A nutrição nitrogenada, apesar de intensamente estudada, continua sendo um desafio aos produtores, especialmente em função da variabilidade encontrada no desenvolvimento da cultura nas áreas de produção comercial, muitas vezes em curtas distâncias. Recentemente esta variabilidade vem sendo associada ao uso de sensores opticos que detectam a refletância do dossel da cultura como forma de estimar a nutrição nitrogenada das plantas, podendo estes serem associados à aplicação em taxa variável em tempo real do fertilizante nitrogenado. Em cana-de-açúcar esses estudos ainda são escassos, e sendo uma cultura voltada para a produção de biomassa para geração de energia, tais sensores podem contribuir para otimizar o saldo positivo em produção de energia e baixar as emissão de carbono no sistema. Este trabalho apresenta o processo e mostra os resultados obtidos utilizando um sensor de nitrogênio e biomassa (N-SensorTM ALS, Yara International ASA) com o objetivo de indicar exigência na aplicação de nitrogênio em plantações comerciais de cana-de-açúcar. Oito talhões em produção comercial da cultura, localizados na região de Ribeirão Preto, SP, variando de 16 a 21 ha cada, foram monitorados. As condições de solo variaram de arenosos a argilosos, se dando a colheita de quatro deles em maio (período seco e frio) e os demais quatro em outubro de 2009 (estação úmida e quente), incluindo três soqueiras (primeira, segunda e terceira) em cada estação e quatro variedades, duas por estação. Cada talhão foi escaneado com o sensor três vezes durante seu desenvolvimento (0,2, 0,4 e 0,6 m de altura de colmo/palmito). Os dados georreferenciados de cada medição foram interpolados gerando mapas contendo cinco classes e em cada classe foram alocados dois pontos amostrais, dez por área, onde foram avaliados número e altura de perfilhos, teor de clorofila com medidor portátil e colhidas amostras para biomassa e extração de nitrogênio, as quais foram comparadas com os valores apresentados pelo sensor nos mesmos locais. Os resultados demonstram não haver relação significativa entre o medidor de clorofila e os parâmetros avaliados, porem alta correlação entre os valores do sensor e da biomassa de cana e sua absorção de nitrogênio, dando suporte à utilização desses dados em forma de um algoritmo para gerenciar a aplicação em taxa variável e tempo real de nitrogênio baseada nas leituras do sensor em áreas cultivadas com cana-de-açúcar. / Nitrogen nutrition of sugarcane, although extensively studied, remains a challenge for producers, especially due variability found in commercial production areas, often in short distances. Recently, this variability has been associated with the use of optical sensors that can detect crop canopy reflectance as a way to estimate the nitrogen nutrition of plants, these measurements can be associated with variable rate application on-the-go of nitrogen fertilizer based on sensor readings. On sugarcane those studies are yet scarce and as a biofuel crop the energy input matters, looking for a high positive energy balance production and low carbon emission on the whole production system. This study presents the procedure and shows the results obtained using a nitrogen and biomass sensor (N-SensorTM ALS, Yara International ASA) aiming to indicate nitrogen application demands on commercial sugar cane fields. Eight commercial fields from one Sugar Mill in the state of São Paulo, Brazil, vary from 16 to 21 hectares each, were monitored. Conditions ranging from sandy to heavy soils and the previous harvesting occurred in May (dry and cold season) and October 2009 (wet and warm season), including first, second, and third ratoon stages over four varieties, two per season. Each field was scanned with the sensor three times in the season (0.2, 0.4, and 0.6 m of stem height). The georeferenced data from each measurement was interpolated generating maps containing five classes, in each class two sample points were allocated, ten per area were the stem height and number, chlorophyll content (Ntester) were evaluated followed by tissue sampling for biomass and nitrogen uptake which were compared with the sensor readings for the same locations. The results show no significant relationship between the chlorophyll meter and the parameters evaluated, but high correlation between the sensor values and sugarcane biomass and their nitrogen uptake, supporting the use of these data as an algorithm to manage onthe- go variable rate application of nitrogen based on sensor readings over sugar cane cultivated areas.

