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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
381

Síntese e estudo da auto-organização de membranas de superredes binárias baseadas em nanopartículas de ferritas / Syntheses and self-assembled binary nanocrystal superlattices of ferrites

Neves, Herbert Rodrigo 08 December 2017 (has links)
O estudo do ordenamento de nanopartículas em estruturas bi e tridimensionais, também conhecidas como superredes, é de grande interesse científico e tecnológico, tanto pelo interesse em se explicar a origem e as consequências deste fenômeno, quanto pelas possibilidades de aplicação oriundas das propriedades observadas nestes sistemas. Quando são utilizados dois tipos de nanomateriais diferentes em tamanho e/ou composição química, tem-se a formação de superredes binárias. Estas estruturas apresentam propriedades que são resultado das propriedades individuais de seus constituintes e, além disso, do conjunto de interações que existem no sistema. Graças a este conjunto de propriedades e interações coletivas, o princípio de se empregar nanopartículas como \"building blocks\" para a criação ou aprimoramento de dispositivos funcionais. Assim, neste trabalho são discutidas as sínteses de óxidos magnéticos do tipo MFe2O4 (com M = Co, Fe ou Mn) e as características necessárias para o emprego destes na formação de superredes de nanopartículas. Os materiais foram sintetizados procurando-se alcançar uma estreita distribuição de tamanho e homogeneidade quanto à forma. Foram empregados sistemas de nanopartículas nos estudos para a formação de superredes que apresentaram polidispersividade entre 6 e 20%, de forma a discutir o efeito desta propriedade no ordenamento das nanopartículas. Observou-se que o ordenamento em escala macroscópica é fortemente influenciado pela tensão de superfície da subfase, enquanto que o arranjo local das nanopartículas em relação aos seus vizinhos mais próximos é mais influenciado pela taxa de evaporação do solvente e pelas interações interpartículas. Para a formação de superestruturas binárias foram empregadas as nanopartículas de CoO/CoFe2O4 com 9,6 nm ou de Fe3O4 de 10,7 nm, com nanopartículas de CdSe de 3,6 nm. Os sistemas de nanopartículas binárias apresentaram arranjos do tipo AlB2 e tiveram, em sua maioria, crescimento na forma de supercristais facetados. A formação de estruturas bidimensionais com crescimento ao longo do plano da membrana foi favorecida pelo aumento na proporção das nanopartículas de maior diâmetro em relação às menores. A compreensão do fenômeno de auto-organização em membranas de superredes binárias possibilita a obtenção de novos materiais nanoestruturados e que apresentem propriedades moduladas. / Self-assembly nanoparticles into superlattices array have attracted significant attention both for the scientific understanding of nanocrystals ordering process and the development of new functional devices using bottom up techniques. The co-assembly of two types of nanoparticles in binary nanoparticles superlattices provides a new way to design metamaterials with unusual and modulated properties. These unusual properties arise from interparticle interactions in the superlattice structure, and from nanoparticles physical properties. To obtain highly ordered structures, it is required that nanocrystals have narrow size distribution. This thesis presents the synthesis of oxide magnetic nanoparticles (MFe2O4; M = Co, Fe, or Mn) and their application as building blocks in nanocrystal superlattices. Nanoparticles presented size distribution from 6% to 20%, and their assemblies has shown amorphous structure when samples have size distribution above 10%. Self-assembled nanoparticles superlattices in the liquid-air interface were obtained using either single or binary components. Single component superlattices were used as model for the understand of self-assembly process, which depends on subphase surface tension and dispersion evaporation rate. Nanocrystals superlattices were obtained from CdSe nanoparticles, with average size of 3,6 nm, and CoO/CoFe2O4 with size of 9,6 nm, and was observed a AlB2-type superstructure. The same superlattice structure was obtained for CdSe and Fe3O4, with average size of 10,7 nm, which indicate that AlB2 is the equilibrium phase for a rage of radii ratios and nanoparticles stoichiometry. These findings enable to better understand self-assembled binary nanocrystal superlattices formation and how to manipulate interparticle interactions in order to synthesize highly ordered structures.
382

