Molybdenum is essential to most organisms, being found in the active site of enzymes that catalyze redox reactions involving carbon, nitrogen and sulfur atoms of key metabolites. Some of the molybdenum-dependent reactions constitute key steps in the global biogeochemical cycles of carbon, nitrogen and sulfur, with particular emphasis on the atmospheric dinitrogen fixation into ammonium. Presently, more than 50 molybdoenzymes are known. The great majority are prokaryotic, with eukaryotes holding only a restricted number of molybdoenzymes. Tungsten, probably because of its limited bioavailability, is less used, being found most often in anaerobic thermophilic prokaryotes.

This chapter provides an overview on the molybdo- and tungstoenzymes.
Their physiological context and significance will be described in Section 1.2,where the recent hypothesis that the lack of molybdenum could have been the limiting factor for the life evolution and expansion on early Earth will receive special attention (Section 1.2.1). A brief introduction to the chemical properties that shape the catalytically competent molybdenum/tungsten centres will be made in Section 1.3. In Section 1.4, the enzymes will be grouped in five main families (Sections 1.4.1 to 1.4.5), according to their metal/cofactor structure, and a general view on the structural (section (a)) and mechanistic (section (b)) versatility of each family will be presented. A brief account of novel heteronuclear centres containing molybdenum, whose physiological function is not yet fully understood, will be made in Section 1.4.6. A final outlook on our present knowledge about these enzymes will conclude this chapter.

http://docentes.fct.unl.pt/lblm/files/mo_w_enzymes-rsc_book-chap_1.pdf

http://docentes.fct.unl.pt/lblm/files/ica-2017-455-350.pdf

Reduced-bias versions of a very simple generalization of the ‘classical’ Hill estimator of a positive extreme value index (EVI) are put forward. The Hill estimator can be regarded as the logarithm of the mean-of-order-0 of a certain set of statistics. Instead of such a geometric mean, it is sensible to consider the mean-of-order-p (MOP) of those statistics, with p real. Under a third-order framework, the asymptotic behaviour of the MOP, optimal MOP and associated reduced-bias classes of EVI-estimators is derived. Information on the dominant non-null asymptotic bias is also provided so that we can deal with an asymptotic comparison at optimal levels of some of those classes. Large-scale Monte-Carlo simulation experiments are undertaken to provide finite sample comparisons.Reduced-bias versions of a very simple generalization of the ‘classical’ Hill estimator of a positive extreme value index (EVI) are put forward. The Hill estimator can be regarded as the logarithm of the mean-of-order-0 of a certain set of statistics. Instead of such a geometric mean, it is sensible to consider the mean-of-order-p (MOP) of those statistics, with p real. Under a third-order framework, the asymptotic behaviour of the MOP, optimal MOP and associated reduced-bias classes of EVI-estimators is derived. Information on the dominant non-null asymptotic bias is also provided so that we can deal with an asymptotic comparison at optimal levels of some of those classes. Large-scale Monte-Carlo simulation experiments are undertaken to provide finite sample comparisons.

Desde que o reforço estrutural começou a utilizar materiais de matriz polimérica reforçada com fibras (FRP) que o fenómeno do descolamento prematuro dos compósitos de FRP da superfície colada tem merecido especial atenção de vários autores. O conhecimento do processo de descolamento completo da ligação CFRP/betão ganhou assim, algum destaque nos últimos anos. Na generalidade, as ligações CFRP/betão têm sido analisadas com recurso métodos analíticos e numéricos sendo que, nos primeiros, se tem vindo a adoptar leis de aderência muito simplificadas das observadas experimentalmente. Apesar das simplificações adoptas nas análises analíticas, as expressões obtidas são muito importantes já que têm grande potencial em serem adoptadas pelos códigos ou normas nacionais e/ou interncionais. Por outro lado, e apesar de adoptarem leis de aderência mais refinadas, as análises numéricas permitem apenas a obtenção de expressões empíricas que podem não contemplar a generalidade dos casos estudados. Neste sentido, este trabalho apresenta um conjunto de soluções analíticas com base numa lei de aderência exponencial capaz de representar todas as não-linearidades envolvidas no descolamento da ligação CFRP/betão. Os resultados analíticos são confrontados com ensaios experimentais em que a técnica de colagem EBR foi utilizada. Contudo, o modelo analítico proposto pode ser também utilizado quando a técnica Near Surface Mounted (NSM) é adoptada. Adicionalmente, são apresentadas soluções analíticas para o caso em que o deslocamento relativo entre o CFRP e o betão é restringido por, e.g., um dispositivo de amarração mecânica instalado na extremidade oposta à aplicação de carga.

