The objective of this thesis is to develop a sequential algorithm to determine accurately and quickly, at which point in time a product is well mixed or reaches a steady state plateau, in terms of the Refractive Index (RI). An algorithm using sequential non-linear model fitting and prediction is proposed. A simulation study representing typical scenarios in a liquid manufacturing process in pharmaceutical industries was performed to evaluate the proposed algorithm. The data simulated included autocorrelated normal errors and used the Gompertz model. A set of 27 different combinations of the parameters of the Gompertz function were considered. The results from the simulation study suggest that the algorithm is insensitive to the functional form and achieves the goal consistently with least number of time points.

Les métamatériaux sont des matériaux artificiels qui possèdent de nouvelles propriétés optiques grâce à leur structuration à l’échelle nanométrique. Un des principaux axes de recherche dans le domaine des métamatériaux s’intéresse aux indices de réfraction négatifs qui permettent la réalisation de lentilles « parfaites » ainsi que d’autres applications excitantes. Dans cette thèse, nous étudions théoriquement les propriétés de métamatériaux optiques de type « fishnet », en particulier l’origine de leur indice de réfraction négatif, ainsi que d’autres problèmes théoriques associés. La thèse peut être divisée en quatre parties.Dans la première partie, nous étudions la diffusion de la lumière à l’interface entre l’air et un métamatériau fishnet semi-infini. A l’aide d’une méthode numérique vectorielle, nous calculons les coefficients de diffusion de l’interface et nous démontrons que le transport de l’énergie est dû à un seul mode de Bloch, le mode fondamental du fishnet. Puis, en s’appuyant sur les coefficients de diffusion de l’interface et sur l’indice effectif de ce mode de Bloch, nous proposons un nouvel algorithme d’extraction des paramètres effectifs du métamatériau. Notre approche met l’accent sur le rôle clé joué par le mode de Bloch fondamental et elle permet d’extraire des paramètres effectifs plus stables que ceux obtenus avec les méthodes classiques basées sur le calcul de la réflexion et la transmission d’une couche de métamatériau d’épaisseur finie. Dans la deuxième partie, nous dérivons grâce à l’orthogonalité des modes de Bloch des expressions analytiques pour les coefficients de diffusion à l’interface entre deux milieux périodiques de périodes légèrement différentes. Nous montrons que les expressions analytiques permettent d’obtenir des résultats très précis pour différentes géométries allant de guides d’onde périodiques diélectriques à des métamatériaux métalliques. Ces expressions analytiques constituent donc un outil utile pour la conception et l’ingénierie de structures photoniques périodiques.Le mode de Bloch fondamental est central pour expliquer le phénomène de réfraction négative dans les métamatériaux fishnet. Dans la troisième partie, nous avons développé un modèle semi-analytique pour la constante de propagation complexe du mode de Bloch fondamental du fishnet. Le modèle est basé sur une analyse fine de la propagation et de la diffusion de la lumière à l’intérieur de la structure. Le modèle montre que l’origine des valeurs négatives de l’indice de réfraction sur une large bande spectrale peut être essentiellement comprise comme le résultat d’une résonance plasmonique dans les canaux transverses métal-insolant-métal du fishnet. La résonance plasmonique exalte la réponse « magnétique » du fishnet et les pertes associées à cette résonance peuvent être compensées en incluant du gain dans les couches diélectriques. En outre, le modèle simplifie l’ingénierie des paramètres géométriques des métamatériaux fishnet. C’est la résonance plasmonique dans des structures de type métal-isolant-métal (MIM) qui induit l’indice de réfraction négatif dans les métamatériaux de type fishnet. Dans la dernière partie, nous étudions le comportement asymptotique de nanorésonateurs MIM lorsque leur taille est réduite sous la limite de diffraction. En particulier, nous montrons que le facteur de qualité augmente d’un ordre de grandeur