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Tableau d’honneur de la Faculté des études supérieures et postdoctorales, 2008-2009 / Le présent mémoire propose une étude sur la caractérisation biophysique et in vivo de peptides formant des canaux ioniques artificiels nommés LS2 et LS3. Ces molécules servant de modèles ont d'abord été mises au point par DeGrado et al en 1988, pour être ensuite caractérisées et modélisées jusqu'en 2007. Nous nous appuyons donc sur ces travaux ainsi que sur des études antérieures effectuées au sein de notre laboratoire pour éclaircir davantage les phénomènes d'auto-assemblage propres à ces peptides modèles. La première partie introduit le sujet des nanostructures peptidiques et la problématique de l'auto-assemblage à l'aide de plusieurs exemples tirés de la littérature récente. Les chapitres 1 et 2 traitent, dans un premier temps, des canaux ioniques naturels et offrent une analyse des éléments structuraux qu'ils partagent. Par la suite, une analyse des critères visés pour la création d'un canal ionique modèle est offerte. Celle-ci est suivie d'une présentation détaillée de LS2 et LS3. Le troisième chapitre présente la synthèse d'analogues fluorescents destinés aux caractérisations biophysiques et in vivo. Les chapitres 4 et 5 se consacrent aux études de dichroïsme circulaire et d'incorporation transmembranaire en infrarouge, respectivement. Le dernier chapitre présente les études de localisation in vivo réalisées avec les analogues fluorescents que nous avons synthétisés.

Surface plasmon resonances at the nanoscale hold great potential for applications in many areas, and the characterization of plasmonic nanostructures plays a critical role in the realization of these applications. Electron energy loss spectroscopy (EELS) has emerged as a powerful characterization tool to study the response of plasmonic nanostructures due to its high spatial-resolution and the capability to probe bright as well as dark plasmonic modes. The main limiting factor of EELS is the energy resolution. However, in this thesis, we overcome this limitation using a combination of electron monochromation and the use of the Richardson-Lucy algorithm. We show that the algorithm could be used to obtain effective energy resolutions up to 10 meV. Using EELS we analyze the resonances of planar nanostructures, and we found that the supported resonances can be described as edge and cavity or film modes, behaving as 1D and 2D modes respectively. We also demonstrate that edge modes are unaffected by the presence of bends up to the critical angle of 90◦ where the modes start self-interacting producing large energy shifts. The interaction of plasmon resonances is also studied, and we show that the coupling can be reduced to three behaviors: coupling through the edge, coupling through a corner, and non-coupling. We propose a method to control the coupling through the edge in offset nanowires, by tuning the nodal alignment and spectral overlap of the edge modes. Finally, we analyze the plasmon modes supported by Koch snowflake fractal antennas, and we demonstrate that modes present in the fractals are formed by the edge modes supported by their characteristic edges. This thesis provides a complete picture of the surface plasmon resonances supported by planar nanostructures and demonstrates the ability of EELS to probe and image a wide variety of plasmonic resonances. / Thesis / Doctor of Philosophy (PhD)

Le présent mémoire expose nos efforts dans le design, la synthèse ainsi que la caractérisation de nouvelles nanostructures peptidiques hélicoïdales pour la détection protéique. Le sujet sera divisé en deux volets. Premièrement, nous présenterons la synthèse de nanotransducteurs peptidiques pour la fonctionnalisation de pointes AFM pour la mesure de force de reconnaissance monomoléculaire. Deuxièmement, nous rapporterons la synthèse canaux ioniques artificiels peptidiques pour la détection de protéines par des essais de fluorescence. Une attention particulière sera portée aux efforts de synthèse ayant permis la fonctionnalisation terminale de peptides avec des espèces glycosidiques servant d’élément de reconnaissance de protéines via une stratégie de couplage de modules par cyclisation azoture-alcyne catalysée au cuivre. / This manuscript reports our results in the design, synthesis and characterization of novel helical peptide nanostructures to be used for the detection of proteins. The work is divided in two parts. The first part deals with the synthesis of peptide-based nanotransducers used for the functionalization AFM tips to perform single molecule recognition force spectroscopy. The second part reports the synthesis of peptide-based artificiel ion channels to be used as sensing elements in fluorescence protein detection assays. A special emphasis is put on our synthetic efforts leading to the terminal functionalization of peptides with glycosidic species for use as a protein recognition elements using a copper catalysed azide-alkyne cycloaddition coupling.

