Hydrogen is currently considered by many as the “fuel of the future”. It is particularly favoured as a replacement for fossil fuels due to its clean-burning properties; the waste product of combustion being water. While hydrogen is relatively easy to produce, there is currently a lack of practical storage methods for molecular H2, and this is greatly hindering the use of hydrogen as a fuel. Gases are normally stored in vessels under only moderate pressures and in liquid form where possible, which yields the highest energy density. However, to store reasonable quantities of hydrogen in similar volume containers, cryogenic temperatures or extreme pressure are required. Many potential hydrogen storage technologies are currently under investigation, including adsorption on metal hydrides, nanotubes and glass microspheres, and the chemical breakdown of compounds containing hydrogen to release H2. Recent studies have sparked interest in hydrates as a potential hydrogen storage material. The molecular storage of hydrogen in clathrate hydrates could offer significant benefits with regard to ease of formation/regeneration, cost and safety, as compared to other storage materials currently under investigation. Here, we present new experimental hydrate stability data for sII forming hydrogen–water (up to pressures of 180 MPa) and hydrogen–water–tetrahydrofuran systems, the structure-H forming hydrogen–water–methyclycohexane system, and semi-clathrate forming hydrogen–water–tetra-n-butyl ammonium bromide/tetra–n-butyl ammonium fluoride systems.

Dans toutes les espèces, les mutations et les réarrangements chromosomiques constituent des moteurs de l’évolution des génomes. Ils génèrent une diversité génétique à l’origine de la variation phénotypique observée entre les individus d’une même espèce. Cette variation est particulièrement importante chez les levures. Elles constituent donc d’excellents modèles pour déterminer les origines génétiques de la variation intra-spécifique. C’est dans ce contexte que ce travail s’est focalisé sur l’étude de la variation de résistance à l’ammonium et aux antifongiques azolés chez deux espèces de levures : Saccharomyces cerevisiae et Lachancea kluyveri. L’analyse des origines génétiques de la résistance à ces composés à mis en évidence que les variations génétiques pouvaient avoir lieu à plusieurs niveaux : séquence codante pour la résistance à l’ammonium et séquence régulatrice pour la résistance aux antifongiques. De plus, la réalisation d’expériences d’évolution adaptative a permis de mettre en évidence que l’adaptation à un nouvel environnement se faisait par dosage génique via l’acquisition d’un chromosome supplémentaire chez les espèces étudiées. / In all species, mutations and chromosomal rearrangements are drivers of genomes evolution. These processes generate the genetic diversity at the origin of the phenotypic variations observed between the individuals of the same species. This variation is essential for their adaptation to a new environment. The yeasts are isolated from various ecological and geographical niches and show an important phenotypic variation. According to these characteristics, they are excellent modelorganisms to determine the genetic origins of the observed phenotypic variation. In this context, the study focused on the variation of resistance to ammonium and azole antifungals within two yeast species: Saccharomyces cerevisiae and Lachancea kluyveri. The analyses of the genetic origin of the resistance to these compounds show that this genetic variation could occur at several levels: coding sequence for resistance to ammonium and regulatory sequence for resistance to antifungal agents. In addition, evolving experiments have showed that the adaptation to a new environment was done by gene dosage, through the acquisition of extrachromosomes in both species studied.

