The research developed a UV Taylor Couette reactor for disinfecting milk as a model opaque fluid. The principal of the reactor was to generate laminar vortices to support efficient mixing and homogenous UV photon distribution. The UV reactor parameters were optimized to generate laminar vortices that were stabilized by modification of the unit with baffles. A model was developed to predict the UV dose required to inactivate model microbes in milk. Through verification trials it was noted the predicted UV dose underestimated that required to support a 5 log cfu reduction of microbes. It was subsequently identified that the deviation from predicted values could be attributed to fat content that enhances the UV inactivation of microbes in milk with proteins providing protection to microbes. In conclusion, the UV Taylor Couette reactor has strong potential for disinfecting opaque fluids although matrix effects need to be considered when undertaking validation trials.

Fumonisins, carcinogenic mycotoxins produced by various Fusarium species, occur naturally in maize and maize-based food products. They are hazards for animal and human health as they cause cancer in rodents and have been associated with oesophageal cancer and neural tube defects in humans. The most abundant naturally occurring fumonisins analogues in maize are fumonisin B1, B2 and B3 (FB1, FB2 and FB3). For analytical determination, they mostly require suitable extraction, clean-up and pre or post-column derivatization together with reversed-phase HPLC separation. o- Phthaldialdehyde (OPA) had been adopted as the most widely used derivatization reagent for fumonisins as they lack useful chromophores or fluorophores. Alternative derivatization reagents, naphthalene-2,3- dicarboxaldehyde (NDA) and dansyl chloride (DnS-Cl), were investigated in this study

Nonlinear optical interaction in quasi-phase-matched structures opens up unique possibilities to build compact and efficient parametric devices such as optical parametric oscillators, generators, and amplifiers with tailored spectral properties. The focus of this thesis is on novel parametric interactions with periodically-poled KTiOPO4 (PPKTP) as the parametric gain medium. Optical parametric oscillators (OPOs) are attractive light sources for many applications, particularly in spectroscopy, and plays a central role in this thesis. Special attention is put on simple, yet powerful, spectral-manipulation and bandwidth-narrowing techniques for OPOs. The overall knowledge gained from these studies has been used for device construction of several tunable ultraviolet sources for biological sensing. In the case of bandwidth narrowing, the observation of decreasing spectral bandwidth in a noncollinear, idler-resonant OPO, as compared with a signal-resonant one, has been found to be due to the interplay between the material properties and the angular dispersion of PPKTP. To further reduce the bandwidth, we have shown that it is very beneficial to replace the output mirror in an OPO with a bulk Bragg grating. In fact, even close to degeneracy, where the bandwidth is typically wide, this approach is able to decrease the bandwidth drastically. Moreover, different OPO cavity designs have been examined in order to spectrally manipulate the resonant waves. By deploying a grating in a ring OPO cavity, it becomes possible to access the resonant wave and spectrally manipulated it in a zero-dispersion arrangement; the filtered wave is subsequently sent back into its own cavity as a seed signal, in a self-seeding arrangement. This particular cavity design decreases the bandwidth close to ~ 1000 times as compare to the free-running mode. An interesting phenomenon arises when two mutually coherent laser beams are used to pump a linear OPO cavity. When the pump beams intersect within the PPKTP crystal, an interference grating is formed and acts as a catalyst for the generation of new spectral sidebands through multiple cascaded four-wave mixing, in the pump, the idler and the signal directions. The spacing of these sidebands is determined geometrically by the incident pump angle, while the signals are continuously tunable over the c-band telecom window (λ ~ 1.5 μm) by rotating the cavity. Ultrabroad bandwidths have been generated in an optical parametric generator (OPG) pumped by an amplified picosecond Ti:sapphire laser. In the collinear direction the output spectrum extends over three octaves in the mid-infrared region. This enormously broad spectrum is also Fourier-filtered and subsequently used for narrowband seeding of an optical parametric amplifier (OPA). Finally, the spectral range between 285 nm and 340 nm is of importance for detection of biological substances through fluorescence spectroscopy. With this spectral region in mind a practical way to generate a tunable parametric device in the ultraviolet region is presented in the thesis. The developed ultraviolet laser is used for studies of the characteristics of biological particles. The ultraviolet source and the results from these studies, will be utilized in an integrated detection system, a so called early-warning system. / QC 20100923

