Spatial and temporal tracking of passively diffusing functionalized colloids continues to be an improving and auspicious approach to measuring weak specific and non-specific biomolecular interactions. Evidence of this is given by the recent increase in published studies involving the development and implementation of these methods. The primary aim of the work presented in this dissertation was to modify and optimize video microscopy (VM) and total internal reflection microscopy (TIRM) methods to permit the collection of equilibrium binding and sampling data from interaction of surface-immobilized biomolecules. Supported lipid bilayers were utilized as model systems for functionalizing colloid and wall surfaces. Preliminary results measuring calcium-specific protein-protein interactions between surface immobilized cadherin fragments demonstrate the potential utility of this experimental system and these methods. Additionally, quantum dot-modified colloids were synthesized and evanescent wave-excited luminescence from these particles was used to construct potential energy profiles. Results from this work demonstrate that colloids can be used as ultra-sensitive probes of equilibrium interactions between biomolecules, and specialized probes, such as those modified with quantum dots, could be used in a spectral multiplexing mode to simultaneously monitor multiple interactions.

Spatial and temporal tracking of passively diffusing functionalized colloids continues to be an improving and auspicious approach to measuring weak specific and non-specific biomolecular interactions. Evidence of this is given by the recent increase in published studies involving the development and implementation of these methods. The primary aim of the work presented in this dissertation was to modify and optimize video microscopy (VM) and total internal reflection microscopy (TIRM) methods to permit the collection of equilibrium binding and sampling data from interaction of surface-immobilized biomolecules. Supported lipid bilayers were utilized as model systems for functionalizing colloid and wall surfaces. Preliminary results measuring calcium-specific protein-protein interactions between surface immobilized cadherin fragments demonstrate the potential utility of this experimental system and these methods. Additionally, quantum dot-modified colloids were synthesized and evanescent wave-excited luminescence from these particles was used to construct potential energy profiles. Results from this work demonstrate that colloids can be used as ultra-sensitive probes of equilibrium interactions between biomolecules, and specialized probes, such as those modified with quantum dots, could be used in a spectral multiplexing mode to simultaneously monitor multiple interactions.

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Cette thèse rapporte l’étude des propriétés de films transparents conducteurs obtenus à partir de dispersions de nanotubes de carbone. La formulation des dispersions représente une étape clé dans le but d’obtenir des films homogènes avec de bonnes propriétés électro-optiques. Plus particulièrement, la création d’interactions attractives en solution entre les nanotubes de carbone permet d’une part de modifier le comportement rhéologique des dispersions et d’améliorer leur dépôt en couche mince par enduction. D’autre part, les travaux présentent une étude concernant l’influence des interactions sur la structuration du réseau de nanotube de carbone qui constitue les films. Ces changements de structuration sont notamment mis en parallèle avec les propriétés électriques des films selon leur épaisseur. L’utilisation de polymères semi-conducteurs a aussi fait l’objet de travaux expérimentaux pour améliorer la formation et les propriétés des films transparents conducteurs. / This thesis reports the study of the properties of transparent conductive films obtained from carbon nanotube dispersions. The dispersion formulation is a key step in order to obtain uniform films with good opto-electrical properties. In particular, the formation of attractive interactions between dissolved carbon nanotubes allows the modification of the rheological behavior of the dispersions and the improvement of their deposition in thin layer by coating. Also, the influence of the interactions on the carbon nanotube network morphology is presented. The structural changes of the networks are then related to both electrical properties and thickness of the films. Finally, the use of semiconducting polymers was analyzed in order to improve the fabrication and the properties of transparent conductive films.

The surface charges of cellulosic fibers contribute to several papermaking operations that influence the manufacture and final properties of paper. This thesis investigates the effect of the surface charges on wet-end chemistry, e.g. through the interaction of cationic polyelectrolytes with the fiber surface charges, and on the network strength of pulp suspensions. The polyelectrolyte titration method was used to investigate the interaction of the fiber charges with cationic polyelectrolytes. Techniques were developed to fluorescent label the adsorbing cationic polyelectrolyte in order to visualize the adsorption behavior. Fluorescent confocal laser scanning microscopy (CLSM) was used to determine the extent to which the cationic polyelectrolyte adsorbs into the porous fiber wall. It was shown that the polyelectrolyte charge density limits the adsorption to the surface under electrolyte-free conditions. Adsorption into the fiber wall only occurs for two conditions: 1) if the molecular mass is sufficiently low or 2) the electrolyte concentration is high enough to screen the charges along the polyelectrolyte backbone but not the interactions between the polyelectrolyte and the fiber charges. Aside from the polyelectrolyte properties, the fiber charge density contributes to the adsorption behavior of cationic polyelectrolytes. The fiber charge profile was altered by bulk and surface carboxymethylation. The electrolyte concentration at which a deviation from 1:1 stoichiometry occurs was shown to be dependent on the amount of surface charges, such that the deviation in stoichiometry occurs at a higher electrolyte concentration for pulps having a higher surface charge. A hypothesis was developed to test the conditions at which the deviation in adsorption stoichiometry occurs, which was defined as the critical electrolyte concentration (CEC). It was found that the CEC corresponded to the electrolyte concentration at which the distance between the fiber charges was on the order of the Debye length. Electron spectroscopy for chemical analysis (ESCA) was used as an independent calibration procedure to validate for which a 1:1 stoichiometry occurs. The analysis with ESCA agreed well with the polyelectrolyte titration method for measurement of fiber surface charges. When measured under appropriate conditions, i.e. electrolyte concentration and molecular properties, the fiber surface charge can accurately be measured by the polyelectrolyte titration method. The charge profiles of various pulp types and treatments were also examined. Having been established as a valid technique, the polyelectrolyte titration method was again used to measure the surface charge while conductometric titration was used to measure the total charge content. The amount of bulk and surface charges vary depending on the pulping method and type of wood, although the ratio between the bulk and surface charge (i.e. the charge ratio) is similar for chemical pulps. The mechanical pulp has a higher charge ratio because it contains more fines material than chemical pulp. Bleaching of the chemical pulp decreases the amount of bulk and surface charges, although the charge ratio remains essentially constant. However, methods such as beating or carboxymethyl cellulose (CMC) grafting are available to increase the charge ratio. The effect of the charge profile on fiber-fiber interactions was studied on both a microscopic and macroscopic level. Colloidal probe microscopy (CPM) was used to investigate the microscopic interactions between two cellulose surfaces. Cellulose surfaces, prepared by spin-coating a dissolving pulp onto silica, were used to model the fiber surface, which is too rough for surface force measurements. The charge density of the model surface was increased by CMC grafting. Results showed that increasing the surface charge density created large electrosteric repulsions, due to CMC the chains protruding out from the surface. These interactions on the microscopic scale affect the fiber network strength, which was measured with a parallel plate rheometer. When the repulsion is increased between the fibers, caused by the increase in the surface charge, fiber flocs break apart more easily due to a reduced friction between the fiber surfaces. The forces acting on the fiber network can also be mechanical in origin. The fiber length and flexibility were altered in order to study the influence of mechanical surface linking and elastic fiber bending on the fiber network strength. Using the storage modulus (G’0) as a measure of fiber network strength, longer fibers were found to create a stronger network due to an increased amount of fiber contacts. Flexible fibers have a lower network strength than stiff fibers because the fibers come to rest in a less strained position such that the the influence of elastic fiber bending on the fiber network strength is predominant. / QC 20100831