Submitted by FÁBIO YOMEI TANAMATI null (fabioyomei@hotmail.com) on 2016-12-21T18:02:23Z No. of bitstreams: 1 Tese- Fábio Final.pdf: 1752648 bytes, checksum: f9b77e3ee591fdbadfb4e16551e1bfc3 (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-12-22T13:34:23Z (GMT) No. of bitstreams: 1 tanamati_fy_dr_bot.pdf: 1752648 bytes, checksum: f9b77e3ee591fdbadfb4e16551e1bfc3 (MD5) / Made available in DSpace on 2016-12-22T13:34:23Z (GMT). No. of bitstreams: 1 tanamati_fy_dr_bot.pdf: 1752648 bytes, checksum: f9b77e3ee591fdbadfb4e16551e1bfc3 (MD5) Previous issue date: 2016-06-02 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O alho é uma hortaliça utilizada como condimento e como planta medicinal. O Brasil é um importante produtor/consumidor desta hortaliça, entretanto a produção nacional é insuficiente e portanto importa de quase 60% do alho consumido. Práticas precisas de manejo na produção e pós-colheita precisas podem resultar em economia na produção, aumento da produtividade e qualidade. Entre as práticas de manejo destaca-se a fertilização destaca-se pela influência direta na produção do alho e constituir um dos principais itens do custo de produção. Após a colheita a deterioração do alho minimamente processado (produto com maior valor agregado) pode ser diminuída através do armazenamento em temperatura controlada e atmosfera modificada. Com o objetivo de avaliar e documentar as melhores fontes e doses de nitrogênio e fontes potássio, bem como o melhor método para o armazenamento do alho minimamente processado foram conduzidos três ensaios que serão apresentados em três capítulos, sendo o primeiro intitulado “Fontes de nitrogênio e potássio sob a produtividade e nutrição mineral do alho”, o segundo capítulo intitulado “Produtividade e nutrição mineral do alho sob diferentes doses de nitrogênio e fontes de potássio”, e o terceiro capítulo intitulado “Efeito de diferentes temperaturas e atmosfera modificada sob as características qualitativas do alho minimamente processado”. Concluiu- se a) Diferentes fontes de N e K podem ser combinadas para a obtenção de máxima produção de alho comercial, b) o teor de nutrientes do alho não é influenciado pelas fontes de N e K ao ponto de constituir um fator crítico à produtividade do alho, c) Recomenda-se a dose 80 kg ha -1 de N como forma de obtenção de máxima eficiência do fertilizante e produtiva do alho vernalizado livre de vírus cv. Caçador, d) Não houve diferenças significativas na produção do alho acima da dose 80 kg ha -1 de N, a partir desta dose, o acúmulo de nutrientes no bulbo, de forma geral, foi inferior nos tratamentos K2SO4, e) baixa temperatura e atmosfera modificada contribuem significativamente para a manutenção da qualidade do alho minimamente processado, f) embalagem a vácuo mantém uma atmosfera consistentes em uma maior gama de temperaturas, g) as atmosferas modificadas com alto teor de CO2 podem influenciar a diminuição do valor de L* durante o armazenamento, h) a pungência do alho é mais bem conservada em embalagens a vácuo. / Garlic is used as a spice and as a medicinal plant, Brazil is an important producer/ consumer of this herb, however small domestic production stimulates import of about 60% the garlic consumed in this country. Management practices in the production and accurate post-harvest can result in savings in production and increasing in yield and quality. Among the management practices, fertilization is distinguished by its direct influence on the production of garlic and constitute one of the main cost items of production and postharvest deterioration of minimally processed garlic (product with higher added value) can be reduced by storing in controlled and modified atmosphere temperature. In order to assess and document the best sources and doses of nitrogen and potassium sources, as well as the more suitable storage method for fresh-peeled garlic we carried out three tests that will be presented in three chapters, the first entitled "Yield and mineral nutrition of vernalized virus free garlic in response to nitrogen and potassium sources topdressing" the second chapter entitled "Yield and mineral nutrition of garlic in response to nitrogen doses and potassium sources topdressing”, "Quality changes in fresh-peeled garlic cloves in relation to storage temperatures and modified atmospheres". From these assays we concluded that a) Different sources of N and K may be combined to obtain maximum production of commercial garlic, b) the garlic mineral content is not influenced by the sources of N and K to be considered a critical factor to garlic productivity, c) 80 kg ha -1 of N is the best way to obtain both maximum fertilizer efficiency and productive of virus free vernalizated garlic cultivar Caçador, d) from the dose 80 kg ha -1 , the lowest accumulation of nutrients in the bulb in SKO treatments suggests that potassium sulfate, alleviates possible effects of toxicity caused by excess NH4 + and reduces minerals export for bulb and thereby the ground, e) both low temperature and modified atmosphere significantly contribute to the maintenance of the quality of fresh-peeled garlic, f) vacuum packaging maintains an atmosphere consistent across a wider range of temperatures, g) modified atmospheres with high CO2 content can influence the decrease in L* value during storage, h) garlic pungency is better preserved in vacuum packaging.