Esta tese descreve a demonstração experimental de dispositivos baseados em fibras de cristal fotônico (PCFs), que aproveitam a flexibilidade estrutural oferecida pela matriz de capilares que compõe a seção reta da fibra, de forma a preencher estes capilares com líquidos e materiais nanoestruturados. Para o caso de materiais nanoestruturados, uma vez preenchida a fibra, os materiais nela inseridos interagem eficientemente com a luz guiada. Essa arquitetura diferenciada em relação às fibras ópticas convencionais abre novas perspectivas no desenvolvimento de aplicações como óptica não-linear e sensoriamento. PCFs de núcleo líquido, por outro lado, impõe dificuldades para a implementação de dispositivos práticos, devido às altas taxas de evaporação dos líquidos inseridos. Por esta razão, foi desenvolvida uma nova técnica para vedar seletivamente ambas as faces externas do núcleo líquido de uma PCF, utilizando um polímero curável. Estes tampões poliméricos evitam a evaporação, causando um impacto mínimo no guiamento da luz, tornando o dispositivo usável por semanas. Esta nova técnica de vedação foi empregada em um experimento para a geração de supercontínuo em uma PCF com núcleo de água destilada, proporcionando uma estabilidade de pelo menos 1 hora. Combinando líquidos e materiais nanoestruturados, foi também foi desenvolvido um sensor de temperatura baseado no preenchimento do núcleo de uma PCF por uma amostra coloidal de nanopartículas semicondutoras de CdSe/ZnS, dispersas em óleo mineral. O espectro de luminescência destes pontos quânticos coloidais é fortemente dependente da temperatura e os resultados obtidos mostraram que a grande interação entre a luz e o colóide, aliada a geometria da fibra, proporcionando uma sensibilidade ~5,5 vezes maior que a apresentada por uma rede de Bragg escrita em uma fibra óptica padrão, com boa relação sinal-ruído. / This thesis describes the experimental demonstration of devices based on photonic crystal fibers (PCFs). PCFs are optical fibers whose core is surrounded by a regular matrix of holes, which runs longitudinally across its length. This singular configuration allows the insertion of liquids and nanostructured material into the fiber. Nanostructured materials embedded inside the fiber efficiently interact with the guided light, opening up possibilities of novel applications regarding the fields of non-linear optics, as well as optical sensing. On the other hand, liquid-core PCFs suffer from some disadvantages concerning practical device applications, on account of the high evaporation of the inserted liquids. In order to address this issue, we developed a novel technique to selectively seal the external faces of a liquid-core PCF, by using a polymer plug. These polymer plugs avoid evaporation while causing a minimum impact on the light guiding characteristics of the PCF. This novel sealing technique was employed in a supercontinuum generation experiment, by using a PCF whose core was water-filled. A temporal stability of at least one-hour on the resulting spectrum was achieved. Combining the above techniques, we also developed a temperature sensor based on the core-filling of a PCF by a colloidal ensemble of CdSe/ZnS semiconductor nanoparticles dispersed in mineral oil. Those colloidal quantum-dots display a luminescence spectrum which is strongly dependent on temperature and the experimental results indicated that the greater interaction between the guided light and the colloidal sample, provided by the fiber geometry, allowed a sensitivity which is approximately 5.5 times than possible with a conventional Bragg grating, while keeping a satisfactory signal-to-noise ratio.

