No / PURPOSE: To estimate refractive indices used by the Lenstar biometer to translate measured optical path lengths into geometrical path lengths within the eye. METHODS: Axial lengths of model eyes were determined using the IOLMaster and Lenstar biometers; comparing those lengths gave an overall eye refractive index estimate for the Lenstar. Using the Lenstar Graphical User Interface, we noticed that boundaries between media could be manipulated and opposite changes in optical path lengths on either side of the boundary could be introduced. Those ratios were combined with the overall eye refractive index to estimate separate refractive indices. Furthermore, Haag-Streit provided us with a template to obtain 'air thicknesses' to compare with geometrical distances. RESULTS: The axial length estimates obtained using the IOLMaster and the Lenstar agreed to within 0.01 mm. Estimates of group refractive indices used in the Lenstar were 1.340, 1.341, 1.415, and 1.354 for cornea, aqueous, lens, and overall eye, respectively. Those refractive indices did not match those of schematic eyes, but were close in the cases of aqueous and lens. Linear equations relating air thicknesses to geometrical thicknesses were consistent with our findings. CONCLUSION: The Lenstar uses different refractive indices for different ocular media. Some of the refractive indices, such as that for the cornea, are not physiological; therefore, it is likely that the calibrations in the instrument correspond to instrument-specific corrections and are not the real optical path lengths.

[ES] La difusión de la luz es un fenómeno ubicuo con implicaciones significativas en gran variedad de disciplinas. Mientras que la mayoría de los estudios de difusión se centran en la extinción u otras mediciones relacionadas con la amplitud, la fase de la onda difusa contiene información importante que puede ser aprovechada para múltiples propósitos. Aunque pocas técnicas de caracterización son adecuadas para esta tarea, la espectroscopía de terahercios (THz) es una técnica coherente que permite esto en un amplio rango de frecuencias con propiedades cuasi ópticas. Para lograrlo, estudiaremos y mejoraremos la metodología existente de pulsos de THz aumentando la velocidad de adquisición de espectros de alta resolución mediante la combinación de diversas técnicas para el muestreo de retardo. Esta tesis aborda la investigación de luz difusa con tecnología de THz para dos desarrollos principales. El primero es un método de caracterización del tamaño de partículas resuelto espectralmente utilizando medidas de extinción y de índice de refracción (IR). Al resolver el problema inverso de luz difusa, se puede obtener una gran información de las propiedades geométricas y químicas de las partículas. Este método tradicionalmente ha empleado solo de datos de extinción del medio heterogéneo. Demostramos que se puede lograr una mejora neta en la reconstrucción de la distribución del tamaño de partícula al combinar datos de extinción con datos de IR. Dado que las mediciones se encuentran en un rango de frecuencia limitado, obtener el IR a partir de relaciones de Kramers-Kronig (KK) no puede sustituir su medición directa utilizando técnicas coherentes. Una razón adicional por la cual las relaciones de KK pueden no ser útiles es que, en el caso de una partícula con una densidad óptica menor que el fondo, el IR efectivo complejo no sigue relaciones de dispersión convencionales. El estudio de este fenómeno y la interpretación de las implicaciones causales que surgen son el foco de la última parte de esta tesis, junto con su posible aplicación para el diseño de ondas con contenido espectral arbitrario. Finalmente, se discuten las conclusiones y las líneas futuras de trabajo derivadas de nuestros hallazgos. / [CA] La difusió de la llum és un fenomen ubic amb implicacions significatives en una gran varietat de disciplines. Mentre que la majoria dels estudis de difusió se centren en l'extinció o altres mesures relacionades amb l'amplitud, la fase de l'ona difusa conté informació important que es pot aprofitar per a múltiples propòsits. Encara que poques tècniques de caracterització són adequades per a aquesta tasca, l'espectroscòpia de teraherços (THz) és una tècnica coherent que permet això en un ampli rang de freqüències amb propietats quasi òptiques. Per a aconseguir-ho, estudiarem i millorem la metodologia existent de polsos de THz augmentant la velocitat d'adquisició d'espectres d'alta resolució mitjançant la combinació de diverses tècniques per al mostreig de retard. Aquesta tesi aborda la investigació de la llum difusa amb tecnologia de THz per a dos desenvolupaments principals. El primer és un mètode de caracterització de la mida de partícules resolt espectralment utilitzant mesures d'extinció i d'índex de refracció (IR). En resoldre el problema invers de llum difusa, es pot obtenir una gran informació sobre les propietats geomètriques i químiques de les partícules. Aquest mètode tradicionalment ha