Análise do circuito de água de refrigeração de uma unidade de regeneração de solventes

A EGEO Solventes S.A. é uma empresa com atividade na área da gestão de resíduos, focando-se na regeneração de solventes. Na unidade industrial da empresa recorre-se à destilação de misturas de solventes usados para obtenção do solvente regenerado. Esta operação exige água para o arrefecimento e condensação dos destilados das misturas de solventes, que, posteriormente, é arrefecida em torres de refrigeração instaladas na unidade. Durante o tempo de operação da unidade foram identificados problemas na condensação dos solventes limpos, obrigando a que se ligassem dois condensadores em série para assegurar a condensação do vapor produzido na destilação e à necessidade de caudais maiores de utilidade fria. Outro dos problemas identificados foi a baixa eficiência das torres de refrigeração, uma vez que a diferença de temperaturas da água à entrada e à saída do equipamento é muito baixa. Assim sendo, o objetivo principal deste trabalho é identificar as principais causas para a baixa eficiência dos equipamentos e propor alterações aos equipamentos ou soluções de melhoria do processo. Para diagnosticar estes problemas foram recolhidas amostras para determinação da composição do solvente limpo obtido e registadas as condições de operação para obtenção da mistura ECOSOLVE MET. Recorrendo a metodologias de projeto determinou-se o fator de resistência do fouling no condensador C1 e seguidamente a geometria, a alocação de correntes e a orientação do condensador mais adequadas e concluiu-se que este está sujeito a uma forte acumulação de material nas paredes e que a melhor opção seria recorrer a um permutador horizontal com condensação na carcaça, mas aumentando o número de passagens da água nos tubos. No que diz respeito à operação da torre de arrefecimento, determinou-se o caudal mínimo de ar para determinadas condições de operação e verificou-se que o caudal de ar alimentado à torre era superior ao mínimo determinado. Foram observadas diferenças quando comparadas as condições de operação experimentais com a performance da unidade usando oito enchimentos estruturados e aleatórios para os quais há dados na literatura São também apresentadas alternativas de operação e o projeto de uma torre de arrefecimento de água, sustentada numa análise económica de todo o processo. As simulações foram realizadas com recurso ao AspenPlus®.

Embolisation of Vertebral Artery Damaged Following Cervical Disc Removal

Introduction: The incidence of vertebral artery (VA) injury during cervical spine surgery is rare. Even though tamponade is effective in many cases, early consultation of an endovascular team is recommended if bleeding cannot be controlled. We report a case of emergent endovascular embolisation of left VA due to iatrogenic injury during anterior cervical disc removal and fusion. Case: A 47-year-old woman was admitted to our emergency department with serious arterial bleeding from the neck only hours after undergoing anterior cervical disc removal and fusion surgery. She was intubated and mechanically ventilated, however hemorrhage could not be successfully controlled by packing with surgical hemostatic agents. Cranial computed tomography, computed tomography of the cervical spine and CT angiography confirmed the suspected diagnosis of injury to the VA. Emergent endovascular embolisation successfully stopped the bleeding. Occlusion of the vessel was achieved by vascular plugging. The patient was discharged from our hospital 14 days after the intervention, receiving a revision surgery of the cervical spine on the day of embolisation. At the date of discharge she presented without any focal neurological deficit. Conclusion: Pre-operative radiographic imaging of the cervical spine should be used routinely to identify anatomic abnormalities of the vertebral arteries. Endovascular embolisation appears to be effective in treating acute iatrogenic dissection of the vertebral arteries.