Reactivity and Coordination Chemistry of Pnictogen-Containing Complexes

Collins, Mary 23 February 2016 (has links)
Only within the last decade has supramolecular chemistry begun to adopt the Group 15 elements into its field of research. This dissertation presents a supramolecular approach to the self-assembly and reactivity of Group 15 metalloids, specifically arsenic and antimony, with organothiolate ligands. Investigating the self-assembly of pnictogen-based coordination complexes allows for in-depth characterization of the chemical behavior of arsenic, antimony and other Group 15 elements. Currently, the infiltration of arsenic into global groundwater systems has developed into a worldwide health concern. There are no chelating agents available for public use in the treatment of arsenic poisoning which are capable of binding arsenic (III) in its preferred coordination geometry thereby hindering the selectivity for rapid chelation. Chapter I is a review covering two important characteristics observed in the Group 15 elements: 1) a stabilizing, non-covalent cation-π interaction aiding in the formation of pnictogen-aryl thiolates, and 2) an observed lack of selectivity in environments containing multiple pnictogen ions which enables transmetalation of the complexes to occur or the generation of heterometallic assemblies. Based on the discovery of this new transmetalation reactivity, the remainder of the dissertation explores the effects of external additives during self-assembly in order to understand how they may affect the reactivity of these self-assembled complexes and provide insight into formation mechanisms. Chapter II identifies a catalyst for the acceleration of a slow self-assembly reaction between AsCl3 and a dithiolate ligand to give an As2L3 cryptand. Chapter III examines the oxidation of the arsenic cryptand using iodine, which leads to the self-assembly of a series of differently sized, discrete disulfide-bridged macrocycles. In Chapter IV, the self-assembly of the first trinuclear arsenic- and antimony-based coordination complexes was studied, revealing interesting solvent dependent conformational isomerism in solution. Chapter V applies the pnictogen-enhanced iodine oxidation to the synthesis of known and new cyclophanes using supramolecular chemistry, including the self-assembly and covalent capture of an unprecedented tetrahedral thiacyclophane. Additionally, an unusual trithioorthoformate capped tricyclophane cage was also synthesized and isolated by pnictogen-activated oxidation. Chapter VI includes the conclusion and future directions for the project. This dissertation includes co-authored material and previously published results. / 10000-01-01
383

Hairy Nanoparticles with Hydrophobic Polystyrene Cores and Hydrophilic Poly(2-hydroxyethylmethacrylate) Hairs: Synthesis and Characterization

Habel, Azza 20 May 2019 (has links)
The self-assembling properties of a core-shell system are considered to be the most desirable characteristics that allow using this class of polymers in different applications. New hairy nanoparticles (HNPs) with hydrophobic polystyrene cores (PS Cores) and hydrophilic poly(2-hydroxyethylmethacrylate) (PHEMA) shells were synthesized by coupling polymerization methods. Living anionic polymerization in one-pot step was used to synthesize cross-linked polystyrene cores functionalized with hydroxyl groups and atom transfer radical polymerization (ATRP) was then carried out to prepare PHEMA hairs following the grafting form technique. The structural characterizations were carried out by FT-IR and NMR spectroscopy (1H NMR, 13C NMR, APT 13C NMR and 1H 13C HMQC). Dynamic light scattering measurements of obtained HNPs show small increase in the order of nanometers of their hydrodynamic radii after the grafting. Thermal properties were studied by TGA and DSC. The thermal stability of PS cores was affected by functionalization with the hydroxyl group. However, the stability of the PS core was not affected by grafting of PHEMA on their surfaces. DSC thermograms of the HNPs shows two distinct transition temperatures corresponding to glass transition temperatures (Tg) of a PS phase and of a PHEMA phase indicating the formation of a hydrophobic-hydrophilic phase separated system. SEM and AFM were utilized to study the morphologies and self-assembly of nanoparticles. The self-assembled HNPs morphologies were dependent on the solvents used. Complexes of the synthesized HNPs and R- or S-mandelic acid were prepared and characterized by circular dichroism (CD) and AFM. CD was used to study the induced chiral properties of the complexes. The CD spectra indicated the formation of enantiomeric chiral structures and the AFM images show toroidal self-assembled structures. Polymer blends of polystyrene functionalized with hydroxyl groups and PHEMA show different morphology and different thermal properties than the core-shell HNP system.
384