La nutrition azotée des bactéries et des plantes est actuellement un sujet de grande importance, notamment pour comprendre comment améliorer les voies métaboliques aboutissant à l’assimilation de l’azote et à plus grande échelle, optimiser des apports d’engrais et augmenter le rendement des cultures. Dans ce contexte, la réaction d’amidation catalysée par la glutamine synthétase (GS), qui fixe l’ammonium (NH₄)⁺ en glutamine, est cruciale car elle est à la fois le point d’entrée de l’azote dans les végétaux, et une étape-clef du recyclage de l’azote (en particulier, NH₄⁺ photorespiratoire). Dans cette étude, nous nous sommes intéressés à la cinétique enzymatique et au mécanisme chimique de la GS. Des systèmes analytiques (HPLC, RMN , GC-MS) ont  été optimisés pour permettre la mesure de l’activité enzymatique in vitro et pour réaliser des analyses par spectrométrie de masse à ratio isotopique. Avec ces techniques, nous avons pu regarder précisément les effets isotopiques ¹²C/¹³C, ¹⁴N/¹⁵N et H₂O/D₂O (solvant) lors de la catalyse, en utilisant la GS d’E. coli et d’Arabidopsis thaliana (GS1,2). Nos résultats montrent qu’il n’y a pas d’effet isotopique ¹²C/¹³C, mais qu’il y a un fractionnement ¹⁴N/¹⁵N de »16‰. En outre, il y a un effet inverse du solvant (réaction 1.5 à 2 fois plus rapide dans D₂O).  Cela suggère que la création de la liaison C----N (amidation) est partiellement limitante (engagement catalytique de »14% seulement) et que le réseau de ponts hydrogènes dans le site actif est crucial pour déterminer la vitesse de la réaction. L’apparition d’effets ¹⁴N/¹⁵N inverses dans certaines circonstances et les effets drastiques causés par une substitution du cofacteur métallique (Mg²⁺) suggèrent en outre que l’étape d’amidation peut être réversible et que la coordination par un métal joue un rôle très important pour stabiliser les intermédiaires de la réaction, en interaction avec le solvant. Ainsi, dans son solvant naturel qu’est H₂O, la GS réalise une réaction ‘chimiquement difficile’ (barrière énergétique élevée de l’amidation) rendue possible par le clivage de l’ATP et son caractère exergonique. / Nitrogen nutrition in bacteria and plants is currently an important topic, in particular to identify key points for metabolic improvements in N assimilation and more generally, to optimize fertilization and crop yield. In such a context, the amidation reaction catalyzed by glutamine synthetase (GS), which fixes ammonium (NH₄)⁺ into glutamine, is of crucial importance since it both represents the N entry in plants and the main step of N recycling (such as photorespiratory (NH₄)⁺. Here, we examined GS kinetics and chemical mechanism. Analytical methods (HPLC, NMR, GC-MS) have been set up so as to measure in vitro activities and isotopic abundance by isotope ratio mass spectrometry. These gave access to isotope effects (¹²C/¹³C, ¹⁴N/¹⁵N et H₂O/D₂O – solvent) during catalysis, with the GS from either E. coli or A. thaliana (GS1,2). Our results show that there no ¹²C/¹³C isotope effect but there is significant ¹⁴N/¹⁵N isotope fractionation of ca. 16‰. In addition, there is an inverse solvent isotope effect (reaction 1.5 to 2 times faster in D₂O). This suggests that forming the C----N bond (amidation) is partially rate-limiting (catalytic commitment of ca. 14% only) and the H-bond network in the active site is of substantial importance for the reaction rate. The occurrence of inverse ¹⁴N/¹⁵N isotope effects under certain circumstances as well as the drastic impact of changing the metal cofactor (Mg²⁺)) indicate that the amidation step can be reversible and that the coordination by the metal plays a key role in stabilizing reaction intermediates, by interfacing the solvent. In other words, in its natural solvent H₂O, the GS catalyses an intrinsically ‘difficult’ reaction (high energy barrier of amidation) made possible by both ATP cleavage and its exergonic nature.

La résistance aux antibiotiques est l'une des menaces les plus graves pour la santé mondiale de nos jours. L'émergence de bactéries multirésistantes encourage les chercheurs à développer de nouveaux antibiotiques et stratégies pour compenser leurs différents mécanismes de résistance. L'un de ces mécanismes de défense est la formation de biofilms. Sous cette forme, les bactéries développent une matrice extracellulaire protectrice les rendant plus résistantes à divers traitements antimicrobiens. Nous avons conçu et synthétisé des composés de déstabilisation des membranes avec des caractéristiques clés : un cation benzimidazolium ou imidazolium, une chaîne apolaire hydrophobe et/ou un site de reconnaissance des anions lipophiles. Ces caractéristiques leur confèrent une activité antimicrobienne accrue et une grande capacité à perturber les membranes cellulaires. Ces composés perturbateurs de la membrane agissent via un mécanisme rapide et efficace et ont montré de bons résultats contre les souches de SARM (staphylococcus aureus résistant à la méthiciline) en tant que candidats antibiofilms prometteurs. Ces nouveaux agents ont le potentiel de se disperser et d'inhiber la formation de biofilms et pourraient avoir un impact positif sur la médecine humaine à l'avenir. / Antibiotic resistance is one of the most serious threats to global health nowadays. Emergence of resistant bacteria encourages researchers to develop new antibiotics and strategies to mitigate their different resistance mechanisms. One of these defense mechanisms is the formation of biofilms. In this form, bacteria develop a protective extracellular matrix making them more resistant to various antimicrobial treatments. We have designed and synthesized membrane destabilizing compounds with three key features: a benzimidazolium or an imidazolium cation, a hydrophobic apolar chain, and a lipophilic anion recognition site. These characteristics give these compounds increased antimicrobial activity and greater ability to disrupt cell membranes. These membrane-disrupting compounds act via a fast and efficient mechanism and showed good results against MRSA (methicillin-resistant staphylococcus aureus) strains as promising antibiofilms candidates. These new agents have the potential to disperse and inhibit the formation of biofilms and could have a positive impact on human medicine in the future.

