Orientador: Salatiér Buzetti / Banca: Marcelo Andreotti / Banca: Renato de Mello Prado / Resumo: O manejo da adubação nitrogenada no feijoeiro é essencial para aumentar a eficiência da planta na utilização do N, possibilitando aumentar a produtividade da cultura. Assim, o trabalho teve como objetivo avaliar o efeito de fontes, doses e épocas de aplicação de nitrogênio e avaliar o uso do clorofilômetro como instrumento indicador da necessidade de adubação nitrogenada em feijoeiro de inverno cultivado em sistema plantio direto irrigado por aspersão em dois anos de cultivo (2008 e 2009). O cultivar utilizado foi o Pérola, que apresenta crescimento indeterminado, hábito do tipo II/III e grãos tipo carioca. O trabalho foi desenvolvido no município de Selvíria - MS, em Latossolo Vermelho Distrófico álico, textura argilosa. O delineamento experimental foi o de blocos casualizados com os tratamentos dispostos em esquema fatorial (5x3x2). Os tratamentos foram constituídos por cinco doses de nitrogênio (zero, 50, 100, 150 e 200 kg ha-1), três fontes de nitrogênio (uréia; Entec® 26 - sulfonitrato de amônio com inibidor de nitrificação - dimetilpirazolfosfato e sulfato de amônio) e duas épocas de aplicação (semeadura ou cobertura), com quatro repetições. Não houve diferença na produtividade do feijoeiro de inverno no cerrado entre as fontes de N utilizadas (uréia, Entec® 26 e sulfato de amônio); a aplicação de todo o nitrogênio na semeadura pode propiciar a obtenção de maiores produtividades de grãos no cultivo do feijoeiro de inverno irrigado; o aumento nas doses de nitrogênio proporcionou incremento na produtividade de grãos, até a máxima dose estudada de 200 kg ha-1 / Abstract: The management of nitrogen in the common bean is essential to increase the efficiency of plant N use, allowing to increase yield. Thus, the study aimed to evaluate the effect of sources, levels and timing of nitrogen application and the use of chlorophyllmeter to indicate the need of nitrogen fertilization in winter common bean grown under no-tillage using sprinkler irrigation in two years of cultivation (2008 and 2009). The cultivar used was the Perola, which has indeterminate growth habit Type II / III and carioca grain type. The study was conducted in Selviria county - MS / Brazil in a clayey alic oxisol. The experimental design was a randomized complete block with treatments in a factorial (5x3x2). The treatments consisted of five nitrogen rates (zero, 50, 100, 150 and 200 kg ha-1), three nitrogen sources (urea, Entec® 26 - ammonium sulphonitrate with nitrification inhibitor - dimetylpirazolphosphate and ammonium sulfate) and two application times (at sowing or at sidedressing), with four replications. There were no differences among N sources (urea, Entec ® 26 and ammonium sulfate) on common bean yield cropped in winter in the savannah soil, implementation of all the nitrogen at sowing can provide higher yields of grain, the increase on nitrogen rates provided an increase in grain yield up to the maximum dose studied of 200 kg ha-1 / Mestre

Made available in DSpace on 2014-06-11T19:29:43Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-03-01Bitstream added on 2014-06-13T20:19:53Z : No. of bitstreams: 1 arf_mv_me_ilha.pdf: 2749537 bytes, checksum: f244b03a161ab1adcab71577daf6b743 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O manejo da adubação nitrogenada no feijoeiro é essencial para aumentar a eficiência da planta na utilização do N, possibilitando aumentar a produtividade da cultura. Assim, o trabalho teve como objetivo avaliar o efeito de fontes, doses e épocas de aplicação de nitrogênio e avaliar o uso do clorofilômetro como instrumento indicador da necessidade de adubação nitrogenada em feijoeiro de inverno cultivado em sistema plantio direto irrigado por aspersão em dois anos de cultivo (2008 e 2009). O cultivar utilizado foi o Pérola, que apresenta crescimento indeterminado, hábito do tipo II/III e grãos tipo carioca. O trabalho foi desenvolvido no município de Selvíria – MS, em Latossolo Vermelho Distrófico álico, textura argilosa. O delineamento experimental foi o de blocos casualizados com os tratamentos dispostos em esquema fatorial (5x3x2). Os tratamentos foram constituídos por cinco doses de nitrogênio (zero, 50, 100, 150 e 200 kg ha-1), três fontes de nitrogênio (uréia; Entec® 26 – sulfonitrato de amônio com inibidor de nitrificação – dimetilpirazolfosfato e sulfato de amônio) e duas épocas de aplicação (semeadura ou cobertura), com quatro repetições. Não houve diferença na produtividade do feijoeiro de inverno no cerrado entre as fontes de N utilizadas (uréia, Entec® 26 e sulfato de amônio); a aplicação de todo o nitrogênio na semeadura pode propiciar a obtenção de maiores produtividades de grãos no