K$_{\alpha , \beta}$ X-ray lines from photon excitation were measured in selected elements from Mg to Cu using a high-resolution double-crystal X-ray spectrometer with a proportional counter, and the K$_beta$/K$_\alpha$ intensity ratio for each element was obtained, after correcting for self-absorption, detection efficiency, and crystal reflectance. This intensity ratio increases rapidly from Mg to Ca but, in the 3d elements region, the increase becomes slower. This is related to the intensity of the Kβ line involving valence electrons. The slow increase of this ratio in the 3d elements region is thought to be due to the correlation between 3d and 4s electrons. Moreover, the chemical shifts, FWHM, asymmetry indices, and Kβ/Kα intensity ratios of the Cr compounds, due to different valences, were also investigated using the same double-crystal X-ray spectrometer. The chemical effects were clearly observed, and the Kβ/Kα intensity ratio was found to be compound-dependent for Cr.

Em Portugal, existe uma ausência de formalização da ciência para assuntos políticos em que a procura de aconselhamento é, em grande medida, informal.

Many proteins naturally carry metal centers, with a large share of them being in the active sites of several enzymes. Paramagnetic effects are a powerful source of structural information and, therefore, if the native metal is paramagnetic, or it can be functionally substituted with a paramagnetic one, paramagnetic effects can be used to study the metal sites, as well as the overall structure of the protein. One notable example is cobalt(II) substitution for zinc(II) in carbonic anhydrase. In this manuscript we investigate the effects of sodium thiocyanate on the chemical environment of the metal ion of the human carbonic anhydrase II. The electron paramagnetic resonance (EPR) titration of the cobalt(II) protein with thiocyanate shows that the EPR spectrum changes from A-type to C-type on passing from 1:1 to 1:1000-fold ligand excess. This indicates the occurrence of a change in the electronic structure, which may reflect a sizable change in the metal coordination environment in turn caused by a modification of the frozen solvent glass. However, paramagnetic nuclear magnetic resonance (NMR) data indicate that the metal coordination cage remains unperturbed even in 1:1000-fold ligand excess. This result proves that the C-type EPR spectrum observed at large ligand concentration should be ascribed to the low temperature at which EPR measurements are performed, which impacts on the structure of the protein when it is destabilized by a high concentration of a chaotropic agent.

This paper presents a comprehensive study of the evidence for ancient tin mining at the Ervedosa mine (Vinhais, Portugal). The geological context of the site indicates a rich cassiterite (SnO2) deposit, which was subject to mining in the twentieth century. Some ancient mining and ore processing stone tools were recovered during the twentieth century mining operations, namely one hammer, one pounder, one flat anvil and five small tools used both as pounders and crushing anvils, evidencing prehistoric mining activities. XRF and SEM–EDS chemical analyses were performed on primary and secondary cassiterite samples from the mining site, demonstrating the abundance and chemical heterogeneity of the tin (Sn) ores. The stone tools can be ascribed to Bronze Age or, at the latest, Early Iron Age (2nd millennium to the first half of 1st millennium BCE) by comparison with similar tools from other Iberian and European archaeological contexts. High-resolution photogrammetric 3D models of the tools are made available in this study. The historical descriptions of the findings and the research made on the technical archives about the mine allowed correlating the tools to mining in a primary context, focused on rich quartz veins in granitic or greisen bedrock, rather than mining in a secondary context. XRF and SEM–EDS analyses performed on the stone material and on surface adherences support their identification as specific types of hard rocks, such as granite, amphibolite and quartzite, and allowed the detection of Sn-rich adherent particles, confirming their use for Sn-material processing. The potential relation between the cassiterite resources and the local later prehistoric (Bronze Age to Early Iron Age) settlement pattern is also discussed. The results raise awareness and provide relevant data about the existence of tin mining in primary contexts during later prehistoric times in the NW Iberian Peninsula.

In this work, we present K- and L- shell fluorescence yield values of the full isonuclear sequence of Fe ions, using a state-of-the-art multiconfiguration Dirac–Fock approach. These results may be of importance for spectral fitting and plasma modeling, both in laboratory and astrophysical studies, where Fe is an important benchmark element. The K-shell fluorescence yields were found to be very similar up to the removal of 14 electrons.

In this paper, we characterize the monoid of endomorphisms of the semigroup of all oriented full transformations of a finite chain, as well as the monoid of endomorphisms of the semigroup of all oriented partial transformations and the monoid of endomorphisms of the semigroup of all oriented partial permutations of a finite chain. Characterizations of the monoids of endomorphisms of the subsemigroups of all orientation-preserving transformations of the three semigroups aforementioned are also given. In addition, we compute the number of endomorphisms of each of these six semigroups.

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An incomplete, yet remarkably-sized dentated rostrum and associated partial cervical vertebrae of a pterosaur (ML 2554) were recently discovered from the Late Jurassic (Late Kimmeridgian-Early Tithonian) Lourinhã Formation of Praia do Caniçal, of central west Portugal. This specimen exhibits features such as a spatulated anterior expansion of the rostrum, robust comb-like dentition, and pronounced rims of the tooth alveoli, indicating gnathosaurine affinities. Based on its further unique tooth and dentary morphology, a new genus and species, \textit{Lusognathus almadrava} gen. et spec. nov., is proposed, making this the first named pterosaur species found within Portugal. The presence of this taxon adds yet another element to the fluvio-deltaic lagoonal environment that has been suggested as representative of the Lourinhã Formation in the Late Jurassic, further contributing to the diversity and distribution of gnathosaurines worldwide.

In this paper we consider the monoid DPC_n of all partial isometries of a n-cycle graph C_n. We show that DPC_n is the submonoid of the monoid of all oriented partial permutations on a n-chain whose elements are precisely all restrictions of a dihedral group of order 2n. Our main aim is to exhibit a presentation of DPC_n. We also describe Green's relations of DPC_n and calculate its cardinality and rank.

In this paper we consider the monoid DPSn of all partial isometries of a star graph Sn with n vertices. Our main objectives are to determine the rank and to exhibit a presentation of DPSn. We also describe Green’s relations of DPSn and calculate its cardinal.

In this paper we consider endomorphisms of a finite directed path from monoid generators perspective. Our main aim is to determine the rank of the monoid wEndP_n of all weak endomorphisms of a directed path with n vertices, which is a submonoid of the widely studied monoid O_n of all order-preserving transformations of a n-chain. Also, we describe the regular elements of wEndP_n and calculate its size and number of idempotents.

Following the new description of an oriented full transformation on a finite chain given recently by Higgins and Vernitsk,
in this short note we present a refinement of this description which is extendable to partial transformations and to injective partial transformations.

In this paper we consider the submonoids OPDI_n, MDI_n and ODI_n of the dihedral inverse monoid DI_n of all orientation-preserving, monotone and order-preserving transformations, respectively. Our goal is to exhibit presentations for each of these three monoids.

Sol-gel production of hybrid materials has, to some extent, revolutionised materials’ engineering and the way science and technology perceive the creation of new materials. Despite that, the method presents some limitations that are circumvented by radiation processing. Electron beam irradiation was used to promote synthesis of hybrid structures while using silanol-terminated PDMS, TEOS and TPOZ as precursors. Evaluation of the method’s performance was executed by gel fraction determination, WDXRF and FTIR-ATR. Results showed that, although there is some pre-irradiation reactivity between precursors, radiolysis induces scission on multiple sites of precursor’s structures, which induces hybrid network formation to a greater extent. Characterisation allowed determining electron beam irradiation to be effective in the creation of Si–O–Zr bonds, resulting in the production of a Class II hybrid material.