Includes bibliographical references.

Self-assembly provides an efficient way to build complex structures with great flexibility in terms of components and properties. This dissertation presents two different forms of self-assembly for technical applications. The first example is the molecular assembly of liquid crystals (LCs). Attaching appropriate side chains on anthracene, oligothiophene, and oligoarenethiophene successfully constructed liquid crystalline organic semiconductors. The phase transitions of the LC semiconductors were analyzed by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The effect of the LC phase change on charge transport was probed by the space-charge limited current (SCLC) method and the field-effect transistor (FET) method. Mobility in the LC phase rose in anthracenyl esters but decreased in oligothiophenes and oligoarenethiophenes. The different electronic behavior of LC semiconductors may be caused by the difference in domain size and/or the difference in response to electric field. The second example of self-assembly in this dissertation is DNA-guided self-assembly of micrometer-sized particles. Patternable bioconjugation polymers were synthesized to allow for lithographic patterning and DNA conjugation. The base pairing of DNA was then used to drive the self-assembly of DNA-conjugated particles. The DNA conjugation chemistry was studied in detail using a fluorescence-based reaction test platform. The conjugated DNA on the polymer surface retained its ability to hybridize with its complement and was efficient in binding microspheres with complementary strands. Highly specific bead-to-bead assembly was analyzed using imaging flow cytometry, and the fractions of self-assembly products were explained on the basis of chemical equilibrium. The process of particle fabrication using photolithography was successfully developed, and the self-assembly of lithographically-patterned particles was demonstrated. We envision that the technologies described in this dissertation will be useful in a variety of fields ranging from microelectronics to biotechnology. / text

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Many materials and biological systems in nature are suspensions composed of disks, such as clay, asphaltenes, and red blood cells. Despite their natural abundance and wide industrial application, disks are least studied compared to spheres and rods, due to the lack of model systems. In our research, disks at micro-scale were mass-produced with unprecedented uniformity in size and shape, and unique flexibility in the control of lateral size, lateral size polydispersity, shape, and aspect ratio (ξ = diameter/thickness). This dissertation focuses on two main areas: the study of the discotic colloidal liquid crystal phase transitions and the application of disk-like colloidal systems as Pickering emulsion and Pickering foam stabilizers. First, we engineered two discotic colloidal systems made from organic and inorganic materials. The former is made of α-eicosene, which is an alkene of 20 carbons. The latter is composed of nano-sheets from exfoliated zirconium phosphate (α-ZrP). Both discotic systems were used to experimentally investigate the liquid crystalline phase transitions (Isotropic-Nematic, Isotropic-Cubic and Isotropic-Columnar). Also, the nematic crystalline phase was studied in detail by embedding it in a translucent and thermo-sensitive hydrogel. This was possible since nematic textures could be formed instantly by ZrP nano-sheets due to their high diameter-thickness ratio. Second, we developed Pickering emulsions and Pickering foams stabilized by high-aspect-ratio nano-sheets. We have also demonstrated for the first time the fabrication of the thinnest amphiphilic Janus and Gemini nano-sheets, which are either surface- or edge-modified plates with a thickness at atomic scale. These nano-sheets were obtained by exfoliating α-ZrP crystals grafted with a coupling agent of hydrophobic molecules on their edges and outer surfaces. Extending this work, we studied crucial fundamental mechanisms that allow Pickering interfacial stabilization, including the effect on the adsorption properties of particle aspect ratio, concentration, and hydrophobicity. Our study is of great interest in the scientific community due to the difficulty in generating a discotic colloidal system of controllable parameters.

