The validation of UV reactors is currently accomplished by biodosimetry, in which the reactor is treated as a "black-box" and hence cannot account for the dependence of the dose delivery on the complex hydrodynamics and the spatial variation in UV intensity. Alternative methods, such as fluorescent microspheres as non-biological surrogates and computational fluid dynamics (CFD) simulations, have been developed; however, each method has its shortcomings. In this study, a novel technique for the spatial and temporal assessment of the hydrodynamics and the UV dose delivered and the link between these two factors in a lab-scale UV reactor using three dimensional laser induced fluorescence (3DLIF) is developed. This tool can also be utilized for the optimization of UV reactors and to provide data for validation of CFD-based simulation techniques. Regions of optimization include areas around the UV lamp where short-circuiting occurred, a longer inlet approach section that enhances the performance of the reactor by reducing short circuiting paths and a longer outlet region to provide greater mixing. 3DLIF allows real time characterization of mixing and dose delivery in a single lamp UV reactor placed perpendicular to flow by capturing fluorescence images emitted from a laser dye, Rhodamine 6G, using a high speed CCD camera. In addition to three-dimensional mixing, the technique successfully visualized the two-dimensional, transient mixing behaviors such as the recirculation zone and the von Karman vortices and the fluence delivery within the reactor, which has not been possible with traditional tracer test techniques. Finally, a decomposition technique was applied to the flow and fluence delivery based concentration data to reveal similar structures that affect these phenomena. Based on this analysis, changing the flow in the reactor, i.e. the Reynolds number, will directly affect the fluence delivery.

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.

It is well known that ultraviolet (UV) B (280-315 nm) and blue light (400-500 nm) radiation can produce phototoxic lesions in the neural retina and the retinal pigment epithelium (RPE). In the first section of this thesis, bovine lens cells (epithelium and superficial cortical fibre cell) and human retinal pigment epithelial (ARPE-19) cells were used to characterize in vitro changes following oxidative stress with UVB radiation in ocular lens optics and cellular function in terms of mitochondrial dynamics. In the second part, human retinal pigment epithelial (ARPE-19) cells and in vitro bioassays were used together to develop an in vitro approach for UV radiation-induced retinal toxicology research. In the third chapter, the in vitro approach developed above was used with intraocular lens (IOL) materials to evaluate the UV radiation blocking efficiency of commercially available IOL’s. Lastly, narrowband blue light irradiation and in vitro assays were used to determine more precisely the wavelengths of blue light responsible for photochemical lesions of the retina as an effort to contribute to future IOL designs. The results from mitochondrial dynamics of lens cells and RPE cells show significant decreases in mitochondrial movement after UVB irradiation in a dose dependent manner. Results obtained from four in vitro assays (Alamar blue assay, confocal microscopy for mitochondrial distribution and nucleic acids damage, phagocytotic activity assay) for evaluating the UVB-induced damage in ARPE-19 show significant decreases in cell viability as well as phagocytotic activity of RPE cells after UVB radiation. In addition, the results show that UV radiation can also induce the degradation of DNA/RNA and mitochondria of RPE cells in a dose dependent manner. The results of the UV blocking efficiency test of commercially available IOL materials show very effective UV blocking ability, allowing no cellular damage at all, in comparison to an IOL uncovered control cell. The results of three different wavelengths of blue light exposure show that only 400 nm blue light radiation can cause significant damage to RPE cells, while 420 and 435.8 nm blue light radiation cause no cellular damage at all. In conclusion, UVB and blue light radiation can cause phototoxic damage to the retinal pigment epithelium as a result of oxidative stress, and in vitro bioassays used for this research may offer a sensitive, and meaningful biomarker approach, not only for evaluating RPE function after oxidative and chemical stress, but also for evaluating IOL effectiveness.

Capacitance-voltage-frequency measurements on n+-GaN/AlxGa1−xN UV/IR dual-band detectors are reported. The presence of shallow Si-donor, deep Si-donor, and C-donor/N-vacancy defect states were found to significantly alter the electrical characteristics of the detectors. The barrier Al fraction was found to change the position of the interface defect states relative to the Fermi level. The sample with Al fraction of 0.1 shows a distinct capacitance-step and hysteresis, which is attributed to C-donor/N-vacancy electron trap states located above the Fermi level (200 meV) at the heterointerface; whereas, the sample with Al fraction of 0.026 shows negative capacitance and dispersion, indicating C-donor/N-vacancy and deep Si-donor defect states located below the Fermi level (88 meV). When an i-GaN buffer layer was added to the structure, an anomalous high-frequency capacitance peak was observed and attributed to resonance scattering due to hybridization of localized Si-donor states in the band gap with conduction band states at the i-GaN/n+-GaN interface.