In many fields, scientific or industrial, optical devices that can be tailored in terms of spectral qualities and output power depending on the application in question are attractive. Nonlinear optics in combination with powerful laser sources provide a tool to achieve essentially any wavelength in the electromagnetic spectrum, and the advancement of material technology during the last decade has opened up new possibilities in terms of realising such devices. The main part of the thesis deals with the development of compact functional lasers based on nonlinear interaction utilising diode-pumped solid-state lasers and also laser diodes. Efficient frequency conversion into the visible and ultraviolet part of the electromagnetic spectrum has been achieved, using both Nd:YAG and Nd:YVO4 lasers as well as a semiconductor laser as the fundamental light sources. For the nonlinear conversion, periodically poled potassium titanyl phosphate (PPKTP), bismuth triborate (BiBO) and beta barium borate (BBO) have been employed. In the search for compact and reliable light sources emitting in the visible part of the spectrum, two different approaches have been explored. First, a scheme based on sum-frequency mixing of a diode-pumped solid-state laser and a laser diode of good beam quality. The idea of this approach is to take advantage of the individual strength of each device, which would be the flexibility in terms of wavelength for the laser diode and the possibility to reach high output power from the diode-pumped solid-state laser. Second, by mixing two different solid-state lasers substantially more output power could be generated albeit at a cost of less freedom in the choice of spectral output. As these two light sources had their central wavelength at 492 nm and 593 nm, respectively, they are highly interesting in biomedical applications since they correspond to the peak absorption of several popular fluorophores. In applications such as lithography, material synthesis and fibre grating fabrication, laser sources emitting in the deep-UV spectrum are desired. An all solid-state 236 nm laser source with 20 mW of average power have been designed and constructed, by frequency-quadrupling a passively Q-switched Nd:YAG laser lasing on a quasi-three level transition. Also, a novel concept for miniaturising solid-state lasers has been examined. Using a heat-conductive polymer carrier, a generic approach especially suited for mass-production of functional laser devices is presented. Finally, it has been proven that GRIN lenses can provide a very compact beam shaping solution to standard laser diodes based on the beam twisting approach. This method offers several advantages such as compactness of the beam shaping system, automated assembly in solid-state laser manufacturing due to the shape of these lenses and polarisation preservation of the laser diode output. / QC 20100903

Le sujet de la thèse initié dans le cadre de l'ANR UV-Borate s'inclut dans le projet UV-Conversion labellisée par 2 pôles de compétitivité (Matériala - Lorraine - et Route des lasers - Aquitaine -) soumis à l'ANR en 2011. Les études se portent particulièrement sur les borates YxLaySc4-(x+y)(BO3)4 (LYSB) et YAl3(BO3)4 (YAB), cristaux Optiques Non Linéaires (ONL) possédant la même structure cristallographique (R32). La croissance de ces cristaux est effectuée par les collaborateurs industriels et universitaires de l'ANR. Ces deux matériaux présentent en effet des possibilités de conversion de fréquence jusqu'à des longueurs d'onde λ < 300 nm, de plus une non hygroscopicité procure une plus grande durée de vie des échantillons et par conséquent un net intérêt pour les applications industrielles. L'endommagement laser étant lié à l'absorption et ainsi, en partie, aux impuretés, une étude de la qualité cristalline et de l'homogénéité de nos cristaux a été effectuée. Les résultats ont permis de relier des défauts de structure (dislocations et etch pits) à la croissance de la maille rhomboédrique via des caractérisations par ombre portée (Photography Schlieren) et par attaque chimique suivi d'une observation par microscopie optique, MEB et MFA. Par ailleurs, des études théoriques et expérimentales d'accord de phase (détermination de θ et φ) lors de conversions de type I principalement ont été réalisées sur les cristaux de YAB, LYSB ainsi que sur des cristaux de référence tel que β-BaB2O4 (β-BBO). L'aspect de l'endommagement laser dans les matériaux ONL a été abordé dans les locaux de l'Institut Fresnel de Marseille au sein de l'équipe Interaction Laser Matière (ILM) sur des échantillons de Li2B4O7 (LTB). L'équipe a effectivement développé un dispositif de mesure de la probabilité d'endommagement laser et de mesure de tenue du seuil d'endommagement laser des matériaux optiques. Par ailleurs, un effort a été mené dans la conception d'un dispositif de mesure de la transmission optique et absorption à température ambiante et aux basses températures afin de révéler des défauts absorbants. Des premiers résultats ont été obtenus et discutés sur des échantillons de β-BBO et LYSB.