Modified atmosphere packaging effects on the postharvest quality of papaya fruit

Export of Fijian papaya (Carica papaya) fruit to destinations such as New Zealand has increased significantly over the last several years. Shipment by sea rather than air is the preferred method, given the capacity for larger volumes and reductions in cost. Long shipping times, however, can compromise fruit quality, although the use of modified atmosphere packaging (MAP) may provide a viable solution for extending fruit storage life. In a collaborative ACIAR project, Australian and Fijian researchers investigated the potential of using MAP to extend storage life of a Fijian papaya ('Fiji Red') fruit based on simulated sea transport conditions. Fruit were packed in one of three MAP environments within cartons, consisting of either a (1) Low Density Polyethylene (LDPE) bag with 10 g of KMnO4, (2) Polyamide Film (PF) bag with macro-perforations or (3) without a bag (control fruit). Fruit were held for 1, 2 or 3 weeks at 10°C before being unpacked, ripened and assessed for quality. On day 6 after outturn, fruit with the highest overall quality were those held in LDPE bags. LDPE fruit generally coloured up faster at outturn than PF or control fruit, had less overall moisture loss and scored high in flavour. Headspace carbon dioxide and oxygen concentrations within the LDPE bags were also near recommended levels for maintaining optimum storage-life quality. The LDPE bag provided the most suitable conditions for long term storage of fresh papaya fruit and is therefore the recommended MAP type for use with sea freight export out of Fiji.

Carbon-carbon bond formation methods for the preparation of shape-persistent architectures

Carbon-rich, conjugated organic scaffolding is a popular basis for functional materials, especially for electronic and photonic applications. However, synthetic methods for generating these types of materials lack diversity and, in many cases, efficiency; the insistence of investigators focusing on the properties of the end product, rather than the process in which it was created, has led to the current state of the relatively homogeneous synthetic chemistry of functional organic materials. Because of this, there is plenty of room for improvement at the most basic level. Problems endemic to the preparation of carbon-rich scaffolding can, in many cases, be solved with modern advances in synthetic methodology. We seek to apply this synthesis-focused paradigm to solve problems in the preparation of carbon-rich scaffolds. Herein, the development and utilization of three methodologies: iridium-catalyzed arene C-H borylation; zinc- mediated alkynylations; and Lewis acid promoted Mo nitride-alkyne metathesis, are presented as improvements for the preparation of carbon-rich architectures. In addition, X-ray crystallographic analysis of two classes of compounds are presented. First, an analysis of carbazole-containing arylene ethynylene macrocycles showcases the significance of alkyl chain identity on solid-state morphology. Second, a class of rigid zwitterionic metal-organic compounds display an unusual propensity to crystallize in the absence of inversion symmetry. Hirshfeld surface analysis of these crystalline materials demonstrates that subtle intermolecular interactions are responsible for the overall packing motifs in this class of compounds.

Modificação da pasta kraft de eucalipto para novas aplicações

Este trabalho constou num estudo da modificação da pasta kraft de eucalipto, utilizando uma técnica de processamento por alta pressão hidrostática com o intuito de melhorar a sua performance para novas aplicações tal como o papel tissue ou o papel para embalagens. Para tal pretendia-se melhorar algumas propriedades da pasta com a utilização da técnica de alta pressão hidrostática. Realizou-se um estudo preliminar onde se submeteu uma pasta branqueada A, não refinada, a um tratamento hiperbárico (TH) numa gama de pressões de 5000-8000 bar. Para uma pressão de 6000 bar constatou-se uma melhoria de cerca de 16 % no alongamento percentual na rotura, 17 % na resistência à tração, 27 % no índice de rebentamento e cerca de 19 % no índice de rasgamento. Posteriormente, e tendo em conta os resultados positivos verificados na pasta A, estudou-se o efeito do TH numa pasta branqueada B variando a consistência de tratamento (1,5% ou 3%) e o tempo de processamento (5 ou 10 minutos). Foi estudado também o efeito do TH quando aplicado antes e após a refinação da pasta. A pasta branca foi submetida à refinação num moinho PFI entre 1000 e 3000 rotações. Os resultados obtidos mostram que o TH realizado a menores consistências apresenta um efeito mais significativo nas propriedades físico-mecânicas de pastas e que o efeito é distinto quando o processamento é aplicado antes e depois da refinação, tendo-se registado melhoramentos das propriedades mecânicas apenas quando o TH ocorre após a refinação. A pasta kraft foi também modificada com anidrido alquenil succínico (ASA). A modificação da pasta de celulose com ASA resultou numa diminuição das propriedades mecânicas e para além disso não gerou qualquer alteração na termoplasticidade do material, no entanto registou-se um aumento na resistência à molhabilidade. Concluiu-se que o TH conduz a alterações ao nível de propriedades mecânicas e estruturais da pasta de interesse para a aplicação em papéis tissue no caso da pasta B. Para além disso a modificação da pasta com ASA resultou em alterações de interesse particular para papéis de embalagem.