It is well known that ultraviolet (UV) B (280-315 nm) and blue light (400-500 nm) radiation can produce phototoxic lesions in the neural retina and the retinal pigment epithelium (RPE). In the first section of this thesis, bovine lens cells (epithelium and superficial cortical fibre cell) and human retinal pigment epithelial (ARPE-19) cells were used to characterize in vitro changes following oxidative stress with UVB radiation in ocular lens optics and cellular function in terms of mitochondrial dynamics. In the second part, human retinal pigment epithelial (ARPE-19) cells and in vitro bioassays were used together to develop an in vitro approach for UV radiation-induced retinal toxicology research. In the third chapter, the in vitro approach developed above was used with intraocular lens (IOL) materials to evaluate the UV radiation blocking efficiency of commercially available IOL’s. Lastly, narrowband blue light irradiation and in vitro assays were used to determine more precisely the wavelengths of blue light responsible for photochemical lesions of the retina as an effort to contribute to future IOL designs. The results from mitochondrial dynamics of lens cells and RPE cells show significant decreases in mitochondrial movement after UVB irradiation in a dose dependent manner. Results obtained from four in vitro assays (Alamar blue assay, confocal microscopy for mitochondrial distribution and nucleic acids damage, phagocytotic activity assay) for evaluating the UVB-induced damage in ARPE-19 show significant decreases in cell viability as well as phagocytotic activity of RPE cells after UVB radiation. In addition, the results show that UV radiation can also induce the degradation of DNA/RNA and mitochondria of RPE cells in a dose dependent manner. The results of the UV blocking efficiency test of commercially available IOL materials show very effective UV blocking ability, allowing no cellular damage at all, in comparison to an IOL uncovered control cell. The results of three different wavelengths of blue light exposure show that only 400 nm blue light radiation can cause significant damage to RPE cells, while 420 and 435.8 nm blue light radiation cause no cellular damage at all. In conclusion, UVB and blue light radiation can cause phototoxic damage to the retinal pigment epithelium as a result of oxidative stress, and in vitro bioassays used for this research may offer a sensitive, and meaningful biomarker approach, not only for evaluating RPE function after oxidative and chemical stress, but also for evaluating IOL effectiveness.

Title from first page of PDF document. Includes bibliographical references.

Many anticancer therapies are based on the interaction of small molecule drugs with nucleic acids, particularly DNA. Electrospray ionization tandem mass spectrometry has established itself as an irreplaceable tool for the characterization of DNA adducts produced by alkylating agents, carcinogens, and antitumor drugs, in addition to the characterization of nucleic acid post-transcriptional modifications. ESI-MS was used to assess the non-covalent binding of a novel series of intercalating anthrapyrazoles to duplexes containing different sequences. Relative binding affinities paralleled the shift in melting point of the DNA duplexes measured from a previous study. Upon collisionally induced dissociation of the duplex/anthrapyrazole complexes, different binding strengths were discerned based on the fragmentation patterns. In addition, the interactions of a new series of sulfur-containing acridine ligands, some that functioned as alklyating mustards, with duplex DNA were also evaluated. Non-covalent and covalent binding of each ligand was determined, and the site of adduction (G > A) was revealed for the covalent modifications. The distribution of cross-linked products and mono-adducts by psoralen analogs was also monitored by both LC-UV and IRMPD-MS methods. Reactions at 5’-TA sites were favored over 5’-AT sites. The sites of interstrand cross-linking were determined by fragmentation of the duplex/psoralen complexes by infrared multiphoton dissociation (IRMPD). Ultraviolet photodissociation (UVPD) at 193 nm caused efficient charge reduction of deprotonated oligodeoxynucleotides via electron detachment. Subsequent CID of the charge-reduced oligodeoxynucleotides formed upon electron detachment, in a net process called electron photodetachment dissociation (EPD), resulted in a diverse array of abundant sequence ions which allowed the modification site(s) of three modified oligodeoxynucleotides to be pinpointed to a more specific location than by conventional CID. Electron transfer dissociation (ETD) caused efficient charge reduction of multi-protonated oligonucleotides. Subsequent CAD of the charge-reduced oligonucleotides formed upon electron transfer, in a net process termed electron transfer collision activated dissociation (ETcaD), resulted in rich backbone fragmentation, with a marked decrease in the abundance of base loss ions and internal fragments. ETcaD of an oligonucleotide duplex resulted in specific backbone cleavages, with conservation of weaker non-covalent bonds. In addition, IRMPD and UVPD were used to activate charge-reduced oligonucleotides formed upon electron transfer. ET-IRMPD afforded tunable characterization of the modified DNA and RNA, allowing for modified bases to be directly analyzed. ET-UVPD promoted higher energy backbone fragmentation pathways and created the most diverse MS/MS spectra. The numerous products generated by the hybrid MS/MS techniques (ETcaD, ET-IRMPD, and ET-UVPD) resulted in specific and extensive backbone cleavages which allowed for the modification sites of multiple oligonucleotides to be pinpointed. / text