Orientador: Salatiér Buzetti / Banca: Marco Eustáquio de Sá / Banca: Orivaldo Arf / Banca: Rita de Cássia Félix Alvarez / Banca: Rogério Peres Soratto / Resumo: A cultura do milho encontra-se entre as de maior potencial de produtividade de grãos, embora no Brasil alguns fatores não permitam que seja expressa a capacidade máxima de produtividade da cultura, que está muito aquém da produtividade média. Para a obtenção de altas produtividades economicamente viáveis, a nutrição mineral adequada é um dos fatores essenciais e o nitrogênio é o nutriente que, via de regra, proporciona os maiores efeitos. O objetivo do trabalho foi comparar os efeitos de diferentes fontes nitrogenadas: sulfonitrato de amônio (SNA), sulfato de amônio (S.A.) e uréia (U), na semeadura e em cobertura, nas características agronômicas do milho, conduzido em solo da região de Selvíria/MS, sob irrigação por aspersão. O trabalho foi desenvolvido na fazenda experimental da Faculdade de Engenharia de Ilha Solteira, UNESP, Selvíria-MS, em um Latossolo Vermelho distrófico, no ano agrícola 2004/05. O delineamento experimental utilizado foi blocos casualizados com quatro repetições, dispostos em esquema fatorial 3x5, sendo: três fontes de nitrogênio (SNA, S.A. e U) aplicadas na semeadura e em cobertura, no estádio de 8 folhas completamente desdobradas, em 5 modos de aplicação (0 + 120; 30 + 90; 60 + 60; 90 + 30 e 120 + 0 kg de N ha-1). A aplicação da fonte nitrogenada sulfonitrato de amônio e o modo... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The corn crop has high productivity potential, although in Brazil it is below of expectation. The mineral nutrition, mainly to concern to nitrogen, is essential to obtain high productivity and feasible economically. The work was conducted at Experimental Station of Universidade Estadual Paulista - UNESP - Ilha Solteira Campus, UNESP/FEIS, located in Selvíria-MS, in a Red dystrophic Latosol (Oxisol), in the agricultural year 2004/05. The objective of this study was to evaluate sources and times of nitrogen application. A randomized blocks design with four repetitions, in a factorial scheme 3x5, was used. Three sources of nitrogen (Sulphonitrate of ammonium, Ammonium sulfate and Urea) applied at sowing and/or covering at stadium of 8 leaves completely unfolded, in 5 combinations (0 + 120; 30 + 90; 60 + 60; 90 + 30 and 120 + 0 kg of N ha-1) constituted the treatments. The nitrogen sources as Sulphonitrate of ammonium and the combination of 60 kg ha-1 at sowing and at 8 leaf stadium provided the larger N leaf content. The grain yield was higher in the treatment that received 30 kg of N ha-1 at sowing + 90 kg of N ha-1 at 8 leaf stadium, and that treatment where N was only supplied at 8 leaf stadium (0 + 120 kg of N ha-1), it provided grain yield of 7,745 kg ha-1 and 7,667 kg ha- 1, respectively... (Complete abstract, click electronic access below) / Doutor

Wasserknappheit und verminderte Wasserqualität sind Folgen des Klimawandels und zu-nehmender menschlichen Aktivitäten in der Landwirtschaft. Um den weltweiten Nahrungsmittelbedarf zu decken, ist der Einsatz von Stickstoffdüngern (hauptsächlich in Form von NH4+) notwendig, um die Qualität und den Ertrag von Nutzpflanzen zu steigern. Eine wachsende Weltbevölkerung macht einen verstärkten Einsatz von Stickstoffdüngern in der Landwirtschaft erforderlich, was zu einem erhöhten Eintrag von reaktivem Stickstoff in den Boden und das Grundwasser führt. Zusammen mit Abwassereinleitungen aus Haus-halten und Industrie in die Umwelt ist die Landwirtschaft Schätzungen zufolge der Hauptverschmutzer von Trinkwasserquellen. Neben Vermeidungs- und Verminderungsstrategien ist die Entwicklung innovativer Technologien zur Entfernung von Stickstoffverbindungen aus Trinkwasserquellen ein vielversprechender Ansatz zur Lösung dieses Problems. Diese Arbeit zeigt die Machbarkeit eines kombinierten Zeolith- und Anammox-Verfahrens zur Entfernung von Stickstoffverbindungen in einer grundwasserähnlichen Matrix für die Trinkwasseraufbereitung auf. Unter Verwendung von natürlichen Zeolithe (Klinoptilolith) als Sorbentien (für NH4+) und als Biofilmträger (für Anammox Bakterien) in einem Festbett-Biofilter wurde ein hocheffizienter, kostensparender, kompakter und wartungsarmer Prozess für dezentrale Anwendungen demonstriert. Darüber hinaus wurden in einer technischen und wirtschaftlichen Bewertung die Chancen und Risiken dieses Verfahrens für die Trinkwasseraufbereitung aufgezeigt. Der Einfluss von Schlüsselparametern auf die Sorption von NH4+ an natürlichen Zeolithe ergab eine hohe NH4+-Selektivität (NH4+ > K+ > Na+ > Mg2+ > Ca2+), hohe Sorptionskapazitäten (bis