quand le volume du résonateur passe de (λ/2n)3 à (λ/50)3. Une étude complète est réalisée avec un modèle Fabry-Perot semi-analytique. Le modèle reste précis sur toute la gamme de tailles étudiées, même dans le régime quasi-statique où des effets de retard ne sont pas attendus. Ce résultat important et contre-intuitif indique que les résonances plasmoniques localisées dans des nanoparticules peuvent être comprises de la même manière que les résonances délocalisées dans des nanofils métalliques, c’est-à-dire comme des problèmes d’antennes basés sur des effets de retard. / Optical metamaterials are artificial media that exhibit new properties from structuring on the nanometric scale. One of the main researches in metamaterials investigates materials with negative refractive index, which can allow the development of perfect lens and other exciting potential applications. In this thesis, we theoretically study the properties of negative-index optical fishnet metamaterials, especially the origin of their negative-valued refractive index, and also associated theoretical problems. The thesis can be divided into 4 parts. In the first part we study the light scattering at an interface between air and a semi-infinite fishnet metamaterial. With a fully-vectorial numerical method, we calculate the scattering coefficients of the interface and find that the energy transport inside the fishnet is due to a single Bloch mode, the fundamental one. Based on the single-interface scattering coefficients and the effective index of this Bloch mode we propose a new algorithm for retrieving effective optical parameters of the metamaterial. The approach emphasizes the key role played by the fundamental Bloch mode and provides retrieved parameters that are more accurate or stable than those obtained by classical methods based only on light reflection and transmission through finite-thickness metamaterial slabs. Due to the importance of the fundamental Bloch mode in the light transport in metamaterials, in the second part, based on the Bloch mode orthogonality we derive closed-form expressions for the scattering coefficients at an interface between two periodic media with slightly different geometrical parameters, which is a computationally demanding electromagnetic problem. We show that the analytical expressions are very accurate for various geometries, including dielectric waveguides and metallic metamaterials. Thus they can be useful for designing and engineering stacks of periodic structures. As shown in the first part, the fundamental Bloch mode is central to explain the negative refraction phenomenon in fishnet metamaterials. In the third part, we derive an accurate semi-analytical model for the complex propagation constant of the fishnet fundamental Bloch mode. This is achieved by analyzing light propagation and scattering inside the fishnet. The model shows that the origin of broad-band negative index of fishnets can be mainly understood as a plasmon resonance in the transversal metal-insulator-metal (MIM) channels. The plasmon resonance enhances the ‘magnetic’ response of fishnet and the losses associated to this resonance can be compensated by including gain in the dielectric layers of the fishnet. Furthermore, the model allows an easy and precise geometrical tailoring of fishnet metamaterials. As shown in the third part, it is the plasmon resonance in metal-insulator-metal (MIM) structures that induces the negative index of fishnet metamaterials. In the last part, we study the asymptotic behavior of 3D MIM nanoresonators, as the resonator size is shrunk below the diffraction limit. In particular we show that the quality factor increases from 10 to 100 when the resonator volume is scaled down from (λ/2n)3 to (λ/50)3. We provide a comprehensive study with a semi-analytical Fabry-Perot model. The model remains accurate over the whole size scale even in the quasi-static regime for which retardation effects are not expected. This important and counterintuitive result indicates that both localized plasmon resonances in nanoparticles and delocalized resonance in elongated plasmonic nanowires can be possibly understood as a wave-retardation based antenna problem.