Esta tese descreve a demonstração experimental de dispositivos baseados em fibras de cristal fotônico (PCFs), que aproveitam a flexibilidade estrutural oferecida pela matriz de capilares que compõe a seção reta da fibra, de forma a preencher estes capilares com líquidos e materiais nanoestruturados. Para o caso de materiais nanoestruturados, uma vez preenchida a fibra, os materiais nela inseridos interagem eficientemente com a luz guiada. Essa arquitetura diferenciada em relação às fibras ópticas convencionais abre novas perspectivas no desenvolvimento de aplicações como óptica não-linear e sensoriamento. PCFs de núcleo líquido, por outro lado, impõe dificuldades para a implementação de dispositivos práticos, devido às altas taxas de evaporação dos líquidos inseridos. Por esta razão, foi desenvolvida uma nova técnica para vedar seletivamente ambas as faces externas do núcleo líquido de uma PCF, utilizando um polímero curável. Estes tampões poliméricos evitam a evaporação, causando um impacto mínimo no guiamento da luz, tornando o dispositivo usável por semanas. Esta nova técnica de vedação foi empregada em um experimento para a geração de supercontínuo em uma PCF com núcleo de água destilada, proporcionando uma estabilidade de pelo menos 1 hora. Combinando líquidos e materiais nanoestruturados, foi também foi desenvolvido um sensor de temperatura baseado no preenchimento do núcleo de uma PCF por uma amostra coloidal de nanopartículas semicondutoras de CdSe/ZnS, dispersas em óleo mineral. O espectro de luminescência destes pontos quânticos coloidais é fortemente dependente da temperatura e os resultados obtidos mostraram que a grande interação entre a luz e o colóide, aliada a geometria da fibra, proporcionando uma sensibilidade ~5,5 vezes maior que a apresentada por uma rede de Bragg escrita em uma fibra óptica padrão, com boa relação sinal-ruído. / This thesis describes the experimental demonstration of devices based on photonic crystal fibers (PCFs). PCFs are optical fibers whose core is surrounded by a regular matrix of holes, which runs longitudinally across its length. This singular configuration allows the insertion of liquids and nanostructured material into the fiber. Nanostructured materials embedded inside the fiber efficiently interact with the guided light, opening up possibilities of novel applications regarding the fields of non-linear optics, as well as optical sensing. On the other hand, liquid-core PCFs suffer from some disadvantages concerning practical device applications, on account of the high evaporation of the inserted liquids. In order to address this issue, we developed a novel technique to selectively seal the external faces of a liquid-core PCF, by using a polymer plug. These polymer plugs avoid evaporation while causing a minimum impact on the light guiding characteristics of the PCF. This novel sealing technique was employed in a supercontinuum generation experiment, by using a PCF whose core was water-filled. A temporal stability of at least one-hour on the resulting spectrum was achieved. Combining the above techniques, we also developed a temperature sensor based on the core-filling of a PCF by a colloidal ensemble of CdSe/ZnS semiconductor nanoparticles dispersed in mineral oil. Those colloidal quantum-dots display a luminescence spectrum which is strongly dependent on temperature and the experimental results indicated that the greater interaction between the guided light and the colloidal sample, provided by the fiber geometry, allowed a sensitivity which is approximately 5.5 times than possible with a conventional Bragg grating, while keeping a satisfactory signal-to-noise ratio.

A nutrição nitrogenada, apesar de intensamente estudada, continua sendo um desafio aos produtores, especialmente em função da variabilidade encontrada no desenvolvimento da cultura nas áreas de produção comercial, muitas vezes em curtas distâncias. Recentemente esta variabilidade vem sendo associada ao uso de sensores opticos que detectam a refletância do dossel da cultura como forma de estimar a nutrição nitrogenada das plantas, podendo estes serem associados à aplicação em taxa variável em tempo real do fertilizante nitrogenado. Em cana-de-açúcar esses estudos ainda são escassos, e sendo uma cultura voltada para a produção de biomassa para geração de energia, tais sensores podem contribuir para otimizar o saldo positivo em produção de energia e baixar as emissão de carbono no sistema. Este trabalho apresenta o processo e mostra os resultados obtidos utilizando um sensor de nitrogênio e biomassa (N-SensorTM ALS, Yara International ASA) com o objetivo de indicar exigência na aplicação de nitrogênio em plantações comerciais de cana-de-açúcar. Oito talhões em produção comercial da cultura, localizados na região de Ribeirão Preto, SP, variando de 16 a 21 ha cada, foram monitorados. As condições de solo variaram de arenosos a argilosos, se dando a colheita de quatro deles em maio (período seco e frio) e os demais quatro em outubro de 2009 (estação úmida e quente), incluindo três soqueiras (primeira, segunda e terceira) em cada estação e quatro variedades, duas por estação. Cada talhão foi escaneado com o sensor três vezes durante seu desenvolvimento (0,2, 0,4 e 0,6 m de altura de colmo/palmito). Os dados georreferenciados de cada medição foram interpolados gerando mapas contendo cinco classes e em cada classe foram alocados dois pontos amostrais, dez por área, onde foram avaliados número e altura de