Dissertations / Theses on the topic 'Failure of UV irradiation'

Atopic dermatitis (AD) is a common, chronic relapsing inflammatory skin disease associated with cutaneous hyper-reactivity to environmental triggers that are innocuous to normal nonatopic individuals. AD affects 10% to 15% of children and 2% to 10% of adults in industrialized countries. There has been increasing interest in this disease triggered by its increasing prevalence in western societies and its contribution to the increasing health care costs. Yet, the underlying pathophysiologic and genetic mechanisms leading to the manifestation of AD are not clear. AD results from a complex interplay between environmental triggers, susceptibility genes including mutations in the keratinocyte protein filaggrin and altered immune responses resulting in allergic CD4+ T cell (Th2) immunity to epidermally encountered antigens. Regulatory T cells (Tregs) play an important role in controlling responsiveness to self-antigens and preventing autoimmune diseases, as well as in limiting inflammatory responses during inflammation and infection. Currently, studies investigating the number and function of Tregs in patients with AD have shown controversial results. It has been long established that symptoms of AD improve on exposure to sunlight. Narrowband UVB (NB-UVB) phototherapy is a common treatment modality for a variety of skin diseases. Considering the adverse effects for systemic treatment for severe adult AD, phototherapy, especially NB-UVB phototherapy may be a more practical long-term treatment. However, approximately 50% of patients over an 8-week treatment course do not improve after NB-UVB phototherapy. Therefore, it is important to identify characteristics of AD patients to determine whether they will respond to phototherapy and to avoid adverse effects for unresponsive patients. UVB exposure has also been associated with induction of Tregs in mice and increasing their numbers and/or functional capacity may offer benefit to patients with chronic AD. Active vitamin D (1,25(OH)2D3), one of the factors induced by UV-B radiation induces Tregs and is suggested to contribute to the suppressive effect of NB-UVB phototherapy. However, UV radiation could also have beneficial effects through other pathways known to affect immunoregulation. UVB exposure upregulates production of nitric oxide (NO) in the skin which also affects immune cell function. The protein filaggrin is broken down in differentiating keratinocytes to form the natural moisturizer of the skin. The gene encoding filaggrin (FLG) has been shown to be a major predisposing factor for AD. A key breakdown product is urocanic acid (UCA) which also acts as a natural sunscreen and undergoes trans-cis isomerisation on exposure to UV-B. Cis-UCA is known to modulate immune responses, however, the mechanisms of its action remain elusive. The production of all three compounds, vitamin D, cis-UCA and NO might all increase in the circulation of patients undergoing UVB phototherapy. While the immunomodulatory effect of Vitamin D is well described, cis-UCA and NO may also affect the behaviour of T lymphocytes systemically. Therefore, I investigated the effect of NO and cis-UCA on the phenotype and function of CD4+T cells and monocyte-derived dendritic cells (Mo-DCs) derived from peripheral blood mononuclear cells (PBMCs) from healthy volunteers. I also investigated the correlation between plasma concentration of 25(OH) vitamin D and nitrate, FLG genotype, circulating Tregs and clinical efficacy of NB-UVB phototherapy. My results showed that NO did not affect the phenotype of human mo-DCs and directly affected peripheral CD4+ T cells by inducing functional CD25+Foxp3+CD127-Tregs from CD4+CD25lo/- effector T cells. Moreover, NO increased expression of the of skin homing marker CLA on these Tregs, suggesting an increased ability of NO-induced Tregs to migrate to the skin. These NO-induced CD25+Foxp3+CD127-Tregs had immunosuppressive functions and inhibited autologous CD4+ T cell proliferation. Cytokines, at least IL-10, secreted by NO-treated CD4+ T cells were not sufficient for the suppressive function of NOinduced Foxp3+Tregs. The immune regulatory function of NO-induced Fopx3+Tregs required cell-cell contact and was mediated by membrane bound TGFβ and PD-1/PD-L1 but not CTLA-4. Results also showed that cis-UCA might have both pro- and anti-inflammatory effects. Cis- UCA significantly decreased the proportion of CD25hi Foxp3+ cells from activated CD4+ T cells. It also decreased the expression of vitamin D receptor in CD4+ T cells which may interfere with the immune regulatory function of vitamin D. These results suggested that there might be a fine balance between UV-induced anti-inflammatory molecules’ effect on CD4+ T cells. However, Cis-UCA also modulated CD4+ T cell directly by decreasing CD4+ T cell proliferation, decreasing phosphorylation of ERK after TCR activation, enhancing immune suppressive cytokines secretion, and inhibiting the percentage of CLA+CD4+T cells suggesting a decreased ability to migrate to the skin, . Cis-UCA also affected the phenotype and function of antigen presenting cells by decreasing the expression of HLA-DR, CD86 and CD40 on immature mo-DCs, which led to increased proportion of CD25+Foxp3+CD127- T cells when co-cultured with allogenic CD4+ T cells. Results generated from the clinical study in which all 29 patients got better after phototherapy suggested although circulating 25 (OH) vitamin D concentration was significantly increased after NB-UVB phototherapy, the change of circulating 25 (OH) vitamin D concentration did not correlate with disease improvement. This suggests that vitamin D is not the only pathway involved and that other molecules contribute to UVB-induced immune-regulation. The data also show that of the levels of circulating nitrate and the FLG genotype did not correlate with improvement / change with phototherapy. However, the expression of CD69 and CLA on circulating CD4+ T cells was decreased after treatment suggesting that UVB affected T cell activation and migration to the skin, and their importance in determining clinical responses requires further investigation. Taken together, the results from my study provide evidence that vitamin D is not the only molecule responsible for the beneficial effect of NB-UVB phototherapy. NO and cis-UCA may down-regulate immune responses by affecting human peripheral CD4+ T cells and mo- DCs phenotype and function. A further understanding of the effect of NO and cis-UCA on skin resident immune cells will provide more insights for narrowing NB-UVB phototherapy which will help to select patients that most likely to benefit from a mechanism-based treatment.

Abstract Electron-ion coincidence spectroscopy has been used to study the fragmentation behaviour of small molecules in two distinct cases: to resolve the state specific fragmentation patterns of HgBr₂ and HgCl₂ subsequent to UV ionization, and to distinguish the dissociation behaviour of various chlorinated methanes (CH₃Cl, CH₂Cl₂, CHCl₃ and CCl₄) subsequent to X-ray irradiation. The mercury-compound work has revealed details on the electronic structure and dissociation dynamics of the valence states which were previously unknown. The study on the chlorinated methanes has found new details on the exact pathways of the appearance of a specific fragment and also investigates the speed of the dissociation in the four different chlorinated methane molecules. The results from the electron-ion coincidence spectroscopic experiments are presented and analysed together with theoretical and computational support.

One of the greatest challenges for the study of photocatalysts is to devise new catalysts that possess high activity under visible light illumination. This would allow the use of an abundant and green energy source, sunlight, to drive chemical reactions. Gold nanoparticles strongly absorb both visible light and UV light. It is therefore possible to drive chemical reactions utilising a significant fraction of full sunlight spectrum. Here we prepared gold nanoparticles supported on various oxide powders, and reported a new finding that gold nanoparticles on oxide supports exhibit significant activity for the oxidation of formaldehyde and methanol in the air at ambient temperature, when illuminated with visible light. We suggested that visible light can greatly enhance local electromagnetic fields and heat gold nanoparticles due to surface plasmon resonance effect which provides activation energy for the oxidation of organic molecules. Moreover, the nature of the oxide support has an important influence on the activity of the gold nanoparticles. The finding reveals the possibility to drive chemical reactions with sunlight on gold nanoparticles at ambient temperature, highlighting a new direction for research on visible light photocatalysts. Gold nanoparticles supported on oxides also exhibit significant dye oxidation activity under visible light irradiation in aqueous solution at ambient temperature. Turnover frequencies of the supported gold nanoparticles for the dye degradation are much higher than titania based photocatalysts under both visible and UV light. These gold photocatalysts can also catalyse phenol degradation as well as selective oxidation of benzyl alcohol under UV light. The reaction mechanism for these photocatalytic oxidations was studied. Gold nanoparticles exhibit photocatalytic activity due to visible light heating gold electrons in 6sp band, while the UV absorption results in electron holes in gold 5d band to oxidise organic molecules. Silver nanoparticles also exhibit considerable visible light and UV light absorption due to surface plasmon resonance effect and the interband transition of 4d electrons to the 5sp band, respectively. Therefore, silver nanoparticles are potentially photocatalysts that utilise the solar spectrum effectively. Here we reported that silver nanoparticles at room temperature can be used to drive chemical reactions when illuminated with light throughout the solar spectrum. The significant activities for dye degradation by silver nanoparticles on oxide supports are even better than those by semiconductor photocatalysts. Moreover, silver photocatalysts also can degrade phenol and drive the oxidation of benzyl alcohol to benzaldehyde under UV light. We suggested that surface plasmon resonance effect and interband transition of silver nanoparticles can activate organic molecule oxidations under light illumination.

Le travail présenté dans ce mémoire a pour objet le développement des revêtements pigmentés de forte épaisseur, opacifiants et photoréticulables par un rayonnement UV-visible. Ces formulations sont destinées à recouvrir des supports bois pour le marché de l'ameublement. Afin d'apporter une réponse à ce problème industriel, une recherche bibliographique exhaustive s'est avérée nécessaire pour définir les différents axes à suivre. Notre premier objectif fut de définir, en milieu épais pigmenté, les performances des photoamorceurs utilisés couramment dans les réactions de photopolymérisation. Pour une meilleure compréhension des limites observées sur les systèmes amorceurs, une étude a été menée ultérieurement sur les propriétés optiques des pigments et a permis de déterminer leur fenêtre de transmission dans le visible. Par conséquent, notre recherche s'est orientée vers des réactions de photopolymérisation sensibilisée par des colorants. Cette nouvelle orientation a permis la mise au point d'une formulation pigmentée pour différents coloris applicable à l'échelle industrielle.