Postharvest handling practices and irradiation increase lenticel discolouration in ‘B74’ mango fruit

ABSTRACT 'B74' mango is a recently commercialised cultivar in Australia, with an appealing skin colour and firm fibreless flesh. However, fruit can develop lenticel discolouration (LD) after harvest, with loss of commercial value, especially after γ-irradiation as a disinfestation treatment. We hypothesised that postharvest practices could increase fruit sensitivity to LD and tested that by sequentially sampling fruit between the orchard and the end of the packing line over two seasons, followed by ripening without and with irradiation treatment. Exposure of 441-610 Gy γ-irradiation significantly increased the severity of LD by 6.8-fold in commercially picked and packed ripe fruit, reducing the proportion of marketable fruit from 98% to 2%, compared to irradiated fruit harvested directly from the trees and not exposed to de-sapping solution and packing operations. Also, LD increased progressively as the fruit passed through the harvesting and packing processes, and exposure to only bore water increased LD severity compared with no water contact. Results suggest that the typical de-sapping process used during harvesting is a major contributor to skin sensitivity to LD in 'B74' mango fruit, and that other packing operations involving wetting of the fruit have an additive effect on it. These effects are exacerbated if fruit is irradiated.

Adsorção de cromo (VI) em leito fixo utilizando partículas de areia recobertas com Quitosana

Neste trabalho foi avaliado o processo de recobrimento de partículas de areia com quitosana utilizando a técnica dip-coating, e analisado o emprego destas partículas como recheio de uma coluna de leito fixo no processo de adsorção de cromo (VI) em solução aquosa. A quitosana foi obtida a partir de resíduos de camarão e caracterizada. O estudo avaliou a influência do tamanho das partículas e da concentração da solução de quitosana no recobrimento das partículas de areia. Foram avaliados parâmetros termodinâmicos, isotermas de equilíbrio e parâmetros relacionados ao funcionamento do leito (vazão e pH da solução, diâmetro de partícula) para o processo de adsorção de cromo (VI) em solução aquosa. No recobrimento das partículas de areia, o tamanho não teve significância na resposta, enquanto a concentração da solução de recobrimento mostrou ter grande influência sobre o resultado, sendo que a menor concentração de quitosana dentro da faixa estudada (0,5% p/v) apresentou o melhor desempenho. O processo de cura física para o recobrimento das partículas de areia mostrou melhor desempenho para a adsorção de cromo (VI) em leito fixo frente ao processo físico-químico. As análises de superfície (MEV) e de difração de raio-X (EDX) comprovaram a mudança na superfície das partículas recobertas e a presença de cromo após a adsorção. O modelo de Sips foi o que melhor representou os dados experimentais de equilíbrio, com R2 >0,99% e EMR<3,5%, sendo que a capacidade máxima de adsorção foi de 46,93 mg g-1 obtida a 298 K. O processo se mostrou espontâneo, exotérmico e favorável, com valores de -4,49 a -4,66kJ mol-1 para e energia livre de Gibbs, -5,97kJ mol-1 para a variação de entalpia e -5,17x10-3 kJ mol-1K -1 para variação de entropia. O aumento do pH diminuiu a adsorção de cromo (VI), sendo que a melhor resposta foi obtida em pH 3, sendo que o diâmetro de partícula não teve efeito significante. O estudo da vazão da solução de cromo (VI) no desempenho do leito mostrou que no menor valor (2,5 mL min-1 ) a concentração de saída do leito foi próxima a zero, mantendo-se com concentrações de saída abaixo de 20% por pelo menos 20 min. O estudo da dessorção do leito mostrou que após cinco ciclos de trabalho o leito manteve 86% da capacidade de adsorção, com taxas de recuperação do cromo no processo de dessorção maiores que 95%.

Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.

