La mise en place de la démarche PAT (Process Analytical Technology), initiée par la FDA (Food and Drug Administration) s’est développée au cours de ces dernières années, au sein de l’industrie pharmaceutique. Grâce à des contrôles en continu au coeur des procédés de fabrication, elle permet une meilleure compréhension et une maîtrise de la formulation et du procédé, afin d’assurer la qualité finale des médicaments.A travers ce travail, nous avons mis en place un suivi en temps réel, par spectroscopie proche infrarouge, d’une opération d’enrobage suite à l’intégration d’une sonde à l’intérieur d’une turbine d’enrobage. La quantité d’enrobage, déterminée par une simple et rapide pesée mais néanmoins soumise à la variabilité de la masse des comprimés nus, ainsi que l’épaisseur du film, obtenue avec précision par imagerie térahertz ont servi de valeurs de référence pour calibrer l’information spectrale. Dans les deux cas, ces deux attributs qualité critiques ont été prédits avec de faibles erreurs de prédiction, qui se sont révélées être similaires. Par ailleurs, la prédiction en temps réel des propriétés de dissolution de comprimés prêts à être libérés, à partir de spectres acquis in-line, a permis de déterminer l’arrêt optimal de l’opération d’enrobage.Suite à un enrobage réalisé à partir d’une dispersion aqueuse de polymère une étape supplémentaire de traitement thermique ou curing est généralement nécessaire afin de stabiliser le film d’enrobage. Un travail de caractérisation mené à partir de techniques innovantes a permis d’apporter un nouvel éclairage sur la compréhension des phénomènes impliqués dans la formation du film au cours du curing. La caractérisation approfondie de la structure d’enrobage de comprimés soumis à un curing en turbine (conditions dynamiques) a mis en évidence la diminution de la porosité, couplée à l’évaporation de l’eau et à une meilleure organisation des chaînes de polymère au cours du curing. L’étude de comprimés soumis à un curing de référence en étuve durant 24 h (conditions statiques) a confirmé l’obtention d’un film stable après 4 h de curing dynamique. De nouveaux phénomènes, indépendants du curing, liés à la cristallisation et à la migration de l’alcool cétylique, couplée à la migration du lauryl sulfate de sodium, au sein de la couche d’enrobage ont été détectés au cours de la conservation des comprimés enrobés. / Implementation of PAT (Process Analytical Technology) approach has recently been promoted by the FDA (Food and Drug Administration) within the pharmaceutical industry. A desired goal of the PAT framework is to enhance understanding and control of the manufacturing process through timely measurements, during processing, to ensure final product quality. Real-time monitoring of a coating operation was performed from in-line Near Infrared (NIR) measurements inside a pan coater. Mass of coating materials, determined by simple and fast weighing but depending on core tablet weight uniformity, and film coating thickness, obtained from accurate and non-destructive Terahertz Pulsed Imaging (TPI) measurements, were used as reference values to calibrate NIR spectral information. In both cases, these two critical quality attributes were predicted with low predictive errors, which were found to be similar. In addition, real-time predictions of drug release from cured tablets were carried out by in-line NIR measurements. The coating operation was successfully stopped when desired dissolution criteria were achieved. A post-coating thermal treatment, known as curing, is generally required to stabilize film coating from aqueous polymer dispersion. Innovative techniques were jointly used to elucidate the underlying mechanisms of film formation along the curing process. This study provided a new insight into the tablet coating structure, highlighting a reduced internal coating porosity, a decrease in water content and showing a better structural rearrangement of polymer chains, with dynamic curing. All investigated techniques confirmed that a stabilized state was reached after a 4 h dynamic curing in comparison with a reference curing carried out in an oven for 24 h. Interestingly even prior to curing, new findings were pointed out, during coated tablets storage, related to the crystallisation and the upward migration of cetyl alcohol, coupled to the downward migration of sodium lauryl sulfate within the coating layer.