The ability to modify the surfaces of polymers and impart desirable functionalities without affecting the bulk-mediated physical properties is vital for advanced materials development. Photochemical approaches to surface modification are particularly attractive as they minimize the need for use of hazardous materials used in conventional wet chemical technologies, and are relatively faster, efficient and convenient to use. In this research, we undertook a combined experimental and computational approach to understand the effect of deep UV irradiation on a broad range of polymeric materials, and develop a scalable and deployable surface modification strategy that could be extended to all. Four polyesters, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate(PBT) and polyethylene napthalate (PEN), Kapton polyimide, a polyolefin and cellulose were the polymers investigated. Technical grades of the material were used in order to understand the fundamental science as well as develop a scalable deployable technology. Surface analysis was done using the X-Ray Photoelectron Spectroscopy (XPS), Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS), Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy(ATR-FTIR), Atomic Force Microscopy (AFM) and contact angle measurements. The experiments were carried out using a high intensity 172 nm xenon microplasma lamp, and the effect of varying doses of UV irradiation, 0, 8, 16, and 32 J/cm2 on the polymer surfaces were characterized. The effect of using two different intensity levels was also compared. In case of the polyesters and polyimide, calculated UV/VIS absorption spectra using the ZINDO//B3LYP/321-G method or the AM1/ZINDO approach were used to give an indication of which orbitals were involved in transitions near 172 nm, a valuable tool for predicting future research and development. It was found that 172 nm excimer UV lamp was successful in creating active surface radicals in all the polymers investigated. The AFM results did not indicate any significant surface roughening at 16 J/cm2 total irradiation dose, which was also found to be the radiation level at which a reaction set point was reached in all the polymers. Vapor phase photo-assisted grafting of an alkane and alkene onto to the polyester surfaces indicated a common trend in the surface chemistry changes. to develop a potentially useful low energy surface that would impart anti soil and cleanibility properties, a fluorocarbon was successfully grafted on each material. Water and light mineral oil contact angle measurements confirmed a marked increase in hydrophobicity and oleophobicity, in some cases reaching that close to pure polytetrafluoroethylene. The grafted surface was found to be significantly wash durable. This is a valuable development as the process is minimally hazardous, relatively simple, fast, efficient, economic, and easily scalable and deployable. Particularly in the case of some polymers, such as polyolefins and cellulose, this method bypasses the challenges of complex processing routes and harmful chemicals that are currently used to achieve the same goal.

En environnement spatial, la contamination moléculaire des surfaces des satellites constitue un problème majeur par la modification de leurs propriétés optiques ou thermo-optiques. En présence de rayonnements UV, les dégradations peuvent être aggravées par la fixation photochimique de contaminants. Le travail présenté dans cette thèse concerne donc les modifications physico-chimiques des contaminants moléculaires sous l’irradiation UV-V (ultraviolet du vide : 100 – 200 nm) entraînant cette fixation. Dans le but de comprendre les mécanismes de ces modifications, nous avons effectué des expériences de contamination et d'irradiation avec des contaminants purs. La formation de produits sous irradiation a été caractérisée de façon massique in situ (dépôt et ATG sur microbalance à quartz) et ex situ par des méthodes morphologiques (MEB), optiques (spectrométrie UV-Visible-PIR et IR) et chimiques (Chromatographie Phase Gazeuse couplée Spectrométrie de Masse). Différentes conditions de dépôt ont été étudiées (croissance d'un dépôt irradié, irradiation d'un dépôt épais) et une étude paramétrique sur les conditions d'irradiation a été menée. Nous avons ainsi pu mettre en évidence la modification et la fixation des contaminants et proposer des mécanismes de modification physico-chimiques des contaminants sous l’effet des UV-V. Des radicaux libres sont formés sous irradiation UV-V des contaminants. Leur addition forme des molécules de volatilités variées dont les petites expliquent la photolyse observée, tandis que les grosses molécules expliquent la fixation de contaminants dégradant les surfaces des satellites.

Ce travail de recherche a été mené dans le cadre d'un projet européen Esprit sur la fabrication assistée par ordinateur de micro-circuits. Notre objectif était de mettre au point un photorésist à base d'acrylates très sensible au rayonnement UV ou visible d'un laser focalisé fonctionnant en mode continu, dans le but de réaliser l'écriture directe de micro-circuits à une vitesse de l'ordre de 1000 m/s. La recherche consacrée à la formulation et à l'optimisation des performances des résines photopolymérisables dans le domaine de l'UV a conduit à un photorésist composé d'un oligomère polyester-amino-tétra-acrylate, d'un monomère monoacrylique contenant une fonction oxazolidone et d'une morpholinocétone comme photoamorceur. Une vitesse d'écriture de 600 m/s a ainsi pu être atteinte. Une étude similaire pour mettre au point un système photosensible à l'émission visible du laser à argon ionisé (488 nm) a conduit à associer un colorant xanthénique avec un titanocène fluoré, une chlorométhyltriazine et une amine aliphatique. Les performances en termes de vitesse de polymérisation et de sensibilité ont été ameliorées en présence d'un composé brome, grâce à son effet d'atomes lourds. La photosensibilité est analogue à celle observée lors de l'irradiation UV en présence d'air. Le champ de nos recherches a été étendu à l'étude des cinétiques de polymérisation des résines acryliques (évaluation des rendements quantiques de polymérisation, des constantes de vitesse) et de disparition des photoamorceurs (évaluation des rendements quantiques de disparition des molécules photosensibles). Les informations quantitatives ainsi obtenues ont permis une meilleure compréhension des mécanismes réactionnels mis en jeu lors de ces réactions photochimiques

La question des détritus marins de plastique et de leur impact sur l'environnement prend de l’ampleur. Il a été démontré que 80% des plastiques sont issus de sources terrestres, tandis que 20% viennent des côtes et mers. De nombreux auteurs soulignent un problème environnemental sérieux lié à l'absorption de POP (Polluants Organiques Persistants) par les débris plastiques, initiant ainsi une source potentielle de contamination de la chaîne alimentaire. Tous les auteurs attribuent la fragmentation en « microplastiques » (taille < 5mm) à des phénomènes liés à la dégradation, en particulier sous UV sans l’avoir jamais réellement ni démontré ni analysé. Les rivières constituant alors un vecteur privilégié de transport des déchets terrestres vers les mers et océans, nous avons décidé de mettre en évidence (et de quantifier) la présence de microplastiques dans une rivière réputée « sauvage » comme l’Allier. Au laboratoire, nous mettons au point des protocoles de simulation de la fragmentation des plastiques sous irradiations UV de différentes matières plastiques dans l'eau (douce). Nous analysons aussi bien les molécules chimiques issues de la dégradation des plastiques et transférées dans le milieu aqueux que les modifications moléculaires que peut subir le matériau
The question of marine litter and their environmental impact gains importance. It was shown that 80% of plastics results from terrestrial sources, while 20% come from coastlines and seas. Many authors point to a serious environmental problem involved to the absorption of POPs (persistent organic pollutants) by plastic detritus, thus initiating a potential source of contamination of the food chain. All authors attribute the fragmentation to "microplastic" (size < 5mm) to phenomena related to degradation, under UV without ever having demonstrated or analysed it. The rivers constituting then a privileged vector of transport of the terrestrial waste towards the seas and oceans, we decided to highlight (and quantify) the presence of microplastics in a river known as "wild" as the Allier. At the laboratory, we develop simulation protocols for the fragmentation of plastics under UV irradiation of various plastic materials in fresh water. We analyse both the chemical molecules resulting from the degradation of plastics and transferred to the aqueous medium as well as the molecular changes that can undergo the material

Consumer demand for fresher and minimally processed foods has brought about a movement to find effective, non-thermal processing technologies for the treatment of milk. The influence of temperature on bacterial reduction in UV irradiated milk was tested. Commercially processed skim, reduced fat (2%), and whole milk samples were inoculated with a naladixic acid resistant E. coli O157:H7 surrogate (ATCC 25922), maintained at or brought to 4oC and 20oC, respectively, and then exposed to a UV light dose between 5.3-6.3 mJ/cm2 for approximately 1.5 sec using the CiderSure 3500 apparatus (FPE Inc., Macedon, NY). Bacterial concentrations before and after UV exposure were enumerated and the results indicated that processing temperature was not significantly related to bacterial reduction (p > 0.05). The results did indicate that skim milk samples had a greater bacterial reduction, regardless of processing temperature compared to reduced fat milk and whole milk samples (p < 0.05). Solids such as milk fat, protein, lactose and minerals, in the milk have a greater effect over bacterial reductions than processing temperatures. Traditional goat cheeses are produced using unpasteurized milk, which increases the food safety concerns for these types of products. Fresh goat's milk was inoculated to 107 cfu/ml with Listeria monocytogenes (L-2289) and exposed to UV light using the CiderSure 3500 apparatus. Inoculated milk was exposed to an ultraviolet dose range between 0 and 20 mJ/cm2 to determine the optimal UV dose. A greater than 5-log reduction was achieved (p < 0.0001) when the milk was processed 12 times for a cumulative exposure time of roughly 18 sec and a cumulative UV dose of 15.8 +/- 1.6 mJ/cm2. The results of this study indicate that UV irradiation could be used for the reduction of L. monocytogenes in goat's milk. Organoleptic consequences of goat's milk treated with UV technology were assessed. Olfactory studies were conducted and a highly significant difference was determined between the odor of fresh goat's milk and UV processed milk (p < 0.05). The extent of lipid oxidation and hydrolytic rancidity was measured by thiobarbituric acid reactive substances (TBARS) and acid degree values (ADVs). Results indicated that as the UV dose increased, there was a significant increase in TBARS values and ADVs of the milk samples (p < 0.05). Milk samples were processed using the UV processor under the same conditions as previously described without exposure to the UV source to determine if the agitation from pumping was causing off-flavors by way of hydrolytic rancidity. The ADVs from these samples increased at the same rate as the UV irradiated samples; however, sensory studies indicated that the increase of free fatty acids (FFA) was not enough to cause detectable off-odors in the milk. Solid phase microextraction and gas chromatography (SPME-GC) was utilized to quantify the production of volatile compounds that were formed due to UV processing. The formation of pentanal, hexanal and heptanal was identified after as little as 1.3 mJ/cm2 UV dose. Peak areas were measured and analyzed after 7.8 mJ/cm2 and 15.6 mJ/cm2 and were determined to increase significantly as UV dose increased (p < 0.05). The chemical analyses supported the findings from the olfactory studies. The outcome of this research showed that UV irradiation at the wavelength 254 nm, was detrimental to certain chemical properties of fluid milk. The properties that were perceived as negative in fluid milk may be considered an attribute in certain types of cheese and future studies in the cheese production sector should be considered. Other applications for this technology could be for use in developing countries where milk is not typically processed because of the high costs of thermal pasteurization. On-farm applications for the treatment of replacement milk should also be considered.
Ph. D.