emprat només dades d'extinció del medi heterogeni. Demostrem que es pot aconseguir una millora neta en la reconstrucció de la distribució de la mida de partícula en combinar dades d'extinció amb dades d'IR. Donat que les mesures es troben en un rang de freqüència limitat, obtenir l'IR a partir de relacions de Kramers-Kronig (KK) no pot substituir la seua mesura directa utilitzant tècniques coherents. Una raó addicional per la qual les relacions de KK poden no ser útils és que, en el cas d'una partícula amb una densitat òptica menor que el fons, l'IR efectiu complex no segueix relacions de dispersió convencionals. L'estudi d'aquest fenomen i la interpretació de les implicacions causals que sorgeixen són el focus de la darrera part d'aquesta tesi, juntament amb la seua possible aplicació per al disseny d'ones amb contingut espectral arbitrari. Finalment, es discuteixen les conclusions i les línies futures de treball derivades dels nostres descobriments. / [EN] Light scattering is a ubiquitous phenomenon with significant implications across various disciplines. While most scattering studies focus on extinction or other amplitude-related measurements, the phase of the scattered wave holds important information that can be harnessed for a multitude of purposes. However, while few characterization techniques are suited for this task, terahertz (THz) spectroscopy is a coherent technique that permits this across a wide range of frequencies with quasi-optical properties. To accomplish this, we will study and improve the existing methodology of pulsed THz by increasing the speed of acquisition of high-resolution spectra with a combination of existing delay sampling techniques. This thesis approaches light scattering research with THz technology for two main developments. The first one is a spectrally resolved particle size characterization method using extinction and refractive index (RI) measurement. By solving the inverse scattering problem, great insight into the geometric and chemical properties of the particles can be gained. This method has traditionally relied only on extinction data from the heterogeneous medium. We demonstrate that a net improvement in the reconstruction of the particle size distribution can be made by combining extinction with RI datasets. Since the measurements are in a limited frequency range, obtaining the RI from Kramers-Kronig (KK) relations cannot substitute for its direct measurement using coherent techniques. One additional reason why KK relations may not be of use is that, for the case of a particle with lower optical density than the background, the measured complex effective RI does not follow conventional dispersion relations. The study of this phenomenon and the interpretation of the causal implications that arise are the subject of the last part of this thesis, along with its possible application to the arbitrary shaping of spectral wave features. Ultimately, the conclusions and future lines of work derived from our findings are discussed. / This thesis has been developed under grant FPI ACIF-2018-163 by GVA, project PID2019-111339GBI00 and project PDC2021-121597-I00 by MCIN/AEI / Báez Chorro, MÁ. (2024). Study of the Complex Spectral Response of Scattering Media with Terahertz Spectroscopy [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/205586

This is a study on the prevalence of refractive errors and patients requiring refractive services at 15 eye clinics in the Amathole, Chris Hani, Joe Gqabi and OR Tambo District Municipalities of the Eastern Cape. This is an area characterised by extreme poverty where the cost of an eye examination and prescription spectacles remains financially unobtainable for most. Optometry services are provided mainly by private optometrists who service the small proportion of the population that can afford them. Adults and children remain house bound or are labelled as dull and unproductive simply because they don’t have access to an eye examination and a pair of spectacles. Purpose The purpose of the study is to identify patients with refractive errors and those requiring refractive services at the 15 eye clinics in the Eastern Cape. Another purpose is to describe the refractive services that are available to patients attending health facilities, where the eye clinics are conducted. Lastly, the purpose is to explore the possibility of nurses providing refractive services independently or under the supervision of optometrists to supplement the lack to refracting and dispensing services. Study Method A quantitative and qualitative non-experimental descriptive design was used. Research involved the analysis of Vision Care’s eye clinic records collected from 15 eye clinics from January 2010-June 2010. Semi-structured interviews were conducted with 30 nurses working at the 15 health facilities where the eye clinics were conducted using purposive sampling. The quantitative data was analysed using excel spreadsheets and graphs and qualitative data was analysed using coding and categorizing methods. Conclusion According to Vision Care’s data of the patients assessed, 19.2 percent had a refractive error and 54 percent of the patients required refractive services. It is estimated that 71.41 percent of the patients had a refractive error according to the optometrist. Although there were some organisations active in the eradication of cataracts, there was little healthcare available in the form of refraction services. xiv Patients needed to travel an average of 63.8kms to access refraction services against the backdrop of poor roads, poverty and unemployment. 