xvii, 203 p. / Gold nanoparticles have garnered recent attention due to their intriguing size- and shape-dependent properties. Routine access to well-defined gold nanoparticle samples in terms of core diameter, shape, peripheral functionality and purity is required in order to carry out fundamental studies of their properties and to utilize these properties in future applications. For this reason, the development of methods for preparing well-defined gold nanoparticle samples remains an area of active research in materials science. In this dissertation, two methods, diafiltration and aptamer mediated synthesis, are explored as possible routes towards well-defined gold nanoparticle samples. It is shown that diafiltration has considerable potential for the efficient and convenient purification and size separation of water-soluble nanoparticles. The suitability of diafiltration for (i) the purification of water-soluble gold nanoparticles, (ii) the separation of a bimodal distribution of nanoparticles into fractions, (iii) the fractionation of a polydisperse sample and (iv) the isolation of [rimers from monomers and aggregates is studied. NMR, thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS) measurements demonstrate that diafiltration produces highly pure nanoparticles. UV-visible spectroscopic and transmission electron microscopic analyses show that diafiltration offers the ability to separate nanoparticles of disparate core size, including linked nanoparticles. These results demonstrate the applicability of diafiltration for the rapid and green preparation of high-purity gold nanoparticle samples and the size separation of heterogeneous nanoparticle samples. In the second half of the dissertation, the identification of materials specific aptamers and their use to synthesize shaped gold nanoparticles is explored. The use of in vitro selection for identifying materials specific peptide and oligonucleotide aptamers is reviewed, outlining the specific requirements of in vitro selection for materials and the ways in which the field can be advanced. A promising new technique, in vitro selection on surfaces (ISOS), is developed and the discovery using ISOS of RNA aptamers that bind to evaporated gold is discussed. Analysis of the isolated gold binding RNA aptamers indicates that they are highly structured with single-stranded polyadenosine binding motifs. These aptamers, and similarly isolated peptide aptamers, are briefly explored for their ability to synthesize gold nanoparticles. This dissertation contains both previously published and unpublished co-authored material. / Adviser: James E. Hutchison

