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.

Centile curves and reference values for height, body mass, body mass index and waist circumference of peruvian children and adolescents

This study aimed to provide height, body mass, BMI and waist circumference (WC) growth centile charts for school-children, aged 4–17 years, from central Peru, and to compare Peruvian data with North-American and Argentinean references. The sample consisted of 8753 children and adolescents (4130 boys and 4623 girls) aged 4 to 17 years, from four Peruvian cities: Barranco, La Merced, San Ramón and Junín. Height, body mass and WC were measured according to standardized techniques. Centile curves for height, body mass, BMI and WC were obtained separately for boys and girls using the LMS method. Student t-tests were used to compare mean values. Overall boys have higher median heights than girls, and the 50th percentile for body mass increases curvilinearly from 4 years of age onwards. In boys, the BMI and WC 50th percentiles increase linearly and in girls, the increase presents a curvilinear pattern. Peruvian children are shorter, lighter and have higher BMI than their counterparts in the U.S. and Argentina; in contrast, age and sex-specific WC values are lower. Height, body mass and WC of Peruvian children increased with age and variability was higher at older ages. The growth patterns for height, body mass, BMI and WC among Peruvian children were similar to those observed in North-American and Argentinean peers.

Edge enhancement improves disruptive camouflage by emphasising false edges and creating pictorial relief

Disruptive colouration is a visual camouflage composed of false edges and boundaries. Many disruptively camouflaged animals feature enhanced edges; light patches are surrounded by a lighter outline and/or a dark patches are surrounded by a darker outline. This camouflage is particularly common in amphibians, reptiles and lepidopterans. We explored the role that this pattern has in creating effective camouflage. In a visual search task utilising an ultra-large display area mimicking search tasks that might be found in nature, edge enhanced disruptive camouflage increases crypsis, even on substrates that do not provide an obvious visual match. Specifically, edge enhanced camouflage is effective on backgrounds both with and without shadows; i.e. this is not solely due to background matching of the dark edge enhancement element with the shadows. Furthermore, when the dark component of the edge enhancement is omitted the camouflage still provided better crypsis than control patterns without edge enhancement. This kind of edge enhancement improved camouflage on all background types. Lastly, we show that edge enhancement can create a perception of multiple surfaces. We conclude that edge enhancement increases the effectiveness of disruptive camouflage through mechanisms that may include the improved disruption of the object outline by implying pictorial relief.

Numerical modelling of braided fibres for reinforced concrete

Fire has been always a major concern for designers of steel and concrete structures. Designing fire-resistant structural elements is not an easy task due to several limitations such as the lack of fire-resistant construction materials. Concrete reinforcement cover and external insulation are the most commonly adopted systems to protect concrete and steel from overheating, while spalling of concrete is minimised by using HPFRC instead of standard concrete. Although these methodologies work very well for low rise concrete structures, this is not the case for high-rise and inaccessible buildings where fire loading is much longer. Fire can permanently damage structures that cost a lot of money. This is unsafe and can lead to loss of life. In this research, the author proposes a new type of main reinforcement for concrete structures which can provide better fire-resistance than steel or FRP re-bars. This consists of continuous braided fibre rope, generally made from fire-resistant materials such as carbon or glass fibre. These fibres have excellent tensile strengths, sometimes in excess of ten times greater than steel. In addition to fire-resistance, these ropes can produce lighter and corrosive resistant structures. Avoiding the use of expensive resin binders, fibres are easily bound together using braiding techniques, ensuring that tensile stress is evenly distributed throughout the reinforcement. In order to consider braided ropes as a form of reinforcement it is first necessary to establish the mechanical performance at room temperature and investigate the pull-out resistance for both unribbed and ribbed ropes. Ribbing of ropes was achieved by braiding the rope over a series of glass beads. Adhesion between the rope and concrete was drastically improved due to ribbing, and further improved by pre-stressing ropes and reducing the slacked fibres. Two types of material have been considered for the ropes: carbon and aramid. An implicit finite element approach is proposed to model braided fibres using Total Lagrangian formulation, based on the theory of small strains and large rotations. Modelling tows and strands as elastic transversely isotropic materials was a good assumption when stiff and brittle fibres such as carbon and glass fibres are considered. The rope-to-concrete and strand-to-strand bond interaction/adhesion was numerically simulated using newly proposed hierarchical higher order interface elements. Elastic and linear damage cohesive models were used effectively to simulate non-penetrative 'free' sliding interaction between strands, and the adhesion between ropes and concrete respectively. Numerical simulation showed similar de-bonding features when compared with experimental pull-out results of braided ribbed rope reinforced concrete.