28 out of 30 nurses either ‘strongly agreed’ or ‘agreed’ that nurses could be trained to perform refractions and dispense spectacles. 29 out of 30 nurses thought that this would have a positive impact on eye care. Further research is necessary to assess the feasibility of implementing a nurse operated refractive program and whether it should be within their scope of practice to refract and dispense spectacles.

MPH / Department of Public Health / See the attached abstract below

Les biocapteurs sont utilisés quotidiennement pour déterminer la présence de molécules biologiques dans une matrice complexe, comme l’urine pour les tests de grossesses ou le sang pour les glucomètres. Les techniques courantes pour la détection des autres maladies nécessitent fréquemment le marquage de l’analyte avec une autre molécule, ce qui est à éviter pour fin de simplicité d’analyse. Ces travaux ont pour but la maximisation de la sensibilité d’une surface d’or ou d’argent nanotrouée, afin de permettre la détection de la liaison de molécules biologiques par résonance des plasmons de surface localisés (LSPR), en utilisant la spectroscopie de transmission. Un biocapteur portable, rapide et sans marquage pour quantifier des analytes d’intérêt médical ou environnemental pourrait être construit à partir de ces travaux. Dans l’objectif d’étudier de nombreuses configurations pour maximiser la sensibilité, le temps et le coût des méthodes de fabrication de nanostructures habituelles auraient limité le nombre de surfaces nanotrouées pouvant être étudiées. Un autre objectif du projet consiste donc au développement d’une technique de fabrication rapide de réseaux de nanotrous, et à moindres coûts, basée sur la lithographie de nanosphères (NSL) et sur la gravure au plasma à l’oxygène (RIE). La sensibilité à la variation d’indice de réfraction associée aux liaisons de molécules sur la surface du métal noble et la longueur d’onde d’excitation du plasmon de surface sont influencées par les caractéristiques des réseaux de nanotrous. Dans les travaux rapportés ici, la nature du métal utilisé, le diamètre ainsi que la périodicité des trous sont variés pour étudier leur influence sur les bandes LSPR du spectre en transmission pour maximiser cette sensibilité, visant la fabrication d’un biocapteur. Les surfaces d’argent, ayant un diamètre de nanotrous inférieur à 200 nm pour une périodicité de 450 nm et les nanotrous d’une périodicité de 650 nm démontre un potentiel de sensibilité supérieur. / Biosensors are used daily to determine the presence of biomolecules in a complex matrix, like urine for pregnancy test or blood with a glucometer. The usual biodetection methods require the addition of a tag on the analyte, which is to be avoided to design a simple analytical method. The objective of this work is to maximize the sensitivity of a gold or silver nanohole arrays to detect the biomolecules liaisons close to the metal surface by localized surface plasmon resonance (LSPR) in transmission spectroscopy. A portable and effective biosensor to quantify analytes could be built based on this work, without a tagging step. To achieve the objective of evaluating numerous configurations for maximal sensitivity, the time and cost of the usual nanostructures fabrication methods would have limited the number of nanohole arrays in metal surface that could have been studied in this project. This fact motivated another objective of this project, the development of a fast and low cost fabrication method for nanohole arrays using nanospheres lithography (NSL) followed by reactive ions etching (RIE). The plasmon sensitivity and wavelength excitation are influenced by the nanohole arrays characteristics. In the work presented here, the chemical composition of the metal surface, the diameter and the periodicity of the nanohole arrays are shown to the influence the LSPR bands. The transmission maximum and minimum position of some LSPR bands are sensitive to refractive index change, which can be exploited in a biosensor format to detect biomolecules. The optimization of these nanohole arrays characteristics allows the maximization of this sensitivity to build a biosensor. The best index refraction sensitive results were with silver surfaces, with nanohole diameters smaller than 200 nm for a periodicity of 450 nm and the nanoholes with a periodicity of 650 nm show a potential for an increased sensitivity.

