Depuis la découverte des propriétés physiques et électroniques du graphène, un très grand nombre de méthodes visant à produire et modifier chimiquement le graphène ont été développées afin d'étendre et améliorer ses capacités en vue de futures applications. Les travaux réalisés au cours de cette thèse ont portés sur une méthode exfoliation du graphite en phase liquide assistée d'une réaction de cycloaddition réversible. Cette approche repose sur la réaction de Diels-Alder entre le graphite et un diène masqué très réactif, et se révèle être très efficace dans des solvants organiques volatils qui ne permettent pas l'exfoliation directe du graphite. L'introduction de groupements fonctionnels sur le diène a permis de moduler les propriétés de surface de films de graphène, ainsi que de post-fonctionnaliser les feuillets de graphène afin d'apporter une plus-value au matériau. / Since the discovery of the exciting properties of graphene, many techniques to produce and chemically modify graphene have been developed in order to expand and improve its properties in view of future applications. The study presented in this thesis focus on a process for the chemically-assisted exfoliation of graphite based on a reversible cycloaddition reaction. It relies on the Diels-Alder reaction between graphite and highly reactive masked diene, and it is effective even in solvents that are otherwise ineffective for exfoliation of graphite. Furthermore, it is possible to introduce functional groups on the diene, thereby enabling the tuning of the surface properties of graphene, as well as the post-functionalization of graphene sheets.

is is a study of the relationship between structure, mechanical properties and relaxing behavior of the polypropylene. The structure was evaluated by the quantity the solid phase content (SPC). This was defined as mathematical result of free induction decay (FID) signal from pulsed 1H-NMR. The solid phase content is a quite new structural parameter representing the quantity for description of semi-crystalline polymers. Whereas pulsed 1H-NMR is non-destructive, accurate and repeatable, it becomes a unique tool for a description of mechanical, structural, physical-mechanical changes of polypropylene within the time and temperature. Particularly, this method registers the small changes in the time-dependant shipments during secondary crystallization with small structure changes.