Neste trabalho investigamos as duas contribuições mais importantes ao índice de refração não-linear, n2, em sólidos dopados: o efeito de Lente Térmica (LT) e o efeito de Lente de População (LP). Nós estudamos cristais fluoretos dopados com Cr+3 e vidros fluoretos dopados com Nd+3. As medidas de n2 foram feitas com a técnica de Z-scan resolvida no tempo, que é uma técnica simples mas muito sensível. Também realizamos medidas usando a técnica de Lente Térmica de modo descasado onde usou-se dois feixes de laser (um de excitação e outro de prova). Nós mostramos que pode-se separar temporalmente as contribuições a n2 devido a LT e LP, através da variação da freqüência do chopper / In this work we investigated the two more important contributions to the index of no-lineal refraction, n2, in ion doped solid: the effects of Thermal Lens (LT) and Population Lens (LP). We studied Cr+3 doped fluoride crystals and Nd+3 doped fluoride glasses. The n2 measurements were made with the time-resolved Z-scan technique that is a simple but very sensitive technique. We also performed time¬ resolved Mode-mismatched Thermal Lens measurements, where two laser beams were used (one excitation beam and another probe beam). We showed that it is possible to temporally separate the contributions of LT and LP for n2, through the variation of the chopper frequency

Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2019-02-12T15:41:23Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Cristiano Santos Lopes.pdf: 29539894 bytes, checksum: f1c58591825997b77f26dff47e244408 (MD5) / Made available in DSpace on 2019-02-12T15:41:23Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Cristiano Santos Lopes.pdf: 29539894 bytes, checksum: f1c58591825997b77f26dff47e244408 (MD5) Previous issue date: 2018-10-24 / Os nanofluidos plasmônicos tem sido empregados em diversas aplicações nos mais variados campos, como por exemplo, fluidos de arrefecimento, coletores solares e agentes teranósticos. Dentro desta área, o entendimento da difusividade térmica é extremamente importante e as diversas técnicas que existem para a sua determinação podemoferecerresultados divergentes.O usodetécnicasfototérmicasapresentamuma grande sensibilidade para medir vários parâmetros dos nanofluidos. Neste trabalho, nanopartículasesféricasdepratacomtamanhomédiode32nmforamsintetizadaspelo métododeTurkevicherevestidascomosurfactantePolivinilpirrolidona(PVP).Medidas de índice de refração não linear e difusividade térmica de nanofluidos de prata foram realizadas por meio das técnicas de Z-Scan e Lente Térmica. Conseguimos obter uma relação entre o índice de refração com a frequência, e também da difusividade térmica com a concentração de nanopartículas. Estes resultados foram corroborados uma vez que a técnica utilizada neste trabalho foi replicada para a análise da difusidade térmica da água, cujo valor adquirido está de acordo com o valor já conhecido na literatura. / Plasmonic nanofluids have been used in several applications in many different fields, such as cooling fluids, solar collectors and theranostic agents. Related to this area, the understanding of thermal diusivity is extremely important and the various techniques that exist for its determination can offer divergent results. The use of photothermal techniques shows presents a great sensitivity to measure various parameters of nanoflu- ids. In this work, silver spherical nanoparticles with a average diameter of 32 nm were synthesized by the Turkevich method and coated with the surfactant Polyvinylpyrroli- done (PVP). Nonlinear refractive index and thermal diffusivity measurements of silver nanofluids were performed using the Z-Scan and Thermal Lens techniques.We obtained a relation that describe the dependence of the refractive index index of refraction with the frequency and also for of the thermal diffusivity with the nanoparticles concentration. These results were corroborated since the technique used in this work was replicated for the water thermal diffusion analysis, whose obtained value is in agreement with the expected literature value.

>Magister Scientiae - MSc / Recent research shows that the study of optical properties of organic material natural dyes has gained much consideration. The specific functional groups in several natural dyes remain essential for the large nonlinear absorption expressed in terms of nonlinear optical susceptibilities or other mechanism of absorption such as two photon absorption (TPA), reverse saturable absorption (RSA) or intensitydependent refractive index characteristic. In this thesis we highlight the optical limiting responses of selected natural dyes as nonlinear response in the femtosecond regime. This technique refers to the decrease of the transmittance of the material with the increased incident light intensity.Three dyes derived from beetroot, flame flower and mimosa flower dyes were investigated. The results showed a limiting behaviour around 795 mW for the beetroot and the flame dye while there is total transmission in the flame dye sample. The performance of the nonlinearity i.e. the optical limiting is related to the existence of alternating single and double bonds(i.e. C-C and C=C bonds) in the molecules that provides the material with the electron delocalization, but also it is related to the light intensity.Beside nonlinearity study, crystallographic investigation was carried out for more possible applicability of the selected dyes and this concerned only the mimosa and flame flower dye thin film samples since the beetroot thin film was very sensitive to strong irradiation (i.e. immediately destroyed when exposed to light with high intensity). For more stability,dye solutions were encapsulated in gels for further measurements.