N-Nitrosamines and N-nitrosamides have been reported to be mutagenic. N-Nitrosamides are direct mutagens that need no activation to be mutagenic, whereas N-nitrosamines need to be enzymatically activated to exert their mutagenicity. Oxidative demethylation of nitrosamines is a commonly accepted activation mechanism. Another pathway of nitroso compounds, denitrosation, has recently been proposed. The mechanism of denitrosation, however, is still unknown. The purpose of this study was to use a photo -reaction model to explore the possible denitrosation mechanism of N-nitroso compounds. An N-nitrosamine, N-nitrosomorpholi ne (NMOR), and an N-nitrosamide, N-methyl-N'-nitrosoguanidine (MMNG), were irradiated with long-wavelength UV light in the presence of phosphate. Denitrosation of these nitroso compounds occurred, and free radicals were generated during the photolysis of N-nitroso compounds. The free radical from NMOR is carbon centered, and the free radical from MNNG is nitrogen centered. They have different responses to phosphate. A stable mutagen is formed during the photolysis of NMOR in the presence of phosphate. The formation of this stable mutagen is through a free-radical mechanism. MNNG appears to be inactivated in terms of mutagenicity by the photodenitrosation. Free radicals produced during the photolysis of NMOR and MNNG are mutagenic through a direct radical interaction mechanism. The results of this study indicate that the newly found pathway of N-nitroso compounds, denitrosation, may be related to a free-radical mechanism.

Les dommages de l'ADN interfèrent avec sa réplication et sa transcription. Ils sont en général éliminés par des mécanismes de réparation, en particulier par la réparation par excision de nucléotides (NER). Ils peuvent également être tolérés grâce à la synthèse translésionnelle (TLS). Au cours de mon travail de thèse, nous avons étudié l'implication de la voie NER et de l'ADN polymérase η (Polη) associée à la TLS dans la réponse aux lésions de l'ADN induites par les rayons ultraviolet (UV) et par une drogue chimiothérapeutique, la doxorubicine. Les principales lésions induites par les rayons UV sont les dimères de pyrimidine cyclobutane (CPDs) et les pyrimidines (6-4) pyrimidones (6-4PPs) qui sont éliminées par la NER. Les données obtenues sur la formation de régions d'ADN simple brin et celles du cycle cellulaire suggèrent que les lésions 6-4PPs sont tolérées par un mécanisme de réparation post-réplicative dans des cellules XP-C déficientes en NER (xeroderma pigmentosum du groupe C). Dans un second temps, mon objectif a été de déterminer la contribution de Polη dans la prise en charge des lésions induites par les rayons UV dans les cellules XP-C. En effet, il est connu que Polη est responsable de la réplication des CPDs, mais l'absence de Polη dans des cellules proficientes en NER ne les rend pas hypersensibles aux rayons UV. De plus, il a été suggéré que Polη soit impliquée dans la TLS des 6-4PPs. En réprimant par shARN l'expression du gène codant Polη dans les cellules XP-C, j'ai réussi à établir la première lignée stable de fibroblastes humains déficients à la fois en NER et en Polη (XP-C/PolηKD). Cette réduction fonctionnelle de l'expression de Polη dans les cellules XP-C irradiées à faible dose d'UV a entraîné un arrêt irréversible du cycle cellulaire, la génération de cassures simple- et double-brin de l'ADN et une mortalité cellulaire significative. Ces résultats montrent un rôle crucial de Polη dans la survie des cellules déficientes en NER après irradiation UV et suggèrent que Polη puisse participer aussi à la TLS des 6-4PPs.Par ailleurs, nous avons montré que les cellules déficientes en NER ou en Polη ont été sensibilisées par un traitement à la doxorubicine indiquant que la NER et Polη participent également de la prise en charge des lésions induites par cet agent. Donc au cours de mon travail de thèse, j'ai mis en évidence des interconnexions complexes entre Polη et la voie NER en réponses à différents agents génotoxiques.

ABSTRACT As far back as the early 1900?s when it was discovered that water could be a mode of transmitting diseases, chlorine was used to disinfect water. In the 1970?s, the formation of disinfection by-products (DBPs) from the reaction of chlorine with natural organic matter was discovered. Since then there have been various studies on alternative disinfectants that could inactivate microorganisms and at the same time form less or no disinfection by-products. More recently the ultraviolet (UV) irradiation has been used to both disinfect and remove organic contaminants in drinking water. Though the use of UV irradiation has been found to be very effective in the inactivation of microorganisms, it does not provide a residual effect to maintain the water?s microbial quality in the distribution system. Due to this, a secondary disinfectant such as chlorine has to be used to achieve microbial stability, suggesting that the formation of chlorination disinfection by-products would still occur but perhaps in different quantities and with different chemical species. In this research, the use of factorial experiments and single factor experiments were used to determine the effects of pH, alkalinity and UV-fluence (dose) on the formation of three classes of disinfection by-products; haloacetic acids (HAAs), haloacetonitriles (HANs) and trihalomethanes (THMs). These disinfection by-products were measured in water samples following post-UV chlorination and the UV treatment was either UV photolysis or UV/H₂O₂. From the factorial experiment results, treatment of synthetic water with UV/H₂O₂, an advanced oxidation process (AOP), produced fewer post-UV chlorination disinfection by-products (PCDBPs) than UV photolysis. For chlorinated PCDBPs, the percentage difference between UV photolysis and UV/H₂O₂ was 55, 65 and 38% for total HAAs (HAA₉), total HANs (THANs) and total THMs (TTHMs) respectively. The percentage difference between UV photolysis and UV/H₂O₂ for brominated PCDBPs was 41 and 42% for HAA9 and TTHMs respectively. Both the use of pH and alkalinity proved to be factors that were significant in affecting the yields of the PCDBPs studied. Increases in alkalinity were found to increase the formation of PCDBPs in the treatment of synthetic water with UV/H₂O₂. Alkalinity had the opposite effect for PCDBP formed under UV photolysis conditions. Increases in pH always decreased the formation of PCDBPs. In the single factor experiments, haloacetic acid concentrations were unaffected as alkalinity was increased but dichloroacetonitrile and chloroform increased in concentration under treatment conditions of UV photolysis followed by chlorination. The UV/H₂O₂ treatment resulted in a decrease in concentration of the PCDBPs. In the pH studies, water samples were subjected only to the UV/H₂O₂ treatments and a reduction in concentration of PCDBPs occurred between pH 7 and 9.

The efficacy of ozone and ultraviolet light, used in combination, to inactivate Listeria monocytogenes in fresh (9% NaCl, 91.86% transmittance at 254 nm) and spent chill brines (20.5% NaCl, 0.01% transmittance at 254 nm) was determined. Preliminary studies were conducted to optimize parameters for the ozonation of â freshâ and â spentâ brines. These include diffuser design, comparison of kit to standard methods to measure residual ozone, studying the effect of ozone on uridine absorbance and determining presence of residual listericidal activity post ozonation. An ozone diffuser was designed using 3/16 inch PVC tubing for the ozonation of brines. The sparger was designed to facilitate better diffusion and its efficiency was tested. The modified sparger diffused 1.44 ppm of ozone after 30 minutes of ozonation and the solution had an excess of 1 ppm in 10 minutes of ozonating fresh brine solution (200ml). Population levels of L. monocytogenes were determined at various time intervals post-ozonation (0, 10, 20, 60 min) to determine the presence of residual listericidal activity. The population post ozonation (0 minutes) was 5.31 Log CFU/ml and was 5.08 Log CFU/ml after a 60 minute interval. Therefore, residual antimicrobial effect was weak. Accuracy of the Vacu-vial Ozone analysis kit was evaluated by comparing the performance of the kit to the standard indigo colorimetric method for measuring residual ozone. The kit was inaccurate in determining residual ozone levels of spent brines and 1% peptone water. Uridine was evaluated as a UV actinometric tool for brine solutions that were ozonated before UV treatment. The absorbance of uridine (A262) decreased after ozonation from 0.1329 to 0.0512 for standard 10 minutes UV exposure duration. Absorbance of uridine was influenced by ozone indicating that the presence of ozone may hamper UV fluence determination accuracy in ozone-treated solutions. Upon completion of diffuser design and ozone/UV analysis studies, the effect of ozone-UV combination on L. monocytogenes in fresh and spent brines was evaluated. Ozonation, when applied for 5 minutes, caused a 5.29 mean Log reduction while 5 minutes of UV exposure resulted in a 1.09 mean Log reduction of L. monocytogenes cells in fresh brines. Ten minutes of ozonation led to a 7.44 mean Log reduction and 10 minutes of UV radiation caused a 1.95 mean Log reduction of Listeria in fresh brine. Spent brines required 60 minutes of ozonation for a 4.97 mean Log reduction in L. monocytogenes counts, while 45 minutes resulted in a 4.04 mean Log reduction. Ten minutes of UV exposure of the spent brines resulted in 0.30 mean Log reduction in Listeria cells. A combination of 60 minutes ozonation and 10 minute UV exposure resulted in an excess of 5 log reduction in cell counts. Ozonation did not cause a sufficient increase in the transmittance of the spent brine to aid UV penetration but resulted in apparent color change as indicated by change in L*a*b* values. Ozonation for sufficient time had considerable listericidal activity in fresh brines and spent brines and when combined with UV treatment, is effective reducing L. monocytogenes to undetectable levels in fresh brines.
Master of Science in Life Sciences

Ce travail de these a pour objectif d'essayer d'ameliorer la capacite de retention des globules blancs (gb) de fibres de pet constitutives des filtres standard utilises en filtration sanguine, par modification de leur surface par greffage d'oligosaccharides presentant une affinite pour les gb. Les oligosaccharides sialyl lewis x sont connus pour etre de bons ligands des l-selectines, proteines presentes a la surface des gb. Le greffage a la surface du pet d'un oligosaccharide sialyl lewis x devrait ainsi permettre de retenir de maniere plus selective les gb lors de la filtration de sang humain. Nous nous sommmes alors interesses a la realisation de modeles de greffage avec des oligosaccharides moins elabores a base de lactose, dans le but de mettre au point des conditions qui permettraient d'obtenir un greffage optimal. La premiere strategie envisagee, un greffage par copolymerisation radicalaire entre des fibres de pet, des monomeres d'acrylamide et des monomeres a base de lactose n'a pas donne de resultats satisfaisants. Un greffage par irradiation aux rayonnements uv a alors ete realise entre le pet et un oligosaccharide hautement photoreactif a base de lactose, sur des films de pet par simple depot d'une solution de l'oligosaccharide, puis sur des fibres de pet par trempage-adsorption et a permis l'obtention d'un greffage quantitatif sur les fibres et d'un greffage quasi-quantitatif sur le film. Nous nous sommes enfin interesses a la synthese d'un hexasaccharide photoreactif de type sialyl lewis x. Lors de la derniere etape, le produit final n'ayant pu etre isole pur, le greffage par irradiation uv et les tests biologiques de deleucocytation n'ont pu etre realises
The objective of the present work is to improve the leukocyte retention ability of pet fibers, constituent in standard deleukocytation filters, by grafting carbohydrates with an affinity to white blood cells. Sialyl lewis x carbohydrates are known to be good ligands for some proteins present on leukocytes surface, the l-selectins. In this way, grafting of a sialyl lewis x carbohydrate on the pet surface should lead to a more selective leukocyte retention during human blood filtration. In this perspective, we have been interested in carrying out grafting models with less elaborate carbohydrates and more exactly with lactose-based carbohydrates to determine optimal grafting conditions. The first considered strategy, a grafting by copolymerization between pet fibers, acrylamide monomers and lactose-based monomers has not led to satisfying results. Grafting of a uv-reactive lactose-based carbohydrate has been then carried out on pet film by a simple deposite of a solution of the photoreactive molecule and on pet fibers by dip-coating. By this uv-grafting method, a quantitative grafting on fibers and a near-quantitative grafting on film were obtained. At least, we have been interested in synthesizing a uv-reactive sialyl lewis x hexasaccharide. Unfortunately, at the last step of the synthesis, the final product has not been pure isolated and consequently, uv-grafting and biological tests of deleukocytation have not been performed