cultivo do feijoeiro de inverno irrigado; o aumento nas doses de nitrogênio proporcionou incremento na produtividade de grãos, até a máxima dose estudada de 200 kg ha-1 / The management of nitrogen in the common bean is essential to increase the efficiency of plant N use, allowing to increase yield. Thus, the study aimed to evaluate the effect of sources, levels and timing of nitrogen application and the use of chlorophyllmeter to indicate the need of nitrogen fertilization in winter common bean grown under no-tillage using sprinkler irrigation in two years of cultivation (2008 and 2009). The cultivar used was the Perola, which has indeterminate growth habit Type II / III and carioca grain type. The study was conducted in Selviria county - MS / Brazil in a clayey alic oxisol. The experimental design was a randomized complete block with treatments in a factorial (5x3x2). The treatments consisted of five nitrogen rates (zero, 50, 100, 150 and 200 kg ha-1), three nitrogen sources (urea, Entec® 26 - ammonium sulphonitrate with nitrification inhibitor - dimetylpirazolphosphate and ammonium sulfate) and two application times (at sowing or at sidedressing), with four replications. There were no differences among N sources (urea, Entec ® 26 and ammonium sulfate) on common bean yield cropped in winter in the savannah soil, implementation of all the nitrogen at sowing can provide higher yields of grain, the increase on nitrogen rates provided an increase in grain yield up to the maximum dose studied of 200 kg ha-1

Les composés diazocétoniques sont des intermédiaires utiles en synthèse organique et l’élaboration de motifs diazocarbonylés est à ce titre un enjeu important. Les diazocétones terminales peuvent subir une addition sur des aldéhydes dans des conditions basiques pour conduire de façon convergente à des composés béta-hydroxy-alpha-diazocétoniques à fort potentiel synthétique. Dans ce contexte, notre projet visait à promouvoir ce type de réaction dans des conditions douces et peu basiques. La stratégie adoptée reposait sur l’utilisation des alpha-trialkylsilyl-alpha-diazoacétones et leur activation nucléophile spécifique par un ion fluorure. Dans un premier temps, la synthèse de la TES-diazoacétone a été optimisée, puis une étude approfondie des paramètres réactionnels a permis la mise au point de la réaction d’aldolisation de la TES-diazoacétone, induite par le TBAF. Deux protocoles expérimentaux faciles de mise en œuvre ont ainsi été mis en place pour conduire à une large gamme de béta-hydroxy-alpha-diazoacétones avec des rendements élevés. L’extension asymétrique de cette méthodologie a ensuite été étudiée en mettant en jeu un fluorure d’ammonium chiral dérivé d’alcaloïde de Cinchona conduisant à la formation des premières béta-hydroxy-alpha-diazoacétones énantioenrichies (e.e = 35%) avec des rendements élevés. Enfin, cette méthodologie a été étendue avec succès à la TIPS-diazoacétone. La robustesse du groupement protecteur TIPS permet d’envisager une large gamme de transformations synthétiques « methyl-side », sans induire une désilylation partielle de la position azométhine du diazo-aldol. Ceci ouvre la voie à l’exploration future de la réactivité des diazoaldols TIPS. / Diazoketones are valuable intermediates in organic synthesis and the elaboration of α-diazocarbonyl scaffolds has aroused a steady interest for many years. The terminal diazoketones can be added to aldehydes under basic conditions to produce beta-hydroxy-alpha-diazoketone compounds with a high synthetic potential. In this context, our project aimed at promoting this type of reaction under mild conditions without using a base. The strategy adopted was based on the use of α-trialkylsilyl-α-diazoacetones and their specific nucleophilic activation by a fluoride ion. Initially, the synthesis of α-trialkylsilyl-α-diazoacetone was optimized and then, an extensive study of the reaction parameters allowed the development of an efficient aldolisation of TES-diazoacetone induced by TBAF. The nucleophilic, weakly basic conditions employed tolerate a wide range of substrates and constitute a practical high-yielding experimental procedure. The asymmetric extension of this methodology was then studied by using a chiral ammonium fluoride derived from Cinchona alkaloid. The condition set up allowed to elaborate the first enantioenriched beta-hydroxy-alpha-diazoacetones (e.e = 35%) in high yields. Finally, this methodology was successfully extended to TIPS-diazoacetone. The robustness of the TIPS protective group makes it possible to envision a range of synthetic « methyl-side » transformations without desilylation of the azomethine position of the diazo-aldol. This study paves the way for future exploration of the reactivity of TIPS diazoaldols.

