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Aminoácidos tipo micosporinas (MAAs) são compostos responsáveis pela fotoproteção no ultravioleta de diversos organismos aquáticos. São sintetizados pela via do ácido chiquímico por algas, bactérias e fungos, de maneira similar à síntese de flavonóides em plantas superiores. Neste trabalho foram conduzidos estudos relacionados a estes compostos em algas. Protocolos de extração de diferentes algas foram testados alterando-se parâmetros como solventes, temperatura e condições de incubação. Os resultados mostraram que dependendo da alga estudada, diferentes condições podem mudar a concentração de MAAs extraída, ressaltando a importância de se testar diversos parâmetros na extração, evitando assim valores sub- ou superestimados de concentrações. O desenvolvimento de um método por HPLC permitiu a separação de 6 MAAs com boa resolução. A caracterização estrutural foi realizada majoritariamente por espectrometria de massas utilizando diferentes tipos de analisadores. Estas análises permitiram a proposição de mecanismos de fragmentação descritos pela primeira vez para esta classe de compostos e possibilitaram a identificação de diferentes MAAs em algumas micro e macroalgas. Ensaios in vitro foram realizados com o extrato obtido da macroalga Gracilaria domingensis no intuito de avaliar seu potencial uso em formulações cosméticas direcionadas à fotoproteção. Os testes de estabilidade quanto ao pH, temperatura e exposição à radiação ultravioleta bem como os ensaios de citotoxicidade, fototoxicidade e avaliação do fator de proteção solar sugeriram que este extrato pode ser promissor quando incorporado em formulações direcionadas para a fotoproteção. Este extrato não apresentou atividade antioxidante significativa. Os estudos com o dinoflagelado Prorocentrum minimum isolado de duas regiões diferentes, quando exposto às radiações ultravioleta, mostraram que houve uma indução das MAAs em ambas linhagens em todos os tratamentos realizados no período de 72 h. A indução foi mais rápida e pronunciada na linhagem oriunda de Lisboa, em Portugal do que na linhagem proveniente de Kattegat, na Dinamarca. Estes dados estão de acordo com as características do local de origem das linhagens, uma vez que os dinoflagelados originários de Portugal em seu meio natural estavam sujeitos a maiores irradiações. Medidas do rendimento quântico do fotossistema II indicaram que a síntese e acúmulo de MAAs em P. minimum isolada de Lisboa ofereceu vantagens na proteção do sistema fotossintético e na supressão de espécies reativas de oxigênio desta microalga quando comparada aos indivíduos da mesma espécie de regiões com menores irradiações. / Mycosporine-like amino acids (MAAs) are chemically related water soluble compounds responsible for UV photoprotection in many aquatic organisms. They are biosynthesized via the shikimate pathway by algae, bacteria and fungi in a similar manner to the biosynthesis of UV-screening flavonoids in terrestrial plants. In this work, studies related to this class of compounds were performed with algae. Extraction protocols of some algae were tested using diverse solvents at different temperature. The results showed that depending on the organism examined, both solvent concentration and temperature affected extraction efficiency and final MAA concentration. The improvement of a HPLC method separated a mix of 6 MAAs with good resolution. The structural characterization was made by mass spectrometry using different analyzers. The analysis by mass spectrometry allowed the proposition of new mechanisms of fragmentation and identification of different MAAs in some micro and macroalgae. In vitro preliminary assays were performed to evaluate the potential use of Gracilaria domingensis extract in suncare products. The extract showed no antioxidant activity, however the pH, temperature and UV exposure stability, as well the citotoxicity, phototoxicity and sun protection factor showed a potential commercial utilization for the extracts. The UV exposure experiments with the dinoflagellate Prorocentrum minimum isolated from Lisbon, Portugal and Kattegat, Denmark, showed that MAAs were induced in all treatments during 72 h. The induction was faster in the species from Lisbon than the ones from Kattegat. These data are in agreement with local isolation place, since the dinoflagellates from Portugal are submitted to high irradiance regime in their natural enviroment. The quantum yield of photosystem II suggested that the over production of MAAs by P. Minimum from Lisbon protects the photosynthetic apparatus, indicating that MAAs act as spectrally specific UV sunscreens in phytoplankton.

