Dix molécules organiques modèles simulant les fonctions chimiques des superplastifiants utilisés dans la formulation des bétons ont été intercalées dans les hydrates cimentiers lamellaires conduisant à la formation de phases AFm hybrides. Les interfaces entre les deux sous-réseaux organiques et inorganiques de ces composés hybrides ont été étudiées afin de caractériser les interactions entre hydrates cimentiers et adjuvants organiques lors de la prise du béton. Les affinités de ces molécules vis-à-vis du feuillet minéral ont pu être comparées et il en ressort les deux séries suivantes : -PO32- > -SO3- > -CO2- pour les parties hydrophiles et C7-R > Φ-R > C5-R > C2-R pour les parties hydrophobes. L’interface organique-inorganique i.e. le mode d’accrochage et l’orientation de la molécule organique au sein de l’espace interlamellaire ont principalement été caractérisés par DRX sur poudre et spectroscopie infrarouge. Différents modes de connexion ont pu être identifiés par intercalation et par greffage. Les molécules organiques examinées sont ainsi orientées soit perpendiculairement, soit parallèlement aux feuillets associés à différents mode d’accroche. Différents taux d’hydratation de ces hydrants hybrides ont ensuite été identifiés et un travail de résolution structurale sur la phase insérant l’anion C6H5SO3- a permis de préciser l’organisation structurale de l’espace interlamellaire. Finalement, une étude sur l’intercalation de quelques superplastifiants commerciaux a mis en évidence un phénomène d’exfoliation de ces hydrates lamellaires. L’étude préalablement réalisée sur des molécules modèles permet alors de mieux comprendre les interactions se produisant au sein du milieu complexe que constitue un béton frais. / Ten organic molecules models simulating the chemical functions of superplasticizers used in concretes formulation were intercalated into lamellar cement hydrates to synthesize hybrid AFm phases. The interfaces between the organic and inorganic networks of these hybrid compounds have been studied to characterize the interactions between cementitious hydrates and organic additives in concrete. The affinities of these molecules toward the mineral layers have been compared and display the following tendencies : -PO32- > -SO3- > -CO2- for the hydrophilic parts and C7-R > Φ-R > C5-R > C2-R for the hydrophobic parts. The organic-inorganic interface (connection mode and orientation of the organic molecule) of the hybrid AFm phases was characterized by powder WRD and infrared spectroscopy. Organic molecules are oriented either perpendicular or parallel to the sheets resulting from different connection modes mainly intercalation and also grafting. The various hydration levels of these hybrids hydrates were then determined, and a structural resolution was attempted on AFm inserting C6H5SO3- anion allowing a description of its interlayer structure. Finally, a study on the intercalation of some commercial superplasticizers highlighted the exfoliation phenomenon for these lamellar hydrates.The present study on model molecules leads to a better understanding of the interactions occuring in complex fresh concrete environment.

