Thesis (Ph. D.)--Rutgers University, 2010. / "Graduate Program in Chemical and Biochemical Engineering." Includes bibliographical references (p. 136-142).

Thesis (Ph. D.)--University of Washington, 1999. / Vita. Includes bibliographical references (leaves 175-188).

Thesis (Ph. D.)--West Virginia University, 2005. / Title from document title page. Document formatted into pages; contains xxiv, 371 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 343-367).

Thesis (M. Sc.)--University of Canterbury, 2007. / Typescript (photocopy). Includes bibliographical references (leaves 76-78). Also available via the World Wide Web.

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (p. 166-172).

The aim of this thesis is to study the structural and thermodynamical properties of polymers at liquid/liquid interfaces by means of multiscale molecular dynamics simulations. This thesis is presented in alternative format, and the results, consisting of three journal articles, are divided into two main parts. The first part of the thesis looks at the structural and dynamical changes as well as the thermodynamic stability of polymers of varying topology (linear and star-shaped) at interfaces by performing molecular dynamics simulations on model systems. It was found that homopolymers are attracted to the interface in both good and poor solvent conditions making them a surface active molecule, despite not being amphiphilic. In most cases changing polymer topology had only a minor effect on the desorption free energy. A noticeable dependence on polymer topology is only seen for relatively high molecular weight polymers at the interface. Examining separately the enthalpic and entropic components of the desorption free energy suggests that its largest contribution is the decrease in the interfacial free energy caused by the adsorption of the polymer at the interface. Furthermore, we propose a simple method to qualitatively predict the trend of the interfacial free energy as a function of the polymer molecular weight. In terms of the dynamics of a linear polymer, the scaling behaviour of the polymer confined between two liquids did not follow that predicted for polymers adsorbed onsolid or soft surfaces such as lipid bilayers. Additionally, the results show that in the diffusive regime the polymer behaves like in bulk solution following the Zimm model and with the hydrodynamic interactions dominating its dynamics. Further simulations carried out when the liquid interface is sandwiched between two solid walls show that when the confinement is a few times larger than the blob size the Rouse dynamics is recovered. The second part of the thesis focuses on optimizing the MARTINI coarse-grained (CG) Model, which retains certain chemical properties of molecules, to reproduce solubility of polymers, in specific polyethylene oxide (PEO), in both polar and non-polar solvents. Performing molecular dynamics simulations using this CG model will then enable us to study the properties PEO in octanol/water and hexane/water systems with increased length and timescales not accessible by atomistic simulations. The MARTINI CG method (Marrink et al., J. Phys. Chem. B, 2007, 111, 7812) is based on developing the optimal Lennard-Jones parameters to reproduce the partition free energy between water (polar solvent) and octanol (apolar solvent). Here we test the MARTINI CG method when modelling the partitioning properties of PEO, with increasing molecular weight between solvents of different polarity by comparing the results with atomistic simulation. We show that using simply the free energy of transfer from water to octanol to obtain the force parameters does not guarantee the transferability of the model to other solvents. Instead one needs to match the solvation (or hydration) free energies to ensure that the polymer has the correct polarity. We propose a simple method to select the Lennard-Jones parameter to match the solvation free energies for different beads. We also show that, even when the partition coefficient of the monomer is correct, even for modestly high molecular weight of the polymer the predicted partitioning properties could be wrong.

