"N-(1-methylpyrene) monoaza-15-crown-5 (P5), N-(1-methylpyrene) monoaza-18-crown-6 (P6), N-(9-anthryl-methyl) monoaza-15-crown-5 (A5), N-(9-anthryl-methyl) monoaza-18crown-6 (A6), were synthesized and tested as fluoroionophores for potassium and sodium cations. Upon metal ion complexation, fluorescence yields increased dramatically due to an internal photoinduced electron transfer quenching mechanism (an off-on fluorescence switch). The results for these model compounds led to the design and synthesis of 1,3 alternate calixarene[4]arenecrown-5 (I) and bicyclic peptide (V). Calixarene I was synthesized and found to selectively complex potassium cations as predicted. The design of bicyclic peptide V is directed toward the selective complexation of ammonium cations. The synthesis of V involved the preparation of an open chain hexa-peptide consisting of two trityl-protected homoserine residues. Addition of an amino methyl pyrene across two homoserine residues was attempted by triflating the alcohols. The cyclization of the peptide ring is expeded to produce a basket-like structure that molecular modeling indicates should have improved selectivity over that of nonactin, the current industry standard."

O nitrogênio compõe cerca de 78% da massa da atmosfera terrestre e é um elemento imprescindível para a construção e manutenção da vida. Porém a abundância de nitrogênio atmosférico da Terra é anômala quando comparada a dos demais planetas telúricos. Isso significa que ou a acresção para esses planetas foi diferente (o que é pouco provável) ou a Terra possui alguma característica única que permita a existência de grandes volumes de nitrogênio em sua atmosfera. A tectônica de placas poderia ser essa característica, uma vez que propicia uma conexão direta entre o manto e superfície (ao mesmo tempo em que material é expelido do manto para a superfície, material é transportado da superfície para o manto). Nesse contexto, este trabalho objetiva compreender, através de simulações em laboratório, o papel das zonas de subducção no transporte global do nitrogênio. Para tal, submeteu-se um material que simula sedimentos pelágicos (esmectitas dioctaédricas) dopado com amônio (NH4-esmectita) a diversas condições de pressão e temperatura: desde pressão ambiente até 7.7 GPa (equivalente a ~270 km de profundidade) e com temperaturas variando entre 200oC e 700oC. Os experimentos foram realizados em uma prensa hidráulica de 1000 tonf com câmaras de perfil toroidal e em um forno de alta temperatura e foram analisados por difração de raios X (DRX), espectroscopia infravermelho por Transformada de Fourier (FTIR) e por imageamento SE-MEV-EDS Além disso, o material inicial foi caracterizado por análise térmica diferencial (DTA) e análise química CHN. Os resultados mostram que as transformações de fase sofridas pela NH4-esmectita agem no sentido de preservar o amônio na estrutura durante o processo de subducção. Também foram observadas fases de pressões mais elevadas capazes de conter amônio (buddingtonita, a 7.7 GPa). Percebeu-se que o regime termal da subducção é fundamental para a eficiência do transporte de nitrogênio, visto que em subducções quentes (litosferas oceânicas jovens que subductam em baixo ângulo) ocorre a fusão parcial do material com liberação de parte do amônio em pressões relativamente baixas (~1 GPa, equivalente a 30 km de profundidade). Por outro lado, em subducções frias (litosferas oceânicas antigas que subductam em alto ângulo) o material aprisiona de forma eficiente o nitrogênio até ~270 km de profundidade (7.7 GPa). / Nitrogen composes around 78 wt% of Earth’s atmosphere and is a vital element for the construction and maintenance of life. However, the abundance of Earth’s atmospheric nitrogen is anomalous when compared to the one from other inner planets. This means that or accretion for these planets was different (which is unlikely) or Earth possesses a unique feature that allows the existence of large volumes of nitrogen in its atmosphere. Plate tectonics could be this feature, since it propitiates a direct connection between mantle and surface (at the same time that material is expelled by the mantle in to the surface, material is transported from the surface in to the mantle). In this context, these work objectives the understanding, through laboratoty simulations, the role of subduction zones in the global transport of nitrogen. For that, a material that simulates pelagic sediments (dioctahedral smectite) doped with ammonium (NH4-smectite) was subjected to a series of pressure and temperature conditions: from ambient pressure up to 7.7 GPa (equivalent to ~270 km depth) and temperatures varying between 200oC and 700oC. Experiments were performed in a 1000 tonf hydraulic press with coupled toroidal chambers and in a high temperature furnace and were analyzed by X ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR) and SE-SEM-EDS imaging. Additionally, the starting material was characterized by differential thermal analysis (DTA and CHN chemical analysis Results show that phase transformations suffered by NH4-smectite tend to preserve ammonium inside the mineral structure during subduction. Also, high-pressure ammonium bearing phases were observed (budingtonite at 7.7 GPa). It was perceived that the thermal setting of the subduction is fundamental for the efficiency of nitrogen’s transportation, as in hot subductions (young oceanic lithospheres subducting at low angle) partial melting with partial liberation of ammonium occur in relatively low pressures (~1 GPa, equivalent to 30 km depth). On the other hand, in cold subductions (ancient oceanic lithopsheres subducting at high angles) the material efficiently imprisons nitrogen until ~270 km depth (7.7 GPa).