La texture de l'albumen de blé tendre (Triticum aestivum) est une propriété importante du grain qui affecte son comportement au fractionnement, ainsi que la qualité des produits finis. Elle est définie par la dureté et la vitrosité qui sont deux propriétés différentes du blé. La dureté est reliée à l'adhésion entre les granules d'amidon et la matrice protéique (principaux constituants de l'albumen) qui est contrôlée génétiquement à travers l'état des puroindolines (sauvages ou mutées). La vitrosité est associée à la porosité de l'albumen et varie principalement en fonction des conditions de culture. Le principal objectif de ce travail de recherche est de contribuer à la compréhension du lien entre la texture de l'albumen et le comportement des grains à la mouture, en fonction de la génétique (puroindolines) et des conditions de culture (porosité). Des grains issus de lignées quasi-isogéniques, ne différant que par l'état allélique de la puroindoline b (Pinb-D1a pour les soft et Pinb-D1b pour les hard) et cultivés dans deux endroits différents (grains vitreux et farineux) ont été spécifiquement sélectionnés pour distinguer le rôle respectif des puroindolines et de la porosité sur la microstructure de l'albumen et sur les propriétés mécaniques à l'échelle de l'albumen et d'une population de grains. Cette analyse multi-échelles a permis de préciser que l'effet de la porosité de l'albumen domine sur la microstructure pour les grains farineux, indépendemment de la génétique, et que l'adhésion amidon-protéines est également impliquée dans le cas des grains vitreux. La porosité et l'adhésion entre les constituants de l'albumen sont tous deux responsables des différences observées de propriétés mécaniques, de comportement des grains à la mouture et de propriétés de la farine. A l'échelle nanométrique, nous avons réussi à mesurer les propriétés mécaniques locales de l'amidon et du gluten en associant une méthode originale utilisant la microscopie à force atomique (AFM) avec un modèle de tribologie. Pour la première fois, nous avons montré que la dureté de l'amidon est quatre fois plus élevée que celle du gluten, indépendamment de leur origine génétique. Nous avons aussi montré pour la première fois que les propriétés mécaniques de l'interface entre amidon et protéines étaient dépendantes de l'origine génétique des blés, et plus précisément des puroindolines. Ces résultats confirment que la dureté du grain n'est pas liée aux propriétés mécaniques des constituants du blé mais plutôt à l'interface amidon-protéine. Ces données ont été intégrées par la suite dans un modèle numérique qui permet de prédire le comportement mécanique global des échantillons en fonction du degré d'adhésion entre amidon et protéines, l'assemblage granulaire des particules d'amidon et la teneur en protéines. Ce modèle a permis de mettre en évidence l'effet de l'assemblage des granules d'amidon sur les propriétés mécaniques, qui a été jusqu'ici négligé dans l'évaluation de la vitrosité. / Endosperm texture is one of the most important grain properties for fractionation behaviour and end-use quality of common wheat (Triticum aestivum). Hardness and vitreousness are distinct grain properties that are both responsible of grain texture. Hardness is related to the starch and protein (endosperm main components) adhesion that is genetically controlled depending on the wild or mutated puroindolines. Vitreousness is associated to endosperm porosity and is mainly affected by the growing conditions. The principal aim of this PhD work is to contribute understanding the link between endosperm texture and the grain milling behaviour, depending on the wheat genetic background (puroindolines) and growth conditions (porosity). Near-isogenic lines differing only by the puroindoline b allelic state (Pinb-D1a for soft and Pinb-D1b for hard) and grown in different locations (vitreous and mealy kernels) were specifically selected to analyse the endosperm microstructure and mechanical properties at the kernel and grain population scales. The multi-scale analysis pointed out, in mealy grains, the dominant effect of porosity on the endosperm microstructure whatever the genetic background, and showed that the starch-protein adhesion is also involved in vitreous kernels. Both endosperm porosity and starch-protein adhesion are responsible for the distinct endosperm mechanical properties, milling behaviour and flour properties. At the nanoscale, an original nanoscratching method using Atomic Force Microscopy (AFM) was associated with a tribological model to measure the mechanical properties of wheat endosperm main components. For the first time, the hardness of starch was found four fold higher than that of gluten, whatever the genetic origin. Most importantly, the AFM methodology clearly revealed differences in the mechanical properties of starch-protein interface between hard and soft grains. These results confirm that grain hardness is related to the mechanical properties of the starch-protein interface and that the puroindolines nature is involved in these properties. The nano-mechanical properties of starch and proteins determined by AFM were integrated in the numerical modelling to predict wheat fractionation according to the starch-protein adhesion, the starch particles assembly and the protein content. The numerical model highlighted the effect of the starch granular assembly on wheat grains mechanical properties, which has not been taken into account before to evaluate the effect of vitreousness.

This thesis deals with monitoring the thermodynamic stability of thaumasite and monitoring it is properties in the long term. The aim was to synthesize thaumasite under different conditions and to evaluate it using X-ray diffraction analysis and thermal analysis.

The thesis is focused on the optimization of the thaumasite preparation in the way of ternesite hydration and further comparison of this approach to the other methods. The thaumasite was prepared by three different methods for this purpose - according to Aguilera et al., Purnell and the hydration method of ternesite clinkers. Finally, the X-ray diffraction analysis was particularly used to evaluate the obtained properties and results.

