DNA nanostructures enable the attachment of functional molecules to nearly any unique location on their underlying structure. Due to their single-base-pair structural resolution, several ligands can be spatially arranged and closely controlled according to the geometry of their desired target, resulting in optimized binding and/or signaling interactions. Here, the efficacy of SWL, an ephrin-mimicking peptide that binds specifically to EphrinA2 (EphA2) receptors, increased by presenting up to three of these peptides on small DNA nanostructures in an oligovalent manner. Ephrin signaling pathways play crucial roles in tumor development and progression. Moreover, Eph receptors are potential targets in cancer diagnosis and treatment. Here, the quantitative impact of SWL valency on binding, phosphorylation (key player for activation) and phenotype regulation in EphA2-expressing prostate cancer cells was demonstrated. EphA2 phosphorylation was significantly increased by DNA trimers carrying three SWL peptides compared to monovalent SWL. In comparison to one of EphA2’s natural ligands ephrin-A1, which is known to bind promiscuously to multiple receptors, pinpointed targeting of EphA2 by oligovalent DNA-SWL constructs showed enhanced cell retraction. Overall, we show that DNA scaffolds can increase the potency of weak signaling peptides through oligovalent presentation and serve as potential tools for examination of complex signaling pathways.

This dissertation presents the development of a synthetic strategy to produce various spiroligomer-based macrocycles that bridge the gap between organic molecules and small proteins. “Spiroligomers” (formerly known as “bis-peptides”) are a class of molecules produced by the assembly of “bis-amino acids”, molecules containing two amino acid regions on a single cyclic core. Each bis-amino acid is connected through pairs of amide bonds to form a diketopiperazine consequently eliminating single bond rotation and, therefore, avoids the complicated folding process common to the field of peptidomimetics. Spiroligomers are shape-programmable since the three-dimensional structure is controlled by the stereochemistry of the bis-amino acid monomers used in the synthesis, the connectivity of the monomers, and the number of monomers used. Furthermore, bis-amino acids can contain additional functional groups attached to multiple locations on the monomer which allows each spiroligomer, once synthesized, the ability to display these functional groups in predictable three-dimensional coordinates, with respect to each other. The synthesis of large spiroligomer-based structures requires the production of large amounts of bis-amino acid monomers. To this end, the scale of the synthesis of proline-based bis-amino acids from inexpensive trans-4-hydroxy-L-proline has been increased roughly 5-fold with respect to the previously published method. In addition to the time and solvent savings as a result of increasing the scale, the synthetic steps have been altered with considerations to ensure the production takes place in a convenient and environmentally friendly manner. Additionally, the desire to synthesize large spiroligomer-based structures means that the synthesis of each spiroligomer fragment must be as efficient and high-yielding as possible. To achieve this goal, a new synthetic approach to highly functionalized spiroligomers on solid support has been developed that results in increased yields relative to previously published methods. This new approach makes use of a protecting group, para-nitrobenzyl carbamate, which has not previously been incorporated in bis-amino acids as well as a pentafluorophenol ester activation strategy that also has not been in the synthesis of spiroligomers. Finally, an extendable synthetic route to spiroligomer-based macrocycles has been developed and representative macrocycles have been synthesized. This approach uses solid support to assemble multiple spiroligomers together through amino acids linkers before being cyclized in solution at dilute concentration to yield the desired macrocycles. Minimal functionality was included in the representative macrocycles to simplify structural information, confirmed by NMR and other means, and the macrocyclic structures were further investigated for host-guest activity using fluorescent, solvatochromic dyes. / Chemistry

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第25400号 / エネ博第479号 / 新制||エネ||89(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 森井 孝, 教授 片平 正人, 教授 佐川 尚 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DGAM