Uppgiften för examensarbetet har varit att göra en bestämning av ammoniumhalten ibiogasslurry med hjälp av jonkromatografi. Resultatet från analysen har sedan jämförtsstatistiskt för att bland annat se repeterbarheten för metoden. Metoden har även jämförts medden spektrofotometriska metoden som finns på Sobacken, så kallad Langemetoden.Ammoniumhalten är en parameter som påverkar biogasbildningen i rötkammaren och det ärdärför viktigt att denna hålls låg.Jonkromatografi är en separtionsmetod som bygger på jonbyteskromatografi. En separationsker i en kolonn innehållande en stationär fas och genom den flödar den mobila fasen ochäven provet. Den stationära fasen och eleuenten har olika laddningar, för katjonkolonnen ärden stationära fasen negativ och den mobila positiv. Jonkromatografens katjonkolonn kräveratt provet är fritt från alkoholer och partiklar större än 0,45 μm. pH ska även ligga mellan 2,5och 3,5 och provet ska spädas med eluenten. Provet har därför beretts i ett antal steg;centrifugering, surgörning samt filtrering. Eventuella alkoholer har testats genom att köraprovet på HPLC och jämfört med en standard innehållande metanol, etanol, propanol ochbutanol. Resultatet från HPLCn gav att provet var fritt från alkoholer och kunde då analyseraspå jonkromatografen. Spädning hundra gånger krävdes för att en god separation skulle skeoch kromatogrammet skulle kunna integreras på ett bra sätt. För att få ut koncentrationengjorde en standardkurva för ammoniumjoner.Resultatet från mätningarna har gett att repeterbarheten för jonkromatografen är god.Jämförelse mellan jonkromatografin och Langemetoden visade att det fanns en signifikantskillnad mellan mätningarna, där jonkromatografin endast ger ca 65 % av värdet frånLangemetoden. En test visade att Langemetoden reagerar med aminosyrakväve, intekvantitativt, men så mycket att det skulle kunna förklara skillnaden mellan metoderna.Resultatet pekar på att de höga koncentrationerna av ammoniumkväve som man uppmäter vidSobacken, i verkligheten är klart lägre. Vidare undersökningar krävs för att klarlägga dettanoggrannare.