Six quadrate bones, of which two almost certainly come from the Kem Kem beds (Cenomanian, Upper Cretaceous) of south-eastern Morocco, are determined to be from juvenile and adult individuals of Spinosaurinae based on phylogenetic, geometric morphometric, and phylogenetic morphometric analyses. Their morphology indicates two morphotypes evidencing the presence of two spinosaurine taxa ascribed to Spinosaurus aegyptiacus and? Sigilmassasaurus brevicollis in the Cenomanian of North Africa, casting doubt on the accuracy of some recent skeletal reconstructions which may be based on elements from several distinct species. Morphofunctional analysis of the mandibular articulation of the quadrate has shown that the jaw mechanics was peculiar in Spinosauridae. In mature spinosaurids, the posterior parts of the two mandibular rami displaced laterally when the jaw was depressed due to a lateromedially oriented intercondylar sulcus of the quadrate. Such lateral movement of the mandibular ramus was possible due to a movable mandibular symphysis in spinosaurids, allowing the pharynx to be widened. Similar jaw mechanics also occur in some pterosaurs and living pelecanids which are both adapted to capture and swallow large prey items. Spinosauridae, which were engaged, at least partially, in a piscivorous lifestyle, were able to consume large fish and may have occasionally fed on other prey such as pterosaurs and juvenile dinosaurs.

Six quadrate bones, of which two almost certainly come from the Kem Kem beds (Cenomanian, Upper Cretaceous) of south-eastern Morocco, are determined to be from juvenile and adult individuals of Spinosaurinae based on phylogenetic, geometric morphometric, and phylogenetic morphometric analyses. Their morphology indicates two morphotypes evidencing the presence of two spinosaurine taxa ascribed to Spinosaurus aegyptiacus and? Sigilmassasaurus brevicollis in the Cenomanian of North Africa, casting doubt on the accuracy of some recent skeletal reconstructions which may be based on elements from several distinct species. Morphofunctional analysis of the mandibular articulation of the quadrate has shown that the jaw mechanics was peculiar in Spinosauridae. In mature spinosaurids, the posterior parts of the two mandibular rami displaced laterally when the jaw was depressed due to a lateromedially oriented intercondylar sulcus of the quadrate. Such lateral movement of the mandibular ramus was possible due to a movable mandibular symphysis in spinosaurids, allowing the pharynx to be widened. Similar jaw mechanics also occur in some pterosaurs and living pelecanids which are both adapted to capture and swallow large prey items. Spinosauridae, which were engaged, at least partially, in a piscivorous lifestyle, were able to consume large fish and may have occasionally fed on other prey such as pterosaurs and juvenile dinosaurs.

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Engineering procedures governing the selection or development of printable nanostructured metal oxide nanoparticles for chromic, photovoltaic, photocatalytic, sensing, electrolyte-gated TFTs, and power storage applications are established in this chapter. The main focus is given on how to perform the material selection and formulation of printable dispersion in order to develop functional films for electrochemical applications. This chapter is divided into four main parts. Firstly, a brief introduction on electrochemically active nanocrystalline metal oxide films developed via printing techniques is given. This is followed by the description of the film morphology, structure, and required functionality. A theoretical approach to understand the impact of size and shape of nanoparticles on an ink formulation and electrochemical performance being the subject of the third section provides a greater control over the material selection. We attempt to describe these properties and show that for a given material, geometry and size of the nanoparticles have a major influence on the electrochemical reactivity and response time. This gives the ability to tune the performance of the film simply by varying the morphology of incorporated nanostructures. This section is completed by the recommendations on each major step of an ink formulation, together with imposed critical constraints concerning the fluid control. Finally, the performance of the ink-jetprinted dual-phase electrochromic films is discussed as a case study. By providing such a rather systematic survey, we aim to stress the importance of proper design strategy that would result in both improved physicochemical properties of nanoparticle-loaded inks and enhanced electrochemical performance of printed functional films. © Springer International Publishing Switzerland 2016.

The present work reports the influence of zinc oxide (ZnO) seed layer annealing temperature on structural, optical and electrical properties of ZnO nanorod arrays, synthesized by hydrothermal method assisted by microwave radiation, to be used as UV sensors. The ZnO seed layer was produced using the spin-coating method and several annealing temperatures, ranging from 100 to 500 °C, have been tested. X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and spectrophotometry measurements have been used to investigate the structure, morphology, and optical properties variations of the produced ZnO nanorod arrays regarding the seed layer annealing temperatures employed. After the growth of ZnO nanorod arrays, the whole structure was tested as UV sensors, showing an increase in the sensitivity with the increase of seed layer annealing temperature. The UV sensor response of ZnO nanorod arrays produced with the seed layer annealed temperature of 500 °C was 50 times superior to the ones produced with a seed layer annealed at 100 °C. © 2016 by the authors.