Municipal wastewater contains a significant amount of nutrients such as phosphorus (P) and nitrogen (N). Therefore have the interest of recovering these nutrients at wastewater treatment plants (WWTP) increased. Nutrient recovery would generate revenue for the WWTP, as it is possible to sell the products as fertiliser. Today, there are several techniques on the market to recover P as magnesium ammonium phosphate (MAP) and N as ammonium sulphate (AMS). Urine is the fraction contributing with the highest concentration of nutrients. Techniques to separate urine from the rest of the wastewater have been developed. These techniques enable the possibility to recover nutrients from the urine fraction separately; this is beneficial since the nutrient concentration would be higher. The purpose with this study was to examine the possibility for increased nutrient recovery at centralised WWTPs through urine separation.   Different techniques for nutrient recovery were compared by their recovery efficiency, chemical demand, and hydraulic retention time (HRT). A WWTP with enhanced biological P removal was modelled with Danish Hydraulic Institute’s (DHI) software WEST. Eight scenarios, with different percentage of the population equivalents using urine separation techniques, were simulated. The P recovery was calculated from phosphate (PO4) in the hydrolysed excess sludge and the separated urine. The N recovery was calculated from the ammonium (NH4) in the supernatant from the anaerobe digester. The theoretical biogas production was also calculated, from the modelled sludge.    The comparison of P recovery techniques showed no substantial differences in their recovery efficiency, chemical demand, and HRT. The comparison of N recovery techniques showed three techniques with a higher efficiency than the other methods. Ekobalans Fenix AB, CMI Europe Environment, and Organics developed these techniques. To determine which method to use, requests for proposal from different providers are recommended. As the urine separation increased, the influent P and N load decreased. When the urine separation increased and the operational parameters were kept constant, the effluent concentration of P and N decreased. The ratio of total Kjeldahl nitrogen (TKN) and total nitrogen (TN) however increased as the urine separation increased. The total MAP production calculated from the modelled hydrolysis showed that the production increased as the urine separation increased. On the other hand, the total MAP production from calculated hydrolysis showed a decrease in production as the urine separation increased. The difference in these results could be because of the performance of the modelled hydrolysis was better with a smaller nutrient load, resulting in a larger release of PO4 as the urine separation increased. The total AMS production increased as the urine separation increased. This, due to the increase of the TKN:TN ratio. The biogas production was not substantially affected by the increased urine separation.