DNA SELF-ASSEMBLY DRIVEN BY BASE STACKING

Longfei Liu (6581096) 10 June 2019 (has links)
<p>DNA nanotechnology has provided programming construction of various nanostructures at nanometer-level precision over the last three decades. DNA self-assembly is usually implemented by annealing process in bulk solution. In recent several years, a new method thrives by fabricating two-dimensional (2D) nanostructures on solid surfaces. My researches mainly focus on this field, surface-assisted DNA assembly driven by base stacking. I have developed methods to fabricate DNA 2D networks via isothermal assembly on mica surfaces. I have further explored the applications to realize quasicrystal fabrication and nanoparticles (NPs) patterning.</p><p><br></p> <p>In this dissertation, I have developed a strategy to assemble DNA structures with 1 or 2 pair(s) of blunt ends. Such weak interactions cannot hold DNA motifs together in solution. However, with DNA-surface attractions, DNA motifs can assemble into large nanostructures on solid surface. Further studies reveal that the DNA-surface attractions can be controlled by the variety and concentration of cation in the bulk solution. Moreover, DNA nanostructures can be fabricated at very low motif concentrations, at which traditional solution assembly cannot render large nanostructures. Finally, assembly time course is also studied to reveal a superfast process for surface-assisted method compared with solution assembly.</p><p><br></p> <p>Based on this approach, I have extended my research scope from 1D to 2D structures assembled from various DNA motifs. In my studies, I have successfully realized conformational change regulated by DNA-surface interaction and steric effect. By introduction of DNA duplex “bridges” and unpaired nucleotide (nt) spacers, we can control the flexibility/rigidity of DNA nanomotifs, which helps to fabricate more delicate dodecagonal quasicrystals. The key point is to design the length of spacers. For 6-point-star motif, a rigid structure is required so that only 1-nt spacers are added. On the other hand, 3-nt spacers are incorporated to enable an inter-branch angle change from 60° to 90° for a more flexible 5-point-star motif. By tuning the ratio of 5 and 6 -point-star motifs in solution, we can obtain 2D networks from snub square tiling, dodecagonal tiling, a mixture of dodecagonal tiling and triangular tiling, and triangular tiling.</p><p><br></p> Finally, I have explored the applications of my assembly method for patterning NPs. Tetragonal and hexagonal DNA 2D networks have been fabricated on mica surfaces and served as templates. Then modify the surfaces with positively-charged “glues”, <i>e.g.</i> poly-L-lysine (PLL) or Ni<sup>2+</sup>. After that, various NPs have been patterned into designated lattices, including individual DNA nanomotifs, gold NPs (AuNPs), proteins, and silica complexes. Observed NP lattices and fast Fourier Transform (FFT) patterns have demonstrated the DNA networks’ patterning effect on NPs.
385