Le rôle du mélanocyte dans la pigmentation de la peau n'est plus a démontré, par contre son rôle photoprotectif est controversé. Le rôle du mélanocyte a été étudié en comparant des épidermes reconstruits avec 100 % de kératinocytes et des épidermes reconstruits avec 95 % de kératinocytes et 5 % de mélanocytes. Dans un premier temps, l'effet d'une irradiation UVB aiguë a été étudié sur ces deux types de reconstructions, puis l'étude a été élargie aux effets des UVA et des UVA+B. Ces études ont permis de montrer, qu'après irradiation, la présence de mélanocytes au sein de l'épiderme reconstruit prévient l'apoptose sans pour autant protéger de façon significative de la formation des lésions directes de l'ADN (CPD et 6-4PP) et permet le maintien du rapport SOD/Catalase (principales enzymes antioxydantes). Par contre, la présence de mélanocytes au sein de l'épiderme amplifie les oxydations lipidiques et protéiques UV-induites mais semble prévenir l'oxydation de l'ADN. Les mélanocytes possèdent en plus de la mélanine, une plus grande concentration en acides gras polyinsaturés membranaires que les kératinocytes. Afin d'estimer quelle est la part de la mélanine et quelle est celle des acides gras polyinsaturés mélanocytaires dans les réponses UV-induites, des épidermes reconstruits avec des kératinocytes ont été suppléméntés avec des acides gras polyinsaturés. Cette étude a permis de mettre en évidence que ce sont les acides gras qui induisent l'amplification des oxydations lipidiques et protéiques alors que la mélanine protège l'ADN de l'oxydation induite par la lipoperoxydation. Ces différentes études ont également permis de montrer que face aux UV, l'épiderme reconstruit se comporte de façon similaire à l'épiderme normal in-vivo. Dans un dernier temps, des crèmes solaires et des antioxydants systémiques ont été testés et ont permis de confirmer que le modèle d'épiderme reconstruit est tout à fait adapté au test de molécules photoprotectrices.

Compte tenu que la capacité de panification de l'amidon aigre, amidon de manioc modifié par fermentation et irradiation UV, n'a pas encore été complètement élucidée, l'influence du génotype et les traitements post-récolte sur le pouvoir de panification de l'amidon aigre a été l'objectif de ce travail. 13 génotypes de manioc de Colombie, cultivés à 1000 m. et 1700 m.p.n.m (3 de plaine et 10 d'altitude, respectivement) modifiés par fermentation (0 ou30 jours) et séchage (four ou soleil) ont été étudiés. Les analyses de la taille des granules, la viscosité d'empesage RVA et la viscosité intrinsèque révèlent que les traitements post-récolte ont été les facteurs prépondérants en vue de l'amélioration de la capacité de panification tandis que le facteur génotype a présenté une influence moins importante. Parmi les traitements post-récolte, la fermentation a présenté un effet plus prononcé sur la structure des granules d'amidon, que le séchage au soleil. Cependant, la combinaison de ces deux traitements a été nécessaire pour obtenir une forte capacité de panification. L'effet d'altitude de culture a été mis en évidence lors de la fermentation par des sensibilités différentes trouvées entre les granules de plaine et d'altitude (exocorrosion et endocorrosion, respectivement). Les génotypes d'altitude, donc, ont montré une bonne capacité de panification. Néanmoins, d'autres facteurs entrent en jeu, la teneur en amylose mesurée par DSC a influencé négativement l'expansion de la pâte, probablement en raison de la formation de complexes amylose-lipide. Par conséquent, la combinaison de génotypes de manioc (la teneur en amylose principalement) et les traitements post-récolte sont un élément clé de la capacité de panification de l'amidon aigre. Ces contributions peuvent aider à l'établissement de standards de qualité de l'amidon aigre vis à vis de leur potentielle utilisation dans la fabrication des produits sans-gluten
The breadmaking ability of sour cassava starch, cassava starch modified by fermentation and UV irradiation, have not been yet fully elucidated. The influence of genotype and postharvest treatments on expansion ability of sour cassava was the objective of this work. Thirteen cassava genotypes have been studied. All genotypes proceeded from Colombia. Two altitudes of origin (1000 m. and 1700 m.a.s.l. refered to respectively as lowland and highland), fermentation treatments (0 or 30 days) and drying treatments (oven or sun) were considered. Analyses of the granule size, RVA pasting behavior and intrinsic viscosity were analysed as indicators of breadmaking ability. Results showed that post-harvest treatments were prevailing factors in improving breadmaking ability while the genotype factors had a smaller influence. Among post-harvest treatments, fermentation had a greater influence than sun-drying on these indicators, in particular on starch granular structure. The combination of both treatments was needed to obtain a high capacity bread. Furthermore, the altitude of origin of cassava genotypes was observed to affect the fermentation process: different sensitivities to fermentation were found between granules of lowland and highland (exocorrosion and endocorrosion, respectively). Highland genotypes showed a better breadmaking ability. Other influencing factor related to genotype was the amylose content measured by DSC: it negatively influenced the expansion of the dough, probably due to the formation of amylose-lipid complex. As a conclusion, the combination of cassava genotypes (mainly amylose content) and post-harvest treatment is key for expansion ability of sour starch. This knowledge is a first, essential step to provide quality standards for sour starch, targeted particularly for use in gluten-free products

L’environnement géostationnaire autour de la Terre présente des conditions complexes influençant les performances ainsi que la durée de vie des satellites. En vol et au cours du temps, les polydiméthylsiloxanes se dégradent ce qui se manifeste par une perte de souplesse, de transparence, ou encore une dégradation de l'état de la surface. Dans ce contexte, le but de cette thèse consiste à étudier l’évolution de la stabilité des polydiméthylsiloxanes en environnement géostationnaire simulé et d’autre part à proposer des solutions qui permettent de limiter la dégradation des propriétés d’intérêts technologiques, optiques en particulier. La stabilisation des polydiméthylsiloxanes soumises aux irradiations UV par l’incorporation de différentes structures d’additifs (Hindered Amine Light Stabilizers, absorbeurs UV, nanocristaux de cellulose) a été étudiée. Une autre approche pour augmenter la stabilité des polydiméthylsiloxanes aux rayonnements UV a été envisagée avec le remplacement du système catalytique actuellement utilisé (catalyseur de Karstedt) par l’emploi de dérivés organométalliques à base de Rhodium ou de Platine. Des solutions concernant la stabilisation de ces polydiméthylsiloxanes aux irradiations H+, comme l’ajout d’additifs tels que le polystyrène, les silsesquioxanes ont également été proposées
The geostationary environment around Earth is complex which strongly influences the satellites performances and lifetime. In flight and over time, polydimethylsiloxanes exhibit degradations like a loss of flexibility and transparency, or a deterioration of the surface state. In this context, the aim of this work was to study the evolution of polydimethylsiloxanes stability in geostationary environment to find solutions to limit the degradation of interest technological properties, in particular the optical one. The stabilization of silicone resins under UV irradiation has been performed by the incorporation of different additives such as Hindered Amine Light Stabilizers, UV Absorbers and cellulose nanocrystals into the PDMS matrix. Generally, polydimethylsiloxanes networks are obtained by hydrosilylation with highly active Karstedt catalyst. Various organometallics derivatives based on Rhodium and Platinum were studied as alternative catalysts for the cross-linking of polydimethylsiloxane in order to improve the UV stability. Finally, different solutions concerning the stabilization of polydimethylsiloxane to proton irradiation, such as the addition of various additives like polystyrene or silsesquioxanes have been investigated

Le développement de nouvelles technologies pour le recyclage des eaux usées est une priorité pour les régions arides et semi-arides tels que les pays du bassin méditerranéen. L'objectif de ce travail a été, dans un premier temps, de développer un système de traitement tertiaire des eaux usées en testant l'efficacité de diodes électroluminescentes émettant des UV-A et/ou des UV-C (DEL-UV) sur l'inactivation de souches bactériennes indicatrices de pollution fécale (Escherichia coli et Enterococcus faecalis) puis sur des effluents urbains, en étudiant la diminution des pollutions microbiennes et chimiques. Cette première étape a mis en évidence l'efficacité accrue du couplage UV-A et UV-C, permettant d'obtenir une eau de qualité répondant aux exigences législatives relatives à la réutilisation des eaux usées pour l'irrigation. La deuxième partie de ce travail était l'étude de l'impact de l'arrosage avec des eaux usées traitées par DEL-UV sur les paramètres du sol et sur le devenir de certain polluant aromatiques dans les sols (anthracène et carbamazépine). L'arrosage avec des eaux usées traitées par DEL-UV ne modifie pas la composition chimique de la matière organique de sol, l'activité catabolique globale des microorganismes, et le nombre et la diversité de bactéries indicatrices de pollution fécale par rapport au sol arrosé avec de l'eau d'irrigation. Certaines activités enzymatiques liées à la dégradation de la matière organique augmentent dans les sols arrosés avec des eaux usées traitées par DEL-UV, montrant que la matière organique apportée par l'effluent est activement dégradée par les microorganismes
The development of new technologies for wastewater reuse is a priority for arid and semi-arid areas such as Mediterranean countries. The objective of this work was, firstly, to develop a system for tertiary treatment of wastewaters testing LEDs emitting UV-A and / or UV-C (UV LEDs) on fecal indicator inactivation (Escherichia coli and Enterococcus faecalis) and then on urban effluents, by studying the decrease in both microbial and chemical pollution. This first step has highlighted a higher efficiency of this system when UV UV-A and UV-C are coupled. Wasterwaters with quality meeting the statutory requirements for the reuse of wastewater for irrigation were obtained and used in the second part of this work was to study the impact of watering with UV-LED- treated wastewaters on soil parameters and on the fate of pollutants (anthracene and carbamazepine) in soils. Watering with UV-LED treated wastewater does not change the chemical composition of soil organic matter, the global catabolic activity of soil microorganisms, and the number and diversity of fecal indicators compared to control (irrigation water). Certain enzymatic activities related to the degradation of organic matter increased in soil watered with UV-LED treated wastewater, showing that the organic matter added by the effluent is actively degraded by microorganisms. In addition, aromatic pollutants are oxidized two to three times faster in soils watered with UV-LED treated wastewater