3D Porous Architecture of Stacks of β-TCP Granules Compared with That of Trabecular Bone: A microCT, Vector Analysis, and Compression Study

International audience

Essays in Greenhouse/Nursery Economics

This dissertation focuses on the greenhouse and nursery industry in the United States. Two major issues are explored: irrigation and plant disease. The first two essays examine wireless soil-moisture sensor networks, an emerging technology that measures soil moisture and optimizes irrigation levels in real time. The first essay describes a study in which a nationwide survey of commercial growers was administered to generate estimates of grower demand and willingness to pay for sensor networks. We find that adoption rates for a base system and demand for expansion components are decreasing in price, as expected. The price elasticity of the probability of adoption suggests that sensor networks are likely to diffuse at a rate somewhat greater than that of drip irrigation. In the second essay, yields, time-to-harvest, and plant quality were analyzed to measure sensor network profitability. Sensor-based irrigation was found to increase revenue by 62% and profit by 65% per year. The third essay investigates greenhouse nursery growers’ response to a quarantine imposed on the west coast of the United States from 2002 to present for the plant pathogen that causes Sudden Oak Death. I investigate whether growers choose to 1) improve their sanitation practices, which reduces the underlying risk of disease without increasing the difficulty of detecting the pathogen, 2) increase fungicide use, which also prevents disease but makes existing infections much harder to detect, or 3) change their crop composition towards more resistant species. First, a theoretical model is derived to formalize hypotheses on grower responses to the quarantine, and then these predictions are empirically tested using several public data sources. I do not find evidence that growers improve their sanitation practices in response to the quarantine. I do, however, find evidence that growers heavily increase their fungicide use in response to a quarantine policy that requires visual (as opposed to laboratory) inspection for the disease before every crop shipment, suggesting that the quarantine may have the adverse effect of making the pathogen harder to identify. I also do find evidence that growers shift away from susceptible crops and towards resistant crops.

Otimização e análise mecânica de pastas geopoliméricas para uso em poços sujeitos à injeção cíclica de vapor

Oil wells subjected to cyclic steam injection present important challenges for the development of well cementing systems, mainly due to tensile stresses caused by thermal gradients during its useful life. Cement sheath failures in wells using conventional high compressive strength systems lead to the use of cement systems that are more flexible and/or ductile, with emphasis on Portland cement systems with latex addition. Recent research efforts have presented geopolymeric systems as alternatives. These cementing systems are based on alkaline activation of amorphous aluminosilicates such as metakaolin or fly ash and display advantageous properties such as high compressive strength, fast setting and thermal stability. Basic geopolymeric formulations can be found in the literature, which meet basic oil industry specifications such as rheology, compressive strength and thickening time. In this work, new geopolymeric formulations were developed, based on metakaolin, potassium silicate, potassium hydroxide, silica fume and mineral fiber, using the state of the art in chemical composition, mixture modeling and additivation to optimize the most relevant properties for oil well cementing. Starting from molar ratios considered ideal in the literature (SiO2/Al2O3 = 3.8 e K2O/Al2O3 = 1.0), a study of dry mixtures was performed,based on the compressive packing model, resulting in an optimal volume of 6% for the added solid material. This material (silica fume and mineral fiber) works both as an additional silica source (in the case of silica fume) and as mechanical reinforcement, especially in the case of mineral fiber, which incremented the tensile strength. The first triaxial mechanical study of this class of materials was performed. For comparison, a mechanical study of conventional latex-based cementing systems was also carried out. Regardless of differences in the failure mode (brittle for geopolymers, ductile for latex-based systems), the superior uniaxial compressive strength (37 MPa for the geopolymeric slurry P5 versus 18 MPa for the conventional slurry P2), similar triaxial behavior (friction angle 21° for P5 and P2) and lower stifness (in the elastic region 5.1 GPa for P5 versus 6.8 GPa for P2) of the geopolymeric systems allowed them to withstand a similar amount of mechanical energy (155 kJ/m3 for P5 versus 208 kJ/m3 for P2), noting that geopolymers work in the elastic regime, without the microcracking present in the case of latex-based systems. Therefore, the geopolymers studied on this work must be designed for application in the elastic region to avoid brittle failure. Finally, the tensile strength of geopolymers is originally poor (1.3 MPa for the geopolymeric slurry P3) due to its brittle structure. However, after additivation with mineral fiber, the tensile strength became equivalent to that of latex-based systems (2.3 MPa for P5 and 2.1 MPa for P2). The technical viability of conventional and proposed formulations was evaluated for the whole well life, including stresses due to cyclic steam injection. This analysis was performed using finite element-based simulation software. It was verified that conventional slurries are viable up to 204ºF (400ºC) and geopolymeric slurries are viable above 500ºF (260ºC)

