abstract: The ability to tolerate bouts of oxygen deprivation varies tremendously across the animal kingdom. Adult humans from different regions show large variation in tolerance to hypoxia; additionally, it is widely known that neonatal mammals are much more tolerant to anoxia than their adult counterparts, including in humans. Drosophila melanogaster are very anoxia-tolerant relative to mammals, with adults able to survive 12 h of anoxia, and represent a well-suited model for studying anoxia tolerance. Drosophila live in rotting, fermenting media and a result are more likely to experience environmental hypoxia; therefore, they could be expected to be more tolerant of anoxia than adults. However, adults have the capacity to survive anoxic exposure times ~8 times longer than larvae. This dissertation focuses on understanding the mechanisms responsible for variation in survival from anoxic exposure in the genetic model organism, Drosophila melanogaster, focused in particular on effects of developmental stage (larval vs. adults) and within-population variation among individuals. Vertebrate studies suggest that surviving anoxia requires the maintenance of ATP despite the loss of aerobic metabolism in a manner that prevents a disruption of ionic homeostasis. Instead, the abilities to maintain a hypometabolic state with low ATP and tolerate large disturbances in ionic status appear to contribute to the higher anoxia tolerance of adults. Furthermore, metabolomics experiments support this notion by showing that larvae had higher metabolic rates during the initial 30 min of anoxia and that protective metabolites were upregulated in adults but not larvae. Lastly, I investigated the genetic variation in anoxia tolerance using a genome wide association study (GWAS) to identify target genes associated with anoxia tolerance. Results from the GWAS also suggest mechanisms related to protection from ionic and oxidative stress, in addition to a protective role for immune function. / Dissertation/Thesis / Results of GWAS for Adults Exposed to 6 H of Anoxia / Results of GWAS for Larvae Exposed to 1 H of Anoxia / Doctoral Dissertation Evolutionary Biology 2018

Le stockage de l'énergie est un domaine en pleine évolution. Le développement des énergies renouvelable et les besoins croissants d'autonomie énergétique (ordinateur portable, Smartphone, voiture électrique) impliquent le développement de nouvelles technologies, plus performantes, moins coûteuses et écologiquement satisfaisantes. Les batteries lithium-air sont vues comme une alternative prometteuse aux batteries lithium- ion, car elles ont une capacité théorique de stockage 2-3 fois plus élevée. La structuration et la réactivité à la cathode est un verrou important. La présente étude se focalise sur le compartiment positif de la cellule, dans lequel les réactions de l’oxygène sont mises en jeu. Dans un premier temps, des modifications de la surface des électrodes de travail qui puissent agir comme fournisseurs de diènes, en utilisant le mécanisme Diels Alder, sont faites afin de changer les propriétés physico-chimiques de surfaces carbonées. Puis, la chimie click a été utilisée comme une deuxième technique de greffage en montrant que l’hydrophobicité des liquides ioniques influe sur la forme de greffage sur la surface des électrodes. Ensuite ces deux mécanismes de greffage sont utilisés pour étudier la réaction de réduction de l’oxygène et la réactivité du superoxyde à l’interface d’une électrode de carbone qui joue le rôle de cathode. / Energy storage is an evolving field. The development of renewable energies and the growing needs for energy autonomy (laptop, smartphone, and electric car) imply the development of new technologies that are more efficient, less costly and ecologically satisfactory. Lithium-air batteries are seen as a promising alternative to lithium-ion batteries, because they have a theoretical storage capacity 2-3 times higher. Structuring and reactivity at the cathode is an important lock. The present study focuses on the positive compartment of the cell, in which the reactions of oxygen are involved. In a first step, modifications of the surface of the working electrodes which can act as diene suppliers, using the Diels Alder mechanism in order to change the physicochemical properties of carbon surfaces. Then click chemistry was used as a second grafting technique showing that the hydrophobicity of the ionic liquids affects the grafting form on the surface of the electrodes. Then these two grafting mechanisms were used to study the oxygen reduction reaction and the reactivity of the superoxide at the interface of a carbon electrode which functions as a cathode.