ENGINEERED 3D DNA CRYSTALS: CHARACTERIZATION, STABILIZATION AND APPLICATIONS

Zhe Li (6581093) 10 June 2019 (has links)
In recent years, DNA nanotechnology has emerged as one of the most powerful strategies for bottom-up construction of nanomaterials. Due to the high programmability of DNA molecules, their self-assembly can be rationally designed. Engineered 3D DNA crystals, as critical products from the design of DNA self-assembly, have been proposed as the structural scaffolds for organizing nano-objects into three-dimensional, macroscopic devices. However, for such applications, many obstacles need to be overcome, including the crystal stability, the characterization methodology, the revision of crystal designs as well as the modulation of crystallization kinetics. My PhD research focuses on solving these problems for engineered 3D DNA crystals to pave the way for their downstream applications.<br>In this thesis, I started by enhancing the stability of engineered 3D DNA crystals. I developed a highly efficient post-assembly modification approach to stabilize DNA crystals. Enzymatic ligation was performed inside the crystal lattice, which was designed to covalently link the sticky ends at the crystal contacts. After ligation, the crystal became a covalently bonded 3D network of DNA motifs. I investigated the stability of ligated DNA crystals under a wide range of solution conditions. Experimental data revealed that ligated DNA crystals had significantly increased stability. With these highly stabilized DNA crystals, we then demonstrated their applications in biocatalysis and protein encapsulation as examples.<br>I also established electron microscope imaging characterization methods for engineered 3D DNA crystals. For crystals from large-size DNA motifs, they are difficult to study by X-ray crystallography because of their limited diffraction resolutions to no better than 10 Å. Therefore, a direct imaging method by TEM was set up. DNA crystals were either crushed or controlled to grow into microcrystals for TEM imaging. To validate the imaging results, we compared the TEM images with predicted models of the crystal lattice. With the advance in crystal characterization, DNA crystals of varying pore size between 5~20 nm were designed, assembled, and validated by TEM imaging.<br>The post-assembly ligation was further developed to prepare a series of new materials derived from engineered 3D DNA crystals, which were inaccessible otherwise. With the directional and spatial control of ligation in DNA crystal, I prepared new DNA-based materials including DNA microtubes, complex-architecture crystals, and an unprecedented reversibly expandable, self-healing DNA crystal. The integration of weak and strong interactions in crystals enabled a lot of new opportunities for DNA crystal engineering.<br>In the final chapter, I investigated the effect of 5’-phosphorylation on DNA crystallization kinetics. I found that phosphorylation significantly enhanced the crystallization kinetics, possibly by strengthening the sticky-ended cohesion. Therefore, DNA crystals can be obtained at much lower ionic strength after phosphorylation. I also applied the result to controling the morphology of DNA crystals by tuning the crystallization kinetics along different crystallographic axes. Together with previously methods to slow down DNA crystallization, the ability to tune DNA crystallization kinetics in both ways is essential for DNA crystal engineering.
386

Caracterização e modificação de membranas de quitosana-PEG com filmes automontados de jacalina e concanavalina A / Characterization and modification of chitosan-PEG membranes with self assembly films of jacalin and concanavalin A

Soares, Andrey Coatrini 07 February 2013 (has links)
O polissacarídeo quitosana é usado em aplicações biológicas, tais como entrega de drogas e engenharia de tecidos como matriz para o crescimento celular, devido à sua biocompatibilidade e biodegradabilidade. Uma das suas utilizações mais frequentes é na forma de membranas obtidas por casting com poli (etileno glicol) (PEG). Neste trabalho, membranas de quitosana-PEG foram modificadas e otimizadas com filmes nanoestruturados de concanavalina A (Con A) e jacalina. O processo de purificação não afetou as propriedades da quitosana, tais como cristalinidade, tamanho de cristalitos, grupos funcionais e grau de acetilação. A única exceção foi a diminuição da massa molecular, provavelmente pela quebra de cadeias por adição de ácido acético à solução. As membranas fabricadas com mistura de quitosana e PEG exibiram superfície mais rugosa, porosa, com energia de superfície mais elevada do que aquelas com quitosana pura. Misturas com 20 e 30% de PEG foram testadas, sendo as que contêm 20% mais adequadas para a funcionalização, devido ao maior tamanho dos poros, de acordo com imagens de microscopia de força atômica. Na funcionalização das membranas de quitosana-PEG com proteínas, o objetivo é obter a cobertura mais uniforme com maior energia de superfície. No processo de otimização, a deposição do filme nanoestruturado de proteína foi confirmada com PM-IRRAS, espectroscopia de fluorescência e dicroísmo circular, e a energia de superfície foi calculada usando o modelo de Owens- Wendt-Rabel-Kaelble a partir dos ângulos de contato para diferentes líquidos. Para Con A e jacalina, propriedades otimizadas foram obtidas com a menor concentração de proteína testada, 0,1 mg/mL, para um tempo de adsorção de 90 minutos. Além disso, o filme de jacalina levou à maior energia de superfície, ou seja, 56,7 mJ/m², comparado com 55,9 mJ/m² para amostras modificadas com Con A. Além disso, sob essas condições de otimização, a atividade da proteína foi mantida por 4 semanas para membranas armazenadas a 4ºC. Portanto, as membranas funcionalizadas são promissoras para crescimento celular e aplicações de engenharia de tecidos / The polysaccharide chitosan is used in various biological applications such as drug delivery and especially in tissue engineering as a matrix for cell growth due to its biocompatibility and biodegradability. One of its most frequent uses is in the form of membranes made via casting blended with poly(ethylene glycol) (PEG). In this work, chitosan-PEG membranes were optimized and modified with nanostructured films of concanavalin A (Con A) and jacalin. The purification process did not affect the chitosan properties, such as crystallinity, crystallite size, functional groups and degree of acetylation. The only exception was a decrease in the molecular mass, probably owing to chain scission by addition of acetic acid to the solution. The membranes made with chitosan and PEG exhibited a rougher, porous surface, with higher surface energy than those with neat chitosan. Blends with 20 and 30% PEG were tested, and those with 20% were considered as more suitable for functionalization owing to the larger size of the pores, according to atomic force microscopy images. The functionalization of the chitosan-PEG membranes with the proteins is aimed at achieving the most uniform coverage with the highest surface energy. In the optimization procedure, the deposition of the protein nanostructured film was confirmed with PM-IRRAS, fluorescence spectroscopy and circular dichroism, while the surface energy was calculated using the Owens-Wendt-Rabel-Kaelble model and the measured contact angles for several liquids. For both Con A and jacalin, optimized properties were obtained with the lowest protein concentration tested, viz. 0.1 mg/mL, for an adsorption time of 90 min. Furthermore, the jacalin film led to the highest surface energy, namely 56.7 mJ/m², to be compared with 55.9 mJ/m² for samples modified with Con A. Under these optimized conditions, the protein activity was kept for ca. 4 weeks if the coated membranes were stored at 4ºC. Therefore, the functionalized membranes are promising for cell growth and tissue engineering applications
387

