Palythine-threonine, a major novel mycosporine-like amino acid (MAA) isolated from the hermatypic coral Pocillopora capitata

Using a high-resolution reverse-phase liquid chromatography method we found that the tissues of the hermatypic coral Pocillopora capitato (collected in Santiago Bay, Mexico) contain a high diversity of primary and secondary mycosporine-like amino acids (MAAs) typical of some reef-building coral species: mycosporine-glycine, shinorine, porphyra-334, mycosporine-methylamine-serine, mycosporine-methylamine-threonine, palythine-serine, palythine and one additional novel predominant MAA, with an absorbance maximum of 320 nm. Here we document the isolation and characterization of this novel MAA from the coral A capitata. Using low multi-stage mass analyses of deuterated and non deuterated compounds, high-resolution mass analyses (Time of Flight, TOF) and other techniques, this novel compound was characterized as palythine-threonine. Palythine-threonine was also present in high concentrations in the corals Pocillopora eydouxi and Stylophora pistillata indicating a wider distribution of this MAA among reef-building corals. From structural considerations we suggest that palythine-threonine is formed by decarboxylation of porphyra-334 followed by demethylation of mycosporine-methylamine-threonine. (C) 2008 Elsevier B.V. All rights reserved.

Biflavonoids from Araucaria angustifolia protect against DNA UV-Induced damage

Ultraviolet radiation is one of the most deleterious forms of radiation to terrestrial organisms and is involved in formation of mutagenic pyrimidine dimers and oxidized nucleotides. The biflavonoid fraction (BFF), extracted from needles of Araucaria angustifolia was capable of protecting calf thymus DNA from damage induced by UV radiation. This occurred through prevention of cyclobutane thymine dimer and 8-oxo-7,8-dihydro-2`-deoxyguanosine formation, this being quantified by high-performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS) in a multiple reaction monitoring mode (MRM) and by HPLC-coulometric detection, respectively. (C) 2009 Elsevier Ltd. All rights reserved.

On the Relaxation Mechanisms of 6-Azauracil

The nonadiabatic photochemistry of 6-azauracil has been studied by means of the CASPT2//CASSCF protocol and double-zeta plus polarization ANO basis sets. Minimum energy states, transition states, minimum energy paths, and surface intersections have been computed in order to obtain an accurate description of several potential energy hypersurfaces. It is concluded that, after absorption of ultraviolet radiation (248 nm), two main relaxation mechanisms may occur, via which the lowest (3)(pi pi*) state can be populated. The first one takes place via a conical intersection involving the bright (1)(pi pi*) and the lowest (1)(n pi*) states, ((1)pi pi*/(1)n pi*)(CI), from which a low energy singlet-triplet crossing, ((1)n pi*/(3)pi pi*)(STC), connecting the (1)(n pi*) state to the lowest (3)(pi pi*) triplet state is accessible. The second mechanism arises via a singlet-triplet crossing, ((1)pi pi*/(3)n pi*)(STC), leading to a conical intersection in the triplet manifold, ((3)n pi*/(3)pi pi*)(CI), evolving to the lowest (3)(pi pi*) state. Further radiationless decay to the ground state is possible through a (gs/(3)pi pi*)(STC).

Crosslinking of Poly(N-vinyl-2-pyrrolidone) in the Coating of Cotton Yarn

Coating of cotton yarn is employed in the textile industry to increase the mechanical resistance of the yarns and resistance to vibration, friction, impact, and elongation, which are some of the forces to which the yarn is subjected during the weaving process. The main objective of this study is to investigate the usage of a synthetic hydrophilic polymer, poly(N-vinyl-2-pyrrolidone) (PVP), to coat 100% cotton textile yarn, aiming to give the yarn a temporary mechanical resistance. For the improvement of the mechanical resistance of the yarn, the following crosslinking processes of PVP were investigated: UV-C (ultraviolet) radiation, the Fenton and photo-Fenton reactions, and sensitized UV-C radiation. The influence of each crosslinking process was determined through tensile testing of the coated yarns. The results indicated that the best crosslinking process employed was UV-C radiation; increasing the mechanical resistance of the yarn up to 44% if compared with the pure cotton yarn, that is, without polymeric coating and crosslinking. POLYM. ENG. SCI., 51:445-453, 2011. (C) 2010 Society of Plastics Engineers