VIANA NETO, Bartolomeu Cruz. Propriedades estruturais e vibracionais de nanotubos e nanofitas de titanato. 2009. 67 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2009. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2014-11-13T22:32:43Z No. of bitstreams: 1 2009_tese_bcviananeto.pdf: 2854187 bytes, checksum: 4f6bd432814c19af95dec1be0d243db2 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2014-11-14T17:50:54Z (GMT) No. of bitstreams: 1 2009_tese_bcviananeto.pdf: 2854187 bytes, checksum: 4f6bd432814c19af95dec1be0d243db2 (MD5) / Made available in DSpace on 2014-11-14T17:50:54Z (GMT). No. of bitstreams: 1 2009_tese_bcviananeto.pdf: 2854187 bytes, checksum: 4f6bd432814c19af95dec1be0d243db2 (MD5) Previous issue date: 2009 / This work reports a study on the structural, morphological and vibrational properties of titanate nanotubes and nanoribbons obtained from hydrothermal treatment of TiO$_2$ in aqueous NaOH solutions. The physical properties of these as-synthesized and heat-treated nanostructures are discussed in comparison with their bulk (Na$_2$Ti$_3$O$_7$ and Na$_2$Ti$_6$O$_{13}$) counterparts. The results obtained from transmission electron microscopy, scanning electron microscopy, atomic emission spectroscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, infrared and Raman spectroscopies allowed us to conclude that the layers of both as-synthesized titanates nanotubes and nanoribbons are isostructural to the Na$_2$Ti$_3$O$_7$ lamellar compound. In the titanate nanotubes the chemical bonds are deformed because of the curvature of walls while in the titanates nanoribbons the layers present structural disorder by size effects. The thermal behavior of titanate nanoribbons is similar to those reported in literature for titanate nanotubes, where structural and morphological changes with increases of temperature are observed and indicated that the nanoribbons, at high temperatures, change to bulk with a phase mixing of Na$_2$Ti$_3$O$_7$ and Na$_2$Ti$_6$O$_{13}$. This is similar to what happens with the bulk Na$_2$Ti$_3$O$_7$ when thermally treated. Thus, we conclude that the chemical composition of both the titanate nanotubes and the titanate nanoribbons is the same, Na$_{2-x}$H$_x$Ti$_3$O$_7$.nH$_2$O (0$leq$x$leq$2). Also, we suggest that Raman spectroscopy can be used for an easy and quick identification of both morphology and structure changes of the nanosized titanates. Furthermore, in this work we report the synthesis, characterization and application of Ce ion-exchanged titanate nanotubes. The physicochemical properties of these nanotubes are discussed in comparison with their pure titanate nanotube counterparts. The transmission electron microscope images showed that the Ce ion-exchanged titanate nanotubes have the same morphology of the pristine nanotubes and their external walls are decorated with cerium oxide nanoparticles. The mechanism of nanoparticle formation is based on the precipitation of Ce ion at the nanotube surface. We observed a shift of the absorption band edge towards the visible region that is attributed to the effects of Ce$^{4+}$ addition (intercalation) and/or the presence of CeO$_2$ nanoparticles decorating the nanotubes surfaces. A red shift of vibrational modes associated with metal ion - oxygen interaction was observed and identified as being due to the effect of Ce addition to the lattice as well as the anchoring of CeO$_2$ nanoparticles to the nanotube wall. We show that this hybrid system is promising for applications in photocatalysis using the blue region of the electromagnetic spectrum and this was demonstrated for photodegradation of reactive blue 19 textile dye using visible light ilumination. / Este trabalho relata o estudo das propriedades estruturais, morfológicas e vibracionais dos nanotubos e das nanofitas de titanato obtidos a partir do tratamento hidrotérmico de TiO2 em solução aquosa de NaOH. As propriedades físicas destas nanoestruturas, como preparadas e tratadas termicamente, são discutidas e comparadas com seus similares sólidos estendidos (Na2Ti3O7 e Na2Ti6O13). Os resultados obtidos por microscopia eletrônica de transmissão, microscopia eletrônica de varredura, espectroscopia de emissão atômica, espectroscopia de energia dispersiva de raios-X, difração de raios-X, espectroscopia de absorção no infravermelho com transformada de Fourier e espectroscopia Raman permitem concluir que as camadas (paredes ou lamelas) de nanotubos e nanofitas de titanato, como preparados, são isoestrutural ao composto lamelar Na2Ti3O7. Nos nanotubos de titanato as ligações químicas são deformadas por causa da curvatura das paredes, enquanto nas nanofitas de titanato as camadas apresentam apenas a desordem estrutural causada pelo efeito do tamanho. O comportamento térmico das nanofitas de titanato é similar ao relatado na literatura para os nanotubos de titanatos, onde mudanças estruturais e morfológicas, com o aumento da temperatura, são observadas e indicam que as nanofitas quando submetidas a altas temperaturas mudam sua morfologia para grandes bastões (sólido estendido) com uma mistura das fases Na2Ti3O7 e Na2Ti6O13. Este resultado é similar ao comportamento do Na2Ti3O7, sólido estendido, quando tratado termicamente. Concluímos que os nanotubos e as nanofitas de titanato têm a mesma composição química Na{2-x}HxTi3O7.nH2O(0·x·2).

abstract: Engineered nanoparticles (NP; 10-9 m) have found use in a variety of consumer goods and medical devices because of the unique changes in material properties that occur when synthesized on the nanoscale. Although many definitions for nanoparticle exist, from the perspective of size, nanoparticle is defined as particles with diameters less than 100 nm in any external dimension. Examples of their use include titanium dioxide added as a pigment in products intended to be ingested by humans, silicon dioxide NPs are used in foods as an anticaking agent, and gold or iron oxide NPs can be used as vectors for drug delivery or contrast agents for specialized medical imaging. Although the intended use of these NPs is often to improve human health, it has come to the attention of investigators that NPs can have unintended or even detrimental effects on the organism. This work describes one such unintended effect of NP exposure from the perspective of exposure via the oral route. First, this Dissertation will explain an event referred to as brush border disruption that occurred after nanoparticles interacted with an in vitro model of the human intestinal epithelium. Second, this Dissertation will identify and characterize several consumer goods that were shown to contain titanium dioxide that are intended to be ingested. Third, this Dissertation shows that sedimentation due to gravity does not artifactually result in disruption of brush borders as a consequence of exposure to food grade titanium dioxide in vitro. Finally, this Dissertation will demonstrate that iron oxide nanoparticles elicited similar effects after exposure to an in vitro brush border expressing model of the human placenta. Together, these data suggest that brush border disruption is not an artifact of the material/cell culture model, but instead represents a bona fide biological response as a result of exposure to nanomaterial. / Dissertation/Thesis / Doctoral Dissertation Biology 2014