Orientador: Keizo Yukimitu / Banca: Antonio Medina Neto / Banca: Elso Drigo Filho / Resumo: Neste trabalho foram estudadas as propriedades ópticas de vidros teluretos do sistema (20-x)Li2O-80TeO2-xTiO2 com x = 0, 5, 10 e 15 mol%. Foram preparadas amostras para cada uma das composições através do convencional método de "meltquenting". Medimos, para cada amostra, o espectro de infravermelho e o espectro na faixa do ultravioleta-visível. Também obtemos os valores de índice de refração de cada amostra para diversos comprimentos de onda na faixa do visível. Para tanto, utilizamos um interferômetro de Michelson-Morley modificado. Medidas de densidade foram feitas utilizando-se o convencional método de Arquimedes. Por fim, foram feitas medidas do coeficiente térmico do caminho óptico através da interferometria. A análise estrutural foi feita através do espectro de infravermelho. Pode-se observar a tendência à formação de pirâmides trigonais em substituição às bipirâmides (encontradas no TeO2 cristalino) quando aumentamos a porcentagem de óxido de lítio. Uma análise qualitativa da absorção na faixa de interesse em comunicações ópticas (~1500 nm) foi feita através do espectro de infravermelho próximo, mostrando que nesta faixa temos a predominância do espalhamento Rayleigh, com o coeficiente de absorção proporcional a λ-4. Usando os dados da espectroscopia na faixa ultravioleta-visível foi possível observar a mudança das freqüências de corte para cada composição e ainda calcular a energia de gap e a energia de cauda de Urbach. Através do modelo clássico de osciladores harmônicos forçados de Wemple, os resultados de índice de refração foram interpretados. Buscou-se ainda relacionar as mudanças observadas para os valores medidos para cada composição com possíveis mudanças estruturais. Concluímos, usando as considerações de Wemple, que o aumento... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this work had been studied tellurite glasses's the optic properties of the system (20-x) Li2O-80TeO2-xTiO2 with x = 0, 5, 10 and 15 mol%. Samples for each one of the compositions through the conventional method of melt-quenting had been prepared. We measure, for each sample, the infra-red ray specter and the specter in the band of the ultraviolet-visible one. Also we get the values of refractive index of each sample for diverse wave lengths in the visible band. For in such a way, we use a modified interferometer of Michelson-Morley. Measures of density had been made using the conventional method of Archimedes. Finally, they had been made measured of the thermal coefficient of the optic way through the interferometry. The structural analysis was made through the infra-red ray specter. The trend to the formation of trigonais pyramids in substitution to the bipyramids can be observed (found in the crystalline TeO2) when increases the lithium oxide percentage. A qualitative analysis of the absorption in the band of interest in optic communications (~1500 nm) was made through the infra-red ray specter, showing that in this band we have the predominance of the Rayleigh scattering, with the coefficient of absorption proportional to λ-4. Using the data of the spectroscopy in the ultraviolet-visible band to each composition was possible to observe the change of the cut-off frequencies and still to calculate the energy of gap and the energy of Urbach. Through the classic model of forced harmonic oscillators of Wemple, the results of refractive index had been interpreted. We still searched to relate the changes observed for the values measured for each composition with possible structural changes. We conclude, using the considerations of Wemple, that the increase for the values of... (Complete abstract click electronic access below) / Mestre

Orientador: Silvana Artioli Schellini / Banca: Milton Ruiz Alves / Banca: Carlos Eduardo Leite Arieta / Banca: Maria Rosa Bet de Moraes Silva / Banca: Flávio Eduardo Hirai / Resumo: Determinar o perfil de distribuição dos erros refracionais em uma amostra populacional do centro-oeste do Estado de São Paulo, suas possíveis associações com características individuais e a influência sobre a acuidade visual. foi desenvolvido estudo de secção transversal com amostragem residencial probabilística e sistemática em nove municípios no sul do centro-oeste paulista, como parte do Projeto de Prevenção à Cegueira na Comunidade. Os indivíduos acima de um ano de idade foram submetidos a entrevista e exame oftalmológico completo. A acuidade visual em sistema Snellen e posterior conversão para logMAR foi obtida antes e após exame de refração e categorizada em quatro segmentos. Os erros refracionais foram classificados em miopia (EE ≤ - 0,50D), hipermetropia (EE ≥ 0,50D), astigmatismo (DC ≤ -0,50D) e anisometropia (diferença de EE ≥ 1,00D entre os olhos). Foi realizada a análise descritiva dos dados de prevalência na amostra, análise univariada e multivariada com modelos de regressão logística múltipla para determinar possíveis associações de prevalências. 