Les mesures des constituants mineurs de l'atmosphère sont souvent réalisées à partir du sol, d'avions, de ballons ou encore par les satellites. Celles-ci sont effectuées régulièrement par des spectromètres fonctionnant dans des régions spectrales différentes, en particulier dans les domaines UV-visible et infrarouge. Or, l'analyse et l'interprétation des spectres atmosphériques requièrent une bonne connaissance des paramètres spectroscopiques. Cependant, les mesures de ces paramètres sont généralement effectuées dans un domaine spectral donné (IR ou UV) et peu d'études de laboratoire ont vérifié la cohérence entre les sections efficaces UV et IR. Il est alors difficile de comparer des profils atmosphériques déduits de mesures effectuées dans différents domaines. Le but de cette étude est donc d'intercalibrer les spectres UV et IR de composés atmosphériques en déterminant et/ou e vérifiant la cohérence des sections efficaces publiées dans la littérature. Ces expériences ont été effectuées dans la chambre de simulation du LISA, en acquérant simultanément des spectres UV et IR à température ambiante et à pression atmosphérique au sein d'une cellule optique commune. Ce travail a porté sur trois molécules clés atmosphériques : le formaldéhyde (et ses isotopes), l'ozone et l'acide nitreux. Ces composés jouent un rôle fondamental dans la physico-chimie atmosphérique puisqu'ils constituent les sources du principal oxydant de l'atmosphère : le radical hydroxyle. Ce travail de laboratoire a permis ainsi d'obtenir des spectres précis et cohérents de l'ozone, du formaldéhyde et de l'acide nitreux dans le moyen infrarouge et l'UV-visible afin d'améliorer la précision de leurs mesures.

Background: A mouse model of combined UVA/riboflavin irradiation to eliminate stromal cells and other antigen-presenting cells in the cornea provides the basis for a probably low risk of corneal transplantation. Methods: After abrasion of the epithelium, the central corneas of mouse eyes were treated with UVA/riboflavin in vitro. Histological studies of hematoxylin-eosin and immunohistochemical staining with caspase 3 were performed. Dissected mouse corneas were analyzed by Western blot. Results: Apoptotic cells were shown on the central corneal stroma; a cell-free zone was displayed in the cornea. Numbers of dead cells increased according to cultivation time. However, the endothelium survived due to the adjustment of the irradiation dose. Conclusions: A cell-free zone in the stroma of the mouse cornea was produced by UVA/riboflavin irradiation in vitro. The technique makes possible to prevent or reduce immunological reactions and the risk of graft rejection by pretreatment of the donor cornea, ultimately prolonging graft survival. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Comprendre l'évolution de la matière organique sur Mars est un enjeu majeur pour interpréter les analyses passées, présentes, et conduire les analyses futures des sondes d'exploration in situ destinées à déterminer si Mars a pu réunir des conditions favorables à l'émergence de la vie. Depuis la planète Mars primitive jusqu'à aujourd'hui, des molécules organiques ont pu être produites par de multiples voies de formation (abiotiques, prébiotiques, voire biologiques) ou apportées sur Mars via le flux météoritique incident. Mais depuis 3 milliards d'années, suite à la perte du champ magnétique de la planète puis d'une grande partie de son atmosphère, le rayonnement ultraviolet, la présence d'oxydants, les particules solaires et les rayons cosmiques peuvent générer des processus physico-chimiques faisant évoluer les molécules organiques à la surface de Mars. Dans ce contexte, quelle est l'évolution des potentielles molécules organiques présentes en surface ? Ce travail présente l'investigation en laboratoire des impacts qualitatif et quantitatif du rayonnement UV et des processus d'oxydation - représentatifs de la surface de Mars - sur une sélection de molécules organiques. L'optimisation du dispositif de simulation MOMIE (pour Mars Organic Molecule Irradiation and Evolution) et la mise en place d'un protocole d'analyse adapté ont permis de déterminer la nature des produits d'évolution (solide ou gazeux) et les paramètres cinétiques (temps de vie extrapolés à la surface de Mars, rendements quantiques) de chaque molécule. Les résultats obtenus indiquent que l'exposition de certaines molécules organiques au rayonnement UV conduit à court terme à la formation de résidus solides, probablement de nature macromoléculaire, pouvant contribuer à une stabilité sur le long terme. D'autre part, l'étude de l'évolution de molécules en interaction chimique avec une argile présente à la surface de Mars, la nontronite, a permis de mettre en évidence pour certaines molécules un effet protecteur marqué vis-à-vis du rayonnement UV, mais pas d'effet catalytique des processus d'altération, et pour d'autres une réactivité particulière avec un possible effet catalytique. Enfin, les paramètres cinétiques déterminés pour chacune des molécules étudiées fournissent des données d'entrée essentielles pour la modélisation numérique spatiale du réservoir actuel de molécules organiques sur Mars.

