ABA type tri-block amphiphilic polyelectrolyte consisting of poly(methyl methacrylate-block-methacrylic acid-block-methyl methacrylate) (P(MMA-b-MAA-b-MMA)) was synthesized by atom transfer radical polymerization technique (ATRP) and the self-assembly behavior of the polymers in aqueous solution was studied over the course of neutralization. Combination of potentiometric and conductometric titrations along with dynamic light scattering (DLS) techniques were used to investigate the size and shape of aggregates at various degrees of neutralization. The effect of hydrophobic-hydrophilic (MMA-MAA) ratio and polymer chain length on the aggregation behavior during neutralization was studied. P(MMA-b-MAA-b-MMA) with longer MMA segment self-assembles via the close association mechanism through stronger self-entanglement of MMA chains, whereas P(MMA-b-MAA-b-MMA) with shorter MMA chain self-assembles via the open association mechanism, as confirmed by transmission electron microscopy (TEM). Conductometric titration was used to determine the counterion condensation during the course of neutralization. When the charge density of micelle approaches a critical value as neutralization progresses, counterion condensation of Na+ ions on the polymer chains occurs. The effect of counterion condensation on the aggregation behavior during neutralization was elucidated. / Singapore-MIT Alliance (SMA)

Based on a Sc.D. thesis in the Dept. of Electrical Engineering, 1969. / Bibliography: p.112-113.

Beta lactoglobulin (βlg) is a major whey protein in the bovine milk. Upon heating above its denaturation temperature (which is pH-dependent), this globular protein undergoes molecular changes leading to the irreversible aggregation. Depending on the pH and ionic strength, either protein aggregates or gels exhibiting various structures and morphologies have been described. Very recently, it was found that in a narrow range of the pH close to iso-electric point, stable suspensions of rather monodisperse spherical particles with a radius of about a hundred nanometers were formed. These spherical particles which were called microgels might be of special interest for the production of liquid dispersions of β-lactoglobulin aggregates exhibiting various functionalities for food applications. The project on which I report here was a collaboration with the Nestlé Reseach Center (Lausanne, Switzerland) and its objective was to study the formation and structural properties of the microgels in different environmental conditions. The first part of the project is to study the influence of the pH on the formation of microgels. Stable suspensions of protein microgels are formed by heating salt free βlg solutions at concentrations up to about C = 50 g.L-1 if the pH is set within a narrow range between 5.75 and 6.1. The internal protein concentration of these spherical particles is about 150 g.L-1 and the average hydrodynamic radius decreases with increasing pH from 200 nm to 75 nm. The formation of the microgels leads to an increase of the pH, which is a necessary condition to obtain stable suspensions. The spontaneous increase of the pH during microgel formation leads to an increase of their surface charge density and inhibits secondary aggregation. This self-stabilization mechanism is not sufficient if the initial pH is below 5.75 in which case secondary aggregation leads to precipitation. Microgels are no longer formed above a critical initial pH, but instead short curved protein strands are obtained with a hydrodynamic radius of about 15-20 nm. The second part of the work is about the formation of microgels driven by the addition of calcium ions. We found that stable suspensions of spherical protein particles (microgels) can be formed by heating βlg solutions in the presence of calcium ions. The conditions for the calcium induced microgel formation were studied at different pH between 5.8 and 7.5 and different protein concentrations between 5 - 100 g.L-1. The results showed that a critical molar ratio of calcium to proteins (R) is needed to form microgels independent of the protein concentration. R decreases with decreasing pH. The microgels have a hydrodynamic radius ranging from 100 to 300 nm and their internal protein concentration ranges from 0.2 to 0.45 g.mL-1. The determination of calcium bound to the microgels suggests that the crucial parameter for microgel formation is the net charge density of the native proteins. The microgel suspensions are stable in a narrow range of R but aggregate at higher Ca2+ concentrations. In the third part, we continued to investigate the formation of microgels at initial step and how it is growing in the presence of calcium ions. We have proposed a mechanism of formation of blg microgels which follows a nucleation and growing process. The nucleus with define size are formed at the initial state and that is growing in size to reach final size of aggregates. At low calcium concentration it stabilizes and then we obtain a stable suspension of microgels. But at high concentrations, the microgels here can jump to form big aggregates and finally a gel. The structure of gel from microgels is heterogenous at the scale of confocal microscopy and similar to those formed in the presence of NaCl 0.3 M. However the process of formation of these gels is not the same...