abstract: This thesis studies three different types of anhydrous proton conducting electrolytes for use in fuel cells. The proton energy level scheme is used to make the first electrolyte which is a rubbery polymer in which the conductivity reaches values typical of activated Nafion, even though it is completely anhydrous. The protons are introduced into a cross-linked polyphospazene rubber by the superacid HOTf, which is absorbed by partial protonation of the backbone nitrogens. The decoupling of conductivity from segmental relaxation times assessed by comparison with conductivity relaxation times amounts to some 10 orders of magnitude, but it cannot be concluded whether it is purely protonic or due equally to a mobile OTf- or H(OTf)2-; component. The second electrolyte is built on the success of phosphoric acid as a fuel cell electrolyte, by designing a variant of the molecular acid that has increased temperature range without sacrifice of high temperature conductivity or open circuit voltage. The success is achieved by introduction of a hybrid component, based on silicon coordination of phosphate groups, which prevents decomposition or water loss to 250ºC, while enhancing free proton motion. Conductivity studies are reported to 285ºC and full H2/O2 cell polarization curves to 226ºC. The current efficiency reported here (current density per unit of fuel supplied per sec) is the highest on record. A power density of 184 (mW.cm-2) is achieved at 226ºC with hydrogen flow rate of 4.1 ml/minute. The third electrolyte is a novel type of ionic liquids which is made by addition of a super strong Brønsted acid to a super weak Brønsted base. Here it is shown that by allowing the proton of transient HAlCl4, to relocate on a very weak base that is also stable to superacids, we can create an anhydrous ionic liquid, itself a superacid, in which the proton is so loosely bound that at least 50% of the electrical conductivity is due to the motion of free protons. The protic ionic liquids (PILs) described, pentafluoropyridinium tetrachloroaluminate and 5-chloro-2,4,6-trifluoropyrimidinium tetrachloroaluminate, might be the forerunner of a class of materials in which the proton plasma state can be approached. / Dissertation/Thesis / Ph.D. Chemistry 2013

abstract: Liquid-liquid interfaces serve as ideal 2-D templates on which solid particles can self-assemble into various structures. These self-assembly processes are important in fabrication of micron-sized devices and emulsion formulation. At oil/water interfaces, these structures can range from close-packed aggregates to ordered lattices. By incorporating an ionic liquid (IL) at the interface, new self-assembly phenomena emerge. ILs are ionic compounds that are liquid at room temperature (essentially molten salts at ambient conditions) that have remarkable properties such as negligible volatility and high chemical stability and can be optimized for nearly any application. The nature of IL-fluid interfaces has not yet been studied in depth. Consequently, the corresponding self-assembly phenomena have not yet been explored. We demonstrate how the unique molecular nature of ILs allows for new self-assembly phenomena to take place at their interfaces. These phenomena include droplet bridging (the self-assembly of both particles and emulsion droplets), spontaneous particle transport through the liquid-liquid interface, and various gelation behaviors. In droplet bridging, self-assembled monolayers of particles effectively "glue" emulsion droplets to one another, allowing the droplets to self-assembly into large networks. With particle transport, it is experimentally demonstrated the ILs overcome the strong adhesive nature of the liquid-liquid interface and extract solid particles from the bulk phase without the aid of external forces. These phenomena are quantified and corresponding mechanisms are proposed. The experimental investigations are supported by molecular dynamics (MD) simulations, which allow for a molecular view of the self-assembly process. In particular, we show that particle self-assembly depends primarily on the surface chemistry of the particles and the non-IL fluid at the interface. Free energy calculations show that the attractive forces between nanoparticles and the liquid-liquid interface are unusually long-ranged, due to capillary waves. Furthermore, IL cations can exhibit molecular ordering at the IL-oil interface, resulting in a slight residual charge at this interface. We also explore the transient IL-IL interface, revealing molecular interactions responsible for the unusually slow mixing dynamics between two ILs. This dissertation, therefore, contributes to both experimental and theoretical understanding of particle self-assembly at IL based interfaces. / Dissertation/Thesis / Ph.D. Chemical Engineering 2013