Determinação da dose eritematosa mínima como marcador de risco e sensibilidade à radiação ultravioleta

Objetivos: Determinar a dose eritematosa mínima (DEM) medida por exposição controlada à radiação ultravioleta-B (RUV-B), como limiar para dano solar agudo nos diversos fototipos, e medir a cor da pele constitucional pelo sistema colorimétrico CIELAB. Pacientes e Métodos: Um total de 194 voluntários, sadios, com idades acima de 18 anos, distribuídos em um mínimo de 30 participantes por fototipo. Todos foram classificados por fototipos segundo os critérios de Fitzpatrick. As regiões infra-axilar torácica e nádega foram irradiadas em 4 áreas de 1 cm2, assim como foi registrada a cor da pele desses locais pelo sistema CIELAB. Delineamento: Estudo transversal. Resultados: A média de idade dos participantes foi de 38 anos, sendo 68% do sexo feminino. A avaliação da associação entre as medidas das DEMs e dos valores colorimétricos da coordenada L*, mostrou uma correlação de Pearson negativa com r = -0,91 para um valor p<0,05. Para os valores das DEMs e os escores da classificação dos voluntários por fototipos, obteve-se correlação de Spearman (rs) de +0,95 para p<0,05 e, correlacionando os valores colorimétricos com os escores dos fototipos, encontrou-se em tórax um rs de -0,93 e em nádega -0,92 para um p < 0,05. Conclusões – Concluiu-se que: 1)- a mensuração dos valores colorimétricos da coordenada L* nas regiões infra-axilar torácica e nádega mostraram uma forte correlação com os valores das DEMs, sendo de menor poder invasivo e de maior praticidade para mensuração de sensibilidade à radiação ultravioleta; 2)- apesar de os escores de Fitzpatrick terem alta correlação com os valores das DEMs, mostraram superposição de valores nos fototipos adjacentes; 3)- o grau de associação das classes dos fototipos com a cor da pele permite dizer que a categoria numérica do fototipo aumenta à medida que a pele fica mais escura.

Efeitos da radiação ultravioleta b na expressão imunoistoquímica das metaloproteinases –2 e –9 em nevos melanocíticos

Introdução: a incidência dos melanomas permanece em ascensão em diversos países. Os nevos melanocíticos podem ser seus precursores ou marcadores de risco. A radiação ultravioleta é o principal fator de risco ambiental para o seu desenvolvimento. Estudos com nevos irradiados mostram que a radiação ultravioleta B (UVB) pode causar alterações morfológicas e bioquímicas semelhantes às de um melanoma in situ. As metaloproteinases da matriz (MMP) são enzimas proteolíticas e, particularmente, as MMP-2 e –9 (gelatinases A e B) parecem estar associadas à invasão tumoral, à formação de metástases e de neoangiogênese em melanomas. O objetivo do presente estudo é avaliar os efeitos da UVB nas expressões imunoistoquímicas de MMP-2 e –9 nas diferentes linhagens celulares de nevos melanocíticos. Métodos: quarenta e dois nevos melanocíticos tiveram suas metades irradiadas com dose de 2 DEM (dose eritematosa mínima) de UVB e foram excisados uma semana após. As expressões imunoistoquímicas das MMP-2 e -9 foram comparadas, quanto à sua intensidade, por três avaliadores diferentes entre os lados irradiados e não irradiados em queratinócitos, melanócitos de epiderme e derme superior, células endoteliais e fibroblastos. Os dados foram analisados pelo teste t pareado para as diferenças de expressão e pelo ICC para avaliação da homogeneidade entre as respostas dos observadores. Resultados: com relação à expressão imunoistoquímica de MMP-2, todas as linhagens celulares mostraram aumento no lado irradiado, especialmente os melanócitos epidérmicos. Quanto à MMP-9, somente nos queratinócitos, não se observou aumento de expressão do lado irradiado, ficando essa evidente nas demais linhagens celulares avaliadas. Conclusões: A UVB na dose de 2 DEM aumenta a expressão imunoistoquímica das MMP-2 e –9 em quase todas as linhagens celulares dos nevos melanocíticos avaliados até uma semana após a irradiação, com exceção feita queratinócitos, com a MMP-9.

