Magnetic resonance imaging (MRI) is a valuable research and clinical imaging modality for the non-invasive detection and characterization of cerebral ischemia. Specifically, diffusion-weighted imaging (DWI), which derives image contrast based on the diffusion of endogenous water molecules, is sensitive to cerebral ischemia within minutes of the onset of stroke. In combination with perfusion-weighted imaging (PWI) and T2-weighted imaging (T2WI), DWI can be used to characterize the temporal and spatial evolution of cerebral ischemia. The primary role of this dissertation is to outline several studies that investigate DWI, PWI, and T2WI changes in a rat stroke model of transient cerebral ischemia. Secondarily, this dissertation will introduce the method and results of an experiment designed to elucidate the relative roles of the intracellular (IC) or extracellular (EC) spaces to the water diffusion coefficient changes that occur as a result of cerebral ischemia. The use of MRI to detect cerebral ischemia is well established; however, the ability to distinguish between reversibly and irreversibly damaged tissues is limited. It has been shown in temporary focal ischemia models that the DWI abnormality (manifested as an image hyperintensity in the DWI) can be resolved if reperfusion is performed soon after the onset of the stroke. Initial studies suggested that the renormalization of water diffusion was associated with permanent restoration of cellular function (i.e., infarction was prevented). However, subsequent studies demonstrated that the disappearance of the acute ischemic lesion following reperfusion is not necessarily permanent and is related to the duration of the transient insult. Following short occlusions [e.g., 10 minutes in a rat middle cerebral artery occlusion (MCAO) model], there is complete tissue renormalization and restoration of normal neurological function. In contrast, following long periods of occlusion (e.g., 90 minutes), there are areas of the brain that do not recover and progress to infarction without delay. Intermediate durations of occlusion (e.g., 30 minutes) exhibit complete renormalization in all regions of ischemia; however, following several hours there is a gradual, secondary decline of the water diffusion coefficient values within the regions initially defined as abnormal. In this dissertation, the significant temporal and spatial heterogeneity in the secondary diffusion changes will be described and evaluated. Ultimately, MR techniques may provide valuable information regarding the response of tissue to transient ischemia as well as potential avenues for therapeutic intervention, which would have major clinical benefit. The significant changes in the apparent diffusion coefficient (ADC) of water that occur in ischemic brain are still not well understood. The leading hypothesis suggests that cellular swelling associated with the failure of the ionic gradient across the cell membrane results in an increase in EC tortuosity of the diffusion paths. Another theory suggests that the influx of fast-diffusing EC water, that occurs during cellular swelling, increases the proportion of water in the IC space, which is more restricted and viscous than the EC space. The final experiment presented herein demonstrates that significant cellular swelling remains in the regions of renormalized of ischemic ADC values that occur following reperfusion in transient ischemia. In short, the changes in the ADC values are not only the result of cellular swelling. Since conventional MR data contains the combined signals from the IC and EC spaces, it is difficult to determine the separate roles of these two compartments to the overall changes in water ADC. First, using a yeast-cell model, a method for separating the NMR signals is introduced. This method utilizes differences in the compartmental relaxation properties to isolate the MR signals from IC and EC spaces, and then secondarily the diffusion coefficients can be calculated. Using a modified version of this method, the experiment was performed in normal and ischemic rat brain. Intracerebroventricular (ICV) infusion of an MR contrast reagent (CR) was used to isolate IC T1, T2, and ADC values in vivo in normal and middle cerebral artery occluded (MCAO) rats using volume-localized, diffusion-weighted inversion-recovery spin-echo (DW-IRSE) spectroscopy and diffusion-weighted echo-planar imaging (DW-EPI). The presence of the EC contrast reagent (CR) selectively enhances the relaxation of water in the EC space and allows the IC and EC signal contributions to be separated based on T1-relaxation time differences between the two compartments. The results presented in this dissertation suggest that the IC ADC value is the major determinant of the overall ADC value measured in the normal rat brain. Further, the data suggests that the ADC decline experienced during acute ischemia is dictated largely by changes in the IC ADC, possibly due to failure of energy-dependent IC microcirculation (cytoplasmic streaming).