Avec l’épuisement progressif des ressources pétrolières, la production de biocarburant est actuellement en plein développement. Utiliser la biomasse en tant que source d’énergie permettrait également de limiter la concentration en dioxyde de carbone dans l’atmosphère et ainsi l’effet de serre. Cependant son processus de transformation implique une étape d’hydrodésoxygénation qui nécessite d’avoir recours à des catalyseurs de type sulfure de molybdène dopé par du cobalt ou du nickel. Ces catalyseurs sont également indispensables au cours du traitement du pétrole lors du procédé d’hydrodésulfuration qui est primordial pour limiter la pollution de l’air par les gaz de combustion des carburants. Cette thèse propose une méthode de synthèse et de structuration de catalyseurs massiques NiMoS facile à mettre en œuvre et rapide. Deux solvants ont été utilisés : l’eau et le formamide. L’ajout d’un polymère hydrosoluble amphiphile, le PEO113-b-PLLA32, dans l’eau et de liquides ioniques (BMIMNTf2 et BMIMBF4) dans le formamide ont permis la structuration des matériaux et l’obtention de surfaces spécifiques atteignant 55 m2g-1. Ceci représente une surface importante pour ce type de composé, en particulier dans le cadre d’une synthèse par chimie douce. Les premiers tests catalytiques réalisés vis-à-vis de la réaction d’hydrodésoxygénation de l’acide décanoïque montrent une activité catalytique très prometteuse pour ces matériaux. / With the progressive decrease of oil resources, the production of biomass fuel is a fast growing field. This could limit the concentration of carbon dioxide in the atmosphere and thus the global warming. The production of this kind of fuel requires the use of catalysts such as nickel or cobalt promoted molybdenum sulfide. These materials are also crucial during the refining of oil, an essential step to limit atmospheric pollution during the classic fuel combustion. New methods to synthesize and structure NiMoS catalysts have been developed in this work. Two solvants have been studied: formamide and water. The addition of an amphiphilic water-soluble polymer (PEO113-b-PLLA32) in water and of ionic liquids (BMIMNTf2 and BMIMBF4) in formamide led to the structuring of the materials with specific surface areas up to 55 m2g-1. This is a high value for this kind of material, especially since the synthesis is carried out under soft conditions. The first catalytic tests dealt with decanoïc acid hydrodesoxygenation and highlighted a promising activity for these materials

Recentemente um efeito piezoelétrico foi encontrado quando um filme polimérico, separando duas soluções de eletrólitos em diferentes concentrações, foi deformado. Este efeito foi atribuído à modulação da mobilidade dos íons no polímero. Foi observado que o efeito diminui com o aumento da concentração de eletrólitos. Para entender mais profundamente este último efeito, foram realizados estudos sobre o transporte de água e sal através do polímero, com e sem deformação, e os resultados podem ser resumidos como segue: a) O aumento da hidratação acarreta um aumento na porosidade e um decréscimo na cristalinidade do polímero. b) O aumento da concentração de sal, no interior do polímero acarreta um aumento na permeabilidade, sendo mais pronunciado na presença de deformação. Esses efeitos tornam mais difícil a modulação dos íons, diminuindo o sinal piezoelétrico observado. / Recently a piezoelectric effect was found when a polymeric film, separating two electrolyte solutions at different concentrations, was deformed. This effect was attributed to the modulation of the mobility of the íons in the polymer. It was observed that the effect decreases as the electrolyte concentrations increases. In order to understand more deeply this last effect a study on water and salt transport through the polymer with and without deformation was carried out, and the results may be summarized as follows: a) An increase in hydration of the polymer leads to an increase in porosity and a decrease in cristallinity. b) An increase in the concentration of the salt leads to an increase in permeability, which is more pronounced in the presence of deformation. The effects make more difficult the modulation of the íons, so lower piezoelectric signals are observed.