Les transistors à effet de champ sensibles aux ions (ISFET) sont des composants électroniques conçus pour fonctionner en phase liquide. Pour résumer, ce sont des MOSFET dont la grille métallique est remplacée par une membrane isolante ionosensible. Au début des années 2000, ces composants ont évolué avec l'introduction des premiers dispositifs à base de nanofils de silicium. Grâce à leurs faibles dimensions, ces capteurs ont ouvert de nouvelles perspectives, comme par exemple, l'étude des métabolismes intracellulaires. L'objectif de cette thèse a été de développer et d'étudier un capteur de type ISFET, à base de nanofils de silicium, ayant comme couche sensible l'alumine Al2O3. Les premiers travaux ont porté sur l'intégration de films minces d'alumine Al2O3 dans un procédé de type MOSFET. Ce matériau devant être déposé sur des nanofils de silicium, la technique de dépôt successif de couches moléculaires (Atomic Layer Deposition ALD) a été retenue. Cette méthode offre la possibilité de déposer des films d'épaisseur homogène tout autour des nanofils. Après l'étude de l'ALD-Al2O3, la deuxième grande partie de ce projet a consisté à développer, en utilisant les techniques de la microélectronique, des structures innovantes à base de nanofils de silicium. Des transistors constitués d'un seul nanofil, et d'autres constitués de réseaux parallèles de nanofils ont été réalisés. Ces capteurs ont été intégrés dans des canaux microfluidiques, permettant ainsi de localiser précisément le liquide sur les nanofils, mais aussi de pouvoir travailler en micro/nanovolumes. La dernière partie de ce projet a consisté à caractériser ces capteurs en phase liquide. Les différentes configurations ont montré leurs avantages et inconvénients en termes de transconductance, courants de fuite, pentes sous le seuil, sensibilités au pH et aux ions interférents (Na+ et K+). Les caractérisations se sont avérées excellentes et laissent entrevoir des perspectives intéressantes pour des applications biologiques. Les principales innovations de ces capteurs concernent : l'utilisation de nanofils suspendus, la réalisation d'une gaine isolante ionosensible bicouche SiO2/Al2O3 tout autour des nanofils, la variation du dopage le long des nanofils ce qui a conduit à la réalisation de jonctions N+/P/N+, et l'intégration des capteurs dans des canaux microfluidiques couverts. / Ion-sensitive field effect transistors (ISFET) are electronic components designed to operate in liquid phase. To summarize, they are MOSFET-based devices whose metal gate is replaced by an ionosensitive insulating layer. In the early 2000s, these components evolved with the introduction of the first device based on silicon nanowires. Thanks to their small dimensions, these sensors opened up new perspectives, such as the study of intracellular metabolisms. The aim of this thesis was to develop and study a type of ISFET sensor, based on silicon nanowires, with Al2O3 alumina as sensitive layer. The first part of this work was focused on the integration of thin alumina Al2O3 films in a MOSFET process. This material had to be deposited on silicon nanowires, that is why Atomic Layer Deposition (ALD) was used. This method allows to deposit films with uniform thickness all around nanowires. After the study of ALD-Al2O3, the second major part of this project was to develop innovative structures, based on silicon nanowires, using microelectronics methods. Transistors consisting of a single nanowire, and others consisting of parallel networks of nanowires were fabricated. These sensors were integrated in microfluidic channels, allowing to precisely locate the liquid on nanowires and also to work in micro/nanovolumes. The last part of this project consisted in characterizing these sensors in liquid phase. The different configurations showed their advantages and disadvantages in terms of transconductance, leakage currents, slopes below the threshold, sensitivities to pH and interfering ions (Na+ and K+). The characterizations proved to be excellent and suggest interesting prospects for biological applications. The main innovations of these sensors are: the use of suspended nanowires, the realisation of a bilayer SiO2/Al2O3 ion-sensitive sheath all around the nanowires, the doping variation along the nanowires which led to the realization of N+/P/N+ junctions, and the integration of sensors into covered microfluidic channels.

No description available.

Patman is a fluorescent membrane probe related to Laurdan. The structural distinctions between the two probes are the lengths of the aliphatic tails (eleven carbons in Laurdan and fifteen in Patman) and the presence of a trimethylammonium group on Patman that produces a positively-charged head. Preliminary studies exploring Patman as a probe to detect membrane properties during apoptosis revealed that the fluorescence intensity of two edges of the emission spectrum (435 and 500 nm) stabilizes at different rates as the probe binds to the cell membrane. To test whether these differences represent dissimilarities in probe binding to ordered and disordered domains, experiments were conducted to monitor Patman equilibration with bilayers composed of various mixtures of saturated and unsaturated phosphatidylcholines at temperatures above, at, and below the main thermotropic phase transition. In general, Patman equilibrated more rapidly with bilayers in the liquid-disordered phase than in the solid-ordered phase. With solid phase membranes, the fluorescence stabilized faster at 500 nm than at 435 nm. Similar, yet more subtle, results occurred in the lipid disordered phase. In contrast, the situation was reversed at the phase transition temperature; equilibration was faster at 435 nm than at 500 nm. To determine whether these results reflected specific properties of Patman, the experiments were repeated with Laurdan, and several distinctions were observed. First, equilibration with solid phase lipids was faster than for Patman and not different from equilibration with the fluid phase. Second, differences in rates between the two wavelengths were less than with Patman for solid phase membranes but greater than with Patman for melted bilayers. Third, at the phase transition temperature, the difference in equilibration rates was the opposite of the result obtained with Patman. Computer simulations were used to assist with interpretation of these results. The data suggest that both probes bind superficially to the membrane before incorporating among the lipid molecules. Once within the membrane, Patman localizes to at least two distinct depths within the bilayer. Probe molecules in the shallow, more hydrated position favor 500 nm emission and those occupying a deeper, dehydrated position emit primarily at 435 nm. Laurdan's equilibration additionally represents movement of the probe between leaflets and multiple bilayers.