Des polyacides lactiques hydroxy téléchélique de masses molaires variées ont été synthétisés par polymérisation par ouverture de cycle du LLA en présence de 1,4 -butane diol. Des polyhydroxybutyrate hydroxy téléchéliques ont été préparés transesterification du PHB et du 1,4-butanediol catalysée par l'acide p-toluène sulfonique .Ces oligomères ont été utilisés pour préparer des polyesters amides fonctionnalisés acrylates ou mercaptans. Dans une approche parallèle, du PCL multi acrylate a été préparé avec succès par copolymérisation par ouverture de cycle de méthacrylate de glycidyle avec du caprolactone. Des copolymères (GMA -co- CL) ayant des masses molaire et de la fonctionnalité variables, ont été préparés en modifiant les paramètres de la réaction tels que le catalyseur, la nature du co-amorceur et le rapport des stœchiométriques des différents réactifs. Les polymères multi acrylates ont été copolymérisés principalement avec l'HEMA sous irradiation UV pour obtenir des réseaux PLA, PHB et PCL segmentés. Les mécanismes de dégradation de ces réseaux ont été étudiés en examinant particulièrement les décompositions des liaisons uréthanes et esters. Des dépolymérisations du PHEMA ont été détectées avec TGA -FTIR à plus haute température (450°C). Pour les réseaux à base de PCL, les propriétés thermo -mécaniques ont été étudiées. Le résultat montre que les phases riches en PCL ont une bonne compatibilité avec le poly HEMA. Les modules caoutchoutiques et l’étendue des températures des zones d’amortissement peuvent être contrôlées en fonction des paramètres réactionnels. Les Polymères multifonctionnels Thiols du PCL, PHA et PLA ont été utilisés pour faire croître des chaines méthacrylates et construire des polymères de type étoile
Hydroxyl telechelic polylactic acids of various molecular weights were synthesized by ring opening polymerization in the presence of LLA and 1,4-butanediol. Telechelic hydroxy polyhydroxybutyrate were prepared transesterification of PHB and 1,4- butanediol catalyzed by p- toluene sulfonic acid. These oligomers were used to prepare polyesteramides functionalised acrylates or mercaptans. In a parallel approach, the PCL multi acrylate was successfully prepared by ring-opening copolymerization of glycidyl methacrylate with caprolactone. Copolymers (GMA-co-CL) with variable molar masses and functionality were prepared by changing the reaction parameters such as catalyst, the nature of the co-initiator and the ratio of different stoichiometric reagents. Multi-acrylated polymers were copolymerized with HEMA under UV irradiation to obtain PLA, PHB and PCL segmented networks. Degradation mechanisms of these networks have been studied by examining particular decomposition of urethane bonds and esters. Depolymerization of the PHEMA was detected with TGA -FTIR at higher temperature (450°C). For PCL based networks, the thermo- mechanical properties were studied. The result shows that the PCL-rich phases have good compatibility with poly HEMA. The rubber and the working temperature range of the damping zones modules can be controlled as a function of reaction parameters. Multi mercapto functionalized polymers with PCL, PLA and PHA segments were used to grow methacrylate polymer chains and build star type

The superhydrophobic materials can be used in manufacturing of the devices and things with the self-cleaning properties (such as solar panels, textiles and building materials, such as glass, tile etc.), coatings with a low friction (such as vehicles), anti-corrosion, anti-icing and antisticking coatings, lab-on-chip devices, drug delivery etc.

Thesis (M. Phil.)--Hong Kong University of Science and Technology, 2004.
Includes bibliographical references (leaves 106-124). Also available in electronic version. Access restricted to campus users.

Titania-based photocatalysts have been extensively studied for the oxidative photodestruction of organic pollutants in wastewaters, releasing non-toxic substances such as CO2, HCl, and water. However, commercial exploitation of this process is limited by the fact that titania is only active under UV irradiation (wavelength below about 388 nm), which is only less than 5% of solar light energy. Sol-gel synthesised catalyst specimens were characterised to determine the correlation between preparation conditions on morphology (XRD, SEM), optical (bandgap energy level) and physicochemical properties (BET surface area, pore volume, acid site density, acid site strength and type) of the photocatalysts. These spesific properties would then be linked to their photoactivity using aqueous aliphatic and aromatic model pollutants. This study has demonstrated that sol-gel synthesised doped titania photocatalysts, especially Pt/TiO2, may be used to effectively degrade non-volatile acids (DL-malic acid, dichloroacetic acid, and p-hydroxybenzoic acid) under visible light and UV irradiation with significant photoactivity suitable for the solar light application of photocatalytic wastewater treatment. A significant drop in band-gap energy was found for all titania sol-gel catalysts doped with Pt, Co, and Ce with values between 1.41 to 1.78 eV. The BET areas of the photocatalysts were also higher (65-117 m2/g) than that of Degussa P25 (50 m2/g). The visible-light photomineralisation of the three pollutants with Pt-TiO2 specimen were further extended to evaluate the effects of major variables in a bubble-column photoreactor on the photodegradation activities. Those major variables were lamp intensity, oxygen concentration, initial pH, catalyst dosage, and inital pollutant concentration. All the three pollutants seemed to follow the Langmuir-Hinselwood model with dual adsorption sites which implicated a bimolecular surface rate-limiting step probably between the adsorbed organic substrate and a surface hydroxyl (or peroxy) radical. A study of the CeyCoxTi(1-x)O3+d perovskite was conducted to investigate the influence of metal composition and pH on the intrinsic optophysical attributes as well as p-hydroxybenzoic acid degradation under UV irradiation. The perovskite UV photoactivities were lower than that of pure TiO2 likely due to excessive loading (metal content) creating new oxide phases act as electron-hole recombination center, regardless better physicochemical attributes of some of the perovskite samples. The role of aging time and calcination temperature on the sol-gel synthesised TiO2 was also explored. Higher calcination temperature (from 250 to 700 0C) resulted in TiO2 photocatalysts with better crystallinity, which is important for OH group formation as active sites for photodegradation. Despite of some advantages from higher temperature preparation, some detrimental effects such as decreased acidity attributes, surface area, and pore volume were also observed. The significant red-shift of sol-gel synthesized TiO2 into visible light, especially for 250 0C specimen since 600 or 700 0C had extremely low activities, has promising implications that this specimen might be used for solar application to substitute Pt-doped TiO2 in order to produce a more cost effective photocatalyst. Aging period (1 to 14 days) did not have any discernible effect on the band-gap value and acid-site density. Even so, the highest acid site strength was obtained with an aging time of 10 days. From the overall perspective, aging time longer than 3 days did not bring noticeable benefits to both catalyst attributes and photoactivities.

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Xanthomonas campestris é uma bactéria fitopatogênica que causa a podridão negra no sistema vascular das plantas da família das cruciferaceaes. Produz um exopolissacarídeo denominado goma xantana, que possui propriedades reológicas únicas sendo utilizada amplamente como agente de suspensão, espessante, emulsionante e estabilizante. É aplicados em indústrias petrolíferas, alimentícias, farmacêuticas, mineração, têxtil, termoquímicas, tintas, cosméticos e produtos agropecuários. O Brasil é um grande produtor mundial de cana de açúcar e álcool etílico. Produtos estes utilizados para a produção de xantana; o primeiro como substrato da fermentação e o segundo para a separação da goma. Apesar de todo esse potencial, o Brasil importa grande quantidade de goma xantana que poderá ser produzida com grande competitividade internacional. Portanto, este trabalho objetivou a utilização da técnica de irradiação ultravioleta, em uma linhagem específica de Xanthomonas campestris, para a obtenção de mutantes estáveis que possam melhorar o rendimento e/ou qualidade de goma obtida. A quantificação foi realizada através da determinação da biomassa, viscosidade, cálculos do rendimento da biomassa e goma. A irradiação UV por 600 segundos causou uma redução de 92,2% na população irradiada e as linhagens sobreviventes foram isoladas e analisadas nos testes de produção e viscosidade da goma xantana. As linhagens I6, I7, I9 e I10 apresentaram um aumento de 102% na produção de goma comparando com a linhagem não irradiada. Em relação à viscosidade do caldo, as linhagens irradiadas obtiveram um aumento de 48% comparadas com as não irradiadas de 20 e 30 rpm. A viscosidade da solução de goma xantana 1%, também foram superiores quando comparadas com a não irradiada. O aumento de...
Xanthomonas campestris is fitopatogenic bacterium that causes the black rotten in the vascular system of the plants of the family of the cruciferaceaes. It produces an exopolysaccharides that forms the xanthan gum, which is used in ample variety as agent of suspension, thicker, emulsifier and stabilizing, and singular rheological properties. It is applied in petroliferous, nourishing, pharmaceutical industries, of mining, textile, thermo chemistries, inks, cosmetics and farming products. Brazil is the worldwide producing greater of sugar cane of sugar and ethyl alcohol. Products theses used for the xanthan production; the first one as substratum of the fermentation, and the second as for the separation of the gum. Despite all this potential, the Brazil imports lot of xanthan gum that could be produced with great international competitiveness. This aimming work the used of the ultraviolet technique of irradiation in a specific strain of Xanthomonas campestris to obtain the mutants that can improve the income and/or quality of produced gum, through the determination of the biomass, viscosity, calculations of the income of the biomass and gum. The UV irradiation during 60 seconds caused a reduce of the 92.2% in the irradiated strains and the survived strains were isolated and analysed in the tests of production and viscosity of xanthan gum. The strains I6, I7, I9 e I10 showed increased in the xanthan production of 102% comparing with the non-irradiated strain. In relation the viscosity of the broth the irradiated strains the increase of 48% in shear rate of 20 and 30 rpm compared with the no irrdiated. The viscosity of the xanthan solution 1% irradiated were higher also whwn compared with no irradiated in both shear rate (20 and 30 rpm. The increase of viscosity was of 17% to rotational speed of 20 rpm and 16% to 30 rpm. The ...(Complete abstract click electronic access below)