Neste trabalho estudamos defeitos pontuais em cristais de NaCl + NaF contendo diversos íons divalentes e em especial o íon Pb++. As técnicas usadas foram as de I.T.C. e absorção ótica. Identificamos três novos defeitos e novos agregados de Pb++. Um modelo microscópico para os defeitos observados foi proposto. Dois dos novos picos de I.T.C. são identificados como relaxação do mesmo defeito constituído do íon divalente e um íon F- em sua proximidade. Pela primeira vez observou-se a conversão da relaxação dielétrica de um íon divalente isolado para a de uma posição perturbada. Os íons F- funcionam como armadilhas eficientes para a difusão do íon Pb++. O efeito do raio iônico sobre a relaxação desses defeitos foi observado e discutido. Atribuiu-se tentativamente a um par de vacâncias ao pico de I.T.C. de mais baixa temperatura / This work report results on the study of point defects in NaCl + NaF single crystals doped with several divalent ions and with more details for Pb++ ions. I.T.C. and u.v. spectroscopy were the used techniques. Three new relaxation peaks were found as well as large aggregates of Pb++ and F- ions. A microscopic model for the observed defects is proposed. Two of the new I.T.C. peaks called B and C, are identified as dielectrics relaxation of one defect - its transverse and the longitudinal relaxation modes. This defect is made of one divalent ion one F anion as its close neighbor and one vacancy. For the first time it was observed the conversion of a Pb++ ion from a normal to a perturbed lattice site. The F anions are efficient traps for divalent ion diffusion. The effect of divalent ion radius on the dielectric relaxation of these perturbed defects was observed and discussed. The lower temperature peak is tentatively attributed to relaxation of a divacancy - a pair of positive and negative vacancy bound together

Compostos intercalados de lítio sac considerados materiais apropriados para eletrodos de baterias recarregáveis de lítio. O conhecimento das taxas de difusão, assim como os mecanismos relacionados com a mobilidade dos íons nos espaços interlaminares são portanto pertinentes para a caracterização das propriedades deste tipo de compostos. Investigações por ressonância magnética nuclear tem um papel ativo no estudo do comportamento dinâmico e estrutural destes compostos de lítio sólidos. Por essa razão este trabalho e baseado nos espectros de RMN obtidos entre 150K e 400K em um campo de 2T. As larguras de linha do 1H e do Li+ foram medidas a partir da transformada de Fourier dos FIDs resultantes da excitação da amostra por um pulse &#960/2. O desacoplamento de 1H foi utilizado, quando necessário, para excluir a contribuição dipolar magnética a destes núcleos a largura de linha do 7Li. Os tempos de relaxação spin-rede para os núcleos 7Li e 1H foram obtidos utilizando-se o método de inversão-recuperação. A partir destas medidas, diversos parâmetros dinâmicos e estruturais destes compostos foram encontrados como: energias de ativação, tempos de correlação e coeficientes de difusão dos íons lítio. / Lithium intercalation compounds are considered suitable materials for electrodes in rechargeable lithium batteries. The knowledge of diffusion rates as well as of mechanistic features related with the mobility of ions in the interlamellar spaces is therefore relevant for the regulation of the properties of this kind of compounds. Nuclear magnetic resonance investigations have played an active role in the study of the dynamic and structural behavior of these solid lithium compounds. For this reason this work is based on NMR spectra recorded between 150K and 400K at 2T. The 1H and Li+ linewidths were measured from the Fourier transform of the FIDs following a &#960/2 excitation. IH decoupling was used, when necessary, to exclude the magnetic dipolar contribution of this nucleus to the 7Li linewidth. The 7Li and 1H spin-lattice relaxation time T1 were measured using the inversion-recovery method. Several dynamic and structural NMR parameters were obtained from these NMR measurements like activation energies, correlation times and diffusion coefficients.