Les lasers à électrons libres (LELs) à simple passage représentent actuellement la possibilité la plus prometteuse pour fournir des impulsions lumineuses de haute énergie (µJ à mJ) à des échelles de durée femtoseconde (1 fs = 10⁻¹⁵s) et des longueurs d'ondes ultra-courtes (résolution nanométrique i.e., jusqu'aux domaines de l'extrême-ultraviolet et des rayons X). Les LELs émettant dans l'extrême-ultraviolet sont une technologie encore jeune, si bien que de nombreuses questions restent ouvertes. Celles posées au sein de ce manuscrit concernent la configuration dite injectée, dans laquelle le processus est initié par une source externe cohérente (le "seed"). Nous nous concentrons particulièrement dans cette thèse sur les caractéristiques transverses et longitudinales de la lumière, sa cohérence, les propriétés de la phase temporelle et les liens directs entre le seed et l'émission LEL. La technique de génération dans un gaz noble d'harmoniques d'ordres élevés d'un laser femtoseconde (GHE) se montre à la fois complémentaire et en compétition avec les LELs. En compétition car les impulsions produites ont des qualités similaires à celles obtenues avec un LEL ; complémentaire car le rayonnement GHE peut être utilisé comme seed ou en combinaison avec la lumière LEL, par exemple pour effectuer des expériences mettant en jeu de multiples faisceaux. Bien que la GHE fournisse des impulsions moins puissantes, l'implémentation d'une telle source requiert un effort significativement moins important. Le taux de conversion harmonique, l'accordabilité et la qualité spatiale du faisceau généré, et la manière dont ces paramètres dépendent du laser générateur sont les problématiques traitées au sein de ce manuscrit. La volonté de la communauté scientifique d'effectuer des expériences novatrices demande des études profondes et l'optimisation des sources de GHE et des LELs. En particulier, sur la source LEL injectée FERMI@Elettra de Trieste, l'induction d'une dérive de fréquence dans le rayonnement a conduit à des résultats marquants. Entre autres, une méthode de génération d'impulsions scindées avec différentes longueurs d'ondes a été analysée et développée. Une telle possibilité ouvre la voie à l'utilisation des LELs injectés en tant que source autonome pour des installations de type pompe-sonde à deux couleurs. Plus généralement, l'étude des phénomènes mis en jeu dans les processus de GHE et du LEL ainsi que la caractérisation des propriétés de leur lumière sont des sujets intrinsèquement excitants, ayant des connexions directes avec de nombreux aspects fondamentaux de la physique.

Mean-field approaches successfully reproduce nuclear bulk properties like masses and radii within the Energy Density Functional (EDF) framework. However, complex correlations are missing in mean-field models and several observables related to single-particle and collective nuclear properties cannot be predicted accurately. The necessity to provide a precise description of the available data as well as reliable predictions in the exotic regions of the nuclear chart motivates the use of more sophisticated beyond-mean-field models. Correlations and higher-order corrections (beyond the leading mean-field order) are introduced. A crucial aspect in these calculations is the choice of the effective interaction to be used when one goes beyond the leading order (available effective interactions are commonly adjusted at the mean-field level). In the first part, we deal with the equation of state of nuclear matter evaluated up to the second order with the phenomenological Skyrme force. We analyze the ultraviolet divergence that is related to the zero range of the interaction and we introduce Skyrme-type regularized interactions that can be used at second order for matter. Cutoff regularization and dimen- sional regularization techniques are explored and applied. In the latter case, connections are naturally established between the EDF framework and some techniques employed in Effective Field Theories. In the second part, we check whether the regularized interactions introduced for nuclear matter can be employed also for finite nuclei. As an illustration, this analysis is performed within the particle- vibration model that represents an example of beyond mean-field models where an ultraviolet divergence appears if zero-range forces are used. These first applications suggest several directions to be explored to finally provide regularized interactions that are specially tailored for beyond- mean-field calculations for finite nuclei. Conclusions and perspectives are finally illustrated.

The material and device characteristics of InGaN/GaN heterojunction bipolar transistors (HBTs) grown by metalorganic chemical vapor deposition are examined. Two structures grown on sapphire with different p-InxGa1-xN base-region compositions, xIn = 0.03 and 0.05, are presented in a comparative study. In a second experiment, NpN-GaN/InGaN/GaN HBTs are grown and fabricated on free-standing GaN (FS-GaN) and sapphire substrates to investigate the effect of dislocations on III-nitride HBT epitaxial structures. The performance characteristics of HBTs on FS-GaN with a 20×20 m2 emitter area exhibit a maximum collector-current density of ~12.3 kA/cm2, a D.C. current gain of ~90, and a maximum differential gain of ~120 without surface passivation. For the development of deep-ultraviolet optoelectronics, several various structures of optically-pumped lasers at 257, 246, and 243 nm are demonstrated on (0001) AlN substrates. The threshold-power density at room temperature was reduced to as low as 297 kW/cm2. The dominating polarization was measured to be transverse electric in all cases. InAlN material was developed to provide lattice matched, high-bandgap energy cladding layers for a III-N UV laser structure. This would alleviate strain and dislocation formation in the structure, and also mitigate the polarization charge. However, a gallium auto-doping mechanism was encountered which prevents the growth of pure ternary InAlN, resulting instead in quaternary InAlGaN. This phenomenon is quantitatively examined and its source is explored.