Compósitos poliméricos a base de fibras de licuri: efeitos da hibridização e do envelhecimento ambiental acelerado

The gradual replacement of conventional materials by the ones called composite materials is becoming a concern about the response of these composites against adverse environmental conditions, such as ultraviolet radiation, high temperature and moist. Also the search for new composite using natural fibers or a blend of it with synthetic fibers as reinforcement has been studied. In this sense, this research begins with a thorough study of microstructural characterization of licuri fiber, as a proposal of alternative reinforcement to polymeric composites. Thus, a study about the development of two composite laminates was done. The first one, involving only the fiber of licuri and the second comprising a hybrid composite based of fiber glass E and the fiber of licuri, in order to know the performance of the fiber when of fiber across the hybridization process. The laminates were made in the form of plates using the tereftálica ortho-polyester resin as matrix. The composite laminate made only by licuri fiber had two reinforcing fabric layers of unidirectional licuri and the hybrid composite had two reinforcing layers of unidirectional licuri fabric and three layers of fiber short glass-E mat. Finally, both laminates was exposed to aging acceleration in order to study the influence of environmental degradation involving the mechanical properties and fracture characteristics thereof. Regarding the mechanical properties of composites, these were determined through uniaxial tensile tests, uniaxial compression and three bending points for both laminates in original state, and uniaxial tensile tests and three bending points after accelerated aging. As regards the study of structural degradation due to aging of the laminates, it was carried out based on microscopic analysis and microstructure, as well as measuring weight loss. The characteristics of the fracture was performed by macroscopic and microscopic (optical and SEM) analysis. In general, the laminated composites based on fiber licuri showed some advantages in their responses to environmental aging. These advantages are observed in the behavior related to stiffness as well as the microstructural degradation and photo-oxidation processes. However, the structural integrity of this laminate was more affected in case the action of uniaxial tensile loads, where it was noted a lower rate of withholding his last resistance property

Síntese hidrotérmica assistida por micro-ondas de tiO2, e aplicação em nanocompósito

In recent decades have seen a sharp growth in the study area of nanoscience and nanotechnology and is included in this area, the study of nanocomposites with self-cleaning properties. Since titanium dioxide (TiO2) has high photocatalytic activity and also antimicrobial, self-cleaning surfaces in your application has been explored. In this study a comparison was made between two synthesis routes to obtain TiO2 nanoparticles by hydrothermal method assisted by microwave. And after analysis of XRD and SEM was considered the best material for use in nanocomposites. It was deposited nanocomposite film of poly (dimethyl siloxane) (PDMS) with 0.5, 1, 1.5 and 2% by weight of nanoparticles of titanium dioxide (TiO2) by the spraying method. The nanocomposite was diluted with hexane and the suspension was deposited onto glass substrate, followed by curing in an oven with forced air circulation. The photocatalytic activity of the nanocomposite impregnated with methylene blue was evaluated by UV- vis spectroscopy from the intensity variation of absorption main peak at 660nm with time of exposure to the UV chamber. Changes in the contact angle and microhardness were analyzed before and after UV aging test. The effect of ultraviolet radiation on the chemical structure of the PDMS matrix was evaluated by spectrophotometry Fourier transform infrared (FTIR).The results indicated that the addition of TiO2 nanoparticles in the coating PDMS gave high photocatalytic activity in the decomposition of methylene blue, an important characteristic for the development of self-cleaning coatings

Modelagem estocástica do índice de radiação ultravioleta na costa leste do nordeste do Brasil