Le présent mémoire porte sur le design, la synthèse et la caractérisation de nanostructures peptidiques longues de 21 acides aminés pouvant servir de composantes moléculaires dans l'élaboration de biosenseurs ultrasensibles. Ces nanostructures utiliseront une biotine comme élément de reconnaissance et toute la structure servira de canal ionique pour la transmission des phénomènes de complexation. Le premier chapitre est consacré à l'introduction, à la description et aux applications de telles molécules dans un système de biosenseurs. Le second chapitre portera sur les concepts et l'élaboration de notre système modèle. La synthèse de nos molécules sera l'objet du troisième chapitre. Finalement, les réalisations et les perspectives futures seront abordées dans le quatrième chapitre.

Ce mémoire présente la synthèse et les études d'autoassemblage de peptides ayant la propriété de s'autoassembler. Ces études ont pour objectif principal de comprendre le processus qui régit l'autoassemblage des nanostructures protéiques de dimensions définies. Nous avons choisi de réaliser ces études d'autoassemblage à partir des peptides amphiphiles, neutres de type (LSLLLSL)3 et (LSSLLSL)3. Dans les quinze dernières années, plusieurs travaux, entre autres du Professeur W.F. DeGrado, démontrent que ces peptides ont la propension à s'autoassembler dans les milieux hydrophobes. Le premier chapitre porte sur les nanostructures protéiques autoassemblantes naturelles et artificielles. Ce chapitre suscite un questionnement sur les règles et les propriétés permettant le processus d'autoassemblage moléculaire. Le deuxième chapitre traite des études antérieures réalisées sur les peptides hélicoïdaux (LSLLLSL)3 et (LSSLLSL)3 communément appelé LS2 et LS3 dans la littérature. Le troisième chapitre décrit les différentes voies de synthèse des dérivés fluorescents LS2 et LS3 dans le but de faire des études d'autoassemblage. Finalement, les chapitres 4, 5 et 6 portent principalement sur la caractérisation de nos peptides fluorescents par dichroïsme circulaire, par fluorescence et par microscopie à force atomique.

Microbial fuel cells (MiFCs) have been suggested as a means to harness energy that is otherwise unutilized during the wastewater treatment process. MiFCs have the unique ability to treat influent waste streams while simultaneously generating power which can offset energy associated with the biological treatment of wastewater. During the oxidation of organic and inorganic wastes, microorganisms known as exoelectrogens have the ability to move electrons extracellularly. MiFCs generate electricity by facilitating the microbial transfer of these electrons from soluble electron donors in feedstocks to a solid-state anode. While MiFCs are a promising renewable energy technology, current systems suffer from low power densities which hinder their practical applicability. In this study, a novel anode design using flame-deposited carbon nanostructures (CNSs) on stainless steel mesh is developed to improve the electron transfer efficiency of electrons from microorganisms to the anode and thus the power densities achievable by MiFCs. These new anodes appear to allow for increased biomass accumulation on the anode and may aid in the direct transfer of electrons to the anode in mediatorless MiFC systems. Experiments were conducted using anaerobic biomass in single-chamber MiFCs with CNS-enhanced and untreated stainless steel anodes. Fuel cells utilizing CNS-enhanced anodes generated currents up to two orders of magnitude greater than cells with untreated metal anodes, with the highest power density achieved being 510 mW m-2. / Master of Science