Les tétraspanines sont des protéines transmembranaires de la membrane plasmique qui forment un réseau d'interactions protéiques, appelé "Tetraspanin Web", entre tétraspanines ou avec d'autres protéines partenaires. Elles ont également la capacité de s'organiser en microdomaines membranaires appelés TEM (Tetraspanin-Enriched Microdomains). Ces protéines sont impliquées dans plusieurs mécanismes cellulaires et associées à de nombreuses pathologies. La diversité de leurs interacteurs reflète la pléiotropie de leurs fonctions.. Entre autres, elles jouent un rôle déterminant au cours des processus infectieux et notamment lors du bourgeonnement du VIH-1. Des études récentes menées au laboratoire ont plus particulièrement démontré, à l’échelle de la molécule unique, que les tétraspanines CD9 et CD81 étaient spécifiquement recrutées au niveau des sites d'assemblage de la protéine virale Gag. Ces travaux ont été faits dans un système modèle de cellules HeLa transfectées par Gag-GFP, dans lesquelles se forment des sites de bourgeonnement de pseudo-particules virales de type VIH-1. Ces observations soulèvent plusieurs questions quant à l’implication des tétraspanines CD9 et CD81 dans le mécanisme d’assemblage du virus, notamment dans le remodelage de la membrane plasmique de la cellule hôte et sa courbure lors du bourgeonnement, deux phénomènes auxquels les tétraspanines sont associées. Dans ce contexte, le principal objectif de ma thèse a été de déterminer l'organisation structurale des sites d'assemblage du VIH-1 en utilisant une nouvelle méthodologie combinant la microscopie à force atomique (AFM) et la microscopie super résolue de type dSTORM. La microscopie dSTORM fait partie des techniques basées sur la localisation de molécules individuelles et permet de cartographier des protéines fluorescentes avec une résolution latérale inférieure à 50nm tandis que l'AFM permet de déterminer la topographie membranaire avec une résolution du même ordre. La première partie de ma thèse a consisté à construire ce nouveau montage expérimental, en collaboration avec l'équipe de Marcelo Nollmann. Nous avons confirmé en premier lieu que les sites regroupant Gag-GFP corrélaient bien avec des protrusions membranaires caractérisés par AFM Nous avons montré que les tétraspanines CD9 étaient spécifiquement recrutées au niveau de ces sites de bourgeonnement et que leur recrutement corrélait avec le degré de maturation des bourgeons Gag-GFP qui dépend du diamètre et de la hauteur des sites de bourgeonnement. En plus d’une redistribution des tétraspanines au cours du processus d’assemblage des nouveaux virions, nous avons pu observer une déplétion des tétraspanines CD9 et CD81 à la surface des cellules exprimant la protéine virale Gag-GFP. Ces résultats préliminaires révèlent la capacité des protéines virales Gag à modifier spécifiquement l’environnement de la cellule hôte en modulant la répartition et l’expression des tétraspanines au niveau de la membrane plasmique, suggérant un rôle déterminant des tétraspanines au cours de la réplication du virus VIH-1. / Tetraspanins are transmembrane proteins forming a network of protein-protein interactions at the cell surface, called "Tetraspanin Web". They can also be organized into membrane microdomains named « TEMs » for « Tetraspanin Enriched Microdomains ». These domains are involved in many cellular functions and pathologies. The role of tetraspanins during infection has been described early on, notably TEMs are implicated in various aspects of the HIV-1 life cycle, including entry and budding. It has been demonstrated recently, at the single molecule level, that the CD9 and CD81 tetraspanins are specifically recruited by HIV-1 Gag to viral assembly and release sites. These observations raise crucial questions about the role of these two tetraspanins in this process and their implication in membrane remodelling and/or bending during assembly and budding of the viral particles. In this context, the main objective of my PhD thesis was to investigate the structural organization of HIV-1 assembly/budding sites by a combination of two advanced microscopy techniques: atomic force microscopy (AFM) and direct Stochastic Optical Reconstruction Microscopy (dSTORM). AFM provides information on the membrane topography with lateral resolution lower than a 50 nm. A similar resolution can be reached with dSTORM that is suitable to map fluorescently labeled proteins at the single molecule level. Combination of these two techniques allowed us to characterize the distribution of CD9 clusters within HIV-1 budding sites in the membrane topography context. The first task of my PhD was to build this new combo in collaboration with Marcelo Nollmann's group. We then performed AFM imaging of HeLa cells transfected with the viral protein Gag fused to GFP and demonstrated that Gag-GFP assembly sites correlate with membrane protrusions. In addition, by dSTORM imaging of the same region, we have shown that CD9 tetraspanins were enriched and recruited at Gag assembly sites and that their distribution depends on the assembly stage of the virus-like particles imaged with AFM (the dimensions of the budding sites relates to the assembly stage of the viral particles). Finally, we documented that Gag mediated depletion of both CD9 and CD81 tetraspanins from the surface of HeLa transfected cells. These results reveal the impact of the viral protein Gag on the host cell environment by modulating the partition and expression of tetraspanins within the plasma membrane, reinforcing an important role of tetraspanins during HIV-1 life cycle.