This document details original numerical studies performed by the author pertaining to the propellant oxidizer, ammonium perchlorate (AP). Detailed kinetic mechanisms have been utilized to model the combustion of the monopropellants AP and ADN, and a two-dimensional diffusion flame model has been developed to examine the flame structure above an AP/HTPB composite propellant. This work was part of an ongoing effort to develop theoretically based, a priori combustion models. The improved numerical model for AP combustion utilizes a “universal” gas-phase kinetic mechanism previously applied to combustion models of HMX, RDX, GAP, GAP/RDX, GAP/HMX, NG, BTTN, TMETN, GAP/BTTN, and GAP/RDX/BTTN. The universal kinetic mechanism has been expanded to include chlorine reactions, thus allowing the numerical modeling of AP. This is seen as a further step in developing a gas-phase kinetic mechanism capable of modeling various practical propellants. The new universal kinetic mechanism consists of 106 species and 611 reactions. Numerical results using this new mechanism provide excellent agreement with AP's burning rate, temperature sensitivity, and final species data. An extensive literature review has been conducted to extract experimental data and qualitative theories concerning ADN combustion. Based on the literature review, the first numerical model has also been developed for ADN that links the condensed and gas phases. The ADN model accurately predicts burning rates, temperature and species profiles, and other combustion characteristics of ADN at pressures below 20 atm. Proposed future work and modifications to the present model are suggested to account for ADN's unstable combustion at pressures between 20 and 100 atm. A two-dimensional model has been developed to study diffusion in composite propellant flames utilizing a vorticity formulation of the transport equations. This formulation allows for a more stable, robust, accurate, and faster solution method compared to the Navier-Stokes formulations of the equations. The model uses a detailed gas-phase kinetic mechanism consisting of 37 species and 127 reactions. Numerical studies have been performed to examine particle size, pressure, and formulation effects on the flame structure above an AP/HTPB propellant. The modeled flame structure was found to be qualitatively similar to the BDP model. Results were consistent with experimental observations. Three different combustion zones, based on particle size and pressure, were predicted: the AP monopropellant limit, the diffusion flame, and a premixed limit. Mechanistic insights are given into AP's unique combustion properties.

In wastewater treatment plants, the amount of ammonium is one example of a measure to determine the quality of the effluent wastewater. Ammonium is regarded as a hazardous chemical for aqueous ecosystems and can cause eutrophication due to its high nitrogen content. The ammonium content in the treated wastewater is controlled by aeration of the biological treatment stage, in which ammonium is converted to nitrate. The aeration process often accounts for the largest energy consumption of the wastewater treatment plant, which motivates automatic control solutions that can both aid in reducing the discharge of ammonium in the effluent and improve the energy efficiency of the aeration process. One such control technique currently used by several large municipal wastewater treatment plants in Sweden is ammonium-based aeration control. In this technique, the aeration process is controlled based on measurements of the effluent ammonium concentration. The purpose of the thesis was to study an extension of ammonium-based aeration control that could better adapt to daily, and often large, fluctuations in the influent load. The proposed method is to use an iterative algorithm to tune the set-point of the ammonium feedback controller. The objective is to, over a given time interval, achieve a flow-proportional mean of the effluent ammonium concentration close to a desired value for a wide range of influent loads. The method was tested by extensive simulations, and the results indicate that the iterative set-point tuning algorithm has the potential to offer a superior ability to achieve a desired flow-proportional mean at the end of a given evaluation period and, in some instances, energy savings compared to standard ammonium feedback control.

No description available.