Magnetoelectric (ME) effect is defined as the change in dielectric polarization (P) of a material under an applied magnetic field (H) or an induced magnetization (M) under an external electric field (E). ME materials have attracted number of investigators due to their potential for improving applications such as magnetic field sensors, filters, transformers, memory devices and energy harvesters. It has been shown both experimentally and theoretically that the composite structures consisting of piezoelectric and magnetostrictive phases possess stronger ME coupling in comparison to that of single phase materials. Giant magnetoelectric effect has been reported in variety of composites consisting of bulk-sized ME composites and thin film ME nanostructures. In this dissertation, novel ME composite systems are proposed, synthesized and characterized in both bulk and thin films to address the existing challenges in meeting the needs of practical applications. Two applications were the focused upon in this study, tunable transformer and dual phase energy harvester, where requirements can be summarized as: high ME coefficient under both on-resonance and off-resonance conditions, broad bandwidth, and low applied DC bias. In the first chapter, three challenges related to the conventional ME behavior in bulk ME composites have been addressed (1) The optimized ME coefficient can be achieved without external DC magnetic field by using a self-biased ME composite with a homogenous magnetostrictive material. The mechanism of such effect and its tunability are studied; (2) A near-flat ME response regardless of external magnetic field is obtained in a self-biased ME composite with geometry gradient structure; (3) By optimizing interfacial coupling with co-firing techniques, the ME coefficient can be dramatically enhanced. Theses co-fired ME laminates not only exhibit high coupling coefficient due to direct bonding, but also illustrate a self-biased effect due to the built-in stress during co-sintering process. These results present significant advancement toward the development of multifunctional ME devices since it eliminates the need for DC bias, expands the working bandwidth and enhances the ME voltage coefficient. Next, magnetoelectric nanocomposites were developed for understanding the nature of the growth of anisotropic thin film structures. In this chapter following aspects were addressed: (1) Controlled growth of nanostructures with well-defined morphology was obtained. Microstructure and surface morphology evolution of the piezoelectric BaTiO3 films was systematically analyzed. A growth model was proposed by considering the anisotropy of surface energy and the formation of twin lamellae structure within the frame work of Structure Zone Model (SZM) and Dynamic Scaling Theory (DST). In parallel to BaTiO3 films, well-ordered nanocomposite arrays [Pb1.1(Zr0.6Ti0.4)O3/CoFe2O4] with controlled grain orientation were developed and investigated by a novel hybrid deposition method. The influence of the pre-deposited template film orientation on the growth of ME composite array was studied. (2) PZT/CFO/PZT thick composite film and BTO/CFO thin film were synthesized using sol-gel deposition (SGD) and pulsed laser deposition (PLD) techniques, respectively. The HRTEM analysis revealed local microstructure at the interface of consecutive constituents. The interfacial property variation of these films was found to affect the coupling coefficient of corresponding ME nanocomposites. Subsequently, a novel complex three-dimensional ME composite with highly anisotropic structure was developed using a hybrid synthesis method. The influence of growth condition on the microstructure and property of the grown complex composites was studied. The film with highly anisotropic structure was found to possess tailored ferroelectric response indicating the promise of this synthesis method and microstructure. Based on the laminated ME composites, three types of ME tunable transformer designs were designed and fabricated. The goal was to develop a novel ME transformer with tunable performance (voltage gain and/or working resonance frequency) under applied DC magnetic field. Conventional ME transformers need either winding coil or large external magnetic field to achieve the tunable feature. Considering the high ME coupling of ME laminate, two ME transformers were developed by epoxy bonding Metglas with transversely/longitudinally poled piezoelectric ceramic transformer. The influence of different operation modes toward magnetoelectric tunability was analyzed. In addressing the concern of the epoxy bonding interface, a co-fired ME transformer with unique piezoelectric transformer/magnetostrictive layer/piezoelectric transformer trilayer structure was designed. The design and development strategy of thin film ME transformer was discussed to illustrate the potential for ME transformer miniaturization and on-chip integration. Lastly, motivated by the increasing demand of energy harvesting (EH) systems to support self-powered sensor nodes in structural health monitoring system, a magnetoelectric composite based energy harvester was developed. The development and design concept of the magnetoelectric energy harvester was systematically discussed. In particular, the first dual-phase self-biased ME energy harvester was designed which can simultaneously harness both vibration and stray magnetic field (Hac) in the absence of DC magnetic field. Strain distribution of the EH was simulated using the finite element model (FEM) at the first three resonance frequencies. Additionally, the potential of transferring this simple EH structure into MEMS scalable components was mentioned. These results provide significant advancement toward high energy density multimode energy harvesting system. / Ph. D.