abstract: This thesis presents systematic studies on angle dependent Raman and Photoluminescence (PL) of a new class of layered materials, Transition Metal Trichalcogenides (TMTCs), which are made up of layers possessing anisotropic structure within the van-der-Waals plane. The crystal structure of individual layer of MX3 compounds consists of aligned nanowire like 1D chains running along the b-axis direction. The work focuses on the growth of two members of this family - ZrS3 and TiS3 - through Chemical Vapor Transport Method (CVT), with consequent angle dependent Raman and PL studies which highlight their in-plane optically anisotropic properties. Results highlight that the optical properties of few-layer flakes are highly anisotropic as evidenced by large PL intensity variation with polarization direction (in ZrS3) and an intense variation in Raman intensity with variation in polarization direction (in both ZrS3 and TiS3). Results suggest that light is efficiently absorbed when E-field of the polarized incident excitation laser is polarized along the chain (b-axis). It is greatly attenuated and absorption is reduced when field is polarized perpendicular to the length of 1D-like chains, as wavelength of the exciting light is much longer than the width of each 1D chain. Observed PL variation with respect to the azimuthal flake angle is similar to what has been previously observed in 1D materials like nanowires. However, in TMTCs, since the 1D chains interact with each other, it gives rise to a unique linear dichroism response that falls between 2D and 1D like behavior. These results not only mark the very first demonstration of high PL polarization anisotropy in 2D systems, but also provide a novel insight into how interaction between adjacent 1D-like chains and the 2D nature of each layer influences the overall optical anisotropy of Quasi-1D materials. The presented results are anticipated to have impact in technologies involving polarized detection, near-field imaging, communication systems, and bio-applications relying on the generation and detection of polarized light. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2016

abstract: This thesis is devoted to the theoretical and computational study of electron transport in molecular junctions where one or more hydrogen bonds are involved in the process. While electron transport through covalent bonds has been extensively studied, in recent work the focus has been shifted towards hydrogen-bonded systems due to their ubiquitous presence in biological systems and their potential in forming nano- junctions between molecular electronic devices and biological systems. This analysis allows us to significantly expand our comprehension of the experimentally observed result that the inclusion of hydrogen bonding in a molecular junc- tion significantly impacts its transport properties, a fact that has important implications for our understanding of transport through DNA, and nano-biological interfaces in general. In part of this work I have explored the implications of quasiresonant transport in short chains of weakly-bonded molecular junctions involving hydrogen bonds. I used theoretical and computational analysis to interpret recent experiments and explain the role of Fano resonances in the transmission properties of the junction. In a different direction, I have undertaken the study of the transversal conduction through nucleotide chains that involve a variable number of different hydrogen bonds, e.g. NH···O, OH···O, and NH···N, which are the three most prevalent hydrogen bonds in biological systems and organic electronics. My effort here has fo- cused on the analysis of electronic descriptors that allow a simplified conceptual and computational understanding of transport properties. Specifically, I have expanded our previous work where the molecular polarizability was used as a conductance de- scriptor to include the possibility of atomic and bond partitions of the molecular polarizability. This is important because it affords an alternative molecular descrip- tion of conductance that is not based on the conventional view of molecular orbitals as transport channels. My findings suggest that the hydrogen-bond networks are crucial in understanding the conductance of these junctions. A broader impact of this work pertains the fact that characterizing transport through hydrogen bonding networks may help in developing faster and cost-effective approaches to personalized medicine, to advance DNA sequencing and implantable electronics, and to progress in the design and application of new drugs. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2017