zu 21.3 mg(NH4+)/g) und hohe Entfernungsleistungen (bis zu 99 %). Untersuchungen in Multisorbat- und natürlichen Wassermatrices ergaben, dass die Konzentrationen von K+ und gelöstem organischem Kohlenstoff (DOC) den größten Einfluss auf die Sorption von NH4+ haben. Die Gleichgewichtsbeladung wurde dabei um bis zu 8% verringert. Der Einfluss von Anionen kann in Grundwasser typischen Konzentrationen bei pH-Werten oberhalb des pHPZC (Point of Zero Charge) vernachlässigt werden. Der pHPZC konnte zwischen pH 6.24 und pH 6.47 bestimmt werden. Zwischen pH 5 und pH 7 wurde eine maximale NH4+-Entfernungsleistung festgestellt, wohingegen aufgrund eines erhöhten Anteils an nicht sorbierbarem NH3(aq) ab pH ≥ 8 die Entfernungsleistung stark abnahm. Bei einer NH4+-Konzentration von 12.8 mg/L konnte der zugrundeliegende Sorptionsmechanismus auf den Ionenaustausch zurückgeführt werden (R² = 0,997). NH4+ beladene Zeolithe ließen sich am besten mit einer K+-Salzlösung regenerieren. Experimentell ermittelte Durchbruchskurven und eine zweifaktorielle Varianzanalyse bestätigten einen starken Einfluss der K+- und DOC-Konzentrationen auf den Durchbruch von NH4+ in natürlichen Wassermatrices. Bei einem Durchbruch von 50% wurde mit dem Einsatz von Elbewasser die Anzahl der behandelten Bettvolumina (BVs) um 69% reduziert. Darüber hinaus wurden die NH4+-Durchbruchskurven mit und ohne den Einfluss von K+ in Reinstwasser sowohl mit dem Linear Driving Force (LDF)- als auch mit dem Thomas-Modell erfolgreich modelliert und durch experimentelle Daten validiert. Die Verwendung solcher Modelle ist ein vielversprechendes Instrument, um zeitaufwändige und umfangreiche Untersuchungen im Labor und im Feld zu reduzieren. Um das Anammox-Verfahren erfolgreich etablieren zu können ist ein stabiler Betrieb der partiellen Nitritation (PN) zur Regulierung des erforderlichen stöchiometrischen NO2-/NH4+-Verhältnisses (1.32:1) entscheidend. Vorläufige Untersuchungen mit einem Fest-bett-Biofilter und einem Sequencing-Batch-Reaktor (SBR) zeigten, dass die folgenden Faktoren bei der Anwendung einer PN berücksichtigt werden müssen: (1) komplexe Wechselbeziehungen zwischen mikrobiellen Gemeinschaften mit unterschiedlichen Substratanforderungen, synergetische/kompetitive Wechselwirkungen, inhibierende Prozesse, und Stoffwechselprodukte; und (2) die Notwendigkeit, verschiedene Inhibierungsstrategien zu etablieren, um die Aktivität NO2- oxidierender Bakterien (NOB) zu unterdrücken. Es ist entscheidend, einen geschichteten und stabilen Biofilm zu etablieren, bevor eine PN unter Grundwasserbedingungen mit erhöhten Temperaturen und hohen NH4+-Konzentrationen eingesetzt wird. Das kombinierte Zeolith- und Anammox-Verfahren wurde in einem sequentiellen Zeolith-Anammox-Biofilter untersucht. Trotz weitaus niedrigerer Substratkonzentrationen und einer 8-fach höheren Filtergeschwindigkeit wurden vergleichbare Entfernungsleistungen für NH4+ (86%) und NO2- (76%) wie mit ähnlichen Zeolith- Anammox-Systemen für die Abwasseraufbereitung ermittelt. Die Entfernungsleistungen für NH4+ und NO2- konnten durch einen Vergleich ihrer Halbwertszeiten mit der effektiven hydraulischen Aufenthaltsdauer im Biofilter bestätigt werden. Die Entfernung von NH4+ erfolgte aufgrund der Sorption über Zeolithe und des Anammox-Stoffwechsel wesentlich schneller als für NO2-, deren Entfernung lediglich auf den Anammox-Stoffwechsel zurückführbar ist. Sowohl die ermittelten Halbwertszeiten als auch das von der Filterhöhe abhängige NO2-/NH4+-Verhältnis konnte eine schnellere NH4+-Entfernung bestätigen. Die Grenzwerte für NO2- der Weltgesundheitsorganisation (WHO: 3 mg/L) und der Vereinigten Staaten von Amerika (USA: 3.2 mg/L)) wurden bei Filtergeschwindigkeiten von 0.032 m/h und 0.043 m/h eingehalten. Bei 0.032 m/h und 0.043 m/h wurden die NH4+-Grenzwerte für China (0.6 mg/L) und Deutschland (0.5 mg/L) leicht überschritten. Durch eine Korrelation der NH4+- und NO2--Entfernung mit der elektrischen Leitfähigkeit konnte darüber hinaus bei allen untersuchten Filtergeschwindigkeiten ein vereinfachtes Verfahren zur Prozessüberwachung demonstriert werden. Eine technisch-wirtschaftliche Bewertung ergab die höchste technische Wertigkeit (X) für das Ionenaustauschverfahren mit Zeolithe (X: 0.79), gefolgt vom Nitrifikationsverfahren (X: 0.68) und dem Verfahren der partiellen Nitritation/Anammox (PN/A) (X: 0.52). Das Ionen-austauschverfahren zeichnet sich dabei vor allem durch eine einfache Handhabung und Anpassung hinsichtlich schwankender NH4+-Konzentrationen im Zulauf sowie eine hohe Betriebssicherheit aus. Dagegen sind vergleichsweise lange Etablierungszeiten, eine un-sichere Betriebssicherheit