The overall objective of this study was to develop and characterise new normoxic polymer gel formulations for evaluation of complex 3-D treatment volumes for application in radiotherapy dosimetry. Throughout this thesis, the essential characteristics of normoxic polymer gels have been extensively investigated. Studies were performed on the chemical components of the MAGIC gel and an improved formulation was proposed. Various anti-oxidants were studied and different versions of the MAGIC gel with fewer chemicals were developed and named MAGAS and MAGAT gel dosimeters. The ascorbic acid anti-oxidant was found to have a slow oxygen scavenging rate and therefore a delay period between manufacture and irradiation of the MAGAS gel was necessary before the gel became radiation sensitive. Vacuum pumping on the MAGAS gel solution to remove dissolved oxygen was shown to initially increase the R2-dose response and sensitivity of the dosimeter, reducing the time between manufacture and irradiation. Studies of the MAGAS gel for measurement of depth dose showed that MAGAS gel has potential as a clinical radiotherapy dosimetry tool. The radiological properties of MAGIC, MAGAS and MAGAT gels were investigated. Due to their high gelatine and monomer concentration, differences with water were observed for the cross-section ratios for attenuation, energy absorption and collision stopping power coefficient ratios through the therapeutic energy range. It was determined that when using and developing normoxic polymer gels the most important consideration for radiological water equivalence are the mass and relative electron densities. A preliminary study was performed with the hypoxic PAG gel dosimeter combined with tetrakis (hydroxymethyl) phosphonium chloride anti-oxidant to form a normoxic PAG gel dosimeter named PAGAT gel. It was found PAGAT gel compared favourably with previous studies of the hypoxic PAG gel. An extensive study was subsequently undertaken in which PAGAT gel was investigated for a number of essential characteristics. The PAGAT gel formulation showed potential as a normoxic polymer gel for clinical radiotherapy dosimetry, which has a significantly reduced manufacturing time and procedure compared with the hypoxic PAG gel dosimeter. The radiological attenuation properties of the PAGAT and MAGAT gels were investigated as a feasibility study for using x-ray computerised tomography (CT) as an evaluation technique of normoxic polymer gels. CT was shown to have potential as an evaluation tool for measuring the dose response of normoxic polymer gel dosimeters. An investigation was performed on the CT diagnostic dose response of normoxic polymer gels. Normoxic polymer gels were found to have potential for use as a specialised tool in measuring computerised tomography dose index (CTDI) for acceptance testing and quality assurance of CT scanners in diagnostic radiology. These findings provide a significant contribution toward the development and successful implementation of normoxic polymer gel dosimetry to clinical radiotherapy.

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T11:34:19Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T11:34:19Z (GMT). No. of bitstreams: 0 / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T11:34:19Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T11:34:19Z (GMT). No. of bitstreams: 0 / A Radioterapia em arco modulado volumétrico (VMAT) é uma das modalidades mais avançadas em teleterapia para o tratamento de câncer. Os diversos avanços tecnológicos, bem como a evolução das técnicas de tratamento tornaram o VMAT como uma das modalidades de estado da arte para o tratamento de alguns cânceres. Parte deste avanço é creditada à melhoria na acurácia e na prescrição de dose absorvida recomendada ao paciente ao longo dos anos. Este avanço permite que atualmente seja possível realizar os cálculos dosimétricos, por meio de sistemas de planejamento computadorizado, considerando as heterogeneidades dos pacientes, tais como: tecidos e órgãos com composições diferentes da água (meio de referência em radioterapia), contorno do paciente individualizado e o movimento dos tumores com a respiração. Tais avanços demandam o controle de qualidade destas ferramentas, com objetivo de assegurar que todo o processo de tratamento seja satisfatório e acurado. A comunidade dispõe poucos sistemas experimentais capazes de avaliar, considerando os níveis de incerteza, se os sistemas de planejamento computadorizados são aptos a considerar a movimentação dos alvos nos tratamentos com VMAT. Neste trabalho serão apresentados os resultados obtidos empregando um objeto simulador Fricke Xylenol Gel, com capacidade de mensurar as diferenças introduzidas pela movimentação, utilizando Imagem por Ressonância Magnética - MRI e comparando qualitativamente e quantitativamente os resultados. São discutidas as principais etapas de desenvolvimento deste objeto simulador, seus resultados experimentais, conclusões. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