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

During recent years the demand for nanoscale materials with tailor-made functional properties as bulk species, is continuously and progressively rising for such fields as e.g. micro- and nano-electronics, plasmonics, spintronics, bio-technology, bio-sensing and life sciences. Preserving and / or improving properties of functional materials with their simultaneous size reduction and high-resolution site-specific positioning is indeed very challenging, for both conductors and insulators. One of the advanced nanoprototyping methods that can be utilized for this purpose is the Electron-Beam-Induced Deposition, or shortly EBID. This process is based on a local decomposition by a focused electron beam of a precursor gas molecules adsorbed on the sample’s surface. The beauty of this method is that it gives a unique possibility of rapid creation of site-specific nanoscale 3D structures of precise shape in a single operation. It’s an additive process that can be easily combined with other patterns. However, besides all the benefits, EBID has some constraints, in particular low purity of the deposited materials, due to the organometallic nature of the used precursors. Chemical composition of EBID patterns is strongly dependent on the chosen gas chemistry, the substrate, many deposition parameters and post-treatment processes applied to the deposited structures. In our research we focused on deposition of Co, Au, SiO2, C, W and Pt, their purification and shape control. And this thesis presents an overview of our accomplishments in this field. Depending on the gas chemistry of interest, three major purification approaches of EBID-grown materials were tested out: - Post-deposition annealing: in air and in the controlled atmosphere, - Deposition onto a preheated substrate, - Deposition in the presence of reactive gases. As a result, a dramatic purity improvement was observed and a significant advancement was achieved in creation of high-purity gold, cobalt and silicon dioxide nanoscale structures. In particular: 1)   For the Me2Au(acac) precursor, we developed a nanofabrication routine combining application of wetting buffer layers, fine tuning of EBID parameters and subsequent post-annealing step, which led to formation of high-purity planar and high aspect ratio periodic Au nanopatterns. We also describe the adopted and gently adjusted wet etching method of undesirable buffer layer removal, required in some cases for the further device application. 2)   For the Co2(CO)8 precursor, in-situ seeded growth in conjunction with EBID at the elevated substrate temperature resulted in a deposition of pure nanocrystalline Co with magnetic and transport properties close to the bulk material. 3)   For the tetraethyl orthosilicate precursor, or shortly TEOS, assisting of the deposition process with the additional oxygen supply led to the EBID of carbon-free amorphous insulating Si-oxide, with the absorption and refraction properties comparable to those for fused silica. Several applications of EBID nanopatterns are also discussed. / <p>QC 20131028</p>

Organic photovoltaic (OPV) cells are advanced, newly emerging technologies that are lightweight, mechanically flexible devices with highthroughput processes from low cost material in a variety of colors. Rathnayake et al. of Western Kentucky University have developed a nanostructure-based OPV cell. Presented in this thesis is a model and simulation of a generalized PV powered system that can predict the performance of solar arrays in various environmental conditions. The simulation has been carried out in Matlab/Simulink, and upon entering the cell’s parameters, it provides key electrical characteristics such as the cell’s I-V curve and efficiency information. The total system that is simulated consists of three elements: a universal two-cell solar array that can account for partial shading and manufacturing variation, a current-controlled power converter, and an energy storage device with charging and discharging capabilities.

GaN and its alloys with Al and In belong to the group III nitride semiconductors and are today the materials of choice for efficient white light emitting diodes (LEDs) enabling energy saving solid state lighting. Currently, there is a great interest in the development of novel inexpensive techniques to fabricate hybrid LEDs combining high quality III-N quantum well (QW) structures with inexpensive colloidal nanoparticles or conjugated polymers. Such hybrid devices are promising for future micro-light sources in full-color displays, sensors and imaging systems. Organics can be engineered to emit at different wavelengths or even white light based on functional groups or by blend of several polymers. This is especially important for the green region, where there is still a lack of efficient LEDs. Besides optoelectronics, other applications such as biochemical sensors or systems for water splitting can be realized using GaN-based nanostructures. Despite a significant progress in the field, there is still a need in fundamental understanding of many problems and phenomena in III-nitride based nanostructures and hybrids to fully utilize material properties on demand of specific applications. In this thesis, hybrid structures based on AlGaN/GaN QWs and colloidal ZnO nano-crystals have been fabricated for down conversion of the QW emission utilizing non-radiative (Förster) resonant energy transfer. Time-resolved photoluminescence (TRPL) was used to investigate the QW exciton dynamics depending on the cap layer thickness in the bare QW and in the hybrid samples. Although the surface potential influences the exciton dynamics, the maximum pumping efficiency assuming a non-radiative energy transfer mechanism was estimated to be ~40 % at 60 K in the structure with thin cap layer of 3 nm. Since bulk GaN of large area is difficult to synthesize, there is a lack of native substrates. Thus, GaN-based structures are usually grown on SiC or sapphire, which results in high threading dislocation density in the active layer of the device and can be the reason of efficiency droop in GaN based LED structures. Fabricating GaN nanorods (NR) can be a way to produce GaN with lower defect density since threading dislocations can be annihilated toward the NR wall during growth. Here, GaN(0001) NRs grown on Si(111) substrates by magnetron sputtering using a liquid Ga target have been investigated. A high quality of NRs have been confirmed by transmission electron microscopy (TEM) and TRPL. Two strong near band gap emission lines at ~3.42 eV and ~3.47 eV related to basal plane stacking faults (SF) and donor-bound exciton (DBE), respectively, have been observed at low temperatures. TRPL properties of the SF PL line suggest that SFs form a regular structure similar to a multiple QWs, which was confirmed by TEM. The SF related PL measured at 5 K for a single NR has a significantly different polarization response compared to the GaN exciton line and is much stronger polarized (&gt; 40 %) in the direction perpendicular to the NR growth axis. Hybrids fabricated using GaN NRs and the green emitting polyfluorene (F8BT) have been studied using micro-TRPL. In contrast to the DBE emission, the recombination time of the SF-related emission was observed to decrease, which might be due to the Förster resonance energy transfer mechanism. Compared to chemical vapor deposition, sputtering allows synthesis at much lower temperatures. Here, sputtering was employed to grow InAlN/GaN heterostructures with an indium content targeted to ~18 %, which is lattice matched to GaN. This means that near strain-free GaN films can be synthesized. It was found that using a lower temperature (~25 C) while depositing the top InAlN results in an improved interface quality compared to deposition at 700 C. In latter case, regions of quaternary alloy of InAlGaN forming structural micro-defects have been observed at the top InAlN/GaN interface in addition to optically active flower-like defect formations.