Inscrite dans le cadre d’un projet ANR, la thèse porte sur l’étude et le développement des revêtements poudres UV en vue du recouvrement de panneaux de bois. La thèse détaille les spécificités de ces formulations et de la technologie associée afin de constituer une bibliographie solide propre à ce domaine. Les travaux expérimentaux se basent sur des formulations modèles comprenant une résine poudre UV (uréthane diacrylate ou polyester diméthacrylate) et un photoamorceur. Une étude mécanistique permet de montrer les influences de la température et de la viscosité, de l’intensité lumineuse et de l’atmosphère sur la réactivité des formulations modèles. Il est également démontré que les mécanismes de terminaison spécifiques à ces systèmes suivent des processus mixtes: bimoléculaire, pseudo-monomoléculaire et recombinaison des radicaux primaires. La prédominance des différents processus dépend de l’avancement de la réaction. La formation du réseau de réticulation est ensuite étudiée en fonction de la source d’irradiation: convoyeur semi-industriel doté de lampes UV ou système LED émettant autour de 395 nm. Les caractéristiques du réseau de réticulation (Tg, densité de réticulation, module d’Young) sont reliées aux propriétés des revêtements finaux (flexibilité, résistance à la rayure ou au solvant). L’utilisation d’acrylates multifonctionnels a un impact sur les longueurs de chaînes et la densité de réticulation. En vue d’applications spécifiques, il est finalement proposé d’incorporer une argile modifiée avec de l’Argent au sein des formulations modèles pour obtenir des revêtements poudres UV antibactériens homogènes possédant de bonnes propriétés de résistance
In the frame of a project of the Agency National Research (France), the thesis deals with the study and the development of UV powder coatings dedicated to wood based panels. The work describes the main features of these formulations and the associated technology in order to offer a strong bibliography specific to this area. The experiments are based on model formulations containing an UV powder resin (diacrylate urethane or dimethacrylate polyester) and a photoinitiator. A mechanistic study allows highlighting the influence of temperature and viscosity, light intensity and atmosphere on the reactivity of the model formulations. It is also shown that the termination mechanisms specific to theses systems follow mixed processes: bimolecular, pseudo-monomolecular and primary radical termination. The predominance of the different processes is related to the reaction conversion. The building of the crosslinking network is then studied depending of the irradiation source: semi-industrial conveyor equipped with UV lamps or LED system emitting around 395 nm. The characteristics of the crosslinking network (Tg, crosslinking density, Young’s modulus) are linked to the final coatings properties (flexibility, scratch and solvent resistance). The incorporation of multifunctional acrylates affects the chains length and crosslinking density. To reach specific applications, it is finally proposed to add a silver-modified clay into model formulations to obtain homogeneous antibacterial UV powder coatings exhibiting good resistance properties

Vitamin D regulation is associated with several human disorders and contributes to various cellular mechanisms. Calcitriol (commercially available as Rocaltrol), an active Vitamin D metabolite, is known as a neuro-protective and anti-cancer drug but most importantly helps maintaining the calcium homeostasis inside the human body. The effectiveness of calcitriol to perform as an effective therapeutic agent is counteracted by its calcemic effects. In order to obtain better therapeutic results, synthetic calcitriol analogs without these calcemic effects have been recently developed but they are not yet cost-effective and their production is time-consuming. In order to determine the best active form of calcitriol that could provide higher chemotherapeutic activity without these calcemic effects, calcitriol mode of action was studied using yeast as a model system. In order to achieve this, we analyzed the calcitriol effects on yeast cellular growth based on calcium intake levels. In this work, we also assessed yeast strains with gene deletions of selected calcium transporter genes to understand the calcitriol metabolism. For the aim of understanding hypercalcemic effects of calcitriol, we developed a hypothesis based on calcitriol interactions with oxygen. Interestingly, use of an anaerobic model validated the oxygen interactions with calcitriol that might possibly cause calcemic effects on patients. Anaerobically grown yeast treated with calcitriol showed significantly less intracellular calcium levels when imaged under indo-1 calcium binding fluorescence dye as compared to calcitriol treated yeast grown under aerobic conditions. Finally, we predict that calcitriol might control free radical generation within the yeast system based on experiments with AAPH and UV- irradiation.

Notre travail presente une etude de quelque couples du type accepteur / donneur qui englobe : - la caracterisation des systemes par plusieurs techniques d'analyse telles que la calorimetrie differentielle a balayage (dsc), la spectroscopie ir, la rmn, la spectroscopie uv en temps reel ; - de la copolymerisation photoinduite des systemes du type accepteur / donneur sans photoamorceur par la photocalorimetrie a compensation de puissance (dpc), la spectroscopie ir en temps reel et la rpe qui permettent de suivre le processus ; - la caracterisation du materiau obtenu complete le travail.

Advances in engineering polymer technology have created a generation of high strength-to-weight materials for medical applications, with virtually no adverse interactions with body fluids. Polycarbonate is a widely used engineering polymer, and is often used in connection with ultra-violet light (UV) cured adhesives. Because of the chemical complexity of polymers, little is known about their actual aging characteristics. By characterizing the effects of aging, storage environment, and sterilization on medical grade polycarbonate/adhesive system properties, more accurate failure predictions can be made. In this thesis, efforts to better understand the effects of accelerated aging on a medical grade polycarbonate and UV cured adhesive system are presented. A case study in which we applied our findings to improve an existing medical device is also described. The resin investigated was DOW Calibre 2081-15 MFR. The adhesives investigated were Dymax 190-M, Loctite 3311, and Loctite 3921. By adapting ASTM test standards, tests were developed to evaluate the effects one type of accelerated aging method had on the polymers. The polycarbonate resin experienced significant changes in material properties after sterilization. The biggest change was in percent elongation which went from 130% to 40%. The Dymax 190-M had the highest shear break values initially; however, the Loctite 3311 was more consistent. The Loctite material experienced a 15% decrease in shear break value over three years accelerated aging, while the Dymax material experienced a 35% decrease. The use of post sterilization or three year accelerated aging properties for polycarbonate designs is better than using published data. This ensures more accurate evaluation for the safety factor and failure profile. It was found that the accelerated aging method used in this study is reliable for general studies through two years, but accuracy declined significantly after this time. By using our findings we were able to significantly improve the case study assembly. Understanding how material properties change over time helped us identify the major contributors to part failure to create a more robust design and final product.

Orientador: Pedro de Oliva Neto
Banca: Valéria Marta Gomes de Lima
Banca: Ivanise Guilherme Branco
Resumo: Xanthomonas campestris é uma bactéria fitopatogênica que causa a podridão negra no sistema vascular das plantas da família das cruciferaceaes. Produz um exopolissacarídeo denominado goma xantana, que possui propriedades reológicas únicas sendo utilizada amplamente como agente de suspensão, espessante, emulsionante e estabilizante. É aplicados em indústrias petrolíferas, alimentícias, farmacêuticas, mineração, têxtil, termoquímicas, tintas, cosméticos e produtos agropecuários. O Brasil é um grande produtor mundial de cana de açúcar e álcool etílico. Produtos estes utilizados para a produção de xantana; o primeiro como substrato da fermentação e o segundo para a separação da goma. Apesar de todo esse potencial, o Brasil importa grande quantidade de goma xantana que poderá ser produzida com grande competitividade internacional. Portanto, este trabalho objetivou a utilização da técnica de irradiação ultravioleta, em uma linhagem específica de Xanthomonas campestris, para a obtenção de mutantes estáveis que possam melhorar o rendimento e/ou qualidade de goma obtida. A quantificação foi realizada através da determinação da biomassa, viscosidade, cálculos do rendimento da biomassa e goma. A irradiação UV por 600 segundos causou uma redução de 92,2% na população irradiada e as linhagens sobreviventes foram isoladas e analisadas nos testes de produção e viscosidade da goma xantana. As linhagens I6, I7, I9 e I10 apresentaram um aumento de 102% na produção de goma comparando com a linhagem não irradiada. Em relação à viscosidade do caldo, as linhagens irradiadas obtiveram um aumento de 48% comparadas com as não irradiadas de 20 e 30 rpm. A viscosidade da solução de goma xantana 1%, também foram superiores quando comparadas com a não irradiada. O aumento de...(Resumo completo, clicar acesso eletrônico abaixo)
Abstract: Xanthomonas campestris is fitopatogenic bacterium that causes the black rotten in the vascular system of the plants of the family of the cruciferaceaes. It produces an exopolysaccharides that forms the xanthan gum, which is used in ample variety as agent of suspension, thicker, emulsifier and stabilizing, and singular rheological properties. It is applied in petroliferous, nourishing, pharmaceutical industries, of mining, textile, thermo chemistries, inks, cosmetics and farming products. Brazil is the worldwide producing greater of sugar cane of sugar and ethyl alcohol. Products theses used for the xanthan production; the first one as substratum of the fermentation, and the second as for the separation of the gum. Despite all this potential, the Brazil imports lot of xanthan gum that could be produced with great international competitiveness. This aimming work the used of the ultraviolet technique of irradiation in a specific strain of Xanthomonas campestris to obtain the mutants that can improve the income and/or quality of produced gum, through the determination of the biomass, viscosity, calculations of the income of the biomass and gum. The UV irradiation during 60 seconds caused a reduce of the 92.2% in the irradiated strains and the survived strains were isolated and analysed in the tests of production and viscosity of xanthan gum. The strains I6, I7, I9 e I10 showed increased in the xanthan production of 102% comparing with the non-irradiated strain. In relation the viscosity of the broth the irradiated strains the increase of 48% in shear rate of 20 and 30 rpm compared with the no irrdiated. The viscosity of the xanthan solution 1% irradiated were higher also whwn compared with no irradiated in both shear rate (20 and 30 rpm. The increase of viscosity was of 17% to rotational speed of 20 rpm and 16% to 30 rpm. The ...(Complete abstract click electronic access below)
Mestre

L’objectif de ce travail est une meilleure compréhension des phénomènes de modification de la couleur du bois soumis à l'irridiation solaire en vue d'une photostabilisation efficace de ce matériau. L'utilisation des spectroscopies UV-visible et infra-rouge à transformées de Fourier a permis de suivre les modifications chimiques engendrées par l'exposition au rayonnement solaire des échantillons d'Abiès grandis et des constituants principaux du bois. Les influences de la répartition spectrale, de l'intensité du rayonnement, de l'oxygène ont pu être dégagées. Il a pu être montré que la lignine est le principal responsable du comportement photochimique du bois soumis à la lumière solaire. Un mécanisme en conformité avec les résultats obtenus en photolyse stationnaire de la lignine et en spectroscopie rapide des molécules modèles de ce composé a été proposé. Ce schéma réactionnel a permis d'aborder scientifiquement l'étude de la protection photochimique du bois et d'interpréter les résultats obtenus avec le salol, absorbeur UV commercial