perfilhos, teor de clorofila com medidor portátil e colhidas amostras para biomassa e extração de nitrogênio, as quais foram comparadas com os valores apresentados pelo sensor nos mesmos locais. Os resultados demonstram não haver relação significativa entre o medidor de clorofila e os parâmetros avaliados, porem alta correlação entre os valores do sensor e da biomassa de cana e sua absorção de nitrogênio, dando suporte à utilização desses dados em forma de um algoritmo para gerenciar a aplicação em taxa variável e tempo real de nitrogênio baseada nas leituras do sensor em áreas cultivadas com cana-de-açúcar. / Nitrogen nutrition of sugarcane, although extensively studied, remains a challenge for producers, especially due variability found in commercial production areas, often in short distances. Recently, this variability has been associated with the use of optical sensors that can detect crop canopy reflectance as a way to estimate the nitrogen nutrition of plants, these measurements can be associated with variable rate application on-the-go of nitrogen fertilizer based on sensor readings. On sugarcane those studies are yet scarce and as a biofuel crop the energy input matters, looking for a high positive energy balance production and low carbon emission on the whole production system. This study presents the procedure and shows the results obtained using a nitrogen and biomass sensor (N-SensorTM ALS, Yara International ASA) aiming to indicate nitrogen application demands on commercial sugar cane fields. Eight commercial fields from one Sugar Mill in the state of São Paulo, Brazil, vary from 16 to 21 hectares each, were monitored. Conditions ranging from sandy to heavy soils and the previous harvesting occurred in May (dry and cold season) and October 2009 (wet and warm season), including first, second, and third ratoon stages over four varieties, two per season. Each field was scanned with the sensor three times in the season (0.2, 0.4, and 0.6 m of stem height). The georeferenced data from each measurement was interpolated generating maps containing five classes, in each class two sample points were allocated, ten per area were the stem height and number, chlorophyll content (Ntester) were evaluated followed by tissue sampling for biomass and nitrogen uptake which were compared with the sensor readings for the same locations. The results show no significant relationship between the chlorophyll meter and the parameters evaluated, but high correlation between the sensor values and sugarcane biomass and their nitrogen uptake, supporting the use of these data as an algorithm to manage onthe- go variable rate application of nitrogen based on sensor readings over sugar cane cultivated areas.

La connaissance de la turbulence atmosphérique en visée horizontale permet de mieux appréhender la physique des flux de chaleur à l’interface sol-atmosphère. Elle permet également, en visée verticale, d’améliorer les performances des futurs systèmes d’optique adaptative grand-champ pour l’observation astronomique. Le profil de Cn² caractérise localement la force de la turbulence. La méthode CO-SLIDAR, développée par l’ONERA, permet de réaliser des profils de Cn² le long de la ligne de visée du télescope à partir des pentes et de scintillations mesurées par un Analyseur de Shack-Hartmann sur source double. Cette méthode a été validée en visée verticale mais n’avait pas encore montré son efficacité en visée horizontale. Les deux expériences à Lannemezan et à Châtillon-Meudon ont vu la mise en place d'un nouveau profilomètre Shack-Hartmann Infrarouge : le SCINDAR. Elles ont été réalisées sur des surfaces respectivement hétérogène et homogène par morceaux, et elles participent à la validation de la méthode pour des applications agronomiques et écologiques. Mon étude consiste à améliorer le traitement du signal du profilomètre SCINDAR et à valider la méthode CO-SLIDAR pour des mesures de la turbulence atmosphérique proche du sol. Cette méthode a été adaptée en utilisant un formalisme de propagation en onde sphérique. L'étude a permis d'identifier et prendre en compte des sources d'erreur dans le traitement : à savoir la vibration de la machine à froid de l'analyseur de front d'onde cryogénique du SCINDAR et l'étendue des sources dans les fonctions de poids du modèle direct posé pour le traitement des données. Mon étude se consacre à l’amélioration du traitement des données du SCINDAR et à la validation expérimentale des profils de Cn² obtenus avec des mesures de Cn² acquises par des scintillomètres. J'ai construit tout d'abord une base de données de pentes et scintillations de qualité vérifiée. Pour l'inversion des données, j'ai choisi la régularisation L1L2 qui est adaptée pour des mesures de Cn² proches du sol. La méthode de réglage des hyperparamètres de cette régularisation est non-supervisée. Elle permet d’augmenter la fiabilité et la précision de l’estimation du profil de Cn² de façon pragmatique à l'aide des erreurs relatives sur les paramètres turbulents macroscopiques. Le profilomètre SCINDAR avec la méthode CO-SLIDAR ainsi améliorée produit finalement des profils de Cn² d'excellente qualité. Ces profils sont comparés avec succès aux mesures des scintillomètres. L’ensemble de ces travaux constitue l'adaptation de la méthode CO-SLIDAR pour des mesures de la turbulence proche du sol. / The knowledge of atmospheric turbulence in horizontal aim allows to better understand the physics of the heat fluxes at the ground-atmosphere