Studying the microstructural features, optical, and electrical properties of the thin-filmperovskite solar cells (PSC) is the main objective of this thesis work. All the PSCs used in thisthesis work were prepared by spin coating assisted with gas quenching process and the samplesreceived from Interuniversity Microelectronics Centre (IMEC), Belgium.Microstructural and architectural details of the stagewise prepared PSCs were investigatedusing a Scanning Electron Microscope (SEM) - Focused Ion Beam (FIB) technique. With thereference to the given specification from IMEC, the SEM-FIB examinations of the as-preparedPSCs confirmed the presence of different layers such as hole transport layer (HTL), perovskitelayer, and electron transport layer (ETL). Further, the thickness of the perovskite layers wasmeasured and found to be 400 and 500 nm which validates the specification of the as-preparedsamples 1 and 2, respectively. The observed average grain size of the perovskite of the asprepared samples 1 and 2 are significantly different and the values are approximately 83 and169 nm, respectively. The average surface roughness values of perovskite layers (as-preparedsamples 1 and 2) and electron transport layer (as-prepared samples 3) were evaluated by atomicforce microscopy (AFM) and the values are 10, 19, and 12 nm, respectively. Furthermore, theconductive-AFM was performed to evaluate the electrical properties of the perovskite layers,and the results confirmed that the as-prepared sample 2 showed a higher mean current value of4.1 nA, than sample 1 resulted in 2.9 nA. The higher electrical performance of the as-preparedsample 2 could be correlated to the larger grain size, higher thickness, and higher surfaceroughness values of the perovskite layer.Moreover, the performance evaluation of a complete perovskite solar device with a similarconfiguration was evaluated between the as-prepared (newly fabricated) and the exposedsamples (tested under sunlight for ten weeks), and their behavior was studied. The optical andelectrical characteristics of the solar cell at the device level were examined with the help ofphotoluminescence (PL), electroluminescence (EL), and solar simulator techniques. The peakand fullwidth half maximum (FWHM) values of the PL emission spectra of the as-prepareddevice are in line with IMEC specification, whereas these values are slightly decreased for theexposed perovskite solar device. Also, during the EL examination, predominantly uniformluminescence was observed for the as-prepared device, whereas discontinuity in the emissionof electrons, and in some parts absence of luminescence-effect was observed for the exposedsolar cell. The current-voltage characteristics obtained from the solar simulator resultsconfirmed that the power conversion efficiency of the as-prepared device is at least 6 timeshigher than the exposed device. Based on the PL, EL, and PCE results it could be confirmedthat the perovskite solar cell exposed to sunlight for 10 weeks has started to degrade.

Extracellular vesicles are important players in cell-to-cell communication and have the potential to be used as biomarkers for decease. The mechanical properties of extracellular vesicles is an active field of research, with new methods and models being developed. In this thesis, two samples of extracellular vesicles containing different levels of membrane protein expressions are investigated using atomic force microscopy. Three models for determining stiffness are applied to the samples: the Hertz model, an adhesion angle dependent model, and the modified Canham-Helfrich model. The Hertz model indicated a higher Young’s Modulus for vesicles without membrane proteins, but with large errors. The adhesion angle dependent model did not provide high enough sensitivity to determine any difference in stiffness between the two samples. The modified Canham-Helfrich model indicated a higher bending modulus for the vesicles with membrane proteins. The results highlight the importance of taking several measurements on each vesicle, in contrast to how the method is currently applied in research. / Extracellulära vesiklar är essentiella komponenter inom cell-till-cell-kommunikation, och har potentialen att kunna användas som sjukdomsmarkörer. Extracellulära vesiklars mekaniska egenskaper är ett aktivt forskningsfält där nya experimentella metoder och teoretiska modeller är under utveckling. I den här arbetet används atomkraftsmikroskopi för att undersöka de mekaniska egenskaperna av två prover av extracellulära vesiklar med olika mängd membranproteiner. Tre modeller för att utvärdera deras styvhet tillämpas: Hertz-modellen, en adhesionsvinkelberoende modell, och den modifierade Canham-Helfrichmodellen. Hertz-modellen indikerade högre elasticitetsmodul för provet med lägre antal membranprotein, men med stora fel i mätningarna. Den adhesionsvinkelbaserade modellen var inte känslig nog att påvisa några skillnader i styvhet mellan proverna. Den modifierade Canham-Helfrich-modellen indikerade att vesiklarna med membranprotein har högre böjmodul än veiklarna utan membranprotein. Resultaten understryker att det är viktigt att göra flertalet mätningar på varje vesikel, i kontrast mot hur modellen tillämpas i dagsläget.