Este trabalho apresenta o estudo de vidros e vitro-cerâmicas oxifluoretos de composição PbGeO3 CdF2 PbF2 (Fluorgermanatos de cádmio e chumbo) e de blendas poliméricas formadas entre o eletrólito polimérico PEO:LiC104 (Poli-óxido de eltileno com perclorato de lítio) e o polímero condutor POMA (Poli-orto metoxianilina). Foram utilizadas as técnicas de ressonância magnética nuclear (RMN), ressonância paramagnética eletrônica (RPE), calorimetria exploratória diferencial (DSC) e impedância complexa. Dentre várias aplicações, estes materiais são importantes devido ao grande potencial como eletrólitos sólidos. Este estudo tem como principal objetivo esclarecer os mecanismos de transporte iônico do flúor e do lítio. Os resultados mostraram que os mecanismos da condução iônica nos vítreos oxifluoretos são caracterizados diferentemente em cada região de temperatura estudada. Em baixas temperaturas (T<300K), o processo de relaxação foi atribuído às excitações de baixas-frequências dos modos desordenados. Acima de 300K, porém abaixo da temperatura de transição vítrea, os movimentos do flúor modulam as interações dipolares F-F. As vitro-cerâmicas, obtidas através de tratamentos térmicos dos vidros de oxifluoretos, são materiais compósitos onde nano ou micro-cristais estão dispersos na matriz vítrea. Os resultados de RMN mostraram no intervalo 100 800K, pelo menos três processos de relaxação, que foram associados com (i) movimentos difusionais dos íons de flúor nos cristais de β-PbF2, (ii) mobilidade iônica na matriz vítrea e (iii) íons de flúor de baixa mobilidade (provavelmente PbGeO3-xFx). Os resultados de RMN 1H mostraram que os tempos de correlação associados aos movimentos das macromoléculas nas blendas poliméricas xii são comparáveis aos encontrados na literatura para o PEO/PMMA. A fim de se garantir resultados reprodutíveis, um cuidadoso método de preparação deve ser seguido, assegurando a estabilidade química e a homogeneidade da blenda / This work reports the study of oxifluorides glasses and glass-ceramics of composition PbGeO3 CdF2 PbF2 (Lead cadmium fluorgermanate) and blends formed by the polymer electrolyte PEO:LiC104 (poly etilene oxide and lithium perclorate) and the conducting polymer POMA (poly ortho methox aniline). Nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), differential scanning calorimetry (DSC) and complex impedance techniques were used. Among several applications, these materiais are important as solid electrolytes. The main objective of this work is to study the fluor or lithium ionic transport mechanisms. Results show that the ionic conduction mechanism in oxifluoride glass systems is characteristic of each temperature region. In low temperatures (T < 300K), the relaxation processes were attributed to low-frequency excitations of disorder modes intrinsic to the glassy state of mater. Above 300 K and below of the glass transition temperature the fluorine motions modulate the dipolar F-F interactions. The glasscerarnics, produced form their respective glasses, are composite materiais where nano- or micro-crystals are dispersed on the glassy matrix. The NMR results, in the range 100-800 K, evidenced three separate relaxation process: (i) diffusional motions of fluorine ions in β-PbF2 crystals; (ii) fluorine mobility in the glass matrix and (iii) fluorine ions of low mobility (probably PbGeO3-xFx). The i ll NMR results shown that the correlation time values, associated to the polymeric chains motion in polymer blends, are comparable to those found for PEO/PMMA. In order to get reproducible results, a careful sample preparation process must be undertaken to ensure chemical stability and blend homogeneity.

Submitted by Liliane Ferreira (ljuvencia30@gmail.com) on 2018-05-25T15:44:48Z No. of bitstreams: 2 Dissertação - Francenya Kelley Lopes da Silva - 2018.pdf: 2672570 bytes, checksum: c14c9fc750994778f5b01e31548559c8 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-05-28T11:22:15Z (GMT) No. of bitstreams: 2 Dissertação - Francenya Kelley Lopes da Silva - 2018.pdf: 2672570 bytes, checksum: c14c9fc750994778f5b01e31548559c8 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-05-28T11:22:15Z (GMT). No. of bitstreams: 2 Dissertação - Francenya Kelley Lopes da Silva - 2018.pdf: 2672570 bytes, checksum: c14c9fc750994778f5b01e31548559c8 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-05-04 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Chitins are enzymes that act in the hydrolysis of chitin, a polysaccharide present in insect exoskeletons, crustacean shells, algae and fungal cell walls. Such enzymes can be applied in the preparation of chitosan and chitoligomers for pharmaceutical use, in the control of pathogenic fungi and in the treatment of chitinous residues derived from fishing. Improvement in the production of chitinase and other enzymes by microorganisms can be achieved by the cell