3012 residências foram entrevistadas e 7654 indivíduos foram incluídos no estudo, sendo 62,7% mulheres, 92,1% considerados com pele branca e média para a idade de 36,89 anos (extremos de 1 a 96 anos). A miopia foi mais prevalente na terceira e quarta décadas de vida, atingindo 43,31% sem diferenças significativas entre sexos, enquanto a hipermetropia foi mais prevalente entre mulheres acima de 60 anos de idade, com uma frequência de 65,6% nesta faixa etária. O astigmatismo apresentou uma frequência progressivamente maior com a idade e semelhante entre os sexos. O eixo do astigmatismo também apresentou variação conforme a idade, com o eixo horizontal mais frequente em jovens e o vertical nos idosos. A prevalência da anisometropia apresentou variação com a idade sendo mais frequente nos extremos de idade, ... / Abstract: Establish the refractive errors distribution in a population sample of the Central São Paulo State, correlations with personal features and its influence in visual acuity. A cross sectional survey was developed with randomized and systematic residential sampling in nine cities of middle region of São Paulo St/Brazil as part of Blindness Prevention Project at Community. Inhabitants above one year old were submitted to an interview and full ophthalmic exam. Visual acuity in logMAR system was determined before and after refraction exam and classified in four categories. Refractive errors were classified in myopia (SE ≤ -0,50D), hyperopia (SE ≥ 0,50D), astigmatism (CD ≤ -0,50D) and anisometrophy (SE difference between eyes ≥ 1,00D). Prevalence data sample were submitted to descriptive analysis, univariate and multivariate logistic regression models to find eventual prevalence associations. 7654 participants were included in this survey, in which 62,7% were women, 92,1% with white skin and middle age of 36,89 years old (1 to 96 years). Myopia was more prevalent at 3rd and 4th decades, achieving 43,31% without significant differences between genders, while hyperopia was more prevalent in women above 60 years old, with 65,5%. Astigmatism prevalence increased by age with no differences between genders. Astigmatism axis changed by age too, when horizontal axis were more frequently observed in youngers and vertical in olders. Anisometrophy prevalence changed by age, more frequent at extremes, achieving 32,66% after 70 years old. No significant differences were found in ethnic categories. Visual acuity increasing prevalence by visual impairment corrected with spectacles (UREN) was 6,53% in the total sample, mainly after 60 years old and high refrective errors. Prevalence associations were found between age and all ametrophic categories, sex and hyperopia and between UREN with myopia, hyperopia and ... / Doutor

Orientador: Keizo Yukimitu / Resumo: Com a crescente populacional a demanda pelos polímeros aumentou significativamente, levando assim a pesquisas cientificas visando adequar materiais as nossas necessidades. O PMMA ou acrílico é muito utilizado em nosso cotidiano, sendo um material muito versátil com aplicabilidade em diversos setores. O intuito deste trabalho foi realizar a produção de um filme de acrílico [Poli(metil-metacrilato)] isento de bolhas e transparente, a qual tivesse uma repetibilidade. Foi realizada a dopagem com terras raras, sendo o Óxido de Érbio e o Óxido de Itérbio escolhidos como dopantes em diferentes concentrações de gramas/mol por gramas/mol (0 % referência, 5 %, 10%, 15% e 20 %). Logo após foi feita a caracterização dos filmes, determinando o índice de refração das amostras utilizando o Interferomêtro de Michelson com laser He-Ne (vermelho) de comprimento de onda de 632,8 nm. Notamos que o índice de refração do PMMA na amostra de referência aumentou gradativamente com as dopagens, o laser diodo na cor verde de comprimento de onda de 532 nm também foi utilizado e os resultados demostraram comportamentos similares. A Espectroscopia no Infravermelho por Transformada de Fourier (FTIR) foi realizada, observando o aparecimento de picos característicos dos elementos dopantes nas amostras e que esses picos aumentavam conforme a concentração de dopagem aumentava. A Difração de Raios-X (DRX) nos mostrou a incidência picos de cristalinidade referentes aos elementos dopantes em contraste com o espec... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: With the growing population demand for polymers has increased significantly, leading to scientific research aimed at adapting materials to our needs. PMMA or acrylic is widely used in our daily lives, being a very versatile material with applicability in several sectors. The purpose of this work was to produce an acrylic film [Poly (methyl-methacrylate)] which had a repeatability. Rare earth doping was performed, with Erbium Oxide and Ytterbium Oxide chosen as dopants in different concentrations of grams / mole per gram / mole (0% reference, 5%, 10%, 15% and 20%). After the characterization of the films, determining the refractive index of the samples using the Michelson Interferometer with He-Ne (red) laser of wavelength of 632.8 nm, we noticed that the refractive index of the PMMA in the sample of reference period increased gradually with doping, the green diode laser wavelength of 532 nm was also used and the results demonstrated similar behaviors. Fourier Transform Infrared Spectroscopy (FTIR) was performed, observing the appearance of characteristic peaks of the dopant elements in the samples and that these peaks increased as the doping concentration increased. X-ray Diffraction (XRD) showed us the incidence of crystallinity peaks relative to the dopant elements in contrast to the normal PMMA spectrum demonstrating the insertion of the rare earths into the matrix structure. / Mestre

A great deal of attention has been paid to brown carbon aerosol in the troposphere because it can both scatter and absorb solar radiation, thus affecting the Earth’s climate. However, knowledge of the optical and chemical properties of brown carbon aerosol is still limited. In this thesis, we have investigated different aspects of the optical and physicochemical properties of various brown carbon aerosol samples of potential atmospheric importance. First, reactions involving the di-carbonyl species methylglyoxal (MG) have been previously suggested as an important pathway for the production of secondary organic aerosol (SOA) in the atmosphere. Reaction in an aqueous inorganic salt solution, such as ammonium sulfate (AS), leads to the formation of light-absorbing brown carbon (BrC) product. In this thesis work, we employed a variety of experimental approaches to investigate the optical and physicochemical properties of BrC aerosol generated from this AS-MG reaction (BrC (AS/MG)). Optical properties of the dried BrC (AS/MG) aerosol particles were studied by Fourier transform infrared (FTIR) extinction spectroscopy in the mid-infrared region, cavity ring-down spectroscopy (CRDS) at 403 nm in the visible, and by measuring the light scattering phase function and polarization profiles at two different visible wavelengths, 532 and 402 nm. In addition, we used UV−vis spectroscopy to measure the mass absorption coefficient (MAC) of the solution-phase reaction products. The different optical properties were measured as a function of reaction time for a period of up to 22 days. The UV-vis absorption spectra showed a clear increase in measured MAC in the visible and near UV as the solution aged. However, analysis of the light scattering data showed no significant differences between AS and BrC aerosol in the derived refractive indices at either 532 or 402 nm, even for the longest reaction times. The FTIR extinction spectra was modeled in a Mie theory simulation to derive the complex refractive index in the mid-IR range (7000-800 cm−1); the results showed no significant changes in either the real or the imaginary parts of the refractive indices for BrC (AS/MG) aerosol particles when compared to unreacted AS aerosol. From the CRDS extinction data, the optical constants for BrC (AS/MG) particles at 403 nm were also determined through a Mie theory based analysis. The retrieved real index of refraction at 403 nm is n = 1.551 ± 0.005, with an imaginary index value of k = 0.000 ± 0.002; these values do not appear to change significantly with aging time over the course of 22 days and are not markedly different from the AS aerosol values. The small imaginary index value suggests that BrC (AS/MG) aerosol formed from this pathway may not significantly contribute to warming. In addition, CRDS measurements of the BrC (AS/MG) aerosol extinction at 403 nm as a function of particle size show a significant deviation from Mie theory simulations for particles with diameters of ≳500 nm, probably as a result of non-spherical particle shape effects. We also employed atomic force microscopy (AFM)-based IR spectroscopy to investigate the morphology and chemical composition of single SOA particles. AFM analysis of the particle morphology shows that a significant fraction of BrC (AS/MG) particles with diameters of ≳500 nm are non-spherical in shape, consistent with our observed breakdown in the applicability of Mie theory for larger particles. In addition to these measurements, we have characterized additional physicochemical properties of the BrC (AS/MG) aerosol particles including hygroscopic growth using a tandem-differential mobility analyzer. Compared to AS, BrC aerosol particles are found to have lower deliquescence relative humidity (DRH), efflorescence relative humidity (ERH), and hygroscopic growth at the same relative humidity