Radiological imaging already has a key role in the detection and management of patients with metastatic colorectal cancer (mCRC). With the evolution of personalised medicine there is a need for non-invasive imaging biomarkers that can detect early tumour response to targeted therapies. Translation from bench to bedside requires a multicentre approach that follows an agreed development roadmap to ensure that the proposed biomarker is precise (reproducible/ repeatable) and accurate in its characterisation of a meaningful physiological, pathological or post treatment response. The following thesis (organized in the alternative format with experimental studies written as individual complete manuscripts) investigates methods to improve precision and accuracy of the Apparent Diffusion Coefficient (ADC), a proposed quantitative imaging biomarker with a potential role in characterisation of post treatment responses in mCRC. The first objective was to establish baseline multicentre reproducibility (n=20) for ADC. A change in ADC greater than 21.1% was required to determine a post treatment response. Using a statistical error model, the dominating factors that influenced reproducibility were motion artefact and tumour volume. In the second study these factors were addressed using a single centre cohort with pre and post treatment data. Correcting for errors due to motion and tumour volume improved sensitivity from 30.3% to 1.7%, so a post treatment response was detected in 6/12 tumours compared to 0/12 using the baseline approach. In the third study, motion correction was implemented and the statistical error model was applied successfully to a multicentre cohort of 15 patients (1.9% sensitivity). The results of this thesis highlights that with careful consideration and correction of factors that negatively influence sensitivity, ADC is a potential imaging biomarker for use in post treatment response for patients with mCRC.

Neste trabalho são apresentados resultados sobre o uso da voltametria com microeletrodos para o estudo de sistemas micelares. Estes estudos se basearam na obtenção de coeficientes de difusão de micelas em solução aquosa. Para tanto, o ferroceno foi utilizado como sonda eletroativa, haja vista que esta molécula é pouco solúvel em água e possui grande afinidade pelo interior micelar. A partir de experimentos envolvendo o tensoativo brometo de hexadecil trimetil amônio (C16TABr) pôde-se calcular parâmetros como o coeficiente de difusão do agregado na concentração micelar crítica e o coeficiente de interação intermicelar com a aplicação dos dados de coeficiente de difusão obtidos pela teoria de interação linear. O coeficiente de interação intermicelar permitiu a estimativa da concentração de eletrólito necessária para a mudança morfológica da micela (micela esférica para micela alongada). O raio hidronâmico da micela foi o calculado a partir da relação Stokes-Einstein. Um estudo complementar envolveu a adição de n-decanol à solução de tensoativo, e comparações dos coeficientes de difusão obtidos na presença e na ausência do álcool foram efetuadas. Estudos subseqüentes foram realizados empregando outros tensoativos (C14TABr, C12TABr e C10TABr) com a finalidade de verificar a dependência do coeficiente de difusão micelar com o comprimento da cauda hidrofóbica da molécula do tensoativo. A influência de outros parâmetros como o raio hidrodinâmico e a concentração de eletrólito necessária para a transição morfológica com o comprimento da cauda hidrofóbica também foi estudada. Em experimentos voltamétricos envolvendo a oxidação eletroquímica do ferroceno em meio de C16TABr e de SDS (dodecil sulfato de sódio) foi verificado que o sinal anódico ocorre em potenciais menos positivos em soluções de SDS, fato justificado pela interação da micela de SDS, negativamente carregada, com a superfície do eletrodo positivamente carregado. A investigação da interação do produto de oxidação eletroquímica do ferroceno, o íon ferrocínio, com as micelas de C16TABr foi realizada em experimentos envolvendo uma microestrutura geradora-coletora. Esta estrutura consiste em dois eletrodos de área similar separados por um canal de espessura micrométrica. A utilização deste dispositivo possibilitou a obtenção do coeficiente de difusão do ferrocínio e, a partir deste dado, foi possível fazer inferências sobre a afinidade deste íon pelo interior micelar. / Voltammetry with platinum disc microelectrodes was employed to gain information on diffusion coefficients, D, of micelles in aqueous solution. Owing to the low solubility in water and