The bachelor thesis submitted deals with properties of electro-insulating lacquer hardenable by ultraviolent radiation and temperature. Within the theoretical part a summary of electro-insulating lacquers used in electrotechnics has been elaborated. Chemical changes that take place in this material group have been described during hardening process. A method of dielectric relaxation spectroscopy specifically focused on mathematic and physical description of polarisation and conductive mechanisms taking place in the structure of the given material has been closely studied. In the experimental part a workplace for hardening and long-term exposition of lacquered samples during simultaneous effect of various climatic elements has been designed and built. The selected electric and mechanical properties have been monitored on three sets of experimental samples prepared by means of different methodical procedures. The results gained have been mathematically evaluated and physically interpreted in term of methodical procedure of hardening and different temperature of measurement.

This work deals with the studies of liquid oligobutadiens properties in AC electric field by dielectric relaxation spectroscopy method. The current issue in the diagnosis of oligomeric and polymeric materials during the activity of various degradation factors and options of their alleviation and suppression was studied. The existing apparatus is modified for monitoring possibilities of polymeric materials during the action of various degradation and operational factors. Effect of climatic factors are experimentally investigated, especially UV radiation and temperature on the course of the frequency dependence of complex permittivity components with respect to the different composition and length of the polymer chain.

We have observed our Universe in many different wavelengths, from gamma ray to radiowaves and have observed countless stars, galaxies, and everything else in between. These measurements slowly add to our understanding of what our Universe is, how it formed, and where it is heading next. In Chapter 2 we introduce the Ultraviolet GAlactic Plane Survey (UVGAPS), which produced a high resolution map of the Milky Way’s Galactic plane in the NUV using the Galaxy Evolution Explorer (GALEX), an orbiting ultraviolet space telescope operated by NASA and Caltech between 2003-2013. Of the many astrophysical phenomena observable in ultraviolet wavelengths, we choose to focus on a few interesting objects: red clump stars and OB type stars, and the Galactic dust that impacts them. We use an image source extractor to obtain the NUV photometry and apply several cuts to clean the data. We present a catalog of 2,843,399 objects with GALEX NUV band mea- surements. Despite the difference in observing strategy and analysis pipeline, we find good agreement between previously targeted GALEX observations and the UVGAPS catalog in overlapping regions. The data were cross matched to Gaia DR2 and Pan-STARRS DR2, two visible-band surveys that have considerable coverage of the Galactic Plane. We characterize matched objects in color-magnitude and color-color space to highlight a range of objects, from main sequence stars to binaries detected with these data. Although core helium-burning red clump (RC) stars are faint at ultraviolet wavelengths, their ultraviolet-optical color is a unique and accessible probe of their physical properties. In Chapter 3, using data from the GALEX All Sky Imaging Survey, Gaia DR2, and the SDSS APOGEE DR14 survey, we find that spectroscopic metallicity is strongly correlated with the location of a RC star in the UV-optical color magnitude diagram. The RC has a wide spread in (NUV - G)0 color of over 4 magnitudes compared to a 0.7-magnitude range in (G BP - G RP )0 . We propose a photometric, dust-corrected, ultraviolet-optical (NUV - G)0 - [Fe/H] color-metallicity relation using a sample of 5,175 RC stars from APOGEE. We show that this relation has a scatter of 0.16 dex and is easier to obtain for large, wide-field samples than spectroscopic metallicities. Importantly, the effect may be comparable to the spread in RC color attributed to extinction in other studies. In Chapter 4 we extend our RC analysis to UVGAPS and include new age and mass measurements. We find that RC stars separate into two distinct populations in the thin and thick disk. Thick disk stars tend to be old, low mass stars while thin disk stars are more heterogeneous, containing mostly young, massive stars but also some old, low-mass stars typical of the thick disk. These last two chapters are just two of many projects that UVGAPS enables.