Problemas de corte : métodos exactos y aproximados para formulaciones mono y multi-objetivo

Los problemas de corte y empaquetado son una familia de problemas de optimización combinatoria que han sido ampliamente estudiados en numerosas áreas de la industria y la investigación, debido a su relevancia en una enorme variedad de aplicaciones reales. Son problemas que surgen en muchas industrias de producción donde se debe realizar la subdivisión de un material o espacio disponible en partes más pequeñas. Existe una gran variedad de métodos para resolver este tipo de problemas de optimización. A la hora de proponer un método de resolución para un problema de optimización, es recomendable tener en cuenta el enfoque y las necesidades que se tienen en relación al problema y su solución. Las aproximaciones exactas encuentran la solución óptima, pero sólo es viable aplicarlas a instancias del problema muy pequeñas. Las heurísticas manejan conocimiento específico del problema para obtener soluciones de alta calidad sin necesitar un excesivo esfuerzo computacional. Por otra parte, las metaheurísticas van un paso más allá, ya que son capaces de resolver una clase muy general de problemas computacionales. Finalmente, las hiperheurísticas tratan de automatizar, normalmente incorporando técnicas de aprendizaje, el proceso de selección, combinación, generación o adaptación de heurísticas más simples para resolver eficientemente problemas de optimización. Para obtener lo mejor de estos métodos se requiere conocer, además del tipo de optimización (mono o multi-objetivo) y el tamaño del problema, los medios computacionales de los que se dispone, puesto que el uso de máquinas e implementaciones paralelas puede reducir considerablemente los tiempos para obtener una solución. En las aplicaciones reales de los problemas de corte y empaquetado en la industria, la diferencia entre usar una solución obtenida rápidamente y usar propuestas más sofisticadas para encontrar la solución óptima puede determinar la supervivencia de la empresa. Sin embargo, el desarrollo de propuestas más sofisticadas y efectivas normalmente involucra un gran esfuerzo computacional, que en las aplicaciones reales puede provocar una reducción de la velocidad del proceso de producción. Por lo tanto, el diseño de propuestas efectivas y, al mismo tiempo, eficientes es fundamental. Por esta razón, el principal objetivo de este trabajo consiste en el diseño e implementación de métodos efectivos y eficientes para resolver distintos problemas de corte y empaquetado. Además, si estos métodos se definen como esquemas lo más generales posible, se podrán aplicar a diferentes problemas de corte y empaquetado sin realizar demasiados cambios para adaptarlos a cada uno. Así, teniendo en cuenta el amplio rango de metodologías de resolución de problemas de optimización y las técnicas disponibles para incrementar su eficiencia, se han diseñado e implementado diversos métodos para resolver varios problemas de corte y empaquetado, tratando de mejorar las propuestas existentes en la literatura. Los problemas que se han abordado han sido: el Two-Dimensional Cutting Stock Problem, el Two-Dimensional Strip Packing Problem, y el Container Loading Problem. Para cada uno de estos problemas se ha realizado una amplia y minuciosa revisión bibliográfica, y se ha obtenido la solución de las distintas variantes escogidas aplicando diferentes métodos de resolución: métodos exactos mono-objetivo y paralelizaciones de los mismos, y métodos aproximados multi-objetivo y paralelizaciones de los mismos. Los métodos exactos mono-objetivo aplicados se han basado en técnicas de búsqueda en árbol. Por otra parte, como métodos aproximados multi-objetivo se han seleccionado unas metaheurísticas multi-objetivo, los MOEAs. Además, para la representación de los individuos utilizados por estos métodos se han empleado codificaciones directas mediante una notación postfija, y codificaciones que usan heurísticas de colocación e hiperheurísticas. Algunas de estas metodologías se han mejorado utilizando esquemas paralelos haciendo uso de las herramientas de programación OpenMP y MPI.