high affinity for the micellar core, ferrocene was used as electroactive probe. Diffusion coefficients of hexadecyl trimethyl ammonium bromide (C16TABr) were determined in solutions containing the surfactant in different concentrations and the data were fitted according to the linear interaction theory. This procedure allowed the diffusion coefficient at the critical micelle concentration to be found, as well as the intermicellar interaction parameter. The latter was used to estimate the minimum concentration of electrolyte that promotes morphological changes in the micelles (sphere to rod transition). The micellar hydrodynamic radius was calculated by using the Stokes-Einstein equation. A complementary study involved the addition of n-decanol to surfactant solutions and the diffusion coefficient was compared with the one obtained in the absence of the fatty alcohol. Experiments were also performed in solutions containing other surfactants (C14TABr, C12TABr e C10TABr) to investigate the dependence of D on the length of the hydrophobic tail. The influence of the hydrodynamic radii and supporting electrolyte concentration for the sphere to rod transition on the surfactant tail was also studied. A brief study on the electrochemical oxidation of ferrocene at two different micellar media (C16TABr and SDS sodium dodecyl sulfate) was done. The voltammetric experiments showed that the anodic process occurs at less positive potentials in solutions containing SDS and a likely explanation involves the electrostatic interaction between the micelle and the electrode surface. Experiments with a homemade twin-electrode thin-layer cell (TETLC) were performed in order to evaluate the interaction of ferrocinium, the product of ferrocene oxidation, with C16TABr micelles. The diffusion coefficient of ferrocinium was obtained and the affinity of this generated electroactive species with the micellar core was discussed.

Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2017-02-15T16:34:59Z No. of bitstreams: 1 2016 - Vitor dos Santos Almeida.pdf: 2652432 bytes, checksum: 7f27ae8d8b345f1dc55ee863302bfda7 (MD5) / Made available in DSpace on 2017-02-15T16:34:59Z (GMT). No. of bitstreams: 1 2016 - Vitor dos Santos Almeida.pdf: 2652432 bytes, checksum: 7f27ae8d8b345f1dc55ee863302bfda7 (MD5) Previous issue date: 2016-04-15 / The analysis of mixtures is a common place challenge in the laboratory. Conventional methods demand a previous treatment which may be time consuming. At present, Nuclear Magnetic Resonance may be employed for the analysis of mixtures by using the DOSY (diffusion ordered spectroscopy) technique, whereby the different components of a mixture are separated by their diffusion coefficients. Pitches, in general, are products which are employed as starting material for the production of a variety of carbon materials, such as anodes for the production of aluminum, graphite electrodes for the steel industry, and carbon fibers. Pitches obtained from coal tar, itself a residue in the production of coke, are the most traditionally used. However, it is a carcinogen and therefore has had its use greatly diminished. Petroleum pitches, which are produced from decanted oil, may be a safer and less expensive alternative. The decanted oil is a heavy fraction obtained from catalytic cracking of petroleum. The difficulties in controlling its processing are derived from its complex composition, which includes paraffins, aromatic and heteroaromatic compounds. The present work investigates the analysis by NMR-DOSY of a mixture of model compounds present in decanted oil. Thus, a mixture of Tetracosane, Phenanthrene, 9-Mehylanthracene, Pyrene, Carbazole, 9-metil Carbazol, Dibenzothiophene, Dibenzofuran, Hexadecane, 1-Methylnaphthalene, Thiophene, Tetrahydrofuran was analyzed by NMR with an Avance III 500 MHz NMR spectrometer equipped with a BBO probe with a gradient on z-axis, at 20?C. To help in the separation by diffusion, the following polymers were used: poly-(ethyleneglycol), poly-(vinylpyrrolidone), poly-(dimethylsiloxan), poly-(butylmethacrylate) e poly-(vinylacetate).The shift reagent Eu(fod)3 was also employed. The results from DOSY-INEPT experiments show that poly-(butylmethacrylate) is the matrix which afforded the best separation of the different components of the mixture, followed by poly-(vinylacetate), poly-(ethyleneglycol) and finally, poly-(vinylpyrrolidone), which showed satisfactory results / Um grande desafio, muitas das vezes at? comum nos laborat?rios, ? a an?lise de misturas. Os m?todos convencionais em sua maioria