Ferroelectric liquid crystals (FLCs) exhibit a bulk electric polarization (PS) that can be coupled to an electric field to produce an ON-OFF light shutter, and are being investigated as an alternative to nematic liquid crystals in display applications. Commercial FLC mixtures normally consist of a small amount of chiral dopant in an achiral smectic C (SmC) liquid crystal host. Because the switching time of FLC display is inversely proportional to the induced polarization, the design of chiral dopants with high polarization powers (p) is a key aspect of FLC research. Such work requires an understanding of the relationship between molecular structure and polar order in the chiral SmC* phase. Previous work in the Lemieux group focused on 2,2’-spirobiindan-1,1’-diones dopants, and a conformational model was proposed to explain the observed host dependence of the polarization power (p) of these dopants. In order to test this model, the 2,2’-spirobiindan-1,1’-dione core has been modified by introducing polar substituents and by modifying the functional groups linking the core to the alkyl side-chains. Specifically, this thesis focuses on implementing this approach via the synthesis and characterization of chloro- and methyl-substituted 2,2’-spirobiindan-1,1’-dione dopants. Four chiral dopants (2.1a, 2.1b, 2.2a and 2.2b) were synthesized, resolved and their absolute configurations assigned by CD spectroscopy. Their polarization powers were measured in four SmC hosts with different core structures. For both the ether-linked and ester-linked dopants, the addition of a substituent at the 6-position of one indanone ring results in lower polarization powers regardless of the size and polarity of the substituent, which is contrary to the original conformational distribution model. A comparative study of the data suggests that the ester-linked dopants exert much stronger perturbations on the host environment than the ether-linked dopants, especially when the 6-position is substituted. We postulate that this perturbation is chiral in nature, and that the feedback effect of chirality transfer causes a shift in the conformational distribution of the dopant favoring conformers with negative polarity. Probe experiments were performed to detect the effect of chirality transfer feedback (CTF) in the case of the chloro-substituted diester dopant (2.1b), showing consistent results with the postulate. / Thesis (Master, Chemistry) -- Queen's University, 2007-09-28 12:26:06.486

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Optical spatial solitons in nematic liquid crystals, termed nematicons, have become an excellent test bed for nonlinear optics, ranging from fundamental effects to potential uses, such as designing and demonstrating all-optical switching and routing circuits in reconfigurable settings and guided-wave formats. Following their demonstration in planar voltage-assisted nematic liquid crystal cells, the spatial routing of nematicons and associated waveguides have been successfully pursued by exploiting birefringent walkoff, interactions between solitons, electro-optic controlling, lensing effects, boundary effects, solitons in twisted arrangements, refraction and total internal reflection and dark solitons. Refraction and total internal reflection, relying on an interface between two dielectric regions in nematic liquid crystals, provides the most striking results in terms of angular steering. In this thesis, the refraction and total internal reflection of self-trapped optical beams in nematic liquid crystals in the case of a planar cell with two separate regions defined by independently applied bias voltages have been investigated with the aim of achieving a broader understanding of the nematicons and their control. The study of the refraction of nematicons is then extended to the equivalent refraction of optical vortices. The equations governing nonlinear optical beam propagation in nematic liquid crystals are a system consisting of a nonlinear Schr¨odinger-type equation for the optical beam and an elliptic Poisson equation for the medium response. This system of equations has no exact solitary wave solution or any other exact solutions. Although numerical solutions of the governing equations can be found, it has been found that modulation theories give insight into the mechanisms behind nonlinear optical beam evolution, while giving approximate solutions in good to excellent agreement with full numerical solutions and experimental results. The modulation theory reduces the infinite-dimensional partial differential equation problem to a finite dynamical system of comparatively simple ordinary differential equations which are, then easily solved numerically. The modulation theory results on the refraction and total internal reflection of nematicons are in excellent agreement with experimental data and numerical simulations, even when accounting for the birefringent walkoff. The modulation theory also gives excellent results for the refraction of optical vortices of +1 topological charge. The modulation theory predicts that the vortices can become unstable on interaction with the nematic interface, which is verified in quantitative detail by full numerical solutions. This prediction of their azimuthal instability and their break-up into bright beams still awaits an experimental demonstration, but the previously obtained agreement of modulation theory models with the behaviour of actual nematicons leads us to expect the forthcoming observation of the predicted effects with vortices as well.

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