Este estudo tem como objetivo analisar a qualidade do lenho das árvores de eucalipto geneticamente modificadas e seus respectivos controles (clones convencionais). Foram selecionadas 70 árvores de eucalipto, ao 12º mês de 14 tratamentos (10 eventos modificados e 4 clones convencionais) representando 5 árvores/tratamento. As amostras do lenho foram coletadas do tronco das árvores com sonda de Pressler para análise das suas características anatômicas, densidade aparente do lenho (microdensitometria dos raios X) e propriedades químicas (espectroscopia no infravermelho próximo). As propriedades anatômicas e a densidade aparente do lenho indicaram poucas diferenças significativas entre as árvores dos tratamentos. Nas análises da espectroscopia no infravermelho próximo (NIR) foram encontrados modelos satisfatórios para a densidade aparente do lenho, a fração parede e para o teor de celulose. O lenho das árvores dos eventos modificados e dos clones convencionais mostrou pequenas diferenças nas características anatômicas e físicas, sendo caracterizado como lenho juvenil; assim as árvores devem ser analisadas em idades mais avançadas, com lenho de transição e adulto. Os resultados constituem-se parte da análise das árvores de eucalipto geneticamente modificadas, subsidiando os estudos genéticos visando obter altos níveis de produtividade. / This study aims to analyze the quality of the wood of genetically modified eucalyptus trees and their respective controls (conventional clones). 70 eucalyptus trees were selected at 12 months of 14 treatments (10 modified events and 4 conventional clones) representing 5 trees / treatment. The wood samples were collected of the trunk of the eucalyptus trees with Pressler increment borer for the analysis of their anatomical features, density of wood (microdensitometry of X-rays) and chemical properties (near infrared spectroscopy). The anatomical properties and wood density of eucalypts trees showed few significant differences between treatments. In the analysis of near infrared spectroscopy (NIR) have been found satisfactory models for the apparent density of the wood, the wall portion and the cellulose content. The wood from the trees of the modified events and conventional clones showed small differences in the anatomical and physical characteristics, being characterized as juvenile wood; so the trees must be analyzed at older ages, with wood transition and adult. The results are a part of the analysis of genetically modified eucalyptus trees, supporting genetic studies to obtain high levels of productivity.

O objetivo deste trabalho foi o desenvolvimento e caracterização de um laser de centro de cor (LCC) sintonizável no infra-vermelho próximo, o qual possui uma cavidade do tipo astigmaticamente compensada, para aplicação em espectroscopia. O meio ativo foi um cristal de KCl:Li+ contendo centros de Fa(II) numa concentração ótima, determinada experimentalmente, para o sinal de saída do LCC, meio ativo foi preparado no próprio laboratório a partir da produção de centros F pelo método de coloração aditiva. A conversão de centros F em Fa(II) foi feita via fotodissociação dos centros F através de bombeamento ótico destes. O intervalo de sintonia do LCC foi de 2,59 a 2,82 &#956m e sua eficiência energéticade 0,14%. A fonte de bombeamento foi um laser de Argônio de 1w de potência em regime de multilinhas / The present work shows the development of a Near-infrared Tunable Color Center Laser (CCL), which optical cavity was astigmatically compensated, for spectroscopy application. The active medium was a KCl:Li+ crystal with Fa(II). The technique used to produce F centers was additive coloration. The F centers was converted into Fa(II) centers by optically pumping the F band of KCl with Tungsten lamp for approximately 20 minutes at room temperature. This laser covered the spectral range from 2.59 to 2.82&#956m, the slope efficiency was 0,14% and the beam divergence was 3.5mrad. The pumping source was a Ar+ laser multilines.