O Rio Grande do Sul é o maior produtor de uvas do Brasil, e as cultivares de Vitis labrusca representam mais de 90% da produção, dentre as quais se destacam as variedades Isabel e Bordô, que se caracterizam por conter altas concentrações de polifenóis, principalmente antocianinas, que exibem propriedades antioxidantes e que podem ser usados como corantes em alimentos. Entretanto, a utilização destes compostos em alimentos se torna difícil devido à sua alta instabilidade, e uma das formas de proteger estes compostos das condições adversas do meio é a microencapsulação. O bagaço da uva, proveniente da fabricação de sucos e vinhos, contém uma elevada concentração de polifenóis, e é composto em grande parte pela casca da uva. Dessa forma, este trabalho de Tese, teve como primeiro objetivo a extração dos polifenóis da casca das uvas Isabel e Bordô, e seu microencapsulamento utilizando diferentes materiais de parede, o qual foi dividido em três etapas. Na primeira etapa, foi realizada a separação dos compostos fenólicos mediante extração aquosa em meio ácido da casca de uva Isabel. A seguir, o extrato foi submetido à atomização para obtenção das micropartículas, utilizando goma arábica, β-ciclodextrina e hidroxipropil-β-ciclodextrina como agentes encapsulantes, combinadas em concentrações máximas de 5%. Os pós obtidos foram avaliados quanto aos fenóis totais, antocianinas monoméricas totais, flavonoides, flavanols, atividade antioxidante (DPPH, CUPRAC e HRSA), cor, umidade, atividade de água, solubilidade, higroscopicidade, temperatura de transição vítrea e microestrutura. De forma geral, os pós obtidos apresentaram alta higroscopicidade e baixa temperatura de transição vítrea, além de aglomeração das partículas. O tratamento elaborado com 3% de goma arábica e 2% de β-ciclodextrina foi considerado o melhor, com maior retenção de flavonoides (67,2%), flavanols (51,1%), atividade antioxidante por DDPH (55%) e CUPRAC (58,8%), menor higroscopicidade (17,33%) e maior temperatura de transição vítrea (32,85 °C). Na segunda etapa, o extrato fenólico aquoso acidificado da casca de uva Bordô foi atomizado e liofilizado para a obtenção das micropartículas, utilizando goma arábica, goma guar parcialmente hidrolisada e polidextrose, em um total de 10% de material de parede. Os pós obtidos foram avaliados quanto ao conteúdo de fenóis totais, antocianinas monoméricas totais, atividade antioxidante (DPPH, CUPRAC, HRSA), cor, umidade, atividade de água, solubilidade, higroscopicidade, temperatura de transição vítrea, tamanho de partícula e microestrutura. Foram obtidas altas retenções, maiores que 80% para fenóis totais e antocianinas monoméricas totais, e entre 45 e 84% para atividade antioxidante em todos os tratamentos estudados. Os pós atomizados tiveram menor umidade, atividade de água e tamanho de partícula, maior solubilidade e temperatura de transição vítrea, além de melhores características morfológicas do que os pós liofilizados. O pó obtido por atomização com 5% de goma guar parcialmente hidrolisada e 5% de polidextrose foi considerado o melhor tratamento, visto que teve maior retenção de fenóis totais (89,0%), antocianinas monoméricas totais (99,5%) e atividade antioxidante por DPPH (57,3%) e CUPRAC (83,2%). Na terceira etapa, dispersões de extrato de casca de uva Bordô com 5% de goma guar parcialmente hidrolisada e 5% de polidextrose, que foi considerado o melhor tratamento dentre todos os elaborados com uva Isabel e Bordô, foram atomizadas e liofilizadas para obtenção das micropartículas, que foram submetidas a testes acelerados de armazenamento (umidades relativas de 75 e 90% em temperaturas de 35, 45 e 55 °C) e de simulação de digestão gastrointestinal (divididos em duas fases: fase gástrica e fase intestinal). Foram avaliados os conteúdos de fenóis totais, antocianinas monoméricas totais e atividade antioxidante por ABTS. Quanto às provas aceleradas, a temperatura teve um efeito significativo na diminuição no conteúdo de fenóis, com retenções de 82,5% a 93,5%. Na redução do conteúdo de antocianinas monoméricas totais foi significativo o efeito da temperatura, umidade relativa e tempo, com retenções de 3,9 a 42,3%. A redução do teor de antocianinas monoméricas totais exibiu cinética de primeira ordem, e os valores de z e Ea indicaram que o pó liofilizado é mais instável às mudanças de temperatura, quando utilizadas temperaturas mais elevadas. Por outro lado, os valores de D e t1/2 foram muito próximos entre os dois pós, o que indica pouca diferença de estabilidade entre eles nas temperaturas utilizadas neste estudo. Os parâmetros termodinâmicos indicaram que a reação foi endotérmica e não espontânea. A atividade antioxidante teve comportamento similar ao dos fenóis totais, com retenção final de 38,5 a 59,5%. Quanto à simulação da digestão gastrointestinal os dois pós tiveram liberação de fenóis de aproximadamente 80% na fase gástrica, e aumento significativo da liberação na fase intestinal, onde, na última hora de experimento, o pó atomizado teve 90,6% de liberação e o liofilizado 94,9%. Comportamento similar foi observado para a atividade antioxidante, onde o pó atomizado e o pó liofilizado tiveram percentuais próximos a 50% na fase gástrica e aumento significativo na fase intestinal, onde na última hora do experimento o pó atomizado teve 69,4% da atividade antioxidante e o pó liofilizado 67,8%. Entretanto, as antocianinas monoméricas tiveram redução significativa de aproximadamente 50% do seu conteúdo na fase intestinal, onde, na última hora de experimento, o pó atomizado teve 39% de liberação e o liofilizado 39,8%. O método de obtenção das micropartículas não influenciou na estabilidade dos pós, tanto nos testes acelerados de armazenamento quanto na simulação da digestão gastrointestinal. Como segundo objetivo foi avaliado o efeito da irradiação UV-C em uvas Bordô, como tratamento pós-colheita. Foram estudadas duas safras de anos diferentes, sendo que na primeira as uvas foram submetidas a 0, 0,5, 1, 4, 10 e 30 minutos de irradiação (120 W) e armazenadas a 22 °C, enquanto que na segunda safra as uvas foram submetidas à irradiações com UV-C (120 W) por 0, 0,5 e 4 minutos, combinada com ultrassom (40 kHz) por 5 minutos e armazenadas a 22 °C. Na primeira safra, as uvas não apresentaram aumento dos compostos bioativos e da atividade antioxidante. Entretanto, na segunda safra, os resultados indicaram o aumento significativo no conteúdo de fenóis totais, antocianinas monoméricas totais e na atividade antioxidante para as uvas irradiadas por 0,5 minutos com UV-C e para as irradiadas com UV-C por 4 minutos em combinação com ultrassom por 5 minutos, com aumentos de 1,2 a 2,0 vezes em relação ao controle, não havendo mudanças significativas na cor das uvas irradiadas.
The state of Rio Grande do Sul, Brazil, is the greatest producer of grapes in the country. Vitis labrusca cultivars constitute more than 90% of production, underscoring Isabel and Bordô varieties, featuring high concentrations of polyphenols, especially antioxidant anthocyanins used as food coloring. Since the use of the compounds in food is rather difficult due to their unstableness, microencapsulation is one of the methods to protect the compounds from adverse environmental condition. Grape pomace, the residue from the manufacture of juice and wine, has high polyphenol concentration and is mainly formed by grape skin. Current thesis aims at extracting polyphenols from the skin of Isabel and Bordô grape varieties and their micro-encapsulation by different wall materials. Research was divided into three stages. The first stage comprised the separation of phenolic compounds by water extraction in the acid medium of the skin of the Isabel grape variety. The extract was spray-dried for microparticles by means of gum arabic, β-cyclodextrin and hydroxypropyl-β-cyclodextrin as encapsulating agents at maximum 5% concentrations. Powders were assessed for total phenols, total monomer anthocyanins, flavonoids, flavanols, antioxidant activity (DPPH, CUPRAC and HRSA), color, humidity, water activity, solubility, hygroscopicity, glass transition temperature and micro-structure. As a rule, the powders featured high hygroscopicity, low glass transition temperature and particle agglomeration. Treatment with 3% of gum arabic 3% and 2% of β-cyclodextrin was the best, with the highest retention rate of flavonoids (67.2%), flavanols (51.1%), antioxidant activity, and with DDPH (55%) and CUPRAC (58.8%), lowest hygroscopicity (17.33%) and highest glass transition temperature (32.85 °C). In the second stage the acidified water phenolic extract from the Bordô grape skin was spray-dried and freeze-dried for microparticles with gum arabic, partially hydrolyzed guar gum and polydextrose, with a total 10% of wall material. Powders were assessed for total phenols, total monomer anthocyanins, antioxidant activity (DPPH, CUPRAC, HRSA), color, humidity, water activity, solubility, hygroscopicity, glass transition temperature, particle size and micro-structure. High retentions occurred, with more than 80% for total phenols and total monomer anthocyanins; and between 45 and 84% for antioxidant activity in all treatments under analysis. Atomized powders had lower humidity, water activity and particle size, greater solubility, higher glass transition temperature, and better morphological characteristics than the freeze-dried powders. The powder obtain by spray-dried with 5% of partially hydrolyzed guar gum and 5% of polydextrose was the best treatment due to greater retention of total phenols (89.0%), total monomer anthocyanins (99,5%) and antioxidant activity for DPPH (57.3%) and CUPRAC (83.2%). The third stage comprised dispersions of the extract of the Bordô grape skin with partially hydrolyzed guar gum 5% and polydextrose 5%, or rather, the best treatment among those prepared with Isabel and Bordô grapes. Dispersions were spray-dried and freeze-dried to obtain microparticles which underwent fast storage tests (relative humidity rates 75 and 90% at 35, 45 and 55 °C) and gastrointestinal digestion simulations (divided into two phases: gastric and intestinal phases). Total phenols, total monomer anthocyanins and antioxidant activity for ABTS were evaluated. Fast tests revealed that temperature had a significant effect on the decrease in phenol contents, with 82.5 - 93.5% retentions. Temperature, relative humidity and time were significant on the reduction of total monomer anthocyanin contents, with 3.9 – 42.3% retentions. Decrease in total monomer anthocyanin rates revealed a first order kinetics, whilst z and Ea rates indicated highly unstable freeze-dried powder for changes in temperature when higher temperatures are employed. On the other hand, D and t1/2 rates were very close between the two powders, revealing slight stability difference between the two at temperatures employed in current study. Thermodynamic parameters demonstrated an endothermic and non-spontaneous reaction. Antioxidant activity behaved similarly to total phenols with a final retention between 38.5 and 59.5%. In the case of gastrointestinal digestion simulation, the two powders released 80% phenols during the gastric phase and a significant increase in release during the intestinal phase in which spray-dried and freeze-dried powders had 90.6% and 94.9% release during the last hour of the experiment. A similar behavior was detected for antioxidant activity in which spray-dried and freeze-dried powders featured 50% during the gastric phase and a significant increase during the intestinal one, with 69.4% and 67.8% of antioxidant activity respectively by the spray-dried and freeze-dried powders during the last hour of the experiment. However, monomer anthocyanins had a significant 50% reduction of contents in the intestinal phase in which the spray-dried and freeze-dried powders had 39% and 39.8% release respectively during the last hour of the experiment. The methods for obtaining microparticles failed to affect the stability of the powder in fast storage tests and in gastrointestinal simulation tests. Current research also evaluated the effect of UV-C irradiation on Bordô grapes for post-harvest treatment. Two harvests in two different years were analyzed: grapes of the first harvest underwent 0, 0.5, 1, 4, 10 and 30 minutes irradiation (120 W) and stored at 22 °C, whereas grapes of the second harvest underwent UV-C irradiations (120 W) during 0, 0.5 and 4 minutes, coupled to ultrasound (40 kHz) for 5 minutes and stored at 22 °C. The former did not have any increase in bioactive compounds and antioxidant activity. Results of the latter, however, demonstrated a significant increase in total phenols, total monomer anthocyanins and antioxidant activity for grapes irradiated during 0.5 minutes with UV-C and for those irradiated with UV-C for 4 minutes plus ultrasound for 5 minutes. There was 1.2 - 2.0 times increase when compared to control, with no change in color in the irradiated grapes.