immobilization technique, which consists in fixing or confining cells in an inert carrier. The cell immobilization confers protection against the shear force, promotes the easy separation of the cells from the culture medium, as well as the product and decrease of the cost of production, since, it allows the reuse of the biocatalyst. Among the materials used as support in a cellular immobilization, biopolymers, such as alginate, have been highlighted as non-toxic, inexpensive and highly available in nature. The present work aims to immobilize Paenibacillus illinoisensis in a polymer matrix of alginate for chitinase production, evaluating the differences in the production of the enzyme between free and immobilized cells. Thus, an anionic alginate solution containing the cells was dripped into a cationic solution of CaCl2, leading to the instant formation of spheres having an average size of 4 mm. The immobilization efficiency was 99.99% ± 0.01. The biomass was determined during enzymatic production and the maximum values were 1.45 x 108 CFU / mL in 96 hours for immobilized cells and 8.95 x 107 CFU / mL in 48 hours for free cells, evidencing an increase of 62.01% in the amount of cells immobilized in comparation to the free cells. The cell leakage from the immobilization support during the process was evaluated and corresponded to 6.46% of the total cells at the end of the fermentation. The enzymatic activity was 0.902 U in 96 hours for the immobilized cells and 0.641 U in 48 hours for the free cells, demonstrating an activity increase of 40.71%. The immobilized cells were also tested for reuse in a sequential batch system and demonstrated stability in the production for 4 cycles of 96 hours each, losing 21.04% of the initial activity at the end of the fourth cycle. The cellular immobilization methodology resulted in spheres with capacity to maintain the cell viability during the bioprocess, increase of the enzymatic activity, low leakage of cells of the support and reuse capacity, being able to be used in the future for the production of chitinase for its various applications. / As quitinases são enzimas que atuam no processo de hidrólise da quitina, um polissacarídeo presente nos exoesqueletos de insetos, carapaças de crustáceos, em algas e na parede celular de fungos. Tais enzimas podem ser aplicadas na preparação de quitosana e quitoligômeros para uso farmacêutico, no controle de fungos patogênicos e no tratamento de resíduos quitinosos derivados da pesca. A melhoria na produção de quitinase e de outras enzimas por microrganismos pode ser alcançada pela técnica da imobilização celular, que consiste na fixação ou confinamento de células em um suporte inerte. A imobilização celular confere proteção contra a força de cisalhamento, promove a fácil separação das células utilizadas do meio de cultura, bem como do produto e diminuição do custo de produção, uma vez que, possibilita o reuso do biocatalisador. Dentre os materiais utilizados como suporte em uma imobilização celular, os biopolímeros, tais como o alginato, têm recebido destaque por serem atóxicos, baratos e de grande disponibilidade na natureza. O presente trabalho teve como objetivo a imobilização de Paenibacillus illinoisensis em matriz polimérica de alginato para produção de quitinase, avaliando-se as diferenças na produção da enzima entre as células livres e imobilizadas. Para tal, uma solução aniônica de alginato contendo as células foi gotejada em uma solução catiônica de CaCl2, levando a formação instantânea das esferas que apresentaram tamanho médio de 4 mm. A eficiência de imobilização foi de 99,99 % ± 0,01, sendo utilizados para produção de quitinase. A biomassa foi determinada durante a produção enzimática e os valores máximos foram de 1,45 x 108 UFC/ mL em 96 horas para células imobilizadas e 8,95 x 107 UFC/ mL em 48 horas para células livres, evidenciando o aumento da quantidade de células imobilizadas em relação as células livres em 62,01 %. A saída de células do suporte de imobilização durante o processo foi avaliada e correspondeu a 6,46 % do total de células ao final da fermentação. A atividade enzimática foi de 0,902 U em 96 horas para as células imobilizadas em comparação com a das células livres de 0,641 U em 48 horas, demonstrando um aumento da atividade em 40,71 %. As células imobilizadas também foram testadas para a reutilização em um sistema de bateladas sequenciais e demonstraram estabilidade para produção por 4 ciclos de 96 horas cada, perdendo 21,04 % da atividade inicial ao final do quarto ciclo. Desse modo, verificou-se que a metodologia de imobilização celular empregada resultou em esferas com capacidade de manutenção da viabilidade celular durante o bioprocesso, aumento da atividade enzimática, baixa saída de células do suporte e capacidade de reuso, podendo futuramente ser empregada para produção de quitinase para suas diversas aplicações.