exigem um tratamento pr?vio das misturas, o que demanda tempo, al?m de interferir diretamente no equil?brio do sistema. Hoje em dia, a t?cnica de Resson?ncia Magn?tica Nuclear pode ser usada na an?lise de misturas medindo-se o coeficiente de difus?o dos componentes da mistura, permitindo a obten??o dos espectros de cada componente individualmente por meio de um experimento r?pido que n?o interfere na mistura em si. O experimento mais comum ? o DOSY, do ingl?s Espectroscopia de Difus?o Ordenada. Piches, em geral, s?o produtos que s?o empregados como mat?rias-primas na produ??o de uma variedade de materiais de carbono, tais como: anodos de carbono para produ??o de alum?nio, eletrodos de grafite para a ind?stria sider?rgia e fibras de carbono. Piches obtidos a partir do alcatr?o da hulha, res?duo da produ??o de coque metal?rgico, s?o os tradicionalmente mais usados, mas apresentam alto potencial carcinog?nico e tem demanda decrescente em fun??o de novas tecnologias empregadas nas coquerias. Piches de petr?leo, produzidos a partir de ?leos decantados, podem potencialmente constituir uma alternativa mais segura e com maior disponibilidade. O ?leo decantado ? uma fra??o pesada obtida nas unidades de craqueamento catal?tico fluido no refino de petr?leo, e o controle de seu processamento ? dificultado pela complexidade de sua composi??o, que inclui compostos paraf?nicos, homoarom?ticos e heteroarom?ticos. O presente trabalho se prop?em a investigar a an?lise por RMN de uma mistura de padr?es de subst?ncias representativas dos tipos de compostos presentes no ?leo decantado. Assim, foram escolhidos padr?es de Tetracosano, Fenantreno, 9-metil Antraceno, Pireno, Carbazol, 9-metil Carbazol, Dibenzotiofeno, Dibenzofurano, Hexadecano, 1-metil Naftaleno, Tiofeno, Tetrahidrofurano. Todos os experimentos foram realizados no laborat?rio de RMN do PPGQ-UFRRJ a 20?C com o espectr?metro de RMN de 500 MHz Bruker Avance III, equipado com sonda BBO, gradiente no eixo z. Para auxiliar na separa??o dos componentes da mistura foram usados o pol?mero poli-(etilenoglicol), poli-(vinilpirrolidona), poli-(dimetilsiloxano), poli-(metacrilato de butila) e poli-(acetato de vinila), al?m do reagente de deslocamento Eu(fod)3. Os resultados obtidos a partir dos experimentos de DOSY-INEPT mostraram que o pol?mero PMAB foi a matriz que mais auxiliou na separa??o dos componentes da mistura em quest?o no presente trabalho, sendo seguido pelas matrizes PAV, PEG e PVP, que tamb?m apresentaram resultados satisfat?rios

Electrostatics plays a crucial role in the membrane biology. Negatively charged lipids (such as PS, PA and PIP2) are subject to redistribution under the action of electrostatic forces during various signalling events. Membrane recruitment of multiple signalling proteins (such as MARCKS or Src kinase) is often maintained by positively charged polybasic domains (PD). Even though adsorption of these proteins to the cellular membrane has been extensively investigated, very little is known about how electrostatic interactions contribute to their membrane lateral dynamics. This thesis presents an investigation of the contribution of electrostatic interactions to the membrane lateral dynamics by means of novel computational tools. First, I developed a dynamic Monte-Carlo automaton that faithfully simulates lateral diffusion of the adsorbed positively charged PD of a peripheral membrane protein, as well as the dynamics of mono- (PS, PA) and polyvalent (PIP2) anionic lipids within the bilayer. This model allowed to investigate the major characteristics of protein-membrane diffusion on the uniform membrane. In agreement with earlier results, the simulations revealed the following microscopic phenomena: 1) Electrostatic lipid demixing in the vicinity of the PD; 2) PD interacts with PIP2 stronger than with monovalent lipids. On the spatially heterogeneous membrane the automaton predicted a directional drift of the PD, which was validated by a simple mean-field analytical model. The predicted phenomenon could potentially play a major role in membrane domain formation. To test this hypothesis and to investigate the membrane dynamics on larger scales I developed a continuous model, which was based on the results of the automaton simulations. The results of the continuous model and the Monte-Carlo simulations were shown to be in quantitative agreement. The continuous model allows one to simulate the electrostatic membrane dynamics on micrometer scales and can be used to describe various biologically important processes, such as endocytic cup initiation.