The signaling mechanisms involved in UVB-induced skin cancer are complex and although the scope of this work is inherently limited in focus, the findings may provide insight into how estrogen receptor signaling impacts cell growth, senescence, and apoptosis to protect keratinocytes. Additional signaling due to E2-activation of the estrogen receptor may provide back-up or redundant pathways in response to UVB.

The present work aims at enhancing the external quantum efficiencies of ultra-violet (UV) sensitive photodetectors (PDs) and light emitting diodes (LEDs)for any light polarization. Deep UV solid state devices are made out of AlGaN or MgZnO and their performances suffer from the high resistivity of their p-doped regions. They require transparent p-contacts; yet the most commonly used transparent contacts have low transmission in the UV: indium tin oxide (ITO) and nickel-gold (Ni/Au 5/5 nms) transmit less than 50% and 30% respectively at 300 nm. Here we investigate the use of surface plasmons (SPs) to design transparent p-contacts for AlGaN devices in the deep UV region of the spectrum. The appeal of using surface plasmon coupling arose from the local electromagnetic field enhancement near the metal surface as well as the increase in interaction time between the field and semiconductor if placed on top of a semiconductor. An in/out-coupling mechanism is achieved by using a grating consisting of two perpendicularly oriented sets of parallel aluminum lines with periods as low as 250 nm. The incident light is first coupled into SPs at the air/aluminum interface which then re-radiate at the aluminum/AlGaN interface and the photons energy is transferred to SP polaritons (SPPs) and back to photons. High transmission can be achieved not only at normal incidence but for a wider range of incident angles. iv A finite difference time domain (FDTD) package from R-Soft was used to simulate and design such aluminum gratings with transparency as high as 100% with tunable peak wavelength, bandwidth and angular acceptance. A rigorous coupled wave analysis (RCWA) was developed in Matlab to validate the FDTD results. The high UV transparency meshes were then fabricated using an e-beam assisted lithography lift-off process. Their electrical and optical properties were investigated. The electrical characterization was very encouraging; the sheet resistances of these meshes were lower than those of the conventionally used transparent contacts. The optical transmissions were lower than expected and the causes for the lower measurements have been investigated. The aluminum oxidation, the large metal grain size and the line edge roughness were identified as the main factors of inconsistency and solutions are proposed to improve these shortcomings. The effect of aluminum oxidation was calculated and the passivation of aluminum with SiO2 was evaluated as a solution. A cold deposition of aluminum reduced the aluminum grain size from 60 nm to 20 nm and the roughness from 5 nm to 0.5 nm. Furthermore, replacing the conventional lift-off process by a dry back-etch process led to much smoother metal line edges and much high optical transparency. The optical measurements were consistent with the simulations. Therefore, reduced roughness and smooth metal line edges were found to be especially critical considerations for deep UV application of the meshes.

Planktonic larvae of marine organisms are increasingly being exposed and required to respond to a changing physical environment. Adult sea urchins occupy both intertidal and subtidal waters and broadcast spawn gametes into the water column to contend with variable physical conditions. To answer how populations of invertebrates residing at different depths adequately prepare their offspring to cope with different levels of ultraviolet radiation (UVR), we collected adult purple sea urchins, Strongylocentrotus purpuratus, from four sites (two intertidal and two subtidal (~15 m deep)) on the central coast of CA to compare UV tolerance in offspring. Our measurements of UVA (321–400 nm) and UVB (280–320 nm) irradiance at all collection sites showed UVA and UVB were low or absent in subtidal sites compared to intertidal sites. Our study found that offspring from intertidal populations experience a less severe developmental delay when exposed to environmentally relevant levels of UVR (using artificial lighting) than offspring from subtidal populations. The mean percent cleavage delay for UV-treated embryos relative to the controls was 16% (± 2.3 SE) for intertidal sites and 21.1% (± 2.7 SE) for subtidal sites. This suggests that environmental UV cues or additional environmental cues experienced by intertidal mothers may prepare offspring to resist effects of UV exposure during early development. To further understand differences in biochemistry of the eggs released from mothers of different populations (i.e. differences in maternal investment), we assessed differences in protein abundance among batches of eggs from intertidal and subtidal populations. We identify a range of candidate proteins involved in various cellular processes such as cell cycle regulation, signaling and transport, oxidative stress and metabolism that may help developing embryos cope with UVR stress. These candidate proteins may also help us understand adaptations important for survival of developing marine organisms in changing ocean conditions.