O confinamento da luz em escala nanométrica, em especial para estruturas metálicas, é conferido graças à ação coletiva dos elétrons livres desses materiais que ao entrarem em ressonância com a frequência da radiação incidente geram campos intensos o suficiente para permitir que uma parcela da luz atravesse as cavidades que formam as estruturas, desafiando os limites clássicos da óptica impostos pela teoria escalar da difração. Designa-se a tal ação coletiva dos elétrons na literatura como plasmons polaritons de superfície, ou SPP da sigla em inglês para Surface Plasmon Polariton, conceito há muito estudado em Física do Estado Sólido. Porém, somente a algumas décadas com o domínio sobre a fabricação de estruturas em escala nanométrica, tornou-se possível a análise experimental e a contribuição de SPP na observação de fenômenos em nano-óptica. A ressonância de plasmons em nanoestruturas confere considerável sensibilidade ao índice de refração dos meios próximos a elas, o que abre mais um canal para estudos no campo da interação entre radiação-matéria. Dentre eles há interação de plasmons com íons de terras-raras (ITR). Estes últimos por apresentarem bandas de absorção estreitas e bem definidas, são excelentes opções como elementos na análise da interação destes com os SPPs gerados nas nanoestruturas. Uma maneira de estabelecer o contato direto entre o campo plasmônico e os ITRs é incorpora-los ao substrato no qual o filme metálico onde as nanoestruturas são fabricadas é depositado. Vidros óxidos à base de Telúrio e Germânio reúnem condições favoráveis para esse propósito, por terem alta solubilidade às terras-raras, janela de transparência relativamente larga (0,4 - 5&mu;m) podendo ser analisados desde o visível até o infravermelho e baixa energia de fônon. O presente trabalho consistiu no esforço de criar uma plataforma para estudo direto de interações SPP com o ITR a partir da nano fabricação via técnica de feixe de íons e medir a luz emitida por processo de conversão ascendente do Érbio diretamente pela nanoestrutura devido ao decaimento do íon em SPP e na consequente remissão através da transmissão óptica extraordinária (TOE). A partir de tais medidas há fortes evidências de que a radiação emitida pelo Érbio apresenta a mesma polarização do campo plasmônico originado nas nanoestruturas. / The confinement of light at the nanoscale, especially for metallic structures is achieved due the collective action of free electrons from the material that resonate with the frequency of the incident radiation, generating enhanced fields enough to allow a portion of the light to cross the cavities that form such structures, challenging the classical limits of optics imposed by the scalar diffraction theory. Such collective action of the electrons is known in the literature as surface plasmon polariton (SPP), a concept which has already been studied in Solid State Physics, but only a few decades ago, with the development of fabrication of nanoscale structures has enabled the experimental analysis and the contribution due SPP on the observation of nanoptics phenomena. The plasmon resonance from nanostructures offers considerable sensitivity to the refractive index from the media that surround them, which opens another topic in matter-radiation interaction. There are interactions of plasmons with rare earth ions (REI). The latter class of emitters, presents narrow and well-defined absorption bands, which make them excellent options as probes to the analysis of interaction with the SPPs generated in the nanostructures. To establish direct contact between the plasmonic field and the REIs consists in embedding them into the substrate for the metallic thin film where the structures are assembled. Tellurium and Germanium oxide based glasses gather the conditions for this purpose, because they present high solubility to rare earths, a relatively wide transparency window (0.4 - 5 &mu;m), which enables spectral analysis from visible to infrared, and low phonon energy. The present work consisted in the effort to create a direct platform to study the SPP interactions with the REI from the milling of the samples by ion beam technique; to measure the light emitted from the Erbium\'s upconversion process directly through the nanostructure due the ion decay to SPP and in the consequent remission by extraordinary optical transmission (EOT). From such measurements there are strong evidences that the radiation emitted by Erbium ions presents the same polarization from the plasmonic field originated in nanostructures.