[pt] A caracterização de cristais osciladores de quartzo (QTF) foi realizada nesta dissertação com o objetivo de implementá–los como sensores de um microscópio de força atômica (AFM). O QTF possui várias vantagens em relação aos cantilevers tradicionais de silício. Utilizado em modos dinâmicos de operação do AFM, o QTF possui maior fator de qualidade e rigidez, permitindo melhor sensibilidade em força e o uso de baixas amplitudes de oscilação para imageamento do que cantilevers tradicionais. Nesse trabalho, parâmetros mecânicos e elétricos do QTF foram medidos. Além disto, um estudo da influência da adição de massa nos braços do QTF foi realizado. Para a implementação do QTF no AFM, um sistema de feedback composto de um amplificador lock–in e um amplificador diferencial foi desenvolvido e testado. Adicionalmente, um novo cabeçote para o microscópio foi desenvolvido para adaptar o QTF ao microscópio. / [en] The characterization of quartz tuning forks (QTF) was performed in this dissertation, aiming to implement them as sensors at an atomic force microscope (AFM). The QTF has several advantages over traditional silicon cantilevers. Used in dynamic AFM modes, the QTF has higher quality factor and stiffness, allowing better force sensitivity and lower amplitudes of oscillation for imaging than traditional cantilevers. In this work, electrical and mechanical parameters of the QTF were obtained. Furthermore, a study of the influence of additional mass on the QTF prongs was performed. To implement the QTF at the AFM, a feedback system composed of a lock–in amplifier and a differential amplifier was developed and tested. Additionally, a new microscope head was designed to adapt the QTF to the microscope.

This dissertation describes new methods for measuring surface forces using evanescent waves, and applications to non-DLVO forces. An evanescent wave, generated at a solid-liquid interface, is scattered by AFM tips or particles attached to AFM cantilevers. The scattering of this wave is used to determine absolute separation between surfaces and/or the refractive index as a function of separation in AFM measurements. This technique is known as evanescent wave atomic force microscopy (EW-AFM). The scattering of an evanescent wave by Si3N4 AFM tips is large and decays exponentially with separation from a refractive index boundary. Thus, scattering is a useful method for measuring the separation between a Si3N4 tip and sample. This method has been used to measure the absolute separation between a tip and sample in the presence of an irreversibly adsorbed polymer film. Measurement of the film thickness and time response of the polymer to applied loads has also been studied. These measurements are not possible using current AFM techniques. In addition to measurements in polymer systems, the simple scattering profile from Si3N4 tips was used to re-examine short range hydration forces between hydrophilic surfaces. Results presented in this thesis suggest this force does not depend on the hydrated radius of the ion between glass and silicon nitride. The scattering generated by a Si3N4 tip has also been used to measure the refractive index of bulk fluids and thin films between hydrophobic surfaces. Based on these results, I have shown that a long-range attraction between hydrophobic surfaces is accompanied by an increase in the refractive index between the tip and surface. From this I have concluded that the attractive force, measured in this study, is the result of an increase in the concentration of organic material between surfaces. Finally, I have shown that the scattering profile depends on the material and size of the scattering object. Scattering from silicon nitride tips is exponential with separation. In contrast, the scattering profile from silicon tips, which are similar in size and geometry, is not a simple exponential. The scattering profile of larger spherical particles attached to cantilevers is also not exponential. It is approximately the sum of two exponentials. The functional form of the scattering profile with separation is consistent with the transmission of evanescent light through flat planar films. This result would suggest that a re-examination of the separation-dependence of scattering in TIRM measurements is necessary. / Ph. D.

Graphene is a material suitable for electronic applications including sensors and biosensors operating in atmospheric conditions and at varying relative humidities. This work concerns the charge diffusion in Hall bar shaped graphene based field effect transistor that is simultaneously investigated by Kelvin probe force microscopy and macroscopic transport measurement. Furthemore it studies the possibilities of graphene Hall bar modification by local anodic oxidation, local cathodic hydrogenation and mechanical lithography.