The loss of central vision subsequent to macular disease is often extremely debilitating. People with central field loss (CFL) must use other peripheral areas of the retina in order to see; areas with inferior resolution capacity, which are also affected by off-axis optical errors. The overall aim of the work encompassed by this thesis was to identify and evaluate methods of improving vision for people with CFL; with focus on the effects of off-axis optical correction and stimulus motion on resolution acuity and contrast sensitivity. Off-axis optical errors were measured using a commercially-available COAS-HD VR open-view aberrometer. We used adaptive psychophysical methods to evaluate grating resolution acuity and contrast sensitivity in the peripheral visual field; drifting gratings were employed to   measure the effect of motion on these two measures of visual performance. The effect of sphero-cylindrical correction and stimulus motion on visual performance in healthy eyes and in subjects with CFL was also studied; in addition, the effect of adaptive optics aberration correction was examined in one subject with CFL. The COAS-HD aberrometer provided rapid and reliable measurements of off-axis refractive errors. Correction of these errors gave improvements in low-contrast resolution acuity in subjects with higher amounts of oblique astigmatism. Optical correction also improved high-contrast resolution acuity in most subjects with CFL, but not for healthy subjects. Adaptive optics correction improved both high and low contrast resolution acuity in the preferred retinal locus of a subject with CFL. The effect of stimulus motion depended on spatial frequency; motion of 7.5 Hz improved contrast sensitivity for stimuli of low spatial frequency in healthy and CFL subjects. Motion of 15 Hz had little effect on contrast sensitivity for low spatial frequency but resulted in reduced contrast sensitivity for higher spatial frequencies in healthy subjects. Finally, high-contrast resolution acuity was relatively insensitive to stimulus motion in the periphery. This thesis has served to broaden the knowledge regarding peripheral optical errors, stimulus motion and their effects on visual function, both in healthy subjects and in people with CFL. Overall it has shown that correction of off-axis refractive errors is important for optimizing peripheral vision in subjects with CFL; the use of an open-view aberrometer simplifies the determination of these errors. In addition, moderate stimulus motion can have a beneficial effect on contrast sensitivity for objects of predominantly low spatial frequency.