interface. It also allows, in vertical aim, to improve the performance of future wide-field adaptive optics systems for astronomical observation. The profile of Cn²locally characterizes the force of turbulence. The CO-SLIDAR method, developed by ONERA, allows profiles of Cn² along the line of sight of the telescope, from the slopes and scintillations of a double source measured by Shack-Hartmann analyzer. This method was validated in vertical aim but had not yet shown its effectiveness in horizontal aim. The two experiments in Lannemezan and Châtillon-Meudon introduced a new Shack-Hartmann Infrared profilometer: the SCINDAR. They were carried out on heterogeneous and piecewise homogeneous surfaces respectively, and they participate in the validation of the method for agronomic and ecological applications. My study consists of improving SCINDAR profilometer signal processing and validating the CO-SLIDAR method for near-ground atmospheric turbulence measurements. This method has been adapted using a spherical wave propagation formalism. The study identified and took into account sources of error in processing: the cold machine vibration of the SCINDAR cryogenic wavefront analyzer and the extent of the sources in the weight functions of the direct model set for data processing. My study focuses on improvement of the SCINDAR data processing and experimental validation profiles Cn² obtained with Cn² measurements acquired by scintillometers. I first built a database of slopes and scintillations of verified quality. For the inversion of the data, I chose the L1L2 regularization which is suitable for near-ground Cn² measurements. The method of setting the hyperparameters of this regularization is unsupervised. It makes it possible to increase the reliability and the accuracy of the Cn² profile estimation in a pragmatic way using the relative errors of the macroscopic turbulent parameters. The SCINDAR profilometer with the improved CO-SLIDAR method finally produces Cn² profiles of excellent quality. These profiles are successfully compared to scintillometer measurements. All of this work constitues the adaptation of the CO-SLIDAR method for measurements of near-ground turbulence.

This dissertation presents the novel creation of a surface relief fiber Bragg grating on the flat surface of a D-shaped optical fiber. In order to produce an efficient surface relief grating the grating must be etched into the surface of the glass fiber close to the core. A short etch that removes the cladding above the core is performed in order to decrease the core-to-flat distance and allow the light to interact with the grating on the flat surface. Due to the unique D-shape of the optical fiber the mechanical integrity of the fiber remains high even after the fabrication process. For traditional fiber Bragg gratings the index modulation occurs in the core of the optical fiber. While this method can produce highly reflective gratings they are not well suited for many sensing applications. For example, the operating temperature range is limited to a few hundred degrees Celsius before the index modulation returns to a more uniform index profile. Also because the gratings are created in the core of the fiber, interaction with the surrounding environment is limited. The surface relief fiber Bragg grating created for this work overcomes some of the sensing challenges of traditional gratings. The major accomplishments of this dissertation show a dramatic increase in operating temperature to over 1000 degrees Celsius, the ability to measure multi-dimensional bend, the ability to measure material changes around the fiber such as chemical concentration, and the ability to use a Vernier effect to dramatically increase the sensors sensitivity. In addition to the sensing applications of this work a more thorough understanding of the reflection and transmission properties of the surface relief grating is also presented. Implementation of the transfer matrix method for simulation of the gratings is also shown to be a fast and accurate modeling tool for predicting the grating response.

Light detection and ranging (lidar) is used for various applications such as remote sensing, altimetry and imaging. In this talk, a linearly chirped pulse source is introduced that generates wavelength-swept pulses exhibiting ~6 nm optical bandwidth with > 20 km coherence length. The chirped pulses are used in an interferometric lidar setup to perform distance measurements with sub-millimeter resolution (using pulses that are a few meters long), at target distances > 10 km, with at least 25 dB signal-to-noise ratio at the receiver. A pulse repetition rate of 20 MHz provides fast update rates, while chirped pulse amplification allows easy amplification of optical signals to high power levels that are required for long range operation. A pulse tagging scheme based on phase modulation is used to demonstrate unambiguous, long range measurements. In addition to this, simultaneous measurement of target range and Doppler velocity is performed using a target moving at a speed of over 330 km/h (205 mph) inside the laboratory. In addition to this, spectral phase modulation of the chirped pulses is demonstrated to compensate for the undesirable ripple in the group delay of the chirped pulses. Moreover, spectral amplitude modulation is used to generate pulses with Gaussian temporal intensity profiles and a two-fold increase in the lidar range resolution (284 um) is observed.