O presente trabalho tem como objetivo contribuir para o conhecimento da morfologia, microestrutura e modulação composicional (perfil da composição química) de recobrimentos NbN/CrN multicamadas nanoestruturados com diferentes periodicidades (entre 4 e 20 nm) depositado por PVD pela técnica de arco catódico. Foi alcançada espessura total do recobrimento de 30 ?m mantendo-se a homogeneidade da periodicidade ao longo de toda a espessura. Análises de difração de Raios-X, aliadas a modelamento computacional (difração dinâmica), e análise de microscopia eletrônica de transmissão (MET), permitiram a determinação da periodicidade das multicamadas e a espessura das camadas individuais de NbN e CrN e análise qualitativa da coerência entre as camadas. O modo de varredura (SMET) acoplado com espectroscopia de perda de energia de elétrons (EELS), permitiu medir a variação da composição química ao longo das nano-camadas individuais. A análise por EELS mostrou que, mesmo para a menor periodicidade estudada - 4nm, não há eliminação da modulação composicional. Assim, um modelo de Análise de Elementos Finitos (FEA) foi utilizado para avaliar a componente das tensões residuais intrínsecas ao longo das multicamadas, alimentado com o cáculo da deformação do parâmetro de rede, que pela Lei de Vergards varia em função da modulação química, ao longo das camadas de NbN e CrN. A microindentação instrumentada e o teste de riscamento mostraram aumento de dureza e maior resistência ao risco com a redução da periodicidade das multicamadas nanoestruturadas de NbN/CrN. O cruzamento dos resultados das diversas técnicas empregadas permitiu análise detalhada da estrutura e morfologia destes recobrimentos e a influência das periodicidades na modulação química das camadas individuais, possibilitando o desenvolvimento de um modelo qualitativo. Este aprendizado irá permitir a deposição de recobrimentos multicamadas nanoestruturados com melhor controle das propriedades mecânicas objetivadas em função da aplicação final do produto. / The present work aims at contributing to the knowledge, microstructure and compositional modulation (Chemical composition profile) of NbN/CrN multilayer nanostructured coatings with different periodicities (between 4 and 20nm) deposited by cathodic arc technique. It was reached a total coating thickness of 30 ?m preserving the periodicity homogeneity along the thickness. X-Ray Diffraction analisys, combined with computational modeling (dinamic diffraction) and Transmission Eletron Microscopy analysis (TEM), allowed the multilayer periodicity determination, the individual NbN and CrN layer thicknesses as well as the qualitative analysis of coherency among layers. The scanning mode (STEM) combined with Electron Energy Loss Spectroscopy (EELS), allowed the measurement of the chemical composition variation along the individual nanolayers. The EELS analysis showed that, even for the lowest periodicity studied - 4nm, there is no elimination of the compositional modulation. Thus, the Finite Element Analysis model (FEA) was used to evaluate the intrinsic residual stress component along the multilayers, fed with the lattice parameter deformation calculation, which, by Vegards Law varies as a function of the chemical modulation, along the NbN and CrN layers. The instrumented microindentation and the Scratch test showed hardness increase and higher scratch resistance as periodicity decreases on the nanostructured multilayer of NbN/CrN. The cross-linking data of the several techniques employed enabled a detailed analysis of the structure and morphology of such coatings and the influence of the periodicities on the individual layer chemical modulation, allowing the development of a qualitative model. This learning will allow multilayer nanostructured coatings deposition with a better control of desired mechanical properties as a function of the final product application.