Un effort mondial existe actuellement dans le but de réaliser un ordinateur quantique. Un tel dispositif permettrait d'implémenter des algorithmes plus rapides que les algorithmes classiques pour certaines tâches (recherche dans des bases de données, factorisation d'entiers). Il permettrait également de simuler des systèmes quantiques de manière beaucoup plus efficace qu'un ordinateur classique. L'obtention de ce gain en puissance nécessite d'intriquer un grand nombre de bits quantiques (qubits). Celle ci suppose de pouvoir déplacer un qubit d'un point à un autre de l'espace. Dans cette thèse, nous démontrons une première étape vers le déplacement d'un qubit de spin électronique : un électron unique est déplacé, à la demande, entre deux boîtes quantiques distantes de quelques microns. Le transport est réalisé à l'aide d'une onde acoustique de surface qui entraîne l'électron. Le transfert a été réalisé avec une efficacité de 90 % et déclenché à la nanoseconde. Ces résultats ouvrent la voie à la réalisation d'expériences d'optique quantique électronique avec une détection évènement par évènement. L'envoi d'un électron sur deux initialement présents ouvre la voie à la génération de paires d'électrons distants et intriqués. / A global effort is pursued to realise a quantum computer. Such a dispositive will allow to implement faster algorithms for tasks like integer factoring and database search. It will also allow to simulate quantum system much more efficiently. than a classical system. This power gain necessitates to entangle a large number of qubits. This in turn requires the ability to transport a qubit in space. In this thesis, we demonstrate a first step: a single electron is transported on demand from one quantum dot to another quantum dot, micrometers away. The transport is realised thanks to a Surface Acoustic Wave (SAW) that drags the electron. The transfer is realised with an efficiency of 90 % and triggered within one nanosecond. These results open the way to the realisation of electron quantum optics experiments with an event per event detection. A work on the separation of two electron initially present in the quantum dot will lead to the generation of distant entangled particles.

abstract: Since its inception about three decades ago, silicon on insulator (SOI) technology has come a long way to be included in the microelectronics roadmap. Earlier, scientists and engineers focused on ways to increase the microprocessor clock frequency and speed. Today, with smart phones and tablets gaining popularity, power consumption has become a major factor. In this thesis, self-heating effects in a 25nm fully depleted (FD) SOI device are studied by implementing a 2-D particle based device simulator coupled self-consistently with the energy balance equations for both acoustic and optical phonons. Semi-analytical expressions for acoustic and optical phonon scattering rates (all modes) are derived and evaluated using quadratic dispersion relationships. Moreover, probability distribution functions for the final polar angle after scattering is also computed and the rejection technique is implemented for its selection. Since the temperature profile varies throughout the device, temperature dependent scattering tables are used for the electron transport kernel. The phonon energy balance equations are also modified to account for inelasticity in acoustic phonon scattering for all branches. Results obtained from this simulation help in understanding self-heating and the effects it has on the device characteristics. The temperature profiles in the device show a decreasing trend which can be attributed to the inelastic interaction between the electrons and the acoustic phonons. This is further proven by comparing the temperature plots with the simulation results that assume the elastic and equipartition approximation for acoustic and the Einstein model for optical phonons. Thus, acoustic phonon inelasticity and the quadratic phonon dispersion relationships play a crucial role in studying self-heating effects. / Dissertation/Thesis / M.S. Electrical Engineering 2013

abstract: Soft lithographic printing techniques can be used to control the surface morphology of titanium dioxide layers on length scales of several hundred nanometers. Controlling surface morphology and volumetric organization of titanium dioxide electrodes can potentially be used in dye-sensitized solar cell devices. This thesis explores how layer-by-layer replication can lead to well defined, dimensionally controlled volumes and details how these control mechanisms influence surface characteristics of the semiconducting oxide. / Dissertation/Thesis / M.S.Tech Engineering 2013

abstract: Current research has identified a specific type of visual experience that leads to faster cortical processing. Specifically, performance on perceptual learning of a directional-motion leads to faster cortical processing. This is important on two levels; first, cortical processing is positively correlated with cognitive functions and inversely related to age, frontal lobe lesions, and some cognitive disorders. Second, temporal processing has been shown to be relatively stable over time. In order to expand on this line of research, we examined the effects of a different, but relevant visual experience (i.e., implied motion) on cortical processing. Previous fMRI studies have indicated that static images that imply motion activate area V5 or middle temporal/medial superior temporal complex (MT/MST+) of the visual cortex, the same brain region that is activated in response to real motion. Therefore, we hypothesized that visual experience of implied motion may parallel the positive relationship between real directional-motion and cortical processing. Seven subjects participated in a visual task of implied motion for 4 days, and a pre- and post-test of cortical processing. The results indicated that performance on implied motion is systematically different from performance on a dot motion task. Despite individual differences in performance, overall cortical processing increased from day 1 to day 4. / Dissertation/Thesis / M.S. Psychology 2014