O objetivo deste trabalho foi desenvolver biosensores de membranas baseados na técnica de Ressonância Plasmônica de Superfície (SPR) e aplicá-los no estudo da interação do citocromo c (cit c) com modelos de membranas. SPR é uma técnica ótica, que através de medidas de variações de índice de refração (n) próximas a uma interface mensura com alta sensibilidade a adsorção ou ligação de moléculas. Inicialmente desenvolvemos um sistema de gradiente de fluxo acoplado ao SPR, denominado FIG-SPR, e demonstramos a determinação automatizada da variação de n em função da concentração (dn/dC) de diferentes compostos e biopolímeros. O desenvolvimento dos biosensores de membranas iniciou-se com o estudo dos fatores que afetam a formação de uma membrana de bicamada híbrida (HBM). HBMs são compostas de uma monocamada de alcanotiol adsorvida sobre o ouro, e sobre esta uma camada fosfolipídica. A formação da HBM depende da fusão de vesículas em superfícies hidrofóbicas e que não é bem compreendido no nível molecular. Nossos estudos mostraram que na presença de cálcio e espermina a formação da HBM é favorecida, de tal forma que a monocamada de fosfolipídio alcança valores de espessura próximos àqueles previstos, cerca de 20 Å\'. Além disso, mostramos que em soluções de baixa força iônica a camada lipídica não é homogênea. Demonstramos também que a presença de cálcio na concentração 150 mM diminui o tempo de formação da monocamada lipídica cerca de 14 vezes quando comparado ao tempo indicado na literatura. A homogeneidade da HBM e a carga superficial da mesma foram verificadas com a adsorção e a dissociação de cit c e de albumina bovina (BSA). Utilizando HBMs de composição lipídica variada demonstramos a adsorção e a dissociação de cit c induzida por cálcio em HBMs mistas, incluindo um modelo mimético da membrana mitocondrial interna (IMM) constituído de fosfatidilcolina, fosfatidiletanolamina e cardiolipina (PC/PE/CL) na proporção (4,5:3,5:2,0). Demonstramos que a adsorção de cit c nativo segue um perfil cooperativo e padrões esperados de variação de afinidade e cooperatividade em pHs 6,8, 7,4 e 8,0. Um modelo matemático foi desenvolvido para tratar as curvas de ligação de cit c, que é uma adaptação do modelo de Hill para adsorção de proteínas em superfícies. Os resultados de SPR juntamente com dados obtidos por Microscopia de Força Atômica (AFM) sugerem que a ligação cooperativa de cit c com HBM ocorre devido à reorganização das moléculas de CL e formação de domínios fosfolipídicos. O tratamento dos resultados cinéticos da dissociação de cit c por cálcio indica a existência de duas constantes de velocidade de dissociação (kd), sendo a primeira constante (kd1) relacionada à perda das interações eletrostáticas entre a proteína e a HBM, e a segunda (kd2) à perda das interações hidrofóbicas. Além disso, a dissociação do cit c do modelo estudado requer uma concentração mínima de cálcio de 30 µM para se tornar significativa. O estudo da interação entre moléculas de cit c foto-oxidadas (citc405) e a HBM de PC/PE/CL sugerem que ela ocorre com menor afinidade, nos três pHs estudados, se comparados aos resultados com cit c nativo. Além disso, nossos resultados sugerem que o citc405 não é facilmente dissociado por cálcio devido à perda da cooperatividade na interação. Possíveis implicações em eventos celulares destas descobertas, como a liberação do cit c da IMM e a iniciação da apoptose, são discutidas / The aim of this work was to develop membrane biosensors based on Surface Plasmon Resonance (SPR) and to apply them to study the interactions between cytochrome c (cyt c) and model membranes. SPR is an optical technique that provides high-sensitivity measurements of refractive index (n), allowing the characterization of the adsorption and desorption of molecules near interfaces. Initially we developed a flow gradient system connected to SPR, which was called FIG-SPR, and demonstrated the automated determination of the concentration gradient of refractive index (dn/dC) of different materials and biopolymers. The development of the membrane biosensors was initiated by studying the factors that affect the formation of a hybrid bilayer membrane (HBM). HBMs are composed of two monolayers: an alcanethiol monolayer adsorbed on gold over which is adsorbed a layer of phospholipids. The formation of an HBM depends on the fusion of phospholipid vesicles on hydrophobic surfaces, a process that is not well understood at the molecular level. Our results showed that in the presence of calcium and spermine the complete formation of an HBM is facilitated, i.e., the phospholipid monolayer reaches the expected thickness of about 20Å\'. However, in low ionic strength solutions the lipid layer that is formed is not homogeneous. We have also demonstrated that in the presence of 150 mM of calcium the time necessary for the formation of the lipid monolayer is reduced 14 times when compared to the times suggested in the literature. The homogeneity of the HBM and its superficial charge were verified with the adsorption