Increased near infrared (NIR) reflection, closely resembling the red edge found in leaves, has been known in frogs for many years. Whereas previously thought of as an isolated rarity, we have shown that it is likely far more prevalent than previously believed, occurring in multiple distinct family groups and world regions. To date, there are now 26 anuran species known to demonstrate increased NIR reflectance, from 12 different genera, 4 families, and 3 ecozones. The visible/NIR reflection spectra of each individual measured was found to be characteristic of its species; whether it was wild or captive bred; and its sex. A machine learning based classification system was demonstrated as a viable method of identifying these properties from a frog's reflection spectra alone. How this reflection spectra developed from a pre-metamorphosis froglet through to adult frog was tracked, with the gradual changes to the reflection spectra of both NIR reflective and other frogs identified as being most likely dominated by the reduction in epidermal melanophores, and the increasing number of dermal iridophores. A modified consumer camera was shown to be a viable method for rapid identification of increased NIR reflection in anurans, and was used to identify that salamanders also show variation in NIR reflection between ground dwelling and leaf sitting species. The overnight colour change in Hylomantis lemur was observed, and found to occur pre-emptively of the frog's future location; with the frogs regularly transitioning from pale green ‘daytime' colouration, to the dark brown ‘night time' colouration, while still on the green leaf surface before becoming active, and undertaking the reverse transition while still active, but shortly before returning to the leaf. It seems likely that this change is for protection from silhouetting whilst active. Optical coherence tomography images were taken of several species of frog, and found to be a viable method for non-invasive investigation of anuran skin structure, with structural differences observed between the two colourations of H. lemur. It was found that the most likely cause of the increased NIR reflection in frogs is a reduction in melanin, either by absence or substitution with pterorhodin. Although the true benefit to the frog is difficult to determine, it seems likely that cryptic thermoregulation plays a key role: the maintenance of body temperature for the purpose of camouflage from animals capable of far-infrared vision. This thesis demonstrates the legitimacy of several techniques and approaches for non-invasive study of anurans, but the ultimate scope of the project is fundamentally limited by the range of frogs available. Further insight is likely to arise from increasing this scope, applying these techniques to more frogs, from more species, in more regions, and the author wishes all future researchers the greatest success in this endeavour.

Chan Jacklynn = 摻近紅外染料溶凝膠薄膜之光學及激光性質研究 / 陳在琳. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (leaves 137-152). / Text in English; abstracts in English and Chinese. / Chan Jacklynn = Shan jin hong wai ran liao rong ning jiao bo mo zhi guang xue ji ji guang xing zhi yan jiu / Chen Zailin. / Abstract --- p.i / Acknowledgements --- p.v / Publications --- p.vii / Table of Contents --- p.viii / List of Figures --- p.xi / List of Tables --- p.xiv / Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Sol-gel Glass Waveguides --- p.3 / Chapter 1.2 --- Ellipsometry --- p.7 / Chapter 1.3 --- Aim of this Research Work and Organization of Thesis --- p.12 / Chapter 2 --- Basics on Ellipsometry --- p.16 / Chapter 2.1 --- Principle of Ellipsometry --- p.17 / Chapter 2.1.1 --- Definition of Ellipsometric Parameters --- p.17 / Chapter 2.1.2 --- Configurations of an Ellipsometer --- p.22 / Chapter 2.2 --- Mathematical Representation of Ellipsometry --- p.26 / Chapter 2.2.1 --- Bulk Material Structure --- p.26 / Chapter 2.2.2 --- Single Layer Structure --- p.28 / Chapter 2.3 --- Parameterization of Optical Functions --- p.31 / Chapter 2.3.1 --- Optical Functions --- p.34 / Chapter 2.3.2 --- Regression Analysis --- p.38 / Chapter 3 --- Modification of Rotating-Polarizer-Analyzer Ellipsometer --- p.40 / Chapter 3.1 --- Principle of RPA System --- p.41 / Chapter 3.2 --- Optical Setup of RPA System --- p.45 / Chapter 3.3 --- Components of the System and Modification for Infrared Measurement --- p.47 / Chapter 3.3.1 --- Light Source --- p.47 / Chapter 3.3.2 --- Monochromator --- p.52 / Chapter 3.3.3 --- Polarizers and Analyzer --- p.53 / Chapter 3.3.4 --- Detector and Data Reduction --- p.54 / Chapter 3.4 --- Optical Alignment --- p.59 / Chapter 3.5 --- Alignment of the Azimuthal Angles of the Polarizers --- p.61 / Chapter 3.6 --- Calibration Procedure --- p.63 / Chapter 3.6.1 --- Calibration by Gold Film on Silicon --- p.63 / Chapter 3.6.2 --- Calibration by Silicon Dioxide Film on Silicon --- p.67 / Chapter 4 --- Near Infrared Dyes in Sol-gel Waveguides --- p.72 / Chapter 4.1 --- Sol-gel Process --- p.73 / Chapter 4.2 --- Near Infrared Dyes in Sol-gel Waveguides --- p.77 / Chapter 4.2.1 --- Development of Near Infrared Dyes --- p.77 / Chapter 4.2.2 --- Studies on Near Infrared Dye Solid State Laser --- p.79 / Chapter 5 --- Optical Properties of Dye-doped Sol-gel Waveguides --- p.83 / Chapter 5.1 --- Experimental Procedure --- p.84 / Chapter 5.1.1 --- Preparation of Samples --- p.84 / Chapter 5.1.1.1 --- Materials --- p.84 / Chapter 5.1.1.2 --- Procedure --- p.86 / Chapter 5.1.2 --- Discussion on Synthesis of Infrared Dye-doped Sol-gel Waveguides --- p.88 / Chapter 5.1.2.1 --- Choice of Solvents --- p.89 / Chapter 5.1.2.2 --- Thermal Treatment and Lifetime --- p.93 / Chapter 5.1.2.3 --- Necessity of Addition of GLYMO --- p.94 / Chapter 5.1.3 --- Sample Characterization --- p.96 / Chapter 5.2 --- Surface Morphology --- p.97 / Chapter 5.3 --- Optical Properties of Dye-doped Zirconia Organically Modified Silicate Waveguides --- p.100 / Chapter 5.3.1 --- Modeling of Ellipsometric Values --- p.101 / Chapter 5.3.2 --- Interpretation of the Modeling Results --- p.107 / Chapter 6 --- Amplified Spontaneous Emission Based on Sol-gel Waveguides --- p.109 / Chapter 6.1 --- Experimental Setup --- p.110 / Chapter 6.2 --- Features of ASE and Fluorescence --- p.112 / Chapter 6.3 --- Prolonged Thermal Treatment Effect on Light Emission --- p.119 / Chapter 6.3.1 --- Difference in Preparation of Samples --- p.121 / Chapter 6.3.2 --- Light Emission of Samples under Extended Thermal Treatment --- p.123 / Chapter 6.3.3 --- Directionality of the Emission --- p.125 / Chapter 6.3.4 --- Some Features of the Emission --- p.127 / Chapter 7 --- Conclusion and Recommendation --- p.133 / Chapter 7.1 --- Conclusion --- p.133 / Chapter 7.2 --- Recommendation --- p.135 / Bibliography --- p.137

The goal of this dissertation is to demonstrate the utility of portable, small-scale diffuse optical spectroscopic (DOS) systems for the diagnosis and treatment monitoring of various diseases. These systems employ near-infrared light (wavelength range of 650nm to 950nm) to probe human tissue and are sensitive to changes in scattering and absorption properties of tissues. The absorption is mainly influenced by the components of blood, namely oxy- and deoxy-hemoglobin (HbO2 and Hb) and parameters that can be derived from them (e.g. total hemoglobin concentration [THb] and oxygen saturation, StO2). Therefore, I focused on diseases in which these parameters change, which includes vascular diseases such as Peripheral Atrial Disease (PAD) and Infantile Hemangiomas (IH) as well as musculoskeletal autoimmune diseases such as Rheumatoid Arthritis (RA). In each of these specific diseases, current monitoring techniques are limited by their sensitivity to disease progression or simply do not exist as a quantitative metric. As part of this project, I first designed and built a wireless handheld DOS device (WHDD) that can perform DOS measurements at various tissue depths. This device was used in a 15-patient pilot study for infantile hemangiomas (IH) to differentiate diseased skin from normal skin and monitor the vascular changes during intervention. In another study, I compare the ultra-small form- factor WHDD’s ability to monitor synovitis and disease progression during a patient’s treatment of RA against the capabilities of a proven frequency domain optical tomographic (FDOT) system that has shown to differentiate patients with and without RA. Learning from clinical utility of the WHDD from these two studies, I adapted the WHDD technology to develop a compact multi- channel DOS measurement system to monitor perfusion changes in the lower extremities before and after surgical intervention for patients with peripheral artery disease (PAD). Using this multi- channel system, which we called the vascular optical spectroscopic measurement (VOSM) system, our group conducted a 20-subject pilot study to quantify its ability to monitor blood perfusion before and after revascularization of stenotic arteries in the lower extremities. This proof-of- concept study demonstrated how DOS may help vascular surgeons perform revascularization procedures in the operating room and assists in post-operative treatment monitoring of vascular diseases.