und eine hohe verfahrenstechnische Komplexität für das PN/A-Verfahren zu erwarten. Die Gesamtkosten jedes Verfahrens wurden unter Berücksichtigung der Anlagengröße, lokaler Strompreise und unterschiedlicher NH4+-Konzentrationen im Zulauf über einen Zeitraum von 20 Jahren berechnet. Auf Grundlage dieser Berechnung können die folgenden Empfehlungen für eine dezentrale Trinkwasseraufbereitung ausgesprochen werden: (1) Das Ionenaustauschverfahren kann für NH4+-Konzentrationen bis zu 21 mg/L empfohlen werden; (2) das PN/A-Verfahren wird bei höheren NH4+-Konzentrationen wirtschaftlicher; und (3) das Nitrifikationsverfahren weist ab einer NH4+-Konzentration von ≥ 14 mg/L im Zulauf eine ungünstige Wirtschaftlichkeit auf, da eine zusätzliche Denitrifikationsstufe eingeplant werden muss um den NO3- Grenzwert von 50 mg/L der WHO und von Deutschland einzuhalten. Werden die Berechnungen mit einem niedrigeren KCl-Preis wiederholt, kann das Ionenaustauschverfahren bis zu einer NH4+-Konzentration von 60 mg/L empfohlen werden. Das PN/A-Verfahren stellt bei NH4+-Konzentrationen ≥ 60 mg/L das wirtschaftlichere Verfahren dar. Insgesamt ist das kombinierte Zeolith- und Anammox-Verfahren ein vielversprechendes Verfahren zur Entfernung von Stickstoffverbindungen in dezentralen Anwendungen für die Trinkwasseraufbereitung in Schwellen- und Entwicklungsländern des globalen Südens. Insbesondere dort, wo erhöhte Temperaturen und hohe NH4+-Konzentrationen in Trinkwasserquellen zu finden sind.:1. Introduction ................................................................................................................. 1 2. Topic and Objective of the Thesis ............................................................................. 3 3. Background and Literature Review ........................................................................... 5 3.1 General Aspects about the Global Nitrogen Cycle ............................................ 5 3.1.1 Nitrogen Reservoirs and Anthropogenic Activities ........................................... 5 3.1.2 Nitrogen Cycle in Riverbank Filtration and Groundwater ................................. 7 3.1.3 Ecological Relevance and Physiological Effects of Nitrogen Compounds ..... 10 3.2 Ammonium Removal Processes – Current State of Knowledge .................... 12 3.2.1 Distinction: Drinking Water vs. Wastewater Treatment .................................. 13 3.2.2 Zeolites: Occurrence, Characteristics and Application ................................... 17 3.2.3 Partial Nitritation and Anammox ..................................................................... 20 4. Results and Discussion ............................................................................................ 25 4.1 Publication 1: Granular Natural Zeolites: Cost-Effective Adsorbents for the Removal of Ammonium from Drinking Water ............................................................ 25 4.2 Publication 2: Natural Zeolites for the Sorption of Ammonium: Breakthrough Curve Evaluation and Modeling .................................................................................. 48 4.3 Preliminary Investigations to the Partial Nitritation ........................................ 66 4.3.1 Material and Methods .................................................................................... 66 4.3.2 Results and Discussion .................................................................................. 70 4.3.3 Conclusions ................................................................................................... 77 4.4 Publication 3: A Sequential Anammox Zeolite-Biofilter for the Removal of Nitrogen Compounds from Drinking Water ............................................................... 79 4.5 Technical-Economic Evaluation ........................................................................ 99 4.5.1 Material and Methods .................................................................................... 99 4.5.2 Results and Discussion ................................................................................ 103 4.5.3 Conclusions ................................................................................................. 114 5. Summary and General Conclusions ...................................................................... 116 6. Outlook ..................................................................................................................... 119 References ..................................................................................................................... 122 List of Tables ................................................................................................................. 