objective of this thesis is to contribute to the understanding of the behavior of the liquid metal eutectic gallium/indium (EGaIn) in composite systems and provide a platform for the development of functional hybrid nanocomposites. Contributions are regarding (i) the investigation of the electromechanical coupling performance of EGaIn as electrodes in a soft electrostatic transducer and (ii) the effectiveness of organic surfactants to stabilize EGaIn nanoparticles in organic solvents. For the first portion, a completely soft dielectric elastomer actuator (DEA) using EGaIn electrodes was fabricated and evaluated. Experimental actuation of the DEA showed high agreement with a generalized NeoHookean constitutive law, assuming uniaxial pre-stretch and considering the device saddle deformation. The expected conductive behavior of the liquid alloy was confirmed, and further efforts have focused on the development and stabilization of EGaIn nanodroplets, which do not exhibit the problems associated with larger pools of EGaIn (such as leakage) and can be applied to soft multifunctional materials. A computational procedure was developed for calculating suspended EGaIn nanoparticle mass in order to determine reaction yields using applied Mie theory and optical characterization techniques (dynamic light scattering and UV/Vis spectrophotometry). This method calculated total mass to within 20% when applied to a known system. A systematic study evaluating particle yield as a function of aliphatic surfactant composition and concentration (and solvent type) revealed a pronounced dependence of nanodroplet formation on the solvent type as well as surfactant structure. Ethanol (EtOH) was found to be the most effective solvent for the formation and stabilization of EGaIn nanodroplets, in which only thiol-based surfactants were found to improve nanodroplet yield. Results suggest a stabilization mechanism other than the expected self-assembled monolayer (SAM) formation. The research has been extended to alternative (e.g. plant based) surfactant systems.

In dieser Arbeit untersuchen wir den Polymorphismus von Biomembranen im Nanometerbereich anhand von Computermodellen. In Kapitel drei werden auf Dissipative Particle Dynamis basierende molekulare Simulationen genutzt, um die Wechselwirkungen zwischen Membranen und Nanotropfen mit hohen Oberflächenspannungen in der Größenordnung von Milli Newton pro Meter zu untersuchen. Wir zeigen, dass Nanotropfen eine negative Linienspannung an der dreiphasigen Kontaktlinie mit der Membran aufweisen. Die negative Linienspannung führt zu einem spontanen Symmetriebruch des Membran-Tropfensystems und zur Bildung eines enggeschlossenen länglichen Membranhalses. In Kapitel vier untersuchen wir Nanotropfen mit niedrigen Grenzflächenspannungen in der Größenordnung von Mikro-Newton pro Meter. Eine Energieminimierung ermöglicht uns, eine Vielzahl von Parametern zu variieren und die Abhängigkeit der Membranbenet-zungsphänomene von der Grenzflächenspannung, der Biegesteifigkeit, der Linienspannung und der spontanen Krümmung systematisch zu bestimmen. Wir beobachten eine neue morphologische Transformation, die sowohl die Vesikel als auch das Tröpfchen betrifft und eine weiter Geometrie mit gebrochener Rotationssymmetrie. Schließlich bestimmen wir die Grenze zwischen symmetrischen und asymmetrischen Kontaktlinien innerhalb des dreidimensionalen Parameterraums bei verschwindender spontanen Krümmung. In Kapitel fünf verwenden wir molekulare Simulationen, um die morphologischen Transformationen einzelner Nanovesikel mit unterschiedlichem Grad an Asymmetrie zwischen den beiden Schichten der Doppelmembranen zu beobachten. Wir beginnen mit kugelförmigen Vesikeln, die ein bestimmtes Wasservolumen einschließen und aus einer bestimmten Gesamtzahl von Lipiden bestehen. Wenn ihr Volumen verringert wird, verwandeln sich die kugelförmigen Vesikel in eine Vielzahl von nicht kugelförmigen Formen. Dieser Polymorphismus kann durch Umverteilung weniger Lipide zwischen der inneren und äußeren Schicht der Membranen kontrolliert werden. / In this thesis, we use computational methods to study polymorphism of biomembranes at the nanoscales. In chapter three, we use molecular simulations based on dissipative particle dynamics to investigate the interaction of membranes with nanodroplets at high interfacial tensions of the order of milli Newton per meter. We find that nanodroplets have negative line tension at the three phase contact line on the membrane. The negative line tension leads to spontaneous symmetry breaking of the membrane-droplet system and formation of a tight-lipped membrane neck. In chapter four, we study nanodroplets with low interfacial tensions of the order of micro Newton per meter. We use energy minimization, which allows us to explore a wide range of parameters and to systemati-cally determine the dependence of membrane wetting phenomena on interfacial tension, bending rigidity, line tension, and spontaneous curvature. We observe a new morphological transformation that involves both vesicles and droplets, leads to another regime with broken rotational symmetry. Finally, we determine the boundary between symmetric and asymmetric contact line geometries within the three-dimensional parameter space in vanishing spontaneous curvature. In chapter five, we use molecular simulations to monitor the morphological transformations of individual nanovesicles with different degrees of asymmetry between the two leaflets of the bilayer membranes. We start with the assembly of spherical vesicles that enclose a certain volume of water and contain a certain total number of lipids. When we reduce their volume, the spherical vesicles transform into a multitude of nonspherical shapes such as oblates and stomatocytes as well as prolates and dumbbells. This polymorphism can be controlled by redistributing a small fraction of lipids between the inner and outer leaflets of the bilayer membranes. As a consequence, the inner and the outer leaflets experience different mechanical tensions.