Les reins jouent un rôle majeur dans la régulation de l'homéostasie acide-base. La production et l'excrétion rénale d'ammonium assurent environ deux tiers de l'excrétion nette d'acides dans les conditions normales et jusqu'à 90% en situation d'acidose métabolique. Bien que l'excrétion d'ammonium soit un processus finement régulé et capital au maintien de l'équilibre acido-basique, à ce jour aucun transporteur spécifique d'ammonium n'a été décrit chez les mammifères. Les protéines Rhésus Rhcg et Rhbg, membres distants de la famille des transporteurs d'ammonium Mep/Amt, semblaient de bons candidats à cette fonction. L'invalidation du gène Rhcg puis celle de Rhbg ont donc été entreprises chez la souris afin d'estimer leur rôle potentiel dans le transport de l'ammonium. / Doctorat en sciences, Spécialisation biologie moléculaire / info:eu-repo/semantics/nonPublished

Le chondrosarcome (CHS), cancer du cartilage est une tumeur chimio- et radiorésistance dont le seul traitement efficace reste la chirurgie. Une prodrogue vectorisée et activable en hypoxie, ICF05016, est actuellement développée par l’UMR 1240, et évaluée en préclinique comme potentielle alternative théra-peutique pour ce cancer. La structure de cette molécule regroupe i) une moutarde cytotoxique, ii) un vecteur ammonium quaternaire chargé positivement possédant un tropisme pour l’aggrécane, protéoglycane majoritaire de la matrice extracellulaire tumorale, iii) une gâchette de type 2-nitroimidazole permettant une activation sélective en situation d’hypoxie, une des caractéristiques principales du CHS.Ces travaux de thèse ont consisté à pharmaco-moduler cette prodrogue bispécifique ICF05016 en modifiant la position du vecteur ainsi que la nature de l’agent cytotoxique. Ainsi sept prodrogues vectorisées ont été synthétisées présentant une chaine vectrice N,N,N-triméthylpropylaminium soit en C-4, soit en N-1 du cycle imidazole. Leur activation par réduction chimique, mimant l’hypoxie, ainsi que leur affinité pour l’aggrécane ont été confirmées in tubo par des analyses de RMN 31P et de SPR, toutefois elles se sont avérées non sélectives en termes de cytotoxicité (CI50 comprises entre 15 et 1 µM, et ce, quelles que soient les conditions d’oxygénation) et faiblement sensibles à une bio-réduction enzymatique. La fonctionnalisation par un vecteur ammonium quaternaire de la gâchette 2-nitroimidazole annihile donc l’activation en hypoxie des prodrogues.Cette stratégie a ensuite été étendue au cancer de la prostate en remplaçant le vecteur ammonium quaternaire par un ligand de type urée affin pour l’antigène membranaire spécifique de la prostate (PSMA). La première molécule synthétisée, qui possède un espaceur triazole, a démontré une affinité pour le récepteur PSMA, par une étude de compétition avec un radioligand, ainsi qu’une activation in tubo par bioréduction enzymatique. Toutefois aucune cytotoxicité n’a été constatée sur les lignées LNCaP-Luc et PC3-Luc. Une seconde molécule combinant un espaceur triazole avec une séquence peptidique identifiée pour la molécule PSMA-617, actuellement en cours d’essai clinique, est actuellement développée mais sa synthèse doit être optimisée, notamment au niveau de l’étape de cycloaddition 1,3-dipolaire. / Chondrosarcoma (CHS), the malignant tumor of the cartilage, is a chemo- and radio-resistant cancer. Surgical resection is still considered the mainstay of treatment of this pathology. A dual targeted hypoxia-activated prodrug, ICF05016 was developed by the UMR 1240 and evaluated in preclinical studies as a potential therapeutic alternative for CHS. The latter is a nitroheteroaryl-based compound designed as follows: a phosphorodiamidic mustard functionalized with a quaternary ammonium (QA) used as targeting function, and a 2-nitroimidazole group to trigger fragmentation and then release the bis-alkylating mustard anion by bioreduction under hypoxic conditions, chemical hallmark of CHS.This project deals with the pharmacomodulation of ICF05016, more specifically by modification of the position of the targeting moiety as well as the nature of the cytotoxic agent. Seven QA-targeted prodrugs have been synthesized with N,N,N-trimethylpropylaminium tethered to the imidazole either in the C-4, or the N-1 position. These prodrugs were cleaved in vitro under chemical reductive conditions, which mimic in vivo hypoxia conditions. In addition, the binding of these derivatives to aggrecan was highlighted by surface plasmon resonance. In vitro assays on human CHS cells (H-EMC-SS) demonstrated quite equivalent cytotoxicities, whatever the oxygen conditions used and their evaluation as substrate of an oxygen-insensitive nitroreductase revealed the almost total lack of activation. A QA targeting moiety grafted on the trigger seems to alter hypoxia activation.New prodrugs with prostate specific membrane antigen (PSMA)-targeting ligand were synthesized to extend this HAP strategy to prostate cancer. The first tested compound, having a triazole spacer, presented selective affinity for PSMA in an in vitro binding experiment as well as activation under enzymatic reduction. However, no cytotoxicity was observed on LNCaP-Luc and PC3-Luc cells. The synthesis of a prodrug combining the spacer of PSMA-617, currently in clinical trial, and a propyltriazole moiety, was initiated but the 1,3-dipolar cycloaddition still need to be optimized.