Resumo: O objetivo do trabalho foi analisar o Ajifer L40 como fonte alternativa de fertilizante nitrogenado na produção de matéria seca, nutrientes da folha e atributos químicos do solo da Brachiaria brizantha cv. Xaraés (capim-Xaraés). O experimento foi conduzido em área do Sindicado Rural no município de Araçatuba, localizado na região da Alta Noroeste do Estado de São Paulo, no período de outubro de 2005 a maio de 2009 em solo classificado como Latossolo Vermelho Amarelo. O delineamento experimental foi em blocos casualizados com 10 tratamentos e três repetições. Os tratamentos foram arranjados em esquema fatorial 3 x 3 + 1, sendo três doses de nitrogênio (100, 200 e 400 kg ha-1 ano-1) e três fontes (uréia, sulfato de amônio e Ajifer L40) e um tratamento adicional (testemunha com dose 0 de N). Os fertilizantes apresentaram resposta máxima média dos quatro anos de avaliação na dose de 322 kg ha-1 de N. O teor de proteína bruta na parte aérea do capim-Xaraés foi linearmente crescente até a dose de 400 kg ha-1 de N para as três fontes estudadas. O Ajifer L40 e o sulfato de amônio foram importante fonte de enxofre para a nutrição das plantas. As fontes nitrogenadas Ajifer L40 e sulfato de amônio apresentaram comportamento semelhante, proporcionando maior acidez na camada superficial do solo em relação à fonte uréia. A utilização dos fertilizantes Ajifer L40, sulfato de amônio e uréia não alterou a concentração de sódio e a condutividade elétrica no solo. A fonte alternativa Ajifer L40 é similar às outras fontes de fertilizantes convencionais / Abstract: The aim was to evaluate the Ajifer L40 as an alternative source of nitrogen fertilizer on dry matter production, leaf nutrients and soil chemical properties of Brachiaria brizantha cv. Xaraés (Xaraés-grass). The experiment was conducted in Syndicate Rural area in the municipality of Araçatuba, located in Upper Northwest of São Paulo, from October 2005 to May of 2009 in a soil classified as Latosol Yellow Red. The experimental design was randomized blocks with 10 treatments and three replications. The treatments were arranged in a 3 x 3 + 1, three nitrogen levels (100, 200 and 400 kg ha-1 yr-1) and three sources (urea, ammonium sulfate and Ajifer L40) and an additional treatment (control dose of 0 N). Fertilizers showed a mean maximum of four years of evaluation at a dose of 322 kg ha-1 N. The crude protein content in leaves of Xaraés-grass was increasing linearly with doses up to 400 kg ha-1 of N for the three sources studied. The Ajifer L40 and ammonium sulfate were an important source of sulfur for plant nutrition. The nitrogen sources, Ajifer L40 and ammonium sulfate were similar, providing greater acidity in the topsoil is in relation to urea. The use of fertilizers Ajifer L40, ammonium sulfate and urea did not alter the concentration of sodium and electrical conductivity in the soil. The alternative source Ajifer L40 is similar to other conventional sources fertilizers / Orientador: Cecílio Viega Soares Filho / Coorientador: Reges Heinrichs / Banca: Ana Cláudia Ruggieri / Banca: Sílvia Helena Venturoli Perri / Mestre

Digitized by Kansas Correctional Industries

by Cheng Sau Wan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves [72]-[76]). / TABLE OF CONTENTS --- p.i / ABSTRACT --- p.iv / LIST OF FIGURES --- p.vi / LIST OF TABLES --- p.x / Chapter CHAPTER ONE --- RESEARCH BACKGROUND --- p.1 / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.2 --- Matrix-assisted laser desorption / ionization mass spectrometry (MALDI) --- p.2 / Chapter 1.2.1 --- Laser desorption methods --- p.2 / Chapter 1.2.2 --- The matrix --- p.3 / Chapter 1.2.2.1 --- Role of the matrix --- p.3 / Chapter 1.2.2.2 --- Features of the matrix --- p.4 / Chapter 1.2.3 --- Mechanisms of ion formation --- p.6 / Chapter 1.2.3.1 --- Desorption process(es) --- p.6 / Chapter 1.2.3.2 --- Ionization process(es) --- p.7 / Chapter 1.3 --- Sequencing of DNA --- p.8 / Chapter 1.3.1 --- DNA sequencing procedure --- p.10 / Chapter 1.3.1.1 --- Generation of the nested set of DNA molecules --- p.11 / Chapter 1.3.1.2 --- Sequence analysis --- p.11 / Chapter 1.3.2 --- MALDI-TOF-MS as a DNA sequencing tool --- p.12 / Chapter 1.3.3 --- MALDI analysis of oligonucleotides --- p.14 / Chapter 1.4 --- Outline of the present