Neste trabalho foram estudadas as propriedades magnéticas e características estruturais de filmes finos bicamadas e multicamadas formados com Ni{x}Cu{1-x} (ferromagneto, 50 x 90 e níquel puro), NiO, FeMn e IrMn (antiferromagnetos). Ligas de níquel-cobre podem ser classificadas como fracamente ferromagnéticas. Ferromagnetismo fraco gera efeitos únicos em propriedades de transporte eletrônico, junções com supercondutores e sistemas de exchange bias. Sendo uma solução sólida extremamente simples, diversas propriedades do NiCu dependem linearmente da estequiometria da liga. Os filmes finos foram depositados via magnetron sputtering em substratos monocristalinos de Si (100) a temperatura ambiente. A estrutura cristalina foi caracterizada por difração de raios-X e a morfologia foi analisada por retroespalhamento Rutherford. Propriedades magnéticas foram medidas com um SQUID a temperaturas entre 5K e 300K (curvas ZFC/FC e de magnetização a diferentes temperaturas) e com um VSM a temperatura ambiente (curvas de magnetização em diferentes ângulos no plano do filme). As amostras com Ni{x}Cu{1-x} mais ricas em cobre apresentam os maiores campos coercivo e de exchange bias a baixas temperaturas, mas os menores em altas temperaturas, geralmente respeitando as temperaturas de bloqueio indicadas nas curvas ZFC/FC. O acoplamento na interface das bicamadas NiO/Ni{x}Cu{1-x} foi muito reduzido em temperaturas mais altas, não sendo observada anisotropia unidirecional nas medidas a temperatura ambiente. As constantes de interação J{int} foram calculadas para as bicamadas Ni{x}Cu{1-x}/FeMn e Ni{x}Cu{1-x}/IrMn a 5K e temperatura ambiente. O sistema Ni/IrMn apresentou o maior valor dessa constante em ambas as temperaturas, diminuindo muito com o acréscimo de cobre na camada Ni{x}Cu{1-x}. O sistema Ni{90}Cu{10}/FeMn apresentou os maiores valores em ambas as temperaturas (excluindo o de níquel puro), comparável até com Ni/IrMn no caso de 5K. Esse comportamento pode ser explicado por uma maior afinidade entre as estruturas do FeMn e Ni{x}Cu{1-x} na direção [111], o que favorece a formação da face (111) no FeMn, mais consistentemente do que no IrMn. Nenhuma das multicamadas estudadas se comportou como uma válvula de spin, mas foi observado um aumento na coercividade e supressão do exchange bias, provavelmente por causa de acoplamento entre as camadas ferromagnéticas. / In this work, a study of magnetic properties and structural characteristics of bilayered and multilayered thin films was carried out. These films were made with Ni{x}Cu{1-x} (ferromagnet, 50 x 90 and pure nickel) and NiO, FeMn or IrMn as antiferromagnets. Nickel-copper alloys may be classified as weakly ferromagnetic. Weak ferromagnetism generates unique effects in electron transport, junctions with superconductors and exchange bias systems. Being an extremely simple solid solution, many properties of the NiCu alloy have a linear dependence with its stoichiometry. The thin films were deposited via magnetron sputtering on Si (100) monocrystalline substracts at room temperature. The crystalline structure was characterized by X-ray diffraction, while the morphology was analyzed by Rutherford back-scattering. Magnetic properties were measured by SQUID at temperatures between 5K and 300K (ZFC/FC curves and magnetization curves at different temperatures) and by VSM at room temperature (magnetization curves at varying angles at the film plan). The samples with copper-richer Ni{x}Cu{1-x} showed the largest coercive and exchange bias fields in lower temperatures, but the lowest ones in higher temperatures, usually following the blocking temperatures denoted by the ZFC/FC curves. The interfacial coupling in NiO/Ni{x}Cu{1-x} was very weak in higher temperatures, not showing unidirectional anisotropy at room temperature. The J{int} exchange interaction constants were calculated for the Ni{x}Cu{1-x}/FeMn and Ni{x}Cu{1-x}/IrMn bilayers at 5K and room temperature. Ni/IrMn had the largest values at both temperatures, heavily decreasing with the copper content in the Ni{x}Cu{1-x} layer. Ni{90}Cu{10}/FeMn showed the largest values at both temperatures (except for the pure Ni sample), even reaching the values of Ni/IrMn at 5K. This behavior may be explaned by a greater matching between the FeMn and Ni{x}Cu{1-x} crystalline structures on the [111] direction, which favors the formation of the (111) FeMn face more consistently than the corresponding IrMn face. All the studied multilayers showed no spin valve behavior, but an increased coercivity and supressed exchange bias were observed, probably because of coupling between the ferromagnetic layers.