Les composés à base de lanthanides luminescents possèdent des propriétés uniques offrant de nombreux avantages pour l’étude de problèmes biologiques et pour le diagnostic. Ils résistent notamment à la photodécomposition, possèdent des temps de vie de luminescence longs ainsi que des bandes d’émissions étroites qui ne se recouvrent pas. De plus, certains lanthanides émettent dans le proche infrarouge, ce qui les rend particulièrement intéressants pour des applications d'’imagerie in vivo. De part l’interdiction des transitions f → f, les cations lanthanides ont des coefficients d’extinction très faibles. C’est la raison pour laquelle, il est nécessaire d’utiliser un ou plusieurs sensibilisateur(s) (comme un chromophore organique) pour exciter le lanthanide par « effet antenne ». Nous proposons ici de nouveaux composés émettant dans le proche infrarouge dont la structure permet d’incorporer une densité importante de lanthanides et de sensibilisateurs par unite de volume : i) les nano-MOF Yb-PVDC-3 constitués de chromophores dérivés de dicarboxylates de phenylènevinylène qui sensibilisent les cations Yb3+ du réseau. ii) les complexes formés avec des ligands dendrimères dérivés de polyamidoamine de génération 3 capables de sensibiliser 8 lanthanides (Eu3+, Yb3+, Nd3+) par le biais de 32 antennes dérivées du groupe 1,8-naphthalimide. La caractérisation physique, photophysique et la biocompatibilité de ces composés ont été réalisées. Ils ont montré une bonne stabilité dans différents environnements. Leur faible cytotoxicité a permis d’obtenir des images de microscopie proche infrarouge sur cellules vivantes. La preuve de principe que les nano-MOFs et les dendrimères complexant des lanthanides peuvent être utilisés comme rapporteurs luminescents in cellulo et in vivo a été ici établie. Les résultats obtenus valident la stratégie d’utiliser ce type de matériel pour augmenter le nombre de photons émis par unité de volume afin d’obtenir une meilleure sensibilité de détection. / Unique properties of luminescent lanthanides reporters explain their emergence for bioanalytical and optical imaging applications. Lanthanide ions possess long emission lifetimes, a good resistance to photodecomposition and sharp emission bands that do not overlap. In addition, several lanthanides emit in the near infrared (NIR) region of the electromagnetic spectrum making them very interesting for in vivo imaging. Free lanthanide cations have low extinction coefficients due to the forbidden nature of the f → f transition. Therefore, lanthanides must be sensitized using a photonic converter such as an organic chromophore through the “antenna effect". We report here new near-infrared emitting compounds whose structure allows to incorporate a high density of lanthanide cations and sensitizers per unit volume: i) nano-MOF Yb-PVDC-3 based on Yb3+ sensitized by phenylenevinylene dicarboxylates. ii) polymetallic dendrimer complexes formed with derivatives of new generation-3 polyamidoamine dendrimers. In these complexes, 8 lanthanide ions (Eu3+, Yb3+, Nd3+) can be sensitized by the 32 antenna derived from 1,8-naphthalimide. These two families of compounds were fully characterised for their physical, photophysical properties as well as for their biological respective compatibilities. They are stable in various media and their low cytotoxicity and emission of a sufficient number of photons are suitable for near-infrared live cell imaging. One of the main goal outcomes of this work is the establishment of the proof of principle that nano- MOFs and lanthanide derived dendrimers can be used for the sensitization of NIR emitting lanthanides to create a new generation of NIR optical imaging agents suitable for both in cellulo and in vivoapplications.The present work also validates the efficiency of the strategy to use both types of nanoscale systems described here to increase the number of emitted photons per unit volume for an improved detection sensitivity and to compensate for low quantum yields.