This thesis presents the results of computer simulation studies of the structure, dynamics, and deformation of cross-linked polymer gels. Obtaining a fundamental understanding of the interrelation between the detailed structure and the properties of polymer gels is a challenge and a key issue towards designing materials for specific purposes. A new off-lattice method for constructing a closed network is presented that is free from defects, such as looping chains and dangling ends. Using these model networks in Brownian dynamics simulations, I show results for the structure and dynamics of bulk gels and describe a novel approach using spherical boundary conditions as an alternative to the periodic boundary conditions commonly used in simulations. This algorithm was also applied for simulating the diffusion of tracer particles within a static and dynamic network, to illustrate the quantitative difference and importance of including network mobility for large particles, as dynamic chains facilitate the escape of particles that become entrapped. I further investigate two technologically relevant properties of polymer gels: their stimuli-responsive behaviour and their mechanical properties. The collapse of core-shell nanogels was studied for a range of parameters, including the cross-linking degree and shell thickness. Two distinct regimes of gel collapse could be observed, with a rapid formation of small clusters followed by a coarsening stage. It is shown that in some cases, a collapsing shell may lead to an inversion of the core-shell particle which exposes the core polymer chains to the environment. This thesis also explores the deformation of bimodal gels consisting of both short and long chains, subject to uniaxial elongation, with the aim to understand the role of both network composition as well as structural heterogeneity on the mechanical response and the reinforcement mechanism of these materials. It is shown that a bimodal molecular weight distribution alone is sufficient to strongly alter the mechanical properties of networks compared to the corresponding unimodal networks with the same number-average chain length. Furthermore, it is shown that heterogeneities in the form of high-density short-chain clusters affect the mechanical properties relative to a homogeneous network, primarily by providing extensibility.

Acceptor copolymers with low lowest unoccupied molecular orbital (LUMO) energy levels are key materials for organic electronics. In the present work, quaternization of pyridine-flanked diketopyrrolopyrrole (PyDPPPy) is used to lower the LUMO energy level of the resulting monomer (MePyDPPPy) by as much as 0.7 eV. The drastically changed electronic properties of MePyDPPPy hinder a second methylation step even in an excess of trimethyloxonium tetrafluoroborate and thereby give access to the asymmetric functionalization of N-heterocycle-flanked DPP building blocks. The corresponding n-type polymeric ionene PMePyDPPPyT2 with bithiophene as comonomer forms thixotropic organogels with the p-type polythiophene P(g42T-TT), indicative of specific cross-interactions between this couple of copolymers. Gelation of polymer blend solutions, which is absent for other couples of p-type/ n-type polymers, is of general interest for (co)processing and orientation of different electronic polymers simultaneously into films or filaments. Detailed optical and electronic characterization reveals that films processed from organogels exhibit ground-state electron transfer (GSET) enabled by suitably positioned highest occupied molecular orbital (HOMO) and LUMO energy levels of P(g42T-TT) (−4.07 eV) and PMePyDPPPyT2 (−4.20 eV), respectively. Furthermore, molecular interactions related to gelation and GSET do not appear to significantly influence the morphology of the polymer blend films.

No description available.

Understanding molecular and ion dynamics in soft materials used for fuel cell, battery, and drug delivery vehicle applications on multiple time and length scales provides critical information for the development of next generation materials. In this dissertation, new insights into transport and kinetic processes such as diffusion coefficients, translational activation energies (Ea), and rate constants for molecular exchange, as well as how these processes depend on material chemistry and morphology are shown. This dissertation also aims to serve as a guide for material scientists wanting to expand their research capabilities via nuclear magnetic resonance (NMR) techniques. By employing variable temperature pulsed-field-gradient (PFG) NMR diffusometry, which can probe molecular transport over nm – μm length scales, I first explore transport and morphology on a series of ion-conducting materials: an organic ionic plastic crystal, a proton-exchange membrane, and a polymer-gel electrolyte. These studies show the dependencies of small molecule and ion transport on modulations to material parameters, including thermal or magnetic treatment, water content, and/or crosslink density. I discuss the fundamental significance of the length scale over which translational Ea reports on these systems (~ 1 nm) and the resulting implications for using the Arrhenius equation parameters to understand and rationally design new ion-conductors. Next, I describe how NMR spectroscopy can be utilized to investigate the effect of loading a small molecule into the core of a spherical block copolymer micelle (to mimic, e.g., drug loading) on the hydrodynamic radius (rH) and polymer chain dynamics. In particular, I present spin-lattice relaxation (T1) results that directly measure single chain exchange rate kexch between micelles and diffusion results that inform on the unimer exchange mechanism. These convenient NMR methods thus offer an economical alternative (or complement) to time-resolved small angle neutron scattering (TR-SANS). / Ph. D.

The work deals with the deposition of layers for electrochromic device with different methods. Transparent electrically conductive layer of SnO2 was deposited by pyrolytic decomposition of peroxostannate solution. Hydrogen peroxide in starting solution contributes to the oxidation process of growth layers and to increase the electrical conductivity. Active electrochromic layer of WO3 was electrolytic deposited from the peroxotungstic acid solution. Optimal deposition time and the optimal annealing temperature of deposited layers were found. Passive electrochromic layer of V2O5 was deposited using dip-coating method from peroxovanadate solution. A contribution of solution diluted with distilled water was investigated. Found results were used to construct complete electrochromic device with polymer gel electrolyte.