For a long time spectrophotometry has been a powerful method of determining optical material properties. Since the technique measures the parameters of interest, reflectance and transmittance, it is in general easy to use and interpret. Certain materials, such as miniature structures or scattering materials, must be given a more careful analysis to avoid incorrect interpretation. General solutions to measurement challenges for thick scattering samples and anisotropically scattering samples are presented. Thorough knowledge about the components of a spectrophotometer gives a solid base which is necessary when trying to design or modify an instrument for the characterisation of miniature components. Focusing optics and pinhole apertures are two methods investigated for studying samples on a millimeter scale. Focusing optics retain a high intensity but might cause internal reflection. Pinhole apertures are easy to build into a sample holder, but they will reduce light intensity which can give problems with signal to noise ratio. Using a microscope as a focusing lens system permits the measurement of samples of a size down to the order of ten micrometers. However, absolute measurements are difficult due to the strong focusing properties of the microscope. Translucent sheets are of interest for daylighting applications, a growing field in today's energy-conscious society. If sunlight is to be used for indoor illumination it is preferable to make it diffuse. By using Transparent Refractive Index Matched Micro (TRIMM) particles in a transparent polymer sheet, it is possible to obtain high transmittance in combination with tailorability of the scattering profile. Such sheets have been characterised experimentally, as well as by Monte Carlo raytracing simulations. The good agreement between simulation and experiment shows that this type of simulation can be used in the materials design process. A more theoretical study of patterns in multiple Mie scattering has been carried out using the Monte Carlo program developed for characterisation of the TRIMM particle sheets.

In the last few years, interest in polymer optical fibers (POF) has increased because of their low cost, easy handling and good flexibility even at large diameters. Moreover, optical cables do not have the problem of electromagnetic interference, which gives, for instance, the problem of cross-talk in copper telephone cables. In the usage of current communication and computer systems the yield has gained a big importance and it has seen from studies that light scattering loss is the only loss, which cannot be eliminated entirely. Besides, this loss causes its attenuation loss intrinsically and determines the lower limit of loss in the POF. In this work, the importance and the dependencies of light scattering were studied, and calculations were done in order to find more appropriate polymer for using as core material of POFs. For this aim, a computer program that calculates the light scattering loss of several amorphous polymers and plots the graph of isotropic scattering loss versus isothermal compressibility and total attenuation loss versus wavelength was written.

The doctoral thesis "Low frequency modes from small nanoparticles (metal nanocrystals) to large nanospheres (viruses): an inelastic light scattering study" is dedicated to investigations of the acoustic properties of different nano-objects : small metal nanoparticles and nanocrystals (D < 30 nm) and large colloid/viral particles (D _ 200 nm). Inelastic light Raman/Brillouin scattering is used as the main research tool to probe the nanoparticle vibrations and to determine their elastic and mechanical parameters. In the first chapter, the well developed theory of elasticity is used to perform a qualitative and nomenclatural analysis of solid sphere vibrations ; several theoretical models allowing to describe the nanoparticle vibrational behavior within a surrounding medium and how the eigenvibrations are modified due to inner crystalline elastic anisotropy are discussed. The second chapter is dedicated to the description of the physics of inelastic light scattering which derives from the fluctuations of the polarizability induced by vibrations. Two types of inelastic light scattering are described : Brillouin scattering which results from the coupling of incident light (photon) with acoustic propagative waves (phonon) in a bulk substance and Raman scattering which is a result of the interaction between an incident photon and localized vibrations, hence nanoparticle vibrations in the present study. As essential in our study, the detailed description and principles of operation of the spectroscopic tools (tandem Fabry-Perot) used to perform these very low frequency inelastic light scattering spectroscopies (between 3 and 300 GHz typically) are given. The third chapter focuses on the study of low frequency modes from small metallic nanoparticles. Three systems are investigated : AuAg and Cu nanoparticles embedded in a vitreous matrix and Au nanocrystals deposited on a surface. The AuAg system allowed to study a notably rich Raman spectrum featuring contributions from fundamental modes and high order harmonics. The experimental data were found to compare rather well with theoretical predictions, thereby providing more insight into the essential ingredients of Raman scattering from nanoparticle modes. The study of deposited Au nanocrystals allowed characterizing the effect of nanocrystalline quality which results in a partial lifting of degeneracy of the nanoparticle modes due to elastic anisotropy. Investigating the wavelength dependence of the Raman spectrum allows a differentiation between single nanocrystals and multiply twinned nanoparticles. Both embedment effects and nanocrystallinity effects are integrated in the study of Cu nanoparticles grown in a glass matrix, where the influence of annealing conditions on the produced nanoparticles was investigated. It was shown that different annealing temperatures [...] result in very different low frequency Raman profiles. [...] The forth chapter reports on the exploration of the possible use of the low frequency inelastic light scattering probe in the characterization of large viruses, as illustrated in the third chapter for small nanoparticles. In order to address the change of the light selection rules as the wavelength of the exciting light becomes comparable to the size of the nanoparticles, the behaviors of the viruses are compared to those of polymer colloids. Ultra Small Angle X-ray Scattering and Atomic Force Microscopy are used to first ensure the comparableness of viruses and polystyrene colloids in terms morphologies. On the basis of the inelastic light scattering data obtained for PS colloids [...], we discuss the difficult interpretation in termsof eigenmodes of the virus counterparts.