139 List of Figures ................................................................................................................ 141 List of Abbreviations ..................................................................................................... 144 List of Formular ............................................................................................................. 146 Appendix ........................................................................................................................ 147 A-1 Supporting Information: Section 3 .................................................................. 147 A-2 Supporting Information: Section 4 .................................................................. 149 A-2.1 Publication 1: Granular Natural Zeolite: Cost-Effective Adsorbents for the Removal of Ammonium from Drinking Water ............................................................ 149 A-2.2 Publication 2: Natural Zeolites for the Sorption of Ammonium: Breakthrough Evaluation and its Modeling ...................................................................................... 157 A-2.3 Preliminary Investigations to Partial Nitritation ............................................. 162 A-2.4 Publication 3: A Sequential Anammox Zeolite-Biofilter for the Removal of Nitrogen Compounds from Drinking Water ............................................................... 168 A-2.5 Technical-Economic Evaluation ................................................................... 179 Journal Articles and Conference Contributions ......................................................... 200 Acknowledgements ....................................................................................................... 201 Declaration ..................................................................................................................... 202

Indiana University-Purdue University Indianapolis (IUPUI) / Both quaternary ammonium bromide (QAB) and furanone derivatives were synthesized, characterized and formulated into dental resin composites for improved antibacterial properties. Compressive strength (CS) and S. mutans viability were used to evaluate the mechanical strength and antibacterial activity of the restoratives. The effects of chain length, loading, saliva and aging on CS and S. mutans viability were investigated. Chapter 2 describes how we studied and evaluated the formulated antibacterial resin composites by incorporating the synthesized QAB-containing oligomers into the formulation. The results show that all the QAB-modified resin composites showed significant antibacterial activity and mechanical strength reduction. Increasing chain length and loading significantly enhanced the antibacterial activity but dramatically reduced the CS as well. The 30-day aging study showed that the incorporation of the QAB accelerated the degradation of the composite, suggesting that the QAB may not be well suitable for development of antibacterial dental resin composites or at least the QAB loading should be well controlled. Chapter 3 describes how we studied and evaluated the formulated antibacterial resin composite by incorporating the synthesized furanone derivative into the formulation. The results show that the modified resin composites showed a significant antibacterial activity without substantially decreasing the mechanical strengths. With 5 to 30% addition of the furanone derivative, the composite kept its original CS unchanged but showed a significant antibacterial activity with a 16-68% reduction in the S. mutans viability. Further, the antibacterial function of the new composite was found not to be affected by human saliva. The aging study indicates that the composite may have a long-lasting antibacterial function. In summary, we have developed a novel QAB- and furanone-containing antibacterial system for dental restoratives. Both QAB- and furanone-modified resin composites have demonstrated significant antibacterial activities. The QAS-modified experimental resin composite may not be well suitable for development of antibacterial dental resin composites due to its accelerated degradation in water unless the QAB loading is well controlled. The furanone-modified resin composite shows nearly no reduction in mechanical strength after incorporation of the antibacterial furanone derivative. It appears that the furanone-modified resin composite is a clinically attractive dental restorative that can be potentially used for long-lasting restorations due to its high mechanical strength and permanent antibacterial function.