Effect of rare earth dopants on structural and mechanical properties of nanoceria synthesized by combustion method

Structural characteristics of combustion synthesized, calcined and densified pure and doped nanoceria with tri-valent cations of Er, Y, Gd, Sm and Nd were analyzed by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). The results showed that the as-synthesized and calcined nanopowders were mesoporous and calculated lattice parameters were close to theoretical ion-packing model. The effect of dopants on elastic modulus, microhardness and fracture toughness of sintered pure and doped ceria were investigated. It was observed that tri-valent cation dopants increased the hardness of the ceria, whereas the fracture toughness and elastic modulus were decreased.

Transporte de juvenis de curimbatá Prochilodus lineatus em diferentes densidades

Transportation of curimbata Prochilodus lineatus juveniles in different densities. Tins study evaluated the effects of curimbata Prochilodus lineatus transportation in three densities (100, 150 and 250 g L-1) on survival, metabolic, ionic and hematological (red series) variables Curimbata juveniles were transported in plastic bag during six hours, and sampled before packing, immediately after die arrival, 24 and 96 hours after transportation During recovery, higher mortality was seen in fish transported in die highest density Water variables, such as conductivity and total ammonia, presented increased values as density increased (p < 005). whereas the opposite occurred with dissolved oxygen Glucose level observed in the arrival was high, significantly reducing after 96 hours Among ionic variables, chloride decreased in higher fish densities and according to sampling times Red series hematological variables, such as hematocrit, red blood cell and hemoglobin, Increased in arrival, but diminished 96 hours after transportation There were no significant differences in the interaction between density and time of sampling for mentioned variables 250 g L-1 density induced the highest mortality rate and the worst variables values measured 96 hours of recovery after the stressing event was enough to return to initial values for hematological variables, but was not sufficient to return to initial values for metabolic and ionic variables.

Étude de propriétés physico-chimiques des membranes lipidiques chargées d’acide palmitique/stérol et de stéarylamine/cholestérol