Erythema is a hallmark skin response to excessive ultraviolet radiation (UVR) and is associated with cutaneous inflammation. Both are mediated by inflammatory mediators including nitric oxide (NO), prostaglandin E2 (PGE2) and chemoattractants such as 12-hydroxyeicosatetraenoic acid (12-HETE) leading to vasodilation and increased leukocyte infiltration. The erythematous response is more pronounced in individuals with low basal melanin levels or who fail to respond to UVR with a robust up-regulation of melanogenesis. While melanin production is a key function of melanocytes, these cells can also produce NO and PGE2, and are located in close proximity to the dermal vasculature. It has been hypothesized that melanocytes with poor melanogenic capacity may participate in the inflammatory response to UVR. The aim of this project was to investigate the inflammatory response in the skin of individuals with either skin phototype (SPT) 1 or 4 to UVR. Sixteen normal healthy individuals were selected for study (8 SPT-1 & 8 SPT-4). Buttock skin was investigated by immunohistochemistry for leukocyte subtypes, eicosanoid producing enzymes and NO synthases under basal and UVR-stimulated conditions. In addition primary cultures of epidermal melanocytes (EM) were established from 16 individuals (8 SPT-1 & 8 SPT-4) and assessed for the presence of eicosanoid-producing enzymes, melanogenic enzymes and NO synthases, by immunocytochemistry, Polymerase Chain Reaction and Western Blotting and for the production of the main pro-inflammatory eicosanoid PGE2 by ELISA and Mass Spectrometry. Moreover, the fatty acid composition of cultured melanocytes was assessed by Gas Chromatography. Results showed that individuals with SPT-1 had significantly greater neutrophil infiltration into the epidermis than those with SPT-4 at 24 hrs post-UVR. Moreover, CD3+ lymphocyte infiltration into the dermis was significantly greater in individuals with SPT-4 than those with SPT-1 at 24 and 72 hrs post-UVR. NOS-1, NOS-3, 12-LOX and COX-2 expression were significantly increased in SPT-1 skin, while NOS-2 and 15-LOX were significantly increased in SPT-4 skin. As 12-LOX and COX-2 products are chemoattractive (for neutrophils) and pro-inflammatory respectively these data could explain the greater observed neutrophil infiltration in SPT-1. The 15-LOX product (15-HETE) is anti-inflammatory and may suggest that 15-LOX up-regulation in SPT-4 skin may aid resolution of the sunburn response, which in part may be mediated by CD3+ lymphocytes and a class-switch in eicosanoid production from COX to LOX products. Melanocyte primary cultures surprisingly showed that SPT was not correlated with melanin content or melanogenic enzyme expression/activity suggesting that all melanocytes in vitro contained the necessary cellular machinery to produce melanin. This finding may reflect also their equal treatment under these enriched culture conditions, which may or may not be available to these cells in situ. Moreover, all melanocytes expressed the necessary machinery (PLA2, COX-1, cPGES) to produce PGE2. However, only some cultures did so at baseline and in response to UVR, and this was not correlated with SPT. A positive correlation was found however between expression level of dopachrome tautomerase (DCT) and protection against PGE2 production in response to UVR, which may suggest a novel role for DCT unrelated to melanogenesis. In summary this research project has generated data that highlights differences between the skin of individuals with SPT-1 and those with SPT-4, and may provide evidence that the keratinocyte partner contributes significantly to the SPT-associated response. This research may also suggest DCT as a novel therapeutic target to protect EM from participation in the UVR-associated inflammatory response in skin. / Wellcome Trust