Stem cells, with the ability to self-renew and differentiate into intended cell types, are a valuable tool for disease modeling and mechanistic study. CRISPR-Cas9 has been widely used for genome editing due to its high efficiency and convenience. However, CRISPR-Cas9 has large-deletion safety issues that dramatically restrict its applications. Wiskott-Aldrich syndrome (WAS) is an inborn immunological disorder caused by WASP deficiency. WASP functions in the nucleus, which may help to understand WAS pathology, are poorly defined. Pannexin 1 (PANX1) forms large plasma membrane pores to exchange intracellular small molecules with the extracellular environment and functions in inflammatory processes. The regulatory mechanisms of the PANX1 channel remain obscure. In this dissertation, I focused on mechanistic studies of CRISPR-Cas9 genome editing, and two immune disease relevant genes, WASP and PANX1 using stem cell-derived immune cells. We first found that CRISPR-induced large deletions (LDs) are predominantly mediated by the MMEJ repair pathway through statistical studies. Further, we found POLQ and RPA play vital roles in CRISPR-induced LDs. Modulation of POLQ and RPA can decrease CRISPR-induced LDs and increase HDR efficiency. Using three isogenic WAS iPSC models generated via gene editing, we successfully recapitulated WAS phenotypes, and for the first time, revealed that WASP regulates RNA splicing via epigenetically controlling the transcription of splicing factors and directly participating in the splicing machinery through a liquid-liquid phase separation process. We established a full-length human PANX1 (hPANX1) channel model via cryo-electron microscopy experiments and molecular dynamics simulation study, and found that hPANX1 channel is a homo-heptamer with both the N- and C-termini stretching deeply into the pore funnel. Functional studies of three selected residues support the new hPANX1 channel model and suggest the potential regulatory role of hPANX1 in pyroptosis upon immune responses. Overall, the mechanistic studies of WASP, PANX1 and CRISPR genome editing revealed new roles of WASP in regulating RNA splicing, new functional insights of PANX1 in pyroptosis, and uncovered two critical players POLQ and RPA in CRISPR-induced LDs.

The work presented has the ultimate aim to increase dynamic mechanical properties by improvements in density and optimisation of microstructure of ultra high carbon PM steels by careful selection of processes, i.e. mixing, binding, alloying, heating profile and intelligent heat treatment. ThermoCalc modelling was employed to predict liquid phase amounts for two different powder grades, Astaloy 85Mo or Astaloy CrL with additive elements such as (0.4-0.6wt%)Si, (1.2-1.4wt%)C and (1-1.5wt%)Mn, in the sintering temperature range 1285-1300ºC and such powder mixes were pressed and liquid phase sintered. In high-C steels carbide networks form at the prior particle boundaries, leading to brittleness, unless the steel is heat-treated. To assist the breaking up of these continuous carbide networks, 0.4-0.6% silicon, in the form of silicon carbide, was added. The water gas shift reaction (C + H2O = CO + H2, start from ~500ºC) and Boudouard reaction (from ~500ºC complete ~930ºC) form CO gas in the early part of sintering and can lead to large porosity, which lowers mechanical properties. With the use of careful powder drying, low dew point atmospheres and optimisation of heating profiles, densities in excess of 7.70g/cm3 were attained. The brittle microstructure, containing carbide networks and free of cracks, is transformed by intelligent heat treatment to a tougher one of ferrite plus sub-micron spheroidised carbides. This gives the potential for production of components, which are both tough and suitable for sizing to improve dimensional tolerance. Yield strengths up to 410 MPa, fracture strengths up to 950 MPa and strains of up to 16 % were attained. Forging experiments were subsequently carried out for spheroidised specimens of Fe-0.85Mo+06Si+1.4C, for different strain rates of 10-3, 10-2, 10-1 and 1sec-1 and heated in argon to 700¿C, density ~7.8g/cm3 and 769 MPa yield strength were obtained. / Libyan Education Ministry Office