Surface plasmon resonance (SPR) sensors using multiwavelength light coupling are investigated to probe changes in refractive index that occur as a result of chemical or biochemical processes. Traditional SPR sensors have used angle modulation to facilitate detection at the sensor surface; however, the multiwavelength approach is novel and brings new functionality to SPR sensors. The multiwavelength sensors are constructed on both fiber optic and bulk waveguides such as prisms. A thin metal film is deposited on the waveguide surface to support the surface plasmon (SP) mode. The evanescent field produced by light propagating through the waveguide can be coupled into the surface plasmon mode thus attenuating the transmitted light. This coupling is dependent upon phase matching between the light wavevector and the surface plasmon wavevector. The wavevectors are directly related to the wavelength of light, thickness of analyte on the sensor surface and the refractive index of the analyte. As these parameters change, the light output from the sensor will be affected. Other thin films can be subsequently deposited on the metal to functionalize the sensor surface for a particular analyte of interest. A theoretical background and details of the sensor construction is given. The developed sensors are tested in a variety of application systems. Experimental results for refractive index sensing in bulk liquid applications is shown. Observed sensitivity approaches that of conventional SPR techniques. Alkyl-thiol monolayer systems are studied to investigate kinetics of formation and the thickness resolution of the sensor. A biochemical system is investigated to compare the sensors with other immunoassay techniques. Ionic self-assembled monolayer (ISAM) systems are investigated to probe structure and determine their usefulness as an immobilization layer for biochemical species. A mathematical model based on Fresnel reflection equations is developed to predict sensor response. This model can be used to selectively vary sensor parameters to optimize the response for a specific analyte system or to calculate system parameters based on experimental results. Results from the various experiments are compared with the model. Experimental results and interpretations are discussed along with future work and potential improvements. Classical SPR sensors are also discussed along with comparisons with the multiwavelength sensors. Future improvements to SPR sensors design are considered, as is the application of the technology to high-throughput drug screening for pharmaceuticals. / Ph. D.

This thesis presents the development and in-vivo applications of wearable and portable devices for the investigation of light interaction with tissue involved in Photodynamic therapy (PDT) and during contraction of muscles. A hand-held device and a clinical method were developed for time course in-vivo imaging of the fluorescence of the photosensitizer Protoporphyrin IX (PpIX) in healthy and diseased skin with the aim to guide improvement of PDT protocols. The device was used in a small clinical study on 11 healthy volunteers and 13 patients diagnosed with non-melanoma skin cancer (NMSC). Two types of PpIX precursors were administered: Ameluz gel and Metvix® cream. The fluorescence was imaged with a 10 minute time step over three hours which was the recommended metabolism time before commencing PDT treatment at Ninewells Hospital, Dundee. The fluorescence time course was calculated by integrating the areas with the highest intensity. The fluorescence continued to grow in all subjects during the three hours. The time course varied between individuals. There was no statistical significance between either healthy volunteers or patients in Ameluz vs Metvix® groups; nor was there statistical difference between the three lesions groups (Actinic keratosis (AK) Ameluz vs AK Metvix® vs Basal cell carcinoma (BCC) Metvix®). The p-value was larger than 0.05 in a two sample t-test with unequal variances for all the groups. However, there was strong body site dependence between the head & neck compared to the lower leg & feet, or the trunk & hands body site groups (p-value < 0.01). One of the possible explanations for this was temperature and vasculature variation in skin at different body sites: the temperature is higher and the vasculature structure is denser at the head and the neck compared to the lower leg or the trunk. The temperature was not measured during the study. So in order to support this hypothesis, typical skin temperatures at the lesion sites were taken from the IR thermal images of healthy skin available in literature. PpIX fluorescence had a positive correlation to temperature. If this hypothesis is true, it will be highly important to PDT treatment. Increasing the temperature could speed up the metabolism and reduce the waiting time before starting the treatment; ambient temperature should be taken