Ultraviolet radiation (UVR) in solar light is important for skin biology. It is involved in the development acute and chronic skin inflammation, aging and cancer, causing erythema, tanning and local or systemic immunosuppression. Omega-3 polyunsaturated fatty acids (n-3 PUFA) are considered anti- inflammatory and could reduce the damage caused by overexposure to UVR. Although, n-3 PUFA have been considered as photoprotective agents, their exact mechanisms of action is not completely understood. The aim of the work is to determine the effect of UVR and the n-3 PUFA eicosapentaenoic acid (EPA), or docosahexaenoic acid (DHA) on human skin cells (in vitro study), specifically on: cell viability, apoptosis and their metabolism through the cyclooxygenase and lipoxygenase pathways. Also, to study the cellular incorporation and effect of n-3 PUFA on the fatty acid profile of skin cells. A clinical study was undertaken to assess the incorporation of n-3 PUFA supplements in human skin. A clinical study was performed in 40 healthy women (active group) supplemented with 4g/day of EPA (70%) and DHA (10%) and 40 healthy women (placebo group) supplemented with 4g/day of glyceryl tricoprylate coprate (GTCC). After 3 months, both blood samples and skin punch biopsies were collected and analysed for fatty acids by gas chromatography (GC). HaCaT keratinocytes and 46BR.1N fibroblasts were cultured and treated with 10 and 50μM of either EPA, or DHA or oleic acid (OA) for 72h and exposed to 15 and 50 mJ/cm2. Cell viability was measured by the MTT assay and cell apoptosis by a colorimetric method, at 24h post UVR. Cells and culture media were analysed by GC and liquid chromatography tandem mass spectrometry (LC/ESI-MS/MS) to assess cellular fatty acids and production of eicosanoids. The clinical a study showed that in RBC saturated fatty acids (SFA) (44.27±7.43%) were the main fatty acid group followed by n-6 PUFA (29.61±5.53%). While in dermal tissue monounsaturated fatty acids (MUFA) (58.90±9.80%) was the main fatty acid group followed by SFA (27.06±6.78%). A significant increase in EPA, DHA and docosapentaenoic acid (DPA) was observed in RBC but only EPA was significantly increased in the dermis post n-3 PUFA supplementation. . The viability of HaCaT keratinocytes and 46BR.1N fibroblasts decreased post UVR and this was further reduced post PUFA treatment. Cell apoptosis increased when cells were exposed to UVR and further increased when cells were treated with EPA and DHA. . In HaCaT keratinocytes MUFA (54.22±8.82%) was the main fatty acid group followed by FAS (37.11±.9.16%), while SFA (51.94±8.68%) was the main group followed by MUFA (27.07±4.79) in 46BR.1N. Treated both cells with EPA and DHA showed significant increased in cellular EPA, DPA and DHA. 46BR.1N fibroblasts produced higher levels of prostaglandins (PG) compared to HaCaT keratinocytes: PGE2 and PGD2 were the main PG in both HaCaT (7.96±3.18 and 1.48±1.19 pg/million cell; respectively) and 46BR.1N with (44.2±23.00 and 17.1±9.71 pg/million cell; respectively). Significant increase in PGE1 and PGE2 occurred when cells were exposed to 15mJ/cm2 UVR. Treatment with n-3 PUFA decreased the level of PGE1 and PGE2, and increase production PGE3 at the baseline and post UVR. Both cell lines produced hydroxy fatty acids and the concentration of these mediators was higher in 46BR.1N than HaCaT. The concentrations of these mediators were significant increased post UVR: treatment with n-3 PUFA decreased the level of HODE and HETE, and increase production of HEPE and HDHA at baseline and post UVR. Overall, n-3PUFA treatment led to increases in the content of EPA and DHA on RBC, dermal tissue and human skin cell lines. EPA and DHA in skin cell lines appear to offer protection by increasing cellular apoptosis, decreasing inflammatory mediators specifically PGE2 and 12-HETE, and increasing anti-inflammatory mediators such as PGE3, 15-HEPE and 17-HDHA.