Imobilização de ftalocianinas em filmes nanoestruturados e aplicações em sensores / Immobilization of phthalocyanines in nanostructured films and sensing applications

Centurion, Lilian Maria Pessôa da Cruz 30 April 2010 (has links)
As metaloftalocianinas (MPcs) são compostos de coordenação macrocíclicos amplamente estudados, e já utilizados em várias aplicações tecnológicas. Sua estabilidade química e térmica e seu caráter semicondutor as tornam materiais promissores no desenvolvimento de dispositivos eletrônicos. A imobilização deste material através da técnica de automontagem tem proporcionado, nos últimos anos, uma nova alternativa de arquitetura e de interação molecular, principalmente entre analitos e transdutores na área de sensores. Neste trabalho, foram produzidos e estudados filmes automontados com ftalocianina tetrassulfonada de cobalto (CoTsPc) e polímeros poli(alilamina hidroclorada) (PAH) ou poli(amido amina) geração 4 (PAMAM G4), com os objetivos de investigar a organização estrutural dos polieletrólitos nos filmes e de utilizar estes sistemas como sensores de umidade. A espectroscopia de absorção no UV-visível revelou que a quantidade de CoTsPc adsorvida nos filmes varia linearmente com o número de bicamadas para substratos de vidro. Medidas de FTIR mostraram que os filmes são formados, principalmente, pela atração eletrostática entre os grupos sulfônicos da ftalocianina e as aminas dos policátions. Um estudo abrangente realizado através da técnica de SPR exibiu a dinâmica de crescimento dos filmes e permitiu a estimativa das espessuras das camadas que os compõem. A condutividade elétrica destas nanoestruturas se mostrou muito sensível à presença de vapor de água. Os valores de corrente variaram três ordens de grandeza para um pequeno intervalo de umidade relativa, indicando o grande potencial destes filmes para sensores. Esta sensibilidade acentuada está profundamente associada à organização dos anéis de ftalocianina nas multicamadas, que é ditada pelo método de automontagem. Estes resultados acenam para a alternativa de obter sensores de umidade com ftalocianinas a partir de uma técnica simples de deposição de filmes finos, cujo destaque é promover uma conformação molecular específica, e consequentemente determinar a sensibilidade dos dispositivos. / Metallophthalocyanines (MPcs) are conjugated macrocyclic compounds that have been widely investigated in different scientific and technological fields. Their chemical and thermal stability, as well as their semiconductor nature make them suitable for the development of electronic devices. Immobilization of MPc molecules in self-assembly films has allowed new possibilities of molecular architecture, from which new, interesting properties may be achieved. This dissertation describes the fabrication of layer-by-layer films obtained from cobalt tetrasulfonated phthalocyanine (CoTsPc) and the polyelectrolytes poly(allylamine hydrochloride) (PAH) and poly(amido amine) generation 4 (PAMAM G4). In addition to the structural investigations that revealed the nanoscale organization of the films, the possibility of using the films as humidity sensors has also been explored. UV-vis spectroscopy showed a linear film growth on glass substrates in both systems, while FTIR measurements provided evidence on the interactions between sulfonate groups from CoTsPc and amines from the polycations. A comprehensive SPR investigation on film growth reproduced dynamically the deposition process and provided an estimation of the layers thicknesses. The electrical conductivity of the films deposited on interdigitated electrodes was found to be very sensitive to water vapor. This sensitivity is caused by the positioning of the Pc rings along the multilayers, which is a consequence of the self-assembly method. These results point to the development of a phthalocyanine-based humidity sensor obtained from a simple thin film deposition technique, whose outstanding ability to tailor molecular organization was crucial to achieve such high sensitivity.
388