and desorption of cyt c and bovine serum albumine (BSA). The adsorption and desorption of cyt c in different HBMs were studied including a model of the internal mitochondrial membrane (IMM), which is made of phosphatidylcholine, phosphatidylethanolamine and cardiolipin (PC/PE/CL) in the ratio (4,5: 3,5: 2,0). We demonstrated that the adsorption of native cyt c follows a cooperative profile showing expected changes in affinity and cooperativity in different solution pHs of 6,8, 7,4 and 8,0. A mathematical model, which is an adaptation of the Hill model for adsorption of proteins in surfaces, was developed to treat the binding curves of cyt c. The results of SPR together with those obtained by Atomic Force Microscopy (AFM) suggested that the cooperative binding of cyt c in HBMs occurs due to the reorganization of CL molecules and formation of phospholipid domains. The kinetic results of the dissociation of cyt c induced by calcium indicates the existence of two velocity constants (kd), being the larger (kd1) related to the dissociation of cyt c interacting electrostatically with the HBM, and the smaller (kd2) related to the dissociation of cyt c interacting hydrophobically with the HBM. Moreover, the dissociation of cyt c from the HBM requires a minimum calcium concentration of 30 µM. The study of the interaction between photo-oxidized cyt c molecules (cytc405) and the PC/PE/CL HBM suggests that it occurs with smaller affinity when compared with the results obtained with the native cyt c. Moreover, cytc405 is not easily dissociated by calcium due to the loss of the interaction cooperativity with the HBM. Possible implications of these discoveries in cellular events, such as the release of cyt c from the IMM and the initiation of apoptosis, are discussed

La réalisation de fonctions de filtrage complexes nécessite une parfaite maîtrise du processus de dépôt ainsi qu’un contrôle précis et en temps réel de l’épaisseur optique des couches déposées. Au cours de ma thèse, consacrée au développement de nouvelles modalités de contrôle optique in situ, je me suis particulièrement intéressé à deux sujets différents, à savoir : - D’une part, la détermination de la dépendance spectrale des constantes optiques (indice de réfraction et coefficient d’extinction) de matériaux diélectriques. Un moyen possible pour effectuer cette détermination consiste à utiliser un système de contrôle optique large bande afin d’enregistrer les spectres de transmission de l’empilement au fur et à mesure de sa formation. En effet, l’évolution temporelle, à chaque longueur d’onde, de ces spectres de transmission contient des informations quantitatives liées aux constantes optiques que nous souhaitons déterminer. - D’autre part, la mesure en temps réel du coefficient de réflexion (r) d’un empilement, en amplitude et en phase, lors de son dépôt. En effet, les méthodes de contrôles optiques en intensité présentent des limitations que la connaissance de l’information de phase devrait permettre de contourner. Cette mesure est réalisée par interférométrie holographique digitale à faible cohérence sur un substrat éclairé par sa face arrière et dont la face avant est équipée d’un masque annulaire. Ceci donne accès aux information de phase et d’amplitude recherchées tout en s’affranchissant des vibrations générées par le fonctionnement de la machine de dépôt ainsi que du mouvement de rotation à 120 tours par minute qu’effectue le porte-substrat. / The realization of complex filtering functions requires a perfect mastering of the deposition process as well as an accurate real time monitoring of the optical thickness of the deposited layers. During my PhD thesis, devoted to the development of new methods of in situ optical monitoring, I was particularly interested in two different subjects, namely:- On the one hand, the determination of the spectral dependence of optical constants (refractive index and extinction coefficient) of dielectric materials. A possible way to achieve this determination consist in using a broadband optical monitoring system in order to record the transmission spectra, in real time, of the stack during its formation. Indeed, the temporal evolution, at each wavelength, of these transmission spectra provide quantitative information related to the optical constants that we wish to determine.- On the other hand, the real time measurement of the reflection coefficient (r) of a stack, in amplitude and phase, during its deposition. Indeed, the optical monitoring methods based on intensity proprieties present some limitations that the knowledge of phase information should overcome. This measurement is performed by low coherence digital holographic interferometry on a substrate illuminated by its rear face and whose front face is equipped with an annular mask. This gives access to desired phase and amplitude information while avoiding the parasitic influence of the substrate motions induced by the vibrations of the deposition machine, and the rotation of the substrate holder at 120 rounds per minute.