into account for daylight PDT; cooling air as pain management should be administered with caution. Potential improvements for wearable PDT light sources were investigated by modelling light transport in skin for the current LED-based Ambulight PDT device, a commercial OLED for future devices and a directional OLED developed in the group. The optical models were implemented in commercial optical software (with intrinsic Monte Carlo ray tracing and Henyey-Greenstein scattering approximation) which was validated on diffuse reflectance and transmittance measurements using in-house made tissue phantoms. The modelling was applied to investigate the benefits from diffusive and forward scattering properties of skin on light transmission in treatment light sources. 1 mm thick skin can only compensate approximately 10% of non-uniform irradiance. It means that uniform illumination is crucial for the treatment light sources. Forward scattering in skin showed a 10% improved light transmission from a collimated emission compared to a wide angle Lambertian emission. However, depth-dependent transmission measurements of directional vs Lambertian emission from organic light emitting films (a nano-imprinted grating was fabricated to provide directional emission in one of the films), collimated vs diffused HeNe laser light through fresh porcine skin did not show the expected improvement. This could be explained by skin roughness which was previously found to change the optical properties and may also affect light coupling. The modelling was applied to guide an optical design of another wearable device – a muscle contraction sensor. Muscle is fibrous and because of that scatters light differently in different directions. The sensor detects the change in backscattered light in parallel and perpendicular directions with respect to muscle fibres. The sensor was implemented on a wearable bandage on fully flexible substrate with flexible OLED and organic photodiodes. The major advantages of organic optoelectronic sensing compared to conventional electromyography (EMG) sensors are the ability to distinguish two types of contractions (isotonic and isometric), insensitivity to electromagnetic interference and the absence of an immune response due to non-invasive electrode-free sensing. Optical modelling was performed to understand the operation of the sensor. A 3D anisotropic optical model of scattering in muscle was created by geometrical manipulations with the standard Henyey-Greenstein scattering volumes. The penetration depth from the Super Yellow OLED was found to be 20-25 mm; the optimal separation between the source and the detector was found to be 20 mm. This distance provided a still detectable signal along with the best discrimination between the two backscatterings. When a 2 mm thick layer of skin and a 2 mm thick layer of adipose tissue were added to the model, the signal was hugely diffused. The discrimination between the two backscatterings decreased by three orders of magnitude, the penetration depth in muscle was reduced, and the intensity of the signal dropped down but was still detectable. With 5 mm thick adipose tissue and 2 mm thick skin the signal was too diffused and interacted with very shallow layers of muscle which approached the limits of the optical sensing of muscle activity.

[pt] A espectroscopia de ressonância de plásmon superficial (SPR) é uma técnica óptica baseada na excitação coletiva dos elétrons livres de metais nobres, tradicionalmente utilizada em sensoriamento de analitos de diferente natureza. Neste trabalho foi otimizado o processo de fabricação de sensores plasmônicos baseados em filmes finos de ouro e interfaces ouro-grafeno. As plataformas de sensoriamento SPR foram usadas para a detecção de íons de metais tóxicos pesados de Pb(2+), Hg(2+) e Cd(2+) em concentrações de 0.1ppm até 1ppm. Os sensores baseados em interfaces ouro-grafeno, onde o grafeno foi crescido mediante o método CVD, demonstraram uma sensitividade entre 3 até 6 vezes maior que os sensores constituídos por filmes finos de ouro, apontando para uma absorção química devida à transferência de elétrons do grafeno para os íons. / [en] Surface plásmon resonance (SPR) spectroscopy is an optical technique based on the collective excitation of free electrons of noble metals, traditionally used in sensing different types of analytes. In this work the fabrication process of plásmonic sensors based on thin gold films and gold-graphene interfaces was optimized. SPR sensing platforms were used for the detection of toxic heavy metals ions Pb(2+), Hg(2+) and Cd(2+) in concentrations ranging from 0.1ppm to 1ppm. The sensors based on gold-graphene interfaces, where graphene was grown using the CVD method, demonstrated a sensitivity between 3 and 6 times greater than the sensor made of thin films of gold, pointing to a chemical absorption due to the transfer of electrons from the graphene to the ions.