Self-Assembled Monolayers and Multilayers for Molecular Scale Device Applications

Soto-Villatoro, Ernesto R 16 August 2005 (has links)
"Self-assembled monolayers (SAMs) are organized molecular assemblies that are formed by spontaneous adsorption of a compound in solution to a surface (e.g. alkanethiols on gold). The design, preparation, and characterization of several self-assembled monolayers and multilayers on surfaces (gold, indium tin oxide and quartz) are described. The systems were chosen based on their ability to form ordered films and to perform a given device function. SAMs were fabricated with selected functional groups at the air-monolayer interface, capable of complexing metal ions (e.g. dicarboxypyridine, dicarboxybenzene, imidazole, 4-hydroxypyridine) with the purpose of using these SAMs to construct multilayered films. Deposition of a second layer consisting of metal ions (e.g. Cu(II), Co(II) and Fe(III)), occurs by non-covalent metal ligand binding interactions between the metal ion layer and the different organic ligands on the surface. Deposition of subsequent layers was achieved by the incorporation of the appropriate organic ligands and metal ions. These monolayers and multilayered films were characterized by contact angle measurements, ellipsometry, grazing angle FT-IR, cyclic voltammetry and impedance spectroscopy following deposition of each layer on the film. Electrochemical analysis of the multilayered films shows alternating insulating/conducting behavior (cyclic voltammetry) and alternating changes in films capacitance (impedance spectroscopy) depending on the outermost layer of the film. Films capped with an organic layer show low conductivity, while films capped with a metal layer show conducting behavior. The electrochemical behavior of the films is related to the degree of “leakiness” or electrolyte solution permeation through the film, which is high for films with metal layers as the top layer and decreases once the film is capped with an organic layer. The alternating conducting/insulating behavior of the films allows for fabrication of multilayered thin films of variable thickness and tunable conducting properties. Ordered films were fabricated with up to seven layers of dicarboxypyridine and Cu(II), and 4-hydroxypyridine and Fe(III) metal-ligand units. The construction of these films provides an example of molecular films that could function as molecular wires or junctions due to their controllable electrochemical properties. Photocurrent generating films were fabricated by incorporation of chromophore groups (e.g. pyrene, porphyrins) into the multilayered structures. These films generate cathodic or anodic current upon photoexcitation of the chromophores. The monolayers functionalized with different organic ligands were also used to study lanthanide complexation on the surfaces. Successful deposition of different lanthanide ions was achieved from DMSO solutions. Monolayers of a bicyclic structure, 4, 7, 13, 16-tetraoxa-1,10,21-triaza-bicycle[8.8.5] tricosane-19,23-dione, attached to a hexadecanethiol molecule were used to study the ability of metal ion detection on the surface using electrochemical (cyclic voltammetry and impedance spectroscopy) techniques. The SAMs show higher complexation affinity for Li+ than for Na+ or K+. Preliminary studies were also carried out to investigate the ability of different SAMs to cell adhesion interactions. Future experiments will help elucidate a systematic relation of cell adherence and the bulk and molecular-level properties of the functionalized surfaces. The different multilayered films described in this dissertation served as preliminary models for different molecular scale device applications. Current work is focused in the design and preparation of more efficient photocurrent generating films, highly selective sensors for different types of ions, surfaces for cell adhesion and microbial interactions, and the study of other potential applications such as the design of micro and nanofluidic devices. "
389