L’incorporation de particules inorganiques dans une matrice polymère confère de nouvelles propriétés au matériau ou améliore de manière significative les propriétés déjà existantes. Cependant, l’apparence visuelle perçue, telle que la transparence, peut être altérée par des phénomènes de diffusion de la lumière par les particules. Cette diffusion de la lumière est principalement conditionnée par la dimension des particules –ou agrégats de particules- et la différence d’indice de réfraction entre la matrice et les charges. Afin de traiter ces deux problèmes, l’objectif de nos travaux était de contrôler simultanément l’état de dispersion des nanoparticules inorganiques dans la matrice polymère et l’indice de réfraction des nanoparticules de façon à l’ajuster à celui de la matrice. Pour élaborer ce nouveau composite, nous avons synthétisé des nanoparticules hybrides cœur@écorce avec un cœur inorganique qui apporte les nouvelles propriétés et une écorce polymère d’épaisseur contrôlée, obtenue par polymérisation radicalaire contrôlée par voie nitroxyde amorcée à la surface des nanoparticules inorganiques. L’écorce polymère limite l’agrégation des particules et permet de modifier l’indice de réfraction moyen des nanoparticules cœur@écorce. En contrôlant l’épaisseur et la nature chimique de l’écorce polymère, nous cherchons à ajuster l’indice de réfraction des nanoparticules cœur@écorce à celui de la matrice. Les nanoparticules ont ensuite été dispersées dans une matrice de poly(méthacrylate de méthyle). Les propriétés optiques des composites ont été caractérisées par spectrogoniophotométrie, afin d’obtenir des informations sur l’intensité et la distribution angulaire de la lumière transmise par le composite. La transparence des nanocomposites a été fortement améliorée en ajustant l’indice de réfraction des nanoparticules cœur@écorce à celui de la matrice. / The incorporation of inorganic particles into a polymer matrix confers new properties to the material or enhances significantly existing properties. However, the perceived visual appearance, such as loss of transparency, might be modified by the scattering of light by the particles. This light scattering is mainly due to the particle –or aggregates of particles- dimensions and the refractive index difference between matrix and fillers. In order to address both issues, the objective of the present work was to control simultaneously the dispersion state of the inorganic nanoparticles into the polymeric matrix and the refractive index of the nanoparticles to match the one of the matrix. To achieve this new composite, we designed hybrid core@shell nanoparticles with an inorganic core that brings new properties and a polymer shell of controlled thickness, obtained by surface-initiated nitroxide mediated controlled radical polymerization. The polymer shell limits the aggregation of the particles and enables us to tune the average refractive index of the hybrid core@shell particle. By controlling the thickness and the chemical nature of the polymeric shell, we targeted to match the refractive index of the hybrid core@shell particle to the one of the polymeric matrix. The nanoparticles were further dispersed into a poly(methyl methacrylate) matrix. Optical properties of composites were characterized by spectrogoniophotometry which gave us informations about the intensity and the angular distribution of the transmitted light by the nanocomposites. The transparency of the nanocomposites was strongly enhanced for core@shell particles fulfilling the refractive index matching conditions.