<p>The redistribution of incident light into scattered fields ultimately limits the ability to image into biological media. However, these scattered fields also contain information about the structure and distribution of protein complexes, organelles, cells and whole tissues that can be used to assess the health of tissue or to enhance imaging contrast by excluding confounding signals. The interpretation of scattered fields depends on a detailed understanding of the scattering process as well as sophisticated measurement systems. In this work, the development of new instruments based on low coherence interferometry (LCI) is presented in order to perform precise, depth-resolved measurements of scattered fields. Combined with LCI, the application of new light scattering models based on both analytic and numerical methods is presented in order to interpret scattered field measurements in terms of scatterer geometry and tissue health. </p><p>The first portion of this work discusses the application of a new light scattering model to the measurement recorded with an existing technique, Angle Resolved Low Coherence Interferometry (a/LCI). In the a/LCI technique, biological samples are interrogated with collimated light and the energy per scattering angle at each depth in the volume is recorded interferometrically. A light scattering model is then used to invert the scattering measurements and measure the geometry of cell nuclei. A new light scattering model is presented that can recover information about the size, refractive index, and for the first time, shape of cell nuclei. This model is validated and then applied to the study of cell biology in a series of experiments measuring cell swelling, cell deformation, and finally detecting the onset of apoptosis.</p><p>The second portion of this work introduces an improved version of a/LCI based on two dimension angle resolved measurement (2D a/LCI) and Fourier domain low coherence interferometry (FD-LCI). Several systems are presenting for high speed and polarization-resolved measurements of scattered fields. An improved light scattering model based on fully polarization and solid angle resolved measurements is presented, and then efficiently implemented using distributed computing techniques. The combined system is validated with phantoms and is shown to be able to uniquely determine the size and shape of scattering particles using a single measurement.</p><p>The third portion of this work develops the use of angle-resolved interferometry for imaging through highly scattering media by exploiting the tendency of scatterers to forward scatter light. A new interferometers is developed that can image through very large numbers of scattering events with acceptable resolution. A computational model capable of reproducing experimental measurements is developed and used to understand the performance of the technique.</p><p>The final portion of the work develops a method for processing 2D angle resolved measurements using optical autocorrelation. In this method, measurements over a range of angles are fused into a single depth scan that incorporates the component of scattered light only from certain spatial scales. The utility of the technique is demonstrated using a gene knockout model of retinal degeneration in mice. Optical autocorrelation is shown to be a potentially useful biomarker of tissue disease.</p> / Dissertation