The increase in ultraviolet radiation (UV) at surface, the high incidence of non-melanoma skin cancer (NMSC) in coast of Northeast of Brazil (NEB) and reduction of total ozone were the motivation for the present study. The overall objective was to identify and understand the variability of UV or Index Ultraviolet Radiation (UV Index) in the capitals of the east coast of the NEB and adjust stochastic models to time series of UV index aiming make predictions (interpolations) and forecasts / projections (extrapolations) followed by trend analysis. The methodology consisted of applying multivariate analysis (principal component analysis and cluster analysis), Predictive Mean Matching method for filling gaps in the data, autoregressive distributed lag (ADL) and Mann-Kendal. The modeling via the ADL consisted of parameter estimation, diagnostics, residuals analysis and evaluation of the quality of the predictions and forecasts via mean squared error and Pearson correlation coefficient. The research results indicated that the annual variability of UV in the capital of Rio Grande do Norte (Natal) has a feature in the months of September and October that consisting of a stabilization / reduction of UV index because of the greater annual concentration total ozone. The increased amount of aerosol during this period contributes in lesser intensity for this event. The increased amount of aerosol during this period contributes in lesser intensity for this event. The application of cluster analysis on the east coast of the NEB showed that this event also occurs in the capitals of Paraiba (João Pessoa) and Pernambuco (Recife). Extreme events of UV in NEB were analyzed from the city of Natal and were associated with absence of cloud cover and levels below the annual average of total ozone and did not occurring in the entire region because of the uneven spatial distribution of these variables. The ADL (4, 1) model, adjusted with data of the UV index and total ozone to period 2001-2012 made a the projection / extrapolation for the next 30 years (2013-2043) indicating in end of that period an increase to the UV index of one unit (approximately), case total ozone maintain the downward trend observed in study period

Transmissão de Radiação Ultravioleta Através do Pelame e da Epiderme de Bovinos

A transmissão de radiação ultravioleta de comprimentos de onda entre 250 e 360 nm através do pelame e da epiderme de bovinos foi determinada em laboratório, usando-se amostras de couro de animais recém-abatidos. A quantidade de radiação transmitida através do pelame depende da coloração e também das características estruturais do pelame (espessura da capa; comprimento, diâmetro, número e inclinação dos pêlos), pelas quais é definido o trajeto médio de um fóton pela massa de pêlos (L). A maior transmissão é proporcionada por pelames brancos com altos valores de L, ao passo que pelames negros em geral apresentam transmissão nula ou muito baixa. Quanto menos pigmentada a epiderme, maior a transmissão de radiação através da sua superfície. A melhor proteção é proporcionada por pelames negros com baixo valor de L sobre epiderme igualmente negra, mas em vista do aquecimento causado pela absorção de radiação térmica (em vacas Holandesas a temperatura das malhas negras atinge 44,1ºC ao mesmo tempo em que a das malhas brancas é 37,7ºC), a combinação ideal para ambientes tropicais é um pelame branco com baixo valor de L sobre epiderme negra, uma combinação dificilmente encontrada em animais de raças européias. Uma alternativa seria um pelame negro com um baixo valor de L. Animais vermelhos apresentam alta transmissão de radiação UV através da epiderme e do pelame, sendo desaconselhados para ambientes tropicais. Entretanto, foi observada uma vaca Holandesa com áreas isoladas de epiderme negra coberta com pelame branco, o que pode trazer perspectivas para uma seleção para combinações mais adequadas de epiderme e pelame em bovinos de raças européias.