DNA driven assembly at solid and liquid interfaces

Joshi, Darshana January 2017 (has links)
This thesis presents work on the DNA directed assembly of colloids at liquid and solid interfaces under specifically sculpted attractive interactions via depletion forces and/or magnetic fields. The highly specific and thermally reversible nature of binding between two complementary single strands of DNA allows us to encode binding rules among various (solid or liquid) components of the system. The thesis begins by presenting a new approach for introducing mobile DNA linkers on oil droplets, enabling a reversible adsorption of colloids at the oil/water interface. In comparison to previous cumbersome approaches involving expensive biotinylated lipids, this simple method provides a relatively higher grafting density of DNA anchors at the interface. Further, it is possible to kinetically control the surface coverage of oil droplets with colloidal particles while preserving fully ergodic colloidal dynamics on the droplets. The equilibrium nature of the absorbed colloids is illustrated by exploring the quasi-two-dimensional (2d) phase behaviour under the influence of depletion interactions. Colloids bound to the oil water interface are found to be significantly less diffusive compared to their bulk counterparts. Simulation studies from collaboration reaffirm the experimentally observed phase behaviour and the nature of compositional arrest. Further, some preliminary results on the phase behaviour of binary colloidal mixtures at the oil/water interface are also presented. The last section of this thesis demonstrates an approach for creating novel superstructures of DNA coated colloids (DNAcc) directed via an externally applied magnetic field. Raspberry-like and long coaxial skeletons of smaller colloids around larger superparamagnetic colloidal cores in a two component system are shown. The rigidity of these mesoscopic superstructures is enhanced by adding a suitably functionalized third component. Finally, the thesis concludes by presenting various dimensions that have emerged out of this work and are being currently pursued.
390

Active Matter and Choreography at the Colloidal Scale

Harder, Joseph January 2017 (has links)
In this thesis, I present numerical simulations that explore the applications of self-propelled particles to the field of self-assembly and to the design of `smart' micromachines. Self-propelled particles, as conceived of here, are colloidal particles that take some energy from their surroundings and turn it into directed motion. These non-equilibrium particles can move persistently for long times in the same direction, a fact that makes the behavior of dense and semi-dilute systems of these particles very different from that of their passive counterparts. The first section of this thesis deals with the interactions between passive components and baths of hard, isotropic self-propelled particles. First, I present simulations showing how the depletion attraction can be made into a short ranged repulsive, or long ranged attractive interaction for passive components with different geometries in a bath of self-propelled particles, and show how the form of these interactions is consistent with how active particles move near fixed walls. In the next chapter, a rigid filament acts as a flexible wall that engages in a feedback loop with an active bath to undergo repeated folding and unfolding events, behavior which would not occur for a filament in a passive environment. The subsequent chapters deal with self-propelled particles that have long ranged and anisotropic interactions. When the orientations of active particles are coupled, they can undergo remarkable collective motion. While the first chapter in this section begins with a discussion of how active disks interacting via an isotropic potential consisting of a long ranged repulsion and short ranged attraction self-assemble into living clusters of controllable size, I show how replacing the disks with anisotropic dumbbells causes these clusters to rotate coherently. In the last chapter, I show that weakly screened active dipoles form lines and clusters that move coherently. These particles can become anchored to the surface of a passive charged colloid in various ways that lead to two different kinds of active motion: rotations of a corona of dipoles around the colloid, and active translation of the colloid, pushed by a tail of dipoles. Finally, a mixture of many charged colloids and dipoles can reproduce the swarming behavior of the pure dipoles at a larger length scale with coherent motion of the colloids. These are all examples of how activity is a useful tool for controlling motion at the micro-scale.

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