Definir los parámetros de polarización de la luz procedente de una muestra aporta una mayor información sobre las propiedades de ésta que la simple medida de la intensidad luminosa difundida. Cuando un haz luminoso sufre una perturbación debida a cualquier interacción con un medio, los campos electromagnéticos del haz incidente y el del haz emergente, expresados en términos de los parámetros de Stokes, pueden ser relacionados mediante la denominada matriz de Mueller. En este aspecto, el conocer la evolución de los parámetros de dicha matriz del sistema, nos permitiría definir cómo se comporta éste frente a la luz incidente. Para tal objetivo, se ha puesto a punto un polarímetro dinámico basado en técnicas de Transformada de Fourier, que permite determinar con una sola medida los 16 elementos de la matriz de Mueller. Ésta nos mostrará los cambios sufridos por la polarización del haz incidente debido a su interacción con una muestra problema.Aplicando el método de Descomposición Polar, se puede ver que cualquier sistema puro, con matriz de Mueller M, responde a la siguiente relación: M=R*D, donde R y D simbolizan las matrices de Mueller de un medio Retardador ideal y de un medio Diatenuador ideal, respectivamente. En una versión extendida de éste teorema, teniendo en cuenta que no todos los medios son ideales, sino que hay medios en los que aparecen efectos de despolarización, la descomposición de la matriz de Mueller daría lugar a: M=Z*R*D, tomando Z como la matriz de Mueller de un sistema despolarizante. De esta forma, utilizando algebra matricial, podemos descomponer la matriz de un sistema problema, en matrices de menor complejidad, con un estricto sentido físico.Partiendo de éstos resultados teóricos, y por medio del uso del polarímetro dinámico para la caracterización polarimétrica de los sistemas, se han analizado muestras de diversos tipos: superficies planas microestructuradas, para evaluar el efecto de la composición, tamaño e interacción; suspensiones de micropartículas y nanopartículas en coloide, para caracterizar su tamaño y composición; y sustancias quirales en medios turbios (en éste aspecto, recientemente ha sido demostrada la validez de éste método para el análisis in situ de tejidos biológicos). Asimismo, se han caracterizado componentes ópticos y polarimétricos por transmisión y reflexión, demostrando la validez del método. Finalmente se han llevado a cabo simulaciones computacionales a fin de estudiar patrones de comportamiento en sistemas complejos por medio del método de Descomposición Polar. / Polarization parameters of light scattered from a sample give more information about its properties than the light scattering intensity measurement. When a light beam interacts with an object or a medium, the electromagnetic fields of the incident and the emerging beam, both expressed in terms of Stokes parameters, can be related by the so-called Mueller matrix. In this respect, the matrix elements are associated to the physical system and define its behaviour. For the analysis of real systems, Mueller matrix must be experimentally obtained. For this purpose, a dynamic polarimeter (DRCP or Dual Rotating Compensator Polarimeter) based on Fourier Transform techniques has been developed, which allow us to determine the 16 elements of the Mueller matrix in a single cycle of measurements.Applying an algebraic tool, as the Polar Decomposition method (PD), we can see that any Mueller matrix corresponding to a pure system satisfies: M = R * D, where R and D are the Mueller matrices of an ideal Retarder and a Diattenuator, respectively. In an extended version of PD, taking into account that not all matrices are ideal, but there are systems in which depolarization effects occur, the decomposition of the Mueller matrix would lead to: M = Z * R * D, with Z representing the depolarization. Thus, using matrix algebra, we can decompose the matrix of a system, in a product of matrices with a strict physical sense.Based on these theoretical results and by using a polarimetric characterization of systems (through PDRC measurements), we have analyzed samples of different types: flat microstructured surfaces to evaluate the effect of the composition, size and interaction; suspensions of microparticles or nanoparticles to characterize their size and composition; chiral substances in turbid media (in this aspect has recently been demonstrated the validity of this method for the analysis of biological tissues "in situ"); characterization and study of polarimetric optics in transmission and reflection, demonstrating the validity of the method. Finally, we have carried out computer simulations to explore patterns in complex systems using PD.

Creating realistic virtual hair consists of several major areas: creating the geometry, moving the hair strands realistically and rendering the hair. In this thesis, a background survey covering each one of these areas is given. A node-based, procedural hair system is presented, which utilizes the capabilities of modern GPUs. The hair system is implemented as a plugin for Autodesk Maya, and a user interface is developed to allow the user to control the various parameters. A number of nodes are developed to create effects such as clumping, noise and frizz. The proposed system can easily handle a variety of hairstyles, and pre-renders the result in real-time using a local shading model.

<p>Cancer is a disease that affects millions of people each year. While methods for the prevention and treatment of the disease continue to advance, the early detection of precancerous development remains a key factor in reducing mortality and morbidity among patients. The current gold standard for cancer detection is the systematic biopsy. While this method has been used for decades, it is not without limitations. Fortunately, optical detection of cancer techniques are particularly well suited to overcome these limitations. This dissertation chronicles the development of one such technique called Fourier domain low coherence interferometry (fLCI). </p><p>The presented work first describes a detailed analysis of temporal and spatial coherence. The study shows that temporal coherence information in time frequency distributions contains valuable structural information about experimental samples. Additionally, the study of spatial coherence demonstrates the necessity of spatial resolution in white light interferometry systems. The coherence analysis also leads to the development of a new data processing technique that generates depth resolved spectroscopic information with simultaneously high depth and spectral resolution. </p><p>The development of two new fLCI optical systems is also presented. These systems are used to complete a series of controlled experiments validating the theoretical basis and functionality of the fLCI system and processing methods. First, the imaging capabilities of the fLCI system are validated through scattering standard experiments and animal tissue imaging. Next, the new processing method is validated by a series of absorption phantom experiments. Additionally, the nuclear sizing capabilities of the fLCI technique are validated by a study measuring the nuclear morphology of in vitro cell monolayers.</p><p>The validation experiments set the stage for two animal studies: an initial, pilot study and a complete animal trial. The results of these animal studies show that fLCI can distinguish between normal and dyplastic epithelial tissue with high sensitivity and specificity. The results of the work presented in this dissertation show that fLCI has great potential to develop into an effective method for early cancer detection.</p> / Dissertation