Theoretical Study of the Thermolysis Reaction and Chemiexcitation of Coelenterazine Dioxetanes

Coelenterazine and other imidazopyrazinones are important bioluminescent substrates widespread in marine species and can be found in eight phyla of luminescent organisms. Light emission from these systems is caused by the formation and subsequent thermolysis of a dioxetanone intermediate, whose decomposition allows for efficient chemiexcitation to singlet excited states. Interestingly, some studies have also reported the involvement of unexpected dioxetane intermediates in the chemiand bioluminescent reactions of Coelenterazine, albeit with little information on the underlying mechanisms of these new species. Herein, we have employed a theoretical approach based on density functional theory to study for the first time the thermolysis reaction and chemiexcitation profile of two Coelenterazine dioxetanes. We have found that the thermolysis reactions of these species are feasible but with relevant energetic differences. More importantly, we found that the singlet chemiexcitation profiles of these dioxetanes are significantly less efficient than the corresponding dioxetanones. Furthermore, we identified triplet chemiexcitation pathways for the Coelenterazine dioxetanes. Given this, the chemiexcitation of these dioxetanes should lead only to minimal luminescence. Thus, our theoretical investigation of these systems indicates that the thermolysis of these dioxetanes should only provide dark pathways for the formation of nonluminescent degradation products of the chemi- and bioluminescent reactions of Coelenterazine and other imidazopyrazinones

Seasonal Patterns of Growth and Senescence in \u3ci\u3eCynodon\u3c/i\u3e spp. cv Tifton 85 Grazed Swards

Growth and senescence are very important determinants of grassland productivity and correspond to key features to be considered for grazing management purposes. The present study was carried out at ESALQ, Piracicaba, S.P., Brazil and evaluated growth and senescence as a function of sward surface height. Mathematical models generated revealed that a similar pattern of response occurred as described in the literature for temperate grass species. However, a seasonal variation in response curves for growth and senescence was also observed and could be related to climatic events. Highest herbage accumulation rates were observed within the range of 15 to 20 cm of sward surface height

Avaliação do sistema radicular de Lima Ácida Tahiti em dois sistemas de manejo.

Para que as plantas cítricas tenham longevidade é necessário que o sistema radicular possa se desenvolver sem limitações. Rezende et al. (2002) registram o desenvolvimento prejudicado do sistema radicular de citros nos solos coesos dos Tabuleiros Costeiros, com as plantas geralmente exibindo sistema radicular superficial e enovelamento da raiz principal. A utilização de práticas de manejo de solo como, uso de coberturas vegetais e subsolagem, melhoram a morfologia da planta, uma melhor distribuição do sistema radicular permite explorar maior volume de solo para absorção de nutrientes e principalmente de água em profundidade. A produção citrícola nos Tabuleiros Costeiros, onde predominam Latossolos Amarelos e Argissolos Amarelos, caracterizados como profundos, ácidos e com presença de horizontes coesos (Jacomine et al., 1977), é realizada praticamente sem uso de irrigação, pois a região dispõe de uma distribuição de chuvas regular durante 9 a 10 meses/ano (CNPMF, 1993). Práticas culturais, como a utilização de leguminosas nas entrelinhas e herbicidas nas linhas, em áreas subsoladas a 0,50 m de profundidade, que foram capazes de aumentar o volume do sistema radicular dos citros neste ecossistema entre 68 e 148% e a produção de frutos entre 28 e 40%, respectivamente (Carvalho et al.,1999). O objetivo deste trabalho foi avaliar o sistema radicular da Lima Ácida Tahiti, verificando a capacidade das raízes de explorar o solo, comparando dois sistemas de cultivo.pdf 220

Strength improvement of adhesively-bonded joints using a reverse-bent geometry

Adhesive bonding of components has become more efficient in recent years due to the developments in adhesive technology, which has resulted in higher peel and shear strengths, and also in allowable ductility up to failure. As a result, fastening and riveting methods are being progressively replaced by adhesive bonding, allowing a big step towards stronger and lighter unions. However, single-lap bonded joints still generate substantial peel and shear stress concentrations at the overlap edges that can be harmful to the structure, especially when using brittle adhesives that do not allow plasticization in these regions. In this work, a numerical and experimental study is performed to evaluate the feasibility of bending the adherends at the ends of the overlap for the strength improvement of single-lap aluminium joints bonded with a brittle and a ductile adhesive. Different combinations of joint eccentricity were tested, including absence of eccentricity, allowing the optimization of the joint. A Finite Element stress and failure analysis in ABAQUS® was also carried out to provide a better understanding of the bent configuration. Results showed a major advantage of using the proposed modification for the brittle adhesive, but the joints with the ductile adhesive were not much affected by the bending technique

Optimization study of hybrid spot-welded/bonded single-lap joints

Joining of components with structural adhesives is currently one of the most widespread techniques for advanced structures (e.g., aerospace or aeronautical). Adhesive bonding does not involve drilling operations and it distributes the load over a larger area than mechanical joints. However, peak stresses tend to develop near the overlap edges because of differential straining of the adherends and load asymmetry. As a result, premature failures can be expected, especially for brittle adhesives. Moreover, bonded joints are very sensitive to the surface treatment of the material, service temperature, humidity and ageing. To surpass these limitations, the combination of adhesive bonding with spot-welding is a choice to be considered, adding a few advantages like superior static strength and stiffness, higher peeling and fatigue strength and easier fabrication, as fixtures during the adhesive curing are not needed. The experimental and numerical study presented here evaluates hybrid spot-welded/bonded single-lap joints in comparison with the purely spot-welded and bonded equivalents. A parametric study on the overlap length (LO) allowed achieving different strength advantages, up to 58% compared to spot-welded joints and 24% over bonded joints. The Finite Element Method (FEM) and Cohesive Zone Models (CZM) for damage growth were also tested in Abaqus® to evaluate this technique for strength prediction, showing accurate estimations for all kinds of joints

Os diplomados em Ciências da Documentação e Informação da Faculdade de Letras da Universidade de Lisboa: Empregabilidade 2008-2017

Objetivo: O objectivo do presente trabalho é analisar a empregabilidade dos diplomados do Mestrado em Ciências da Documentação e Informação da Universidade de Lisboa. Metodología: O presente estudo, como qualquer estudo de índole científica, assenta numa metodologia de investigação que nos permite apresentar resultados válidos e legitima o próprio trabalho. Neste sentido, o trabalho foi realizado completando as seguintes fases (Quivy & Campenhoudt, 1992): Elaboração da Pergunta de partida; Revisão da Literatura; Problematização; Instrumento de Análise; Recolha de Dados; e Análise dos Dados. É, ainda, um estudo exploratório de natureza qualitativa e quantitativa, suportado, sobretudo na revisão da literatura, pelo método de pesquisa documental (Saint-Georges, 1997:15). Resultados: Em termos absolutos, os valores da empregabilidade apresentados nos três momentos que foram inquiridos – à data de candidatura, à data de conclusão e atualmente, são de, respetivamente, 83%, 82% e 87%. Estes valores são ainda firmados pelo facto de 65% dos adjetivos utilizados sobre a formação do Mestrado ser: boa, abrangente, interessante, pertinente, atual, excelente, relevante, diversificada, prática, útil, enriquecedora, científica, eficiente, fundamental e rigorosa. Em suma, o presente estudo evidencia uma elevada empregabilidade dos diplomados em Ciências da Documentação e Informação pela Faculdade de Letras da Universidade de Lisboa, entre 2008 e 2017.info:eu-repo/semantics/draf