work --- p.16 / Chapter CHAPTER TWO --- INSTRUMENTATION AND EXPERIMENTAL --- p.18 / Chapter 2.1 --- Time-of-flight mass spectrometry (TOF-MS) --- p.18 / Chapter 2.1.1 --- Linear time-of-flight mass spectrometry --- p.18 / Chapter 2.1.2 --- Reflectron time-of-flight mass spectrometry --- p.21 / Chapter 2.1.3 --- Ion detection --- p.22 / Chapter 2.1.4 --- Vacuum system --- p.22 / Chapter 2.2 --- Instrumentation --- p.24 / Chapter 2.2.1 --- The laser system --- p.24 / Chapter 2.2.2 --- Ion source and vacuum system --- p.24 / Chapter 2.2.3 --- Flight tube and reflector --- p.27 / Chapter 2.2.4 --- The detector --- p.28 / Chapter 2.2.5 --- Data acquisition and computer control --- p.28 / Chapter 2.3 --- Experimental --- p.29 / Chapter 2.3.1 --- Sample preparation --- p.29 / Chapter 2.3.2 --- Mass spectrometric analysis --- p.30 / Chapter CHAPTER THREE --- USE OF AMMONIUM SALTS AS CO-MATRICES --- p.32 / Chapter 3.1 --- Introduction --- p.32 / Chapter 3.2 --- Experimental --- p.35 / Chapter 3.3 --- Results and Discussion --- p.36 / Chapter 3.3.1 --- Effects of counter-anions --- p.36 / Chapter 3.3.2 --- Effects of matrix materials --- p.40 / Chapter 3.4 --- Conclusions --- p.43 / Chapter CHAPTER FOUR --- USE OF POTASSIUM SALTS AS CO-MATRICES --- p.44 / Chapter 4.1 --- Introduction --- p.44 / Chapter 4.2 --- Experimental --- p.44 / Chapter 4.3 --- Results and Discussion --- p.44 / Chapter 4.3.1 --- Adduct formation --- p.49 / Chapter 4.3.2 --- Signal enhancement --- p.50 / Chapter 4.4 --- Conclusions --- p.52 / Chapter CHAPTER FIVE --- ANALYSIS OF HIGH MASS OLIGONUCLEOTIDES --- p.53 / Chapter 5.1 --- Introduction --- p.53 / Chapter 5.2 --- Experimental --- p.53 / Chapter 5.3 --- Results and Discussion --- p.54 / Chapter 5.4 --- Conclusions --- p.67 / Chapter CHAPTER SIX --- CONCLUSIONS AND FURTHER WORK --- p.68 / Chapter 6.1 --- Conclusions --- p.68 / Chapter 6.2 --- Further work --- p.70 / ACKNOWLEDGMENT --- p.A1 / REFERENCES --- p.R1 - R5

O etanol é o combustível que mais se destaca como alternativa à gasolina no setor do transporte. No entanto, a melhoria da eficiência da fermentação, aprimorando o processo de conversão de biomassa em etanol combustível e reduzindo o custo de produção são desafios ainda pertinentes. Neste cenário, as fermentações com alta concentração de açúcar ou VHG (very high gravity) estão sendo cada vez mais estudadas. A adição de compostos como fonte de nitrogênio pode gerar benefícios para a produção de etanol, entretanto, a maioria dos estudos com suplementação de fontes nitrogenadas é realizada em sistema descontínuo simples e em escala laboratorial, embora os processos fermentativos industriais sejam conduzidos em sistema descontínuo alimentado. Neste contexto, este trabalho visou avaliar o perfil fermentativo da linhagem CAT-1 em mosto contendo alta concentração de açúcar fermentescível e suplementado com as fontes nitrogenadas peptona e sulfato de amônio, nas concentrações 5 e 10 g/L, em sistema de descontínuo simples e descontínuo alimentado com reciclo de células, utilizando diferentes escalas produtivas. Nos experimentos em sistema descontínuo simples, os tratamentos controle e peptona (5 g/L) apresentaram uma melhor produção de etanol, maior rendimento e produtividade em comparação com os demais tratamentos. Nos experimentos em sistema descontínuo alimentado não houve diferença significativa entre os tratamentos controle e peptona 5 e 10g/L, porém, o tratamento com sulfato de amônio (10 g/L) apresentou parâmetros fermentativos de produção de etanol e produtividade superiores ao tratamento controle, o oposto do descontínuo simples. Os resultados mostraram que quando as células de levedura foram submetidas a concentrações crescentes de açúcar, como é o caso do sistema descontínuo alimentado, ocorre uma adaptação das mesmas, proporcionando melhores resultados, com uma redução no tempo de fermentação para 16h. Além disso, a alta concentração de etanol no meio fermentativo causa um efeito prejudicial às células, já que nos tratamentos onde houve teores mais elevados de etanol ocorreu menor viabilidade e maior quantidade de açúcar residual. / Ethanol is the fuel that stands out as an alternative to gasoline in the transportation sector. However, improving the efficiency of fermentation, improving the process