Neste trabalho são apresentados resultados sobre o uso da voltametria com microeletrodos para o estudo de sistemas micelares. Estes estudos se basearam na obtenção de coeficientes de difusão de micelas em solução aquosa. Para tanto, o ferroceno foi utilizado como sonda eletroativa, haja vista que esta molécula é pouco solúvel em água e possui grande afinidade pelo interior micelar. A partir de experimentos envolvendo o tensoativo brometo de hexadecil trimetil amônio (C16TABr) pôde-se calcular parâmetros como o coeficiente de difusão do agregado na concentração micelar crítica e o coeficiente de interação intermicelar com a aplicação dos dados de coeficiente de difusão obtidos pela teoria de interação linear. O coeficiente de interação intermicelar permitiu a estimativa da concentração de eletrólito necessária para a mudança morfológica da micela (micela esférica para micela alongada). O raio hidronâmico da micela foi o calculado a partir da relação Stokes-Einstein. Um estudo complementar envolveu a adição de n-decanol à solução de tensoativo, e comparações dos coeficientes de difusão obtidos na presença e na ausência do álcool foram efetuadas. Estudos subseqüentes foram realizados empregando outros tensoativos (C14TABr, C12TABr e C10TABr) com a finalidade de verificar a dependência do coeficiente de difusão micelar com o comprimento da cauda hidrofóbica da molécula do tensoativo. A influência de outros parâmetros como o raio hidrodinâmico e a concentração de eletrólito necessária para a transição morfológica com o comprimento da cauda hidrofóbica também foi estudada. Em experimentos voltamétricos envolvendo a oxidação eletroquímica do ferroceno em meio de C16TABr e de SDS (dodecil sulfato de sódio) foi verificado que o sinal anódico ocorre em potenciais menos positivos em soluções de SDS, fato justificado pela interação da micela de SDS, negativamente carregada, com a superfície do eletrodo positivamente carregado. A investigação da interação do produto de oxidação eletroquímica do ferroceno, o íon ferrocínio, com as micelas de C16TABr foi realizada em experimentos envolvendo uma microestrutura geradora-coletora. Esta estrutura consiste em dois eletrodos de área similar separados por um canal de espessura micrométrica. A utilização deste dispositivo possibilitou a obtenção do coeficiente de difusão do ferrocínio e, a partir deste dado, foi possível fazer inferências sobre a afinidade deste íon pelo interior micelar. / Voltammetry with platinum disc microelectrodes was employed to gain information on diffusion coefficients, D, of micelles in aqueous solution. Owing to the low solubility in water and high affinity for the micellar core, ferrocene was used as electroactive probe. Diffusion coefficients of hexadecyl trimethyl ammonium bromide (C16TABr) were determined in solutions containing the surfactant in different concentrations and the data were fitted according to the linear interaction theory. This procedure allowed the diffusion coefficient at the critical micelle concentration to be found, as well as the intermicellar interaction parameter. The latter was used to estimate the minimum concentration of electrolyte that promotes morphological changes in the micelles (sphere to rod transition). The micellar hydrodynamic radius was calculated by using the Stokes-Einstein equation. A complementary study involved the addition of n-decanol to surfactant solutions and the diffusion coefficient was compared with the one obtained in the absence of the fatty alcohol. Experiments were also performed in solutions containing other surfactants (C14TABr, C12TABr e C10TABr) to investigate the dependence of D on the length of the hydrophobic tail. The influence of the hydrodynamic radii and supporting electrolyte concentration for the sphere to rod transition on the surfactant tail was also studied. A brief study on the electrochemical oxidation of ferrocene at two different micellar media (C16TABr and SDS sodium dodecyl sulfate) was done. The voltammetric experiments showed that the anodic process occurs at less positive potentials in solutions containing SDS and a likely explanation involves the electrostatic interaction between the micelle and the electrode surface. Experiments with a homemade twin-electrode thin-layer cell (TETLC) were performed in order to evaluate the interaction of ferrocinium, the product of ferrocene oxidation, with C16TABr micelles. The diffusion coefficient of ferrocinium was obtained and the affinity of this generated electroactive species with the micellar core was discussed.

