Thesis (Ph. D.)--University of Wisconsin--Madison, 1971. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 1998. / Vita. Includes bibliographical references (leaves 128-138). Available also in a digital version from Dissertation Abstracts.

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Type III-B rotaxane dendrimers (T3B-RDs) are hyperbranched macromolecules with mechanical bonds on every branching unit. First to third (G1-G3), and up to the fourth (G4) generation (MW>22,000 Da) of pure organic T3B-RDs and dendrons were successfully synthesized through the copper catalyzed alkyne-azide cycloaddition (CuAAC) reaction. By utilizing multiple molecular shuttling of the mechanical bonds within the sphere-like macromolecule, a collective three-dimensional contract-extend molecular motion was demonstrated by diffusion ordered spectroscopy (DOSY). The discrete T3B-RDs were further observed and characterized by atomic force microscopy (AFM), dynamic light scattering (DLS), and mass spectrometry (MS). The binding of chlorambucil and pH-triggered switching of the T3B-RDs were also characterized by 1H NMR spectroscopy.;Type III-C rotaxane dendrimer is a new type of rotaxane dendrimer where in the mechanical bonds are in between and constituing the branchning point to form the macromolecules. First and second (G1-G2) type III-C rotaxane dendrimers were synthesized successfully as a prototypical example. Two different shuttling processes have been deomostrated by the non-methylated and methylated type III-C rotaxane dendrimers, and characterized by 1H NMR spectroscopy.

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This research project focuses on the synthesis of fluorescent polymers with pendant triazole-substituted coumarin side chain units. Copper(I)-catalyzed Huisgen’s 1,3-dipolar cycloaddition of alkynes with azides to form a 1,2,3-triazole ring, a typical example of “click” reaction, has been utilized for the synthesis of a novel vinyl monomer, 2-oxo-3-(4- vinyl-1H-1,2,3-triazol-1-yl)-2H-chromen-7-yl acetate 62. The monomer and its precursors were synthesised and characterized using 1D- and 2D-NMR and FT-IR. Coumarin-containing triazole polymers were synthesised using free radical polymerization. Reversible Addition-Fragmentation Chain Transfer (RAFT)-mediated polymerization was used to synthesise well defined coumarin-containing triazole polymers with moderate PDI values. The polymers were characterised using 1H-NMR and FT-IR. Modelling of the monomer precursor 61 and the monomer 62 at DFT level of approximation provided useful insights into possible conformations adopted by the monomer precursor 61 and the monomer 62. The photophysical properties of the novel monomer and the synthesised polymers were investigated in a polar solvent.

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No description available.

Nanoparticulas magnéticas de óxido de ferro tem sido amplamente utilizadas em diversas áreas da biotecnologia e biomedicina, tais como no tratamento de câncer, marcação de célula e como agentes de contraste em imagem por ressonância magnética. O intuito deste trabalho foi sintetizar as nanopartículas magnéticas com magnetização de saturação intensificadas via processo do poliol modificado, e usando agentes de superfície para melhorar as propriedades de superfície. Carboximetildextrana, metilpolietilenoglicol (MPEG), quitosana, sílica e 3-aminopropiltrimetoxisilano (APTMS) foram utilizados para a modificação da superfície. Através da microscopia eletrônica de transmissão (TEM), foi obtido que as nanopartículas magnéticas de magnetita obtiveram um diâmetro médio de 5nm, em uma estreita distribuição de tamanho. A difração de raios-X (DRX) indicou a formação de magnetita em todos os sistemas em que o método do poliol modificado foi utilizado. As medidas de espectroscopia no infravermelho (FTIR) evidenciaram a presença de modos de vibração relacionados às macromoléculas e compostos inorgânicos utilizados na modificação de superfície das nanopartículas magnéticas. A TEM das diferentes modificações de superfície mostram a formação de aglomerados dependendo do modificador utilizado. As nanopartículas recobertas com APTMS foram funcionalizadas com ácido fólico, mostrando resultados satisfatórios, porém serão necessárias outras técnicas de caracterização. Para a funcionalização foi determinada a quantidade de amina livre na superfície da nanopartícula recoberta com APTMS e a técnica de UV-Vis determinou um bom resultado. A magnetometria de amostra vibrante (VSM) mostrou comportamentos semelhantes para todas as amostras recobertas em comparação a amostra sem recobrimento. Estes resultados evidenciam que a modificação de superfície foi realizada satisfatoriamente. Os métodos utilizados para realizar a mudança para hidrofóbica a superfície inicialmente hidrofílica se mostraram efetivos, porém a quantidade de agentes modificadores deve ser melhor estudada. Portanto, as nanopartículas magnéticas funcionalizadas com diferentes superfícies foram obtidas e possuem um alto potencial para serem utilizadas em aplicações em biomedicina. / Superparamagnetic iron oxides nanoparticles (SPION) have been highlighted in several areas of biotechnology and biomedicine, for example in cancer treatment, in labeling of cells and as contrast agent in magnetic resonance imaging (MRI). The purpose of this study was synthesizing SPION with intensified saturation magnetization by modified polyol process, and using surface agents to enhance the surface properties. Carboxymethildextran, metylpolietileneglycol, chitosan, silica and 3-aminopropyltrimethoxysilane (APTMS) were utilized as surface modifiers. By transmission electron microscopy (TEM), SPION showed narrow particle size distribution, with an average diameter around 5 nm. The X-ray diffraction studies indicated the formation of magnetite in all synthesized systems in which the modified polyol process was utilized. FTIR measurements showed the presence of vibration modes related to the macromolecules and inorganic compounds used to SPION surface modifications. TEM of the different surface modifications showed the agglomerate formation, which depends on the used surface modifier. SPION coated with APTMS was functionalized with folic acid, showing satisfactory results. However other characterization techniques will be necessary for study this modification. Quantity of free amine groups was determinate in the amount coated with APTMS for functionalization, and UV-Vis spectroscopy determinates a good result. Vibrating sample magnetometry (VSM) indicates similar behaviors in all cases against SPION without surface modifiers. These results suggest that the surface modifications were performed satisfactorily. Utilized methods for changing the hydrophobic to hydrophilic surface showed effectives, however, the quantity of surface modifiers should be better studied. Therefore, SPION functionalized with different hydrophilic surfaces were obtained, which possess high potential to be used as devices in biomedical applications.

Coarse-graining and multi-scale approaches are rapidly becoming important tools for computer simulations of large complex molecular systems. Such theoretical models are powerful tools because they allow one to probe the essential features of a complex, many-bodied system on length and time scales over which emergent phenomena may occur. Because of the computational advantages and fundamental insight made available through coarse-grained methods, a vast array of various phenomenological potentials to describe coarse-grained interactions have been developed; nonetheless, the ability of these potentials to provide quantitative information about several different properties of the same system is not evident. On a theoretical level, it is not well-understood how small correlations in the long-range structure propagate through the coarse-graining procedure into the effective potential and lead to incorrect thermodynamics. Taking an alternative approach, this dissertation will discuss an analytical coarse-graining method for synthetic polymer chains of specific chemical structure, where a group of atoms on a polymer chain are represented by a variable number of soft interacting effective sites. The approach is based in liquid-state theory, providing a theoretical framework to address questions of thermodynamic consistency. It will be shown that the proposed method of coarse-graining maintains thermodynamic consistency for a variety of polymer models. In a multi-scale modeling scheme simulations of the same system represented by several different levels of detail may be joined to provide a complete description of the system at all length and time scales of interest. This dissertation includes previously published and unpublished co-authored material.