Centile curves and reference values for height, body mass, body mass index and waist circumference of peruvian children and adolescents

This study aimed to provide height, body mass, BMI and waist circumference (WC) growth centile charts for school-children, aged 4–17 years, from central Peru, and to compare Peruvian data with North-American and Argentinean references. The sample consisted of 8753 children and adolescents (4130 boys and 4623 girls) aged 4 to 17 years, from four Peruvian cities: Barranco, La Merced, San Ramón and Junín. Height, body mass and WC were measured according to standardized techniques. Centile curves for height, body mass, BMI and WC were obtained separately for boys and girls using the LMS method. Student t-tests were used to compare mean values. Overall boys have higher median heights than girls, and the 50th percentile for body mass increases curvilinearly from 4 years of age onwards. In boys, the BMI and WC 50th percentiles increase linearly and in girls, the increase presents a curvilinear pattern. Peruvian children are shorter, lighter and have higher BMI than their counterparts in the U.S. and Argentina; in contrast, age and sex-specific WC values are lower. Height, body mass and WC of Peruvian children increased with age and variability was higher at older ages. The growth patterns for height, body mass, BMI and WC among Peruvian children were similar to those observed in North-American and Argentinean peers.

Emergetic evaluation of cattle rearing in a montado farm

O Montado, em Portugal, é um complexo sistema silvopastoril de uso da terra, tipicamente Mediterrânico, com diversos estratos de vegetação, incluindo sobreiro e azinheira em várias densidades, onde é frequente a criação de gado. Esta actividade pecuária beneficia das pastagens no sob-coberto, de algumas espécies arbustivas e também das bolotas que caem do coberto arbóreo, contribuindo para evitar a invasão da pastagem por matos. No entanto, dependendo da sua gestão, este gado pode comprometer a regeneração do sistema. Nos últimos 20 anos, os subsídios no âmbito da Política Agrícola Comum da União Europeia têm promovido a criação de gado bovino em detrimento de outras espécies e raças mais leves, bem como a intensificação desta produção. Esta intensificação pode impossibilitar a regeneração natural das árvores ameaçando o equilíbrio do Montado. Por esta razão é necessária uma avaliação focada na criação de gado bovino e nos seus impactos sobre o sistema. O objectivo deste estudo foi obter uma melhor compreensão do funcionamento de uma exploração silvopastoril num sistema de Montado, através da aplicação do Método de Avaliação Emergética e do cálculo de índices emergéticos. Pretende-se assim compreender a melhor forma de o gerir, bem como conceber estratégias que maximizem o fluxo de emergia na exploração. Uma comparação deste método com a avaliação económica permitiu perceber em que aspectos esta pode ser complementada pelo método da avaliação emergética. O método da avaliação emergética permite a avaliação de sistemas multifuncionais complexos à escala de uma exploração individual, fornecendo informação extra em relação à avaliação económica como a renovabilidade dos inputs do sistema, ou a quantidade de fluxos livres da natureza que é valorada por preços de mercado. Este método permite a integração das emternalidades e das externalidades à contabilização económica, transformando uma avaliação tendencialmente separada do seu sistema mais vasto, numa avaliação de um sistema em conexão com aqueles mais vastos nos quais se integra; Abstract: The Montado, in Portugal, is a complex silvo-pastoral system of land use, typically Mediterranean, with different strata of vegetation, including cork and holm oaks in various densities, and where cattle rearing is common. This stockfarm benefits from the herbaceous layer under the trees, as well as from some species in the shrub layer, and also from the acorns faling down from the tree cover, while contributing to prevent the invasion of pastures by shrubs. Nevertheless, depending on its management, livestock can affect the system regeneration. Over the past 20 years, subsidies of the European Union's common agricultural policy have promoted the cattle rearing at expense of other lighter species and breeds, as well as its intensification. This intensification may impair the natural regeneration of trees threatening the balance of the Montado. Therefore an assessment focused on cattle and their impact on the system is required. The purpose of this study was to obtain a better understanding of the functioning of a silvo-pastoral farm in a Montado system, by applying the emergy evaluation method and through the calculation of emergy indices. It is intended to understand the best way to manage and design strategies that maximize the emergy flow on the farm. A comparison of this method with the economic evaluation allowed to realize in what aspects it can be complemented by the emergy evaluation method. The emergy evaluation method alows the assessment of complex multi-functional systems at the scale of an individual farm, providing extra information in relation to economic avaluation as the renewability of the inputs to a system and the amount of free flows of nature that is valued by market prices. This method allows the integration of the emternalities and the externalities to the economic accounting, transforming an evaluation tended separated from its wider system, in an evaluation of a system in connection with the larger ones on which it is incorporated.