Objetivo: Investigar as alterações biomecânicas da córnea de suínos induzidas pela confecção de lamelas pediculadas de diferentes espessuras pelo laser de femtossegundo. Métodos: Para a formação dos dois grupos, 12 olhos de porcos foram usados: lamelas pediculadas de 100 e de 300 micrômetros confeccionadas pelo laser de femtossegundo. Cada olho foi submetido aos seguintes exames, antes da criação das lamelas: topografia por rasterstereography, Ocular Response Analyzer (ORA), tomografia do segmento anterior por coerência óptica para a avaliação paquimétrica corneal e das lamelas criadas e sistema de velocidade de onda (SVO), que mede a velocidade de propagação de ondas acústicas entre dois transdutores posicionados na superfície corneal antes e imediatamente, após a feitura da lamela. O primerio passo foi desenhado para o estudo das diferenças em relação à histerese corneal, fator de resistência corneal, mudanças na curvatura e velocidade de propagação de onda acústica entre córneas com lamelas finas e espessas. Posteriormente, as lamelas foram amputadas, e as medidas do sistema de velocidade de onda foram repetidas. Resultados: A média de espessura das lamelas ± desviopadrão (DP) foi de 108,5±6,9 (8,5% da espessura total) e 307,8±11,5 m (22,9% da espessura total), para os grupos de lamelas finas e espessas, respectivamente (p< 0,001). Histerese corneal e o fator de resistência corneal não apresentaram diferença estatística, após a criação de lamelas finas (p = 0,81 e p = 0,62, respectivamente). Histerese corneal foi significantemente mais baixa, depois da confecção de lamelas mais espessas (8,0±1,0 para 5,1±1,5 mmHg para medidas pré e pós-operatórias, respectivamente, p = 0,003, diminuição de 36,25%) e fator de resistência corneal também mostrou significante diminuição nesse grupo, após o procedimento cirúrgico; valores médios pré e pós-operatórios de 8,2±1,6 e 4,1±2,5 mmHg respectivamente (p= 0,007), diminuição de 50%. A ceratometria média simulada apresentou maiores valores, após a confecção das lamelas mais espessas em relação ao pré-operatório (ceratometria pré e pós-operatória de 39,5±1 D e 45,9±1,2 D, respectivamente, p= 0,003). Para o grupo de lamelas finas, não houve diferença estatisticamente significante (ceratometria pré e pós-operatória de 40,6±0,6 D e 41,4±1,0 D, respectivamente, p=0,55). Em relação ao Sistema de Velocidade de Onda, após a criação das lamelas e sua amputação, houve diminuição da velocidade de propagação acústica, embora na maior parte das posições não fosse estatisticamente significante. Conclusão: Nas condições experimentais estabelecidas por este estudo, a criação de lamelas de maior espessura pareceu exercer efeito mais relevante sobre a biomecânica da córnea de suínos / Purpose: To study the impact of programmed flaps at two different thicknesses on the biomechanical properties of the swine corneas. Methods: Twelve pig eyes were enrolled in this study and were formed two groups: 100m and 300 m flaps performed with the femtosecond laser. Each eye had the following procedure before the flap creation: raster photograph topographic maps, Ocular Response Analyzer (ORA), Optical Coherence Tomography to measure the pachymetry and flap thickness and Surface Wave Velocity system which is a prototype system that measures sonic wave propagation time between two transducers positioned on the corneal surface before and after flap creation. This first step was designed to investigate the differences in respect to corneal hysteresis, corneal resistance factor, curvature change and ultrasonic wave propagation between the groups with thinner and thicker flaps. After this initial procedure, flap amputation was performed and new measurements with the surface wave velocity system were taken again. Results: Measured flap thicknesses averaged 108.5±6.9 (8.5% of the total cornea) and 307.8±11.5 m (22.9% of the total cornea) for thin and thick flap groups, respectively (p< 0.001). Hysteresis and corneal resistance factor did not change significantly after flap creation in the thin flap group (p = 0.81 and p = 0.62, respectively). With thicker flaps, both parameters decreased significantly from 8.0±1.0 to 5.1±1.5 mmHg (p=0.003, reduction of 36.25%) and from 8.2±1.6 to 4.1±2.5 mmHg, respectively (p = 0.007), reduction of 50%. Simulated keratometry values increased in the thick flap group (from 39.5±1 D to 45.9±1.2 D, p=0.003) after flap creation and not in the thin flap group (from 40.6±0.6D to 41.4±1.0D, p= 0.55). Regarding surface wave velocity analysis, the surgical procedures induced lower values in some positions although most of them did not present statistically different results. Conclusion: In this experimental model, thicker flaps seemed to have a greater effect on the biomechanics of the swinish cornea