Raman spectroscopy is a form of vibrational spectroscopy that is capable of probing biological samples at a molecular level. In this work it was used in the analysis of ionizing radiation-induced damage in DNA. Spectra of both simple, short-stranded DNA oligomers (SS-DNA) and the more complicated calf-thymus DNA (CT-DNA) were acquired before and after irradiation to a variety of doses from 0 to ~2000 Gy. In a technique known as ultraviolet resonance Raman spectroscopy (UVRRS), three UV wavelengths of 248, 257 and 264 nm were utilized in order to selectively enhance contributions from different molecular groups within the samples. Assignment of the spectral peaks was aided by the literature, as well as through analysis of UVRR spectra of short strands of the individual DNA bases obtained at each of the three incident UV wavelengths. Difference spectra between the irradiated and unirradiated samples were calculated and the samples exposed to ~2000 Gy showed significant radiation-induced features. Intensity increases of spectral peaks, observed primarily in the CT-DNA, indicated unstacking of the DNA bases and disruption of Watson-Crick hydrogen bonds, while intensity decreases of spectral peaks, observed only in the SS-DNA, indicated both base damage and the loss of structural integrity of the DNA molecule. The high molecular specificity of UVRRS allowed for precise identification of the specific bonds affected by the radiation, and the use of the varying incident wavelengths allowed for the observation of damage to moieties that would otherwise have been excluded. The use of UVRRS shows promise in the study of radiation-induced damage to DNA and would be well suited for extension to the study of more complicated biological systems.

Thermal degradation during composite fabrication is the main impediment for the wide use of agro-based fibers as filler and reinforcement in engineering thermoplastic composites. Different thermal, chemical and physical techniques (e.g., alkali, steam explosion and retting) aiming to increase the fiber-matrix adhesion or reduce the plant fibers water absorption have been presented in the literature. However, there have been very few attempts to solve the difficulties associated with processing engineering thermoplastics with plant fibers. Most of these attempts involved the use of additives (such as plasticizers and salts) to lower the polymers processing temperature and plant fibers with inherent higher thermal stability (such as Curaua and cellulose). Despite all these efforts, no important progress has been achieved. Therefore, to explore the full potential of wheat straw and expand its use in commercial applications, an experimental study was carried out to develop different methodologies to improve the thermal stability of wheat straw fiber. In this thesis, most attention is given to wheat straw because of the relevance and potential of entering the market as commercial filler today. It is reported here that the thermal stability and chemical composition of wheat straw do not seem to significantly vary with wheat straw type and cultivation region. For example, the main thermal degradation of wheat straw samples starts in a narrow window of temperature which goes from 220.8 to 237.8 °C and from 224.8 to 238.1 °C for air and nitrogen atmospheres, respectively. On the other hand, lignin and inorganic materials are the wheat straw components with the highest relative variation. In addition, it is showed here that silane modification is an efficient method to increase the temperature of degradation of wheat straw. The highest improvements were achieved with chlorosilane modifiers and combinations of alkoxysilane and chlorosilane modifiers. In fact, the silane treated samples have lower thermal degradation during the fabrication of composites with polyamide-6. It is observed here that the extruded and injection molded composites containing silane treated wheat straw samples have significant smaller thermal degradation than those utilizing untreated wheat straw samples. Equally important, it seems that the mechanical properties of the composites are not affected by the addition of silane treated samples in comparison with untreated wheat straw. In addition, another efficient treatment method is presented in this thesis. This method employs ultraviolet light to modify and improve the thermal stability of wheat straw. This method offers important economical and environmental benefits. Significant improvements (e.g., 40 ºC increase on the temperature at 2% of weight loss) were achieved after treatment for short periods of time (up to 15 minutes) and without the use of any pre-treatment or production of toxic by-products. This treatment method represents a novel application for ultraviolet light with potential for industrial use.