CFD Applications for Wave Energy Conversion Devices (MoonWEC) and Turbulent Fountains for Environmental Fluid Mechanics

This thesis is based on two studies that are related to floating wave energy conversion (WEC) devices and turbulent fountains. The ability of the open-source CFD software OpenFOAM® has been studied to simulate these phenomena. The CFD model has been compared with the physical experimental results. The first study presents a model of a WEC device, called MoonWEC, which is patented by the University of Bologna. The CFD model of the MoonWEC under the action of waves has been simulated using OpenFOAM and the results are promising. The reliability of the CFD model is confirmed by the laboratory experiments, conducted at the University of Bologna, for which a small-scale prototype of the MoonWEC was made from wood and brass. The second part of the thesis is related to the turbulent fountains which are formed when a heavier source fluid is injected upward into a lighter ambient fluid, or else a lighter source fluid is injected downward into a heavier ambient fluid. For this study, the first case is considered for laboratory experiments and the corresponding CFD model. The vertical releases of the source fluids into a quiescent, uniform ambient fluid, from a circular source, were studied with different densities in the laboratory experiments, conducted at the University of Parma. The CFD model has been set up for these experiments. Favourable results have been observed from the OpenFOAM simulations for the turbulent fountains as well, indicating that it can be a reliable tool for the simulation of such phenomena.

PCM-based battery thermal management systems, energy saving materials and LCA strategy for automotive

This PhD work arises from the necessity to give a contribution to the energy saving field, regarding automotive applications. The aim was to produce a multidisciplinary work to show how much important is to consider different aspects of an electric car realization: from innovative materials to cutting-edge battery thermal management systems (BTMSs), also dealing with the life cycle assessment (LCA) of the battery packs (BPs). Regarding the materials, it has been chosen to focus on carbon fiber composites as their use allows realizing light products with great mechanical properties. Processes and methods to produce carbon fiber goods have been analysed with a special attention on the university solar car Emilia 4. The work proceeds dealing with the common BTMSs on the market (air-cooled, cooling plates, heat pipes) and then it deepens some of the most innovative systems such as the PCM-based BTMSs after a previous experimental campaign to characterize the PCMs. After that, a complex experimental campaign regarding the PCM-based BTMSs has been carried on, considering both uninsulated and insulated systems. About the first category the tested systems have been pure PCM-based and copper-foam-loaded-PCM-based BTMSs; the insulated tested systems have been pure PCM-based and copper-foam-loaded-PCM-based BTMSs and both of these systems equipped with a liquid cooling circuit. The choice of lighter building materials and the optimization of the BTMS are strategies which helps in reducing the energy consumption, considering both the energy required by the car to move and the BP state of health (SOH). Focusing on this last factor, a clear explanation regarding the importance of taking care about the SOH is given by the analysis of a BP production energy consumption. This is why a final dissertation about the life cycle assessment (LCA) of a BP unit has been presented in this thesis.