A classificação e caracterização do petróleo cru em tempo real é um dos mais importantes desafios atuais da indústria petroquímica e agencias ambientais. Um método rápido e econômico antes da destilação do petróleo iria a fornecer informações químicas de grande importância para o ajuste em tempo real dos parâmetros críticos de uma refinaria, permitindo a otimização do processo, resultando em benefícios econômicos e ambientais. Uma variedade de técnicas espectroscópicas está sendo utilizadas nas ultima décadas para as analises, classificação e caracterização de petróleo cru nos campos de perfuração, para as análises dos produtos petrolíferos e para detecção de derrames. As vantagens do uso desta técnica incluem uma rápida resposta, requerimento mínimo de preparação da amostra e equipamentos relativamente econômicos. As técnicas espectroscópicas envolvidas na tese (NIR) mostraram o maior potencial no campo. No entanto, os estudos realizados com todas estas técnicas não foram enfocados em aplicações em linha. O NIR é tradicionalmente a técnica espectroscópica mais utilizada para a análise de petróleo cru. Mas os problemas típicos que esta técnica apresenta são sobreposição das diferentes bandas de absorção e saturação do sinal devido à alta absorbância característico do petróleo cru. A Fluorescência é um fenômeno mais complexo do que a absorção (NIR) e efeitos como quenchinge transferência de energia têm que ser consideradas. No entanto, a espectroscopia de fluorescência pode fornecer sinais bidimensionais com muito mais informação do que uma emissão unidimensional do espectro de absorção. Enquanto a espectrometria de massa, a técnica MALDI TOF faz possível a ionização de macromoléculas que são difíceis de serem ionizadas por não ser facilmente decompostas. Neste trabalho, as vantagens e limitações das técnicas disponíveis são analisadas e o potencial do analises remoto em linha do petróleo cru é avaliado. A pesar da boa analise e classificação obtida com algumas técnicas, nem sempre é possível integrá-los em um sistema em linha quando uma preparação previa da amostra é necessária ou quando o sistema é demasiado complexo. Para a extração da informação química contida nos espectros foram utilizados métodos matemáticos e estatísticos (quimiométricos) nos espectros: Mínimos Quadrados Parciais (PLS). / Online remote characterization and real-time classification of crude petroleum is one of the most important current challenges faced by the petrochemical industry and environmental agencies. A rapid and inexpensive method for the remote analysis and classification of petroleum prior to distillation of the crude would provide chemical information of great importance for real time adjustment of the critical parameters of a refinery, permitting an optimization of the process and resulting in economic and environmental benefits. A variety of spectroscopic techniques have been used over the last few decades for the analysis, characterization and classification of crude oil in drilling fields, for the analysis of petroleum products and for the detection of oil-spills. The advantages of using these techniques include rapid response, the requirement of minimal sample preparation and relatively inexpensive equipment costs. The spectroscopic techniques involved in the thesis (NIR, fluorescence and mass spectrometry) showed the greatest potential in the field. Nevertheless, the studies carried out with these techniques typically do not focus on online applications. NIR is traditionally the spectroscopic techniques most used for crude petroleum analysis. Overlap of the different absorption bands and saturation of the signal due to the high absorbance of crude petroleum are typical problems encountered with this technique. Fluorescence is a more complex phenomenon than absorption (NIR) and effects such as quenching and energy transfer have to be considered. However, fluorescence spectroscopy can provide two-dimensional signals with much more information than a one-dimensional emission or absorption spectrum. While mass spectrometry, MALDI TOF technique makes possible the ionization of macromolecules that are difficult to be ionized not be easily broken. In this work, the advantages and limitations of the available techniques are analyzed and the potential for remote on-line analysis of crude petroleum is evaluated. In spite of the good analysis and classification obtained with some of the techniques, it is not always possible to integrate them into a remote on-line analytical system when some prior sample preparation is required or when the system is too complex. For the extraction of chemical information contained in the spectra were used mathematical and statistical (chemometric) in the spectra: Partial Least Squares (PLS).