Att följa ammonium i reningsverk är avgörande för att förbättra reningsprocessen och kontrollera flödet av föroreningar ut till ekosystemet. Jonselektiva elektroder (ion-selective electrodes, ISEs) är en lovande teknik inom området, där polymermembran baserade på nonactin är de mest studerade membranen för ammoniumsensorer. Membranet droppas tillsammans med ett jon-till-elektron transducerande material på ett elektrodsubstrat av grafit eller glasartat kol. Nonactin-baserade jonselektiva elektroder har typiskt en detektionsgräns inom storleksordningen 10-5 M, men uppvisar betydande kaliuminterferenser. Ett elektrodsystem baserat på grafitelektroder, inkluderande en ISE och en referenselektrod (RE), studerades i detta examensarbete. De jonselektiva elektroderna producerades genom att droppa jon-till-elektron trandsducerande funktionella flerväggiga kolnanotuber (functional multiwalled carbon nanotubes, f-MWCNTs) lösta i tetrahydrofuran (THF) och en membrancocktail innehållande polyvinylklorid (PVC), mjukgörare och nonactin löst i THF på grafitelektroder. Membranet täcktes sedan med en buffrad polyvinylalkohol (PVA) hydrogel med pH 7 och ett gas-permeabelt membran. Referenselektroderna producerades genom att droppa en membrancocktail av polyvinylbutyral (PVB) mättat med NaCl på grafitelektroder. Jonselektiva elektroder med f-MWCNTs som jon-till-elektron transducerande lager och ett PVC-baserat ammonium-selektivt membran med nonactin producerades framgångsrikt. Elektroderna hade en detektionsgräns i storleksordningen 10-5 M, vilket kan jämföras med tidigare artiklar publicerade inom området. Ytterligare producerades PVB-baserade referenselektroder mättade med NaCl framgångsrikt. Referenselektroderna uppvisade små variationer när koncentrationer av olika salt varierades. Arbetet visade att det gaspermeabla membranet Hyflon AD i kombination med en PVA hydrogel inte var lämplig i den föreslagna konfigurationen, då hålrum formades i torkningsprocessen av det gaspermeabla membranet och membranet delaminerade. Det föreslogs att beteendet kunde vara en konsekvens av inkompatibilitet mellan PVC och det gaspermeable membranet, till följd av deras skillnad i polaritet. / Monitoring ammonium in wastewater is vital to improve the treatment process and monitor the release of the pollutant into the ecosystem. Ion-selective electrodes (ISEs) is a promising technique in the area where the ISE is often based on a polymeric membrane containing the ionophore nonactin. The polymeric ion-selective membrane is drop-cast onto graphite or glassy carbon electrode substrates together with an ion-to-electron transducing layer. Nonactin-based ISEs typically demonstrate a limit of detection (LOD) in the range of 10-5 M, but exhibit significant potassium interferences. A solid-state system based on graphite electrodes, including an ISE and a reference electrode (RE), was investigated in this study. The ISEs were produced by drop-casting ion-to-electron transducing functional multi-walled carbon nanotubes (f-MWCNTs) dispersed in tetrahydrofuran (THF) and a membrane cocktail comprising poly(vinyl chloride) (PVC), plasticizer, and nonactin dispersed in THF onto graphite electrodes. The membrane was then covered with a buffered poly(vinyl alcohol) (PVA) hydrogel of pH 7 and a gas-permeable membrane (GPM). The solid-state RE was produced by drop-casting a poly(vinyl butyral) (PVB) membrane cocktail saturated with NaCl onto the graphite electrode.  ISEs using f-MWCNTs as ion-to-electron transducers and a PVC-based ammonium-sensitive membrane with nonactin were successfully produced. The electrodes exhibited LODs in the range of 10-5 M, which is comparable to previous articles published on the subject. Additionally, PVB-based solid-state REs saturated with NaCl were successfully produced. The reference electrodes exhibited minor influences when varying the concentrations of various salts. The study showed that the GPM Hyflon AD combined with a PVA hydrogel was not suitable in this configuration, as air voids were formed in the drying process, and the membrane was easily delaminated. It was suggested that this behavior could be a consequence of the incompatibility of PVC and the GPM due to their difference in polarity.

Call number: LD2668 .T4 1984 M93 / Master of Science