An einer rieselfeldbürtigen Altlast werden Ausbreitungs- und Abbaumechanismen von Ammonium basierend auf hydrogeochemischen Parametern und stabilen Isotopen identifiziert und modelliert. Da das Rieselfeld seit fast 20 Jahren geschlossen ist, können auch die Dekontaminationsprozesse untersucht werden. Die Ammoniumausbreitung wird durch Kationenaustausch gesteuert, der durch Eintrag und Akkumulation von abwasserbürtigem organischem Material (OM) zusätzlich erhöht ist. Die stabilen Isotope von Ammonium und Nitrat zeigen vollständigen Abbau des reaktiv verfügbaren Ammoniums durch Nitrifikation in der aeroben Zone direkt an der Schadstoffquelle an. Das entstehende Nitrat wird abstromig durch heterotrophe Denitrifikation abgebaut. Wie die reaktive Stofftransportmodellierung zeigt, sind die am oberen Rand der Fahne im Abstrom des Rieselfeldes auftretenden erhöhten delta15N-Signaturen von Ammonium entweder auf dortige Nitrifikation oder Anammox nahe der Schadstoffquelle zurückzuführen. Das akkumulierte OM liefert durch seine Austauschwirksamkeit zusätzliches Ammonium während der Dekontaminationsphase. Andererseits ermöglicht eingelöstes DOC die Entfernung des sekundären Nitrats durch heterotrophe Denitrifikation. Sollte OM aufgebraucht werden, besteht die Gefahr der Ausbreitung von Nitrat. Sollte innerhalb der Ammoniumfahne Sulfidminerale akkumuliert worden sein, bestünde dann die Gefahr erhöhter Sulfatfrachten durch autotrophe Denitrifikation. Es kann gezeigt werden, dass mit einem reaktiven Multikomponenten-Transportmodell das Langzeitverhalten von Ammonium im Feldmaßstab besser simuliert werden kann als mit einem auf Sorptionsisothermen (Henry, Freundlich) beruhenden Transportmodell. Prognosesimulationen liefern einen deutlich längeren Dekontaminationszeitraum bei Verwendung des reaktiven Modells. Die Anwendbarkeit der Sorptionsisothermen im Feldmaßstab ist deshalb, vor allem bei der Ermittlung von Dekontaminationszeiträumen, grundsätzlich in Frage zu stellen. / Using the example of a contaminant site caused by sewage farm operation ammonium fate and attenuation are identified and modelled based upon hydrogeochemical parameters and stable isotopes. A feature of the site is the chance to investigate the decontamination processes in a contaminant source, which was closed 20 years ago. The ammonium plume migration is controlled by cation exchange, which is increased due to infiltration and accumulation of sewage based organic matter (OM). Complete nitrification of available, i.e. desorbed, ammonium in the aerobic zone directly below the sewage farm is detectable based upon stable isotopes of ammonium and nitrate. The secondary nitrate is degraded downstream the contamination source by heterotrophic denitrification. It is shown by reactive contaminant transport modelling, that increased delta15N signatures at the upper fringe of the plume downstream of the source are caused by nitrification on site or by Anammox close to the contaminant source. The exchange affecting accumulated OM cause a release of additional ammonium. On the other hand DOC dissolved from OM facilitates degradation of secondary nitrate due to heterotrophic denitrification. In the case of depleted OM the risk of nitrate migration is arising. In the case of accumulated sulphide minerals which are precipitated due to redox processes during the sewage water infiltration, there may be a risk of increased sulphate loads due to autotrophic denitrification. It can be shown that a reactive multicomponent transport model is better suited to simulate the long term migration of ammonium in field scale than a transport model based on sorption isotherms (Henry, Freundlich). With regard to the aquifer decontamination the application of the reactive transport model yields a longer future decontamination period than the simple retardation model. Hence the applicability of sorption isotherms in field scale is doubtful, especially for investigations of aquifer decontamination.