<p>Preparing silicon wafers is a tedious multi-step process that includes etching, polishing, and cleaning. The minimum wafer thickness attainable in current high volume wafer production processes is generally 160 to 300 μm, and the kerf loss for these processes is up to 40% of the total volume. Thin silicon wafers (~30 to 100μm) are very expensive to produce and the wafering process is not cost effective due to the high amount of material loss (more than 80% at these dimensions) during the process and the risk of breakage of the wafers during wafering. In this thesis, a new method called Vapour-Liquid Interface Growth (VLIG) is proposed. VLIG is capable of directly growing a sheet of single crystal silicon without wafering with a thickness of about 30 to 50μm. The features of the process are 1) low temperature operation; 2) the resulting silicon sheet is easily detachable and self-supporting; 3) the resulting sheet has uniform thickness and is single crystal. The system operates in a supersaturated growth solution of an indium-silicon melt. A seed line in a substrate facing down is employed. A layer of single crystal silicon grows on the seed line at the melt surface due to surface segregation during the super cooling process. The grown silicon can grow laterally due to the limited thickness of the melt depth that minimizes growth in the vertical growth direction. The grown silicon can be easily peeled off from the seed line substrate due to the presence of a gap between the grown silicon sheet and the oxide layer on the seed line substrate. The self-supporting silicon sheet now comprises a very thin silicon substrate or sheet.</p> <p>VLIG silicon sheet is characterized by X-ray diffraction to determine the crystallinity. Hall Effect measurements are performed to measure the electrical properties. VLIG silicon sheet is (111) oriented single crystal and it exhibits the same orientation as the substrate. The growth temperature is from 975 to 850^oC, and the VLIG silicon is p-type doped with indium. The resistivity is 4.181x10^-3 ohm-cm, and the doping level is around 5.3.0x10¹⁸ /cm3. The measured mobility is ranging from 280 cm²/V.s. In this study, VLIG demonstrates the potential of growing thin sheet of single crystal silicon with qualities that feasible for photovoltaic application.</p> / Master of Applied Science (MASc)

No / Transient liquid phase (TLP) brazing of Mg–AZ31 alloy and Ti–6Al–4V alloy was performed using double Ni and Cu sandwich foils. Two configurations were tested; first, Mg–AZ31/Cu–Ni/Ti–6Al–4V and second, Mg–AZ31/Ni–Cu/Ti–6Al–4V. The effect of set-up configuration of the foils on microstructural developments, mechanical properties and mechanism of joint formation was examined. The results showed that different reaction layers formed inside the joint region depending on the configuration chosen. The formation of e phase (Mg), r (CuMg2), d (Mg2Ni) and Mg3AlNi2 was observed in both configurations. Maximum shear strength obtained was 57 MPa for Mg–AZ31/Ni–Cu/Ti–6Al–4V configuration and in both configurations, the increase in bonding time resulted in a decrease in joint strength to 13 MPa. The mechanism of joint formation includes three stages; solid state diffusion, dissolution and widening of the joint, and isothermal solidification. / The authors would like to acknowledge The German Jordanian University (GJU), and NSERC Canada for the financial support for this research.

Yes / Cocrystals consist of two molecules bonded together in a single crystal lattice giving rise to wide applications including improving solubility of poorly soluble pharmaceuticals. Cocrystallization reaction occurs in the oily phase of liquid–liquid phase separation (LLPS) after it is mixed with coformers. Indomethacin–saccharin cocrystal formation was monitored in situ, and the kinetics of crystallization were determined. The crystallization rates show that the process can be proposed to prevent unwanted oily phase formation during LLPS. / Research Development Fund Publication Prize Award winner, Sep 2022.