In this thesis, we studied the self-assembly of nanoparticles at liquid metal-water interfaces and oil-water interfaces. We demonstrated a simple approach to form nanostructured electronic devices by self-assembly of nanoparticles at liquid metal surfaces. In this approach, two liquid-metal droplets, which were coated with a monolayer of ligand-stabilized nanoparticles, were brought into contact. They did not coalesce but instead remained separated by the nanoparticles assembled at the interface. Devices formed by this method showed electron transport between droplets that was characteristic of the Coulomb blockade, where current was suppressed below a tunable threshold voltage because of the energy of charging individual nanoparticles. Further studies of this approach demonstrated the potential of interfacial assembly in fabricating microscopic electronic devices over a large area in a cost-effective and time-efficient fashion. Micrometer-scale Ga droplets coated with nanoparticles were fabricated using ultrasonication and then deposited on patterned substrates to form microscopic devices. I-V measurements showed Coulomb blockade effect in the devices containing more than one nanoparticle junction. The measured threshold voltages increased with number of junctions as expected for devices arranged in series. We also studied experimentally the energy of adsorption of nanoparticles and microparticles at the oil-water and Ga-water interfaces by monitoring the decrease of interfacial tension as the particles bind. For citrate-stabilized gold nanoparticles assembling on a droplet of octafluoropentyl acrylate, we found adsorption energy =-5.1 kBT for particle radius R = 2.5 nm, and adsorption energy scales R^2 for larger sizes. Gold nanoparticles with (1-mercaptoundec-11-yl) tetra(ethylene glycol) ligand had a much larger binding energy (-60.4 kBT) and an energy barrier against adsorption. For polystyrene spheres with R = 1.05 micrometer, we found adsorption energy =-0.9*10^6 kBT. We also found that the binding energy depended on the composition of the oil phase and could be tuned by the salt concentration of the nanoparticle suspension. At Ga-water interfaces, we found that adsorption energy of Au-cit and Au-TEG nanoparticles were much larger. We have also studied desorption of polystyrene microparticles from oil-water interfaces by changing experimental conditions, including addition of nanoparticles, cross-linking ligand molecules or in response to chemical interactions between the particles and the oil. We found that microparticles can desorb even though the adsorption energy is large. We also found that the desorbed particle formed a surprising `tail'-like structure.

Ce travail de thèse est consacré à la manipulation et la déformation optique d'interfaces liquides molles, cela dans deux géométries fondamentales: plane et sphérique. Nous montrons alors que les déformations induites par pression de radiation optique permettent de déduire les propriétés des interfaces, comme la tension interfaciale par exemple. Dans le cadre de la déformation d'une interface liquide plane par pression de radiation, nous généralisons pour la première fois la manifestation électro-hydrodynamique des cônes de Taylor au régime optique, en montrant que des cônes liquides peuvent émerger sous fortes excitation laser. Nous avons alors caractérisé la morphologie de ces « cônes optiques » et nous montrons que l'angle de ces derniers dépend à la fois des paramètres de l'excitation laser mais aussi des caractéristiques des fluides. Une étude analytique ainsi qu'une étude numérique ont alors été menées afin de rendre compte des comportements observés.Afin d'étudier la déformation d'interfaces molles en géométrie sphérique, nous avons développé un double piège optique fibré en dispositif microfluidique dans une configuration inédite en termes de longueur d'onde excitatrice et de puissance laser. Nous avons alors appliqué notre dispositif à la déformation de vésicules en tant qu'objets modèles mous et nous montrons que notre double piège est bien adapté à la caractérisation rhéologique d'objets micrométriques déformables. Grâce à l'utilisation de faisceaux laser de forte puissance, nous mettons ici en évidence expérimentalement l'apparition d'un régime non-linéaire de déformation au sein de notre double piège optique. / This thesis work is devoted to the optical manipulation and deformation of soft liquid interfaces, in two fundamental geometries: plane and spherical. We then show that the deformations induced by optical radiation pressure allow to deduce the properties of interfaces, such as interfacial tension for example. In the framework of the deformation of a plane liquid interface by optical radiation pressure, we generalize for the first time the electro-hydrodynamic manifestation of Taylor cones to the optical regime, showing that liquid cones can emerge under intense laser excitation.We then characterized the morphology of these "optical cones" and we show that their angle depends both on the parameters of the laser excitation and on the characteristics of the fluids. An analytical study as well as a numerical investigation were then conducted to account for the observed behaviors. In order to study the deformation of soft interfaces in spherical geometry, we have developed a fiber-based dual-beam optical trap in a microfluidic device in a novel configuration in terms of excitation wavelength and laser power. We then applied our device to the deformation of vesicles as soft model objects and we show that our dual-beam trap is well adapted to the rheological characterization of deformable micron-sized objects. Thanks to the use of high laser power beams, we experimentally highlight the appearance of a non-linear deformation regime within our double optical trap.