The movement towards a more sustainable energy economy may require not only the generation of cleaner fuel sources, but the conversion of waste streams into value-added products. Phototrophic purple non-sulfur bacteria are capable of metabolizing VFAs (volatile fatty acids)and generate hydrogen as a byproduct of nitrogen fixation using energy absorbed from light. VFAs are easily produced from dark anaerobic fermentation of food, agricultural, and municipal wastes, which could then be fed into photobioreactors of purple bacteria for hydrogen production. The process of photofermentation by purple bacteria for hydrogen production remains attractive due to the capability of reaching high substrate conversions under mild operating conditions, but increasing the efficiency of converting light energy into hydrogen remains challenging. Purple bacteria cannot utilize the entire solar spectrum, and the dominant region of absorption lies in the near-infrared region above 800 nm. In this work, the model purple non-sulfur bacteria Rhodopseudomonas palustris was used to study different strategies to increase light utilization and hydrogen production. Near-infrared LED arrays were selected to match the target bacteriochlorophyll absorption range, and were tested to be used as a sole illumination source for photofermentation. Additionally, plasmonic nanoparticles with resonant frequencies matching bacterial absorbance were added in solution to increase light utilization through scattering and near field electric enhancement effects at intensities around 100 W/m2 . Both of these approaches proved to increase cellular growth rate and hydrogen production, which opens the door to utilizing more advanced photonic structures for use in bacterial phototrophic processes.

Doctor of Philosophy / In this thesis, three experiments were conducted to monitor: (i) muscle oxygenation and electromyographic activity of the biceps brachii after exercise-induced muscle damage (ii) muscle oxygenation after downhill walking-induced muscle damage, and, (iii) muscle oxygenation following a bout of vigorous concentric exercise. Maximal eccentric exercise (EE) of biceps brachii resulted in significantly increased mean resting oxygen saturation and decreased deoxyhaemoglobin. During isometric contractions at 50% and 80% of subjects’ maximum voluntary torque (MVT), oxygen desaturation and resaturation kinetics and volume were significantly decreased after EE, and these declines were significantly prevalent over the following 6 days. Additionally, a significant shift in median frequency intercept (measured by electromyography; EMG) towards lower frequencies was observed during isometric contractions at both 50% and 80% MVT after EE in the exercised arm. After an exhaustive session of downhill walking, another form of EE, resting total haemoglobin and oxyhaemoglobin decreased. Furthermore, during isometric contractions at 30%, 50% and 80% of MVT, prolonged and significant increases were observed in oxygen desaturation and resaturation kinetics and volumes after ambulatory EE. In contrast to the two EE experiments, concentric contractions did not evoke any prolonged changes in muscle oxygenation. Collectively, the findings of this thesis revealed significant and prolonged changes in muscle oxygenation at rest and during exercise, following sessions of strenuous eccentric exercise. Although not clear, the possible mechanism responsible for the changes in muscle oxygenation after EE could be increased resting muscle oxygen utilization due to probable muscle damage and a subsequent requirement of energy demanding repair processes. Concentric exercise resulted in fatigue, but it did not affect muscle oxygenation. Although a prolonged reduction in EMG median frequency intercept was observed after EE, this was not closely time-associated with the biochemical, anthropometric or functional markers of muscle damage.