Estimation of effective diffusion coefficients is essential to be able to describe the diffusive transport of solutes in porous media. It has been shown in theory that in the case of uncharged porous materials the effective diffusion coefficient of solutes is a function of the pore morphology of the material and can be described by their tortuosity (tensor). To estimate the apparent diffusion coefficients, the values of tortuosity and porosity should be known first. In contrast with calculation of porosity, which can be easily obtained, estimation of tortuosity is intricate, particularly with increasing micro-geometry complexity in porous media. Moreover, many engineering materials (e.g, clays and shales) are characterized by electrical surface charges on particles of the porous material which can strongly affect the diffusive transport properties of ions. For these materials, estimation of effective diffusion coefficients have been mostly based on phenomenological equations with no link to underlying microscale properties of these charged materials although a few recent studies have used alternative methods to obtain the diffusion parameters. / In the first part of this thesis a numerical method based on a recently proposed up-scaled Poisson-Nernst-Planck type of equation (PNP) and its microscale counterpart is employed to estimate the tortuosity and thus the effective and apparent diffusion coefficients in thin charged membranes. Beside this, a new mathematical approach for estimation of tortuosity is applied and validated. This mathematical approach is also derived while upscaling of micro-scale Poisson-Nernst-Planck system of equations using the volume averaging method. A variety of different pore 2D and 3D micro-geometries together with different electrochemical conditions are studied here. To validate the new approaches, the relation between porosity and tortuosity has been obtained using a multi-scale approach and compared with published results. These include comparison with the results from a recently developed numerical method that is based on macro and micro-scale PNP equations. / Results confirm that the tortuosity value is the same for porous media with electrically uncharged and charged particles but only when using a consistent set of PNP equations. The effects of charged particles are captured by the ratio of average concentration to effective intrinsic concentration in the macroscopic PNP equations. Using this ratio allows to consistently take into account electro-chemical interactions of ions and charges on particles and so excludes any ambiguity generally encountered in phenomenological equations. / Steady-state diffusion studies dominate this thesis; however, understanding of transient ion transport in porous media is also important. The last section of this thesis briefly introduces transient diffusion through bentonite. To do so, the micro Nernst-Planck equation with electro-neutrality condition (NPE) is solved for a porous medium which consists of compacted bentonite. This system has been studied before in another research using an experimental approach and the results are available for both transient and steady-state phases. Three different conditions are assumed for NPE governing equations and then the numerical results from these three conditions are compared to the experimental values and analytical phenomenological solution. The tortuosity is treated as a fitting parameter and the effective diffusion coefficient can be calculated based on these tortuosity values. The results show that including a sorption term in the NPE equations can render similar results as the experimental values in transient and steady state phases. Also, as a fitting parameter, the tortuosity values were found varying with background concentration. This highlights the need to monitor multiple diffusing ion fluxes and membrane potential to fully characterize electro-diffusive transport from fundamental principles (which have been investigated in first part of this thesis) rather than phenomenological equations for predictive studies. / This research has lead to two different journal articles submissions, one already accepted in Computers and Geotechnics (October 22, 2009, 5-yrs Impact Factor 0.884) and the other one still under review.