In the atmosphere in the height of 18000ft to 25000ft, there are some metastable droplets called supercooled liquid water in the temperature range of 0◦C to 40◦C. When these droplets impinge on the wings of an airplane, a very thin layer of ice is formed on the surface. This natural phenomenon calls “impact icing”. In this research, I studied the nanoscale impact icing on structured graphite surfaces, as the substrates at the atomistic scale using Molecular Dynamics (MD) simulations. This research focuses on the first steps of the development of a predictive multiscale strategy for molecular simulations of impact ice adhesion on nanostructured substrates. Through the simulations, the molecular level physics such as molecular interactions, interfacial energy, and nanoscale surface roughness are processed into a “microscopic ice adhesion strength” that describes the energy cost for breaking the nanoscale interfacial layer. In this work, the simulation strategy is designed based on the postulate that at the nanoscale the fracture strength of impact ice on a given substrate is controlled by the extent of the ice interdigitating the substrate. The interdigitating interfacial structure is then determined by the process of wetting the substrate by a supercooled impinged water droplet and the process of penetrating of supercooled water crystallizing into ice crystals under graphene nanoconfinement. Following this line of reasoning, I divided my impact icing simulations into three separate sections including (1) simulations of dynamic wetting of supercooled water on nanostructured graphene substrate, (2) simulations of water crystallization under nano-confinement, and (3) simulations of fracture of prescribed ice-substrate interfacial structure. Based on the results, it is concluded that the degree of surface hydrophobicity, depth of penetrated water, the order of interlocked water molecules, size of surface roughness, texture structure of the surface, and ice temperature are the key roles that dominate the investigation of fracture strength of impact ice at the solid interface. Furthermore, MD simulation results demonstrate that the surface roughness lower than 3.0nm is enabled to stop water from crystallization, a piece of useful information to design anti-icing surfaces.

Les systèmes moléculaires sous irradiation sont présents dans le monde vivant et la matière inerte. D’un point de vue macroscopique, ils sont constitués d’un très grand nombre de molécules mais l’action d’un rayonnement agit à travers les électrons localisés sur une molécule, créant ainsi, localement et sur des échelles de temps courts, une situation manifestement très éloignée de l’équilibre thermodynamique. Etudier les nanosystèmes moléculaires sous irradiation permet d’accéder à la manière dont l’énergie déposée dans une molécule va être redistribuée dans le système, via les interactions entre molécules. Les distributions de vitesses d’une molécule évaporée mesurées pour les nanogouttes de méthanol protonées présentent un comportement bimodal avec, comme observé pour l’eau, l’évaporation de molécules avec des vitesses nettement supérieures à celles attendues après redistribution complète de l’énergie. De plus, une réaction dans l’agrégat, conduisant à la formation du diméthyléther protoné avec élimination d’une molécule d’eau, a été observée. La possibilité d’étudier la compétition suite à l’irradiation entre l’évaporation moléculaire et une réaction d’élimination pourra contribuer à contraindre les hypothèses quant à la formation de molécules prébiotiques en conditions interstellaires.Les résultats sur les nanogouttes mixtes eau-méthanol ont été comparés à ceux obtenus avec celles dopées en pyridine et celles d’eau pure. L’analyse de la partie basse vitesse des distributions de vitesses des molécules d’eau évaporées montrent que l’évaporation intervient avant la redistribution complète de l’énergie dans l’ensemble de l’agrégat. Il apparaît qu’il y a moins d’énergie disponible pour l’évaporation d’une molécule d’eau quand l’excitation initiale est déposée sur le méthanol protoné ou sur l’ion pyrimidium. Ainsi, à la différence de l’ion hydronium qui est parfaitement solvaté, les impuretés favorisent la croissance de ces petits agrégats d’eau dont la présence dans l’atmosphère facilite les premières étapes de la formation des aérosols / Molecular systems under irradiation are present in the living as well as in inert matter. From a macroscopic point of view, the matter is made up of a very large number of molecules but the action of radiation acts through the electrons located on a molecule and thus, creating locally and on short time scales a situation clearly far from the thermodynamic equilibrium. Studying molecular nanosystems