values. Second, we investigated the optical properties of the water soluble products of limonene BrC generated from ozonolysis of d-limonene with further aging by AS. Optical constants for the dried limonene BrC aerosol product were measured at 403 nm by CRDS over the course of 9 days of aging. While the fresh limonene BrC aerosol showed a significant non-zero absorption index, the aged samples showed absorption index values consistent with zero. This result was somewhat unexpected because UV-vis absorption spectra of the bulk reaction solution showed a continued increase in absorption as the solution aged. One possible explanation for this result is that there could be an increase in the fraction of volatile chromophores as the solution ages, that are then removed in the aerosol drying process. Third, we investigated optical properties and chemical compositions of several humic substance (HS) reference samples including humic acid (HA) and fulvic acid (FA) standards by CRDS, UV-vis spectroscopy, elemental analysis, and 13C NMR spectroscopy. Measurements of the optical properties of HS is important in atmospheric science, because it is thought that HS samples have similar optical properties to organic materials, such as HUmic-Like Substances (HULIS), that exist in clouds, fogs, rainwater, and atmospheric aerosol. The humic acid aerosol samples generally showed higher absorption index values than the fulvic acid aerosol samples. We also found a correlation between the absorption index and chemical composition, with the value for k generally increasing with both increasing carbon-to-oxygen atomic ratio and sample aromaticity. In addition, we compared our measured optical constants for the HS aerosol samples with results from previous studies of field collected HULIS. The absorption index values for the fulvic acid aerosol samples give a better match than the humic acid samples when compared to the results from the field collected samples. Overall, these studies provide new details of the optical and physicochemical properties of a class of brown carbon organic aerosol which may have important implications for atmospheric chemistry and climate.

Purpose: To improve the predictability, accuracy and stability of laser in-situ keratomileusis (LASIK), by evaluating the clinical, procedural and tissue response factors that affect refractive outcomes. Methods: Myopic LASIK surgeries (n=5,978) were carried out using the Technolas planoscan and Nidek EC-5000 excimer lasers. Clinical variables associated with a refractive outcome of within ??0.50 D of the target were identified using regression analysis. Possible procedural variations such as the timing of the procedure and accuracy of both the chosen keratome and excimer laser were evaluated. The predictability and accuracy of the ablation was assessed by measuring changes in corneal thickness during and after the procedure. Factors influencing the stability of refractive outcome were assessed. Results: Clinical factors associated with a refractive outcome of within ??0.50 D of the target included; corrections less than 5.00 DS (OR 0.21x, 95% CI 0.11-0.40x compared with corrections over -5.00 DS[referent]), patients younger than 40 years (patients over 50 OR 8.27x, 95% CI 3.41-20.03x, patients 40 to 50 years OR 1.93x, 95% CI 0.96-3.90x, compared with patients under 40[referent]) and average pre-operative curvatures between 43.50 and 45.50D (OR 0.39x, 95% CI 0.18-0.83 compared with curvatures of less than 43.50D [referent]). Refractive stability was improved using optic zone sizes between 5.5-6.0 mm, reduced myopic corrections, flatter pre-operative corneal curvatures and thicker corneal flaps (R??=25%, p&lt0.001). Procedural factors associated with poorer outcomes included: thinner measured flap thickness, deeper ablations and the use of the automated corneal shaper (ACS) microkeratome with a novice surgical team (R??=34%, p &lt 0.001). Delaying the ablation from 20 to 90 seconds (s) after flap lift was associated with a more stable refractive outcome at three months (p=0.017). In the 90 s following flap lift, the cornea thinned by 5??3%. The ablation rate per scan varied between procedures, however, the effect on refractive outcome was small (r=0.15, p=0.267). Changes in central corneal thickness indicated refractive stability (p=0.039). Conclusions: Applying the optimal clinical and procedural factors as described afforded a refractive outcome in a further 8% of cases, resulting in 94% to 96% of cases within ??0.50 DS of target. Refractive predictability was limited due to the inability of the keratome to produce a consistent corneal flap thickness and unexpected changes in corneal thickness. The accuracy of refractive outcome will decrease with larger ablations. The degree of refractive inaccuracy with high refractive corrections (&gt -10.00 D) can be over 1.00 D.