Deep space orbit determination and guidance of the LICIACube microsatellite mission

Recently, the JPL's MarCO mission demonstrated that these probes are also mature enough to be employed in the deep space, even though with the limitations related to the employed commercial components. Currently, other deep space CubeSats are planned either as stand-alone missions or as companions of a traditional large probe. Therefore, developing a dedicated navigation suite is crucial to reaching the mission's goals, considering the limitations of the onboard components compared to typical deep space missions. In this framework, the LICIACube mission represents an ideal candidate test-bench, as it performs a flyby of the Didymos asteroid system subject to a strong position, epochs, and pointing requirements. This mission will also allow us to infer the capabilities of such microsatellites and highlight their limitations compared with the benefits of a lighter design and tailoring efforts. In this work, the OD and guidance methods and tools adopted for classical deep space missions have been tailored for the CubeSat applications and validated through extensive analyses. In addition, navigation procedures and interfaces have been designed in view of the operations foreseen in late 2022. The pre-launch covariance analysis has been performed to assess the mission's feasibility for the nominal trajectory and its associated uncertainties, based on conservative assumptions on the main parameters. Extensive sensitivity analyses have been carried out to understand the main mission parameters affecting the performance and to demonstrate the robustness of the designed trajectory and operation schedule in fulfilling the mission requirements. The developed system was also stressed by tuning the models to access different reconstruction methods for the maneuvers. The analysis demonstrated the feasibility of the LICIACube mission navigation in compliance with the mission requirements, compatible with the limited resources available, both in space and on the ground.

Many-body approach to the BCS-BEC crossover for an imbalanced ultra-cold Fermi gas

The aim of this thesis is the study of the normal phase of a mass imbalanced and polarized ultra-cold Fermi gas in the context of the BCS-BEC crossover, using a diagrammatic approach known as t-matrix approximation. More specifically, the calculations are implemented using the fully self-consistent t-matrix (or Luttinger- Ward) approach, which is already experimentally and numerically validated for the balanced case. An imbalance (polarization) between the two spin populations works against pairing and superfluidity. For sufficiently large polarization (and not too strong attraction) the system remains in the normal phase even at zero temperature. This phase is expected to be well described by the Landau’s Fermi liquid theory. By reducing the spin polarization, a critical imbalance is reached where a quantum phase transition towards a superfluid phase occurs and the Fermi liquid description breaks down. Depending on the strength of the interaction, the exotic superfluid phase at the quantum critical point (QCP) can be either a FFLO phase (Fulde-Ferrell-Larkin-Ovchinnikov) or a Sarma phase. In this regard, the presence of mass imbalance can strongly influence the nature of the QCP, by favouring one of these two exotic types of pairing over the other, depending on whether the majority of the two species is heavier or lighter than the minority. The analysis of the system is made by focusing on the temperature-coupling-polarization phase diagram for different mass ratios of the two components and on the study of different thermodynamic quantities at finite temperature. The evolution towards a non-Fermi liquid behavior at the QCP is investigated by calculating the fermionic quasi-particle residues, the effective masses and the self-energies at zero temperature.

Instrument transformers with Digital outputting high voltage power networks

In recent years, energy modernization has focused on smart engineering advancements. This entails designing complicated software and hardware for variable-voltage digital substations. A digital substation consists of electrical and auxiliary devices, control and monitoring devices, computers, and control software. Intelligent measurement systems use digital instrument transformers and IEC 61850-compliant information exchange protocols in digital substations. Digital instrument transformers used for real-time high-voltage measurements should combine advanced digital, measuring, information, and communication technologies. Digital instrument transformers should be cheap, small, light, and fire- and explosion-safe. These smaller and lighter transformers allow long-distance transmission of an optical signal that gauges direct or alternating current. Cost-prohibitive optical converters are a problem. To improve the tool's accuracy, amorphous alloys are used in the magnetic circuits and compensating feedback. Large-scale voltage converters can be made cheaper by using resistive, capacitive, or hybrid voltage dividers. In known electronic voltage transformers, the voltage divider output is generally on the low-voltage side, facilitating power supply organization. Combining current and voltage transformers reduces equipment size, installation, and maintenance costs. These two gadgets cost less together than individually. To increase commercial power metering accuracy, current and voltage converters should be included into digital instrument transformers so that simultaneous analogue-to-digital samples are obtained. Multichannel ADC microcircuits with synchronous conversion start allow natural parallel sample drawing. Digital instrument transformers are created adaptable to substation operating circumstances and environmental variables, especially ambient temperature. An embedded microprocessor auto-diagnoses and auto-calibrates the proposed digital instrument transformer.