under irradiation provides access to understanding of how the energy deposited in a molecule will be redistributed into the system through interactions between surrounding molecules.The velocity distributions of evaporated molecules measured for irradiated protonated methanol nanodroplets have a bimodal behaviour, as observed for water, including evaporation of molecules with much higher velocities than expected after complete redistribution of energy. In addition, a reaction in the cluster leading to the formation of protonated dimethyl-ether with elimination of a water molecule was observed. The possibility of studying the competition between molecular evaporation and an elimination reaction following irradiation of a nanodroplet will contribute to constrain the hypothesis on the formation of prebiotic molecules under interstellar conditions. The results for the water-methanol mixed nanodroplets were compared with those obtained with pyridine doped water nanodroplets and protonated water nanodroplets. Analysis of the low velocity part of the velocity distributions of the evaporated water molecules shows that evaporation occurs before the complete redistribution of energy in the cluster. It appears that there is less energy available for evaporation of a water molecule when the initial excitation is located on the protonated methanol ion or on the pyrimidium. Thus, unlike the hydronium ion which is fully solvated, impurities promote the growth of these small water clusters, whose presence in the atmosphere facilitates the early stages of aerosol formation

<p>Miniaturization of technologies to milli-, micro- and nanoscale offers numerous advantages for diagnostic and therapeutic biomedical applications. In comparison to their macro-scale counterparts, these small-scale systems are more portable, less invasive and less costly. They can facilitate rapid, sensitive and high throughput detection of abnormalities, help track disease progression, reduce sample consumption and improve therapeutic efficacy of drug delivery while decreasing systemic toxicity. Thus, there is clearly a need for creating innovative milli-, micro- and nanoscale tools that can uncover new possibilities in detection and treatment of various types of diseases. The overall objective of this dissertation was to develop novel small-scale technologies that could help enhance diagnostic and/or therapeutic outcomes in patients with cancer, opioid addiction and inflammatory bowel disease. First, we developed an echogenically stable nanodroplet ultrasound contrast agent with potential applications in extravascular molecular imaging of tumors and targeted cancer therapies. Then, we created a polymer blend microsphere system that could be integrated in prescription opioid tablets to develop an abuse-deterrent formulation against smoking. Finally, we designed a release system for localized delivery of aminosalicylates from magnetically actuated millirobots in the colon to improve therapeutic outcomes in patients suffering from inflammatory bowel disease. Overall, the technologies we developed could serve as a basis for designing diagnostic and therapeutic tools that are superior to currently existing platforms.</p>

<p dir="ltr">Nanoparticles have seen immense development in the past several decades due to their intriguing physicochemical properties. The modern chemist is interested not only in methods of synthesizing nanoparticles with tunable properties but also in the chemistry that nanoparticles can drive. While several methods exist to synthesize nanoparticles, it is often advantageous to put nanoparticles on a variety of conductive substrates for multiple applications (such as energy storage and conversion). Despite enjoying over 200 years of development, the electrodeposition of nanoparticles suffers from a lack of control over nanoparticle size and morphology. Understanding that structure-function studies are imperative to understand the chemistry of nanoparticles, new methods are necessary to electrodeposit a variety of nanoparticles with control over macro-morphology but also microstructure. When a nanodroplet full of a metal salt precursor is incident on the electrode biased sufficiently negative to drive electroplating, nanoparticles form at a shocking rate (on the order of microseconds to milliseconds). We start with the general nuts-and-bolts of the experiment (nanodroplet formation and methods for electrodeposition). The deposition of new nanomaterials often requires one to develop new methods of measurement, and we detail new measurement tools for quantifying nanoparticle porosity and nanopore tortuosity within single nanodroplets. Owing to the small size of the nanodroplets and fast mass transfer, the use of nanodroplets