Efeitos do envelhecimento ambiental acelerado em compósitos poliméricos

The advantages of the use of vegetable fibers on the synthetic fibers, such as glass fibers, in the reinforcements in composites are: low cost, low density, good tenacity, good thermal properties and reduced use of instruments for their treatment or processing. However, problems related to poor performance of some mechanical natural fibers, have hindered its direct use in structural elements. In this sense, the emergence of alternative materials such as hybrids composites, involving natural and synthetic fibers, has been encouraged by seeking to improve the performance of structural composites based only on natural fibers. The differences between the physical, chemical and mechanical properties of these fibers, especially facing the adverse environmental conditions such as the presence of moisture and ultraviolet radiation, is also becoming a concern in the final response of these composites. This piece of research presents a comparative study of the strength and stiffness between two composite, both of ortoftalic polyester matrix, one reinforced with fibers of glass-E (CV) and other hybrid reinforced with natural fibers of curauá and fiberglass-E (CH). All the comparative study is based on the influence of exposure to UV rays and steam heated water in composites, simulating the aging environment. The conditions for the tests are accelerated through the use of the aging chamber. The composites will be evaluated through tests of uniaxial static mechanical traction and bending on three points. The composite of glass fiber and hybrid manufacturing industry are using the rolling manual (hand lay-up) and have been developed in the form of composites. All were designed to meet possible structural applications such as tanks and pipes. The reinforcements used in composites were in the forms of short fiber glass-E quilts (450g/m2 - 5cm) of continuous wires and fuses (whose title was of 0.9 dtex) for the curauá fibers. The results clearly show the influence of aging on the environmental mechanical performance of the composite CV and CH. The issues concerning the final characteristics of the fracture for all types of cargoes studied were also analyzed

Estudo da radiação ultravioleta na Cidade de Natal-RN

There were studied the variation of the solar ultraviolet radiation (UVR) in four wavelengths (305 nm, 320 nm, 340 nm e 380 nm) and erythemic dose, measured in Natal RN Brazil, from January 2001 until December 2007, using the ground ultraviolet radiometer of the Instituto Nacional de Pesquisas Espaciais / Centro Regional do Nordeste INPE-CRN, fixed on the roof of the Laboratório de Variáveis Ambientais Tropiciais LAVAT-INPE-CRN. It was verified that the mean value of the UVR in the city reachs the HIGH index before 09h00 a.m. and VERY HIGH before 09h40 a.m.; it was also verified that, except in the months of June and July, in the other months of the year the UVR reachs the HIGH index before 10h00 a.m., despite of the recommendations broadcasting in the media about the safe time to people stay ashore on the beaches of the city. After 14h30 p.m., the UVR reachs the MODERATE index in any month of the year. These evidence are valid to all years of the period studied, i.e., 2001 to 2007. The year of 2004 presented the lower mean values of UVR indices, and the year of 2007 presented the higher mean values of UVR index. It was prove, by means of the analysis of variance (ANOVA), the variation in the four wavelengths and in the erythemic dose. Considering that the city has high indices of skin cancer and cataract, the results of the research may be use as a data source to studies that intend to support programs of public health. At the same time, the results of the research may be applied to material science and agriculture studies

Efeitos da radiação uv, temperatura e vapor aquecido nos compósitos poliméricos: monitoramento, instabilidade estrutural e fratura

The application of composite materials and in particular the fiber-reinforced plastics (FRP) has gradually conquered space from the so called conventional materials. However, challenges have arisen when their application occurs in equipment and mechanical structures which will be exposed to harsh environmental conditions, especially when there is the influence of environmental degradation due to temperature, UV radiation and moisture in the mechanical performance of these structures, causing irreversible structural damage such as loss of dimensional stability, interfacial degradation, loss of mass, loss of structural properties and changes in the damage mechanism. In this context, the objective of this thesis is the development of a process for monitoring and modeling structural degradation, and the study of the physical and mechanical properties in FRP when in the presence of adverse environmental conditions (ageing). The mechanism of ageing is characterized by controlled environmental conditions of heated steam and ultraviolet radiation. For the research, it was necessary to develop three polymer composites. The first was a lamina of polyester resin reinforced with a short glass-E fiber mat (representing the layer exposed to ageing), and the other two were laminates, both of seven layers of reinforcement, one being made up only of short fibers of glass-E, and the other a hybrid type reinforced with fibers of glass-E/ fibers of curaua. It should be noted that the two laminates have the lamina of short glass-E fibers as a layer of the ageing process incidence. The specimens were removed from the composites mentioned and submitted to environmental ageing accelerated by an ageing chamber. To study the monitoring and modeling of degradation, the ageing cycles to which the lamina was exposed were: alternating cycles of UV radiation and heated steam, a cycle only of UV radiation and a cycle only of heated steam, for a period defined by norm. The laminates have already undergone only the alternating cycle of UV and heated steam. At the end of the exposure period the specimens were subjected to a structural stability assessment by means of the developed measurement of thickness variation technique (MTVT) and the measurement of mass variation technique (MMVT). Then they were subjected to the mechanical tests of uniaxial tension for the lamina and all the laminates, besides the bending test on three points for the laminates. This study was followed by characterization of the fracture and the surface degradation. Finally, a model was developed for the composites called Ageing Zone Diagram (AZD) for monitoring and predicting the tensile strength after the ageing processes. From the results it was observed that the process of degradation occurs Abstract Raimundo Nonato Barbosa Felipe xiv differently for each composite studied, although all were affected in certain way and that the most aggressive ageing process was that of UV radiation, and that the hybrid laminated fibers of glass-E/curaua composite was most affected in its mechanical properties