of converting biomass to fuel ethanol and reducing the cost of production are still relevant challenges. In this scenario, fermentations with high sugar concentration or very high gravity (VHG) are being studied more and more. The addition of compounds as a source of nitrogen can generate benefits for ethanol production, however, most of the studies with nitrogen supplementation are carried out in a simple discontinuous system and in laboratory scale, although the industrial fermentation processes are conducted in a fed batch system . In this context, the objective of this work was to evaluate the fermentation profile of the CAT-1 strain in must containing high fermentable sugar concentration and supplemented with nitrogen peptone and ammonium sulfate at 5 and 10 g / L in a simple discontinuous system and fed batch system, fed with recycle of cells, using different productive scales. In the simple discontinuous system experiments, the control and peptone treatments (5 g / L) presented better ethanol production, higher yield and productivity in comparison to the other treatments. However, the treatment with ammonium sulfate (10 g / L) showed fermentative parameters of ethanol production and productivity higher than the control treatment, the opposite of simple discontinuity. The results showed that when the yeast cells were submitted to increasing concentrations of sugar, as is the case of the fed batch system, an adaptation occurs, providing better results, with a reduction in the fermentation time to 16h. In addition, the high concentration of ethanol in the fermentation medium causes a detrimental effect on the cells, since in the treatments with higher levels of ethanol; less viability and more residual sugar were observed.

Acid-base disturbances have serious clinical consequences and are particularly critical in patients whose cardiopulmonary function is compromised. Cellular transport of NH3 and NH4+ has important physiological significance in the regulation of acid-base balance. In the kidney, production and excretion of NH3/NH4+ is critical for net acid excretion. Recently, two non-erythroid glycoproteins (Rhbg and Rhcg) belonging to the Rh family were suggested to be involved in NH3/NH4+ transport. Thus far, the functional properties of these membrane proteins as transport mechanisms are not resolved. In this study, we expressed Rh proteins in Xenopus oocytes and demonstrated that they transport both NH4+ and NH3. As such, the Rh transporters are unique in being able to transport both the ionic and the neutral gaseous components of ammonia. Previous studies have shown that DIDS, a stilbene derivative known to inhibit anion exchangers, was shown to inhibit CO2 transport by AQP1. This led us to hypothesize that DIDS might also inhibit transport of other gases such as NH3 by Rh proteins. We therefore conducted the present study to test the effects of DIDS on NH4+ and NH3 transport by Rh glycoproteins. To do so we used ion-selective microelectrodes and two-electrode voltage clamp to measure changes in surface pH (pHs) and whole cell currents (I) induced by NH3/NH4+ and methyl ammonium (MA/MA+) with or without DIDS. All experiments were conducted in Xenopus oocytes expressing Rhbg. Rhbg was expressed by injecting the oocytes with cRNA of the cloned genes. Control oocytes were injected with H2O. Our results indicate that in oocytes expressing Rhbg, exposure to 5mM NH4Cl (NH3/NH4+) caused a decrease in surface pH (pHs) and an inward current. The decrease in pHs is caused by NH3 influx whereas the inward current is due to electrogenic NH4+ influx. In the presence of DIDS, exposure to 5mM NH4Cl caused a significantly smaller decrease in pHs and current. The %inhibition of pHs and ΔI were 33% and 49%, respectively (P<0.05). Similarly, exposing oocytes expressing Rhbg to 5mM MA/MA+ (a substitute to NH3/NH4+) caused a decrease in pHs and an inward current. In the presence of DIDS, the MA/MA+ induced changes in pHs and current were also inhibited (37% and 63%, respectively; P<0.05). DIDS had no effect on NH3/NH4+ transport in H2O-injected oocytes (not expressing Rhbg). In summary, our data support the following conclusions: 1) RhAG and Rhbg transport both the ionic NH4+ and the neutral NH3 species. 2) Transport of NH4+ is electrogenic. 