Steady-state ultraviolet (UV) irradiation for potable water production is becoming an important global alternative to traditional disinfection by chlorination. Failure of UV to reduce the number of viable contaminant pathogens however can lead to enduring health legacies (with or without fatalities). To better understand vulnerability of UV operations to failure, the probabilistic Fr 13 risk framework of Davey and co-workers1 is applied for the first time in this thesis. Fr 13 is predicated on underlying chemical engineering unit-operations. It is based on the hypothesis that naturally occurring, chance (stochastic) fluctuations about the value of ‘set’ process parameters can unexpectedly combine and accumulate in one direction and leverage significant change across a binary ‘failure– not failure’ boundary. Process failures can result from the accumulation of these fluctuations within an apparent steady-state process itself. That is to say, even with good design and operation of plant, there can be unexpected (surprise and sudden) occasional failures without ‘human error’ or ‘faulty fittings’. Importantly, the impact of these naturally occurring random fluctuations is not accounted for explicitly in traditional chemical engineering. Here, the Fr 13 risk framework is applied for the first time to quantitatively assess operations of logically increasing complexity, namely, a laminar flow-through UV reactor, with turbulent flow in a concentric annular-reactor, both with and without suspended solids present (Davey, Abdul-Halim and Lewis, 2012; Davey and Abdul-Halim, 2013; Abdul-Halim and Davey, 2015; 2016), and; a two-step ‘global’ risk model of combined rapid-sand-filtration and UV irradiation (SF-UV) (Abdul-Halim and Davey, 2017). The work is illustrated with extensive independent data for the survival of viable Escherichia coli - a pathogenic species of faecal bacteria widely used as an indicator for health risk. A logical and step-wise approach was implemented as a research strategy. UV reactor unit-operations models are first synthesized and developed. A failure factor is defined in terms of the design reduction and actual reduction in viable E. coli contaminants. UV reactor operation is simulated using a refined Monte Carlo (with Latin Hypercube) sampling of UV lamp intensity (I), suspended solids concentrations [conc] and water flow (Q). A preliminary Fr 13 failure simulation of a single UV reactor unit-operation (one-step), developed for both simplified laminar flow and turbulent flow models, showed vulnerability to failure with unwanted survival of E. coli of, respectively, 0.4 % and 16 %, averaged over the long term, of all apparently successful steady-state continuous operations. A practical tolerance, as a design margin of safety, of 10 % was assumed. Results from applied ‘second-tier’ studies to assess re-design to improve UV operation reliability and safety and to reduce vulnerability to Fr 13 failure showed that any increased costs to improve control and reduce fluctuations in raw feed-water flow, together with reductions in UV lamp fluence, would be readily justified. The Fr 13 analysis was shown to be an advance on alternate risk assessments because it produced all possible practical UV outcomes, including failures. A more developed and practically realistic model for UV irradiation for potable water production was then synthesized to investigate the impact of the presence of suspended solids (SS) (median particle size 23 μm) as UV shielding and UV absorbing agents, on overall UV efficacy. This resulted in, respectively, some 32.1 % and 43.7 %, of apparent successful operations could unexpectedly fail over the long term due, respectively, to combined impact of random fluctuations in feed-water flow (Q), lamp intensity (I0) and shielding and absorption of UV by SS [conc]. This translated to four (4) failures each calendar month (the comparison rate without suspended solids was two (2) failures per month). Results highlighted that the efficacy of UV irradiation decreased with the presence of SS to 1-log10 reduction, compared with a 4.35-log10 reduction without solids present in the raw feed-water. An unexpected outcome was that UV failure is highly significantly dependent on naturally occurring fluctuations in the raw feed-water flow, and not on fluctuations in the concentration of solids in the feed-water. It was found that the initial presence of solids significantly reduced the practically achievable reductions in viable bacterial contaminants in the annular reactor, but that fluctuations in concentration of solids in the feed-water did not meaningfully impact overall vulnerability of UV efficacy. This finding pointed to a pre-treatment that would be necessary to remove suspended solids prior to the UV reactor, and; the necessity to improve control in feed-water flow to reduce fluctuations. The original synthesis was extended therefore for the first time to include a rapid sand-filter (SF) for pre-treatment of the raw feed-water flow to the UV reactor, and; a Fr 13 risk assessment on both the SF, and sequential, integrated rapid sand-filtration and UV reactor (SF-UV). For the global two-step SF-UV results showed vulnerability to failure of some 40.4 % in overall operations over the long term with a safety margin (tolerance) of 10 %. Pre-treatment with SF removed SS with a mean of 1-log10 reduction (90 %). Subsequently, an overall removal of viable E. coli from the integrated SF-UV reactor was a 3-log10 reduction (99.9 %). This is because the efficacy of UV light to penetrate and inactivate viable E. coli, and other pathogens, is not inhibited by SS in the UV reactor. This showed that the physical removal of E. coli was accomplished by a properly functioning SF and subsequently disinfection was done by UV irradiation to inactivate viable E. coli in the water. Because the Regulatory standard for potable water is a 4-log10 reduction, it was concluded that flocculation and sedimentation prior to SF was needed to exploit these findings. Flocculation is a mixing process to increase particle size from submicroscopic microfloc to visible suspended particles prior to sedimentation and SF. This research will aid understanding of factors that contribute to UV failure and increase confidence in UV operations. It is original, and not incremental, work. Findings will be of immediate interest to risk analysts, water processors and designers of UV reactors for potable water production.
Thesis (Ph.D.) -- University of Adelaide, School of Chemical Engineering & Advanced Materials, 2017

碩士
長庚大學
基礎醫學研究所
94
Our previous study demonstrated that human DDB2, a DNA repair protein known to participate in genomic DNA repair of UV damage, is a modulator of UV-induced apoptosis, and that UV resistance can be overcome by inhibition of DDB2 in mammalian cell culture. However, the molecular mechanism underlying the protective role of DDB2 is not fully understood. Fruit fly (Drosophila melagaster) that lacks DDB2 homologue has been used as an animal model for studying numerous protein functions including DNA repair. In previous study, we revealed that hDDB2 could protect fly from UV-irradiation in third-instar larvae, but is not sufficient to attenuate major apoptosis pathways. Here, we demonstrated the protective roles of hDDB2 in UV-irradiated embryo. Using UAS-Gal4 expression system, hDDB2 was absolutely detected in cell nuclei of Drosophila embryo no matter with UV-irradiation or not. In contrast, dDDB1 was diffusely distributed in cells. Following UV-irradiation, however, dDDB1 was concentrated in embryonic nuclei. Moreover, the cyclobutane pyrimidine dimers (CPD) repair assay indicated that the amounts of UV-induced CPD are accumulated in nuclei in a dose-dependent manner; CPD was then gradually removed following repair incubation. From the gel shift assay, hDDB2 also elevated the activity of UV-DDB, the key step in DNA repair ability. Confocal microscopy analysis indicated that hDDB2 co-localizes with CPD in nuclei immediately after UV-irradiation, and also elevates the CPD repair efficiency. Colocalization between hDDB2 and dDDB1 were demonstrated by fluorescent immunolabeling assay. These findings reveal that hDDB2 could protect fly against UV along various developmental stages. These results suggest that heterologous molecules, hDDB2 and dDDB1, may act in concert to participate in DNA repair and provide a possible explanation for UV protection in both cultured cells and organism.

碩士
國立清華大學
生命科學系
88
Cell death following exposure to genotoxin, for example, ultraviolet, can occur via several routes, including mitotic catastrophe, extended or permanent cell cycle arrest, and apoptosis. Previously, the massive cell death induced by colcemid after UV exposed in CHO.K1 cells has been proved. Colcemid, a mitosis inhibitor, caused the synergistic cell death cooperated with UV damage and this effect was incubation time and drug dose dependent. Upon exposure to 0.5 mg/ml of colcemid after UV 26 j/m2 treatment, cell morphology was severely altered, cell volume decrease, and condensation of the chromosome was clearly noticeable. Besides this, the fragmentation of genomic DNA indicated cell death caused by drug and UV was probably due to apoptosis. To determine if other cell cycle inhibitors would promote cell death in the same situation, mimosine, the G1 phase inhibitor were tested and synergistic apoptosis was observed of this drugs also. Different modes of cell death can occur within individual cell type to the genotoxin, so two different cell lines, NIH3T3 and HF-E6, were treated. The results show that there was no obvious diversity between two data of UV exposed alone and coexist with colcemid. The outcomes of HF-E6 cells that lack of p53 protein functions, indicate the synergistic apoptosis might be not due to p53 disruption. Recent work has suggested that cell cycle inhibitors could induce synergistic apoptosis after UV damage dependents on cell type, medicinal dose and incubation time, but not for dysfunction of p53 protein.