also allows the electrodeposition of high entropy alloy nanoparticles at room temperature. Electrodeposition in aqueous nanodroplets can also be combined with stochastic electrochemistry for a variety of interesting studies. We detail the quantification of the growth kinetics of single nanoparticles in single aqueous nanodroplets. Nanodroplets can also be used as tiny reactors to trap only a few molecules, and the reactivity of those molecules can be electrochemically probed and evaluated with time. Overall, this burgeoning synthetic tool is providing unexpected avenues of tunability of metal nanoparticles on conductive substrates. Moreover, there is little understanding of how ion transfer can affect the fundamental of nanoparticle synthesis with nanodroplet-mediated electrodeposition. This thesis details different experiments performed to study the role of ion transfer during the nucleation and growth of nanoparticles.</p>

L'évaporation d'une molécule d'eau se traduit par la rupture d'une ou plusieurs liaisons hydrogène. Ces liaisons hydrogène sont à l'origine de nombreuses propriétés remarquables de l'eau. A l'échelle macroscopique, l'eau est connue pour son efficacité à thermaliser un système, tandis qu'au niveau microscopique, un transfert ultrarapide d'énergie vibrationnelle par l'intermédiaire des liaisons hydrogène a été observé. Qu'en est-il à l'échelle d'une nanogoutte lorsque qu'un nombre limité de molécules entre en jeu? Dans l'expérience réalisée auprès du dispositif DIAM de l'IPN Lyon, la relaxation d'une nanogoutte d'eau protonée est observée après excitation électronique d'une de ses molécules. La mise en œuvre d'une méthode d'imagerie de vecteur vitesse associée à la technique COINTOF (COrrelated Ion and Neutral Time-Of-Flight) a permis la mesure de la distribution de vitesse de molécules évaporées d'agrégats d'eau protonés, préalablement sélectionnés en masse et en énergie. La forme des distributions de vitesse mesurées montre que, même pour des nanogouttes composées de quelques molécules d'eau, l'énergie est redistribuée dans la goutte avant évaporation. Pour des nanogouttes contenant moins d'une dizaine de molécules d'eau, les distributions de vitesse mesurées sont proches de celles attendues pour des gouttes macroscopiques. La redistribution statistique de l'énergie apparaît comme un processus de relaxation dominant. Cependant, la mesure de la distribution des vitesses met aussi en évidence une contribution distincte à haute vitesse correspondant à l'éjection d'une molécule avant redistribution complète de l'énergie. Les distributions de vitesse mesurées pour des nanogouttes d'eau lourdes deutérées mettent en évidence une proportion d'événements non ergodiques plus importante que pour l'eau normale. Les mesures réalisées avec différents atomes cibles montrent que la proportion d'événements non ergodique diminue avec la diminution de l'énergie déposée dans la nanogoutte / The evaporation of a water molecule resulting in the rupture of one or more hydrogen bonds. These hydrogen bonds are responsible for many remarkable properties of water. At the macroscopic scale, water is well known for its ability to thermalize a system, while at the microscopic level, a high-speed transfer of vibrational energy through hydrogen bonding was observed. What scale of nanogoutte when a limited number of molecules come into play? In the experiment carried out with the device DIAM IPN Lyon, the relaxation of a nanogoutte of protonated water is observed after electronic excitation of one of its molecules. The implementation of a velocity vector imaging method associated with the technical COINTOF (Correlated Ion and Neutral Time-Of-Flight) allowed the measurement of the velocity distribution of molecules of evaporated protonated water clusters, mass and energy preselected. The shape of the measured velocity distributions shows that even for some nanodroplets composed of few water molecules, the energy is redistributed in the drop before evaporation. For nanodroplets containing less than ten water molecules, the measured velocity distributions are closed to those expected for macroscopic droplets. The statistical redistribution of energy appears as a dominant relaxation process. However, the measurement of the velocity distribution also highlights a distinct contribution at high velocity corresponding to the ejection of a molecule before complete redistribution of energy. The measured velocity distributions for heavy water nanodroplets deuterated show a proportion of non-ergodic most important events that for normal water. The measurements carried out with different target atoms show that the proportion of non-ergodic events decreases with decreasing the energy deposited in the nanogoutte