3) RhAG and Rhbg expression both enhance MA transport, an electroneutral component. 4) Like Rhbg, RhAG also transports MA+, an electrogenic component. The charged MA+ seems to be a direct substrate for RhAG whose transport likely resembles that of NH4 +. 5) Rhcg is likely to be a predominantly NH3 transporter. 6) RhAG and Rhbg are unlikely to be NH4 +/H+ exchangers. Regarding the effect of DIDS, our data also indicate that 1) DIDS partially inhibits the transport of NH3 and MA by Rhbg without affecting endogenous NH3 and MA transport. 2) DIDS also inhibits the electrogenic transport of NH4 + and MA+ by Rhbg. 3) DIDS is the only inhibitor shown to block both gas (NH3) and ionic (NH4 +) transport by Rhbg. / acase@tulane.edu

Crops grown in sandy soils require frequent irrigation. As a result, nitrogen (N) fertilizers. such as ammonium sulfate((NH4)2SO4), are leached from the rooting zone of crops. This loss of N increases N fertilizer use and the potential for nitrate (NO3-) contamination of water. Ammonium-loaded clinoptilolite (NH4+-Cp) may reduce this N leaching, increase N fertilizer use-efficiency, and prevent NO3- contamination of water while sustaining normal crop growth. The potential of NH4+-Cp as a N fertilizer was assessed in three leaching experiments without plants and two leaching experiments with plants. Pots containing rounded quartz sand were amended with (NH4)2SO4 and one of three NH4+-Cp size fractions: small ( Finally, in two leaching studies, pots containing the sandy soil were planted with sweet corn and grown for 35 d and 42 d, respectively. No differences were found among N sources in corn relative growth rates, leaf area ratios, and net assimilation rates, even though the corn plants that were fertilized with NH4+-Cp assimilated significantly more N than the (NH4)2SO4-fertilized plants. The pots fertilized with NH5+-Cp leached In the greenhouse, NH4+-Cp is a slow-release fertilizer that will reduce N leaching while maintaining normal plant growth. However, field studies are needed to confirm the suitability of NH4+-Cp as a slow-release fertilizer under field conditions.

Investigations were carried out to study the effect of alternate wetting and drying cycles on the mineralization, nitrification, and denitrification of soil nitrogen in two soils, in the presence or absence of added ammonium and nitrite. Soils were analyzed at the end of each drying cycle for total inorganic nitrogen, ammonium, and nitrite nitrogen. Gaseous products, i.e., ammonia, and the oxides of nitrogen (NO and NO2) were collected in the course of drying for determination. The drying cycles accelerated the rate of nitrogen mineralization in both soils and further increased the oxidation of applied and available ammonium. The rate of ammonium transformation was faster in Yolo clay loam soil than in Miami silt loam. A faster rate of nitrification was also observed in Yolo clay loam. This may be because of a higher pH of the Yolo clay loam soil. The successive drying cycles had a pronounced effect on the nitrate formation in both soils. The extent of nitrite decomposition was inversely related to soil pH. The amount of nitrogen oxides (NO and NO2) evolved were inversely related to soil pH, but significant amounts of NO and N02 were evolved from even the slightly alkaline Yolo clay loam. The loss of nitrogen oxides increased with increased number of drying cycles and, further, the losses of nitrogen increased with increase in nitrite level. The majority of the nitrogen losses from these soils may be due to the direct decomposition of nitrite and possibly slight losses due to an interaction of nitrite and ammonium ions during the course of drying the soil. A considerable amount of nitrogen remained as undetected in treatments receiving either ammonium or nitrite or both. These losses of nitrogen apparently are other than by the release of NO, NO2, and NH3. The undetected nitrogen loss from the soil system may be either in the form of N2O or N2. No volatile losses of ammonia were recorded from the acid Miami silt loam soil. The greatest amount of applied ammonium nitrogen volatilized as ammonia in Yolo clay loam during the initial drying cycles. The rate of ammonia volatilization increased with increase in applied ammonium concentration.