Electrochromic iridium oxide (IrOx) and iridium-tantalum oxide (IrTaOx) thin films were prepared by reactive magnetron sputtering. Composition, density, and structure were determined using Rutherford backscattering spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and electron energy loss spectroscopy. The electronic density of states (DOS) and the solid phase chemical diffusion coefficient (D) were determined for hydrogen in IrOx and IrTaOx by potentiostatic intermittent titration technique (PITT), and electrochemical impedance spectroscopy (EIS). The complex refractive indices were determined for colored and bleached IrOx and IrTaOx by inverting transmission and reflectance, measured using spectrophotometry in the 300-2500 nm wavelength range. A very porous structure, with a stoichiometry of IrO2.2, was found for IrOx. It contained ~4 nm sized grains. The IrTaOx had a denser structure built up by ~4 nm sized grains. The composition of IrTaOx was found to vary on a nanometer scale, with an average composition of IrTa1.4O5.6. It was found that DOS can be measured using PITT and EIS in the presence of spontaneous side reactions, even for systems influenced by non-negligible charge transfer kinetics and Ohmic drops. It was found that the measured DOS is 30-50% of the theoretically calculated DOS and that D is in the 10-10 – 10-11 cm2/s range for both materials. The hydrogen diffusion mechanism was described by an anomalous diffusion model, possibly indicating percolation or diffusion paths described by a fractal network. The refractive indices were found to be ~1.3 and ~2 for IrOx and IrTaOx, respectively, and independent of coloration state, whereas the extinction coefficients were found to modulate by ~30% for IrOx and ~50% for IrTaOx, making IrTaOx more favorable for electrochromic applications. A modulation peak was found at ~660 nm for both IrOx and IrTaOx associated with the removal of intraband transitions within the Ir t2g band.

This project considers the diffusion of water molecules through a cellular medium in which the cells are modeled by square compartments placed symmetrically in a square domain. We assume the diffusion process is governed by the 2D diffusion equations and the solution is provided by implementing the Crank-Nicolson scheme. These results are verified and illustrated to agree well with the finite element method using the Comsol Multiphysics package. The model is used to compute the values of the apparent diffusion coefficient, (ADC) which is a measure that is derived from diffusion weighted MRI data and can be used to identify, e.g., regions of ischemia in the brain. With our model, it is possible to examine how the value of the apparent diffusion coefficient is affected whenever the extracellular space is varied. We observe that the average distance that the water molecules travel in a definite time is highly dependent on the geometrical properties of the cellular media. / UOIT

The behavior of polymeric systems confined into thin films is a situation that has numerous practical consequences. One particular application in which the properties of thin polymer films is becoming crucially important is in the design, formulation, and processing of photoresists for semiconductor microlithography. As devices continue to be scaled down into the nano-regime, the microelectronics industry will ultimately rely upon a molecular understanding of materials for process development. The majority of these devices are now confined in planar geometries; thus, thin films have played an ever-increasing role in manufacturing of modern electronic devices. This movement towards thinner resist films creates larger surface to volume ratios, and hence thin films can exhibit thermodynamic, structural, and dynamic properties that are different from those of the bulk material. It is thus extremely important to understand the properties of polymers when confined in such geometries for various applications including resists for lithographic patterning. In present work, the influence of a variety of factors including film thickness, molecular weight, and substrate interactions on the polymer thin film physical properties such as the glass transition temperature, coefficient of thermal expansion, dissolution rate, and diffusion coefficient was studied in detail using a combination of experimental characterization and molecular modeling simulation techniques.