Les phénomènes électrocinétiques couplés au sein d'un nanocanal sont d'intérêt pour la conversion d'énergie et la production d'électricité reposant sur le mélange contrôlé d'eau douce et d'eau salée aussi appelée "énergie bleue". L'origine des phénomènes est lié à l'interaction avec des parois chargées et au transport d'ions au sein de ce qu'on nomme les couches de Debye. Ce travail vise à une meilleure compréhension de la physique et des phénomènes de transport dans ces couches dans le cadre de solutions confinées dans des nanocanaux.Une instrumentation spécifique a été développée pendant la thèse pour étudier les mécanismes qui gouvernent ces flux couplés. L'idée est de caractériser simultanément le transport de masse et le courant électrique au sein d'un nanocanal soumis à une différence de salinité de pression ou de tension électrique. Ce travail est divisé en trois parties.Dans la première partie, est décrite une cellule conçue pour la mesure et le contrôle de courant et tension électrique en présence de différence de pression ou de salinité au bornes d'un nanopores. L'utilisation de la cellule est illustrer dans le cas d'une membrane nanoporeuse de nafion.La seconde partie est focalisée sur une méthode simple de préparation d'un nanocanal directement connectable à un dispositif macroscopique. Le nanocanal, d'un micromètre de long, présente une géométrie conique, d'angle ajustable, et des extrémités équipées d'électrode déposées par pulvérisation cathodique.La troisième partie, concerne le développement d'une méthode pour la mesure directe de débit jusqu'à 10 pL/min s'écoulant au sein d'un nanocanal. Cette méthode combinée à une caractérisation électrique, pourra être utilisée, en présence de gradient de pression, de tension ou de salinité pour mesurer le débit et le courant électrique au sein d'un nanocanal de manière simultanée et indépendante. / Coupled electrokinetic phenomena within nanochannel are of interest for energy harvestingand production of electricity based on the controlled mixing of river water with sea water known as "blue energy". The origin of the phenomena is related to interaction with charged walls and transport of ions within the so called Debye layer. This work aims at a better understanding of the physics and transport phenomena in this layer associated with solution confined in nanochannel.A specific instrumentation has been developed during this thesis to study the mechanisms governing coupled nanofluics fluxes. The idea is to characterize simultaneously the mass transport within the nanochannel and the electrical current driven through the nanochannel by the application of either salinity difference , pressure difference or voltage difference across the channel. The thesis is divided into three parts.In the first part, a custom made flow cell and experimental conditions to control and measure various fluxes is presented. The capability of cell to measure current or voltage under applied pressure or salinity gradient is presented taking the benefit of commercial nanoporous Nafion membrane.The second part is focused on an easy way of preparation of nanochannel sample in the form of single chip, in which nanochannel is interfaced to micro and macroscopic world. A well-controlled, 1.4µm long nanochannel of conical geometry with a maximum aspect ratio of 10 is fabricated. The minimum apex size of nanochannel achieved here is 50 nm which is about 30 times less than the length of channel. The presence of electrode directly at the interface of nano to micro cavity allow to perform electrical characterization of nanochannel with high precision.The third part of the thesis is devoted to the development of a method for the direct measurement of flow rate as low as 10 pL/min across a single nanochannel. This measurement approach combined with electrical measurement, could be used, in presence of pressure, voltage or salinity gradient, to measure the flow rate and the electrical current across a single nanochannel simultaneously and independently.

Thesis (Ph. D.)--University of Oregon, 2007. / Typescript. Includes vita and abstract. Includes bibliographical references (leaves 146-156). Also available for download via the World Wide Web; free to University of Oregon users.