Envelhecimento ambiental em compósitos poliméricos à base de tecidos de reforços híbridos

The utilization of synthetic fibers for plastic reinforcement is more and more frequent and this growing interest requires that their mechanic behavior under the most variable conditions of structural applications be known. The use of such materials in the open and exposed to the elements is one of them. In this case, it becomes extremely necessary to study their mechanical properties (strength, stiffness) and the mechanism of fracture by which the environment aging them out. In order to do that, the material must be submitted to hot steam and ultraviolet radiation exposure cycles, according to periods of time determined by the norms. This study proposal deals with the investigation of accelerated environmental aging in two laminated polymeric composites reinforced by hybrid woven made up of synthetic fibers. The configurations of the laminated composites are defined as: one laminate reinforced with hybrid woven of glass fibers/E and Kevlar fibers/49 (LHVK) and the other laminate is reinforced with hybrid tissue of glass fibers/E and of carbon fibers AS4 (LHVC). The woven are plane and bidirectional. Both laminates are impregnated with a thermofix resin called Derakane 470-300 Epoxy Vinyl-Ester and they form a total of four layers. The laminates were industrially manufactured and were made through the process of hand-lay-up. Comparative analyses were carried out between their mechanical properties by submitting specimen to uniaxial loading tractions and three-point flexion. The specimen were tested both from their original state, that is, without being environmentally aging out, and after environmental aging. This last state was reached by using the environmental aging chamber

Degradação do fungicida tiofanato metílico pelo processo foto-Fenton em reatores anular e solar

Effluents from pesticide industries have great difficulty to decontaminate the environment and, moreover, are characterized by high organic charge and toxicity. The research group Center for Chemical Systems Engineering (CESQ) at the Department of Chemical Engineering of Polytechnical School of University of São Paulo and Department of Chemical Engineering, Federal University of Rio Grande do Norte have been applying the Advanced Oxidation Processes (AOP's) for the degradation of various types of pollutants. These processes are based on the generation of hydroxyl radicals, highly reactive substances. Thus, this dissertation aims to explore this process, since it has been proven to be quite effective in removing organic charge. Therefore, it was decided by photo-Fenton process applied to the degradation of the fungicide Thiophanate methyl in aqueous system using annular reactor (with lamp Philips HPLN 125W) and solar. The samples were collected during the experiment and analyzed for dissolved organic carbon (TOC) using a Shimadzu TOC (Shimadzu 5050A e VCP). The Doehlert experimental design has been used to evaluate the influence of ultraviolet radiation, the concentrations of methyl thiophanate (C12H14N4O4S2), hydrogen peroxide (H2O2) and iron ions (Fe2+), among these parameters, was considered the best experimental conditions, [Fe2+] = 0.6 mmol/L and [H2O2] = 0.038 mol/L in EXP 5 experiment and in SOL 5 experiment, obtaining a percentage of TOC removal of 60% in the annular reactor and 75% in the solar reactor