensable precursors in order to continue the project. We were able to show that the activation of the acidic partner involved in the key reaction of Mitsunobu usually obtained by the use of the phtalimide group, could be advantageously realized by the introduction of a hydrazone moiety with strong electron-withdrawing character. An extension of this method on solid support is a result which constitutes an effective application of a Mitsunobu protocol in Solid Phase Organic Chemistry. The N­aminodipeptides thus obtained were studied in reactions of oligomérisation. A preliminary study in liquid phase allowed to demonstrate that a classic peptidic coupling reaction could occur between two pseudopeptidic units. The continuation of the study was made on solid phase and allowed us to obtain the first [alpha-N-amino]peptides never synthesized to this day. Finally, in the third chapter, these oligomers were studied by molecular modelling and various spectroscopic methods (NMR, IR) who allowed to suggest a folding by the establishment of intramolecular hydrogen bonds

Ce travail étudie le potentiel du silicium de type n purifié par voie métallurgique pour la fabrication de cellules photovoltaïques à bas coût. Les teneurs élevées en dopants conduisent à des gammes de résistivités larges et faibles, ainsi qu’à une diminution de la durée de vie des porteurs de charge.La fabrication de cellules photovoltaïques a permis d’obtenir des rendements de conversion variant de 13.7% à 15.0% sur 148.6cm². Avec un procédé de fabrication amélioré, des rendements de 16.0% pourraient être obtenus. La résistivité des plaquettes a été identifiée comme facteur limitant les performances des cellules. Le co-dopage au gallium a été proposé pour augmenter la gamme de résistivité.Les cellules photovoltaïques réalisées montrent une excellente stabilité sous illumination et de faibles coefficients en température de la tension de circuit-ouvert. Ces travaux de thèse ont permis de définir le potentiel du silicium de type n purifié par voie métallurgique et de définir les spécifications nécessaires initiales au niveau de la charge à purifier pour permettre la fabrication de cellules photovoltaïques efficaces. / This work studies the potential of n-type silicon purified via the metallurgical route for the fabrication of low cost photovoltaic cells. The high level of doping species leads to a large range of low resistivity, as well as reduced carriers’ lifetime. The fabrication of photovoltaic cells led to conversion efficiencies varying from 13.7% to 15.0% on 148.6 cm². With an improved fabrication process, efficiencies of 16.0% could be obtained. The resistivity has been identified as the limiting factor on the cells’ efficiency. Gallium co-doping has been proposed in order to increase the resistivity range.The fabricated photovoltaic cells show an excellent stability under illumination with weak temperature coefficients of the open circuit voltage. This PhD work led to the knowledge of the potential of n-type silicon purified via the metallurgical route, and to define the charge specifications required to the fabrication of efficient photovoltaic cells.