Les stérosomes, des vésicules artificielles composées d’amphiphiles monoalkylés et d’un grand pourcentage de stérols, sont prometteurs dans plusieurs domaines comme les industries pharmaceutiques et alimentaires. Il existe des stérosomes chargés négativement, positivement et neutres. Dans ce mémoire, nous avons approfondi nos connaissances sur les propriétés physico-chimiques des stérosomes chargés : acide palmitique (PA)/stérol et stéarylamine (SA)/cholestérol (Chol). Premièrement, afin de mesurer la diffusion latérale de PA dans les membranes PA/stérol (30/70 mol/mol) par RMN à gradients pulsés, nous avons tenté de former des bicouches liquide-ordonnées (lo) orientées magnétiquement avec ce mélange. En s'inspirant de l’idée que l’ajout de 1,2-dihexanoyl-sn-glycéro-3-phosphocholine (DHPC), un lipide à courtes chaînes, dans le système 1,2-dimyristoyl-sn-glycéro-3-phosphocholine (DMPC) mène à la formation de bicouches orientées, nous avons étudié la formulation PA perdeutéré/acide hexanoïque (HA)/Chol avec une proportion molaire de 25/18/57 à plusieurs températures; aucune formation de bicouches orientées n’a été observée. Ce résultat pourrait être expliqué par la solubilisation partielle de HA en milieu aqueux. Alors, une quantité insuffisante serait insérée dans la bicouche pour induire son orientation. La formulation PA perdeutéré/DHPC/Chol n’a pas conduit, elle non plus, à des bicouches orientées magnétiquement à des températures et concentrations lipidiques variées. En étudiant le mélange DMPC/DHPC/Chol (67/17/14), nous avons remarqué que la présence de Chol inhibait l'orientation magnétique des bicouches. Tandis que le mélange DMPC/DHPC/stigmastérol (SS) avec les proportions molaires 67/19/14 et 72/21/7 conduisait à des bicouches orientées avec leur normale (n) perpendiculaire au champ magnétique à 40 °C et 50 °C. Ces résultats suggèrent que le mélange PA/SS avec une proportion de lipide à courtes chaînes, HA et DHPC, pourrait mener à des bicouches orientées magnétiquement. Le mélange PA/Chol avec un lipide à courtes chaînes pourrait aussi être étudié en présence des lanthanides. Deuxièmement, nous avons examiné la possibilité de moduler la libération de matériel encapsulé dans des liposomes essentiellement composés de PA et d’un stérol. Il est connu que le mélange PA/Chol (30/70) à pH ≥ 7,5 forme des liposomes très peu perméables. Il est avantageux de pouvoir moduler la perméabilité pour avoir un contrôle sur le temps de libération de leur contenu, qui est un paramètre de grande importance pour les formulations liposomales de médicaments. D’abord, il a été montré que l’acide oléique (OA)/Chol (30/70) est capable de former des vésicules, ce qui n’avait jamais été prouvé auparavant. Par contre, les bicouches OA/Chol (30/70) ne sont pas plus perméables que les bicouches PA/Chol (30/70). L’ajout de 1-palmitoyl-2-oléoyl-sn-glycéro-3-phosphatidylcholine (POPC) dans le mélange PA/Chol n’augmente pas plus la perméabilité. En effet, les cinétiques de relargage de calcéine des vésicules PA/POPC/Chol (15/27.5/57.5), POPC/Chol (40/60) et POPC étaient très semblables à celle de PA/Chol (30/70). Il a été remarqué que les études littéraires se contredisent à propos de la perméabilité à la calcéine des bicouches de phosphatidylcholine (PC). L’explication de ces divergences est inconnue pour le moment. En remplaçant la moitié de la proportion molaire de Chol par le cholate de sodium (SC) dans le mélange PA/Chol (30/70), la membrane n’était pas plus apte à libérer son contenu. Il se pourrait que le SC se retrouvant dans la bicouche n’induit pas une diminution d’empilement. Il est aussi possible que le SC ne s'insère pas dans la membrane à cause de son hydrophilie considérable et il pourrait alors former seul des micelles. En remplaçant complètement le Chol par le sulfate de cholestérol (SChol), un stérol chargé négativement, et en préparant les vésicules à un bas pH, la formulation PA/SChol (30/70) mène à une très grande perméabilité à pH 7.5; le relargage est provoqué par un saut de pH. Nos travaux suggèrent qu'il serait possible de moduler la perméabilité des liposomes en les préparant avec le mélange PA/SChol/Chol en variant les proportions entre 30/63/7 à 30/70/0. Le diagramme pH-composition du mélange PA/SChol/Chol indique que ces proportions conduisent, à pH 7.4, à la coexistence de phases solide et lo en différentes proportions, ce qui pourrait moduler la perméabilité membranaire. Troisièmement, les résultats de perméabilité obtenus avec la calcéine et les difficultés survenues lors de l’extrusion des vésicules encapsulant cette sonde nous ont amené à nous demander si la calcéine interagit avec les bicouches chargées. L’impact de certains anions, dont la calcéine, a été examiné sur les bicouches chargées positivement SA/Chol (50/50). La calorimétrie différentielle à balayage (DSC, de l’anglais differential scanning calorimetry), indique qu’il n’y a aucune transition entre 25 et 90 °C pour les liposomes SA/Chol (50/50) à pH = 7.4. L’ajout de chlorure de sodim (375 mM) n’a pas mené à la formation d’agrégats et aucune transition n’a été observée sur le thermogramme. La formation d’agrégats macroscopiques instantanément après l’ajout d’hydrogénophosphate de sodium (125 mM), de sulfate de sodium (125 mM) et de calcéine (3 mM) a été observée. Une transition a été observée sur les thermogrammes en présence de ces sels. Les agrégats observés pourraient être associés à la transition de phase. L’effet des anions sur la température et l’enthalpie de transition suivent le même ordre que la série d’Hofmeister : sulfate > hydrogénophosphate > chlorure (pas de pic). La calcéine avait l’impact le plus prononcé sur l’agrégation; ceci illustre que la calcéine n’est pas une sonde fluorescente inerte avec le mélange SA/Chol. Elle pourrait être un chaotrope volumineux. De plus, les interactions SA-calcéine plus fortes, menant à l’agrégation des vésicules, que les interactions PC-calcéine pourraient s’expliquer par le fait que la SA est chargée positivement.